Control Calidad Componentes Pinturas Ambos01

TOMO IV.
01
CONTROL DE CALIDAD
DE LOS COMPONENTES
DE LAS PINTURAS
PFC. EUETIB
CONTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS
PROYECTO FINAL DE CARRERA
FABRICACIÓN DE UNA PINTURA
José Miguel Rando Cardalda
Rubén Rafael González Rivero
JUNIO 2005
PFC. EUETIB COTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS I
PROYECTO FINAL DE CARRERA. FABRICACIÓN DE UNA PINTURA
JUNIO 2005
4. TOMO IV. CONTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS.............Página
4.1. Introducción. 1
4.2. Determinaciones generales. 3
4.2.1. Densidad
4.2.2. Puntos de fusión y de solidificación
4.2.3. Temperaturas de ebullición y de destilación
4.2.4. Determinación del índice de refracción
4.2.5. Dosificado de las sustancias
4.2.5.1. Procedimientos de volumetría. Soluciones normales
4.2.5.2. Procedimientos de gravimetría. Análisis de una barita
4.3. Pigmentos. 19
4.3.1. Color básico
4.3.2. Poder colorante de los pigmentos coloreados
4.3.3. Tonos secundarios de los pigmentos coloreados
4.3.4. Poder colorante de los pigmentos blancos
4.3.5. Absorción de aceite
4.3.6. Peso específico
4.3.7. Dureza
4.3.8. Distribución del tamaño de las partículas
4.3.8.1. Método de estudio
4.3.8.2. Ejemplos prácticos de calculo teórico de densidades
4.3.9. Estabilidad
4.3.10. Opacidad
PFC. EUETIB COTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS II
JUNIO 2005
4.3.11. Determinación de la humedad y de la pérdida por calcinación
4.3.12. Valoración de un blanco de zinc
4.3.13. Análisis de un litopón
4.3.14. Determinaciones del hierro, del aluminio y del titano
4.3.15. Determinación del anhídrido carbónico
4.3.16. Determinación del cobre y del arsénico
4.3.17. Valoración del cromato de plomo y del verde de zinc
4.3.18. Coloración de perlas de bórax
4.3.19. Método Kappelmeier
4.3.20. Ensayo de los pigmentos negros y de las lacas
4.3.21. Especificaciones sobre pigmentos
4.3.21.1. Pigmentos blancos
4.3.21.2. Pigmentos amarillos, ocres o pardos
4.3.21.3. Pigmentos rojos
4.3.21.4. Pigmentos verdes
4.3.21.5. Pigmentos azules
4.3.21.6. Pigmentos negros
4.4. Formadores de película. 77
4.4.1. Color
4.4.2. Temperatura de reblandecimiento de sólidos
4.4.3. Peso por litro y densidad
4.4.4. Contenido total de no volátiles
4.4.5. Viscosidad de los líquidos

PFC. EUETIB COTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS III
JUNIO 2005
4.4.6. Determinación del grado de acidez
4.4.7. Determinación del índice de saponificación
4.4.8. Determinación del índice de yodo
4.4.9. Determinación del índice de Maumené
4.4.10. Determinación de los ácidos grasos
4.4.11. Determinación de los bromocompuestos
4.4.12. Determinación de la glicerina
4.4.13. Comportamiento con el ácido nitroso
4.4.14. Investigación de aceites minerales
4.4.15. Diferenciación de los aceites animales y vegetales
4.4.16. Determinación del poder secante
4.4.17. Índice de dienos
4.4.18. Índice de rodán
4.4.19. Punto de precipitación
4.4.20. Especificaciones de formadores de película
4.4.20.1. Barnices
4.4.20.2. Aceites, diluentes, aparejos y secativos
4.5. Disolventes. 121
4.5.1. Color
4.5.2. Olor
4.5.4. Toxicidad
4.5.5. Intervalo de destilación
4.5.6. Velocidad de evaporación

PFC. EUETIB COTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS IV
JUNIO 2005
4.5.7. Punto de inflamación
4.5.8. Poder de disolución
4.5.9. Efecto sobre la viscosidad del vehículo
4.11. Bibliografía. 128
4.12. Normativa ASTM. 129

PFC. EUETIB CONTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS 1
JUNIO 2005
4. CONTROL CALIDAD DE LOS COMPONENTES
DE LAS PINTURAS
4.1. Introducción.
Casi todos los métodos de ensayo se pueden usar para la evaluación de

nuevas materias primas o fuentes de abastecimiento. En los ensayos normales
de control de los materiales de las partidas que llegan, se emplea un número
mucho más restringido de métodos de ensayo, para los cuales se han
establecido normas. Muchas de estas pruebas consisten únicamente en
comparaciones con patrones conocidos. Estas comprenden todas las
características de funcionamiento de las materias primas en la medida que
ellas pueden afectar a las propiedades de los recubrimientos de superficies.
Pocas veces es necesario un análisis químico real de las materias primas

utilizadas por la industria de la pintura, para el control de calidad de los envíos
que llegan, o para la evaluación de nuevas fuentes de abastecimiento, aunque
las determinaciones del contenido de humedad se realicen regularmente.
Normalmente se pueden detectar grandes cantidades de adulterantes por sus
efectos sobre las propiedades físicas. Muchas materias primas contienen
porcentajes pequeños, y hasta grandes porcentajes de materias extrañas
añadidas por sus fabricantes para mejorar sus propiedades, y no pueden
considerarse como adulterantes. En consecuencia, los análisis químicos no
dan una información suficiente como para justificar lo costoso de su realización.
Muchas de las propiedades de las materias primas se pueden determinar

únicamente al incorporarlas realmente a los recubrimientos determinados de
superficies y observando sus efectos sobre las características funcionales. Por
ejemplo, las propiedades de los pigmentos tales como cubrimiento, brillo,
fluidez, estabilidad y su efecto sobre la viscosidad del vehículo se deben
determinar de esta manera.
JUNIO 2005
Los ensayos de que se dispone, son el resultado de muchos años de trabajo de

organizaciones tales como la Federation of Societies for Paint Technology
(FSPT), la Technical Division of the National Paint, Varnish and Lacquer
Association (NPVLA), la American Society for Testing Materials (ASTM), la
National Bureau of Standards (NBS), otros organismos oficiales y los
laboratorios de muchas compañías de la industria de la pintura. Gracias al
esfuerzo de estas organizaciones, los ensayos existentes se mejoran
constantemente y se añaden otros nuevos a la larga lista de métodos útiles.
La mayoría de estas pruebas se describen con detalle en publicaciones tales

como Standards and Methods of Test, FSPT; Standards on Paint, Varnish,
Lacquers and Related Products, ASTM; Paint, Lacquer and Related Materials;
Methods of Inspection, Sampling and Testing, Especificación Federal
TT-P-141b. En los casos en que existe más de una prueba para una misma
propiedad, se da preferencia a los ensayos FSPT, seguidos de los ASTM y de
las pruebas Federales correspondientes. Muchas de las pruebas FSPT y ASTM
son idénticas, en cuyo caso se dan ambos resultados. Algunos ensayos para
los cuales no hay ningún procedimiento normalizado se describen para
información general.
También se incluyen pruebas sobre pigmentos, formadores de película y

disolventes, puesto que las propiedades de los plastificantes, secantes y
aditivos, se deben determinar en la mayoría de los casos en recubrimientos de
superficies reales, y se deben probar mediante algunos diversos
procedimientos.
JUNIO 2005
4.2. Determinaciones generales.
4.2.1. Densidad
La densidad se determina generalmente por el método del picnómetro para los

cuerpos sólidos y por el método de MOHR-WESTPHAL para los líquidos.
Para determinar una densidad con el método del picnómetro (llamándose así a
un pequeño frasco con tapón tubulado que tiene marcado un aforo), se llena de
agua dicho matracito hasta la señal de enrase, se seca cuidadosamente
anotando la temperatura y se pesa en la balanza de precisión. Sea este peso
P. Luego se pesan uno o varios trocitos del cuerpo, o del polvo cuya densidad
se desea obtener: sea P’ este nuevo peso. Destapado el picnómetro, se
introduce dentro este peso P’, recogiendo el agua que sobre con un papel de
filtro que la absorba, se coloca bajo una campana de vacío a fin de que no
queden burbujas de aire adheridas a los trozos, durante el tiempo necesario; se
tapa y enrasa nuevamente cuidando que esté a igual temperatura que antes, y
se pesa otra vez. Sea este nuevo peso P”.
La densidad de un cuerpo es igual a su peso dividido por su volumen

(rigurosamente, esto es el peso específico, que se expresa por la misma cifra
que la densidad y en la práctica se llama así), referido a los mismos valores del
agua. Por tanto:
Siendo d la densidad del agua a la temperatura a que se opere. Esta densidad

debería ser 1, pero como en realidad sólo tiene este valor a 4°C, hay que tener
en cuenta tal corrección. El cuerpo acostumbra tomarse a 15°C. No obstante,
las densidades se dan muchas veces con relación al agua a 15°C, evitando
correcciones. El empleo del factor d, que vale:
JUNIO 2005
No excluye el pesar el cuerpo a 15° C para tener la densidad a esta

temperatura, referida al agua a 4° C, o sea D, 15 ºC/4 ºC; para tenerla con
relación al agua a 15° C, o sea D, 15°C/15 ºC, por cálculo, bastará multiplicar
por 0,9991; es decir:
Inversamente,
Las cantidades pesadas de cuerpo varían alrededor de 2 gr, aunque según las
necesidades se puede operar con mayor o menor cantidad. Para la cifra
indicada será normal el empleo de un picnómetro de 25 ml de capacidad. El
peso P’ se puede determinar vaciando y secando cuidadosamente el
picnómetro, pesándolo vacío y con una porción del producto dentro. El
aumento de peso será el del cuerpo. El peso P se habrá determinado
primeramente y el P” se determinará llenándolo de nuevo. En estas
manipulaciones hay que vigilar cuidadosamente que no varíen las temperaturas
al hacer las pesadas.
Para hallar la densidad de los pigmentos extraídos de una pintura o de un

barniz mediante un disolvente, a causa de su dificultad en mojarse por el agua,
se suele emplear como líquido para la determinación el éter sulfúrico, o
cualquier otro líquido a propósito. En este caso el factor se substituye por la
densidad de dicho líquido.
Con el fin de facilitar el trabajo en relación a la exigencia de hacer las pesadas

a la misma temperatura, hay modelos de picnómetros que llevan en una
tubuladura auxiliar un termómetro.
La determinación de densidades en los líquidos con la balanza de MOHR-

WESTPHAL requiere menos operaciones que el método anterior. La balanza
JUNIO 2005
tiene dos brazos desiguales, el largo dividido en diez partes por unas muescas
y el corto constituido por un contrapeso terminado en un índice, que señala el
equilibrio. El conjunto va sostenido por una columna extensible y un pie con
tornillos nivelantes, y del extremo del brazo largo, coincidiendo con la división
diez, cuelga un cilindro de vidrio tarado que actúa de inmersor; siendo
simultáneamente un termómetro. Las pesas son unos jinetillos de los que cada
uno vale la décima parte del anterior, y existe otra, que pesa como la mayor de
ellas, que sirve para equilibrar la balanza. La cruz puede ascender y descender
dentro de la columna que la sostiene, y fijarse con un tornillo, y el pie puede
nivelarse cómodamente.
El líquido cuya densidad quiere determinarse, se coloca en una probeta, se fija

la cruz a altura conveniente y se introduce el inmersor de vidrio dentro del
líquido, de modo que quede en su seno sin tocar a las paredes del recipiente;
primeramente se habrá puesto la balanza en equilibrio, que se alterará. Se
pone una pieza mayor en el gancho de donde cuelga el inmersor: si el líquido
fuera de mayor densidad que el agua, la admitiría; si fuese de menor densidad,
no ocurriría así. Se emplea luego la segunda pieza mayor, colgándola del
mismo sitio: si la admite se deja ahí y si no la tolera se prueba en cada una de
las diez muescas, en la que indicará centésimas, después la tercera, que
señalará milésimas y finalmente la cuarta, que designará décimas de milésima.
Las piezas se pueden colgar una de la otra si concurriesen en la misma
división. Si se supone que un líquido ha requerido para llevar la balanza al
equilibrio:
La pérdida de peso del inmersor en el líquido será, siendo P el peso de las

piezas mayores:
JUNIO 2005
Ahora bien, por construcción se ha hecho en el aparato P igual a la pérdida de

peso del inmersor en el agua, luego la densidad será:
Si no se hubiese podido poner una pieza mayor en el gancho, el resultado sería

D = 0,3517. Las balanzas de MOHR-WESTPHAL dan generalmente las
densidades referidas al agua a 15° C, debiendo ponerse el líquido en examen a
dicha temperatura, y hacer luego las oportunas correcciones indicadas para el
picnómetro, si se desean referir a 4° C de temperatura del agua. El cuarto
decimal no acostumbra a ser muy exacto con este aparato.
De quererla precisar, o de no tener la suficiente cantidad de muestra para

emplear el método de MOHR, hay que emplear un picnómetro para líquidos, lo
que no excluye trabajar con serias precauciones de precisión. Buscando de
este modo la densidad 15 ºC/15 ºC:
Si se desea en otra forma, téngase presente lo dicho en el caso del picnómetro

para sólidos.
4.2.2. Puntos de fusión y de solidificación
El punto de fusión se determina generalmente por el método de BUNSEN, o del

tubo capilar. Estos tubos, que se prepara el mismo químico, deben tener unos
cuatro centímetros de longitud y alrededor de un milímetro y medio de
diámetro, cerrados al fuego por un extremo.
La sustancia seca y pulverizada se introduce en uno de ellos, ayudando con

una ligera trepidación del tubo, en cantidad suficiente; y el tubito se coloca al
lado del depósito de un termómetro, sujeto con una abrazadera de caucho. El
JUNIO 2005
conjunto se introduce en un matraz de cuello largo, lleno hasta su mitad con

ácido sulfúrico o aceite de vaselina, que sirve de baño de calefacción, y que no
debe penetrar dentro del tubito.
Un primer ensayo da idea de la temperatura de fusión aproximada, y luego

operando con cuidado al llegar cerca de aquélla, calentando con lentitud, se lee
el termómetro en el momento en que se torna líquida la sustancia.
En el estudio de las grasas se usa mucho el sistema llamado de punto de gota:

a un porta objetos de microscopio se adhieren las substancias que van a
estudiarse, en porciones del tamaño de una lenteja y en cantidad de cuatro de
modo corriente, según los vértices de un cuadrado cuyo centro se hace
coincidir con el bulbo del termómetro, al que se sujeta el porta objetos con dos
abrazaderas de caucho. Todo esto se coloca dentro de un tubo de ensayo
suficientemente ancho y vacío, que a su vez se introduce en un matraz de
cuello ancho y corto que contiene el baño de calefacción. El conjunto se
sostiene convenientemente y se calienta; al fundir las substancias, se ve la
gota que se escurre del sitio primitivo que ocupaban aquéllas.
Con este sistema se pueden comparar diferentes cuerpos a una temperatura

determinada en cuanto a su comportamiento respecto a la fusión. En el caso de
resinas, es conveniente seguir los dos métodos, pues muchas de aquéllas no
tienen un punto de fusión franco, sino que presentan primero el llamado punto
de reblandecimiento, que se aprecia fácilmente con el punto de gota por la
deformación que presenta la lenteja al llegar su temperatura a dicho punto de
reblandecimiento. En cambio, el punto de transparencia, anotado en el
momento de su aparición, y que denota la fusión propiamente dicha, se
apreciará en este caso con mayor exactitud por el procedimiento del tubo
capilar.
Se utiliza también con muy buenos resultados el bloque de MAQUENNE, en los

estudios propios de la industria de pinturas, y barnices relacionados con la
fusión. Consiste en un semicilindro metálico con una cara plana, que tiene unos
pocillos en parejas, y un termómetro que corre por su interior, de modo que su
JUNIO 2005
bulbo puede ponerse en el centro entre cada dos pocillos. El aparato lleva un
soporte que permite calentar la parte cilíndrica del bloque.
Puestas las substancias en los pocillos, se siguen claramente con la vista las
incidencias de la fusión, cuya temperatura se lee en el termómetro colocado en
posición conveniente. Las mediciones no son de precisión.
El punto de solidificación es difícil de determinar a causa de los fenómenos

físicos que le acompañan. No obstante a veces tiene interés. En este caso, el
mejor método es poner unos 20 gr. de sustancia en un tubo de ensayo,
fundirlos e introducir el bulbo de un termómetro. Luego se pone a enfriar dentro
de una probeta suficientemente ancha, sostenida por un tapón de corcho,
ancho y delgado, a cuyo través pasa el tubo de ensayo y que obtura la probeta.
Se anota la temperatura en las distintas fases que pueden ocurrir: si se trata de

un ácido graso, la primera aparición de cristales, la formación de los mismos en
masa; después de unos momentos de descenso, la temperatura vuelve en
muchos casos a aumentar.
Se agita periódicamente con el termómetro, cuyo bulbo estará completamente

sumergido en la sustancia. Las temperaturas leídas se anotan, construyendo
una curva con varios puntos, y la temperatura más elevada constituye
generalmente la temperatura de solidificación.
4.2.3. Temperaturas de ebullición y de destilación
Una característica de la mayor importancia está constituida por la expresión de

la temperatura de ebullición de un cuerpo líquido. Cuando el cuerpo no es puro
o está formado por mezclas, se utilizan las temperaturas de destilación, que
detallan las cantidades de destilado en porcentajes que pasan a cada
temperatura indicada.
Para las determinaciones de temperaturas de destilación se emplean matraces

de destilación fraccionada, es decir, con tubuladura lateral, a la que se acopla
un refrigerante condensador, recogiéndose el destilado en una probeta
graduada suficientemente exacta. En el matraz se pone una cantidad
JUNIO 2005
determinada de líquido y generalmente algunos trozos de vidrio o arena silícea

limpia para conseguir una ebullición tranquila.
El bulbo del termómetro se pondrá delante de la salida de la tubuladura,

procurando que quede además gran parte de la columna termométrica dentro
del cuello del matraz. Las cantidades con que suele trabajarse oscilan de 100 a
200 ml. En muchos casos, como petróleos, disolventes derivados del alquitrán
y otros, los aparatos tienen dimensiones convenidas.
Como manantiales de calor para las destilaciones, se adoptará el baño maría

para los líquidos que hiervan a baja temperatura. A temperaturas más elevadas
se puede emplear el baño de aire, y a mayores se emplean baños de aceite o
de parafina.
El punto de ebullición se determina por el método de SIWOLOBOFF; un tubito

de unos 5 cm de longitud y unos 3 mm de diámetro, se adapta a un termómetro
y a un baño como para la determinación de los puntos de fusión. El líquido se
introduce en dicho tubito hasta la altura que tenga el bulbo del termómetro, y
dentro del líquido se introduce un tubo capilar con un punto cerrado cerca del
JUNIO 2005
final, de modo que forme una pequeña campanita que servirá de manantial de
burbujas de aire para conseguir una ebullición regular. Así que se consiga ésta,
se lee la temperatura.
Se hacen dos o tres determinaciones y se toma el promedio. En

determinaciones muy precisas de puntos de destilación y ebullición, debería
tenerse en cuenta la presión atmosférica. En general, por cada 5 mm de
diferencia de altura barométrica, varía el punto de ebullición en unas 2 décimas
de grado centígrado.
4.2.4. Determinación del índice de refracción
Este valor físico con referencia al aire en una sustancia, constituye otra de las
constantes que se emplean para contribuir a la caracterización de muchos
materiales que tienen importancia en la tecnología de los barnices y pinturas.
Se emplea generalmente para su determinación el refractrómetro de ABBE,

que consiste en dos prismas ópticos entre cuyas caras hipotenusa se puede
introducir una cantidad de sustancia, pues se abren por una charnela.
Un anteojo permite recibir los rayos de luz que manda un espejo a través de los
prismas y que permite medir los ángulos sobre un limbo graduado. Los prismas
van encerrados en una montura metálica.
Puesto el aparato de manera que la luz reflejada en el espejo ilumine bien, se

introduce el líquido entre los dos prismas. Mirando por el anteojo y girando el
sistema óptico, y combinando un compensador que lleva el aparato a fin de
quitar las irisaciones que aparecen, se consigue el campo dividido en dos
mitades con una línea de separación bien definida, que debe coincidir con un
retículo que lleva el anteojo.
Entonces se lee en el limbo graduado directamente el valor del índice de

refracción, pues la escala está adaptada no a la lectura de ángulos, sino que
llevando las operaciones calculatorias ya resueltas (el valor del índice de
refracción depende del ángulo que debe leerse) da el valor buscado sin más
JUNIO 2005
preocupaciones. Operando debidamente se pueden apreciar hasta cuatro

decimales.
Como el índice de refracción depende de la temperatura, hay montado en el

aparato un dispositivo que permite hacer circular agua caliente alrededor de los
prismas ópticos que contienen la sustancia sobre que se opera. Generalmente
la determinación se hace a 15 ºC, pero en otros casos hay que operar a
temperaturas más altas, por requerirlo la naturaleza de la sustancia, como los
sebos, cuyo índice de refracción se da a 40° C. De un modo general, por cada
grado de temperatura el índice de refracción disminuye en 0,0004. Después de
cada determinación hay que limpiar cuidadosamente el aparato.
El índice de refracción es la relación que existe entre el seno del ángulo de

incidencia y el seno del ángulo de refracción. Así, pues, varía con la luz que se
emplee. Con el refractómetro de ABBE se usa luz blanca, natural o artificial.
Para determinaciones científicas delicadas, se emplea el refractómetro de
PULFRICH, que requiere luz monocromática.
Corrientemente el refractómetro de ABBE lleva una placa auxiliar o placa de

verificación, que puede ponerse fácilmente en el aparato y cuyo índice de
refracción, con cuatro decimales, va escrito en ella. Esto permite comprobar la
exactitud del instrumento cuando convenga.
4.2.5. Dosificado de las sustancias
Los procedimientos de Análisis químico que permiten el dosificado de

substancias mediante las reacciones llevadas a cabo con soluciones que
contienen uno de los reactivos en cantidad conocida, son extensamente
usados en la práctica industrial. Mientras en los métodos gravimétricos se pesa
una sustancia obtenida por precipitación con un reactivo en exceso, en los
volumétricos la cantidad de reactivo usada es la exactamente necesaria; se
requiere, pues, en general el empleo de un indicador que señale el fin de la
operación.
JUNIO 2005
La pesada es también indispensable en estos métodos, puesto que debe

operarse sobre una cantidad determinada del producto a investigar, y las
soluciones empleadas deben contener una cantidad fijada de reactivo: pero
este reactivo se mide en volúmenes, y una vez preparado puede servir para
varios ensayos en cada uno de los cuales se consuma una parte alícuota de la
cantidad preparada.
4.2.5.1. Procedimientos de volumetría. Soluciones normales
Los aparatos usados son las buretas y las pipetas, exactamente calibradas;
asimismo se emplean los matraces aforados. Todas las vasijas graduadas lo
estarán en las mismas condiciones de temperatura; se acostumbra a llamar
graduación normal la verificada a 15°C de temperatura en la vasija, llenada con
agua a 4° C. Como ello no es posible, se opera por cálculo, y los aforos así
obtenidos corresponden a la definición del litro, que es el volumen ocupado por
1 kg de agua a 4° C, en cuyo momento su densidad es igual a 1.
Las soluciones utilizadas pueden ser empíricas y normales. Las empíricas

contienen disuelto en 1 litro de disolución una cantidad determinada del
reactivo, según el fin que se persigue en su empleo; y las normales contienen
en 1 litro de disolución una cantidad de reactivo que de un modo directo o
indirecto se corresponde con un átomo gramo de hidrógeno, llamándose a esta
cantidad un equivalente gramo de la sustancia.
Así, pues, la solución normal de ácido sulfúrico contendrá 1/2 mol de éste, ya
que con tiene 2 H, y la solución normal de sosa cáustica contendrá 1 mol de
ésta, puesto que la reacción entre los dos compuestos será:
en la que se ve que 1 átomo de Na substituye a 1 átomo de H, o sea que se

equivalen. En los métodos volumétricos por oxidación con el permanganato
potásico:
JUNIO 2005
cada 2 moles de permanganato ocasionan el desprendimiento de 5 átomos

gramo de oxígeno, que equivaliendo a 10 de H, hacen que cada mol de
permanganato potásico se equivalga con 5 átomos gramo de H; así pues la
disolución normal de dicho permanganato deberá contener en 1 litro de
disolución la 1/5 parte de 1 mol.
Las soluciones normales reaccionan exactamente con volúmenes iguales de

ellas, de manera que 1 ml de ácido sulfúrico normal requerirá para una
neutralización completa 1 ml de sosa cáustica normal. En estas condiciones se
podrá proceder a valorar una cantidad de sosa cáustica desconocida, con un
número de centímetros cúbicos de ácido sulfúrico conocidos, gastados en una
neutralización cuyo final señalará un indicador adecuado.
Solución normal de ClH. En 1000 ml de solución debe haber 1 mol de

HCl=36,46 gr. Se pesan 120 gr, o se miden 100 ml en un matraz con dos
aforos (uno a 1000 ml otro a 1100 ml hasta el segundo aforo. Se pesan
exactamente en la balanza de precisión 2 gr de bicarbonato potásico puro,
tomados de una cantidad del mismo que previamente se ha disuelto en 4,5
veces su peso de agua, filtrado y precipitado con 2 veces su peso de alcohol de
90°; los cristales separados se secan en el desecador con ácido sulfúrico, y de
esta porción se pesan los 2 gr.
Se disuelve el bicarbonato en un Erlenmeyer con 20 ml de agua, se añaden 3

gotas de disolución de anaranjado de metilo al 0,1 % en agua destilada y
después con una bureta se añade el ácido clorhídrico preparado, hasta viraje
rojo. Para tener un punto de referencia exacta aconseja KOLTHOFF, como
coloración final a obtener, la que tenga otro Erlenmeyer con 40 ml de agua
destilada y 3 gotas del indicador. Si se quiere mayor precisión se añaden
también 1,5 gr de cloruro potásico puro y neutro. Antes de llegar a la coloración
final, hay que hervir el líquido unos minutos a fin de expulsar el ácido
carbónico.
JUNIO 2005
Las últimas adiciones de ácido se harán con sumo cuidado, de gota en gota,
muy lentamente y agitando bien. La reacción que tiene lugar es:
por tanto, 2 gr de CO3HK necesitan
de ClH para quedar neutralizados, apareciendo el viraje rojo en el líquido

amarillo. Pero 0,7284 gr de ClH están contenidos en
de la solución normal del ácido; de modo que si para el viraje se ha gastado

esta cantidad, la solución está bien: si se ha gastado menos, la solución es
demasiado concentrada, y si se ha gastado más, es demasiado diluida.
En el primer caso, y suponiendo que se han gastado como promedio de dos

ensayos, 19,5 ml: a 19,5 ml de la solución preparada hay que añadir 19,98-
19,50=0,48 ml de agua para que sea normal; a 1000 habrá que añadir
Como se pueden medir fácilmente los 1000 ml, pues se han preparado 1100ml,
se vacía cuidadosamente con una pipeta el matraz hasta el enrase 1000 ml y
entonces con una bureta se añaden 24,6 ml exactamente medidos,
procediendo luego a comprobar la operación con un nuevo ensayo.
En el segundo caso, la manipulación sería más engorrosa, pero como se ha

preparado la disolución intencionadamente algo más concentrada, puede
quedar excluido en la práctica. Si no se hubiese querido modificar la solución, o
no se hubiese podido, se calcula el factor de ella, diciendo: 19,5:19,98=1: x, de
JUNIO 2005
donde x=1,0247 y se tendría que tener la precaución de multiplicar siempre los

ml gastados, antes de proceder a cualquier cálculo, por dicho factor, a cuyo fin
se apunta en la etiqueta del frasco que contiene la solución.
Si en lugar de gastar menos ácido del requerido se hubiese gastado más, o sea
el segundo caso citado, el factor de la solución valdría, suponiendo que se
hubiesen gastado 20,4 ml 20,4: 19,98 = 1: x, de donde x 0,9794, y se debería
multiplicar por dicho valor todos los consumos de ácido efectuados.
Solución de ácido sulfúrico. La normal contendrá ½ mol de ácido por litro o sea
49,04 gr y la decinormal la vigésima parte de un mol, o sea 4,9 gr.
Solución de sosa cáustica decinormal. Debe contener 4 gr de NaOH por litro.
Solución de potasa cáustica decinornial. Debe contener 5,6 gr de KOH por litro.
Solución normal de tiosulfato sódico. Se emplea para determinar el yodo

puesto en libertad en algunas valoraciones. La reacción es:
de modo que 1 molécula gramo de tiosulfato reacciona con un átomo gramo de

1 que equivale a un átomo gramo de H. Por tanto la solución normal contendrá
por litro un peso molecular en gramos de tiosuifato; como la sal cristaliza con 5
moléculas de agua, este peso será:
La solución normal contendrá esta cantidad y la decinormal 24,822 gr.
4.2.5.2. Procedimientos de gravimetría. Análisis de una barita
Los métodos ponderales tienen su mayor aplicación en el examen de los

pigmentos empleados en la confección de las pinturas. Las pesadas se harán
en balanzas de precisión sensibles a la décima de miligramo y las disoluciones
y precipitaciones se llevan a cabo en vasos de precipitados; las filtraciones y
loción de éstos exigen la debida atención y cuidados para no tener pérdidas de
JUNIO 2005
materias; asimismo la desecación y la calcinación. Citase un dosificado de

sulfato bárico en una barita, a título documental.
Dada la insolubilidad de esta sustancia en los ácidos, es preciso disgregarla en

un en sol de platino. Para ello se pesa exactamente el crisol, se echa dentro
cerca de 1/2 gramo del producto y por nueva pesada se sabe la cantidad
exacta sobre que se opera; se añaden entonces unos 4 gr de mezcla en partes
iguales de carbonatos sódico y potásico anhidros y secos, y se calienta el crisol
progresivamente, sin que salten proyecciones. La masa se mantiene fundida al
rojo unos 20 minutos.
Para evitar que el producto de la fusión quede adherido al crisol, con unas
pinzas se mueve de modo que la masa forme una costra uniforme en las
paredes, dejando luego enfriar sobre una plancha de hierro. Se introduce en un
vaso con agua y calentando nuevamente se consigue la disolución completa y
se puede sacar el crisol limpio con las pinzas, enjuagándolo con el chorro del
frasco lavador y cayendo las aguas de loción dentro del vaso. El contenido de
éste queda compuesto por sulfatos sódico y potásico disueltos y carbonato
bárico insoluble. Filtrando, quedan los dos primeros en el líquido y el carbonato
bárico sobre el filtro, lavándolo cuidadosamente a fin de que no queden
porciones de sulfatos impregnando su masa.
Determinación del bario. Se disuelve íntegramente el precipitado de carbonato

bárico en ácido clorhídrico diluido y se precipita al estado de sulfato bárico
insoluble, con ácido sulfúrico diluido, en caliente.
Determinación del SO42- Los líquidos filtrados y de loción se acidulan con ácido
clorhídrico y se precipita el SO42-con disolución de cloruro bárico al estado de
sulfato bárico insoluble, con las precauciones recomendadas por el análisis
químico.
Las precipitaciones deben hacerse, tal como se acaba de decir, con

determinadas precauciones propias de cada caso. Así, en los dos casos
anteriores, que en realidad son el mismo, es preciso operar en caliente, cerca
del punto de ebullición, y añadir los reactivos también calientes. Ocurre si no
JUNIO 2005
que el precipitado es tan tenue, que atraviesa el papel de filtro, con la

consiguiente pérdida de material que falsearía completamente el análisis.
El precipitado, recogido en un filtro, debe lavarse cuidadosamente con el frasco

lavador a fin de eliminar las impurezas solubles que puedan quedar retenidas
en él, y en este caso procedentes de las aguas madres, pudiéndose conocer
que está bien lavado cuando añadiendo solución de nitrato de plata a las aguas
de loción, éstas no den enturbiamiento.
La calcinación se verifica en un crisol de porcelana, introduciendo en él el filtro

lleno del precipitado, y húmedo. Esto es posible en este caso, pero
generalmente hay que incinerar primeramente el filtro mediante una espiral de
platino y luego añadir sus cenizas al crisol con el precipitado. Debe tomarse
esta precaución a fin de evitar reacciones entre el carbón procedente de
quemar el filtro y el precipitado, que falsearían los resultados.
En los métodos gravimétricos, los cálculos se establecen mediante las

respectivas reacciones y los pesos moleculares de los componentes:
de donde,
Valor que se llama factor de transformación del sulfato bárico en bario. El peso
hallado de sulfato bárico al pesar el crisol, multiplicado por este factor, dará la
cantidad de bario contenida en la cantidad de sustancia de que procede el
sulfato bárico que hay en dicho crisol. Entonces se reduce a 100 mediante la
proporción:
Cantidad de muestra: cantidad de bario = 100: x. x = % de Ba.

JUNIO 2005
Este valor no interesa, puesto que lo que se desea saber es la cantidad de

sulfato bárico contenida en la barita examinada. Para ello, se calcula la
cantidad que corresponde al Ba hallado:
Lo que dará la cantidad de sulfato bárico en 100 de barita. La diferencia serán

sustancias extrañas.
El compuesto insoluble pesado es el mismo (aunque ahora puro) de que se

partió: en efecto, se buscaba sulfato de bario y se ha pesado sulfato de bario;
lo que no ocurre a menudo, pues generalmente el cuerpo hallado contiene el
elemento químico común en distinta combinación del que se busca. En
realidad, en el caso expuesto, los cálculos hechos pueden simplificarse.
JUNIO 2005
4.3. Pigmentos.
Las características funcionales de los pigmentos en relación con las

propiedades, se pueden determinar únicamente mediante pruebas realizadas
en los recubrimientos de superficies a los que han sido incorporados.
4.3.1. Color básico
Véase FSPT At-2-32 o ASTM D387- 52T, secciones 1-5 Color básico y poder
colorante de los pigmentos coloreados.
Para medir el color de un pigmento, uno de los procedimientos es comprobar

su color básico o dominante amasando o dispersando el pigmento con el barniz
litográfico transparente número 2. El color básico de la muestra, que es el color
de la luz reflejada desde la superficie de la pasta oleosa, se compara con el
color básico de la pasta patrón yuxtapuestas sobre un panel de vidrio
transparente. Algunos de los términos más corrientes utilizados para describir
las diferencias entre la muestra y el color son lechoso, más claro, más sucio,
más intenso, más limpio, más rojizo, más amarillento, etc. El amasado del
pigmento se puede hacer a mano sobre una placa de pulimentar de cristal
esmerilado, o sobre una trituradora automática Hoover que es un sistema
mecánico de molienda. Sin embargo, ambos requieren un pesaje exacto del
pigmento y aceite, una operación de amasado constante y uniforme y una
fuente de luz patrón para la observación de las pastas. La cantidad de
pigmento y aceite utilizados depende de la absorción de aceite del pigmento.
4.3.2. Poder colorante de los pigmentos coloreados
Véase FSPT At 2-32 o ASTM D387-52T, sección 6, Color básico y poder

Los ensayos del poder colorante determinan la capacidad de un pigmento para

colorear una cantidad dada de blanco patrón, bien en seco o bien como pasta
dispersada en algún líquido. El pigmento blanco puede ser óxido de cinc o
bióxido de titanio en aceite. En este ensayo, los pesos conocidos de las pastas
obtenidas a partir de la muestra del pigmento y del patrón de referencia, se
JUNIO 2005
mezclan cada uno en una amasadora con un peso conocido de la pasta blanca.
Se suele utilizar una muestra de la misma pasta preparada para la prueba de
tono básico. Las intensidades de color de las mezclas se comparan por
yuxtaposición sobre un panel de vidrio transparente. Cuanto más intenso es el
color, mayor es el poder cubriente de coloración del pigmento.
Si el poder colorante del pigmento y del patrón no son iguales, se mezcla con la
pasta blanca una cantidad más pequeña del pigmento más fuerte (patrón o
muestra), hasta que los colores igualen en intensidad. El poder colorante de la
muestra se calcula hallando la relación del peso de la pasta patrón y el de la
pasta de la muestra y multiplicando por cien para obtener el resultado en
porcentajes.
Se entiende por poder colorante de un pigmento la intensidad con que da su

propio color a un pigmento blanco, tomando estas relaciones en peso. Para
comparar el poder colorante de dos muestras de un pigmento, o de dos
distintos pigmentos de dolor semejante o distinto, se pesa una cantidad igual
de cada uno, del orden al menos de 1 gr, se colocan en dos cápsulas de
porcelana iguales, se añade a cada una la misma cantidad pesada de 2 gr o3
de blanco de zinc (o el color blanco que se prefiera), y añadiendo aceite de
linaza con una bureta se empastan con una varilla de vidrio terminada con
pequeña espátula. Luego se examina el resultado obtenido, y se sacan las
consecuencias, en general por examen a simple vista y a criterio del
observador; de desear más exactitud, habría que proceder midiendo la
intensidad colorante lograda. (fotómetro gradual de PULFRICH).
Las cantidades a mezclar de pigmento y blanco, estarán relacionadas con el fin

perseguido en la determinación, siendo ínfimas para el negro y el azul, de los
que se pesarán nada más que unos decígramos, o aún centígramos.
Cuando se quiere un valor del poder colorante que pueda compararse con
otros obtenidos en las mismas condiciones, será preciso que el tono buscado
en la mezcla sea un término fijo y definido. Para que los valores sean además
JUNIO 2005
comparables, es necesario que las densidades de los pigmentos estudiados

sean sensiblemente iguales.
En algunos casos el poder colorante se hallará con mejor éxito procediendo

inversamente de como se ha descrito, mezclando al pigmento a estudiar un
pigmento negro o azul, como el azul de ultramar, hasta llegar al tono deseado.
Finalmente, para lograr resultados ciertos, aún será necesario que la cantidad
de aceite empleada en las muestras sea la misma, y que la amalgamación
entre éste y los pigmentos sea efectuada en buenas condiciones de
empastado.
Los valores obtenidos se-expresarán numéricamente de la siguiente manera:

Se da el valor 100 al tono buscado como término de comparación; este tono ha
sido alcanzado en la preparación de una muestra con 2 gr de blanco de zinc, y
0,5 gr del pigmento en examen, se han necesitado 0,3 gr para otra muestra,
correspondiente a un segundo pigmento
Se tiene:
puesto que el poder colorante del pigmento varía directamente con el peso de
blanco, o sea que cuanta mayor cantidad de este entra en la mezcla, mas
elevado es el poder colorante del pigmento. En el primer caso, el contenido en
blanco es del 80 % y en el segundo del 86 %.
4.3.3. Tonos secundarios de los pigmentos coloreados
Véase FSPT At 2-32 o ASTM D387-52T, sección 6, Color básico y poder

Este ensayo del poder colorante puede ser útil en la determinación del matiz o
tono secundario de los pigmentos. El color secundario es importante si el
JUNIO 2005
pigmento se va a usar para la coloración de otros pigmentos, como el blanco

en los tonos pastel. Una partida de pigmento puede ser satisfactoria en su tono
fundamental, pero puede estar fuera de tolerancia en el matiz o tono
secundario. Los pigmentos de tipos químicos diferentes pueden ser bastante
similares en tonos fundamentales, pero mostrarán amplias diferencias en los
tonos secundarios y en intensidad.
4.3.4. Poder colorante de los pigmentos blancos
Véase FSPT At-1-32. o ASTM D332-36, Poder colorante de los pigmentos

blancos.
El procedimiento para la medida del poder colorante de los pigmentos blancos

es similar al usado para medir el poder colorante de los pigmentos coloreados,
excepto que el negro de humo o el azul ultramar se usa como pasta patrón. En
este caso nos puede interesar el poder colorante de los pigmentos blancos,
tales como plomo blanco, óxido de cinc, y bióxido de titanio.
Se añade un peso determinado del material colorante a dos gramos del

pigmento blanco patrón de referencia, y la mezcla se amasa cuidadosamente.
Con cada muestra se fricciona cien veces sobre una placa de pulimentar de
cristal esmerilado o en una amasadora automática Hoover. La pasta
homogénea, obtenida mediante este método de dispersión, se compara a la
muestra del pigmento ensayado, tratado de la misma manera, detectándose
cualquier diferencia de intensidad.
Si existe una diferencia en el poder colorante entre el patrón y la muestra, se

debe realizar una serie de mezclas nuevas con cantidades variantes del
material colorante y dos gramos de pigmento blanco patrón. Tan pronto como
se determine la combinación de material colorante y de pigmento patrón que
iguale la muestra de la prueba, se puede calcular el poder de coloración de la
muestra:
Poder de coloración = (A / B) x T ,
JUNIO 2005
A = peso en gramos del material colorante usado con el patrón para

igualar el tinte;
B = peso en gramos del material colorante usado con la muestra;
T = valor empírico del poder colorante del patrón.
4.3.5. Absorción de aceite
Véase ASTM D281-31, Método de ensayo para la absorción de aceite de los

pigmentos. TT-P-141b, Método 419,1, Absorción de aceite (Rub-Out). Método
419,2, Absorción de aceite (Gardner-Coleman).
La absorción de aceite de un pigmento es la cantidad de aceite requerida por

un peso determinado de pigmento para formar una pasta, mediante un
mezclado mecánico, hasta obtener una consistencia específica. La absorción
de aceite se expresa en gramos de aceite por cien gramos de pigmento. Los
resultados variarán con la consistencia de la pasta formada (el punto final), el
tiempo requerido para realizar la prueba, el grado de amasado, la temperatura
y la humedad.
Puesto que la absorción de aceite está regida por el tamaño de las partículas,
la actividad química del pigmento, las características de la superficie de las
partículas, y otras propiedades, la absorción de aceite se usa en los
laboratorios para comparar la uniformidad de los pigmentos de cada lote y
como un medio de comparar tipos similares de pigmentos obtenidos de
diversas procedencias. En términos generales, cuanto más grandes son las
partículas menos superficie hay que humedecer, lo que significa una absorción
de aceite más pequeña.
Los procedimientos para la determinación de la absorción de aceite varían

ampliamente en la industria de la pintura. Esto es debido a la ausencia de una
prueba satisfactoria que pueda dar resultados exactos y consistentes entre los
distintos laboratorios. Sin embargo, el método más aceptado es el
procedimiento ASTM.
JUNIO 2005
La prueba de absorción de aceite consiste en amasar una muestra de pigmento

exactamente pesada, con aceite de linaza mediante una espátula metálica. El
aceite se añade gota a gota mezclándose con el pigmento hasta que forma una
pasta espesa como un emplaste que no se separa ni se rompe.
La cantidad de aceite usado se determinará en relación con el pigmento. En

esta prueba un operador puede duplicar con facilidad sus propios resultados,
pero los valores obtenidos variarán de un operador a otro.
Otra prueba utilizada es el método Gardner-Coleman, descrito en las

Especificaciones Federales TT-T-141b. Se comienza poniendo una muestra del
pigmento exactamente pesada en una taza de porcelana, o sobre un vaso de
250 ml. El aceite de linaza se incorpora gota a gota y se mezcla con el
pigmento con una varilla agitadora de vidrio. El punto final se alcanza cuando
toda la masa del pigmento permanece reunida en un bloque.
Teniendo las partículas de los pigmentos diferentes formas según su

procedencia, ya se trate de un color mineral, u obtenido industrialmente por
precipitación química; en cuyo caso suelen ser más o menos irregulares y en
de variadas formas según la naturaleza de su formación cuando llenan un
depósito o recipiente dejan espacios entre partículas, que quedan ocupados
por aire.
El volumen aparente, por tanto, ocupado por el material, tiene importancia

especialmente en la molienda con aceite, pues influye en la cantidad de éste
que debe emplearse, ya que no se hace en aquélla más que reemplazar el aire
por el aceite. La forma de las partículas se estudia al microscopio con facilidad
usando los aumentos que cada caso requiera, que no suelen ser
considerables.
Para la determinación, se emplea un aparato que consiste en una vasija

metálica cilíndrica, de una capacidad de 1000 ml, con una tapa también
metálica e igualmente cilíndrica, que sobresale un centímetro alrededor y que
JUNIO 2005
colocada sobre ella tapándola, alcance la mitad aproximadamente de la altura

de la vasija.
Se llena el recipiente con el pigmento sobre que se opere, se dan dos o tres
sacudidas golpeando el fondo plano de lleno sobre la mesa del laboratorio
otras tantas veces, y se acaba de llenar en cúpula sobre el borde. Se tapa
entonces con la otra mitad, que deberá tener un peso de unos 200 gr, sin
apretar; se levanta la tapa y con una regla que quite el exceso de pigmento se
allana la superficie del recipiente con los bordes del mismo. Se limpia con un
trapo el exterior y se pesa en una balanza que aprecie bien el medio gramo.
Si después de sacada la tapa no hubiese lugar al paso de la regla para allanar,

se empezaría nuevamente toda la operación. Previamente la vasija se habrá
pesado vacía y limpia, restando este peso del obtenido.
El volumen específico de un cuerpo es el inverso de su densidad. Por tanto, el

volumen aparente será el inverso de la densidad aparente:
En la fabricación de pinturas hay que distinguir entre el aceite absorbido por un

pigmento en la molienda para transformarlo en pasta, y el que se necesita para
que cada partícula quede rodeada suficientemente para formar una pintura.
Puede tratarse de otro medio que el aceite de linaza, tanto en un caso como en
otro, pero en general el dato de interés es la cantidad de aceite de linaza
necesario para obtener una pasta normal; aunque no haya definición teórica de
este extremo, sino coincidencia práctica en la apreciación.
Cada fabricante de pinturas puede preparar otros tipos que dicho normal de
pasta, según las necesidades de su clientela u otros motivos, pero no puede
disminuir aquella proporción de aceite, en realidad; y si la aumenta tiende hacia
JUNIO 2005
el empleo de la cantidad necesaria para la fluidez, es decir la segunda

acepción indicada, que constituye una pintura líquida, aunque ello no quiera
decir apta para su uso.
Este segundo valor es más relativo que el primero; la molienda de pigmentos

se hace casi siempre con aceite de linaza u otra clase, de modo que la
variación no suele ser considerable. En cambio, una pintura puede prepararse
con muy diversos vehículos según los fines a que se destine, pudiendo ser la
variación del respectivo valor muy grande. Ambos suelen expresarse en aceite,
y en porcentajes, llamándose al uno aceite absorbido en la molienda y al otro
aceite necesario para la fluidez.
El segundo dato corresponde a la cantidad de vehículo preciso para la

extensión y formación del gel coloidal que aprisiona en sus mallas las
partículas del pigmento.
La pasta correspondiente al aceite absorbido en la molienda, necesita para su

aplicación ser diluida, con aceite u otro vehículo, al menos hasta la situación
determinada por el segundo valor, o pintura líquida para poder formar la
película. Los valores dependen del estado de división del pigmento, o sea de la
finura del polvo; de la forma de las partículas, es decir de su superficie; y de la
resistencia a dejarse mojar dichas partículas, o poder mojante relativo del
medio, relacionado con la tensión superficial y entre fases.
Las condiciones de resistencia que se exijan a la película formada, aunque en

la pintura al aceite coinciden a veces con la cantidad de aceite absorbido en la
molienda, como mínimo para algunos de los servicios pedidos a la capa de
pintura, así como las posibilidades de aplicación práctica necesarias del
material, no entran en consideración en estos valores.
Ambos datos para un pigmento están también en relación con la densidad del
mismo, de modo que la cantidad de aceite necesario para formar la pintura en
pasta es inversamente proporcional a la densidad, cosa por otra parte natural.
JUNIO 2005
Esta proporcionalidad se pierde en el caso de trabajar con pigmentos de

distinta composición o procedencia, y con una mezcla de pigmentos, tanto más
cuanto más distintos son sus volúmenes secos (que a su vez dependen de la
finura y de la forma de las partículas del pigmento) y que son uno de los
factores determinantes de la cantidad de aceite necesario para la molienda;
que dependerá aún de los medios mecánicos puestos en juego para lograr la
formación de la pintura en pasta.
La absorción de aceite se puede determinar en el laboratorio pesando 25 gr del

pigmento en cuestión y poniéndolos en el centro de una placa de mármol. Del
montoncito formado se separan con una espátula unos 3 gr, y el resto se
empasta con el aceite que se deja caer de una bureta, hasta la consistencia de
pasta que se desea, por medio de la espátula.
Cuando se ha llegado a aquel punto, se emplea la moleta sobre el mármol; la

pasta se afina y se vuelve menos espesa. Entonces se añade nuevamente con
la espátula la porción separada de pigmento, con lo que puede llevarse otra
vez a la consistencia requerida. El número de centímetros cúbicos de aceite
gastados, multiplicado por 4, da la cantidad necesaria por 100 de polvo para la
molienda. Generalmente los porcentajes en la práctica son inferiores a los
hallados y varían según el tipo de molino que se use y el procedimiento de
empastado que se emplee.
La cantidad de aceite necesaria para la formación de pintura fluida, se puede

determinar continuando en el ensayo anterior, aunque juntadas dos pruebas, la
adición de aceite a la pasta íntegramente colocada en un mortero de vidrio de
gran capacidad; se agita enérgicamente con su mano hasta que tomando una
muestra de la masa, cada vez menos espesa, e introduciendo en ella 1/2 cm
una varilla de vidrio de unos 4 mm de diámetro, al levantarla y mantenerla
vertical, la pintura escurra y forme bola en su extremo, previamente
redondeado al fuego, sin formar reborde.
El aceite contenido en las dos pruebas que se han juntado, más el nuevamente
añadido, multiplicado todo por 2, será el resultado. En ambas determinaciones
JUNIO 2005
de absorción de aceite, hay que hacer cinco ensayos y tomar el promedio como
valor de la determinación. Es evidente que las dos, y de modo especial la
segunda, requieren habilidad y suficiente experiencia por parte del operador,
para conseguir cifras de un valor adecuado.
Véase FSPT At-10-54 y ASTM D153-54, Peso específico de los pigmentos.
Se coloca en un picnómetro una muestra del pigmento y se cubre con

keroseno. El aire ocluido entre las partículas del pigmento se separa some-
tiendo el picnómetro al vacío. A continuación se llena el picnómetro por
completo con keroseno. La densidad del pigmento se calcula de la siguiente
manera:
JUNIO 2005
Peso específico = S / ( K – X )
S = peso de pigmento en el picnómetro;
K = volumen de keroseno requerido para llenar el picnómetro sin pigmento

presente;
X = volumen de keroseno requerido para llenar el picnómetro con

pigmentos;
K - X = volumen ocupado por el peso S del pigmento.
4.3.7. Dureza
Se entiende corrientemente en Mineralogía por dureza la resistencia de unos

cuerpos al ser rayados por otros. Se aprecia en general esta propiedad
mediante la inclusión de los minerales en una escala establecida por MOHS:
1. Talco.
2. Yeso.
3. Calcita.
4. Pluorita.
5. Apatita.
6. Ortosa.
7. Cuarzo.
8. Topacio.
9. Zafiro.
10. Diamante.
La dureza se determina buscando un cuerpo de esta escala que raye al mineral

en examen mientras que este mismo raya al cuerpo que le antecede. La dureza
JUNIO 2005
estará comprendida entre las dos correspondientes de la escala, y se

expresará con el número del más blando más 5 décimas. Así, un cuerpo
situado entre los 4 y 5 tendrá una dureza de 4,5. Los dos primeros números de
la escala se rayan con la uña; del 3.° al 6.º se rayan con un estilete de acero.
Este modo de determinación es suficiente para indicar la dureza de los colores
minerales.
La resistencia de un cuerpo a dejarse dividir en partículas más o menos finas

en la molienda, depende de su dureza. Por tanto, desde este punto de vista,
para el fabricante de pinturas en pasta y de esmaltes, tiene importancia la
dureza del pigmento, no solamente en cuanto atañe al material a emplear para
conseguir una preparación correcta en la molienda, sino también en lo que
afecta a consumo de fuerza motriz.
La molienda en buenas condiciones no permitirá, además, moler

simultáneamente pigmentos de muy distinta dureza en mezcla más o menos
uniforme. El fabricante de pinturas busca en realidad más que la pulverización
o reducción de tamaño, la amalgamación perfecta, o lo más perfecta posible,
con el aceite o vehículo del pigmento, previa mente molido y reducido al
tamaño de partícula conveniente por el fabricante de colores, operación que
éste habrá practicado ya en húmedo ya en seco, según el pigmento de que se
trata o el fin a que se destine.
En el caso de una pintura o esmalte, la resistencia a la abrasión de la película

resaltante, será influida por la mayor o menor dureza del pigmento empleado
en la manufactura, en igualdad de condiciones de vehículo empleado.
4.3.8. Distribución del tamaño de las partículas
El grado de división mecánica de un pigmento, o sea el tamaño de las

partículas, varía según la naturaleza del mismo, y aún dentro de su masa. Las
dimensiones se dan en micras, siendo la micra la milésima parte de un
milímetro. La medición debe hacerse en un microscopio, con un micrómetro
objetivo y un micrómetro ocular, tomando algunas precauciones.
JUNIO 2005
En la técnica, el procedimiento consiste en pesar 10 gr. del pigmento, que se

pasan por una colección de tamices de unos 8 cm de diámetro por unos 4 de
alto, que pueden adaptarse a un cilindro metálico recipiente, de unos 10 cm de
altura, fácil de pesar en una balanza que aprecie bien el miligramo; con cuya
precisión se habrán pesado los 10 gr. del pigmento. Los tamices pueden
taparse cómodamente y desmontarse.
Teniendo preparada una colección con números de mallas decreciente, se

ponen los 10 gr. en el primer cedazo, junto con algunas bolas de acero, de
cojinete, de unos 5 mm de diámetro. Se tapa, y puesto sobre el depósito, que
previamente, se habrá tarado, se agita en sentido circular y dando pequeños
golpes, para que tenga lugar el tamizado. Se pesa luego el recipiente, se
coloca otra vez el cedazo y se repite la operación, volviéndose a pesar al cabo
de un rato y así hasta peso constante. Cambiando luego el cedazo por el
siguiente, de modo que todo el polvo y las bolas que quedan en el primero, por
medio de un pincel caigan en el segundo, se continúa la operación. Los
aumentos de peso del depósito indican la cantidad de pigmento que ha pasado
por cada tamiz.
Otro modo de manipular consiste en mezclar primeramente el pigmento con

agua, o alcohol, y lavar los tamices con el chorro de un frasco lavador lleno de
estos líquidos, en lugar del pincel o cepillo. Operando en seco como en
húmedo, no debe perderse nada de polvo y hay que pasar por el número de
tamices requerido los 10 gr. completos del pigmento. De trabajar en húmedo, la
última pesada correspondiente a cada tamiz se hará previo secado del polvo.
JUNIO 2005
Para una pintura en pasta o un color mineral molido con aceite, en lugar de
agua o alcohol se empleará esencia de trementina, u otro disolvente
conveniente. En este caso el pigmento separado debe lavarse con éter y
secarse antes de la pesada definitiva. Si queda un residuo de impurezas, se
pesará también para su valoración. Puede estar constituido por substancias
extrañas al pigmento, procedentes de las distintas operaciones por las que
haya pasado durante su fabricación, u otras causas.
El tamaño de las partículas queda expresado algo mejor, por las cantidades de
pigmento retenidas en los tamices de una colección de número de mallas
creciente.
Se emplean para ello unas columnas de cedazos circulares con borde alto, la
parte inferior de cada uno de los cuales encaja con la superior del siguiente.
Una tapa y un fondo completan el sistema.
Se carga el tamiz superior con 100 gr, en general, de pigmento, y sacudiendo

horizontalmente se hace pasar el polvo por la columna, de modo que en cada
tamiz va quedando lo que no atraviesa sus mallas, siendo necesario que en el
fondo no se recoja nada.
El peso de cada fracción conseguida en estas condiciones, expresa el residuo

al tamiz de los distintos números de mallas que constituyen la escala.
JUNIO 2005
Los tamices tienen un número de mallas que se expresa por centímetro o por
pulgada lineales, y también por centímetro cuadrado. Un tamiz de 39 mallas
por centímetro lineal equivale a 100 mallas por pulgada inglesa (25,4 mm), y el
polvo que lo atraviesa se llama corrientemente un polvo fino; pero el empleado
en la confección de un esmalte debe tener una finura correspondiente a 250
mallas para que quede uniforme y liso; y hasta 350 si el esmalte es
nitrocelulósico.
En los Estados Unidos, si en una muestra examinada con relación al tamiz de

200 mallas, 5 gr. han pasado por el de 250; 2,5 gr. por el de 200; y 2,5 gr. por
el de 150, se suele decir que el porcentaje de finura es:
Esto mismo, con relación al tamiz de 250 mallas, daría un porcentaje de finura
de:
JUNIO 2005
Es preciso indicar los límites que se admiten y los tamices tolerados, en cada
caso, teniendo en cuenta que el sistema es relativo.
Los cedazos se construyen generalmente de madera, y las telas de bronce

fosforoso, latón, níquel. La magnitud de los orificios depende del diámetro de
los alambres que forman el tejido (luz de la malla). Como el milímetro tiene
1000 micras, a un tamiz de 200 mallas por pulgada, corresponderá por malla:
25400: 200 = 127 micras,
Contadas del centro de un hilo al centro del siguiente. Para saber la luz de la
malla, hay que restar el diámetro de un hilo (dos medios: el tejido metálico que
forma el matiz está estructuraclo por alambres que se cruzan generalmente
según los vértices de un cuadrado).
El diámetro del hilo varía según los números, y en el caso que se cita, es de 53
micras, por lo que queda como orificio útil un cuadro de 74 micras de lado, para
que pasen a su través las partículas del pigmento (TYLER Co.).
En España es corriente numerar los tamices por pulgada francesa (27,070mm),

en lugar de pulgada inglesa. Los números exigidos en las prescripciones de los
usuarios importantes para los pigmentos suelen variar del 300 al 200. La luz de
las mallas es de 50 micras para el número 300, 58 micras para el número 250,
y 75 micras para el número 200; y el grosor del hilo de 40, 50 y 60 micras,
respectivamente, en tales condiciones. La finura se expresa indicando el
porcentaje admisible de residuo para el tamiz requerido.
Véase ASTM E-20-51T, Análisis por métodos microscópicos de la distribución

del tamaño de partículas de sustancias particuladas que pasan por el tamiz de
325 mallas.
Se dispersan bien unos pocos miligramos del pigmento en algún medio líquido,
de manera que los aglomerados se disgreguen en sus partículas primarias
JUNIO 2005
discretas. La dispersión se extiende en una película fina sobre el portaobjetos

de un microscopio, con las partículas lo suficientemente separadas, de modo
que sus contornos se distingan y las pequeñas no queden ocultas por las
grandes.
Se hace una microfotografía de la dispersión, en la cual se puedan contar las

partículas comprendidas en cada escala de tamaños; el negativo puede
también proyectarse sobre una pantalla para incrementar el tamaño aparente
de las partículas y poderlas contar más fácilmente.
Este método es útil para el intervalo de tamaños de 1,0 µ-37 µ. El límite inferior
viene impuesto por el poder de resolución del microscopio. La distribución de
los tamaños de partículas por encima de 37 µ se puede determinar mediante
tamices. El método microscópico es tedioso y requiere una considerable
experiencia y pericia en las técnicas microscópicas y fotográficas, pero produce
resultados exactos y tiene la ventaja de mostrar al mismo tiempo la forma de
las partículas. Cuando se aplica a dispersiones reales, aquél puede también
mostrar si existen pigmentos aglomerados.
La distribución del tamaño de partículas de los pigmentos para diámetros

comprendidos entre 1,0 y 0,001 µ, se puede determinar con el microscopio
electrónico, pero estas determinaciones requieren aún más tiempo y
operadores muy experimentados, por no decir nada del costo del microscopio
electrónico en sí.
Las pruebas de sedimentación se utilizan también para determinar la

distribución del tamaño de las partículas. Se basan en el hecho de que las
partículas esféricas, suspendidas en líquidos, sedimentan a diferentes
velocidades proporcionales al cuadrado de sus diámetros. Al diámetro más
grande corresponde la velocidad de sedimentación más rápida. El tiempo
requerido por las partículas de un diámetro dado, para recorrer en su caída una
distancia fija, en un líquido determinado, se puede calcular por la ley de Stokes.
La ecuación se puede escribir de la siguiente manera:
T = [18HV / (S1 - S2)GD2 ] x108

JUNIO 2005
T = tiempo en segundos;
H = altura de caída en centímetros;
V = viscosidad del líquido en poises;
S1 = peso específico de la partícula;
S2 = peso específico del líquido;
G = aceleración de la gravedad = 980 cm/s2;
D = diámetro de las partículas en micrones.
C. K. Williams and Company utiliza una prueba de sedimentación bastante

sencilla para determinar la distribución del tamaño de partículas en el intervalo
de 0,5 a 40 µ en pigmentos inorgánicos esféricos que normalmente no forman
aglomerados muy coherentes.
Se obtiene una dispersión de unos 25 g de pigmento en 200 ml de agua en un

mezclador Waring y 0,5 g de Calgon como agente dispersante.
La dispersión se coloca en una pipeta de Andreason que consiste en un cilindro

de vidrio unido a un tapón de vidrio esmerilado, a través del cual desciende la
varilla de la pipeta hasta unos 5 cm del fondo. El cilindro está calibrado en
centímetros, de 0-20, partiendo desde el nivel del fondo de la pipeta. Se añade
agua para llevar el nivel de la dispersión en el cilindro, hasta la marca de 20cm.
Por tanto, H en la ecuación anterior es 20. Se calcula T para los diversos
diámetros de partículas desde 40 µ hasta 0, 5 µ.
El cilindro se lleva a 30 ºC en un baño de agua y se agita enérgicamente. Se

toma una muestra de 10 ml. El peso del pigmento seco (W) en esta muestra se
usa para calcular la distribución del tamaño de partículas. Se deja entonces
que la dispersión se sedimente.
JUNIO 2005
Para T40 todas las partículas mayores que 40 µ habrán pasado la marca 0. Se
toma una muestra de 10 mI. En esta muestra todas las partículas son más
pequeñas que 40 µ y el peso del pigmento seco es W40.
• ( W40 x 100 ) / W = % de pigmento en una muestra menor que 40 µ de

diámetro.
Para T30 se toma otra muestra de 10 ml.
• ( W30 x 100 ) / W = % de pigmento en una muestra menor que 30 µ de

diámetro.
Se toman otras muestras adicionales en los intervalos de tiempo adecuados

hasta T0,5.
Datos correspondientes a las distribuciones del tamaño de partículas de dos

pigmentos, obtenidos por este método.
Se observa que el pigmento B es mucho más fino que el pigmento A. El

pigmento B no contiene ninguna partícula mayor de 10 µ, y el 41 % es más
pequeño que 1 µ; el 39 % del pigmento A es más pequeño que 5 µ, y
solamente el 11 % es menor que 1 µ.
Datos de la distribución del tamaño de partículas
Esta prueba proporciona resultados aproximados para pigmentos con forma de

placas o de agujas, ya que éstos no siguen la ley de Stokes. Se puede utilizar
JUNIO 2005
también para pigmentos dispersos en cualquier líquido. Los aglomerados de

partículas primarias tienden a comportarse en la prueba como partículas
primarias de un diámetro mayor, de manera que la prueba se puede utilizar
como una prueba del grado de dispersión.
4.3.8.1. Método de estudio
• Tamaño de las partículas
Un pigmento se puede considerar finamente molido, según CRUICKSHANK

SMITH:
1. Cuando el diámetro medio de las partículas menores no excede

de 5 micras.
2. Cuando el diámetro medio de las partículas mayores no excede

de 25 micras.
3. Cuando el diámetro medio de todas las partículas no excede de

10 micras.
Se considera que un pigmento se puede emplear para la confección de

esmaltes:
1. Cuando contiene de 75 a 85 % de partículas menores de 3 micras

de diámetro.
2. Cuando contiene de 20 a 12 % de partículas de 3 a 5 micras de

diámetro.
3. Cuando contiene el resto de partículas de más de 5 micras de

diámetro, hasta 8.
Un pigmento de tales condiciones se podría llamar suficientemente molido.
• Densidades (pesos específicos) y volúmenes específicos de varios

pigmentos minerales e industriales
JUNIO 2005
• Absorciones de aceite por algunos pigmentos
• Mezclas de pigmentos
La regla aritmética de aligación permite resolver los dos siguientes problemas:
1. Dadas ciertas cantidades de pigmentos y sus densidades, hallar

la densidad de la mezcla resultante.
2. Dadas las densidades de ciertos pigmentos, hallar las cantidades

en que se deben mezclar para obtener una densidad
determinada.
JUNIO 2005
4.3.8.2. Ejemplos prácticos de calculo teórico de densidades
• Primer caso
Una mezcla de 66,5 partes de óxido de zinc de densidad 5,7, y 33,5 partes de
blanco de España de densidad 2,6. Densidad de la mezcla:
• Segundo caso
Para obtener una mezcla con óxido de zinc cuya densidad es 5,7, y blanco de
España cuya densidad es 2,6, de modo que se obtenga una densidad de 4,66,
se tendrá:
Composición de la mezcla:
La unidad “partes” utilizada en los casos, corresponde a partes en volumen.

Para pasar a partes en peso, es preciso multiplicar los resultados del segundo
caso por su densidad respectiva:
JUNIO 2005
y el porcentaje de pesos será:
Para resolver el primer caso partiendo de unas proporciones en peso, se

empleará el volumen específico en lugar de la densidad:
4.3.9. Estabilidad
La estabilidad de un pigmento es una característica del mismo que debe ser

considerada en distintos casos. Podrá ser estudiada en relación al vehículo en
que debe ponerse en suspensión y frente a los agentes que deban actuar
sobre él.
• Estabilidad respecto al vehículo
Siendo uno de los objetivos asignados a un esmalte o pintura el opacimiento de

la superficie sobre la que se aplican, el comportamiento del pigmento frente al
medio empleado será primeramente de insolubilidad.
Cuando existe una solubilidad del pigmento en el medio dispersante, al aplicar

una capa de pintura sobre otra anterior suele ocurrir, si ésta es de distinto color,
especialmente un color blanco o claro, que esta segunda capa se enmascara
con el color de la primera.
Se dice entonces que la pintura “resuda”, y naturalmente el fin conseguido no

es el deseado.
JUNIO 2005
Esto ocurre especialmente con pigmentos lacados rojos de colorantes no

adecuados.
Se puede ensayar esta posibilidad de accidente tomando una pequeña

cantidad del pigmento, mezclándolo con otra del medio que quiera usarse y
pintando un papel secante blanco, o papel de filtro, por una cara; examinando
luego la otra del papel, o incluso el halo que se formara alrededor del trozo
pintado en la misma cara, por absorción.
Al aplicar una pintura sobre otra no hay que olvidar que esto también puede
ocurrir si el disolvente de la segunda capa remueve la película de la primera en
mayor o menor proporción. En el oficio de pintor es corriente, aunque no se
hace sólo con este fin, quemar una capa de pintura antigua antes de proceder
a la aplicación de otra nueva, o quitarla mediante preparados especialmente
concebidos para la eliminación de capas secas de pintura,
Se acostumbra a llamar impropiamente a estos productos “desoxidantes”, y

suelen estar compuestos por soluciones alcalinas, o pastas que contienen
estos cuerpos. También se emplean compuestos de disolventes, como mezclas
de acetona, bencina y benzol, que hinchan y desintegran la linoxina.
El modo de aplicar unos y otros consiste en extender el desoxidante sobre la

superficie a tratar, y al cabo de poco tiempo, cuando la capa de pintura se ha
reblandecido, eliminarla mediante raspado con una espátula. Luego se lava y
se deja secar completamente.
• Estabilidad a la luz y color
Al tratar del amarilleamiento de las películas, se ha excluido la parte de culpa

correspondiente al pigmento, si éste no corresponde a lo que se le exige. La luz
difusa causa en general poca alteración en el color de los pigmentos, no así la
luz solar directa, que ocasiona a veces con facilidad el agrisado de ciertos
litopones, y el descoloramiento de muchos colores lacados, cuando los
colorantes de anilina empleados en los mismos no tienen resistencia suficiente
a la luz.
JUNIO 2005
Un ensayo preliminar pintando un tablero de los empleados en ensayos de

pinturas, orienta con facilidad después de un tiempo oportuno de exposición a
la luz del sol, o en lámparas de rayos ultravioletas. Se emplean para el examen
de resistencia a la luz de pigmentos y pinturas, cajas de palastro provistas de
un tubo luminoso de cuarzo, dentro de las que se introducen los tableros que
se comparan, quedando sujetas a la acción intensa de los rayos actínicos las
superficies pintadas.
Los materiales destinados a la pintura de radiadores de calefacción, máquinas

de tren y otros objetos sometidos a la acción del calor, deben ser concebidos
para dicho fin en cuanto a los vehículos empleados, pero igualmente los
pigmentos que en ellos se utilicen deberán ser escogidos con la suficiente
estabilidad química y física al calor, a fin de que no experimenten cambios.
Los pigmentos obtenidos a altas temperaturas se hallan generalmente en este

caso, pero un ensayo preliminar pintando una plancha y manteniéndola en la
estufa a una temperatura y una duración conveniente, orientará con bastante
facilidad respecto este punto.
Con respecto a la humedad o agua de hidratación contenida en los pigmentos.

No dejará nunca de practicar su determinación cuando se trata de proyectar
pinturas para altas temperaturas, pues la eliminación de agua en caso de tener
el contenido en ésta un valor no tolerado, ocasionaría el demérito o la
destrucción de la pintura.
La resistencia al calor, que ciertos pigmentos, como los carbonatos, se alteran

descomponiéndose en otros cuerpos y desprendiendo gases.
Otros pigmentos, como el óxido de zinc, cambian de color con la temperatura y

vuelven al primitivo cuando cesa el aumento.
• Estabilidad en las mezclas
Es corriente en la práctica industrial o por el pintor en la confección de los

materiales empleados en pintura, obtener matices mediante mezcla de distintos
pigmentos. Es preciso en estos casos que los compuestos mezclados sean
JUNIO 2005
cuerpos que no reaccionen entre sí, pues a medida que va ocurriendo la

reacción, el color obtenido se va alterando.
Como el número de pigmentos, lacas y colores minerales ha ido aumentando,

para una gran mayoría de matices y colores se halla el correspondiente
material en el mercado y la necesidad del conocimiento de las
incompatibilidades entre colores ha ido disminuyendo para el práctico, dejando
de ocupar un lugar interesante en la técnica de la pintura, como antes ocurría.
No pueden mezclarse pigmentos que contengan azufre con colores de plomo;

que ennegrecen a causa de la formación de sulfuro de plomo negro. Lo mismo
ocurre con los verdes de cobre. Cuando en la confección de tintes pálidos
verdes y azules se emplea azul de Prusia, si el resto de carga lo constituyen
productos básicos, como blanco de España, blanco de plomo, dichos tintes
pueden resultar fugaces.
• Datos especiales de estabilidad
Puesto que las pinturas, al ser ejecutadas, pueden tomar contacto con
materiales alcalinos como la sosa y jabones, que el óxido de zinc es soluble en
sosa cáustica y el azul de Prusia se descompone con los álcalis. Esto deberá
tenerse en cuenta en la aplicación de pinturas o esmaltes sobre superficies que
han sido lavadas con álcalis, o tratadas con los materiales llamados
“desoxidantes” para remover capas de pinturas antiguas.
También se tendrá en cuenta en la aplicación de materiales sobre paredes

revocadas a la cal o con materiales alcalinos. Inversamente al azul de Prusia,
el azul de ultramar resiste mejor la acción de los álcalis, pero en cambio es
destruido por los ácidos.
Es preciso tener en cuenta que la estabilidad de un pigmento en cuanto a

duración de la pintura, depende en parte también de la cantidad de aceite
empleado en su preparación, si se trata de una pintura al óleo, ya que cuanto
mayor es dicha cantidad, más resistente es la pintura y mayor solidez tiene.
JUNIO 2005
También dependerá de que la preparación de la superficie sobre que se aplica

la pintura sea la adecuada, o esté incorrectamente tratada.
4.3.10. Opacidad
No debe confundirse con el opacimiento de las películas, ni con el poder

cubriente.
Índice de refracción de varios pigmentos:
4.3.11. Determinación de la humedad y de la pérdida por calcinación
Para la determinación de la humedad de un pigmento, se pesan de 5 a 10 gr

del material en una capsulita de vidrio, previamente tarada, que se mantiene en
la estufa de 100 a 110ºC hasta peso constante. Conocida la cantidad de agua
contenida en la muestra pesada, se reduce a tanto por ciento mediante el
correspondiente cálculo.
Muchas veces interesa conocer la pérdida que experimenta el color mineral en

su calcinación. Para ello, se pesan en un crisolito de porcelana, previamente
enrojecido, enfriado y tarado, cerca de 2 gr del producto, que se someten a la
calcinación con las debidas precauciones.
4.3.12. Valoración de un blanco de zinc
Los métodos aplicados al análisis de pigmentos, son generalmente

gravimétricos; como la determinación de la riqueza de una barita en sulfato
bárico.
JUNIO 2005
Para determinar el Zn de un blanco de zinc, (y conocido aquél por el cálculo se

conoce la riqueza del producto examinado), se toman 2 gr que se tratan con
ácido nítrico diluido, transformándose así el zinc en nitrato, que queda disuelto.
Se filtra para separar el residuo insoluble (constituido por sulfatos de plomo o
de bario generalmente), que calcinado se puede pesar si interesa, y la solución
nítrica obtenida se trata con ácido sulfúrico, concentrándola luego hasta
aparición de humos blancos.
Se deja enfriar y se añade agua alcohólica, recogiendo el precipitado de sulfato

de plomo, que se habrá formado si el blanco de zinc contenía carbonato de
plomo, que se puede determinar.
El líquido filtrado se hace hervir para expulsar el alcohol, y se concentra casi a

sequedad, para disolverlo luego en agua acidulada con ácido clorhídrico, a fin
de pasar una corriente de ácido sulfhídrico, que precipitará los metales
correspondientes que puedan hallarse presentes. Separados éstos por
filtración, se hace hervir el filtrado para eliminar el sulfhídrico; se neutraliza la
solución con hidróxido sódico, se acidifica con ácido acético y se añade acetato
sódico; y se precipita nuevamente con corriente de ácido sulfhídrico, a unos 50°
C durante 1/4 de hora al menos.
A fin de no tener inconvenientes de naturaleza coloidal en la filtración del SZn

formado, se aconseja añadir antes de ésta algo de cloruro mercúrico en
disolución acuosa (que transformándose en sulfuro mercúrico se volatilizará
durante la calcinación).
El precipitado de sulfuro de zinc se calcina en un crisol de Rose, con adición de

azufre y en corriente de hidrógeno. El peso obtenido de SZn, multiplicado por
0,8351 da la cantidad de OZn contenida en los 2 gr de producto del que se
partió.
Las demás determinaciones que suelen hacerse para el reconocimiento de la

calidad de un blanco de zinc, en el orden químico, son la de humedad, y la de
los compuestos de plomo.
JUNIO 2005
Para éstos es mejor pesar 5 gr del producto inicial, disolverlos en 40 ml de

ácido nítrico, diluir a doble volumen con agua destilada caliente y hervir. Se
deja enfriar y se filtra.
El residuo se calienta con solución concentrada de acetato amónico en una

cápsula de porcelana, solubilizándose el sulfato de plomo, que una nueva
filtración separa del resto, esta vez en el filtrado.
Sobre este líquido filtrado se precipita el plomo procedente del sulfato de plomo
contenido en el blanco de zinc, con ácido sulfhídrico, y el sulfuro de plomo
separado se disuelve en ácido nítrico diluido. Se adiciona ahora ácido sulfúrico,
se evapora hasta aparición de humos blancos, se deja enfriar, se trata con
agua, se añade alcohol, se deja depositar, se filtra y se pesa, obteniéndose la
cantidad de sulfato de plomo contenida en 5 gr de blanco de zinc.
La solución nítrica primitiva, contiene los compuestos de plomo procedentes del

carbonato (albayalde) o de los óxidos existentes en el blanco de zinc.
A una alícuota de la disolución obtenida y adicionada de las aguas de loción del

residuo filtrado, se añade ácido sulfúrico que se evapora a baño maría hasta la
aparición de humos blancos, se deja enfriar, se trata con agua, se añade
alcohol, se deja depositar, se filtra, se seca a 100 ºC, y se pesa. El peso de
sulfato de plomo ahora obtenido, multiplicado por 0,7358, expresa el PbO.
4.3.13. Análisis de un litopón
Si el Zn que se quiere determinar es el de un litopón, se pesan igualmente 2 gr

de producto, que colocados en un matraz se tratan con ácido clorhídrico de D =
1,12, unos 50 ml, haciendo hervir hasta que no se desprenda más SH2. Se
filtra, con lo que se separa el sulfato bárico y queda en solución Cl2Zn.
Se puede precipitar el Zn con sulfuro amónico, añadiendo previamente cloruro

amónico y amoníaco en exceso. El sulfuro amónico será poco coloreado.
Si se quiere determinar el contenido en sulfato bárico, se lava, seca y calcina el

precipitado que se separa del tratamiento con ácido clorhídrico.
JUNIO 2005
4.3.14. Determinaciones del hierro, del aluminio y del titano
Para determinar la cantidad de óxido férrico en un rojo de Venecia, o en un

minio de hierro, se pesan 2 gr de la sustancia, que se tratan con ácido
clorhídrico concentrado, mediante calefacción prolongada y substituyendo el
ácido que pueda evaporarse, hasta conseguir la disolución de todo el hierro. Si
ésta es muy lenta, pueden añadirse unas gotas de ácido nítrico.
Verificada la disolución, se lleva a sequedad la cápsula en que se operaba, en

baño maría, evitando las proyecciones (pérdida de sustancia con el
consiguiente falseo de los resultados del análisis). Se insolubiliza la sílice
dejando la cápsula media hora a 110 ºC en la estufa y se añade agua caliente y
ácido clorhídrico. Se filtra.
El residuo que queda en el filtro es el total de materias insolubles, incluida la

sílice; se seca, calcina y pesa para conocer su cantidad. La solución filtrada se
precipita con amoníaco en presencia de cloruro amónico, y el precipitado se
lava, seca, calcina y pesa. Se tiene así la cantidad de óxidos férrico y
alumínico, Fe2O3 + Al2O3 conjuntamente. Si se quiere el detalle de cada uno de
ellos, debe procederse a su separación.
Teniendo en cuenta que el rojo inglés está constituido esencialmente de óxido

férrico, el rojo de Venecia es generalmente el mismo cargado con barita o yeso,
y el minio de hierro contiene una proporción de sílice y silicatos; a no ser que
se busque alguna adulteración, se podrá proceder a determinar la alúmina
únicamente en el último material. El primero, en efecto, no habrá dado en la
determinación cantidad importante de sílice, como tampoco el segundo; en
cambio el tercero la dará.
Habiendo sílice en abundancia, seguramente habrá alúmina, de modo que

interesará saber su proporción, ya que rebaja el contenido en hierro del
pigmento objeto del análisis. Para determinar la alúmina, el contenido del crisol
después de la calcinación y de la pesada, se disuelve en ácido clorhídrico
concentrado, calentando a baño maría, y la disolución se evapora luego a
JUNIO 2005
sequedad, añadiendo entonces ácido sulfúrico concentrado y calentando hasta

la aparición de humos blancos.
Se disuelve el residuo en agua y se determina el hierro volumétricamente. Si

hubiese mucha alúmina, sería mejor disgregar el contenido de óxidos de hierro
y aluminio del crisol con bisulfato potásico; y luego de verificada la disgregación
con las debidas precauciones, proceder igualmente al dosado volumétrico del
hierro después de disolver el producto de la operación en agua acidulada con
ácido sulfúrico.
En los dos casos se llega a una disolución de sulfato férrico, que hay que
transformar en ferroso para poder valorarlo con la solución decinormal de
permanganato. Para ello se adapta al matracito que contiene la disolución, una
válvula de Bunsen (tubo de goma con un corte lateral, obturado en un extremo
por una varilla de vidrio), y se le añaden unos 3 gr de zinc metálico,
reduciéndose la sal férrica a ferrosa con hidrógeno, fuera del contacto del aire.
Luego se añade ácido sulfúrico y se valora con el permanganato contenido en
una bureta, añadiéndolo hasta coloración rosa persistente.
La reacción es:
La cantidad de óxido férrico, restada del total de óxidos hallados, dará la

cantidad de óxido alumínico, Al2O3.
Es necesario, a menudo, una vez conocida la riqueza de un pigmento en

determinado compuesto, averiguar la naturaleza de otros que pueden hallarse
en el mismo, en concepto de cargas o de impurezas.
En el caso actual, la presencia de carbonato de cal, señalada cualitativamente

por la efervescencia producida por tratamiento con ácido clorhídrico, indicará la
JUNIO 2005
conveniencia de determinar la pérdida por calcinación. Ésta, menos la

humedad, dará la pérdida correspondiente al agua combinada y al anhídrido
carbónico, en general.
La resistencia a los ácidos de los pigmentos de hierro para pinturas de

protección, se determina por digestión de 1 gr de materia en 1 litro de ácido
sulfúrico al 10 %.
Cada 24 horas se toma una muestra del líquido, y se determina la cantidad de

hierro disuelta.
En los ocres, se hace la determinación de la humedad, de la pérdida por

calcinación, del hierro, del aluminio, y de la sílice, de modo principal.
El dosado del óxido de titano en un pigmento, se consigue disgregando 1 gr de

sustancia, fundiéndola en un crisol de platino con bisulfato potásico. La masa
fundida y enfriada se hace hervir con agua, quedando un residuo que contiene
la barita y la sílice, que se separan por filtración. En el filtrado se halla el sulfato
de titano.
Si el pigmento contenía como carga sulfato cálcico, quedará en el residuo, pero

una porción pasará al filtrado también. Este filtrado deberá tener un volumen de
unos 200 ml y a él se añaden unos 30 ml de amoníaco de peso específico 0,91,
quedando entonces con una acidez cercana al 10 % de SO4H2.
Para el dosado del titano contenido en esta disolución, se recomiendan varios

métodos, que exigen una ejecución muy cuidadosa. Como menos complicada
la gravimétrica, por separación de ácido titánico mediante ebullición prolongada
de dicha solución, pesándose TiO2 después de calcinación cuidadosa.
La separación del titano del hierro o del aluminio, requiere igualmente

manipulaciones analíticas delicadas.
JUNIO 2005
4.3.15. Determinación del anhídrido carbónico
Las técnicas para la determinación del ácido carbónico de los carbonatos,

como blanco de España o albayalde, son varias. Generalmente se usa un
aparatito consistente en un pequeño matraz con una tubuladura lateral para
introducir la sustancia y dos anexos en la parte superior: el uno es un embudo
de llave con tapón esmerilado, y el otro un barboteador por el que se expele el
CO2 a través de ácido sulfúrico concentrado, de que se habrá llenado, para
absorber la humedad que pueda arrastrar en su desprendimiento.
En el embudo de llave se pone ácido clorhídrico diluido. Por la tubuladura

lateral se introduce cerca 1 gr del material a ensayar, mediante un tubito que se
pesa lleno, se vacía en el matraz, y vuelto a pesar da el peso exacto, y algo de
agua destilada.
Luego se pesa el aparato en la balanza de precisión, y se deja caer

suavemente el ácido clorhídrico sobre el carbonato mediante la llave del
embudo, de modo que el desprendimiento de CO2 sea regular a través del
barboteador con ácido sulfúrico. Terminado el desprendimiento, se pesa
nuevamente el aparato y por la pérdida de peso se conoce la cantidad de CO2
contenida en la muestra.
Es preciso al final de la reacción calentar a baño maría para que todo el

carbonato se haya disuelto, y una vez terminado todo el ácido del embudo,
pasar una corriente de aire que se lleve el CO2 que llena el aparato, aspirando
con un tubo de goma enchufado a la salida del barboteador de ácido sulfúrico.
El aire entrará por el embudo vacío.
4.3.16. Determinación del cobre y del arsénico
El cobre en un pigmento que lo contenga, como el verde montaña, se puede

determinar disolviendo 1 gr de la sustancia en ácido clorhídrico y precipitando
con una disolución de potasa cáustica. El precipitado obtenido se filtra, se seca
a la estufa y se calcina en un crisol de porcelana, incinerando primero el filtro,
cuyas cenizas se añaden al precipitado.
JUNIO 2005
Se pesa óxido cúprico, y puede escribirse:
De modo que el peso de CuO hallado, multiplicado por 0,7989, dará la cantidad
de Cu en la muestra examinada.
Si en el verde de Schweinfurt, constituido por acetato y arsenito de cobre, se

quiere determinar el arsénico, se opera del modo siguiente: Cerca de 0,3 gr de
sustancia finamente pulverizada se tratan con 25 ml de agua, y se añade ácido
clorhídrico concentrado, gota a gota y agitando, hasta disolución del pigmento;
bastan generalmente 10 gotas. Si hay anhídrido arsenioso libre, queda
insoluble en estas condiciones, y se puede recoger sobre un filtro.
Al filtrado se le añade carbonato sódico hasta precipitación incipiente, y luego

una disolución de 2 a 3 gr de tartrato sádico-potásico; se diluye a 200 ml, se
añaden 5 gr de bicarbonato sódico sólido, se valora con solución decinormal de
yodo en presencia de engrudo de almidón, con lo que se determina el anhídrido
arsenioso combinado.
El anhídrido arsenioso que quedó sobre el filtro, se pone en un Erlenmeyer con

agua y se hace hervir con bicarbonato sódico hasta disolución, determinándose
igualmente con la solución de yodo (según VILLAVECCHIA). Las reacciones
que ocurren son:
El ácido yodhídrico, que convierte la reacción en reversible, se elimina desde

su formación con el bicarbonato sódico que se añade. Como
JUNIO 2005
4.3.17. Valoración del cromato de plomo y del verde de zinc
Para la valoración del cromato de plomo neutro, en un amarillo de cromo (que

se encuentra en distintos tipos en el mercado según el grado de carga que
lleva, generalmente sulfato bárico, carbonato cálcico, sulfato cálcico y sulfato o
carbonato de plomo) VILLAVECCHIA aconseja el siguiente método,
suficientemente exacto:
Se pesan exactamente 2,154 gr de sustancia, se trituran en un mortero con

algunos centímetros cúbicos de agua y otros tantos de ácido clorhídrico de D =
1,18. Se echa todo en un matraz de 200 ml, lavando el mortero con agua y se
añaden 3 ó 4 gr de yoduro potásico puro. Se agita y se deja reposar 15
minutos.
Se añade agua hasta el enrase y después de agitar, se deja en reposo 2 horas.

100 ml de este líquido se valoran con solución decinormal de tiosulfato sódico,
añadiendo cuando el líquido está aún amarillento, una solución indicadora de
engrudo de almidón, continuando la adición de tiosulfato hasta la desaparición
del color azul. En estas condiciones, el número de centímetros cúbicos de
solución decinormal de tiosulfato gastados, da directamente el porcentaje de
CrO4Pb en la sustancia examinada.
El verde de zinc, mezcla de cromato de zinc y azul de Prusia con algún

diluyente, tiene como determinaciones más interesantes el zinc y el hierro.
Para el análisis, se parte de 1 gr de pigmento, que se trata con solución

caliente de potasa cáustica, disolviéndose el cromato de zinc y
transformándose el azul de Prusia en hidróxido férrico y ferrocianuro potásico.
El hidróxido férrico se separa por filtración, y se hace el dosado del hierro

volumétricamente. Como el precipitado contiene el sulfato bárico o cálcico, u
otra carga análoga insoluble y no atacada procedente del pigmento, se trata el
precipitado con ácido clorhídrico diluido caliente, que permite la separación de
los mismos, quedando el hierro en disolución clorhídrica.
JUNIO 2005
En el primer filtrado se hallan el zinc en forma de zincato potásico, el cromo en

forma de cromato potásico, y el ferrocianuro potásico.
El zinc se precipita con corriente de anhídrido carbónico, al estado de

carbonato básico, que permite el dosado por calcinación al estado de óxido de
zinc.
4.3.18. Coloración de perlas de bórax
Los ensayos con las llamadas perlas de bórax o de sal de fósforo (fosfato
sódico-amónico), orientan muy a menudo sobre los materiales que se
investigan. Se ejecutan valiéndose de un alambre de platino con un cabo
formando anillo; el alambre se sujeta por fusión del extremo de una varilla de
vidrio.
Primeramente se obtiene una perla transparente e incolora mediante fusión al

mechero de una pequeña cantidad de sal cogida en el anillo. Tocando el polvo
del cuerpo a ensayar con esta perla aún blanda y caliente, se consigue que una
partícula adhiera a ella, procediéndose a una nueva fusión, calentando a la
llama de oxidación, a la de reducción del mechero, y examinando las
coloraciones que adquiere.
Cuando la coloración obtenida es oscura y no se distingue bien, debe

procederse a una nueva operación con menor cantidad de sustancia a ensayar,
que la tomada en la operación antecedente. Los hilos de platino se limpian
sumergiéndolos en ácido clorhídrico. Empleando el bórax, las coloraciones
obtenidas son:
JUNIO 2005
La caracterización de los componentes de un material exige la práctica de un

análisis químico cualitativo completo, siguiendo la marcha analítica de
investigación de cationes y de aniones, una vez disuelto el pigmento.
Todos los tratados de Análisis químico cualitativo contienen las reacciones

características por vía húmeda de los elementos que forman ácidos, bases, o
sales, y la serie ordenada de investigaciones que, llamada la marcha analítica
mineral, permiten su reconocimiento y separación con relativa facilidad.
4.3.19. Método Kappelmeier
KAPPELMEIER ha establecido un método especial para el análisis cualitativo

de pigmentos. Comprende cinco grupos:
1. Tratamiento con ácido clorhídrico 4N.
2. Tratamiento con ácido acético 2N.
3. Tratamiento con sosa cáustica 4N.
4. Tratamiento con carbonato sódico 2N.
5. Tratamiento con una solución en partes iguales de amoníaco 27 % y

carbonato amónico 4N.
Se pueden reconocer unos 13 pigmentos blancos y cargas; 5 rojos y violetas; 5

amarillos y pardos; 7 azules y verdes, y 9 negros y grises. (CHIMIE DES
PEINTURES, 1939).
Se indica acto seguido la investigación más utilizada para el reconocimiento de

pigmentos.
Tratamiento de un color mineral en un tubo de ensayo en cantidad aproximada

de 1 gr con ácido clorhídrico.
JUNIO 2005
Los colores minerales blancos, pueden presentar tres modos de reacción:
1. Desprenden un gas inodoro que enturbia el agua de barita (anhídrido

carbónico).
2. Como el albayalde (la disolución cristaliza Cl2Pb por enfriamiento), la

creta. El gas desprendido tiene olor a ácido sulfhídrico: Como el litopón.
3. Se disuelven sin desprendimiento gaseoso: Como el blanco de zinc.
4. No se disuelven: Como el sulfato de plomo y el de bario.
Los colores minerales rojos, pueden presentar los siguientes casos de

reacción:
1. Desprenden olor a cloro calentando, como el nimio de plomo.
2. Se disuelven sin desprendimiento gaseoso, con ferrocianuro potásico

dan color azul; colores que contienen óxido de hierro.
3. Insoluble, y se volatiliza calentándolo, cinabrio.
Tratándose en la misma forma, los colores minerales amarillos dan:
1. Con ácido diluido solución amarilla y con ácido concentrado solución

verde y olor a cloro, separándose cristales al enfriar (cloruro de plomo),
amarillo de cromo. No cristaliza al enfriar: amarillo de zinc.
2. Soluble con olor a sulfhídrico: amarillo de cadmio.
3. Insoluble: amarillo de Nápoles (antimoniato básico de plomo).

JUNIO 2005
Los colores minerales verdes y azules, cuando se tratan con ácido clorhídrico
diluido en caliente, reaccionan de las siguientes maneras:
1. Se decoloran dando olor a sulfhídrico, como el ultramar.
2. Se disuelven, con coloración verde que pasa a azul cuando se añade

exceso de amoníaco: Colores minerales que contienen cobre, tales son
el verde montaña, el verde Schweinfurt, el verde Scheele.
3. Se disuelven en parte: Con ferrocianuro potásico dan coloración azul,

como la tierra verde.
4. Se disuelven apenas: Tratados con ácido concentrado la solubilidad

aumenta con coloración verde: Como el verde de cromo, el azul de
Prusia.
5. No se disuelven: Como el azul de cobalto.
4.3.20. Ensayo de los pigmentos negros y de las lacas
Los colores minerales negros, o pardos oscuros, se reconocen mediante

calefacción al aire.
1. Si la sustancia se quema, ocurren los siguientes casos:
a) No da olor bituminoso y no deja cenizas: negro de humo. Deja pocas

cenizas: negros vegetales. Deja muchas cenizas: negro animal.
b) Da olor bituminoso: Como la tierra de Colonia.
2. Si la sustancia no se quema, y cambia de color: Tierra de sombra o de

Siena naturales. Si no cambia, las mismas, tostadas.
Los colores de laca permiten una extracción del colorante con alcohol en mayor
o menor escala, o con algún otro disolvente adecuado; esta extracción se hace
en caliente. La solución alcohólica se evapora y se puede obtener el colorante
que se empleó en el lacado. El reconocimiento del mismo requiere una
JUNIO 2005
investigación de colorantes orgánicos semejantes a la que se sigue en la

industria textil, con toda su complejidad.
No acostumbra a hacerse más que en contadas ocasiones. La naturaleza del

substrato se averigua eliminando todo el colorante por calcinación, tratando el
residuo por ácido clorhídrico, y luego con los demás métodos de investigación.
4.3.21. Especificaciones sobre pigmentos
4.3.21.1. Pigmentos blancos
• Blanco de España
Se clasifica en dos calidades: especial y corriente.
1. Molido. No debe dejar un residuo mayor del 2 % a su paso por el

tamiz del núm. 300 (luz, 0,05 mm) o su equivalente de 53 micras
(núm. 270) de la A. S. T. M. (American Society for Testing
Materials).
2. Análisis químico. Determinada la riqueza en carbonato cálcico por

el dosado del anhídrido carbónico (CO2 y del óxido cálcico (CaO),
deberá resultar:
• Blanco do zinc
Existe una categoría única y puede solicitarse en polvo o en pasta.
1. Molido. Tanto el óxido de zinc en polvo como el empastado no

deben dejar un residuo mayor del 1,5 % en peso a su paso por el
tamiz núm. 300 (luz, 0,05 mm) o su equivalente de la A. S. T. M.
de 53 micras (núm. 270)
JUNIO 2005
2. Propiedades generales. El óxido de zinc no debe contener

partículas de zinc metálico. El polvo debe ser ligero, fino y de un
blanco puro. La pasta debe ser homogénea, flexible y sin grumos.
3. Análisis químico:
a) El blanco de zinc empastado debe contener:
b) El óxido de zinc en polvo debe contener:
• Albayalde en polvo y empastado
Hay una calidad única correspondiente al producto industrial puro de carbonato

básico de plomo, y puede ser expedida en polvo finamente molido, y
empastado con aceite de linaza crudo.
Proporción de pigmento y aceite del empastado. Por disolución en cloroformo y

lavado con alcohol absoluto y filtrado se separa el pigmento del aceite. La
proporción de pigmento retenida en el filtro estará comprendida entre 88 y 93
%, y el aceite separado por destilación de los disolventes, entre el 7 y el 12 %,
según lo indicado por el fabricante en su oferta.
2. Características del pigmento. Humedad: la pérdida a 100-119° C

no será superior al 0,5 %.
3. Agua combinada. Desecado previamente, la pérdida de peso,

calentado, entre 155 y 165° C, no será inferior al 1,38 % ni
superior al 3,55 %.
JUNIO 2005
4. Protóxido de plomo. Desecado previamente y calcinado después,

la pérdida de peso (CO2 y agua combinada) estará comprendida
entre 12,21 y 14,82 %, y quedará un residuo de protóxido de
plomo (PbO) comprendido entre el 85,18 y el 87,7 %.
5. Disolución en ácido nítrico. Se disolverá íntegramente.
6. Anhídrido carbónico. La proporción de CO desprendida y recogida

en el aparato de potasa estará comprendida entre el 8,66 y el
13,44 %.
7. Otros ensayos. Comprobación de que no contiene materias

extrañas, como plomo metálico, litargirio, acetato de plomo,
sulfatos de plomo, bario o calcio, litopón, carbonato cálcico o
bárico, caolín, etc., tolerándose un máximo de 2 % de dichas
materias en conjunto.
• Litopón
Hay una sola categoría de litopón y puede ser pedido en polvo o en pasta.
Debe consistir en una mezcla de sulfuro de zinc y sulfato bárico.
El litopón en polvo debe tener color blanco, ser de grano fino y estar exento de
productos grasos.
El litopón en pasta debe diluirse perfectamente en aceite de linaza, esencia de

trementina o cualquier otro diluente volátil o mezcla de los mismos.
a) Litopón en polvo:
No debe obscurecerse en contacto con el ácido sulfhídrico ni a la luz del sol.

JUNIO 2005
b) Litopón en pasta:
Estará constituido por una mezcla de pigmento en polvo que reúna las
condiciones mencionadas, aceite de linaza y un diluente.
La proporción de pigmento oscilará entre el 75 y 85 %, debiendo indicar la casa

ofertante la composición del producto.
4.3.21.2. Pigmentos amarillos, ocres o pardos
• Tierras para pintura
Las tierras para pintura se clasifican en cinco categorías:
1. Molido. Las tierras no deben dejar un residuo mayor del 2 % en

peso a su paso por el tamiz núm. 300 (luz, 0,05 mm). El residuo
debe pasar por el tamiz núm. 240 (luz, 0,062).
2. Análisis químico. La tierra es previamente calcinada para

determinar la pérdida al fuego, que debe ser:
Incluyendo en estas cifras la humedad, que se evapora antes de

los 105° C.
JUNIO 2005
Después de la calcinación, el análisis ponderal debe dar los siguientes

resultados:
• Amarillo de cromo
Existen varias categorías dependientes del tono de color que se pida, y que
será semejante al de una muestra tipo, o, cuando ésta no se indique, se
adaptará a uno de los tonos siguientes: amarillo limón, amarillo oro, amarillo
naranja. El pigmento puede ser pedido en polvo o en pasta.
1. Molido. Tanto en polvo como en pasta, el amarillo de cromo no

debe dejar un residuo superior al 2 % en peso a su paso por el
tamiz del núm. 300 (luz, 0,05 mm).
2. Análisis químico. El análisis ponderal debe satisfacer

completamente las condiciones siguientes:
a) Amarillo de cromo empastado:
b) Amarillo de cromo en polvo:

JUNIO 2005
• Ocre amarillo y ocre rojo
Los ocres (amarillo y rojo) se clasifican en dos categorías, corriente y superior,

y pueden solicitarse en polvo o en pasta.
Son pigmentos naturales que provienen de tierras arcillosas, trituradas,

levigadas y, si es preciso, calcinadas. La adición de toda carga o colorante,
mineral u orgánico, está prohibida.
1. Molido. Los ocres en polvo o en pasta no deben dejar un residuo

superior al 2 % a su paso por el tamiz del núm. 300 (luz, 0,05
mm).
El residuo debe pasar totalmente por el tamiz del núm. 240 (luz, 0,062).
2. Propiedades generales. La pasta debe ser homogénea y sin

grumos, y debe poder diluirse en aceite de linaza, esencia de
trementina, white-spirit o en una mezcla cualquiera de estos
diluentes.
El polvo mezclado con diez veces su peso de blanco de zinc en polvo y diluido
en aceite, o la pasta mezclada con diez veces su peso de blanco de zinc en
pasta, se aplican sobre una placa de vidrio; el tono obtenido debe ser igual al
de una muestra tipo.
Una capa de pintura que contenga un 60 % en peso de ocre en polvo debe

cubrir un fondo verde.
a) Ocres en pasta. Deben contener las siguientes proporciones en peso:

JUNIO 2005
b) Ocres en polvo:
El producto calcinado debe contener:
• Pardo Van Dyck
Es clasificado, según el matiz, en dos categorías, rojo y violeta, y puede ser

pedido en polvo, en pasta al aceite y en pasta a la esencia.
El pardo Van Dyck en polvo proviene de la calcinación de óxidos de hierro

naturales o artificiales. La adición de cualquier otro colorante, mineral u
orgánico, y de cualquier carga, queda prohibida.
1. Molido. El pardo Van Dyck, en polvo o en pasta, no debe dejar un

residuo superior al 1 por 100 en peso sobre el tamiz del núm. 300
(luz, 0,05 mm), y el residuo debe pasar completamente por el
tamiz del núm. 240 (luz, 0,062 mm).
a) Pardo Van Dyck en polvo:

JUNIO 2005
b) Pardo Van Dyck empastado:
4.3.21.3. Pigmentos rojos
• Carmín fino de primera
Existe una categoría única de este pigmento que debe ser obtenido,
exclusivamente, de la cochinilla «coccus cacti», quedando prohibida la adición
de toda sustancia extraña, como, por ejemplo, pigmentos minerales o
colorantes orgánicos y otra materia cualquiera, trozos de insectos, restos
vegetales, etc.
El pigmento no debe contener más de un 15 % de humedad ni más de un 10 %

de cenizas. Debe ser insoluble en agua, alcohol, éter, esencia de trementina y
aceite, y disolverse en los ácidos minerales fuertes y totalmente en el
amoniaco.
• Bermellón
El bermellón de mercurio es de una sola categoría y puede pedirse en polvo o

en pasta.
Es un sulfuro mercúrico artificial obtenido por vía seca o por vía húmeda. La
adición de cualquier colorante mineral u orgánico y e cualquier carga está
prohibida.
1. Molido. Tanto en polvo como empastado no debe dejar más del

0,5 % en peso de pigmento seco, sobre el tamiz del núm. 300 (luz
0,05 mm).
JUNIO 2005
a) Bermellón en polvo:
b) Bermellón empastado:
• Minio de hierro
El minio de hierro es de una categoría única y puede interesarse en polvo o en

pasta.
1. Molido. El minio en polvo no debe dejar un residuo mayor de 3 %

en peso a su paso por el tamiz ni 250 (luz 0,058 mm), ni el
empastado más del 3,5 %.
2. Propiedades generales. El minio en polvo debe estar

prácticamente exento de todo compuesto de azufre, cloro y
arsénico. No ha de contener más del 1 % en peso de materias
solubles en agua a + 15° C, y la solución obtenida debe ser
neutra.
a) El minio de hierro empastado debe contener:
b) El minio de hierro en polvo no dará una pérdida a la calcinación mayor del 6

%, comprendida en esta cifra la humedad que se evapora antes de los 105° C,
la cual no debe exceder del 1 %.
JUNIO 2005
Después de la calcinación debe obtenerse:
1. Ensayo de aplicación. Se prepararán y aplicarán con brocha

sobre una chapa vertical las pinturas siguientes:
2. Resultados. Doce horas después de la aplicación, la pintura no

debe manchar los dedos. Debe secar sin resbalar ni arrugarse y
formar una capa unida y dura.
• Minio de plomo (minio)
El minio de plomo es de una categoría única y se puede pedir en polvo o en

pasta.
1. Molido. El minio en polvo o en pasta no debe dejar un residuo

mayor del 1,5 % en peso a su paso por el tamiz del núm. 300 (luz,
0,05 mm), o su equivalente A. S. T. M. de 53 micras (núm. 270).
a) Minio empastado. La composición ponderal será:

JUNIO 2005
b) Minio en polvo. La composición en peso será la siguiente:
1. Ensayo de aplicación. Preparar y aplicar con brocha sobre una

chapa vertical las siguientes pinturas:
2. Resultado. La pintura debe ser lo suficientemente fluida para

poder ser extendida sin dificultad, incluso después de estar en
reposo 24 horas.
La pintura ha de secar, sin correrse ni arrugarse, y formar una capa unida, dura
y elástica.
• Minio alumino-férrico y minio titano-férrico
Son cada uno de una sola categoría y pueden solicitarse en polvo o en pasta.
El minio alúmino-férrico en polvo es un pigmento que proviene de las bauxitas

rojas o de los residuos de la fabricación de la alúmina. Cuando contienen sosa
estos residuos deben sufrir previamente un tratamiento de neutralización.
El minio titano-férrico en polvo es un pigmento que proviene de la ilmenita o de

los residuos del tratamiento de ésta para la fabricación del blanco de titanio.
La adición de toda materia mineral (sulfato bárico, sulfato o carbonato cálcico,

etc.), está prohibida.
JUNIO 2005
1. Molido. Los minios en polvo no deben dejar un residuo mayor del

3 % en peso:
a) El titano-férrico en el tamiz núm. 250 (luz, 0,058 mm).
b) El alúmino-férrico en el tamiz núm. 300 (luz, 0,05 mm).
a) Minios en polvo:
• Los minios en polvo no deben contener más del 1 % en

peso de materias solubles en agua a 15° C; la solución
obtenida debe ser neutra.
• Pérdida a la calcinación:
(comprendida en estas cifras la humedad que se evapora antes de los 105° C,

que no debe ser superior al 1 %).
• La composición ponderal después de la calcinación será:

JUNIO 2005
b) Minios en pasta.
Las proporciones ponderales serán las siguientes:
3. Ensayo de aplicación. Se preparan y extienden con brocha sobre

una chapa vertical, pinturas de la composición siguiente en tanto
por ciento en peso.
4. Resultados: Ocho horas después de la aplicación la pintura debe

haber secado sin correrse ni arrugarse y formar una capa unida y
dura.
4.3.21.4. Pigmentos verdes
• Verde cromo-férrico (verde de cromo)
Existe una sola categoría y se puede pedir en polvo, en pasta al aceite o en

pasta a la esencia de trementina.
Es una mezcla de amarillo de cromo, azul de hierro (azul de Prusia) y negro de

hueso o de humo, cargado con sulfato bárico. La adición de cualquier otra
carga está prohibida. Disuelto el polvo en aceite de linaza o en trementina, y
aplicado sobre una placa de vidrio, debe dar un tono igual al de una muestra
tipo.
JUNIO 2005
1. Molido. Tanto en polvo como en pasta no dejará un residuo

superior al 2 % en peso sobre el tamiz del núm. 300 (luz 0,05).
2. Análisis químico.
a) En pasta. La composición ponderal será:
b) En polvo:
• Verde cobalto en polvo
Existen categorías variables dependientes del tono de color que se pida.
El tono del color es semejante al de una muestra tipo o, cuando ésta no se

indique, se adaptará al tono claro, medio u oscuro que se estipule, pero en
ningún caso la cantidad de óxido cobaltoso (CoO) deberá descender del 8 %, ni
del 70 % la de óxido de zinc (ZnO).
1. Molido. El pigmento no debe dejar un residuo mayor del 2 % a su

paso por el tamiz del número 300 (luz de las mallas 0,05 mm), o
su equivalente de 53 micras (número 270) de la A. S. T. M.
2. Análisis químico. Los resultados mínimos a obtener se indican en

la tabla siguiente:
JUNIO 2005
4.3.21.5. Pigmentos azules
• Azul de Prusia (Azul de hierro)
El azul de Prusia es de una categoría única, y puede ser pedido en polvo o

empastado.
1. Molido. Tanto en polvo como empastado no debe dejar un residuo

superior al 2 % en peso a su paso por el tamiz del número 300
(luz de las mallas 0,05 mm).
2. Análisis químico.
a) Las proporciones de pigmento y aceite del azul de Prusia empastado serán

las siguientes:
b) El azul de Prusia en polvo debe satisfacer las condiciones siguientes:
• Azul de ultramar
Existe una categoría única y puede pedirse en polvo o en pasta.
1. Molido. El azul de ultramar, en polvo o en pasta, no debe dejar un

residuo superior al 1 % en peso de pigmento seco sobre el tamiz
número 300 (luz 0,05 mm).
JUNIO 2005
2. Análisis químico. Las proporciones ponderales deben ser las

siguientes:
a) Azul de ultramar en pasta:
b) Azul de ultramar en polvo:
• Azul cobalto en polvo
Existen categorías variables dependientes del tono de color que se pida.
1. Molido. El pigmento no debe dejar un residuo mayor del 2 % a su

paso por el tamiz del número 300 (luz 0,05 mm), o su equivalente
de 53 micras (número 270) de la A. S. T. M.
2. Análisis químico. Los resultados a obtener serán los siguientes:
4.3.21.6. Pigmentos negros
• Negro de hueso
El negro de hueso es de una sola categoría y puede ser pedido en polvo o

empastado con aceite, esencia de trementina o barniz.
1. Molido. El negro de hueso, en polvo o en pasta, no debe dejar un

residuo superior al 3 % en peso de pigmento seco, a su paso por
el tamiz del número 300 (luz de las mallas 0,05 mm).
JUNIO 2005
2. Propiedades generales. El tono del pigmento no debe ser ni

grisáceo ni rojizo.
Mezclado en proporción de 1 a 10 con óxido de zinc en polvo (1 de negro y 10

de blanco) debe dar un tono gris-azulado claro. Conservado al abrigo de la
humedad, el polvo no ha de aglomerarse.
La pasta debe ser homogénea y sin grumos. Debe poder diluirse fácilmente en
aceite de linaza, esencia de trementina y barnices grasos o en una mezcla
cualquiera de estos diluentes.
a) Negro de hueso empastado. Las proporciones en peso serán las siguientes:
El diluente consistirá en aceite de linaza crudo, esencia de trementina o barniz

de tintes rápido, llamado «Cola de oro», según el pedido.
b) Negro de hueso en polvo:
Las cenizas deben contener aproximadamente un 90 % de su peso de fosfato

tricálcico (PO4)Ca3, y tratadas por los ácidos no tienen que dejar más de 1 %
de residuo insoluble.
• Negro de humo
Es de una sola categoría y se puede pedir en polvo o en pasta.
1. Molido. En polvo o en pasta no debe dejar más del 1 % de su

peso de residuo a su paso por el tamiz del número 300 (luz 0,05
mm).
JUNIO 2005
2. Propiedades generales. El negro de humo en polvo debe provenir

únicamente de la combustión incompleta de materias orgánicas
hidrocarbonadas: resinas, grasas, aceites, naftalina, petróleo,
alquitrán, etc. La adición de cualquiera otro pigmento negro,
mineral, vegetal o animal, está prohibida. Ha de entregarse un
mes después de su fabricación.
El negro de humo en polvo debe tener una densidad real comprendida entre
1,69 y 1,80.
Mezclado con óxido de zinc (en polvo o en pasta, según el caso), en la

proporción de 1 de negro por 10 de blanco, en peso, y aplicado al aceite sobre
una placa de vidrio, debe dar un tono gris-azulado claro.
3. Densidad aparente (para el pigmento en polvo solamente):
Llenando un depósito metálico de 100 ml de negro de humo, por simple caída,

sin aplastamiento, y enrasándolo, el contenido no debe pesar más de 13gr.
El ensayo se efectuará según la especificación y aparato de la ASTM.
a) Negro de humo empastado. Las proporciones en peso serán las siguientes:
b) Negro de humo en polvo. El análisis ponderal debe dar:
• Grafito en polvo para pinturas
Existe una sola categoría, que corresponde a la calidad comercial llamada

“grafito plateado”. Debe consistir, exclusivamente, en carbono natural
cristalizado. Se considera como fraude la adición de cualquier materia de
JUNIO 2005
substitución o de adulteración, tales como: plombagina amorfa, carbón de

madera, carbón de retorta, negro de humo, negro de acetileno, etc.
Es de color gris plata con reflejo metálico, graso y untuoso al tacto, y

examinado al microscopio, con luz reflejada, debe dar las franjas de
interferencia características.
1. Molido. Debe pasar totalmente por el tamiz del número 200 (luz
0,075 mm), y no dejar un residuo mayor del 10 %, en peso, sobre
el tamiz del número 240 (luz 0,062).
Su densidad aparente (sin apisonar) no tiene que ser superior a 0,5.
2. Análisis químico. Los resultados en peso a obtener son los

siguientes:
• Negro de hierro
Es de una sola categoría y se pide en polvo.
Es un pigmento a base de óxido de hierro magnético, que debe ser atraído por
el imán y que no ha de contener mezcla de ningún otro negro extraño.
1. Molido. Debe pasar por el tamiz del número 300 (luz 0,05 mm) sin
dejar un residuo superior al 1,5 % en peso.
El residuo anterior ha de pasar completamente por el tamiz del número 240 (luz
0,062 mm).
2. Análisis químico. Materias solubles en agua a 15 ºC, 0,5 %

máximo en peso, y la solución obtenida debe ser neutra al
tornasol. Pérdida a la calcinación (comprendida la humedad que
se evapora antes de los 105° C), 3 % máximo. Oxido de hierro
magnético (Fe3O4) en el producto calcinado, 75 % mínimo.
JUNIO 2005
4.4. Formadores de película.
Las propiedades y composición de los aceites y resinas, usados en, la industria

de los recubrimientos de superficies, varían tan ampliamente que una misma
serie de pruebas no es aplicable a todas. Cada clase de formadores de
película, debido a su composición y a sus características físicas, requiere
pruebas especiales adecuadas a cada grupo particular. Sin embargo, unos
pocos ensayos tienen aplicación general a diversos aglomerantes.
Es difícil establecer ensayos patrones para muchas propiedades de los aceites

y resinas, tales como solubilidad en diversos disolventes, compatibilidad con
otros formadores de película, mojabilidad de los pigmentos y características de
dispersión y reactividad con los pigmentos. Estas propiedades se pueden
determinar solamente mediante ensayos reales en cada combinación particular
sobre la que se desee información.
4.4.1. Color
Véase ASTM D154-50, secciones 5-7, Método de ensayo de barnices. FSPT

Ct-1 -49, o ASTM D365-39, secciones 8-12,- Ensayos para soluciones de base
de nitrocelulosa. ASTM D1209-54, Color de líquidos transparentes (escala
platino-cobalto). ASTM D509-52, sección 2, E y F, Métodos de muestreo y
clasificación de la colofonia.
El color de una solución de resina se determina normalmente comparándola

con los patrones de color Gardner 1933. Los patrones Gardner consisten en
soluciones de referencia, de dieciocho colores permanentes, desde el blanco
agua, al ámbar oscuro. Se toman como patrones los colores obtenidos
disolviendo diversas cantidades de bicromato potásico en ácido sulfúrico
concentrado. Puesto que el color de la muestra de ácido sulfúrico y bicromato
potásico no es estable, los patrones mismos se hacen de cloruro férrico, cloruro
de cobalto y ácido clorhídrico.
La muestra de la solución de resina se pone en un tubo de ensayo pequeño y

se compara con los patrones frente a un fondo bien iluminado. Al color se le
JUNIO 2005
asigna un número del 1 al 18 según el patrón al cual se aproxima más la

muestra.
También se puede usar el comparador de colores de barnices Hellige. Este

instrumento consta de 18 muestras de colores de referencia permanentes de
cristal sobre dos discos de plástico de 100 mm de diámetro con las cuales se
compara el color de la solución de la resina.
En la prueba de color de los materiales de nitrocelulosa, se usan soluciones

patrones de cobalto-platino, en lugar de las de ácido sulfúrico-bicromato. Estos
patrones se emplean para líquidos transparentes y por esta razón se parecen
más al color natural de las soluciones de nitrocelulosa. Los patrones se
fabrican con una mezcla de cloruro de cobalto, cloroplatinato potásico y ácido
clorhídrico y se les asignan los números 5, 10, 15, 20, 25, 30, 35, 40, 50, 60,
70, 100 y 500. Los números más bajos corresponden a los Colores más claros.
El color de las resinas sólidas o de los formadores de películas, se puede

determinar, bien disolviendo la resina a una concentración determinada y
comparando el color obtenido con los de los patrones Gardner, o bien
comparándolos directamente con los doce patrones de color de vidrio incluidos
en los patrones oficiales de Estados Unidos para la colofonia. En lugar de
valores numéricos, a las colofonias patrones se les dan las designaciones X,
WW, WG, N, M, K, I, H, G, F, E y D. X corresponde al color más claro y D al
color más oscuro.
4.4.2. Temperatura de reblandecimiento de sólidos
Véase ASTM E-28-51T, Temperatura de reblandecimiento mediante el aparato

del anillo y bola.
La temperatura de reblandecimiento de las resinas sólidas y de las colas se

utiliza como un medio de control de la calidad y uniformidad de estos
materiales. Se elige el punto de reblandecimiento porque estos materiales no
tienen un punto de fusión definido. Al calentarlos se reblandecen y funden en
un amplio intervalo de temperatura.
JUNIO 2005
Uno de los medios más populares para determinar el punto de

reblandecimiento es el método del anillo y la bola. En esta determinación el
punto de fusión es la temperatura a la cual un disco hecho del material a
ensayar es forzado hacia abajo una pulgada por el peso de una bola de acero
de dimensiones y peso especificados, a medida que se calienta en un baño de
agua o glicerina.
La muestra se funde y entonces se vierte en un anillo de latón que tiene un

diámetro máximo interior de 3/4 de pulgada. El anillo frío que contiene la resina
o cola se suspende horizontalmente en un soporte hecho especialmente. Se
coloca en el centro de la muestra una bola de acero de 9,53 mm de diámetro
que pesa aproximadamente 3,50 g. Después que el conjunto se ha suspendido
en un recipiente con el líquido del baño, se va elevando lentamente la
temperatura a una velocidad normalizada. El punto de reblandecimiento es la
temperatura a la cual la bola de acero penetra en el material y desciende hasta
que la resina reblandecida, empujada por ella, toca una placa horizontal 2,50
cm por debajo,
Existen otros métodos de determinar el punto de reblandecimiento. En uno, una

muestra de resina finamente molida se pone en un tubo capilar que se coloca
después en un baño caliente adecuado. El baño se calienta lentamente y la
temperatura a la cual se derrite y funde se lee como punto de fusión.
En el método de Durrans se funden aproximadamente 3 g de resina o cola en

un tubo de ensayo que permanece en un baño de ácido sulfúrico. Después de
que se coloca un termómetro en la materia fundida, el tubo se retira del baño y
se deja enfriar. Después se vierte sobre la resina 50 g de mercurio. El tubo de
ensayo que contiene la resina, el termómetro y el mercurio, se vuelve otra vez
al baño frío y se calienta a una velocidad de 2 ºC/min. El punto de
reblandecimiento es la temperatura a la cual la resina aparece por primera vez
por encima del mercurio.
JUNIO 2005
4.4.3. Peso por litro y densidad
Uno de los métodos más convenientes para obtener el peso por litro de un
aceite, pintura, pasta, barniz o una solución de laca, es determinar el peso del
material que se requiere para llenar un recipiente patrón que tiene capacidad
para exactamente 100,0 ± 0,1 ml de agua a 25 ± 0,5 ºC o 100,2 g de agua.
Este recipiente se pesa vacío y después se llena con la muestra a 25 ºC. El
peso en gramos de la muestra dividido por 10 da el peso en kilos por litros. El
peso específico de la muestra se obtiene multiplicando el peso de la muestra
del recipiente expresado en gramos por el factor 0,012.
4.4.4. Contenido total de no volátiles
Véase ASTM D154-50, sección 14, Ensayos para barnices. TT-P-141b,

métodos 404,1 y 404,2, Contenido volátil y no volátil.
Los ensayos de peso por litro y del contenido total no volátil se usan como
medio de comparar la proporción de sólidos de una solución de resinas. Puesto
que el peso específico de la resina sólida es más alto que el del volátil o el del
disolvente en la solución de la resina, aquél da una indicación aproximada de la
cantidad de sólido existente. Las disoluciones de resina compradas se pueden
controlar de esta manera para asegurarse que en cada lote existe el contenido
de sólidos correcto desde el punto de vista del control de producción y del
económico.
Para una determinación más exacta de los sólidos totales en una solución de
resina se debe realizar un ensayo de no volátiles. Brevemente el procedimiento
es como sigue: pesar un pequeño platillo metálico de 75 mm de diámetro y 22
mm de profundidad, perfectamente seco, en una balanza analítica. Pesar, por
diferencia, en el platillo 1 g de muestra con una botella con tapón o una jeringa.
Después de dar vueltas y extender la solución de resina por igual en el fondo
del platillo, poner éste en un horno mantenido a 100 ºC ± 5 ºC durante 3-4
horas. Enfriar y volver a pesar. El peso final de la muestra, dividido por el peso
primitivo y multiplicado por 100 da el % de material sólido presente.
JUNIO 2005
4.4.5. Viscosidad de los líquidos
Véase FSPT Bt-1-51, o ASTM D553-53, secciones 71-76, Ensayos para

aceites secantes. ASTM D1343-54T, Viscosidad de los derivados de la celulosa
por el método de la caída de bola. ASTM D154-50, secciones 8-12, Ensayos
para barnices.
Puesto que no se requiere una gran precisión en las medidas de la viscosidad

de los formadores de películas, en la industria de la pintura se utilizan
normalmente los tubos de burbujas Gardner-Holdt. Este aparato que consiste
en una serie de tubos conteniendo líquidos transparentes con Viscosidades
que varían de 0,5 a 148 poises es rápido y suficientemente preciso y exacto. La
longitud interior de los tubos es 112 mm; su diámetro interior preciso es de
10,75 mm, y hay dos líneas grabadas una a 5 mm y otra 13 mm por debajo de
los extremos abiertos. Estos tubos patrones se llenan de líquido hasta la línea
de 13 mm y se cierran, dejando un espacio de aire determinado o burbuja de
dimensión conocida. La longitud de la burbuja no debe ser más grande que el
diámetro del tubo. Cuando el tubo se invierte, la burbuja asciende con una
velocidad que depende de la viscosidad del líquido en el tubo. Un tubo vacío
del mismo tamaño patrón se llena con la muestra hasta la señal de 5 mm y se
tapa con un corcho. Ensayando la serie de tubos Gardner-Holdt se selecciona
un tubo que iguale la velocidad de ascensión de la burbuja a 25 + 0,25 ºC. Los
tubos patrones se clasifican alfabéticamente desde la A a la Z. El más viscoso
Z, se subdivide en patrones de viscosidad creciente. A la viscosidad de la
muestra se la designa con la letra de la muestra patrón a la que más se
aproxima.
Para determinar la viscosidad de soluciones de derivados celulósicos tales

como nitrocelulosa, acetato de celulosa y otros líquidos viscosos transparentes
similares se utiliza el método de la caída de la bola. En este método se deja
caer una bola de acero de peso y dimensiones conocidas a través de un tubo
de vidrio que contiene la muestra y se mide el tiempo de caída entre dos
puntos del tubo.
JUNIO 2005
Una variante de este método es la utilizada por Hércules Powder Company.

Existen muchos más procedimientos e instrumentos, pero todos son
fundamentalmente parecidos. El instrumento en este caso es un tubo de 4
pulgadas de largo y 1 de diámetro, tapado por el extremo inferior. Existen dos
líneas marcadas en el tubo, una de las cuales está a 2 pulgadas del extremo
superior y la otra a 2 pulgadas del fondo. La solución a medir se vierte en el
tubo y se mantiene a la temperatura de 25 ± 0,25 ºC. Una bola de acero de
5/16 pulgadas de diámetro (el método ASTM requiere una bola de acero
inoxidable de 3/32 pulgadas) y 2,043 g de peso se moja con el disolvente y se
deja caer dentro del tubo. El tiempo que tarda la bola en caer entre las dos
marcas indica la viscosidad. Los resultados se pueden dar en segundos o en
poises. La proporción de sólidos de las soluciones de resinas es normalmente
de 12,2 %, pero para materiales de viscosidad más baja se incrementa aquélla
de manera que la caída de la bola pueda medirse con más exactitud. Las
resinas que dan soluciones muy viscosas, pueden requerir concentraciones
menores para permitir que la bola caiga en un tiempo razonable.
Para fines de control los diversos grados de resina son diferenciados por
pruebas de viscosidad normalizadas similares que dan una indicación de los
pesos moleculares medios relativos y se conocen como índice de “viscosidad
inherente” o “viscosidad específica”. A la viscosidad más alta corresponde el
peso molecular medio más alto. Existen especificaciones ASTM para medidas
de viscosidad inherentes de diversos tipos de resinas poliméricas.
4.4.6. Determinación del grado de acidez
Véase FSPT Bt-1-51, o ASTM D555-53, secciones 10-13, Ensayos para

aceites secantes. ASTM D154-50, secciones 26-28, Ensayos para barnices.
El índice de acidez de cualquier sustancia se define como el número de

miligramos de hidróxido de potasio requeridos para neutralizar los grupos
carboxílicos libres o sin reaccionar en 1 g de aceite, cera, resina o cola.
En España se llama grado de acidez la que presenta un aceite a causa de los

ácidos libres que contiene, expresada en ácido oleico por 100 gramos.
JUNIO 2005
La importancia del índice de acidez estriba en que es una buena indicación del
comportamiento que cabe esperar del material del producto acabado. Dos de
los factores implicados son los siguientes:
• La reactividad con pigmentos básicos es aproximadamente proporcional al

índice de acidez debido a la formación de jabones y ésteres.
• Las características de mojabilidad y dispersión de los pigmentos se

relacionan con la concentración de grupos carboxílicos libres.
Una muestra del material se pesa exactamente en un vaso Erlenmeyer de 250

ml; para materiales de bajo índice de acidez se emplean muestras de 20 g y
para materiales de alto índice se emplean muestras de 1 g. Se añaden 50 ml
de una mezcla neutra de alcohol-benceno, seguido de unas cuantas gotas de
fenolftaleína como indicador. Se agita hasta la disolución completa. Entonces
se valora rápidamente con una solución N/10 de hidróxido potásico hasta una
tenue coloración rosa. Este es el punto final. El índice de acidez se calcula:
Índice de acidez = ( N x ml (KOH usados) x 56,1) / peso de la muestra
N = es la normalidad de la solución de hidróxido potásico.
Para aceites oscuros y materiales asfálticos en los que es difícil o imposible ver
el cambio del indicador, debe observarse el color en la capa de alcohol encima
de la muestra después que se ha dejado sedimentar.
JUNIO 2005
La determinación de los valores que toman los índices químicos que

caracterizan los aceites, hace falta aplicar los mismos índices a las resinas.
El índice de acidez de las resinas expresa los miligramos de potasa cáustica,

KOH, necesarios para saturar los ácidos resínicos libres solubles en alcohol, de
1 gr de resina. La determinación tiene lugar disolviendo 5 gr de resma en 50 ml
de alcohol de 95°. Como la disolución de muchas resinas no es fácil, se puede
proceder de distintos modos, según un ensayo previo de solubilidad:
1. Con refrigerante a reflujo, en un matracito, de modo que el alcohol hierva

en él a bañomaría y se condense en el refrigerante, volviendo al matraz.
Como generalmente queda un residuo, las correspondientes pesadas
permiten su evaluación.
2. Con una mezcla de alcohol éter, en proporción de 1 volumen de alcohol

de 95° por 1 a 4 volúmenes de éter; o con una mezcla de 1 volumen de
alcohol de 95° por 1 a 2 volúmenes de alcohol amílico; o con una mezcla
de 1 volumen de alcohol absoluto por 1 volumen de benzol (método
Marcusson y Winterfield). Este método opera con refrigerante a reflujo y
200 ml de mezcla.
Con las de alcohol y éter o alcohol etílico y alcohol amílico, se opera en frío, en
una cápsula en la que se coloca la resina y 50 ml del disolvente, que se
decantan en un vaso de precipitados. Se trata de nuevo por otros 50 ml
procediendo a otra decantación, y aún puede repetirse con otros 50 ml si se
cree oportuno, antes de evaluar el peso del residuo previa desecación de la
cápsula en estufa. Este método es el más empleado, usando la mezcla de
alcoholes etílico y amílico.
En todos los casos hay que proceder a un ensayo de acidez de los disolventes,
añadiendo a una muestra de ellos unas gotas de solución de fenolftaleína, y
unas gotas de solución decinormal de potasa cáustica alcohólica, si fuese
necesario para lograr la aparición del color rosado característico.
JUNIO 2005
La valoración de la acidez de la resina disuelta se hace igualmente con potasa

alcohólica decinormal, debiendo agitar enérgicamente durante la
determinación, especialmente si se separan dos capas o hay formación de
precipitados. Se opera tal como se ha indicado en el caso de los aceites.
Para los distintos tipos de resinas, depende la acidez de tal modo de su origen
y naturaleza, que las variaciones son de importancia. La determinación tiene
interés en la fabricación de pinturas, pues cuanto más ácida es una resina de
un barniz para pinturas o esmalte, más difícil, hasta imposible, es el empleo de
ciertos pigmentos básicos.
c) El cálculo del número del ácido se hace multiplicando por 5,61 el número de
centímetros cúbicos de solución decinormal de hidróxido potásico gastados en
la titulación, y dividiendo por el número de gramos de resina disuelta tomados.
Si se desea expresarlo en ácido oleico, se aplicará la fórmula que se ha dado
para los aceites en la determinación de su grado de acidez. Si se desea
expresar, como algunas veces se hace, en anhídrido sulfúrico SO3 se empleará
la siguiente fórmula:
que da el tanto por ciento de SO3 siendo n el número de centímetros cúbicos

de hidróxido potásico decinormal empleados en la titulación, y 75 el peso de la
sustancia.
Para la determinación del índice de acidez de los copales Albertol, se aconseja

el siguiente método: Se disuelven 10 gr de resina en 100 cm3 de una mezcla
previamente neutralizada de 2 volúmenes de benzol y 1 de alcohol. Se añaden
50 cm3 de solución de cloruro sódico saturada en caliente, enfriada y
neutralizada; 15 ó 20 gr de cloruro sódico en polvo fino, y 20 gotas de solución
de fenolftaleína al 1 %.
La valoración se hace con disolución normal de sosa cáustica, hasta coloración

rosada. Luego se añaden tantos centímetros cúbicos de alcohol neutralizado
JUNIO 2005
como disolución alcalina se empleó, y se continúa añadiendo disolución

alcalina hasta coloración rojo intenso, valorándose el exceso de sosa con
solución normal de ácido sulfúrico hasta que desaparezca el color rojo y quede
sólo el color rosado débil. El cálculo se hace con la siguiente fórmula:
Este procedimiento tiene por objeto la determinación precisa del punto de viraje
y, por tanto, del consumo exacto de álcali, pudiéndose aplicar fácilmente a
resinas y aceites muy obscuros de color.
4.4.7. Determinación del índice de saponificación
Este valor llamado también número de KÖTTSTORFER, expresa los

miligramos de hidróxido potásico necesarios para saponificar 1 gr de aceite;
indica pues la cantidad de potasa cáustica KOH por mil necesaria para escindir
los glicéridos del aceite. Estrictamente hablando, esta segunda acepción
corresponde al llamado propiamente índice de éster; ambos valores son
solamente iguales cuando la grasa es neutra.
Para determinarlo se pesa en la balanza un vaso de unos 25 ml medio lleno de

aceite y con un cuentagotas se echan unos 2 gr en un vaso de Erlenmeyer de
unos 150 ml de capacidad. Por una nueva pesada del vaso con aceite se
conoce el peso exacto empleado en la determinación que va a efectuarse.
Se adapta al Erlenmeyer un tapón de corcho atravesado por un tubo de vidrio

de unos 75 cm de altura que deberá actuar como refrigerante. Luego se
añaden, medidos con una pipeta, 25 ml de disolución alcohólica de potasa y se
calienta el aparato al baño maría durante 30 minutos, agitando de cuando en
cuando. La ebullición será tranquila. El tubo de vidrio entrará 1 cm más que el
tapón dentro del Erlenmeyer.
Se añaden entonces unas gotas de fenolftaleína y se coloca el Erlenmeyer

debajo de una bureta con ácido clorhídrico 0,5 normal. Se añade solución hasta
que el líquido se decolore.
JUNIO 2005
Se repiten las mismas operaciones otra vez, pero ésta sin poner el aceite en el
Erlenmeyer, es decir, se hace una prueba en blanco. Se operará en ella
exactamente como en el caso anterior.
Restando del número de centímetros cúbicos de ácido gastados en este caso,

los que se gastaron en el ensayo con la muestra de aceite, se tendrá el número
de centímetros cúbicos de ácido precisos para descomponer las sales
potásicas formadas en la saponificación. Sean a; sea p el peso de aceite
empleado. 1 ml de ácido clorhídrico 0,5 normal satura 28 mg de potasa
cáustica; y el número de KÖTTSTORFER será:
La solución de potasa alcohólica se prepara disolviendo 16 gr de potasa

cáustica al alcohol en unos 15 ml de agua en un matraz aforado de 500 ml. La
disolución se diluye hasta el enrase con alcohol de 96° de buena calidad.
Después de un día de reposo, se filtra en un frasco de tapón esmerilado.
Si se opera con aceites de pescado, no debe emplearse fenolftaleína, pues

durante la saponificación se oscurecen y no dejan ver el viraje del indicador.
Empléese como a tal azul alcalino, que es rojo por la acción de los álcalis y
azul por la de los ácidos, con lo que se puede operar cómodamente. Se
prepara por disolución en alcohol al 2 % y se usa en proporción de 2 ó 3 ml
para los ensayos descritos.
La fenolftaleína se emplea en solución alcohólica, disolviendo 1 gr de

fenolftaleína en 100 ml de alcohol de 96°. Finalmente, el índice de
saponificación, que señala los kilogramos de potasa cáustica pura y sólida
necesarios para transformar 1000 kg de aceite en ácidos grasos y glicerina,
multiplicado por 0,713 da la misma cantidad expresada en sosa cáustica
NaOH.
La naturaleza de los ácidos grasos influye en el valor del índice de

saponificación. Es muy corriente un valor de 190 a 200. Cuando el peso
JUNIO 2005
molecular de los ácidos grasos es pequeño, el índice es mayor; los aceites de

crucíferas tienen un índice de saponificación alrededor de 175, por contener
ácido erúcico, de peso molecular alto.
El índice de saponificación, o de KÖTTSTORFER, da a conocer no solamente

la cantidad de hidróxido potásico en miligramos necesarios para saponificar 1gr
de la resina, sino también lleva incluidos los que corresponden a la
determinación anterior, es decir, al número de ácido, correspondiente a los
ácidos resínicos libres, o no combinados.
Para su determinación, se hierve 1 gr de la resina con refrigerante a reflujo, con

25 cm3 de disolución N/2 de potasa cáustica alcohólica. Después de 1/4 de
hora de ebullición, se añaden 100 cm3 de alcohol de 95°, y se valora el exceso
de potasa cáustica con disolución N/2 de ácido clorhídrico. El índice de
saponificación vendrá dado por:
siendo ir el número de centímetros cúbicos de ácido gastados en la titulación.
4.4.8. Determinación del índice de yodo
Véase FSPT Bt-1-51 o ASTM D555-53, secciones 23-25, Ensayos para aceites
secantes.
El índice de yodo es el número de centigramos de yodo que reacciona con un

gramo de aceite. Este valor se determina no sólo como un modo de controlar la
uniformidad de los aceites, sino como un medio para medir la capacidad del
aceite para combinarse con el oxígeno y así secar en forma de película. Cuanto
mayor es el índice de yodo, mayor será la insaturación de la molécula y mayor
la capacidad de secado del aceite. En presencia de dobles enlaces conjugados
el valor del índice de yodo no es una medida exacta del número de dobles
enlaces existentes, pero se puede usar como medio de controlar la uniformidad
de los aceites que los contienen tales como aceite de palo (aceite de tung) y de
oiticica.
JUNIO 2005
El método Wijs se basa en la adición de yodo al aceite en una disolución de

ácido acético glacial anhidro. En la prueba se añade un exceso de monohaluro
de yodo a un peso conocido de aceite en un Erlenmeyer con tapón de vidrio y
de 500 ml de capacidad. Después de un tiempo de reacción de una hora en la
oscuridad, se determina la cantidad de yodo sin reaccionar valorándolo con una
solución N/10 de tiosulfato sódico. Esto muestra indirectamente la cantidad de
yodo que ha reaccionado con el aceite. Puesto que el tiempo de reacción, la
temperatura, y la presencia de luz y humedad, afectan a los resultados
definitivos, se deben controlar cuidadosamente.
Perteneciente en su determinación a los métodos volumétricos, acostumbra a

emplearse en el reconocimiento de las materias grasas. Es de suma
importancia, ya que permite, en efecto, determinar en un aceite la cantidad de
ácidos grasos no saturados que contiene; la combinación del yodo con los
ácidos grasos tiene lugar igualmente cuando éstos se hallan formando con la
glicerina los glicéridos constituyentes del aceite.
La cantidad de yodo absorbida por el aceite será determinada por su

composición. Se toma como índice de yodo la cantidad calculada en
centígramos que absorbe 1 gr de grasa: tanto por ciento de yodo.
El motivo de esta combinación es la facultad que tienen los halógenos, en

especial el bromo y el yodo, de adicionarse a los átomos de carbono unidos por
dobles enlaces, rompiendo éstos y transformándolos en uniones sencillas. Así,
el ácido oleico se transforma en el ácido oleico yodado:
El ácido linólico que tiene dos dobles enlaces absorberá más yodo; su índice
será mayor que el ácido oleico, que tiene uno. El ácido linolénico, que tiene tres
dobles uniones, lo tendrá mayor aún.
Se ha hablado de la importancia del número de dobles enlaces en un aceite en

relación con su poder secante al tratar de los ácidos linólico y linolénico; por
JUNIO 2005
tanto, es fácil de imaginar la importancia y el interés que el índice de yodo

presenta en el reconocimiento de primeras materias para barnices y pinturas.
Soluciones empíricas de este cuerpo que se requieren:
• Para la determinación por el método Hübl
25 gr de yodo se disuelven en 500 ml de alcohol de 95°, puro; 30 gr de cloruro

mercúrico se disuelven en otros 500 ml del mismo alcohol. Ambos productos
químicos serán purísimos para análisis. Las dos soluciones se conservan en
botellas color topacio separadamente, tapadas con precaución, y se mezclan
en la forma requerida antes de su uso.
• Para la determinación por el método de Wijs
7,8 gr de tricloruro de yodo purísimo y 8,5 gr de yodo se disuelven

separadamente en porciones de ácido acético glacial puro, calentando a baño
maría, en dos matraces de Erlenmeyer. Obtenidas las dos disoluciones, se
mezclan entre sí y se lleva el volumen total a 1 litro, con más ácido acético de
la misma clase; el ácido deberá ser del 99 % de pureza y una muestra del
mismo calentada con algo de bicarbonato potásico y ácido sulfúrico, no dará
coloración verde (ausencia de cuerpos reductores).
No disponiendo de tricloruro de yodo en el laboratorio, se procede del siguiente

modo: 13 gr de yodo bisublimado se disuelven en 1 litro de ácido acético glacial
y se determina la cantidad en ml de solución decinormal de tiosulfato que
necesitan 20 ml de la solución de yodo, previa adición de yoduro potásico al
10%, agua y engrudo de almidón, para decolorarse con toda exactitud.
Luego se coloca la solución de yodo en un matraz apropiado, y se hace pasar

una corriente de cloro, lavado y seco, hasta cambio de color neto del líquido.
Este cambio es una guía, pues entonces se procede a una nueva valoración
del líquido, debiendo gastar 20 ml del mismo, valorados como antes, doble
número exacto de cm3 de solución de tiosulfato.
JUNIO 2005
• Para la determinación por el método de Hanus
10 gr de monobromuro de yodo se disuelven en 500 ml de ácido acético glacial

puro. El reactivo se puede preparar también disolviendo en caliente en ácido
acético, 6,5 gr de yodo; dejando enfriar, añadiendo luego 4 gr de bromo con
cuidado, y completando a 500 ml con más ácido acético glacial puro.
Determinación por el método clásico de HÜBL, por el método de WIJS y por el

método de HANUS, recomendado por la Comisión Internacional de Métodos
para Análisis de Grasas.
Método de Hübl. Los reactivos necesarios son: Solución de yodo. Solución de

yoduro potásico: 10 gr de yoduro potásico purísimo en 100ml de agua. Solución
de almidón: 1 gr de almidón se empasta con agua destilada, y se echa en 300
ml de agua hirviente. Se deja enfriar y se decanta la parte líquida, que es la que
se emplea. Solución de tiosulfato sódico decinormal.
Se determina su título con respecto al yodo mediante el método de VOLHARD:

Una solución acuosa de dicromato potásico purificado por cristalización y
desecado a 130° C que contenga 0,4903 gr en 100 cm3 de la cual se toman 20
cm3 a los que se añaden 10 cm3 de solución de yoduro potásico y 5 cm3 de
ácido clorhídrico de D 1,10, diluido en unos 100 cm3 de agua; es valorada en
cuanto al yodo liberado con la solución de tiosulfato que se prueba:
Durante la adición de tiosulfato se va aclarando el color, y antes de la

desaparición del mismo se añaden unos 4 cm3 de solución indicadora de
almidón; el viraje es la desaparición total de la coloración azul, obtenida al
añadir el indicador.
JUNIO 2005
El modo de operar es el siguiente: Se pesan tinos 0,2 gr del aceite en ensayo si

es secante y el doble si no lo es o se trata de una grasa sólida. Se disuelven en
un Erlenmeyer con tapón esmerilado en 15 cm3 de cloroformo; y se añaden 25
cm3 de una mezcla en volúmenes iguales de las soluciones de yodo y de
cloruro mercúrico, preparada con unas 48 horas de anterioridad.
Se agita y se deja unas 12 horas en lugar oscuro a unos 18° C. Luego se

introducen en el Erlenmeyer 20 cm3 de la solución de yoduro potásico y 200
cm3 de agua destilada, titulando el exceso de yodo con la solución decinormal
de tiosulfato, agitando continuamente e introduciendo al final 5 cm3 de la
solución de almidón para conocer el punto exacto de viraje.
Simultáneamente, se habrá operado de idéntico modo en otro Erlernmeyer,

pero sin la sustancia grasa: prueba en blanco. La diferencia entre las dos
cantidades de tiosulfato consumidas, transformada en yodo, da el número de
yodo.
Método de Wijs. Los reactivos necesarios que varían respecto al anterior son:
la solución de yodo y el disolvente de la grasa, que es el tetracloruro de
carbono. Se procede como en el método de HÜBL pero la solución de yodo no
requiere la mezcla previa, por no alterarse con el tiempo, ni más allá de dos
horas de contacto con la grasa en ensayo. El método es, pues, más cómodo y
más usado, siendo el utilizado normalmente en el examen de los aceites
secantes.
El índice de yodo de la grasa es:
en la que: p expresa cantidad de grasa; a, centímetros cúbicos de tiosulfato en

la prueba en blanco; b, centímetros cúbicos de tiosulfato promedio de las
determinaciones en la grasa.
JUNIO 2005
Método de Hanus. Los reactivos necesarios son: Solución de monobromuro de

yodo. Solución de tiosulfato decinormal, cuya valoración se ha expuesto.
Engrudo de almidón, como se ha indicado. Solución de yoduro potásico al 15%.
Se pesan de 0,2 a 0,4 gr de la sustancia, y el doble si el índice de yodo es bajo,

que se disuelven en 10 ml de cloroformo. Se añaden 25 ml de la solución de
yodo. La reacción tiene lugar en una media hora. Se añaden luego 10 cm3 de la
solución de yoduro potásico, 50 ml de agua destilada y se valora el yodo como
anteriormente.
La determinación exacta de índices de yodo requiere varias determinaciones

promediadas. Es preciso además que la cantidad absorbida por la grasa sea
aproximadamente la mitad de la que queda libre para la valoración, y por ello
deben guardar relación las cantidades de grasa pesadas con la solución de
yodo empleada, según sea más o menos secante el aceite analizado. En el
método de HÜBL, a menudo se prepara la solución de dicromato con 3,865 gr
de éste por litro, para la valoración del tiosulfato. Entonces 20 ml de la solución
de dicromato liberan 0,2 gr de 1 del yoduro potásico, y el número de
centímetros cúbicos de solución de tiosulfato gastada equivale a 0,2 gr de
yodo.
4.4.9. Determinación del índice de Maumené
Llamado también grado termosulfúrico, de importancia para la industria de

pinturas y barnices, expresa el aumento de temperatura que se produce
cuando se mezcla una sustancia grasa con ácido sulfúrico. Los aparatos más
usados son el termómetro de TORTELLI, y el de JEAN. El primero consiste en
un recipiente de dobles paredes, constituyendo una cámara intermedia en la
que se ha hecho el vacío.
Un termómetro especial, con unas aletas agitadoras a ambos lados del bulbo,
permite apoyándose en el fondo y mediante un movimiento de rotación
alternativo dado con los dedos, leer los aumentos de temperatura y una
agitación adecuada. 20 ml del aceite en examen se introducen en el recipiente,
se agita y lee la temperatura. Luego se introducen 5 ml de ácido sulfúrico de
JUNIO 2005
D=1,8413, y se agita vigilando la subida del termómetro, hasta el punto

máximo.
Es preciso que 20 ml de agua destilada, puestos en el aparato y añadidos de

los 5 ml de ácido de la densidad señalada, den un índice térmico de 50. En el
ensayo, ácido y aceite estarán a la misma temperatura. A menudo se hace el
grado de MAUMENÉ con 50 gr de ácido sulfúrico de 66° Bé, en un vaso
corriente, agitando con un termómetro ordinario. Desde luego, la concentración
del ácido es factor principalísimo.
4.4.10. Determinación de los ácidos grasos
Para separar de los aceites los ácidos grasos que los constituyen, se emplea
generalmente el método de DALICAN. Se parte de 50 gr de la materia grasa, a
los que se añaden, en una cápsula de porcelana, 40 gr de potasa cáustica
disueltos en 20 ml de agua y 40 ml de alcohol etílico de 96°. Se efectúa la
saponificación calentando al baño maría y agitando, y una vez completa, se
añade agua caliente hasta 1 litro de volumen total, haciéndose hervir para que
se marche el alcohol, 1 hora.
La cápsula deberá ser, pues, suficientemente grande. Se añade ahora ácido

sulfúrico diluido para separar los ácidos grasos, que quedan formando una
capa en la superficie; que una vez completa, limpia y transparente, se deja
enfriar si son sólidos y se pasan a un vaso donde se lavan con agua hirviendo
por fusión y nueva solidificación.
Si hay líquidos, se filtra el contenido caliente de la cápsula, con su capa

aceitosa de ácidos grasos al través de un filtro tarado, lleno de agua hasta su
mitad, pasando los líquidos acuosos y quedando los ácidos grasos sin pasar.
Hay que hacer varios lavados tanto en un caso, como en otro hasta que las
aguas de loción no sean ácidas; para pesar los ácidos grasos hay que
introducir el filtro lleno de ellos y en el momento en que escurrida el agua vayan
a escurrir ácidos grasos, en un vaso tarado: secado a la estufa, como se
conoce el peso del vaso y el del filtro, se puede hallar por diferencia el de
JUNIO 2005
ácidos grasos. Los pesos obtenidos se reducen luego por cálculo a 100 de
grasa.
El residuo insaponificable contenido en los aceites, va en este método incluido

en los ácidos grasos separados. Sobre los ácidos grasos obtenidos se
determina el punto de fusión, según se ha expuesto en el lugar adecuado;
como asimismo la temperatura de solidificación.
Los ácidos grasos líquidos no saturados, oxidables con facilidad, necesitan que
el secado se haga en atmósfera inerte de anhídrido carbónico o de nitrógeno.
La separación cuantitativa de ácidos grasos sólidos y líquidos, requiere la

obtención de sus sales de plomo.
Para ello se saponifican al baño maría en un Erlenmeyer de 150 ml, 3 gr del

aceite con 25 ml de potasa alcohólica mitad normal. La solución de jabón
conseguida se neutraliza con ácido acético y fenolftaleína como indicador, y se
vierte en un Erlenmeyer que contiene a la ebullición 200 ml de agua y 30 ml de
acetato de plomo al 10 %.
Agitando entonces bajo el grifo de agua fría, se forma el jabón de plomo

adherido a las paredes del Erlenmeyer. Se decanta la parte líquida y se lava el
jabón con dos o tres aguas, y una vez vertida la última, se añaden 100 ml de
éter. Montado un refrigerante a reflujo, se calienta al baño maría hasta que el
residuo insoluble en el éter sea pulverulento. Se recoge este residuo por
filtración, lavándose el Erlenmeyer con algo de éter que se filtra igualmente, y
se lava también con éter el precipitado obtenido en el filtro.
Este jabón de plomo corresponde a los ácidos grasos sólidos contenidos en la

grasa en examen. Tratado con ácido clorhídrico diluido en caliente, se escinde
en un matracito el cloruro de plomo y ácidos grasos, que extraídos con éter y
evaporado el disolvente, se pueden pesar.
El filtrado etéreo procedente de la separación de este jabón de plomo, contiene

disuelto el jabón de plomo correspondiente a los ácidos grasos líquidos.
Colocado en un embudo de separación, se le adiciona ácido clorhídrico diluido
JUNIO 2005
para escindirlo por agitación. Una vez separadas las dos capas y eliminada la
acuosa y las aguas de lavado, la solución de ácidos grasos líquidos en la capa
etérea se trasvasa a un matracito tarado y se destila al baño maría
cuidadosamente, quedando como residuo los ácidos grasos líquidos, que se
pueden pesar.
Los ácidos grasos oxidables de los aceites secantes deben ser protegidos
durante la destilación por una atmósfera de gas inerte (carbónico, nitrógeno) en
el matraz, cuyo tapón tendrá un tubo de entrada de gas, que barboteará en el
líquido, desalojando el aire.
Las sales de plomo de los ácidos grasos líquidos no saturados oleico, linólico,
linolénico y clupanodónico, son solubles en éter sulfúrico y en éter de petróleo;
las de los ácidos grasos sólidos saturados láurico, mirístico, palmítico y
esteárico, son insolubles; los ácidos grasos sólidos no saturados elaidínico,
erúcico, brasídico y eleosteárico, tienen sus sales igualmente insolubles.
La separación cuantitativa de los ácidos grasos no saturados de los saturados,

se hace a partir de los ácidos grasos totales separados de la grasa en examen,
según el método descrito al principio de este apartado. Eliminando los
insaponificables, lo que se consigue una vez suprimido el alcohol de la solución
jabonosa y antes de separar los ácidos grasos con el ácido sulfúrico,
extrayéndolos de dicha solución jabonosa con éter en un embudo de
separación, resulta desprovista aquélla de substancias extrañas, que quedan
en la capa etérea.
Con los ácidos grasos totales obtenidos, se preparan los ésteres metílicos o
etílicos de los ácidos, por esterificación con el alcohol, siendo esta una
operación larga. Después de verificada, se procede a la destilación fraccionada
de los ésteres conseguidos, manipulación que requiere rigurosos cuidados.
El contenido en ácidos grasos líquidos no saturados de un aceite, se puede

deducir del número de yodo de la sustancia grasa, y del número de yodo de los
ácidos grasos líquidos separados de ella.
JUNIO 2005
Siendo el primero I, y el segundo I (líq.), se tiene:
4.4.11. Determinación de los bromocompuestos
Los bromocompuestos, que se obtienen por adición de Br con rotura de

enlaces, a los ácidos grasos no saturados constituyentes de los aceites,
suministran datos de gran interés.
Del ácido oleico se obtiene el ácido dibromoesteárico, soluble en alcohol, éter,

benzol.
Punto de fusión.: 29°C. De los ácidos erúcico y brasídico, se obtienen los

derivados dibromados correspondientes, que funden a 43 y a 54°C
respectivamente, solubles en los mismos disolventes dichos.
Del ácido linólico, en sus isómeros cis y trans existentes en los aceites
naturales, o sea el α-linólico y el β-linólico, se obtiene el ácido
tetrabromoesteárico, soluble en alcohol, éter, benzol. Punto ebullición: 114°C el
derivado tetrabromado del ácido α-linólico, y líquido a la temperatura ordinaria
el del ácido β-linólico.
El ácido linolénico da el hexabromoesteárico, soluble en benzol, cloroformo;

insoluble en éter. Punto ebullición: 175-180°C.
Los ácidos grasos de los aceites de pescados, dan octo y

decabromocompuestos, que se descomponen sin fundir cerca de los 200 ºC, y
son insolubles en los disolventes indicados para los bromocompuestos
anteriores.
El índice de hexa-bromocompuestos para reconocimiento del aceite de linaza,

que mide su riqueza en ácido linolénico, y el de octo-bromocompuestos (deca-
bromocompuestos) para reconocimiento de los aceites de pescado, se
practican sobre los ácidos grasos por el método de HAIPHEN, mediante su
JUNIO 2005
reactivo brómico, compuesto de 280 ml de ácido acético glacial, 40 ml de

nitrobenzol y 10 ml de bromo.
Para la primera reacción, se puede partir de 5 ml de aceite de linaza, que se

baten enérgicamente en una probeta con tapón esmerilado, con 100 ml del
reactivo, durante algunos minutos. Por reposo se separa un precipitado
amarillo del compuesto que se forma con el ácido linolénico.
Para la segunda es preciso partir de los ácidos grasos separados: 10 ml de

ellos se tratan similarmente con 200 ml de reactivo brómico, obteniéndose un
precipitado semejante de los bromocompuestos de los ácidos del aceite de
pescado.
Ambos precipitados se pueden diferenciar por su solubilidad en benzol

hirviente, en el que se disuelve el procedente del aceite de linaza y en el que
no se disuelve el procedente del aceite de pescado.
Para la determinación cuantitativa de los índices de bromocompuestos, se

parte siempre de los ácidos grasos separados. Estos índices designan la
cantidad de bromocompuestos que dan 100 gr de ácidos grasos.
Método de Hehner y Mitchell para el aceite de linaza: 2 gr de ácidos grasos

separados como se ha indicado se disuelven en 40 ml de éter y 5 ml de ácido
acético glacial. Se enfría a 0 ºC y se añade bromo gota a gota hasta coloración
rosa persistente. Luego de un reposo de unas 3 horas se filtra sobre filtro
secado a 100 ºC y tarado. El precipitado se lava con alcohol, luego con éter, se
deseca en la estufa y se pesa. Se determina el punto de fusión, que será de
175 a 180°C, si se han eliminado bien en el lavado los derivados bromados
solubles en alcohol y en éter.
Se calcula la cantidad de hexabromuro que corresponde a 100 gr de sustancia

grasa, o sea el índice, y éste multiplicado por 0,357 da el porcentaje de ácido
linolénico en aquélla.
Método de Halphen y Marcuson para el aceite de pescado: 10 ml de ácidos

grasos separados como se ha indicado, se agitan enérgicamente con 200 ml
JUNIO 2005
del reactivo brómico de HALPHEN. Se deja en reposo unas 3 horas y se opera

como en el método de HEHNER y MITCHELL.
Para el examen de la solubilidad en benzol, se emplean 50 ml del mismo por

1gr del precipitado; y se hace hervir a baño maría en un Erlenmeyer con
refrigerante a reflujo (un largo tubo basta). Caso de tratarse de una mezcla de
aceites de pescado y aceite de linaza el precipitado es soluble parcialmente en
benzol, pudiéndose deducir de la proporción disuelta, las de la mezcla.
Otros aceites secantes que tienen ácido linolénico dan en mayor o menor
proporción hexa-bromocompuestos; y que con el método de HEHNER y
MITCHELL, los aceites de animales marinos dan también octo-
bromocompuestos.
4.4.12. Determinación de la glicerina
La glicerina se investiga en una sustancia calentándola con algunos cristalitos

de bisulfato potásico, desprendiéndose un irritante olor a acroleína. Se
determina saponificando 20 gr de la materia grasa, similarmente a como se ha
expuesto en la separación de los ácidos grasos. Una vez disuelto el jabón,
evaporado el alcohol y precipitados aquéllos con ácido sulfúrico, se separan
por filtración, tanto sólidos como líquidos, mediante filtro.
El líquido acuoso ácido (a causa del ácido sulfúrico) que contiene la glicerina,
se concentra a baño maría hasta pequeño volumen, se alcaliniza con una
lechada de hidrato cálcico (obtenida apagando 150 gr de óxido cálcico con
agua hasta un volumen total de 500 ml) hasta reacción alcalina fuerte. Se
añaden unos gramos de arena limpia y lavada, y se concentra al baño maría
hasta pasta blanda, agitando con una varilla, en cuyo momento se extrae la
glicerina añadiendo alcohol de 96°, debiendo quedar atacada toda la masa.
Se filtra entonces en un matracito, lavando con alcohol de 96º el contenido del

filtro; y poniendo un refrigerante al matraz, que deberá contener unos 150 ml de
líquido, se destila el alcohol, evaporando las últimas porciones quitando el
refrigerante, siempre a baño maría.
JUNIO 2005
Queda en el matracito un residuo espeso, como un jarabe, que se disuelve

entonces en alcohol absoluto en el mismo balón; se añade luego un volumen
de éter anhidro igual a una vez y media el de alcohol absoluto empleado,
apareciendo por reposo un precipitado de impurezas que se separa después
por filtración a través de un filtro pequeño, recogiendo la solución
alcohólicoetérea de glicerina en un vaso tarado, cuyo contenido se concentra a
baño maría, sin que llegue a hervir, hasta expulsión de la mezcla alcohol-éter;
hallándose por diferencia el peso de glicerina correspondiente a los 20 gr de
sustancia grasa de que se partió.
4.4.13. Comportamiento con el ácido nitroso
La reacción de la elaidina se practica poniendo en un tubo de ensayo 10 gr de

aceite y añadiendo 5 ml de ácido nítrico de D = 1,40. Se agita unos minutos
hasta homogeneidad, y se añade 1 gr de mercurio metálico, agitando después
enérgicamente y dejando luego en reposo unas 24 horas. Se observa que el
aceite de oliva da una masa sólida; los aceites de colza, sésamo, algodón y
pescado, dan una masa pastosa; los aceites de linaza, nuez y adormidera dan
una masa líquida. La masa sólida es amarillenta, la pastosa es más o menos
coloreada, y la líquida es anaranjada. Con mezclas de aceites se obtiene una
gama de resultados intermedios.
4.4.14. Investigación de aceites minerales
La adición de aceites minerales a las grasas naturales puede investigarse

saponificando con 5 ml de lejía alcohólica de sosa, normal, 2 gr del aceite o
grasa en cuestión; en un tubo de ensayo grande o en un pequeño matracito,
que se hace hervir en un baño maría un tiempo suficiente.
Luego se añade un volumen tres veces mayor que el total, de agua, y se

calienta; observando si la solución es completa o no. Es transparente si no hay
parte mineral insaponificable, y se produce un enturbiamiento mayor o menor si
aquélla existe.
JUNIO 2005
Las sustancias insaponificables que se hallan en los aceites, pueden ser de

procedencia natural, o en el caso de las primeras materias para barnices y
pinturas, haber sido añadidas con fines de adulteración, hallándose incluidos
en este caso los aceites minerales.
Para la determinación cuantitativa de las sustancias insaponificables, se tratan

a la ebullición en un Erlenmeyer provisto de refrigerante a reflujo y calentado a
baño maría, 10 gr de aceite con 5 gr de potasa cáustica disueltos en 20 ml de
agua destilada y 50 ml de alcohol de 95°, hasta saponificación completa.
Se añaden luego unos 80 ml de agua, y frío, se pasa todo a un embudo de

separación en el que se agitan con 50 ml de éter de petróleo de punto de
ebullición no superior a 60° en ninguna de sus fracciones. Separada la capa
etérea, se repite la extracción con otros 50 ml de éter de petróleo, luego una
tercera vez con otros 50 ml.
Los 150 ml de éter de petróleo recogidos, en los que se hallan los

insaponificables, se colocan en un aparato de destilación calentando a baño
maría, cuyo matraz ha sido tarado previamente con las precauciones del caso.
Verificada la destilación y colocado el matraz a la estufa de 80 a 90° C hasta
peso constante, el peso obtenido corresponde a los insaponificables contenidos
en los 10 gr de aceite empleados, con lo que fácilmente se tiene el tanto por
ciento en el aceite examinado.
Si el residuo insaponificable está formado por substancias naturales, alcanza

hasta un 2 % en general (fitosterina o colesterina e su mayor parte) y es soluble
en alcohol de 90°. Si está constituido además por aceites minerales, la solución
es turbia.
4.4.15. Diferenciación de los aceites animales y vegetales
Algunas veces tiene mucha importancia en la industria de pinturas y barnices,

dictaminar si un aceite es de procedencia animal o vegetal. Esta diferenciación
se consigue con el examen del residuo insaponificable: en el caso de proceder
éste de una grasa animal, contiene siempre un alcohol cíclico superior, la
JUNIO 2005
colesterina; y en el caso de proceder de una grasa vegetal, contiene siempre

otro alcohol cíclico superior, la fitosterina, ambos cristalizables.
Se opera generalmente con el método de BÖMER: 100 gr de aceite se

saponifican en un Erlenmeyer de 1 litro de capacidad con 60 ml de solución
acuosa de potasa (obtenida disolviendo 100 gr de potasa pura en 150 ml de
agua destilada), y 140 ml de alcohol de 95º. Se calienta a baño maría con
refrigerante a reflujo (un tubo largo basta).
Verificada la saponificación y bien homogénea la solución de jabón, se pasa a

un embudo de llave de capacidad suficiente al que se añaden también las
aguas de loción del Erlenmeyer, y en el que habíanse colocado 300 ml de agua
destilada.
Una vez todo frío, se echan en el embudo 800 ml de éter sulfúrico, y se agita.
Separado el éter, se saca la capa acuosa y aquél se coloca en un aparato de
destilación apropiado: téngase sumo cuidado en el manejo de tal cantidad de
éter, y para la agitación en el embudo así como para la destilación, tórnense las
precauciones aconsejadas para su manejo.
Con los 400 ml primeros de éter recogidos, se repite la extracción de la

solución jabonosa, así como con los siguientes 400 ml añadiéndolos al matraz
del aparato de destilación, que llevará un embudo de llave. Destilado todo el
éter, queda en el matraz el insaponificable.
El residuo obtenido en el matraz de destilación, se disuelve en alcohol absoluto

caliente, y puesto en una capsulita de vidrio, se deja cristalizar, cosa que tarda
a veces varias horas. Luego se examina al microscopio: los cristales de
colesterina forman laminitas transparentes; los de fitosterina, agujas largas y
sedosas. Si el aceite fuese una mezcla de grasas vegetales y animales, los
cristales toman una nueva forma.
Si se quiere determinar el punto de fusión de los acetatos de colesterina y de

fitosterina, que es de 114,5° C para el primero y de 130° C en promedio para el
JUNIO 2005
segundo, se trata el residuo cristalino con anhídrido acético. Es operación que

exige varias cristalizaciones.
4.4.16. Determinación del poder secante
Método de Livache, que exige preparar primeramente plomo precipitado,

sumergiendo una lámina de zinc en una solución de acetato o de nitrato de
plomo al 10 % acidulada con ácido nítrico.
El precipitado se lava con agua, alcohol y éter y se deseca. Puesto en una

capsulita de vidrio, se pesa 1 gr de este plomo; se le añade 0,5 gr del aceite a
examinar, de modo que verificando la operación gota a gota quede humedecida
toda la masa, poniendo las gotas en distintos lugares de ella. Se expone a la
acción del aire, de la luz, y a temperatura constante, pesando y determinando
el aumento de peso debido a la absorción de oxígeno, durante varios días,
hasta peso constante.
Con las debidas variaciones, este método permite medir el poder secante de
los productos empleados con tal fin, generalmente resinatos y linoleatos
metálicos. Para ello se substituye el plomo precipitado por arena silícea fina y
limpia, lavada con ácido clorhídrico diluído y luego con agua.
Se disuelve el secante en el aceite a ensayar y una vez enfriada la solución, se

toma nota del tiempo que tarda en conseguirse el aumento máximo, hasta peso
constante; que expresa la capacidad del agente para cumplir su misión
aceleradora del proceso de oxidación del aceite.
El proceso de la desecación y el momento de producirse el secado superficial

completo, se pueden seguir y determinar mediante los métodos de GARDNER
y de SANDERSON, para barnices, aceites y secantes.
El primero consiste en un tambor con movimiento de relojería, en el que se

arrollan lentamente unas tiras pintadas con el aceite o barniz en estudio,
simultáneamente con otra cinta de papel. Conocida la velocidad del tambor, se
puede conocer el tiempo empleado en el arrollamiento de cierta cantidad de
cinta. Al desarrollar éstas, una vez terminado el experimento, se halla el
JUNIO 2005
momento preciso en que la tira pintada y la de papel no se han pegado,

determinándose el tiempo que ha sido necesario, por la longitud de la cinta
arrollada.
El aparato de SANDERSON consiste en un disco que gira lentamente, sobre el

que se extiende el aceite o barniz en estudio. Por un embudito cae arena fina
sobre el disco, de tal modo que al terminar el experimento, invirtiéndolo y
haciendo caer la arenilla no pegada, se puede conocer el momento en que dejó
de pegarse. El resultado puede reducirse a tiempo, sabiendo el empleado por
el disco en dar una revolución completa.
Según un primer ensayo, se determina la velocidad del disco que será

necesaria para graduar el movimiento de manera que no caiga arena dos
veces consecutivas sobre un mismo lugar, lo que impediría conocer el
momento final. Se indicó en el estudio del aceite de linaza el método de
determinación del poder secante por extensión del material sobre láminas de
vidrio, empleado corrientemente en la práctica, expresando el tiempo necesario
para el secado.
4.4.17. Índice de dienos
Los dobles enlaces conjugados adicionan anhídrido maleico, de tal modo que
desaparece uno de aquéllos que se reemplaza por una nueva combinación; el
hecho es de importancia en el estudio de las resinas artificiales. KAUFMAN ha
podido establecer un método que permite determinar el número de dobles
enlaces conjugados existentes en una sustancia, puesto que cada molécula
gramo de ésta adiciona anhídrido maleico según normas determinadas.
JUNIO 2005
Para la determinación del índice de dienos, el reactivo empleado se prepara

con 10 gr de anhídrido maleico purísimo, que se disuelven en 1000 ml de
acetona purísima, igualmente. A 10 ml de esta solución se añaden 100 ml de
agua destilada y se valora con solución decinormal de hidróxido sódico y
fenolftaleína como indicador, empleando esta última al 1 % como siempre, pero
disuelta en acetona en lugar de alcohol.
La determinación tiene lugar colocando en un tubito de vidrio cerrado a la

lámpara por un extremo, de 0,10 a 0,25 gr de la sustancia a ensayar, e
introduciéndolo en un matracito o ampolla de vidrio de unos 20 ml de capacidad
y cuello largo, que pueda cerrarse a la lámpara también después de haber
introducido en él 10 ml del reactivo maleico.
Cerrado el cuello de la ampolla, se coloca ésta en un baño de parafina a 100ºC

durante 20 horas. Verificada la reacción, se abre la ampolla una vez enfriada,
se pasa su contenido y las aguas de loción a un Erlenmeyer y se añade un
poco de cloruro sódico puro.
Después de un reposo de 6 horas, se filtra y se añade al filtrado el indicador

fenolftaleina acetónica; se valora con solución decinormal de sosa cáustica.
Siendo a (los centímetros cúbicos de solución empleados en la titulación del
reactivo) y b (los empleados en la titulación del producto obtenido), su
diferencia será el equivalente al anhídrido maleico consumido en la operación
(habrá siempre, naturalmente, exceso de éste en ella). El índice de dienos es:
siendo p el peso de sustancia tomada.
Este índice se expresa, como se puede deducir de la fórmula, por el tanto por
ciento de yodo equivalente al anhídrido maleico absorbido por la sustancia en
examen.
Como dimensiones para el tubito se indican 12 mm de largo por 6,5 mm de

diámetro exterior, y para el cuello de la ampolla, 10 cm de largo y 8 mm de
JUNIO 2005
diámetro interior. La cabida del Erlenmeyer será de 250 ml y las aguas de

loción serán en total unos 100 ml. La adición de cloruro sódico tiene por objeto
destruir la emulsión formada.
La evaluación del índice de dienos se considera más exacta neutralizando por

yodometría. Para ello, el contenido de la ampolla se pasa al Erlenmeyer,
lavando con 20 ml de benzol y 20 ml de agua. Se añaden 15 ml de una
solución conteniendo en 100 ml, 4 gr de yodato y 24 gr de yoduro potásicos; y
25 ml de solución decinorinal de tiosulfato, dejando 2 horas en reposo. Luego
se añaden 25 ml de solución decinormal de yodo, preparada disolviendo en
agua destilada 12,692 gr de yodo bisublimado y 20 gr de yoduro potásico y
completando a 1000 ml y se valora con solución decinormal de tiosulfato.
4.4.18. Índice de rodán
KAUFMAN ha establecido un procedimiento para determinación del índice de

yodo rodanométrico, que expresa semejantemente en tanto por ciento de yodo
la proporción de tiocianógeno (SCN) adicionada por la grasa.
Para la determinación del índice de rodán se añade a 250 ml de ácido acético

glacial destilado sobre anhídrido fosfórico 15 gr de sulfocianuro de plomo puro
y bien seco. A otros 250 cm3 del mismo ácido acético se añaden 4 gr de bromo;
se mezclan cuidadosamente ambas soluciones y se filtra. Ocurre la reacción:
Quedando el sulfocianógeno libre en el filtrado. Se valora la solución tomando

20 ml de ella, añadiendo 20 ml de solución de yoduro potásico al 10 %, 20 ml
de agua y valorando el yodo liberado con tiosulfato sódico decinomal.
El índice se determina pesando 0,2 gr de aceite en un matracito con tapón

esmerilado, añadiendo 20 ml de solución de sulfocianógeno, dejando en reposo
24 horas en sitio oscuro; luego se añade solución de yoduro potásico 20 ml (si
ha habido necesidad de tomar más sulfocianógeno a causa de requerirlo el
aceite que se determina, se pondrá el mismo volumen que se tomó), otro tanto
JUNIO 2005
volumen de agua destilada y se valora el yodo con solución decinormal de

tiosulfato.
Se tendrá:
Siendo a, los centímetros cúbicos de tiosulfato empleados en la valoración en

blanco, y b, los empleados en la determinación; p, es la cantidad pesada de
sustancia. La solución de tiocianógeno es inestable.
Con el índice de yodo (I), y el índice de rodán (R), se puede calcular la

composición de los ácidos grasos de un aceite.
Cuando éste contiene ácido oleico, ácido linólico y ácido linolénico, caso del
aceite de linaza, se tiene, siendo los ácidos grasos sólidos separados ácidos
saturados, adicionándoles los insaponificables y la glicerina, valor (N) de las
fórmulas:
Cuando el aceite contiene además ácido eleosteárico, caso del aceite de

madera o de mezclas de éste con el de linaza, se necesita también el índice de
dienos (D):
El valor (N) no comprenderá el ácido eleosteárico, sólido, no saturado.

JUNIO 2005
4.4.19. Punto de precipitación
Una investigación que tiene a menudo interés en el examen de las resinas

destinadas a la preparación de barnices al alcohol es la del punto de
precipitación. Se entiende por éste el momento en que empieza a separarse un
precipitado en una disolución alcohólica de resina, cuando se le añade agua
destilada. Para la determinación se toman 3 gr de resina, que se disuelven en
12 ml de alcohol de 95°; se filtra y se recogen 9 ml del filtrado, que colocados
debajo de una bureta en un vasito de precipitados, y llenada aquélla con agua
destilada, permite medir la cantidad, en centímetros cúbicos o en décimas,
necesaria que hay que añadir para la aparición del punto de precipitación
(WOLFF).
4.4.20. Especificaciones de formadores de película
4.4.20.1. Barnices
• Barniz graso para pulimentar y acabar
Existen dos categorías:
Consisten en una disolución en esencia de trementina de soluciones de gomas

naturales duras en aceite de linaza. La secatividad se obtiene indiferentemente
por medio de óxidos o sales de plomo, manganeso o cobalto. Las proporciones
en peso de goma, G, y aceite, A, son tales que:
JUNIO 2005
Los barnices no deben contener aceites o esencias minerales ni colofonia o

resinatos, cuyas trazas pueden provenir de impurezas de la trementina. No
pueden ser servidos hasta después de madurados 1 año como mínimo.
Extendidos con brocha deben correr bien, sin tirar, cubrir bien y formar una vez
secos una capa delgada, lisa y brillante.
El barniz de pulimentar debe poder pulimentarse a las 18 horas de su

aplicación y dar una superficie mate 24 horas después del pulimentado.
Una capa de barniz de acabar, aplicada sobre un fondo terminado por dos
capas de barniz pulimento debe resistir sin agrietarse 2 años de exposición
vertical a la intemperie y a mediodía.
o Ensayos en estado líquido.
1. Ensayo de limpidez y colorimétrico. Un tubo de ensayo de vidrio

incoloro se llena de barniz y se compara, por observación
transversal con luz directa, con una solución reciente colocada en
otro tubo idéntico y compuesta de
El barniz deber ser límpido y su color no será más oscuro que el de esta
solución.
2. Viscosidad. La viscosidad a 25° C debe estar comprendida en los

límites.
3. Neutralidad. El barniz debe ser neutro al tornasol.
4. Secatividad. Extendido a brocha sobre placa de vidrio y puesto a

secar en una habitación bien aireada a 15-20 ºC y grado
higrométrico de 0,45 a 0,85, el barniz debe secar en los límites.
JUNIO 2005
5. Volatilidad. 2 gramos de barniz en un cristalizador de 70 mm de

diámetro, colocado 4 horas en una estufa a 105-110° C, no deben
dar, por evaporación, una pérdida superior al 50 % en peso.
6. Inflamabilidad. El punto de inflamabilidad en el LUCHAIRE debe

ser superior a + 30° C.
• Barniz graso de tintes
Existen dos categorías:
El barniz de tintes está constituido por una disolución en esencia de trementina

de soluciones de gomas naturales duras en aceite de linaza. La secatividad se
obtiene indiferentemente por medio de óxidos o sales de plomo, manganeso o
cobalto. En cualquier caso la proporción ponderal de plomo no debe exceder
del 5 %.
Las proporciones ponderales de goma, G, y aceite, A, serán tales que:
El barniz no debe contener aceites o esencias minerales, ni colofonia o

resinatos, cuyas trazas pueden provenir de impurezas de la esencia de
trementina.
Los barnices deben ser límpidos y no tienen que formar depósitos.

JUNIO 2005
o Ensayos en estado líquido.
1. Ensayo de limpidez y colorimetría. Comparar un tubo de ensayo

de vidrio incoloro, por observación transversal y luz directa, lleno
de barniz, con otro idéntico lleno de una solución recién
preparada y de la siguiente composición:
El barniz debe ser límpido y su color no será más oscuro que el

de esta solución.
2. Ensayo de viscosidad. La viscosidad a 25° C ha de estar

comprendida dentro de los límites fijados en la clasificación.
3. Neutralidad. Los barnices deben ser neutros al tornasol.
4. Volatilidad. La pérdida de peso por evaporación de 2 gramos de

barniz, colocados en un cristalizador de 70 mm de diámetro en
una estufa a 105-110° C durante 4 horas no será superior al 55%.
5. Inflamabilidad. El punto de inflamabilidad en el LUCHAIRE debe

ser superior a 30°C.
6. Secatividad. Preparar una pintura de la composición siguiente, en

peso:
Aplicada con brocha sobre una placa de vidrio debe secar en los
límites marcados en la clasificación.
JUNIO 2005
• Barniz negro mineral
Es una disolución de brea de hulla en benzol. La proporción en peso de brea

seca que funde a 70°C (método de KRAEMER-SARNOW) no es inferior a 45%.
El barniz tiene que ser homogéneo, no debe depositarse ni dar vapores

molestos.
Extendido a la brocha debe correr sin tirar, y formar, al secar, una capa de color
francamente negro, lisa, brillante y muy opaca.
1. Viscosidad. A 25°C la viscosidad estará comprendida entre 110 y 220

centistokes.
2. Secatividad. Extendida una capa normal de barniz sobre una placa de

vidrio (9 x 12 cm), y dejado secar en una habitación bien aireada a 15-
20° C, y un grado higrométrico de 0,45 a 0,85, al cabo de 10 horas el
barniz no dejará huella al paso de los dedos.
3. Volatilidad. La pérdida a 105-110° C en una estufa durante 4 horas de 2

gr de barniz colocados en un cristalizador de vidrio de 70 mm de
diámetro, no será superior al 55%.
4. Inflamabilidad. En vaso cerrado (LUCHAIRE) el punto de inflamabilidad

debe ser superior a los 30°C.
5. Neutralidad. Ha de ser neutro al tornasol.
6. Resistencia al calor. Una chapa lisa y desengrasada con una capa de

barniz se deja secar, verticalmente, en una habitación a 15-20°C y de
0,45 a 0,85 de humedad, durante 120 horas. Transcurrido este tiempo
se introduce verticalmente durante 8 horas en una estufa de 60 a 65°C.
El barniz no debe hincharse, descolgarse ni correrse.

JUNIO 2005
4.4.20.2. Aceites, diluentes, aparejos y secativos
• Aceite de linaza crudo
a) Especificaciones de los ferrocarriles franceses.
El aceite deberá provenir exclusivamente del tratamiento de los granos del lino
Estará exento de toda mezcla de otros aceites o de cualquier otra materia
extraña al estado de disolución, suspensión o deposito.
1. Aspecto. El aceite debe estar y quedar límpido después de agitado

enérgicamente y no enturbiarse o formar deposito.
2. Densidad. La densidad a + 15° C estará comprendida entre 0,930 y

0,936.
3. Índice de ácido. Será inferior o igual a 4.
4. Impurezas sólidas. Separadas por dilución del aceite en el benceno

puro, filtrando y lavando con el mismo disolvente, no pasaran de
0,2%.
5. Secatividad. Se deposita en el centro de una placa de vidrio

finamente pulida unas gotas de aceite que se extiende por toda la
superficie con ayuda de una varilla de vidrio cilíndrica y bien recta El
exceso de aceite se lleva a los bordes y se quita Se obtiene así una
capa regular cuyo peso es de 0,5 a 1 mg por centímetro cuadrado La
placa se coloca bien horizontal en una estufa a 100° C con
ventilación interior Al cabo de 3 horas, como máximo, la película
debe estar seca y formar un barniz transparente, sen incoloro y
resistente al frotamiento de los dedos.
b) Especificaciones de la American Society for Testing Materials (ASTM).
El aceite de linaza debe ser aceite puro obtenido por el prensado de la linaza, y
ha de tener las siguientes características:
JUNIO 2005
Color no más oscuro que una solución recientemente preparada de 1,0 gr de

K2Cr2O7 en 100 ml. de H2SO4 puro (densidad 1,84).
Si se desea un tipo de aceite de linaza de alto índice de yodo, el mínimo índice

de yodo será 188.
• Aceite de linaza cocido
a) Especificaciones de los ferrocarriles franceses.
Debe ser obtenido por cocción del aceite de linaza puro con óxidos de plomo y
de manganeso.
1. Pureza. Estará exento de cualquier otra materia y particularmente de

resinas, resinatos y productos volátiles.
2. Aspecto. Debe ser límpido, sin dar lugar a enturbiamientos o depósitos

en los recipientes que lo contienen.
3. Densidad. A 15°C estará comprendida entre 0,940 y 0,960.
4. Proporción de plomo y manganeso. Se pesan 5 ó 10 gr de aceite en una

cápsula de porcelana y se carbonizan a baja temperatura. El residuo se
disuelve en ácido nítrico puro, diluido con un volumen igual de agua
destilada. En el líquido y en las aguas de lavado se pesa el plomo y el
manganeso por los procedimientos clásicos, debiendo encontrarse:
5. Secatividad. Efectuado el ensayo como se indica para el aceite crudo, la

película debe estar seca al cabo de 45 minutos y formar un barniz
JUNIO 2005
transparente, sensiblemente incoloro y resistente al frotamiento de los

dedos.
b) Especificaciones de la American Society for Testing Materials (A. S. T. M.).
1. Propiedades. Debe ser aceite de linaza puro, que haya sido cocido
incorporándole compuestos de plomo y, a elección del fabricante,
compuestos apropiados de otros metales secantes. Así se obtiene un
producto que puede secar rápidamente. Ha de ser claro, no presentar
sedimentos y tener las siguientes características:
Modo de efectuar el ensayo de secatividad. Se extiende el aceite sobre una

placa de cristal perfectamente limpio y se coloca en posición vertical al aire, a
una temperatura de 30° C y un grado higrométrico de 0,32. Transcurridas 2
horas se prueba a intervalos el secado, tocando con un dedo a la placa a una
distancia del borde no menor de 2,5 cm. La película de aceite puede
considerarse seca cuando el dedo no se adhiere a ella ni deja ninguna huella al
frotar ligeramente su superficie con el dedo.
• Esencia de trementina
Los resultados a obtener en los ensayos que se indican a continuación son

límites absolutos. Toda muestra que no cumpla completamente las condiciones
fijadas puede originar el rechazo del lote correspondiente.
1. Aspecto y pureza. La esencia debe estar bien rectificada; es incolora o

muy ligeramente verdosa o amarillenta. Será completamente límpida, no
contendrá agua ni dará lugar a depósito alguno. Ha de estar
completamente exenta de esencia mineral.
JUNIO 2005
2. Índice de ácido. Será inferior o igual a 1,5.
3. Densidad. Medida a + 15 ºC, será superior a 0,860.
4. Índice de refracción. Para la raya D, a la temperatura de + 15 ºC, será de

1,470, con una tolerancia de 0,005 en más o en menos.
5. Residuo de evaporación. Poner 50 gr de esencia en un cristalizador de

70 mm de diámetro. Evaporar al aire en bailo de aceite a temperatura de
158° C. El residuo de la evaporación debe estar comprendido entre 2 y
4%.
6. Destilación. La esencia comienza a hervir, a la presión de 760 mm de

mercurio, a una temperatura superior a 152° C. Por bajo de los 170° C
debe haber destilado al menos el 90 % de su peso.
• «Filling-up»
Está constituido a base de polvo de pizarra.
Las otras materias que entren en su composición se dejan al arbitrio del

fabricante, siempre que el producto cumpla las condiciones del análisis
químico.
Es un polvo ligero y fino de color neutro, grisáceo, azulado o rojizo. Debe pasar
por el tamiz número 100 (luz 0,160 mm) sin dejar un residuo mayor del 2 %.
1. Análisis químico. La proporción ponderal debe ser:
El carbonato cálcico que entre en «varios» no debe exceder del 3 % del peso
total.
JUNIO 2005
2. Ensayo de apreciación y lijado. Sobre una chapa pulida y desengrasada

se aplican a brocha, con 6 horas de intervalo, dos capas de la
composición siguiente:
Después de 12 horas secando, la capa debe ser suficientemente dura para

dejarse lijar al agua con piedra pómez o papel de lija sin estropearse.
La superficie lijada debe ser lisa, mate y no absorbente.
• Aparejo graso para fondos de pintura
Se obtiene por disolución en esencia de trementina de una mezcla de materias

pigmentarias y barnices a base de gomas naturales duras.
Las proporciones de pigmento, (P), gomas naturales, (G), y aceite secante, (A),
seré tales que:
La proporción de plomo no pasará de 1,5 %.
El aparejo graso no debe contener: cerusa, aceites o esencias minerales,

colofonia o resinatos (las trazas de éstos pueden provenir de impurezas de la
trementina).
El aparejo debe pasar completamente por el tamiz número 180 (luz 0,084 mm).
Debe ser de color neutro, grisáceo, azulado o rojizo. Su densidad a 15-20° C

estará comprendida entre 1,6 y 1,8. Debe cubrir bien, secar rápidamente y
JUNIO 2005
soportar el recubrimiento de cualquier pintura grasa o celulósica sin originar

ampollas ni grietas, tanto durante la aplicación como durante el secado.
o Ensayo al estado líquido.
1. Viscosidad. Se determina en un aparato que en esencia está

formado por un depósito cilíndrico de 85 mm de altura y 80 mm de
diámetro, con fondo troncocónico, provisto de un orificio calibrado
de 3 mm de diámetro. Los 50 primeros centímetros cúbicos deben
tardar en salir de 1,5 a 5 minutos, a la temperatura de 15-20°C.
2. Volatilidad. La pérdida de peso por evaporación en una estufa a

105-110° centígrados, durante 4 horas, de 2 gr, colocados en un
cristalizador de vidrio de 70 mm de diámetro, no debe exceder del
30 %.
3. Inflamabilidad. En el Luchaire el punto de inflamabilidad debe ser

superior a 30° C.
4. Neutralidad. Debe ser neutro al tornasol.
o Ensayos al estado seco.
Las probetas para estos ensayos son chapas pulidas y desengrasadas con una
mano de imprimación de la composición siguiente, en peso:
No deben ser utilizados hasta 24 horas después de la imprimación.
1. Ensayo de lijado. Sobre la mitad de una de las probetas,

preparadas como se indica anteriormente, se dan 2 capas del
aparejo graso, con 6 horas de intervalo.
JUNIO 2005
Doce horas después de la aplicación de la segunda capa, el aparejo debe estar

lo bastante duro para permitir lijarlo al agua con piedra pómez o papel de lija
sin estropearse. La superficie obtenida debe ser lisa y mate.
2. Ensayo de revestimiento. La probeta utilizada en el ensayo

anterior, lavada y seca durante 24 horas, se recubre en toda su
superficie de una capa de pintura de laca verde. La parte con
aparejo no debe ser absorbente.
Después del secado el tono y brillo debe ser idéntico en toda la superficie de la
chapa, no distinguiéndose una mitad de otra.
3. Ensayo de doblado. Se efectuará en la forma que se indica para

este ensayo en general.
El aparejo debe resistir dos flexiones sin desprenderse, agrietarse ni

pulverizarse por el frotamiento con los dedos.
• Secativos para pinturas
Los secativos para pinturas se clasifican en dos categorías:
a) Secativo en polvo.
El secativo en polvo está compuesto por una mezcla de borato de manganeso

y sulfato cálcico natural. La proporción mínima en peso de manganeso metálico
será de 1,5 %.
b) Secativo líquido.
El secativo líquido es una mezcla de esencia de trementina y aceite de linaza

cocido en presencia de óxidos o sales de manganeso, plomo o cobalto. La
proporción total en peso de metal no será inferior a 5 %, cuando entre un
compuesto de plomo, y a 2 % en el caso contrario. La proporción de esencia de
trementina no debe exceder de 75 %. El secativo no ha de contener aceites o
esencias minerales, ni colofonia o resinatos, cuyas trazas pueden provenir de
impurezas de la esencia de trementina.
JUNIO 2005
1. Aspecto. El secativo en polvo es impalpable y francamente

blanco. No debe aglomerarse El secativo liquido es límpido. No
debe formar grumos ni depósitos.
2. Ensayo de secatividad. Preparar una pintura de la composición

siguiente:
Extender con brocha, sobre una placa de vidrio, una capa de esta pintura, a
razón de 1 gr por decímetro cuadrado. Ponerla a secar en una sala bien
aireada a 15-20° C y grado higrométrico de 0,45 a 0,85.
Pasar suavemente la yema de un dedo sobre la capa a 2 cm por lo menos, del

borde de la placa, y anotar el momento en que comienza a no dejar huella.
Resultados:
a) Al secarse, la capa no debe arrugarse ni agrietarse.
b) El dedo no debe dejar huella al cabo de un tiempo comprendido entre 3 y 5

horas para el secativo líquido y de 9 a 15 horas para el secativo en polvo.
JUNIO 2005
4.5. Disolventes.
En la norma ASTM D-268-49 se indican diversos ensayos para la composición

y las impurezas de los disolventes. Entre ellos están el contenido de agua, la
acidez, la alcalinidad, el índice de éster de los disolventes ésteres, y la
corrosión del cobre y del mercurio. Los disolventes afectan a muchas de las
propiedades de los recubrimientos de superficies, tales como el brillo, la fluidez
y la resistencia al enrojecimiento.
4.5.1. Color
Véase ASTM D268-49, Pruebas para disolventes y diluyentes de lacas.

Sección 4.
El color es importante, particularmente si el disolvente se utiliza para pinturas

blancas o de colores pastel. La decoloración puede indicar la presencia de
grupos no saturados, tales como olefinas u otros contaminantes que pueden
causar con el tiempo un posterior oscurecimiento.
Para este ensayo se utilizan dos tubos Nessler de 100 ml, los cuales, excepto
en los extremos del fondo, han sido cubiertos con papel. Se llena un tubo con
la solución patrón que se forma disolviendo 0,003 g de bicromato potásico en
un litro de agua destilada. La muestra se coloca en el segundo tubo y se
compara con el patrón. Las comparaciones se realizan colocando los fondos de
los tubos Nessler contra una hoja de papel blanco. La muestra es blanco-agua
si es más claro que el color patrón.
Véase ASTM D1209-54, Color de los líquidos transparentes.
Recientemente en lugar del patrón de bicromato, se han usado los patrones de

color platino-cobalto para medir el color de los líquidos transparentes. Estos
patrones se obtienen de una mezcla de cloruro de cobalto y cloroplatinato
potásico en una solución de ácido clorhídrico débil.
JUNIO 2005
4.5.2. Olor
Véase FSPT Dt-4-49, Procedimiento 7, ASTM D268-49, Procedimiento 7.
El olor, especialmente de mercaptanos o compuestos de azufre, puede

significar contaminación o una purificación defectuosa de la producción. Este
olor molesto llega hasta la pintura final, pero se puede comprobar mojando una
tira de papel filtro con la muestra sospechosa y dejando que el disolvente se
evapore. La materia residual sobre el papel de filtro se comprueba para ver si
contiene sustancias odoríferas.
Véase TT-P-141b, método 418.3, Peso específico de los hidrocarburos

aromáticos.
El peso específico se puede usar para diferenciar entre hidrocarburos alifáticos

y aromáticos, ya que los alifáticos tienden a ser más ligeros en peso que los
aromáticos. El peso específico se mide con un hidrómetro, una balanza
Westphal (balanza para el peso específico) o un picnómetro.
4.5.4. Toxicidad
No hay ensayos de laboratorio específicos para los efectos tóxicos de los

disolventes. Sin embargo, para investigar los nuevos disolventes que se han de
usar, es una buena norma consultar el U.S. Public Health Service, o un buen
libro de consulta. Una de las fuentes recomendadas para esta información es
Toxicity of Industrial Organic Solvents por Ethel Browning, Chemical Publishing
Co., New York, 1953.
4.5.5. Intervalo de destilación
Véase FSPT-Dt-2-48 o ASTM D86-54, Destilación de gasolina, nafta, keroseno

y productos similares del petróleo. TT-P-141 b, método 430,1. Destilación de
los alcoholes minerales y disolventes volátiles similares.
JUNIO 2005
El ensayo de destilación vale para estimar la pureza de un disolvente y para

obtener una idea general de su velocidad de evaporación. El aparato
empleado, la velocidad de destilación y aun la posición del termómetro en el
frasco de destilación afecta el intervalo de temperaturas de destilación del
disolvente. Para controlar estas condiciones se utiliza normalmente el pro-
cedimiento FSPT o el ASTM en la industria de la pintura. El procedimiento es
destilar 100 ml de disolvente, a una velocidad de 4-5 ml/min, y registrar las
temperaturas cuando se recoge el destilado. Todo el equipo, así como la
velocidad de calentamiento, están normalizados.
4.5.6. Velocidad de evaporación
Véase la Especificación Federal TT-P-141b, método 536.1.
Se pone en la tapa de un bote de 100 cm3 un gramo del volátil a ensayar, y se

determina a intervalos la pérdida por evaporación pesando la tapa y el
contenido. En lugar de este ensayo se puede emplear otro similar, en
condiciones idénticas de temperatura y de flujo de aire, en el cual se sustituye
la muestra por tolueno. Después se comparan las curvas de pérdida de tiempo
en función del tiempo. Este ensayo es lento y no muy exacto.
Un ensayo de velocidad de evaporación, que se considera más rápido y más

exacto, fue ideado en 1955 por la New York Society for Paint Technology. En
este procedimiento, se ponen 2 ml del disolvente en un tubo de centrifugación
modificado, que se sumerge horizontalmente en un baño, mantenido a la
temperatura constante de 25 ºC. A través del tubo y con un flujo constante, se
pasa hidrógeno o aire seco a 25 ºC. A intervalos, dependiendo de la velocidad
de evaporación del disolvente, el tubo se pone en la posición vertical y se lee el
volumen del disolvente que queda en la escala. Se puede entonces trazar una
curva de los porcentajes del volumen evaporado en función del tiempo.
Las velocidades de evaporación de los disolventes de las lacas se expresan

frecuentemente relacionadas con las del acetato de butilo, el cual tendrá por
tanto una velocidad de evaporación igual a 1,0. Por ejemplo, el valor de la
JUNIO 2005
velocidad de evaporación para la acetona es 7,7. Esto significa que la acetona

se evapora 7,7 veces más rápidamente que el acetato de butilo.
4.5.7. Punto de inflamación
Véase ASTM D-1310-54T. Ensayo para determinar el punto de inflamación de

materiales volátiles inflamables mediante el aparato Tag en crisol abierto. FSPT
Dt-1-48 o ASTM D56-52, Ensayo para determinar el punto de inflamación
mediante el probador Tag cerrado.
Los disolventes de bajo punto de inflamación pueden ser peligrosos, a menos

que se tomen las debidas precauciones en su manejo y uso. Las
reglamentaciones de transportes requieren que todos los materiales de pinturas
que se inflamen por debajo de 215 ºC lleven una marca roja y se manipulen de
un modo especial.
En todos los ensayos de punto de inflamación el material se coloca en

recipientes y se incrementa la temperatura a velocidades específicas en baños
adecuados. A medida que aumenta la temperatura del material, aumenta
también la presión de vapor y la concentración de los vapores del disolvente
inflamable en los recipientes. En intervalos determinados entran en contacto
con los vapores pequeñas llamas de determinado tamaño. La temperatura del
material a la cual los vapores arden es el punto de inflamación.
4.5.8. Poder de disolución
Véase FSPT Dt-7-51 o ASTM D1133-54T, Índice de Kauri-Butanol de los

disolventes hidrocarburos.
El disolvente se vierte desde una bureta en una cantidad de una solución

normalizada de goma Kauri en butanol, agitando continuamente. Cuando hay la
cantidad suficiente de disolvente, la goma Kauri se descompondrá, enturbiando
la solución y oscureciendo la impresión en un trozo de periódico colocado
debajo. La solución tolera mayores cantidades de disolventes de alto poder de
disolución que los que tienen poder de disolución bajo antes de que tenga lugar
la descomposición. La cantidad de disolvente que tolera la solución de Kauri en
JUNIO 2005
butanol es, por tanto, la medida del poder del disolvente. Los valores elevados
KB indican un gran poder de disolución.
Véase FSPT Dt-6-52 o ASTM D1012-51, Punto de anilina y punto de anilina

mezclada de disolventes hidrocarburos.
El punto de anilina es la temperatura a la cual un volumen de hidrocarburo

disuelve un volumen igual de anilina químicamente pura recientemente
destilada. Si la mezcla es transparente a la temperatura ambiente, se enfría
hasta que la solución empiece a enturbiarse. Si se enturbia a la temperatura
ambiente se calienta hasta que tenga lugar la disolución. La temperatura de la
interfase entre el enturbiamiento y la transparencia se llama punto de anilina.
Para disolventes cuyo punto de anilina es lo suficientemente bajo como para

que congele la anilina, se utiliza el punto de anilina mezclada. Este es también
la temperatura mínima de la solución de una mezcla de dos volúmenes de
anilina, uno del disolvente y otro de heptano normalizado. Los procedimientos
de ensayo son los mismos que para la determinación del punto de anilina.
ASTM D1132-50T, Índice de heptano de los disolventes hidrocarburos.
Este ensayo se realiza para determinar el poder de disolución de los

hidrocarburos de gran poder de disolución para cualquier resina que sea
soluble en ellos. Es útil porque algunas de las modernas resinas sintéticas,
tales como las fenólicas, pueden comportarse de manera diferente que la goma
Kauri.
Con el disolvente a ensayar se forma una solución del 50 % en peso de una

resina. La solución se valora con heptano, que tiene un poder de disolución
pequeño, hasta que un enturbiamiento oscurece la impresión de un trozo de
papel situado debajo. Se hace una solución similar de la resina en tolueno, que
tiene casi el mayor poder disolvente que es posible alcanzar con un
hidrocarburo como disolvente. La solución de tolueno se valora también hasta
el punto de enturbiamiento con heptano normal.
JUNIO 2005
Cuanto mayor es la capacidad de disolución del disolvente a ensayar, mayor

cantidad de heptano tolerará la solución de resina hecha a partir de él. El índice
heptano del disolvente se calculará como sigue:
Índice de heptano = ( A / B )x 100,
A = volumen de heptano tolerado por la solución resina-disolvente;
B = volumen de heptano tolerado por la solución de tolueno-resina.
Véase FSPT Dt-4-49 o ASTM D268-53, Ensayos para disolventes y diluyentes

de lacas; sección 32-36, Relación de dilución del tolueno.
La relación de disolución del tolueno se utiliza para determinar el poder de

solubilidad para la nitrocelulosa de los disolventes activos de la laca. Se
expresa como el número máximo de volúmenes de tolueno que se pueden
añadir a un volumen del disolvente a ensayar hasta que se produzca la
descomposición de una concentración de 8 g de nitrocelulosa por 100 ml de la
mezcla de disolvente-tolueno.
Por supuesto, se puede utilizar en mezclas de disolventes activos, o mezclas

de disolventes activos y latentes, siendo un ensayo práctico porque es simple y
da una idea exacta de la cantidad de diluyente que se puede usar para
abaratar una mezcla de disolvente de laca.
Una solución de nitrocelulosa en el disolvente o en la mezcla de disolventes se

valora con tolueno bajo una vigorosa agitación hasta que se alcance el punto
final con la primera aparición definida y persistente de enturbiamiento o gel. El
ensayo se hace de nuevo con la composición de la solución corregida de
acuerdo con el contenido de sólidos seleccionados arbitrariamente de 8 ± 1 g
de nitrocelulosa a 100 ml de disolvente y tolueno combinados, ya que el
porcentaje total de nitrocelulosa en la solución afecta considerablemente a los
resultados obtenidos.
Un punto a estudiar del poder de disolución, es la selección del disolvente

adecuado o de la mezcla de disolventes para utilizarlos con resinas nuevas.
JUNIO 2005
Cuando se crea una resina nueva se debe encontrar un disolvente adecuado

para ella o no será práctica para usar en los recubrimientos de superficies.
Estos ensayos sobre disolución no se pueden normalizar. El disolvente más
adecuado para un tipo determinado de resina se puede determinar únicamente
mediante un estudio sistemático de las características de disolución de los
diferentes disolventes en la resina en cuestión.
4.5.9. Efecto sobre la viscosidad del vehículo
Además de la capacidad de un disolvente para disolver una resina

determinada, es muy importante la viscosidad de la solución así obtenida.
Normalmente es conveniente que las disoluciones de las resinas en los
disolventes tengan baja viscosidad, puesto que la viscosidad baja hace posible
un contenido mayor de sólidos en los recubrimientos de superficies, y por tanto
películas secas más gruesas por mano de pintura.
Por consiguiente, la viscosidad de las soluciones de resinas obtenidas con

diversos disolventes se indica con frecuencia dentro de las características de
funcionamiento.
JUNIO 2005
4.11. Bibliografía.
• Tecnología de los recubrimientos de superficie. Dean H. Parker. Ed.

Urmo (1970).
• Tecnología de pinturas. Tomo II. Henry Fleming Payne. Editorial

BLUME. España, (1973).
• Química y tecnología de pinturas y revestimientos. J. Bentley y G. P.A.

Turner. (1980).
• Tecnología química de barnices y pinturas. Antonio Campins. Ed.

Reverté. (1951).
• Normativa ASTM. 1995.

JUNIO 2005
4.12. Normativa ASTM.
(Ver documentación adjunta)

Designation: D 12 – 88 (Reapproved 1998)
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Specification for

Raw Tung Oil1
This standard is issued under the fixed designation D 12; the number immediately following the designation indicates the year of original
adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript
epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 2090 Test Method for Clarity and Cleanness of Paint and
1.1 This specification covers raw tung oil derived from Ink Liquids3
Aleurites fordii Hemsley. D 3278 Test Methods for Flash Point of Liquids by Small
Scale Closed-Cup Apparatus4
2. Referenced Documents
3. Properties
2.1 ASTM Standards:
3.1 Raw tung oil shall conform to the requirements given in
D 93 Test Methods for Flash Point by Pensky-Martens
Table 1 .
Closed Tester2
D 555 Guide for Testing Drying Oils3 TABLE 1 Properties of Raw Tung OilA
D 1466 Test Method for Sampling Liquid Oils and Fatty ASTM
Acids Commonly Used in Paints, Varnishes, and Related Requirements Test
Materials3 Method
D 1541 Test Method for Total Iodine Value of Drying Oils Specific gravity, 25/25°C 0.933 to 0.938 D 1963
Acid value, max 5.0 D 1639
and Their Derivatives3 Saponification value 189 to 195 D 1962
D 1544 Test Method for Color of Transparent Liquids Unsaponifiable matter, max, % 0.75 D 1965
(Gardner Color Scale)4 Iodine value (Wijs), min 163 D 1959
Total iodine value, min 220 D 1541
D 1639 Test Method for Acid Value of Organic Coating Clarity clear and transparent D 2090
Materials3 at 25°C
D 1955 Test Method for Gel Time of Drying Oils3 Color (Gardner), max 12 D 1544
Flash point, min 203°F (95°C) D 3278B
D 1959 Test Method for Iodine Value of Drying Oils and 250°F (121°C) D 93
Fatty Acids3 Gel time, minutes, max 12 D 1955
D 1962 Test Method for Saponification Value of Drying Tung oil quality test pass D 1964
Refractive index, 25°C 1.5160 to 1.5200
Oils, Fatty Acids, and Polymerized Fatty Acids3 A
A relationship between refractive index and tung oil adulteration with other oils
D 1963 Test Method for Specific Gravity of Drying Oils, is described in “Paint Testing Manual,” Gardner-Sward-13th Edition, 1972, Chapter
Varnishes, Resins, and Related Materials at 25/25°C3 2.1, Section 12.1, p. 62.
D 1964 Test Method for Tung Oil Quality3 B
Test Methods D 3278 are useful only at temperatures up to 230°F, but may be
used to test for the presence of volatile solvents as evidenced by a flash point of
D 1965 Test Method for Unsaponifiable Matter in Drying 230°F or lower.
Oils, Fatty Acids, and Polymerized Fatty Acids3
4. Test Methods
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 4.1 Sampling—Sampling shall be conducted in accordance
and Related Coatings, Materials, and Applications and is the direct responsibility of with Test Method D 1466.
Subcommittee D01.32 on Drying Oils. 4.2 The significance of the test methods enumerated under
Current edition approved Oct. 31, 1988. Published December 1988. Originally
published as D 12 – 15 T. Last previous edition D 12 – 87. properties in this specification is discussed in Guide D 555.
2
Annual Book of ASTM Standards, Vol 05.01. 5. Keywords
3
Annual Book of ASTM Standards, Vol 06.03.
4
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; tung oil
The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connection
with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such
patent rights, and the risk of infringement of such rights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your
views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
1
Designation: D 13 – 97

Spirits of Turpentine1
This standard has been approved for use by agencies of the Department of Defense.
1. Scope 2.2 Other Standard:

1.1 This specification covers the following kinds of spirits Naval Stores Act of 1923 (42 Stat 1435.7 U.S.C.-91-99) as
of turpentine as defined by the Naval Stores Act and Termi- amended in 19513
nology D 8042: gum spirits of turpentine, steam-distilled wood 3. Properties
turpentine, sulfate wood turpentine, and destructively-distilled
wood turpentine. 3.1 Spirits of turpentine shall be pure and shall conform to
1.2 The purchaser should specify the kind of spirits of the requirements prescribed in Table 1.
turpentine desired. 4. Appearance
1.3 This specification is no longer widely used as it only
specifies physical characteristics and not chemical composi- 4.1 Spirits of turpentine shall be clear and free from
tion. This specification was developed when the chief use for suspended matter and water.
turpentine was as a solvent. Currently, especially in the United 5. Color
States, only a very limited quantity of turpentine is used as a
solvent. Its main end use is as a raw material for the 5.1 The color shall be “standard” or better.
preparation of polyterpene type resins and synthetic organic 6. Odor
chemicals. In spite of its limited application as a solvent, and
6.1 The odor shall be characteristic of the kind of spirits of
hence the limited use of this specification, it is considered to be
turpentine specified. If desired, deliveries shall conform to the
important to retain this specification. When information is
odor of the sample agreed upon between the purchaser and the
required on chemical composition, gas chromatography is the
seller.
recommended procedure (see Test Method D 30092).
2. Referenced Documents 7. Test Methods
2.1 ASTM Standards: 7.1 The material shall be sampled and the properties enu-
D 233 Methods of Sampling and Testing Turpentine2 merated in this specification determined in accordance with the
D 804 Terminology Relating to Naval Stores, and Related Methods D 233.
Products2 8. Keywords
D 3009 Test Method for Composition of Turpentine by Gas
8.1 turpentine
Chromatography2
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of
Subcommittee D01.34 on Naval Stores.
Current edition approved July 10, 1997. Published September 1997. Originally
3
published as D 13 – 14 T. Last previous edition D 13 – 92. Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
2
Annual Book of ASTM Standards, Vol 06.03. Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.
1
D 13
TABLE 1 Physical Requirements
Gum Spirits of
Wood Turpentine
Turpentine
Destructively
Steam Distilled Sulfate
max min Distilled
max min max min max min
Specific gravity, 15.6/15.6°C 0.875 0.860 0.875 0.860 0.875 0.860 0.865 0.850
Refractive index at 20°C, D line 1.478 1.465 1.478 1.465 1.478 1.465 1.483 1.463
Initial boiling point at 760-mm Hg 160 150 160 150 160 150 157 150
pressure,° C
Distilling below 170°C at 760-mm Hg ... 90 ... 90 ... 90 ... 60
pressure, %
Distilling below 180°C at 760-mm Hg ... ... ... ... ... ... ... 90
pressure, %
2
Standard Test Methods for

Sampling and Testing Lac Resins1
1. Scope by Bubble Time Method5

1.1 These test methods cover procedures for sampling and D 1959 Test Method for Iodine Value of Drying Oils and
testing orange shellac, button lac, garnet lac, and bleached lac. Fatty Acids5
1.2 The sampling procedures and test methods appear in the E 11 Specification for Wire-Cloth Sieves for Testing Pur-
following order: poses6
Sections
Sampling: SAMPLING
Orange Shellac, Button Lac, and Garnet Lac 3
Bleached Lac 4 3. Orange Shellac, Button Lac, and Garnet Lac
Identification of Samples 5
General Requirements for Test Methods: 3.1 Lot Size—For the purpose of sampling, the quantity of a
Reagents 6 lot of any one of these types of lac resin shall not exceed 500
Source and Preparation of Portions of Sample for bags or packages. The net weight of lac resin in each bag or
Tests 7
Insoluble Matter 8 to 9.5 package shall not exceed 75 kg.
Iodine Value 10 to 10.3 3.2 Source and Number of Samples—Only original un-
Purity 11 to 13.2 opened bags or packages shall be sampled. Ten percent of the
Volatile Matter (Moisture) 14 to 15.2
Wax 16 to 16.4 containers in every lot of lac resin shall be taken at random, but
Matter Soluble in Water 17 to 17.2 not less than 5 nor more than 25 containers shall be taken.
Ash 18 to 18.2 3.3 Free-Flowing Lac Resins—In sampling free-flowing lac
Color 19 to 19.4.3
Color of Orange Shellac 20 to 20.4.4 resins, samples shall be drawn from different places in each
Acid Value 21 to 21.4 container in double handfuls or by means of a suitable sampler
Orpiment 22 to 22.4 such as a grain sampler. A total of approximately 2.7 kg shall
Saponification Value 23 to 23.4
be taken.
1.3 This standard does not purport to address all of the 3.4 Blocked or Matted Lac Resin—Pieces of blocked or
safety concerns, if any, associated with its use. It is the matted lac resin shall be chipped with an axe, pick, or other
responsibility of the user of this standard to establish appro- suitable instrument from each container taken for sampling.
priate safety and health practices and determine the applica- Approximately the same amount shall be taken from each
bility of regulatory limitations prior to use. Specific hazard container and the total amount taken shall be about 2.7 kg. The
statements are given in Note 1. pieces of lac resin shall then be ground to pass a No. 4
(4.75-mm) sieve. All sieves referenced must conform to the
requirements of Specification E 11 .
2.1 ASTM Standards: 3.5 Preparation of Samples for Observation or Analysis—
D 304 Specification for n-Butyl Alcohol (Butanol)2 Whether free-flowing or rough ground, as in the case of
D 331 Specification for 2-Ethoxyethanol2 blocked lac resin, the entire sample representing any lot shall
D 1193 Specification for Reagent Water3 be thoroughly mixed and divided into halves. The use of a
D 1544 Test Method for Color of Transparent Liquids mechanical mixer is recommended for mixing the resin and a
(Gardner Color Scale)4 riffle sampler for dividing it into quarters. When these devices
D 1545 Test Method for Viscosity of Transparent Liquids are not available for use, the entire sample shall be mixed,
heaped, and quartered along two diameters that intersect at
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint
right angles and the opposite quarters combined. One half the
and Related Coatings, Materials, and Applications and are the direct responsibility sample, thus obtained, shall then be mixed and divided into
of Subcommittee D 01.33 on Polymers and Resins. quarters as before. Each quarter shall be placed in an airtight
Current edition approved June 10, 1998. Published October 1998. Originally
published as D 29 – 14 T. Last previous edition D 29 – 81(l993){1.
2
3 5
Annual Book of ASTM Standards, Vol 11.01. Annual Book of ASTM Standards, Vol 06.03.
4 6
1
D 29
container, sealed, labeled (Section 5), and sent to the interested packages sampled, total number of containers in the lot,
parties as the “original observation sample.” When agreed condition of the containers and their contents, manufacturer’s
upon between the seller and the purchaser, the “original name, lot and code numbers of the containers, and the purpose
observation sample” shall be used for the determination of identification, namely “original observation sample” or
volatile matter (moisture) (Sections 14 to 15, as applicable). “sample for determination of volatile matter (moisture)”,
The other half of the sample shall be ground to pass a No. 10 “reserve sample” or “prepared sample” as may apply.
(2.00-mm) sieve, mixed thoroughly, and divided into two equal
portions A and B. Portion A shall be labeled the “reserve TEST METHODS
sample.” Portion B shall then be ground to pass a No. 25
(710-µm) sieve, mixed thoroughly, and quartered as described 6. Reagents
above. Each quarter shall be packaged in an airtight container,
6.1 Purity of Reagents—Reagent grade chemicals shall be
sealed, labeled “prepared sample,” and sent to the testing
used in all tests. Unless otherwise indicated, it is intended that
laboratory for analysis.
all reagents shall conform to the Specifications of the American
4. Bleached Lac Chemical Society, where such specifications are available.7
Other grades may be used, provided it is first ascertained that
4.1 Lot Size—For the purpose of sampling, the quantity of a
the reagent is of sufficiently high purity to permit its use
lot shall not exceed 200 packages.
without lessening the accuracy of the determination.
4.2 Source and Number of Samples—Only original un-
opened packages shall be sampled. Twenty percent of the 6.2 Purity of Water—Unless otherwise indicated, references
containers in every lot shall be taken at random, but not less to water shall be understood to mean reagent water conforming
than two containers in any lot shall be taken, except in the case to Type II of Specification D 1193.
where the entire lot is packaged in a single container.
4.3 Dry Bleached Lac (Free-Flowing)—Samples shall be 7. Source and Preparation of Specimens for Tests
drawn with a scoop or suitable sampler from different parts of 7.1 Each portion of sample for use in a given test shall be
each container directly after the packages are opened or bored. taken from the sample of lac resin only after it has been mixed,
Approximately 450 g shall be drawn from each container. The either by rolling on paper or by rolling and tumbling in its
samples shall be combined, mixed thoroughly, and where airtight container, as the condition of the sample requires, a
larger than 1.4 kg, shall be reduced by quartering as prescribed sufficient number of times to ensure uniformity of the specimen
in 3.5 to a sample of this size. taken. The test specimens shall be taken from the“ prepared
4.4 Dry Bleached Lac (Blocked or Matted)—Samples ag- sample” (3.5 or 4.6), as received, except in the following cases:
gregating at least 450 g shall be chopped or chiseled from 7.1.1 When it has been previously agreed upon between the
different parts of each container. The composite sample from seller and the purchaser that the “original observation sample”
all the containers shall be quickly crushed to lumps about 25 shall be used for the determination of volatile matter (mois-
mm square or smaller. The crushed lac resin shall be well ture). In this case, the “original observation sample” shall be
mixed and where the amount is larger than 1.4 kg, it shall be mixed, quartered, ground, and sieved in accordance with the
reduced by quartering, as prescribed in 3.5, to a sample of procedure described in 3.5 for obtaining the “prepared
approximately this size. sample.” All operations shall be done as expeditiously as
4.5 Hanks, Bars, or Crushed Free-Ground Bleached Lac— possible and the test specimen taken immediately after the
This material, which generally contains approximately 25 % sieved sample has been thoroughly mixed, to avoid any
moisture, shall be sampled by the procedures described in 4.3 possible loss by evaporation.
or 4.4, as applicable. 7.1.2 When the “prepared sample” is known to have a high
4.6 Preparation of Samples for Analysis—The composite moisture content, as in the case of certain forms of bleached lac
sample obtained as described in 4.3 or 4.4 shall be mixed (4.5), it shall be dried to a moisture content of 6 % before the
thoroughly and divided into two equal portions A and B as test specimens are taken. The lac resin shall be dried by placing
prescribed in 3.5. Each portion shall be placed in a clean, dry it in a thin layer in a flat-bottom dish (loosely covered to
glass jar provided with a rubber-sealed cap or an airtight prevent dust contamination) and exposing it to the atmosphere
friction-top tin can. Portion A shall be labeled “reserve at room temperature for 24 h and then desiccating it over
sample.” Portion B obtained in accordance with 4.3 or 4.4 shall anhydrous calcium chloride. The partially dried lac resin shall
be further ground to pass a No. 20 (850-µm) sieve, thoroughly be kept in a clean, dry, airtight container, and shall be
mixed and replaced in the jar, sealed and labeled “prepared thoroughly mixed by rolling and tumbling in the container
sample.” Portion B obtained in accordance with 4.5 shall be before the specimens are taken for analysis.
further ground to pass a No. 10 (2.00-mm) sieve, thoroughly
mixed, replaced in the jar, sealed, labeled “prepared sample,”
and sent to the laboratory for analysis.
7
Reagent Chemicals, American Chemical Society Specifications, American
5. Identification of Samples Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
5.1 The following information shall be legibly placed on the Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
label, which shall be securely attached to each sample con- and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
tainer: date of the sampling, number of bags, barrels or MD.
2
D 29
INSOLUBLE MATTER
8. Test Method A—For Orange Shellac, Button Lac,
Garnet Lac, and Regular Bleached
8.1 Apparatus:
8.1.1 Condenser—A four-bulb Allihn condenser of the di-
mensions and design shown in Fig. 1.
8.1.2 Siphon Tube—A Knoefler siphon tube of the dimen-
sions shown in Fig. 1. FIG. 2 Hot-Water Bath for Insoluble Matter,
8.1.3 Filter Tube—A carbon filter tube of the dimensions Test Method A
shown in Fig. 1.
8.1.4 Flask—A borosilicate glass Erlenmeyer flask 176 6 3
mm in height and 48 6 1.5 mm in inside diameter at the top. Safe laboratory handling procedures and all applicable OSHA regulations
are to be followed.
8.1.5 Flask Support—A suitable ring support with an iron
clamp and a Nichrome or iron wire gauze square without an 8.3 Preparation of Extraction Thimble:
asbestos center. 8.3.1 Pass the stem of the condenser through a hole cut in
8.1.6 Extraction Thimble—Extraction thimble 26 6 1 mm the center of a cork stopper of such size that it will tightly fit
in diameter and 60 6 1 mm in height. the flask. Adjust the cork on the stem so that the bottom of the
8.1.7 Water Bath—A metal container with cover of the size cork is just above the holes in the stem. Place an extraction
and design shown in Fig. 2. The container and cover shall be thimble (use new thimbles only) in the siphon tube. Suspend
made of 26-oz copper sheet. The cover shall have a flanged the siphon tube from the stem of the condenser by passing a
hole 57 6 1 mm in diameter for a 200-mL beaker and also a piece of copper wire through the holes in the stem and
hole 35 6 1 mm in diameter for the carbon filter tube. Directly fastening the ends of the wire through the holes in the siphon
below this hole in the bottom of the container shall be a flanged tube. The wire shall be sufficiently long to leave about 6-mm
hole 25 6 1 mm in diameter. space between the tip of the condenser and the top of the
8.1.8 Heating Device—An electric hot plate or bunsen siphon tube.
burner equipped with a draft shield. 8.3.2 Place 125 mL of ethyl alcohol in the flask and attach
8.1.9 Weighing Bottle—A glass-stoppered weighing bottle the flask to the condenser by means of the cork stopper. Place
of the dimensions shown in Fig. 1. the flask on an electric hot plate or a flask support. Run a steady
8.2 Solvent—Specially denatured 95 % (190 proof) ethyl stream of cold water through the condenser. Adjust the flame of
alcohol conforming to Formula No. 1 or No. 3A of the Alcohol, the burner or the hot plate setting so as to give a cycle of filling
Tobacco and Firearms Division of Internal Revenue Service, and emptying of the siphon tube every 2 min, and extract the
U.S. Treasury Department. thimble for 30 min. Remove the extraction thimble from the
siphon tube and allow to drain and air-dry for several minutes.
NOTE 1—Precaution: The reagents and samples used in these methods
may, under some conditions, be hazardous. Refer to the supplier’s
8.3.3 Place the thimble in a weighing bottle and dry in an
Material Safety Data Sheet for specific handling and safety precautions. oven for 2 h at 105 6 2°C. Remove and stopper the weighing
bottle and cool in a desiccator. Weigh the bottle and thimble
lifting the stopper momentarily before weighing. Continue
drying and weighing as before after each hour of drying until
the loss in weight between successive weighings does not
exceed 2 mg.
8.3.4 A number of thimbles may be extracted and kept in
weighing bottles or a desiccator until needed.
8.4 Procedure:
8.4.1 Weigh to 1 mg 5 6 0.2 g of the mixed sample (Section
7) and place in a 200-mL tall-form beaker. Add 125 mL of ethyl
alcohol to the beaker and place it in the hot-water bath (Fig. 2),
which has been previously heated to not less than 90°C.
Maintain the bath at this temperature, or above, during the
solution and filtration of the sample. Boil the solution for 30
min, keeping the volume of alcohol constant to ensure com-
plete solution of the lac resin.
8.4.2 Place an extracted, weighed extraction thimble (8.3) in
the carbon filter tube (Fig. 2). Wet the thimble with hot alcohol
and decant the boiling solution into the warm thimble until the
beaker is nearly empty. Wash the remaining solution and
insoluble matter into the thimble with a stream of hot alcohol
FIG. 1 Extraction Apparatus for Insoluble Matter, from a wash bottle using a “policeman” if necessary. Finally,
Test Method A wash the thimble from the top down. The transfer of the
3
D 29
insoluble matter from the beaker and the washing down of the 9.1.2 Filter Tube—A carbon filter tube made of borosilicate
thimble will require at least 75 mL of hot alcohol. to fit the crucible.
8.4.3 Transfer the thimble with the insoluble matter to the 9.1.3 Heating Coil—A heating coil made of 3-mm diameter
siphon tube of the extraction apparatus (Fig. 1). Place 125 mL copper tubing of such size and shape that the filter crucible and
of alcohol in the flask and attach the condenser. Adjust the the large part of the carbon tube will fit snugly within it. The
heating device so that a complete filling and emptying of the outside shall be insulated with sheet asbestos paper.
siphon tube with hot alcohol requires 2 min or 30 cycles per 9.2 Solvent—Either of the following materials may be used
hour (Note 2), and extract for exactly 1 h (Note 3). Remove the as the solvent for the lac resin:
thimble, and allow it to drain in an upright position. 9.2.1 2-Ethoxyethanol, conforming to the requirements of
Specification D 331.
NOTE 2—Occasionally, lac resins are encountered that will not yield the
required 30 siphons per hour due to slow filtration. In these instances the 9.2.2 Normal Butyl Alcohol (n-Butanol), conforming to the
extraction shall be continued until 30 cycles have occurred and the requirements of Specification D 304.
determination reported as abnormal or slow filtering. 9.3 Preparation of Filtering Unit:
NOTE 3—During the 1-h extraction, all the remaining soluble matter 9.3.1 Cut a disk of rapid, ashless filter paper to fit inside the
should be extracted by the hot alcohol, leaving only the insoluble matter crucible and place it on top of the glass filter. Introduce upon
in the thimble. the filter paper, in the customary manner, an asbestos mat
8.4.4 Place the thimble in the weighed weighing bottle and approximately 3 mm in thickness. Dry the crucible at 105 6
dry in an oven at 105 6 2°C for 2 h. Remove the weighing 2°C; then cool in a desiccator to constant weight. Weigh the
bottle from the oven, insert its stopper, cool in a desiccator, and prepared crucible and place it within the carbon tube, using
weigh, lifting the stopper momentarily to break the vacuum thin rubber tubing to form an airtight connection. Place the
before weighing. Continue drying and weighing as before after combined filtering unit within the heating unit, attach to a
each hour of heating until the loss in weight between succes- suction flask, and pass a current of steam through the coil.
sive weighings does not exceed 2 mg. 9.4 Procedure:
8.5 Calculation—Calculate the percent of matter insoluble 9.4.1 Weigh to 1 mg 5 6 0.2 of the mixed sample (Section
in hot alcohol as follows: 7 and Note 4) into a 200-mL beaker. Add 75 mL of the solvent
Insoluble matter, % 5 @R/S~1 2 M!# 3 100 (1) (9.29.2) and bring the solution to boiling on an electric hot
plate. Keep the solution boiling slowly for 5 min to ensure
where: complete solution.
R 5 insoluble matter obtained, g,
S 5 sample used, g, and NOTE 4—For refined bleached shellac and other shellacs having a very
low insoluble matter content take a 10 to 20-g specimen using
M 5 volatile matter (moisture) content of the sample,
proportionally more solvent.
expressed as a decimal fraction.
9.4.2 Pour about 10 mL of the boiling solvent from a wash
9. Test Method B—For All Grades of Lac Resins bottle into the heated crucible. Gently apply suction and
Including Refined Bleached Lac8 immediately pour the boiling solution into the crucible so as to
9.1 Apparatus (Fig. 3): retain as much as possible of the insoluble residue in the
9.1.1 Crucible—A borosilicate glass Gooch crucible having beaker. Wash the insoluble residue successively with three
a capacity of 30 mL with a fritted-glass filter disk having a 20-mL portions of the solvent, boiling the solution on the
medium porosity. electric hot plate for about 1 min before each filtration.
9.4.3 Transfer the residue from the beaker to the crucible
with a stream of the boiling solvent from a wash bottle, using
8
a policeman when necessary. Wash down the inner walls of the
Hartman, C. C., “Determination of Insoluble Matter in Shellac,” Journal of
Research, Nat. Bureau Standards, Vol 7, No. 6, 1931, p. 1105.
crucible with the boiling solvent. The total volume of the
solvent used will be approximately 175 mL. It is advisable to
keep the crucible covered with a small watch glass at all times,
except when actually transferring the solution from the beaker
to crucible, or when washing down the inside walls of the
crucible to maintain a higher temperature within the crucible.
Allow the crucible to remain inside the heating coil with the
suction on for a few minutes, so as to suck it as dry as possible.
NOTE 5—The insoluble matter can be easily removed together with the
asbestos mat and filler paper. The crucible may be used several times
without further cleaning. Additional cleaning when necessary is easily
accomplished by immersing the crucible in a hot mixture of sulfuric and
nitric acids for a few minutes.
9.4.4 Remove the crucible and wash the outside with
boiling solvent. Dry in an oven at 105 6 2°C for 2 h, cool in
FIG. 3 Apparatus for Insoluble Matter, a desiccator, and weigh.
Test Method B 9.5 Calculation—Calculate the percent of matter insoluble
4
D 29
in the hot solvent as follows: Gently swirl the contents of the bottle occasionally during the
Insoluble, % 5 @R/S~1 2 M!# 3 100 hour. Remove the bottle from the bath and add 10 mL of the KI
(2) solution washing into the bottle any Wijs solution on the
stopper with the same.
where: 10.2.3 Immediately titrate with the standard Na2S2O3
R 5 insoluble matter obtained, g, solution, allowing the solution to run rapidly and swirling the
S 5 sample used, g, and contents of the bottle vigorously and continuously until the
M 5 volatile matter (moisture) content of the sample, solution becomes a straw color. Add 5 mL of the starch
expressed as a decimal fraction. indicator solution and continue the titration dropwise until the
blue color just disappears. The end point is sharp and any blue
10. Iodine Value
color returning after 30 s should be disregarded.
10.1 Reagents: 10.2.4 Blank—Run a blank determination on the reagents at
10.1.1 Potassium Iodide Solution (100 g/L)—Dissolve 10 g the same time and through the entire procedure. The blank is
of iodate-free potassium iodide (KI) in water and dilute to 100 necessary because of the effect of temperature changes on
mL. volume and possible loss in strength of the Wijs solution.
10.1.2 Reference Standard Shellac—Pure shellac of known 10.2.5 Reference Standard—Run a determination on a
iodine value.9 sample of pure shellac of known iodine value (10.1.2) with
10.1.3 Sodium Thiosulfate, Standard Solution —(0.1 N)— each set of test specimens.
Prepare and standardize in accordance with Section 5 of 10.3 Calculation—Calculate the iodine value as follows:
Method D 1959.
Iodine value 5 @~B 2 V!N 3 12.69#/S
10.1.4 Starch Indicator Solution—Prepare in accordance
(3)
with Test Method D 1959.
10.1.5 Wijs Solution—Prepare in accordance with Test where:
Method D 1959. The Wijs solution should be tested against an V 5 Na2S2O3 solution required for titration of the
orange shellac the iodine value of which is accurately known. specimen, mL,
The iodine value thus obtained should be within 60.5 of the B 5 Na2S2O3 solution required for titration of the blank,
known iodine value. mL,
10.2 Procedure: N 5 normality of the Na2S2O3 solution, and
10.2.1 Weigh to 0.1 mg about 0.2 g of the mixed sample S 5 sample used, g.
(Section 7 and Note 6 and Note 7) into a 250-mL dry, clear PURITY
glass bottle having a ground-glass stopper. Add 20 mL of
glacial acetic acid and heat at 65 to 70°C on a hot-water bath, 11. Qualitative Test for Rosin
gently swirling the contents of the bottle occasionally, until 11.1 Reagents:
solution is complete, except for the wax. This should not 11.1.1 Acetic Acid (Glacial).
require more than 15 min. Add 10 mL of chloroform and cool 11.1.2 Ethyl Alcohol (Absolute).
at 21.5 to 22.5°C for 1⁄2 h in an insulated, thermostatically 11.1.3 Halphen-Hicks Reagent10—Prepare the following
controlled water bath. two solutions:
NOTE 6—In the case of grossly adulterated samples, a smaller quantity 11.1.3.1 Solution A—One part by volume of phenol
(0.15 or 0.1 g) should be used instead of 0.2 g of the material in order that dissolved in 2 parts by volume of carbon tetrachloride.
the excess of iodine monochloride may not be too greatly reduced, since 11.1.3.2 Solution B—One part by volume of bromine
the excess of halogen is one of the factors in determining the amount of dissolved in 4 parts by volume of carbon tetrachloride.
absorption. In case less than 25 mL of the Na2S2O3 solution is required, 11.2 Procedure:
another test should be made using a smaller quantity of the lac resin.
11.2.1 Weigh 2 6 0.1 g of the mixed sample (Section 7) into
NOTE 7—In weighing lac resin some difficulty is at times experienced
on account of its electrical resistance properties. In very dry weather it a 2-L Florence flask and dissolve in 20 mL of either absolute
may be found that the necessary handling to prepare it for weighing has ethyl alcohol or glacial acetic acid, warming on a steam bath if
electrostatically charged it, and that it may be necessary to leave it in the necessary. Cool, add 100 mL of petroleum ether, and mix
balance pan at rest for a few minutes before determining the weight. thoroughly.
NOTE 8—If a number of samples are being run, allow at least 5 min 11.2.2 Add sufficient water to bring the petroleum ether
between the additions of the Wijs solution. layer into the neck of the flask when separated. Add the water
10.2.2 Add 20 mL of the Wijs solution to the bottle, using a portionwise, shaking the flask between additions to prevent
pipet. Replace the stopper and half immerse the bottle in the coagulation of the precipitated lac resin. Allow to stand until
water bath held from 21.5 to 22.5°C for exactly 1 h (Note 8). the petroleum ether separates into a distinct layer.
11.2.3 Siphon off at least 50 mL of the petroleum ether
solution, filter if cloudy, and heat on an electric hot plate or
9
The sole source of supply of Standard samples of pure orange shellac, steam bath until the petroleum ether is completely removed.
rosin-free of accurately known iodine known to the committee at this time is the
U. S. Shellac Importers Assn., Inc., 425 Park Ave., New York, NY 10022. If you are
10
aware of alternative suppliers, please provide this information to ASTM For more detailed information, reference may be made to Hicks, E. F.,“ New
Headquarters. Your comments will receive careful consideration at a meeting of the Color Reactions for Some of the Resins with Halphen’s Reagent for Colophony,”
responsible technical committee,1 which you may attend. Industrial and Engineering Chemistry, Vol 3, 1911, p. 86.
5
D 29
11.2.4 Dissolve the residue in several millilitres of Solution VOLATILE MATTER (MOISTURE)
A, and transfer 1 to 2 mL of the mixture to one of the cavities
of a white porcelain spot plate. Immediately fill an adjacent 14. Test Method A—For Orange Shellac, Button Lac,
cavity with Solution B. Cover the plate with an inverted watch Garnet Lac, and Dry Bleached Lac
glass and note the color developed in the Solution A mixture by 14.1 Procedure:
the bromine vapors from Solution B. The development of a 14.1.1 Weigh to 0.1 mg approximately 2 g of the mixed
fugitive violet color, best observed on the flat portion of the sample from the air-tight container (7.1.1 or 7.1.2) into a
spot plate, indicates the presence of rosin. A control sample weighed, clean, dry, flat-bottom glass dish about 4 in. (100
containing rosin should be run simultaneously, as a guide in mm) in diameter and provided with a ground-glass cover. Place
judging the color developed with the test specimen. the dish, with the cover removed, in a well-ventilated oven
maintained at 40 6 1°C for 6 h.
12. Qualitative Test for Copal 14.1.2 Transfer the dish and cover to a vacuum desiccator
12.1 Reagents: containing concentrated sulfuric acid (H2SO4, sp gr 1.84).
12.1.1 Ethyl Alcohol, Denatured—(See 8.2). Immediately evacuate the desiccator and keep the specimen
12.1.2 Methyl Alcohol (99 %). uncovered in the vacuum for 18 h. Release the vacuum, replace
the cover on the dish, and weigh immediately.
12.2 Procedure:
14.2 Calculation—Calculate the percent volatile matter
12.2.1 Weigh to 0.1 g about 15 g of the mixed sample (moisture) in the sample as follows:
(Section 7) into an Erlenmeyer flask. Add twice its weight of
the denatured alcohol, stopper the flask and let stand with Volatile matter ~moisture!, % 5 @1 2 ~S2/S1!# 3 100 (5)
periodic shaking until the sample is in the solution. Filter the where:
solution through a folded filter paper, discarding the first 5 mL S1 5 sample used, g, and
of filtrate. S2 5 dried specimen, g.
12.2.2 Transfer 10 mL of the filtrate to a large test tube (6 by
3⁄4 in.) (150 by 20 mm) and nearly fill the tube with methyl 15. Test Method B—For Bleached Lac in Form of
alcohol. Stopper the tube and mix its contents thoroughly. Hanks, Bars, and Crushed Fresh-Ground
Immediate formation of a cloudiness or precipitate indicates 15.1 Procedure:
the presence of copal. Lac resin free of copal should remain 15.1.1 Thoroughly mix the “original observation’’ sample
clear. in its original airtight container by rolling and tumbling.
Transfer 25 to 50 g to a mortar and crush as rapidly as possible
13. Estimation of Adulteration into fine granules. Keep the mortar covered as well as possible
13.1 Since the variation between the highest and lowest to avoid any loss of moisture. Immediately transfer
iodine values of a pure lac resin is not great, it is recommended approximately 10 g of the crushed lac to a weighed, clean, dry,
that the following assumptions (Note 9) be made: flat-bottom glass dish about 100 mm in diameter, provided with
Assumed a ground-glass cover, and weigh to 0.1 mg. Record the weight
Type of Lac Resin Iodine Value of the lac taken for use as S1.
Rosin-free and copal-free shellac, button lac, and 15
15.1.2 Place the dish and contents in a vacuum desiccator
garnet lac containing H2SO4(sp gr 1.84). Remove the cover from the dish
Rosin-free and copal-free bleached lac 10 and immediately evacuate the desiccator. Keep the dish in the
Rosin 228
Copal 130
vacuum at room temperature for 18 to 24 h. Replace the cover
on the dish, remove from the desiccator, and weigh. Record the
13.2 Calculate the percent of adulteration as follows: weight of the partially dried lac for use as S2.
Percent of rosin in orange shellac, button lac, and garnet lac 15.1.3 Grind the partially dried lac resin until it entirely
passes a No. 40 (425-µm) sieve. Thoroughly mix the sieved lac
5 @~x 2 15!/~228 2 15!# 3 100 (4) on a mixing sheet (7.1). Transfer approximately a 2-g specimen
Percent of rosin in bleached lac 5 @~x 2 10!/~228 2 10!# 3 100 of it from the mixing sheet to a weighed, covered dish of the
Percent of copal in orange shellac, button lac, and garnet lac type described in 15.1.1, and weigh to 0.1 mg. Record the
weight of the specimen taken for use as S3.
5 @~x 2 15!/~130 2 15!# 3 100 15.1.4 Heat the dish with cover removed in a well-
Percent of copal in bleached lac 5 @~x 2 10!/~130 2 10!# 3 100 ventilated oven at 40 6 1°C for 18 h. Replace the cover on the
dish, cool in a desiccator, and weigh. Record the weight of
where: dried lac obtained for use as S4.
x 5 iodine value of the sample under test, determined in 15.2 Calculation—Calculate the percent of volatile matter
accordance with 10.2. (moisture) in the original lac sample as follows:
NOTE 9—The results obtained by assuming the values of 15 and 10 as Volatile matter ~moisture!, % 5 @1 2 ~S4 3 S2!/~S3 3 S1!# 3 100
the iodine value of orange and bleached shellac, respectively, and 228 as (6)
the iodine value of rosin may give a slightly lower percent rosin, under
some circumstances, than that which is actually present.
where:
6
D 29
S1 5 crushed wet lac taken for drying in vacuum, g, desiccator and weigh.
(15.1.1) 16.4 Calculation—Calculate the percent of wax in the lac
S2 5 partially dried lac, g, (15.1.2), resin as follows:
S3 5 partially dried, sieved lac used as specimen for final Wax, % 5 @R/S~1 2 M!# 3 100 (7)
oven drying, g, (15.1.3), and
S4 5 completely dried lac specimen obtained in 15.1.4, g. where:
R 5 wax obtained, g,
S 5 sample used, g, and
16. Wax M 5 volatile matter (moisture) content of the sample,
16.1 Apparatus: expressed as a decimal fraction.
16.1.1 Extraction Apparatus—An assembly suitable for
continuous extraction with hot solvent, such as that used for the 17. Matter Soluble in Water
determination of insoluble matter (Section 8). 17.1 Procedure:
16.1.2 Filtering Medium—A Büchner funnel, having an 17.1.1 Weigh to 0.1 g 10 g of the mixed sample (Section 7)
inside diameter of 55 to 90 mm, and prepared just before use into a 400-mL beaker. Add 200 mL of water and stir
in the following manner. Fit a disk of filter paper snugly over thoroughly. Cover the beaker with a watch glass and let stand
the bottom of the funnel and then with the suction on pour over with occasional stirring for 4 h at 25 6 2°C.
the filter paper in a layer of uniform thickness 1 g of filter aid 17.1.2 Filter the water solution through a filter paper into a
(16.2.3) suspended in water. 400-mL beaker. Transfer all the lac resin from the beaker to the
16.1.3 Extraction Thimble—A thimble, such as prescribed filter paper with a stream of water from a wash bottle using a
in 8.1.6, that has been previously extracted with chloroform by policeman if necessary. Finally wash the lac resin and filter
the procedure given in 8.3. paper with approximately 100 mL of water.
16.2 Reagents: 17.1.3 Evaporate the filtrate almost to dryness in a weighed
16.2.1 Chloroform, redistilled, free of nonvolatile residue. evaporating dish on a steam bath. Dry the extracted residue for
16.2.2 Ethyl Alcohol, Denatured, as prescribed in 8.2. 1-h periods in an oven maintained at 105 6 2°C until the
16.2.3 Filter Aid—A suitable filter aid, extracted with difference in successive weighings does not exceed 1 mg. Cool
chloroform and dried before using. in a desiccator and weigh.
16.2.4 Sodium Carbonate (Na2CO3). 17.2 Calculation—Calculate the percent of matter soluble
16.3 Procedure: in water as follows:
16.3.1 Weigh to 1 mg approximately 10 g of the mixed Matter soluble in water, % 5 @R/S~1 2 M!# 3 100 (8)
sample (Section 7) into a 200-mL tall-form beaker. Dissolve
2.5 g of Na2CO3 in 150 mL of hot water and add to the beaker. where:
Immerse the beaker in a boiling water bath and stir until the lac R 5 residue obtained, g,
resin is in solution. Cover the beaker with a watch glass and S 5 sample used, g, and
allow to remain in the bath for 2 to 3 h, without agitation. M 5 volatile matter (moisture) content of the sample,
16.3.2 Remove the beaker from the bath and place it in cold expressed as a decimal fraction.
water. The wax will come to the top of the solution where it
will solidify as a layer or float as small, hard particles. Add 0.5 18. Ash
g of the filter aid to the lac solution and filter through the 18.1 Procedure:
Büchner funnel with the aid of suction. Transfer all of the wax 18.1.1 Weigh to 1 mg between 3 and 5 g of the mixed
from the beaker to the filter with a stream of water from a wash sample (Section 7) into a weighed porcelain crucible. Place the
bottle, using a policeman if necessary. Finally pour a few crucible in a hood and heat with a low flame until the contents
millilitres of the alcohol over the filter to facilitate drying. of the crucible are a dry, charred mass. Transfer to a muffle
Place the funnel in an oven and dry its contents at 60 6 2°C for furnace and ignite the residue at a dull red heat (not exceeding
several hours. 600°C) until the ash is free of carbon. Cool in a desiccator and
16.3.3 Insert a thin spatula under the edge of the filter paper weigh. Repeat the ignition, cooling and weighing until the
and transfer the contents of the funnel to a sheet of filter paper. difference between successive weighings does not exceed 1
Securely wrap the transferred material in the filter paper, and mg.
bind it firmly with fine copper wire. Place the packet in the 18.1.2 If a carbon-free ash cannot be obtained in this
prepared extraction thimble. Wash out both the beaker in which manner, add water to the crucible, bring the water to a slow boil
the lac resin was originally dissolved and the Büchner funnel and digest the ash for 5 to 10 min. Filter through an ashless
with portions of hot chloroform, filtering the chloroform filter paper, washing out the crucible with a stream of hot water
solutions through the extraction thimble into the flask to be from a wash bottle using a policeman if necessary. Retain the
used in the extraction. Place the thimble in the extraction filtrate. Transfer the filter paper with the insoluble residue to
apparatus, and extract with hot chloroform for 2 h. the crucible and ignite at a dull red heat in a muffle furnace
16.3.4 Transfer the chloroform extract to a weighed beaker until all the carbon is consumed. Then add the filtrate to the
and heat on a steam-bath until most of the chloroform has been crucible and evaporate to dryness over a low flame or hot plate.
evaporated. Finally heat the residue in the beaker in an oven at Finally ignite the crucible and its contents at dull red heat to
105 6 2°C to constant weight (within 10 mg). Cool in a constant weight (within 1 mg) as prescribed in 18.1.1.
7
D 29
18.2 Calculation—Calculate the percent ash of the lac resin 20. Color of Orange Shellac
as follows: 20.1 Apparatus:
Ash, % 5 @R/S~1 2 M!# 3 100 (9) 20.1.1 Funnel—Porcelain No. 1 Büchner funnel 55 mm in
inside diameter.
where: 20.1.2 Colorimetric Tubes—Nessler color comparison
R 5 ash obtained, g,
tubes, approximately 20 mm in diameter and 300 mm in length.
M 5 volatile of matter (moisture) content of the sample, 20.1.3 Standard Light Source—A light source consisting of
expressed as a decimal fraction. a 100-W frosted daylight bulb mounted at the center of the
back wall of a 255-mm cubic box so that the tip of the bulb
faces the front. The front opening of the box shall be covered
19. Color
with a white opaque paper or a ground-glass plate. The lamp
19.1 Apparatus: shall be inserted in a socket which just protrudes through the
19.1.1 Glass Tubes—Clear glass tubes with closed, flat, wall of the box so that the distance from the tip of the lamp to
even bottom, an external length of approximately 114 mm, and the paper or glass is approximately 115 mm. The five inside
a uniform internal diameter of 10.65 6 0.025 mm throughout walls of the box shall be painted white. Any other suitable
the length of the tube. Viscosity tubes described in Test Method apparatus or standard daylight lamp may be used, provided it
D 1545 are satisfactory. produces light of the same characteristics as specified above.
19.1.2 Glass Plate—White Carrara or Vitrolite glass plate See Test Method D 1544 for using the Gardner Color Scale.
approximately 150 by 200 mm, one side of which has been 20.2 Reagents:
polished to a smooth, high gloss surface. 20.2.1 Ethyl Alcohol—Specially denatured 95 % (190
19.1.3 Film Applicator—Film applicator to case a film proof) ethyl alcohol; either formula No. 1 or formula No. 30 of
50-mm wide and 50-µm thick. A clearance of 4 mils should the U.S. Internal Revenue Bureau.
provide the required thickness. 20.2.2 Filter Aid—Any high-grade analytical filter aid for
rapid flow.
19.2 Reagent—Ethyl Alcohol, Denatured, as prescribed in
20.2.3 Ferric Sulfate—(Fe2(SO4)3·xH2O)—Any hydrated
8.2.
analytical reagent.
19.3 Color Comparison Material—The lac resin mutually 20.2.4 Sodium Hydroxide, Standard Solution (1N)—
agreed upon by the purchaser and the seller for the color Dissolve 40 g of pure NaOH in 500 mL of distilled water and
comparison. dilute to 1 L in a volumetric flask. Standardize against pure
19.4 Procedure: oxalic acid dihydrate.
19.4.1 Weigh 10 6 0.1 g each of the mixed sample (Section 20.2.5 Sodium Thiosulfate, Standard Solution (0.2N)—
7) and the comparison lac resin, which shall have been Dissolve 49.66 g sodium thiosulfate (Na2S2O3·5H2O) in
similarly prepared, into separate Erlenmeyer flasks. Add to distilled water that has been previously boiled to free it from
each flask an amount of alcohol equal to twice the weight of the carbon dioxide and dilute to 1 L of the solution. It is best to let
resin and stopper the flasks. Keep the flasks at 21 to 32°C and this solution stand about 2 weeks before standardizing with
shake at frequent intervals until the resins are completely pure resublimed iodine or potassium bi-iodate. Preserve in a
dissolved (cut). Allow the flasks to stand undisturbed for 1⁄2 h. brown stock bottle with a guard tube filled with soda lime.
Compare the color of the lac solutions by one or both of the 20.2.6 Starch Solution—Make a paste of 0.2 g of soluble
following procedures as agreed upon between the purchaser starch (potato starch) in cold water and pour into 100 mL of
and the seller. boiling water, cool and bottle or use the solution prepared for
19.4.2 Comparison of Solutions—Fill separate glass tubes the iodine number determination (10.1.5).
to their bottom lines with each of the solutions, being careful 20.2.7 Potassium Iodide (KI)—Iodate-free crystal.
not to disturb any settlement that may have occurred in either 20.2.8 Nickel Sulfate—Reagent grade (NiSO4·6H2O).
flask. Place the tubes side by side and make the color 20.3 Preparation of Color Standards
comparison by viewing the liquids while they are held against 20.3.1 Ferric Sulfate—Dissolve 400 g of Fe2(SO4)3·xH2O
a background substantially equal in illumination to that of a in about 600 mL of water by heating to boiling while stirring
fairly light overcast northern sky. constantly. After complete solution, cool to room temperature
19.4.3 Comparison of Films—Without disturbing any and dilute to 1 L in a volumetric flask. Standardize this stock
settlement that may have occurred in the flask, decant a solution by titrating with iodine in the following manner:
suitable portion of the solution of the sample and draw down Dissolve 20 g of KI in 30 mL of water and add 5 mL of the
on the white glass plate with a film, 50-mm wide and 50-µm stock solution. Add to this approximately 2 weight % of
thick, using the apparatus described in 19.1.3. In a similar H2SO4(sp gr 1.84). Allow to stand for 5 min and titrate with 0.2
manner, draw down a film of the comparison solution on the N sodium thiosulfate solution in the usual manner, not adding
same plate keeping the films as close together as possible. the starch indicator until near the end of the titration. Run at the
Air-dry the films at 21 to 32°C for 24 h. Compare the color of same time a blank determination on the KI solution and correct
the dried films by viewing them by reflected light at an for any nonuniformity of this reagent. Adjust the stock solution
illumination substantially equal to that of a fairly overcast to approximately 0.725 M Fe2(SO4)3 solution (Note 10); 5 mL
northern sky. of the stock solution should then be equivalent to 36.2 6 0.8
8
D 29
mL of 0.2 N sodium thiosulfate solution. NOTE 12—Most filtered solutions made by dissolving shellac that has
been ground for analysis will darken appreciably in color if allowed to
NOTE 10—The amount of coordinated water in ferric sulfate may vary, stand for periods longer than 12 h.
and has to be taken into account in weighing out the required amount of
ferric salt. It is usually about 6 mols per mol of ferric sulfate for the 21. Acid Value
powdered analyzed reagent. 21.1 Definition:
20.3.2 Nickel Sulfate—Dissolve 50 g of NiSO4·6H2O in 21.1.1 acid value—the number of milligrams of potassium
about 300 mL of water. After complete solution, dilute to 500 hydroxide required to neutralize 1 g of moisture-free lac resin.
mL in a volumetric flask. 21.2 Reagents:
20.3.3 Reference Standard for All Grades11—Transfer 21.2.1 Neutral Ethyl Alcohol—Alcohol, as described in
exactly 20 mL of the stock ferric sulfate solution (20.3.1) to a Section 8, that has been neutralized with standard KOH or
100-mL volumetric flask. Add 11.5 mL of the 1.0 N NaOH NaOH solution, using the phenolphthalein indicator to a faint
solution from a buret, and shake until all the precipitate formed but persistent pink color just prior to use.
has dissolved. Then, add 10 mL of the nickel sulfate solution 21.2.2 Phenolphthalein Indicator Solution—Dissolve 1 g of
and dilute to 100 mL with distilled water. If any of the solutions phenolphthalein in 100 mL of ethanol (8.2), methanol, or
show permanent precipitates, prepare fresh solution. isopropanol.
20.4 Procedure: 21.2.3 Potassium Hydroxide or Sodium Hydroxide Solution,
20.4.1 Transfer exactly 5 g of the sample to a clean 120-mL Standard Aqueous or Alcoholic (0.1 N):
wide-mouth bottle and add exactly 50 mL of alcohol. Shake 21.2.3.1 Preparation of Aqueous Solution—Prepare a stock
until solution is complete and then cool to 10°C. concentrated solution by dissolving potassium hydroxide
20.4.2 Place a 55-mm tough, hard, close texture filter paper (KOH) or sodium hydroxide (NaOH) in water in the proportion
or its equivalent in the Büchner funnel which has been of 112 g of KOH, or 85 g of NaOH in 200 mL of water. Allow
mounted in the neck of a 2-L suction flask with a rubber the solution to cool and settle in a stoppered bottle for several
stopper. Pour evenly upon the filter paper a 1-g suspension of days. Decant the clear liquid from the carbonate precipitate
filter aid in 50 mL of alcohol, and suck completely dry with a into another clean bottle. Add clear barium hydroxide
partial vacuum, using a water suction pump. Remove the (Ba(OH)2) solution until no further precipitate forms. Again
funnel and add about 400 mL of alcohol to the flask. (Note 11) allow to settle until clear. Draw off 175 mL and dilute to 10 L
Place an 200-mm test tube in the suction flask, supporting, if with water. Preserve in a stock bottle provided with a guard
necessary, with filter paper, so that the tip of the Büchner tube filled with soda-lime.
funnel when inserted in the neck of the flask will come well 21.2.3.2 Preparation of Alcoholic Solution—Place 5 to 10 g
within the open test tube. Reinsert the funnel in the flask. of KOH in a 2-L flask and add 1 to 1.5 L of alcohol prescribed
20.4.3 Add 1 g of filter aid to the cold shellac solution and in 8.2. Boil on a water bath under a reflux condenser for 30 to
stir thoroughly. Transfer completely to the Büchner funnel and 60 min. Distill and collect the alcohol. Dissolve 5.6 g of KOH
filter at the rate of 2 drops per second by means of a carefully or 4 g of NaOH in 1 L of the distilled alcohol, keeping the
regulated vacuum. This may be conveniently done by the use temperature below 15.5°C while the alkali is being dissolved.
of a water pump to which has been attached a trap carrying a This solution should remain clear.
stopcock to admit air. Slowly increase the amount of vacuum 21.2.3.3 Standardization of Solution—Standardize either
toward the end of the filtration in order to maintain a constant solution by titrating against pure potassium acid phthalate,12
filtration rate until the filtration is practically complete, and using phenolphthalein indicator. The solution will be
then suck dry. The final volume in the test tube should be 49 to approximately 0.1 N. Determine its exact normality to 60.001
50 mL. If it is less than 48 mL, repeat the procedure. N.
21.2.4 Thymol Blue Indicator Solution—Dissolve 0.04 g of
NOTE 11—The method used in preparing the solution for comparison is
very important. A slight loss in alcohol will materially affect the color
thymol blue (thymol sulfonphthalein) in 100 mL of the alcohol
when diluted for comparison. Alcohol is placed in the flask to avoid undue prescribed in 8.2.
evaporation of the solution during filtration. The rate of filtration is an 21.3 Procedure:
important factor. 21.3.1 Weigh to 1 mg approximately 2 g of the mixed
20.4.4 Transfer 10 mL of filtered solution to one of the sample (Section 7) into a 250-mL Erlenmeyer flask and add
colorimetric tubes, and compare with 10 mL of the standard 100 mL of the neutral alcohol. The sample should completely
color solution by viewing the tubes transversely in front of the dissolve at room temperature within a few hours with the aid of
standard light source. Dilute the shellac solution with alcohol periodic gentle swirling. Titrate in accordance with 21.3.2 or
until it matches the reference standard color. Report the volume 21.3.3.
in millilitres of the diluted solution; this is taken as the color 21.3.2 In case of bleached lac, add 1 mL of the
number of the sample. Determine the color of the filtered phenolphthalein indicator solution and titrate with 0.1 N KOH
solution the same day upon which the samples are dissolved. or NaOH solution, with constant swirling of the contents of the
flask. Take as the end point when a faint pink color remains
after continuous swirling for 30 s.
11
This standard color solution was designed to match the No. 5 iodine color
12
standard of the Angelo color method which has been used by various laboratories for National Institute of Standards and Technology standard reference material
obtaining numerical color values for lacs. It is closer in hue to most lacs than the No. 84d is recommended for this purpose and should be handled as directed in the
iodine solution and hence easier to match. certificate of analysis accompanying the sample.
9
D 29
21.3.3 In case of orange shellac, place several drops of the sample (Section 7) into a 500-mL Kjeldahl flask. Add 450 mL
thymol blue indicator solution on a white porcelain spot plate. of the alcohol to the flask and heat its contents in a hot water
Titrate the solution with 0.1 N KOH or NaOH solution, with bath at a gentle boil until the lac resin is completely dissolved.
constant swirling, and determine the end point by transferring 22.3.2 Remove the flask from the bath and wait just long
1 or 2 drops of the solution on a glass rod to the indicator. The enough to permit settlement of the bulk of the insoluble matter
end point is reached when the first blue color is developed in from the solution. Decant the solution from the flask to the
the indicator. filter paper held in the jacketed funnel which must be kept hot
21.4 Calculation—Calculate the acid value as follows: during the entire filtration by passing steam through the coil or
Acid value 5 ~VN 3 56.1!/S~1 2 M! (10) jacket. Keep a watch glass over the funnel when not pouring
the solution into it (Note 13).
where: 22.3.3 Wash the sediment layer in the flask with four
V 5 KOH or NaOH solution required for the titration, mL successive 50-mL portions of boiling alcohol, and decant the
N 5 normality of the KOH or NaOH solution, washings through the filter. Finally wash the filter paper with
S 5 sample used, g, and 50 mL of the boiling alcohol. Continue heating the funnel to
M 5 volatile matter (moisture) content of the sample drive off most of the alcohol. Pour slowly over the entire
expressed as a decimal fraction. surface of the filter paper approximately 200 mL of boiling
carbon tetrachloride to dissolve any of the lac wax that may
22. Orpiment
have remained on the filter paper (Note 14). Now leave the
22.1 Reagents and Materials: watch glass off and continue passing the steam through the
22.1.1 In addition to conforming to the requirements of funnel jacket to dry the solvent from the paper.
Section 6, all reagents shall be free of arsenic.
22.1.2 Ammonium Hydroxide (NH4OH)—Concentrated NOTE 13—If the funnel and its contents are not kept hot the wax will
congeal and clog the filter paper, thus slowing up the filtration.
ammonium hydroxide (sp gr 0.90).
NOTE 14—All wax should be removed from the filter paper and inside
22.1.3 Carbon Disulfide (CS2).
of the flask, as otherwise the subsequent digestion procedure may be
22.1.4 Carbon Tetrachloride (CCl4). materially prolonged.
22.1.5 Ethyl Alcohol, Denatured, as prescribed in 8.2.
22.1.6 Ferrous Sulfate or Ferrous Ammonium Sulfate 22.3.4 Carefully transfer the filter paper and its contents to
(FeSO4 or FeSO4(NH4)2SO4). the flask. Add 25 mL of HNO3 (sp gr 1.42) to the flask, and
22.1.7 Hydrochloric Acid (HCl)—Concentrated apply gentle heat, digesting the contents of the flask for 20 min.
hydrochloric acid (sp gr 1.19). Cool, add 25 mL of H2SO4 and again heat gently until most of
22.1.8 Hydrogen Peroxide (H2O2)—Concentrated hydrogen the nitrous fumes have been driven off. Increase the heat and
peroxide 30% . continue boiling until the evolution of sulfur trioxide (SO3)
22.1.9 Hydrogen Sulfide (H2S)—A supply or source of fumes occurs.
gaseous hydrogen sulfide. 22.3.5 If organic matter or charring is evident at this point,
22.1.10 Nitric Acid (HNO3)—Concentrated nitric acid (sp allow the flask to cool to room temperature. Rinse down the
gr 1.42). inside of the flask with a small amount of water and carefully
22.1.11 Sulfuric Acid (H2SO4)—Concentrated sulfuric acid add 3 to 4 mL of H2O2. After any initial violent gas evolution
(sp gr 1.84). has subsided again heat to SO3 fumes. If discoloration
22.2 Apparatus: reappears, repeat the hydrogen peroxide treatment and heating
22.2.1 Filter Paper—Ashless, medium-porosity filter paper. until a clear carbon-free solution is obtained.
22.2.2 Funnel—A jacketed-glass funnel or funnel about 22.3.6 Transfer the clear solution to the 300-mL Kjeldahl
which has been wound a coil of copper or tin tubing through flask, rinsing the flask thoroughly with small portions of water
which steam may be passed to heat it. until the volume of the solution and washing is between 125
22.2.3 Gooch Crucible—A Gooch crucible that has been and 150 mL. Heat the solution rapidly to boiling and evaporate
prepared with an asbestos mat in the usual manner, ignited, just short of fuming to ensure complete removal of both HNO3
cooled, and stored in a desiccator. and H2O2.
22.2.4 Distillation Assembly—A 300-mL Kjeldahl flask, 22.3.7 Add 20 g of either ferrous sulfate or ferrous
fitted with a 2-hole rubber stopper, and attached to a bulb-type ammonium sulfate to the flask and connect the flask to the
glass condenser by a U-tube having about 6.4-mm bore and a distillation assembly. Place 50 mL of water in the beaker,
distance of 205 mm between arms. Through the other hole in serving as receiver, and raise the beaker on its support until the
the stopper a double-bulb safety tube or a small separatory end of the condenser is immersed in the water. Start H2S
funnel with a long, slim stem is inserted. The tip of the safety bubbling into the water in the beaker (Note 15) and cold water
tube or funnel is bent to form a short U, the orifice of which flowing through the condenser. Place 50 mL of HCl in the
points upward. The tube or funnel is fitted into the flask so that safety tube or separatory funnel and adjust the stopcock so that
the U tip nearly touches the bottom of the flask. A250-mL the acid runs in a slow stream into the flask. Apply gentle heat
beaker, which serves as a receiver, is held on a movable and bring the solution to a steady boil. If orpiment is present a
support, immediately under the condenser tip. yellow precipitate will appear in the receiver when distillation
22.3 Procedure: starts. Discontinue the distillation when bumping begins.
22.3.1 Weigh to 0.1 g approximately 50 g of the mixed 22.3.8 Remove the flame, change the receiver, add another
10
D 29
50-mL portion of the HCl to the contents of the flask and repeat 23.2 Reagents:
the distillation procedure (Note 16). When the second 23.2.1 Hydrochloric Acid, Standard (0.5 N)—Add 45 mL
distillation is completed, lower the receiver, and wash down of concentrated hydrochloric acid (HCl, sp gr 1.19) to about
the inside of the condenser and the outside of the condenser tip 900 mL of water, cool, and dilute to 1 L. Standardize against
with water. If any orpiment adheres to the walls of the freshly standardized NaOH solution or by any other accurate
condenser, wash it off with a small amount of NH4OH, allow method.
it to drain into the receiver, and then rinse again with water.
23.2.2 Neutral Alcohol, as prescribed in 21.2.1.
Check the contents of the beaker for acidity, adding more acid
if necessary, and allow the H2S to bubble through the solution 23.2.3 Phenolphthalein Indicator Solution, as prescribed in
for a few minutes longer. 21.2.2.
23.2.4 Potassium Hydroxide, Alcoholic Solution (0.5 N)—
NOTE 15—The H2S supply should be of sufficient amount to afford a
Prepare the solution as prescribed in 21.2.3, Item 2, except use
uniform and good rate of flow during the entire distillation.
NOTE 16—With a properly prepared specimen, practically all of the 33 g of KOH in 1 L of the alcohol.
arsenic comes over in the first distillation, the second one serving mainly 23.2.5 Thymol Blue Indicator Solution, as prescribed in
as a safeguard. 21.2.4.
22.3.9 Filter the contents of both beakers through the 23.3 Procedure:
prepared and weighed Gooch crucible. Wash all of the 23.3.1 Weigh to 1 mg approximately 1 g of the mixed
precipitate from each beaker into the crucible with a stream of sample (Section 7) into an alkali-resistant, standard-taper,
hot water from a wash bottle, using a policeman if necessary. ground-glass joint, 250-mL Erlenmeyer flask. Using a constant
Next, wash out the beaker with two 50-mL portions of alcohol volume pipet, add 25 mL of the alcoholic KOH solution to the
followed by two 50-mL portions of boiling CS2 (Note 17). flask containing the specimen and to a second flask for use as
When filtering these washings, adjust the suction so that each a blank. Add 25 mL of the neutral alcohol to each flask and
portion will be retained in the crucible for approximately 5 min attach a standard-taper, ground-glass joint condenser to each
(Note 18). Dry the crucible and its contents at 105 6 2°C for flask. Connect the condensers with soda-lime tubes and reflux
2 h. Cool in a desiccator and weigh. on a steam bath for at least 1 h. Wash down the condensers and
NOTE 17—Bring the CS2 to a boil on a steam bath, making sure there the sides of the flasks with 20 mL of the neutral alcohol and
is no gas flame or electric arc in the immediate area in which the CS2 is titrate in accordance with 23.3.2 or 23.3.3.
being used. 23.3.2 In the case of bleached lac, add several drops of the
NOTE 18—This treatment ensures complete removal of all traces of phenolphthalein solution to each flask and titrate with 0.5 N
sulfur that may have precipitated with the orpiment and which, if left in,
would materially affect the final result, especially with a sample quite low
HCl, with constant swirling of the contents of the flask, until
in arsenic. the pink color just disappears.
22.3.10 If there is any reason for believing that the reagents 23.3.3 In the case of orange shellac place several drops of
used are not arsenic-free, run blank determinations the thymol blue indicator sulution on a white porcelain spon
concurrently, using the same reagents in the same amounts and plate. Titrate the solutions with 0.5 N HCl, with constant
make the proper correction for the amount of orpiment thus swirling, and determine the end point by transferring one or
found. two drops of the solution on a glass rod to the indicator. The
22.4 Calculation—Calculate the percentage of orpiment end point is when the color of the indicator changes to red.
(As2S3) as follows: 23.4 Calculation—Calculate the saponification value as
follows:
Orpiment, % 5 @~R 2 B!/S~1 2 M!# 3 100 (11)
Saponification value 5 @~B 2 V!N 3 56.1#/S~1 2 M!
where: (12)
R 5 residue from specimen, g (22.3.9),
B 5 residue from blank, g (if any) (22.3.10), where:
S 5 sample used, g, and V 5 HCl required for titration of the specimen, mL,
M 5 volatile matter (moisture) content of the sample, B 5 HCl required for titration of the blank, mL,
expressed as a decimal fraction. N 5 normality of the HCl,
23. Saponification Value M 5 volatile matter (moisture) content of the sample
expressed as a decimal fraction.
23.1 Definition:
23.1.1 saponification value—the number of milligrams of
24. Keywords
potassium hydroxide that react with 1 g of the moisture-free
sample. It is a measure of the alkali reactive groups in lac 24.1 bleached lac; button lac; insoluble content; matted lac;
resins. orange lac; saponification value; shellac; volatile content
11
D 29
12
Standard Guide for

Chemical Analysis of White Pigments1
1. Scope D 1394 Test Methods for Chemical Analysis of White

1.1 This guide covers procedures for the chemical analysis Titanium Pigments3
of white pigments. D 3280 Test Methods for Analysis of White Zinc Pigments3
2. Referenced Documents 3. Significance and Use

2.1 ASTM Standards: 3.1 This compilation of available ASTM methods for the
C 471M Test Methods for Chemical Analysis of Gypsum analysis of white pigment serves as a guide to chemists.
and Gypsum Products2 4. Test Methods
D 715 Test Methods for Analysis of Barium Sulfate Pig-
ment3 4.1 Tests shall be conducted in accordance with the follow-
D 717 Test Methods for Analysis of Magnesium Silicate ing ASTM methods. Test procedures not covered by ASTM
Pigment3 methods shall be agreed upon by the purchaser and seller.
D 718 Test Methods for Analysis of Aluminum Silicate 4.2 Lead Pigments—Test Method D 1301.
Pigment3 4.3 Zinc Pigments—Test Methods D 3280.
D 719 Test Methods for Analysis of Diatomaceous Silica 4.4 Titanium Dioxide Pigments—Test Methods D 1394.
Pigment3 4.5 Calcium Carbonate Pigments: Whiting, Paris White,
D 1199 Specification for Calcium Carbonate Pigments3 Spanish White, Chalk—Specification D 1199.
D 1301 Test Methods for Chemical Analysis of White Lead 4.6 Calcium Sulfate Pigments: Gypsum, Terra Alba, Plaster
Pigments3 of Paris—Test Methods C 471M.
4.7 Barium Pigments: Barytes or Barite and Blanc Fixe—
Test Methods D 715.
1
This guide is under the jurisdiction of ASTM Committee D-1 on Paint and 4.8 Silica Pigments—Test Methods D 719.
Related Coatings, Materials, and Applications and is the direct responsibility of 4.9 China Clay—Test Method D 718.
Subcommittee D01.31 on Pigment Specifications. 4.10 Magnesium Silicate—Test Methods D 717.
Current edition approved Sept. 15, 1991. Published November 1991. Originally
published as D 34 – 15. Last previous edition D 34 – 87. 5. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.03. 5.1 chemical analysis; white pigment
1
Designation: D 49 – 83 (Reapproved 1996)e1
Standard Test Methods of

Chemical Analysis of Red Lead1
e1 NOTE—Keywords and References were added editorially in May 1996.
1. Scope 4. Purity of Reagents

1.1 These test methods cover procedures for the chemical 4.1 Reagent grade chemicals shall be used in all tests.
analysis of red lead having the approximate formula Pb3O4 Unless otherwise indicated, it is intended that all reagents shall
(probably PbO2·2PbO). conform to the specifications of the Committee on Analytical
1.2 This standard does not purport to address all of the Reagents of the American Chemical Society where such
safety concerns, if any, associated with its use. It is the specifications are available.5 Other grades may be used pro-
responsibility of the user of this standard to establish appro- vided it is first ascertained that the reagent is of sufficiently
priate safety and health practices and determine the applica- high purity to permit its use without lessening the accuracy of
bility of regulatory limitations prior to use. the determination.
4.2 Unless otherwise indicated, references to water shall be
2. Referenced Documents understood to mean reagent water conforming to Type II of
2.1 ASTM Standards: Specification D 1193.
D 50 Test Methods for Chemical Analysis of Yellow, Or-
ange, Red, and Brown Pigments Containing Iron and 5. Moisture
Manganese2 5.1 Determine moisture content with a 2-g specimen in
D 215 Practice for Chemical Analysis of White Linseed Oil accordance with Method A of Test Method D 280. The speci-
Paints3 men is dried for 2 h at 105°C. The loss in weight is considered
D 280 Test Methods for Hygroscopic Moisture (and Other as moisture.
Matter Volatile Under the Test Conditions) in Pigments2
D 1193 Specification for Reagent Water4 6. Organic Color
D 1208 Test Methods for Common Properties of Certain 6.1 Boil 2 g of the sample with 25 mL of 95 % ethyl alcohol,
Pigments2 let settle, decant the supernatant liquid; boil the residue with 25
D 1301 Test Methods for Chemical Analysis of White Lead mL of distilled water and decant as before; boil the residue
Pigments2 with 25 mL of diluted NH4OH (1 + 4) and again decant. Boil
D 1959 Test Method for Iodine Value of Drying Oils and another 2-g portion of the sample with 25 mL of chloroform,
Fatty Acids2 let settle, and decant the supernatant liquid. If any one of the
above solutions is colored, organic coloring matter is indicated.
3. Treatment of Sample If the solutions remain colorless, organic colors are probably
3.1 If the pigment is lumpy or not finely ground, grind it to absent.
a fine powder and mix thoroughly. Large samples may be NOTE 1—If it is desired to test for organic colors resistant to the above
thoroughly mixed and a representative portion taken and reagents, the test procedures described in the following books may be
powdered if lumpy or not finely ground. The sample in all used, taking into account the nature of the pigment involved (1,2,3).6
cases shall be thoroughly mixed before taking portions for
analysis. All samples shall be preserved in stoppered bottles or 7. Total Lead and Insoluble Matter
containers. 7.1 Treat 1 g of the sample with 15 mL of HNO3(1 + 1) and
sufficient H2O2 to dissolve all PbO2 on warming. If any
1 5
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Reagent Chemicals, American Chemical Society Specifications, American
and Related Coatings, Materials, and Applications and are the direct responsibility Chemical Society, Washington, DC. For suggestions on the testing of reagents not
of Subcommittee D 01.31 on Pigment Specifications. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved Dec. 20, 1983. Published January 1984. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 49 – 17 T. Last previous edition D 49 – 82. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
Annual Book of ASTM Standards, Vol 06.03. MD.
3 6
Annual Book of ASTM Standards, Vol 06.01. The boldface numbers in parentheses refer to a list of references at the end of
4
Annual Book of ASTM Standards, Vol 11.01. these test methods.
1
D 49
insoluble matter is present, add 25 mL of water, boil, filter, and in 25 mL of the acetic acid (1 + 3), warming gently and stirring
wash with hot water. The insoluble matter contains free SiO2 until a clear solution is obtained. Cool this solution to room
and should be examined for BaSO4 and silicates, if appreciable. temperature, dilute to 50 mL with the acetic acid solution
7.2 To the original solution or filtrate from the insoluble (1 + 3), and mix thoroughly.
matter add 20 mL of H2SO4 (sp gr 1.84) and evaporate to SO3 8.2 Sodium Thiosulfate Solution (0.1N)—Dissolve 24.83 g
fumes. Cool, add 150 mL of water, and 150 mL of 95 % ethyl of sodium thiosulfate (Na2S2O3·5H2O), freshly pulverized and
alcohol, let stand cold for 2 h, filter, on a Gooch crucible, wash dried between filter paper, and dilute with water to 1 litre at the
with 95 % alcohol, dry at 105 to 110°C, and weigh as PbSO4. temperature at which the titrations are to be made. The solution
Calculate to PbO. is best made with well-boiled water free from CO2, or let stand
7.3 Red lead is rarely adulterated, but should the specimen 8 to 14 days before standardizing, as described in Section 5 of
contain soluble barium compounds, the PbSO4 obtained in 8.2 Test Method D 1959.
will contain BaSO4. In this case, precipitate the lead as sulfide 8.3 Starch Solution—Stir 2 to 3 g of potato starch with 100
from a slightly acid (HCl) solution, dissolve the PbS in hot mL of salicylic acid solution (1 %), and boil the mixture until
diluted HNO3, and determine the lead as sulfate or chromate. the starch is practically dissolved, then dilute to 1 L (Note 3),
7.4 If the specimen contains significant amounts of calcium or prepare as described in 7.8.2 of Test Method D 1959.
or magnesium, boil the HNO3 − H2O2 solution (7.1) until all NOTE 3—Lead Peroxide—If the pigment contains an appreciable
the lead is converted into nitrate and then determine the lead as amount of nitrite (nitrate has no effect on the method), leach out
PbCrO4. water-soluble matter as below, dry the residue and determine PbO2 as
7.5 If soluble barium, calcium, or magnesium are to be above, calculating to basis of original specimen.
determined, precipitate the lead as sulfide from a slightly acid
solution (HCl), dissolve the PbS in hot diluted HNO3, and 9. Procedure
determine the lead as sulfate. Boil the filtrate from the PbS to 9.1 Weigh 1 g of the finely ground sample, transfer to a
expel H2S, add a little bromine water to oxidize iron (if 200-mL Erlenmeyer flask, add 20 mL of water; then add as
present), boil to expel bromine, and precipitate the barium with quickly as possible 40 mL of the “red lead solution” at room
a few millilitres of H2SO4 (1 + 3). Filter and weigh as BaSO4. temperature. If the sample is red lead that has been extracted
Calculate to BaO or BaCO3. To the filtrate from the BaSO4 add from a paint or paste, in place of the water use 10 mL of a
NH4OH in slight excess, filter off any precipitate of mixture of 7 parts by volume of chloroform and 3 parts by
Fe(OH)3 + Al(OH)3, wash with hot water. Manganese, if volume of glacial acetic acid, and then add without delay the
present, can be precipitated by adding bromine and NH4OH red lead solution. Add 30 mL of water containing 5 or 6 g of
and warming. Filter, wash with hot water, ignite, and weigh as sodium acetate and titrate at once with 0.1 N Na2S2O3 solution,
Mn3O4. Unite all the filtrates, make slightly acid with acetic adding the latter rather slowly and keeping the liquid con-
acid, heat to boiling and pass H2S into the hot solution until stantly in motion by whirling the flask. When the solution has
saturated (20 to 30 min); add 5 g of NH4Cl and let stand 5 h, become light yellow, rub-up any undissolved particles with the
filter off any ZnS, wash with H2S water, dissolve the ZnS in hot rod until free iodine no longer forms, wash off rod, add the
diluted HCl and determine the zinc by titration with Na2S2O3 solution until pale yellow, add starch solution, and
K4Fe(CN)6. Or, boil off the H2S, filter out any separated sulfur titrate until colorless. Add the 0.1 N iodine solution until blue
and determine the zinc as Zn2P2O7. Calcium may be deter- color is just restored and subtract the amount used for the
mined in the filtrate from the ZnS by expelling H2S and then volume of Na2S2O3 that had been added.
adding NH4OH and ammonium oxalate. Titrate the calcium
oxide precipitate using the procedure described in 13.3 of Test 10. Calculation
Methods D 50. In the filtrate from calcium determine magne- 10.1 Calculate the lead peroxide and true red lead contents
sium by precipitating with sodium phosphate solution, finally as follows:
weighing as Mg2P2O7.
8. Lead Peroxide (PbO2) and True Red Lead (Pb3O4) PbO2 5 I 3 0.942
Pb3O4 5 PbO2 3 2.866 5 I 3 2.7
NOTE 2—Method of Diehl (4) modified by Topf (5)—not applicable
when substances are present, other than oxides of lead, that liberate iodine
where: I 5 iodine value of the Na2S2O3 solution,
under conditions given, or substances such as metallic lead which reduce PbO2 239.19
PbO2 to PbO without the liberation of iodine. 0.942 5 I 5 253.81 , and (1)
2
8.1 Solutions Required: (a) Red Lead Solution—Dissolve in Pb3O4 685.57
2.86616 5 PbO 5 239.19
1-L beaker 600 g of crystallized sodium acetate and 48 g of KI 2
in about 500 mL of acetic acid (1 + 3) (made by mixing 150
mL of glacial acetic acid with 450 mL of water). Warm the 11. Zinc
beaker and contents on a steam bath, stirring occasionally, until 11.1 If the volume is appreciable, evaporate off the alcohol
a clear solution is obtained. Cool this solution to room from the filtrate from total lead, make alkaline with NH4OH,
temperature, dilute to exactly 1000 mL with the acetic acid then acid with HCl (sp gr 1.19), add 3 mL more of HCl, dilute
(1 + 3) and mix thoroughly. If preferred, the red lead solution to about 250 mL with water, heat nearly to boiling and titrate
may be prepared separately for each titration, as follows: with standard K4Fe(CN)6 solution in accordance with 16.1.11
Dissolve 30 g of the crystallized sodium acetate and 2.4 g of KI of Method D 215. Report as ZnO (includes cadmium). Iron,
2
D 49
copper, or other interfering substances should first be removed 15.2 Or, dissolve 0.5 g of the sample in 25 mL of water, 10
as described in 25.2.3 of Practice D 215. mL of NH4OH (sp gr 0.90) and HCl in slight excess; dilute to
about 150 mL with water and add a piece of aluminum foil
12. Matter Soluble in Water which should about cover the bottom of the beaker (being held
12.1 Determine the amount of water soluble material on the bottom by means of a stirring rod). Heat gently till all
present in accordance with the procedure in Section 5 of Test lead is precipitated, decant through a filter, pressing the lead
Methods D 1208 or determine in accordance with Test Method sponge with a flattened rod, and washing with hot water. Add
D 1301. to the filtrate a little bromine water, boil until bromine is
expelled, add 15 mL of BaCl2 solution (10 %), let stand on a
13. Total Silica steam bath for 1 h, filter, wash with hot water, ignite, and weigh
13.1 Digest 5 g of the sample in a covered casserole with 5 as BaSO4 (any SrSO4 present is not decomposed in this
mL of HCl and 15 mL of HNO3 (1 + 1). Evaporate to dryness method).7
to dehydrate. Cool, treat with hot water and HNO3, boil, filter,
wash with hot acid ammonium acetate solution, then dilute 16. Iron Oxide
HCl and finally hot water. Ignite and weigh as SiO2. The 16.1 Determine iron oxide in accordance with Section 12 of
residue may be treated with H2SO4 and HF in cases of doubt as Method D 50, or in a large beaker, treat 20 g of the sample with
to purity. 20 mL of water, 20 mL of HNO3 (sp gr 1.42), and 3 mL of
14. Carbon Dioxide formaldehyde solution. Warm until all PbO2 is dissolved, dilute
with water, warm, filter off insoluble matter, and wash with hot
14.1 Determine carbon dioxide by the evolution method, water. Ignite filter and insoluble matter, and evaporate with
using diluted HCl and stannous chloride. H2SO4 and HF. To filtrate from insoluble matter add 14 mL of
15. Soluble Sulfates H2SO4 (1 + 1), filter off PbSO4, and wash. Dissolve the residue
from HF and H2SO4 in H2SO4 and add to the filtrate from
15.1 Sulfates Other Than Barium Sulfate—Treat 0.5 g of the PbSO4. Dilute to 500 mL and determine iron colorimetrically
sample with 5 mL of water, 3 g of NH4Cl, and 5 mL of HCl in an aliquot, using the same amounts of HNO3, H2SO4, and
saturated with bromine. Digest (covered) on steam bath about formaldehyde in the comparison solution Ref (7). Calculate to
15 min. Add 25 mL of water, neutralize with dry Na2CO3, and Fe2O3.
add about 2 g more. Boil 10 to 15 min, let settle, dilute with hot
water, filter, and wash with hot water. Redissolve in HCl, 17. Keywords
reprecipitate as above, and wash thoroughly with hot water.
Acidify the united filtrates with HCl, adding a slight excess; 17.1 chemicals analysis; lead dioxide; red lead; tetra lead
boil and add a slight excess of BaCl2 solution (10 %). Let stand oxide
on a steam bath for 1 h. Filter and wash with hot water. Ignite
and weigh as BaSO4. Calculate to SO3 (includes SO3 formed
from SO2). 7
The solubility of BaSO4 is increased by the presence of aluminum chloride (6).
REFERENCES
(1) Zerr, and Mayer, Tests for Coal Tar Colors in Aniline Lakes. (5) Zeitschrift für Analytische Chemie, ZANCA, Vol 26, p. 296.
(2) Schultz, and Julius, A Systematic Survey of the Organic Coloring (6) Skoog, D. A. and West, D. M., Fundamentals of Analytical Chemistry,
Matters. Holt, Rinehart and Winston, Inc., New York, 1969, p. 192.
(3) Mulliken, Identification of Pure Organic Compounds; Commercial
(7) Lunge-Berl, “Chemische-technisch Untersuchungs-Methoden,” Vol 2,
Dyestuffs, Vol III.
(4) Dinglers, Dinglers Polytechnisches Journal, DPJOA, Vol 246, p. 196. p. 95, 6th Ed.
3

Chemical Analysis of Yellow, Orange, Red, and Brown
Pigments Containing Iron and Manganese1
1. Scope Quicklime, and Hydrated Lime2

1.1 These test methods cover procedures for the chemical D 185 Test Methods for Coarse Particles in Pigments,
analysis of yellow, orange, red, and brown pigments containing Pastes, and Paints3
iron and manganese. The test methods apply specifically to the D 280 Test Methods for Hygroscopic Moisture (and Other
following pigments: synthetic hydrated yellow iron oxide, Matter Volatile Under the Test Conditions) in Pigments3
yellow ocher, red and brown iron oxides, raw and burnt umber, D 562 Test Method for Consistency of Paints Using the
raw and burnt sienna, and venetian red. Stormer Viscometer4
1.2 The analytical procedures appear in the following order: D 1193 Specification for Reagent Water5
ASTM
D 1208 Test Methods for Common Properties of Certain
Method Pigments3
Refer- E 11 Specification for Wire Cloth Sieves for Testing Pur-
Dry Pigments Sections ences
poses6
Moisture and Other Volatile Matter 6 D 280
Loss on Ignition 7 3. Significance and Use
Coarse Particles 8 D 185
Matter Soluble in Water 9 D 1208
3.1 These test methods compile in one place, recommended
Organic Coloring Matter 10 procedures for analyzing inorganic colored pigments. These
Iron Oxide 11 and 12 pigments are used extensively in paints, and for this reason
Calcium Compounds (Reported as CaO) 13 and 14
Sulfates Soluble in Hydrochloric Acid 15 and 16
their compositions are important to the formulators and user.
Lead Chromate (in Ochers) 17
Calcium Carbonate (in Venetian Red) 18 C 25 4. Preparation of Sample
Manganese (in Siennas and Umbers) 19 and 20
4.1 Mix the sample thoroughly and take a representative
Pigment Pastes in Oil portion for analysis. Reduce any lumps or coarse particles to a
fine powder by grinding. Grind extracted pigments to pass a
Pigment Content 21 D 1208
Moisture and Other Volatile Matter 22 D 1208
No. 80 (180-µm) sieve (see Specification E 11 for detailed
Nonvolatile Matter in Vehicle 23 requirements). Discard any skins that do not pass through the
Moisture by Distillation 24 D 1208 sieve. Mix the finely ground pigment thoroughly.
Coarse Particles and Skins 25 D 185
Consistency (Stormer) 26 D 562
5. Purity of Reagents
1.3 This standard does not purport to address all of the 5.1 Purity of Reagents—Unless otherwise indicated, it is
safety concerns, if any, associated with its use. It is the intended that all reagents shall conform to the specifications of
responsibility of the user of this standard to establish appro- the Committee on Analytical Reagents of the American Chemi-
priate safety and health practices and determine the applica- cal Society, where such specifications are available.7 Other
bility of regulatory limitations prior to use. grades may be used, provided it is first ascertained that the
2
2.1 ASTM Standards: 3
C 25 Test Methods for Chemical Analysis of Limestone, 4
5
6
7
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Chemical Society, Washington, DC. For suggestions on the testing of reagents not
and Related Coatings, Materials, and Applications and are the direct responsibility listed by the American Chemical Society, see Analar Standards for Laboratory
of Subcommittee D01.31 on Pigment Specification. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Current edition approved May 25, 1990. Published July 1990. Originally and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
published as D 50 – 17 T. Last previous edition D 50 – 81. MD.
1
D 50
reagent is of sufficiently high purity to permit its use without NOTE 2—With this class of pigments indication of presence of an
lessening the accuracy of the determination. organic color may often be noted by the characteristic odor given off on
5.2 Purity of Water—Unless otherwise indicated, references ignition.
to water shall be understood to mean Type II reagent water Iron Oxide
conforming to Specification D 1193.
11. Reagents
DRY PIGMENTS 11.1 Stannous Chloride Solution (SnCl 2·2H2O)—Dissolve
Moisture and Other Volatile Matter 50 g of SnCl 2·2H2O in 300 mL of hydrochloric acid (HCl) (sp
gr 1.19) and dilute with water to 500 mL. Keep the clear
6. Procedure solution in a tightly stoppered bottle containing some metallic
6.1 Determine moisture and other volatile matter in accor- tin.
dance with Method A of Test Methods D 280. 11.2 Mercuric Chloride Solution (HgCl 2)—Prepare a satu-
rated solution of HgCl2(60 to 100 g/L).
Loss on Ignition 11.3 Sulfuric-Phosphoric Acid Mixture— Mix 150 mL of
sulfuric acid (H2SO4) (sp gr 1.84) with 150 mL of phosphoric
7. Procedure
acid (H3PO4) (85 %) and dilute with water to 1 L.
7.1 Weigh accurately approximately 1 g of pigment into a 11.4 Diphenylamine Indicator—Dissolve 1 g of dipheny-
previously weighed and ignited porcelain crucible (Note 1). lamine in 100 mL of H2SO4 (sp gr 1.84).
Cover and ignite to constant weight over a bunsen or Meker 11.5 Standard Potassium Dichromate Solution—(K2Cr2O7)
burner or in an electric furnace at a temperature of approxi- (0.1 N)—Dissolve 4.904 g of K2Cr2O7 in water and dilute to 1
mately 900°C. Cool in a desiccator, weigh, and calculate the L. Standardize against the National Bureau of Standards
percent loss on ignition. This figure may include combined standard sample No. 27 of Sibley iron ore.
water, carbon dioxide (CO2), organic matter, and some sulfuric 11.6 Potassium Ferricyanide Solution (K3Fe(CN)6)—A
oxide (SO3) if much calcium sulfate (CaSO4) is present. The very dilute solution is most satisfactory. Dissolve approxi-
CO2 may be determined on a separate portion if desired. mately 0.01 g of K3Fe(CN) 6 in 50 mL of water. This solution
NOTE 1—It is inadvisable to use platinum unless it is known that must be made fresh when wanted because it does not keep.
attacking substances are absent.
12. Procedure
Coarse Particles 12.1 According to the amount of iron in the pigment, weigh
0.3 to 1.0 g of the pigment and ignite in a porcelain crucible at
8. Procedure a dull red heat to destroy organic matter. Transfer to a 400-mL
8.1 Determine coarse particles in accordance with Test beaker and add 25 mL of HCl (sp gr 1.19). Cover with a
Method D 185. watchglass and digest just short of boiling (80 to 90°C) until no
dark specks can be seen in the insoluble residue. The addition
Matter Soluble in Water of a few drops of SnCl2 solution after adding the acid greatly
assists dissolving of the iron. When the residue is light in color,
9. Procedure the solution of iron may be considered complete. This may take
9.1 Determine matter soluble in water in accordance with from 15 min to 1 h, or longer.
Test Methods D 1208. 12.2 Add 25 to 50 mL of water and heat to gentle boiling
(avoid vigorous prolonged boiling). Slowly add SnCl2 solution
Organic Coloring Matter dropwise until the last drop makes the solution colorless or free
from any tinge of yellow, then add 1 or 2 drops in excess. It is
10. Procedure best to keep the watchglass on the beaker while adding the
10.1 Boil 2 g of the sample with 25 mL of water, let settle, SnCl2 solution, with agitation of the hot iron solution after each
and decant the supernatant liquid. Boil the residue with 25 mL addition. If too much SnCl2 is added by mistake, add potassium
of ethyl alcohol (95 %) and decant as before. Boil the residue permanganate (KMnO4) to the solution until a yellow color
with 25 mL of 1 N alcoholic sodium hydroxide (NaOH) appears, then again add SnCl2 dropwise until the yellow color
solution and again decant. Boil another 2-g portion of the just disappears, again adding one or two drops in excess. Dilute
sample with 25 mL of chloroform, let settle, and decant the with 200 mL of cold water; then add all at once with vigorous
supernatant liquid. If any one of the above solutions is colored, stirring 15 mL of HgCl2 solution. Let stand 3 to 4 min. A slight
organic coloring matter is indicated (Note 2). If the solutions white precipitate should form. If none, or a heavy grayish
remain colorless, organic colors are probably absent, but may precipitate forms, the determination should be discarded and
be tested for by reference to procedures given in standard repeated.
reference works, taking into account the nature of the pigment 12.3 Add 15 mL of H2SO4-H 3PO4 mixture and 3 drops of
involved.8 diphenylamine indicator solution. Titrate with K2Cr2O7 solu-
tion, taking the sudden change of the dark green color to a
blue-black color as the end point.
8
Reference may be made to the following: Payne, H. F., “Organic Coatings 12.4 If preferred, K3Fe(CN)6 may be used as an external
Technology,” Vol II, John Wiley & Sons, Inc., New York, N. Y., 1961. indicator. In this case omit the addition of the H 2SO4-H3PO4
2
D 50
mixture and the diphenylamine indicator. Titrate with the Digest just short of boiling until no dark specks can be seen in
K2Cr2O7 solution as in 12.3, except toward the end take out a the insoluble residue. Add ammonium hydroxide (NH4OH) (sp
very small drop of the solution being titrated and touch this to gr 0.90) in slight excess and about 2 mL of H2O2 (30 %). Cool,
a drop of the K3Fe(CN) 6 solution, best placed on a paraffined transfer to a 500-mL graduated flask, and dilute to 500 mL.
surface. Toward the end point the blue is replaced by a Mix thoroughly and filter through a dry paper.
bluish-green coloration, perceptible at the junction of the two 14.2 Take 100 mL of the filtrate (corresponding to 0.5 g of
solutions. Take as the end point when no trace of the bluish- sample), add a few drops of NH4OH, heat to boiling, and add
green coloration can be detected. an excess of saturated ammonium oxalate solution. Continue
12.5 Calculation—Calculate the percent of iron oxide the boiling until the precipitate becomes granular. Let stand
(Fe2O3), A, as follows: about 30 min, filter, and wash three times with 20-mL aliquots
A 5 ~FV/S! 3 100 (1) of hot water until free of ammonium oxalate.
14.3 Place the beaker in which precipitation was made
where: under the funnel, pierce the apex of the filter with a stirring rod,
F 5 Fe2O3 equivalent of the K2Cr2O 7 solution, g/mL, and wash the precipitate into the beaker with hot water. Pour
V 5 K 2Cr2O7 solution required, mL, and warm H2SO 4 (1 + 4) through the paper and wash a few times.
S 5 sample used, g. Add about 30 mL of H2SO4 (1 + 4) and dilute to about 250 mL.
Heat to 90°C and titrate at once with KMnO4 solution. (The
Calcium Compounds (Reported as CaO) temperature of the solution should not be below 60°C when the
13. Reagents end point is reached.)
14.4 Calculation—Calculate the percent of calcium com-
13.1 Ammonium Oxalate Saturated Solution—Heat to boil- pounds, A, in terms of CaO, as follows:
ing 5 g powdered ammonium oxalate [(NH4) 2C2O4·H2O] and
A 5 ~V2C/0.5! 3 100 (4)
100 mL of water. Allow to cool.
13.2 Hydrogen Peroxide (H2O2) (30 %). where:
13.3 Potassium Permanganate, Standard Solution— V 2 5 KMnO4 solution required by the specimen, mL, and
(KMnO4) (0.1 N)—Dissolve 3.16 g of KMnO4 in water and C 5 CaO equivalent of the KMnO4 solution, g/mL.
dilute to 1 L. Let stand 8 to 14 days, siphon off the clear
solution (or filter through a medium porosity fritted disk), and Sulfates Soluble in Hydrochloric Acid
standardize against the National Institute of Standards and 15. Reagent
Technology (NIST) standard sample No. 40 of sodium oxalate 15.1 Barium Chloride Solution—Dissolve 117 g of barium
(Na2C2O 4) as follows: In a 400-mL beaker dissolve 0.2500 to chloride (BaCl2·2H2O) in water and dilute to 1 L.
0.3000 g of the NIST Na2C2O4 in 250 mL of hot water (80 to
90°C) and add 15 mL of H2SO4 (1 + 1). Titrate at once with 16. Procedure
KMnO4 solution, stirring the liquid vigorously and continu- 16.1 Weigh 1 g of the sample and add 30 mL of HCl (sp gr
ously. The KMnO4 must not be added more rapidly than 10 to 1.19). Boil 10 min, add about 50 mL of water, boil, filter, and
15 mL/min, and the last 0.5 to 1 mL must be added dropwise wash with hot water. Heat the solution to boiling, add NH4OH
with particular care to allow each drop to be fully decolorized in excess, filter, and wash the precipitate several times with hot
before the next is introduced. The solution shall not be below water. Dissolve the precipitate in hot HCl (1 + 1), reprecipitate
60°C by the time the end point has been reached. (More rapid with NH4OH, and wash well with hot water.
cooling may be prevented by allowing the beaker to stand on 16.2 Combine the united filtrates and make distinctly acid
a small asbestos-covered hot plate during the titration.) The use with HCl, boil, and add dropwise, while stirring, an excess of
of a small thermometer (nonmercury type) as a stirring rod is BaCl 2 solution. Boil about 10 min. The BaSO4 precipitate
most convenient. Keep the KMnO4 solution in a glass- should normally stand for 2 to 4 h before filtering in order to
stoppered bottle painted black to keep out light, or in a brown coagulate the precipitate. If the pad is thick enough on the
glass bottle stored in a dark place. Gooch crucible and filtrate is free of sulfate, then standing may
13.4 Calculate the calcium oxide (CaO) value of the solu- not be necessary. Filter on a Gooch crucible, and wash with hot
tion as follows: water. Ignite at 900°C, and weigh as barium sulfate (BaSO4).
C 5 ~W 1 3 V1! 3 0.4185 (2) 16.3 Calculation—Calculate the percent of SO3, A, as
follows:
where:
A 5 @~P 3 0.343!/S# 3 100 (5)
C 5 CaO equivalent of the KMnO4 solution, g/mL,
W1 5 sodium oxalate used, g, and where:
V1 5 KMnO4 solution required for the titration, mL. P 5 weight of BaSO4, g, and
0.4185 5 CaO/Na2C2O4 5 56.08 / 134.01 (3) S 5 weight of original sample, g.
0.343 5 SO3/BaSO 4 5 80.06/233.42
14. Procedure
Lead Chromate (in Ochers)
14.1 Weigh 2.5 g of sample, transfer to a porcelain crucible,
and ignite at a dull red heat to destroy organic matter. Cool, 17. Procedure
transfer to a 600-mL beaker, and add 100 mL of HCl (1 + 1). 17.1 Test for lead by any standard method of qualitative
3
D 50
analysis. The following method is suggested: Dissolve a small addition of a little HNO3, add to the main filtrate, and
portion of the pigment in cold nitric acid (HNO3) (1 + 5), evaporate nearly to dryness. Take up in HNO 3 (1 + 3) and
stirring vigorously. Add a few millilitres of potassium iodide transfer to the flask as before.
(KI) solution (100 g/L). The appearance of yellow crystals 20.2 Pipet a 10-mL aliquot into a 200-mL Erlenmeyer flask
indicates the presence of lead. and add 30 mL of water and 10 mL of HNO3 (sp gr 1.42). Add
about 0.5 g of NaBiO3 and heat for a few minutes, or until the
Calcium Carbonate (in Venetian Red) pink color has disappeared with or without the precipitation of
18. Procedure magnesium dioxide (MnO2). Add a few small crystals of
sodium nitrite (NaNO 2) or potassium nitrite (KNO2) to
18.1 Determine carbon dioxide (CO2) in accordance with dissolve the MnO2 and boil the solution several minutes to
Test Methods C 25. expel nitrous oxide fumes (a little anhydrous sodium carbonate
18.2 Calculation—Calculate the percent of calcium carbon- (Na2CO3) will aid this). Add water to bring the volume up to
ate (CaCO3), A, as follows: 50 mL and cool to about 15°C. Add about 0.5 g of bismuthate
A 5 @~W3 3 2.274!/S# 3 100 (6) and shake the flask well. Add 50 mL of HNO 3 (3 + 97), filter
by suction through an asbestos felt into a 300-mL Erlenmeyer
where: flask, and wash with 50 to 100 mL of the HNO 3 (3 + 97). Run
W 3 5 CO2, g, and
in exactly 25 mL of ferrous ammonium sulfate solution and
S 5 sample used, g. 2.274 5 CaCO3/CO 2 5 100.09/
titrate to a faint pink color with KMnO4 solution.
44.0
NOTE 3—If 25 mL of ferrous ammonium sulfate solution is not
Manganese (in Siennas and Umbers) sufficient to decolorize the solution, add a further 10 mL or more as
required. Adjust the blank (19.3) accordingly.
19. Reagents
20.3 Calculation—Calculate the percent of manganese, A,
19.1 Standard Potassium Permanganate Solution (KMnO4) as follows:
(1 mL 5 0.00035 g Mn)—Dissolve 1 g of KMnO4 in 1 L of
water. Age and standardize the solution as in Section 13, using A 5 @~B2 2 V 4!M/W5# 3 100 (8)
one third the quantities of reagents specified therein. Calculate where:
the manganese value of the solution as follows: B 2 5 KMnO4 solution required for titration of the blank
M 5 ~W4/V 3! 3 0.165 (7) (19.2), mL,
V4 5 KMnO4 solution required for back-titration of the
where: specimen (19.2), mL,
M 5 manganese equivalent of the KMnO4 solution, g/mL, M 5 manganese equivalent of the KMnO4 solution, g/mL,
W4 5 sodium oxalate used, g, and and
V3 5 KMnO4 solution required for the titration, mL. W5 5 sample in the aliquot, g.
19.2 Sodium Bismuthate (NaBiO3).
19.3 Ferrous Ammonium Sulfate Solution— To 12 g of PIGMENT PASTES IN OIL
ferrous ammonium sulfate (Fe(NH4)2(SO 4)2·6H2O) add 25 mL
of H2SO 4 (sp gr 1.84) and 25 mL of H3PO4 (85 %) and dilute 21. Pigment Content
to 1 L with water. Each day the solution is used run a blank 21.1 Determine pigment content in accordance with Test
titration against the KMnO4 as follows: Measure into a 200-mL Methods D 1208.
Erlenmeyer flask 50 mL of HNO3 (1 + 3), cool, and add about
0.2 g of NaBiO3. Dilute with 50 mL of HNO3 (3 + 97), filter by 22. Moisture and Other Volatile Matter
suction through Gooch crucible with a medium porosity fritted 22.1 Determine moisture and other volatile matter in accor-
disk into a 300-mL Erlenmeyer flask, and wash with 50 mL of dance with Test Methods D 1208.
HNO3 (3 + 97). Run in exactly 25 mL of the ferrous solution
and titrate to a faint pink color with the KMnO4 solution. 23. Nonvolatile Matter in Vehicle
23.1 Subtract the percent pigment content and percent
20. Procedure volatile matter from 100 and report as percent vehicle.
20.1 Ignite 1 g of the sample in a porcelain crucible at a dull
red heat to destroy organic matter. Transfer to a platinum dish 24. Moisture by Distillation
and add 10 mL of water, 4 mL of H2SO4 (sp gr 1.84), 20 mL 24.1 Determine moisture by distillation in accordance with
of HF (48 %), and a few drops of H2SO3. Evaporate until the Test Methods D 1208.
H2SO4 fumes freely, cool, and add 25 mL of HNO3 (1 + 3). If
no appreciable residue remains, transfer to a 100-mL volumet- 25. Coarse Particles and Skins
ric flask, using 25 mL of HNO3 (1 + 3) to rinse the dish, dilute 25.1 Determine coarse particles and skins in accordance
to the mark with water, and mix thoroughly. If there is an with Test Methods D 185.
appreciable residue, filter through a small qualitative filter
paper and wash with water. Ignite the residue in a platinum 26. Consistency (Stormer)
crucible, and fuse with a little sodium pyrosulfate (Na2S 2O7) 26.1 Determine consistency in accordance with Test Method
or potassium pyrosulfate (K2S2O 7). Dissolve in water, with the D 562.
4
D 50
27. Keywords
27.1 brown pigment (iron and manganese); calcium; col-
ored pigment; iron oxide; red pigment; soluble sulfate; yellow
pigment
5
Designation: D 79 – 86 (Reapproved 1999) American Association State
Highway and Transportation Officials Standard
AASHTO No.: M124

Zinc Oxide Pigments1
1. Scope 4. Composition and Properties

1.1 This specification covers the pigments commercially 4.1 Dry Pigment, French Process—In the manufacture of
known as “zinc white” or zinc oxide. The pigments may be French process zinc oxide, metallic zinc is vaporized, either in
purchased in the dry form or as a paste in oil. a boiler or a refining column, and the resulting vapor is burned
in a controlled manner in an orifice. The fine particles of zinc
NOTE 1—Zinc oxides are used in many industries. For additional
information, see Specification D 4295 and Test Methods D 4315 for oxide are cooled enough to agglomerate and are collected by a
descriptions of zinc oxide use in rubber compounding. system of fabric bags. French process oxide shall conform to
the properties listed in Table 1.
2. Referenced Documents 4.2 Dry Pigment, American Process— In the manufacture
2.1 ASTM Standards: of American process zinc oxide, zinc ore is reduced in the
D 185 Test Methods for Coarse Particles in Pigments, presence of a carbonaceous fuel. The resulting vapor is burned
Pastes, and Paints2 in a combustion chamber, and the fine particles of zinc oxide
D 280 Test Methods for Hygroscopic Moisture (and Other are cooled enough to agglomerate and are collected by a
Matter Volatile Under the Test Conditions) in Pigments2 system of fabric bags. American process oxide shall conform to
D 281 Test Method for Oil Absorption of Pigments by the properties listed in Table 1.
Spatula Rub-Out3 4.3 Paste in Oil—The paste shall be made by thoroughly
D 332 Test Method for Relative Tinting Strength of White grinding the specified pigment with linseed oil. As received it
Pigments by Visual Observation3 shall not be caked in the container and shall break up readily in
D 1483 Test Method for Oil Absorption of Pigments by oil to form a smooth paint of brushing consistency. The paste
Gardner-Coleman Method3 shall conform to the following requirements:
D 2745 Test Method for Relative Tinting Strength of White Pigment, % 80 to 86
Pigments by Reflectance Measurements3 Linseed oil, % 14 to 20
Moisture and other volatile matter, max, % 0.5
D 3280 Test Methods for Analysis of White Zinc Pigments2 Coarse particles and skins (total residue retained on a 1.5
D 4295 Classification for Rubber Compounding No. 325 (45-µm) sieve), max, % of the dry pigment
Materials—Zinc Oxide4 4.4 In such physical properties as are specified by the
D 4315 Test Methods for Rubber Compounding Material— purchaser, the pigment shall satisfactorily match a reference
Zinc Oxide4 sample mutually agreed upon by the purchaser and the seller.
E 20 Practice for Particle Size Analysis of Particulate Sub- The most frequently specified properties are oil absorption,
stances in the Range of 0.2 to 75 µm by Optical Micros- tinting strength, and particle shape. Appropriate test methods
copy5 are listed in Section 6. In the event that either an acicular type
3. Significance and Use or a nodular (spherical) type of zinc oxide is desired, the
particle shape shall be determined by examining or photo-
3.1 Zinc oxide functions as both a chemical and a pigment. graphing microscopic mounts (10003 or more) of the sample
It is used in a variety of applications including rubber, paint, and the mutually agreed upon standard that are to be prepared
reprography, glass, chemicals, etc. In paint, it contributes to as specified in Practice E 20.
mildew protection, ultraviolet absorption, hiding power, and
neutralization of acids formed upon oxidation of the paint film. 5. Sampling
5.1 Two samples shall be taken at random from different
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint packages from each lot, batch, day’s pack, or other unit of
and Related Coatings, Materials, and Applications, and is the direct responsibility of production in a shipment. When no markings distinguishing
Subcommittee D01.31 on Pigment Specifications.
Current edition approved April 25, 1986. Published June 1986. Originally
between units of production appear, samples shall be taken
published as D 79 – 21 T. Last previous edition D 79 – 80. from different packages in the ratio of two samples for each
2
3
Annual Book of ASTM Standards, Vol 06.03. 10 000 lb (4540 kg), except that for shipments of less than
Annual Book of ASTM Standards, Vol 06.01. 10 000 lb, two samples shall be taken. At the option of the
4
5
Discontinued; See 1993 Annual Book of ASTM Standards, Vol 14.02. purchaser, the samples may be tested separately or after
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
1
D 79
TABLE 1 Composition 6.1.1 Coarse Particles—Test Methods D 185.
French American 6.1.2 Moisture in Pigments—Test Methods D 280.
Process Process
6.1.3 Chemical Analysis of Dry Pigments— Methods
Zinc oxide, min, % 99 98.5
Total sulfur, max, % 0.1 0.2
D 3280.
Moisture and other volatile matter, max, % 0.5 0.5 6.1.4 Oil Absorption of Pigments by Gardner-Coleman
Total impurities, including moisture and 1.0 1.5 Method—Test Method D 1483.
other volatile matter, max, %
Coarse particles (total residue retained on 0.10 0.25 6.1.5 Oil Absorption of Pigments by Spatula Rub-Out—Test
a No. 325 (45-µm) sieve), max, % Method D 281.
6.1.6 Instrumental Tinting Strength of White Pigments—
blending in equal quantities the samples from the same Test Method D 2745.
production unit to form a composite sample. 6.1.7 Tinting Strength of White Pigments— Test Method
6. Test Methods D 332.
6.1 Tests shall be conducted in accordance with the appro-
priate ASTM test methods, where applicable. Test procedures 7. Keywords
not covered by ASTM test methods shall be mutually agreed 7.1 American process; French process; mildew protection;
upon by the purchaser and the seller. ultraviolet absorption; zinc oxide; zinc white
This standard is copyrighted by ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States. Individual
reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585
(phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (http://www.astm.org).
2

Basic Carbonate White Lead Pigment1
1. Scope Pigment, min, % 89

Linseed oil, max, % 11
1.1 This specification covers the material commercially Moisture and other volatile matter, max, % 0.7
known as basic carbonate white lead, used as a pigment and in Coarse particles and skins (total residue retained on a 1.5
putty. The pigment may be purchased in the dry form or as a No. 325 (45-µm) sieve), max, % of the dry
pigment
paste in oil.
3.3 Semipaste Containing Volatile Thinner—The semi-paste
2. Referenced Documents shall be made by thoroughly grinding the specified pigment
2.1 ASTM Standards: with a mixture of linseed oil and a small amount of volatile
D 185 Test Methods for Coarse Particles in Pigments, thinner. The semipaste shall not be caked in the container and
Pastes, and Paints2 shall be readily stirred to a uniform mixture which shall mix
D 280 Test Methods for Hygroscopic Moisture (and Other readily with oil, turpentine, or volatile petroleum spirits to form
Matter Volatile Under the Test Conditions) in Pigments2 a smooth paint of brushing consistency. The odor of the
D 1208 Test Methods for Common Properties of Certain semipaste, as taken from the container, while drying or after
Pigments2 drying, shall be not abnormally pungent or disagreeable. The
D 1301 Test Methods for Chemical Analysis of White Lead semipaste shall conform to the following requirements:
Pigments2 Pigment, min, % 87.5
Linseed oil, max, % 10.5
3. Composition and Properties Moisture and other volatile matter, %A 1.5 to 3.0
Moisture, max, % 0.7
3.1 Dry Pigment—The pigment shall be free of adulterants Coarse particles and skins (total residue retained 1.5
and shall contain not more than traces of impurities incident to on a No. 325 (45-µm) sieve), max, % of the
dry pigment
well-controlled manufacture of high-grade basic carbonate __________
white lead. The pigment shall conform to the following A
The volatile matter shall be turpentine, volatile petroleum spirits, or any mixture
requirements: thereof.
Lead carbonate, % 62 to 75 3.4 The color and color strength, when specified, shall be
Moisture and other volatile matter, max, % 0.7 within mutually agreed upon limits of a standard acceptable to
Total other impurities, max, % 1.0 both the purchaser and the seller.
Coarse particles (total residue retained on a No. 1.0
325 (45-µm) sieve), max, %
4. Sampling
3.2 Paste in Oil—The paste shall be made by thoroughly 4.1 Two samples shall be taken at random from different
grinding the specified pigment with linseed oil. The paste shall packages from each lot, batch, day’s pack, or other unit of
not be caked in the container and shall break up readily in oil production in a shipment. When no markings distinguishing
to form a smooth paint of brushing consistency. The paste shall between units of production appear, samples shall be taken
conform to the following requirements: from different packages in the ratio of two samples for each 5
tons (inch-pound or SI), except that for shipments of less than
10 000 lb two samples shall be taken. At the option of the
1
purchaser, the samples may be tested separately or after
and Related Coatings, Materials, and Applications, and is the direct responsibility of blending in equal quantities the samples from the same
Subcommittee D01.31 on Pigment Specifications. production unit to form a composite sample.
Current edition approved May 29, 1987. Published July 1987. Originally
published as D 81 – 21 T. Last previous edition D 81 – 80 (1986) e1. 5. Test Methods
2
priate ASTM test methods. Test procedures not covered by
ASTM test methods shall be mutually agreed upon by the
purchaser and the seller.
5.1.1 Coarse Particles—Test Methods D 185.
5.1.2 Moisture in Pigment—Test Methods D 280.
1
D 81
5.1.3 Lead Carbonate and Total Other Impurities—Test 6. Keywords
Methods D 1301.
6.1 basic carbonate; dry pigment; lead carbonate; linseed
5.1.4 Pigment, Linseed Oil, and Moisture and Other Volatile
oil; paste; putty; white lead
Matter in Paste in Oil—Test Methods D 1208.
2

Red Lead Pigment1
e1 NOTE—Keywords were added editorially in May 1996.
1. Scope paste as shipped by the seller, and for three months thereafter,
1.1 This specification covers four grades of red pigment shall not be caked in the container, and shall break up readily
commercially known as red lead. The pigment may be pur- in oil to form a smooth paint of brushing consistency. The paste
chased in the dry form or as a paste in oil. shall conform to the following requirements:
Pigment, % 92 to 94
2. Referenced Documents Linseed oil, % 6.0 to 8.0
2.1 ASTM Standards: Coarse particles and skins (total residue retained on 1.5
D 49 Test Methods for Chemical Analysis of Red Lead2 a No. 325 (45-µm) sieve), max, % of the dry pigment
D 185 Test Methods for Coarse Particles in Pigments, When mixed as indicated in the following table, the resulting
Pastes, and Paints2 paint, brushed on a smooth, vertical iron surface, shall dry hard
D 1208 Test Methods for Common Properties of Certain and elastic without running, streaking, or sagging:
Pigments2 Red lead paste 20 lb (9.1 kg)
Raw linseed oil 3 pt (1.4 L)
3. Composition and Properties Turpentine 2 gills (0.24 L)
Liquid drier 2 gills (0.24 L)
3.1 Dry Pigment—The pigment shall be made by roasting
litharge or metallic lead, or compounds of lead that yield NOTE 1—The storage of paste red lead in places of high temperature
litharge by heating, and shall consist entirely of oxides of lead, should be avoided, as heat accelerates the tendency of this material to cake
or harden. Purchasers are cautioned that 85 % grade red lead should not be
free of adulterants. The four grades of pigment shall conform
bought in paste form. The 95 % grade, if made into paste, should be used
to the following requirements: within a short period of time after grinding. When pure red lead paste is
True red lead (Pb3O4), min, %: to be stored for a considerable period of time, the 97 % or 98 % grade of
85 % grade 85 red lead should be specified. Therefore the manufacturer shall identify the
95 % grade 95
grade of red lead used in the paste and the date of manufacture.
97 % grade 97
98 % grade 98
Total impurities including moisture, water soluble 1.0 4. Sampling
matter, and matter insoluble in a mixture of
nitric acid and hydrogen peroxide, max, %
Lead monoxide, PbO remainder packages from each lot, batch, day’s pack, or other unit of
Coarse particles (total residue retained on a 45-µm 1.0 production in a shipment. When no markings distinguishing
(No. 325) sieve), max, %
When mixed as indicated in the following table, the resulting from different packages in the ratio of two samples for each
paint, brushed on a smooth vertical iron surface, shall dry hard 10 000 lb (5000 kg), except that for shipments of less than
and elastic without running, streaking, or sagging: 10 000 lb two samples shall be taken. At the option of the
Dry red lead 20 lb (9.1 kg) purchaser, the samples may be tested separately or after
Raw linseed oil 5 pt (2.4 L) blending in equal quantities the samples from the production
Turpentine 2 gills (0.24 L)
Liquid drier 2 gills (0.24 L)
unit to form a composite sample.
3.2 Paste in Oil—The paste shall be made by thoroughly 5. Test Methods
grinding the specified pigment with linseed oil (Note 1). The 5.1 Tests shall be conducted in accordance with the follow-
ing ASTM test methods. Test procedures not covered by ASTM
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint test methods shall be mutually agreed upon between the
and Related Coatings, Materials, and Applications and is the direct responsibility of purchaser and the seller.
Current edition approved Aug. 31, 1984. Published December 1984. Originally 5.1.1 Chemical Analysis—Test Methods D 49.
published as D 83 – 21 T. Last previous edition D 83 – 73 (1984)e1. 5.1.2 Coarse Particles—Test Methods D 185.
2
1
D 83
5.1.3 Pigment, Linseed Oil, and Moisture and Other Volatile 6. Keywords
Matter in Paste in Oil—Test Methods D 1208. 6.1 lead oxide; lead tetra oxide; pigment; red lead
2

Ochre Pigment1
1. Scope Organic coloring matter none

1.1 This specification covers ferrous earthy pigment in- Coarse particles (total residue retained on a No. 325 1.0
cluded under the general term “ochre.” The pigment may be (45-µm) sieve), max, %
purchased in the dry form. 3.2 The mass color and character of the tint and the tinting
2. Referenced Documents strength formed by a mixture with a white pigment shall be
within mutually agreed upon limits of a standard acceptable to
2.1 ASTM Standards:
both the purchaser and the seller.
D 50 Test Methods for Chemical Analysis of Yellow, Or-
ange, Red, and Brown Pigments Containing Iron and 4. Sampling
Manganese2 4.1 Two samples shall be taken at random from different
D 185 Test Methods for Coarse Particles in Pigments, packages from each lot, batch, day’s pack, or other unit of
Pastes, and Paints2 production in a shipment. When no markings distinguishing
D 280 Test Methods for Hygroscopic Moisture (and Other between units of production appear, samples shall be taken
Matter Volatile under the Test Conditions) in Pigments2 from different packages in the ratio of two samples for each 5
D 387 Test Method for Color and Strength of Color Pig- tons (inch-pound or SI), except that for shipments of less than
ments with a Mechanical Muller3 10 000 lb two samples shall be taken. At the option of the
D 1208 Test Methods for Common Properties of Certain purchaser, the samples may be tested separately or after
Pigments2 blending in equal quantities the samples from the same
3. Composition and Properties production unit to form a composite sample.
3.1 The pigment shall be a hydrated oxide of iron permeat- 5. Test Methods
ing a siliceous base and shall be free from added impurities and 5.1 Tests shall be conducted in accordance with the follow-
added coloring matter. The pigment shall conform to the ing ASTM test methods. Test procedures not covered by ASTM
following requirements: methods shall be mutually agreed upon between the purchaser
Ferric oxide, min, % 17
Calcium oxide, max, % 5
and the seller.
Lead chromate none 5.2 Chemical Analysis of Dry Pigment— Test Methods
D 50.
5.3 Coarse Particles—Test Methods D 185.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.4 Mass Color and Tinting Strength— Test Method D 387.
and Related Coatings, Materials, and Applications and is the direct responsibility of 5.5 Volatile Matter—Test Methods D 1208.
Subcommittee D 01.31 on Pigment Specifications. 5.6 Moisture—Test Methods D 280.
Current edition approved June 26, 1987. Published August 1987. Originally
published as D 85 – 21. Last previous edition D 85 – 81 (1986)e1. 6. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 6.1 ferrous; hydrated iron oxide; ochre; pigment
views known to the ASTM Committee on Standards, at the address shown below.
1
D 85
This standard is copyrighted by ASTM, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at
610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (www.astm.org).
2

Degummed Soybean Oil1
This standard is issued under the fixed designation D 124; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 1967 Test Method for Measuring Color After Heating of

1.1 This specification covers degummed soybean oil suit- Drying Oils3
able for use in the paint and varnish industry. D 2090 Test Method for Clarity and Cleanness of Paint and
Ink Liquids3
2. Referenced Documents D 3278 Test Methods for Flash Point of Liquids by Small
2.1 ASTM Standards: Scale Closed-Cup Apparatus4
D 93 Test Methods for Flash Point by Pensky-Martens
Closed Tester2 3. Properties
D 555 Guide for Testing Drying Oils3 3.1 Degummed soybean oil shall conform to the require-
D 1466 Test Method for Sampling Liquid Oils and Fatty ments in Table 1 .
Acids Commonly Used in Paints, Varnishes, and Related
Materials3 TABLE 1 Physical Properties
D 1475 Test Method for Density of Paint, Varnish, Lacquer, ASTM Test
Property Requirement
and Related Products4 Method
D 1544 Test Method for Color of Transparent Liquids Specific gravity, 25/25°C 0.917 to 0.924 D 1963, D 1475
(Gardner Color Scale)4 Acid value, max 3.0 D 1639
Saponification value 189 to 195 D 1962
D 1639 Test Method for Acid Value of Organic Coating Unsaponification matter, max, % 1.5 D 1965
Materials3 Break, max, % 0.10 D 1952
D 1952 Test Method for Quantitative Determination of Iodine value (Wijs), min 126 D 1959
Loss on heating at 105 to 0.3 D 1960
Break in Drying Oils3 110°C, max, %
D 1959 Test Method for Iodine Value of Drying Oils and Clarity clear and transparent D 2090
Fatty Acids3 at 65°C
Color (Gardner 1933), max 12 D 1544
D 1960 Test Method for Loss on Heating of Drying Oils3 Color (after heating), max 12 D 1967
D 1962 Test Method for Saponification Value of Drying Flash point over 203°F (95°C) D 93, D 3278
D 1963 Test Method for Specific Gravity of Drying Oils, 4. Test Methods
Varnishes, Resins, and Related Materials at 25/25°C3
D 1965 Test Method for Unsaponifiable Matter in Drying 4.1 Sampling—Sampling shall be conducted in accordance
Oils, Fatty Acids, and Polymerized Fatty Acids3 with Test Method D 1466.
4.2 The properties enumerated in this specification shall be
1 determined in accordance with the applicable ASTM test
This specification is under the jurisdiction of ASTM Commitee D-1 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of methods listed in Table 1. The significance of the methods of
Subcommittee D01.32 on Drying Oils. testing enumerated under properties in this specification is
Current edition approved Oct. 31, 1988. Published December 1988. Originally discussed in Guide D 555.
published as D 124 – 22. Last previous edition D 124 – 87.
2
3
4
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; soybean oil
1

Analysis of Yellow, Orange, and Green Pigments Containing
Lead Chromate and Chromium Oxide Green1
1. Scope D 280 Test Methods for Hygroscopic Moisture (and Other

1.1 These test methods cover procedures for the chemical Matter Volatile Under the Test Conditions) in Pigments2
analysis of yellow, orange, and green pigments containing lead D 521 Test Methods for Chemical Analysis of Zinc Dust
chromate and chromium oxide green. (Metallic Zinc Powder)2
1.2 The analytical procedures appear in the following order: D 1013 Test Method for Determining Total Nitrogen in
Sections
Resins and Plastics2
CHROME YELLOW, CHROME ORANGE, AND MOLYBDATE ORANGE D 1193 Specification for Reagent Water3
Organic Colors and Lakes 7 E 11 Specification for Wire-Cloth Sieves for Testing Pur-
Moisture and Other Volatile Matter 8
Matter Soluble in Water 9
poses4
Lead Chromate 10 and 11
3. Summary of Test Methods
Total Lead 12
Sulfate 13 and 14 3.1 Chrome Yellow, Chrome Orange, and Molybdate Or-
Carbon Dioxide 15
Molybdenum 16 and 17
ange:
Extenders 18-22 3.1.1 Organic colors and lakes are determined qualitatively
Calculation of Substances Other than Insoluble Lead by boiling the sample in water, then ethyl alcohol, and finally
Compounds 23 and 24
PURE CHROME GREEN AND REDUCED CHROME GREEN
chloroform.
Organic Colors and Lakes 25 3.1.2 Moisture and other volatile matter are determined in
Moisture and Other Volatile Matter 26 accordance with Test Method A of Test Methods D 280.
Iron Blue 28
3.1.3 Matter soluble in water is determined by boiling in
Lead Chromate 29 and 30 water and filtering.
Barium Sulfate and Insoluble Siliceous Material 31 3.1.4 Lead chromate is determined by dissolving the sample
Total Lead 32
Sulfate 33
in dilute HCl, filtering and titrating potentiometrically with
Calcium Oxide Soluble in Acid 34 and 35 FeSO4 solution after addition of HClO4.
Extenders 36 3.1.5 Total lead is determined by precipitation as lead
Calculation of Insoluble Lead Com-
pounds 37
sulfide solution with H2SO4 and final precipitation as lead
CHROMIUM OXIDE GREEN sulfate.
Organic Colors and Lakes 38 3.1.6 Sulfate is determined by dissolving the sample in
acetic acid, neutralizing with sodium carbonate, plus addition
Total Chromium as Chromium Oxide 41 of HCl to an aliquot followed by addition of BaCl2 to
precipitate as barium sulfate.
1.3 This standard does not purport to address all of the
3.1.7 Carbon dioxide is determined by evolution.
safety problems, if any, associated with its use. It is the
3.1.8 Molybdenum is determined by precipitation as the
responsibility of the user of this standard to establish appro-
sulfide, solution in HNO3 and H2SO4, addition of NH4OH and
priate safety and health practices and determine the applica-
H2SO4. The solution is reduced in a Jones reductor, collected
bility of regulatory limitations prior to use. Specific hazard
under Fe2(SO4)3 solution and titrated with KMnO4 solution.
statements are given in Note 3.
3.1.9 Extenders are either:
2. Referenced Documents 3.1.9.1 Calcium carbonate, calcium sulfate, magnesium car-
2.1 ASTM Standards: bonate or;
(a) The compounds in 3.1.9.1 are determined qualitatively
1
by precipitation with ammonium solution.
and Related Coatings, Materials, and Applications and are the direct responsibility
2
of Subcommittee D01.31 on Pigment Specifications. Annual Book of ASTM Standards, Vol 06.03.
3
Current edition approved May 29, 1987. Published July 1987. Originally Annual Book of ASTM Standards, Vol 11.01.
published as D 126 – 22. Last previous edition D 126 – 65 (1981)e1. 4
1
D 126
(b) If chromium is present, it is reduced and the lead salts of sufficiently high purity to permit its use without lessening
dissolved in dissolving solution. Hydroxides and hydrous the accuracy of the determination.
oxides are precipitated by addition of HCl and NH4OH and 5.2 Water—Unless otherwise indicated, references to water
filtered. CaC2O4 is precipitated with calcium oxalate solution for use in the preparation of reagents and in analytical
and filtered, ashed and weighed as CaO. Alternatively, the procedures shall be understood to mean reagent water con-
precipitate is dissolved in H2SO4 and titrated with KMnO4. forming to Type II of Specification D 1193.
Magnesium is determined on the filtrate from calcium deter-
mination by precipitation as the phosphate with ammonium 6. Preparation of Sample
phosphate solution. 6.1 Mix the sample thoroughly and take a representative
3.2 Chromium Oxide Green: portion for analysis. Reduce any lumps or coarse particles to a
3.2.1 Organic colors and lakes are determined qualitatively fine powder by grinding. Grind extracted pigments to pass a
by boiling the sample in water, then ethyl alcohol, and finally No. 80 (180-µm) sieve (Note 1). Discard any skins that do not
choloroform. pass through the sieve. Thoroughly mix the finely ground
3.2.2 Moisture and other volatile matter are determined in pigment and preserve in stoppered and suitably identified
accordance with Test Method A of Test Methods D 280. bottles or containers.
3.2.3 Matter soluble in water is determined by boiling in NOTE 1—Detailed requirements for this sieve are given in Specification
water and filtering. E 11.
3.2.4 Total chromium as chromium oxide is determined by 6.2 Moisten the weighed portions of extracted pigments
dissolving the sample in dilute HCl, filtering and titrating with a small amount of suitable wetting agent (Note 1) before
potentiometrically with FeSO4 solution after addition of adding reagents for analysis.
HClO4. NOTE 2—A 0.1 % solution of sodium dioctylsuccinosulfonate has been
found satisfactory. (This material is sold under the trade name of Aerosol
4. Significance and Use OT.) Wetting agents containing mineral salts, sulfates, or sulfonates which
may be hydrolyzed to sulfates, should be avoided; the use of alcohol is
4.1 These test methods are for analysis designed as an aid in also undesirable because of its tendency to reduce chromates.
quality of yellow, orange, and green pigments containing lead NOTE 3—Precaution: As the National Institute for Occupational Safety
chromate and chromium oxide green. Some sections may be and Health has stated that hexavalent chromium compounds are hazardous
applicable to analysis of these pigments when extracted from to health, care should be exercised in preparation of the sample. The
whole paints. wearing of a respirator and rubber or synthetic gloves are recommended.
If hexavalent chromium materials come in contact with the skin, wash
thoroughly with soap and water.
5. Purity of Reagents and Water
5.1 Reagents—Unless otherwise indicated, it is intended
5
that all reagents shall conform to the specifications of the “Reagent Chemicals, American Chemical Society, Specifications,” Am. Chem.
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
Committee on Analytical Reagents of the American Chemical
American Chemical Society, see “Reagent Chemicals and Standards,” by Joseph
Society, where such specifications are available.5 Other grades Rosin, D. Van Nostrand Co., Inc., New York, NY, and the “United States
may be used, provided it is first ascertained that the reagent is Pharmacopeia.”
CHROME YELLOW, CHROME ORANGE, AND MOLYBDATE ORANGE

(Primrose, Lemon, and Medium Yellows; Chrome Oranges; Lead Molybdate or Basic Lead Chromate; Molybdate Orange)
ORGANIC COLORS AND LAKES MOISTURE AND OTHER VOLATILE MATTER
7. Procedure 8. Procedure
7.1 Boil 2 g of the sample 2 min with 25 mL of water, let 8.1 Determine moisture and other volatile matter in
settle, and decant the supernatant liquid. Similarly, boil the accordance with Test Method A of Test Method D 280.
residue with 25 mL of ethyl alcohol (absolute or 95 %) and
decant as before. Likewise boil with 25 mL of chloroform and MATTER SOLUBLE IN WATER
again decant. If any one of the above solutions is colored,
9. Procedure
organic colors are present. If all solutions remain colorless,
organic colors are presumably absent. The presence of organic 9.1 Place 2.5 g of the sample in a graduated 250-mL flask.
colors resistant to the above reagents is unlikely, but may be Add 100 mL of water and boil for 5 min. Cool, dilute to exactly
tested for by reference to procedures given in standard refer- 250 mL, mix, and allow to settle. Filter the supernatant liquid
ence works.6 through a dry paper and discard the first 20 mL. Evaporate 100
mL of the clear filtrate to dryness in a weighed dish, heat for 1
h at 105 to 110°C, cool, and weigh.
6
Reference may be made to the following: Payne, H. F., “Organic Coatings 9.2 Calculation—Calculate the % of matter soluble in water
Technology,” Vol II, John Wiley & Sons, Inc., New York, NY, 1961. as follows:
2
D 126
Matter soluble in water, % 5 ~R3 2.5 3 100!/S (1) 12.2 Rinse the precipitate from the filter (Note 5) into a
beaker containing 25 mL of HNO3(1+3) and boil until all PbS
where: has dissolved. Add 10 mL of H2SO4(1+1) and evaporate to
R 5 weight of residue, and
strong fumes of SO3. Cool and add 50 mL of water and 50 mL
S 5 specimen weight, g.
of ethyl alcohol (95 %) (Note 6). Let stand 1 h; then filter on
LEAD CHROMATE7 a tarred Gooch crucible. Wash with ethyl alcohol (95 %), dry,
ignite at 500 to 600°C, and weigh as PbSO4.
10. Reagents
NOTE 5—If a trace of sulfide remains on the paper, the stained portion
10.1 Dissolving Solution—Saturate 1 L of water with NaCl. of the paper may be separately treated with bromine water, the paper
Filter. Add to the filtered solution 150 mL of water and 100 mL filtered off, and the filtrate added to the body of the solution.
of HCl (sp gr 1.19). NOTE 6—Any sulfur remaining from decomposition of the sulfides may
10.2 Ferrous Sulfate, Standard Solution (0.3 N)—Dissolve be mechanically removed as a globule of solidified sulfur at this point.
86 g of FeSO4 · 7H2O in 500 mL of water to which 30 mL of SULFATE7
H2SO4 (sp gr 1.84) has been added with constant stirring.
Dilute to 1 L and standardize not more than 6 h before use by 13. Reagents
potentiometric titration against 0.7-g portions of K2Cr2O7.
13.1 Barium Chloride Solution—Dissolve 117 g of BaCl2 ·
11. Procedure 2H2O in water and dilute to 1 L.
13.2 Dissolving Solution—See 10.1.
11.1 Dissolve 1 g of the sample in 150 mL of the dissolving
13.3 Sodium Carbonate Solution —(saturated)—Prepare a
solution. Agitate for 10 to 15 min, keeping the solution cold
solution containing excess Na2CO3 at laboratory temperature,
until dissolution is complete (Note 4). If dissolution is not
and free of SO4. Decant the clear solution for use as required.
complete, filter through fine grade filter paper and wash with
three 10-mL portions of cold dissolving solution. Add 10 mL of 14. Procedure
HClO4 (70 %), dilute to 250 mL, and titrate potentiometrically
with FeSO4 solution. 14.1 Digest 1.25 g of the sample with 100 mL of dissolving
solution at 100°C for 5 min. Add 25 mL of glacial acetic acid
NOTE 4—Incomplete solution of the pigment is evidence of the possible and 15 mL of ethyl alcohol and heat gently for 10 min to
presence of barium sulfate, silica, silicates, or other acid-insoluble reduce chromium, as indicated by the green color of the
extenders (see Section 18). Some chrome yellows may contain organic
addition agents and will give a turbid solution at this point.
solution. Cool. Neutralize with saturated Na2CO3 solution and
Newer chemically resistant-type lead chromate type pigments (silica add a slight excess. Transfer to a 250-mL volumetric flask,
encapsulated) cannot be decomposed by the procedures described in this dilute to the mark with distilled water, and mix. Filter without
method. Pigments of this type may require treatment with strong alkali washing through a dry filter paper, discarding the first 10 to 15
hydroxide or hydrofluoric acid. mL.
Also, if trivalent antimony has been used in manufacturing the product, 14.2 Take a 200-mL aliquot of the filtrate, neutralize with
pentavalent antimony may be present which would interfere in the HCl (1+1), and add 10 mL excess. Heat to boiling and boil for
determination of lead chromate.
5 min. To the gently boiling solution, add 15 mL of BaCl2
11.2 Alternatively, the solution may be reduced by a known solution dropwise with constant stirring. Digest on a steam
excess of FeSO4 solution and back-titrated with KMnO4 bath for 2 h. Filter through an ignited tarred Gooch crucible,
solution in the presence of MnSO4, or excess KI may be added wash with HCl (1+99), and finally with hot water. Dry at 105
and the liberated iodine titrated with Na2S2O3 solution, using to 110°C, ignite at 900°C, and weigh.
starch indicator. The iodine liberation method is not applicable
in the presence of molybdenum. CARBON DIOXIDE7
TOTAL LEAD7 15. Procedure
12. Procedure 15.1 Determine CO2 by the evolution method on 2.5 g of the
sample, using dilute HNO3 free of NO or NO2 and absorbing
12.1 Dissolve 0.5 g of sample as described in Section 11. the CO2 in soda lime or in KOH solution.
Add 5 mL of ethyl alcohol (95 % or absolute) and boil until the
chromium is reduced, as indicated by a green color. Filter if MOLYBDENUM7
any insoluble residue is present, retaining the filtrate and
washings for the determination. Add NH4OH (sp gr 0.90) to 16. Reagents
this solution until a faint precipitate begins to form; then add 5 16.1 Ferric Sulfate Solution—Dissolve 20 g of Fe2(SO4)3 ·
mL of HCl (sp gr 1.19) slowly, dilute to 500 mL, and pass a (NH4)2SO4 · 24H2O in 200 mL of water to which has been
rapid current of H2S into the solution until precipitation is added 50 mL of H2SO4 (sp gr 1.84) and 20 mL of H3PO4
complete. Settle, filter, and wash with water containing H2S. (85 %), and dilute to 1 L.
16.2 Jones Reductor—The reductor shall contain at least a
7
Sections 23 and 24 under “Calculation of Substances Other than Insoluble Lead
35-cm column of amalgamated zinc, prepared by shaking 20 to
Compounds” should be read carefully before proceeding with the analyses described 30-mesh zinc free of iron or carbon with HgCl2 solution (20
in Sections 10 to 22. g/L) in sufficient quantity to produce an amalgam containing 1
3
D 126
to 5 % of mercury, and supported by a suitable inert pad of 18.2 Extenders of group A may be present if the analysis
asbestos, glass wool, or other inert material. shows sulfates and carbonates to be in the pigment, and are
16.3 Potassium Permanganate, Standard Solution (0.1 absent if sulfate and carbonate are absent. Since the latter
N)—Dissolve 3.16 g of KMnO4 in water and dilute to 1 L. Let situation rarely exists, it is advisable to test for the presence of
stand 8 to 14 days, siphon off the clear solution (or filter calcium and magnesium to determine if extenders are present.
through a medium porosity fritted disk), and standardize Extenders of group B are recognized as an insoluble residue
against the National Bureau of Standards standard sample No. following acid solution of the pigment, and may be determined
40 of sodium oxalate (Na2C2O4) as follows: In a 400-mL quantitatively if desired, by the method described in Section
beaker dissolve 0.2500 to 0.3000 g of the Bureau of Standards 31. Extenders of group A, if present, may affect the calculation
sodium oxalate in 250 mL of hot water (80 to 90°C) and add 15 of insoluble lead compounds as given in Section 23. Their
mL of H2SO4 (1+1). Titrate at once with KMnO4 solution, qualitative or quantitative estimation may be necessary.
stirring the liquid vigorously and continuously. The KMnO4 NOTE 7—Some lead chromates may contain zirconium or titanium
must not be added more rapidly than 10 to 15 mL/min, and the compounds, some of which are insoluble in the dissolving solution, but are
last 0.5 to 1 mL must be added dropwise with particular care to not to be considered as extenders, since they have been added to improve
allow each drop to be fully decolorized before the next is the properties of the pigment.
introduced. The solution shall not be below 60°C by the time
the end point has been reached. (More rapid cooling may be Qualitative Detection of Extenders of Group A
prevented by allowing the beaker to stand on a small asbestos-
19. Reagents
covered hot plate during the titration. The use of a small
thermometer (non-mercury type) as a stirring rod is most 19.1 Ammonium Phosphate Solution—Dissolve 100 g of
convenient.) Keep the KMnO4 solution in a glass-stoppered (NH4)2HPO4 in water and dilute to 1 L.
bottle painted black to keep out light, or in a brown glass bottle
stored in a dark place. 20. Procedure
20.1 Dissolve 1 g of the sample as described in Section 11.
17. Procedure Add 5 mL of ethyl alcohol (95 % or absolute) and boil until the
17.1 Dissolve 1 g of the sample as described in Section 11. chromium is reduced. An insoluble residue at this point denotes
Add 5 mL of ethyl alcohol (95 % or absolute) and boil until the presence of extenders of Group B. Filter if necessary and
chromium is reduced. Filter if any insoluble residue is present, wash well.
retaining the filtrate and washings. Add NH4OH (sp gr 0.90) 20.2 To the filtrate, add NH4OH (1+4) until just
cautiously until a faint precipitate begins to form, then add 15 ammoniacal, boil 5 min, and allow to digest in a warm place
mL of H2SO4 (sp gr 1.84) and dilute to 300 mL. Heat to until the precipitate has coagulated. Filter, washing well with
boiling, pass in a rapid stream of H2S for 15 min, and dilute hot water and reserving the filtrate. Dissolve the precipitate on
with 300 mL of hot water. Pass in H2S for 10 min, boil for 3 the filter with HCl (1+1), washing back into the original beaker.
min, and cool. Pass in H2S for 10 min, and let stand at room Reprecipitate, filter, and wash as before.
temperature for 1 h. Filter and wash with H2SO4 (1+99) 20.3 Combine the washings, make just acid with HCl (1+1),
saturated with H2S. and evaporate to a volume of about 250 mL. Add 50 mL of
17.2 Rinse the sulfide precipitate into the original beaker (NH4)2HPO4 solution, cool, and add 50 mL of NH4OH (sp gr
and add 20 mL of HNO3 (sp gr 1.42) and 5 mL of H2SO4(sp gr 0.90). Allow to stand overnight. A precipitate indicates the
1.84) (see Note 5). Cover and heat to fumes. Cool, add 10 mL presence of extenders of Group A.
of HNO3 (sp gr 1.42), and again fume. Repeat this operation if
necessary until a light-colored solution is obtained. Wash the Quantitative Determination of Extenders of
cover and inside of the beaker and fume again to remove all Group A
HNO3. Dilute to 200 mL and add NH4OH (1+4) until neutral;
then add 10 mL of H2SO4(sp gr 1.84). 21. Reagents
17.3 Cool the solution and reduce by passing through a 21.1 Ammonium Oxalate Solution—Dissolve 30 g of
Jones reductor at a rate not exceeding 100 mL/min, collecting ammonium oxalate in water and dilute to 1 L.
the effluent under 200 mL of Fe2(SO4)3 solution. Titrate with 21.2 Ammonium Phosphate Solution—See Section 19.
KMnO4 solution. A blank determination should also be made.
22. Procedure
EXTENDERS7
22.1 If the sample is a chrome yellow or orange use the
18. General Considerations procedure given in Section 14 for dissolving and reducing
18.1 Extenders fall into two groups, depending on their chromium. For other chromium pigments heat gently 2 g of
solubility or insolubility in the dissolving solution described in sample in a porcelain dish without ignition until iron blue, if
Section 10, as follows: present, is just decomposed. Transfer to a beaker and dissolve
A. Extenders Soluble in Dissolving Solution—Calcium the lead salts in 150 mL of dissolving solution as described in
sulfate (gypsum), calcium carbonate (whiting), and magnesium Section 11.
carbonate. 22.2 Add 20 ml of HCl (sp gr 1.19) and digest 1 h at 100°C.
B. Extenders Insoluble in Dissolving Solution—Silica, Dilute to 300 mL, filter and wash thoroughly. Add NH4OH
magnesium silicate, and clay (Note 7). (1+4) to the filtrate and washings until just ammoniacal, boil 5
4
D 126
min and allow to digest in a warm place until the hydroxides E 5 SO3, % 5 grams of BaSO4 3 34.3 (8)
and hydrous oxides are coagulated. Filter, washing well with 23.5.1 If E is equal to or greater than 0.3587 D, the % of
diluted water and reserve the filtrate. Redissolve the precipitate PbSO4 equals 1.3587 D, and the % total insoluble lead
with HCl (1+1) washing back into the original beaker.
compounds equals A + B + 1.3587 D.
Reprecipitate, filter and wash as before. Combine the washings
with the original filtrate and add 50 mL of ammonium oxalate 23.5.2 If E is less than 0.3587 D, the percentage of PbSO4
solution. Filter off the CaC2O4 precipitate on quantitative equals 3.788 E, and a new excess of PbO is calculated as
paper. Transfer to a tarred crucible, ash, ignite at 1300°C, cool follows:
in a desiccator, and weigh as CaO. Alternatively, the washed F 5 Excess PbO, % 5 D 2 2.788 E (9)
precipitate may be dissolved in H2SO4(1+1) and the resulting
23.6 Calculate the percent of CO2 from the analysis of
solution titrated hot with 0.1 N KMnO4 solution, as described
Section 15 as follows:
in the Procedure section under Calcium in Test Methods D 521.
22.3 Make the filtrate from the calcium determination G 5 CO2, % 5 grams of CO2 3 40 (10)
slightly acid with HCl (1+1) and evaporate to 250 mL volume. 23.6.1 If G is equal to or greater than 0.1314 F, the percent
Add 50 mL of (NH4)2HPO4 solution, cool, and add 50 mL of of basic lead carbonate (2 PbCO3 · Pb(OH)2) is 1.1584 F and
NH4OH (sp gr 0.90). Allow to stand overnight. Filter on the percent of total insoluble lead compounds is A + B + 3.788
suitable quantitative paper, wash with NH4OH (1+19), ignite in E + 1.1584 F.
a platinum crucible at 1050°C for 1 h and weigh. Care must be
23.6.2 If G is appreciably in excess, extenders are probably
taken to char the paper slowly before igniting.
present. If G is less than 0.1314 F, the percent of 2
22.4 Calculation—Calculate the percent of extenders (as
PbCO3·Pb(OH)2 is 8.813 G and the excess PbO is:
oxides) as follows:
H 5 Excess PbO, % 5 F 2 7.608 G (11)
Calcium oxide, % 5 weight of CaO 3 50 (2)
Magnesium oxide, % 5 weight of Mg2P2O7 3 18.11 (3) 23.6.2.1 The percent of total insoluble lead compounds is
A + B + 3.788 E + 8.813 G + H.
The calculation of the amount of extenders as carbonates or
sulfates is described in Section 24.
24. Calculations Where Extenders Are Present
CALCULATION OF SUBSTANCES OTHER THAN 24.1 If extenders are present, calculate the CO2 equivalent
INSOLUBLE LEAD COMPOUNDS as follows:
23. Calculations Where Extenders Are Absent I 5 CO2 equivalent of extenders (12)
23.1 “Insoluble lead compounds” in chrome yellow and 5 CaO, % 3 0.786 1 MgO, % 3 1.100
chrome orange may consist of PbCrO4, PbSO4, 2PbCO3 · 24.2 If I is less than G, use G − I as the net CO2 for purposes
Pb(OH)2, PbO, or PbMoO4. The first two are characteristic of calculating the 2PbCO3·Pb(OH)2 content of the pigment.
the chrome yellows, the first, third, and fourth of the basic
chrome oranges, and the first, second, and last of molybdate Total extenders 5 CaO, % 1 MgO, % 1 I (13)
oranges. For purpose of determining conformance with 24.3 If I is greater than G, some of the extender is present as
specification requirements, where “insoluble lead compounds” CaSO4 (Note 8). Calculate the total percent of extenders as
are defined as above, make the following calculations if follows:
extenders are absent: J 5 CO2 equivalent of MgO 5 MgO % 3 1.100 (14)
23.2 If molybdenum is present, calculate the percent of
PbMoO4 from the titration of Section 17 as follows: K 5 CO2 present as CaCO3 5 G – J (15)
CaCO3, % 5 2.73 K (16)
A 5 PbMoO4, % 5 mL titration 3 normality of KMnO4 3 12.24
(4) L 5 CaO present as sulfate, % 5 CaO, % 6 1.27 K (17)
23.3 Calculate the percent of PbCrO4 from the titration of CaSO4, % 5 2.43 L (18)
Section 11 as follows: SO3 combined as CaSO4, % 5 1.43 L (19)
B 5 PbCrO4, % 5 mL titration 3 normality of FeSO4 3 10.77 (5)
24.3.1 E − 1.43 L equals the net SO3 to be used for
23.4 Calculate the percent of total lead as oxide and the calculating the PbSO4 content of the pigment. If I is greater
percent of excess PbO from the analysis of Section 12 as than G, no calculation of 2PbCO3 · Pb(OH)2 is necessary, and
follows: the excess PbO is given by F.
C 5 PbO, % 5 grams of PbSO4 3 147.2 (6) Total extenders, % 5 2.100 3 MgO, % 1 2.73 K 1 2.43 L (20)
D 5 excess PbO, % 5 C – ~0.6906 B 1 0.6078 A! (7)
NOTE 8—It is impractical to detect by chemical means whether a
23.5 Calculate the sulfate as SO3 from the analysis of pigment contains CaCO3 and PbSO4, or CaSO4 and 2PbCO3 · Pb(OH)2.
Section 14 as follows: This calculation assumes the former as more probable.
5
D 126
PURE CHROME GREEN AND REDUCED CHROME GREEN
ORGANIC COLORS AND LAKES BARIUM SULFATE AND INSOLUBLE SILICEOUS

MATERIAL8
25. Procedure
31. Procedure
25.1 Determine organic colors and lakes in accordance with
Section 7. 31.1 Heat gently 1 g of sample in a porcelain dish without
ignition until the iron blue is just decomposed. Transfer to a
MOISTURE AND OTHER VOLATILE MATTER beaker and dissolve the lead salts as described in Section 11,
warming if necessary. Filter through a tared Gooch crucible,
26. Procedure wash thoroughly, ignite at 600 to 800°C, and weigh.
26.1 Determine moisture and other volatile matter in 31.2 Calculation—Calculate the percent of BaSO4 and
accordance with Section 8. insoluble siliceous material as follows:
MATTER SOLUBLE IN WATER BaSO4 and insoluble siliceous material, % (22)
5 weight of precipitate 3 100
27. Procedure
TOTAL LEAD
27.1 Determine matter soluble in water in accordance with
Section 9. 32. Procedure
32.1 Determine total lead on the filtrate from the
IRON BLUE
determination of BaSO4 and insoluble matter (Section 31) in
28. Procedure accordance with the directions of Section 12.
28.1 Determine the total nitrogen (by the Kjeldahl-Gunning SULFATE
method) (Note 9) on 1 g of the sample, adding 2 g of FeSO4 ·
33. Procedure
7H2O before digestion for at least 21⁄2 h.
33.1 After decomposition of the iron blue in 1.25 g of
NOTE 9—For further details refer to Test Method D 1013.
sample as described in Section 31, digest the residue with 20
28.2 Calculation—Calculate the percent of iron blue as mL of HCl (sp gr 1.19) at 100°C until solution is complete.
follows: Add 300 mL of water and heat to boiling. Filter and wash
Iron blue, % 5 nitrogen, % 3 3.4 (21) thoroughly. Determine sulfate on the filtrate and washings as
described in Section 14.
NOTE 10—Qualitative tests may be made for other nitrogen-containing
blue pigments. CALCIUM OXIDE SOLUBLE IN ACID
LEAD CHROMATE 34. Reagents
34.1 Ammonium Oxalate Solution—See 21.1.
29. Reagents
29.1 Ferrous Sulfate, Standard Solution (0.3 N)—See 10.2. 35. Procedure
29.2 Potassium Permanganate Standard Solution (0.1 N)— 35.1 Decompose 2 g of sample as described in Section 31.
Prepare as described in 16.3. Standardization is unnecessary Add 20 mL of HCl (sp gr 1.19) and proceed in accordance with
except for the alternative procedure given in Section 30. 21.1 to the end of the calcium determination.
35.2 Calculation—Calculate the percent of CaO soluble in
30. Procedure acid as follows:
30.1 Mix thoroughly 1 g of sample with at least 10 g of CaO soluble in acid, % 5 grams CaO 3 50 (23)
Na2O2 in a 30-mL pure iron crucible. Heat gently until the
fusion is complete; then heat strongly, rotating the crucible EXTENDERS
with iron tongs (not Nichrome or chromium plate) for a few 36. Procedure
minutes to ensure complete fusion. Allow to cool; then transfer
36.1 The method described in Sections 31, 34, and 35
the crucible and cover to a beaker containing 250 mL of water.
suffices for the detection and estimation of all common
When the action has ceased, rinse and remove the crucible and
extenders except MgCO3. This may be tested for the filtrate
cover, and boil for at least 10 min to destroy excess peroxide.
from the CaO determination by the method described in
Make just acid with H2SO4 (1+1) and add about 35 mL in
Section 22.
excess. Add 2.5 mL of 0.1 N KMnO4 solution and heat to
boiling. Add 10 mL of HCl (1+4) and boil to reduce manganese CALCULATION OF INSOLUBLE LEAD
and lead as indicated by clearing of the solution. If the solution COMPOUNDS
is not clear after 5 min boiling, add 5 mL of additional HCl
37. Procedure
(1+4), and repeat until a clear solution is obtained. Cool and
titrate with FeSO4 solution on a potentiometric apparatus; or 37.1 The insoluble lead compounds may be calculated by
alternatively, add a measured excess of FeSO4 and back-titrate
with KMnO4 solution in the presence of MnSO4. 8
See Note 7 of Section 18.
6
D 126
the methods of Sections 23 and 24.
CHROMIUM OXIDE GREEN
ORGANIC COLORS AND LAKES 41.2 Calculation—Calculate the percent of chromium as

Cr2O3 as follows:
38. Procedure
Cr2O3, % 5 mL titration 3 normality of FeSO4 3 63.34 (24)
38.1 Determine organic colors and lakes in accordance with
Section 7. 42. Precision and Bias
MOISTURE AND OTHER VOLATILE MATTER 42.1 Data are not available to determine the precision and
39. Procedure bias of these test methods. There are no plans at present to
obtain such data.
39.1 Determine in accordance with Section 8.
MATTER SOLUBLE IN WATER 43. Keywords
40. Procedure 43.1 chromium oxide green pigment; green pigment

containing lead chromate and chromium oxide; lead chromate
40.1 Determine in accordance with Section 9. pigment; lead containing pigment; molybdate pigment; orange
TOTAL CHROMIUM AS CHROMIUM OXIDE pigment containing lead chromate and chromium oxide; yellow
pigment containing lead chromate and chromium oxide
41. Procedure
41.1 Using 0.4 g of the sample proceed as in Section 30.
7

Specific Gravity of Pigments1
1. Scope under the capillary tube than with types having the ground glass seal on
the inside of the neck.
1.1 These test methods cover three procedures for determin-
ing the specific gravity of pigments, as follows: 4.2 Water Bath, maintained at 25 6 0.5°C and equipped
Test Method A—For Routine Testing of Several Samples with a stirring device.
Simultaneously. 4.3 Manometer, open- or closed-tube (see Part f of the
Test Method B—For Tests Requiring Greater Accuracy than apparatus for Test Method C), made of glass tubing 6 mm in
Test Method A. diameter, fitted with rubber pressure tubing attached to a
Test Method C—For Rapid and Accurate Testing of Single T-joint leading to the desiccator and the pump. For the
Samples. open-tube type 860 mm of mercury shall be used. The
1.2 The specific gravity value obtained by these procedures difference in levels of the mercury in the manometer when the
may be used with the weight of a dry pigment to determine the system is in operation, subtracted from the barometer reading
volume occupied by the pigment in a coating formulation. taken at the same time, shall be considered the absolute
1.3 This standard does not purport to address all of the pressure of the system in millimetres of mercury.
safety concerns, if any, associated with its use. It is the 4.4 Desiccator, glass, constructed with heavy walls to
responsibility of the user of this standard to establish appro- withstand a vacuum of one atmosphere, and with an opening at
priate safety and health practices and determine the applica- the side.
bility of regulatory limitations prior to use. For specific hazard 4.5 Vacuum Pumps—A laboratory water vacuum-type pump
statements, see Sections 5, 11, and 15. (Note 2), to remove the greater portion of air in the desiccator,
and an oil vacuum-type pump, motor-driven, and capable of
2. Referenced Documents reducing the absolute pressure of the system to 3 mm.
2.1 ASTM Standards: NOTE 2—The water vacuum pump may be omitted if the rate of
D 1193 Specification for Reagent Water2 evacuation with the oil pump can be controlled so as to avoid a rapid
ebullition of entrapped air and possible loss of specimen.
4.6 Thermometer, having a range from 0 to 60°C, and
3.1 Purity of Water—Reference to water shall be understood graduated in 0.1°C divisions.
to mean reagent water as defined by Type II of Specification 4.7 Weighing Bottle, wide-mouth cylindrical glass (about 30
D 1193. mm in height and 70 mm in diameter), provided with a
TEST METHOD A—FOR ROUTINE TESTING OF ground-glass stopper.
SEVERAL SAMPLES SIMULTANEOUSLY 4.8 Immersion Liquid—Kerosine has been found to be a
good wetting vehicle for most pigments, and shall be used
4. Apparatus and Materials generally as the immersion liquid. Refined, white kerosine of
4.1 Pycnometer—A pycnometer (Note 1) having a 50-mL narrow evaporation and boiling range shall be used. With some
capacity. pigments that are not wetted well with kerosine, other immer-
sion liquids such as glycerin, ethylene glycol, tetrahydronaph-
NOTE 1—The Weld type with the cap seal on the outside of the neck of thalene, etc., may be substituted. The liquid must have a low
the bottle is preferred because there is less danger of trapping air just
evaporation rate and narrow boiling range, and the same
procedure shall be followed as with kerosine. Water is not a
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint preferred liquid because of the possibility of frothing.
and Related Coatings, Materials, and Applications, and are the direct responsibility
of Subcommittee D01.31 on Pigment Specifications. 5. Hazards
Current edition approved Oct. 26, 1984. Published January 1985. Originally
published as D 153 – 23 T. Last previous edition D 153 – 82. 5.1 Before a desiccator is used for the first time, wrap it in
2
Annual Book of ASTM Standards, Vol 11.01. a towel and test under an absolute pressure of under 3 mm.
1
D 153
Exercise care in handling the desiccator when under vacuum, Take the pycnometer out of the bath, allow to come to room
since a sudden jar may cause it to collapse. temperature, and weigh.
6. Standardization of Pycnometer 8. Calculation

6.1 Fill the pycnometer with freshly boiled water at 23 to 8.1 Calculate the specific gravity, S, of the pigment as
24°C, gradually bring to 25 6 0.5°C, and then dry and weigh follows:
as specified in 7.6. Empty the pycnometer, and clean, dry, and P1
reweigh it. Next fill the pycnometer with kerosine at 23 to S5 K1 (2)
24°C, bring to 25 6 0.5°C, dry, and weigh as before. Calculate W2 D
the specific gravity, S, of the kerosine at 25/25°C as follows:
S 5 A/B (1) where:
P1 5 weight of pigment used, g,
where: W 5 weight of water to fill the pycnometer, g,
A 5 weight of kerosine, g, and K1 5 weight of kerosine added to the pigment, g, and
B 5 weight of water, g. D 5 specific gravity of the kerosine.
7. Procedure 9. Precision
7.1 Drying—Dry the pigment, preferably in an electric 9.1 Duplicate determinations by this test method should not
oven, at 105 6 2°C for 2 h. differ by more than 0.02.
7.2 Weighing—Transfer to a clean, dry, weighed pycnom-
eter, sufficient sample to form a layer approximately 3⁄4 in. (20 TEST METHOD B—FOR TESTS REQUIRING
mm) deep. For black, blue, and lake pigments of low specific GREATER ACCURACY THAN TEST METHOD A
gravity, use about 1 g of sample; for inert crystalline pigments,
about 4 g; for opaque white pigments, 7 to 10 g; and for red 10. Apparatus (see Fig. 1 and Fig. 2)
lead, from 15 to 20 g. Weigh pigments of a hydroscopic nature 10.1 Pycnometer, Water Bath, Manometer, Vacuum Pump,
from the weighing bottle. Thermometer, Weighing Bottle, and Immersion Liquid—See
7.3 Number of Specimens—Run all samples at least in Section 4; also Fig. 2 (e) and (f ).
duplicate. 10.2 Bell Jar, glass, with a two-hole rubber stopper. Into one
7.4 Addition of Kerosine—Add enough kerosine to the hole of the stopper shall be fitted a separatory funnel with a
pycnometer to form a clear layer approximately 1⁄4 in. (6 mm) well-ground stopcock (Fig. 1 (c)), extending into the pycnom-
above the pigment. When necessary, stir the specimen with a eter. Into the other hole of the stopper shall be fitted a glass
polished round-bottom glass rod until completely covered by tube with a well-ground three-way stopcock (Fig. 2 (d)) and
kerosine, adding more kerosine if necessary. Wash the rod with connected with the vacuum pump (Fig. 2 (e)). The bell jar shall
kerosine, adding the washings to the pycnometer. rest on a sheet of rubber, cemented or vulcanized to a glass or
7.5 Removal of Occluded Air—Place the pycnometer in the iron plate. With stopcock c closed and stopcock d open to the
desiccator. Close the desiccator and attach to the water pump pump, the system shall maintain an absolute pressure of at
until the greater part of the air is removed from the system. most 3 mm. A desiccator may be used instead of a bell jar.
Complete this procedure within a period of 5 to 10 min. Close 10.3 Bottle, storage, (Fig. 2 (h)) for kerosine or other
the system with a pinchcock and attach the desiccator to the oil wetting liquid.
pump for the removal of the small amounts of air given off at
the low pressures obtainable with the oil pump. Use the 11. Hazards
manometer to indicate whether the oil pump is giving the 11.1 Before a bell jar (or desiccator) is used for the first
proper vacuum. When the manometer indicates that the abso- time, test under a vacuum as described in Section 5.
lute pressure is 3 mm and constant, cut off the oil pump for 11.2 Use a buret stopcock (Fig. 2 (c)) that is well ground
short periods, taking care that the vacuum does not change and lubricated with silicone lubricants or use a PTFE-coated
materially due to leakage. At first bubbles of air rise from the stopcock.
pigments very rapidly, then this action gradually decreases and
finally stops. The time required for complete removal of air
may vary from 30 min to 24 h, depending upon the nature of
the pigment. When no more bubbles can be seen, it may be
assumed that the occluded air has been removed and that the
pigment is thoroughly wet with kerosine. Then slowly admit
air to the desiccator by means of the pinchcock.
7.6 Filling and Bringing to Temperature—Remove the py-
cnometer from the desiccator, fill with kerosine at 24 to 25°C
taking care to add a sufficient quantity to prevent air bubbles
where the pycnometer is closed, and permit to come to constant
temperature at 25 6 0.5°C in the water bath. Carefully stopper
the pycnometer and remove excess kerosine with lens paper. FIG. 1 Apparatus for Test Method B
2
D 153
FIG. 2 Apparatus for Test Method C
12. Procedure 14.4 Vacuum Pump—See 4.5; also Fig. 2 (e). In this
12.1 Place the pycnometer containing the weighed, dried procedure the oil vacuum pump shall be capable of reducing
pigment under the bell jar. Close stopcocks c and d, start the the absolute pressure of the system to 1 mm.
vacuum pump, and then gradually open stopcock d to the 14.5 Manometer, Thermometer, Weighing Bottle, and Im-
pump. When an absolute pressure of 3 mm has been attained mersion Liquid—See Section 4; also Fig. 2 (f ).
and can be maintained, fill the separatory funnel with kerosine, 14.6 Bottle—See 10.3.
close stopcock d, and gradually open stopcock c, adding
15. Hazards
sufficient kerosine to cover the pigment. Then stop the pump
and release the suction at stopcock d. Finally, fill the pycnom- 15.1 The variations that occur under normal conditions in a
eter with kerosine, and complete the test as described in 7.6 and room do not materially affect the specific gravity of a pigment.
Section 8, under Test Method A. However, take care that the temperature of the liquid after
transferring to the flask is approximately the same as it was
13. Precision when in the buret.
13.1 Duplicate determinations by this test method should 15.2 Since in determining both K2 and V the tip of the buret
not differ by more than 0.01. and bore of the stopcock plug are empty, no correction is to be
made; but stopcock c must be so well ground that under an
TEST METHOD C—FOR RAPID AND ACCURATE absolute pressure of 1 mm for 30 min no leakage of kerosine
TESTING OF A SINGLE SPECIMEN shall take place. The usual sources of error are failure to
remove all the air from the pigment, and leaks in the system.
14. Apparatus (see Fig. 2 and Fig. 3) Use a minimum amount of rubber tubing in the system and,
14.1 Buret, 100-mL, with a 75-mL bulb in the upper part, wherever it is used, coat the joints between rubber and glass
and with the lower part (25 mL) graduated in 0.05-mL with a melted mixture of beeswax and rosin.
divisions (see Fig. 3). 15.3 In cleaning the flask of kerosine only, a rinsing two or
14.2 Flask—A special 100-mL graduated flask (Fig. 2 (b)) three times with ether, followed by dry air (dried over sulfuric
with ground-glass stopper. The flask shall be thick enough to acid and calcium chloride), is considered sufficient. When
withstand an absolute pressure of 1 mm, and shall weigh pigment is also present, remove both pigment and kerosine and
between 50 and 60 g. The neck of the flask shall be graduated follow with ether rinses until no more pigment remains. Add
in 0.05-mL divisions between the 99 and 100-mL marks. The some filter pulp (macerated filter paper) and water (with or
dimensions of the flask shall be as shown in Fig. 2. without glass beads), and shake vigorously. Repeat if neces-
14.3 Stopcocks—A tightly ground stopcock (Fig. 2 (c)) as sary. Rinse the flask with reagent water, and either dry in an
part of buret, a, and a three-way stopcock (Fig. 2 (d)) oven, or rinse with alcohol and ether followed by dry air.
connecting with the vacuum pump, e. To prevent leakage of
kerosine use a buret stopcock (Fig. 2 (c)) that is well ground 16. Standardization of Apparatus
and lubricated with silicone lubricant or use a PTFE-coated 16.1 Connect the flask to the buret and the pump by means
stopcock. of a two-holed rubber stopper. Evacuate the system with the
3
D 153
neck. Read the buret, calling this reading K2 (the volume of the
flask).3
17. Procedure
17.1 Clean the flask dry, and weigh. Transfer a quantity of
the dry pigment to be tested to the flask by means of a clean,
dry, glass funnel with the stem reaching to the bottom of the
bulb. A piece of stiff nickel wire is convenient to push the
powder down the stem. Nearly fill the bulb of the flask with the
pigment, which, however, shall occupy a volume of less than
25 mL after all air is expelled. Greater accuracy may be
obtained with a large specimen than with a small one. Wipe the
inside stem as well as the entire outside of the flask with a clean
piece of dry, lintless cloth. Weigh the flask and pigment, and
calculate the weight of pigment by deducting the weight of the
empty flask. With the buret clean and dry, attach the flask to the
evacuating system as shown in Fig. 2. After closing stopcocks
c and d, start the pump and carefully open stopcock d to the
pump. Continue evacuation until the pump maintains an
absolute pressure of 1 mm in the flask, or until all the air is
removed from the system. Then fill the buret from the top as
described in Section 16, close stopcock d, gradually open
stopcock c, and add kerosine until the pigment is covered. Tap
the flask gently to dislodge any air bubbles. Stop the pump,
open stopcock d to the air, and fill the flask up to the same mark
as was obtained in determining its volume. Designate the
volume of kerosine required as V. Read the height of the liquid
in the buret to the nearest estimated 0.01 mL.
Buret: Geissler, straight; glass stopcock, ground accurately.
Total capacity 100 mL 18. Calculation
Capacity of bulb 0 to 75 mL
Graduated 75 to 100 mL 18.1 Calculate the specific gravity, SG, of the pigment as
Subdivisions 0.05 mL follows:
Rate of outflow about 2 min
Permissible variations: SG 5 P2 / ~K2 2 V!
Capacity, total 6 0.10 mL
Capacity graduated portion 6 0.03 mL where:
Markings on graduations shall be in conformity with the National Bureau of P2 5 weight of pigment used, g,
Standards Circular No. 9.3
K2 5 volume of kerosine required to fill the flask when
FIG. 3 Buret in Apparatus empty, mL, and
V 5 volume of kerosine required to fill the flask when the
pigment is present, mL.
buret stopcock (Fig. 2 (c)) closed until the pump maintains an
absolute pressure of 1 mm in the flask. Close the three-way 19. Precision
stopcock, d, for 30 s, and again open to the pump. There shall 19.1 Duplicate determinations by this test method should
be no appreciable change in the mercury levels in the manom- not differ by more than 0.01.
eter, indicating that the system beyond stopcock d is tight. With
the vacuum still maintained, fill the buret from the top with 20. Keywords
kerosine, adjusting the level to the zero mark with a piece of 20.1 pigments; specific gravity
capillary tubing. Now close stopcock d, and carefully open
stopcock c, admitting about 75 mL of kerosine into the flask.
Open stopcock d to the air, thus releasing the vacuum in the 3
Available from National Institute of Standards and Technology, Gaithersburg,
flask, and fill the flask with kerosine to a definite mark on the MD 20899.
4
D 153
5
Standard Guide for

Testing Varnishes1
1. Scope D 1310 Test Method for Flash Point and Fire Point of
1.1 This guide covers the selection and use of procedures Liquids by Tag Open-Cup Apparatus4
for testing varnishes. Some test methods are included, but most D 1469 Test Method for Total Rosin Acids Content of
sections refer to specific ASTM test methods. Coating Vehicles6
1.2 Varnishes may be applied under such diverse conditions D 1475 Test Method for Density of Paint, Varnish, Lacquer,
to so many different surfaces and their dried films may be and Related Products4
subjected to so many kinds of wear and exposure, that it is not D 1542 Test Method for Qualitative Detection of Rosin in
possible to assure desired performance from a single selection Varnishes6
of test methods and numerical results. Those skilled in varnish D 1544 Test Method for Color of Transparent Liquids
technology may find partial assurance of obtaining desired (Gardner Color Scale)4
qualities in various types of varnishes through careful selection D 1545 Test Method for Viscosity of Transparent Liquids
of the methods covered and intelligent interpretation of results. by Bubble Time Method6
1.3 This standard does not purport to address all of the D 1546 Test Method for Performance Tests of Clear Floor
safety concerns, if any, associated with its use. It is the Sealers7
responsibility of the user of this standard to establish appro- D 1639 Test Method for Acid Value of Organic Coating
priate safety and health practices and determine the applica- Materials6
bility of regulatory limitations prior to use. D 1640 Test Methods for Drying, Curing, or Film Forma-
tion of Organic Coatings at Room Temperature4
2. Referenced Documents D 1641 Test Method for Exterior Durability of Varnishes7
2.1 ASTM Standards: D 1644 Test Methods for Nonvolatile Content of Varnishes4
D 56 Test Method for Flash Point by Tag Closed Tester2 D 1647 Test Method for Resistance of Dried Films of
D 93 Test Methods for Flash Point by Pensky-Martens Varnishes to Water and Alkali6
Closed Cup Tester2 D 1729 Practice for Visual Evaluation of Color Differences
D 445 Test Method for Kinematic Viscosity of Transparent of Opaque Materials4
and Opaque Liquids (and the Calculation of Dynamic D 2090 Test Method for Clarity and Cleanness of Paint and
Viscosity)2 Ink Liquids6
D 479 Test Method for Reactivity of Paint Liquids3 D 2244 Test Method for Calculation of Color Differences
D 523 Test Method for Specular Gloss4 from Instrumentally Measured Color Coordinates4
D 658 Test Method for Abrasion Resistance of Organic D 2369 Test Method for Volatile Content of Coatings4
Coatings by Air Blast Abrasive4 D 2805 Test Method for Hiding Power of Paints by Reflec-
D 968 Test Methods for Abrasion Resistance of Organic tometry4
Coatings by Falling Abrasive4 D 3278 Test Method for Flash Point of Liquids by Small
D 1200 Test Method for Viscosity by Ford Viscosity Cup4 Scale Closed Cup Apparatus4
D 1209 Test Method for Color of Clear Liquids (Platinum- D 3964 Practice for Selection of Coating Specimens for
Cobalt Scale)5 Appearance Measurements4
D 4039 Test Method for Reflection Haze of High-Gloss
Surfaces4
1
This guide is under the jurisdiction of ASTM Committee D-1 on Paint and D 4060 Test Method for Abrasion Resistance of Organic
Related Coatings, Materials, and Applications and is the direct responsibility of
Coatings by the Taber Abraser4
Subcommittee D01.33 on Polymers and Resins.
2
3
Discontinued; see 1983 Annual Book of ASTM Standards, Vol 06.01.
4 6
5 7
1
D 154
E 308 Practice for Computing the Colors of Objects by TABLE 1 List of Test Methods
Using the CIE System Test Method Section
ASTM
4
Designation
LIQUID VARNISH PROPERTIES Liquid Varnish Properties:
Appearance 3 D 2090
3. Appearance Color (Gardner) 4.1 D 1544
Color, Platinum-Cobalt Scale 4.2 D 1209
3.1 Appearance of the liquid varnish is important both for Color, tristimulus 4.3 E 308
aesthetic reasons and because it indicates whether the dried Viscosity: 5
Bubble time (Gardner-Holdt) 5.2 D 1545
film is likely to have a satisfactory appearance. Examine the Ford cup efflux 5.3 D 1200
liquid varnish for foreign matter, sediment or skins in accor- Kinematic, high precision 5.4 D 445
dance with Test Method D 2090. Specific gravity 6 D 1475
Volatile content 7 D 2369
Nonvolatile matter 8 D 1644
4. Color Flash point: 9
4.1 Most varnishes are predominantly yellow, but the color Tag closed-cup D 56
Pensky Martens D 93
of the liquid varnish is only a preliminary indication of the Tag open-cup D 1310
color of the dried varnish film. The initial color may bleach or Setaflash closed tester D 3278
may darken depending upon the conditions of exposure. Skinning 10
Acid value 11 D 1639
Determine approximately and quickly the liquid color of small Reactivity of paint liquids 12 D 479
specimens in Gardner-Holdt tubes by comparison with the Rosin content, quantitative 13 D 1469
Gardner Color Standards in accordance with Test Method Rosin content, qualitative (Lieber-
man-Storch and Halphen-Hicks) 13 D 1542
D 1544.
4.2 Measure the color of extremely pale varnishes by using Drying and Curing Properties:
larger specimens in 100-mL cylinders, 300 mm deep, in Drying time 14 D 1640
Print free time 15 D 1640
accordance with Test Method D 1209.
4.3 A more precise measure of color, in terms of tristimulus Dry Varnish Properties:
values, may be made on small specimens in 10-mm cells with Gloss: 16
Specular gloss D 523
parallel walls in accordance with Practice E 308. Reflective haze D 4039
Resistance of dried films to water
5. Viscosity and alkali 17 D 1647
Abrasion resistance:
5.1 The viscosity of a varnish or clear vehicle is a property Carborundum air blast 18
important in ease of application; varnishes for brush applica- Falling abrasive D 658
Taber abraser D 968
tion are typically 1 to 2 St whereas varnishes with viscosities Exterior durability D 4060
as high as 100 St may sometimes be added to lithography Color of dried film 19 D 1641
coatings or used as mixing vehicles for producing enamels. 20.1 D 2244
20.2 D 1729
Viscosity is commonly measured at 77°F (25°C).
5.2 For the rapid, approximate measurement of the viscosity Clear floor sealers 21 D 1546
of transparent varnishes, determine the bubble time by Test
Method D 1545. Report the viscosity either in stokes or in
Gardner-Holdt letter designations as described in Table 1 of
Test Method D 1545. upon the method of application, the time required to vaporize
5.3 For a rapid, approximate measurement of the viscosity the volatile, and the conditions of the atmosphere surrounding
of translucent varnishes, determine the Ford cup efflux time in the application, it is recommended that Test Method D 2369 be
accordance with Test Method D 1200. used to determine the volatile content of a varnish.
5.4 For the precise measurement of viscosity, use capillary
viscometers as described in Test Method D 445. 8. Nonvolatile Matter
8.1 Nonvolatile content is an indication of the amount of
6. Specific Gravity permanent film-forming material contained in a varnish. The
6.1 Specific gravity of a varnish is the ratio of the weight of normal drying of a varnish film may involve varying amounts
a given volume of the varnish at a given temperature to the of absorption of oxygen from the air, loss of volatile solvents,
weight of an equal volume of distilled water at the same and continuing decomposition of the dried film. The net result
temperature. Determine specific gravity or density at 77°F of this process may differ somewhat from a nonvolatile
(25°C) or other agreed temperature in accordance with Test determination at a temperature higher than the normal drying
Method D 1475 which allows use of either a pycnometer or a conditions.
weight per gallon cup. 8.2 With due regard to the composition of the varnish,
determine the nonvolatile matter in accordance with either
7. Volatile Content Method A (3 h at 220°F (105°C)) or Method B (10 min at
7.1 Volatile matter determination is an indication of the 300°F (149°C)) of Test Methods D 1644.
amount of material in the coating that will be given off to the 8.3 As noted in Test Method D 2369, nonvolatile matter can
atmosphere in the area where the coating is applied. Depending also be calculated by subtracting the volatile content from 100.
2
D 154
9. Flash Point humidity, and exposure to light and other radiation may affect
9.1 Determine the flash point of varnishes having a viscosity drying times by 65 %.
of less than 9.5 cSt at 77°F (25°C) (45 SUS at 100°F) by Test 14.2 Determine the drying stages appropriate to the varnish
Method D 56, and of varnishes having a viscosity of more than under test in accordance with the applicable sections of Test
9.5 cSt at 77°F by Test Methods D 93. Alternatively, use Test Methods D 1640.
Method D 3278, which gives comparable results to Test
15. Print-Free Time
Methods D 56, D 93, and Test Method D 1310.
15.1 Varnishes intended for floors, furniture, etc., are ex-
NOTE 1—Due to various U.S. Government and State regulations, it is pected to bear heavy objects for long periods without marring
now necessary to check with appropriate departments to determine which
ASTM Test Method is applicable.
of the surface or adhering to the object.
15.2 Determine the print-free time in accordance with that
10. Skinning section of Test Methods D 1640.
10.1 Varnishes, which dry by oxidation, may form a skin in DRY VARNISH PROPERTIES
a partially filled can or in a filled can that is stored for a long
time. Since skins are insoluble in the varnish, they must be 16. Gloss
removed before use if a satisfactory film is to be obtained. Use
16.1 Because varnishes are transparent or translucent, gloss
the following test to determine if a varnish has an objectionable
must be measured on films applied to a nonreflecting substrate.
tendency to early skin formation:
The usual material is plane, black glass as described in Test
10.1.1 Container—A wide-mouth jar with a capacity of 8
Method D 2805 and similar to the gloss standards used in Test
fluid oz (235 mL) and dimensions of 41⁄2 in. (115 mm) in height
Method D 523. Gloss measurements of varnishes on wood
and 2 in. (50 mm) in diameter.
substrates are generally not valid because the reflectance of the
10.1.2 Procedure—Measure a 6-fluid oz (180-mL) speci-
substrate can affect the result, but comparative tests in one
men of the varnish into the glass container. Screw the cover on
laboratory of different varnishes on the same substrate may be
tightly, invert the jar, and leave in an inverted position, at rest,
helpful.
and in the dark (placing under a box or in a drawer is
16.2 Gloss is usually measured in accordance with Test
satisfactory). Examine the varnish for skinning at specified
Method D 523 using 60° geometry. For greater sensitivity in
time intervals.
evaluating high gloss varnishes, the 20° geometry may be used
11. Acid Value or Test Method D 4039 which uses both 20° and 60° geom-
etries.
11.1 The acid value of a varnish is an indication of reactivity
16.3 Prepare specimens in accordance with Practice
with basic pigments and, within any one type of composition,
D 3964, applying the varnish to black glass panels with a film
may indicate conformity to a standard method of preparation.
applicator that has a clearance of 3 mils (75 µm) for varnishes
It is not a general criterion of excellence in a protective
with a nonvolatile content of 35 % or more and 6 mils (150
coating.
µm) for those with a nonvolatile content less than 35 %.
11.2 Determine the acid value in accordance with Test
16.4 Allow the films to dry under the conditions specified in
Method D 1639.
Test Methods D 1640 for at least 24 h. For a rapid control test
12. Reactivity of Paint Liquids the films may be force dried at 120°F (50°C) for 1 h, providing
it has been established that heat acceleration does not affect the
12.1 Reactivity of a varnish with zinc oxide is a partial
gloss of the varnish.
indication of the stability of the consistency of enamels made
16.5 Measure the gloss in accordance with Test Methods
from it and various basic pigments.
D 523 or D 4039 and report.
12.2 Determine the reactivity in accordance with Test
Method D 479. 17. Resistance of Dried Films to Water and Alkali
13. Rosin Content 17.1 Performance of varnish films is indicated in part by
13.1 Improper use of rosin and its derivatives is sometimes measurement of resistances of their dried films to water, alkali,
associated with inferior performance of varnishes containing and other reagents.
them. Qualitative tests for rosin may be employed to detect the 17.2 Determine the resistance to water and alkali in accor-
use of a significant amount in varnishes. Quantitative determi- dance with Test Method D 1647.
nation of rosin may be used to control rosin content within 18. Abrasion Resistance
limits agreeable to the purchaser and the seller.
13.2 Determine the rosin content quantitatively in accor- 18.1 The durability and general performance of varnish
dance with Test Method D 1469 and qualitatively with Test films on floors is influenced by many factors such as mechani-
Method D 1542. cal properties, film thickness, and exposure to light, cleaning
materials, various types of soil, and foot or vehicular traffic, so
DRYING AND CURING PROPERTIES that no one set of tests are adequate to ensure universally
satisfactory service.
14. Drying Time 18.2 An indication of the resistance to abrasion in service
14.1 Small variations in film thickness, air temperature and may be determined by Test Methods D 658, D 968, or D 4060.
3
D 154
All these test methods are suitable for interlaboratory use only 21. Clear Floor Sealers
when results are compared by ranking instead of numerical
21.1 Clear floor sealers are varnishes of relatively low
values.
viscosity for application to wooden or other porous surfaces
19. Exterior Durability and are variously used as either the sole coating or for making
19.1 Durability of varnish films varies so widely with the substrate more uniform for application of wax, varnish, or
exposure to varying conditions of atmosphere and light or other other coatings.
radiation, that any one set of conditions is only a preliminary 21.2 Evaluate clear floor sealers in accordance with Test
indication of general durability. Method D 1546.
19.2 Determine the exterior durability in accordance with
Test Method D 1641. 22. Precision
20. Color of Dried Film 22.1 No specific precision statement is made for this guide
20.1 The color of the dry film is usually more significant since this information is included in the referenced methods, if
than that of the liquid varnish in establishing whether the color available.
of a varnished object will be acceptable. This can be evaluated
by determining, in accordance with Test Method D 2244, the 23. Keywords
color difference of white structural glass before and after 23.1 drying and curing properties; varnish acid value; var-
application and drying of a varnish film. nish flash point; varnish nonvolatile contents; varnish physical
20.2 If a varnish with a dry color known to be satisfactory properties; varnish specific gravity; varnish volatile contents;
is available, a standard panel can be prepared and used for varnish viscosity
visual color comparison in accordance with Practice D 1729.
4

Coarse Particles in Pigments, Pastes, and Paints1
1. Scope weigh on an analytical balance, recording the weight to 1 mg.
1.1 These test methods cover the determination of the 5.2 Weigh a specimen (25 g for basic carbonate and basic
amount of coarse particles in dry pigments and of coarse sulfate white leads, 25 g for red lead and mercuric oxide, 2 g
particles and skins in mixtures of pigments and vehicles. for black pigments of low specific gravity, 3 g for Prussian
1.2 The values stated in inch-pound units are to be regarded blues and graphite, and 10 g for all other pigments) of the
as the standard. The values given in parentheses are for pigment to be tested on an analytical balance to 1 mg. Wet the
information only. sieve on both sides with alcohol and transfer the specimen of
1.3 This standard does not purport to address all of the pigment to the sieve and wet with alcohol.
safety concerns, if any, associated with its use. It is the 5.3 Hold the sieve under a tap delivering about 300 to 500
responsibility of the user of this standard to establish appro- mL of the wash liquid (water) per minute. By slightly shaking
priate safety and health practices and determine the applica- the sieve, the pigment will be rapidly carried through. A soft
bility of regulatory limitations prior to use. camel’s-hair brush may be used in aiding the operation. If the
sieve is held at a slight angle so that the pigment gradually
2. Referenced Documents collects at one edge during the washing process, and then
2.1 ASTM Standards: rotated, the pigment may be brushed out rapidly, with no risk
E 11 Specification for Wire-Cloth Sieves for Testing Pur- of clogging the sieve.
poses2 5.4 After most of the finely divided portion of the pigment
has passed through the sieve (from 2 min to 1 h, according to
3. Significance and Use the kind of pigment), place the sieve in an 8-in. (200-mm)
3.1 In production of paints, smoothness of the paint film is porcelain dish containing 250 mL of the wash liquid so that the
of paramount importance. Agglomerates or coarse particles sieve is covered to a depth of about 1⁄2 in. Brush the pigment
larger than 45 µm are difficult to disperse and may prevent remaining on the sieve with a soft 1-in. (25-mm) camel’s-hair
obtaining a smooth film. These test methods are a valuable brush at the rate of two strokes per second during two periods
quality control test for grading raw materials. of 10 s each. Raise the sieve from the dish after each 10-s
period to let the liquid on the sieve run through. Change the
4. Apparatus liquid in the dish after every two brushing periods. Continue
4.1 The apparatus shall consist of a 3-in. (75-mm) 45-µm this operation until the wash liquid passing over the residue and
(No. 325) sieve conforming to Specification E 11. A3-in. through the sieve is clear and free from solid particles. When
45-µm sieve for comparison purposes should be retained in the the washing appears to be complete, collect about 200 mL of
laboratory as a reference standard. Whenever a new sieve is the wash liquid, after passing over the residue and through the
secured, a practical test of its accuracy should be made by sieve, in a clean 400-mL beaker. Stir the liquid vigorously, and
running on it and on the reference standard sieve a comparison set the beaker on a black surface in the case of white pigments
test, using a pigment that has a considerable amount of coarse and on a white surface in the case of colored pigments. The
particles. A reserve stock of such a pigment should be kept for washing is not considered complete until such a test fails to
this purpose. show any particles collected about the middle of the bottom of
the beaker.
5. Procedure for Insoluble Dry Pigments, Except Metallic
NOTE 1—Occasionally, pigments will be found that foam when water is
Aluminum and Bronze Powders
used as the wash liquid. In such instances, during the last washing in the
5.1 Dry the sieve in an oven at 105 6 2°C, cool, and then porcelain dish the use of a liquid that breaks down the foaming and is
1
of Subcommittee D01.31 on Pigment Specifications.
published as D 185–37. Last previous edition D 185–78.
2
1
D 185
readily miscible with water, such as alcohol, will usually overcome this the paper with the finger. When no further real blackening of
difficulty. the paper occurs, carefully transfer the residue to the balance
5.5 When the washing is complete wash the pigment par- pan, weigh, and recalculate the percent of coarse particles.
ticles adhering to the brush back onto the sieve and wipe off the
water below the sieve. Add a few drops of alcohol and then of 8. Procedure for Water-Soluble Pigments, Pastes in Oil,
ether to expedite drying. Dry the sieve for 1 h at 105°C, cool, Pastes in Japan, and Mixed Paints
and weigh as described in 5.1. Calculate the percent of coarse 8.1 Dry, cool, and weigh the sieve as described in 5.1.
particles. 8.2 For water-soluble pigments use 10 6 1 g as the
specimen. For pastes in oil, pastes in Japan, and mixed paints
6. Procedure for Metallic Aluminum and Bronze use 256 1 g as the specimen. For white leads and red lead use
Powders 50 6 1 g as the specimen.
6.1 In the case of metallic aluminum and bronze powders 8.3 Weigh the specimen to 1 mg and transfer to a 250-mL
follow the procedure described in Section 5 except use 5 g of beaker. Slowly add 100 mL of kerosine to the contents of the
the material as the specimen and denatured alcohol, instead of beaker, mixing thoroughly by use of a stirring rod with
water, as the wash liquid. flattened end. Break up all lumps but do not grind the material.
8.4 Wet the sieve on both sides with kerosine; then transfer
7. Procedure for Carbon Black in Pellet Form the contents of the beaker to the sieve using a wash bottle filled
7.1 Dry, cool, and weigh the sieve as described in 5.1. with kerosine.
7.2 Prepare a stock solution of dispersing agent3 in water, 8.5 Remove small particles retained on the stirring rod or
using as high a concentration of dispersing agent as possible beaker walls with a camel’s-hair brush. Rinse the brush with
without losing fluidity. When solution has been obtained, filter kerosine.
through coarse filter paper. A quart of this solution will be 8.6 When the washing is complete, wash the pigment
sufficient for several tests. particles adhering to the brush back onto the sieve and wipe off
7.3 Crush the pellets between two glass plates approxi- kerosine below the sieve. Dry the sieve for 1 h at 105°C, cool,
mately 12-in. (305-mm) square, using a gentle rotating motion. and weigh as described in 5.1. Calculate the percent of
If 10 g of carbon black are taken, crush about 2 g at a time. particles.
Weigh into a 600-mL beaker 10 g of the crushed particles. Add
enough of the dispersing solution to make a heavy paste and 9. Procedure for Ship-Bottom Paints Containing Resins
mix well to incorporate thoroughly the carbon black. Dilute and Alcohol
with water to about 300 mL; then pour into the clean 45-µm 9.1 In the case of ship-bottom paints containing resins and
(No. 325) sieve. First pass the tap water through a 45-µm sieve. alcohol follow the procedure described in Section 8, with
7.4 Using a small camel’s-hair brush, gently brush the mix specimen weight of 25 6 1 g, but use denatured alcohol,
through the sieve, running tap water slowly through at the same instead of kerosine, as the wetting medium, for mixing with
time. When it appears that all the dispersed black has gone paint, and as the wash liquid.
through, stop the tap water and continue brushing until most of
the water remaining on the sieve has gone through. Add a few 10. Procedure for Cellulose Ester Lacquers
millilitres of the stock solution of the dispersing agent, thor- 10.1 In the case of cellulose ester lacquers follow the
oughly mix with the brush, then turn on the tap water again and procedure described in Section 8, with specimen weight of 25
wash through as before. Repeat this operation until no dis- 6 1 g of the material but use a mixture of equal parts of ethyl
persed black comes through the sieve. When about 0.5 g of acetate, toluene, and denatured alcohol, instead of kerosine, as
sand-like material is left on the sieve, the end point is being the wetting medium, for mixing with the lacquer, and as the
approached. At this point, adding the dispersing solution and wash liquid.
gently rubbing it into the residue with the finger still produces
11. Procedure for Latex and Emulsion Paints
a colloidal dispersion of black which easily passes through the
sieve. From this point on, before each addition of dispersing 11.1 Apparatus—As described in Section 4 except that
agent, work the residue into the center of the sieve with the tap sieves used shall be as follows:
water. Many washings and many additions of dispersing 11.1.1 Flat Paints, a 3-in. (75-mm) 90-µm (No. 170) sieve.
solution are required in order to reach the end point. Take care 11.1.2 Gloss and Semi-Gloss Paints, a 3-in. (75-mm) 75-µm
to make certain that all the black has been washed through the (No. 200) sieve.
sieve. 11.2 Dry, cool, and weigh the sieve as described in 5.1.
7.5 Dry the sieve in an oven at 105°C for 1 h, cool, and 11.3 Weigh 25 g of paint to 61 g into a tared 250-mL
weigh the residue. Calculate the percent of coarse particles. If beaker. Without delay, start adding 100 mL of water to the paint
the value thus obtained is greater than that specified, proceed as in the beaker, slowly and with hand stirring sufficient to
follows to remove any adhered carbon that will pass through thoroughly mix the paint with the water. Wet the sieve on both
the 45-µm (No. 325) sieve: Transfer the particles on the sieve sides with water and transfer the contents of the beaker
to a piece of white bond paper and gently rub the carbon onto gradually to the sieve, using a wash bottle containing water.
Small particles retained on the stirrer or beaker walls may be
removed with a camel’s-hair brush. Instead of tap water, use
3
Any dispersing agent specific for carbon black may be used. reagent water for diluting the paint sample, in the wash bottle,
2
D 185
and for washing the paint through the sieve. The water may be 12. Precision
delivered from a reservoir for the last step.
12.1 Precision data are not available at this time. When
11.4 Follow the procedure described in 5.3. In using the
available the appropriate precision statements will be added.
camel’s-hair brush, take care not to crush agglomerates that
would not be broken down in normal application of the paint.
Rinse the brush into the sieve at end of use. 13. Keywords
11.5 Finally, dry, cool, and weigh the sieve for 1 h, as 13.1 agglomerates; coarse particles; paints; paste; pigments;
described in 5.1. Then calculate the percent of coarse particles skins
and skins.
3

Lampblack Pigment1
1. Scope with linseed oil, turpentine, or volatile petroleum spirits, or any

1.1 This specification covers the pigment commercially mixture of these substances. The paste shall conform to the
known as lamp-black. The pigment may be purchased in the following requirements:
dry form or as a paste in oil. Pigment, min, % 25
2. Referenced Documents Coarse particles and skins (total residue retained on a 1.0
2.1 ASTM Standards: 45-µm (No. 325) sieve), max, % of the dry pigment
D 185 Test Methods for Coarse Particles in Pigments,
Pastes, and Paints2 3.3 The mass color and character of the tint and the tinting
D 387 Test Method for Color and Strength of Color Pig- strength formed by a mixture with a white pigment shall be
ments with a Mechanical Muller3 within mutually agreed upon limits of a standard acceptable to
D 1208 Test Methods for Common Properties of Certain both the purchaser and the seller.
Pigments2 4. Sampling
3. Composition and Properties 4.1 Two samples shall be taken at random from different
3.1 Dry Pigment—The pigment shall be made by burning packages from each lot, batch, day’s pack, or other unit of
oils or tars in such a manner as to form a deposit of carbon or production in a shipment. When no markings distinguishing
soot. It shall be high grade in every respect and shall be free between units of production appear, samples shall be taken
from oil, greasy matter, and admixture of any other substance. from different packages in the ratio of two samples for each
The pigment shall conform to the following requirements: 10 000 lb (4540 kg), except that for shipments of less than
Ash, max, % 0.5
Acetone extract, max, % 1.0 purchaser, the samples may be tested separately or after
Moisture and other volatile matter, max, % 3.0 blending in equal quantities the samples from the same
Coarse particles, (total residue retained on a 0.5 production unit to form a composite sample.
45-µm (No. 325) sieve), max, %
Tone when diluted with zinc oxide clear-blue-gray
5. Test Methods
3.2 Paste in Oil—The paste in oil shall be made by 5.1 Tests shall be conducted in accordance with the follow-
thoroughly grinding the specified pigment with linseed oil. As ing test methods. Test procedures not covered by ASTM test
received it shall not be caked in the container and shall break methods shall be mutually agreed upon between the purchaser
up readily in oil to form a smooth paint of brushing consis- and the seller.
tency. It shall mix readily in all proportions, without curdling, 5.2 Coarse Particles—Test Methods D 185.
5.3 Pigment, Linseed Oil, and Moisture and Other Volatile
Matter in Paste in Oil—Test Methods D 1208.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.4 Mass Color and Tinting Strength—Test Method D 387.
and Related Coatings, Materials, and Applications, and is the direct responsibility of
Current edition approved Aug. 31, 1981. Published October 1981. Originally
6. Keywords
published as D 209 – 24. Last previous edition D 209 – 47 (1974).
2
6.1 carbon; lampblack; linseed oil; pigment; soot
3
1
D 209
2
Designation: D 210 – 81a (Reapproved 1999)

Bone Black Pigment1
1. Scope with linseed oil, turpentine, or volatile petroleum spirits, or any

1.1 This specification covers the pigment commercially mixture of these substances. The paste shall conform to the
known as bone black, ivory black, or drop black. The pigment following requirements:
may be purchased in the dry form or as a paste in oil. Pigment, min, % 45
Coarse particles and skins (total residue retained on a 2.5
2. Referenced Documents No. 325 (45-µm) sieve), max, % of the dry pigment
2.1 ASTM Standards:
3.3 The mass color and character of the tint and the tinting
strength formed by a mixture with a white pigment shall be
Pastes, and Paints2
D 387 Test Method for Color and Strength of Color Pig-
ments with a Mechanical Muller3
D 1208 Test Methods for Common Properties of Certain 4. Sampling
Pigments2 4.1 Two samples shall be taken at random from different
3. Composition and Properties packages from each lot, batch, day’s pack, or other unit of
production in a shipment. When no markings distinguishing
3.1 Dry Pigment—The pigment shall be made by the
calcination of bones, shall be unmixed with any other sub-
from different packages in the ratio of two samples for each
stance, and shall conform to the following requirements:
10 000 lb (5000 kg), except that for shipments of less than
Ash (pigment dried at 105°C), %, max 88
Ash insoluble in acids, max, % 3.0
Acetone extract, max, % 2.0 purchaser, the samples may be tested separately or after
Coarse particles (total residue retained on a No. 325 2.0 blending in equal quantities the samples from the same
(45-µm) sieve), max, %
production unit to form a composite sample.
3.2 Paste in Oil—The paste in oil shall be made by
thoroughly grinding the specified pigment with linseed oil. As 5. Test Methods
received it shall not be caked in the container and shall break 5.1 Tests shall be conducted in accordance with the follow-
up readily in oil to form a smooth paint of brushing consis- ing ASTM test methods. Test procedures not covered by ASTM
tency. It shall mix readily in all proportions, without curdling, test methods shall be mutually agreed upon by the purchaser
and the seller.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.3 Pigment and Linseed Oil in Paste in Oil—Test Methods
and Related Coatings, Materials, and Applications, and is the direct responsibility of D 1208.
Subcommittee D01.31 on Pigment Specifications. 5.4 Mass Color and Tinting Strength— Test Method D 387.
2
3
Annual Book of ASTM Standards, Vol 06.01. 6.1 Black pigment; drop black; ivory black; pigment.
1

Chrome Yellow and Chrome Orange Pigments1
e1 NOTE—Keywords were added editorially in August 1996.
1. Scope Carbon-Arc Light and Water Exposure Apparatus4

1.1 This specification covers six types of commercially pure D 1210 Test Method for Fineness of Dispersion of Pigment-
lead chromate pigments as follows: Vehicle Systems4
Type I—Primrose Chrome Yellow, E 97 Test Method for Directional Reflectance Factor, 45-
Type II—Lemon Chrome Yellow, deg 0-deg, of Opaque Specimens for Broad-Band Filter
Type III—Medium Chrome Yellow, Reflectometry5
Type IV—Light Chrome Orange, 2.2 Federal Specification:6
Type V—Dark Chrome Orange, and TT-R-266 Resin, Alkyd; Solutions
Type VI—Chrome Yellow for Green. 3. Composition and Properties
1.2 The following hazard caveat applies to the test method
portion of this specification only. This standard does not 3.1 The pigments shall be chemical precipitates consisting
purport to address all of the safety concerns, if any, associated of normal or basic lead chromates, or mixtures of these, with or
with its use. It is the responsibility of the user of this standard without admixtures of other insoluble compounds of lead or
to establish appropriate safety and health practices and other materials used in manufacture to control certain proper-
determine the applicability of regulatory limitations prior to ties. The pigments shall conform to the requirements for
use. composition as prescribed in Table 1.
3.2 The mass color and character of the tint formed by
2. Referenced Documents mixture with a white pigment shall be the same as, and the
2.1 ASTM Standards: strength shall be within mutually agreed upon limits of a
D 126 Test Methods for Analysis of Yellow, Orange, and standard acceptable to both the purchaser and the seller.
Green Pigments Containing Lead Chromate and Chro- 3.3 When mutually agreed upon between the purchaser and
mium Oxide Green2 the seller as being essential to the end use of the pigment,
D 185 Test Methods for Coarse Particles in Pigments, resistance to loss of gloss, chalking, and color change shall be
Pastes, and Paints2 tested as specified in 5.1.4. The exposed panel shall show no
D 235 Specification for Mineral Spirits (Petroleum Spirits) chalking, a loss of not more than 30 % of the original gloss,
(Hydrocarbon Dry Cleaning Solvents)3 and a color change no greater than the lightness difference. DL,
D 387 Test Method for Color and Strength of Color Pig- shown for each pigment type in Table 2.
ments With a Mechanical Muller4
4. Sampling
D 523 Test Method for Specular Gloss4
D 562 Test Method for Consistency of Paints Using the 4.1 Two samples shall be taken at random from different
Stormer Viscometer4 packages from each lot, batch, day’s pack, or other unit of
D 600 Specification for Liquid Paint Driers3 production in a shipment. When no markings distinguishing
D 822 Practice for Conducting Tests on Paint and Related between units of production appear, samples shall be taken
Coatings and Materials Using Filtered Open-Flame from different packages in the ratio of two samples for each
1
and Related Coatings, Materials, and Applications, and is the direct responsibility of purchaser, the samples may be tested separately, or samples
Subcommittee D01.31 on Pigment Specifications. from the same production unit may be blended in equal
Current edition approved Sept. 8, 1967. Originally published as D211 – 25T. Last
previous edition D211 – 63 T.
2 5
Annual Book of ASTM Standards, Vol 06.03. Discontinued; see 1992 Annual Book of ASTM Standards, Vol 06.01.
3 6
Annual Book of ASTM Standards, Vol 06.04. Available from Standardization Documents Order Desk, Bldg. 4, Section D,
4
Annual Book of ASTM Standards, Vol 06.01. 700 Robbins Ave., Philadelphia, PA 19111-5094.
1
D 211
TABLE 1 Requirements for Composition
Type I Type II Type III Type IV Type V Type VI
Lead chromate (PbCrO4), min % 50 65 87 55 55 75
Total matter soluble in water, max % 1.0 1.0 1.0 1.0 1.0 1.0
Total of all substances other than insoluble compounds of lead, max % 8.0 10.0 10.0 10.0 3.0 10.0
Moisture and other volatile matter, max % 1.5 1.5 1.5 1.5 1.5 1.5
Coarse particles (total residue retained on a 45-µm (No. 325) sieve), max % 1.0 1.0 1.0 1.0 1.0 1.0
Organic colors and lakes none none none none none none
TABLE 2 Permissible Lightness Difference (DL) prescribed in Test Method D 562.

D
See Class B in Specification D 600.
Type Pigment DL E
As required to obtain set-to-touch in 2 h and dry-hard in 8 h.
I Primrose chrome yellow 35 5.1.4.2 The enamel shall have a fineness of grind, aspre-
II Lemon chrome yellow 8
III Medium chrome yellow 6
scribed in Test Method D 1210, of 1.5 mils or less. Apply the
IV Light chrome orange 3 enamel to duplicate flat metal panels by spray or applicator to
V Dark chrome orange 3 complete hiding and allow to dry 72 h. Measure the gloss at
VI Chrome yellow for green 6
60° in accordance with Test Method D 523. Measure the
directional reflectance of the coating in accordance with Test
quantities to form a composite sample. Method E 97. Subject the coated panels for 168 h to acceler-
ated weathering under the conditions prescribed in Practice
5. Test Methods D 822. Examine the exposed coating for chalking. Wash the
5.1 Tests shall be conducted in accordance with the follow- exposed panel under running water with a thoroughly de-
ing test methods. Test procedures not covered by ASTM greased lamb’s wool pad to remove scum or dirt. Wipe off
methods shall be mutually agreed upon between the purchaser water with clean cheesecloth and dry the panel for 2 h.
and the seller. Calculate the loss of gloss from gloss measurements made
5.1.1 Chemical Analysis of Dry Pigment—Test Methods before and after exposure. After exposure, determine the
D 126. The lead chromate analysis should be conducted in directional reflectance for each panel as described in Test
accordance with 11.1 of Test Methods D 126; the procedure Method E 97. Calculate the color change or lightness-
outlined in 11.2 is not applicable. difference estimate (DL) as follows:
5.1.2 Coarse Particles—Test Methods D 185. DL 5 K~Y2½ 2 Y1½! (1)
5.1.3 Mass Color and Tinting Strength—Test Method
D 387. where:
5.1.4 Resistance to Loss of Gloss, Chalking, and Color Y1 5 luminous directional reflectance of the panel mea-
Change: sured before exposure,
5.1.4.1 A test enamel shall be prepared consisting of ingre- Y2 5 reflectance measured after exposure, and
K 5 100 when the reflectances are expressed as decimal
dients conforming to the applicable specifications in the
fractions or 10 if reflectances are expressed in
following proportions:
percent.
Weight
Ingredient Percent The color change for the coating shall be the average
Pigment under test 30 to 34
obtained for the two panels.7
Alkyd resin vehicle solids, minA 28
Total solids, min 60 6. Keywords
B, C
Mineral spirits
Driers D, E 6.1 chrome orange; chrome yellow; lead chromate; orange
_________________ pigments; pigments; yellow pigments
A
An alkyd resin solution conforming to Type III of Federal Specification
7
TT-R-266 is suggested. The method of determining the lightness-difference estimate is described in
B detail in example 4, “Photoelectric Tristimulus Colorimetry with Three Filters,”
See Specification D 235.
C
As required to give a Stormer consistency of 100 to 150 g at 200 r/min as Circular C429, Nat. Bureau Standards.
2

Sampling and Testing Turpentine1
1. Scope D 3009 Test Method for Composition of Turpentine by Gas

1.1 These test methods cover procedures for sampling and Chromatography5
testing turpentine, as defined by the Naval Stores Act2 and E 1 Specification for ASTM Thermometers7
Terminology D 804.3 These test methods are also used for the 3. Significance and Use
sampling and testing of pinenes, the major components of most
turpentines. 3.1 The test procedures described in this standard were
1.2 These test methods primarily measure the physical developed when the chief use for turpentine was as a solvent.
rather than the chemical properties of turpentines and pinenes. Currently however, the chief use for turpentine (and pinenes) is
As turpentines and pinenes are currently used chiefly as as raw materials for the production of resins and synthetic
chemical raw materials for the production of resins and organic chemicals. Thus the chemical composition of turpen-
synthetic organic chemicals, chemical composition is also very tines and pinenes is extremely important and tests, in addition
important. Consequently, testing the chemical composition of to the ones described in these test methods, are required in
turpentines and pinenes by gas chromatography has displaced order to fully characterize turpentines and pinenes. The most
these test methods to a large extent. (See for example Test widely used technique for determining the chemical composi-
Method D 3009.) tion of turpentines (and pinenes) is gas chromatography (see
1.3 The values stated in inch-pound units are tobe regarded Test Method D 3009).
as the standard. The values given in parentheses are for 4. Purity of Reagents
information only.
1.4 This standard does not purport to address all of the 4.1 Reagent grade chemicals shall be used in all tests.
safety concerns, if any, associated with its use. It is the Unless otherwise indicated, it is intended that all reagents shall
responsibility of the user of this standard to establish appro- conform to the specifications of the Committee on Analytical
priate safety and health practices and determine the applica- Reagents of the American Chemical Society, where such
bility of regulatory limitations prior to use. specifications are available.8 Other grades may be used, pro-
vided it is first ascertained that the reagent is of sufficiently
2. Referenced Documents high purity to permit its use without lessening the accuracy of
2.1 ASTM Standards: the determination.
D 86 Test Method for Distillation of Petroleum Products3 4.2 Unless otherwise indicated, references to water shall be
D 270 Method of Sampling Petroleum and Petroleum Prod- understood to mean reagent water conforming to Specification
ucts4 D 1193.
D 804 Terminology Relating to Naval Stores, Including Tall SAMPLING
Oil and Related Products5
D 1193 Specification for Reagent Water6 5. Sampling
5.1 The method of sampling specified in 5.2 or 5.3 shall be
used, according to the special conditions that apply.
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint 5.2 From Loaded Tank Car or Other Large Vessel—The
and Related Coatings, Materials, and Applications, and are the direct responsibility composite sample taken shall be not less than 1⁄2 gal (1.9 L) and
of Subcommittee D01.34 on Naval Stores.
Current edition approved Nov. 10, 1997. Published June 1998. Originally
7
published as D233 – 26. Last previous edition D233 – 92. Annual Book of ASTM Standards, Vol 14.03.
2 8
Naval Stores Act of 1923 (42 Stat 1435.7 USC-91-99) as amended in 1950 and Reagent Chemicals, American Chemical Society Specifications, American
regulations promulgated thereunder by the United States Department of Agriculture. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
3
Annual Book of ASTM Standards, Vol 05.01. listed by the American Chemical Society, see Analar Standards for Laboratory
4
Discontinued, See 1983 Annual Book of ASTM Standards, Vol 05.01. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
5
Annual Book of ASTM Standards, Vol 06.03. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
6
1
D 233
should consist of small samples of not more than 1 qt (0.9 L) the temperature of the liquid is above or below 15.6°C. If the
each, taken from near the top and bottom by means of a metal determination is made with apparatus calibrated for a tempera-
or glass container with removable stopper or top.9 This device, ture other than 15.6°C, the observed reading shall first be
attached to a suitable pole, shall be lowered to the desired calculated to density at the temperature of observation, then
depth, the stopper or top removed, and the container allowed to converted to density at 15.6°C by applying the above factor,
fill. If a sample from close to the bottom of a tank shows a and finally converted to specific gravity by dividing the
decided difference in color or appearance from samples taken calculated density by 0.999 (the density of water at 15.6°C).
at other depths, an extra bottom sample shall be taken and
examined separately from the composite sample. In such case, REFRACTIVE INDEX
the composite sample shall not include any portion of such 10. Procedure
bottom sampling.
10.1 Determine the refractive index with an accurate instru-
5.3 From Barrels and Drums—At least 5 % of the packages
ment, at 20°C if possible. If determined at any other tempera-
in any shipment shall be represented in the sample. The
ture, correct the reading obtained to 20°C by adding or
purchaser may increase the percentage of packages to be
subtracting 0.00045 for each degree Celsius that the tempera-
sampled at his direction, and it is recommended that every
ture at which the determination was made is, respectively,
package be sampled in the case of expensive terpene hydro-
above or below 20°C.
carbons that are bought in small quantity. A portion shall be
withdrawn from about the center of each package sampled by DISTILLATION
means of a “thief” or other sampling device. The composite
sample thus obtained shall be not less than 1 qt (0.9 L) and 11. Apparatus
shall consist of equal portions of not less than 1⁄2 pt (0.24 L) 11.1 Use the type of distillation apparatus described in Test
from each package sampled. Method D 86, with the following exceptions:
11.1.1 For testing turpentine or pinene use an ASTM Tur-
DETECTION AND REMOVAL OF SEPARATED pentine Distillation Thermometer, 3-in. (76-mm) partial im-
WATER mersion, having a range from 147 to 182°C, and conforming to
the requirements for Thermometer 27C as prescribed in Speci-
6. Procedure
fication E 1, or an ASTM Solvents Distillation Thermometer,
6.1 Draw a portion by means of a glass or metal container 3.94-in. (100-mm) partial immersion, having a range from 95
with a removable stopper or top,9 or with a “thief,” from the to 255°C, and conforming to the requirements for Thermom-
lowest part of the container, or by opening the bottom valve of eter 42C as prescribed in Specification E 1.
the perfectly level tank car. If water is found in this sample, 11.1.2 Ice is not necessary in the condenser bath. It is
draw it all out, record the quantity, and deduct it from the total permissible to use a glass Liebig condenser 22 in. (560 mm) in
volume of liquid delivered. length with 16 in. (410 mm) in contact with the cooling water
and filled with an adapter to extend 1 in. (51 mm) into the
APPEARANCE receiving graduate.
7.1 Examine a portion of the sample after agitation to 12.1 Using the receiving graduate, transfer exactly 100 mL
determine whether its appearance conforms to specifications. of the sample directly into the flask, allowing none to run into
the side tube. If the sample contains dissolved or suspended
ODOR
water it is advisable to add a few small pieces of pumice or
8. Procedure broken glass to promote smooth distillation. Insert the ther-
mometer, so that the top of the mercury bulb (or the top of the
8.1 Compare the odor of the sample with an agreed-upon
contraction chamber if the Solvents Distillation Thermometer
water-free reference sample kept in the dark in a completely
is used) is level with the bottom of the side tube. Connect the
filled, well-stoppered bottle. In the absence of such a sample,
side tube to the condenser, with the bottom of the flask resting
compare with samples of known purity similarly preserved.
securely in the opening in the asbestos board. Apply heat
SPECIFIC GRAVITY cautiously, and regulate it so that the first drop of condensate
falls from the condenser in not less than 5 nor more than 10
9. Procedure min. Record as the initial boiling point the thermometer
9.1 Determine the specific gravity at 15.6/15.6°C by any reading when the first drop falls from the end of the condenser,
convenient method having a precision of 0.0005. Determina- correcting for barometric pressure as described in Section 13.
tions made at any other temperature using apparatus standard- When the distillation begins, regulate the heat so that the
ized at 15.6°C shall be corrected by adding to or subtracting distillate is collected at a rate of not less than 4 nor more than
from the observed reading 0.00082 for each degree Celsius that 5 mL/min (approximately 2 drops/s). Discontinue the distilla-
tion when the temperature reaches that specified for the
minimum percentage requirement (usually 170°C for turpen-
9
Detailed description of equipment suitable for such sampling is given in tine), after correcting for barometric pressure. Allow the
Method D 270. condenser to drain and read the percentage distilled.
2
D 233
12.2 The percentages distilled below successive selected TABLE 1 Temperature Corrections for Barometric PressureA
temperatures and the temperature at which each successive 10 Observed Mercurial Barometer
mL distills may also be determined, if desired, making the Barometric Aneroid Temperature of Barometer
Pressure, Barometer
necessary correction of the temperature for barometric pres- mm 20°C 25°C 30°C 35°C
sure. 780 − 1.04 − 0.91 − 0.88 − 0.84 − 0.81
770 − 0.52 − 0.39 − 0.36 − 0.32 − 0.29
13. Barometric Correction 760 0.00 + 0.13 + 0.16 + 0.19 + 0.22
750 + 0.52 + 0.65 + 0.68 + 0.71 + 0.74
13.1 The distilling temperature of turpentine (and pinene) is 740 + 1.04 + 1.17 + 1.20 + 1.23 + 1.26
affected by 0.052°C for each millimetre (1.32°C for each inch) 730 + 1.56 + 1.68 + 1.71 + 1.75 + 1.78
variation of the atmospheric pressure. Therefore, the distilla- 720 + 2.08 + 2.20 + 2.23 + 2.26 + 2.29
710 + 2.62 + 2.72 + 2.75 + 2.78 + 2.81
tion temperatures observed or specified shall be corrected to 700 + 3.16 + 3.24 + 3.27 + 3.30 + 3.33
permit distillation to be conducted as though the barometer A
These corrections are calculated as follows: The observed barometric pres-
reading, corrected to 0°C, were exactly 760 mm (30 in.). sure is first corrected to what it would be at 0°C, by means of the table in Circular
13.2 When about to begin the distillation, observe and F, Instrument Division, U. S. Weather Bureau. The corrected barometric pressure
is then subtracted from 760 mm (or vice versa) and the difference multiplied by
record the barometric pressure and the temperature of the 0.052°C to give the temperature correction shown in this table. The correction
barometer. (No temperature correction is necessary for factor, C, of 0.052°C was calculated using the Sydney-Young equation:
aneroid-type barometers.) From Table 1 determine the proper C 5 0.00012(760 − P)(273 + T)
where:
temperature correction corresponding to these atmospheric P 5 observed pressure, corrected to 0°C, in millimetres, and
conditions, interpolating to the nearest 0.1°C. If the barometric T 5 median boiling temperature for turpentine, 160°C.
pressure, corrected to 0°C, is below 760 mm, the temperature
correction must be added to the initial boiling point and
designated apparatus with the accepted or specific color
subtracted from the minimum percentage requirement tempera-
ture; if above 760 mm, the correction must be subtracted from standard.
the initial boiling point and added to the minimum percentage
requirement temperature. 15. Precision and Bias
NOTE 1—Example—Suppose the observed barometric pressure is 748 15.1 The procedures described in these test methods were
mm at 32°C, and the initial boiling point is observed to be 155.2°C. From developed many years ago and were once widely used for the
Table 1 the temperature correction is seen to be 0.8°C. Therefore, the sampling and testing of turpentines and pinenes. Currently they
corrected boiling point is 155.2 + 0.8 5 156°C. Furthermore, the tempera- are not widely used and it is not considered practical to
ture observation point at the minimum percentage requirement (170°C at
redetermine the precision and bias of the individual methods at
760 mm) must be altered to the same extent. Since the turpentine is
distilling 0.8°C below what it would at normal pressure, distillation must this time.
be discontinued at 169.2°C to determine the percentage distilling below
170°C at 760 mm pressure. 16. Keywords
14. Color
16.1 pinene; sampling; turpentine
14.1 Compare the color of the sample in any suitable or
3

Raw Linseed Oil1
1. Scope TABLE 1 Properties of Raw Linseed Oil
1.1 This specification covers raw linseed oil. ASTM

Property Requirement
Method
2. Referenced Documents Specific gravity, 25/25°C 0.926 to 0.931 D 1963

2.1 ASTM Standards: Saponification value 189.0 to 195.0 D 1962
D 93 Test Methods for Flash Point by Pensky-Martens Unsaponifiable matter, max, % 1.50 D 1965
Iodine value (Wijs), min 177 D 1959
Closed Tester2 Loss on heating at 105 to 110°C, 0.2 D 1960
D 555 Guide for Testing Drying Oils3 max, %
D 1466 Test Method for Sampling Liquid Oils and Fatty Clarity clear and transpar- D 2090
ent at 65°C
Acids Commonly Used in Paints, Varnishes, and Related Color (Gardner), max 13 D 1544
Materials3 Foots, volumetric, heated oil, max, % 1.0 D 1954
D 1544 Test Method for Color of Transparent Liquids Foots, volumetric, chilled oil, max, % 4.0 D 1954
Gravimetric foots, max % 0.25 D 1966
(Gardner Color Scale)4 Flash point, min, °F 250 D 93
D 1639 Test Method for Acid Value of Organic Coating
Materials3
D 1954 Test Method for Foots in Raw Linseed Oil (Volu- D 2090 Test Method for Clarity and Cleanness of Paint and
metric Method)3 Ink Liquids3
D 1959 Test Method for Iodine Value of Drying Oils and 3. Properties
Fatty Acids3
3.1 Linseed oil shall be the oil obtained from flaxseed and
D 1960 Test Method for Loss on Heating of Drying Oils3
shall conform to the requirements given in Table 1.
D 1962 Test Method for Saponification Value of Drying
Oils, Fatty Acids, and Polymerized Fatty Acids3 NOTE 1—It is recognized that raw linseed oil is a natural product and
D 1963 Test Method for Specific Gravity of Drying Oils, that, in unusual crop years, the color, iodine value and acid value may vary
from the stated specification limits. In this case the limits shall be agreed
upon between the purchaser and the supplier.
D 1965 Test Method for Unsaponifiable Matter in Drying
Oils, Fatty Acids, and Polymerized Fatty Acids3 4. Test Methods
D 1966 Test Method for Foots in Raw Linseed Oil (Gravi- 4.1 Sampling—Sampling should be conducted in accor-
metric Method)3 dance with Test Method D 1466.
1
determined in accordance with the applicable ASTM methods
and Related Coatings, Materials, and Applications, and is the direct responsibility of listed in Table 1. The significance of the methods of testing
D01.32 on Drying Oils. enumerated under properties in this specification is discussed
Current edition approved June 25, 1982. Published September 1982. Originally in Guide D 555.
published as D234 – 26 T. Last previous edition D234 – 72 (1976).
2
3
4
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; linseed oil
1

Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry
Cleaning Solvent)1
1. Scope * D 1296 Test Method for Odor of Volatile Solvents and

1.1 This specification covers four types of hydrocarbon Diluents3
solvents, normally petroleum distillates, used primarily in the D 2710 Test Method for Bromine Index of Petroleum Hy-
coatings and dry-cleaning industries. “Mineral spirits” is the drocarbons by Electrometric Titration4
most common name for these solvents. They are also called D 3227 Test Method for Mercaptan Sulfur in Gasoline,
“Stoddard Solvents” when used for dry cleaning. Kerosine, Aviation Turbine, and Distillate Fuels (Potentio-
1.2 For specific hazard information and guidance, see the metric Method)4
supplier’s Material Safety Data Sheet for materials listed in this D 3257 Test Method for Aromatics in Mineral Spirits by
specification. Gas Chromatography3
1.3 The following hazard caveat pertains only to the test D 3278 Test Method for Flash Point of Liquids by Small
method portion, 6.1.10, of this specification. This standard Scale Closed-Cup Apparatus5
does not purport to address all of the safety concerns, if any, E 300 Practice for Sampling Industrial Chemicals6
associated with its use. It is the responsibility of the user of this 2.2 U.S. Federal Specification:
standard to establish appropriate safety and health practices PPP-C-2020 Chemical, Liquid, Dry, and Paste: Packaging
and determine the applicability of regulatory limitations prior of7
to use. 3. Classification
2. Referenced Documents 3.1 Mineral spirits shall be of the following types as
2.1 ASTM Standards: specified:
D 56 Test Method for Flash Point by Tag Closed Tester2 3.1.1 Type I—Full Range.
D 86 Test Method for Distillation of Petroleum Products at 3.1.2 Type II—High Flash Point.
Atmospheric Pressure2 3.1.3 Type III—Odorless.
D 130 Test Method for Detection of Copper Corrosion from 3.1.4 Type IV—Low Dry Point.
Petroleum Products by the Copper Strip Tarnish Test2 3.2 Mineral spirits types may be further differentiated based
D 156 Test Method for Saybolt Color of Petroleum Prod- on aromatics content as follows:
ucts (Saybolt Chromometer Method)2 3.2.1 Class A—8 to 22 vol % aromatics.
D 268 Guide for Sampling and Testing Volatile Solvents 3.2.2 Class B—2 to 8 max vol % aromatics.
and Chemical Intermediates for Use in Paint and Related 3.2.3 Class C—less than 2 vol % aromatics.
Coatings and Materials3
4. Properties
D 1133 Test Method for Kauri-Butanol Value of Hydrocar-
bon Solvents3 4.1 The physical and chemical properties of the different
D 1159 Test Method for Bromine Number of Petroleum types and classes of mineral spirits shall conform to the
Distillates and Commercial Aliphatic Olefins by Electro- requirements specified in Table 1.
metric Titration2 5. Sampling
D 1209 Test Method for Color of Clear Liquids (Platinum-
Cobalt Scale)3 5.1 The material shall be sampled in accordance with
Practice E 300.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paints
4
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Annual Book of ASTM Standards, Vol 05.02.
5
Current edition approved Dec. 10, 1999. Published February 2000. Originally Annual Book of ASTM Standards, Vol 06.01.
6
published as D 235 – 26. Last previous edition D 235 – 95. Annual Book of ASTM Standards, Vol 15.05.
2 7
Annual Book of ASTM Standards, Vol 05.01. Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
3
Annual Book of ASTM Standards, Vol 06.04. Robbins Ave., Philadelphia, PA 19111-5094.
*A Summary of Changes section appears at the end of this standard.

1
D 235
TABLE 1 Physical and Chemical Properties of Mineral Spirits
Type I Full Range Mineral Spirits ? Type II High Flash Point
Class A Class B A
Class C A
? Class A Class BA Class CA
Aromatic Content, range, vol % 8–22 2–8 max 0–2 8–22 2–8 max 0–2
Commercial reference regular rule 66 low aromatic regular rule 66 low aromatic
Appearance clear and free of suspended matter when observed at 60–78°F
Flash point, °F (°C), min 100 (38) 100 (38) 100 (38) 142 (61) 142 (61) 142 (61)
Color, min not darker than + 25 on Saybolt Scale or 25 on Pt-Co Scale
Kauri-Butanol value,
min 29 29 28 29 29 28
max 45 45 40 45 45 40
Bromine Number, max 5 1 0.1 5 1 0.1
OdorB characteristic, as agreed between purchaser and supplier
Doctor test negative
Distillation, °F (°C)
Initial boiling point, min 300 (149) 300 (149) 300 (149) 350 (177) 350 (177) 350 (177)
50 % Recovered, max 360 (182) 360 (182) 360 (182) 390 (199) 390 (199) 390 (199)
Dry point, max 415 (213) 415 (213) 415 (213) 415 (213) 415 (213) 415 (213)
Residue from distillation:
Vol %, max 1.5
Acidity neutral
Copper corrosion, max rating 2A
Apparent Specific Gravity 60/60°F
(15.6/15.6°C)
min 0.754 0.754 0.754 0.768 0.768 0.768
max 0.820 10.810 0.800 0.820 0.810 0.810
Type III OdorlessC ? Type IV Low Dry Point
Class C-1A Class C-2A ? Class A Class BA Class CA
Aromatic Content, range, vol % 0–0.25 0–0.25 8–22 2–8 max 0–2
Commercial Reference odorless odorless regular rule 66 low aromatic
Appearance clear and free of suspended matter when observed at 60–78°F
Flash Point, °F (°C), min 100 (38) 100 (38) 100 (38) 100 (38) 100 (38)
Color, min not darker than + 25 on Saybolt Scale or 25 on Pt-Co Scale
Kauri-Butanol value,
min ... ... 29 29 28
max 29 29 45 45 40
Bromine Number, max 0.1 5 5 1 0.1
OdorB characteristic as agreed between purchaser and supplier
Doctor Test negative
Distillation, °F (°C)
Initial boiling point, min 300 (149) 300 (149) 300 (149) 300 (149) 300 (149)
50 % Recovered, max 385 (196) 385 (196) 345 (174) 345 (174) 345 (174)
Dry point, max 415 (213) 415 (213) 365 (185) 365 (185) 365 (185)
Residue from distillation
Vol% , max 1.5
Acidity neutral
Copper Corrosion, max rating 2A
Apparent Specific Gravity 60/60°F
(15.6/15.6°C)
min 0.740 0.740 0.754 0.754 0.754
max 0.775 0.775 0.810 0.800 0.790
A
Mineral Spirits of Types I, II, III, and IV may be commercially available as Classes B and C to meet certain air pollution regulations (for example, “Rule 66”) which set
maximum limits on certain constituents as follows: toluene and ethylbenzene 20 vol %, C8 and higher aromatics 8 vol %, olefins 5 vol %; the sum of all restricted
constituents not to exceed 20 vol %.
B
Optional: Test for odor only when agreed as necessary by purchaser and supplier.
C
Only products that have a very high isoparaffinic hydrocarbon content, that is, approaching 100 %, are considered to fit the odorless category. Type III Class C-1 is
hydrogenated product; Class C-2 is a distillation fraction.
6. Test Methods 6.1.4 Distillation—Test Method D 86.

6.1 The properties enumerated in this specification shall be 6.1.5 Flash Point—Test Method D 56 or Test Method
determined in accordance with the following ASTM test D 3278. In case of dispute, Test Method D 56 shall be the
methods: referee method.
6.1.1 Bromine Number—Test Method D 1159. Bromine 6.1.6 Kauri-Butanol Value—Test Method D 1133.
number is expressed as g bromine reacted per 100-g sample. 6.1.7 Odor—Test Method D 1296. Samples of particular
For products having low olefin contents, Bromine Index (mg types of products being tested, having odor characteristics
bromine reacted per 100-g sample) by Test Method D 2710 satisfactory to consumer and producer, are to be used as
may be used. reference standards for comparison.
6.1.2 Color—Test Method D 156 or Test Method D 1209. In 6.1.8 Mercaptan Sulfur—Test Method D 3227.
case of dispute, Test Method D 156 shall be the referee method. 6.1.9 Apparent Specific Gravity—Determine the apparent
6.1.3 Corrosion—Test Method D 130. Perform test under specific gravity by any convenient method that is accurate to
the prescribed conditions for 3 h at 100°C. the third decimal place, the temperature of both specimen and
2
D 235
water being 15.6°C. See Guide D 268. masked, consider the test positive and the solvent as “sour”. If
6.1.10 Doctor Test: the sample remains unchanged in color and the sulfur film is
6.1.10.1 Preparation of Doctor (Sodium Plumbite) bright yellow or only slightly discolored with gray or flecked
Solution—Dissolve approximately 125 g of sodium hydroxide with black, consider the test negative and the solvent as
(NaOH) in 1 L of reagent water. Add 60 g of lead monoxide “sweet”.
(PbO) and shake vigorously for 15 min., or let stand with 6.1.10.4 If the doctor test result is positive, mercaptan
occasional shakings for at least a day. Allow to settle and content may be determined using Test Method D 3227 and
decant or siphon off the clear liquid. If the solution does not reported.
settle clear, filter it through filter paper. Keep the solution in a 6.1.11 Aromatics—Test Method D 3257.
tightly corked bottle and refilter before use if not perfectly
clear. 7. Packaging and Package Marking
6.1.10.2 Procedure—Shake vigorously together in a test 7.1 Package size shall be agreed upon by the purchaser and
tube 10 mL of the solvent being tested and 5 mL of sodium the supplier.
plumbite solution for about 15 s. Add a small amount of pure, 7.2 Packaging shall conform to applicable carrier rules and
dry flowers of sulfur so that practically all of it floats on the regulations or when specified shall conform to Fed. Spec.
interface between the solvent and the sodium plumbite solution PPP-C-2020.
after shaking. Again shake for 15 s, allow to settle and observe
within 2 min. 8. Keywords
6.1.10.3 Interpretation of Results—If the solvent is discol- 8.1 Doctor test; hydrocarbon dry cleaning solvents; mineral
ored or if the yellow color of the sulfur film is noticeably spirits; solvents; Stoddard Solvent
SUMMARY OF CHANGES
Committee D-1 has identified the location of selected changes to this standard since the last date of issue that
may impact the use of this standard.
(1) Added Test Method D 2710, Test Method for Bromine (4) In Table 1, Type III Odorless, changed current Class C to
Index, to Referenced Documents section. Class C-1, and added Class C-2 (which has much higher olefin
(2) Under Test Methods, 6.1.1 Bromine Number, added Test content and bromine number) to distinguish it from Class C-1
Method D 2710 Bromine Index, as an optional test method that products. Class C-2 has a bromine number of 5 max.
may be used for products having low olefin contents. Defined (5) In Table 1 FootnoteC, indicated that Type III Class C-1 is
units of bromine number and bromine index. hydrogenated product; Class C-2 is a distillation fraction.
(3) In Table 1, changed maximum apparent specific gravity of
Type II Class C from 0.800 to 0.810 to reflect current
commercial products.
3

Orange Shellac and Other Lacs1
1. Scope 3. Physical Properties

1.1 This specification covers three types and four grades of 3.1 The material shall conform to the requirements pre-
orange shellac and other lac, as follows: scribed in Table 1.
1.1.1 Type I, orange shallac, grades A, B, C, and D, NOTE 1—Type II customarily occurs in the form of circular disks about
1.1.2 Type II, button lac, and 3 in. (76 mm) in diameter and 1⁄8 in. (3.2 mm) in thickness and is known
1.1.3 Type III, garnet lac. to the trade as pure button lac. Type III is dark garnet in color and is
1.2 Stick-lac and seed-lac are not covered by this specifica- known to the trade as pure garnet lac. Garnet lac also is manufactured in
tion. admixture with rosin and as a dewaxed lac, but these are not covered by
this specification.
4. Test Methods
2.1 ASTM Standards:
D 29 Test Methods for Sampling and Testing Lac Resins2 4.1 The material shall be sampled and the properties enu-
merated in this specification shall be determined in accordance
1
with Test Methods D 29.
and Related Coatings Materials and Applications and is the direct responsibility of 5. Keywords
Current edition approved Sept. 30, 1957. Published November 1957. Originally 5.1 lac; orange shellac; shellac
published as D237 – 26. Last previous edition D237 – 55.
2
1
D 237
TABLE 1 Requirements for Orange Shellac and Other Lacs
Type I Type II Type III
Grade A Grade B Grade C Grade D ... ...
Matter insoluble in specified hot solvents, max, % 1.00 1.25 1.50 3.00 1.00 0.50
Iodine number, max 15.0 15.0 15.0 15.0 15.0 18.0
Moisture, max, % 2.0 2.0 2.0 2.0 2.0 2.0
Wax, max,% 5.5 5.5 5.5 5.5 5.5 3.5
Orpiment, max, % 0.03 0.03 0.03 0.2 0.03 0.03
Matter soluble in water, max, % 0.5 0.5 0.5 0.5 0.5 0.5
Ash, max, % 1.0 1.0 1.0 1.0 0.5 0.5
Rosin none none none none none ...
Color when specified, the color shall be no darker than that of a sample agreed upon between the seller and the
purchaserA
A
Attention is called to the fact that the seller and the purchaser must agree upon one of the two methods for determining color appearing in Test Methods D 29.
2

Boiled Linseed Oil1
1. Scope D 1960 Test Method for Loss on Heating of Drying Oils3

1.1 This specification covers two types of boiled linseed oil: D 1962 Test Method for Saponification Value of Drying
1.1.1 Type I, Regular Boiled, and Oils, Fatty Acids, and Polymerized Fatty Acids3
1.1.2 Type II, Double Boiled. D 1963 Test Method for Specific Gravity of Drying Oils,
2. Referenced Documents D 1965 Test Method for Unsaponifiable Matter in Drying
2.1 ASTM Standards: Oils, Fatty Acids, and Polymerized Fatty Acids3
D 564 Test Methods for Liquid Paint Driers2 D 2090 Test Method for Clarity and Cleanness of Paint and
D 1475 Test Method for Density of Paint, Varnish, Lacquer, Ink Liquids3
and Related Products2
3. Properties
D 1544 Test Method for Color of Transparent Liquids
(Gardner Color Scale)2 3.1 Boiled linseed oil shall conform to the requirements
D 1639 Test Method for Acid Value of Organic Coating shown in .
Materials3
4. Test Methods
D 1951 Test Method for Ash in Drying Oils and Fatty
Acids3 4.1 The properties enumerated in this specification shall be
D 1953 Test Method for Drying Properties of Drying Oils4 determined in accordance with the appropriate ASTM methods
D 1959 Test Method for Iodine Value of Drying Oils and given in Table 1.
Fatty Acids3 5. Keywords
5.1 boiled linseed oil; linseed oil
1
Subcommittee D01.32 on Drying Oils.
Current edition approved March 27, 1986. Published May 1986. Originally
published as D 260 – 27 T. Last previous edition D 260 – 80.
2
3 4
Annual Book of ASTM Standards, Vol 06.03. Discontinued; see 1980 Annual Book of ASTM Standards, Part 29.
1
D 260
TABLE 1 Physical Properties

Type I Type II ASTM Methods
Specific gravity, 25/25°C 0.928 to 0.938 0.930 to 0.945 D 1963, D 1475
Acid value, max 7.5 8.0 D 1639
Saponification value 189 to 195 190 to 198 D 1962
Unsaponifiable matter, max, % 1.5 1.5 D 1965
Iodine value (Wijs), min 170 165 D 1959
Loss on heating at 105 to 110°C, max, % 0.4 0.6 D 1960
Appearance at 65°C clear and transparent clear and transparent D 2090
Gardner color, max 15, approximately 15, approximately D 1544
Set-to-touch time, max, h 16 8 D 1953
Ash, max, % 0.50 0.60 D 1951, D 564
2

Iron Blue Pigment1
1. Scope tinting strength, are considered a better measure of value than the
percentages of chemical constituents.
1.1 This specification covers the dry pigment commercially
known as Prussian blue, Chinese blue, Milori blue, or iron 4. Sampling
blue. 4.1 Two samples shall be taken at random from different
2. Referenced Documents packages from each lot, batch, day’s pack, or other unit or
2.1 ASTM Standards:
between units or production appear, samples shall be taken
D 387 Test Method for Color and Strength of Color Pig-
from different packages in the ratio of two samples for each 5
tons (inch-pound or SWI), except that for shipments of less
D 1135 Test Methods for Chemical Analysis of Blue Pig-
than 10 000 lb two samples shall be taken. At the option of the
ments3
3. Composition and Properties blending in equal quantities the samples from the same
3.1 The pigment shall be the blue product formed by the
reaction of a solution of iron salts with a ferrocyanide or 5. Test Methods
ferricyanide solution. It shall be free from admixture of any
substances other than those added during manufacture, in small
priate ASTM test methods. Test procedures not covered by
amounts up to a total of 5 %, for the purpose of improving the
ASTM test methods shall be mutually agreed upon between the
quality or working properties, or both, of the pigment. Extend-
ers, and diluents such as barium sulfate, silica, silicates,
5.2 Identification—Test Methods D 1135.
calcium carbonate, calcium sulfate, magnesium carbonate, etc.,
5.3 Extenders and Diluents—Test Methods D 1135.
shall be absent. The pigment shall conform to the following
5.4 Total Matter Soluble in Water— Matter soluble in water
requirements:
shall be determined by either of the following methods, as
Total matter soluble in water, max, % 1.0
Moisture, max, % 8.0
mutually agreed upon between the purchaser and the seller:
Organic colors or lakes none 5.4.1 Water-Soluble Matter by Extraction— Test Methods
Acidity or alkalinity—the acidity or alkalinity of the aqueous extract, with methyl D 1135.
orange indicator, shall not exceed the chemical equivalent of 0.1 % of sulfuric
acid, calculated on the dry pigment.
5.4.2 Water-Soluble Salts by Electrical Conductivity—Test
Methods D 1135.
3.2 The mass color and character of the tint and the tinting 5.5 Moisture in Dry Pigment—Moisture shall be determined
strength formed by a mixture with a white pigment shall be by either of the following methods, as mutually agreed upon
within mutually agreed upon limits of a standard acceptable to between the purchaser and the seller:
both the purchaser and the seller. 5.5.1 Brabender Moisture Tester—Test Methods D 1135.
5.5.2 Toluene Distillation—Test Methods D 1135.
NOTE 1—The physical properties and tests of iron blue, particularly the
5.6 Organic Colors or Lakes—Test Methods D 1135.
5.7 Mass Color and Tinting Strength— Test Method D 387.
1
and Related Coatings, Materials, and Applications, and is the direct responsibility of 6. Keywords
Subcommittee D 01.31 on Pigment Specifications. 6.1 iron blue; Milori blue; pigment; Prussian blue; tint;
Current edition approved Oct. 31,1975. Published December 1975. Originally
published as D 261 – 27 T. Last previous edition D 261 – 47 (1970).
tinting strength
2
3
1
D 261
2

Ultramarine Blue Pigment1
1. Scope Matter soluble in water, max, % 1.5

1.1 This specification covers the dry pigment commercially Coarse particles (total residue retained on a No. 325 1.0
known as ultramarine blue, suitable for use in paints, enamels, (45-µm) sieve), max, %
lacquers, and similar products. Organic colors or lakes none
strength formed by mixture with a white pigment shall be
2.1 ASTM Standards: within mutually agreed upon limits of a standard acceptable to
D 185 Test Methods for Coarse Particles in Pigments, both the purchaser and the seller.
Pastes, and Paints2
D 280 Test Methods for Hygroscopic Moisture (and Other 4. Sampling
Matter Volatile Under the Test Conditions) in Pigments2 4.1 Two samples shall be taken at random from different
D 387 Test Method for Color and Strength of Color Pig- packages from each lot, batch, day’s pack, or other unit of
ments with a Mechanical Muller3 production in a shipment. When no markings distinguishing
D 1135 Test Methods for Chemical Analysis of Blue Pig- between units of production appear, samples shall be taken
ments2 from different packages in the ratio of two samples for each 5
D 1208 Test Methods for Common Properties of Certain tons (inch-pound or SI), except that for shipments of less than
Pigments2 10 000 lb two samples shall be taken. At the option of the
3. Composition and Properties
blending in equal quantities the samples from the same
3.1 The pigment shall be a manufactured product obtained production unit to form a composite sample.
by the calcining of mixtures of clays and silicas with sodium
salts, sulfur, and carbonaceous material. It shall be a soft, dry, 5. Test Methods
finely ground powder of good blue color, free of admixtures of 5.1 Tests shall be conducted in accordance with the follow-
color substances, and shall conform to the following require- ing methods. Test procedures not covered by ASTM methods
ments: shall be mutually agreed upon between the purchaser and the
seller.
5.2 Identification—Test Methods D 1135.
5.3 Matter Soluble in Water—Test Methods D 1135.
5.4 Moisture and Other Volatile Matter in Dry Pigment—
Method A of Test Methods D 280 or Test Method D 1208.
5.6 Organic Colors or Lakes—Section 18 of Test Methods
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint D 1135.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.7 Mass Color and Tinting Strength— Test Method D 387.
Subcommittee D 01.31 on Pigment Specifications.
Current edition approved Oct. 30, 1981. Published December 1981. Originally 6. Keywords
published as D 262 – 41 T. Last previous edition D 262– 75.
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 pigment; tint; tinting strength; ultramarine blue; white
3
Annual Book of ASTM Standards, Vol 06.01. pigment
1
D 262
2

Chrome Oxide Green Pigment1
1. Scope strength formed by a mixture with a white pigment shall be

1.1 This specification covers the dry pigment commercially within mutually agreed upon limits of a standard acceptable to
known as chrome oxide green. both the purchaser and the seller.
2. Referenced Documents 4. Sampling

2.1 ASTM Standards: 4.1 Two samples shall be taken at random from different
D 126 Test Methods for Analysis of Yellow, Orange, and packages from each lot, batch, day’s pack, or other unit of
Green Pigments Containing Lead Chromate and Chro- production in a shipment. When no markings distinguishing
mium Oxide Green2 between units of production appear, samples shall be taken
D 185 Test Methods for Coarse Particles in Pigments, from different packages in the ratio of two samples for each
Pastes, and Paints2 10 000 lb (4540 kg) except that for shipments of less than
D 280 Test Methods for Hygroscopic Moisture (and Other 10 000 lb two samples shall be taken. At the option of the
Matter Volatile Under the Test Conditions) in Pigments2 purchaser, the samples may be tested separately or after
3. Composition and Properties production unit to form a composite sample.
3.1 The pigment shall consist of practically pure chromium
5. Test Methods
sesqui-oxide (Cr2O3) without any admixture, and shall con-
form to the following requirements: 5.1 Tests shall be conducted in accordance with the follow-
Total chromium (calculated as Cr2O3), min, % 97
ing methods where applicable. Test procedures not covered by
Total matter soluble in water, max, % 0.5 ASTM test methods shall be mutually agreed upon between the
Moisture and other volatile matter, max, % 0.5 purchaser and the seller.
325 (45-µm) sieve), max, %
5.2 Chromium Content—Test Methods D 126.
Organic colors or lakes none 5.3 Total Matter Soluble in Water— Test Methods D 126.
5.4 Moisture Content—Test Method D 280.
3.2 The mass color and character of the tint and the tinting 5.5 Coarse Particles— Test Methods D 185.
5.6 Organic Colors and Lakes—Test Methods D 126.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 6. Keywords
Subcommittee D01.31 on Pigment Specifications. 6.1 chrome oxide green; chromium sesqui-oxide; pigment;
Current edition approved Oct. 31, 1975. Published December 1975. Originally tint; tinting strength; white pigment
2
1

Gold Bronze Powder1
1. Scope properties the powder shall be mixed in the proportion of 3 to

1.1 This specification covers the materials commercially 4 lb (370 to 475 g/L) to a gallon (3.8 L) of the liquid. As thus
known as gold bronze, pale gold bronze, and rich gold bronze mixed it shall also give a free flowing, smooth, continuous
powders. coating in accordance with Test Method D 480.
NOTE 1—A suitable liquid is made by mixing spar varnish conforming
2. Referenced Documents to the U. S. Federal Specification for Water-Resisting Spar Varnish (No.
2.1 ASTM Standards: TT-V-121 h) with turpentine conforming to Specification D 13 in such
D 13 Specification for Spirits of Turpentine2 proportions that the mixture will have a viscosity of 0.65 to 0.85 poises (B
D 185 Test Methods for Coarse Particles in Pigments, to C on the Gardner-Holdt scale).
Pastes, and Paints2 3.4 The gold bronze powder shall be suitable for making
D 480 Test Methods for Sampling and Testing of Flaked gold bronze paint. It shall match in shade and fineness a
Aluminum Powders and Pastes2 reference sample mutually agreed upon by the purchaser and
2.2 U.S. Federal Specification: the seller.
TT-V-121h Water-Resisting Spar Varnish3
4. Sampling
3. Composition and Properties 4.1 Two samples shall be taken at random from different
3.1 The bronze powder shall be made from new ingot packages from each lot, batch, day’s pack, or other unit of
metals. It shall consist of fine polished flakes containing not production in a shipment. When no markings distinguishing
less than 3 % of fatty or oily matter (polishing lubricant) to between units of production appear, samples shall be taken
give good “leafing” properties. from different packages in the ratio of two samples for each 5
3.2 The residue retained on a No. 100 (150-µm) sieve, using tons (inch-pound or SI), except that for shipments of less than
alcohol as the wash liquid, shall not exceed 0.2 % (in accor- 10 000 lb two samples shall be taken. At the option of the
dance with Test Methods D 185). purchaser, the samples may be tested separately or after
3.3 The powder shall have good “leafing” properties. (By blending in equal quantities the samples from the same
“leafing” is understood the property of forming an apparently production unit to form a composite sample.
continuous brilliant film over the entire free surface of a
mixture of the powder in a suitable liquid (Note), within 1 min 5. Test Methods
after cessation of stirring the mixture.) In testing for leafing 5.1 Test shall be conducted in accordance with the appro-
priate methods of the American Society for Testing and
Materials, where applicable. Test procedures not covered by
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint ASTM methods shall be mutually agreed upon between the
Subcommittee D01.31 on Pigment Specifications. purchaser and the seller.
Current edition approved June 25, 1982. Published October 1982. Originally
published as D 267 – 27 T. Last previous edition D 267– 41 (1975). 6. Keywords
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 bronze powders; leafing; spar varnish
3
Available from Standardization Documents Order Desk, Bldg. 4, Section D,
700 Robbins Ave., Philadelphia, PA 19111-5094.
1
D 267
2
Standard Guide for

Sampling and Testing Volatile Solvents and Chemical
Intermediates for Use in Paint and Related Coatings and
Material1
1. Scope TABLE 1 List of Test Methods
1.1 This guide covers procedures for the sampling and Test Method Section ASTM Method
testing of volatile solvents used in the manufacture of paint, Acidity in:

Aromatic hydrocarbons 11 D 847
lacquer, varnish, and related products. The test methods are Volatile solvents 11 D 1613
listed in Table 1. Acid wash color of aromatics 23 D 848
1.2 This standard does not purport to address the safety Alcohols in ketones 18 D 2804, D 3329
Alkalinity in acetone 12 D 1614
concerns, if any, associated with its use. It is the responsibility Aromatics in mineral spirits 25 D 3257
of the user of this standard to consult and establish appropriate Color, platinum cobalt scale 6 D 1209
safety and health practices and determine the applicability of Copper corrosion test:
Aromatic hydrocarbons 14 D 849
regulatory limitations prior to use. Mineral spirits 14 D 1616
Distillation range:
2. Referenced Documents Aromatic hydrocarbons 7 D 850
Mineral spirits, turpentine 7 D 86
2.1 ASTM Standards: Volatile organic liquids 7 D 1078
D 13 Specification for Spirits of Turpentine2 Ester value 13 D 1617
D 56 Test Method for Flash Point by Tag Closed Tester3 Esters, purity 13 D 3545
Flash point:
D 86 Test Method for Distillation of Petroleum Products3 Pensky-Martens closed cup 17 D 93
D 93 Test Methods for Flash Point by Pensky-Martens Tag closed cup 17 D 56
Closed Cup Tester3 Tag open cup 17 D 1310
Setaflash tester 17 D 3278
D 156 Test Method for Saybolt Color of Petroleum Prod- Method surveys:
ucts (Saybolt Chromometer Method)3 Ethylene and propylene glycols 22 E 202
D 233 Methods of Sampling and Testing Turpentine2 Methanol 21 E 346
Nonaromatics in aromatics 24 D 2360
D 235 Specification for Mineral Spirits (Petroleum Spirits) Nonvolatile matter 8 D 1353
(Hydrocarbon Dry Cleaning Solvent)4 Odor 9 D 1296
D 329 Specification for Acetone4 Paraffins in aromatics 24 D 2360
Permanganate time for acetone and meth- 16 D 1363
D 611 Test Method for Aniline Point and Mixed Aniline anol
Point of Petroleum Products and Hydrocarbon Solvents3 Purity of ketones 18 D 2192,
D 847 Test Method for Acidity of Benzene, Toluene, Xy- D 2804,
D 3329, D 3893
lenes, Solvent Naphthas, and Similar Industrial Aromatic Sampling 4 E 300
Hydrocarbons4 Solvent power evaluation:
D 848 Test Method for Acid Wash Color of Industrial Aniline point and mixed aniline point of 19 D 611
petroleum products and hydrocarbon
Aromatic Hydrocarbons4 solvents
D 849 Test Method for Copper Strip Corrosion of Industrial Kauri-butanol value of hydrocarbon 19 D 1133
Aromatic Hydrocarbons4 solvents
Dilution ratio in cellulose nitrate solution 19 D 1720
D 850 Test Method for Distillation of Industrial Aromatic for active solvents, hydrocarbon dilu-
ents, and cellulose nitrates
Specific gravity 5 D 891, D 2935,
1
This guide is under the jurisdiction of ASTM Committee D-1 on Paint and D 3505, D 1555
Related Coatings, Materials, and Applications and is the direct responsibility of Sulfur as hydrogen sulfide and sulfur dioxide 15 D 853
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Water:
Current edition approved May 10, 1996. Published July 1996. Originally Fischer reagent titration method 10 D 1364, E 203
published as D 268 – 27 T. Last previous edition D 268 – 90 (1993)e1. Turbidity method 10 D 1476
2
Annual Book of ASTM Standards, Vol 06.03. Water miscibility of water-soluble solvents 20 D 1722
3
4
1
D 268
Hydrocarbons and Related Materials4 D 3545 Test Method for Alcohol Content and Purity of
D 853 Test Method for Hydrogen Sulfide and Sulfur Diox- Acetate Esters by Gas Chromatography4
ide Content (Qualitative) of Industrial Aromatic Hydrocar- D 3893 Test Method for Purity of Methyl Amyl Ketone and
bons4 Methyl Isoamyl Ketone by Gas Chromatography4
D 891 Test Methods for Specific Gravity, Apparent, of E 12 Terminology Relating to Density and Specific Gravity
Liquid Industrial Chemicals5 of Solids, Liquids, and Gases5
D 1078 Test Method for Distillation Range of Volatile E 201 Test Method for Calculation of Volume and Weight of
Organic Liquids4 Industrial Chemical Liquids5
D 1133 Test Method for Kauri-Butanol Value of Hydrocar- E 202 Test Methods for Analysis of Ethylene Glycols and
bon Solvents4 Propylene Glycols5
D 1209 Test Method for Color of Clear Liquids (Platinum- E 203 Test Method for Water Using Karl Fischer Reagent5
Cobalt Scale)4 E 300 Practice for Sampling Industrial Chemicals5
D 1296 Test Method for Odor of Volatile Solvents and E 346 Method for Analysis of Methanol5
Diluents4
D 1310 Test Method for Flash Point and Fire Point of 3. Significance and Use
Liquids by Tag Open-Cup Apparatus6 3.1 A brief discussion of each test method is given with the
D 1353 Test Method for Nonvolatile Matter in Volatile intent of helping the user in the selection of the most applicable
Solvents for Use in Paint, Varnish, Lacquer, and Related procedure where more than one is available.
Products4
D 1363 Test Method for Permanganate Time of Acetone 4. Sampling
and Methanol4 4.1 Representative samples are a prerequisite for the evalu-
D 1364 Test Method for Water in Volatile Solvents (Karl ation of any product. The directions for obtaining representa-
Fischer Reagent Titration Method)4 tive samples cannot be made explicit to cover all cases and
D 1476 Test Method for Heptane Miscibility of Lacquer must be supplemented by judgment, skill, and sampling
Solvents4 experience. It is recommended that Practice E 300 be em-
D 1555 Test Method for Calculation of Volume and Weight ployed in sampling liquid solvents.
of Industrial Aromatic Hydrocarbons4
5. Specific Gravity
D 1613 Test Method for Acidity in Volatile Solvents and
Chemical Intermediates Used in Paint, Varnish, Lacquer, 5.1 Specific gravity of liquids is defined in Terminology
and Related Products4 E 12 as “the ratio of the mass of a unit volume of a material to
D 1614 Test Method for Alkalinity in Acetone4 the mass of the same volume of gas-free distilled water at a
D 1616 Test Method for Copper Corrosion by Mineral stated temperature.” When the stated temperature of the water
Spirits7 is 4.0°C, specific gravity and density are numerically equal.
D 1617 Test Method for Ester Value of Solvents and Thin- 5.2 The apparent specific gravity of liquid is defined in
ners4 Terminology E 12 as “the ratio of the weight in air of a unit
D 1720 Test Method for Dilution Ratio of Active Solvents volume of material at a stated temperature to the weight in air
in Cellulose Nitrate Solutions4 of equal density of an equal volume of gas-free, distilled water
D 1722 Test Method for Water Miscibility of Water-Soluble at a stated temperature.”
Solvents4 NOTE 1—Specific gravity or density is an intrinsic property of all
D 2192 Test Method for Purity of Aldehydes and Ketones4 substances and can to a degree be used to identify them. When such
D 2360 Test Method for Trace Impurities in Monocyclic substances are of high purity, specific gravity may be used in support of
Aromatic Hydrocarbons by Gas Chromatography4 other properties to define their degree of purity. The use of specific gravity
D 2804 Test Method for Purity of Methyl Ethyl Ketone by for such purposes, however, is valid only when all components and their
relative effects upon the specific gravity of the system are known.
Gas Chromatography4
D 2935 Test Method for Apparent Density of Industrial 5.3 The choice of test method for determining specific
Aromatic Hydrocarbons4 gravity is largely dependent on the degree of accuracy required.
D 3257 Test Methods for Aromatics in Mineral Spirits by In general, when the product specification requires an accuracy
Gas Chromatography4 to the third decimal place, the hydrometer or specific gravity
D 3278 Test Method for Flash Point of Liquids by Setaflash balance method may be employed. When the product specifi-
Closed–Cup Apparatus6 cation requires an accuracy to the fourth decimal place, a
D 3329 Test Method for Purity of Methyl Isobutyl Ketone pycnometer method should be employed. Test Methods D 891
by Gas Chromatography4 give procedures using all three techniques.
D 3505 Test Method for Density or Relative Density of 5.4 With specific reference to the determination of density
Pure Liquid Chemicals4 or specific gravity of a number of aromatic and cyclic
hydrocarbon solvents, Test Method D 3505 describes a simpli-
5
fied procedure for this measurement.
6 5.5 Methods for converting specific gravity data to weight
7
Discontinued, see 1981 Annual Book of ASTM Standards, Part 29. Replaced by and volume data at various temperatures are given in Method
Test Method D 130. E 201 for oxygenated and chlorinated compounds, and for
2
D 268
aromatic hydrocarbons in Test Method D 1555. 7.2 Three test methods are available for determining the
5.6 The measurement of density of aromatic hydrocarbons distillation range of solvents. The major differences among the
at any convenient temperature, and the conversion of the data three methods are the size of distillation flasks and type of
to an applicable specification or storage temperature are thermometers (partial or total immersion) employed. Flask size
described in Test Method D 2935. has little to no effect on the results obtained between labora-
tories beyond the limits of error noted for each test method.
6. Color The advantage of the larger size flask is to prevent “boil over”
6.1 The property of color of a solvent will vary in impor- when high-boiling products, processing relatively high coeffi-
tance with the application for which it is intended, the amount cients of expansion are being tested. On the other hand,
of color that can be tolerated being dependent on the color differences between laboratories will be large when one labo-
characteristics of the material in which it is used. The paint, ratory employs a partial immersion thermometer and another a
varnish, and lacquer solvents, or diluents commercially avail- total immersion instrument. The spread between results will
able on today’s market normally have little or no color. The increase as the boiling range rises above 100°C. Partial
presence or absence of color in such material is an indication immersion thermometers are preferred for narrow boiling
of the degree of refinement to which the solvent has been products since they require no emergent stem temperature
subjected or of the cleanliness of the shipping or storage correction. The type of heat source may affect the distillation
container in which it is handled, or both (see Test Method range of products boiling within 1 or 2°C. This is especially
D 1209). true for low-boiling solvents such as methyl alcohol or acetone.
NOTE 2—For a number of years the term “water-white” was considered A large electric heater tends to distort the dry point due to the
sufficient as a measurement of solvent color. Several expressions for heating effect of infrared radiation on the bulb of the thermom-
defining“ water-white” gradually appeared and it became evident that a eter, while a properly adjusted gas burner minimizes this effect.
more precise color standard was needed. This was accomplished in 1952 The following test methods are commonly used in determining
with the adoption of Test Method D 1209 using the platinum cobalt scale. distillation ranges:
This method is similar to the description given in the Standard Methods 7.2.1 Test Method D 1078, using a 200-mL flask, high-
for the Examination of Water and Waste Water of the American Public
Health Assn., 14th Ed., p. 65 and is referred to by many as “APHA Color.”
precision partial immersion thermometers, and gas or electric
The preparation of these platinum-cobalt color standards was originally heat. The latter may be used only after it has proven to give
described by Hazen, A., American Chemical Journal, Vol. XIV, 1892, p. results comparable to those obtained when using gas heat. The
300, in which he assigned the number 5 (parts per ten thousand) to his method was designed specifically for determining the distilla-
platinum-cobalt stock solution. Subsequently, in their first edition (1905) tion range of volatile solvents used in coating compositions,
of Standard Methods for the Examination of Water, the American Public but is applicable to any volatile organic liquid that boils
Health Assn., using exactly the same concentration of reagents, assigned between 30 and 300°C, and is chemically stable during the
to color designation 500 (parts per million) which is the same ratio. The
parts per million nomenclature is not used since color is not referred
distillation process.
directly to a weight relationship. It is therefore recommended that the 7.2.2 Test Method D 850, using a 200-mL flask, partial
incorrect term “Hazen Color” should not be used. Also, because it refers immersion thermometer, and electric or gas heat. This method
primarily to water, the term “APHA Color” is undesirable. The recom- is applicable to industrial aromatic hydrocarbons and related
mended nomenclature for referring to the color of organic liquids is products. It is particularly suited to narrow boiling hydrocar-
“Platinum-Cobalt Color, Test Method D 1209.” bons or mixtures of hydrocarbons.
NOTE 3—The petroleum industry uses the Saybolt colorimeter Test
7.2.3 Method D 86, using a 100-mL flask for products
Method D 156 for measuring and defining the color of hydrocarbon
solvents; however, this system of color measurement is not commonly showing an end point below 250°C, a 125-mL flask for
employed outside of the petroleum industry. It has been reported by products showing an end point above 250°C, total immersion
various sources that a Saybolt color of + 25 is equivalent to 25 in the thermometers, and electric or gas heat. This method is appli-
platinum-cobalt system or to colors produced by masses of potassium cable to mineral spirits conforming to Specification D 235, and
dichromate ranging between 4.8 and 5.6 mg. dissolved in 1 L of distilled to spirits of turpentine conforming to Specification D 13, using
water. Because of the differences in the spectral characteristics of the partial immersion thermometers in accordance with Test Meth-
several color systems being compared and the subjective manner in which
the measurements are made, exact equivalencies are difficult to obtain.
ods D 233, and to other hydrocarbon mixtures that have wide
boiling ranges.
7. Distillation Range
8. Nonvolatile Matter
7.1 The distillation range of an organic solvent is an
empirical set of data peculiar to the solvent under study and the 8.1 The nonvolatile matter test is run usually on volatile
apparatus used giving the purchaser an indication of the solvents capable of evaporating in a reasonable period of time
product quality available to him. at 105°C. The finding of a residue significantly higher than 5
mg/100 mL indicates the presence of either contamination or
NOTE 4—The distillation range provides information on the initial impurities inherent in the solvent. In certain cases this may
boiling point, percent distilled at certain temperatures, and the dry point. adversely affect a product or coating system into which the
These parameters may be affected by improper refining techniques,
solvent is introduced. See Test Method D 1353.
impurities inherent in the sample, or contamination. It is absolutely
necessary that the purchaser and seller employ the same type of apparatus, 9. Odor
including thermometers, and follow an identical procedure as agreed
upon. If these factors are not followed precisely, it is quite possible 9.1 The evaluation of the characteristic odor of a solvent is
disagreement will result between the parties. a quick and simple means of identifying a material as well as
3
D 268
determining its suitability from an odor point of view for use in of an ester, the remaining portion of the material usually being
a solvent system. Note, however, that inhaling certain solvent the alcohol associated with the original reaction to produce the
fumes may be hazardous. Several ASTM standard specifica- ester. The method also may be employed to obtain the total
tions for solvents list the odor test as an option to be agreed ester content of a lacquer thinner.
upon between the buyer and the seller. Residual odor may be 13.2 Essentially pure and urethane grade acetate esters may
due to improper refining techniques, impurities inherent in the also be analyzed by the gas chromatographic procedure, Test
solvent, or contamination. Whatever the source, a pronounced Method D 3545, which provides not only the ester content but
residual odor may find its way into a finished product and thus also the concentration of the remaining parent alcohol. The
adversely affect the coating system. See Test Method D 1296. alcohol content is of special interest with urethane grade
solvents.
10. Water
14. Copper Corrosion Test
10.1 Two test methods are available for determining the
moisture or water content of a solvent: 14.1 The copper corrosion test normally is applied to
10.1.1 Test Method D 1364, covers the determination of hydrocarbon solvents (aliphatic and aromatic). However, the
moisture concentration in absolute terms. It is not only sensi- test also may be used in connection with oxygenated solvents.
tive and accurate for the level of water found in commercially The test is a visual estimate of the presence of free and
available solvents, but is applicable to a wide range of combined sulfur and is not a measure of the corrosiveness of
materials including hydrocarbon and oxygenated hydrocarbon solvent to other metals. See Test Methods D 849 and D 1616.
solvents. The principles of the procedure are based on the use 15. Sulfur
of the Karl Fischer reagent, Test Method E 203. 15.1 Test Method D 853 indicates the presence of sulfur
10.1.2 Test Method D 1476 may be used to determine dioxide or hydrogen sulfide in aromatic hydrocarbons. No
whether there is sufficient moisture in a solvent to cause absolute analysis of the sulfur content is obtained. The method
turbidity when the solvent is mixed with n-heptane. This is not sensitive to organic sulfur compounds. The presence in
method is limited in its usefulness in that it does not cover a solvent of detectable sulfur compounds using this method
measurement of water in absolute terms and is subject to a indicates the possibility of odor-forming bodies, as well as
wide range of sensitivity. For example, when applied to esters color-forming agents (color degradation in the final product).
and higher molecular weight ketones (methyl ethyl ketone and
higher) its lower limit for detecting water ranges from 0.1 to 16. Permanganate Time Test for Acetone and Methanol
0.3 %, depending on the particular solvent being tested. When 16.1 The measurement of permanganate time is a sensitive
applied to acetone and most alcohols, its lower limit of means for detecting trace quantities of reducing substances
sensitivity ranges from 0.5 to 2 %, again depending on the such as aldehydes and unsaturates that might be present in
particular material. Its main advantage is to detect the gross acetone and methanol. Determine the permanganate time of
contamination of a solvent by water. acetone and methanol in accordance with Test Method D 1363.
11. Acidity NOTE 6—The significance of the impurities detected using this test is
open to some question; however, the presence of trace quantities of
11.1 Acidity in a solvent may be due to improper refining reducing substances may have harmful effects in some chemical reactions,
techniques, instability in storage, or contamination. Some either alone or in combination with other reactants.
processes are highly sensitive to acidity while others are not.
Despite the fact that various acids might be involved, two 17. Flash Point
calculations are commonly given for determining acidity, that 17.1 The flash point is the lowest temperature, corrected to
is, weight percent as acetic acid, and acid number (milligrams 101.3 kPa (760 mm Hg) of pressure, of a solvent at which
of potassium hydroxide consumed per gram of sample). The application of an ignition source causes the vapor of the
purchaser and seller must agree as to which calculation should specimen to ignite under specified conditions of test.
be used for purchase specifications. See Test Methods D 847 17.2 There are four methods currently used to determine the
and D 1613. flash points of volatile solvents. One uses an open cup that
allows the solvent vapors to disperse into ambient air during
12. Alkalinity the determination while three use a closed cup that confines the
NOTE 5—Alkalinity is so rarely encountered in commercially available solvent vapors. Flash point values obtained with the open cup
solvents that among the solvents under the jurisdiction of Committee D-1, are higher than those measured in closed cups. Current United
only Specification D 329 for acetone contains a requirement for alkalinity. States Department of Transportation regulations require the
12.1 If alkalinity is suspected as a contaminant in a solvent, measurement of flash points by the applicable closed cup
determine the alkalinity in accordance with Test Method procedure to define the characteristics of a product for labelling
D 1614. This method may be adapted to water-immiscible and transport purposes. Flash points may be determined by the
solvents by substituting isopropyl, or ethyl alcohol conforming following methods:
to Formula No. 3A of the U. S. Bureau of Internal Revenue, for 17.2.1 Test Method D 1310, Tag Open Cup—A temperature
water in the test procedure. range from − 18 to 168°C (0 to 325°F) is covered by this
instrument.
13. Ester Value 17.2.2 Test Method D 56, Tag Closed Cup—This apparatus
13.1 Test Method D 1617 may be used to estimate the purity is applicable to solvents with a viscosity at 38°C (100°F) below
4
D 268
45 SUS (9.5 cSt or mm2/s at 25°C) and which flash below 93°C Solvents, Hydrocarbon Diluents, and Cellulose Nitrate—
(200°F). Determine the dilution ratio in accordance with Test Method
17.2.3 Test Methods D 93, Pensky-Martens Closed Cup— D 1720. This method covers (a) the amount of standard toluene
With a range from 20 to 700°F (−7 to 370°C), this unit is that can be added to a standard solution of nitrocellulose in a
applicable to products with flash points higher than those given oxygenated solvent, (b) the amount of a given diluent
obtainable with either the Tag Closed Tester or the Setaflash that can be added to a standard solution of nitrocellulose in
Tester. In addition, with its stirrer it is applicable to liquids standard n-butyl acetate, and (c) the amount of standard
having a viscosity greater than 9.5 cSt (mm2/s) at 25°C, having toluene that can be added to standard n-butyl acetate in a
a tendency to skin over, or containing suspended solids. prescribed solution of nitrocellulose of varying solubility
17.2.4 Test Methods D 3278, Setaflash Closed Tester—The characteristics.
construction of this instrument permits the use of a small, 19.4.1 Item (a) supplies information dealing with the ability
2-mL, specimen and is applicable in the range from 0 to 110°C of the oxygenated solvent to withstand dilution by a standard
(32 to 230°F) to liquids with viscosities below 150 St (1.50 diluent. Superior solvent power is characterized by a high
mm2/s) at 25°C (77°F). One may determine the finite flash dilution ratio.
point of a liquid or whether the liquid will or will not flash at 19.4.2 Item (b) refers to the ability of the diluent (or
a certain temperature. nonsolvent) to dilute a standard oxygenated solvent in a
standard nitrocellulose solution. Superior solvent power is
18. Purity of Ketones characterized by a high dilution ratio.
18.1 Methyl ethyl ketone and methyl isobutyl ketone may 19.4.3 Item (c) deals with the nitrocellulose itself and its
contain small quantities of alcohols and other impurities, ability to withstand dilution by a standard diluent in a standard
depending upon the process by which they were manufactured. solvent.
Test Method D 2804 may be used to determine the impurities
in methyl ethyl ketone by gas chromatography and Method 20. Water Miscibility of Water-Soluble Solvents
D 3329 is applicable to methyl isobutyl ketone. An equivalent 20.1 Determine water miscibility of these materials in
procedure for the analysis of methyl amyl ketone and methyl accordance with Test Method D 1722. This method is designed
isoamyl ketone Test Method D 3893. to detect the presence of trace amounts of a hydrocarbon
18.2 Hydroxylamine will react quantitatively with ketones impurity, or other water-insoluble contaminants.
to provide a wet chemical test for assay. This procedure may be
NOTE 7—Because of modern refining techniques, there is little likeli-
found in Test Method D 2192. hood of any commercially available acetone, isopropyl alcohol or other
water-soluble solvents containing even a trace of a water-insoluble
19. Solvent Power Evaluation
impurity. However, this method is of value in detecting such contamina-
19.1 The following three methods may be used singly, or in tion that might occur as a result of an improperly cleaned shipping or
combination with each other, to characterize the solvency storage container, or both.
power of hydrocarbon solvents. The test method described in
18.4 also gives a procedure for evaluating the solvency of 21. Analysis of Methanol
oxygenated hydrocarbons. 21.1 A compilation of analytical methods, both general and
19.2 Aniline Point and Mixed Aniline Point of Hydrocarbon specific to methanol is presented in Method E 346.
Solvents—Determine the aniline point and mixed aniline point
in accordance with Test Method D 611. This method covers the 22. Analysis of Ethylene and Propylene Glycols
determination of solvent power in terms of miscibility tem- 22.1 A survey of analytical methods for the specification
peratures in the presence of aniline. High aniline points testing of mono-, di-, and triethylene glycol, and mono- and
indicate the presence of saturated hydrocarbons in major dipropylene glycol is presented in Test Method E 202.
proportions. Aromatics produce low aniline points and, when
present in major quantities, low mixed aniline points. 23. Acid Wash Color of Aromatic Hydrocarbons
19.3 Kauri-Butanol Value of Hydrocarbon Solvents— 23.1 Chemically reactive impurities in aromatic hydrocar-
Determine the kauri-butanol value in accordance with Test bons may impart color to a final product. An estimate of the
Method D 1133. Numbers obtained by means of the kauri- quantity of these compounds in aromatic hydrocarbons may be
butanol value determination represent relative solvent power of obtained by Test Method D 848.
hydrocarbon solvents used in coating formulations. Results,
however, cannot necessarily be translated into terms derived by 24. Paraffins and Other Nonaromatic Hydrocarbons in
other test methods, since hydrocarbon solvents vary in com- Aromatics
position (ratio of aromatics to paraffins to naphthenes). Sol- 24.1 For the determination of less than 1 % nonaromatic
vents from different suppliers may show identical kauri- hydrocarbons in monocyclic aromatics, the applicable proce-
butanol values but quite different resin solution viscosities. The dure is Test Method D 2360.
method, therefore, is suitable for routine testing of solvents
from a particular source. It also may be used as a guide in 25. Aromatics in Mineral Spirits
determining whether a solvent from a new source should be 25.1 Determine the aromatics in mineral spirits in accor-
considered. dance with Test Method D 3257. Part A of this gas chromato-
19.4 Dilution Ratio in Cellulose Nitrate Solutions for Active graphic procedure permits the identification and calculation of
5
D 268
concentrations of aromatic components in accordance with the 26. Keywords
scope of the method. Part B measures only the ethyl benzene
26.1 solvents; volatile solvents
content by a rapid procedure.
6
Standard Test Method for

Insoluble Matter in Rosin and Rosin Derivatives1
1. Scope 0.0014-in. wire diameter. (44-µm openings) as described in

1.1 This test method covers the determination of the amount Specification E 11.
of insoluble matter in rosin and rosin derivatives as described 4.4 Two-Piece Filter Apparatus, appropriate to hold the
in Terminology D 804. stainless steel screens without leaking.
1.2 This standard does not purport to address all of the 4.5 Analytical Balance, capable of weighing 0.0001 g.
safety problems, if any, associated with its use. It is the 4.6 Laboratory Tweezers.
responsibility of the user of this standard to establish appro- 4.7 Forced Draft Oven.
priate safety and health practices and determine the applica- 5. Reagents
bility of regulatory limitations prior to use.
5.1 Clean Toluene, Hexane, Mineral Spirits, or other suit-
2. Referenced Documents able solvent for the specific material to be checked in, as
2.1 ASTM Standards: agreed upon between the customer and the supplier.
D 804 Terminology Relating to Naval Stores Including Tall 6. Procedure
Oil and Related Products2
E 11 Specification for Wire-Cloth Sieves for Testing Pur- 6.1 Rinse the pre-cut screen thoroughly with the solvent to
poses3 clean it before use.
6.1.1 Dry the clean screen at 105 to 110°C for 30 min, cool
3. Significance and Use in a desiccator, and weigh.
3.1 Rosin, particularly gum and wood rosin, occasionally 6.1.2 Record the weight of the dry screen to the nearest
contains small amounts of contamination such as sand, dirt or 0.0001 g.
bark. Rosin derivatives occasionally contain traces of insoluble 6.1.3 Place the screen in the filter apparatus and secure it to
material as a result of the raw materials used in their production prevent leakage.
or they may be generated during the production process. In all NOTE 1—Always use tweezers when handling the pre-cut screen.
instances the presence of such insoluble material should be
6.2 Weigh 100 6 0.1 g of freshly powdered material to be
minimal. This test method describes a rapid and reliable
tested into an 800-mL beaker. Add 150 mL of solvent. Place a
procedure for determining the amount of such insoluble matter.
PTFE-coated magnetic stir bar into the beaker, and place the
It is based on the knowledge that rosin and most of its
beaker on a hot plate. Heat and stir the material until it is
derivatives are soluble in numerous organic solvents whereas
completely dissolved. Do not boil the solvent.
most common contaminants are not. It is especially useful for
6.3 Immediately pour the solution through the screen. Rinse
internal quality control rather than sales specifications.
the beaker and filter apparatus three times with additional hot
4. Apparatus solvent.
6.4 Disassemble the filter apparatus, remove the screen, and
4.1 Beaker, 800 mL.
place it in a forced draft oven, contaminated side up. Dry the
4.2 Magnetic Stirring Hot Plate with Polytetrafluoroethyl-
screen to constant weight at 105 to 110°C. (1 h is usually
ene (PTFE) Stirbar, or hot plate with manual stirring rod.
sufficient), cool in a desiccator, and weigh. Record the weight
4.3 Precut Stainless Steel Circular Screen, 325 mesh with
of the dry contaminated screen to the nearest 0.0001 g.
7. Calculation
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint, weight contaminanted screen
Related Coatings, Materials, and Applications and is the direct responsibility of 2weight clean screen.
Subcommittee D01.34 on Naval Stores. Percent insolubles 5 weight of sample 3 100
Current edition approved July 10, 1997. Published September 1997. Originally
2
3
1
D 269
8. Report primarily used for internal quality control purposes rather than
8.1 Report the percent insoluble matter to the nearest for customer specification purposes.
0.01 %.
10. Keywords
9. Precision and Bias
10.1 insoluble; rosin; rosin derivatives
9.1 It is not practical to measure the precision and bias of
the procedure in this test method because this test method is
2

Bleeding of Pigments1
1. Scope a stopper, shake well for 10 s, and let stand 15 min. Repeat the
1.1 These test methods cover procedures for determining 10-s shake and let stand 45 min.
the bleeding characteristics of dry pigments by direct solvent NOTE 1—Additional amounts of pigment may be used by prior agree-
extraction of the pigment and by overstriping a film with a ment for denser inorganic pigments. A maximum of 1.5 g is recommended
white coating and observing for the color migration from the for even the dense lead chromate pigments.
base coat containing the pigment. NOTE 2—Other solvents may be used, by mutual agreement between
1.2 This standard does not purport to address all of the the parties involved, in place of toluene in a specific pigment bleed
evaluation.
safety problems, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 4.2 Filter through a glass funnel using double filter paper
priate safety and health practices and determine the applica- that has first been wet with toluene and collect approximately
bility of regulatory limitations prior to use. 10 mL of filtrate. If the filtrate is cloudy, refilter to get a clear
filtrate.
NOTE 3—In the case of colloidal particles, it may be necessary to
2.1 Test Method A—The pigment is shaken with toluene, centrifuge the filtrate.
filtered, and the filtrate observed for color. 4.3 Hold the test tube containing the filtrate above a white
2.2 Test Method B—A coating using the pigment under test background and look down through the filtrate for coloration
is prepared and applied to one half of a panel. A white finish is caused by pigment bleed. Describe the degree or severity of
applied over the dried colored coating and extended to the bleed according to the following terminology:
uncoated portion of the panel. The dried overstripe coating is 4.3.1 None—No perceptible color (that is, no bleed).
examined for color migration from the base coat. 4.3.2 Slight—A faint but distinct coloration.
3. Significance and Use 4.3.3 Moderate—A pronounced but not severe coloration.
4.3.4 Severe—An intense coloration.
3.1 Test Method A determines the amount of color produced
when the pigment is in direct contact with a selected solvent TEST METHOD B, WHITE OVERSTRIPE OF A
such as toluene. It is useful as a rapid, easily conducted test of PIGMENTED FILM
the general bleeding characteristics of pigments. 5. Procedure
3.2 Test Method B determines the amount of color migra- 5.1 Prepare a coating of agreed upon composition, using the
tion into a white film applied over a base coat containing the pigment under test, and prepare a film of this coating by any
pigment. It may give a more practical evaluation of whether a method that will give a smooth and uniform film of normal
pigment will meet specific requirements for bleed resistance. coating thickness (that is, in the range from 2 to 3 mils) (50 to
3.3 Both Test Method A and Test Method B measure the 75 µm) leaving a portion of the substrate uncoated. Cure the
extent of bleed. film under conditions appropriate to the end use. For air dry
TEST METHOD A, DIRECT SOLVENT CONTACT films, dry at room temperature, approximately 25°C (77°F) for
WITH PIGMENT a minimum of 24 h.
5.2 Pretreatments of the colored coating, such as sanding or
4. Procedure solvent wipe, or both, may be used before the overstripe, as
4.1 Place 0.50 g of pigment (Note 1) in a 25-mL test tube agreed upon by the purchaser and seller.
and add 20-mL of reagent grade toluene (Note 2). Close with 5.3 Overstripe with a white finish of agreed upon composi-
tion. Ensure that the overstripe film is of uniform thickness and
applied at complete hiding; otherwise, color show-through may
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint be erroneously interpreted as bleed.
5.4 Extend the overstripe film to the uncoated portion of the
Current edition approved May 29, 1987. Published July 1987. Originally panel. Dry the overstripe under conditions mutually agreed
published as D 279 – 28 T. Last previous edition D 279 – 73 (1979). upon by the involved parties.
1
D 279
5.5 Examine for color migration from the base coat into the in Test Method A and with the type of base coat and type of
white topcoat. Within 2 h after drying rate the extent of bleed overstriping used in Test Method B.
in accordance with the scale in Test Method A (4.3).
7. Keywords
6.1 The precision and bias are considered to be undetermin- 7.1 bleeding pigments; pigment bleeding test
able as they will vary with the solvent or solvent blends used
2

Hygroscopic Moisture (and Other Matter Volatile Under the
Test Conditions) in Pigments1
1. Scope METHOD B—FOR PIGMENTS THAT DECOMPOSE

1.1 These test methods cover procedures for determining AT 110°C
hygroscopic moisture (and other matter volatile under the test 4. Apparatus
conditions) in pigments.
1.2 This standard does not purport to address all of the 4.1 Weighing Bottle, glass, as described in 2.1.
safety concerns, if any, associated with its use. It is the 4.2 Open-Tube Manometer made of glass tubing 6 mm in
responsibility of the user of this standard to establish appro- diameter, filled with mercury to approximately 860 mm, fitted
priate safety and health practices and determine the applica- with rubber pressure tubing attached to a T-joint leading to the
bility of regulatory limitations prior to use. desiccator and the pump. A suitable low-pressure gage may be
used in place of the manometer.
METHOD A—FOR PIGMENTS THAT DO NOT NOTE 1—The difference in levels of the mercury in the manometer
DECOMPOSE AT 110°C when the system is in operation, subtracted from the barometer reading
taken at the same time, gives the pressure of the system in millimetres of
2. Apparatus mercury.
2.1 Weighing Bottle, wide-mouth, cylindrical, glass (flat 4.3 Desiccator, glass, having a hole at the side or in the
form, about 30 mm in height and about 70 mm in diameter), cover, constructed with heavy walls to withstand a vacuum of
provided with a ground-in glass stopper. Or, an aluminum one atmosphere. The hole at the side shall be closed with a
moisture dish (about 90 mm in diameter and about 50 mm in one-hole rubber stopper carrying a glass tube with a rubber
depth) with a tightly fitting cover. tube connection and a pinchcock or with a glass stopcock
2.2 Oven in which a temperature of from 110 6 2°C is ground to fit the tubulature.
maintained. 4.4 Oil Vacuum Pump, 2 able to achieve and hold a vacuum
2.3 Analytical Balance. of 3 mm.
3. Procedure 4.5 Analytical Balance.
3.1 Weigh accurately the glass weighing bottle and stopper 5. Procedure
or the aluminum moisture dish with cover. Place a specimen of 5.1 Weigh accurately the glass weighing bottle and stopper.
from 3 to 5 g of the pigment in the clean, dry weighing bottle Place a specimen of from 1 to 3 g of the pigment in the clean,
or in the clean, dry aluminum moisture dish. Insert the stopper dry weighing bottle, insert the stopper and weigh to 0.1 mg.
(or cover) and weigh to 0.1 mg. Subtract the weight of the Subtract the weight of the vessel from the total weight to obtain
vessel from the total weight to obtain the weight of sample the weight of sample used in the test.
used in the test. Remove the stopper (or cover) and place it and 5.2 Remove the stopper and place it and the bottle contain-
the bottle (or dish) containing the specimen in an oven that has ing the specimen in the desiccator containing fresh, anhydrous
been previously heated to 110 6 2°C, heat for 2 h at a magnesium perchlorate.3 Close the desiccator, attach to the
temperature of 105 to 110°C. Replace the stopper (or cover), pump, and gradually evacuate until the pressure is constant at
cool in a desiccator, and weigh. Calculate the total loss in 3 mm or less (Note 2). Close the pinchcock or stopcock, stop
weight as percent of moisture and other volatile matter. the pump, and let stand at room temperature (70 to 90°F) for 24
h.
5.3 Slowly admit air that has been dried by passage through
1
fresh magnesium perchlorate to the desiccator by means of the
and Related Coatings, Materials, and Applications and are the direct responsibility pinchcock or stopcock, remove the cover, quickly replace the
Current edition approved Oct. 30, 1981. Published December 1981. Originally 2
published as D280 – 28. Last previous edition D280 – 75. The “Hyvac” oil pump is satisfactory.
3
Available from Chemical Suppliers under the name Anhydrous or Dehydrite.
1
D 280
stopper in the weighing bottle, and weigh. Repeat the evacu- lubricant is applied to the ground surfaces. Desiccators when evacuated
ations and weighings until the loss in weight does not exceed should be wrapped in towels or covered by other means to prevent
0.5 mg in 24 h. Calculate the total loss in weight as percent of possible injury to the operator.
moisture and other volatile matter (Note 3). NOTE 3—This is an empirical method and the details should be strictly
followed. The determination of the true hygroscopic moisture content of
NOTE 2—Caution should be used in evacuating glass desiccators. The very finely divided pigments is very difficult, if not impossible in some
vacuum should be applied gradually. Desiccators will maintain a vacuum cases.
for a greater length of time when a thin film of a suitable stopcock
2

Chemical Analysis of Cuprous Oxide and Copper
Pigments1
1. Scope fine powder and thoroughly mix (Note 1). Large samples may
1.1 These test methods cover procedures for the chemical be thoroughly mixed and a representative portion taken and
analysis of cuprous oxide and copper pigments. powdered if lumpy or not finely ground. In all cases thoroughly
1.2 The analytical procedures appear in the following order: mix the sample before taking portions for analysis. Preserve all
Sections
samples in dry, dark, airtight and completely filled bottles or
Total Copper 7 containers to prevent oxidation. Some commercial copper
Total Reducing Power as Cuprous Oxide 8 and 9 oxides appear to segregate or oxidize rather easily. Therefore,
Metallic Copper 10 and 11
Cuprous Oxide 12
the thorough mixing of the sample to ensure homogeneity and
Cupric Oxide 13 the rapid handling of the sample, when exposed to light and air,
Metals Other than Copper 14-16 are extremely important factors in obtaining accurate results.
Chlorides and Sulfates 17 and 18
Acetone-Soluble Matter 19 NOTE 1—It is very important that the sample be thoroughly mixed.
Water 20 Some samples of cuprous oxide are not homogeneous so are likely to give
Stability 21
trouble when an attempt is made to obtain concordant results. By placing
Coarse Particles 22
Coarse Particles Insoluble in Nitric Acid 23 a few grams of a sample on a sheet of white paper and drawing it out with
a spatula, it is frequently found that the sample contains coarse particles
1.3 This standard does not purport to address all of the of black scale, along with small balls of bright red cuprous oxide. Thus,
safety concerns , if any, associated with its use. It is the it may be necessary to pass the pigment through a No. 60 (250-µm) sieve,
responsibility of the user of this standard to establish appro- break up any lumps of ground pigment by gentle pressure, and grind any
priate safety and health practices and determine the applica- coarse particles failing to pass through the sieve. Since oxidation of slight
or even considerable magnitude may take place, these operations should
bility of regulatory limitations prior to use. Specific hazard
be performed quickly, avoiding prolonged grinding and exposure to light
statements are given in Section 6. and air.
2. Referenced Documents 5. Reagents
2.1 ASTM Standards: 5.1 Purity of Reagents—Reagent grade chemicals shall be
D 185 Test Methods for Coarse Particles in Pigments, used in all tests. Unless otherwise indicated, it is intended that
Pastes, and Paints2 all reagents shall conform to the specifications of the Commit-
D 1193 Specification for Reagent Water3 tee on Analytical Reagents of the American Chemical Society,
D 1208 Test Methods for Common Properties of Certain where such specifications are available.4 Other grades may be
Pigments2 used, provided it is first ascertained that the reagent is of
3. Significance and Use sufficiently high purity to permit its use without lessening the
accuracy of the determination.
3.1 This collection of test methods is used by pigment 5.2 Purity of Water—Unless otherwise indicated, references
producers and paint manufacturers for process control, product to water shall be understood to mean reagent water conforming
acceptance, and research and development. to Type II of Specification D 1193.
4. Treatment of Sample 5.3 Ammonium Sulfate—((NH4) 2SO4).
5.4 Nitric Acid (sp gr 1.42)—Concentration nitric acid
4.1 Grind dry pigments, if lumpy or not finely ground, to a (HNO3).
1
4
and Related Coatings, Materials, and Applications and are the direct responsibility Reagent Chemicals, American Chemical Society Specifications, American
of Subcommittee D01.31 on Pigment Specifications. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Oct. 26, 1984. Published January 1984. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 283 – 28. Last previous edition D 283 – 52 (1978) e2. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 283
5.5 Perchloric Acid (70 %)—Concentrated perchloric acid place in a 250-mL, vented, glass-stoppered Erlenmeyer flask
(HClO4). previously filled with carbon dioxide (CO2) or other inert gas.
Add a few small glass beads and 10 mL of FeCl3 solution. Heat
6. Hazards
gently for 15 min, stirring occasionally and maintaining at all
6.1 Warning—Concentrated mineral acids cause burns of times an atmosphere of CO2 or other inert gas.
the skin and eyes. Concentrated bases are also hazardous.
Avoid contact with skin or eyes. In case of contact immediately NOTE 2—The use of a 0.4-mL micro beaker for weighing the specimen
is advised. The beaker is weighed first and the sample introduced into the
flush skin or eyes with plenty of water. See appropriate MCA
beaker, the correct weight obtained, and the entire beaker and its contents
Safety Data Sheets for further information before handling dropped into the flask. This eliminates errors in weighing caused by
dangerous chemicals. brushing the sample from glass balance pans.
6.2 Chemicals that have been declared toxic should be
9.2 After the specimen has been dissolved, cool, add 50 mL
disposed of as hazardous chemicals and not discharged into a
of distilled water, and titrate at once with 0.1 N ceric ammo-
sink.
nium nitrate solution until near the end point. Add 2 drops of
TOTAL COPPER orthophenanthroline indicator solution and complete the titra-
tion. A sharp, distinct color change from orange to pale green
7. Procedure
occurs at the end point. Back-titrate with 0.03 N ferrous
7.1 Weigh accurately 1.0 g of the sample and transfer to a ammonium sulfate solution to the orange color.
300-mL electrolytic beaker. Add 10 mL of concentrated nitric 9.3 Calculation—Calculate the percent of total reducing
acid (HNO 3) and boil several minutes. Add 10 mL of HClO4 power, A, as cuprous oxide (Cu 2O) as follows:
(70 %) and fume for 5 min. Cool, dilute to a volume of
V1N1 – V2N2 3 0.07154
approximately 150 mL, and add 1 mL of HNO3 and 1 g of A5 3 100 (1)
S1
(NH4)2SO 4.
7.2 Carefully weigh the platinum electrode to 0.1 mg. where:
Electroplate the copper on a rotating platinum electrode at a V1 5 Ce(NH4)2(No3) 6 solution required to titrate the
current of 2 A for 2 h. Dilute with water and continue the specimen, mL,
electrolysis for 15 min. When the deposition is complete, N1 5 normality of the Ce(NH4)2(No3)6 solution,
remove the electrode, wash with water and acetone, dry, and V2 5 Fe(NH4) 2(SO4)2 solution required for the back-
weigh to 0.1 mg. Save the electrolyte for the determination of titration, mL,
metals other than copper (Section 15). N2 5 normality of the Fe(NH4)2(SO4)2 solution,
7.3 Calculate the percent of total copper, Cu. S1 5 specimen weight, g, and
0.07154 5 equivalent weight of Cu 2O/1000.
TOTAL REDUCING POWER AS CUPROUS OXIDE
8. Reagents METALLIC COPPER5
8.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)— 10. Reagents
Mix 54.826 g of ceric ammonium nitrate (Ce(NH4)2(NO3) 6) 10.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)—
(either reagent grade or reference standard purity) with 56 mL See 8.1.
of sulfuric acid (H2SO4) (1+1). Dissolve the salt and acid in 10.2 Denatured Alcohol (Formula No. 2B)
water, cool to room temperature, and dilute to 1 L. Standardize 10.3 Extraction Solution—Add 40 mL of HCl (sp gr 1.19)
this solution against analyzed bright copper foil that has been to 1 L of denatured alcohol. Mix thoroughly. Add 40 g of
freed from all oxide coating. stannous chloride (SnCl2 ·2H2O) and stir until completely
8.2 Ferric Chloride Solution—Dissolve 75 g of ferric chlo- dissolved.
ride (FeCl3 ·6 H2O) in a mixture of 150 mL of hydrochloric 10.4 Ferric Chloride Solution—See 8.2.
acid (HCl) (sp gr 1.19) and 400 mL of distilled water. Add 5 10.5 Orthophenanthroline Indicator— See 5.4.
mL of hydrogen peroxide (H2O2) (30 %) and boil to remove
the excess. 11. Procedure
8.3 Ferrous Ammonium Sulfate, Standard Solution (0.03 11.1 Add approximately 20 mL of 4-mm diameter glass
N)—Dissolve 12 g of ferrous ammonium sulfate beads to a 250-mL Phillips beaker (assay flask). Weigh
(Fe(NH4)2(SO4) 2 ·6 H2O) in 200 to 300 mL of water and add accurately 0.15 g of sample on a tared, glazed paper approxi-
40 mL of H2SO4 (sp gr 1.84), while stirring constantly. Dilute mately 1⁄2 in. (13 mm) square or a small watch glass that will
to 1 L in a volumetric flask. A few pieces of mossy aluminum fit into the Phillips beaker, and transfer the specimen and paper
may be added to stabilize the solution. The solution should be or watch glass to the beaker.
restandardized frequently against 0.1 N ceric ammonium ni- 11.2 Add 25 mL of denatured alcohol and swirl vigorously
trate solution. for approximately 1 min to remove any surface coating and
8.4 Orthophenanthroline Indicator Solution (0.5 % in
water)—Orthophenanthroline ferrous complex (ferroin) shall
be used as the indicator. 5
This test method is based on the procedure described by Irvin Baker and R.
9. Procedure Stevens Gibbs, “Determination of Metallic Copper in Cuprous Oxide—Cupric
Oxide Mixtures,” Industrial and Engineering Chemistry, Analytical Edition, Vol 13,
9.1 Weigh accurately (Note 2) 0.15 g of the sample and February 15, 1946, p. 124.
2
D 283
break up lumps. While swirling the flask, slowly add 100 mL CUPROUS OXIDE
of the extraction solution.
11.3 After the addition of the extraction solution, swirl the 12. Calculation
flask vigorously for 5 min, adding lumps of dry ice (solid 12.1 Calculate the percent of cuprous oxide (Cu 2O), D, as
carbon dioxide) (Note 3) continuously during this time to lower follows:
the temperature of the solution to approximately −10°C. Break D 5 A 2 2.252B (3)
up any lumps in the solution with a glass rod or policeman.
where:
11.4 Filter off the metallic copper-cupric oxide residue A 5 total reducing power as cuprous oxide (Section 9), %,
using a 125-mm close-texture paper, a filter cone to support the and
paper, and suction (Note 4). Continue the addition of dry ice to B 5 metallic copper (Section 11), %.
the flask and filter paper during the filtration to keep the
solution cold. Wash the flask and filter paper with 150 to 200 CUPRIC OXIDE
mL of denatured alcohol, continuing the use of suction.
13. Calculation
NOTE 3—During the 5-min swirling period approximately 25 to 30 g of
13.1 Calculate the percent of cupric oxide (CuO), E, as
dry ice is added in approximately 5-g portions. The initial lumps of dry ice
volatilize rapidly due to the temperature of the solution. Approximately 15 follows:
g of dry ice is added in the first 2 min with a subsequent temperature drop E 5 1.252~F 2 B! 2 1.112D (4)
to 0°C. The remaining 15 g volatilizes more slowly and gradually lowers
the temperature to the vicinity of −10°C. These directions are not critical, where:
but merely serve as a guide. The solution must be kept very cold in order F 5 total copper (Section 7), %,
to obtain correct and reproducible results. During the filtration period, B 5 metallic copper (Section 11), %, and
additions of dry ice to the flask should be continued to keep the solution D 5 cuprous oxide (Section 12),% .
cold until all of the extraction solution has been filtered.
NOTE 4—In the great majority of cases, the metallic copper-cupric METALS OTHER THAN COPPER
oxide residue is completely retained by the use of a suitable close-texture
filter paper. The filtration is rapid and can be readily completed in 5 min 14. Reagents
with proper suction. The filtrate should be carefully examined for the 14.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)—
presence of finely divided particles of copper. In the event that extremely
See 8.1.
finely divided particles of copper are present and pass through the filter
paper, as evidenced by the presence in the filtrate of a reddish color, which
14.2 Diphenylamine Indicator—Dissolve 1 g of dipheny-
may be transient, the following method of filtration should be used: Place lamine in 100 mL of H2SO4 (sp gr 1.84).
a 25-mm diameter, beveled-edge, perforated porcelain filter disk in a 60°, 14.3 Potassium Ferricyanide Solution (50 g/L)—Dissolve 5
75-mm diameter glass funnel. Using suction, prepare an asbestos filter pad g of potassium ferricyanide (K 3Fe(CN)6), in 100 mL of
on the porcelain disk of sufficient thickness and retentiveness to hold the distilled water. Keep tightly stoppered in a dark bottle.
finely divided residue. Wash the asbestos pad several times with denatured 14.4 Potassium Ferrocyanide, Standard Solution (1
alcohol to remove all water from the pad. Filter the metallic copper-cupric mL 5 0.001 g Zn)—Dissolve 5.0 g of potassium ferrocyanide
oxide residue on this asbestos pad with the suction on at the start of the (K4Fe(CN)6 ·3H 2O) in distilled water and dilute to 1 L.
filtration. Keep the solution cold by the addition of dry ice and proceed
Standardize with analyzed reagent grade zinc prior to use.
with washing the residue, transferring it to the original extraction flask,
and the subsequent titration as directed in Section 11.
15. Procedure
11.5 Transfer the entire residue, filter paper, and beads to the 15.1 Filter the electrolyte from the determination of total
original extraction flask and dissolve the residue in 25 mL of copper (Section 7). Add 5 mL of H2SO 4 (sp gr 1.84) and
FeCl3 solution, keeping an atmosphere of CO2 above the evaporate just to dryness to remove all HClO 4 and HNO3. Add
sample by addition of dry ice. Heat on a steam bath to dissolve approximately 150 mL of water and neutralize with NH4OH
the copper. Add 50 mL of distilled water and 3 drops of (sp gr 0.90), adding 5 mL in excess. Add 10 g of NH 4Cl. Boil
orthophenanthroline indicator solution. Titrate with 0.1 N ceric the solution gently for several minutes and allow the precipitate
ammonium nitrate solution until the color changes from orange to settle. Filter through a close-texture paper, and wash the
to pale green. precipitate with 50 mL of hot NH4Cl solution (20 g/L).
11.6 Calculation—Calculate the percent of metallic copper 15.2 Determination of Iron—Dissolve the precipitate from
content, B, as follows: the filter paper with hot HCl (1+1). Determine iron by the
procedure of reduction with SnCl2 solution, followed by
V3C
B 5 S 3 100 (2) addition of HgCl2 and titration with 0.1 N ceric ammonium
2
nitrate solution.
where: 15.2.1 Calculation—Calculate the percent of iron, G, as
V 3 5 ceric ammonium nitrate solution required for titra- follows:
tion of the sample, mL, V4N1 3 0.056
C 5 copper equivalent of the ceric ammonium nitrate G5 S 3 100 (5)
solution, g/mL, and
S2 5 specimen weight, g. where:
3
D 283
V4 5 ceric ammonium nitrate solution required to titrate 18.3.1 Calculation—Calculate the percent of chlorides as
the specimen, mL, Cl, J, as follows:
N1 5 normality of the ceric ammonium nitrate solution, P1 3 0.247
and J 5 S 3 0.1 3 100 (7)
3
S 5 specimen weight (Section 7), g.
15.3 Determination of Cobalt and Nickel— Evaporate the where:
filtrate (see 15.1) to 15 to 20 mL. If the solution is colored, the P 1 5 AgCl, g, and
presence of nickel or cobalt, or both, may be indicated. If S3 5 specimen weight, g.
present, they must be removed before determining zinc, 18.4 Determination of Sulfates—Dilute the second 50-mL
determined by any standard procedure and reported as percent aliquot (18.1) to approximately 200 mL. Add approximately 1
of cobalt or nickel, or both. mL of HCl (1+1). Heat to boiling and add slowly an excess (10
15.4 Determination of Zinc—Neutralize the solution (see mL) of BaCl 2 solution. Let settle, filter through a Gooch
15.4) with H2SO4 (1+2) and add 15 mL in excess. Dilute to 300 crucible, and wash. Dry, ignite at full red heat, cool in a
mL with water. Add 10 drops of K 3Fe(CN)6 solution and 5 desiccator, and weigh.
drops of diphenylamine indicator solution. Heat to 75°C and 18.4.1 Calculation—Calculate the percent of sulfates as
titrate with standard K4Fe(CN) 6 solution. A color change from SO4, K, as follows:
blue to greenish yellow occurs at the end point. P2 3 0.412
K 5 S 3 0.1 3 100 (8)
15.4.1 Calculation—Calculate the percent of zinc, H, as 3
follows:
where:
V5Z
H 5 S 3 100 (6) P 2 5 BaSO4, g, and
S3 5 specimen weight, g.
where: ACETONE-SOLUBLE MATTER
V 5 5 K4Fe(CN)6 solution required for titration of the
specimen, mL, 19. Procedure
Z 5 zinc equivalent of the K4Fe(CN)6 solution, and
19.1 Weigh accurately 5.0 g of the well-mixed sample and
S 5 specimen weight (Section 7), g.
transfer to a 250-mL glass stoppered Erlenmeyer flask. Add
16. Report 100 mL of acetone and shake vigorously for 15 min. Allow to
settle and filter through a double, close-texture paper into a
16.1 Report as percent of metals other than copper the total 250-mL Griffin beaker. Wash the flask and paper well with
percent of metals determined in accordance with Section 15. acetone to remove all acetone-soluble matter.
CHLORIDES AND SULFATES 19.2 Evaporate the acetone on a water bath to a low volume
and transfer to a 15 by 55-mm weighed aluminum moisture
17. Reagents dish. Wash out the beaker with a small amount of acetone.
Finally evaporate all acetone and heat the residue for 30 min in
17.1 Barium Chloride Solution (100 g/L)—Dissolve 117 g
an oven at 105°C.
of BaCl2 · 2H 2O in water and dilute to 1 L.
19.3 Report the weight of the dried residue as acetone-
17.2 Silver Nitrate Solution—Dissolve 5 g of silver nitrate
soluble matter.
(AgNO3) in 100 mL of water.
17.3 Sodium Carbonate Solution—Prepare a saturated so- WATER
lution of sodium carbonate (Na2CO3) that is free of both
chlorine (Cl) and sulfate (SO4). 20. Procedure
20.1 Determine the water content in accordance with Test
18. Procedure
Methods D 1208.
18.1 Weigh accurately approximately 10 g of the sample,
add an excess of concentrated HNO3, and heat gently until the STABILITY
sample is decomposed. Dilute with water to approximately 150
mL. Add an excess of Na2CO3 solution (16.3), and bring to a 21. Procedure
boil. Transfer to a 500-mL volumetric flask and dilute to the 21.1 Spread approximately 100 g of the sample on a watch
mark with water. Let settle. glass and heat in an oven at a temperature of 100°F (40°C) and
18.2 Draw off two separate 50-mL aliquots of the clear approximately 95 % relative humidity for a period of 72 h.
solution. Make each slightly acid with HNO3. Remove from the oven. Note any change in color of the
18.3 Determination of Chlorides—To one of the 50-mL pigment. Determine its total reducing power in accordance
aliquots (18.2), add a few drops of AgNO3 solution. If no with Section 9.
precipitate forms, report no chlorides present. If a precipitate 21.2 Determine the percent of moisture on 50 g of the
forms, add slowly an excess of AgNO3 solution. Heat to sample remaining from the test described in 18.1 using the
boiling after the precipitate has settled, filter through a Gooch distillation method specified in Section 20.
crucible, and wash with cold water. Dry at 130°C, cool, and 21.3 Calculation—Calculate the percent decrease in total
weigh. reducing power, L, as follows:
4
D 283
N sieve to a beaker, add 50 mL of HNO3 (1+3), and boil for 5
L 5 100 2 M (9)
min. Cool and filter through a tared Gooch crucible, previously
where: washed with HNO 3 (1+3), or a fritted-glass filter of appropri-
L 5 total reducing power after stability test calculated on ate porosity. Wash the insoluble residue on the filter with hot
dry basis, water. Dry the crucible or fritted-glass filter and contents at 105
N 5 total reducing power after stability test as determined to 110°C and weigh.
in 21.1, and 23.2 Calculation—Calculate the percent of coarse particles
M 5 moisture (21.2),% . insoluble in nitric acid, T, as follows:
A2E R
L5 T 5 S 3 100 (11)
A 3 100 (10)
where: where:
L 5 decrease in total reducing power (from stability test), R 5 weight of residue, g, and
% and S 5 weight of original specimen, g.
A 5 total reducing power before stability test as calculated
in 9.3. 24. Precision
COARSE PARTICLES 24.1 Precision data are not available at this time. When
available the appropriate precision statements will be added.
22. Procedure
22.1 Determine the percent of coarse particles on a 25-g 25. Keywords
specimen as described in Test Methods D 185 using both a No. 25.1 chemical analysis; copper pigments; cuprous oxide
200 (75-µm) and a No. 325 (45-µm) sieve. pigments
COARSE PARTICLES INSOLUBLE IN NITRIC ACID
23. Procedure
23.1 Transfer the residue retained on a No. 200 (75-µm)
5

Chemical Analysis of Mercuric Oxide Pigment1
1. Scope 5. Preparation of Sample

1.1 These test methods cover procedures for the chemical 5.1 If the sample is large, mix it thoroughly before taking a
analysis of mercuric oxide pigment. representative portion. Grind the representative portion to a
1.2 This standard does not purport to address all of the fine powder and thoroughly mix before taking portions for
safety concerns, if any, associated with its use. It is the analysis. Keep the sample in a stoppered glass bottle.
priate safety and health practices and determine the applica- 6. Precision
bility of regulatory limitations prior to use. A specific hazard 6.1 Repeatability and reproducibility are believed to be well
statement is given in the Note 1 of 11.1. within the limits usually obtained on similar chemical test
methods, but no actual figures on precision are available.
2.1 ASTM Standards: ALKALINITY OR ACIDITY
D 1193 Specification for Reagent Water2 7. Procedure
Pigments3 7.1 Determine alkalinity or acidity in accordance with Test
Methods D 1208.
3. Significance and Use
FREE MERCURY
3.1 These test methods are intended as a quick and reliable
procedure for measuring purity of mercuric oxide pigment to 8. Procedure
determine if it meets purity standards as agreed upon between 8.1 Examine a representative specimen of the dry mercuric
the producer and the consumer. oxide under a microscope for the presence of free mercury.
4. Purity of Reagents and Materials TOTAL MERCURY
4.1 Reagent grade chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall 9. Reagents and Materials
conform to the specifications of the Committee on Analytical 9.1 Ammonium Thiocyanate, Standard Solution (1
Reagents of the American Chemical Society, where such mL 5 0.012 g Hg)—Dissolve 9 g of ammonium thiocyanate
specifications are available.4 Other grades may be used, pro- (NH4CNS) in water and dilute to 1 L. Standardize the solution
vided it is first ascertained that the reagent is of sufficiently against mercury, as follows: Weigh to 0.1 mg about 4.6 g of
high purity to permit its use without lessening the accuracy of mercury, and dissolve it in 40 mL of warm HNO3 (1+1). Dilute
the determination. to 200 mL with water and add KMnO4 solution (50 g/L)
4.2 Unless otherwise indicated, references to water shall be dropwise until the pink color persists for 5 min in order to
understood to mean reagent water conforming to Type II of ensure the absence of nitrous acid (HNO2) and monovalent
Specification D 1193. mercury. Add FeSO 4 solution (50 g/L) dropwise to destroy
excess permanganate. Add 4 mL of ferric ammonium sulfate
1
indicator solution, and titrate with the NH 4CNS solution.
and Related Coatings, Materials, and Applications and are the direct responsibility 9.2 Calculate the mercury equivalent M of the NH4CNS
of Subcommittee D 01.31 on Pigment Specifications. solution, in grams per millilitre, as follows:
published as D 284 – 28 T. Last previous edition D 284 – 74 (1987)e 1. M 5 W1/V1
2
3
Annual Book of ASTM Standards, Vol 06.03. where:
4
Reagent Chemicals, American Chemical Society Specifications, American W 1 5 mercury used, g, and
Chemical Society, Washington, DC. For suggestions on the testing of reagents not V1 5 NH4CNS solution required for titration, g.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
9.3 Ferric Ammonium Sulfate Indicator Solution—Dissolve
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, enough ferric ammonium sulfate (Fe2(SO4) 3·(NH4)2SO4·24H
MD.
1
D 284
2O) in water to make a saturated solution at room temperature 11. Calculation
and add HNO3 (sp gr 1.42) dropwise to bleach the brown color
11.1 Calculate the percent of mercury P as follows:
of the solution. About 30 g of ferric ammonium sulfate per 100
mL of water will be required for the saturated solution. P 5 @~V 2 3 M!/S# 3 100
9.4 Ferrous Sulfate Solution (50 g/L)—Dissolve 5 g of
where:
ferrous sulfate (FeSO 4·7H2O) in water and dilute to 100 mL. V 2 5 NH4CNS solution required for titration of the speci-
9.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid men, mL
(NHO3). M 5 mercury equivalent of the NH4CNS solution, g/mL,
9.6 Nitric Acid (1+1)—Mix 1 volume of HNO3 (sp gr 1.42) and
with 1 volume of water. This acid must be free of nitrous acid S 5 dried specimen, g.
(HNO2).
9.7 Potassium Permanganate Solution (50 g/L)—Dissolve ASH
5 g of potassium permanganate (KMnO 4) in water and dilute
to 100 mL.
12. Procedure
10. Procedure 12.1 Ignite 2.0 g of a dry specimen in a weighed porcelain
10.1 Weigh to 1 mg about 0.5 g of the sample, previously crucible or dish under a well-ventilated hood. ( Warning—See
dried for 1 h at 150°C into a 750-mL Erlenmeyer flask. Add 40 Note 1) Cool and weigh the residue. Calculate the percent of
mL of HNO3 (1+1), and warm gently until the specimen is ash.
dissolved.
10.2 Dilute to 200 mL with water, and add 4 mL of ferric NOTE 1—Warning: The fumes are poisonous.
ammonium sulfate indicator solution. Titrate with 0.1 N
13. Keywords
NH4CNS solution until a distinct pink color persists after
vigorous shaking. 13.1 mercuric oxide; pigments (mercuric oxide)
2
Designation: D 301 – 95 (Reapproved 1999) Federation of Societies for
Paint Technology Standard No. Cs-2-58

Soluble Cellulose Nitrate1
1. Scope m) beneath the surface of the material in the barrel. These

1.1 These test methods cover the material known as soluble samples shall then be composited to represent each lot or batch
cellulose nitrate (also known as soluble nitrocellulose), which in the shipment.
is shipped wet in conformance with regulations of the Interstate 3.2 The samples shall meet the following requirements:
Commerce Commission. 3.2.1 Appearance—The cellulose nitrate shall not be discol-
1.2 The test methods appear in the following sections: ored and shall be free of lumps and foreign matter, such as
Sections
charred particles.
3.2.2 Ash—Ash content shall not exceed 0.30 %, calculated
Ash 5-7 on the basis of dry-weight soluble cellulose nitrate.
Drying Samples 4
Nitrogen 8-10
3.2.3 Nitrogen—The percent nitrogen, calculated on the
Stability 11-13 basis of dry-weight soluble cellulose nitrate, shall be within the
Toluene Dilution 22-24 limits agreed upon by the purchaser and the manufacturer for
Viscosity 14-18
the particular type of soluble cellulose nitrate.
1.3 This standard does not purport to address all of the 3.2.4 Stability—The stability as determined by the 134.5 C
safety concerns, if any, associated with its use. It is the test shall be not less than 25 min.
responsibility of the user of this standard to establish appro- 3.2.5 Viscosity—The viscosity shall be within the limits
priate safety and health practices and determine the applica- agreed upon by the purchaser and the manufacturer for the
bility of regulatory limitations prior to use. For specific hazard particular type of soluble cellulose nitrate.
statements, see Notes 2-5. 3.2.6 Solubility and Appearance of the Solution—The solu-
bility and appearance of the sample shall be equal to the
2. Referenced Documents reference standard for the particular type of soluble cellulose
2.1 ASTM Standards: nitrate.
D 302 Specification for Ethyl Acetate (85 to 88 Percent 3.2.7 Film Test—The film test of the sample shall be equal
Grade)2 to that of the reference standard for the particular type of
D 303 Specification for n-Butyl Acetate (90 to 92 % soluble cellulose nitrate.
Grade)2 3.2.8 Toluene Dilution Test—The toluene dilution value of
D 362 Specification for Industrial Grade Toluene2 the sample shall be equivalent to that of the reference standard
D 1343 Test Method for Viscosity of Cellulose Derivatives for the particular type of soluble cellulose nitrate.
by Ball-Drop Method3
D 4795 Test Method for Nitrogen Content of Soluble DRYING SAMPLES
Nitrocellulose—Alternative Method3
4. Procedure
E 1 Specification for ASTM Thermometers4
4.1 Soluble cellulose nitrate is a flammable material, the
3. Sampling degree of flammability varying with the extent and nature of
3.1 Samples shall be taken from not less than 10 % (at least the wetting medium. Cellulose nitrate is always wet with water
two barrels) of each lot or batch in the shipment. In sampling or alcohol in commercial handling, shipping, and storage, in
the barrels, two samples of approximately 1 pt (0.5 dm3) each which condition it presents no unusual hazard. Dry cellulose
shall be taken from two well-separated points at least 1 ft (0.3 nitrate, if ignited by fire, spark, or static electricity, burns very
rapidly. Samples of dry cellulose nitrate must not be stored at
any time. Dry only that portion required for immediate test.
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Wet the excess material and the samples left after testing with
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. water and dispose of by burning on a safe burning ground.
Current edition approved Sept. 15, 1995. Published November 1995. Originally 4.2 Dry small quantities required for ash and nitrogen tests
2
by spreading in a thin layer on a tray at room temperature for
Discontinued, see 1986 Annual Book of ASTM Standards, Vol 06.03.
3 12 to 16 h, followed by oven-drying in crucibles or weighing
4
Annual Book of ASTM Standards, Vol 14.03. bottles 1 h at 100 to 105°C. The oven used for drying cellulose
1
D 301
nitrate should have the latch removed. Wear a face mask (see 10.2 Bias—No statement of bias can be made as no suitable
12.2) when the oven is opened after samples have been heated. reference material is available as a standard.
4.3 Dry larger quantities of water-wet material required for NITROGEN
viscosity and toluene dilution tests, or a small quantity for
stability tests, by blowing warm compressed air (at a tempera- 11. Significance and Use
ture of 60 to 65°C, and a pressure of 40 to 60 psi (275 to 415 11.1 The nature and strength of solvent systems required for
kPa)) through the sample placed in a cylindrical holder with a cellulose nitrate are dependent upon the nitrogen content.
screen over one end for 1⁄2 to 1 h. Provide the compressed air Mismatches of solvent with nitrogen level can result in poor
line with a safety plug (Note 1) of Wood’s metal, which melts solution quality and colloid and gel formation.
at 70 to 75°C, so the air will be diverted from the sample if a 11.2 An alternative preferred method can be found in Test
temperature of 70°C is exceeded. Method D 4795.
NOTE 1—Information on the availability of a suitable fusible plug 12. Apparatus
assembly may be obtained from ASTM Headquarters.
12.1 Nitrometer—Use the duPont Nitrometer, which is il-
4.4 If the material is alcohol-wet, it is necessary to modify lustrated in Figs. 1-4.
the drying procedure. After placing the required amount of 12.2 Face Mask—A face mask, so constructed that a heavy
cellulose nitrate in the cylindrical holder, pour in sufficient piece of cellulose acetate sheeting protects the face.
distilled or iron-free water to fill it. Allow the bulk of the liquid
NOTE 2—Precaution: The cellulose acetate mask must be worn during
to drain off. Then dry by blowing warm air through the holder
the generation and measurement of the gas as a precaution in case of an
as described in 4.3. explosion.
ASH 13. Procedure
5. Significance and Use 13.1 Calibrate the measuring tube accurately in the usual
manner, using mercury as the calibrating liquid.
5.1 Ash accounts for the nonsoluble, nonfilm forming por-
13.2 Standardize the apparatus as follows:
tion of the polymer. It may affect solution clarity and film
13.2.1 Fill the compensating, measuring, and reaction tubes
properties.
and their rubber connections with mercury. Run 20 to 30 mL of
6. Apparatus H 2SO4 (ACS grade, 94.5 6 0.5 %) into the reaction bulb
through the cup at the top and admit about 210 mL of air. Close
6.1 Porcelain Crucibles, Coors No. 3 or equivalent. the stopcocks, shake the bulb well, and allow to stand
6.2 Muffle Furnace, maintained at 550 6 25°C. overnight. This desiccates the air which is then run into the
7. Reagents compensating tube until the mercury is about on a level with
the 12.50 % mark on the measuring tube, the two tubes being
7.1 Ethyl Alcohol. held at the same height. Then seal the compensating tube using
7.2 Acetone. a small blowpipe flame.
7.3 Castor Oil. 13.2.2 As a preferred alternative, nitrogen may be used in
8. Procedure place of air.
13.2.3 Place in weighing bottles 0.95 6 0.05-g portions of
8.1 Dry the cellulose nitrate as described in 4.2 and place a ACS grade KNO3 that has been recrystallized twice from
specimen of approximately 4.0 g in a tared and ignited distilled water and ground to pass a No. 100 (150-µm) sieve.
crucible. Moisten the sample in the crucible with ethyl alcohol, Dry the specimens 2 to 3 h at 135 to 150°C. Stopper the bottles,
then gelatinize by adding a sufficient amount of 5 % solution of cool in a desiccator, and weigh accurately. Transfer the KNO3
castor oil into the acetone. Place the crucible in a draft-free to the cup of the reaction bulb and weigh the weighing bottle
hood and ignite the contents with a Bunsen flame. Allow the to obtain the weight of sample used. Add 1.0 mL of water and
material to burn without further addition of heat until a charred stir the mixture in the cup with a small glass stirring rod to
residue remains. Place the crucible in a muffle furnace at 550 liberate the entrained bubbles of air; work the undissolved
6 25°C for 90 min. Remove carefully the crucible from the crystals into the lower part of the cup, keeping them below the
muffle furnace to avoid loss of ash, cool in a desiccator, and surface of the solution. It is not necessary that the KNO3
weigh accurately. dissolve before drawing it into the reaction bulb. Make sure the
9. Calculation lower stopcock is open; then admit the mixture to the bulb by
a series of quick openings of the upper stopcock, in the
9.1 Calculate the percent ash as follows: meantime keeping the crystals below the surface of the liquid.
Ash, % 5 ~wt of ash/wt of dry sample! 3 100 In this way, all but a small amount of the KNO3 may be run
into the bulb. Rinse the cup with a second 1.0-mL portion of
10. Precision and Bias water; then repeat with a third 1.0-mL portion (3 mL in all).
10.1 Precision—Statistical analysis of intralaboratory (re- This should be sufficient to dissolve all remaining particles of
peatability) test results on a sample containing approximately KNO3 in the cup. Transfer 25 mL of the H2SO4 (94.5 6
0.015 % ash indicates a precision of 60.015 % absolute at the 0.5 %), divided in several portions, to the cup, and subse-
95 % confidence level. quently to the bulb by lowering the reservoir slightly and
2
D 301
NOTE 1—1 in. = 25.4 mm.

FIG. 1 General Assembly of Apparatus for Nitrogen Determination
opening and closing the upper stopcock, care being taken that tube at the level of the mercury, and the standardization is
no air enters even the bore hole in the stopcock. There must completed. It is advisable to make several check determina-
always be a slight suction when introducing the specimen, the tions, preferably on different days, to ensure accurate standard-
wash water, and the acid, but never enough to cause air to be ization. Determinations should check within 60.01 %.
sucked into the reaction bulb. The quantities of water and 13.5 Dry the cellulose nitrate as described in 4.2 and place
H2SO4 used should be constant. Then with the bottom stopcock a specimen of 1.0 to 1.2 g in a weighing bottle. After drying at
still open, lower the reservoir bulb to give reduced pressure in 100 to 105°C for 1 h, stopper, cool in a desiccator, and weigh
the reaction bulb and gently shake the reaction bulb to start the accurately. Transfer the specimen to the cup of the decompo-
decomposition. sition bulb; then reweigh the empty bottle to get the weight of
13.3 After the evolution of NO has become slow (Precau- the specimen by difference. Add 5 to 10 mL of H2SO4 (94.5 6
tion, see Note 3), lower the reservoir bulb until all but 25 mL 0.5 %) to the cup and stir the mixture with a small stirring rod.
of the mercury in the reaction bulb is withdrawn, close the Lower the mercury reservoir and then, with the lower stopcock
bottom stopcock, and shake the reaction bulb vigorously for 5 open, draw the mixture in by opening the upper stopcock. Take
min. care that no air is drawn in. Rinse the cup of the decomposing
NOTE 3—Precaution: It is extremely important that the bottom stop-
bulb several times with H2SO4, using a total of 25 mL for
cock be left open until the major part of the decomposition has occurred; dissolving and rinsing. Complete the determination in accor-
otherwise, sudden evolution of gas will burst the bulb, scattering acid and dance with the procedure described in 10.2 for standardization
glass. of the apparatus, and take a reading after adjusting the level of
13.4 When the reaction is completed, allow the gas to cool the mercury in the reading tube to the mark on the compen-
for 20 min; then transfer the gas to a measuring tube. By means sating tube. The reading divided by the weight of the specimen
of the leveling device make careful adjustment of the mercury gives the percent nitrogen.
levels so that the mercury in the measuring tube is at the STABILITY
13.85 % mark (the theoretical percent nitrogen in KNO3) if an
exactly 1.000-g specimen was used, or a proportional reading 14. Significance and Use
if less was used. Paste a strip of paper on the compensating 14.1 Nitrocellulose stability is measured by detecting the
3
D 301
NOTE 1—1 in. = 25.4 mm.

FIG. 3 Reaction Bulb
15.2 Test Tubes—Heat-resistant glass5 tubes, with an out-

NOTE 1—1 in. = 25.4 mm. side diameter of 18 mm, a wall thickness of 1.5 mm, and a
FIG. 2 Measuring Tube for Nitrogen Determination length of 290 mm.
15.3 Heater—An electric hot plate for heating the bath.
15.4 Face Mask—See 12.2.
evolution of nitrogen oxides under elevated temperature. The 15.5 Gloves—A pair of heavy gloves.
results are not necessarily a predictor of shelf life. 15.6 Pincers—Long pincers for handling the test tubes.
15.7 Thermometer—An ASTM Stability Test Thermometer
having a range from 130 to 140°C and conforming to the
15. Apparatus
requirements for Thermometer 26C as prescribed in Specifi-
15.1 Copper Bath—Copper bath with copper or brass con- cation E 1. The thermometer should be fitted with a cork
denser, as shown in Fig. 5 and Fig. 6. These baths are usually stopper and placed in an empty glass tube in the bath.
made to hold 13 to 15 test tubes. To aid in heat transfer, add 15 15.8 Methyl Violet Test Paper.
to 25 mL of mineral oil to each copper well, in order to fill the
16. Procedure
space between the glass tube and the well. To maintain the bath
at a temperature of 134.5 6 0.5°C, fill to within 3 in. (76 mm) 16.1 Conduct the test in a room that is free of acid fumes.
of the top with a mixture consisting of ten parts of a NOTE 4—Precaution: It is important that the operator wear the cellu-
commercial ethylene glycol solution (automobile radiator an- lose acetate mask and heavy gloves and the tubes be handled with long
tifreeze containing a corrosion inhibitor) and one part of water. pincers.
Adjust the temperature of the boiling liquid in the bath to 134.5
6 0.5°C by adding more glycol or water, as necessary. 5
Borosilicate glass has been found satisfactory for this purpose.
4
D 301
NOTE 1—1 in. = 25.4 mm.

FIG. 5 Copper Bath for Stability Test
NOTE 1—1 in. = 25.4 mm.

FIG. 4 Compensating Tube
16.2 Dry the sample as described in 4.2. Weigh duplicate

specimens of 2.5 6 0.1 g into test tubes and press the
specimens down so that they occupy the lower 2 in. (51 mm)
of the tubes; then swab out all cellulose nitrate particles
adhering to the inside wall of the tubes. Crease a piece (20 by
70 mm) of normal methyl violet test paper for one half its
length; then insert it in the tube with the uncreased portion
downward, until the lower edge is 1 in. above the top of the
specimen. The paper must remain in this portion throughout
the test. Stopper the tube with a cork provided with hole or
notch 4 mm in diameter. Place the tube, without jarring, in the
heating bath maintained at 134.5 6 0.5°C. Beginning at the
end of the first 20 min, inspect the tube at 5-min intervals by
lifting the tube until the methyl violet paper, but not the FIG. 6 Brass Condenser for Stability Test Apparatus
cellulose nitrate, is visible above the surface of the bath. The
end point is reached when the entire test paper changes in color 17. Precision and Bias
to salmon pink. For example, if the color is not completely 17.1 Precision—Statistical analysis of intralaboratory (re-
changed at 20 min but is completely changed at 25 min, record peatability) test results indicates a precision of 65 min at the
the stability of the specimen as 25 min. 95 % confidence level.
NOTE 5—Precaution: As a safety measure, immerse the specimen in 17.2 Bias—No statement of bias can be made as no suitable
cold water immediately upon completion of the test. reference material is available as a standard.
5
D 301
VISCOSITY where:
n = viscosity at the specified temperature, P,
18. Significance and Use a = ball density, g/mL,
b = solution density, g/mL, and
18.1 Coating and lacquer formulations are based on percent t = time of fall, s.
solids in a solvent system. Viscosity is a determining factor in
limiting the percent solids in a given solvent system. 22. Precision and Bias
22.1 Precision—Statistical analysis of intralaboratory (re-
19. Solutions Required peatability) test results indicates a precision of 65.2 % at the
19.1 Determine viscosity by dissolving the cellulose nitrate, 95 % confidence level. The results of an interlaboratory (re-
dried as described in 4.3, according to a standard formula producibility) test study are shown in Test Method D 1343.
(Table 1) and noting the time for a steel ball to fall through a 22.2 Bias—No statement on bias can be made at this time
measured depth of the solution at 25°C. Use formula A for as no material is available to serve as a standard.
types designated as 5 s or over. Use formula B for types TOLUENE DILUTION
designated as 1⁄2 and 3⁄4. Use formula C for types designated as 23. Significance and Use
1⁄4 s and 30 to 35 cp. Cellulose nitrate will dissolve more
23.1 This test method can ascertain whether cellulose nitrate
quickly if it is first wet with alcohol and toluene and the
of a given percent nitrogen is contaminated with material of a
mixture then allowed to stand a few minutes before the ethyl
significantly different nitrogen content. Such cross contamina-
acetate is added. Completely dissolve the sample in the solvent
tion may adversely affect solution and film quality.
mixture by agitating in a tightly closed bottle.
24. Procedure
20. Viscosity Determination 24.1 Prepare a solution containing 12.2 weight percent of
20.1 Measure the viscosity, using the apparatus and follow- cellulose nitrate dried as described in 4.3, and 87.8 weight
ing the procedure described in Test Method D 1343. percent of butyl acetate conforming to Specification D 303. To
50 mL of this solution in a stoppered bottle add toluene,
21. Report conforming to Specification D 362 in small quantities from a
buret, shaking well after each addition.
21.1 Report the results in seconds (Note 6) for a 3⁄32-in.
(2.4-mm) steel ball (density 7.7 6 0.1) and a 2.00 6 0.02-in. 25. Calculation and Report
(50.8 6 0.5-mm) drop. The viscosity value shall be prefixed 25.1 Report as the dilution value the volume of toluene
with the letter A, B, or C, corresponding to the formula of the required to effect the first permanent separation of cellulose
solution employed. nitrate, calculated as a percent by volume of the original
solution, as follows:
NOTE 6—Results in seconds for a 3⁄32-in. steel ball may be converted to
poises as follows: Dilution value 5 ~mL toluene 3 100!/50
5 mL toluene 3 2
n 5 0.560 ~a 2 b! t
NOTE 7—Large quantities of butyl acetate and toluene should be
reserved for this test to avoid possible variation between different lots. The
TABLE 1 Solutions for Viscosity and Film Tests test should be run at 25°C.
Formula Formula Formula 26. Precision and Bias
A B C
Ingredients:
Soluble cellulose nitrate (dried), 12.2 20.0 25.0 peatability) test results indicates a precision of 62 mL at the
weight percent 95 % confidence level.
Completely denatured ethyl alcohol 22.0 20.0 18.75 26.2 Bias—No statement of bias can be made as no suitable
(188 to 190 proof), weight percent
Toluene,A weight percent 48.3 44.0 41.25 reference material is available as a standard.
Ethyl acetate,B weight percent 17.5 16.0 15.0
Density of solution at 25°C (g/mL) 0.90 0.93 0.97
27. Keywords
A
Toluene conforming to Specification D 362. 27.1 ash; cellulose nitrate; drying; nitrogen content; stabil-
B
Ethyl acetate conforming to Specification D 302. ity; toluene dilution; viscosity
6

n-Butyl Alcohol (Butanol)1
1. Scope 3. Properties
1.1 This specification covers n-butyl alcohol (butanol). 3.1 n-butyl alcohol (butanol) shall conform to the following
1.2 For hazard information and guidance, see the supplier’s requirements:
Material Safety Data Sheets. Apparent specific gravity:
20/20°C 0.810 to 0.813
2. Referenced Documents 25/25°C 0.807 to 0.810
Color, Pt-Co scale, max 10
2.1 ASTM Standards: Distillation range, 760 mmHg A
D 268 Guide for Sampling and Testing Volatile Solvents Nonvolatile matter, max, mg/100 mL 5
Water, max, weight % 0.1B
and Chemical Intermediates for Use in Paint and Related Acidity, as acetic acid, max, weight % 0.005C
Coatings and Materials2 ______________
D 891 Test Methods for Specific Gravity, Apparent, of A
Shall distill entirely within a 1.5°C range which shall include 117.7°C.
Liquid Industrial Chemicals3 B
This quantitative water limit ensures that the material is miscible without
D 1078 Test Method for Distillation Range of Volatile turbidity with 19 volumes of 99 % heptane at 20°C.
Organic Liquids2 C
Equivalent to 0.047 mg of KOH per gram of sample.
Cobalt Scale)2 4. Sampling
D 1353 Test Method for Nonvolatile Matter in Volatile 4.1 The material shall be sampled in accordance with
Solvents for Use in Paint, Varnish, Lacquer, and Related Practice E 300.
Products2
D 1364 Test Method for Water in Volatile Solvents (Karl 5. Test Methods
Fischer Reagent Titration Method)2 5.1 The properties enumerated in this specification shall be
D 1476 Test Method for Heptane Miscibility of Lacquer determined in accordance with the following ASTM methods:
Solvents2 5.1.1 Apparent Specific Gravity—Determine the apparent
D 1613 Test Method for Acidity in Volatile Solvents and specific gravity at 20 or 25°C by a convenient method that is
Chemical Intermediates Used in Paint, Varnish, Lacquer, accurate to the third decimal place. See Methods D 268 or Test
and Related Products2 Methods D 891 or D 4052.
D 4052 Test Method for Density and Relative Density of 5.1.2 Color—Test Method D 1209.
Liquids by Digital Density Meter4 5.1.3 Distillation Range—Test Method D 1078 using an
E 1 Specification for ASTM Thermometers5 ASTM Solvents Distillation Thermometer 40C having a range
E 300 Practice for Sampling Industrial Chemicals3 from 72 to 126°C and conforming to the requirements of
2.2 U.S. Federal Specification: Specification E 1.
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging 5.1.4 Nonvolatile Matter—Test Method D 1353.
of 6 5.1.5 Water—Test Methods D 1364 and D 1476.
5.1.6 Acidity—Test Method D 1613.
1
This specification is under the jurisdiction of the ASTM Committee D-1 on 6. Packaging and Package Marking
Paint and Related Coatings, Materials, and Applications and is the direct responsi-
bility of Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermedi- 6.1 Package size shall be agreed upon between the pur-
ates. chaser and the supplier.
Current edition approved Feb. 15, 1995. Published April 1995. Originally 6.2 Packaging shall conform to applicable carrier rules and
2
Annual Book of ASTM Standards, Vol 06.04. regulations, or when specified, shall conform to Fed. Spec.
3
Annual Book of ASTM Standards, Vol 15.05. PPP-C-2020.
4
5
6
Available from Standardization Documents Order Desk, Bldg 4 Section D, 700
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. 7.1 n-butanol; n-butyl alcohol; 1-butanol; propyl carbinol
1
D 304
2

Solvent-Extractable Material in Black Pigments1
1. Scope
1.1 This test method covers the determination of the
solvent-extractable material in black pigments such as carbon
black, lampblack, and bone black.
safety concerns, if any, associated with its use. It is the
2.1 ASTM Standards:
D 329 Specification for Acetone2
3.1 This test method is used by black pigment producers and
users for product acceptance.
4. Apparatus
4.1 Extraction Apparatus, consisting of a flask, siphon cup,
and a condenser similar to the apparatus shown in either Fig. 1
or Fig. 2.
NOTE 1—A Sophlet apparatus may be used as an alternative.
4.2 Extraction Thimbles—The thimble must be made of FIG. 1 Extraction Apparatus
greaseless paper and be of correct size to fill the selected
apparatus. used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
NOTE 2—The recommended thimble size for each of the apparatus
shown in Fig. 1 is listed below: tee on Analytical Reagents of the American Chemical Society,
Fig. 1 Fig. 2
where such specifications are available.3 Other grades may be
Height 70 mm 62 mm used, provided it is first ascertained that the reagent is of
Inside diameter 28 mm 22 mm sufficiently high purity to permit its use without lessening the
Outside diameter 30 mm 24 mm
4.3 The thimbles are available in various heights and widths 5.2 Solvent—Acetone and benzene are the most commonly
with two thickness levels, single thickness or double thickness. used solvents (see Specification D 329); however, other sol-
Single-thickness thimbles are recommended for this extraction vents may be used as agreed upon.
procedure. 5.3 Glass Wool.
5. Reagents and Material 6. Procedure
5.1 Purity of Reagents—Reagent grade chemicals shall be 6.1 Weight approximately 10 g of pigment (moisture-free)
1 3
This test method is under the jurisdiction of ASTM Committee D-1 on Paint Reagent Chemicals, American Chemical Society Specifications, American
and Related Coatings, Materials, and Applications and is the direct responsibility of Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Subcommittee D01.31 on Pigment Specifications. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved Aug. 31, 1984. Published October 1984. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 305 – 29 T. Last previous edition D 305 – 72 (1978). and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
1
D 305
6.2 When using acetone as the extraction solvent, extract
continuously for 4 h, heating at a rate such that the time
required to fill and empty the siphon cup will not exceed 8 min.
With other solvents extract for 16 h.
NOTE 3—If particles of carbon have escaped from the cup into the
extraction liquid, filter the liquid, wash the paper with solvent, and return
the total filtrate to the extraction flask, prior to continuing with 6.3.
6.3 Transfer quantitatively the extract solution to a 400-mL
beaker that has been weighed to the nearest 0.1 g, and
evaporate off the solvent on a steam bath or plate. Remove the
beaker from the bath or hot plate just before the last trace of the
solvent disappears. Dry the dish for 1 h at 105°C (221°F). Cool
and weigh to the nearest 0.1 g.
7. Calculation
7.1 Calculate the percent extractable material, E, to the
nearest 0.05 % as follows:
E 5 @~R 2 B!/~S 2 W!# 3 100
where:
R 5 weight of extractable material and weighed dish, g,
B 5 weight of weighed dish, g,
S 5 weight of thimble and specimen, g, and
W 5 weight of thimble, g.
FIG. 2 Extraction Apparatus

8. Precision
8.1 Precision data are not available at this time. When they
into a weighed thimble and record the weight to 0.1 g. For are available the appropriate precision statements will be
pigments with high apparent density (bone black, iron oxides, added.
etc.) a 40-g sample is recommended. Plug the open end of the
thimble with glass wool and place in the siphon cup. Add 200 9. Keywords
to 250 mL of the solvent to the previously dried flask. 9.1 black pigment; solvent extractable
2

Amyl Alcohol (Synthetic)1,2
1.1 This specification covers synthetic amyl alcohol. 3.1 Amyl alcohol (synthetic) shall conform to the following
1.2 For hazard information and guidance, see the supplier’s requirements:
Material Safety Data Sheet. Apparent specific gravity
20/20°C 0.812–0.820
2. Referenced Documents 25/25°C 0.809–0.817
2.1 ASTM Standards: Distillation range, 760 mmHg, °C as:
D 268 Guide for Sampling and Testing Volatile Solvents Initial boiling point, min 127.5
Dry point, max 139.0
and Chemical Intermediates for Use in Paint and Related Water, max, weight % 0.3A
Coatings and Materials3 Acidity, as acetic acid, max, weight % 0.01B
D 891 Test Methods for Specific Gravity, Apparent, of ______________
Liquid Industrial Chemicals4
A
D 1078 Test Method for Distillation Range of Volatile turbidity with 19 volumes of 99 % heptane at 20°C.
Organic Liquids3 B
D 1364 Test Method for Water in Volatile Solvents (Karl 4.1 The material shall be sampled in accordance with
Fischer Reagent Titration Method)3 Practice E 300.
D 1476 Test Method for Heptane Miscibility of Lacquer
Solvents3 5. Test Methods
D 1613 Test Method for Acidity in Volatile Solvents and 5.1 The properties enumerated in this specification shall be
Chemical Intermediates Used in Paint, Varnish, Lacquer determined in accordance with the following ASTM methods:
and Related Products3 5.1.1 Apparent Specific Gravity—Determine the apparent
D 4052 Test Method for Density and Relative Density of specific gravity at 20 or 25°C by a convenient method that is
Liquids by Digital Density Meter5 accurate to the third decimal place. See Methods D 268 or Test
E 1 Specification for ASTM Thermometers6 Methods D 891 or D 4052.
E 300 Practice for Sampling Industrial Chemicals4 5.1.2 Color—Test Method D 1209.
2.2 U.S. Federal Specification: 5.1.3 Distillation Range—Test Method D 1078, using an
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging ASTM Solvents Distillation Thermometer 41C having a range
of 7 from 98 to 152°C and conforming to the requirements in
Specification E 1.
5.1.4 Water—Test Methods D 1364 and D 1476.
1
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
6. Packaging and Package Marking
Current edition approved Feb. 15, 1995. Published April 1995. Originally 6.1 Package size shall be agreed upon between the pur-
published as D 319 – 30. Last previous edition D 319 – 90. chaser and the supplier.
2
Amyl alcohol is also known as pentanol. This material is a mixture of the
isomers of amyl alcohol. 6.2 Packaging shall conform to applicable carrier rules and
3
Annual Book of ASTM Standards, Vol 06.04. regulations, or when specified, shall conform to Fed. Spec.
4
5
6
7
Available from Standardization Documents Order Desk, Bldg 4 Section D, 700
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. 7.1 amyl alcohol; pentanols
1
D 319
2

Acetone1,2
1. Scope * and Related Products3

1.1 This specification covers acetone (99.5 % grade). D 1614 Test Method for Alkalinity in Acetone3
1.2 This standard does not purport to address all of the D 1722 Test Method for Water Miscibility of Water-Soluble
safety concerns, if any, associated with its use. It is the Solvents3
responsibility of the user of this standard to establish appro- D 4052 Test Method for Density and Relative Density of
priate safety and health practices and determine the applica- Liquids by Digital Density Meter4
bility of regulatory limitations prior to use. Specific hazard E 1 Specification for ASTM Thermometers5
statements are given in 1.3 and 4.1. E 300 Practice for Sampling Industrial Chemicals6
1.3 This specification specifies the use of a U.S. Occupa- 2.2 U.S. Federal Specification:7
tional Safety and Health Administration (OSHA)-designated PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging
hazardous chemical, acetone. For hazard information and of
guidance see the supplier’s Material Safety Data Sheet. 3. Properties
2. Referenced Documents 3.1 Acetone (99.5 % grade) shall conform to the following
2.1 ASTM Standards: requirements:
D 268 Guide for Sampling and Testing Volatile Solvents Acidity (free acid as acetic) 0.002 (equivalent to 0.019 mg of KOH/g of
wt %, max sample)
and Chemical Intermediates for Use in Paint and Related Aldehydes passes test
Coatings and Materials3 Alkalinity (as ammonia) 0.001
D 1078 Test Method for Distillation Range of Volatile wt %, max
Apparent specific gravity:
Organic Liquids3 20/20°C 0.7910 to 0.7930
D 1209 Test Method for Color of Clear Liquids (Platinum- 25/25°C 0.7865 to 0.7885
Cobalt Scale)3 Assay wt %, min 99.5
Color Pt-Co, max 5
D 1296 Test Method for Odor of Volatile Solvents and Distillation range 760 shall distill entirely within a 1.0°C range
Diluents3 mmHg which shall include 56.1°C
D 1353 Test Method for Nonvolatile Matter in Volatile Nonvolatile matter 5
mg/100 mL, max
Solvents for Use in Paint, Varnish, Lacquer, and Related Odor (Note 2) nonresidual
Products3 Permanganate time color of added KMnO4 must be retained for
D 1363 Test Method for Permanganate Time of Acetone at least 30 minutes at 25°C in the dark
Water wt %, max 0.5 (Note 1)
and Methanol3 Water miscibility passes test
D 1364 Test Method for Water in Volatile Solvents (Karl ____________
Fischer Reagent Titration Method)3 NOTE 1— This quantitative water limit ensures that the material is
D 1476 Test Method for Heptane Miscibility of Lacquer miscible without turbidity with 19 volumes of 99 % heptane at 20°C.
Solvents3 NOTE 2—Optional: Test for odor only when agreed upon as necessary
D 1613 Test Method for Acidity in Volatile Solvents and between the purchaser and the supplier.
Chemical Intermediates Used in Paint, Varnish, Lacquer,
4. Sampling
1
4.1 The material shall be sampled in accordance with
4
5
published as D 329 – 31 T. Last previous edition D 329 – 95. Annual Book of ASTM Standards, Vol 14.03.
2 6
The compound is also known under the names dimethyl ketone and Annual Book of ASTM Standards, Vol 15.05.
7
2-propanone. Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
3

1
D 329
Practice E 300. Warning: Acetone is highly flammable. 5.1.6 Color—Test Method D 1209.
5.1.7 Distillation Range—Test Method D 1078 using an
5. Test Methods ASTM Solvents Distillation Thermometer 39C having a range
5.1 The properties enumerated in this specification shall be from 48 to 102°C in 0.2°C subdivisions or Thermometer 14 C
determined in accordance with the following ASTM methods: having a range from 38 to 82°C in 0.1°C subdivisions, and
5.1.1 Acidity—Test Method D 1613. conforming to the requirements in Specification E 1.
5.1.2 Aldehydes—Dilute 2.5 mL of the specimen with water 5.1.8 Nonvolatile Matter—Test Method D 1353.
to 10 mL. Prepare a control containing 0.04 mg of formalde- 5.1.9 Odor—Test Method D 1296.
hyde in 10 mL of water. To both the specimen solution and the 5.1.10 Permanganate Time—Test Method D 1363.
control, add 0.15 mL of a 5 % solution of 5,5-dimethyl-1,3- 5.1.11 Water—Test Methods D 1364 for quantitative deter-
cyclohexanedione in alcohol. Evaporate each on a steam bath mination and D 1476 for qualitative determination.
until the acetone is volatilized. Dilute each to 10 mL and cool 5.1.12 Water Miscibility—Test Method D 1722.
quickly in an ice bath with vigorous stirring. Any turbidity
produced in the specimen solution shall be no greater than that 6. Packaging and Package Marking
produced in the control.
5.1.3 Alkalinity—Test Method D 1614. 6.1 Package size shall be agreed upon between the pur-
5.1.4 Apparent Specific Gravity—Determine the apparent chaser and the supplier.
specific gravity by any convenient method that is accurate to 6.2 Packaging shall conform to applicable carrier rules and
the fourth decimal place, the temperature of both specimen and regulations or when specified shall conform to Federal Speci-
water being 20 or 25°C. See Guide D 268 and Test Method fication PPP-C-2020.
D 4052.
5.1.5 Assay—Assay is determined by difference; 100 % 7. Keywords
minus (% water + % acidity), assuming that no other impuri- 7.1 acetone; aldehydes test; dimethyl ketone; 2-propanone;
ties are present. solvents
SUMMARY OF CHANGES
(1) Deletion of reference to Federal Specification O-A-51, (3) In 5.1.2 Aldehydes, deletion of the parenthetical statement
which has been cancelled and defers to ASTM Specification D “(no odor of acetone remains)” so that the person performing
329. the test is not required to breathe acetone vapor.
(2) Deletion of Note 1 which indicates that the aldehydes test
is a requirement of Federal Specification O-A-51.
2
Designation: D 330 – 93 (Reapproved l997)

2-Butoxyethanol1,2
1.1 This specification covers 2-butoxyethanol. 3.1 2-Butoxyethanol shall conform to the following require-
1.2 For specific hazard information and guidance, see the ments:
supplier’s Material Safety Data Sheet for materials listed in this Apparent specific gravity
specification. 20/20°C 0.901 to 0.904
25/25°C 0.898 to 0.901
2. Referenced Documents Distillation range, 760 mm Hg
2.1 ASTM Standards: Initial boiling point, °C, min 168
Dry point, °C, max 173
D 268 Guide for Sampling and Testing Volatile Solvents Water, weight %, max 0.1
and Chemical Intermediates for Use in Paint and Related Acidity (free acid as acetic acid), 0.01 equivalent to 0.093 mg KOH per
Coatings and Materials3 weight %, max gram of material
D 1078 Test Method for Distillation Range of Volatile 4. Sampling
Organic Liquids3
D 1209 Test Method for Color of Clear Liquids (Platinum- 4.1 The material shall be sampled in accordance with
Cobalt Scale)3 Practice E 300.
D 1364 Test Method for Water in Volatile Solvents (Fischer 5. Test Methods
Reagent Titration Method)3
Chemical Intermediates Used in Paint, Varnish, Lacquer, determined in accordance with the following ASTM methods:
D 4052 Test Method for Density and Relative Density of specific gravity by any convenient method that is accurate to
Liquids by Digital Density Meter4 the third decimal place, the temperature of both specimen and
E 1 Specification for ASTM Thermometers5 water being 20 or 25°C (See Guide D 268 or Test Methods
E 300 Practice for Sampling Industrial Chemicals6 D 4052.)
2.2 U.S. Federal Standard: 5.1.2 Color—Test Method D 1209.
PPP-C-2020 Specification for Packaging of Chemicals, Liq- 5.1.3 Distillation Range—Test Method D 1078 using an
uid, Dry, and Paste7 ASTM Solvents Distillation Thermometer 103C having a
range from 148 to 202°C and conforming to the requirements
in Specification E 1.
5.1.4 Water—Test Method D 1364.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.5 Acidity—Test Method D 1613.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 6. Packaging and Package Marking
Current edition approved Sept. 15, 1993. Published November 1993. Originally 6.1 Package size to be agreed upon between the purchaser
2
This compound is also known under the name ethylene glycol monobutyl ether. and the supplier.
3
Annual Book of ASTM Standards, Vol 06.04. 6.2 Packaging shall conform to applicable carrier rules and
4
Annual Book of ASTM Standards, Vol 05.02. regulations or when specified shall conform to PPP-C-2020.
5
6
7
Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
Robbins Ave., Philadelphia, PA 19111-5094. 7.1 ethylene glycol monobutyl ether; 2–butoxyethanol
1
D 330
2

2-Ethoxyethanol1,2
1.1 This specification covers 2-ethoxyethanol. 3.1 2-Ethoxyethanol shall conform to the following require-
1.2 For hazard information and guidance, see the supplier’s ments:
Material Safety Data Sheets. Apparent specific gravity:
20/20°C 0.929 to 0.932
2.1 ASTM Standards: Distillation range, 760 mm Hg, °C as:
D 268 Guide for Sampling and Testing Volatile Solvents Initial boiling point, min 134.0
and Chemical Intermediates for Use in Paint and Related Nonvolatile matter, max, mg/100 mL 5
Coatings and Materials3 Water, max, weight % 0.1A
D 1078 Test Method for Distillation Range of Volatile Acidity (free acid as acetic acid), max, weight % 0.01B
__________
Organic Liquids3
A
D 1209 Test Method for Color of Clear Liquids (Platinum- This quantitative water limit ensures that the material is miscible without
turbidity with 19 volumes of 99 % heptane at 20°C.
Cobalt Scale)3 B
Equivalent to 0.1 mg of KOH per gram of material.
D 1353 Test Method for Nonvolatile Matter in Volatile
Solvents for Use in Paint, Varnish, Lacquer, and Related 4. Sampling
Products3
D 1364 Test Method for Water in Volatile Solvents (Karl
Practice E 300.
Fischer Reagent Titration Method)3
D 1613 Test Method for Acidity in Volatile Solvents and 5. Test Methods
Chemical Intermediates Used in Paint, Varnish, Lacquer 5.1 The properties enumerated in this specification shall be
and Related Products3 determined in accordance with the following ASTM methods:
D 4052 Test Method for Density and Relative Density of 5.1.1 Apparent Specific Gravity—Determine the apparent
Liquids by Digital Density Meter4 specific gravity by any convenient method that is accurate to
E 1 Specification for ASTM Thermometers5 the third decimal place, the temperature of both specimen and
E 300 Practice for Sampling Industrial Chemicals6 water being 20°C or 25°C. See Methods D 268 or Test Method
2.2 U. S. Federal Specification: D 4052.
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging 5.1.2 Color—Test Method D 1209.
of 7 5.1.3 Distillation Range—Test Method D 1078 using an
ASTM Solvents Distillation Thermometer 102C having a
range from 123 to 177°C and conforming to the requirements
of Specification E 1.
1
5.1.4 Nonvolatile Matter—Test Method D 1353.
and Related Coatings, Materials, and Applications and is the direct responsibility of 5.1.5 Water—Test Method D 1364.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 5.1.6 Acidity—Test Method D 1613.
Current edition approved Feb. 15, 1995. Published April 1995. Originally
published as D 331 – 32 T. Last previous edition D 331 – 90. 6. Packaging and Package Marking
2
This compound is also known under the name ethylene glycol monoethyl ether.
3
Annual Book of ASTM Standards, Vol 06.04. 6.1 Package size to be agreed upon between the purchaser
4
5
Annual Book of ASTM Standards, Vol 05.02. and the supplier.
Annual Book of ASTM Standards, Vol 14.03. 6.2 Packaging shall conform to applicable carrier rules and
6
7
Available from Standardization Documents Order Desk, Bldg,4 Section D, 700 regulations, or when specified, shall conform to Fed. Spec.
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. PPP-C-2020.
1
D 331
7. Keywords
7.1 ethylene glycol monoethyl ether; 2-ethoxyethanol
2

Shellac Varnishes1
e1 NOTE—Keywords were added editorially in October 1996.
1. Scope agreement between the purchaser and the seller.

1.1 This specification covers shellac varnish consisting of a 6. Body and Cut
solution or “cut” of a specified type and grade of dry lac resin
in specially denatured alcohol. Ninety-five percent (190 proof) 6.1 The body and cut of the respective types and grades
ethyl alcohol, specially denatured according to Formula No. 1 shall be based on the percent of nonvolatile matter and shall
of the Alcohol, Tobacco, and Firearms of the Treasury Dept., is conform to the following minimum requirements:
the solvent most commonly used. However, other specially Nonvolatile Matter, min,
%
denatured alcohols and proprietary solvents are also used for Bleached,
this purpose. Orange, Regular
Grades and
2. Referenced Documents A and B Refined
2.1 ASTM Standards: Very light body (3-lb (1.4-kg) cut) 28.5 28.0
D 29 Test Methods of Sampling and Testing Lac Resins2 varnish
Light body (4-lb (1.8-kg) cut) varnish 35.0 34.5
D 207 Specification for Dry Bleached Lac2 Medium body (4.5-lb (2.0-kg) cut) 37.5 37.0
D 237 Specification for Orange Shellac and Other Lacs2 varnish
Heavy body (5-lb (2.3-kg) cut) varnish 40.0 39.5
3. Types, Grades, and Bodies Very heavy body (6-lb (2.7-kg) cut) 44.0 43.5
varnish
3.1 This specification covers two grades, A and B, of orange Extra heavy body (8-lb (3.6-kg) cut) 51.0 50.5
shellac varnish and two grades, regular and refined, of bleached varnish
lac varnish. Each type and grade may be furnished in very NOTE 2—The term “cut” is defined as the number of pounds of dry lac
light, light, medium, heavy, very heavy, or extra heavy body resin (containing only that amount of moisture acceptable for proper
varnish, as specified. cutting with the solvent to ensure a satisfactory varnish) that were added
to 1 gal (3.8 L) of specified solvent in manufacturing the varnish.
4. Color Allowance has, therefore, been made for 2 % maximum moisture and
other volatile matter and 3 % insoluble matter in orange shellac, and for
4.1 The color of shellac varnish shall be no darker than the 6 % moisture and other volatile matter in bleached lac, in arriving at a
color of a standard varnish of the same nonvolatile matter minimum value. Varnishes of the above specified bodies or “cuts” should
content mutually agreed upon between the purchaser and the accordingly conform to the respective minimum requirements specified
seller. for nonvolatile matter.
NOTE 1—Attention is called to the fact that the purchaser and the seller 7. Properties of Dry Lac
must agree upon one of the two methods for determining color appearing
in Test Methods D 29. 7.1 The nonvolatile matter in the varnish shall conform to
the Properties section of Specification D 207 and Table 1 of
5. Drying Time Specification D 237.
5.1 Shellac varnish shall dry hard in 1 h. Shellac varnishes
8. Packaging and Marking
having a body greater than that for a light body varnish shall be
thinned to the nonvolatile matter content of a light body 8.1 Shellac varnish shall be packaged in standard commer-
varnish. Special conditions for this test may be made by mutual cial containers of the type and size mutually agreed upon
between the purchaser and the seller. The label of the container
shall show the type, grade, body or cut, and date of manufac-
1
This specification is under the jurisdiction of the ASTM Committee D-1 on ture of the varnish contained therein.
Paint and Related Coatings, Materials, and Applications, and is the direct respon-
sibility of Subcommittee D01.33 on Polymers and Resins. 9. Test Methods
published as D 360 – 33. Last previous edition D 360 – 73 (1981). 9.1 The sampling and methods of testing shall be conducted
2
1
D 360
in accordance with Test Methods D 29. 10. Keywords
10.1 denatured alcohol; dry lac resin; orange shellac; shellac
varnish
2

Tricresyl Phosphate1
1.1 This specification covers tricresyl phosphate (99.0 % 3.1 Tricresyl phosphate shall conform to the following
grade) prepared from commercial cresylic acid. requirements:
1.2 For specific hazard information and guidance, see the Apparent specific gravity:
supplier’s Material Safety Data Sheets for materials listed in 20/20°C 1.150 to 1.180
25/25°C 1.147 to 1.177
this specification. Color, Pt-Co scale, max 100
Volatile matter, max, weight % 0.20
2. Referenced Documents Potassium permanganate test A
Unsaponifiable matter, max, weight % 0.5

2.1 ASTM Standards: Water content, max, weight % 0.1
D 268 Guide for Sampling and Testing Volatile Solvents Acidity, mg of KOH per gram 0.1
and Chemical Intermediates for Use in Paint and Related of sample, max
____________
Coatings and Materials2 A
Color of added KMnO4 to be retained at least 30 min.
D 1364 Test Method for Water in Volatile Solvents (Fischer
Reagent Titration Method)2
Practice E 300.
D 1399 Test Method for Unsaponifiable Contents of Tricr-
esyl Phosphate2 5. Test Methods
D 1468 Test Method for Volatile Matter in Tricresyl Phos-
phate2
determined in accordance with the following ASTM methods:
5.1.1 Apparent Specific Gravity—Determine the apparent
Chemical Intermediates Used in Paint, Varnish, Lacquer
specific gravity at 20°C or 25°C by a convenient method that
is accurate to the third decimal place. See Guide D 268 or Test
D 1721 Test Method for Permanganate Time of Tricresyl
Method D 4052.
Phosphate2
5.1.2 Color—Test Method D 1209.
D 4052 Test Method for Density and Relative Density of
5.1.3 Volatile Matter—Test Method D 1468.
Liquids by Digital Density Meter3
5.1.4 Potassium Permanganate Test—Test Method D 1721.
E 300 Practice for Sampling Industrial Chemicals4
5.1.5 Unsaponifiable Matter—Test Method D 1399.
2.2 U.S. Federal Specification:
5.1.6 Water—Test Method D 1364.
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging
of5
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 6.1 Package size shall be agreed upon between the pur-
and Related Coatings, Materials, and Applications and is the direct responsibility of chaser and the supplier.
Current edition approved May 25, 1990. Published July 1990. Originally 6.2 Packaging shall conform to applicable carrier rules and
published as D 363 – 33. Last previous edition D 363 – 85. regulations or when specified shall conform to Fed. Spec.
2
3
4
5
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. 7.1 tricresyl phosphate
1
D 363
2

Chemical Analysis of Zinc Yellow Pigment (Zinc Chromate
Yellow)1
1. Scope E 50 Practices for Apparatus, Reagents, and Safety Precau-

1.1 These test methods cover procedures for the chemical tions for Chemical Analysis of Metals5
analysis of the pigment known commercially as “zinc yellow”
or“ zinc chromate yellow.”
1.2 The analytical procedures appear in the following order: 3.1 This test method has been developed to standardize the
Sections
chemical analysis of zinc chromate yellow pigment and to
Moisture and Other Volatile Matter 7 provide alternate methods of analysis for chromium and zinc.
Combined Water 8
Chromium: 4. Preparation of Sample
Dichromate Method 9-11
Thiosulfate Method 9, 12, and 13 4.1 Mix the laboratory sample thoroughly. Take a sufficient
Zinc: quantity for the chemical analyses and pass it through a
Hydroxyquinoline Method 9, 14, and 15
Ferrocyanide Method 9, 16, and 17
180-µm (No. 80) sieve, grinding in a mortar if necessary.
Alkaline Salts 18 and 19 NOTE 1—Detailed requirements for this sieve are given in Specification
Sulfates 20 and 21
Chlorides 22 and 23
E 11.
Matter Insoluble in Dilute Acetic 24
Acid 5. Reagents
Coarse Particles 25
5.1 Purity of Reagents—Unless otherwise indicated, it is
1.3 This standard does not purport to address all of the intended that all reagents shall conform to the specifications of
safety concerns, if any, associated with its use. It is the the Committee on Analytical Reagents of the American Chemi-
responsibility of the user of this standard to establish appro- cal Society, where such specifications are available.6 Other
priate safety and health practices and determine the applica- grades may be used, provided it is first ascertained that the
bility of regulatory limitations prior to use. reagent is of sufficiently high purity to permit its use without
lessening the accuracy of the determination.
2. Referenced Documents 5.2 Purity of Water—Unless otherwise indicated, references
2.1 ASTM Standards: to water for use in the preparation of reagents and in analytical
D 185 Test Methods for Coarse Particles in Pigments, procedures shall conform to Type II reagent water, in Specifi-
Pastes, and Paints2 cation D 1193.
D 280 Test Methods for Hygroscopic Moisture (and Other
Matter Volatile Under the Test Conditions) in Pigments3 6. Precision
D 478 Specification for Zinc Yellow (Zinc Chromate)3 6.1 Precision statements have not been established.
D 1193 Specification for Reagent Water3
E 11 Specification for Wire-Cloth Sieves for Testing Pur-
poses4
1
5
and Related Coatings, Materials, and Applications and are the direct responsibility Annual Book of ASTM Standards, Vol 03.05.
6
of Subcommittee D 01.31 on Pigment Specifications. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Oct. 31, 1988. Published December 1988. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 444 – 37. Last previous edition D 444 – 81(1987)e1. listed by the American Chemical Society, see Analar Standards for Laboratory
2
Annual Book of ASTM Standards, Vol 06.03. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
3
4
1
D 444
MOISTURE AND OTHER VOLATILE MATTER of H2SO4 (sp gr 1.84). Cool to 35°C or below.
11.2 Add an excess of ferrous ammonium sulfate solution
7. Procedure and back-titrate with 0.1 N K2Cr 2O7 solution, using ortho-
7.1 Determine moisture and other volatile matter in accor- phenanthroline indicator. Carry out a blank titration of the
dance with Test Method A of Test Method D 280. same amount of ferrous ammonium sulfate solution at the same
time and in the same manner.
COMBINED WATER
11.3 Calculation—Calculate the percent of chromium C as
8. Procedure CrO3, as follows:
8.1 Weigh to 0.1 mg 3 g of the oven-dried material from the C 5 ~B1 2 V 1!N1 3 0.03334/S1 3 100
determination of moisture and other volatile matter (Note 2 and
Note 3), and place in a porcelain boat. Introduce the boat with where:
the charge into a refractory combustion tube in an electrically- B1 5 K2Cr2O7 solution required for titration of the
heated combustion furnace of the type used for the determina- blank, mL,
V1 5 K2Cr2O 7 solution required for back-titration of
tion of carbon in steel by direct combustion (Note 4). Place the
the specimen, mL,
boat at the center of the combustion tube maintained at a
N1 5 normality of the K2Cr2O7 solution, and
temperature of 1000°C for 4 h. Draw a current of pure dry air S1 5 specimen in the aliquot used, g.
or dry nitrogen through the tube to sweep the evolved moisture 0.03334 5 milliequivalents weight of CrO3.
into a previously weighed absorption tube containing anhy- 11.4 Alternatively, the solution of the specimen may be
drous magnesium perchlorate (Mg(ClO4)2) or other efficient titrated directly with the ferrous ammonium sulfate solution,
desiccant. The weight increase of the absorption tube repre- using an electrometric titration assembly to detect the end
sents the “combined water.” point. Standardize the ferrous solution against K2Cr2O7.
NOTE 2—Loss on ignition of the pigment does not suffice for the
determination of combined water in zinc yellow. CHROMIUM BY THE THIOSULFATE TEST
NOTE 3—If the pigment contains an organic treating agent, first remove METHOD
this treating agent by washing with ether or chloroform.
NOTE 4—See Apparatus No. 1 for the determination of total carbon by 12. Reagents
direct combustion as described in Practices E 50.
12.1 Potassium Iodide Solution (150 g/L)—Dissolve 150 g
SPECIMEN SOLUTION FOR DETERMINATION OF of potassium iodide (KI) in water and dilute to 1 L.
CHROMIUM AND ZINC 12.2 Sodium Thiosulfate, Standard Solution (0.1 N)—
Dissolve 24.8 g of sodium thiosulfate of (Na2S2O3 · 5H2O) in
9. Procedure 1 L of freshly boiled and cooled water contained in a sterile
9.1 Weigh to 0.1 mg about a 4-g specimen and mix with 50 glass bottle. If sulfur precipitates during preparation or upon
mL of cold sulfuric acid (H2SO4) (1+5). It should dissolve subsequent use, discard the solution and prepare a new one.
completely at this stage (Note 5). Dilute the solution to 500 mL Standardize against iodine.
in a volumetric flask. 12.3 Starch Indicator Solution—Stir up 2 to 3 g of potato
starch with 100 mL salicylic acid solution (1 %), and boil the
NOTE 5—A cloudy solution may result if the pigment contains a
surface-treating agent. In this case, it usually can be cleared by cooling in
mixture until the starch is practically dissolved, then dilute to
an ice-bath and filtering through a medium porosity fritted disk. If the 1 L with water.
solution is not clarified by this treatment, extract a portion of the original
sample with a solvent such as chloroform before the analysis is begun. 13. Procedure
13.1 Pipet a 25-mL aliquot of the solution of the specimen
CHROMIUM BY THE DICHROMATE TEST (Section 9) into a 500-mL glass-stoppered Erlenmeyer iodi-
METHOD metric flask or other suitable glass-stoppered bottle containing
10. Reagents 200 mL of H 2SO4 (1+39). Add 20 mL of KI solution (150 g/L),
stopper, and allow the solution to stand for approximately 5
10.1 Ferrous Ammonium Sulfate Solution— Dissolve 80 g
min.
of ferrous ammonium sulfate (FeSO4 · (NH 4)2SO4 · 6H2O) in
13.2 Titrate the liberated iodine with 0.1 N Na2S2O3 solu-
50 mL of H2SO4 (sp gr 1.84) and enough water to make 1 L of
tion at room temperature until the reddish brown iodine color
solution. Mix thoroughly before use. This solution is approxi-
becomes quite faint. Add 5 mL of starch solution and continue
mately 0.2 N.
the titration until the final color change becomes pale green
10.2 Ortho-Phenanthroline Indicator Solution—0.5 % in
with no blue tinge. Titrate this final titration by swirling the
water.
flask at least three times after each addition of the Na2S2O 3
10.3 Potassium Dichromate, Standard Solution (0.1 N)—
solution, being sure that there is no further color change,
Dissolve 4.9035 g of dried potassium dichromate (K2Cr2O7) in
especially at the final stage of the titration. The green end point
water and dilute to 1 L in a volumetric flask.
is definite and sharp.
11. Procedure 13.3 Calculation—Calculate the percent of chromium C as
11.1 Pipet 50 mL of the solution of the specimen (Section 7) CrO3 as follows:
into a 600-mL beaker. Add 200 to 250 mL of water and 10 mL C 5 @~V2N2 3 0.03334!/S 2# 3 100
2
D 444
where: with hot water and heat nearly to boiling. Run in the
V 2 5 Na2S2O3 solution required for titration of the speci- K4Fe(CN)6 solution slowly from a buret, while stirring con-
men, mL stantly, until a drop tested on a white porcelain plate with a
N2 5 normality of the Na2S 2O3 solution, and drop of the uranyl indicator solution shows a brown tinge after
S 2 5 specimen in the aliquot used, g. standing 1 min. Do not allow the temperature of the solution to
fall below 70°C during the titration. Run a blank using the
ZINC BY THE HYDROXYQUINOLINE TEST same amounts of reagents and water as in the standardization.
METHOD
The standardization must be made under the same conditions
(Suitable if No Interfering Substances Are Present) of temperature, volume, and acidity as obtained when the
specimen is titrated. Calculate the strength of the K4Fe(CN)6
14. Reagents
solution in terms of grams of zinc as follows:
14.1 Acetone Solution of 8-Hydroxyquinoline (50 g/L)—
Z 5 W/~V3 2 B2!
Dissolve 5 g of 8-hydroxyquinoline in 100 mL of acetone.
where:
15. Procedure Z 5 zinc equivalent of the K4Fe(CN)6 solution, g/mL,
15.1 Pipet 50 mL of the solution of the specimen (Section 9) W 5 zinc used (or equivalent to the ZnO used), g,
into a 250-mL beaker and dilute to 100 mL with water. Add 5 V3 5 K4Fe(CN)6 solution required for titration of the
to 10 g of ammonium chloride (NH4Cl) and heat to boiling. standard, g, and
Add a slight excess of ammonium hydroxide (NH4OH) and let B 2 5 K4Fe(CN)6 solution required for titration of the
stand a few minutes to allow any precipitate to coagulate. Filter blank, mL.
through an ashless, rapid paper into a 400-mL beaker and 16.3 Thymol Blue Indicator Solution (0.5 g/L)—Dissolve
wash. 0.1 g of thymol blue indicator in 200-mL of methanol, ethanol,
15.2 Heat the filtrate to boiling and add 5 mL of NH 4OH (sp or isopropanol.
gr 0.90). Add dropwise 10 mL of the acetone solution of 16.4 Uranyl Acetate Indicator Solution (50 g/L)—Dissolve
8-hydroxyquinoline (Note 6). Let stand 10 to 20 min and filter
5 g of UO2(C2H 3O2)2 · H2O in water made slightly acid with
through a medium-porosity sintered-glass crucible. Wash well
acetic acid and dilute to 100 mL.
with water.
NOTE 6—The reagent is used in acetone solution rather than alcohol 17. Procedure
solution to eliminate the danger of reducing some of the chromate by
alcohol. Avoid adding an excess of reagent and lengthy boiling after its 17.1 Pipet 50 mL of the solution of the specimen (Section 9)
addition. Ten millilitres of hydroxyquinoline (50 g/L) is sufficient for a into a 400-mL beaker. Add 35 mL of H2SO4 (1+5) and 3 to 4
normal zinc yellow. The solution can be tested for complete precipitation, drops of thymol blue indicator solution. First add NH 4OH (sp
but since the reagent itself is rather insoluble, the results may be
gr 0.90) and finally NH4OH (1+10) until the color of the
misleading. The insoluble reagent will dissolve in a hot solution and also
in an excess of alcohol or acetone, whereas the zinc oxyquinolate will not. indicator changes to a salmon shade intermediate between pink
and yellow. This gives a pH of about 2.4. Dilute the solution to
15.3 Dry the precipitate at 165°C for at least 2 h and weigh
300 mL and heat to just under boiling. Pass in H2S at a
as zinc oxyquinolate.
moderate rate for 40 min. Allow the precipitate to settle for 1
15.4 Calculation—Calculate the percent zinc A as zinc
oxide (ZnO), as follows: h and filter. Wash the filter ten times with water saturated with
hydrogen sulfide gas (H2S).
A 5 @~P 3 0.2303!/S 3# 3 100
17.2 Dissolve the precipitate in hot HCl (1+3) and wash the
where: filter paper well with hot water. Boil out the H2S, neutralize to
P 5 zinc oxyquinolate, g, and methyl orange with NH4OH, and dilute to 300 mL. Add 2 g of
S3 5 specimen in aliquot used, g. NH 4Cl and 3 mL of HCl (sp gr 1.19), and heat to boiling.
0.2303 5 ZnO/zinc oxyquinolate 5 81.38/353.37 17.3 Titrate the hot solution with K4Fe(CN) 6 solution
ZINC BY THE FERROCYANIDE TEST METHOD (16.2), using uranyl acetate as an external indicator on a spot
plate or 1 to 2 drops of ferrous ammonium sulfate solution as
16. Reagents an internal indicator.
16.1 Methyl Orange Indicator Solution— Dissolve 0.1 g of 17.4 Calculation—Calculate the percent zinc A as ZnO, as
methyl orange in 100 mL of water. follows:
16.2 Potassium Ferrocyanide, Standard Solution—Dissolve A 5 ~V4Z/S4! 3 100
22 g of potassium ferrocyanide (K4Fe(CN)6· 3H2O) in water
and dilute to 1 L. To standardize, transfer 0.2 g of metallic zinc where:
or freshly ignited ZnO to a 400-mL beaker. Dissolve in 10 mL V 4 5 K4Fe(CN)6 solution required for titration of the
of hydrochloric acid (HCl, sp gr 1.19) and 20 mL of water. specimen, mL,
Drop in a small piece of litmus paper, add ammonium Z 5 ZnO equivalent of the K4Fe(CN)6 solution, g/mL,
hydroxide (NH4OH) until slightly alkaline, then add HCl until and
S4 5 specimen in the aliquot used, g.
just acid, and then 3 mL more of HCl. Dilute to about 250 mL
3
D 444
ALKALINE SALTS Add 75 mL of HCl (sp gr 1.19). Boil the solution under a hood
until the rapid evolution of chlorine has subsided. Add 5 mL of
18. Reagents methyl alcohol and boil to a volume of about 35 mL (Note 9).
18.1 Gelatin Solution (0.2 g/L)—Dissolve 0.2 g of low-ash Add 25 mL of HCl and continue boiling. Add 5 mL of methyl
gelatin in water and dilute to 1 L. alcohol and again boil to a volume of about 35 mL.
18.2 Lead Acetate Solution (100 g/L)—Dissolve 117 g of NOTE 9—If the volume is reduced below 35 mL, a precipitate may form
Pb(C2H3O 2)2·3H2O in water and dilute to 1 L. that will not dissolve upon dilution. It is imperative, however, that all the
chromium be reduced.
19. Procedure
21.2 Dilute the solution to 400 mL with water. If the
19.1 Dissolve exactly 1 g (Note 7) of a specimen in 10 mL
solution is not clear at this point, filter it. Heat to boiling and
of acetic acid (1+1) and add 25 mL of water. Heat until
add 50 mL of glacial acetic acid. Add 10 mL of BaCl2 solution
dissolved. Dilute to 250 mL and heat to boiling. Add 20 mL of
(100 g/L) dropwise, while stirring. Boil for 30 min and allow
lead acetate solution (100 g/L) and allow the precipitate to
to stand overnight (Note 10). Filter through a tared Gooch
settle. Filter and wash the precipitate with hot water.
crucible and wash with hot water.
NOTE 7—The specimen should not be greater than 1 g because above 1
NOTE 10—The acetic acid is necessary to minimize the tendency of
g the loss in alkali metals due to adsorption on the precipitate becomes
sulfate to form an inner complex with the trivalent chromium. It is
excessive.
necessary that the solution stand overnight to ensure the precipitation of
19.2 Saturate the filtrate with hydrogen sulfide (H 2S) for 40 all the sulfate.
min. Add 10 mL of gelatin solution (0.2 g/L) and stir 21.3 Dry the precipitate in an oven, and ignite at 900°C to
vigorously. Filter and wash with H2S water acidified with a few constant weight. Weigh as barium sulfate (BaSO4).
drops of H 2SO4 (1+1).
19.3 Add 5 mL of H2SO4 (1+1) to the filtrate and boil to a NOTE 11—If the wet precipitate has a yellow appearance, all the
volume of 50 mL. Transfer to a silica dish and evaporate to chromate was not previously reduced. The results will be high and the
specimen should be discarded. Greater attention should then be given to
dryness. Ignite gently.
the reduction of the chromium. A slight greenish color cannot be avoided
19.4 Leach the residue with hot distilled water, transferring but does not indicate a serious error.
the entire contents of the silica dish to a small beaker. Saturate
with H 2S for about 15 min (Note 8). Add 10 mL of gelatin 21.4 Calculation—Calculate the percent sulfates E as sulfur
solution (0.2 g/L) and stir vigorously. Filter and wash the trioxide (SO3), as follows:
precipitate with H 2S water, catching the filtrate in a tared silica E 5 @~P 2 3 0.343!/S6# 3 100
dish.
where:
NOTE 8—A second treatment with H2S is necessary because some of P 2 5 BaSO4, g, and
the heavy metals pass through to the alkali metal filtrate. S6 5 sample used, g.
19.5 Add about 2 mL of H2SO4 (1+1) to the filtrate,
evaporate to dryness, and again ignite gently. During the CHLORIDES
ignition process add small portions of solid ammonium car-
bonate ((NH 4)2CO3). Cool in a desiccator and weigh. 22. Reagent
19.6 Test the residue for calcium. If present, determine the 22.1 Silver Nitrate Solution (17 g/L)—Dissolve 17.0 g of
amount, calculate to calcium sulfate (CaSO4), and deduct from AgNO3 in water and dilute to 1 L.
the weight of the ignited residue.
19.7 Calculation—Calculate the percent of alkaline salts D 23. Procedure
as potassium oxide (K2O), as follows: 23.1 Weigh a 10-g specimen into a 600-mL beaker. Add 200
D 5 @~R 2 W 2! 3 0.541!/S5# 3 100 mL of water and 50 mL of nitric acid (HNO3) (2+3). Warm just
enough to dissolve the specimen. Filter to remove insoluble
where: material. Add a slight excess of AgNO3 solution (17 g/L) (Note
R 5 ignited residue (see 16.5), g, 12). Boil for 5 min and let stand for about 2 h.
W2 5 CaSO4 (if any) (see 16.6), g, and
S5 5 sample used, g. NOTE 12—If care is exercised in adding but a slight excess of AgNO3
solution, no silver chromate (Ag2CrO4) will form. About 10 to 15 mL of
SULFATES AgNO3 solution (17 g/L) is usually not too much.
23.2 If no crystals of Ag2CrO4 are present, filter at room
20. Reagent temperature through a tared, fine-porosity sintered-glass cru-
20.1 Barium Chloride Solution (100 g/L)—Dissolve 117 g cible, using suction. Wash the precipitate free of AgNO3 with
BaCl2· H 2O in water and dilute to 1 L. HNO3 (1+99). To be sure that an excess of AgNO3 was used,
test the filtrate by adding a few drops of HCl (2+3). Dry the
21. Procedure precipitate at 105 6 2°C for 2 h, cool, and weigh as silver
21.1 For this determination take about 20 g of Type I chloride (AgCl).
pigment or about 5 g of Type II pigment as defined in 23.3 If crystals of Ag2CrO4 are present (Note 13), filter the
Specification D 478. Weigh the specimen into a 1-L beaker. solution through a fine-porosity sintered-glass crucible and
4
D 444
discard the filtrate containing most of the chromium. Dissolve place in a 600-mL beaker. Add 300 mL of acetic acid (1+9).
the AgCl precipitate by pouring 100 mL of hot ammonium Heat the mixture to 80°C and maintain at 80 6 5°C, while
hydroxide (NH4OH) (1+5) slowly through the crucible while stirring, until nothing further dissolves. Filter while hot through
applying gentle suction. Catch the filtrate in a clean flask, a tared Gooch crucible. Wash the insoluble residue on the filter
taking care not to lose any of it. Wash with a few millilitres of with hot water.
HNO3 (sp gr 1.42) and then with a little more NH4OH (1+5).
NOTE 14—If the pigment contains an organic treating agent, first
NOTE 13—Silver chromate is difficult to dissolve completely by wash- remove this treating agent by washing with ether or chloroform.
ing with dilute HNO3; hence, in such cases, it is necessary to dissolve in
NH4OH and reprecipitate. 24.2 Dry the crucible at 105 6 2°C and weigh.
23.4 Transfer the solution to a beaker and make it faintly 24.3 Calculation—Calculate the percent of matter insoluble
acid by adjusting with either HNO3 (1+5) or NH4OH (1+5) as in 10 % (by volume) acetic acid F as follows:
required. Add a few drops of AgNO3 solution (17 g/L) and boil F 5 ~R 1/S8! 3 100
for 5 min. Let stand at least 2 h in a dark place. Filter through
a tared, fine-porosity sintered-glass crucible, using suction. where:
23.5 Wash the precipitate free of AgNO3 with 1 % (by R 1 5 residue, g, and
volume) HNO3, and dry at 105 6 2°C for 2 h. Cool and weigh S8 5 specimen used, g.
as AgCl.
23.6 Calculation—Calculate the percent chlorides E as COARSE PARTICLES
chlorine, as follows:
E 5 @~P3 3 0.247!/S 7# 3 100 25. Procedure
where: 25.1 Determine the percent of coarse particles in the pig-
P3 5 AgCl, g, ment as received, in accordance with Test Methods D 185.
S7 5 specimen used, g, and
0.247 5 Cl/AgCl 5 34.45/143.32. 26. Keywords
MATTER INSOLUBLE IN DILUTE ACETIC ACID 26.1 pigments—zinc chromate; zinc chromate
24. Procedure
24.1 Weigh to 0.1 mg about a 10-g specimen (Note 14) and
5

Saponification Number of Naval Store Products Including
Tall Oil and Other Related Products1
1. Scope deleted when test methods D 803 are revised. Test Methods
1.1 These test methods cover the determination of the D 803 will reference these test methods.
saponification number of tall oil and products obtained by the 3.2 The saponification number is an important property of
fractionation of tall oil such as rosin, fatty acids and distilled tall oil and the products obtained by the fractionation of tall oil.
tall oil as defined in Terminology D 804.2 These test methods It is the test method widely used to determine the total acid
are also applicable to gum and wood rosin. Two test methods content, both free and combined, of these products.
are covered as follows: 3.3 The potentiometric test method should be used when the
1.1.1 Test method using a potentiometric method, and most reproducible results are required.
1.1.2 Test method using an internal indicator method. 4. Preparation of Sample
1.2 The potentiometric method is suitable for use with both
light- and dark-colored test samples. It should be considered 4.1 If the sample for analysis is rosin, it shall consist of
the referee method. The internal indicator method is suitable small pieces of rosin chipped from a freshly exposed part of a
for use only with light- and medium-colored test samples. It lump or lumps, and thereafter crushed to facilitate weighing
should be considered the alternate method. and dissolution. Prepare the sample the same day on which the
1.3 This standard does not purport to address all of the test is begun in order to avoid changes in properties due to
safety concerns, if any, associated with its use. It is the surface oxidation. Changes are very pronounced on ground
responsibility of the user of this standard to establish appro- rosin that has a large surface area exposed to air. Existing rosin
priate safety and health practices and determine the applica- dust and powdered rosin must not be used.
bility of regulatory limitations prior to use. 4.2 If the sample is a nonhomogeneous liquid, heat the
entire sample in a closed container fitted with a capillary vent
2. Referenced Documents or the equivalent. Some kind of agitation, even if done
2.1 ASTM Standards: occasionally by hand, saves much time. Heat by immersion in
D 803 Test Methods for Testing Tall Oil2 open steam or hot water bath to avoid overheating. When
D 804 Terminology Relating to Naval Stores, Including Tall dealing with crystallized rosin, a higher temperature of ap-
Oil and Other Related Products2 proximately 160°C may be needed. Remove samples for
E 70 Test Method for pH of Aqueous Solutions with the testing only when the entire sample is homogeneous and has
Glass Electrode3 been well stirred.
3. Significance and Use 5. Purity of Reagents and Water

3.1 These test methods are designed to broaden the scope of 5.1 Unless otherwise indicated, it is intended that all re-
the previous edition of the test method by the inclusion of tall agents shall conform to the specifications established by the
oil and tall oil derived products as test materials. Test Methods Committee on Analytical Reagents of the American Chemical
D 803 currently includes a method for the determination of Society,4 where such specifications are available. References to
saponification number. The details of that procedure will be water shall be understood to mean distilled or deionized water.
1
4
of Subcommittee D01.34 on Naval Stores. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Sept. 15, 1995. Published November 1995. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 464 – 37 T. Last previous edition D 464 – 92. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 464
POTENTIOMETRIC TEST METHOD (Referee Method) isopropyl alcohol-toluene solution (1:1) can be added to the
flask to predissolve the sample. Using a constant delivery pipet
6. Apparatus or volumetric pipet add 50.0 mL of the alkali solution. Add
6.1 Erlenmeyer Flask, 250-mL, of chemically resistant several PTFE boiling stones or glass beads and connect the
glass5 with standard-taper glass joint. flask to the condenser.
6.2 Hot Plates. 8.2 Place the flask on a hot plate and maintain the solution
6.3 Water-Cooled Reflux Condenser, with standard-taper at reflux for 1 h. At the end of the reflux time, while the sample
joint to fit the Erlenmeyer flask. is still warm, transfer the contents of the Erlenmeyer flask into
6.4 Buret, with 0.1 mL divisions. a 400-mL tall-form beaker rinsing with 100 mL of isopropyl
6.5 Stirrer, variable-speed, with a polytetrafluoroethylene alcohol in three washings. Place samples on a heated surface
(PTFE) coated magnetic stir bar. until they can be titrated. In order to avoid highly variable
6.6 Delivery or Volumetric Pipet, 50-mL constant. results, make sure that the temperature of the samples is
6.7 PTFE Boiling Stones, or glass beads. approximately 60 to 70°C when titrated.
6.8 Beaker, 400-mL tall-form. 8.3 Titrate with 0.5 N acid, recording the buret and pH meter
6.9 Glass Electrode pH Meter, conforming to the require- readings. Sufficient acid may be added initially to bring the pH
ments of Test Method E 70. Use either standard or alkali- of the solution to about 12. Allow sufficient time for the
resistant electrodes for this test. Alternatively, an automatic electrode system to reach equilibrium. Add acid in 1.0-mL
potentiometric titrator may be used. portions until the change in pH per addition exceeds 0.3 pH
units. Reduce the additions of acid to 0.1 mL or smaller until
7. Reagents the end point has been passed, as indicated by a significant
7.1 Ethyl Alcohol (95 %) denatured by Formula No. 3A or decrease in pH units per 0.1 mL of acid added. Continue the
No. 30 of the U.S. Bureau of Internal Revenue.6 titration with 1.0-mL portions until it becomes apparent that the
7.2 Isopropyl Alcohol, Reagent grade. inflection point has been well defined.
7.3 Toluene, Reagent grade. 8.4 Determine the inflection point (point of maximum
7.4 Alkali Solution, Standard Alcoholic (0.5 N)—Dissolve change in pH per millilitre of acid) to the nearest 0.05 mL. This
33 g of potassium hydroxide (KOH), preferably in pellet form, may be found by inspection of a plot of pH against millilitres
in ethyl alcohol conforming to 7.1 and dilute to 1 L with 3A of acid added. For greater accuracy, a plot may be made of the
ethyl alcohol. Standardize to 60.001 N by dissolving potas- change in pH per millilitre of acid added, against the pH. The
sium acid phthalate (C6H4 COOKCOOH) in 60 mL of water inflection point is considered as the end point of the titration.
followed by the addition of 40 mL of isopropyl alcohol. Once Alternatively if an automatic titrator is used, the endpoint is
the potassium acid phthalate has dissolved, 2.553 g of potas- either the inflection point from the plotted curve or the pH
sium acid phthalate will be neutralized by 25.0 mL of 0.5 N determined to coincide with the inflection point in the labora-
KOH solution. Protect the standardized solution against evapo- tory performing the analysis. The value of 10.8 is the average
ration and absorption of carbon dioxide (CO2) from the air. The pH encountered at the inflection point by this procedure.
solution should be standardized either potentiometrically or 8.5 Blank—Make duplicate blank determinations using 50.0
colorimetrically using either phenolphthalein or thymol blue as mL of the alkali solution. If 10 mL of isopropyl alcohol-toluene
the indicator. The standardization should use the same equip- solution (1:1) is used as a solvent in 8.1, then use the same
ment and techniques as used in the actual saponification amount in the blank determination.
number determination.
7.5 Acid, Standard (0.5 N)—Standardize a 0.5 N solution of 9. Calculation and Report
HCl to 60.001 N by any accepted procedure. 9.1 Calculate the saponification number, expressed as mil-
7.6 Borax Buffer, Standard Solution (0.01 M, pH 9.18 at ligrams of KOH per gram of sample as follows:
25°C)—Dissolve 3.81 6 0.01 g of disodium tetraborate Saponification number 5 @~B 2 A! N 3 56.1#/C
(Na2B407·10 H2O) in water and dilute to 1 L in a volumetric
flask. Use the special grade7 of borax prepared specifically for where:
use as a pH standard. As an alternative, commercially available B 5 acid required for titration of the blank, mL,
buffer with a pH between 9 and 11 may be used. A 5 acid required for titration of the sample, mL,
N 5 normality of the acid, and
8. Procedure C 5 sample weight, g.
8.1 Transfer 2.95 to 3.05 g of the sample, weighed to the Report the saponification number to the nearest whole
nearest 0.001 g, to the Erlenmeyer flask. If necessary, 10 mL of number.
INTERNAL INDICATOR TEST METHOD (Alternative
5
Alkali-resistant glasses, or equivalent, are suitable for this purpose. Borosilicate Method)
flasks may be used, but they should either be new or be cleaned by rinsing with a
hot solution of HF (2 or 3 %). This removes from the flasks the adhering partially 10. Apparatus
disintegrated silicates that would interfere with the determination. 10.1 Same apparatus as 6.1-6.7.
6
Available from the U.S. Bureau of Alcohol, Tobacco, and Firearms, Distilled
Spirits and Tobacco Branch, 1200 Pennsylvania Ave., NW, Washington DC 20226. 11. Reagents
7
The National Institute of Standards and Technology standard sample of borax
No. 187 is satisfactory for this purpose. 11.1 Phenolphthalein Indicator Solution— Dissolve 1 g of
2
D 464
phenolphthalein in 100 mL of methanol. 13. Calculation and Report
11.2 Thymol Blue Indicator Solution— Dissolve 0.1 g of
13.1 Calculate the saponification number as described in
thymol blue in 100 mL of methanol.
Section 9. Report the results to the nearest whole number.
11.3 Same as 7.1-7.5.
8
12. Procedure 14. Precision and Bias
12.1 Transfer 2.95 to 3.05 g of the sample, weighed to the 14.1 Precision—The precision of these test methods was
nearest 0.001 g to the Erlenmeyer flask. If necessary, 10 mL of determined through a multilaboratory round-robin testing pro-
isopropyl alcohol-toluene (1:1) can be added to the flask to gram using two substances: tall oil fatty acid and distilled tall
predissolve the sample. Using a constant delivery pipet or oil. The results were combined to give the conclusions given
volumetric pipet, add 50.0 mL of the alkali solution. Add below.
several PTFE boiling stones or glass beads, and connect the 14.1.1 Single operator precision—The single operator stan-
flask to the condenser. dard deviation was found to be 0.9 %. Therefore, results of two
12.2 Place the flask on a hot plate and maintain the solution properly conducted tests by the same operator on the same
at reflux for 1 h. At the end of the reflux time, place samples on
sample should not differ by more than 2.5 %.
a heated surface until they can be titrated. In order to avoid
highly variable results, make sure that the temperature of the 14.1.2 Multilaboratory precision—The multilaboratory
samples is approximately 60 to 70°C when titrated. standard deviation was found to be 2.2 %. Therefore, results of
12.3 Titrate with 0.5 N HCl using either 4 to 5 drops of two properly conducted tests on the same sample from two
phenolphthalein indicator to a clear endpoint or 4 to 5 drops of laboratories should not differ by more than 6.1 %.
thymol blue indicator. With thymol blue, the end point is 14.2 Bias—The procedure in this test method for measuring
indicated when the color undergoes the first change from a acid number has no bias because the value of the acid number
distinct blue to a blue-green, just short of clear yellow. If is defined only in the terms of these test methods.
needed, more indicator may be used. Read the buret to 0.05-mL
titrant. If less than 20 mL of titrant is consumed, decrease the 15. Keywords
sample size.
15.1 rosin; saponification number; tall oil; tall oil fatty acids
12.4 Blank—Make duplicate blank determinations using
50.0 mL of the alkali solution and following the same
procedure as for the sample. If 10 mL of isopropyl alcohol-
toluene solution (1:1) was used as a solvent in 12.1, then use 8
Supporting data are available from ASTM Headquarters. Request RR:
the same amount in the blank determinations. D01–1091.
3

Acid Number of Naval Stores Products Including Tall Oil
and Other Related Products1
1. Scope oil and tall oil derived products as test materials. Test Methods
1.1 These test methods are intended for determining the acid D 803 currently includes a method for the determination of
number of naval store products as defined in Terminology acid number. The details of that procedure will be deleted when
D 8042 including tall oil products, wood and gum rosin, and Test Methods D 803 are revised.
other related materials. These test methods may not be appli- 3.2 The acid number is an important property of naval stores
cable to all modified rosin products. Two test methods are products, tall oil, and the products obtained by the fractionation
covered, as follows: of tall oil. It is the test method widely used to determine the
1.1.1 Potentiometric method (referee), and total free acid content of these products.
1.1.2 Internal indicator method (alternate). 3.3 The potentiometric test method should be used when the
1.2 The potentiometric method is suitable for use with both most reproducible results are required.
light- and dark-colored products. It should be considered the 4. Preparation of Sample
referee method. The internal indicator method is suitable for
use only with light- and medium-colored products with a 4.1 If the sample for analysis is rosin, it shall consist of
Gardner color of less than 12. It should be considered the small pieces of rosin chipped from a freshly exposed part of a
alternate method. lump or lumps, and thereafter crushed to facilitate weighing
1.3 This standard does not purport to address all of the and dissolution. Prepare the sample the same day on which the
safety concerns, if any, associated with its use. It is the test is begun, in order to avoid changes in properties due to
responsibility of the user of this standard to establish appro- surface oxidation. This is very pronounced on ground rosin
priate safety and health practices and determine the applica- having a large surface area exposed to the air. Existing rosin
bility of regulatory limitations prior to use. dust and powdered rosin must not be used.
4.2 If the sample is a nonhomogenous liquid, heat the entire
2. Referenced Documents sample in a closed container fitted with a capillary vent or the
2.1 ASTM Standards: equivalent. Some kind of agitation, even if done occasionally
D 803 Test Methods of Testing Tall Oil2 by hand, saves much time. Heat by immersion in open steam or
D 804 Terminology Relating to Naval Stores, Including Tall hot water bath to avoid overheating. When dealing with
Oil and Other Related Products2 crystallized rosin a temperature of approximately 160°C may
E 70 Test Method for pH of Aqueous Solutions with the be needed. Sampling should take place only when the entire
Glass Electrode3 sample is homogeneous and has been well stirred.
E 177 Practice for the Use of the Terms Precision and Bias 4.3 For other products no special preparation is necessary
in ASTM Test Methods4 except storage in a closed container prior to testing.
E 691 Practice for Conducting an Interlaboratory Study to 4.4 Guideline for sample size, solvent, and titrant:
Determine the Precision of a Test Method4 Sample Size, Solvent I, Solvent II, Titrant,
Sample g mL mL KOH
3. Significance and Use Fatty acids 4.0 6 0.05 Isopropyl al- None 0.5N
3.1 These test methods are designed to broaden the scope of DTOA cohol 100
Rosin soap
the previous edition of the test method by the inclusion of tall
FA esters 20 6 0.1 Isopropyl al- None 0.1N
cohol 100
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Rosin 4.0 6 0.05 Toluene 25 Isopropyl al- 0.5N
and Related Coatings, Materials, and Applications, and are the direct responsibility CTOA cohol 75
of Subcommittee D01.34 on Naval Stores. Pitch
Current edition approved Jan. 10, 1996. Published March 1996. Originally
published as D 465 – 37 T. Last previous edition D 465 – 92. Rosin esters 10 6 0.1 Toluene 25 Isopropyl al- 0.1N
2
Annual Book of ASTM Standards, Vol 06.03. 10 6 0.1 g cohol 75
3
Annual Book of ASTM Standards, Vol 15.05. ____________
4 A
Annual Book of ASTM Standards, Vol 14.02. DTO represents distilled tall oil, while CTO represents crude tall oil.
1
D 465
5. Purity of Reagents and Water 7.6 Borax Buffer, Standard Solution (0.01 M, pH 9.18 at
5.1 Unless otherwise indicated, it is intended that all re- 25°C)—Dissolve 3.81 6 0.01 g of disodium tetraborate
agents shall conform to the specifications established by the (Na2B4O7 10H2O) in water and dilute to 1 L in a volumetric
Committee on Analytical Reagents of the American Chemical flask. Use the special grade6 of borax prepared specifically for
Society, where such specifications are available. References to use as a pH standard. As an alternative, a commercially
water shall be understood to mean distilled or deionized water.5 available buffer with a pH between 9 and 11 may be used
instead of self-prepared standard.
POTENTIOMETRIC METHOD (REFEREE METHOD)
8. Standardization of Apparatus
6. Apparatus 8.1 Adjust the pH meter with the standard buffer solution
6.1 Glass Electrode pH Meter, conforming to the require- from 7.6, following essentially the same procedure as de-
ments of Test Method E 70. Use either standard or alkali- scribed in Test Method E 70.
resistant electrodes for this test. An automatic potentiometric
titrator may be used in place of a pH meter. 9. Procedure
6.2 Buret, 50 mL with 0.1 mL divisions. 9.1 Transfer the prescribed amount of sample recommended
6.3 Stirrer, variable-speed with polytetrafluoroethylene in 4.4, weighed to the nearest 0.001 g, to a 400-mL tall-form
(PTFE) coated magnetic stir bar or other type mechanical beaker. Add the proper amount of solvent I (see 4.4) and swirl
stirrer. to dissolve. Heat gently if necessary to dissolve the sample.
6.4 Beaker, 400-mL tall-form. 9.2 Add the correct amount of solvent II (see 4.4), if
required, and cool to near room temperature.
7. Reagents 9.3 Adjust the beaker so the lower half of each electrode of
7.1 Alkali, Standard Solution (0.5 N)—Dissolve 33 g of the pH meter is immersed in the solution. Start the stirrer and
potassium hydroxide (KOH) (pellets or sticks) in methyl adjust the speed so that there is vigorous stirring without
alcohol conforming to 5.1, and dilute to 1 L with the same spattering.
solvent. Standardize to 6 0.001 N by dissolving potassium acid NOTE 1—Glass electrodes tend to dehydrate in nearly anhydrous
phthalate (KHP) in 60 mL of water followed by the addition of solvent medium. Condition the electrode in water between tests and check
40 mL of isopropyl alcohol once the KHP has dissolved; 2.553 with known pH buffers frequently.
g of KHP will be neutralized by 25.0 mL of 0.5 N KOH 9.4 Titrate with the standard alkali solution, recording the
solution. Protect the standardized solution against evaporation buret and pH meter readings. Sufficient alkali may be added
and absorption of carbon dioxide (CO2) from the air. The initially to bring the pH of the solution to about 8. Allow
solution should be standardized frequently, either potentio- sufficient time for the electrode system to reach equilibrium.
metrically or colorimetrically using either phenolphthalein or Add alkali in 1.0-mL portions until the change in pH per
thymol blue as the indicator. The standardization should use increment added amounts to about 0.3 pH unit. Reduce the
the same equipment and techniques as used in the actual acid additions of alkali to 0.1 mL or smaller until the end point has
number determination. been passed, as indicated by a significant decrease in pH units
7.2 Alkali, Standard Solution (0.1 N)—Dissolve 6.6 g of per 0.1 mL added. Continue the titration with 1.0-mL portions
potassium hydroxide (KOH) (pellets or sticks) in methyl until it becomes apparent that the inflection point has been well
alcohol conforming to 7.4, and dilute to 1 L with the same defined.
solvent. Standardize to 6 0.001 N by dissolving potassium acid 9.5 Determine the inflection point (point of maximum
phthalate (KHP) in 60 mL of water followed by the addition of change in pH per millilitre of alkali solution) to the nearest
40 mL of isopropyl alcohol once the KHP has dissolved; 0.05 mL by plotting the pH readings against the millilitres of
0.5106 g of KHP will be neutralized by 25.0 mL of 0.1 N KOH alkali used. For greater accuracy, a plot may be made of the
solution. Protect the standardized solution against evaporation change in pH per millilitre of alkali, against the pH. The peak
and absorption of carbon dioxide (CO2) from the air. The of this curve will indicate the exact inflection point. The
solution should be standardized frequently, either potentio- inflection point is considered as the end point of the titration.
metrically or colorimetrically using either phenolphthalein or Alternatively, if an automatic titrator is used, the end point is
thymol blue as the indicator. The standardization should use either as inflection point from the plotted curve or the pH
the same equipment and techniques as used in the actual acid determined to coincide with the inflection point in the labora-
number determination. tory performing the analysis.
7.3 Isopropyl Alcohol, as in 5.1.
7.4 Methyl Alcohol, as in 5.1. NOTE 2—The value of 10.8 is the average pH encountered at the
inflection point by the above procedure using closely controlled condi-
7.5 Toluene, as in 5.1.
tions, solvent, etc.
10. Calculation and Report

5
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 10.1 Calculate the acid number of the sample, expressed as
6
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, The National Institute for Standards and Testing standard sample of borax No.
MD. 187 is satisfactory for this purpose.
2
D 465
milligrams of KOH per gram of sample, as follows, and report NOTE 3—If less than 20 mL of titrant is consumed the sample size
to the nearest whole number: should be increased.
Acid number 5 ~A 3 N 3 56.1!/B 14. Calculation and Report

where: 14.1 Calculate the acid number as described in Section 10
A 5 alkali solution required for titration of the specimen, and report to the nearest whole number.
mL
N 5 normality of the alkali solution, and 15. Precision and Bias
B 5 specimen weight, g. 15.1 Interlaboratory Test Program—An interlaboratory
study of the acid number of three substances, tall oil fatty acids,
INTERNAL INDICATOR METHOD (ALTERNATE
distilled tall oil, and rosin, was run in 1994. Each of 14
METHOD)
laboratories tested each of the three materials. The design of
11. Reagents the experiment, similar to that of Practice E 691 and a
within-between analysis of the data are given in ASTM
11.1 Prepare or use, as required, the reagents described in
Research Report.7
7.1-7.5.
15.2 Test Result—The precision information given below
11.2 Phenolphthalein Indicator Solution—Dissolve 1 g of
for the acid number of naval stores products is for the
phenolphthalein in 100 mL of methyl alcohol.
comparison of two test results, each of which is the average of
11.3 Thymol Blue Indicator Solution—Dissolve 0.1 g of
three test determinations as follows:
thymol blue in 100 mL of methyl alcohol.
15.2.1 Repeatability Limit, 95 % (within laboratory) 5 1.2.
12. Apparatus 15.2.2 Reproducibility Limit, 95 % (between laborato-
ries) 5 3.3.
12.1 Same apparatus as 6.2 and 6.3.
15.3 These terms (repeatability limit and reproducibility
12.2 Erlenmeyer flask, 250-mL.
limit) are used as specified in Practice E 177. The respective
13. Procedure standard deviations among test results, related to the above
numbers by the factor of 2.8, are as follows:
13.1 Transfer the prescribed amount of sample recom-
15.3.1 Repeatability standard deviation 5 0.4.
mended in 4.4, weighed to the nearest 0.001 g, to a 250-mL
15.3.2 Reproducibility standard deviation 5 1.2.
Erlenmeyer flask. Add the proper amount of solvent I (see 4.4)
15.4 Bias—These test methods have no bias because acid
and swirl to dissolve. Heat gently if necessary to dissolve.
number is defined only in terms of these test methods.
13.2 Add the correct amount of solvent II (see 4.4) if
required and cool to near room temperature.
16. Keywords
13.3 Titrate the solution with the standard alkali solution
using 4 to 5 drops of either phenolphthalein or thymol blue 16.1 acid number; rosin; tall oil; tall oil fatty acids
indicator solution. Dark colored samples may require addi-
tional indicator to be added to the solution. With phenolphtha-
lein titrate to the first persistent faint pink color, or with thymol 7
Supporting data are available from ASTM Headquarters. Request RR:D01–
blue titrate to a blue-green color. Read buret to 0.05-mL titrant. 1086.
3

Pure Para Red Toner Pigment1
1. Scope Moisture and other volatile 1.0 1.0

matter, max, %
1.1 This specification covers the red pigment commercially Coarse particles (total residue 1.5 1.5
known as pure para red toner. It is available in two Types: Type retained on a 45-µm
I, light, and Type II, dark. (No.325) sieve), max, %
Solubility in chloroform complete ...
Resistance to acids to pass test to pass test
2. Referenced Documents Resistance to alkalis to pass test equal to standard
2.1 ASTM Standards: Identity test to pass test to pass test
D 970 Test Methods for Para Red and Toluidine Red Pig- 3.3 The mass color and character of the tint formed by
ments2 mixture with a white pigment shall be the same as, and the
strength not less than, that of a reference sample mutually
agreed upon by the purchaser and the seller.
3.1 Dry Pigment:
3.1.1 Type I—The pigment shall be in a soft dry form and 4. Sampling
shall consist of para red toner, light (1-(p-nitro-phenyl-azo)-2- 4.1 Two samples shall be taken at random from different
naphthol) free of any substrate. packages from each lot, batch, day’s pack, or other unit of
3.1.2 Type II—The pigment shall be in a soft dry form and production in a shipment. When no markings distinguishing
shall consist of para red toner, light (1-(p-nitro-phenyl-azo)-2- between units of production appear, samples shall be taken
naphthol) mixed with a small quantity of 1-(p-nitro-phenyl- from different packages in the ratio of two samples for each
azo)-2-naphthol-7-sulfonic acid free of any substrate. 10 000 lb (5 000 kg), except that for shipments of less than
3.2 The pigments shall conform to the following require- 10 000 lb two samples shall be taken. At the option of the
ments: purchaser, the samples may be tested separately, or after
Type I Type II blending in equal quantities the samples from the same
Ash, max, % 3.0 3.0
5. Test Methods
5.1 Tests shall be conducted in accordance with Test Meth-
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint ods D 970.
Subcommittee D01.31 on Pigment Specifications. 6. Keywords
Current edition approved Nov. 30, 1967. Originally published as D 475– 38 T.
Last previous edition D 475– 49. 6.1 pigment; pure para red; red toner; toluidine red pigment;
2
Annual Book of ASTM Standards, Vol 06.03. toner pigment
1
Standard Classification for

Dry Pigmentary Titanium Dioxide Products1
1. Scope differences, while allowing maximum flexibility.

1.1 This classification describes seven types of dry pigmen- 5. Composition and Properties
tary titanium dioxide products, grouped by composition, typi-
cal end use application, and some performance properties. 5.1 Titanium Dioxide Pigments, should conform to the
1.2 The values stated in SI units are to be regarded as the requirements for composition prescribed in Table 1. They are
standard. The values given in parentheses are for information chemically prepared pigments consisting of anatase or rutile
only. titanium dioxide with or without modifications with water-
insoluble oxides of aluminum, silicon, zinc, etc., or other
2. Referenced Documents agents; these reagent materials are introduced specifically to
2.1 ASTM Standards: improve those properties for which the pigment is used. The
D 34 Guide for Chemical Analysis of White Pigments2 titanium dioxide pigments shall be free of extenders such as
D 153 Test Methods for Specific Gravity of Pigments2 barium sulfate, clay, magnesium silicate, whiting, etc.
D 185 Test Methods for Coarse Particles in Pigments, 5.2 The desired properties of the pigment, other than as
Pastes, and Paints2 herein indicated, shall be subject to agreement between the
D 280 Test Methods for Hygroscopic Moisture (and Other purchaser and the seller and shall be based on a satisfactory
Matter Volatile Under the Test Conditions) in Pigments2 match between the submitted pigment sample and a previously
D 1394 Test Methods for Chemical Analysis of White agreed upon reference sample (see 6.1.6).
Titanium Pigments2 6. Test Methods
D 2448 Test Method for Water-Soluble Salts in Pigments by
Measuring the Specific Resistance of the Leachate of the 6.1 Tests shall be conducted in accordance with the follow-
Pigment2 ing test methods. Test procedures not covered by ASTM test
D 3720 Test Method for Ratio of Anatase to Rutile in methods shall be mutually agreed upon between the purchaser
Titanium Dioxide Pigments by X-ray Diffraction2 and the seller.
6.1.1 Chemical Analysis—Guide D 34 or Test Methods
3. Significance and Use D 1394.
3.1 This classification is given as an aid in determining the 6.1.2 Specific Gravity—Test Methods D 153.
fitness for use of a titanium dioxide pigment for a coating 6.1.3 Coarse Particles—Test Methods D 185.
application. It is limited to dry, hiding pigments. It excludes 6.1.4 Moisture—Test Method D 280.
pigment dispersions, and non-hiding specialty titanium dioxide 6.1.5 Matter Soluble in Water, Specific Resistance—Test
products. Method D 2448. The measured specific resistance of the
aqueous leachage from the pigment is an index of the level of
4. Basis for Classification water-soluble salts.
4.1 Titanium dioxide pigments can differ in many ways 6.1.6 Chalking Resistance—It is recommended that pur-
including composition and performance. This classification chaser and seller agree upon standards and methods of test
outlines differences between pigment types that should be suitable for their requirements (see 5.2). Comparison in a good
considered when selecting a product for a coating application. quality exterior air-dry alkyd enamel (trade sales or industrial)
A minimum number of properties are given to highlight major and exposure in Florida at 45° facing south are recommended.
Chalking differences are minimized by less durable vehicles,
1
while required exposure times are prolonged by more durable
This classification is under the jurisdiction of ASTM Committee D01 on Paint
vehicles. Once the reference sample agreed upon between the
Subcommittee D01.31 on Pigment Specifications. purchaser and seller has qualified, subsequent shipments of that
Current edition approved July 10, 2000. Published September 2000. Originally product may be compared with the reference sample by an
published as D 476 – 38. Last previous edition D 476 – 84 (1995)e1. agreed upon accelerated weathering test.
2
1
TABLE 1 Classification of Dry, Pigmentary Titanium Dioxide Pigments
Typical Properties
ASTM
Classification Type I II III IV V VI VII
Standards
Crystal type anataseA rutile rutile rutile rutile rutile rutile D 3720
Chalking resistance, relative free chalking low-medium medium high high medium-high medium-high
Typical end use application(s) white exterior house low-medium high exterior coatings exterior coatings int-ext coatings int-ext coatings
paint and interior uses % PVC % PVC requiring excellent requiring excellent medium-high low-high
durability durability with % PVC % PVC
high gloss
Titanium dioxide (TiO2) content, min., % 94 92 80 80 90 90 92 D 1394

Specific resistance, min, V 5000 5000 3000 3000 3000 5000 5000 D 2448
Moisture content as packed, min, % 0.7 0.7 1.5 1.5 1 0.7 0.7 D 280
Specific gravity 3.8–4.0 4.0–4.3 3.6–4.3 3.6–4.3 3.6–4.3 3.6–4.3 4.0–4.3 D 153
45-µm screen residue, max, % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 D 185
A
Identification of anatase or rutile or mixtures thereof is made by X-ray analysis (Test Method D 3720).
2
D 476
D 476
7. Keywords
7.1 anatase; dioxide pigments; rutile; titanium; white pig-
ments
3

Zinc Yellow (Zinc Chromate) Pigments1
1. Scope TABLE 1 Composition Requirements
1.1 This specification covers the pigments commercially Type I Type II
known as zinc yellow (zinc chromate). Zinc (calculated as ZnO), % 35 to 40 35 to 40

Chromium (calculated as CrO3), 41 41
1.2 Two types are included: min, %
1.2.1 Type I—High-purity, low sulfate and chloride content. Sulfates (calculated as SO3), max, % 0.20 3.0A
1.2.2 Type II—Regular grade. Chlorides (calculated as Cl), max, % 0.10 0.8A
Alkaline salts (calculated as K2O), max, % 13 13
2. Referenced Documents Matter insoluble in acetic acid 0.3 0.3
(1+9) at 80°C, max, %
2.1 ASTM Standards: Moisture and other volatile matter, max, % 1.0 1.0
D 185 Test Methods for Coarse Particles in Pigments, Coarse particles (total residue retained on 1.0 1.0
No. 325 (45-µm) sieve), max, %
Pastes, and Paints2
A
The maximum percent of sulfates or chlorides given in the table for Type II
D 387 Test Method for Color and Strength of Color Pig- pigment apply if only one or the other is present (for this purpose amounts of less
ments with a Mechanical Muller3 than 0.05 % shall be disregarded). If both sulfates and chlorides are present, the
D 444 Test Methods for Chemical Analysis of Zinc Yellow sum of the percentages of each divided by its respective maximum permissible
percentage (3.0 for SO3 and 0.8 for Cl) shall not exceed 1.0. For example, if a
Pigment (Zinc Chromate Yellow)2 sample contains 1.8 % SO3 (0.6 of the maximum for sulfates) and 0.3 % chlorides
(0.4 of the maximum for chlorides), the sample just conforms to the maximum
3. Significance and Use requirements of the specification in this respect.
3.1 Zinc yellow is used in rust-inhibiting protective coatings
and metal primers for ferrous and non-ferrous metals.
packages from each lot, batch, day’s pack, or other unit of
4.1 Dry Pigment—The pigment shall be a reaction precipi- between units of production appear, samples shall be taken
tate of soluble chromates and a suitable zinc compound and from different packages in the ratio of two samples for each
shall be free of extenders, carbonates, and organic color in any 10 000 lb (5000 kg), except that for shipments of less than
form. The pigment shall conform to the requirements for 10 000 lb two samples shall be taken. At the option of the
composition prescribed in Table 1 . purchaser, the samples may be tested separately or after
4.2 The mass color and character of the tint and the tinting blending in equal quantities the samples from the same
strength formed by a mixture with a white pigment shall be production unit to form a composite sample.
both the purchaser and the seller. 6. Test Methods
5. Sampling 6.1 Tests shall be conducted in accordance with the follow-
5.1 Two samples shall be taken at random from different ing ASTM test methods:
6.2 Chemical Analysis—Test Methods D 444.
1
and Related Coatings, Materials, and Applications, and is the direct responsibility of 6.4 Mass Color and Tinting Strength—Test Method D 387.
Current edition approved April 25, 1986. Published June 1986. Originally 7. Keywords
published as D478 – 38 T. Last previous edition D478 – 49 (1981)e1.
2
Annual Book of ASTM Standards, Vol 06.03. 7.1 chromatic; inhibitor metal primer; pigment; zinc chro-
3
Annual Book of ASTM Standards, Vol 06.01. mate; zinc yellow
1
D 478
2

Sampling and Testing of Flaked Aluminum Powders and
Pastes1
1. Scope Determine the Precision of a Test Method8

1.1 These test methods cover procedures for sampling, 3. Significance and Use
qualitative analysis, and physical testing of flaked aluminum
powders and pastes (leafing and nonleafing) for coatings. 3.1 Flaked aluminum pigments are produced in a variety of
1.2 These test methods apply equally to leafing and non- forms. These test methods allow the user to determine the
leafing flaked aluminum powders and pastes except where applicability of a given product to this use.
noted to the contrary. 4. Sampling
safety concerns, if any, associated with its use. It is the 4.1 Sampling is subject to mutual agreement between the
responsibility of the user of this standard to establish appro- seller and the purchaser. Place each sample in a clean, dry
priate safety and health practices and determine the applica- metal or glass container which shall be nearly filled, then close
bility of regulatory limitations prior to use. For a specific with a tight cover, seal, mark, and send to the laboratory for
hazard statement, see Note 1. testing.
4.2 When requested, duplicate samples may be taken from
2. Referenced Documents the same container and delivered to the seller, and the inspector
2.1 ASTM Standards: may take a third set of samples to hold for test in case of
D 185 Test Methods for Coarse Particles in Pigments, disagreement.
Pastes, and Paints2 5. Qualitative Analysis
D 235 Specification for Mineral Spirits (Petroleum Spirits)
(Hydrocarbon Drycleaning Solvent)3 5.1 Significance and Use—This test method determines if
D 329 Specification for Acetone3 there are chemical impurities, other than fatty and oily matter,
D 962 Specification for Aluminum Powder and Paste Pig- as specified in Specification D 962, to ensure the absence of
ments for Paints2 fillers or extender pigments.
D 3980 Practice for Interlaboratory Testing of Paint and 5.2 Procedure:
Related Materials4 5.2.1 Total Impurities—Determine the total impurities by
E 11 Specification for Wire-Cloth Sieves for Testing Pur- weight in accordance with Test Methods E 34 and E 607 or by
poses5 atomic absorption.
E 34 Test Methods for Chemical Analysis of Aluminum and 5.2.2 Total Aluminum—Determine the total aluminum by
Aluminum Alloys6 weight difference with elemental impurities in accordance with
E 607 Test Method for Optical Emission Spectrometric 5.2.1.
Analysis of Aluminum and Aluminum Alloys by the 6. Leafing Properties
Point-to-Plane Technique, Nitrogen Atmosphere7
E 691 Practice for Conducting an Interlaboratory Study to 6.1 The leafing test conditions specified are selected arbi-
trarily, and even though the numerical leafing value obtained
1
by this test method appears to be low, the pigment may give
substantially perfect leafing under the conditions of practical
Subcommittee D01.31 on Pigment Specifications. application in a paint.
Current edition approved July 29, 1988. Published December 1988. Originally 6.2 Significance and Use—This leafing test method has
published as D 480 – 38. Last previous edition D 480 – 70 (1976). been established to determine the percent of leafed aluminum
2
3
flakes at the surface of a simulated paint formula to ensure a
4
Annual Book of ASTM Standards, Vol 06.01. bright metallic luster. Minimum leafing characteristics must
5
6
7 8
1
D 480
conform to Specification D 962. the vehicle and continue stirring to obtain complete dispersion.
6.3 Apparatus: Transfer the mixture to the test tube to give a depth of about
6.3.1 Leafing Spatula, nonmagnetic, stainless steel spatula 110 mm when the specified spatula is immersed. Avoid
having the following dimensions: formation of bubbles. Dip the spatula to the bottom of the
Length of blade min, in. (mm) 5.5 (139.7) mixture and rotate it gently through an arc of about 90° for 10
Width of blade, in. (mm) 0.540 6 0.002 (13.72 6 0.05) s. Withdraw the spatula at a uniform rate of about 2 in. (50
Thickness of blade, in. (mm):
10 mm from tip 0.0136 0.003 (0.33 6 0.08)
mm)/s. The spatula should not touch the wall of the test tube
100 mm from tip 0.038 6 0.004 (0.97 6 0.10) above the liquid level. Immediately suspend the spatula verti-
Shape of tip rounded or straight cally in the glass cylinder with leafing liquid in it and allow to
The surface of the spatula shall be polished with 3/0 emery remain for 3 min. Measure the height of immersion and the
or silicon carbide metallographic paper wet with mineral height of complete leafing on both sides of the spatula,
spirits; polishing shall be repeated for 1-min intervals until a measuring to the bottom of the meniscus in each case. Clean
consistent minimum leafing result is obtained in a typical the spatula by rinsing it in petroleum spirits and wipe dry with
leafing test. a clean cloth. Stir (do not shake) the mixture in the test tube
6.3.2 Test Tube, 6 in. (152 mm) in length by 0.75 in. (19.0 and repeat the determination.
mm) in diameter. 6.8 Calculation—Calculate the leafing value L as follows:
6.3.3 Glass Cylinder, 8 in. (203 mm) in length and 1.5 to 2.0 L 5 A/B 3 100 5 A 3 100/B
in. (38.1 to 50.8 mm) in inside diameter. A stopper shall be
used and the spatula shall be attached to the stopper so as to where:
hang vertically in the cylinder with the tip about 1 in. (25 mm) A 5 height of complete leafing, in. (mm), and
B 5 height of immersion, in. (mm).
from the bottom.
6.4 Reagents: 7. Coarse Particles
6.4.1 Coumarone-Idene Resin—The form commercially
known as “chipped” and having the following properties: 7.1 This section provides two test methods for determining
the percent residue retained on a sieve by wet-screening
Softening point, °C 109 to 117
Specific gravity 1.12 to 1.16 techniques.
Acid value, max 0.5 7.2 Significance and Use—These procedures determine the
Cloud point, °C, max −7 percent of coarse particles present in aluminum pigments to
6.4.2 Petroleum Spirits—Conforming to Specification ensure a smooth appearance, as required in Specification
D 235 and having the following additional properties: D 962.
Specific gravity at 60°F (16°C) 0.800 to 0.810 7.3 Procedure A:
Surface tension at 70°F (21°C), 24.5 7.3.1 Aluminum Powder—Fill two “straight wall” contain-
N/m, min
Kauri butanol value 42 to 44
ers not less than 12 in. (305 mm) in diameter to a depth of not
Aniline point, °F (°C) 105 to 115 (40 to 45) less than 4 in. (102 mm) with petroleum spirits, and fill a third
similar container to a depth of not less than 3 in. (76 mm) with
6.5 Preparation of Leaf-Testing Vehicle—Prepare solution
acetone. The petroleum spirits used for the test shall conform
by dissolving 30.0 g of resin, in the form of small chips, in 100
to Specification D 235, and the acetone shall conform to
mL of petroleum spirits, while heating gently at about 140°F
Specification D 329. Weigh 5 g of the aliquot, transfer to a
(60°C). The specific gravity of the solution shall be between
250-mL beaker, and add in small portions a total of about 150
0.877 and 0.881 at 60°F (16°C). Allow the solution to settle
mL of petroleum spirits, mixing thoroughly to a uniform
and retain the clear portion for use.
consistency after each addition. Clamp a standard sieve 8 in.
6.6 Aliquot—Unless otherwise specified, the aliquot weight
(203 mm) in diameter conforming to Specification E 11, just
shall be as follows:
above the level of the petroleum spirits in the first container
Aliquot
Classification ASTM Designation Class
Weight, g
and pour the specimen on the sieve, using a 45-µm (No. 325)
sieve for Classes A, B, and C powder and in addition a 150-µm
Flaked aluminum powder D 962, Type 1 A 1.0 (No. 100) sieve for Class C powder. Rinse the beaker with clear
B 1.0
C 2.0
petroleum spirits and transfer the rinsings to the sieve. Holding
Aluminum paste D 962, Type 2 A 1.5 the sieve at a slight angle to prevent air lock, shake it backward
B 1.5 and forward working the sieve alternately just under and just
C 3.0
above the level of the liquid with rotation, avoiding spillage
6.7 Procedure—Perform the test at a room temperature of from the screen, at a rate of approximately 60 to 100 cpm. It is
25 6 2°C. Place approximately 5 mL of the leaf-testing vehicle important that the material be thoroughly sieved in each
in the glass cylinder and cover with a watch glass. Transfer container. After the bulk of the aliquot has passed through the
25.06 1.0 mL of the vehicle to a clean container. Weigh the sieve (usually about 2 min) repeat the procedure in the second
required aliquot of aluminum powder or paste to the nearest container for about 2 min. When it is evident that practically
0.01 g and transfer to a small dish. Add about 2.5 mL of the none of the residue on the sieve is passing through it, repeat the
25-mL quantity of vehicle and mix to a stiff paste with a spatula procedure in the acetone container for about 2 to 3 min until
or small stiff brush. Add approximately 5 mL more of the nothing more passes through the sieve. Rinse the sides of the
vehicle and stir to a smooth mixture, then add the remainder of sieve with a small stream of acetone, and collect the residue at
2
D 480
one side of the sieve. Transfer the residue to a dried and conforming to Specification D 329. Heat the mixture to boiling
weighed aluminum cup or small evaporating dish with a small while occasionally agitating. Cool, fill to the 200-mL mark
stream of acetone, using not less than 15 to 25 mL. Place the with acetone, and mix. Allow the mixture to settle. Draw off
aluminum cup or dish in an oven, evaporate to dryness at 105 approximately one half of the supernatant liquid and filter
to 100°C, and continue heating at this temperature for 15 min. through dry paper. Discard the first 10 mL of the filtrate.
Transfer 100 mL of the clear filtrate to a weighed dish.
NOTE 1—Warning: Do not close the door of the oven while evaporat-
ing the acetone, as there is danger of explosion or flash of acetone vapor. Evaporate the acetone at a temperature not above 75°C. Heat
the dish for 15 min in an oven at 105 to 110°C. Cool and weigh
7.3.2 Aluminum Paste—Determine the percent of coarse the amount of fatty oily matter.
particles in accordance with the procedure described in 7.3.1
8.3.2 Aluminum Paste—Determine the percent of easily
using a 45-µm (No. 325) sieve for Classes A, B, and C paste
extracted fatty and oily matter in aluminum paste in accordance
and in addition a 150-µm (No. 100) sieve for Class C paste.
with the procedure described in 8.3.1.
7.3.3 Calculation—Calculate the weight percent of the
residue retained on the sieve R from the increase in weight as 8.4 Calculation—Calculate the weight percent of fatty and
follows: oily matter F as follows:
F 5 @2 3 ~A/W!# 3 100
R 5 @~A/W! 3 CF# 3 100
where: where:
A 5 weight of dried residue, g, A 5 weight of residue in 100 mL of acetone, g, and
CF 5 correction factor (1.0 for NIST sieves), and W 5 weight of aliquot, g.
W 5 aliquot weight, g.
9. Nonvolatile Matter
NOTE 2—A correction factor shall be applied in the case of sieves used
in the test that have not been certified by the National Institute of 9.1 Determine the percent of nonvolatile matter in alumi-
Standards and Technology. Sieves having a correction factor above 1.2 or num paste consisting of aluminum, fatty acids, additives, and
below 0.8 should not be used. The correction factor may be calculated as their inter-reaction products.
follows: Determine the coarse particles of an aliquot on a master sieve 9.2 Significance and Use—This test method determines the
certified by the National Institute of Standards and Technology following combined percent of aluminum and other nonvolatile matter,
the procedure described in 7.3.1. Sieve the same aliquot on the unknown
sieve by the same procedure. Calculate the correction factor, CF, as
such as fatty acids and their inter-reaction products, in alumi-
follows: num pigments and their conformance with Specification D 962.
CF 5 X/Y 9.3 Procedure—Aluminum Paste and Powder—Weigh into
an evaporating dish 5 g of paste or powder to within 0.01 g.
where: Evaporate in an oven at a temperature of 105 to 110°C for 3 h.
X 5 weight of residue on the NIST sieve, g, and Cool to room temperature and weigh.
Y 5 weight of residue on the unknown screen, g.
9.4 Calculation—Calculate the weight percent of nonvola-
7.4 Procedure B—Test in accordance with Test Methods tile matter NV as follows:
D 185 to determine conformance of flaked aluminum powders NV 5 A/W 3 100
and pastes to Specification D 235.
where:
8. Easily Extracted Fatty and Oily Matter
A 5 weight of residue, g, and
8.1 Easily extracted fatty and oily matter is determined by W 5 weight of aliquot, g.
the following arbitrary test method. Details of the test proce-
dure shall be strictly followed. 10. Precision and Bias
8.2 Significance and Use—This test method determines the
percent of easily extracted fatty and oily matter in aluminum 10.1 Precision and Bias—Determine in accordance with
pigments in accordance with Specification D 962. Practices D 3980 and E 691.
8.3 Procedure:
8.3.1 Aluminum Powder—Weigh accurately (to within 0.01 11. Keywords
g) approximately 2 g of the aliquot. Transfer to a 200-mL 11.1 flaked powders; leafing properties; aluminum powders
volumetric flask and add about 50 mL of redistilled acetone and pastes
3

Sampling and Grading Rosin1
1. Scope 3.2 Although these test methods are still applicable, many
1.1 These test methods cover procedures for sampling and modifications of these methods and many additional test
determining the grade of rosin delivered in commercial bags, methods are now used to grade rosin. For example, Test
barrels, drums or in molten form. Methods E 28, D 465, and D 5974 are widely used to assess the
quality of rosin in addition to the color grading described in
NOTE 1—All rosin sold in interstate commerce must be described by those methods. Further, as rosin is often available in molten
reference to the U. S. Standards for rosin, and is therefore subject to
grading prior to such sale. The grading procedure described in these test
form, it is common practice to pour liquid rosin into molds in
methods is used for checking grades or regrading after the rosin has order to prepare specimens for color grading. The need for a
moved from the primary markets to distributing or consuming points. test method describing such a technique is under discussion by
Subcommittee D01.34. Thus, even though some parts of these
1.2 The values stated in inch-pound units are to be regarded
test methods are somewhat outdated, these test methods are
as the standard. The values given in parentheses are for
still important from both a practical and historical viewpoint.
information only.
1.3 This standard does not purport to address all of the 4. Apparatus
4.1 Offıcial Rosin Standards—The official standards for use
in grading rosin ( G, Fig. 1, plus three standards lighter than
“X”) consists of assemblies of colored glass plates, cemented
together, as issued on loan by the U.S. Department of Agricul-
2. Referenced Documents ture.4 The grades and standards are designated as follows: XC,
XB, XA, X, WW, WG, N, M, K, I, H, G, F, E, and D. A special
2.1 ASTM Standards:
grade, FF, is used for dark wood rosins. Grades XA, XB, and
D 465 Test Methods for Acid Number of Naval Stores
XC are not available from the U.S. Department of Agriculture
Products Including Tall Oil and Other Related Products2
but may be purchased commercially.5 The standards issued by
D 5974 Test Method for Fatty and Rosin Acids in Tall Oil
the Department of Agriculture (except FF), consist of combi-
Fractionation Products by Capillary Gas Chromatography2
nations of plates cut, ground, and polished to specified thick-
D 6090 Standard Test Method for Softening Point of Resins
nesses from selected melts of Corning and Jena colored glass.
(Mettler Cup and Ball Method)2
The colorimetric specifications of the standards, based on the
E 28 Test Method for Softening Point by Ring-and-Ball
1931 CIE Coordinate System, for a standard observer using
Apparatus2
standard Illuminant C, are given in Table 1. The colorimetric
3. Significance and Use specifications for the U.S. Rosin Standards, Master Cubes XA,
3.1 Rosin is an important product of the centuries old Naval XB, and XC, are given in Table 2.
Stores industry and is produced and consumed in many 4.2 Secondary standards or “type samples” are sometimes
countries throughout the world. Consequently, reliable meth- used for approximate grading, in the absence of permanent
ods of sampling and grading rosin are necessary. The test official standards of glass.5 Such samples may consist of cubes
methods described herein were developed many years ago for
the sampling and grading of rosin and are similar to those 4
The U.S. Rosin Standards are issued only by the Agricultural Marketing
included in the Naval Stores Act.3 Service, Tobacco Division, U.S. Department of Agriculture, P.O. Box 96456,
Washington, DC 20090-6456. To obtain a set of standards, a Form N.S.A. 2“
Request for Loan of Official United States Rosin Standards” and a security deposit
of $100.00 should be sent to the above address.
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint If an applicant is unable to borrow a set of the U. S. Rosin Standards, because
and Related Coatings, Materials, and Applications and are the direct responsibility of the limited number of sets in existence, secondary sets are available. These
of Subcommittee D01.34 on Naval Stores. standards are excellent duplicates of the U. S. Rosin Standards but could not be
Current edition approved June 10, 1998. Published August 1998. Originally classified as identical and do not have official recognition of the U.S. Department of
issued as D 509 – 38. Last previous edition D 509 – 70 (1993). Agriculture.
2 5
Annual Book of ASTM Standards, Vol 06.03. The Standards XA, XB, and XC and secondary standards may be purchased
3
Naval Stores Act of 1923 (42 Stat 1435.7 USC-91-99) as amended in 1951 and directly from Tintometer, Ltd., Salisbury, England, or from their United States
regulations promulgated thereunder by the United States Department of Agriculture. representative HF Scientific Inc. 3170 Metro Parkway Fort Myers, FL 33916.
1
D 509
A—Rosin spike. F—Rosin type samples.

B—Comparison box. G—Official rosin standards.
C—Sampling hatchet. H—Spiked lump sample.
D—Sampling adz. I—Sample for grading.
E—Smoothing device.
FIG. 1 Apparatus for Sampling and Grading Rosin
TABLE 1 Colorimetric Specifications for U.S. Rosin Standards they should be tested periodically by comparison with perma-
(Master Set No. 200)A nent glass standards.
Grade x y T l p
NOTE 2—It is not possible to dissolve a specified quantity of rosin in a
X 0.4339 0.4663 0.609 575.0 0.755
WW 0.4579 0.4732 0.531 576.8 0.851
solvent and use such solution as a standard for grading the rosin because
WG 0.4785 0.4741 0.466 578.5 0.905 there is no constant relationship between the color of the original solid
N 0.5001 0.4704 0.396 580.5 0.944 rosin and the color of the rosin after being put in solution. Consequently,
M 0.5212 0.4619 0.322 582.8 0.969 the color of such solution is not a criterion of the color of the rosin itself.
K 0.5430 0.4483 0.245 585.5 0.985
I 0.5649 0.4310 0.178 588.7 0.993 4.3 Rosin Color Molds, 7⁄8 in. (22.225 mm), standard size or
H 0.5879 0.4102 0.1114 592.4 0.997 Rosin Sample Trays, 7⁄8 by 7⁄8 by 1 in. (22.225 by 22.225 by
G 0.6116 0.3874 0.0723 596.8 0.999
F 0.6364 0.3632 0.0398 602.1 1.000 22.225 mm), white cover without labels.
E 0.6640 0.3358 0.0131 609.4 1.000
D 0.6943 0.3057 0.0021 621.4 1.000 5. Sampling
A
x and y are CIE trilinear coordinates; T is the luminous transmission factor; l
is the dominant wavelength in nanometers; p is the colorimetric purity.
5.1 Number of Packages to Be Sampled— A preliminary
sampling of 20 % of the entire lot or shipment shall be made.
TABLE 2 Colorimetric Specifications for U. S. Rosin Standards If the grade of 85 % or more of the number of such preliminary
(Master Cubes XA, XB, and XC)A samples agrees with the grade indicated on the package or
Grade x y T invoice, with none of the samples disagreeing by more than
one grade, the original grading shall be considered confirmed
XA 0.4048 0.4443 0.708
XB 0.3724 0.4117 0.788 and the shipment accepted as a good delivery. If the grades of
XC 0.3406 0.3696 0.848 more than 15 % of the preliminary samples are in disagree-
A
x and y are CIE trilinear coordinates; T is the luminous transmission factor. ment, or if any appreciable number are under grade by more
than one grade, additional packages in the lot to make up a total
of specially selected rosin or other colored transparent me- equal to not less than 50 % of the entire shipment (preferably
dium; solutions are also sometimes used (Note 2). Secondary the entire shipment if accessible and not too great) shall be
standards or “types” are usually not permanent in color and sampled. The findings on such larger quantity shall be accepted
must be protected from excessive exposure to sunlight or heat. as the basis for settlement between the purchaser and the seller.
Wrapping and storage in a cool dark place when not in use is 5.2 Method of Sampling—Take samples that are approxi-
recommended. To ensure correctness of grading therewith, mately cubical in shape and exactly 7⁄8-in. (22.225-mm) thick
2
D 509
in the direction in which they are to be viewed, by any of the hue, ( 2) a more saturated hue, and (3) a lower brightness.
following methods: 6.2 A sample showing two distinct colors, usually evi-
(a) By cutting or cleaving the same from a lump of rosin denced by darker streaks through the rosin, indicates a mixture
removed from the solid mass in the barrel or drum, the top side of rosins in the package, in which case the darkest part of the
of which lump shall come from not less than 4 in. (101.6 mm) sample or darkest rosin to be found in the package shall
below the surface of the rosin. determine the grade.
(b) By means of a tin mold of suitable design which has been 6.3 A check sample taken from close to the bottom of a
placed inside the barrel or drum through an opening in the side, barrel or drum shall not be considered representative, because
the top of which opening is not less than 8 in. (203.2 mm) from of a natural variation in color sometimes found between the top
the top of the container, in order to provide a sample that shall and bottom rosin as well as a reduced brightness of the bottom
have come from a position not less than 4 in. below the surface rosin due to a settling of finely divided suspended matter
of the rosin. The mold thus placed must be entirely within the usually present in normal gum rosin. Should such bottom
barrel or drum and completely encased in the rosin. sample show not more than one grade lower than the top
(c) By suspending in the barrel or drum of molten rosin a sample, the latter shall determine the grade of the rosin in the
clean tin plate mold 7⁄8in 2 (22.225 mm2) (inside) and 1.5 in. barrel. If, however, the bottom-head sample is more than one
(38.1 mm) or more in length, in such a manner that it will be grade lower than the top sample, double filling or“ mixed-
in a horizontal position at least 4 in. below the surface of the packing” is indicated, and the bottom-head sample shall
rosin after it has thoroughly cooled. Such samples shall not be determine the grade of the rosin in the package.
spiked from the barrel until it is completely cooled. 6.4 Rosin that is only slightly cloudy or opaque (caused by
(d) By withdrawing from a full package of 150 lb (67.5 kg) occluded moisture or separation of crystals in the solid mass)
or less, a quantity of the molten rosin, and allowing the same shall be graded in the usual way if the condition is not such as
to cool and solidify in any suitable mold. Samples representing to prevent an accurate evaluation of the color in comparison
a single charge (or intermittent distillation) of oleoresin shall with the standards. If, however, the opaqueness is of such a
be taken from not less than 2 packages, one of which shall be degree that the grade cannot be definitely determined in
selected after 1⁄4 of the rosin has been placed in the containers, comparison with the standards, the rosin shall be designated
and the other shall be the last package filled. “OPAQUE” and graded “OP,” in which case its acceptance and
(e) By withdrawing a quantity of molten rosin from a full value shall be a matter for settlement between the purchaser
drum, filled after a preliminary cooling period, and taken 1 h and the seller without reference to grade. Such opaque rosin
after the drum was filled, and pouring some withdrawn portion may be further identified or described as pale, medium, or dark
into a suitable mold. opaque.
(f) By pouring a portion of molten rosin sampled during
production into a color mold. 7. Tolerance
7.1 The tolerance or allowance of 15 % variation (Note 4)
6. Grading described in Section 5 is necessary because careful competent
6.1 The sample or “type” shall be compared with the graders rarely get exact duplicate results on all individual
appropriate standard, preferably against an open direct north samples when regrading a large number of rosin samples.
sky light, or in a direction that excludes direct rays from the Moreover, a regrade sample, coming from a different position
sun from passing through the rosin to the eye. The grade in the package, and after storage and weathering for an
assigned to the rosin shall be considered that of the highest or indefinite period, may be slightly darker than the original
lightest colored standard which the sample equals or excels (is sample on which the grade was based. An allowance for such
lighter than) in color (Note 3). Should the color or appearance slight variation must therefore be made.
of the rosin be such that there is a doubt whether the rosin is as NOTE 4—This tolerance is that recognized by the Federal Government
light or bright as the standard, the sample and the standard shall in the administration of the U. S. Naval Stores Act.
be viewed through a suitable colorimeter. Then in case of
uncertainty the rosin shall be given the benefit of the doubt. For 8. Softening Point
example, if a rosin sample is definitely darker than the WW 8.1 Determine the softening point in accordance with Test
standard but lighter than the WG standard, it is WG grade. If Method E 28.
however, the grader is undecided whether the total color of the 8.2 Test Method D 6090 may be used to determine the
rosin is “as good as” or equals, or is darker than that of the WW softening point provided the user determines the starting
standard, the grade is WW. temperature and heating rate that give results equivalent to the
ring and ball softening point in Test Method E 28.
NOTE 3—The “color” of a sample of rosin is made up of three
attributes: hue, saturation, and brightness. “Hue” alludes to the character- 9. Acid Number
istic described by the words “yellow” or “red.” “Saturation” describes the
9.1 Determine the acid number in accordance with Test
purity or strength of the yellowness or redness of the color.“ Brightness”
depends on the relative amount of light transmitted by the rosin. The Method D 465.
cleanliness of the rosin affects its transparency and therefore its brightness. 10. Gas Chromatographic Analysis
The terms “lighter than” and its inverse, “darker than” are convenient to
describe the difference between a sample and a standard. The rosin may be 10.1 Determine the amounts of the major rosin acid isomers
darker than the standard in one or more of the following ways: (1) a redder present in the rosin in accordance with Test Method D 5974.
3
D 509
11. Precision and Bias no longer widely used by industry and insufficient data could
11.1 Where the test method listed in this standard references be developed to give meaningful statements.
another ASTM method, that method should be studied to
determine the precision and bias. It is not practical to specify 12. Keywords
the precision and bias of the other procedures in this standard 12.1 colorimetric standards; rosin; USRG color
method for sampling and grading rosin, as the procedures are
4

Zinc Dust Pigment1
1. Scope TABLE 1 Requirements for Composition
1.1 This specification covers three types of zinc dust, for use Type I Type II Type III
as a pigment in paints. Total zinc, calculated as Zn, min, % 97.5 98.0 99.0
Metallic zinc, min, % 94.0 94.0 96.0
1.2 The values stated in SI units are to be regarded as the Material other than metallic zinc, ZnO,
standard. The values given in parentheses are for information and admixed CaO, where applicable
only. max % 0.75 ... ...
Calcium, calculated as CaO, max, % 0.7 0.7 ...
Lead, calculated as Pb, max, % ... 0.01 0.002
2. Referenced Documents Iron, calculated as Fe, max, % ... 0.02 0.002
2.1 ASTM Standards: Cadmium, calculated as Cd, max, % ... 0.01 0.001
Chlorine, calculated as Cl, max, % ... 0.01 ...
B 214 Test Method for Sieve Analysis of Granular Metal Sulfur, calculated as SO2, max, % ... 0.01 ...
Powders2 Moisture and other volatile matter, max, %
D 185 Test Methods for Coarse Particles in Pigments, 0.10 0.10 0.10
Oily or fatty matter, or both, max, % ... 0.05 ...
Pastes, and Paints3 Zinc oxide (ZnO), max, % 6.0 remainder remainder
D 521 Test Methods for Chemical Analysis of Zinc Dust Coarse particles, max, %:
(Metallic Zinc Powder)3 Total residue retained on a 150-µm none 0.1 0.1
(No. 100) sieve
E 40 Test Methods for Chemical Analysis of Slab Zinc Total residue retained on a 75-µm ... 0.8 0.8
(Spelter)4 (No. 200) sieve
Total residue retained on a 45-µm 4.0 3.0 3.0
3. Composition and Properties (No. 325) sieve
3.1 The pigments shall consist substantially of metallic zinc

and shall conform to the requirements for composition pre-
scribed in Table 1. 5000 kg (10 000 lb), except that for shipments of less than
3.2 In such physical properties as are specified by the 5000 kg, two samples shall be taken. At the option of the
purchaser, the pigment shall satisfactorily match a reference purchaser, the samples may be tested separately or after
sample mutually agreed upon between the purchaser and the blending in equal quantities the samples from the same
seller. production unit to form a composite sample.
4. Sampling 5. Test Methods
4.1 Two samples shall be taken at random from different 5.1 Tests shall be conducted in accordance with the follow-
packages from each lot, batch, day’s pack, or other unit of ing ASTM test methods. Test procedures not covered by these
production in a shipment. When no markings distinguishing ASTM test methods shall be mutually agreed upon between the
between units of production appear, samples shall be taken purchaser and the seller.
from different packages in the ratio of two samples for each 5.1.1 Total and Metallic Zinc—Test Methods D 521.
5.1.2 Lead, Cadmium, and Iron—Sections 8, 18.2, and 22,
1
respectively, of Test Methods E 40.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.1.3 Oily or Fatty Matter, or Both—Test Methods D 521.
Subcommittee D01.31 on Pigment Specifications. 5.1.4 Coarse Particles—Test Method B 214 or Test Meth-
Current edition approved April 10, 2000. Published June 2000. Originally ods D 185.
published as D520 – 39 T. Last previous edition D520 – 84 (1995)e1.
2
3
4
Annual Book of ASTM Standards, Vol 03.05. 6.1 pigment; zinc
1
D 520
2

Chemical Analysis of Zinc Dust (Metallic Zinc Powder)1
1. Scope 3. Significance and Use

1.1 These test methods cover procedures for the chemical 3.1 These test methods compile procedures which can be
analysis of metallic zinc powder in the form commercially used to check the composition of purity of metallic zinc
known as zinc dust for use as a pigment in paints. powder. This information is useful to both the formulator and
1.2 The analytical procedures appear in the following order: users.
Sections
Moisture and Other Volatile Matter 7 4. Treatment of Sample
Coarse Particles 8
Matter Soluble in Hexane 9 and 10
4.1 Store the laboratory sample in a tightly stoppered bottle
Total Zinc 11 and 12 to protect it from oxidation. Mix the whole sample thoroughly
Metallic Zinc 13 and 14 before taking portions for analysis.
Zinc Oxide 15
Calcium 16 and 17
Lead 18
Iron 19 5.1 Purity of Reagents—Unless otherwise indicated, it is
Cadmium 20
Chlorine 21 and 22
intended that all reagents shall conform to the specifications of
Sulfur 23 and 24 the Committee on Analytical Reagents of the American Chemi-
cal Society, where such spedcifications are available.7 Other
grades may be used, provided it is first ascertained that the
reagent is of sufficiently high purity to permit its use without
5.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water conforming
2. Referenced Documents to Type II of Specification D 1193.
2.1 ASTM Standards: 6. Precision
B 214 Test Method for Sieve Analysis of Metal Powders2
6.1 Precision statements have not been established.
Pastes, and Paints3 MOISTURE AND OTHER VOLATILE MATTER
Matter Volatile Under the Test Conditions) in Pigments3 7. Procedure
D 1193 Specification for Reagent Water4 7.1 Determine moisture and other volatile matter in accor-
E 40 Test Methods for Chemical Analysis of Slab Zinc dance with Method A of Test Methods D 280, except heat the
(Spelter)5 sample for only 1 h.
E 68 Method for Polarographic Determination of Lead and
Cadmium in Zinc6 COARSE PARTICLES
8. Procedure
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint 8.1 Determine the percent of coarse particles in the pigment
and Related Coatings, Materials, and Applications and are the direct responsibility in accordance with Test Methods D 185 or B 214.
7
published as D 521 – 39 T. Last previous edition D 521 – 81. Reagent Chemicals, American Chemical Society Specifications, American
2
Annual Book of ASTM Standards, Vol 02.05. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
3
4
5
6
Discontinued—See 1979 Annual Book of ASTM Standards, Part 12. MD.
1
D 521
MATTER SOLUBLE IN HEXANE addition of the litmus paper and the adjustment of the acidity
with NH4OH and HCl.
9. Reagent 12.3 Calculation—Calculate the percent of total zinc, T, as
9.1 Hexane—Pure hexane or commercial hexane or petro- follows:
leum ether of boiling point not higher than 75°C. Redistill T 5 @~V2 2 B2!Z/S1# 3 100 (2)
before using.
where:
10. Procedure V 2 5 K4Fe(CN)6 solution required for titration of the
10.1 Place 100 g of the pigment in an extraction thimble in specimen, mL,
a Soxhlet extraction apparatus. Record the tare weight of the B2 5 K4Fe(CN) 6 solution required for titration of the
receiving flask. Charge the flask with a suitable volume of blank, mL,
hexane and extract the sample for 4 h, subjecting the specimen Z 5 zinc equivalent of the K4Fe(CN)6 solution, g/mL,
to not less than 20 extractions in this time. Make a blank and
determination at the same time. S1 5 sample used, g.
10.2 Remove the receiving flask, evaporate or distill off the
hexane on a steam bath, and dry the flask at 105 6 2°C for 1 METALLIC ZINC
h. Cool and weigh. NOTE 1—Sections 12 and 13 cover a rapid method for determining
10.3 Calculate the percent of matter soluble in hexane, metallic zinc, intended for routine analysis. The results are inclined to be
allowing for any material found in the blank. somewhat low, and for highest accuracy and particularly for referee tests,
the hydrogen evolution method should be used.8
TOTAL ZINC
13. Reagents
11. Reagents
13.1 Ferric Chloride Solution—Prepare a solution contain-
11.1 Potassium Ferrocyanide, Standard Solution—Dissolve ing 20 g of ferric chloride (FeCl3·6H 2O) and 20 mL of 20 %
22 g of potassium ferrocyanide (K4Fe(CN)6·3H 2O) in water sodium acetate (NaC2H3O2) solution per 100 mL. It is advis-
and dilute to 1 L. To standardize, transfer 0.2 g of metallic zinc able to make up only one day’s supply at a time (50 mL are
or freshly ignited zinc oxide (ZnO) to a 400-mL beaker. required for each determination).
Dissolve in 10 mL of hydrochloric acid (HCl), sp gr 1.19 and 13.2 Potassium Permanganate, Standard Solution (0.1 N, 1
20 mL of water. Drop in a small piece of litmus paper, add mL 5 0.008 g TiO2)—Dissolve 3.16 g of KMnO4 in water and
ammonium hydroxide (NH4OH) until slightly alkaline, then dilute to 1 L. Let stand 8 to 14 days, siphon off the clear
add HCl until just acid, and then 3 mL more of HCl. Dilute to solution (or filter through a medium porosity fritted disk), and
about 250 mL with hot water and heat nearly to boiling. Run in standardize against the National Institute of Standards and
the K 4Fe(CN)6 solution slowly from a buret, while stirring Technology (NIST) standard chemical No. 40 of sodium
constantly, until a drop tested on a white porcelain plate with a oxalate (Na2C2O4) as follows: In a 400-mL beaker dissolve
drop of the uranyl indicator solution shows a brown tinge after 0.2500 to 0.3000 g of the NIST sodium oxalate in 250 mL of
standing 1 min. Do not allow the temperature of the solution to hot water (80 to 90°C) and add 15 mL of H2SO4 (1+1). Titrate
fall below 70°C during the titration. Run a blank using the at once with the KMnO4 solution, stirring the liquid vigorously
same amounts of reagents and water as in the standardization. and continuously. The KMnO4 must not be added more rapidly
The standardization must be made under the same conditions than 10 to 15 mL/min, and the last 0.5 to 1 mL must be added
of temperature, volume, and acidity as obtained when the dropwise with particular care to allow each drop to be fully
sample is titrated. Calculate the strength of the K 4Fe(CN)6 decolorized before the next is introduced. The solution shall
solution in terms of grams of zinc as follows: not be below 60°C by the time the end point has been reached.
Z 5 W/~V1 2 B! (1) (More rapid cooling may be prevented by allowing the beaker
to stand on a small hot plate during the titration. The use of a
where: small nonmercury type thermometer as a stirring rod is most
Z 5 zinc equivalent of the K4Fe(CN)6 solution, g/mL,
convenient.) Keep the KMnO4 solution in a glass-stoppered
W 5 zinc used (or equivalent to the ZnO used), g,
V1 5 K4Fe(CN) 6 solution required for titration of the bottle painted black to keep out light, or in a brown glass bottle
standard, mL, and stored in a dark place.
B 5 K4Fe(CN)6 solution required for titration of the 13.3 Sodium Acetate Solution (200 g/L)—Dissolve 200 g of
blank, mL. sodium acetate (NaC2H 3O2) or 332 g of NaC2H3O2·3H 2O, in
11.2 Uranyl Nitrate Indicator Solution— Dissolve 5 g of water and dilute to 1 L.
uranyl nitrate (UO2(NO3)2·6H 2O) in 100 mL of water. 13.4 Zimmerman-Reinhardt Solution—Prepare a solution
containing 67 g of manganese sulfate (MnSO4·4H 2O) 130 mL
12. Procedure of H2SO4 (sp gr 1.84), and 138 mL of phosphoric acid (H3PO4)
12.1 Transfer 0.25 g of the sample to a 400-mL beaker, (85 %) per L.
moisten with alcohol, and dissolve in 10 mL of HCl (sp gr
1.19) and 20 mL of water.
12.2 Continue with the procedure used in standardizing the 8
Wilson, L. A., “The Evaluation of Zinc Dust: A Proposed Method of Analysis,”
K4Fe(CN)6 solution as described in 10.1, beginning with the Proceedings, ASTEA, Am. Soc. Testing and Mats., Vol 18, Part II, 1918, p. 220.
2
D 521
14. Procedure out as hydroxide at this point.) Add NH4OH (sp gr 0.90)
14.1 Weigh 0.2 g of the sample, transfer immediately to a dropwise, stirring until the solution becomes clear. Heat nearly
dry, 600-mL heavy-wall Erlenmeyer flask, and add 50 mL of to boiling and add 75 mL of saturated ammonium oxalate
the FeCl 3 solution. Tightly stopper the flask and agitate solution. Boil until the precipitate assumes a dense crystalline
constantly for approximately 15 min. As soon as the zinc dust appearance. Allow to settle on a steam bath for 20 min and then
is all dissolved, add 50 mL of the Zimmerman-Reinhardt cool. Filter on close-grained paper and wash five times with a
solution and 250 mL of water. Titrate with 0.1 N KMnO4 cold ammonium oxalate solution (10 g/L).
solution. 17.2 Carefully dissolve the precipitate from the filter paper,
using alternately hot HCl (1+3) and hot water. Catch in a clean
NOTE 2—If preferred, the reduced iron may be titrated with 0.1 N 400-mL beaker, dilute (if necessary) to a volume of about 250
potassium dichromate (K2Cr2O7) solution, using sodium diphenylamine
sulfonate in the presence of phosphoric acid (H 3PO4) as an internal
mL, and add 25 mL of saturated ammonium oxalate solution.
indicator.9 Bring to a boil, and add NH4OH in slight excess. Boil until the
precipitate becomes crystalline and dense. Let stand 1 h on a
14.2 Blank—Make a blank determination, following the steam bath. Allow to cool. Filter and wash with small amounts
same procedure and using the same amounts of all reagents of hot water until all ammonium oxalate is removed.
prior to the titration. (The blank is usually 0.1 to 0.2 mL of 0.1 17.3 Remove the paper from the funnel and spread it out on
N KMnO4 solution.) the inside of a 600-mL beaker above 300 mL of warm water to
14.3 Calculation—Calculate the percent of metallic zinc, which has been added 20 mL of H2SO4 (1+1). Rinse the
M, as follows: precipitate off the paper with water from a wash bottle and
M 5 @~V3 2 B 3!~N 3 0.0327!/S2# 3 100 (3) warm the solution to 80°C. Titrate at this temperature with
KMnO4 solution. As soon as a persistent pink end point is
where:
obtained, drop the paper into the liquid, rinse the side of the
V3 5 KMnO4 solution required for titration of the
beaker, and quickly complete the titration.
specimen, mL,
B3 5 KMnO4 solution required for titration of the 17.4 Calculation—Calculate the percent of calcium, C, as
blank, mL, CaO, as follows:
N 5 normality of the KMnO4 solution, C 5 @~V4N 3 0.02804!/S 3# 3 100 (5)
S2 5 sample used, g, and
0.327 5 milliequivalent weight of Zn. where:
V 4 5 KMnO4 solution required for titration of the sample,
ZINC OXIDE mL,
N 5 normality of the KMnO4 solution, and
15. Calculation S 3 5 specimen used, g.
15.1 Calculate the percent of zinc oxide (ZnO), Z, as
LEAD
follows:
Z 5 ~A 2 C! 3 1.2447 (4) 18. Procedure
18.1 Determine the lead content in accordance with Section
where:
A 5 total zinc, % (Section 10), and 6 of Test Methods E 40.
C 5 metallic zinc, % (Section 12). NOTE 3—Lead may also be determined in accordance with Test Method
E 68.
CALCIUM
IRON
16. Reagents
16.1 Ammonium Oxalate, Saturated Solution—Mix 50 g of 19. Procedure
ammonium oxalate and 1 L of water. 19.1 Determine the iron content in accordance with Section
16.2 Ammonium Oxalate Solution (10 g/L)—Dissolve 10 g 22 of Test Method E 40.
of ammonium oxalate in water and dilute to 1 L.
16.3 Potassium Permanganate, Standard Solution (0.1 CADMIUM
N)—See 13.2. 20. Procedure
17. Procedure 20.1 Determine the cadmium content in accordance with
17.1 Transfer 10 g of the sample, weighed to 0.1 g, to a 18.1 and 18.3 of Test Method E 40.
400-mL beaker. Dissolve in 30 mL of HCl (1 + 1), keeping the NOTE 4—Cadmium may also be determined in accordance with Test
beaker covered. Dilute to 200 mL. The solution at this point Method E 68.
should be clear and transparent. Neutralize with NH4OH.
CHLORINE
(Some zinc, because of its high concentration, will precipitate
21. Reagents
9
Kolthoff, I. M., and Sandell, E. B., Textbook of Quantitative Inorganic Analysis, 21.1 Silver Nitrate Solution (3.5 g/L)—Dissolve 3.5 g of
1945, p. 608. silver nitrate (AgNO3) in water and dilute to 1 L.
3
D 521
21.2 Sodium Chloride, Standard Solution (0.01 N)— saturated bromine water and then cautiously add HNO3(sp gr
Dissolve 0.5850 g of pure sodium chloride (NaCl) in water and 1.42) until solution is complete.
dilute to 1 L. 24.2 Add 1 g of anhydrous sodium carbonate (Na 2CO3) and
boil down until salts just begin to separate, then add 75 mL of
22. Procedure
HCl (sp gr 1.19) and again boil down until salts begin to
22.1 Transfer 1.000 g of the sample to a 200-mL electrolytic separate. Repeat this operation and, finally, dilute to 100 mL,
beaker. Add 20 mL of water and then cautiously add 5 mL of heat until solution is complete, and filter into a 400-mL beaker
nitric acid (HNO 3) (sp gr 1.42). Cover with a watch glass and through close-texture paper.
heat on a steam bath with frequent stirring for 5 min, or until
24.3 Wash the paper with hot water, make the filtrate
a clear solution results. Add 70 mL of water and cool to room
alkaline with NH4OH, and then just acid with HCl. Heat to
temperature.
boiling and hold at boiling temperature at least 5 to 10 min to
22.2 To the specimen and to a blank (prepared in similar
drive out CO 2 then slowly add with stirring 5 mL of BaCl2
fashion) add 5.0 mL of AgNO3 solution (3.5 g/L) and stir. To
solution. Allow to stand at least 5 h (preferably overnight).
the blank, add dropwise from a 10-mL buret, with thorough
mixing, enough NaCl solution to develop a turbidity matching 24.4 Filter on a weighed Gooch crucible, wash free from
that of the sample. Keep the contents of both beakers well chlorides with hot water, dry, and ignite carefully at 900°C.
stirred and view against a black background in equal illumi- Cool and weigh. The difference between the original and final
nation. weight is BaSO 4.
22.3 Calculation—Calculate the percent of chlorine, C, as 24.5 Blank—Make a blank determination, following the
follows: same procedure and using the same amounts of all reagents.
C 5 0.035 V5 (6) 24.6 Calculation—Calculate the percent of sulfur, S, as
follows:
where V5 5 0.01 N NaCl solution added to the blank, mL.
S 5 @~~W1 2 B 4! 3 0.1374!/S4# 3 100 (7)
SULFUR
where:
23. Reagents W1 5 BaSO4, g,
23.1 Barium Chloride Solution (100 g/L)—Dissolve 117 g B4 5 correction for blank, g,
S4 5 sample used, g, and
of barium chloride (BaCl2·2H 2O) in water and dilute to 1 L.
0.1374 5 S/BaSO4 5 32.06/233.42.
23.2 Bromine Water (saturated).
24. Procedure 25. Keywords
24.1 Transfer 20 g of the specimen, weighed to the nearest 25.1 calcium; chlorine; potassium ferrocyanide; zinc dust;
0.1 g, to a 600-mL beaker. Cover the sample with 50 mL of zinc powder
views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428. This standard is
copyrighted by ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, Unite d States. Individual reprints (single or
multiple copies) of this standard may be obtained by conta cting ASTM at the above address or at 610-832-9585 (phone),
610-832-9555 (fax) or service[@000a]stm.org (e-mail); or through the ASTM website (http://www.astm.org). []
4
Standard Guide for Testing

Drying Oils1
1. Scope responsibility of whoever uses this standard to consult and

1.1 This guide covers the selection and use of procedures establish appropriate safety and health practices and deter-
for testing drying oils commonly used in paints, varnishes, and mine the applicability of regulatory limitations prior to use.
related products.
1.2 The test methods included are as follows: 2. Referenced Documents
ASTM 2.1 ASTM Standards:
Test Method Section Test Method D 56 Test Method for Flash Point by Tag Closed Tester2
Acetone Tolerance 13 D 1950 D 93 Test Methods for Flash Point by Pensky-Martens
Acid Value 6 D 1639
Ash 10 D 1951, Closed Tester2
D 564 D 445 Test Method for Kinematic Viscosity of Transparent
Break 12 D 1952 and Opaque Liquids (and the Calculation of Dynamic
Clarity 5 D 2090
Color 19 D 1544, Viscosity)2
D 1209 D 564 Test Methods for Liquid Paint Driers3
Color after Heating of Drying Oils 25 D 1967 D 1209 Test Method for Color of Clear Liquids (Platinum-
Drying Properties 23 D 1640
Flash Point 24 D 93, Cobalt Scale)4
D 1310, D 1259 Test Method for Nonvolatile Content of Resin
D 56
Foots Volumetric 11 D 1954
Solutions3
Foots Gravimetric 11 D 1966 D 1310 Test Method for Flash Point and Fire Points of
Gel Time 14 D 1955 Liquids by Tag Open-Cup Apparatus3
Hydroxyl Value 16 D 1957
Loss on Heating 17 D 1960,
D 1358 Test Method for Spectrophotometric Diene Value of
D 93 Dehaydrated Castor Oil and Its Derivatives5
Matter Insoluble in Chloroform 18 D 1958 D 1466 Test Method for Sampling Liquid Oils and Fatty
Preparation of Sample 4 ...
Refractive Index 21 ...
Sampling 3 D 1466 Materials5
Saponification Value 8 D 1962 D 1475 Test Method for Density of Paint, Varnish, Lacquer,
Specific Gravity 20 D 1963,
D 1475
Tung Oil Quality Test 15 D 1964 D 1541 Test Method for Total Iodine Value of Drying Oils
Unsaponifiable Matter 9 D 1965 and Their Derivatives5
Unsaturation:
Diene Value:
Spectrophotometric 7 D 1358 (Gardner Color Scale)3
Method D 1545 Test Method for Viscosity of Transparent Liquids
Iodine Value:
Rosenmund-Kuhn- 7 D 1541
by Bubble-Time Method5
henn Method D 1639 Test Method for Acid Value of Organic Coating
Wijs Method 7 D 1959 Materials5
Viscosity 22 D 1545,
D 445 D 1640 Test Methods for Drying, Curing, or Film Forma-
1.3 This standard does not purport to address all of the D 1644 Test Methods for Nonvolatile Content of Varnishes3
safety concerns, if any, associated with its use. It is the D 1950 Test Method for Acetone Tolerance of Heat-Bodied
Drying Oils5
1
This Guide is under the jurisdiction of ASTM Committee D-1 on Paint and
2
Subcommittee D01.32 on Drying Oils. Annual Book of ASTM Standards, Vol 05.01.
3
Current edition approved April 27, 1984. Published August 1984. Originally Annual Book of ASTM Standards, Vol 06.01.
4
published as D 555 – 39, replacing methods appearing in D 12, D 124, D 125, Annual Book of ASTM Standards, Vol 06.04.
5
D 234, and D 260. Last previous edition D 555 – 78. Annual Book of ASTM Standards, Vol 06.03.
1
D 555
D 1951 Test Method for Ash in Drying Oils and Fatty a number of established liquid samplers may be used with good
Acids5 results.
D 1952 Test Method for Quantitative Determination of
Break in Drying Oils5 4. Preparation of Sample
D 1954 Test Method for Foots in Raw Linseed Oil (Volu- 4.1 Melt the sample if it is not already completely liquid.
metric Method)5 The temperature during melting should not exceed 10 to 15°C
D 1955 Test Method for Gel Time of Drying Oils5 above the melting point of the sample.
D 1957 Test Method for Hydroxyl Value of Fatty Oils and 4.2 Mix the laboratory sample thoroughly by shaking,
Acids5 stirring, or pouring from one vessel to another. Take the
D 1958 Test Method for Chloroform–Insoluble Matter in specimens for the individual tests from this thoroughly mixed
Oiticica Oil5 sample.
D 1959 Test Method for Iodine Value of Drying Oils and
5. Clarity
Fatty Acids5
D 1960 Test Method for Loss on Heating of Drying Oils5 5.1 This requirement provides for the quick rejection of
D 1962 Test Method for Saponification Value of Drying natural oils that are obviously contaminated by solid matter,
Oils, Fatty Acids and Polymerized Fatty Acids5 such as dirt, or water in excess of the solubility limit.
D 1963 Test Method for Specific Gravity of Drying Oils, 5.2 Most natural oils contain some saturated glycerides,
Varnishes, Resins, and Related Materials at 25/25°C5 which may crystallize out at low temperatures giving a cloudy
D 1964 Test Method for Tung Oil Quality5 appearance. If the cloudiness disappears on warming, it is
D 1965 Test Method for Unsaponifiable Matter in Drying probably due to these saturated glycerides and should be
Oils, Fatty Acids and Polymerized Fatty Acids5 disregarded.
D 1966 Test Method for Foots in Raw Linseed Oil (Gravi- 5.3 Some processed oils are naturally hazy, as a result of the
metric Method)5 processing methods used, and a clarity requirement should not
D 1967 Test Method for Measuring Color After Heating of be included in specifications for processed oils unless it is
Drying Oils5 known that properly processed oils of the type desired will
D 1983 Test Method for Fatty Acid Composition by Gas- meet the requirements.
Liquid Chromatography of Methyl Esters5 5.4 Determine the clarity in accordance with Test Method
D 2090 Test Method for Clarity and Cleanness of Paint and D 2090.
Ink Liquids5 6. Acid Value
D 2245 Test Method for Identification of Oils and Oil Acids
in Solvent-Reducible Paints3 6.1 The acid value of an oil is an indication of the condition
D 2800 Test Method for Preparation of Methyl Esters from of the seed from which the oil has been extracted and of the
Oils for Determination of Fatty Acid Composition by Gas refining to which it has been subjected. It is not useful for the
Chromatography5 identification of the type of oil.
D 3457 Test Method for Preparation of Methyl Esters from 6.2 Test Method D 1639 is generally most satisfactory as to
Fatty Acids for Determination of Fatty Acid Composition precision. There is no choice between sodium and potassium
by Gas-Liquid Chromatography5 hydroxides except personal preference.
D 3725 Test Method for Semiquantitative Determination of 6.3 If the percent of free fatty acids calculated as oleic is
Fish Oil in Drying Oils and Drying Oil Fatty Acids by required, the following equation may be used for the transfor-
Gas-Liquid Chromatography5 mation:
Free fatty acids, % 5 0.503 3 acid value (1)
3. Sampling
7. Unsaturation
3.1 Sample the material in accordance with Test Method 7.1 The drying properties of fats and oils are indicated by
D 1466. This test method covers in considerable detail a the amount and nature of unsaturation they contain. The
procedure for obtaining representative samples of liquid oils amount is conventionally expressed as the iodine value, that is,
and fatty materials from drums, barrels, casks, and tank cars. centigrams of iodine absorbed per gram of sample (weight
The test method gives instructions on obtaining representative percent of iodine absorbed). The iodine value is a fairly
samples from 4000, 6000, 8000, 10 000 and 12 000-gal (15, satisfactory measure of the relative drying time and speed of
23, 30, 38, and 45-m3) cars. Additional directions must be heat-polymerization among a group of oils of the same type.
obtained for sampling cars of other capacities. However, because both drying time and heat-polymerization
3.2 Test Method D 1466 takes into consideration the pos- are affected by the kind and distribution of fatty acids in the oil,
sible presence of settled solid or “footy” materials that may these methods are not so useful in comparing oils of different
exist in the container. The test method requires that drums or types. The measurement of unsaturation is an alternative to the
casks be thoroughly mixed by rolling before a sample is taken. determination of the individual fatty acids for the identification
However, with regard to tank cars, the procedure, if followed of natural oils, since each natural oil has its own range of
carefully, will yield representative samples from cars that unsaturation values.
contain considerable quantities of settled solid material. If it is 7.2 Determine the unsaturation of natural drying oils that do
known that there is no settled material in a tank car, any one of not contain conjugated double bonds by the Wijs method as
2
D 555
described in Test Method D 1959, which gives fairly good nonglyceride matter, such as mineral oil, hydrocarbon resins,
accuracy and precision. It has largely superseded the Hanus etc.
and other methods that tend to give high results. When the Wijs 9.2 Determine the unsaponifiable matter in accordance with
method is applied to oils containing conjugated double bonds, Test Method D 1965, which is the referee method. Since the
such as tung oil and dehydrated castor oil, an empirical figure exact amount of unsaponifiable matter obtained is governed by
is obtained that is indicative of the relative amount of the partition coefficient of the matter between the soap solution
unsaturation present, but is not a measure of the total and the solvent, different results may be expected if some other
unsaturation. With careful control of the reaction conditions, solvent such as ethyl ether is used. A rapid, qualitative test for
however, reproducible and useful results may be obtained. excessive unsaponifiable matter consists in saponifying a small
Where the total unsaturation is required, make the quantity of the oil and diluting with water. A milky emulsion
determination using a modification of the Rosenmund- indicates excess unsaponifiable matter.
Kuhnhenn method as described in Test Method D 1541. This
method gives an accurate measure of total unsaturation on 10. Ash
conjugated oils and is also satisfactory for nonconjugated oil, 10.1 Ash is determined by igniting the oil, under specified
although somewhat more difficult to run than the Wijs method. conditions, and weighing the noncombustible material. Most
Quantitative hydrogenation will also yield an accurate measure natural and processed oils contain small amounts of ash, but
of the total unsaturation. There is no standard procedure for this the amount is insignificant. Certain, synthetic drying oils may
method. It is the only satisfactory method for oils containing contain residual catalyst or other materials, thus giving larger
acetylenic bonds, such as isano oil. amounts of ash. Although the ash and metal content of boiled
7.3 The iodine value is useful for the identification of oils may be specified, the trend with new and improved driers
linseed, soybean, safflower, and similar natural oils. The is toward the specification of drying time, allowing the
amount of conjugated diene (or triene) is useful for identifying manufacturer to obtain this in any way desired.
tung and oiticica oils, as well as dehydrated castor oil. 10.2 Determine the ash in accordance with Test Method
Conjugated diene is a measure of the quality of dehydrated D 1951. Determine the drier metal content of the ash in
castor oil, although it is not the only measure that should be accordance with Test Methods D 564. Wet ashing or extraction
used. Determine the amount of conjugated diene by methods may give more accurate results.
spectrophotometric measurement using Test Methods D 1358.
11. Foots
8. Saponification Value 11.1 “Foots” is the term applied to nonoil material that will
settle out of natural oils on storage. Since the material
8.1 The saponification value is, essentially, a measure of the
measured as foots is usually suspended rather than dissolved in
molecular weight of the fatty acid portion of the glyceride,
the oil, extreme care in sampling is necessary to get a
varying inversely with the weight, except for certain modified
representative sample for measurement. This applies not only
oils. It is not a measure of the quality or identity of the oil. The
to the sampling of the bulk oil but also to the taking of
value is useful for certain calculations in the use of the oil, such
specimens for running the test. Careful agitation to ensure
as in the manufacture of alkyd resins.
thorough mixing before sampling is absolutely essential.
8.2 Determine the saponification value in accordance with
11.2 Some of the materials included in the foots hydrate
Test Method D 1962, which is satisfactory for all normal oils
readily in the presence of moisture, particularly at low
and for many special and synthetic products. As indicated in
temperatures, and these hydrated materials have a much larger
the test method, longer saponification times are required for
volume than they had originally. Therefore, oils exposed to
certain synthetic oils, and some special products may require
moisture for periods of time, particularly with chilling, may be
the use of a higher-boiling solvent, such as ethylene glycol, for
expected to show a substantial increase in volumetric foots
complete saponification.
with time.
8.3 Saponification value is not changed significantly by 11.3 Determine volumetric foots in accordance with Test
polymerization but increases rapidly with oxidation. A Method D 1954. Very careful control of all variables in the test
saponification value significantly higher than normal indicates is absolutely necessary, as the test is empirical. Even under the
the presence of oxidized or blown oils or else modification with best conditions, the reproducibility is not good. The test is
chemicals such as maleic or fumaric acids. usually used for raw linseed oil. It has no meaning when
applied to oils that have been processed to any marked degree.
9. Unsaponifiable Matter 11.4 Determine gravimetric foots in accordance with Test
9.1 The unsaponifiable matter is a measure of the materials Method D 1966. The precision of this procedure is much better
present in the oil that are oil-soluble and are not converted to than the older volumetric method. Internationally the
water-soluble soaps by the saponification conditions used. A procedure is known as the P.A.T. test and its use is increasing
small amount of unsaponifiable matter is characteristic of all in oil trading.
natural oils, varying with the extraction and refining
conditions. Within the limits of the individual oil 12. Break
specifications, the amount of unsaponifiable matter is no 12.1 “Break” is the nonoil material that separates from
measure of the quality or identity of the oil. An excessive natural oil on heating. It is usually reported by weight. Break
amount of unsaponifiable matter indicates contamination with is not significant except in oils that are to be heated, as in the
3
D 555
manufacture of varnishes or alkyd resins, and this requirement 16. Hydroxyl Value
should not be included in a specification unless necessary for 16.1 The hydroxyl value is a measure of hydroxyl content of
the proposed end use. an oil, expressed as milligrams of potassium hydroxide
12.2 Determine break in accordance with Test Method equivalent to the hydroxyl content of 1 g of oil. It is used to
D 1952. Test Method D 1952 is empirical, and the conditions determine the efficiency of the dehydration of dehydrated
prescribed must be carefully followed, but results correlate castor oil. It is also a measure of the residual hydroxyl groups
well with practical performance. of processed oils, when other interfering groups are not
13. Acetone Tolerance present.
16.2 Determine the hydroxyl value in accordance with Test
13.1 The acetone tolerance is a measure of the amount of Method D 1957. This test method involves the acetylation of
high polymer in a heat-bodied oil when no nonfatty material is hydroxyl-containing fatty oils and acids using pyridine as
present. It is only applicable to heat-bodied oils and should solvent. Other groups that will react with acetic anhydride
only be used to assure uniformity of deliveries. There is no under the conditions of the test method will be reported as
correlation between the acetone tolerance and the usefulness of hydroxyl. A correction is applied for acid groups present and,
an oil, but, if acetone tolerance and other properties of an oil if necessary, similar corrections may be applied for other
are the same as those of an accepted sample, the two probably interfering groups.
have been produced by the same technique.
13.2 Determine the acetone tolerance in accordance with 17. Loss on Heating
Test Method D 1950. The test method consists of adding 17.1 Determine the loss on heating in accordance with Test
acetone until a cloudy dispersion persists. Temperature is Method D 1960, which is a quick method for detecting
extremely important and must be controlled very closely. This contamination or adulteration of natural oils with volatile
determination may be made as a “cloud point,” measuring the solvents. It is not a true loss measure since small amounts of
temperature at which cloudiness appears for a given acetone oxygen, if any, in the inert gas used will be absorbed by the oil,
concentration, but this is a more difficult technique, resulting in a small gain in weight, that may more than offset
experimentally, for this particular solvent-solute combination. small losses. This method should be used only for gross
Quantities greater than the smallest traces of water in the contamination. When small amounts of flammable volatile
acetone also affect the result significantly, and the amount must solvent are to be qualitatively detected, as in solvent-extracted
be kept within the prescribed limits. oil, use Test Method D 93. For oils containing larger amounts
of volatile matter where an accurate determination is required,
14. Gel Time use Test Methods D 1259 or D 1644.
14.1 Gel time is a measure of the tendency of oils to solidify
under certain specified conditions. The test is designed 18. Matter Insoluble in Chloroform
primarily for the detection of adulteration in tung and oiticica 18.1 The matter insoluble in chloroform, in a drying oil,
oils. The method, usually at a higher temperature, may also be represents mineral contamination, since all materials naturally
used to evaluate oils treated to produce rapid polymerization as occurring in such oils are soluble under the conditions outlined
well as dehydrated castor oil. The method is not applicable to in this test method.
natural oils such as linseed and soybean that do not show a 18.2 Determine insoluble matter in accordance with Test
sharp end point at practicable temperatures. Other natural oils Method D 1958. This test method is rarely applied to drying
such as tung and oiticica are subject to some variation, oils other than oiticica oil which, because of the production
depending upon many factors. Slight variations from the process, may be contaminated with mineral matter.
standard values should not at first glance be taken as sufficient 19. Color
evidence of adulteration.
14.2 Determine the gel time in accordance with Test Method 19.1 The color of an oil, in bulk, is usually relatively useful
D 1955. In this test method, since the volume of the oil bath is in predicting how it will behave in use in comparison with
relatively small, the bath is chilled by the introduction of the other similar oils. However, since some oils darken on heating
specimens, and must be raised above the operating temperature or oxidation and others bleach, the color in bulk is rarely
in order to be correct after insertion of the tubes. Since the helpful in comparing oils of different types.
control of temperature is very important and is difficult to 19.2 Determine the color by comparison with standards,
maintain accurately by manual means over a long period of either liquid or glass, as described in Test Method D 1544
time, oils that gel slowly should be tested at higher (but which is the fastest method and, in general, is sufficiently
accurately defined) temperatures, in order that gelation may accurate. For extremely light-colored oils (Gardner color No. 3
take place in a reasonable time. or lower) use the APHA or Hazen method as described in Test
Method D 1209. Since this test method uses a much thicker
15. Tung Oil Quality Test layer of oil than Test Method D 1544, light colors may be
15.1 Determine the quality of tung oil in accordance with judged more precisely. However, because of this thickness
Test Method D 1964, which is designed to detect adulteration difference, there is no precise correlation between the two
of tung oil with nonconjugated oils. It is not intended for use methods and the method specified must be used.
with any other oil. Temperature is extremely important, and the NOTE 1—For edible oils, methods based on Lovibond glasses
correct thermometer, used in the correct way, is essential. (American Oil Chemists’ Society Method Cc 13b) or, rarely, on
4
D 555
spectrophotometric measurements (AOCS Method Cc 13c) are used. For and many processed oils have measurable (by the tube method)
tallows and certain other inedible oils, the FAC Method (AOCS Method viscosities, but in the case of processed oils the viscosity is a
Cc 13a) is commonly specified. These methods should not be used for result of the method of processing and is in no way related to
drying oils.
the merit of the oil.
19.3 In making visual comparisons of the color of specimen 22.3 Determine the viscosity of drying oils in accordance
and standard, careful control of the conditions of illumination with Test Method D 1545. This test method describes a means
and view are necessary if high precision is called for. Care for measuring the travel of an air bubble in a cylindrical tube
must be taken that the observer has normal color perception. either by timing or by comparison with standard tubes of
19.4 Standards darker than Gardner color No. 18 are not known viscosity. The results are very close to the true viscosity
very useful, since comparison of specimen and standard under in stokes, but are not exactly correct, so that viscosity
the conditions specified is difficult. When it is necessary to determined by this test method should be reported in
specify the color of very dark oils, it is usually more “approximate stokes” or “bubble seconds.” More precise
satisfactory to specify the color of the oil diluted with a results may be obtained for viscosities of less than 4 s by
standard amount of solvent sufficient to bring the color into the comparison with standards, and for more viscous oils by
range of the standard color-measuring methods. The nature of timing. If higher precision is required, use capillary
the solvent and the dilution must be specified exactly. viscometers such as those described in Test Method D 445.
20. Specific Gravity Results obtained in poises should be divided by the density to
give stokes.
20.1 Specific gravity of an oil is a useful measure, since
22.4 When tube methods are used, results are affected by the
translation from volume to weight, or vice versa, is often
size and shape of the air bubble. Therefore, if precise results
required. For this reason it should be determined with care.
are required, tubes conforming exactly to the standard must be
Specific gravity is not a measure of the quality of the oil, and
used, and the air bubble must be adjusted to the correct size. A
an oil that deviates slightly from the specified limits, but
difference in tube diameter of 0.05 mm will result in an error
otherwise conforms, is usually completely satisfactory.
of approximately 2 %. All viscosity measurements are very
Specific gravity increases with polymerization or oxidation in
sensitive to temperature and extremely close temperature
a regular manner, and for every bodied or blown oil of a given
control (60.1°C) is necessary for precise results.
viscosity there is an appropriate specific gravity.
20.2 Determine the specific gravity in accordance with Test 23. Drying Properties
Method D 1963, which is capable of high precision and is the 23.1 Since drying oils, by definition, set to a solid film, the
referee method. If less accurate results (3 significant figures) time required for this to take place is an important property of
are adequate, “weight-per-gallon” cups as described in Test all such oils. Unfortunately, the time required is greatly
Method D 1475 may be used. Specific gravity is very sensitive affected by a number of variables including temperature, drier
to temperature, and the temperature of measurement must be content, light, humidity, film thickness, air circulation, etc. All
controlled, or at least known, with high precision. If these must be controlled with great care to assure reproducible
measurements are made at other than the standard temperature, results. Furthermore, results obtained under one set of
or if the value of the specific gravity is required at some conditions do not necessarily allow prediction of results that
temperature other than the standard, the approximate value might be obtained under other conditions.
may be calculated as described in Test Method D 1963. 23.2 Empirical measures of drying properties are useful in
21. Refractive Index comparing one oil with others of the same general type, but
21.1 Refractive index is a scientifically defined property and must be used cautiously otherwise. Because of the effect of
numerous accurate instruments are available for its pigmentation and other variables, it is difficult to predict the
determination. Since the method used depends upon the drying time of a paint from the drying time of the oil used in
instrument, no method for its determination is given. Any one its manufacture.
of a large number of instruments operated according to the 23.3 Select from Test Methods D 1640 one set of generally
manufacturer’s instructions will give satisfactory results. acceptable conditions (except for drier content, which must be
21.2 Refractive index is not a very useful means of specified). These conditions may, of course, be varied as
specifying drying oils. It is useful in detecting adulteration in required, but any variation must be outlined carefully if
oils containing substantial amounts of conjugation, such as agreement is to be obtained. Numerous other methods of
tung, oiticica, and dehydrated castor oils. Since refractive measuring drying time have been proposed. Most of these use
index varies with iodine value, it can be used as a quick some mechanical device to determine the end point. However,
approximation of iodine value. many of these devices interfere, in an unpredictable manner,
with the circulation of air, the amount of oxygen, and the
22. Viscosity amount of light available to the film so that results are likely to
22.1 Viscosity is the resistance experienced by one portion be erratic. The most widely used device, the Sanderson
of a liquid flowing over another portion. It is expressed in machine which drops sand on the film, gives results between
poises, the absolute unit, or in stokes, equivalent to poises the“ set-to-touch” and “dry” times.
divided by density. 23.4 Since the drying of oils is a continuing process that
22.2 The viscosity of most natural oils is very low and its goes on indefinitely, it is difficult to select sharp end points that
specification serves no useful purpose. Tung, oiticica, castor, may be measured precisely. The “set-to-touch” point, where
5
D 555
the internal cohesion of the film exceeds its adhesion to the traces of flammable solvents may evaporate and be lost without ever
finger, is probably the sharpest. This point coincides very igniting and an unduly high result may be obtained. Since many oils are
closely with the point where the film changes from a liquid to fairly viscous liquids, the use of test methods that do not provide for
stirring, such as Test Method D 56, may give anomalous results.
a gel. The “dry time” is more subjective, and it is difficult to get
close agreement between laboratories, especially for oils with 25. Color After Heating of Drying Oils
relatively long drying times. Agreement, however, is better as
to whether or not a film is dry at a specified time. 25.1 Some drying oils darken on heating to polymerization
temperatures while others may lighten in color. The procedure
24. Flash Point in Test Method D 1967 gives an indication of this color change.
24.1 The flash point of a liquid is defined as the lowest
temperature, corrected to 101.3 kPa (760 mmHg) of pressure, 26. Composition of Drying Oils and Fatty Acids by Gas-
of the material under test at which application of an ignition Liquid Chromatography
source causes its vapor to ignite under specified conditions of 26.1 Gas-liquid chromatography has proven to be a very
test. effective tool for the determination of the fatty acid
24.2 Most natural and synthetic drying oils have very high composition of fats and oils. It is often beneficial to know the
flash points of about 500°F (260°C), unless they contain traces actual chemical composition of a fatty mixture. This can be
of volatile, flammable materials. If the contaminating solvent is obtained by the use of several applicable related ASTM test
known, it is possible to set up a relationship between the methods.
solvent content and the flash point. 26.2 The oil or fatty acid to be tested must first be converted
24.3 Flash point of vegetable oils is helpful in determining to the methyl ester for the gas-liquid chromatographic
that no hazardous amounts of solvents have been left in determination. This is accomplished using Test Method D 2800
solvent-extracted oils, or that the oils have been contaminated in the case of oils and Test Method D 3457 for fatty acids.
with such solvents. If flammable solvents are not present, the 26.3 Test Method D 1983 is the general method for the
flash point of natural oils is meaningless as far as specifications determination of composition by gas chromatography. Test
are concerned. Method D 3725 shows the modifications to Test Method
24.4 Determine the flash point in accordance with Test D 1983 needed to determine fish oil present in other drying
Method D 93 which uses the Pensky-Martens Closed Cup. Use oils. This gas-liquid chromatography method is more reliable
Method B for Testing flash point of highly viscous materials. than the old bromination procedures referred to in X1.3.
The exact flash point obtained is empirical, depending upon the 26.4 Typical composition of oils used in paint products are
rate of heating and other factors set forth in the test method. shown in Table 1 of Method D 2245.
These must be followed carefully if reasonable precision is to
be obtained. 27. Keywords
NOTE 2—If open-cup methods, such as Test Method D 1310 are used, 27.1 drying oils
APPENDIX
(Nonmandatory Information)
X1. REFERENCES TO DELETED METHODS
X1.1 ASTM Method D 1956, Test for Heat Bodying Rate appeared in Part 29 of the 1978 Annual Book of ASTM
of Drying Oils, last appeared in Part 29 of the 1974 Annual Standards. Last approved in 1974. Withdrawn in 1978. This
Book of ASTM Standards. Last approved in 1969. Withdrawn method is still used in ISO 150, Specification for Raw, Boiled,
in April 1975. and Refined Linseed Oil.
X1.2 ASTM Method D 1961, Test for Maleic Diene Value
X1.4 The preceding methods have been deleted due to
of Drying Oils, last appeared in Part 29 of the 1974 Annual
nonuse or due to replacement by other more reproducible
Book of ASTM Standards. Last approved in 1969. Withdrawn
in April 1975. methods. If the instrumentation or equipment needed for the
new methods is not available then by mutual agreement
X1.3 ASTM Method D 1724, Qualitative Determination of between concerned parties the older methods, copies of which
Fish Oil in Drying Oils and Drying Oil Fatty Acids, last may be obtained from ASTM Headquarters, may be used.
6
D 555
7

Carbon Black Pigment for Paint1
1. Scope TABLE 1 Composition and Properties
1.1 This specification covers the pigment commercially Type I Type II ASTM Test Method
known as carbon black, which is suitable for use in the Ash, max, % 0.2A 1.0A D 1506
Acetone extract, max, % 0.5A 1.0A D 305
manufacture of protective or decorative coatings. Moisture (loss at 105°C) max, % 8.0B 8.0B D 1509
Coarse particles (total residue 0.2 0.2 D 1514
2. Referenced Documents retained on 45-µm (No. 325)
screen, max), %
2.1 ASTM Standards: Organic dyes none none D 50
D 305 Test Method for Solvent-Extractable Material in A
When mutually agreed upon by the purchaser and the seller, higher maximum
Black Pigments2 ash and acetone extract values may be allowed if final product requirements
D 387 Test Method for Color and Strength of Color Pig- necessitate the use of additional treating agents.
B
ments with a Mechanical Muller3 It may be necessary for the purchaser and the seller to agree upon a higher
maximum moisture content in high-color black. High-color blacks are very hygro-
D 1506 Test Method for Carbon Black—Ash Content4 scopic and should be protected against moisture during storage.
D 1509 Test Method for Carbon Black—Heating Loss4
D 1514 Test Method for Carbon Black—Sieve Residue4
3. Composition and Properties production in a shipment. When no markings distinguishing
3.1 The pigment shall be made by burning natural gas (Type between units of production appear, samples shall be taken
I) or oil (Type II) in such a manner as to form a deposit of from different packages in the ratio of two samples for each
carbon. It shall be free of adulterants and be in the form of 10 000 lb (5000 kg), except that for shipments of less than
powder or dustless pellets and shall conform to the require- 10 000 lb two samples shall be taken.
ments specified in Table 1. 4.2 At the option of the purchaser, the samples may be
3.2 The mass color and character of the tint and tinting tested separately or, after blending the samples from the same
strength formed by a mixture with a white pigment shall be production unit in equal quantities, tested as a composite
within mutually agreed upon limits of a standard acceptable to sample.
both the purchaser and the seller when tested in accordance 5. Test Methods
with Test Method D 387.
5.1 Tests shall be conducted in accordance with the follow-
NOTE 1—For the tinting strength test a ratio of 100 parts of white to 1 ing ASTM test methods. Test procedures not covered by ASTM
part of black is usually suitable. test methods shall be mutually agreed upon between the
4. Sampling purchaser and the seller.
5.1.1 Solvent Extractable Material—Test Method D 305.
4.1 Two samples shall be taken at random from different 5.1.2 Color and Tinting Strength—Test Method D 387.
5.1.3 Carbon Black—Ash Content—Test Method D 1506.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.4 Heating Loss—Test Method D 1509.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.1.5 Sieve Residue—Test Method D 1514.
Current edition approved Oct. 29, 1982. Published February 1983. Originally 6. Keywords
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 carbon black; natural gas; oil; pigment
3
4
1
D 561
2
Designation: D 563 – 88 (Reapproved 1996)e1 An American National Standard

Phthalic Anhydride Content of Alkyd Resins and Resin
Solutions1
1. Scope 5. Reagents
1.1 This test method covers the determination of the ph- 5.1 Purity of Reagents—Reagent grade chemicals shall be
thalic anhydride content (Note 1) of alkyd resins and resin used in all tests. Unless otherwise indicated, it is intended that
solutions, including those containing styrene. all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
NOTE 1—This test method is not applicable for the determination of
phthalic anhydride in alkyd resins containing other dibasic acids such as where such specifications are available.3 Other grades may be
maleic or fumaric, or modifying agents such as urea, melamine, and used, provided it is first ascertained that the reagent is of
phenolic resins. sufficiently high purity to permit its use without lessening the
1.2 This standard does not purport to address all of the accuracy of the determination.
safety concerns, if any, associated with its use. It is the 5.2 Purity of Water—Unless otherwise indicated, references
responsibility of the user of this standard to establish appro- to water shall be understood to mean reagent water as defined
priate safety and health practices and determine the applica- by Type II of Specification D 1193.
bility of regulatory limitations prior to use. 5.3 Alcohol-Benzene Wash Solution—Mix one volume of
absolute ethyl alcohol (Note 2) with three volumes of benzene.
2. Referenced Documents NOTE 2—The alcohol may be denatured, formula 2B, but must be
2.1 ASTM Standards: absolute.
D 1193 Specification for Reagent Water2 5.4 Benzene.
3. Significance and Use 5.5 Ether—Anhydrous analytical reagent-grade ether.
5.6 Hydrochloric Acid, Standard (0.1 N).
3.1 The phthalic anhydride content of alkyd resins controls 5.7 Potassium Hydroxide, Alcoholic Solution—Dissolve 66
the properties of the final film. g of reagent-grade potassium hydroxide (KOH) in 1 L of
4. Apparatus absolute ethyl alcohol (Note 2). Filter just before use.
4.1 Flask and Condenser—A 500-mL Erlenmeyer flask 6. Procedure
fitted with an air-cooled glass reflux condenser 30 in. (760 mm) 6.1 Weigh by difference, from a closed container into the
in length. The connection between the flask and condenser 500-mL Erlenmeyer flask, a specimen of resin or resin solution
shall be a 24/40 standard taper ground-glass joint. sufficient to yield from 0.8 to 1.2 g of potassium alcohol
4.2 Water Bath. phthalate. Add 150 mL of benzene, warming slightly on the
4.3 Fritted-Glass Filter Crucible, fine or medium porosity, steam bath if necessary, to effect solution. Add 60 mL of
of 30-mL capacity. alcoholic KOH solution and attach the condenser. Place the
4.4 Desiccator, containing concentrated H2SO4 (sp gr 1.84) flask in a water bath to a depth approximately equal to that of
as the desiccant. the contents of the flask. Warm the bath, maintaining a
4.5 Filter Flasks. temperature of 40°C for 1 h, then gradually raise the tempera-
4.6 Crucible Holder. ture until the alcoholic solution boils gently. Reflux for 11⁄2 h.
1 3
This method is under the jurisdiction of ASTM Committee D-1 on Paint and Reagent Chemicals, American Chemical Society Specifications, American
Related Coatings, Materials, and Applications and is the direct responsibility of Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Subcommittee D01.33 on Polymers and Resins. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved May 27, 1988. Published October 1988. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
1
D 563
6.2 Remove the flask from the bath and wash down the may be a source of error. If a correction for K2CO3 is desired,
inside of the condenser with a few millilitres of alcohol- proceed as follows: Dissolve the weighed precipitate in about
benzene wash solution. Remove the condenser, cap the flask 50 mL of distilled water that has been neutralized to phenol-
with the soda-lime guard tube, and cool by means of running phthalein. Add 3 to 4 drops of phenolphthalein indicator
water or an ice bath. solution, and if the solution is alkaline, titrate with 0.1 N HCl.
6.3 When cool, filter immediately and as rapidly as possible,
through a fritted-glass crucible that previously has been tared, 7. Calculation
using the alcohol-benzene wash solution for transferring the
7.1 Calculate the percent of phthalic anhydride A in the
precipitate and washing the reaction flask. Wash the precipitate
specimen as follows:
with successive portions of alcohol-benzene wash solution
until a few millilitres of washings collected in a second suction K 5 VN 3 0.1382
flask are no longer alkaline to phenolphthalein. (Normally A 5 @~~P 2 K! 3 0.5136!/S# 3 100
about 75 mL of wash solution are sufficient.) Do not allow air
to be drawn through the crystals, as they are hygroscopic. where:
Finally pour 25-mL of ether into the crucible and draw through K 5 correction for K2CO3 (if determined), g,
V 5 HCl used for titration (see 6.5), mL,
the precipitate with the aid of suction.
N 5 normality of HCl,
6.4 Wipe the outer surface of the crucible with a clean cloth P 5 potassium alcohol phthalate (see 6.5), g, and
and place in a gravity convection oven at 60°C for 1 h (Note 3). S 5 specimen used, g.
Cool to room temperature in a desiccator and weigh.
NOTE 3—The precipitate is the alcoholate (C6H4(COOH)2·(C2H5OH)), 8. Precision and Bias
and the alcohol of crystallization will be slowly driven off on prolonged
heating. It is safe, however, to dry the alcoholate at temperatures up to 8.1 Precision and bias are being determined.
60°C for as long as 1 h.
9. Keywords
6.5 Correction for Carbonates—Coprecipitation of potas-
sium carbonate (K2CO3) with the potassium alcohol phthalate 9.1 alkyd resins; phthalic anhydride content; resin solutions
2

Liquid Paint Driers1
1. Scope D 1545 Test Method for Viscosity of Transparent Liquids

1.1 This specification covers liquids for use in paints, by Bubble Time Method3
varnishes, enamels, and similar organic coatings and are 2.2 U.S. Federal Specification:
solutions of metallic salts of: PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging
1.1.1 Class A—2-Ethyl hexanoic acids in petroleum spirits. of 4
1.1.2 Class B—Naphthenic acids in petroleum spirits. 3. Chemical and Physical Requirements
1.1.3 Class C—Neodecanoic acids in petroleum spirits.
1.1.4 Class D—Tall oil fatty acids in petroleum spirits. 3.1 Quantitative Requirements—The drier shall conform to
1.1.5 Class E—Any of the above acids or acid blends, but the quantitative requirements as specified in Table 1 for
containing additives that make the liquid drier water dispers- metallic content, color, and viscosity.
ible. Some other driers may also contain complexing agents. 3.2 Physical Appearance—Each type of drier shall be a
1.1.6 Class F—Other acids and acid blends unidentified by mobile liquid free of sediment and suspended matter and shall
their producers. be stable and miscible with oil as listed in Test Methods D 564.
1.2 For specific hazard information and guidance, see the 4. Significance and Use
supplier’s Material Safety Data Sheets for materials listed in
this specification. 4.1 This specification covers the general requirements for
liquid paint driers used in paints, varnishes, enamels, and
2. Referenced Documents similar organic coatings.
2.1 ASTM Standards: 4.2 The values listed should be considered as general guides
D 564 Test Methods for Liquid Paint Driers2 to the character of the products, rather than reproducible
D 1544 Test Method for Color of Transparent Liquids constants.
(Gardner Color Scale)2 5. Test Methods
determined in accordance with Test Methods D 564, except as
1
otherwise provided in this specification.
3
Current edition approved May 25, 1990. Published July 1990. Originally Annual Book of ASTM Standards, Vol 06.03.
4
published as D600 – 73 (1978). Last previous edition D600 – 85. Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
2
TABLE 1 Typical Requirements of Liquid Paint DriersA
Nonvolative Typical Specific Color,B Gardner

Metal Concentration, % G-H Viscosity (Test
Class Metal Matter, % Gravity 25/25°C (Test Method
Method D 1545)
min max max min max D 1544)
A Calcium 3.9 4.1 50 0.884C — 3 A

A Calcium 4.9 5.1 60 0.894 0.912 5 C
B Calcium 3.9 4.1 70 0.902 0.937 10 D
B Calcium 4.9 5.1 85 0.932 0.970 11 T
C Calcium 4.9 5.1 46 0.888 — 2 A
D Calcium 3.9 4.1 66 0.890 0.918 9 B
E Calcium 3.9 4.1 63 0.905 0.930 8 G
E Calcium 5.9 6.1 76 0.922 0.960 5 N
F Calcium 3.9 4.1 50 0.850 0.884 3 A
F Calcium 4.9 5.1 60 0.900 0.936 4 B
F Calcium 5.9 6.1 74 0.873 0.948 6 N
F Calcium 7.9 8.1 70 0.958 — 5 B
1
D 600
TABLE
1 Continued
Nonvolative Typical Specific Color,B Gardner
Metal Concentration, % G-H Viscosity (Test
Class Metal Matter, % Gravity 25/25°C (Test Method
Method D 1545)
min max max min max D 1544)
F Calcium 9.9 10.1 65 1.000 1.030 7–8 K

A Cerium 5.9 6.1 30 0.856 — 8 A
B Cerium 5.9 6.1 57 0.925 — 17 A1
A Cobalt 5.9 6.1 45 0.875 0.900 blue/purple A
A Cobalt 11.8 12.2 90 1.008 1.060 blue/purple J
B Cobalt 5.9 6.1 67 0.918 0.970 blue/purple B
C Cobalt 11.8 12.2 65 0.984 — blue A
D Cobalt 5.9 6.1 72 0.912 0.956 purple C
E Cobalt 4.9 5.1 60 0.926 — red/purple A
E Cobalt 5.9 6.1 71 0.945 0.960 blue/purple I
F Cobalt 5.9 6.1 70 0.870 0.958 blue/violet A
F Cobalt 11.8 12.2 80 1.014 1.040 blue/violet J
A Iron 5.9 6.1 50 0.900 0.930 dark brown A
B Iron 5.9 6.1 67 0.960 0.990 dark brown M
F Iron 5.9 6.1 50 0.905 0.930 brown A
F Iron 8.9 9.1 78 0.950 0.985 brown A
F Iron 11.8 12.2 75 1.068 — brown A
A Lead 23.8 24.2 65 1.090 1.110 3 A
B Lead 23.8 24.2 67 1.125 1.160 11 B
C Lead 23.8 24.2 61 1.100 — 2 A2
D Lead 23.8 24.2 66 1.100 1.125 10 A
E Lead 23.8 24.2 71 1.125 1.150 7 A
F Lead 23.8 24.2 67 1.080 1.140 10 A
F Lead 35.8 36.2 81 1.350 1.393 8 H
A Manganese 5.9 6.1 50 0.888 0.920 red/brown A
B Manganese 5.9 6.1 66 0.930 0.965 17 D
C Manganese 5.9 6.1 50 0.870 — 10 A
D Manganese 5.9 6.1 72 0.942 0.972 brown E
E Manganese 4.9 5.1 42 0.911 — brown A
E Manganese 5.9 6.1 69 0.942 0.965 brown E
F Manganese 5.9 6.1 55 0.870 1.020 18 A
F Manganese 8.9 9.1 80 0.950 1.020 18 H
F Manganese 11.8 12.2 75 1.044 — 16 C
A Nickel 9.9 10.1 70 1.032 — sh. green A
A Rare earthD 5.9 6.1 30 0.630 0.880 6 E
A Rare earth 11.8 12.2 55 0.977 — yel.-green C
B Rare earth 3.9 4.1 35 0.840 0.855 10 A
C Rare earth 5.9 6.1 35 0.876 — 8 A5
A Zinc 7.9 8.1 50 0.880 0.906 6 G
A Zinc 17.8 18.2 90 1.068 1.130 7 Z
B Zinc 7.9 8.1 70 0.915 0.960 9 A
B Zinc 9.9 10.1 75 0.980 1.044 8 L
D Zinc 7.9 8.1 70 1.008 — 11 D
E Zinc 7.9 8.1 42 0.946 — 2 A
F Zinc 7.9 8.1 60 0.855 0.963 7 C
F Zinc 15.8 16.2 80 1.020 1.100 3 B
A Zirconium 5.9 6.1 30 0.860 0.864 2 A
A Zirconium 11.8 12.2 56 0.960 0.992 4 A
A Zirconium 17.8 18.2 55 1.070 1.074 3 A
A Zirconium 23.8 24.2 77 1.240 — 2 J
C Zirconium 5.9 6.1 23 0.864 — 2 A5
C Zirconium 11.8 12.2 46 0.976 — 2 A
E Zirconium 5.9 6.1 31 0.864 — 4 A
E Zirconium 11.8 12.2 55 0.975 1.020 4 A
F Zirconium 5.9 6.1 28 0.855 0.870 2 A5
F Zirconium 11.8 12.2 55 — — — —
F Zirconium 17.8 18.2 80 1.090 1.130 4 Z
F Zirconium 23.8 24.2 93 1.240 1.260 6 J
A
Source: “Raw Material Index,” National Paint and Coatings Association Guide, Chemical Specialties Section, April 1978. Available from National Paint and Coatings
Assn., 1500 Rhode Island Ave. NW, Washington, DC 20005.
B
Per Gardner Test Method D 1544. If off the scale, as observed by the unaided eye.
C
Only one drier was listed in this category.
D
The metal content represents total rare earth metals calculated as cerium, but the drier contains cerium and lanthanum, as well as minor amounts of other rare earth
metals.
6. Packaging and Package Marking 6.2 Packaging shall conform to applicable carrier rules and
6.1 Package size shall be agreed upon between the pur- regulations or when specified shall conform to Fed. Spec.
chaser and the supplier. PPP-C-2020.
2
D 600
7. Keywords
7.1 liquid paint driers
3

Oiticica Oil (Permanently Liquid)1
1. Scope D 1959 Test Method for Iodine Value of Drying Oils and
1.1 This specification covers oiticica oil that has been Fatty Acids3
treated to render it permanently liquid. D 1963 Test Method for Specific Gravity of Drying Oils,
Varnishes, Resins, and Related Materials at 25/25 C3
2.1 ASTM Standards: 3. Properties
D 445 Test Method for Kinematic Viscosity of Transparent 3.1 Oiticica oil (permanently liquid) shall conform to the
and Opaque Liquids (and the Calculation of Dynamic requirements in Table 1 .
Viscosity)2
D 555 Guide for Testing Drying Oils3 TABLE 1 Physical Properties
D 1466 Test Method for Sampling Liquid Oils and Fatty
Property Requirement ASTM Method
Specific gravity, 25/25°C, min 0.972 D 1963, D1475
Materials3 Viscosity at 25°C, approximate 11 to 23 D 1545, D445
D 1475 Test Method for Density of Paint, Varnish, Lacquer, Stokes
and Related Products4 Acid value, max 8.0 D 1639
Iodine value (Wijs), min 135 D 1959
D 1544 Test Method for Color of Transparent Liquids Color (Gardner 1933 Standards), max 11 D 1544
(Gardner Color Scale)4 Gel time, minutes, max 17 D 1955
D 1545 Test Method for Viscosity of Transparent Liquids Refractive index at 25°C, min 1.5100 ...
Matter insoluble in chloroform, max, % 0.1 D 1958
by Bubble Time Method3
Materials3
D 1955 Test Method for Gel Time of Drying Oils3 4. Test Methods
D 1958 Test Method for Chloroform Insoluble Matter in 4.1 Sampling—Sampling shall be conducted in accordance
Oiticica Oil3 with Test Method D 1466.
1
determined in accordance with the applicable ASTM test
methods listed in Table 1. The significance of these test
Subcommittee D 01.32 on Drying Oils. methods enumerated under properties in this specification is
Current edition approved Oct. 30, 1987. Published December 1987. Originally discussed in Methods D 555.
published as D 601 – 41. Last previous edition D 601 – 55 (1981)e1.
2
3
4
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; oiticica oil
1

Barium Sulfate Pigments1
1. Scope TABLE Continued

1.1 This specification covers the barium sulfate pigments Blanc
commercially known as barytes and blanc fixe. Barytes Fixe
Moisture and other volatile matter, max, % 0.5 0.5

2. Referenced Documents Coarse particles (total residue retained on 0.5 0.5
2.1 ASTM Standards: No. 325 (45-µm sieve), max, %
Free silica (quartz, clays, or other foreign 2.0 2.0
D 185 Test Methods for Coarse Particles in Pigments, materials), max, %
Pastes, and Paints2
D 280 Test Methods for Hygroscopic Moisture (and Other 3.2 In such physical properties as are specified by the
Matter Volatile Under the Test Conditions) in Pigments2 purchaser, the pigment shall satisfactorily match a reference
D 715 Test Methods for Analysis of Barium Sulfate Pig- sample mutually agreed upon by the purchaser and the seller.
ment2 4. Sampling
3.1 The pigment shall consist of barium sulfate (BaSO 4) between units of production appear, samples shall be taken
without any admixture of other materials in the case of blanc from different packages in the ratio of two samples of each
fixe, and without any admixture of other materials not naturally 10 000 lb (5000 kg), except that for shipments of less than
occurring in the barite ore in the case of barytes, and which 10 000 lb two samples shall be taken. At the option of the
conform to the following requirements: purchaser, the samples may be tested separately or after
Blanc production unit to form a composite sample.
Barytes Fixe
5. Test Methods
Barium sulfate, min, % 94 97
Ferric oxide, max, % 0.05 0.02 5.1 Tests shall be conducted in accordance with the follow-
pH, min 3.5 3.5 ing ASTM test methods. Test procedures not covered by ASTM
Matter soluble in water, max, % 0.2 0.2
test methods shall be mutually agreed upon by the purchaser
and the seller.
5.2 Coarse Particles in Pigment—Test Methods D 185.
5.3 Moisture—Test Methods D 280.
5.4 Barium Sulfate, Ferric Oxide, and Free Silica—Test
Methods D 715.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.5 Hydrogen Ion Concentration and Matter Soluble in
and Related Coatings, Materials, and Applications, and is the direct responsibility of Water—Test Methods D 1208.
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 barium sulfate; barytes; blanc fixe; pigments
1
D 602
2

Aluminum Silicate Pigments (Hydrous)1
1. Scope TABLE 1 Pigment Composition Requirements
1.1 This specification covers the white pigments that consist Ideal Typical Range Max
substantially of natural hydrous aluminum silicate2 (of the 1:1 Aluminum oxide, Al2O3, % 39.50 38.8 37 to 42A ...
Silicon dioxide, SiO2, % 46.54 45.4 48 to 43B ...
layer type), and are restricted to those minerals which conform Iron oxide, Fe2O3, % ... 0.3 ... 0.5
to the chemical limits prescribed herein and which can be Titanium dioxide, TiO2, % ... 1.5 ... 2.0
suitably processed to what is commercially known as paint Calcium oxide, CaO,% ... 0.1 ... 0.2
Sodium oxide, Na2O, % ... 0.1 ... 0.3
pigment quality. Potassium oxide, K2O, % ... 0.1 ... 2.0
Other oxides, % ... trace ... 0.1
2. Referenced Documents Free moisture (105°C), % ... ... ... 1.0
Loss on ignition 13.96 13.8 ... 15.0
2.1 ASTM Standards: (1000°C), %
D 281 Test Method for Oil Absorption of Pigments by A
Permitting up to 5 % excess Al2O3, for example as allophane.
Spatula Rub-Out3 B
Permitting up to 5 % excess SiO2, for example as quartz.
D 422 Test Method for Particle-Size Analysis of Soils4
D 718 Test Methods for Analysis of Aluminum Silicate
Pigment5 3.3 Water-Soluble Matter—The water-soluble matter shall
D 1208 Test Methods for Common Properties of Certain be not more than 0.50 %.
Pigments5 3.4 Wet-Sieve Residue—The pigment shall contain no more
D 1483 Test Method for Oil Absorption of Pigments by than 0.5 % wet-sieve residue retained on a 45-µm (No. 325)
Gardner-Coleman Method3 sieve (“grit” or “coarse particles”) except as may be agreed
D 2448 Test Method for Water-Soluble Salts in Pigments by upon between the purchaser and the seller.
Measuring the Specific Resistance of the Leachate of the 3.5 Color—The color (brightness, reflectance) shall con-
Pigment5 form to the following requirements:
E 70 Test Method for pH of Aqueous Solution with the 3.5.1 The color shall be equal, within agreed upon toler-
Glass Electrode6 ances, to that of a reference standard agreed upon between the
purchaser and the seller, or
3. Composition of Properties 3.5.2 The color shall be not less than a guaranteed minimum
3.1 Preparation—The pigment shall be made by grinding, expressed as percent reflectance of standard illuminant C at
milling, washing, purifying, size-fractionating, or otherwise 457 nm compared to a freshly smoked standard magnesium
processing, natural hydrous aluminum silicates, and shall oxide surface by means of an accepted integrating sphere
conform to the composition requirements (weight percent) reflectance spectrophotometer7 or a monochromatic reflectance
given in Table 1. meter,7 or
3.2 pH—The pH of a water slurry of the pigment shall be 3.5.3 The color shall be specified by actual determination of
within a range as agreed upon between the purchaser and the dominant wavelength, hue, and spectral efficiency as can be
seller. calculated from the tristimulus integration of the reflectance
curve.
3.6 Oil Absorption—The oil absorption shall be equal,
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint within agreed upon tolerances, to that of a reference standard
and Related Coatings, Materials, and Applications, and is the direct responsibility of agreed upon between the purchaser and the seller.
Current edition approved Sept. 20, 1966. Originally issued 1941. Replaces 3.7 Aluminum silicate pigments may be furnished in several
D 603 – 42 (1955). types or grades whose various properties are dependent in part
2
Synonymous terms are china clay and kaolinite.
3
4
5 7
Annual Book of ASTM Standards, Vol 06.03. The General Electric Reflectance Spectrophotometer and the General Electric
6
Annual Book of ASTM Standards, Vol 15.05. Reflectance Meter, respectively, have been found satisfactory for this purpose.
1
D 603
on average size or particle size distribution about the average, not covered by ASTM test methods shall be agreed upon
or both. The particle size shall be equal within agreed upon between the purchaser and the seller, except as follows:
tolerances to that of a reference standard agreed upon between 5.1.1 Hydrogen Ion Concentration (pH)—Prepare a sample
the purchaser and the seller. having 20 % solids, but otherwise in accordance with Test
4. Number of Tests Methods D 1208. Determine the pH in accordance with Test
Method E 70 except to maintain sufficient agitation of the
slurry such that all particles are in suspension at time of
measurement.
between units of production appear, samples shall be taken 5.1.2 Water-Soluble Matter—Test Method D 2448.
from different packages in the ratio of two samples for each 5.1.3 Coarse Particles—Test Methods D 718.
10 000 lb (4540 kg), except that for shipments of less than 5.1.4 Oil Absorption—Test Method D 281 or D 1483.
10 000 lb two samples shall be taken. At the option of the 5.1.5 Particle Size Distribution—Method D 422.
blending in equal quantities the samples from the same 5.1.6 Chemical Analysis—Test Method D 718.
6. Keywords
5. Test Methods
6.1 aluminum silicate (hydrous); clay; pigments
priate ASTM test methods, where applicable. Test procedures
2

Diatomaceous Silica Pigment1
1. Scope Loss on ignition, max., % 1.0

Matter soluble in HCl (1+2), max, % 3.0
1.1 This specification covers two types of diatomaceous Moisture and other volatile matter, max, % 1.0
silica pigments for use in paints: Volume of settled pigment in petroleum spirits
1.1.1 Type A—Standard fineness for general paint use. after 1 h, min, mL:
Type A 35
1.1.2 Type B—Extra fine, for special uses. Type B 25
Coarse particles (total residue retained on a
NOTE 1—Silica pigments originating from crystalline rocks or sands are 45-µm (No. 325) sieve), %:
not covered by this specification. Type A 5.0 to 15.0
NOTE 2—For additional information, see Test Methods D 719. Type B 1.0 max
2. Referenced Documents 3.2 The color shall be within mutually agreed upon limits of
a reference sample acceptable to both the purchaser and the
2.1 ASTM Standards:
seller.
Pastes, and Paints2 4. Sampling
D 719 Test Methods for Analysis of Diatomaceous Silica
Pigment2
Pigments2
3. Composition and Properties from different packages in the ratio of two samples for each
3.1 The pigment shall be a diatomaceous silica especially
produced by chemical, heat, and grading processes, and se-
lected for use in paints and shall conform to the following
requirements:
5. Test Methods
5.1 Test shall be conducted in accordance with the follow-
ing ASTM test methods, where applicable. Test procedures not
covered by ASTM test methods shall be mutually agreed upon
between the purchaser and the seller.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.2 Coarse Particles—Test Methods D 185.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.3 Loss on Ignition and Moisture—Test Methods D 1208.
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 diatomaceous earth; diatomaceous silica; pigment
1

Magnesium Silicate Pigment (Talc)1
e1 NOTE—Keywords and unit of measurement statement were added editorially in July 1996.
1. Scope processing natural, hydrous magnesium silicate and shall

1.1 This specification covers pigments that consist substan- conform to the following requirements:
tially of natural hydrous magnesium silicate, and is restricted to Weight %
min max
those minerals that conform to the chemical limits prescribed Combined magnesium and calcium sili- 88 ...
herein and can be suitably processed to what is commercially cates (MgO plus SiO2 plus CaO)
known as paint pigment quality. Calcium oxide (CaO) ... 10
Aluminum and iron oxides (R2O3) ... 6
1.2 The values stated in inch-pound units are to be regarded Loss on ignition ... 7
as the standard. The values given in parentheses are for Moisture and other volatile material ... 1
information only. 3.2 Color—The color shall be equal, within agreed upon
1.3 The following hazard caveat applies to the test method tolerances, to that of a reference sample agreed upon between
portion of this specification only. This standard does not the purchaser and the seller.
purport to address all of the safety concerns, if any, associated 3.3 Coarse Particles—The pigment shall contain no more
with its use. It is the responsibility of the user of this standard than 2 % of coarse particles, retained on a 45-µm (No. 325)
to establish appropriate safety and health practices and sieve except as may be agreed upon between the purchaser and
determine the applicability of regulatory limitations prior to the seller.
use. 3.4 Water-Soluble Matter—The pigment shall contain no
2. Referenced Documents more than 1 % water-soluble matter except as may be agreed
upon between the purchaser and the seller.
2.1 ASTM Standards:
3.5 Oil Absorption—The oil absorption shall be equal,
within agreed upon tolerances, to that of a reference sample
agreed upon between the purchaser and the seller.
D 281 Test Method for Oil Absorption of Pigments by
3.6 Consistency—When consistency is included in the pur-
Spatula Rub-Out3
chaser’s specification, it shall be equal, within agreed upon
D 562 Test Method for Consistency of Paints Using the
tolerances, to that of a reference sample agreed upon between
Stormer Viscometer3
the purchaser and the seller.
D 717 Test Methods for Analysis of Magnesium Silicate
3.7 Fineness—The paint fineness shall be equal, within
Pigment2
agreed upon tolerances, to that of a reference sample agreed
upon between the purchaser and the seller.
Pigments2
D 1210 Test Method for Fineness of Dispersion of Pigment- 4. Sampling
Vehicle Systems3 4.1 Two samples shall be taken at random from different
3. Composition and Properties packages from each lot, batch, day’s pack, or other unit of
3.1 The pigment shall be made by grinding or otherwise
1
from different packages in the ratio of two samples for each
Subcommittee D01.31 on Pigment Specifications. 10 000 lb, two samples shall be taken. At the option of the
Current edition approved June 25, 1982. Published August 1982. Originally purchaser, the samples may be tested separately or after
published as D 605 – 41 T. Last previous edition D 605 – 69 (1976). blending in equal quantities, the samples from the same
2
3
production unit form a composite sample.
1
D 605
5. Test Methods spatula. Weigh in 160 g of magnesium silicate and stir with a
5.1 Tests shall be conducted in accordance with the follow- spatula to wet all lumps. Stir with a motor-driven propeller-
ing ASTM test methods, where applicable. Test procedures not type stirrer for 5 min at approximately 800 r/min. Weigh in an
covered by ASTM test methods shall be mutually agreed upon additional 180 g of linseed oil and stir an additional 2 min with
between the purchaser and the seller. the electric stirrer. Determine the consistency in accordance
5.1.1 Color, Composition, and Coarse Particles—Test with Test Method D 562.
Methods D 717. 5.1.5 Fineness—Test Method D 1210. The test mixture may
5.1.2 Water-Soluble Matter and Loss on Ignition—Test be the same as that used for the consistency test.
Methods D 1208. 5.1.6 Moisture—Test Methods D 280.
5.1.3 Oil Absorption—Test Method D 281.
5.1.4 Consistency—Use the pigment to prepare a mixture
6. Keywords
according to the following directions: Weigh 78 g of petroleum
spirits and 80 g of linseed oil (viscosity, 21 to 24 P; acid 6.1 hydrous magnesium silicate; magnesium silicate; pig-
number, 4 to 8) into a pint can and thoroughly mix with a ment; talc
2

Wet Ground Mica Pigments1
1. Scope Types
A
1.1 This specification covers two types of finely divided Regular 325 M B
muscovite mica, commercially known as wet ground mica, Grade Fine Grade
suitable for use in the manufacture of protective coatings.
Total residue retained on a 0.1 0.01
No. 140 (106-µm) sieve
2. Referenced Documents Total residue retained on a 12.0 3.0
2.1 ASTM Standards: No. 325 (45-µm) sieve
Ignition loss, max, weight % 5.0 5.0
D 185 Test Methods for Coarse Particles in Pigments, (dry basis)
Pastes, and Paints2
D 280 Test Methods for Hygroscopic Moisture (and Other 3.2 The color shall be within mutually agreed upon limits of
Matter Volatile Under Test Conditions) in Pigment2 a standard acceptable to both the purchaser and the seller.
D 716 Test Methods for Evaluating Mica Pigment2 4. Sampling
3.1 The pigments shall be made by wet grinding muscovite between units of production appear, samples shall be taken
mica and shall conform to the requirements for properties from different packages in the ratio of two samples for each 5
prescribed as follows: tons (inch-pound or SI), except that for shipments of less than
Types
A purchaser the samples may be tested separately or after
Regular 325 M B blending in equal quantities the samples from the same
Grade Fine Grade
Apparent density, max, lb/ft3 12.0 (0.2) 12.0 (0.2)
(g/cm3) 5. Test Methods
Moisture and other volatile 0.5 0.5
matter, max, weight %
Grit, max, weight % 0.5 0.5 priate ASTM methods. Test procedures not covered by ASTM
Coarse particles, max, weight %: methods shall be mutually agreed upon between the purchaser
and the seller.
5.1.1 Apparent Density—Test Method D 716.
5.1.2 Moisture—Test Method D 280.
5.1.3 Grit—Test Method D 716.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.4 Coarse Particles—Test Method D 185.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.1.5 Ignition Loss—Test Method D 1208.
Current edition approved June 25, 1982. Published August 1982. Originally 6. Keywords
2
Annual Book of ASTM Standards, Vol 06.03. 6.1 mica; muscovite; wet ground
1
D 607
2

Dibutyl Phthalate1
1.1 This specification covers dibutyl phthalate (99 % grade). 3.1 Dibutyl phthalate (99 % grade) shall conform to the
1.2 For specific hazard information and guidance, see the following requirements:
supplier’s Material Safety Data Sheet for materials listed in this Apparent specific gravity:
specification. 20/20°C 1.046 to 1.050
25/25°C 1.043 to 1.047
2. Referenced Documents Odor nonresidual
2.1 ASTM Standards: Water, max, weight % 0.2A
Acidity (free acid as phthalic 0.01B
D 268 Guide for Sampling and Testing Volatile Solvents acid), max, weight %
and Chemical Intermediates for Use in Paint and Related Ester value, max, weight % not less than 99.0
Coatings and Materials2 ______________
A
D 1209 Test Method for Color of Clear Liquids (Platinum- This quantitative limit ensures that the material is miscible without turbidity with
19 volumes of 99 % heptane at 20°C.
Cobalt Scale)2 B
D 1296 Test Method for Odor of Volatile Solvents and
Diluents2 4. Sampling
D 1364 Test Method for Water in Volatile Solvents (Fischer 4.1 The material shall be sampled in accordance with
Reagent Titration Method)2 Practice E 300.
D 1476 Test Method for Heptane Miscibility of Lacquer
Chemical Intermediates Used in Paint, Varnish, Lacquer, determined in accordance with the following ASTM methods:
D 1617 Test Method for Ester Value of Lacquer Solvents specific gravity at 20 or 25°C by a convenient method that is
and Thinners2 accurate to the third decimal place. See Guide D 268 or Test
D 4052 Test Method for Density and Relative Density of Method D 4052.
Liquids by Digital Density Meter3 5.1.2 Color—Test Method D 1209.
E 300 Practice for Sampling Industrial Chemicals4 5.1.3 Odor—Test Method D 1296.
2.2 U.S. Federal Specification: 5.1.4 Water—Test Methods D 1364 and D 1476.
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging 5.1.5 Acidity—Test Method D 1613.
of5 5.1.6 Ester Value—Test Method D 1617.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 6.1 Package size shall be agreed upon between the pur-
and Related Coatings, Materials, and Applications and is the direct responsibility of chaser and the supplier.
Current edition approved May 25, 1990. Published July 1990. Originally 6.2 Packaging shall conform to applicable carrier rules and
published as D 608 – 41 T. Previous edition D 608 – 90. regulations or when specified shall conform to Fed. Spec.
2
3
4
5
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. 7.1 dibutyl phthalate
1
D 608
2

Pure Toluidine Red Toner1
1. Scope Ash, max, % 1.0

1.1 This specification covers the red pigment commercially Coarse particles (total residue retained on a No. 1.0
known as pure toluidine red toner. The pigment may be 325 (45-µm) sieve), max, %
purchased in the dry form or as a paste in oil. Paranitraniline red none
Solubility in chloroform complete
Resistance to acids and alkalis to pass test
2. Referenced Documents Identity test to pass test
2.1 ASTM Standards:
strength formed by a mixture with a white pigment shall be
Pastes, and Paints2
D 387 Test Method for Color and Strength of Color Pig- 4. Sampling
ments with a Mechanical Muller3 4.1 Two samples shall be taken at random from different
D 970 Test Methods for Para Red and Toluidine Red Pig- packages from each lot, batch, day’s pack, or other unit of
ments2 production in a shipment. When no markings distinguishing
3. Composition and Properties between units of production appear, samples shall be taken
from different packages in the ratio of two samples for each 5
3.1 Dry Pigment—The pigment shall consist of toluidine
tons (inch-pound or SI), except that for shipments of less than
red toner (1-(2-nitro-p-tolylazo)-2-naphthol) with or without
admixture with a small quantity of (1-(2-nitro-
purchaser, the samples may be tested separately, or after
p-methoxyphenyl-azo)-2-naphthol). It shall be free of any
substrate and shall conform to the following requirements:
5. Test Methods
priate test methods. Test procedures not covered by ASTM
methods shall be mutually agreed upon between the purchaser
and the seller.
5.3 Moisture—Test Methods D 280.
5.4 Color and Tint—Test Method D 387.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.5 Solubility—Test Methods D 970.
and Related Coatings, Materials, and Applications , and is the direct responsibility 5.6 Identity—Test Methods D 970.
of Subcommittee D01.31 on Pigment Specifications. 5.7 Ash—Test Methods D 970.
published as D 656 – 42 T. Last previous edition D 656 – 81. 6. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 6.1 tint; tinting strength; toluidine; white pigment
1
D 656
2

Analysis of Barium Sulfate Pigment1
1. Scope high purity to permit its use without lessening the accuracy of
1.1 These test methods cover the analysis of barium sulfate the determination.
pigment. 4.2 Unless otherwise indicated, references to water shall be
1.2 This standard does not purport to address the safety understood to mean reagent water conforming to Type II of
concerns associated with its use. It is the responsibility of the Specification D 1193.
user of this standard to establish appropriate safety and health BARIUM SULFATE
practices and determine the applicability of regulatory limita-
tions prior to use. 5. Reagents
2. Referenced Documents 5.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
monium hydroxide (NH4OH).
2.1 ASTM Standards: 5.2 Ammonium Sulfate ((NH4)2SO4).
D 185 Test Methods for Coarse Particles in Pigments, 5.3 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
Pastes, and Paints2 chloric acid (HCl).
5.4 Hydrochloric Acid (1+1)—Mix equal volumes of con-
centrated HCl (sp gr 1.19) and water.
5.5 Methyl Red Indicator Solution—Dissolve 0.2 g of me-
thyl red in 100 mL of methanol, ethanol, or isopropanol.
Pigments2
5.6 Sodium Carbonate Solution (30 g/L)—Dissolve 30 g of
E 832 Specification for Laboratory Filter Papers4
Na2CO3 in water and dilute to 1 L.
6. Procedure
3.1 These test methods are used to determine the purity of
6.1 Weigh to 0.1 mg approximately 0.5 g of the sample into
barium sulfate and to determine the concentration of known
a platinum crucible, add 3 g of Na2CO3, mix thoroughly, and
impurities. This information is useful to producers and users as
fuse until the melt is clear. Allow the melt to cool and then
an aid in the manufacture of coatings.
leach in a platinum dish with hot water until it is entirely
4. Purity of Reagents disintegrated. Filter on a close-texture paper and wash thor-
oughly with hot Na2CO 3 solution (30 g/L).
6.2 Transfer the filter paper containing the insoluble carbon-
Unless otherwise indicated, it is intended that all reagents shall
ates to a 250-mL beaker and acidify with concentrated HCl (sp
conform to the specifications of the Committee on Analytical
gr 1.19). Wash the fusion crucible with HCl (sp gr 1.19) so that
Reagents of the American Chemical Society, where such
no barium is lost. Boil the solution, filter into a 600-mL beaker,
specifications are available.5 Other grades may be used, pro-
and wash well with water. Add methyl red indicator solution,
and add NH4OH (sp gr 0.90) until the solution is slightly
alkaline. Add 6 mL of HCl (1+1), and dilute to 300 mL.
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint 6.3 Heat the solution to boiling, and add 5 g of (NH 4)2SO4
and Related Coatings, Materials, and Applications and are the direct responsibility dissolved in 40 mL of water. If low-grade material is being
of Committee D01.31 on Pigment Specifications.
analyzed, the (NH4)2SO4 solution should be added drop by
published as D 715 – 43. Last previous edition D 715 – 75 (1981) e1. drop from a buret to minimize inclusion. If the barytes is a
2
Annual Book of ASTM Standards, Vol 06.03. rather pure product (95 to 99 % BaSO4), this is not necessary,
3
Annual Book of ASTM Standards, Vol 11.01. since the only nonvolatile constituents of the solution will be
4
5
barium salts. Allow the precipitate of BaSO4 to digest for 4 h
Chemical Society, Washington, DC. For suggestions on the testing of reagents not or overnight, and filter through a close-texture paper. Wash the
listed by the American Chemical Society, see Analar Standards for Laboratory precipitate with as little cold water as possible (consistent with
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia the purity of the precipitate), ignite in an oxidizing atmosphere,
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. and weigh as BaSO4.
1
D 715
7. Calculation HYDROGEN ION CONCENTRATION
7.1 Calculate the percent of BaSO4 as follows:
12. Procedure
BaSO4, % 5 ~P/S 1! 3 100 (1)
12.1 Determine the pH in accordance with Test Methods
where: D 1208.
P 5 BaSO4, g, and
S1 5 sample used, g. MATTER SOLUBLE IN WATER
FERRIC OXIDE 13. Procedure

13.1 Determine the amount of water soluble material
8. Apparatus present in accordance with Test Methods D 1208.
8.1 Colorimetric Apparatus—Nessler type or other similar
100-mL colorimetric tubes. MOISTURE AND OTHER VOLATILE MATTER
9. Reagents 14. Procedure

9.1 Ammonium Thiocyanate Solution (76.1 g/L)—Dissolve 14.1 Determine the moisture and other volatile matter in
76 g of ammonium thiocyanate (NH 4CNS) in water and dilute accordance with Test Method D 280.
to 1 L.
COARSE PARTICLES
9.2 Iron, Standard Solution (100 mL 5 0.00002 g Fe)—
(Total Residue Retained on No. 325 (45-µm) Sieve)
Dilute and divide a ferric solution of known iron content so as
to obtain 0.4 mg of iron. Dilute the solution to 2 L with water 15. Procedure
containing 200 mL of iron-free H2SO 4.
15.1 Determine the coarse particles in accordance with Test
9.3 Potassium Permanganate Solution (0.1 g/L)—Dissolve
Methods D 185.
0.1 g of potassium permanganate (KMnO 4) in water and dilute
to 1 L. FREE SILICA
9.4 Standard Color Solution—Mix thoroughly 10 parts by
volume of NH4CNS and 90 parts by volume of standard iron 16. Reagent
solution (100 mL 5 0.02 mg Fe). One hundred millilitres of
16.1 Heavy Liquid (sp gr 2.9)—Dissolve 4 parts by weight
the solution will thus contain 0.000018 mg of Fe.
of potassium iodide (KI) in 6 parts of warm water, and add,
9.5 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
while stirring constantly, 5 parts of mercuric iodide (HgI 2).
(H2SO4).
Evaporate over a hot plate or gas flame, protected by screen
9.6 Sulfuric Acid (1+1)—Carefully mix 1 volume of con-
cloth, until a light crystalline scum forms. Cool, and filter
centrated H2SO4 (sp gr 1.84) with 1 volume of water.
through heavy paper. The solution will be a clear, deep, amber
10. Procedure color of about 3.2 specific gravity. All filter washings showing
a yellow color should be saved and evaporated. Determine the
10.1 Dissolve the soluble portion of a 1-g specimen in 3.2 specific gravity accurately by means of a specific gravity
H2SO4 (1+1), filter, and wash, keeping the volume of the bottle, and correct the solution to a specific gravity of 2.9 at
solution under 100 mL. Oxidize any iron present in the filtrate room temperature by adding water. Prepare approximately 200
by adding potassium permanganate (KMnO4) until a faint pink mL of the solution.
color is obtained. Dilute the solution to 100 mL and pour into
a buret graduated in 0.1-mL divisions. 17. Procedure
10.2 Pour 100 mL of the standard color solution into a 17.1 Carefully weigh 10 g of the finely ground dry barium
100-mL colorimetric tube. Into a second colorimetric tube pour sulfate pigment and transfer to a carefully dried 125-mL clear
10 mL of concentrated H2SO4 (sp gr 1.84) and 10 mL of NH glass separatory funnel of the long narrow type. Add 100 mL
4CNS, dilute to 60 or 70 mL and then add the test solution from
of the heavy liquid (sp gr 2.9), stopper, and shake well to
the buret until the depth of color thus produced on dilution to liberate any air bubbles that might adhere to the particles, and
100 mL exactly matches that of the standard. Record the also to break up all agglomerates. Set the separatory funnel
number of millilitres required. aside and allow to stand in a perpendicular position for 2 h, or
for a sufficient time for the particles to rise or sink.
11. Calculation
17.2 Draw off the heavy particles through the stopcock into
11.1 Calculate the percent of Fe2O3 as follows: a beaker along with 75 mL of the liquid. Add 50 mL of fresh
Fe 2O3, % 5 @~I 3 1.4298!/S2# 3 100 (2) heavy liquid (sp gr 2.9) to the float particles and liquid
remaining in the separatory funnel and repeat the procedure as
where: described in 17.1.
I 5 iron in standard, g, 17.3 Draw off the heavy particles along with 75 mL of the
1.4298 5 Fe2O3 159.694
liquid and add to those drawn off in accordance with 17.1,
Fe2 5 111.694, and leaving the float particles in the funnel. Wash the particles
S2 5 sample used, g.
remaining in the funnel with fresh heavy liquid (sp gr 2.9),
2
D 715
filter through a No. 2/0 paper (see Specification E 832), and Free SiO 2, % 5 ~A/S3! 3 100 (3)
wash free of solution with warm water.
17.4 Transfer the filter paper and silica to an ignition cup, where:
A 5 SiO2, g, and
dry, and ignite carefully in an electric furnace or over a flame
S3 5 sample used, g.
to keep mechanical loss at a minimum. Weigh the floated
material, and transfer to a tared platinum dish or crucible. Add 19. Precision and Bias
20 mL of hydrofluoric acid (HF) and 3 drops of H2SO4 (1+1), 19.1 The precision and bias of these test methods has not
evaporate to dryness, and ignite carefully to expel all fumes. been determined.
Cool and weigh. The loss in weight represents the free silica in
the floated material. 20. Keywords
20.1 analysis of pigment; barium sulfate; barium sulfate
18. Calculation content; barium sulfate pigment; ferric oxide in barium sulfate;
18.1 Calculate the percent of free SiO2 as follows: free silica in barium sulfate
3

Evaluating Mica Pigment1
1. Scope mm) in diameter. It may be found necessary to replace the top

1.1 These test methods cover the evaluation of mica pig- glass baffle with one that is longer to ensure that all of the sifted
ment. mica is caught.
1.2 The values stated in SI units are to be regarded as the 5. Procedure
standard. The values given in parentheses are for information
only. 5.1 Transfer convenient quantities of the mica pigment to
1.3 This standard does not purport to address all of the the funnel of the modified volumeter and brush the pigment
safety concerns associated with its use. It is the responsibility through the screen with a camel-hair brush until the receiver is
of the user of this standard to establish appropriate safety and slightly more than full. Scrape off the excess and weigh the
health practices and determine the applicability of regulatory pigment. Care must be taken not to jar the apparatus during the
limitations prior to use. procedure.
2. Referenced Documents 6. Calculation

2.1 ASTM Standards: 6.1 Calculate the apparent density of the mica pigment and
D 185 Test Methods for Coarse Particles in Pigments, convert to pounds per cubic foot.
Pastes, and Paints2 7. Report
Matter Volatile Under the Test Conditions) in Pigments2 7.1 Report the mean of three determinations as the apparent
E 11 Specification for Wire-Cloth Sieves for Testing Pur- density of the mica pigment.
poses3 8. Reproducibility of Results
3. Significance and Use 8.1 The mean of the three determinations should check
3.1 These test methods are used to determine apparent within 5 %.
density of mica pigments and the grit level. This information is MOISTURE AND OTHER VOLATILE MATTER
significant to the user of mica pigments for inclusion in
coatings. 9. Procedure
APPARENT DENSITY 9.1 Determine the moisture and other volatile matter in
accordance with Test Methods D 280.
4. Apparatus
GRIT
4.1 Volumeter4—A Scott volumeter or similar apparatus
modified as follows: The screen used shall conform to the 10. Apparatus
requirements of a No. 40 (425-µm) sieve as prescribed in 10.1 Beaker, 600-mL, low-form.
Specification E 11. The funnel below the screen shall be 10.2 Metal Tubing—An L-shape metal tube (Fig. 1) 6.4 mm
replaced by a conical funnel having a bottom opening 1 in. (25 (1⁄4in.) in outside diameter with a foot 25 mm (1 in.) in length.
The foot of the tube shall be drilled to 4.4 mm (0173 in.) (No.
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint 17 drill) in inside diameter for a depth of 12.7 mm (1⁄2 in.). The
and Related Coatings, Materials, and Applications and are the direct responsibility tube shall be placed in the beaker with the long arm in the
vertical position, and the foot of the L parallel to the bottom of
published as D 716 – 43. Last previous edition D 716 – 75 (1981)e1. the beaker and perpendicular to the radius of the bottom at a
2
Annual Book of ASTM Standards, Vol 06.03. point such that there is about 1.5-mm (1⁄16-in.) clearance
3
Annual Book of ASTM Standards, Vol 14.02. between the tubing and both the bottom and side of the beaker.
4
The volumeter is no longer generally available. As of June 1986 only one
supplier, Sargent Welch Co., Skokie, IL, was known. The device is Scott-Schaeffer The center of the foot shall be placed 90° from the lip of the
and White Volumeter listed on p. 932 of Catalog No. 133 (1985–86). beaker.
1
D 716
G, % 5 @~A 2 B!/S# 3 100 (1)
where:
A 5 ash, g,
B 5 filter paper ash, g, and
S 5 sample used, g.
COARSE PARTICLES
13. Procedure
13.1 Determine the course particles in accordance with Test
Methods D 185.
COLOR
14. Standard Pigments

14.1 Standard Mica Pigment.
14.2 Standard Zinc Oxide.
15. Procedure
FIG. 1 Grit Test Apparatus 15.1 Compare pastes made by rubbing a standard mica
pigment and standard zinc oxide, mutually agreed upon by the
11. Procedure purchaser and the seller, in linseed oil with a similar paste
11.1 Transfer 10 g of the sample to the 600-mL beaker, add using the sample to be tested. Rub 9 g of zinc oxide, and 3 g
100 mL of water, and swirl the beaker until the mica is of mica pigment on a glass plate with a glass muller or rubber
dispersed. Insert the metal tubing into the beaker as described spatula to avoid staining, with 4 mL of bleached linseed oil.
in 10.2 and connect the upper end to a water faucet. Regulate Spread the pastes adjacently on a clear glass plate and
the flow of water by a constant head to a rate of 800 mL/min determine the color by viewing the spreadouts on the glass.
over the lip of the beaker. When the elutriation has progressed
so that the body of the water in the beaker is clear, stop the 16. Precision and Bias
flow, and lower the water level to prevent spilling. 16.1 Insufficient data are available to develop acceptable
11.2 Swirl the beaker again to bring the remaining mica precision and bias statements. The information presented in
pigment into suspension and repeat the elutriation procedure as Section 8 (Reproducibility of Results) was obtained in 1943,
described in 11.1 three times. After final clearing, decant part and no documentation is currently available. The information
of the water, and filter the residue. Transfer the paper and will remain in Section 8.
residue to a weighed crucible, and ash slowly, cool, and weigh.
17. Keywords
12. Calculation 17.1 grit; detection in mica pigment; mica pigment; analy-
12.1 Calculate the percent grit, G, as follows: sis of; pigment
2

Analysis of Magnesium Silicate Pigment1
1. Scope conform to the specifications of the Committee on Analytical

1.1 These test methods cover the analysis of magnesium Reagents of the American Chemical Society, where such
silicate pigment. specifications are available.5 Other grades may be used, pro-
1.2 This standard does not purport to address the safety vided it is first ascertained that the reagent is of sufficiently
concerns associated with its use. It is the responsibility of the high purity to permit its use without lessening the accuracy of
user of this standard to establish appropriate safety and health the determination.
practices and determine the applicability of regulatory limita- 5.2 Unless otherwise indicated, references to water shall be
tions prior to use. understood to mean Type II of Specification D 1193.
2. Referenced Documents SILICON DIOXIDE

2.1 ASTM Standards: 6. Reagents
D 234 Specification for Raw Linseed Oil2 6.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl).
6.2 Hydrochloric Acid (1+20)—Mix 1 volume of concen-
D 718 Test Methods for Analysis of Aluminum Silicate trated hydrochloric acid (HCl, sp gr 1.19) with 20 volumes of
Pigment2 water.
6.3 Hydrofluoric Acid (48 %)—Concentrated hydrofluoric
D 1208 Test Methods for Common Properties of Certain acid (HF).
Pigments2 6.4 Sodium Carbonate (Na2CO3).
D 2448 Test Method for Water-Soluble Salts in Pigments by 6.5 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
Measuring the Specific Resistance of the Leachate of the (H2SO4).
Pigment2
E 97 Test Method for Directional Reflectance Factor, 45- 7. Procedure
deg 0-deg, of Opaque Specimens by Broad-Band Filter 7.1 Transfer 1 g of the sample weighed to 0.1 mg to a
Reflectometry4 platinum crucible and fuse with 5 g of Na2CO3 until the entire
3. Significance and Use contents of the crucible are in a molten state. Continue heating
for 20 min. Keep a close-fitting platinum cover on the crucible
3.1 These test methods may be used to confirm the stated
during the fusion. When the fusion is complete, allow the
SiO2, CaO, and MgO content of magnesium silicate for quality crucible and contents to cool, and transfer to a 600-mL
control. porcelain casserole containing 200 mL of water (Note 1). Boil
4. Apparatus until the melt is disintegrated.
4.1 Platinum Crucible. NOTE 1—If, during the cooling period, the crucible is partially im-
4.2 Electric Furnace, capable of 1200°C. mersed several times in cold water to chill the outer portions of the melt,
the subsequent removal of the melt is facilitated. Do not allow the water
5. Purity of Reagents to enter the crucible while the contents are hot to avoid spattering.
5.1 Reagent grade chemicals shall be used in all tests. 7.2 Remove crucible and lid, being careful to scrub and
Unless otherwise indicated, it is intended that all reagents shall rinse out any adhering particles of the melt. Carefully acidify
the contents of the casserole with concentrated HCl (sp gr
1
5
of Subcommittee D01.31 on Pigment Specifications. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved April 25, 1986. Published June 1986. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 717 – 43. Last previous edition D 717 – 73 (1979)e2. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
Discontinued; see 1992 Annual Book of ASTM Standards, Vol 14.02. MD.
1
D 717
1.19); introduce the HCl in small portions, keeping a watch was effected. Dissolve the precipitate with 40 mL of hot HCl
glass over the crucible to avoid loss by spattering. Add 30 mL (1+3), dilute the solution to about 100 mL, and reprecipitate the
of HCl in excess and evaporate to dryness on a steam bath; take hydroxides as described in 10.2. Filter and wash the precipitate
care to break up any crusts that form. When the material four times with hot NH4Cl. Combine the filtrate and washings
appears completely dry, and no odor of HCl can be detected, with the filtrate set aside and reserve for the determination of
remove the casserole from the steam bath, and allow to cool. CaO (Section 10).
7.3 Wash down the sides of the casserole with 20 mL of HCl 10.4 Place the precipitate in a weighed platinum crucible,
(sp gr 1.19) and then with water. Repeat the evaporation as heat slowly until the papers are charred, and finally ignite to
described in 7.2, then bake for 1 h in an oven at 105°C. Cool constant weight at 1050 to 1100°C with care to prevent
the residue, drench with 25 mL of HCl (sp gr 1.19), add 175 reduction. Cool and weigh as R 2O3(aluminum and iron
mL of water, and warm, while stirring, until all soluble salts are oxides).
dissolved. Filter off the silica on a close-texture paper, wash
five times with HCl (1+20), wash five times with hot water, and 11. Calculation
reserve the filtrate for determination of other oxides (Section 11.1 Calculate the percent of R2O3 as follows:
9). R2O 3, % 5 ~P2/S! 3 100 (2)
7.4 Transfer the paper and washed silica to a clean platinum
crucible, ignite, first gently until the filter paper is consumed, where:
and then at 1200°C for 20 min, cool, and weigh. Moisten the P 2 5 R2O3, g, and
residue with water, add 5 drops of H2SO4 (sp gr 1.84), and 15 S 5 sample used, g.
mL of HF. Evaporate to dryness on a steam bath, heat gently
until H2SO 4 has been expelled, and ignite at 1200°C for 5 min. CALCIUM OXIDE
Cool and weigh. The loss in weight represents the SiO2.
12. Reagents
8. Calculation 12.1 Ammonium Hydroxide (1+1)—Mix 1 volume of con-
8.1 Calculate the percent of silica as follows: centrated NH4OH (sp gr 0.90) with 1 volume of water.
12.2 Ammonium Oxalate Solution—((NH 4)2C2O4·H2O),
SiO2, % 5 ~P/S! 3 100 (1)
saturated.
where: 12.3 Ammonium Oxalate Solution (1 g/L)—Dilute 1.0 g of
P 5 SiO2, g, and ammonium oxalate ((NH4) 2C2O4·H2O) in 1 L of water.
S 5 sample used, g. 12.4 Hydrochloric Acid (1+3)—See 9.3.
AMMONIUM HYDROXIDE GROUP trated hydrochloric acid (HCl, sp gr 1.19) with 1 volume of
(Alumina and Iron Oxide) water.
12.6 Methyl Red Indicator Solution— See 9.4.
9. Reagents
9.1 Ammonium Chloride Solution (2 g/100 mL)—Dissolve 13. Procedure
2 g of ammonium chloride (NH 4Cl) in 100 mL of water. 13.1 Acidify the combined filtrates obtained in the precipi-
9.2 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- tations of the ammonium hydroxide group (Section 10) with
monium hydroxide (NH4OH). HCl and evaporate them to a volume of about 300 mL. Add 5
9.3 Hydrochloric Acid (1+3)—Mix 1 volume of concen- mL of HCl (1+1), a few drops of methyl red indicator solution,
trated HCl (sp gr 1.19) with 3 volumes of water. and 30 mL of warm ammonium oxalate solution (saturated).
9.4 Methyl Red Indicator Solution— Dissolve 0.2 g of Heat the solution to 70 to 80°C and add NH 4OH (1+1)
methyl red in 100 mL of methanol, ethanol, or isopropanol. dropwise while stirring, until the color changes from red to
9.5 Potassium Pyrosulfate—(K2S2O7). yellow. Allow the solution to stand without further heating for
1 h (no longer) with occasional stirring during the first 30 min.
10. Procedure Filter and wash moderately with cold dilute ammonium oxalate
10.1 If an appreciable residue remains after the treatment solution. Reserve the filtrate and washings.
with HF in accordance with 7.4, fuse the residue with a small 13.2 Transfer the precipitate and filter paper to the beaker in
amount of K2S2O7 until it is dissolved. Leach the pyrosulfate which the precipitate was effected. Dissolve the oxalate in 40
melt out of the crucible with water and combine the solution mL of hot HCl (1+3) and macerate the filter paper. Dilute to
with the filtrate reserved in accordance with 7.3. 200 mL with water, add a few drops of methyl red indicator
10.2 Using the methyl red indicator solution, neutralize the solution and 5 mL of ammonium oxalate solution (saturated).
combined solutions from the silica determination with NH4OH Heat the solution nearly to boiling, and precipitate calcium
and add an excess of 2 drops. Bring to a boil adding NH4OH oxalate again by neutralizing the acid solution with NH4OH as
1 drop at a time if necessary to maintain a slight alkalinity. described in 13.1. Allow the solution to stand 1 to 2 h and wash
Allow the precipitate to settle (not more than 5 min) and filter. as before. Combine the filtrate with that already obtained and
Wash four times with hot NH 4Cl solution. reserve for the determination of MgO (Section 16).
10.3 Set aside the filtrate and transfer the precipitate and 13.3 Dry the precipitate in a weighed covered platinum
filter paper to the same beaker in which the first precipitation crucible. Char the paper without inflaming, burn the carbon at
2
D 717
as low a temperature as possible, and, finally, heat with the where:
crucible tightly covered in an electric furnace or over a blast P 4 5 Mg2P2O7, g, and
lamp at a temperature of 1100 to 1200°C. Cool in a desiccator S 5 sample used, g.
and weigh as CaO. Repeat the ignition to a constant weight. molecular weight 0.2 MgO 2 3 40.32
molecular weight Mg 2P2O7 5 222.60 5 0.3623 (5)
14. Calculation
14.1 Calculate the percent of CaO as follows: 17.2 Consider the sum of MgO, CaO, and SiO2 as combined
magnesium and calcium silicate.
CaO, % 5 ~P 3/S! 3 100 (3)
LOSS ON IGNITION
where:
P 3 5 CaO, g, and 18. Procedure
S 5 sample used, g.
18.1 Determine the loss on ignition in accordance with Test
MAGNESIUM OXIDE Methods D 1208.
15. Reagents MOISTURE AND OTHER VOLATILE MATTER

15.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- 19. Procedure
15.2 Ammonium Hydroxide (5+95)—Mix 5 volumes of 19.1 Determine the moisture and other volatile matter by
concentrated NH4OH (sp gr 0.90) with 95 volumes of water. Test Methods D 280.
15.3 Diammonium Phosphate Solution (250 g/L)—Dissolve
COARSE PARTICLES
250 g of diammonium phosphate (NH 4)2HPO4 in enough
(Total Residue Retained on a No. 325 (45-µm) Sieve)
water to yield 1 L of solution.
15.4 Hydrochloric Acid (1+3)—See 9.3. 20. Procedure
16. Procedure 20.1 Determine the coarse particles in accordance with Test
Methods D 718, except that the specimen weight should be
16.1 Acidify the filtrates reserved in the determination of
adjusted to provide appropriate sensitivity for the residual
CaO (Section 13) with HCl and concentrate to about 400 mL.
weight determination. Any difficulty encountered in wetting-
Add to this solution about 50 mL of (NH4)2HPO 4(250 g/L) and
out the specimen can be overcome by prewetting with a 50+50
if the solution becomes alkaline, add HCl (1+3) to keep the
mixture of acetone or alcohol and water.
solution acidic. Cool the solution by placing the beaker in a
cold water trough or in a tray of ice water. After cooling add MATTER SOLUBLE IN WATER
NH4OH drop by drop, while stirring constantly, until the
crystalline magnesium ammonium phosphate begins to form, 21. Procedure
and then in moderate excess (5 to 10 % of the volume of the 21.1 Determine the matter soluble in water by Test Method
solution), the stirring being continued for several minutes. Set D 2448 or alternatively by Test Methods D 1208.
the solution aside for at least 8 h in a cool atmosphere.
16.2 Filter the solution on a close-texture paper and wash COLOR
with NH4OH (5+95). Unfold the filter paper and, using hot
water, wash the precipitate into the beaker in which the 22. Standard Pigment
precipitation was effected. Rinse the filter paper with hot HCl 22.1 Standard Extender Pigment.
(1+3) and again with hot water; if necessary add more hot HCl 22.2 Standard Zinc Oxide.
(1+3) to dissolve the precipitate. Dilute the solution to about
250 mL, add 1 mL of (NH4)2HPO 4 solution, and then add 23. Procedure
concentrated NH4OH drop by drop, while stirring constantly, 23.1 Carefully weigh out the proportions of the standard
until the precipitate is again formed as described in the NH4OH extender pigment and standard zinc oxide mutually agreed
is in moderate excess. Cool and allow to stand for about 4 h. upon, and rub up to a fairly stiff paste with a glass muller on a
16.3 Filter the solution on a close-texture paper and wash glass plate or stone slab with raw linseed oil conforming to
six times with NH4OH (5+95). Transfer the precipitate Specification D 234. Note the volume of the oil required.
wrapped in the moist paper to a weighed platinum or porcelain Prepare a similar paste with the sample, using the same weight
crucible, slowly char the paper without allowing it to ignite and of pigment, volume of oil, and number of strokes of the glass
carefully burn off the carbon over a gradually increasing flame muller as used in the preparation of the paste of the standard
which shall never heat the crucible to more than the faintest pigments. Spread the pastes adjacently on a microscope slide,
red. Finally ignite at 1000 to 1100°C to constant weight, taking draw a scraper lightly across them so as to present them on an
care to avoid melting the pyrophosphate. even plane, and judge the color immediately.
17. Calculation 24. Dry Brightness
17.1 Calculate the percent of MgO to 0.1 as follows: 24.1 The test sample and reference sample shall be prepared
MgO, % 5 @~P 4 3 0.3623!/S# 3 100 (4) into suitable smooth, dry, packed surfaces in accordance with
3
D 717
accepted practice and tested for reflectance using the green obtain such information. The methods have been in use for
filter in accordance with Test Method E 97. several years and are considered acceptable.
PRECISION 26. Keywords
25. Precision and Bias 26.1 calcium oxide in magnesium silicate; magnesium ox-
25.1 Data are not available to determine the precision and ide in magnesium silicate; magnesium silicate pigment, analy-
bias of these test methods. There are no plans at present to sis of; silicon dioxide, analysis of
4

Analysis of Aluminum Silicate Pigment1

1.1 These test methods cover the analysis of aluminum 5.1 Reagent grade chemicals shall be used in all tests.
silicate pigment. Unless otherwise indicated, it is intended that all reagents shall
1.2 This standard does not purport to address the safety conform to the specifications of the Committee on Analytical
concerns associated with its use. It is the responsibility of the Reagents of the American Chemical Society,5 where such
user of this standard to establish appropriate safety and health specifications are available. Other grades may be used, pro-
practices and determine the applicability of regulatory limita- vided it is first ascertained that the reagent is of sufficiently
tions prior to use. high purity to permit its use without lessening the accuracy of
the determination.
2. Referenced Documents 5.2 Unless otherwise indicated, references to water shall be
2.1 ASTM Standards: understood to mean Type II of Specification D 1193.
D 234 Specification for Raw Linseed Oil2
D 280 Test Methods for Hygroscopic Moisture (and Other SILICON DIOXIDE
6. Procedure
D 717 Test Methods for Analysis of Magnesium Silicate
Pigment2 6.1 Determine the silicon dioxide content in accordance
D 1193 Specification for Reagent Water3 with Test Methods D 717.
D 1208 Test Methods for Common Properties of Certain ALUMINUM OXIDE
Pigments2
D 2448 Test Methods for Water-Soluble Salts in Pigments 7. Reagents
by Measuring the Specific Resistance of the Leachate of 7.1 Ammonium Acetate (20 %)—Dissolve 200 g of ammo-
the Pigment2 nium acetate (NH4C 2H3O2) in 1 L of distilled water.
E 11 Specification for Wire-Cloth Sieves for Testing Pur- 7.2 Ammonium Chloride Solution (20 g/L)—Dissolve 20 g
poses4 of ammonium chloride (NH 4Cl) in water and dilute to 1 L.
3. Significance and Use 7.3 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
3.1 These test methods may be used to confirm the stated 7.4 Diphenylamine Indicator Solution (1 g/100 mL)—
aluminum oxide and SiO2 content of aluminum silicate for Dissolve 1 g of diphenylamine in 100 mL of concentrated
quality control. sulfuric acid (H2SO4, sp gr 1.84).
4. Apparatus 7.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl).
4.1 Platinum Crucible.
4.2 Electric furnace (or gas burner), capable of 1050 to
trated HCl (sp gr 1.19) with 3 volumes of water.
1100°C.
7.7 Hydrofluoric Acid (48 %)—Concentrated hydrofluoric
4.3 Volumetric flask, 100 and 250 mL.
acid (HF).
4.4 Colorimeter, with transmission range from 400 to 550
7.8 Hydrogen Peroxide (H2O2, 3 %, freshly prepared)—
nm. Mix 1 volume of H2O2 (30 %) with 9 volumes of distilled
4.5 High Silica Crucible. water.
7.9 Hydroxylamine Hydrochloride (10 %)—Dissolve 10 g
1
5
published as D 718 – 43. Last previous edition D 718 – 73 (1979) e1. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
1
D 718
of NH2OH · HCl in 100 mL of distilled water. Prepare fresh increasing the heat gradually until the oxides have all dis-
weekly. solved. Take up the melt with 5 mL of H2SO4 (1+1) in 150 mL
7.10 Iron Standard—Dissolve 0.1 g of analytical grade iron of water and warm to effect solution. Transfer the solution to a
wire in 10 mL of HCl (1+1) and dilute to 1 L. Each millilitre 250-mL volumetric flask, dilute to volume, and mix well.
contains 0.1 mg of Fe. Reserve for TiO2 and Fe2O3 determinations.
7.11 Mercuric Chloride Solution (HgCl2), saturated. 8.5 Determine the percent of TiO2 as follows: Pipet an
7.12 Methyl Red Indicator Solution— Dissolve 0.2 g of aliquot containing 0.2 to 3.0 mg of TiO2 into a 100-mL
methyl red in 100 mL of methanol, ethanol, or isopropanol. volumetric flask. For samples containing 0.5 to 3 % TiO2, a
7.13 Potassium Dichromate, Standard Solution (0.05 N)— 20-mL aliquot is suitable. Add 5 mL of H2O2 (3 %), dilute to
Dissolve 2.457 g of potassium dichromate (K2Cr2O7) in water volume with H2SO4 (1+9) and mix well. Obtain the colorimet-
and dilute to 1 L. Standardize against National Bureau of ric reading in a suitable colorimeter using a filter with
Standards’ standard sample No. 27b of Sibley iron ore, using transmission limits of 400 to 450 nm or at 410 nm with a prism
such an amount as to give approximately the same titration as or grating spectrometer. Compare the readings to a curve
the sample to be analyzed. plotted from a set of TiO2 standards similarly treated and read
7.14 Phosphoric Acid (H3PO 4, 85 %)—Concentrated phos- on the same instrument.
phoric acid. 8.6 Determine the percent of Fe2O3 as follows: Pipet a
7.15 Potassium Pyrosulfate (K2S2O7). 25-mL aliquot into a 100-mL volumetric flask. Add the
7.16 o-Phenanthroline (0.1 %)—Dissolve 1.0 g of following in the order given, mixing well after each addition:
o-phenanthroline in 1 L of hot distilled water. 2 mL of NH2OH · HCl (10 %), 10 mL of NH4C 2H3O2 (20 %),
7.17 Stannous Chloride Solution (5 g/100 mL)—Dissolve 5 and 10 mL of o-phenanthroline (0.1 %). Roll a small piece of
g of stannous chloride (SnCl 3, 2H2O) in 10 mL of concentrated congo red paper into a ball and introduce into the flask. Add
HCl (sp gr 1.19) and dilute to 100 mL with water. Add scraps concentrated NH4OH dropwise until indicator turns red and 1
of iron-free granulated tin, and boil until the solution is clear. drop in excess. Dilute to volume and let stand for 10 to 20 min.
Keep the solution in a closed dropping bottle containing Obtain the colorimetric reading in a suitable colorimeter using
metallic tin. a filter with transmission limits 485 to 550 nm, or at 510 nm
7.18 Sulfuric Acid (1+1)—Add carefully 1 volume of con- with a prism or grating spectrometer. Compare the readings to
centrated sulfuric acid (H2SO 4, sp gr 1.84) to 1 volume of a curve plotted from a set of Fe2O3 standards similarly treated
distilled water. and read on the same instrument.
7.19 Sulfuric Acid (1+9)—Add carefully 1 volume of con- 8.7 Alternatively the Fe2O3 may be determined by titration
centrated H2SO4 (sp gr 1.84) to 9 volumes of distilled water. as follows: Fuse 1 g of sample with 10 g of K2S2O7 in a
high-silica crucible starting at low temperature and increasing
8. Procedure the heat gradually until the crucible glows with a dull red color
8.1 If an appreciable residue remains after the treatment and decomposition is judged to be complete. Leach the melt
with HF in accordance with 7.4 of Test Methods D 717, fuse with 10 mL of concentrated HCl in 100 mL of water and digest
the residue with a small amount of K2S 2O7 until it is dissolved. at low heat to disintegrate the cake. Filter and wash free of
Leach the pyrosulfate melt out of the crucible with water and chlorides with hot water. Save filtrate. Ignite the insoluble
combine the solution with the filtrate reserved in accordance residue in a platinum crucible. Treat with 5 mL of H2SO4 (1+1)
with 7.3 or Test Methods D 717. and 15 mL of HF (48 %), and heat until fumes of H2SO4
8.2 Bring the volume of the combined solution to 250 mL, appear. Bring the residue into solution with the addition of a
and, if necessary, add HCl in order to ensure a total of 10 to 15 few drops more of H2SO 4 (1+1) and combine the solution with
mL of HCl, add a few drops of methyl red indicator solution, the bulk of the iron. Add 5 mL of HCl to the combined
and heat to boiling. Add concentrated NH4OH (sp gr 0.90) solutions and evaporate to 50-mL volume.
dropwise until 1 drop changes the color of the solution to a 8.8 To the hot solution add SnCl2 solution, dropwise, while
distinct yellow. Reheat the solution containing the precipitated stirring, until the solution is decolorized, and then add 2 to 3
hydroxides to boiling, boil for 1 or 2 min, and filter. Wash the drops more. Cool the solution to room temperature, wash down
precipitate once by decantation and then slightly on the filter the inside of the beaker with water, and add at one stroke 10
with hot NH4Cl. mL of cool HgCl2 solution (saturated). Stir the solution
8.3 Transfer the precipitate and paper to the original beaker vigorously for 1 min, add 5 mL of phosphoric acid (85 %) and
in which the precipitation was made. Dissolve the precipitate in 3 drops of diphenylamine indicator solution. Titrate with 0.05
hot HCl (1+3), dilute to 100 mL, and precipitate again as N K2Cr2O 7 solution to an intense deep-blue end point that
described in 8.2. After filtering, wash the precipitate ten times remains unchanged on further addition of K2Cr2O7 solution.
with small portions of hot NH4Cl solution. Transfer the 8.9 Calculate the percent of Fe2O3 as follows:
precipitate to a weighed platinum crucible, heat slowly until
Fe 2O3 % 5 @~N 3 V 3 0.0798!/S# 3 100 (1)
the paper is charred, and finally ignite to constant weight at
1050 to 1100°C in an electric furnace or over a burner, taking where:
care to avoid reduction. Weigh the precipitate as Al2O3 + TiO S 5 sample used, g,
2 + Fe2O3. V 5 K2Cr 2O7, mL, and
8.4 Fuse the combined oxides from 8.3 with 9 to 10 g of N 5 normality of the K2Cr2O7.
K2S2O7 in a platinum crucible, starting at low temperature and 8.10 Calculate the percent of Al2O3 as follows:
2
D 718
Al 2O3, % 5 100~P/S! 2 C (2) type wash bottle is very convenient) to ensure complete
transfer of the specimen to the sieve. Spray the sieve surface
where: gently with a low pressure fan-shaped spray (tap water at about
P 5 weight of combined oxides Al2O3 + TiO 2 + Fe2O3,
5 psig (30 kPa) back pressure) and continue washing until all
S 5 specimen weight, g, and
C 5 Fe2O3 + TiO2, %. the pigment has been washed through and the water passing the
sieve is clear. Dry the sieve for 1 h at 105 to 110°C, cool and
LOSS ON IGNITION weigh.
12.2 Calculation:
9. Procedure Percent of coarse particles (3)
9.1 Determine loss on ignition in accordance with Test 5 ~increase in weight of sieve/specimen weight! 3 100!
Methods D 1208.
MATTER SOLUBLE IN WATER
MOISTURE AND OTHER VOLATILE MATTER
13. Procedure
10. Procedure
13.1 Determine the matter soluble in water by Test Method
10.1 Determine moisture and other volatile matter in accor- D 2448.
dance with Test Methods D 280.
COLOR
COARSE PARTICLES
(Total Residue Retained on a No. 325 (45-µm) Sieve) 14. Standard Pigment
14.1 Standard Extender Pigment.
11. Apparatus
14.2 Standard Zinc Oxide.
11.1 Sieve—A No. 325 (45-µm) 3-in. (76 mm) diameter
high form sieve conforming to Specification E 11, shall be 15. Procedure
used. 15.1 Carefully weigh out the proportion of the standard
11.2 Stirring Apparatus, consisting of: extender pigment and standard zinc oxide mutually agreed
11.2.1 Mixing Cup—A stainless steel cup, about 7 in. (178 upon, and rub up to a fairly stiff paste with a glass muller on a
mm) deep, and slightly tapered from an outside diameter at the glass plate or stone slab with raw linseed oil conforming to
top of about 4 in. (102 mm) to about 23⁄4 in. (70 mm) at the Specification D 234. Note the volume of the oil required.
bottom, such as is characteristic of a usual malted-milk type Prepare a similar paste with the sample using the same weight
mixing cup. of pigment, volume of oil, and number of strokes of the glass
11.2.2 Mechanically Operated Stirring Device, in which a muller as used in the preparation of the paste of the standard
suitably mounted electric motor turns a vertical shaft at a speed pigments. Spread the pastes adjacently on a microscope slide,
of not less than 10 000 r/min without load. The shaft shall be draw a scraper lightly across them to present them on an even
equipped with a replaceable stirring button not more than 1 in. plane, and judge the color immediately.
(25 mm) in diameter, and of such length that the stirring button
shall operate not less than 3⁄4 in. (19.0 mm) nor more than 11⁄2 PRECISION AND BIAS
in. (38 mm) above the bottom of the dispersion cup. A common
malted milk-type mixer of high quality meets this specification. 16. Precision and Bias
16.1 Data are not available to determine the precision and
12. Procedure bias of these methods. There are no plans at present to obtain
12.1 Dry a No. 325 (45-µm) sieve in an oven at 1056 2°C, such information. The methods have been in use for several
cool, and weigh accurately. Transfer 100 6 0.5 g of the years and are considered acceptable.
specimen to the mixing cup containing approximately 250 mL
of water to which has been added about 2 drops of 0.5 % 17. Keywords
solution sodium silicate, and stir for about 10 min at high 17.1 aluminum oxide in aluminum silicate pigment; alu-
speed. Pour the resulting slurry slowly through the sieve and minum silicate pigment, analysis of; pigment, aluminum sili-
wash out the mixing cup carefully (a polyethylene squeeze- cate
3

Analysis of Diatomaceous Silica Pigment1
1. Scope MATTER SOLUBLE IN HYDROCHLORIC ACID

1.1 These test methods cover the analysis of diatomaceous 6. Procedure
silica pigment.
1.2 This standard does not purport to address the safety 6.1 Transfer about 2 g (weighed to 0.1 mg) of the dried
concerns, if any, associated with its use. It is the responsibility material (Section 3) to a 150-mL flask or beaker. Add 45 mL of
of the user of this standard to establish appropriate safety and hydrochloric acid (HCl, 1 + 2) and boil for 5 min. Add 50 mL
health practices and determine the applicability of regulatory of water and boil for 5 min. Filter through a previously dried
limitations prior to use. and weighed Gooch crucible. Wash the insoluble residue on the
filter with hot water until free of chlorides and then with
2. Referenced Documents methanol. Dry the crucible and contents at 105 6 2°C for 2 h.
2.1 ASTM Standards: 7. Calculation
Pastes, and Paints2 7.1 Calculate the percent of matter soluble in HCl as
D 234 Specification for Raw Linseed Oil2 follows:
D 235 Specification for Mineral Spirits (Petroleum Spirits) Matter soluble in HCl, % 5 @~S 2 R!/S# 3 100 (1)
(Hydrocarbon Dry Cleaning Solvent)3
D 280 Test Methods for Hygroscopic Moisture (and Other where:
Matter Volatile Under the Test Conditions) in Pigments2 S 5 sample used, g, and
R 5 residue, g.
Pigments2 VOLUME OF SETTLING IN PETROLEUM
SPIRITS
3.1 These test methods are used to determine the purity and 8. Procedure
some physical properties of diatomaceous silica pigment. The 8.1 Transfer 3 g of the sample to a 100-mL, glass-stoppered,
information is significant to pigment producers and coatings graduated cylinder. Add mineral spirits, conforming to Speci-
manufacture. fication D 235 until a total volume of 100 mL is obtained.
Disperse the mixture by inverting the cylinder 50 times, and
MOISTURE AND OTHER VOLATILE MATTER then allow to stand for 1 h. Read the volume of the settled
4. Procedure pigment.
4.1 Determine the moisture and other volatile matter by Test COLOR
Methods D 280.
9. Standard Pigments
LOSS ON IGNITION 9.1 Standard Extender Pigment.
5. Procedure 9.2 Standard Zinc Oxide.
5.1 Determine the loss on ignition in accordance with Test 10. Procedure
Methods D 1208. 10.1 Carefully weigh out the proportions of the standard
extender pigment and standard zinc oxide mutually agreed
upon, and rub up to a fairly stiff paste with a glass muller on a
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint glass plate or stone slab with raw linseed oil conforming to
and Related Coatings, Materials, and Applications and are the direct responsibility Specification D 234. Note the volume of oil required. Prepare
of Subcommittee D01.31 on Pigment Specifications. a similar paste with the sample, using the same weight of
pigment, volume of oil, and number of strokes of the glass
2
Annual Book of ASTM Standards, Vol 06.03. muller as used in the preparation of the paste of the standard
3
Annual Book of ASTM Standards, Vol 06.04. pigments. Spread the pastes adjacently on a microscope slide,
1
D 719
draw a scraper lightly across them so as to present them on an 12. Precision and Bias
even plane, and judge the color immediately. 12.1 Precision and bias for these test methods have not been
COARSE PARTICLES determined.

11.1 Determine the percent of coarse particles in accordance 13.1 diatomaceous silica pigment; analysis of; pigment;
with Test Methods D 185. diatomaceous silica
2

Methyl Ethyl Ketone1,2
1. Scope PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging

1.1 This specification covers two types of methyl ethyl of7
ketone that are used primarily as solvents in lacquers and
3. Classification
industrial coatings, but also in adhesives, printing inks, lube oil
dewaxing, and as chemical intermediates. 3.1 Methyl ethyl ketone shall be of the following types, as
1.2 For specific hazard information and guidance, see the specified:
supplier’s Material Safety Data Sheet for materials listed in this 3.1.1 Type I—regular, and
specification. 3.1.2 Type II—urethane grade. This type may be suited for
use in urethane coatings, provided that the water content and
2. Referenced Documents alcohol content are acceptable.
2.1 ASTM Standards:
4. Properties
D 268 Guide for Sampling and Testing Volatile Solvents
and Chemical Intermediates for Use in Paint and Related 4.1 The physical and chemical properties of methyl ethyl
Coatings and Materials3 ketone shall conform to the requirements specified in Table 1.
D 1078 Test Method for Distillation Range of Volatile 5. Sampling
Organic Liquids3
D 1209 Test Method for Color of Clear Liquids (Platinum- 5.1 The material shall be sampled in accordance with
Cobalt Scale)3 Practice E 300.
D 1353 Test Method for Nonvolatile Matter in Volatile 6. Test Methods
Solvents for Use in Paint, Varnish, Lacquer, and Related
Products3 6.1 The properties enumerated in this specification shall be
D 1364 Test Method for Water in Volatile Solvents (Fischer determined in accordance with the following ASTM test
Reagent Titration Method)3 methods:
D 1613 Test Method for Acidity in Volatile Solvents and 6.1.1 Acidity—Test Method D 1613.
Chemical Intermediates Used in Paint, Varnish, Lacquer 6.1.2 Alcohol—Test Method D 2804.
and Related Products3 6.1.3 Color—Test Method D 1209.
D 2804 Test Method for Purity of Methyl Ethyl Ketone 6.1.4 Distillation Range—Test Method D 1078, using an
Using Gas Chromatography3 ASTM Solvents Distillation Thermometer 39C having a range
D 4052 Test Method for Density and Relative Density of from 48 to 102°C and conforming to the requirements in
Liquids by Digital Density Meter4 Specifications E 1.
E 1 Specification for ASTM Thermometers5 6.1.5 Nonvolatile Matter—Test Method D 1353.
E 300 Practice for Sampling Industrial Chemicals6 6.1.6 Purity—Test Method D 2804.
2.2 U.S. Federal Specification: 6.1.7 Apparent Specific Gravity—Determine the apparent
specific gravity by any method that is accurate to the third
decimal place, the temperature of both specimen and water
being 20°C or 25°C. (See Specific Gravity section of Guide
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint D 268, or Test Method D 4052.)
and Related Coatings, Materials, and Applications and is the direct responsibility of 6.1.8 Water—Test Method D 1364.
Current edition approved March 15, 1994. Published May 1994. Originally 7. Packaging and Package Marking
2
Also known as butanone and 2–butanone. 7.1 Package size shall be agreed upon between the pur-
3
4
Annual Book of ASTM Standards, Vol 06.04. chaser and the supplier.
5
7
6
Robbins Ave., Philadelphia, PA 19111-5094.
1
D 740
TABLE 1 Physical and Chemical Properties of Methyl Ethyl 8. Keywords
Ketone
Type I Type II
8.1 solvents; methyl ethyl ketone; regular grade; 2–bu-
tanone; urethane grade
Commerical reference regular urethane-grade
AcidityA, weight %, max 0.005 0.003
AlcoholB, weight %, max ... 0.5
Color, Pt-Co scale, max 10 10
Distillation range, 760 mm Hg,° C
Initial boiling point, min 78.5 78.5
Dry point, max 81.0 81.0
Nonvolatile matter, mg/100 mL, max 5 5
Purity, weight %, min 99.5 99.5
Specific gravity, apparent
20/20°C 0.805 to 0.807 0.805 to 0.807
25/25°C 0.801 to 0.803 0.801 to 0.803
Water, weight %, max 0.2 0.05
A
Free acid as acetic acid. Equivalent to 0.047 mg potassium hydroxide (KOH)
per gram of material.
B
Calculated as 2-butanol or sec-butyl alcohol.
7.2 Packaging shall conform to applicable carrier rules and

regulations or when specified shall conform to Fed. Spec.
PPP-C-2020.
2

Raw and Burnt Umber Pigments1
1. Scope TABLE 1 Requirements for Composition of Raw and Burnt

Umber
1.1 This specification covers the pigments commercially
Raw Burnt
known as raw umber and burnt umber. Umber Umber
2. Referenced Documents Iron oxide (Fe2O3), min, % 37 42

Calcium compounds (as CaO), max, % 5.0 5.0
D 50 Test Methods for Chemical Analysis of Yellow, Or- Coarse particles (total residue retained on a No. 325 2.0 2.0
ange, Red, and Brown Pigments Containing Iron and Organic colors, max, % none none
Manganese2
Pastes, and Paints2 container and shall break up readily in linseed oil to form a
D 280 Test Methods for Hygroscopic Moisture (and Other smooth paint of brushing consistency. It shall mix readily in all
Matter Volatile Under the Test Conditions) in Pigments2 proportions, without curdling, with linseed oil, turpentine, or
D 387 Test Method for Color and Strength of Color Pig- volatile petroleum spirits, or any mixture of these substances.
ments with a Mechanical Muller3 The paste shall conform to the following requirements:
D 1208 Test Methods for Common Properties of Certain Pigment, min, % 55
Pigments2 Nonvolatile vehicle, min, % 80
Moisture by distillation, max, % 2.0
3. Composition and Properties Coarse particles and skins (total residue retained on a 1.0
No. 325 (45-µm sieve), max, % of dry pigment
3.1 Dry Pigments—The pigments shall conform to the
following requirements: 3.3 The mass color and character of the tint and the tinting
3.1.1 Raw Umber—The pigment shall be in a soft, dry form strength formed by a mixture with a white pigment shall be
and shall be a hydrated oxide of iron (together with such within mutually agreed upon limits of a standard acceptable to
manganese that is naturally associated with it) permeating a both the purchaser and the seller.
siliceous base and shall be free of admixtures of other
4. Sampling
substances except carbon pigments. The pigment shall conform
to the requirements for composition prescribed in Table 1. 4.1 Two samples shall be taken at random from different
3.1.2 Burnt Umber—The pigment shall be produced by the packages from each lot, batch, day’s pack, or other unit of
calcination of raw umber and shall be free of admixtures of production in a shipment. When no markings distinguishing
other substances except carbon pigments. The pigment shall between units of production appear, samples shall be taken
conform to the requirements for composition prescribed in from different packages in the ratio of two samples for each
Table 1. 10 000 lb (4540 kg), except that for shipments of less than
3.2 Paste in Oil—For both raw and burnt umber, the paste 10 000 lb two samples shall be taken. At the option of the
in oil shall be made by thoroughly grinding the pigment with purchaser, the samples may be tested separately or after
linseed oil (with or without a small amount of volatile thinner) blending in equal quantities the samples from the same
together with (where necessary) small amounts of wetting or production unit to form a composite sample.
dispersing agents to produce a paste or semipaste of satisfac-
5. Test Methods
tory consistency. As received, it shall not be caked in the
ing ASTM test methods. Test procedures not covered by ASTM
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint test methods shall be mutually agreed upon by the purchaser
and Related Coatings, Materials, and Applications, and is the direct responsibility of and the seller.
Subcommittee D01.31 on Pigment Specifications. 5.2 Chemical Analysis of Dry Pigment—Test Methods
published as D763 – 44 T. Last previous edition D763 – 48 (1974).
D 50.
2
Annual Book of ASTM Standards, Vol 06.03. 5.3 Moisture in Paste in Oil—Test Method D 280, except
3
Annual Book of ASTM Standards, Vol 06.01. that the sample shall be weighed instead of measured and the
1
D 763
results shall be expressed as weight percentage instead of 5.5 Pigment and Linseed Oil in Paste in Oil—Test Methods
volume. D 1208.
5.4 Coarse Particles—Test Methods D 185. 5.6 Mass Color and Tinting Strength—Test Method D 387.
2

Raw and Burnt Sienna Pigments1
1. Scope TABLE 1 Requirements for Composition of Raw and Burnt

Sienna
1.1 This specification covers the pigments commercially
Raw Burnt
known as raw sienna and burnt sienna. Sienna Sienna
2. Referenced Documents Iron oxide (Fe2O2), min, % 38 40

Calcium compounds (as CaO) max, % 5.0 5.0
D 50 Test Methods for Chemical Analysis of Yellow, Or- Coarse particles (total residue retained on a No. 325 2.0 2.0
ange, Red, and Brown Pigments Containing Iron and Organic colors, max, % none none
Manganese2
Pastes, and Paints2 Pigment, min, % 60
D 280 Test Methods of Hygroscopic Moisture (and Other Nonvolatile vehicle, min, of vehicle 80
Matter Volatile Under the Test Conditions) in Pigments2 Moisture by distillation, max, % 2.0
Coarse particles and skins (total residue retained on a No. 325 (45-µm) 1.0
D 387 Test Method for Color and Strength of Color Pig- sieve), max, % of dry pigment
D 1208 Test Methods for Common Properties of Certain 3.3 The mass color and character of the tint and the tinting
Pigments3 strength formed by a mixture with a white pigment shall be
3. Composition and Properties both the purchaser and the seller.
3.1 Dry Pigments—The pigments shall conform to the
4. Sampling
following requirements:
3.1.1 Raw Sienna—The pigment shall be in a soft, dry form 4.1 Two samples shall be taken at random from different
and shall be a hydrated oxide of iron permeating a siliceous packages from each lot, batch, day’s pack, or other unit of
base. The pigment shall conform to the requirements for production in a shipment. When no markings distinguishing
composition prescribed in Table 1. between units of production appear, samples shall be taken
3.1.2 Burnt Sienna—The pigment shall be produced by the from different packages in the ratio of two samples for each 5
calcination of raw sienna and shall conform to the requirements tons (inch-pound or SI), except that for shipments of less than
for composition prescribed in Table 1. 10 000 lb two samples shall be taken. At the option of the
3.2 Paste in Oil—For both raw and burnt sienna, the paste purchaser, the samples may be tested separately or after
in oil shall be made by thoroughly grinding the pigment with blending in equal quantities the samples from the same
linseed oil (with or without a small amount of volatile thinner) production unit to form a composite sample.
together with (where necessary) small amounts of wetting or
5. Test Methods
dispersing agents to produce a paste or semipaste of satisfac-
tory consistency. As received, it shall not be caked in the 5.1 Tests shall be conducted in accordance with the appro-
container and shall break up readily in linseed oil to form a priate ASTM test methods. Test procedures not covered by
smooth paint of brushing consistency. It shall mix readily in all ASTM test methods shall be mutually agreed upon by the
proportions, without curdling, with linseed oil, turpentine, or purchaser and the seller.
volatile petroleum spirits, or any mixture of these substances. 5.1.1 Total Iron Oxide, Calcium Compound, and Organic
The paste shall conform to the following requirements: Coloring Matter—Test Methods D 50.
5.1.2 Coarse Particles—Test Methods D 185.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.3 Pigment and Linseed Oil in Paste in Oil—Test Meth-
and Related Coatings, Materials, and Applications, and is the direct responsibility of ods D 1208.
Subcommittee D01.31 on Pigment Specifications. 5.1.4 Moisture in Paste in Oil—Test Methods D 280, except
that the sample shall be weighed instead of measuredand the
2
Annual Book of ASTM Standards, Vol 06.03. results shall be expressed as percentage by weight instead of
3
Annual Book of ASTM Standards, Vol 06.01. volume.
1
D 765
5.1.5 Mass Color and Tinting Strength— Test Method 6. Keywords
D 387. 6.1 burnt sienna; iron; manganese; pigment; raw sienna
2

Yellow Iron Oxide Hydrated1
1. Scope shall not be caked in the container and shall break up readily in
1.1 This specification covers the pigment commercially oil to form a smooth paint of brushing consistency. It shall mix
known as yellow iron oxide, hydrated. readily in all porportions, without curdling, with linseed oil,
turpentine, or volatile petroleum spirits, or any mixtures of
2. Referenced Documents these substances. The paste shall conform to the following
2.1 ASTM Standards: requirements:
D 50 Test Methods for Chemical Analysis of Yellow, Or- Pigment, min, % 55
Nonvolatile vehicle, min, % of vehicle 80
ange, Red, and Brown Pigments Containing Iron and Moisture by distillation, max, % 2.0
Manganese2 Coarse particles and skins (total residue retained on a 1.0
D 185 Test Methods for Coarse Particles in Pigments, No. 325 (45-µm) sieve), max, percent of the dry
pigment
Pastes, and Paints2 Consistency by the Stormer viscometer:
D 280 Test Methods for Hygroscopic Moisture (and Other At shearing rate of 100 revolutions/30 s, min, g 700A
Matter Volatile Under the Test Conditions) in Pigments2 At shearing rate of 100 revolutions/35 s, max, g 1200B
__________
Pigments2 A
Equivalent to a rating of 125 Krebs’ Units.
B
Equivalent to a rating of 145 Krebs’ Units.
3. Composition and Properties 3.3 The mass color character of the tint and the tinting
3.1 The pigment shall be a manufactured yellow iron oxide strength formed by a mixture with a white pigment shall be
obtained by chemical reaction. It shall be a soft, finely within mutually agreed upon limits of a standard acceptable to
powdered pigment, free of admixtures of other substances and both the purchaser and the seller.
shall conform to the following requirements:
4. Sampling
Total hydrated oxide of iron, min, % 93
Total oxide of iron,A min, % 83 4.1 Two samples shall be taken at random from different
Loss on ignition,A max, % 13 packages from each lot, batch, day’s pack, or other unit of
Water soluble matter, max, % 0.50
Coarse particles (total residue retained on a No. 325 0.5 between units of production appear, samples shall be taken
(45-µm) sieve), max, % from different packages in the ratio of two samples for each 5
Hydrogen ion concentration (pH value) 4.5 to 8.0
__________ tons (inch-pound or SI), except that for shipments of less than
A
Total hydrated oxide of iron shall be the sum of iron oxide and loss on ignition.
Loss on ignition shall be calculated on the dry material. purchaser, the samples may be tested separately or after
3.2 Paste in Oil—The paste in oil shall be made by blending in equal quantities the samples from the same
thoroughly grinding the specified pigment with linseed oil production unit to form a composite sample.
(with or without a small amount of volatile thinner) together
with (where necessary) small amounts of wetting or dispersing 5. Test Methods
agents to a semipaste or fluid type consistency. As received, it 5.1 General—Tests shall be conducted in accordance with
the appropriate ASTM test methods. Test procedures not
covered by ASTM test methods shall be mutually agreed upon
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint between the purchaser and the seller.
and Related Coatings, Materials, and Applications, and is the direct responsibility of 5.1.1 Chemical Analysis—Test Methods D 50.
5.1.2 Coarse Particles in Pigments—Test Method D 185.
published as D 768 – 44T. Last previous edition D 768 – 47 (1974). 5.1.3 Moisture in Pigments—Test Method D 280.
2
Annual Book of ASTM Standards, Vol 06.03. 5.1.4 Water Soluble Matter—Test Method D 1208.
1
D 768
5.1.5 Hydrogen Ion Concentration—Test Method D 1208. 6. Keywords
5.1.6 Pigment and Linseed Oil in Paste in Oil—Test Meth-
6.1 hydrated; pigment; yellow iron oxide
ods D 1208.
2

Black Synthetic Iron Oxide1
e1 NOTE—Additional keywords were added editorially in May 1995.
1. Scope strength formed by a mixture with a white pigment shall be

1.1 This specification covers the pigment commercially within mutually agreed upon limits of a standard acceptable to
known as black synthetic iron oxide. both the purchaser and the seller.

D 50 Test Methods for Chemical Analysis of Yellow, Or- packages from each lot, batch, day’s pack, or other unit of
ange, Red, and Brown Pigments Containing Iron and production in a shipment. When no markings distinguishing
Manganese2 between units of production appear, samples shall be taken
D 185 Test Methods for Coarse Particles in Pigments, from different packages in the ratio of two samples for each 5
Pastes, and Paints2 tons (inch-pound or SI), except that for shipments of less than
D 280 Test Methods for Hygroscopic Moisture (and Other 10 000 lb two samples shall be taken. At the option of the
Matter Volatile Under the Test Conditions) in Pigments2 purchaser, the samples may be tested separately or after
D 387 Test Method for Color and Strength of Color Pig- blending in equal quantities the samples from the same
ments with a Mechanical Muller3 production unit to form a composite sample.
D 1208 Test Methods for Common Properties of Certain 5. Test Methods
Pigments2
D 3872 Test Method for Ferrous Iron in Iron Oxides2 5.1 Tests shall be conducted in accordance with the appro-
priate test methods. Test procedures not covered by ASTM test
3. Composition and Properties methods shall be mutually agreed upon between the purchaser
3.1 The pigment shall be a manufactured ferrous-ferric and the seller.
oxide obtained by chemical reaction. It shall be a soft dry finely 5.1.1 Total Iron Oxides—Test Methods D 50.
powdered pigment, free of admixtures of other substances and 5.1.2 Ferrous Iron in Iron Oxides—Test Method D 3872.
shall conform to the following requirements: 5.1.3 Water Soluble Matter, Maximum, Percent—Test Meth-
Total ferrous and ferric oxide, min % 93
ods D 1208.
Ferrous oxide (FeO), min, % 20 5.1.4 Moisture and Other Volatile Matter, Maximum,
Water-soluble matter, max, % 0.5 Percent—Test Methods D 280.
5.1.5 Coarse Particles (Total Residue Retained on a 325-
325 (45-µm) sieve), max, % mesh sieve (45 µm), Maximum, Percent—Test Methods D 185.
Hydrogen ion concentration (pH value) 4.5 to 8.5 5.1.6 Hydrogen Ion Concentration (pH value)—Test Meth-
ods D 1208.
3.2 The mass color and character of the tint and the tinting 5.1.7 Mass Color and Tinting Strength—Test Method
D 387.
1
6. Keywords
Subcommittee D01.31 on Pigment Specifications. 6.1 black iron oxide; ferric oxide; ferrous oxide; iron oxide;
Current edition approved May 29, 1987. Published July 1987. Originally manganese; pigment; synthetic iron oxide
2
3
1
D 769
2

Isopropyl Alcohol1,2
1. Scope E 300 Practice for Sampling Industrial Chemicals6

1.1 This specification covers isopropyl alcohol (99 % 2.2 U.S. Federal Specification:
grade). PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging
1.2 This standard does not purport to address all of the of7
safety concerns, if any, associated with its use. It is the 3. Properties
priate safety and health practices and determine the applica- 3.1 Isopropyl alcohol shall conform to the following re-
bility of regulatory limitations prior to use. quirements:
1.3 For hazard information and guidance, see the supplier’s Apparent specific gravity,
20/20°C 0.785 to 0.787
Material Safety Data Sheet. 25/25°C 0.782 to 0.784
2. Referenced Documents Distillation range, 760 mmHg A
Nonvolatile matter, max, mg/100 mL 5

2.1 ASTM Standards: Odor nonresidualB
D 268 Guide for Sampling and Testing Volatile Solvents Water, max, weight % 0.2C
and Chemical Intermediates for Use in Paint and Related Acidity, acetic acid, max, weight % 0.002D
Water miscibility passes test
Coatings and Materials3 _______________
D 1078 Test Method for Distillation Range of Volatile
Organic Liquids3 A
Distill entirely within a 1.5°C range which shall include 82.3°C.
D 1209 Test Method for Color of Clear Liquids (Platinum- B
Optional, when required, as agreed upon between the supplier and the
consumer.
Cobalt Scale)3 C
D 1296 Test Method for Odor of Volatile Solvents and turbidity with 19 volumes of 99 % heptane at 20°C.
Diluents3 D
0Equivalent to 0.019 mg KOH per gram of sample.
Products3 4.1 The material shall be sampled in accordance with
D 1364 Test Method for Water in Volatile Solvents (Karl Practice E 300.
D 1476 Test Method for Heptane Miscibility of Lacquer 5. Test Methods
Solvents3 5.1 The properties enumerated in this specification shall be
D 1613 Test Method for Acidity in Volatile Solvents and determined in accordance with the following ASTM methods:
Chemical Intermediates Used in Paint, Varnish, Lacquer, 5.1.1 Apparent Specific Gravity—Determine the apparent
and Related Products3 specific gravity at 20 or 25°C by a convenient method that is
D 1722 Test Method for Water Miscibility of Water-Soluble accurate to the third decimal place. See Guide D 268 or Test
Solvents3 Method D 4052.
Liquids by Digital Density Meter4 5.1.3 Distillation Range—Test Method D 1078, using an
E 1 Specification for ASTM Thermometers5 ASTM Solvents Distillation Thermometer 40C having a range
from 72 to 126°C and conforming to the requirements in
1
Specification E 1.
and Related Coatings, Materials, and Applications and is the direct responsibility of 5.1.4 Nonvolatile Matter—Test Method D 1353.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 5.1.5 Odor—Test Method D 1296.
2
This compound is also known under the name propanol-2 and isopropanol.
3 6
4 7
Annual Book of ASTM Standards, Vol 05.02. Available from Standardization Documents Order Desk, Bldg 4 Section D, 700
5
1
D 770
5.1.6 Water—Test Methods D 1364 and D 1476. 6.2 Packaging shall conform to applicable carrier rules and
5.1.7 Acidity—Test Method D 1613. regulations, or when specified, shall conform to Fed. Spec.
5.1.8 Water Miscibility—Test Method D 1722. PPP-C-2020.
6. Packaging and Package Marking 7. Keywords
6.1 Package size shall be agreed upon between the pur- 7.1 isopropanol; isopropyl alcohol; petrohol; 2–propanol;
chaser and the supplier. secondary propyl alcohol
2

Sampling and Testing Dipentene1
1. Scope These procedures were sufficient when dipentene was used

1.1 These test methods cover procedures for sampling and primarily as a solvent. Currently, however, dipentene finds
testing dipentene and related terpene solvents, consisting application as a chemical raw material and a knowledge of its
chiefly of monocyclic terpene hydrocarbons distilling above chemical composition is therefore important. Gas chromatog-
the range for turpentine. raphy is the accepted method for determining the chemical
1.2 The procedures given in these test methods appear in the composition of dipentene. An ASTM test method using an
following order: existing ASTM test method using packed column gas chroma-
Section
tography can be used for the major compounds in dipentene. A
Sampling 4 capillary GC procedure is currently being written which is
Detection and Removal of Separated Wa- 5 suitable for both the major and minor components.
ter
Appearance 6
Color 7
4. Sampling
Odor 8 4.1 Sample the material in accordance with the procedure
Specific Gravity 9
Refractive Index 10
described in Guide D 268 and Practice E 300. If a sample from
Composition 11 close to the bottom of a tank shows a decided difference in
Flash Point 12 color or appearance from samples taken at other depths, take an
Moisture 13
extra bottom sample and examine it separately from the
1.3 This standard does not purport to address all of the composite sample. In such case the composite sample shall not
safety concerns, if any, associated with its use. It is the include any portion of such bottom sample.
priate safety and health practices and determine the applica- 5. Detection and Removal of Separated Water
bility of regulatory limitations prior to use. 5.1 Draw a portion of the dipentene by means of a glass or
metal container with a removable stopper or top,5 or with a
2. Referenced Documents thief, from the lowest part of the container, or by opening the
2.1 ASTM Standards: bottom valve of the level tank car. If water is found to be
D 268 Guide for Sampling and Testing Volatile Solvents present, draw it all out, record the quantity, and deduct it from
and Chemical Intermediates for Use in Paint and Related the total volume of liquid delivered.
Coatings and Materials2
D 803 Standard Test Methods for Testing Tall Oil3 6. Appearance
D 890 Test Method for Water in Liquid Naval Stores3 6.1 Examine a portion of the sample after agitation to
D 3009 Standard Test Method for Composition of Turpen- determine its clarity and freedom from foreign matter and
tine by Gas Chromatography3 separated water.
7. Color
3. Significance and Use 7.1 Compare the color of the sample in any suitable or
3.1 The testing procedures described in these test methods designated apparatus with the accepted or specified color
have been in use for many years and emphasize the physical standard.
properties rather than the chemical composition of dipentene.
8. Odor
1
8.1 Compare the odor of the sample with an agreed upon
water-free reference sample kept in the dark in a completely
of Subcommittee D01.34 on Naval Stores. filled well-stoppered bottle. In the absence of such a reference
2
3 5
Annual Book of ASTM Standards, Vol 06.03. Detailed description of equipment suitable for such sampling is given in
4
Annual Book of ASTM Standards, Vol 15.05. Practice E 300.
1
D 801
sample, compare with samples of known purity similarly agreed upon between the producer and the customer.
preserved.
8.2 The use of an odor panel made up of personnel trained 13. Moisture
to small terpenic odors is recommended.
13.1 The recommended method for the determination of
9. Specific Gravity dissolved water uses the Karl Fischer reagent and is described
9.1 Determine the specific gravity at 15.6/15.6°C by any in Test Method D 890. This method is more rapid than the
convenient method, reporting the value to the nearest 0.0005. distillation method described in 13.2 and is applicable to
Correct determinations made at any other temperature, using oxidized products.
apparatus standardized at 15.6°C by adding to or subtracting 13.2 Alternative Method—Distillation:
from the observed reading 0.00082 for each degree Celsius that 13.2.1 The azeotropic distillation method described in the
the temperature of the liquid is above or below 15.6°C. procedure section of Test Methods D 803 can be used for
10. Refractive Index moisture analysis of dipentene.
10.1 Determine the refractive index with an instrument 14. Precision and Bias
having a resolution of 6 0.0001 at 20°C, if possible. If tested
at any other temperature, correct the reading obtained to 20°C 14.1 Some of the procedures described in these test methods
by adding or subtracting 0.00045 for each degree Celsius that were developed many years ago and were once used widely for
the temperature at which the determination was made is the sampling and testing of dipentene. Currently these test
respectively above or below 20°C. methods are less widely used and it is not considered practical
to determine the precision and bias of the individual test
11. Composition methods at this time.
11.1 Determine the component concentration of dipentene 14.2 Where reference is made to other ASTM test methods,
using gas chromatography. The referenced method employs these test methods should be examined to determine their
packed column technology (see Test Method D 3009). An
precision and bias.
improved test method employing a capillary column is cur-
rently being written by the Subcommittee D01.34.
15. Keywords
12. Flash Point 15.1 dipentene; gas chromatography; sampling
12.1 Determine the flash point by any acceptable means
2

Sampling and Testing Pine Oils1
1. Scope chromatography is the accepted method for determining the

1.1 These test methods cover procedures for sampling and chemical composition of pine oil. An ASTM test method based
testing pine oils, and are applicable to both natural pine oils on capillary gas chromatography can be used for the major
derived from pine stumps either by the steam and solvent components of pine oil. A capillary GC procedure is currently
process or by destructive distillation, and also to synthetic pine being written which is suitable for both major and minor
oils obtained by the chemical hydration of terpene hydrocar- components.
bons. 4. Sampling
1.2 The procedures given in these test methods appear in the
following order: 4.1 Sample the material in accordance with the procedure
Section
described in Guide D 268 and Practice E 300.
Sampling 4
Appearance 5 5. Appearance
Color 6
Specific Gravity 7
5.1 Examine a portion of the sample after agitation to
Refractive Index 8 determine its clarity and freedom from foreign matter and
Composition 9 separated water.
Moisture 10
1.3 This standard does not purport to address all of the 6. Color
safety concerns, if any, associated with its use. It is the 6.1 Compare the color of the sample in any suitable or
responsibility of the user of this standard to establish appro- designated apparatus with the accepted or specified color
priate safety and health practices and determine the applica- standard.
7. Specific Gravity
2. Referenced Documents 7.1 Determine the specific gravity at 15.6/15.6°C by any
2.1 ASTM Standards: convenient method, reporting the value to the nearest 0.0005.
D 268 Guide for Sampling and Testing Volatile Solvents (A pycnometer or specific gravity balance is recommended. A
and Chemical Intermediates for Use in Paint and Related hydrometer should not be used, on account of errors caused by
Coatings and Materials2 surface tension on the hydrometer stem.) Correct determina-
D 803 Test Methods for Testing Tall Oil3 tions made at any other temperature, using apparatus standard-
D 890 Test Method for Water in Liquid Naval Stores3 ized at 15.6°C by adding to or subtracting from the observed
D 3009 Test Method for Compositon of Turpentine by Gas reading 0.00080 for each degree Celsius that the temperature of
Chromatography3 the liquid is above or below 15.6°C.
8. Refractive Index
3. Significance and Use 8.1 Determine the refractive index with an instrument hav-
3.1 The testing procedures described in these test methods ing a resolution of 6 0.0001 at 20°C, if possible. If tested at
have been in use for many years and emphasize the physical any other temperature, correct the reading obtained to 20°C by
properties of pine oil rather than its chemical composition. Gas adding or subtracting 0.00045 for each degree Celsius that the
temperature at which the determination was made is, respec-
tively, above or below 20°C.
1
and Related Coatings, Materials, and Applications and are the direct responsibility 9. Composition
of Subcommittee D01.34 on Naval Stores. 9.1 Determine the component concentration of pine oil
using gas chromatography. The referenced method employs
2
Annual Book of ASTM Standards, Vol 06.04. packed column technology (see Test Method D 3009). An
3
4
1
D 802
improved test method employing a capillary column is cur- 11. Precision and Bias
rently being written by Subcommittee D01.34.
11.1 Some of the procedures described in these test methods
10. Moisture were developed many years ago and were once used widely for
10.1 The recommended method for measuring the moisture the sampling and testing of pine oils. Currently these test
content of pine oil is the use of the Karl Fischer reagent and is methods are less widely used and it is not considered practical
described in Test Method D 890. This test method is more rapid to determine the precision and bias of the individual methods
and more reliable than the alternative method described in at this time.
10.2. 11.2 Where reference is made to other ASTM test methods,
10.2 Alternative Method, Distillation— these test methods should be examined to determine their
10.2.1 The azeoitropic distillation method described in the precision and bias.
procedure section of Test Methods D 803 can be used for
moisture analysis of pine oil. 12. Keywords
NOTE 1—It is important that the flask be scrupulously clean. If it shows 12.1 gas chromatography; pine oil; sampling; terpene alco-
any white deposits (such as might be caused from attack by alkalies during hols
previous use), the percentage of water may be erroneously high due to a
slight decomposition of the terpene alcohols in the pine oil.
2

Testing Tall Oil1
1. Scope D 97 Test Methods for Pour Point of Petroleum Oils2

1.1 These test methods cover the test procedures to be D 269 Test Method for Insoluble Matter in Rosin and Rosin
applied to whole tall oils or refined tall oils. Previous editions Derivatives3
of these test methods have described test procedures that are D 464 Test Methods for Saponification Number of Naval
used to test tall oil fatty acid, rosin, and other tall oil-derived Store Products Including Tall Oil and Other Related
products as well as test crude and refined tall oil. Consequently, Products3
these test methods are widely cited in reference books and D 465 Test Methods for Acid Number of Naval Store
industry literature for the testing of tall oil-derived products. Products Including Tall Oil and Other Related Products3
1.1.1 In this current revision, procedural details of some of D 890 Test Method for Water in Liquid Naval Stores3
the often-cited test methods have been removed and the test D 1065 Test Method for Unsaponifiable Matter in Naval
methods consolidated with other existing test methods. In such Stores, Including Rosin, Tall Oil, and Related Products3
cases the consolidated methods, applicable to all tall oil- D 1240 Test Method for Rosin Acids Content of Naval
derived products, are referenced. Stores, Including Rosin, Tall Oil, and Related Products3
1.2 The procedures appear in the following order: D 1466 Test Method for Sampling Liquid Oils and Fatty
Physical Tests Sections
Viscosity: Materials3
Brookfield Method (Preferred Method) 7 D 1544 Test Method for Transparent Liquids (Gardner
Bubble Time Method 8
Pour Point 9
Color Scale)4
Flash Point 10 D 1545 Test Method for Viscosity of Transparent Liquids
Color 11 by Bubble Time Method3
Moisture: 12
Insoluble Matter 13
D 1585 Test Methods for Fatty Acids Content of Naval
Ash 14 Stores Including Rosin, Tall Oil, and Related Products3
Chemical Analysis D 2196 Test Methods for Rheological Properties of Non-
Acid Number 17
Saponification Number 18 Newtonian Materials by Rotational (Brookfield) Viscom-
Rosin Acids 19 eter4
Unsaponifiable Matter 20 D 3278 Test Methods for Flash Points of Liquids by Set-
Fatty Acids 21
aflash Closed Cup Apparatus4
1.3 This standard does not purport to address all of the E 300 Practice for Sampling Industrial Chemicals5
responsibility of the user of this standard to establish appro- 3. Significance and Use
priate safety and health practices and determine the applica- 3.1 Tall oil, both crude and refined, is an important by-
bility of regulatory limitations prior to use. product of the alkaline (kraft) pulping of pine wood. It consists
primarily of fatty acids, resin acids, and neutral materials; the
2. Referenced Documents levels of these various components depend on factors such as
2.1 ASTM Standards: the species of pine tree, geographic location, climate, etc.
D 92 Test Method for Flash and Fire Points by Cleveland 3.1.1 Tall oil is used primarily as a commercial source of
Open Cup2 fatty acids and rosin, and, therefore, reliable methods for the
D 93 Test Methods for Flash Point by Pensky-Martens analysis of these components is necessary.
Closed Tester2
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Unless otherwise indicated, it is intended that all reagents shall
of Subcommittee D01.34 on Naval Stores.
3
4
2 5
1
D 803
conform to the specifications of the Committee on Analytical Methods D 97, reporting only the lower pour point. The upper
Reagents of the American Chemical Society, where such pour point is not always reproducible because of the tendency
specifications are available.6 Other grades may be used, proof some tall oils to crystallize.
high purity to permit its use without lessening the accuracy of FLASH POINT
the determination.
4.2 Unless otherwise indicated, references to water shall be 10. Procedure
understood to mean distilled water or deionized water. 10.1 Determine the flash point in accordance with any
referenced method (see Test Methods D 92, D 93, and D 3278).
5. Sampling
5.1 As with many industrial chemicals, the procedure for COLOR
obtaining a representative sample of tall oil depends on the
container to be sampled and the uniformity of the material to be 11. Procedure
sampled. No specific standard procedure for sampling tall oil 11.1 Determine the color in accordance with Test Method
has been developed but Test Method D 1466 and Practice D 1544.
E 300 describe applicable methods when the tall oil contains
no separated solids or separated water. If rosin has separated, MOISTURE CONTENT
the rosin can be redissolved by heating and agitating the
material to be sampled until it is homogeneous. If separated 12. Procedure
water is present, special procedures should be followed to 12.1 Determine the moisture content in accordance with the
ensure that a representative sample be obtained. The selection methods described in Test Method D 890. The Karl Fischer
of an appropriate procedure will depend on the water content method is the preferred method.
and the type of container being sampled.
6. Conditioning INSOLUBLE MATTER
6.1 Heat the entire sample in a closed container fitted with 13. Procedure
a capillary vent or its equivalent. Some kind of agitation, even
if done occasionally by hand, saves much time. Heat in a 13.1 Determine the insoluble matter in accordance with Test
forced-air oven in order to dissolve any crystalline material. A Method D 269.
temperature of 100°C is usually sufficient to dissolve crystals
ASH
present in crude tall oil, but a temperature as high as 160°C
may be required to remove rosin crystals from distilled tall oil. 14. Apparatus
Withdraw the specimens only when all crystalline matter has
dissolved and when the entire sample becomes a homogeneous 14.1 Platinum Dish—A platinum dish of 50 to 100-mL
fluid after thorough stirring. capacity.
NOTE 1—A porcelain or silica dish may be used in place of platinum,
VISCOSITY BY THE BROOKFIELD METHOD
if the ash is not to be analyzed.
(Preferred Method)
7.1 Determine the viscosity in centipoise in accordance with 15.1 Heat the platinum dish to redness and, after cooling in
Test Methods D 2196. The testing temperature shall be 210°F a desiccator, weigh to the nearest 0.0001 g. Place an approxi-
(99°C) unless a lower temperature is specified. mately 20-g sample of tall oil in the dish and weigh to the
nearest 0.1 g (Note 2). Heat the dish gently by means of a
VISCOSITY BY THE BUBBLE TIME METHOD bunsen burner until the oil can be ignited at the surface (Note
(Alternative Method) 3). Remove the burner and allow the oil to burn completely.
8. Procedure Burn all free carbon on the sides of the dish and heat the
residue with a strong flame, or in a muffle furnace, until all
8.1 Determine the viscosity in accordance with Test Method
carbonaceous matter disappears. After cooling in a desiccator
D 1545. The testing temperature shall be 210°F (99°C) unless
weigh the dish to the nearest 0.0001 g. Repeat the heating until
a lower temperature is specified.
a constant weight is obtained.
POUR POINT
NOTE 2—This size is suitable for ash contents in the range from 0.02 to
9. Procedure 0.2 %, but in the case of lower or higher ash contents, a larger or smaller
sample may be used. In such cases the result shall be specified or reported
9.1 Determine the pour point in accordance with Test
as follows:“ Ash (...g sample) ... percent.”
NOTE 3—To avoid foaming and loss of sample in the case of samples
6
Reagent Chemicals, American Chemical Society Specifications, American containing moisture, it is advisable to add 1 to 2 mL of absolute alcohol
Chemical Society, Washington, DC. For suggestions on the testing of reagents not before heating.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 16. Calculation
MD. 16.1 Calculate the percentage of ash as follows:
2
D 803
Ash. % 5 ~R/W! 3 100 20. Unsaponifiable Matter
(1)
20.1 Determine the unsaponifiable matter in accordance
where: with Test Method D 1065.
R 5 residue, g, and
W 5 sample, dry basis, g. 21. Fatty Acid Content
16.2 Report the percentage of ash to the third decimal place.
21.1 Determine the fatty acid content in accordance with
CHEMICAL ANALYSIS Test Methods D 1585.
17. Acid Number 22. Precision and Bias (General Statement)

17.1 Determine the acid number in accordance with Test 22.1 Where the test method listed in this standard references
Methods D 465.
another ASTM method, that method should be studied to
18. Saponification Number determine the precision and bias. Other methods listed are well
established, and determination of precision and bias is not
18.1 Determine the saponification number in accordance
practical.
19. Rosin Acid Content 23. Keywords

19.1 Determine the rosin acid content in accordance with 23.1 acid number; fatty acids; rosin acids; saponification
Test Method D 1240. number; tall oil
3
Terminology Relating to
Naval Stores, Including Tall Oil and Related Products1
1. Scope destructively distilled dipentene, n—from the lighter portions

1.1 Although the naval stores industry has been a continuing of the oil recovered during the destructive distillation of pine
producer of chemical products for many centuries, the nature wood.
of the industry, its products, and its terminology have changed. steam-distilled dipentene, n—fractionated from the crude oleo-
In particular, the original practice of recovering naval stores resinous extract during the processing of related steam-
through the processing of the exudate from pine trees (gum distilled wood naval stores.
naval stores) has been supplemented by their extraction by sulfate dipentene, n—from the crude condensate of the vapors
solvent (wood naval stores) and by wood pulping chemicals generated in the digestion of wood in the sulfate paper pulp
(sulfate naval stores). Thus, this terminology contains some old process.
terms now mostly of historic value, together with the terms of ester gum, n—a resin made from rosin and a polyhydric
the modern naval stores industry2. alcohol, generally glycerol or pentaerythritol.
gloss oil, n—a solution of limed rosin or limed rosin acids in
2. Terminology a volatile solvent, used chiefly in surface coatings. (When
made from tall oil, the source is usually indicated.)
abietic acid, commercial grade, n—a product consisting
gum thus, n—botanically, the oleoresin from trees of
chiefly of rosin acids in substantially pure form, separated
Boswellia species native to Arabia and Somaliland.
either from rosin or tall oil commercially for specific
purposes and in which abietic acid and its isomers are the DISCUSSION—Also known as olibanum or frankincense. As applied to
principal components. the naval stores industry, the term refers to the crystallized pine
colophony, n—a term denoting medium and high grades of oleoresin or “scrape” collected from scarified “faces” of trees being
worked for turpentine.
rosin.
crude stripper oil, n—a by-product of the manufacture of d-limonene, n—a purified optically active terpene hydrocar-
citrus juice, composed largely of d-limonene and containing bon recovered from by-products of the citrus industry.
up to 1.5 % of aldehydes. (See also d-limonene.)
DISCUSSION—It is used as a chemical intermediate and as a monomer
dipentene, n—chemically defined as the optically inactive in terpene resins.
form of the monocyclic terpene hydrocarbon limonene.
metallic resinates, n—rosin in which part or all of the rosin
DISCUSSION—Commercial dipentenes contain substantial portions of
acids have been chemically reacted with those metals that
other monocyclic and bicyclic, as well as some oxygenated, terpenes
having closely related boiling ranges. They are generally obtained by give soaps or salts which are water insoluble.
fractional distillation from crude oils recovered in the several commer- DISCUSSION—Limed rosin, zinc-treated rosin, and the resinates of
cial methods of utilizing pine wood, also by isomerization during the lead, cobalt, copper, and manganese, are of the greatest industrial
chemical processing of terpenes. There is no legal requirement under importance.
the Naval Stores Act that the source, origin, or kind of dipentene be
shown in the commercial designation. Consequently, coined trade modified rosin, n—rosin that has been treated with heat or
names are sometimes used in selling this product. The four kinds of catalysts, or both with or without added chemical substances,
commercial dipentene are: so as to cause substantial change in the structure of the rosin
chemically processed dipentene, n—recovered as a product or acids, as isomerization, hydrogenation, dehydrogenation, or
a by-product in connection with the chemical treatment and polymerization, without substantial effect on the carboxyl
conversion of other terpenes. group.
DISCUSSION—The following are types of modified rosin:
1 disproportionated (dehydrogenated) rosin, n—rosin that has been
This terminology is under the jurisdiction of ASTM Committee D-1 on Paint,
Related Coatings, Materials, and Applicationsand is the direct responsibility of
subjected to chemical or physical treatment, or both, so as to cause
Subcommittee D01.34on Naval Stores. substantial simultaneous hydrogenation and dehydrogenation of the
Current edition approved Dec. 10, 1997. Published June 1998. Originally rosin acids to form their hydrogenated and dehydrogenated counter-
published as D 804 – 44 T. Last previous edition D 804 – 92. parts.
2
Zinkel, D. F., and Russell, J., eds., Naval Stores: Production, Chemistry and heat-treated rosin, n—rosin in which a reduction of acid number and a
Utilization, Pulp Chemicals Association, NY, 1989.
1
D 804
positive shift in optical rotation has been brought about by controlled destructively distilled pine oil, n—obtained from the lighter distillate
heat treatment only, in order to improve its suitability for specific uses. from the destructive distillation (carbonization) of pine wood.
hydrogenated rosin, n—rosin that has been treated with hydrogen under steam-distilled pine oil, n—obtained from the crude oleoresinous
conditions that cause a partial or complete saturation of the resin acids extract of pinewood during the processing of related steam-distilled
present, best indicated by a drop in the refractive index. Commercial wood naval stores . sulfate pine oil, n—a high boiling fraction obtained
hydrogenated rosin is usually only partially saturated. in the refining and fractional distillation of crude sulfate turpentine.
synthetic pine oil, n—obtained by chemical hydration of pinenes to
polymerized rosin, n—rosin that has been treated by chemical form monocyclic terpene alcohols, mainly alpha-terpineol.
or physical means, or both, in a manner so as to cause a
union of a part of the rosin acids to form dimers to such an pine tar, n—A product of the destructive distillation of pine
extent that the average molecular weight of such rosin will wood.
be measurably greater than that of the original rosin. Also DISCUSSION—There are several types of pine tar as follows:
known as “dimerged resin.”
monocyclic terpenes, n—a designation sometimes used in the kiln burned, pine tar, n—the heavy, oily liquid resulting from
trade to describe a heterogeneous mixture of monocyclic, controlled carbonization (slow burning) of pine knots and
bicyclic, and other related terpene C10H16 hydrocarbons stump-wood to charcoal in earth-covered piles or 88kilns,”
recovered or removed in the fractionation of certain terpenes with introduction of insufficient air to permit complete
or other essential oils, or as a by-product in the chemical combustion; contains undecomposed resin acids along with
conversion of pinenes generally sold under trade names. the decomposition products. This product is sometimes
called “country tar.”
DISCUSSION—The term “other monocyclic hydrocarbons,” used in pine tar oil, n—the oil obtained by condensing the vapors from
statistical reports of the U.S. Department of Agriculture, covers this the retorts in which resinous pine wood is destructively
type of material.
distilled (carbonized).
naval stores, n—chemically reactive oils, resins, tars, and retort, pine tar, n—the tar produced by removal of volatile oils
pitches derived from the oleoresin contained in, exuded by, from pine tar oil by steam distillation. Several grades are
or extracted from wood chiefly of the pine species ( Genus marketed, namely: Thin, Medium, Heavy, and Extra Heavy,
Pinus). so classified on the basis of viscosity, and depending upon
neutral content, n—the total amount of material contained in the quantity of volatile oils removed.
naval stores, such as rosin, tall oil, and their derivatives that Stockholm, pine tar, n—kiln-burned pine tar produced in
do not contain any acidic functionality. Scandinavian countries from wood of the Northern Euro-
DISCUSSION—Neutral content includes unsaponifiable matter and any
pean pine, Pinus sylvestris.
combined acidic material present as derivatives, such as esters, anhy- pitch—a term to describe a variety of solid or semi solid
drides, or lactones. products isolated from trees as follows:
Archangel pitch, n—originally a genuine pine pitch made from
oil of (pine) tar, n—certain heavier fractions of the volatile oil pine tar in the Archangel district of Russia; in this country a
recovered by distilling pine-tar oil to convert it into pine tar. similar product is made from residues of pine origin blended
oil of turpentine, n—the pharmaceutical name for spirits of with various oils to make a pitch for caulking boats.
turpentine that conforms to the requirements of the National Brewer’s pitch, n—a term used to designate a type of pitch
Formulary. made by blending certain oils, waxes or other ingredients
oleoresin, n—pine gum, the nonaqueous secretion of resin with rosin for the coating of beer barrels.
acids dissolved in a terpene hydrocarbon oil that is produced Burgundy pitch, n—originally the solidified resin obtained by
or exuded from the intercellular resin ducts of a living tree, heating and straining the air-dried solid oleoresin exuded by
and is present, together with oxidation products, in the dead the Norway spruce (Picea excelsa) and European silver fir
wood of weathered limbs and stumps. (Abies pectinata); now denotes an artificial mixture made by
pine needle oil, n—an essential oil of typical fragrance heating rosin with certain fixed oils, the combination being
obtained by steam distillation of the leaves (needles) of used for adhesive plasters.
certain species of pine. Navy pitch, n—a pitch obtained by melting rosin with pine tar,
DISCUSSION—Some imported oils derived from other conifers are with or without rosin distillation residues. The terms Arch-
classified as pine needle oil. angel pitch, Brewer’s pitch, Burgundy pitch, and Navy pitch
pinenes, n—bicyclic terpene hydrocarbons, the principal con- have been in use in the naval stores industry for many years.
stituent of all turpentines and existing therein in two iso- They cover a wide variety of compounded products in which
meric forms, alpha-pinene and beta-pinene. the one constituent common to all is a large proportion of
pine oil, n—a colorless to amber colored volatile oil with rosin.
characteristic pinaceous odor, consisting principally of iso- reclaimed, rosin, n—rosin that has been recovered or re-
meric tertiary and secondary cyclic terpene alcohols, with claimed by any means from waste or deteriorated material,
variable quantities of terpene hydrocarbons, ethers, ketones, provided that the concentration of rosin acids is not below
phenols, and phenolic ethers, the amount and character of that normal for rosin, and any residual or contaminating
which depend on the source and method of manufacture. component from the waste material itself or from any article
used in the recovery process is not in sufficient quantity to
DISCUSSION—The four commercial kinds of pine oil are:
2
D 804
cause the physical or chemical properties of the reclaimed agency. The official grades established by or under authority of the
product to differ materially from those of rosin. Federal Naval Stores Act, for which standards are provided, are as
rectified tar oil, n—the volatile oil that is rectified by steam follows in order of increasing color XC, XB, XA, X, WW, WG, N, M, K,
I, H, G, F, E, D, and FF (the latter grade is used only for wood rosin).
distillation of pine tar, obtained by destructive distillation of Rosin darker in color than the standard for Grade D or FF is graded B.
various species of Pinus. The designation Opaque with the grade letters OP is used to describe
DISCUSSION—It is a thin liquid, having a dark reddish-brown color rosin that, because of a turbid, cloudy, or nontransparent condition due
and a strong empyreumatic odor and taste. It is miscible in all to occluded moisture, excessive crystallization, or presence of foreign
proportions with ethyl alcohol and is used in certain pharmaceutical matter other than dirt, cannot be accurately graded by comparison with
preparations. The specific gravity of rectified tar oil is not less than any of the described rosin grade standards.
0.960 nor more than 0.990 at 77°F (25°C). rosin type (sample), n—a sample of rosin, or a mold of
resinates, metallic—See metallic resinates. thermosetting plastic material, used as an unofficial standard
rosin, n—a specific kind of natural resin obtained as a vitreous in grading rosin.
water-insoluble material from pine oleoresin by removal of DISCUSSION—Such sample shall be so selected, sized, and surface-
the volatile oils, or from tall oil by the removal of the fatty finished that it will have the form of an approximate 7⁄8-in. (22 mm)
acid components thereof. cube with at least two opposite faces having smooth parallel surfaces,
and shall have a color when viewed through these faces which matches
DISCUSSION—It consists primarily of several diterpenoid isomers of within rather narrow tolerances the color of the corresponding official
tricyclic monocarboxylic acids having the general empirical formula Government standard made of glass.
C20H 30O2, with small quantities of compounds saponifiable with
boiling alcoholic potassium or sodium hydroxide, and some unsaponi- scrape, n—the crystallized pine oleoresin collected from the
fiable matter. The three general classifications or kinds of rosin in scarified faces of trees being worked for turpentine.
commerce are: skimmings (tall oil), n—the curd, not acidified or otherwise
gum rosin, n—obtained from the oleoresin collected from living trees.
tall oil rosin, n—obtained by the fractional distillation of tall oil. Such
processed, skimmed from the black liquor of the alkaline
rosin shall have the characteristic form, appearance, and other physical paper pulp industry, from which tall oil is obtained.
and chemical properties normal for other kinds of rosin. spirits of turpentine, n—the volatile oil consisting primarily
wood rosin, n—obtained from the oleoresin contained in dead wood of a number of terpene hydrocarbons of the general formula
such as stumps and knots. C10H16.
rosin acids or resin acids, n—principally monocarboxylic DISCUSSION—Four kinds of turpentine are now recognized:
acids with the empirical formula C19H20—COOH. destructively distilled wood turpentine, n—obtained by fractionation of
certain oils recovered by condensing the vapors formed during the
DISCUSSION—They are classified into two groups: the abietic type and destructive distillation of pine wood.
the pimaric type. Both types and their derivatives are found in wood, gum turpentine or gum spirits, n—obtained by distilling the crude
gum, and tall oil rosins. exuded gum or oleoresin collected from living pine trees.
steam-distilled wood turpentine, n—obtained from the oleoresin within
rosin adducts, n—the addition product between rosin and an
the wood of pine stumps or cuttings, either by direct steaming of the
a, b unsaturated carboxylic acid such as fumaric acid, mechanically disintegrated wood or after solvent extraction of the
acrylic acid or maleic anhydride. oleoresin from the wood.
rosin based resins, n—resinous products derived from rosin or sulfate turpentine, n—recovered during the conversion of wood to
rosin adducts through chemical reaction with raw materials paper pulp by the sulfate process. Refined turpentine is the name for a
such as alcohols (especially polyhydric alcohols), formalde- commercially available grade that is produced by removing primarily
hyde, a,b unsaturated carboxylic acids, phenols etc., or sulfur compounds from sulfate wood turpentine.
DISCUSSION—Various other products use the descriptor “turpentine”.
combinations of these materials. Examples are as follows:
DISCUSSION—Rosin based resins are used extensively in printing inks
and adhesives.
Canada turpentine—same as Canada balsam, the oleoresin
obtained from trees of the Canadian silver fir (Abies bal-
rosin oil, n—the relatively viscous, oily portion of the con- samea).
densate obtained when rosin is subjected to dry destructive sulfite turpentine—this term is not in good usage, because the
distillation; also used to describe specially compounded oils volatile oil recovered in the conversion of wood to pulp by
having a rosin oil base. the sulfite process consists chiefly of cymene (C10H14) rather
rosin reclaimed—See reclaimed rosin. than pinene and other terpenes.
rosin spirits, n—the relatively light, volatile portion of the Venice turpentine—same as larch turpentine, the oleoresin of
condensate obtained in the first stages when rosin is sub- the European larch tree, Larix europea or
jected to dry destructive distillation. Larix decidua—the term is also now used widely to describe
rosin standards, n—the combinations of assembled colored the clear yellow liquid portion of pine oleoresin, or a
glasses having the colors designated as representative of the synthetic product of similar composition made by dissolving
established U.S. grades used in classifying rosin. rosin in a terpene solvent.
DISCUSSION—The recognized official standards are those developed tall oil, n—a generic name for a number of products obtained
and issued by the U.S. Department of Agriculture, or similar standards from the manufacture of wood pulp by the alkali (sulfate)
made of Lovibond glass, when certified by the same Government process or more popularly known as the kraft process.
3
D 804
DISCUSSION—To provide some distinction between the various prod- tall oil rosin—See rosin.
ucts, designations are often applied in accordance with the process or tall oil heads (light ends), n—the low-boiling fractions
composition, some of which are crude tall oil, acid refined tall oil, obtained by the fractional distillation of crude tall oil under
distilled tall oil, tall oil fatty acids, and tall oil rosin. The following
designations for tall oil shall be considered obsolete:
reduced pressure.
Crude resinous liquid Swedish pine oil DISCUSSION—The composition of these products varies over a wide
Finn oil Swedish resin range but includes palmitic, oleic, linoleic, and stearic acids with lesser
Liquid resin Swedish rosin amounts of other saturated and unsaturated acids. The neutral materials
Liquid rosin Swedish rosin oil
content is normally high.
Resin oil Syulvic oil
Sulfate pitch Talloel
Sulfate resin Tallol
tall oil pitch, n—the residue from the distillation of crude tall
Sulfate rosin oil. It is generally recognized that tall oil pitches contain
some high-boiling esters and neutral materials with lesser
acid refined tall oil, n—the product obtained by treating crude
amounts of rosin and fatty acids.
tall oil in solvent solution with sulfuric acid under controlled
tall oil soap, n—the product formed by the saponification or
conditions to remove dark color bodies and odoriferous
neutralization of tall oil with organic or inorganic bases.
materials. Removal of the solvent yields a product with
terpenes, n—a class of unsaturated organic compounds having
lighter color and higher viscosity than crude tall oil with
the empirical formula C10H16 occurring in most essential
approximately the same fatty acids-to-rosin ratio.
oils and oleoresinous plants.
crude tall oil, n—a dark brown mixture of fatty acids, rosin,
and neutral materials liberated by the acidification of soap DISCUSSION—Structurally the important terpenes and their derivatives
skimmings. The fatty acids are a mixture of oleic acid and are classified as monocyclic (dipentene), bicyclic (pinene), and acyclic
(myrcene).
linoleic acid with lesser amounts of saturated and other
unsaturated fatty acids. The rosin is composed of resin acids terpene alcohol, n—an alcohol directly related to or derived
similar to those found in gum and wood rosin. The neutral from a terpene hydrocarbon.
materials are composed mostly of polycyclic hydrocarbons,
DISCUSSION—The following are common examples: terpineol (ter-
sterols, and other high-molecular weight alcohols. tiary cyclic), borneol (secondary cyclic), geraniol (primary, acyclic),
distilled tall oil, n—the class of products obtained by distilling linalool (tertiary, acyclic).
crude tall oil in fractionating equipment under reduced
pressure under such conditions that the ratio of rosin acids to terpene resins, n—the products formed by polymerization of
fatty acids is varied over a wide range. The products that b -pinene, a-pinene, limonene and other terpene hydrocar-
generally contain less than 90 % of fatty acids, are known as bons.
distilled tall oils. turpentine, oil of— See oil of turpentine.
turpentine, spirits of— See spirits of turpentine.
DISCUSSION—The fatty acids are a mixture of oleic and linoleic acids turpentine substitute, n—this term is not recommended,
with lesser amounts of saturated and other unsaturated fatty acids. The because its use to describe a paint thinner of mineral oil
remainder consists of rosin and neutral materials.
origin is illegal under the U.S. Federal Naval Stores Act.
tall oil fatty acids, n—the class of products containing 90 % or unsaponifiable matter, n—the total amount of non-acidic
more fatty acids obtained by fractionation of crude tall oil. organic material, both free and combined, present in naval
stores products such as rosin, tall oil, and their derivatives
DISCUSSION—The fatty acids are a mixture of oleic and linoleic acids after saponification. Unsaponifiable matter is composed
with lesser amounts of saturated and other unsaturated fatty acids. The
remainder consists of rosin and neutral materials.
primarily of alcohols, sterols, aldehydes, and hydrocarbons.
For example, it is material that will not form a soluble soap
tall oil, distilled— See distilled tall oil under tall oil. when refluxed with alcoholic potassium hydroxide.
4
Standard Test Methods of Testing

Cellulose Acetate Propionate and Cellulose Acetate
Butyrate1
1.1 These test methods cover procedures for the testing of 3.1 Purity of Reagents—Reagent grade chemicals shall be
cellulose acetate propionates and acetate butyrates. These used in all tests. Unless otherwise indicated, it is intended that
esters may vary widely in composition and properties, so all reagents shall conform to the specifications of the Commit-
certain of the procedures can be used only in the ranges of tee on Analytical Reagents of the American Chemical Society,
composition where they are suitable. where such specifications are available.4 Other grades may be
1.2 The test procedures appear in the following sections: used, provided it is first ascertained that the reagent is of
Sections sufficiently high purity to permit its use without lessening the
Acetyl Propionyl or Butyryl Contents 28-37 accuracy of the determination.
Acetyl Content, Apparent 18-27
Acidity, Free 12-17
Ash 7-10
4. Conditioning
Color and Haze 77-81 4.1 Conditioning—Condition the test specimens at 23 6
Heat Stability 57-65
Hydroxyl Content 38-44
2°C (73.4 6 3.6°F) and 50 6 5 percent relative humidity for
Hydroxyl Content, Primary 46-50 not less than 40 h prior to test in accordance with Procedure A
Intrinsic Viscosity 67-71 of Methods D 618, for those tests where conditioning is
Moisture Content 5-6
Sulfur or Sulfate Content 51-56
required. In cases of disagreement, the tolerances shall be6
Viscosity 74-75 1°C (61.8°F) and 62 percent relative humidity.
Limiting Viscosity Number 67-71 4.2 Test Conditions—Conduct tests in the Standard Labora-
1.3 This standard does not purport to address the safety tory Atmosphere of 23 6 2°C (73.4 6 3.6°F) and 50 6 5 %
concerns, if any, associated with its use. It is the responsibility relative humidity, unless otherwise specified in the test meth-
of the user of this standard to establish appropriate safety and ods. In cases of disagreements, the tolerances shall be 61°C
health practices and determine the applicability of regulatory (61.8°F) and6 2 % relative humidity.
limitations prior to use.
MOISTURE CONTENT
5. Procedure
2.1 ASTM Standards:
5.1 Transfer about 5 g of the sample to a tared, low,
D 618 Practice for Conditioning Plastics and Electrical
wide-form weighing bottle and weigh to the nearest 0.001 g.
Insulating Materials for Testing2
Dry in an oven for 2 h at 105 6 3°C. Remove the bottle from
D 1343 Test Method for Viscosity of Cellulose Derivatives
the oven, cover, cool in a desiccator, and weigh.
by Ball-Drop Method3
D 2929 Test Method for Sulfur Content of Cellulosic Ma- 6. Calculation
terials by X-Ray Fluorescence3
6.1 Calculate the percentage of moisture as follows:
D 5897 Test Method for Determination of Percent Hydroxyl
on Cellulose Esters by Potentiometric Titration— Moisture, % 5 ~A/B! 3 100 (1)
Alternative Method3 where:
A 5 weight loss on heating, g, and
1
4
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Nov. 10, 1996. Published January 1997. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 817 – 44 T. Last previous edition D 817 – 91. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
MD.
1
D 817
B 5 sample used, g. Test Method A—For Samples Containing Not More than
About 30 % Propionyl or Butyryl
ASH
13. Procedure
7. Significance and Use 13.1 Shake 5 g of the sample, corrected for moisture content
7.1 Ash content gives an estimate of the inorganic content if necessary, in a 250-mL Erlenmeyer flask with 150 mL of
of cellulose ester samples. The presence of high levels of freshly boiled, cold water. Stopper the flask and allow it to
inorganic content (ash) can be detrimental to the melt stability stand for 3 h. Filter off the cellulose ester and wash it with
and optical clarity of a cellulose ester in melt processing or act water. Titrate the combined filtrate and washings with 0.01 N
as a potential source of insolubles when the ester is used in NaOH solution, using phenolphthalein indicator solution.
solution. 13.2 Run a blank determination on the water, using the same
volume as was used in extracting the sample.
8. Procedure
14. Calculation
8.1 Dry the sample for 2 h at 105 6 3°C and weigh 10 to 50
g, to the nearest 0.01 to 0.1 g, depending on its ash content and 14.1 Calculate the percentage of acidity as free acetic acid
the accuracy desired. Burn directly over a flame in a 100-mL as follows:
tared platinum crucible that has been heated to constant weight Free acetic acid, % 5 $@~A 2 B!C 3 0.06#/W% 3 100 (3)
and weighed to the nearest 0.1 mg. Add the sample in portions
if more than 10 g is taken. The sample should burn gently and where:
the portions should be added as the flame subsides. Continue A 5 NaOH solution used to titrate the sample, mL,
heating with a burner only as long as the residue burns with a B 5 NaOH solution used to titrate the blank, mL,
C 5 normality of the NaOH solution, and
flame. Transfer the crucible to a muffle furnace and heat at 550
W 5 sample used, g.
to 600°C for 3 h, or longer if required, to burn all the carbon.
Allow the crucible to cool and then transfer it, while still warm, Test Method B—For Samples Containing More than About
to a desiccator. When the crucible has cooled to room tem- 7 % Propionyl or Butyryl and Particularly Suitable for
perature, weigh accurately to the nearest 0.1 mg. Samples Containing More than 30 % Propionyl or Butyryl
9. Calculation 15. Procedure
9.1 Calculate the percentage of ash as follows: 15.1 Dissolve 10.0 g of the sample, corrected for moisture
Ash, % 5 ~A/B! 3 100 (2) content if necessary, in 200 mL of neutral acetone plus 20 mL
of water. When completely dissolved, add 50 mL of water and
where: shake well to precipitate the ester in a finely divided form. Add
A 5 ash, g, and 3 drops of methyl red indicator solution and titrate to a
B 5 sample used, g. lemon-yellow end point and 0.01 N NaOH solution.
15.2 Make a blank determination on the reagents.
10.1 No statement on bias can be made as no reference 16. Calculation
material is available as a standard. 16.1 Calculate the free acid content as acetic acid as
directed in Section 14.
FREE ACIDITY
17.1 No statement on bias can be made as no reference
11.1 Free acidity is a measure of unesterified organic acid in material is available as a standard.
the ester. The presence of high levels of free acid is potentially
detrimental to melt processing of the ester and can impact the APPARENT ACETYL CONTENT
odor of the ester.
18. Scope
12. Reagents 18.1 The test methods described in the following 20 to 26
12.1 Acetone, neutral. cover the determination of the saponification value of the
12.2 Methyl Red Indicator Solution (0.4 g/L)—Dissolve 0.1 sample calculated as percentage of apparent acetyl, equivalent
g of methyl red in 3.72 mL of 0.1000 N NaOH solution and weight 43. This value is required in the calculation of acetyl
dilute to 250 mL with water. Filter if necessary. and propionyl or butyryl contents in 36.1.
12.3 Phenolphthalein Indicator Solution (1 g/100 mL)— 18.2 The test method used should be specified or agreed
Dissolve 1 g phenolphthalein in 100 mL of ethyl alco- upon. The choice depends on the propionyl or butyryl content
hol (95 % ). and the physical condition of the sample. Ordinarily, Test
12.4 Sodium Hydroxide, Standard Solution (0.01 N)— Method A is recommended for samples having less than about
Prepare and standardize a 0.01 N solution of sodium hydroxide 35 % propionyl or butyryl and Test Method B for samples
(NaOH). having more than that amount.
2
D 817
19. Significance and Use NOTE 1—Potassium acid phthalate is used so that the concentration of
the NaOH in contact with the solvent in the blank will be approximately
19.1 Apparent acetyl content is a measure of the saponifi- the same as that in contact with the sample and so that the titration of the
cation value of the ester. Apparent acetyl value is required in blank will be approximately the same as the titration of the sample, thus
the calculation of acetyl, propionyl, and butyryl content in avoiding errors caused by using a different buret for the titration of the
36.1. blank and the sample or by refilling the 15-mL buret. If desired, however,
the potassium acid phthalate may be omitted.
Test Method A—For Samples Containing Less than About
35 % Propionyl or Butyryl 22.2 For acetone-soluble sample, put the sample into solu-
tion as follows: Add 150 mL of acetone and 5 to 10 mL of
20. Apparatus water and swirl to mix. Stopper the flask and allow it to stand
20.1 Weighing Bottle, glass-stoppered, 15-mL capacity, with occasional swirling until solution is complete. Solution
25-mm diameter by 50 mm high. may be hastened by magnetic stirring or by any suitable
20.2 Tray, copper or aluminum, approximately 137 mm mechanical shaking that will provide a gentle rocking type of
square, containing 25 compartments 25 mm square. Each agitation to avoid splashing the solution on the stopper. It is
compartment shall have the correct dimensions to contain one essential that complete solution be effected.
weighing bottle. The entire tray shall fit inside a desiccator and 22.3 For acetone-insoluble samples of low propionyl or
should have a basket-type handle to facilitate the introduction butyryl content, dissolve the sample by either of the following
and removal of the tray (convenient but not essential). two methods:
20.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem 22.3.1 Gently rotate the flask by hand to distribute and
graduated from 25 to 35 mL in 0.05-mL increments; or pipet, spread the sample in a thin layer over the bottom of the flask.
automatic zero, 30-mL for NaOH solution (40 g/L). Add 70 mL of acetone to the flask and swirl gently until the
20.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem sample particles are completely wetted and evenly dispersed.
graduated from 10 to 15 mL in 0.05-mL increments, for 1 N Stopper the flask and allow it to stand undisturbed for 10 min.
H2SO4. Carefully add 30 mL of dimethyl sulfoxide from a graduate to
20.5 Buret, 5-mL, in 0.01 or 0.1-mL divisions, for back the flask, pouring the solvent down the sides of the flask to
titration with 0.1 N NaOH solution. wash down any sample particles clinging to the side. Stopper
20.6 Magnetic Stirrer, for single flask. the flask and allow it to stand with occasional swirling until
20.7 Magnetic Stirrer, capacity twelve or more flasks. solution is complete. Magnetic stirring or gentle mechanical
20.8 Stirring Bars, stainless steel Type 416, length 50 mm, agitation that will not splash the solution is recommended.
diameter 5 to 6 mm or equivalent, dimensions not critical. When solution appears to be complete, add 50 mL of acetone
and swirl or stir for 5 min. Proceed in accordance with 22.4.
21. Reagents 22.3.2 Dimethyl sulfoxide is the preferred solvent, but if it
21.1 Acetone—Add one 30-mL portion of 1.0 N NaOH is not available, spread the sample in a thin layer over the
solution to a mixture of 150 mL acetone and 100 mL hot water, bottom of the flask, add 15 mL of acetone, swirl to wet the
allow to stand with frequent swirling for 30 min, and titrate particles with acetone, stopper the flask, and allow the mixture
with 1.0 N H2SO4. Add another 30-mL portion of 1.0 N NaOH to stand undisturbed for 20 min. Add 75 mL of pyridine
solution to 100 mL of hot water, allow to stand for 30 min, and without shaking or swirling and allow the mixture to stand for
titrate as above. The difference between the two titrations shall 10 min. Heat the solution just to boiling and swirl or stir for 5
not exceed 0.05 mL. min. Again heat to boiling and swirl or stir for 10 min.
21.2 Dimethyl Sulfoxide. Continue to heat and stir until the mixture is homogeneous and
21.3 Pyridine. all large gel masses are broken down into individual highly
21.4 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of swollen particles. When these highly swollen gel particles are
sodium hydroxide (NaOH) in water and dilute to 1 L. well dispersed and are not fused together in large gel masses,
21.5 Sodium Hydroxide, Standard Solution (0.1 N)— no further heating is necessary. Cool the flask, add 30 mL of
Prepare and standardize a 0.1 N solution of NaOH. acetone, and swirl or stir for 5 min.
21.6 Sulfuric Acid Standard (1.0 N)—Prepare and stan- 22.4 Add 30 mL of NaOH solution (40 g/L) with constant
dardize a 1.0 N solution of sulfuric acid (H2SO4). swirling or stirring to the solution of the sample and also to the
21.7 Phenolphthalein Indicator Solution (1 g/100 mL)— blank. Use of a magnetic stirrer is recommended (Note 2). It is
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol absolutely necessary that a finely divided precipitate of regen-
(95 %). erated cellulose, free of lumps, be obtained. Stopper the flask
and let the mixture stand with occasional swirling or stir on the
22. Procedure magnetic stirring unit. Allow 30 min for saponification of
22.1 Dry the ground well-mixed sample in weighing bottle lower acetyl samples, 2 h for high acetyl samples when
for 2 h at 105 6 3°C and weigh 1.9 6 0.05 g of the dried dimethyl sulfoxide is the solvent, and 3 h when pyridine is the
sample by difference to the nearest 1 mg into a 500-mL solvent. At the end of the saponification period, add 100 mL of
Erlenmeyer flask. Prepare a blank by drying approximately 3.8 hot water, washing down the sides of the flask, and stir for 1 or
g of potassium acid phthalate and weighing it by difference into 2 min. Add 4 or 5 drops of phenolphthalein indicator solution
a flask as described above. Carry the blank through the entire and titrate the excess NaOH solution with 1.0 N H2SO4 (Note
procedure. 3). Titrate rapidly with constant swirling or stirring until the
3
D 817
end point is reached; then add an excess of 0.2 or 0.3 mL of Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol
H2SO4. Allow the mixture to stand with occasional stirring or (95 %).
preferably stir on the magnetic stirrer for at least 10 min. Then 24.4 Pyridine – Alcohol Mixture—Mix equal volumes of
add 3 drops of phenolphthalein indicator solution to each flask pyridine and methyl alcohol.
and titrate the same excess of acid with 0.1 N NaOH solution 24.5 Sodium Hydroxide, Aqueous Solution (20 g/L)—
to a persistent phenolphthalein end point. Take extreme care to Dissolve 20 g of sodium hydroxide (NaOH) in water and dilute
locate this end point; after the sample is titrated to a faint pink to 1 L with water.
end point, swirl the mixture vigorously or place it for a moment 24.6 Sodium Hydroxide, Methanol Solution (20 g/L)—
on the magnetic stirrer. If the end point fades because of acid Dissolve 20 g of NaOH in 20 mL of water and dilute to 1 L
soaking from the cellulose, continue the addition of 0.1 N with methyl alcohol.
NaOH solution until a faint persistent end point remains after
vigorous swirling or stirring. Titrate the blank in the same 25. Procedure
manner as the sample. 25.1 Dry the sample for 2 h at 105 6 3°C and cool in a
NOTE 2—While the amount of magnetic stirring is somewhat optional, desiccator. Weigh 0.5-g portions of the sample to the nearest
such stirring during the entire period of the determination is strongly 0.005 g and transfer to 250-mL glass-stoppered Erlenmeyer
recommended. Solution is more rapid, titrations are more rapid, and the flasks. Dissolve each sample in 100 mL of appropriate solvent
end point can be approached directly and without a back titration. (see 25.2 and 25.3) and prepare at least two blanks, which shall
NOTE 3—It is important to correct all 1.0 N H2SO4 buret readings for be carried through all steps of the procedure.
temperature and buret corrections. 25.2 Samples Containing 30 to 45 % Propionyl or
23. Calculation Butyryl—Dissolve in 100 mL of the acetone–alcohol mixture.
Add water and aqueous NaOH solution from a buret or pipet in
23.1 Calculate the percentage by weight of acetyl as fol- the following order and swirl the contents of the flask vigor-
lows: ously during all additions: 10 mL of NaOH solution, 10 mL of
Acetyl, % 5 $@~D 2 C!Na 2 ~B 2 A!Nb 1 P# 3 0.04305%/W 3 100 water, 10 mL of NaOH solution, 5 mL of water, 20 mL of
(4) NaOH solution, and 5 mL of water. Stopper and allow to stand
P 5 ~GH 3 1000!/204.2 ~Note 4! at room temperature for 16 to 24 h.
25.3 Samples Containing More than 45 % Propionyl or
where: Butyryl—Dissolve in 100 mL of the pyridine–alcohol mixture.
A 5 NaOH solution required for titration of the sample,
Add 30 mL of the methanol solution of NaOH from a pipet or
mL,
buret slowly, with swirling. Add 20 mL of water slowly in
B 5 NaOH solution required for titration of the blank,
about 2-mL portions, with swirling, and swirl the flask until the
mL,
Nb 5 normality of the NaOH solution, solution becomes turbid. Stopper and allow to stand overnight
C 5 H2SO4 required for titration of the sample, mL at room temperature.
D 5 H2SO4 required for titration of the blank, mL, 25.4 Back-titrate the excess NaOH with 0.5 N HCl just to
Na 5 normality of the H2SO4, the disappearance of color, using phenolphthalein indicator
P 5 milliequivalents of potassium acid phthalate, solution.
G 5 potassium acid phthalate used, g,
H 5 purity factor for potassium acid phthalate, and 26. Calculation
W 5 sample used, g. 26.1 Calculate the apparent acetyl content as follows:
NOTE 4—When equal volumes of alkali or acid are added to samples Apparent acetyl, % 5 $@~A 2 B!Na 3 0.04305#/W% 3 100 (5)
and blank, these amounts cancel out. Thus only the amounts of each added
in the titration enter into the calculations. Use of potassium acid phthalate where:
in the blank is recommended. When it is not used, the term P drops out of A 5 HCl required for titration of the blank, mL,
the equation. B 5 HCl required for titration of the sample, mL,
Na 5 normality of the HCl, and
Test Method B—For Cellulose Esters Containing More than W 5 sample used, g.
30 % Propionyl or Butyryl, by Varying the Reagents5
24. Reagents
24.1 Acetone–Alcohol Mixture—Mix equal volumes of ac- material is available as a standard.
etone and methyl alcohol.
24.2 Hydrochloric Acid, Standard (0.5 N)—Prepare and ACETYL AND PROPIONYL OR BUTYRYL
standardize a 0.5 N solution of hydrochloric acid (HCl). CONTENTS
24.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
28. Scope
5
28.1 The test methods described in the following Sections
Malm, C. J., Genung, L. B., Williams, R. F., Jr., and Pile, M. A., “Analysis of
Cellulose Derivatives: Total Acyl in Cellulose Organic Esters by Saponification in
30 to 36 cover the determination of acetyl and propionyl or
Solution,” Industrial and Engineering Chemistry, Analytical Edition, IENAA, Vol butyryl contents of cellulose mixed esters by calculation from
16, 1944, pp. 501–504. the apparent acetyl content, determined in accordance with
4
D 817
Sections 18 to 26, and the molar ratio of acetyl and propionyl
or butyryl, determined in accordance with Sections 30 to 35.
The molar ratio of acetyl and propionyl or butyryl is deter-
mined by saponifying, acidifying, vacuum distilling off the
mixture of acids, and determining the distribution ratio of the
acids between n-butyl acetate and water. The distribution ratios
are also determined for acetic, propionic, and butyric acids,
using samples of known high purity, and the molar ratio of the
acids in the sample is calculated from these values.6
28.2 The saponification conditions are varied depending on
the propionyl or butyryl content of the sample. Use Procedure
A (Section 32) for samples containing less than about 35 %
propionyl or butyryl, and use Procedure B (Section 33) for
samples containing more than that amount.
28.3 Analyses for combined acetic, propionic, and butyric
acids may be done by gas chromatographic methods. Difficul-
ties encountered include ghosting in the columns, variation of
factors with composition, and inconsistencies in the use of pure
acids as standards. When such methods are used for this
purpose, they shall be cross checked with the following
partition method using suitable check batches to establish
accuracy.
29.1 Acetyl and propionyl or butyryl content is a measure of
the amount of each of these acids esterified onto the cellulose
A—Flask containing sample (500-mL, round-bottom).
backbone of the polymer. The amount of substitution of these B—Capillary inlet tube.
esters has a very strong effect on the polymer’s solubility and C—Kjeldahl distilling head.
physical properties. D—Condenser.
E—Receiver (500-mL distilling flask).
F—Opening for adding water.
30. Apparatus G—Water bath for heating sample.
30.1 Vacuum Distillation Apparatus—The vacuum distilla- H—Cooling bath for receiver.
I—Side arm, connected to vacuum line.
tion apparatus shown in Fig. 1 will be required. The 500-mL FIG. 1 Vacuum Distillation Apparatus for Mixed-Ester Analysis
round-bottom flask, A, shall be fitted with a stopper carrying a
very small capillary inlet tube, B, and a Kjeldahl distilling
head, C. The Kjeldahl distilling head shall be connected to a mL of the n-butyl acetate with 30 mL of water in a 125-mL
vertical condenser, D, having an outlet tube long enough to separatory funnel for about 1 min. Allow to settle, draw off the
reach within 76.2 mm of the bottom of the 500-mL distilling water layer, and titrate with 0.1 N NaOH solution, using
flask, E, used as a receiver. The Kjeldahl distilling head shall be phenolphthalein as the indicator. If this requires more than 0.02
equipped with a funnel or stoppered opening, F, for adding mL of 0.1 N NaOH solution, the butyl acetate should be
extra water during the distillation. A water bath, G, for heating purified or a correction for acidity applied to each titration.
the sample and a cooling bath, H, for cooling the receiver shall 31.4 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured).
be provided. 31.5 Phosphoric Acid (1 + 14)—Dilute 68 mL of phospho-
ric acid (H3PO4, 85 %) to 1 L with water. Titrate the NaOH
31. Reagents solution (20 g/L) with this acid to a yellow end point, using
31.1 Acetic, Propionic, and Butyric Acids—Acetic, propi- bromcresol green indicator solution, and calculate the volume
onic, and butyric acids of tested purity. of the acid (approximately 50 mL) required for 100 mL of the
31.2 Bromcresol Green Indicator Solution (0.4 g/L)—Grind NaOH solution.
0.1 g of tetrabromo-m-cresolsulfonphthalein in a mortar with 31.6 Sodium Hydroxide Solution (20 g/L)—Dissolve 20 g of
14.3 mL of 0.01 N NaOH solution and dilute to 250 mL. sodium hydroxide (NaOH) in water and dilute to 1 L.
31.3 n-Butyl Acetate—Prepare n-butyl acetate for use as an 31.7 Sodium Hydroxide, Standard Solution (0.1 N)—
extraction solvent, free of acidity and water and containing not Prepare and standardize a 0.1 N solution of NaOH.
more than 2 % butyl alcohol. Check for acidity by shaking 60
Isolation of the Mixed Acids
6
Malm, C. J., Nadeau, G. F., and Genung, L. B., “Analysis of Cellulose 32. Procedure A—For Samples Containing Less than
Derivatives: Analysis of Cellulose Mixed Esters by the Partition Method,” Indus- About 35 % Propionyl or Butyryl
trial and Engineering Chemistry, Analytical Edition, IENAA, Vol. 14, 1942, pp.
292–297. This reference may be consulted for application to other mixed esters and 32.1 Heat duplicate 3-g portions of the sample, not espe-
to three-component mixtures. cially dried nor accurately weighed, with 100 mL of NaOH
5
D 817
solution (20 g/L) in 500-mL, round-bottom, chemically resis- K 5 ~M1/M! 3 100 (6)
tant glass flasks in a water bath at 40°C for 48 to 72 h. At the NOTE 6—It should be kept in mind that all these determination are
end of this time add the required amount (approximately 50 ratios and not quantitative; however, accuracy of duplication is very
mL) of H3PO4 (1 + 14) to each flask to form monosodium important. All measurements must be made as exactly as those made by
phosphate, which liberates the organic acids from their sodium standardizations of the solutions and equipment.
salts. 34.2 In the same manner determine the distribution ratios
32.2 Assemble the vacuum distillation apparatus as illus- for acetic, propionic, and butyric acids. Dilute a sample of each
trated in Fig. 1. Heat the 500-mL round-bottom flask contain- acid of tested purity with water to give an approximately 0.1 N
ing the sample in a water bath, and vacuum-distill the acid solution. Titrate 25-mL portions and extract 30-mL portions,
solutions to dryness, allowing a small stream of air bubbles to following exactly the same procedure as used for the mixtures
enter to avoid bumping. Keep the receiver cooled to 0°C. Add (34.1). Calculate the partition ratios for the pure acids, as
25 mL of water to the residue in each flask and again distill to decimal fractions, as follows (Note 7):
dryness. Repeat the distillation to dryness with a second 25-mL k 5 M1/M (7)
portion of water.
where:
NOTE 5—In this operation it is not necessary to work with quantitative
accuracy at all stages, but it is necessary to obtain water solutions of the
ka 5 distribution ratio for acetic acid under the conditions
acids in the same ratios as they occur in the esters. The volume of the described,
distillate and rinsings is usually 200 to 250 mL, which in the majority of kp 5 distribution ratio for propionic acid under the condi-
cases automatically adjusts the acidity of the distillate to 0.06 to 0.12 N, tions described, and
the range desired for subsequent extractions. kb 5 distribution ratio for butyric acid under the conditions
32.3 Continue as directed in Section 34. described.
NOTE 7—The constants must be checked occasionally and must be
33. Procedure B—For Samples Containing More than determined by each operator for each supply of butyl acetate. Blanks
About 35 % Propionyl or Butyryl should be run on the butyl acetate, since it may develop acidity on
33.1 Weigh duplicate 3-g samples, not especially dried nor standing, particularly if it contains a little water. All measurements should
accurately weighed, into 500-mL round-bottom flasks and add be made with good pipets or burets and extreme care and cleanliness
observed during the whole operation. The accuracy of the procedure can
100 mL of Formula 2B, 3A, or 30 denatured ethyl alcohol and be checked by testing an acid mixture of known composition.
100 mL of NaOH solution (20 g/L) to each flask. Allow the
samples to stand stoppered at room temperature for 48 to 72 h. 35. Calculation
At the end of this period, filter off the regenerated cellulose, 35.1 Calculate the molar ratios of acetic and propionic or
collecting the filtrates in 500-mL round-bottom flasks. butyric acids in the mixed acids as follows (Note 8):
33.2 Assemble the vacuum-distillation apparatus as illus- P 5 ~100ka 2 K!/~ka 2 kp! (8)
trated in Fig. 1. Heat the flasks in the water bath and
A 5 100 2 P (9)
vacuum-distill off all the alcohol. After distilling to dryness,
release the vacuum, rinse out the distillation heads, condensers, B 5 ~100ka 2 K!/~ka 2 kb! (10)
and receivers, and discard the distillates and rinsings. A 5 100 2 B (11)
33.3 Add the required amount, about 50 mL, of H3PO4
(1 + 14) to form monosodium phosphate, which liberates the where:
P 5 percentage of propionic acid, mol,
organic acids from their sodium salts. Also add 100 mL of
B 5 percentage of butyric acid, mol,
water to each flask and reassemble the distillation apparatus. A 5 percentage of acetic acid, mol,
Vacuum-distill the volatile acids as described in 32.2. K 5 percentage distribution ratio of the acids in the distil-
33.4 Continue as directed in Section 34. late (34.1),
Determination of the Molar Ratios of the Acids ka 5 distribution ratio of acetic acid (34.2),
kp 5 distribution ratio of propionic acid (34.2), and
34. Procedure kb 5 distribution ratio of butyric acid (34.2).
34.1 Titrate a 25-mL portion of the distillate (32.2) with 0.1 NOTE 8—In order to evaluate two unknowns, two simultaneous alge-
N NaOH solution, using phenolphthalein as the indicator. braic equations involving the two unknown quantities are necessary. In the
Designate the volume of NaOH solution required as M. Shake case of a binary acid mixture, the sum of the mol percentages of the acids
present represents the total acidity, or 100 %. If A and B represent the mole
30 mL of the distillate in a small separatory funnel with 15 mL
percentages of acetic and butyric acids, respectively:
of n-butyl acetate. Measure these volumes accurately using
A 1 B 5 100 (12)
pipets and burets. Shake the mixture thoroughly for 1 min,
allow the layers to separate for 2 min, and draw off the aqueous Aka 1 Bkb 5 K (13)
(lower) layer. Pipet out 25 mL of the solution and titrate with The distribution ratios ka and kb are known and refer to the
0.1 N NaOH solution (Note 6). Designate the volume of NaOH pure individual acids, whereas the distribution ratio K refers to
solution required as M1. Calculate K, the percentage partition the binary mixture. By solving these equations for B, the
ratio of the acids in the distillate, as follows: equations given in this section may be derived.
6
D 817
Calculation of Acetyl, Propionyl, and Butyryl Contents strong effect on the polymer’s solubility and physical proper-
ties. Hydroxyl content also impacts the propensity for this
36. Calculation polymer to crosslink with various crosslinking agents.
36.1 Calculate the percentages by weight of acetyl, propio-
nyl, and butyryl as follows: 41. Apparatus
Acetyl, % 5 AC/100 (14) 41.1 Spectrophotometer, complete with hydrogen light
Propionyl, % 5 ~PC/100! 3 ~57/43! (15)
source and a set of four 1.00-cm quartz cells or an equally
suitable apparatus. The wavelength calibration, as checked
Butyryl, % 5 ~BC/100! 3 ~71/43! (16)
against a mercury lamp, shall be within the manufacturer’s
where: tolerances. As a further check, measure the density of a
A 5 percentage of acetic acid (Section 35), mol, potassium chromate (K2CrO4) solution prepared as follows:
P 5 percentage of propionic acid (Section 35), mol, Dissolve 0.0400 g of K2CrO4 or 0.0303 g of potassium
B 5 percentage of butyric acid (Section 35), mol, and dichromate (K2Cr2O7) in 0.05 N potassium hydroxide (KOH)
C 5 percentages by weight of apparent acetyl (Sections 23 solution and dilute to 1 L in a volumetric flask with 0.05 N
and 26). KOH solution. Using the hydrogen lamp measure the absor-
36.2 Hydroxyl can be measured precisely, particularly at bance at 280 nm of a silica cell filled with the K2CrO4 solution
high degrees of esterification (Sections 38 to 44). It is therefore and also of the same cell filled with water. The absorbance of
sometimes advantageous to base the calculation of weight the solution minus that of the blank shall be 0.723 6 0.023.
percentages of acetyl, propionyl, and butyryl on hydroxyl 41.2 Bottles, 112-g (4-oz), with screw caps, for washing the
content rather than on apparent acetyl as in 36.1. The equations samples.
for this calculation are as follows: 41.3 Special Reflux Tubes for the carbanilation, constructed
For cellulose acetate propionates: as follows (see Fig. 2): Make a test tube approximately 20 by
Acetyl, % 5 9.15A ~31.5 2 h!/~786 2 A! (17) 150 mm from the outer part of a standard-taper 24/40 ground-
glass joint by closing the open end in a blast lamp. Draw the
Propionyl, % 5 2.93P ~31.5 2 h!/~786 2 A! (18)
tubing on the inner joint to a constriction just above the joint.
For cellulose acetate butyrates: Cut the glass at the point and seal on a short length of 8-mm
Acetyl, % 5 4.88A ~31.5 2 h!/~443 2 A! (19) tubing to provide a bearing for a glass stirrer. Make a stirrer of
Butyryl, % 5 8.05B ~31.5 2 h!/~443 2 A! (20)
4-mm glass rod with a semicircle at right angles to the shaft at
the bottom and small enough to fit into the test tube. When
where, in addition to the definitions of terms in 36.1:
h 5 weight percentage of hydroxyl (Section 44).
NOTE 9—This calculation involves the assumption that there are
exactly three hydroxyls, free plus esterified, for each anhydroglucose unit
of cellulose.

material is available as a standard.
HYDROXYL CONTENT
38. Scope
38.1 This test method is applicable to pyridine-soluble
cellulose esters and is especially useful when the hydroxyl
content is low. (Samples containing plasticizer may be ana-
lyzed directly by this test method because the plasticizer is
removed during washing of the carbanilate).
38.2 A preferred method is available in Test Method
D 5897.
39. Summary of Test Method
39.1 Hydroxyl in cellulose esters is determined by reaction
with phenyl isocyanate in pyridine solution under anhydrous
conditions to form the carbanilate derivative. The derivative is
then analyzed for its carbanilate content by ultraviolet absorp-
tion.
40.1 Hydroxyl content is a measure of the free hydroxyl on
the cellulose backbone of the polymer. Hydroxyl content has a FIG. 2 Special Reflux Tube for Carbanilation
7
D 817
properly constructed this unit acts as an air condenser, thus was precipitated in cold 80 % alcohol. In this case, wash the
preventing the loss of solvent by evaporation. precipitate in cold 90 % alcohol. Washing is best accomplished
41.4 Pipet, serological type, 5-mL capacity, graduated in by transferring the precipitate to a 4-oz screw cap bottle
0.1-mL divisions. containing about 75 mL of alcohol and shaking for 1⁄2 h on an
41.5 Büchner Funnel, of a size accommodating 90-mm automatic shaker. Filter, pressing out as much liquid as
filter paper. possible with a glass stopper. Repeat the washing and filtering
41.6 Automatic Shaker, with speed regulator mechanism. operations twice more.
41.7 Electric Oven, maintained at 105 6 3°C.
NOTE 10—Samples of high hydroxyl content and large amounts of
41.8 Oil Bath, equipped with a rack to hold several of the propionyl or butyryl may give gummy precipitates when poured into cold
special reflux tubes. This bath shall be kept between 115 and 80 % alcohol. Samples of this type give improved precipitates when
120°C. precipitated in the reverse manner. Pour the diluted reaction solution into
a 600-mL beaker, taking care to distribute the solution evenly on the
42. Reagents bottom. Chill the beaker in a brine bath for 30 to 60 s. Pour about 200 mL
42.1 Acetone. of cold 80 % alcohol onto the chilled liquid. Wash the resulting precipitate
and filter in the usual manner using cold 90 % alcohol.
42.2 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured).
42.3 Methylene Chloride–Methyl Alcohol Mixture—Mix 9 43.5 Allow the precipitate to air-dry 1 to 2 h at room
parts by weight of methylene chloride with 1 part of methyl temperature with good ventilation or preferably overnight to
alcohol. This mixture should have an absorbance of less than ensure complete removal of the alcohol. (Samples wet with
0.2 at 280 nm in a 1.00-cm silica cell measured against air. alcohol may sinter and stick to paper or glass when dried at
Pure methylene chloride has an absorbance of about 0.05, but 105°C.) Dry the sample at 105°C in the oven for 1 h and cool
the commercial product may have an absorbance as high as in a desiccator. Small manila envelopes are convenient for
1.00. The methylene chloride and methyl alcohol should be drying and cooling the samples.
selected to have low absorbance; otherwise, they should be 43.6 Weigh 0.1231 g of the dry precipitate into a 100-mL
redistilled. volumetric flask fitted with a ground-glass stopper. Add 60 to
42.4 Phenyl Isocyanate. 80 mL of methylene chloride-methyl alcohol mixture, and
42.5 Pyridine, redistilled, of low water content, preferably shake occasionally until complete solution occurs. Dilute to
less than 0.05 %. 100 mL and mix thoroughly. Using the spectrophotometer with
a 1-cm silica cell, measure the absorbance of the solution at
43. Procedure 280 nm against the solvent mixture as a reference.
43.1 In the following procedure the phenyl isocyanate
reagent shall be used under anhydrous conditions. Therefore, 44. Calculations
the sample, containers, pipet, and all other equipment shall be 44.1 Calculate the percentage of carbanilate, c, for a sample
thoroughly dried. weight of 0.1231 g as follows:7
43.2 Place a 0.5-g sample in a special reflux tube and dry in Carbanilate, % 5 A 3 17.1 (21)
an electric oven at 105 6 3°C for 2 h. Remove the tube from
the oven, add 5 mL of pyridine, assemble the reflux apparatus where:
complete with glass stirring rod, and place in the 115 to 120°C A 5 absorbance.
oil bath. Stir occasionally until the sample is completely 44.2 Calculate the percentage of hydroxyl as follows:
dissolved. Add 0.5 mL of phenyl isocyanate, stir thoroughly, Hydroxyl, % 5 14.3c / ~100 2 c! (22)
and reflux in the oil bath for 1⁄2 h to complete the reaction. Use
0.1 mL of phenyl isocyanate for each 1 % of estimated 45. Precision and Bias
hydroxyl content, but never less than 0.5 mL. 45.1 No statement on bias can be made as no reference
43.3 At the end of the reaction time, remove the sample and material is available as a standard.
dilute it with acetone to the proper viscosity for precipitation.
The amount of acetone used to thin the solution is a critical PRIMARY HYDROXYL CONTENT
factor in acquiring a good precipitate. Samples having low 46. Summary of Test Method
viscosity require little, if any, dilution. The average sample
46.1 The primary hydroxyl content of cellulose ester is
requires the addition of about an equal volume of acetone.
determined by formation of the triphenylmethyl (trityl) ether
Precipitate the carbanilate by pouring the solution into about
and measurement of the trityl group by ultraviolet absorbance.7
200 mL of ethyl alcohol, or if the ester contains more than 20
Trityl chloride reacts preferentially with primary hydroxyls.
percent propionyl or butyryl, into the same volume of cold
Since there is also a slight reaction with secondary hydroxyls,
80 % alcohol. Stir the alcohol vigorously during the precipita-
standardized reaction conditions are important.8
tion. The precipitate should be fluffy and white. Sticky precipi-
tates indicate too little dilution. Filter off the precipitate using
paper on a Büchner funnel, with suction applied only as long as 7
Malm, C. J., Tanghe, L. J., Laird, B. C., and Smith, G. D., “Determination of
is necessary to remove the bulk of the solvent; prolonged Total and Primary Hydroxyl in Cellulose Esters by Ultraviolet Absorption Meth-
ods,” Analytical Chemistry, ANCHA, Vol 26, 1954, p. 189.
suction may cause undesirable clumping together of the 8
Malm, C. J., Tanghe, L. J., and Laird, B. C., “Primary Hydroxyl Groups in
precipitate. Hydrolyzed Cellulose Acetate,” Journal of the American Chemical Society, JACSA,
43.4 Wash the precipitate with alcohol, unless the sample Vol 72, 1950, p. 2674.
8
D 817
47. Apparatus derivative into a 100-mL volumetric flask fitted with a ground-
47.1 See Section 41. glass stopper, and dissolve in the methylene chloride-methyl
alcohol mixture. Dilute to 100 mL and mix thoroughly.
48. Reagents Measure the absorbance of this solution in a 1-cm silica cell
48.1 Acetone. using a spectrophotometer at 259 nm against the solvent as a
48.2 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured). reference.
48.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9
parts by weight of methylene chloride with 1 part of methyl 50. Calculation
alcohol. This mixture should have an absorbance of less than 50.1 Calculate the trityl content, t, for this concentration of
0.2 at 259 mm in a 1-cm silica cell measured against air; 0.1 g/100 g and with a correction of 0.015 for the absorbance
otherwise, the solvents should be redistilled. of the cellulose acetate as follows:8
48.4 Pyridine, redistilled to a water content less than Trityl, % 5 25.25~A 2 0.015! (23)
0.05 %. The water content may be reduced further by storing
over a suitable drying agent, such as a molecular sieve, Type where:
4A. A 5 absorbance.
48.5 Trityl Chloride (Chlorotriphenylmethane or Triph- 50.2 Calculate the weight percentage of primary hydroxyl
enylmethyl Chloride). as follows:
49. Procedure Primary hydroxyl, % 5 7.02 t/~100.4 2 t! (24)
49.1 The reagents must be used under anhydrous condi- 50.3 Calculate the percentage primary hydroxyl of the total
tions. It is imperative that the sample and all equipment be hydroxyl as follows:
thoroughly dry. Primary hydroxyl of total hydroxyl, % 5 ~B/C! 3 100 (25)
49.2 Place a 0.5-g sample in the test tube of the special
reflux apparatus and dry for 2 h at 105 6 3°C. Add 5 mL of where:
pyridine, insert the top of the reflux apparatus and the stirring, B 5 value of primary hydroxyl as determined in 50.2, and
and heat with stirring in a 115 to 120°C oil bath. After the C 5 value of total hydroxyl as determined in 44.2.
sample has dissolved, add 0.5 g of trityl chloride. If the total
SULFUR OR SULFATE CONTENT
hydroxyl content exceeds 3 %, use an additional 0.075 g of
trityl chloride for each additional 1 % hydroxyl. Stir the 51. Summary of Test Method
mixture thoroughly and reflux in the oil bath for exactly 2 h at
115 to 120°C. Remove the tube and cool. 51.1 The sulfur or sulfate content of cellulose acetate is
49.3 Dilute the sample with acetone to the proper viscosity measured by oxidizing the sample in a nitric acid-perchloric
for precipitation. The amount of acetone used to thin the acid mixture and determined gravimetrically as barium sulfate.
solution is a critical factor in obtaining a good precipitate. To determine combined sulfur the sample must first be repre-
Samples having low viscosity require little, if any, dilution. The cipitated into dilute acid to remove noncombined sulfur com-
average sample requires the addition of about an equal volume pounds.
of acetone. Precipitate the trityl derivative by pouring the 51.2 The sulfur or sulfate content may also be determined
solution into about 200 mL of ethyl alcohol with vigorous by Test Method D 2929, The X-ray method shall be calibrated
stirring. The precipitate should be fluffy and white. Sticky against the chemical method following in Sections 53 to 54,
precipitates indicate too little dilution. Separate the precipitate and the sample shall be treated in accordance with 53.1, if
by filtering through paper on a Büchner funnel, with suction combined sulfur is to be determined.
applied only as long as necessary to remove the bulk of the
solvent; prolonged suction may evaporate the alcohol and
cause the precipitate to partially redissolve in the remaining 52.1 Sulfur and sulfate content indicates the amount of
pyridine. sulfur in the cellulose ester either as inorganic salts (usually
49.4 Wash the precipitate by transferring it to a 4-oz screw sulfates) or as organic sulfate (usually as sulfate ester com-
cap bottle containing 75 mL of ethyl alcohol, capping securely, bined to the cellulose backbone). The presence of high levels of
and shaking for 1⁄2 h on a shaker at medium speed. Again sulfur and sulfate can be detrimental to the melt stability of the
collect the precipitate on a Büchner funnel, pressing out as ester.
much liquid as possible with a glass stopper. Repeat this
washing and filtering operation twice more, or until the 53. Apparatus
absorbance of the filtrate at 259 nm is about the same as that of 53.1 Funnel, modified by cutting the stem off at the apex of
an alcohol blank. Allow the precipitate to air-dry on the filter the funnel and fire polishing.
paper for 1⁄2 h at room temperature with good ventilation, or 53.2 Crucibles, 30-mL, extra-fine porosity.
preferably overnight, to remove most of the alcohol. (Samples 53.3 Oven, controlled at 120 to 125°C.
wet with alcohol may sinter or stick to paper or glass when 53.4 Muffle Furnace, controlled at 800 6 50°C.
dried at 105°C). Transfer the sample to a manila envelope, dry
it for 1 h at 105°C, and cool in a desiccator. 54. Reagents
49.5 Weigh a 0.1231-g sample of the dry trityl ether 54.1 Acetone.
9
D 817
54.2 Acetic Acid (1 + 49)—Mix 1 volume of glacial acetic front of the hood until the reaction is complete. Place the flask
acid with 49 volumes of water. back on the hot plate and continue the digestion until the
54.3 Barium Chloride Solution (100 g/L)—Dissolve 100 g HClO4 refluxes about half way up the side of the Erlenmeyer
of barium chloride (BaCl2·2H2O) in water and dilute to 1 L. flask and about 5 mL is left in the flask. The HNO3–HClO4
54.4 Hydrochloric Acid (1 + 1)—Mix 1 volume of concen- mixture should be clear and colorless. If it is not, set the flask
trated hydrochloric acid (sp gr 1.19) with 1 volume of water. off the hot plate to cool and then add 3 to 5 mL of HNO3 (sp
54.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid gr 1.42). Replace the flask on the hot plate and continue heating
(HNO3). until the HClO4 refluxes half way up the flask. Remove the
54.6 Nitric Acid (2 + 3)—Mix 2 volumes of concentrated flask from the hot plate and allow the flask and its contents to
nitric acid (sp gr 1.42) with 3 volumes of water. cool.
54.7 Nitric Acid-Perchloric Acid Mixture—Mix 5 volumes
of concentrated HNO3 with 1 volume of concentrated perchlo- Determination of Barium Sulfate
ric acid (HClO4, 70 %). 55.5 Wash the modified funnel top thoroughly with water,
54.8 Phenolphthalein Indicator Solution (1 g/100 ml)— collecting the rinsings in the flask. Add 50 mL of water. Swirl
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol the flask to mix the solution thoroughly. Add 2 drops of
(95 %). phenolphthalein indicator solution and neutralize the acid with
54.9 Silver Nitrate Solution (50 g/L)—Dissolve 50 g of the NaOH solution to a faint pink. Acidify immediately with
silver nitrate (AgNO3) in water and dilute to 1 L. HCl (1 + 1), dropwise, until the solution is just acid to
54.10 Sodium Carbonate—(Na2CO3). phenolphthalein; then add 2 mL of HCl (1 + 1).
54.11 Sodium Hydroxide Solution (400 g/L)—Dissolve 400 55.6 Filter through a 12.5-cm fine-porosity paper into a
g of sodium hydroxide (NaOH) in water and dilute to 1 L. clean 400-mL beaker. Wash the flask thoroughly with water,
filtering the washings through the paper. Finally wash the paper
55. Procedure
thoroughly with ten portions of hot water. Dilute the filtrate to
Treatment Prior to Analysis approximately 200 mL. Place the beaker on the hot plate and
55.1 Remove uncombined sulfur as follows (Note 11): heat almost to boiling. Slowly add 10 mL of BaCl2 solution
Dissolve 25 g of sample in approximately 300 mL of acetone, from a pipet, stirring the solution during the addition. Do not
depending on the viscosity. If the sample is of too high acetyl add the BaCl2 solution rapidly, as from a graduate, since the
content to be directly soluble in acetone, cool in a dry ice rapid addition will produce an impure precipitate. Remove the
cabinet overnight; then allow to come to room temperature stirring rod from the beaker and wash it with a stream of water
while tumbling or stirring. Filter the solution, if necessary, from the wash bottle, collecting the washings in the beaker.
through felt or a coarse sintered-glass crucible. Precipitate with Cover the beaker with a watch glass and keep the mixture near
rapid stirring into a beaker or pail containing 2 to 3 L of acetic the boiling temperature for 6 h or overnight. Do not allow the
acid (1 + 49). Filter through a cloth bag or a Büchner funnel liquid to evaporate to dryness.
and give two 15-min washes with water using mechanical 55.7 Using suction, decant the supernatant liquid through an
agitation. A little Na2CO3 may be added to the last wash to extra-fine porosity porcelain filter crucible that has been
stabilize samples of high sulfur content. Filter and dry over- previously rinsed with acetone, ignited, and weighed to the
night at 60°C. nearest 0.1 mg. Transfer the precipitate with the aid of a stream
of hot water. Always use a stirring rod in this transfer. Scrub the
NOTE 11—To analyze for total sulfur content omit this treatment.
sides and bottom of the beaker with a rubber policeman to
Decomposition remove any adhering precipitate. The crucibles may be used to
collect several precipitates one on top of the other. Close
55.2 Weigh 10 6 0.1 g of cellulose acetate and transfer to a
control of temperature and time of heating and cooling are
clean wide-mouth, 500-mL Erlenmeyer flask. Add 50 mL of
necessary. Cleaning with hot water is generally sufficient;
the HNO3–HClO4 mixture to the flask, and swirl the flask
drastic attack with cleaning solution should be avoided.
gently to wet the sample thoroughly. Place the modified funnel
55.8 Wash the precipitate on the filter until free of chlorides
in the mouth of the flask and heat the flask carefully on a hot
by the following test: To 5 mL of wash water, collected in a
plate in a fume hood.
separate test tube or on a watch glass, add 1 mL of HNO3
NOTE 12—Precaution: Use the utmost care in handling the (2 + 3) and 1 mL of AgNO3 solution. The appearance of a
HNO3–HClO4 mixture. If a spill occurs, wash down with plenty of water. milky white precipitate indicates the presence of chlorides, and
Wear safety glasses or a face shield. the washing should therefore continue until the test is negative.
55.3 After the mixture becomes hot and less viscous, Do not attempt to get a completely negative test for chloride.
increase the heat of the hot plate. Continue the digestion until Discontinue washing when no more than a faint opalescence is
all the sample has been oxidized and the thick reddish-brown produced in the test.
fumes of nitric oxide have been expelled. At this point, white 55.9 Finally pour a few millilitres of pure acetone through
fumes will appear and a rather vigorous reaction will occur that the filter and suck it dry. Place the crucible in a larger crucible
is caused by the last traces of organic material being oxidized or in a metal tray with perforated sides and bottom for
and the nitric acid fuming off. protection and place it in an oven at 120 to 125°C for 1 h. Do
55.4 When this reaction starts, remove the flask from the hot not handle the crucibles with the fingers between ignition and
plate, swirl gently for a few seconds, and set it on the shelf in the completion of weighing; use forceps.
10
D 817
55.10 Remove the crucible from the oven and ignite it for 61. Heat Treatment
10 min in a muffle furnace at 800 6 50°C. Cool in a desiccator 61.1 Place the sample, ground to pass a No. 20 (841-µm)
for 75 6 15 min and weigh to the nearest 0.0001 g. It is sieve, in a clean, dry test tube and pack it firmly and uniformly.
permissible to return the crucible to the oven for at least 15 min Stopper with a cork having a notch or tube as described in 59.2.
before transferring to the desiccator. Heat the tube and contents for 8 h at 180°C or as otherwise
55.11 From time to time, and especially when using new specified.
reagents, run a blank in duplicate in the reagents. If the weight
of the precipitate exceeds 0.0005 g, investigate and eliminate 62. Dry Color Evaluation
the cause. This is equivalent to an error of 0.002 % on a 10-g 62.1 Examine the heated sample for uniformity of color and
sample. for the presence of charred or decomposed spots. Compare the
56. Calculation color of the material at the bottom of the tube with standards
prepared as follows: Heat portions of a check batch of similar
56.1 Calculate the percentage of sulfur and sulfate as
particle size, representative quality and stability, and accepted
follows:
by mutual agreement between the purchaser and the seller.
Sulfur, % 5 $@~C 2 B! 2 ~E 2 D!# 3 0.1374/A% 3 100 (26) Pack portions of this check batch firmly in each of twelve
Sulfate, % 5 $@~C 2 B! 2 ~E 2 D!# 3 0.4115/A% 3 100 (27) clean, dry test tubes and stopper with corks as described in
59.2. Heat the tubes at 180°C, or as otherwise specified,
where: remove one tube each 2 h, and mark the time of heating in
A 5 weight of sample, g, hours on each tube. This set of numbered tubes serves as the
B 5 weight of crucible for sample, g, color standards. They should be checked and renewed if
C 5 weight of crucible and BaSO4 for sample, g,
necessary every 6 months.
C−B 5 weight of BaSO4 for sample, g,
D 5 weight of crucible for blank, g, 63. Solution Color Using Platinum–Cobalt Standards
E 5 weight of crucible and BaSO4 for blank, g, and
E−D 5 weight of BaSO4 for blank, g. 63.1 Heat a 1-g sample for the specified time and tempera-
ture and, after cooling, examine for charred or decomposed
HEAT STABILITY spots. Dissolve the heated sample in 15 mL of the methylene
57. Summary of Test Method chloride–methyl alcohol mixture. Compare the color of the
solution (viewing transversely) with test tubes of platinum-
57.1 The heat stability of a cellulose ester is one indication
cobalt color standards, prepared as described in Section 80. (It
of its quality. It is measured by heating the sample for a
may be necessary to prepare standards having as much as 2000
specified time and temperature, observing it for amount and
ppm of platinum for this purpose or to dilute the sample
uniformity of color developed, and possibly also measuring the
solution before grading.)
loss of viscosity as a result of heating. Suggested times of
heating are 8 h at 160°C, 8 h at 180°C, or 2 h at 190°C. The 64. Solution Color by Spectrophotometer
time and temperature of heating, method of grading, and limits
64.1 The color of the solution prepared as described in
are matters for agreement between the purchaser and the seller.
Section 63 may also be measured spectrophotometrically.
58. Significance and Use Measure the absorbance at 400 nm against the solvent, using a
58.1 The heat stability of a cellulose ester is one indication suitable spectrophotometer with a 1-cm silica cell.
of its quality.
65. Viscosity Change
59. Apparatus 65.1 Measure the limiting viscosity number of the heated
59.1 Heater Block—A metal block of suitable size heated sample and of an unheated sample as described in Sections 67
electrically and maintained at the specified temperature to 71 of this test method. The percentage loss of viscosity as the
within6 1°C. This is best accomplished by providing continu- result of heating is a measure of heat stability.
ous heat to hold the temperature a few degrees below the
specified temperature, and providing intermittent additional 66. Precision and Bias
heat thermostatically controlled. Holes shall be drilled in the 66.1 No statement on bias can be made as no reference
top of the block to hold test tubes, a thermoregulator, and a material is available as a standard.
thermometer. The block should be insulated.
59.2 Test Tubes, either 18 by 150-mm or 20 by 150-mm, LIMITING VISCOSITY NUMBER
fitted with corks. The corks shall be fitted with glass tubes the
length of the cork and 4 mm in inside diameter or shall have a
small V-shaped notch of equivalent cross-section cut in a 67.1 Limiting viscosity number, expressed in millilitres of
vertical position. solution per gram of solute, is determined by measuring the
flow times of a solution of known concentration and also of the
60. Solvent solvent used and making a calculation by means of the
60.1 Methylene Chloride-Methyl Alcohol Mixture—Mix 9 modified Baker-Philippoff equation.
parts by weight of methylene chloride with 1 part of methyl 67.2 Intrinsic viscosity, expressed in decilitres per gram of
alcohol. solute, is determined in the same way by expressing c in grams
11
D 817
TABLE 1 Solvents for Limiting Viscosity Number Determination
Value of
A Ingredients, % k for Cal-
Solvent
by weight culation
(71.2)
A 90 % acetoneB 10
10 % ethyl alcoholC
B acetoneB 10
C or D 90 % methylene chlorideD 3
10 % ethyl alcoholC
E 96 % acetoneB 10
4 % water
F 90 % methylene chlorideD 3
10 % methanolE
A
Solvent designations conform to those used in Table 2 for viscosity determi-
nations.
B
Acetone (99.4 6 0.1 %) containing 0.3 to 0.5 % water and under 0.3 % ethyl
alcohol.
C
Ethyl alcohol (95 % by volume). Formula 2B or 3A denatured ethyl alcohol may
be used.
D
Methylene chloride having a boiling range of 39.2 to 40.0°C and less than
0.001 % acidity calculated as HCl.
E
Methyl alcohol (sp gr 20/20°C 5 0.785 to 0.795).
ing this conditioning period, water at 25°C should be circulat-

ing through the water jacket of the viscometer to allow ample
FIG. 3 Wagner Capillary Tube Viscometer9
time for the pipet to reach temperature equilibrium.
70.2 Viscosity Measurements—Rinse the reservoir and the
per 100 mL in 71.2. Limiting viscosity number is thus outside of the capillary tube thoroughly with solvent. Rinse the
100 3 intrinsic viscosity. inside of the capillary tube twice by alternately applying
pressure at points B and A (see Fig. 3). Discard the wash
68. Significance and Use portion of the solvent. Pour more solvent into the reservoir and
68.1 Limiting viscosity number can be used to estimate the allow several minutes for complete drainage and thermal
molecular weight of a cellulose ester by using the Mark- equilibrium to be obtained. Adjust the outer meniscus to a
Houwink equation and constants measured for the solvent, reference point, D, that will give a flow time between 70 and
temperature, and ester of concern. 100 s. Apply air pressure at B to force the solvent up through
the capillary past the upper timing mark, C, on the measuring
69. Apparatus bulb, E. Record the time in seconds required for the meniscus
69.1 Capillary Viscometer, such as the Wagner apparatus to fall between the timing marks, C and F. Take a minimum of
(see Fig. 3)9 or an Ostwald-Fenske-Cannon pipet, that will give two readings. Repeat these operations, substituting the solution
a flow time for the solvent of not less than 70 s. for the solvent.
69.2 Water Bath—A constant-temperature water bath con-
trolled at 25.0 6 0.1°C and with a pump for circulating the 71. Calculation
water through the viscometer jacket or tank. 71.1 Calculate the viscosity ratio, h/h0 as follows:
69.3 Stop Clock or Watch, calibrated in 1⁄10 s. Viscosity ratio 5 t1 / t2 (28)
70. Procedure where:
70.1 Sample Preparation—Dry about 0.26 g of sample in a t1 5 efflux time of solution, and
weighing bottle at 105 6 3°C for 2 h, stopper, and cool in a t2 5 efflux time of solvent.
desiccator. Weigh the bottle containing the sample to the NOTE 13—Strictly, the viscosity ratio is defined as h/h0 where h and h0
nearest 0.001 g, transfer the sample to a 250-mL flask, and are the viscosities of the solution and solvent, respectively, and are related
reweigh the bottle. Pipet into the flask 100 mL of solvent at 25 to the corresponding efflux times by:
6 0.1°C. The solvent used should be mutually agreed upon by h 5 Ct 2 Er/t2 (29)
the purchaser and the seller. Suitable solvents are listed in
h0 5 Ct0 2 Er0/t02 (30)
Table 1. After the sample is completely dissolved, place it in
where:
the constant-temperature bath at 25°C along with a portion of C and E are constants for the particular viscometer used.
the solvent used, and allow sufficient time for both to come to The equation in 71.1 follows if the second term in these relations, a kinetic
temperature before making the viscosity measurements. Dur- energy correction, is negligible and the respective solvent and solution
densities, r0 and r, are substantially equal.
71.2 Calculate the limiting viscosity number, [h], as fol-
9
Wagner, R. H., and Russell, John, “Capillary Tube Viscometer for Routine lows:
Measurement of Dilute High Polymer Solutions,” Analytical Chemistry, Vol 20,
1948, pp. 151–7. @h# 5 ~k/c!@antilog ~~log h/h0! / k! 2 1 (31)
12
D 817
where: COLOR AND HAZE

k 5 values from Table 1 (Note 14), and
c 5 concentration in g/mL. 77. Summary of Test Method
77.1 Color and haze determinations on cellulose ester solu-
NOTE 14—Different values may be used by agreement between the
tions are made by comparison with standards. Simultaneous
measurement of these properties is desirable because haze
71.3 Calculate intrinsic viscosity, h, in accordance with reduces the amount of color observed.
71.2, but express c in grams per 100 mL.
78.1 Solution color and haze of a cellulose ester is a
72.1 No statement on bias can be made as no reference measurement of the optical properties of cellulose esters when
material is available as a standard. dissolved in a specific solvent.
VISCOSITY 79. Apparatus
73. Significance and Use 79.1 Light Box—A suitable light box (Fig. 4) is described as
73.1 A measurement of viscosity is of great practical utility follows: The light source consists of a mercury vapor bulb
in determining the proper processing equipment and process which requires an autotransformer for the current source. The
concentrations for cellulose esters. bulb is mounted horizontally across the lower front part of a
plywood box 356 mm (14 in.) wide, 430 mm (17 in.) high, and
74. Procedure 330 mm (13 in.) deep. This box is lined with a heat resistant
74.1 Solution—Dry the sample for 1 to 2 h at 105 6 3°C board and is painted black inside, except that the inside back
and cool in a desiccator. Prepare a solution of the dried sample surface toward the viewer is white. A bottle holder large
in a solvent and at a concentration mutually agreed upon by the enough to hold four bottles is built onto the front of the light
purchaser and the seller. Suitable solutions are listed in Table 2. box, and a 64 by 150-mm (21⁄2 by 6-in) horizontal viewing hole
74.2 Viscosity Determination—Prepare the solution and is cut through the front of the box. This opening is covered with
measure the viscosity in accordance with Test Method D 1343, clear glass, and a 6-mm (1⁄4-in.) strip of black tape is fastened
(see Note 17 in Section 81). to the glass horizontally to aid in judging haze in the solution.
Holes are cut in the bottom and top of the box for cooling by
75. Report air convection. For continuous use, forced circulation of air
75.1 Report the results in poises, unless otherwise specified. would be desirable. A black metal baffle over the bulb prevents
The viscosity value shall be prefixed with the letter A, B, C, direct light on the viewing glass.10
etc., corresponding to the formula of the solution employed. 79.2 Sample Bottles—The bottles used for the sample solu-
tions are French square bottles, 470-mL (16-oz), with screw
76. Precision and Bias caps. These same bottles may be used for the color and haze
76.1 No statement on bias can be made as no reference standards.
NOTE 15—These bottles may also be used for determination of viscos-
ity, as described in 74.2.
TABLE 2 Solutions for Viscosity Determination
Formula
10
A B C D E F A detailed drawing of the color and haze apparatus may be obtained from
Ingredients, Weight %
ASTM Headquarters. Request Adjunct No. 12-408170-00.
Cellulose ester 20A 20A 20B 15C 20A 10C

AcetoneD 72 80 ... ... ... ...
Acetone, 96 percent ... ... ... ... 80 ...
Water, 4 percent
Ethyl alcoholE 8 ... 8 8.5 ... ...
Methyl alcoholF ... ... ... ... ... 9
Methylene chlorideG ... ... 72 76.5 ... 81
Typical Solution Densities, g/mL at 25°C
0.85 0.86 1.25 1.23 0.86 1.24
A
Suitable for most mixed esters having less than about 40 % acetyl and more
than about 8 % propionyl or butyryl.
B
Suitable for most of the commercial cellulose acetate propionates and acetate
butyrates.
C
Suitable for most of the commercial cellulose acetate propionates and acetate
butyrates. Particularly good for esters containing more than 40 % acetyl.
D
alcohol.
E
Ethyl alcohol (95 % by Vol). Formula 2B, 3A, or 30 denatured ethyl alcohol may
be used.
F
Methyl alcohol (sp gr 20/20C 5 0.785 to 0.795).
G
0.001 % acidity calculated as HCl. FIG. 4 Color and Haze Apparatus
13
D 817
79.3 Cap Liners—Cap liners shall be of a composition not one of the square bottles. See Table 2 for suitable solutions. At
affected by the solvents used. Liners of fiber board covered least 350 mL are required. Tumble until a uniform solution is
with cellophane or aluminum foil are usually satisfactory, but obtained. Allow the solution to stand until it is free of bubbles
vinyl resin or waxed liners may cause interference with before grading it for color and haze.
viscosity, color, or haze measurements. 81.2 Place the bottle containing the solution to be graded at
80. Reference Standards the front of the shelf on the apparatus and place a similar bottle
containing water behind it. Place the freshly shaken haze
80.1 Color Standards—A color standard containing 500
standard at the front of the shelf beside the bottle containing the
ppm of platinum may be purchased or the solution may also be
solution to be tested and place the color standard behind it.
prepared as follows: Dissolve 1.245 g of potassium platinum
chloride (K2PtCl6), containing 0.500 g of platinum, and 1.000 Determine the amount of color and haze in the solution by
g of crystallized cobalt chloride (CoCl2·6H2O), containing changing the color and haze standards until as good a match as
0.248 g of cobalt, in water, add 100 mL of HCl (sp gr 1.19), and possible has been obtained. The haze standards settle out
dilute to 1 L with water. Prepare standards containing 50, 60, quickly so they must be reshaken at short intervals. Report
70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400 and 500 results in parts per million for both color and haze.
ppm of platinum by diluting suitable aliquots of the standard NOTE 17—When viscosity, color, and haze determinations, and an
solution to 500 mL with water. Place these standards in the observation of general appearance are to be made on a cellulose ester
special bottles (see 79.2), taking care to select bottles with sample, a considerable saving in time can be made by using one solution
good clarity and free of flaws. Label and cap tightly. in a square bottle for all three determinations. Dry the cellulose ester as
80.2 Haze Standards—Prepare haze standards by diluting a required for the viscosity determination, prepare the solution carefully,
stock solution having a turbidity of 1000 ppm. Prepare bottles and allow the bottle to stand long enough to form a thick solution before
containing 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, tumbling, to avoid solvent loss around the cap. Use a large enough sample
175, 200, and 400 ppm of turbidity, label, and cap tightly. to provide at least 350 mL of solution in the bottle. Measure the viscosity
as described in Test Method D 1343.
NOTE 16—The previously recommended stock solution for preparing
these standards was made from fuller’s earth, water, and hydrochloric 82. Precision and Bias
acid. This solution is no longer available. A comparable stock solution can
be made using diatomaceous earth. To obtain haze levels equivalent to the 82.1 No statement on bias can be made as no reference
fuller’s earth standard, 1.1 parts of diatomaceous should be used in place material is available as a standard.
of 1.0 parts of fuller’s earth in preparing the aqueous suspension. No
hydrochloric acid is needed.
83. Keywords
81. Procedure 83.1 apparent acetyl; ash; cellulose acetate butyrate; cellu-
81.1 Prepare the solution to be graded by dissolving the lose acetate propionate; cellulose esters; color; free acidity;
cellulose ester in the specified amount and kind of solvent, in haze; hydroxyl; limiting; partition; sulfate content; viscosity
14

Nitration Grade Toluene1,2
1. Scope Determine Conformance with Specifications5

1.1 This specification covers nitration grade toluene. 2.2 Federal Specification:6
1.2 The following applies to all specified limits in this PPP-2020 Packaging of Chemicals, Liquid, Dry, and Paste
standard: for purposes of determining conformance with this 2.3 Other Document:
standard, an observed value or a calculated value shall be OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
rounded off “to the nearest unit” in the last right-hand digit 1910.12007
used in expressing the specification limit, in accordance with 3. Properties
the rounding-off method of Practice E 29.
1.3 Consult OSHA regulations, supplier’s Material Safety 3.1 Nitration grade toluene shall conform to the following
Data Sheets, and local regulations for all materials used in this requirements:
specification. ASTM Test
Property Specification Method
Nonaromatic hydrocarbons, max, volume % 1.5 D 2360
2. Referenced Documents Acid wash color, max pass with 2 D 848
2.1 ASTM Standards: Copper corrosion pass (1A or 1B) D 849
A
Appearance ...
D 848 Test Method for Acid Wash Color of Industrial Color, Pt/Co scale, max 20 D 1209 or
Aromatic Hydrocarbons3 D 5386
D 849 Test Method for Copper Strip Corrosion of Industrial Relative density, 15.56/15.56°C 0.869 to 0.873 D 3505 or
D 4052
Aromatic Hydrocarbons3 or
D 850 Test Method for Distillation of Industrial Aromatic Density, 20°C, g/mL 0.865 to 0.870 ...
Hydrocarbons and Related Materials3 Distillation range including the temperature 1.0 D 850
110.6°C at 101.3 kPa (760 mm Hg pressure),
D 1209 Test Method for Color of Clear Liquids (Platinum- max,° C
Cobalt Scale)3
D 2360 Test Method for Trace Impurities in Monocyclic A
Clear liquid free of sediment and haze when observed at 18.3 to 25.6°C (65 to
Aromatic Hydrocarbons by Gas Chromatography3 78°F).
D 3437 Practice for Sampling and Handling Liquid Cyclic 4. Sampling
Products3
D 3505 Test Method for Density or Relative Density of 4.1 The material shall be sampled in accordance with
Pure Liquid Chemicals3 Practice D 3437.
D 4052 Test Method for Density and Relative Density of 5. Packaging and Labeling for U.S. Government
Liquids by Digital Density Meter4 Procurements
D 5386 Test Methods for Color of Liquids Using Tristimu-
lus Colorimetry3 5.1 United States Government procurements shall be pack-
E 29 Practice for Using Significant Digits in Test Data to aged and labeled in accordance with the applicable paragraphs
of Fed. Spec. PPP-C-2020.
1
This specification is under the jurisdiction of ASTM Committee D-16 on
6. Keywords
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of 6.1 toluene
Subcommittee D 16.0A on BTX, Cyclohexane, and Their Derivatives.
5
Current edition approved Dec. 10, 1997. Published August 1998. Originally Annual Book of ASTM Standards, Vol 14.02.
6
published as D 841 – 45 T. Previous edition D 841 – 95. Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
2
This material was formerly known as “nitration pure toluol.” Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.
3 7
Annual Book of ASTM Standards, Vol 06.04. Available from Superintendent of Documents, U.S. Government Printing
4
Annual Book of ASTM Standards, Vol 05.02. Office, Washington, DC 20402.
1
D 841
2

Nitration Grade Xylene1,2
1. Scope D 5386 Test Method for Color of Liquids Using Tristimulus

1.1 This specification covers nitration grade xylene. Colorimetry3
1.2 The following applies to all specified limits in this E 29 Practrice for Using Significant Digits in Test Data to
standard: for purposes of determining conformance with this Determine Conformance with Specifications4
standard, an observed value or a calculated value shall be 2.2 Other Document:
round off “to the nearest unit” in the last right-hand digit used OSHA Regulations 29 CFR, paragraphs 1910.1000 and
in expressing the specification limit, in accordance with the 1910.12005
round-off method of Practice E 29. 3. Properties
1.3 Consult OSHA regulations, supplier’s Material Safety
Data Sheets, and local regulations for all materials used in this 3.1 Nitration grade xylene shall conform to the following
specification. requirements:
ASTM Test
2. Referenced Documents Property Specification Method
Nonaromatic hydrocarbons, max, volume % 4.0 D 2360
2.1 ASTM Standards: Acid wash color, max pass with 6 D 848
D 848 Test Method for Acid Wash Color of Industrial Copper corrosion pass (1A or 1B) D 849
A
Appearance ...
Aromatic Hydrocarbons3 Color, Pt/Co scale, max 20 D 1209 or
D 849 Test Method for Copper for Corrosion of Industrial D 5386
Aromatic Hydrocarbons3 Distillation range at 101.3 kPa (760 mm Hg 5 D 850
pressure), max,° C
D 850 Test Method of Distillation of Industrial Aromatic Initial distillation temperature, min,° C 137 D 850
Hydrocarbons and Related Materials3 Dry point, max,° C 143 D 850
D 1209 Test Method for Color of Clear Liquids (Platinum- A
Clear liquid free of sediment and haze when observed at 18.3 to 25.6°C (65 to
Cobalt Scale)3 78°F).
D 2360 Test Method for Trace Impurities in Monocyclic
Aromatic Hydrocarbons by Gas Chromatography3 4. Sampling
D 3437 Practice for Sampling and Handling Liquid Cyclic 4.1 The material shall be sampled in accordance with
Products3 Practice D 3437.
1
5. Keywords
This specification is under the jurisdiction of ASTM Committee D-16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of 5.1 xylene
Subcommittee D16.0A on BTX, Cyclohexane, and Their Derivatives.
Current edition approved Dec. 10, 1997. Published August 1998. Originally
4
2 5
This material was formerly known as “3° xylol.” Available from Superintendent of Documents, U.S. Government Printing
3
1

Acidity of Benzene, Toluene, Xylenes, Solvent Naphthas,
and Similar Industrial Aromatic Hydrocarbons1
1. Scope the conditions prescribed in this test method.

1.1 This test method is intended for the detection of acidity 3.1.2 acid reaction—a characteristic of materials producing
and for the quantitative determination of acidity of benzene, the acid-color of the indicator used under the conditions
toluene, xylenes, solvent naphthas, and similar industrial aro- prescribed in this test method.
matic hydrocarbons. 3.1.3 alkaline or basic reaction—a characteristic of the
1.2 The following applies to all specified limits in this test materials producing the alkali-color of the indicator used under
method: for purposes of determining conformance with this the conditions prescribed in this test method.
test method, an observed value or a calculated value shall be 4. Summary of Test Method
rounded off “to the nearest unit” in the last right-hand digit
used in expressing the specification limit, in accordance with 4.1 The acidity of aromatic hydrocarbons is detected and
the rounding-off method of Practice E 29. determined quantitatively using a sodium hydroxide titration
1.3 This standard does not purport to address all of the and a color change in a phenolphthalein indicator.
safety concerns, if any, associated with its use. It is the 5. Significance and Use
priate safety and health practices and determine the applica- 5.1 This test method is suitable for setting specifications, for
bility of regulatory limitations prior to use. For specific hazard use as an internal quality control tool, and for use in develop-
statements see Section 8. ment or research work on industrial aromatic hydrocarbons and
related materials. This test method gives an indication of
2. Referenced Documents residual acidity and is a measure of the quality of the finished
2.1 ASTM Standards: product. It is an indication of the tendency of the product to
D 1193 Specification for Reagent Water2 corrode equipment.
D 3437 Practice for Sampling and Handling Liquid Cyclic 6. Interferences
Products3
E 29 Practice for Using Significant Digits in Test Data to 6.1 Tests for acidity are not applicable in the presence of
Determine Conformance with Specifications4 contaminating acidic or alkaline gases, soaps, salts, or other
2.2 Other Documents: compounds derived from the atmosphere or apparatus. The
OSHA Regulations, 29 CFR, Paragraphs 1910.1000 and container holding the specimen, and the apparatus, water,
1910.12005 indicator, and other materials used in the test shall be chosen so
that they themselves shall not appreciably affect the results.
3. Terminology Since new corks used in specimen bottles often are bleached
3.1 Definitions: with oxalic acid, it is advisable to rinse them thoroughly and
3.1.1 acidity—the number of milligrams of sodium hydrox- check them for neutrality with the indicator used in the test.
ide consumed when 100 mL of the specimen are titrated under Glassware shall be of acid-resistant and alkali-resistant glass6
and shall be rinsed with neutral distilled water before use. The
1
room in which the test is performed shall be chosen so as to
This test method is under the jurisdiction of ASTM Committee D-16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of
prevent undue contamination by carbon dioxide, ammonia, or
Subcommittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their other interfering substances that may be present in the atmo-
Derivatives. sphere.
Current edition approved June 10, 1996. Published August 1996. Originally 6.2 The distilled water used in the test shall not alter the
2
Annual Book of ASTM Standards, Vol 11.01. composition of the specimen nor otherwise interfere with the
3
Annual Book of ASTM Standards, Vol 06.04. purpose of the work. Although inert impurities often may be
4
5
Available from Superintendent of Documents, U.S. Government Printing
6
Office, Washington, DC 20402. Borosilicate glass or the equivalent has been found satisfactory for this purpose.
1
D 847
neglected, care must be exercised to correct for impurities or to Safety Data Sheets, and local regulations for all materials used
eliminate them entirely if they are likely to interfere. When the in this test method.
distilled water does not show an acid or alkaline reaction, it
may be used without further adjustment to neutrality. However, 10. Sampling
if the water shows an acid or alkaline reaction, it shall be 10.1 Sample the material in accordance with Practice
brought to a persistent pink end point before use by titration D 3437.
with standard 0.01 N NaOH solution (see 8.5) or standard 0.01
N H2SO4, respectively. 11. Procedure
11.1 Measure out 100 mL of the sample into the 500-mL
7. Apparatus bottle. Add 100 mL of neutral distilled water (see 8.2) and 2
7.1 Graduate, 100-mL.6 drops of phenolphthalein indicator solution. Stopper and shake
7.2 Bottle, 500-mL glass-stoppered.6 thoroughly. Without separating the layers, titrate the acidity, if
7.3 Buret, 10-mL, graduated in 0.05-mL subdivisions. any, with standard 0.1 N NaOH solution to the first persistent
8. Reagents shade of pink, while shaking thoroughly.
11.2 If more than 2 drops (0.10 mL) of 0.1 N NaOH solution
8.1 Purity of Reagents—Reagent grade chemicals shall be is required to produce a persistent pink end point, discard the
used in all tests. Unless otherwise indicated, it is intended that results of the test. While taking precautions to avoid contami-
all reagents shall conform to the specifications of the Commit- nation from the apparatus and atmosphere, proceed as follows:
tee on Analytical Reagents of the American Chemical Society, Rinse the 100-mL graduated cylinder and the 500-mL bottle
where such specifications are available.7 Other grades may be and glass stopper with neutral distilled water. To the bottle, add
used, provided it is first ascertained that the reagent is of 100 mL of the sample and 100 mL of neutral distilled water.
sufficiently high purity to permit its use without lessening the Add 2 drops of phenolphthalein indicator solution, and shake
accuracy of the determination. vigorously for 10 s. Bring the temperature to between 15 and
8.2 Phenolphthalein Indicator Solution— Dissolve 0.5 g of 18.5°C (60 and 65°F). Add 1 drop of 0.1 N NaOH solution,
phenolphthalein in 100 mL of cp ethyl alcohol (95 %). Add stopper, and shake vigorously for 10 s. Repeat the addition of
0.01 N NaOH solution cautiously until a faint pink color 1 drop of NaOH solution, stoppering, and shaking for 10 s,
appears; then just remove the color with a drop or two of 0.01 until a sharp pink end point is secured. Repeat this procedure
N acid. on a blank run with 100 mL of the neutral distilled water.
8.3 Sodium Hydroxide, Standard Solution (0.1 N).
8.4 Sodium Hydroxide, Standard Solution (0.01 N). 12. Interpretation of Results and Calculation
8.5 Sulfuric Acid, Standard (0.01 N). 12.1 Unless otherwise indicated in the applicable specifica-
8.6 Purity of Water: Distilled Water, Neutral——Boil vig- tions, the test results shall be interpreted as follows:
orously for 30 min, 1 to 2 L of distilled water conforming to 12.1.1 A specimen shall be said to contain no free acid, that
Type III of Specification D 1193. Insert a stopper carrying a is, show no evidence of acidity, if 2 drops or less of 0.1 N
guard tube of soda lime. Rinse a 200-mL flask with this NaOH solution produces a persistent pink end point in the test
distilled water, add a 100-mL portion, and titrate in a closed bottle.
system with 0.01 N NaOH solution: or heat to boiling and 12.1.2 When more than 2 drops (0.10 mL) of 0.1 N NaOH
titrate immediately, taking care that the temperature does not solution is required to produce a persistent pink end point in the
fall below 80°C during the titration. If more than 1 drop (0.05 test bottle, the acidity shall be reported in terms of milligrams
mL) of 0.01 N NaOH solution is required to obtain an end point of NaOH required for 100 mL of specimen, and shall be
with phenolphthalein, adjust the pH of the water to be used by calculated as follows:
adding the calculated amount of NaOH solution. Repeat the
Acidity, mg NaOH per 100 mL 5 4 ~A 2 B! (1)
blank titration, and readjust if necessary until the blank titration
on 100 mL of the distilled water is 1 drop (0.05 mL) or less of where:
the 0.01 N NaOH solution. The distilled water now will be A = 0.1 N NaOH solution required for titration of the
neutral or very slightly acid to the phenolphthalein indicator. sample, mL, and
9. Hazards B = 0.1 N NaOH solution required for titration of the blank,
mL.
9.1 Consult current OSHA regulations, supplier’s Material
7
Reagent Chemicals, American Chemical Society Specifications, American 13.1 In the case of pass/fail data, no generally accepted
Chemical Society, Washington, DC. For suggestions on the testing of reagents not method for determining precision is currently available.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 14. Keywords
MD. 14.1 acidity
2
D 847
3

Acid Wash Color of Industrial Aromatic Hydrocarbons1
1. Scope internal quality control tool and in development or research

1.1 This test method covers the determination of the acid work.
wash color of benzene, toluene, xylenes, refined solvent 5.2 The color developed in the acid layer gives an indication
naphthas, and similar industrial aromatic hydrocarbons. of impurities which if sulfonated would cause the material to
1.2 This standard does not purport to address all of the be discolored.
safety concerns, if any, associated with its use. It is the 6. Apparatus
priate safety and health practices and determine the applica- 6.1 Containers for Color Standards—Clear and unblem-
bility of regulatory limitations prior to use. For specific hazard ished, clean, French square, flint-glass, flat-bottom, glass-
statements, see Section 8 and Note 1. stoppered, 1-oz capacity bottles holding 31 to 33 mL when
filled to the neck. The bottles shall be numbered consecutively
2. Referenced Documents from 0 to 14.
2.1 ASTM Standards: 6.2 Test Containers—Containers exactly like those de-
D 1193 Specification for Reagent Water2 scribed in 6.1 except that each French square bottle shall be
D 3437 Practice for Sampling and Handling Liquid Cyclic marked by etching to show when the bottle contains the
Products3 volume of 7 and 28 mL, respectively. Colored crayons and
D 4790 Terminology of Aromatic Hydrocarbons and Re- similar markers shall not be used for marking the bottles.
lated Chemicals3 7. Reagents
2.2 Other Document:
OSHA Regulations. 29 CFR, paragraphs 1910.1000 and 7.1 Purity of Reagents—Reagent grade chemicals shall be
1910.12004 used in all tests. Unless otherwise indicated, it is intended that
3. Terminology tee on Analytical Reagents of the American Chemical Society,
3.1 See Terminology D 4790 for definitions of terms used in where such specifications are available.5 Other grades may be
this test method. used provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
4. Summary of Test Method accuracy of the determination.
4.1 A mixture of the aromatic hydrocarbon and sulfuric acid 7.2 Purity of Water—Unless otherwise indicated, references
is vigorously shaken and the color of the acid layer is compared to water shall be understood to mean distilled water, Type I or
with that of color standards prepared from CoCl2 and FeCl3. II as described in Specification D 1193.
7.3 Cobalt Chloride (CoCl2· 6H2O).
5. Significance and Use 7.4 Ferric Chloride (FeCl3· 6H2O).
5.1 This test method is suitable for setting specifications on 7.5 Hydrochloric Acid (1 + 39)—Mix 25 mL of hydrochlo-
the materials referenced in 1.1. It may also be used as an ric acid (31 weight % HCl) with 975 mL of water.
7.6 Potassium Chromate (K2CrO4).
7.7 Potassium Dichromate (K2Cr2O7).
1
7.8 Sulfuric Acid (96 6 0.5 weight % H2SO4).
7.9 Sulfuric Acid (78 6 0.5 weight % H2SO4).
Subcommittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their
Derivatives.
5
Current edition approved June 10, 1997. Published September 1997. Originally Reagent Chemicals, American Chemical Society Specifications, American
published as D 848 – 45. Last previous edition D 848 – 93. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
3
4
Available from Superintendent of Documents, U.S. Government Printing and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Office, Washington, DC 20402. MD.
1
D 848
8. Hazards paraffin to prevent loss by evaporation or seepage.
8.1 Consult current OSHA regulations, supplier’s Material 12. Procedure
Safety Data Sheets, and local regulations for all materials used
in this test method. 12.1 Rinse a test container (5.2) twice with acid of the
8.2 When handling strong acids or acid cleaning solutions, strength specified in Table 1 for the type of sample to be tested
wear proper personnel protective equipment. (Note 1). Drain the rinsings and fill with the acid up to the
7-mL mark. Add sufficient sample to bring the total volume to
9. Sampling the 28-mL mark (Note 2). Insert the stopper, hold a finger over
9.1 Sample the material in accordance with Practice the stopper, and give vigorous shakes with a stroke of 13 to 25
D 3437. cm (5 to 10 in.), shaking for a total of 150 cycles over a period
of 40 to 50 s, that is at a rate of 3 to 3.75 cycles/s.
10. Cleaning of Containers
NOTE 1—Precaution: Concentrated sulfuric acid will cause severe
10.1 Clean the containers (Section 6) with a cleaning burns on contact with the skin. As a precaution the test container should
solution that will not impact the results, such as a chromatic be wrapped in a towel or enclosed in a plastic bag during the shaking
acid substitute, rinse with tap water followed by distilled water, period.
and dry in an oven set at a minimum of 105°C for at least 1 h. NOTE 2—If the room temperature is above 85°F, maintain the acid,
sample, and reference color standards at a temperature between 77 and
Likewise, clean all other glassware used in this test method.
85°F (25 and 29°C) through the test, and insulate the test container in
11. Preparation of Reference Color Standards some convenient way, such as wrapping with a cloth, during the shaking
period.
11.1 Stock Solutions—Prepare the following basic reagent
solutions for use in preparing the reference color standards: 12.2 Allow the container to stand, protected from direct
11.1.1 Solution A—Dissolve 59.50 g of CoCl2·6H2O in HCl sunlight, for the period of time shown in Table 1. Without
(1 + 39) and make up to 1 L in a volumetric flask with HCl further delay, invert the container gently once or twice to
(1 + 39). obtain a uniform color in the acid layer, and compare the color
11.1.2 Solution B—Dissolve 45.054 g of FeCl3·6H2O in of the acid layer with that of the standards (10.3). Make the
HCl (1 + 39) and make up to 1 L in a volumetric flask with HCl comparison against a white background or against daylight,
(1 + 39). using transmitted light (Note 3). When testing samples in
11.1.3 Solution C—Mix 31⁄2 volumes of Solution A with Group 1 (Table 1), observe the color of the oil layer as well as
361⁄2 volumes of Solution B and dilute with 90 volumes of that of the acid layer.
water. NOTE 3—Agreement of results may be improved by using a color
11.1.4 Solution D—Mix 31⁄2 volumes of Solution A with comparator of a suitable type for observing the color of the acid layer in
361⁄2 volumes of Solution B. comparison with the reference standard color solution.
11.1.5 Solution E—Prepare an aqueous solution of K2CrO4 12.3 Designate the color of the acid layer by the number of
saturated at 21°C. the nearest matching standard, following the number with a
11.1.6 Solution F—Prepare an aqueous solution of K2Cr2O7 plus or minus sign if the sample is darker or lighter, respec-
saturated at 21°C and dilute with an equal volume of water. tively, than the standard. Disregard any difference in hue and
11.2 Prepare reference color standard solutions having the determine only whether the color of the acid layer is darker or
following compositions and numbered from 0 to 14: lighter than the color of the reference standard to which the
No. 0—Distilled water. sample most nearly corresponds. If the hue of the acid color is
No. 1—1 volume of Solution C plus 1 volume of water. different from the hue of the reference color standard, record
No. 2—51⁄2 volumes of Solution C plus 2 volumes of water.
No. 3—Solution C. the color number followed by (X). Thus “No. 4 − (X)” means
No. 4—1 volume of Solution D plus 1 volume of water. that the acid wash test color is slightly lighter than No. 4 color
No. 5—51⁄2 volumes of Solution D plus 2 volumes of water. standard and that the hue of the No. 4 color standard is not the
No. 6—Solution D.
No. 7—5 volumes of Solution E plus 2 volumes of water. same as the hue of the acid layer.
No. 8—Solution E.
No. 9—7 volumes of Solution E plus 1⁄2 volume of Solution F. TABLE 1 Acid Strengths and Standing Times
No. 10—61⁄2 volumes of Solution E plus 1 volume of Solution F.
No. 11—51⁄2 volumes of Solution E plus 2 volumes of Solution F. Acid Standing
No. 12—1 volume of Solution E plus 1 volume of Solution F. Sample Strength, Time,
No. 13—2 volumes of Solution E plus 5 volumes of Solution F. % min
No. 14—Solution F. Group 1 Benzene, all ASTM grades
Toluene, all ASTM grades
11.3 Rinse the No. 0 container (5.1) and its glass stopper Xylene, nitration grade 96 15
three times with water, fill with water, and stopper. Rinse the Xylene, 5°
No. 1 container and its stopper three times with reference color Xylene, 10°
Any other more highly refined
standard solution No. 1 (Section 11.2), fill with this solution, products
and stopper. In this way, prepare the set of containers of color
Group 2 Xylene, industrial grade 96 5
standards from 0 through 14 having the compositions shown Refined solvent naphtha
for the corresponding color solution standards in 11.2. When
filling the French square bottles, leave 1⁄4 in. (6 mm) of vapor Group 3 Hi-flash solvent 78 5
Heavy solvent naphtha
space below the neck of the bottle. Seal each container with
2
D 848
13. Interpretation of Results tests were conducted in 1961, principally to establish equality
13.1 Report Group 1 samples (Table 1) as passing the test with the previously used shaking procedure. Precision esti-
only when the oil layer shows no change in color and when the mates taken from these data are as follows:
acid layer is not darker than the specified color standard. A Repeatability Reproducibility
Degrees 95 % Degrees 95 %
cloudiness or haze in the oil layer should not be interpreted as Average Acid
of Repeat- of Repro-
a change in color. Wash Color
Freedom ability Freedom ducibility
13.2 When testing samples of Groups 2 or 3, disregard the
Benzene 1.4 11 0.75 9 2.34
color of the oil layer and report the sample as passing the test 6.1 12 1.85 10 4.47
when the acid layer is not darker than the specified color
standard. Xylene 4.7 12 0.40 10 1.39
10.2 12 1.14 10 3.52
15. Keywords
14.1 Precision data have not been established for all types of
samples on which this test method is used. Limited cooperative 15.1 acid wash color; aromatic hydrocarbons
3

Copper Strip Corrosion by Industrial Aromatic
Hydrocarbons1
1. Scope aluminum strips; includes Method D 130)6

1.1 This test method determines the corrosiveness of indus- 3. Terminology
trial aromatic hydrocarbons to a copper strip.
3.1 See Terminology D 4790 for definition of terms used in
NOTE 1—For a similar copper strip test applicable to other petroleum this test method.
products, see Method D 130 and Test Method D 1838.
1.2 The values stated in SI units are to be regarded as the 4. Summary of Test Method
standard. The values given in parentheses are for information 4.1 A polished copper strip is immersed in 200 mL of
only. specimen in a flask with a condenser and placed in boiling
1.3 This standard does not purport to address all of the water for 30 min. At the end of this period, the copper strip is
safety concerns, if any, associated with its use. It is the removed and compared with the ASTM Copper Strip Corro-
responsibility of the user of this standard to establish appro- sion Standards.
bility of regulatory limitations prior to use. For specific hazard 5. Significance and Use
statements, see Section 8. 5.1 This test method is suitable for setting specifications, for
use as an internal quality control tool, and for use in develop-
2. Referenced Documents ment or research work on industrial aromatic hydrocarbons and
2.1 ASTM Standards: related materials. It also gives an indication of the presence of
B 152 Specification for Copper Sheet, Strip, Plate, and certain corrosive substances which may corrode equipment,
Rolled Bar2 such as acidic compounds or sulfur compounds.
D 130 Test Method for Detection of Copper Corrosion from
Petroleum Products by the Copper Strip Tarnish Test3 6. Apparatus
D 1838 Test Method for Copper Strip Corrosion by Lique- 6.1 Flask, 250-mL, of chemically resistant glass with flat
fied Petroleum (LP) Gases3 bottom and vial mouth.
D 4790 Terminology of Aromatic Hydrocarbons and Re- 6.2 Glass Condenser, 30-mm, with the inside diameter of
lated Chemicals4 the condenser tube not less than 10 mm. A cork is used to
2.2 Other Documents: connect the flask with the condenser. A condenser and flask
OSHA Regulations, 29 CFR, paragraphs 1910.1000 and with ground-glass joints may also be used.
1910.12005 6.3 Strip Polishing Vise, to hold the copper strip firmly
2.3 ASTM Adjuncts: without marring the edges. For convenient vises see Method
ASTM Copper Strip Corrosion Standards (13 photolithed D 130.
6.4 Water Bath, of convenient design, able to maintain
boiling water such that the contents of the flask are submerged
during the test.
1
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of 7. Reagents and Materials
Subcommittee D16.0A on BTX Cyclohexane and Their Derivatives.
Current edition approved June 10, 1997. Published September 1997. Originally 7.1 Wash Solvent—Any volatile, sulfur-free hydrocarbon
2
solvent may be used provided that it shows no tarnish at all
Annual Book of ASTM Standards, Vol 02.01. when tested at 100°C (212°F) for 1 h. Knock-test grade
3
4
5
Office, Washington, DC 20402. 6
Available from ASTM Headquarters. Request PCN 12-401300-00. Names of
suppliers in the United Kingdom can be obtained from the Institute of Petroleum.
Two master standards are held by the IP for reference.
1
D 849
isooctane (Warning—See 8.2) is a suitable solvent and should silicon-carbide grains picked up from a clean glass plate with
be used in case of dispute. a pad of absorbent cotton moistened with a drop of wash
7.2 Polishing Materials—Silicon carbide grit paper of vary- solvent. Wipe vigorously with fresh pads of absorbent cotton
ing degrees of fineness including 65-µm (240-grit) paper or and subsequently handle only with stainless-steel forceps; do
cloth; also a supply of 105-µm (150-mesh) silicon carbide grain not touch with the fingers. Clamp in a vise and polish the main
and pharmaceutical grade absorbent cotton (cotton wool). surfaces with silicon carbide grains on absorbent cotton. Rub in
7.3 Copper Strips—Use strips 12.5 mm (1⁄2 in.) wide, 1.5 to the direction of the long axis of the strip, carrying the stroke
3.0 mm (1⁄16 to 1⁄8 in.) thick, cut 75 mm (3 in.) long from beyond the end of the strip before reversing the direction.
smooth-surfaced, hard-tempered, cold-finished copper of Clean all metal dust from the strip by rubbing vigorously with
99.9 + % purity. Electrical bus-bar stock is generally suitable clean pads of absorbent cotton until a fresh pad remains
(hard-temper, cold-finished type-electrolytic tough pitch (ETP) unsoiled. When the strip is clean immediately attach the copper
copper conforming to UNS C11000 in Specification B 152. wire and immerse the strip in the specimen flask.
Drill a 3.2-mm (1⁄8-in.) hole approximately 3.2 mm (1⁄8 in.) NOTE 3—It is important to polish the whole surface of the strip
from one end in the center of the strip. The strips may be used uniformly to obtain a uniformly stained strip. If the edges show wear
repeatedly but should be discarded when surfaces become (surface elliptical) they will likely show more corrosion than the center.
deformed on handling. The use of a vise will facilitate uniform polishing.
7.4 Copper wire, soft, about 150 mm (6 in.) in length.
7.5 ASTM Copper Strip Corrosion Standards, consisting of 10. Procedure
reproductions in color of typical test strips representing in- 10.1 Fasten the 150-mm (6-in.) length of soft copper wire
creasing degrees of tarnish and corrosion. The reproductions through the hole provided near one end of the strip, taking care
are encased in plastic in the form of a plaque. Instructions for not to touch the strip with the fingers after polishing. Place the
care and use are given on the reverse side of each plaque and strip in the flask and add 200 mL of the sample. The specimen
in Method D 130. must not contain separated water. Filter through a dry filter
paper, if necessary, to remove water. Connect the flask to the
8. Hazards vertical reflux condenser by means of a properly bored cork
8.1 Consult current OSHA regulations, supplier’s Material stopper. It is absolutely necessary that a cork, not rubber,
Safety Data Sheets, and local regulations for all materials used stopper be used, in order to avoid contamination of the
in this test method. specimen by sulfur from rubber stoppers. The copper wire may
8.2 Isooctane is Extremely Flammable. Harmful if inhaled. be allowed to extend into the condenser tube for convenience
Vapors may cause flash fire. Keep away from heat, sparks, and in removing the strip. Completely immerse the strip which
open flame. Keep container closed. Use with adequate venti- should preferably lie flat and touch the flask only at the ends of
lation. Avoid buildup of vapors and eliminate all sources of the strip. Place the flask in the gently boiling water bath, and
ignition, especially non-explosion-proof electrical apparatus immerse the flask to the liquid line of the specimen within the
and heaters. Avoid prolonged breathing of vapor or spray mist. flask. Remove the copper strip 30 min from the time the flask
Avoid prolonged or repeated skin contact. was immersed in the bath. Do not touch the copper strip, but
remove it by the wire that has been provided. Do not allow the
9. Preparation of Strips strip to come in contact with separated water during any part of
9.1 Surface Preparation—Remove all surface blemishes the test, since water causes bad local staining of the copper. If
from all six sides of the strip with silicon carbide grit paper of it is desired to preserve the strip for future reference, dip it
such degrees of fineness as are needed to accomplish the immediately into white shellac or lacquer.
desired results efficiently. Finish with 65-µm (240-grit) silicon-
11. Interpretation of Results
carbide paper or cloth, removing all marks that may have been
made by other grades of paper used previously. Immediately 11.1 Compare the exposed strip with the ASTM Copper
immerse the strip in wash solvent from which it may be Strip Corrosion Standards described in 7.5. Hold the test strip
withdrawn for final polishing or in which it may be stored for and the Standard in such a manner that light reflected from
future use. them at an angle of approximately 45° will be observed. Report
as passing strips shown in the Slight Tarnish catagory or better
NOTE 2—As a practical manual polishing procedure, place a sheet of (1A or 1B); all others shall be considered failures.
the paper on a flat surface, moisten it with wash solvent, and rub the strip
against the paper with a rotary motion, protecting the strip from contact 12. Precision and Bias
with the fingers with an ashless filter paper. Alternatively, the strip may be 12.1 In the case of pass/fail data, no generally accepted
prepared by use of motor-driven machines using appropriate grades of dry
paper or cloth.
method for determining precision and bias is currently avail-
able.
9.2 Final Polishing—Remove a strip from the wash solvent.
Holding it in the fingers protected with ashless filter paper, 13. Keywords
polish first the ends and then the sides with the 150-mesh 13.1 copper corrosion test
2
D 849
3

Distillation of Industrial Aromatic Hydrocarbons and Related
Materials1
1. Scope * E 133 Specification for Distillation Equipment5

1.1 This test method covers the distillation of industrial E 220 Test Method for Calibration of Thermocouples by
aromatic hydrocarbons and related materials of relatively Comparison Techniques3
narrow boiling ranges from 30 to 250°C. E 691 Practice for Conducting an Interlaboratory Study to
1.2 The values stated in SI units are to be regarded as the Determine the Precision of a Test Method4
standard. The values given in parentheses are for information 2.2 Other Document:
only. OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
1.3 The following applies to all specified limits in this test 1910.12006
method: for the purposes of determining conformance to this 3. Terminology
test method, an observed or calculated value shall be rounded
off “to the nearest unit” in the last right-hand digit used in 3.1 Definitions:
expressing the specification limit, in accordance with the 3.1.1 See Terminolgy D 4790 for definitions of terms used
rounding-off method of Practice E 29. in this test method.
1.4 This standard does not purport to address all of the 4. Summary of Test Method
responsibility of the user of this standard to establish appro- 4.1 The distillation of a 100-mL sample of industrial aro-
priate safety and health practices and determine the applica- matic hydrocarbons and related materials is carried out via a
bility of regulatory limitations prior to use. For specific hazard carefully controlled distillation wherein temperature readings
statements, see 6.6 and Section 7. are noted for the first drop of distillate and when 5, 10, and
each additional 10 up to 90, and 95 % of the sample has
2. Referenced Documents distilled over. The temperature corresponding to the dry point
2.1 ASTM Standards: is also noted.
D 1078 Test Method for Distillation Range of Volatile 5. Significance and Use
Organic Liquids2
D 3437 Practice for Sampling and Handling Liquid Cyclic 5.1 This test method is suitable for setting specifications, for
Products2 use as an internal quality control tool, and for use in develop-
D 4790 Terminology of Aromatic Hydrocarbons and Re- ment or research work on industrial aromatic hydrocarbons and
lated Chemicals2 related materials.
E 1 Specification for ASTM Thermometers3 5.2 This test method gives a broad indication of general
E 29 Practice for Using Significant Digits in Test Data to purity and can also indicate presence of excessive moisture. It
Determine Conformance with Specifications4 will not differentiate between products of similar boiling range.
6. Apparatus
1
This test method is under the jurisdiction of ASTM Committee D16 on 6.1 Distillation Flask—A standard 200-mL side-tube, heat-
resistant glass distillation flask as shown in Fig. 1, conforming
Subcommittee D16.0E on Instrumental Analysis.
Current edition approved Dec. 10, 2000. Published January 2001. Originally
published as D 850 – 45. Last previous edition D 850 – 99a.
2 5
3 6
4

1
D 850
to be done at regular intervals. This may be accomplished as
prescribed in Test Method E 220, or some similar means using
a precision resistance decade box. Another technique is to
distill pure toluene and compare the temperature indicated by
the thermocouple or resistance thermometer with that shown
by the thermometer.
6.2.2.1 Automatic Distillation Temperature Sensor Center-
ing Device—The temperature sensor shall be mounted through
a snug-fitting device designed to mechanically center the
sensor in the neck of the flask. The use of a cork or silicone
stopper with a hole drilled through the center is not acceptable
for this purpose. Examples of acceptable centering devices are
shown in Fig. 2.
6.2.2.2 The electronic circuitry or algorithms, or both, used
shall include the capability to simulate the temperature lag of
a mercury-in-glass thermometer.
6.2.2.3 Alternatively, the sensor can also be placed in a
FIG. 1 Distillation Flask
casing with the tip of the sensor covered, so that the assembly,
because of its adjusted thermal mass and conductivity, has a
to the following dimensions: temperature lag similar to that of a mercury-in-glass thermom-
Diameter of bulb, outside, mm 76 6 1.5 eter.
Diameter of neck, inside, mm 21 6 1
Height of flask, outside, mm 179 6 3 NOTE 1—In a region where the temperature is changing rapidly during
Vertical distance from bottom of bulb outside to 120 6 3 the distillation, the temperature lag of a thermometer can be as much as 3
bottom of vapor-tube opening in neck, mm s.
Length of side tube, mm 100 6 3
Diameter of side tube, outside, mm 7 6 0.5 6.3 Condenser and Cooling Bath:
Angle of side tube with vertical axis of bulb and 75 6 3
neck, ° 6.3.1 Manual Distillation Condenser and Cooling Bath:
6.3.1.1 The manual distillation condenser and cooling bath
The flask does not comply with Flask C of Specification shall be as specified in Section 5, and Fig. 1 of Specification
E 133. E 133.
6.2 Temperature Measurement Devices: 6.3.1.2 As an alternative, the condenser tube may consist of
6.2.1 Manual Distillation Thermometer— The ASTM Sol- a straight glass tube 600 to 610 mm in length and 12 mm in
vents Distillation Thermometer used in the test shall be as inside diameter, of standard wall thickness (about 1.25 mm)
prescribed in the specifications for the material being tested. If with the exit end cut off square and ground flat. It shall be set
no thermometer is specified in the material specification, select in a cooling trough so that at least 380 mm of the tube is in
one from Table 1 with the smallest graduations that will cover contact with the water. Clearance between the condenser tube
the entire distillation range of the material being tested. Table and any parallel side of the trough shall be not less than 19 mm.
1 lists several ASTM solvents distillation thermometers which The water in the cooling trough shall be maintained at 10 to
are suitable for testing industrial aromatic hydrocarbons, and 20°C. This may be done by adding ice to the water or by
which meet the requirements of Specification E 1. circulating chilled water through the trough. The trough shall
6.2.2 Automatic Distillation Temperature Sensor— be so mounted that the condenser tube is set at an angle of 75°
Temperature measurement systems using thermocouples or with the vertical.
resistance thermometers, otherwise referred to as the “tempera-
6.3.2 Automatic Distillation and Cooling Bath—The auto-
ture measuring devices,” must exhibit the same temperature lag
matic distillation and cooling bath shall be as specified in
and accuracy as the equivalent mercury glass thermometer.
Section 5, Fig. 2 of Specification E 133.
Confirmation of the calibration of these temperature sensors is
6.4 Distillation Receiver:
6.4.1 Manual Distillation Receiver—A graduate of the cy-
TABLE 1 ASTM Thermometers for Distillation Test of Industrial lindrical type, of uniform diameter, with a pressed or molded
Aromatic Hydrocarbons
base and a lipped top. The cylinder shall be marked to contain
ASTM
Ther- Subdivision,
100 mL, and the 0 to 100 mL receiver portion shall be not less
Name Range, °C than 178 nor more than 203 mm in length. It shall be graduated
mometer °C
No. in single millilitres and each fifth mark shall be distinguished
39C solvents distillation 48 to 102 0.2 by a longer line. It shall be numbered from the bottom up at
40C solvents distillation 72 to 126 0.2 intervals of 10 mL. The overall height of the receiver shall not
41C solvents distillation 98 to 152 0.2
42C solvents distillation 95 to 255 0.5 be less than 248 nor more than 260 mm. The graduations shall
102C solvents distillation 123 to 177 0.2 not be in error by more than 1 mL at any point on the scale. The
103C solvents distillation 148 to 202 0.2 bottom 1-mL graduation may be omitted. The receiver com-
104C solvents distillation 173 to 227 0.2
105C solvents distillation 198 to 252 0.2 plies with Section 9, Graduate B Fig. 4, of Specification E 133.
6.4.2 Automatic Distillation Receiver—A receiver to be
2
D 850
FIG. 2 Examples of Centering Device Designs for Straight-Bore Neck Flasks
used with measurements in accordance with the instrument 8. Sampling

manufacturer and conform to the physical specifications de- 8.1 Sampling should follow safe rules in order to adhere to
scribed in this section, with the exception of the graduations. all safety precautions as outlined in the latest OSHA regula-
6.4.2.1 Automatic Distillation Level Follower—For auto- tions. Refer to Practice D 3437 for proper sampling and
matic apparatus, the level follower or recording mechanism of handling of aromatic hydrocarbons analyzed by this test
the apparatus will have a resolution of 0.1 mL with an accuracy method.
of 6 1 mL. The calibration of the assembly should be 8.2 The sample under test shall be transparent and free of
confirmed according to the manufacturer’s instructions at separated water. Any separated water may ordinarily be elimi-
regular intervals. The typical calibration procedure involves nated by care in pouring the 100-mL specimen (10.1) into the
verifying the output with the receiver containing 5 and 100 mL graduated cylinder. If necessary, any separated water or cloudi-
of material respectively. ness may be removed by filtration, in which case the following
6.5 Support for Flask—A sheet of 3 to 6-mm hard insulation precautions shall be taken: Use a soft paper through which the
board 152 mm square with a circular hole in the center, specimen filters rapidly, avoid drafts, cover the funnel with a
supported on a circular metal shield enclosing the bunsen watch glass, and filter at least 200 mL from which to take the
burner, and approximately 50 mm higher than the top of the 100 mL for distillation. Dehydration (that is, removal of
burner. For tests of benzene and toluene, the hole shall be 25 dissolved water) is not permissible. Note, however, that certain
mm in diameter; for tests of materials boiling above toluene but materials, especially benzene, may absorb traces of water that
mostly below 145°C, the hole shall be 38 mm in diameter, and can be significant with respect to this test. When it can be
for higher boiling materials, it shall be 50 mm in diameter. shown that failure to pass this distillation test is due to the
6.6 Heater: presence of dissolved water, it shall be permissible, if mutually
6.6.1 Manual Distillation Heater—An electric heater or a agreeable to the purchaser and the seller, to dry the specimen
bunsen burner, fully adjustable and capable of giving sufficient by any method agreed to by both the purchaser and the seller.
heat to distill the product at the required rate. When a bunsen
burner is used, as described in 7.1 and Fig. 1 of Specification 9. Assembly of Apparatus
E 133, the burner shall be adjusted so as to produce an entirely 9.1 Manual Distillation Apparatus:
blue flame. 9.1.1 Remove any residual liquid in the condenser tube by
swabbing with a piece of lint-free cloth attached to a cord or
NOTE 2—Caution: Superheating of the flask can cause erroneous
results and is more likely to occur with electric heaters than with bunsen wire.
burners as heat sources. This problem is discussed in the section on 9.1.2 Assemble the apparatus as shown in Fig. 2. Mount the
Preparation of Apparatus in Test Method D 1078. flask on the insulation board of appropriate dimensions, with
the side tube extending through a tightly fitting silicone or cork
7. Hazards stopper about 50 mm into the condenser tube.
7.1 Consult current OSHA regulations’ and supplier’s Ma- 9.1.3 Support the distillation thermometer in the neck of the
terial Safety Data Sheets, and local regulations, for all materi- flask by means of a cork or silicone stopper with the thermom-
als used in this test method. eter vertical and centered in the neck of the flask and in such
3
D 850
a position that the top of the bulb (or top of contraction bulb if Regulate the rate of heating so that the ring of condensing
present) is level with the lowest point of juncture between the vapor on the wall of the flask reaches the lower edge of the side
side tube and the neck of the flask (see Fig. 3). arm in not less than 90 s, and preferably approximately 120 s,
9.1.4 Place the burner directly under the center of the hole from the start of the rise of the vapor ring. The total time from
in the insulation board. the start of heating until the first drop falls into the receiver
9.2 Automatic Distillation Apparatus—For assembly of au- should be not less than 5 nor more than 10 min. Avoid major
tomatic distillation apparatus, consult the instrument manufac- changes in heating rate. Even operation is best gained through
turer’s operating manual. experience with the method. When distillation starts, adjust the
NOTE 3—The centering device must be as stated in 6.2.2.1 (Fig. 2). receiver to allow condensation to flow down its inner wall to
prevent loss by spattering; then adjust the heater to continue the
9.3 Carefully measure a 100-mL specimen of the material to distillation at the rate of 5 to 7 mL/min (about 2 drops/s).
be tested in the 100-mL graduated cylinder at room tempera- Maintain this rate, and continue the distillation to dryness. The
ture and transfer to the distillation flask, draining the cylinder total yield of distillate when testing close boiling benzenes,
at least 15 s. This is preferably done before mounting the flask toluenes, and xylenes shall be not less than 97 %, and when
in position, in order to prevent liquid from entering the side testing wider boiling refined products and light oils, shall be
arm. Do not rinse out the graduated cylinder used to measure not less than 95 %; otherwise, the test shall be repeated.
the sample for distillation, but place under the lower end of the
condenser tube to receive the distillate. 10.1.3 Take the temperature reading when the first drop of
9.4 Fit the flask vapor tube, provided with a snug fitting distillate falls into the receiving cylinder and report as the
silicone rubber stopper, tightly into the condenser tube. Adjust initial boiling point (IBP). If necessary, take additional read-
the flask in a vertical position so that the vapor tube extends ings when 5, 10, each additional 10 up through 90, and 95 %
into the condenser tube for a distance of 25 to 50 mm (1 to 2 of the specimen has just distilled over. Take a final reading
in.). Raise and adjust the flask support board to fit snugly when the liquid just disappears from the lowest point in the
against the bottom of the flask. flask, and report this reading as the dry point temperature.
9.5 Place the cylinder which was used to measure the When testing crude materials, a decomposition point, rather
charge, without drying, into its position under the lower end of than a dry point, may be obtained. When a decomposition point
the condenser tube so that the end of the condenser tube is is reached at the end of a distillation, the temperature will
centered in the graduate and extends in for a distance of at least frequently cease to rise and begin to fall. In this case, take the
25 mm (1 in.). temperature at the decomposition point as the maximum
temperature observed. The decomposition point may also be
10. Procedure indicated by the appearance of heavy fumes in the flask.
10.1 Manual Distillation Procedure: Should that occur, record the temperature at the time the bulb
10.1.1 Connect the flask to the condenser apparatus as of the flask becomes substantially full of fumes. If a decom-
described in Section 9. Fit the thermometer to the flask as position rather than a dry point is observed, so note when
described in 9.1. recording results.
10.1.2 Heat the flask slowly, especially after boiling has 10.1.4 Observe and record any correction for inaccuracy of
begun, so as to allow the mercury column of the thermometer the thermometer at the time and place of the distillation test.
to become fully expanded before the first drop distills over. 10.2 Automatic Distillation Procedure:
FIG. 3 Position of Thermometer in Measuring Device in Distillation Flask
4
D 850
10.2.1 Connect the distillation flask to the automatic distil- TABLE 3 Boiling Points of Hydrocarbons
lation equipment as described in 9.2. Fit the temperature Boiling Point, °C
measuring device to the flask for automatic distillation equip- Cyclohexane 78.0
ment according to the manufacturer’s instructions. Benzene 80.1
Ethylbenzene 136.2
10.3 Barometer Reading and Temperature of the Pyridine 115.5
Barometer—The observed barometric pressure shall be cor- Toluene 110.6
rected by reference to standard tables and reported in terms of m-Xylene 139.1
o-Xylene 144.4
millimeters of mercury at 0°C. p-Xylene 138.3
11. Temperature Corrections

11.1 Corrections of temperature should be applied in the
12.2 In the ASTM specifications where Test Method D 850
following cases:
is cited, the distillation range is defined as:
11.1.1 When required by the specifications,
11.1.2 When there is any question of compliance with the Distillation range, °C 5 DPT–IBP (2)
specifications, and where DPT is the dry point temperature and IBP is the initial
11.1.3 When tests of the sample are to be checked against boiling point.
results obtained by another investigator. 12.3 In cases where decomposition points occur, the distil-
NOTE 4—When corrected temperatures are reported, notation should be
lation range is defined as:
made of the type of corrections applied. Distillation Range °C 5 DCPT 2 IBP (3)
11.2 Inaccuracy of Thermometer—This correction shall be where:
obtained by calibration of the thermometer used in the test and DCPT = the temperature at the decomposition point, and
applied to the observed thermometer reading. IBP = the initial boiling point.
11.3 Variation from Standard Barometric Pressure—This
correction shall be applied to the observed temperature after 13. Precision and Bias
correcting for inaccuracy of the thermometer and is determined 13.1 Precision: Manual Distillation Method—The follow-
by the following equation: ing criteria should be used for judging the acceptability of
C 5 @A 1 $B 3 ~760 2 P!%# 3 ~760 2 P! (1) results (95 % confidence) on distillation determined by the
manual method:
where: 13.1.1 Intermediate Precision—Duplicate results by the
C = the correction in degrees Celsius, same operator should be considered suspect if they differ by
A, B = constants from Table 2, more than the following amounts:
P = the measured barometric pressure in millimetres of
°C
mercury corrected to 0°C.
11.4 Combined Corrections—If the overall distillation Cyclohexane 0.17
range of the sample does not exceed 2°C, a combined correc- Benzene 0.16
Toluene 0.23
tion for thermometer inaccuracy and barometric pressure may Xylene 0.26
be made on the basis of the difference between the observed
50 % boiling point and the true boiling point at 760 mm as 13.1.2 Reproducibility—Results submitted by each of two
given in Table 3. laboratories should be considered suspect if the two results
differ by more than the following amounts:
12. Report °C
12.1 Report observed temperatures to the nearest 0.1°C, in Benzene 0.42

a manner conforming to the specifications of the material Toluene 0.47
tested. If no definite manner of reporting is specified, report the Xylene 0.42
corrected temperatures at each observed volume, and report the NOTE 5—There was insufficient data for cyclohexane to determine
volume percentages of residue, recovery, and distillation loss. reproducibility.
13.2 Precision: Automatic Distillation Method—The fol-
TABLE 2 Constants for Correction for Variations in Barometric lowing criteria should be used for judging the acceptability of
Pressure (600 to 800-mm Hg)
results (95 % confidence) on distillation range determined by
Material A B the automatic method. The precision criteria was derived from
Benzene 0.0427 0.000025 the interlaboratory data submitted by nine different laborato-
Toluene 0.0463 0.000027
Ethylbenzene 0.0490 0.000028
ries. Each sample was run twice in two days by two different
o-Xylene 0.0497 0.000029 operators. Results were analyzed in accordance with Practice
m-Xylene 0.0490 0.000029 E 691.
p-Xylene 0.0492 0.000029
Mixed xylenes 0.0493 0.000029
13.2.1 Intermediate Precision—Duplicate tests by the same
Grade xylene operator should be considered suspect if they differ by more
Solvent naphtha 0.0493 0.000029 than the following amounts:
Hi-flash solvent 0.0530 0.000032
Response Intermediate Precision
5
D 850
Toluene (Automatic Method) IBP 0.238
Dry Pt 0.230 Response Reproducibility
Xylene (Automatic Method) IBP 0.964
Response Intermediate Precision 50 % Pt 0.439
Xylene (Automatic Method) IBP 0.409 Dry Pt 0.390
50 % Pt 0.239
Dry Pt 0.264 NOTE 7—There was insufficient data for cresol to determine reproduc-
ibility.
Response Intermediate Precision
Cresol (Automatic Method) IBP 0.681 13.3 Bias: Manual and Automatic Distillation Methods—
50 % Pt 0.423
Dry Pt 0.675
There was no significant bias found between data for this test
method, as none of the T values for toluene or mixed xylene are
NOTE 6—Cresol data was analyzed with ANOVA (due to insufficient significant at the 95 % confidence level.
data to analyze with Practice E 691).
NOTE 8—For this test method, automatic distillation data are based on
13.2.2 Reproducibility— Results submitted by each of two
automatic distillation apparatus (ADA) with dry point sensors. The
laboratories should be considered suspect if the two results precision and bias statements for this test method are therefore only valid
differ by more than the following amounts: for ADA units with dry point sensing devices.
Response Reproducibility
Toluene (Automatic Method) IBP 0.581 14. Keywords
50 % Pt 0.156
Dry Pt 0.456 14.1 aromatic hydrocarbons; distillation
SUMMARY OF CHANGES
Committee D 16 has identified the location of selected changes to this standard since the last issue that may
impact the use of this standard.
(1) 13.2 Automatic Distillation Method: The removal of diate precision was not practically attainable. Since the 50 %
toluene 50 % was initially included using research report data point for pure products such as toluene must meet 110.6 in
for which the baraometric pressure had been corrected. Due to accordance with this test method, it was deemed by those in
the accuracy of the thermocouples, the variance and corre- attendance at the June 2000 ASTM D16 meetings that the
sponding intermediate precision was very tight. It was brought inclusion of the Toluene Intermediate Precision was not nec-
to the attention of the D16.OE Subcommittee that the interme- essary.
6

Solidification Point of Benzene1
1. Scope * 3.1.1 solidification point—an empirical constant defined as

1.1 This test method covers the determination of the solidi- the temperature at which the liquid phase of a substance is in
fication point of benzene. approximate equilibrium with a relatively small portion of the
1.2 The following applies to all specified limits in this test solid phase.
method: for purposes of determining conformance with this 3.1.1.1 Discussion—Solidification point is distinguished
test method, an observed value or a calculated value shall be from freezing point which is described in Test Method D 1015.
rounded off “to the nearest unit” in the last right-hand digit An interpretation of mol percent purity in terms of freezing
used in expressing the specification limit, in accordance with point is given in Test Method D 1016.
the rounding-off method of Practice E 29. 4. Summary of Test Method
safety concerns, if any, associated with its use. It is the 4.1 Solidification point is measured by noting the maximum
responsibility of the user of this standard to establish appro- temperature reached during a controlled cooling cycle after the
priate safety and health practices and determine the applica- appearance of a solid phase.
bility of regulatory limitations prior to use. For specific hazard 5. Significance and Use
statements, see Section 7.
5.1 This test method may be used as a criteria for determin-
2. Referenced Documents ing the purity of benzene. The closer the solidification point
2.1 ASTM Standards: reaches that of pure benzene, the purer the sample.
D 1015 Test Method for Freezing Points of High-Purity 6. Apparatus
Hydrocarbons2
D 1016 Test Method for Purity of Hydrocarbons from 6.1 Benzene Container (Air Jacketed):
Freezing Points2 6.1.1 Inner Container, a test tube 15 mm in outside diameter
D 1193 Specification for Reagent Water3 and 125 mm in length.
D 3437 Practice for Sampling and Handling Liquid Cyclic 6.1.2 Air Jacket, a standard test tube 25 mm in outside
Products4 diameter and 150 mm in length.
E 1 Specification for ASTM Thermometers5 6.1.3 Insulation—Dry absorbent cotton or glass wool.
E 29 Practice for Using Significant Digits in Test Data to 6.2 Benzene Container (thick walled), a glass test tube 18
Determine Conformance with Specifications6 mm in outside diameter, 14 mm in inside diameter and 150 mm
2.2 Other Document: in length.
OSHA Regulations, 29CFR, paragraphs 1910.1000 and 6.3 Ice Bath, a 1-L beaker, or similar suitable container,
1910.12007 having an effective depth of at least 127 mm and filled with
chipped or shaved ice.
3. Terminology 6.4 Stirrer, consisting of a 1-mm wire (copper or stainless
3.1 Definitions: steel) or a 2-mm glass rod with one end bent into a circular
form at right angles to the shaft so that it will move freely in
1
the annular space between the thermometer stem and the wall
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of of the smaller test tube.
Subcommittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their 6.5 Temperature Measurement Device, either device de-
Derivatives. scribed below has been found satisfactory.
6.5.1 Thermometer, an ASTM Benzene Freezing Point
2
Annual Book of ASTM Standards, Vol 05.01. Thermometer having a range from 4.0 to 6.0°C and conform-
3
Annual Book of ASTM Standards, Vol 11.01. ing to the requirements for Thermometer 112C as prescribed in
4
Annual Book of ASTM Standards, Vol 06.04. Specification E 1.
5
6
Annual Book of ASTM Standards, Vol 14.02. 6.5.2 Thermistor, Type CSP with accuracy of 0.01° C with
7
Available from Superintendent of Documents, U.S. Government Printing a nominal resistance at 2500 V at 25°C. The thermistor shall be
Office, Washington, DC 20402.

1
D 852
equipped with an ohm meter capable of reading resistance to termistor should be inserted so as to contact the benzene
the nearest 0.1 V. solution. Through the other hole insert shaft of the stirrer.
6.6 Stirring Apparatus (Optional), the apparatus illustrated 9.2 If using the benzene container (air jacketed), place a
in Fig. 1 has been demonstrated to be an acceptable replace- 1⁄8-in. (3.2-mm) layer of dry absorbent cotton or glass wool in
ment for manually stirring the benzene solution. the bottom of the larger test tube and insert the inner container
up to the lip into a cork stopper or annular ring of cork that just
7. Hazards fits into the mouth of the air jacket.
7.1 Consult the latest OSHA regulations, supplier’s Material
Safety Data Sheets, and local regulations for all materials used 10. Calibration of Temperature Measuring Device
in this test method. 10.1 Calibration of ASTM thermometer 112C is accom-
plished with the small scale etched on the lower portion of the
8. Sampling thermometer. Prepare an ice bath by filling a small Dewar flask
8.1 Sample the material in accordance with Practice with crushed ice made from Type I or Type II water (as
D 3437. specified in Specification D 1193) and add just enough chilled
Type I or Type II water to make a slurry. Immerse the
9. Preparation of Apparatus thermometer in the ice bath, allow 5 min for the system to
9.1 Fit the benzene container with a two-hole cork stopper. reach equilibrium and read the thermometer. When using a
Through one hole insert the temperature measurement device. thermistor, the ohmic value is readand converted to tempera-
The thermometer should be inserted up to the 4.0°C mark. The ture by using the calibration data supplied by the manufacturer.
FIG. 1 Benzene Solidification Point Apparatus Set Up
2
D 852
Solidification point values are subsequently adjusted by adding the determination is actually made on water-saturated benzene,
(or subtracting) the number of degrees the thermometer is the solidification point shall be corrected to the anhydrous basis
below (or above) 0.00°C. by adding 0.09°C to the observed maximum temperature
following the minimum. Corrections for accuracy of the
11. Procedure
thermometer shall be made.
11.1 Saturate the sample of benzene with water as follows:
Place 7 to 8 mL of the sample in the benzene container, add 1 13. Precision and Bias
drop of water, and shake the tube and contents vigorously.
11.2 Place the cork stopper onto the benzene container and 13.1 Precision—The following criteria shoud be used to
onto the stirring apparatus, if available. judge the acceptability (95 % probability level) of results
11.3 When using the benzene container (air jacket), the obtained by this test method. The criteria were derived from an
operator may cool the smaller test tube and contents rapidly to interlaboratory study between six laboratories. One sample was
about 6°C in the ice bath, while stirring. Wipe dry the outside analyzed in triplicate in one day using a thermistor and a thick
of the smaller test tube and insert it into the larger test tube. walled glass test tube.
Place the assembled tubes in the ice bath. 13.1.1 Repeatability—Results in the same laboratory should
11.4 Stir the benzene continuously and observe the ther- not be considered suspect unless they differ more than 0.03 °C.
mometer reading closely. The temperature will fall to a On the basis of test error alone, the difference between two
minimum, then rise to a maximum, remain constant at this results obtained in the same laboratory on the same material
maximum for approximately 15 s, and then fall again (Note 1). will be expected to exceed this value only 5 % of the time.
The minimum temperature is due to super-cooling before
solidification starts and shall not be more than 0.7°C below the 13.1.2 Reproducibility—Results submitted by each of two
maximum. Record the maximum constant temperature ob- laboratories should not be considered suspect unless they differ
served to the nearest 0.01°C and designate it as “wet” (Note 2). by more than 005 °C. On the basis of test error alone, the
difference between two test results obtained in different labo-
NOTE 1—If distinct minimum and maximum points are not evident, or ratories on the same material will be expected to exceed this
if the temperature does not remain constant at the maximum for at least 15
s, the determination shall be repeated. value only 5 % of the time.
NOTE 2—The precision can be increased to 60.01°C by using a 13.2 Bias—ce there is no accepted reference material suit-
magnifying glass that ensures a reading perpendicular to the stem of the able for determining the bias for the procedure, bias has not
thermometer. In such cases it may be necessary to correct for stem been determined.
exposure, that under ordinary conditions this correction will be less than
0.01°C.
14. Keywords
12. Report
14.1 benzene; solidification point
12.1 Results shall be reported on the anhydrous basis. Since
SUMMARY OF CHANGES
(1) Correction of temperature in Fig. 1. 2) Addition of new Precision and Bias statement.
3

Hydrogen Sulfide and Sulfur Dioxide Content (Qualitative) of
Industrial Aromatic Hydrocarbons1

1.1 This test method covers the determination of the hydro- 5.1 This test method is suitable for setting specifications on
gen sulfide and sulfur dioxide content (qualitative) of industrial industrial aromatic hydrocarbons and related materials and for
aromatic hydrocarbons. use as an internal quality control tool.
1.2 This standard does not purport to address all of the 5.2 This test method is a qualitative one for hydrogen
safety concerns, if any, associated with its use. It is the sulfide (H2S) and sulfur dioxide (SO2). It should not be
responsibility of the user of this standard to establish appro- considered quantitative. It gives an indication of the presence
priate safety and health practices and determine the applica- of H2S or SO2, or both, which may cause objectionable odors
bility of regulatory limitations prior to use. For specific hazard or be corrosive to certain materials of construction.
statements see Section 6.
6. Reagents
2. Referenced Documents 6.1 Lead Acetate Solution (saturated).
2.1 ASTM Standards: 6.2 Potassium Iodate Solution (100 g/L)—Dissolve 10 g of
D 850 Test Method for Distillation of Industrial Aromatic potassium iodate (KIO3) in water and dilute to 100 mL.
Hydrocarbons and Related Materials2 6.3 Starch Paper—Dip strips of filter paper in starch solu-
D 3437 Practice for Sampling and Handling Liquid Cyclic tion and dry.
Products2
D 4790 Terminology of Aromatic Hydrocarbons and Re- 7. Hazards
lated Chemicals2 7.1 Consult current OSHA regulations, supplier’s Material
2.2 Other Documents: Safety Data Sheets, and local regulations for all materials used
OSHA Regulations, 29 CFR, Paragraphs 1910.1000 and in this test method.
1910.12003
8. Sampling
3. Terminology 8.1 Sampling should follow safe rules in order to adhere to
3.1 See Terminology D 4790 for Definition of terms used in all safety precautions as outlined in the latest OSHA regula-
this test method. tions. Refer to Practice D 3437 for sampling and handling of
aromatic hydrocarbons analyzed by this test method.
4.1 This test method involves a qualitative color test for H2S 9. Procedure
and SO2 that utilizes filter paper containing lead acetate and 9.1 Make a qualitative test for H2S and SO2, at the time of
starch paper containing potassium iodate. The test is performed performing the distillation test, see Test Method D 850. This is
when carrying out the Test Method D 850 distillation test. done by hanging a strip of filter paper moistened with the lead
acetate solution and a strip of starch paper moistened with the
potassium iodate solution on the end of the condenser tube.
1
This test method is under the jurisdiction of ASTM Committee D-16 on The strips are placed so that they are suspended in the upper
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of part of the receiving cylinder so that drops of condensate pass
Subcommittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their
Derivatives.
between the strips without touching them. If, at the end of the
Current edition approved June 10, 1997. Published September 1997. Originally test, the lead acetate paper shows discoloration, H2S is present
published as D 853 – 45 T. Last previous edition D 853 – 91. but not SO2. If the lead acetate paper shows no discoloration
2
Annual Book of ASTM Standards, Vol 06.04. but the starch iodate paper develops a blue color, SO2 is present
3
1
D 853
but not H2S. If neither paper shows discoloration, neither H2S 11. Keywords
nor SO2 is present.
11.1 hydrogen sulfide; sulfur dioxide
10.1 In the case of pass/fail data, no generally accepted
method for determining precision and bias is currently avail-
able.
2

Cellulose Acetate1
1. Scope specifications are available.4 Other grades may be used, pro-

1.1 These test methods cover procedures for testing cellu- vided it is first ascertained that the reagent is of sufficiently
lose acetate. high purity to permit its use without lessening the accuracy of
1.2 The test procedures appear in the following sections: the determination.
Sections
Ash 8 to 11 understood to mean reagent tared, low, wide-form weighing
Color and Haze 67 to 72 bottle and water, conforming to Specification D 1193.
Combined Acetyl or Acetic Acid Content
Test Method A. Solution Method 17, 19 to 23
Test Method B. Heterogeneous Saponification Method 17, 24 to 26
MOISTURE CONTENT
Free Acidity 12 to 16
Heat Stability 47 to 56 4. Significance and Use
Hydroxyl Content 27 to 33
Intrinsic Viscosity 57 to 62
4.1 Moisture content of the cellulose ester can be used to
Moisture Content 4 to 7 estimate the dry weight of the cellulose ester. Since cellulose
Primary Hydroxyl Content 34 to 39 esters are desiccants, their moisture content can vary greatly
Sulfur or Sulfate Content 40 to 45
Viscosity 63 to 66
depending on storage.
This standard does not purport to address the safety con- 5. Procedure
cerns, if any, associated with its use. It is the responsibility of 5.1 Transfer about 5 g of the sample to a tared, low,
the user of this standard to establish appropriate safety and wide-form weighing bottle and weigh to the nearest 0.001 g.
health practices and determine the applicability of regulatory Dry in an oven for 2 h at 105 6 3 C. Remove the bottle from
limitations prior to use. the oven, cover, cool in a desiccator, and weigh.
2. Referenced Documents 6. Calculation
2.1 ASTM Standards: 6.1 Calculate the percentage of moisture as follows:
Moisture, % 5 ~A/B! 3 100
D 1343 Test Method for Viscosity of Cellulose Derivatives
by Ball-Drop Method3 where:
D 2929 Test Method for Sulfur Content of Cellulosic Ma- A 5 weight loss on heating, g, and
terials by X-Ray Fluorescence3 B 5 sample used, g.
D 5897 Test Method for Determination of Percent Hydroxyl
on Cellulose Esters by Potentiometric Titration— 7. Precision and Bias
Alternative Method3 7.1 No statement on bias can be made as no reference
3.1 Reagent grade chemicals shall be used in all tests. ASH
Unless otherwise indicated, it is intended that all reagents shall 8. Significance and Use
Reagents of the American Chemical Society, where such 8.1 Ash content gives an estimate of the inorganic content
of cellulose ester samples. The presence of high levels of
inorganic content (ash) can be detrimental to the melt stability
1
and Related Coatings, Materials, and Applications and are the direct responsibility 4
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Nov. 10, 1996. Published January 1997. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 871 – 46. Last previous edition D871 – 91. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 871
and optical clarity of a cellulose ester in melt processing or act 15. Calculation
as a potential source of insolubles when the ester is used in 15.1 Calculate the percentage of acidity as free acetic acid
solution. as follows:
9. Procedure Free acetic acid, % 5 @~A 2 B!N 3 0.06 3 100#/W (1)
9.1 Dry the sample for 2 h at 105 6 3°C and weigh 10 to 50 where:
g, to the nearest 0.01 to 0.1 g, depending on its ash content and A 5 NaOH solution used to titrate the sample, mL,
the accuracy desired. An air-dried sample may be used and B 5 NaOH solution used to titrate the blank, mL,
calculated to dry weight using the value for moisture deter- N 5 normality of the NaOH solution, and
mined as in Sections 5 and 6. Burn directly over a flame in a W 5 sample used, g.
100-mL tared platinum crucible that has been heated to
constant weight and weighed to the nearest 0.1 mg. Add the 16. Precision and Bias
sample in portions if more than 10 g is taken. The sample 16.1 No statement on bias can be made as no reference
should burn gently and the portions should be added as the material is available as a standard.
flame subsides. Continue heating with a burner only as long as
the residue burns with a flame. Transfer the crucible to a muffle COMBINED ACETYL OR ACETIC ACID
furnace and heat at 550 to 600°C for 3 h, or longer if required, CONTENT
to burn all the carbon. Allow the crucible to cool and then
transfer it, while still warm, to a desiccator. When the crucible 17. Scope
has cooled to room temperature, weigh accurately to the 17.1 Two test methods are described for determining the
nearest 0.1 mg. combined acetyl or acetic acid content. The first, described in
Sections 19 to 22, is more precise, but less widely applicable,
10. Calculation than the method described in Sections 24 to 26.
10.1 Calculate the percentage of ash as follows:
Ash, % 5 ~A/B! 3 100
18.1 Acetyl or acetic acid content is a measure of the
where: amount of acetic acid esterified onto the cellulose backbone of
A 5 ash, g, and the polymer. The amount of substitution of acetate ester has a
B 5 sample used, g. very strong effect on the polymer’s solubility and physical
11. Precision and Bias properties.
11.1 No statement on bias can be made as no reference Test Method A—Solution Method
19. Apparatus
FREE ACIDITY
19.1 Weighing Bottle, glass-stoppered, 15-mL capacity,
12. Significance and Use 25-mm diameter by 50-mm high.
12.1 Free Acidity is a measure of unesterified organic acid 19.2 Tray, copper or aluminum, approximately 5 3⁄8 in.
in the ester. The presence of high levels of free acid is (136.5 mm) square, containing 25 compartments 1 in. (25.4
potentially detrimental to the melt processing of the ester and mm) square. Each compartment shall have the correct dimen-
can impact the odor of the ester. sions to contain one weighing bottle. The entire tray shall fit
inside a desiccator and should have a basket-type handle to
13. Reagents facilitate the introduction and removal of the tray (convenient
13.1 Phenolphthalein Indicator Solution (1 g/100 mL)— but not essential).
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol 19.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem
(95 %). graduated from 25 to 35 mL in 0.05-ml increments; or pipet,
13.2 Sodium Hydroxide, Standard Solution (0.01 N)— automatic zero, 30-mL, for 1.0 N NaOH solution.
Prepare and standardize a 0.01 N solution of sodium hydroxide 19.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem
(NaOH). graduated from 10 to 15 mL in 0.05-mL increments, for 1 N
H2SO4.
14. Procedure 19.5 Buret, 5-ml, in 0.01 or 0.1-mL divisions, for back
14.1 Shake 5 g of the sample, ground to pass a No. 20 (850 titration with 0.1 N NaOH solution.
µm) sieve and corrected for moisture content if necessary, in a 19.6 Magnetic Stirrer, for single flask.
250-mL Erlenmeyer flask with 150 mL of freshly boiled, cold 19.7 Magnetic Stirrer, capacity twelve or more flasks.
water. Stopper the flask and allow it to stand for 3 h. Filter off 19.8 Stirring Bars, stainless steel Type 416, length 50 mm,
the cellulose acetate and wash it with water. Titrate the diameter 5 to 6 mm, or equivalent, dimensions not critical.
combined filtrate and washings with 0.01 N NaOH solution,
using phenolphthalein indicator solution. 20. Reagents
14.2 Run a blank determination on the water, using the same 20.1 Acetone—Add one 30-mL portion of 1.0 N NaOH
volume as was used in extracting the sample. solution to a mixture of 150 mL acetone and 100 mL hot water,
2
D 871
allow to stand with frequent swirling for 30 min, and titrate is not available, spread the sample in a thin layer over the
with 1.0 N H2SO4. Add another 30-mL portion of 1.0 N NaOH bottom of the flask, add 15 mL of acetone, swirl to wet the
solution to 100 mL of hot water, allow to stand for 30 min, and particles with acetone, stopper the flask, and allow the mixture
titrate. The difference between the two titrations shall not to stand undisturbed for 20 min. Add 75 mL of pyridine
exceed 0.05 mL. without shaking or swirling, and allow to stand for 10 min.
20.2 Dimethyl Sulfoxide. Heat the solution just to boiling and swirl or stir for 5 min.
20.3 Pyridine. Again heat to boiling and swirl or stir for 10 min. Continue to
20.4 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of heat and stir until the mixture is homogeneous and all large gel
sodium hydroxide (NaOH) in water and dilute to 1 L. masses are broken down into individual highly swollen par-
20.5 Sodium Hydroxide, Standard Solution (0.1 N)— ticles. When these highly swollen gel particles are well
Prepare and standardize a 0.1 N solution of NaOH. dispersed and are not fused together in large gel masses, no
20.6 Sulfuric Acid (1.0 N)—Prepare and standardize a 1.0 further heating is necessary. Cool the flask, add 30 mL of
N solution of sulfuric acid (H2SO4). acetone, and swirl or stir for 5 min. Proceed in accordance with
20.7 Phenolphthalein Indicator Solution (1 g/100 mL)— 21.4.
Dissolve 1 g of phenolphthalein in 100 ml of ethyl alcohol 21.4 Add 30 mL of NaOH solution (40 g/L) with constant
(95 %). swirling or stirring to the solution of the sample and also to the
blank. Use of a magnetic stirrer is recommended (Note 2). It is
21. Procedure absolutely necessary that a finely divided precipitate of regen-
21.1 Dry 1.9 6 0.05 g of the ground well-mixed sample in erated cellulose, free from lumps, be obtained. Stopper the
a weighing bottle for 2 h at 105 6 3°C and weigh the dried flask and let the mixture stand with occasional swirling, or stir
sample by difference to the nearest 1 mg into a 500-mL on the magnetic stirring unit. Allow 30 min for saponification
wide-mouth Erlenmeyer flask. Prepare a blank by drying of lower acetyl samples, 2 h for high acetyl samples when
approximately 3.8 g of potassium acid phthalate and weighing dimethyl sulfoxide is the solvent, and 3 h when pyridine is the
it by difference into a flask as described. Carry the blank solvent. At the end of the saponification period, add 100 mL of
through the entire procedure. hot water, washing down the sides of the flask, and stir for 1 or
NOTE 1—Potassium acid phthalate is used so that the concentration of 2 min. Add 4 or 5 drops of phenolphthalein indicator solution
the NaOH in contact with the solvent in the blank will be approximately and titrate the excess NaOH solution with 1.0 N H2SO4 (Note
the same as that in contact with the sample and so that the titration of the 3). Titrate rapidly with constant swirling or stirring ring until
blank will be approximately the same as the titration of the sample, thus the end point is reached; then add an excess of 0.2 or 0.3 mL
avoiding errors caused by using a different buret for the titration of the of H2SO4. Allow the mixture to stand with occasional stirring
blank and the sample or by refilling the 15-mL buret. If desired, however, or preferably stir on the magnetic stirrer for at least 10 min.
the potassium acid phthalate may be omitted.
Then add 3 drops of phenolphthalein indicator solution to each
21.2 If the acetyl content is 32 to 41 % or the acetic acid flask and titrate the small excess of acid with 0.1 N NaOH
content is 45 to 57 %, put the sample into solution as follows: solution to a persistent phenolphthalein end point. Take ex-
Add 150 mL of acetone and 5 to 10 mL of water and swirl to treme care to locate this end point; after the sample is titrated
mix. Stopper the flask and allow it to stand with occasional to a faint pink end point, swirl the mixture vigorously or place
swirling until solution is complete. Solution may be hastened it for a moment on the magnetic stirrer. If the end point fades
by magnetic stirring or by any suitable mechanical shaking that because of acid soaking from the cellulose, continue the
will provide a gentle rocking type of agitation to avoid addition of 0.1 N NaOH solution until a faint persistent end
splashing the solution on the stopper. It is essential that point remains after vigorous swirling or stirring. Titrate the
complete solution be effected. Proceed in accordance with blank in the same manner as the sample.
21.4.
21.3 If the acetyl content is 41 to 44.8 % or the acetic acid NOTE 2—While the amount of magnetic stirring is somewhat optional,
such stirring during the entire period of the determination is strongly
content is 57 to 62.5 %, dissolve the sample by either of the recommended. Solution is more rapid, titrations are more rapid, and the
following two methods: end point can be approached directly and without a back titration.
21.3.1 Gently rotate the flask by hand to distribute and NOTE 3—It is important to correct all 1.0 N H2SO4 buret readings for
spread the sample in a thin layer over the bottom of the flask. temperature and buret corrections.
Add 70 mL of acetone to the flask and swirl gently until the
sample particles are completely wetted and evenly dispersed. 22. Calculation
Stopper the flask and allow it to stand undisturbed for 10 min. 22.1 Calculate the percentage by weight of acetyl and acetic
Carefully add 30 mL of dimethyl sulfoxide from a graduate to acid as follows:
the flask, pouring the solvent down the sides of the flask to
Acetyl or acetic acid, % (2)
wash down any sample particles clinging to the side. Stopper
the flask and allow it to stand with occasional swirling until 5 @~D 2 C!Na 1 ~A 2 B!Nb 1 P# 3 ~F/W! ~Note 4!
solution is complete. Magnetic stirring or gentle mechanical P 5 ~GH 3 1000!/204.2
agitation that will not splash the solution is recommended.
When solution appears to be complete, add 50 mL of acetone where:
and swirl or stir for 5 min. Proceed in accordance with 21.4.
mL,
21.3.2 Dimethyl sulfoxide is the preferred solvent, but if it
3
D 871
B 5 NaOH solution required for titration of the blank, mL, of HCl with 0.5 N NaOH solution to a phenolphthalein end
Nb 5 normality of the NaOH solution, point. Extreme care must be taken to locate this end point.
C 5 H2SO4 required for titration of the sample, mL, After the sample is titrated to a faint pink end point, stopper the
D 5 H2SO4 required for titration of the blank, mL, flask and shake vigorously. The end point may fade because of
Na 5 normality the H2SO4, acid diffusing from the cellulose. Continue the addition of 0.5
F 5 4.305 for acetyl and 6.005 for acetic acid, N NaOH solution and shaking until the faint pink end point
P 5 milliequivalents of potassium acid phthalate, persists after vigorous shaking of the flask.
G 5 potassium acid phthalate used, g,
H 5 purity factor for potassium acid phthalate, and 26. Calculation
W 5 sample used, g.
26.1 Calculate the percentage of combined acetyl or acetic
NOTE 4—When equal volumes of alkali or acid are added to samples acid as follows:
and blank, these amounts cancel out. Thus only the amounts of each added
acetyl or acetic acid, % 5 @~D 2 C!Na 1 ~A 2 B!Nb# 3 ~F/W! (3)
in the titration enter into the calculations. Use of potassium acid phthalate
in the blank is recommended. When it is not used, the term P drops out of
where:
the equation.
23. Precision and Bias mL,
B 5 NaOH solution required for titration of the blank, mL,
23.1 No statement on bias can be made as no reference Nb 5 normality of the NaOH solution,
material is available as a standard. C 5 HCl required for titration of the sample, mL,
Test Method B—Heterogeneous D 5 HCl required for titration of the blank, mL,
Saponification Method Na 5 normality of the HCl solution,
F 5 4.305 for acetyl or 6.005 for acetic acid, and
24. Reagents W 5 sample used, g.
24.1 Ethyl Alcohol (75 Volume %)—Mix 790 mL of For- HYDROXYL CONTENT
mula 2B, 3A, or 30 denatured ethyl alcohol and 210 mL of
water. 27. Scope
24.2 Hydrochloric Acid (0.5 N)—Prepare and standardize a
27.1 This test method is applicable to pyridine-soluble
0.5 N solution of hydrochloric acid (HCl).
cellulose esters and is especially useful when the hydroxyl
24.3 Sodium Hydroxide, Standard Solution (0.5 N)—
content is low. Samples containing plasticizer may be analyzed
Prepare and standardize a 0.5 N solution of sodium hydroxide
directly by this test method because the plasticizer is removed
(NaOH).
during washing of the carbanilate.
25. Procedure 27.2 A preferred method is available in Test Method
25.1 Grind the sample in a Wiley mill or other suitable D 5897.
grinder so that 100 % will pass a No. 20 (850-µm). (Grinding
may be omitted if the sample has suitable texture.) Dry about
1 g of the sample in a weighing bottle at 105 6 3°C for 2 h, 28.1 Hydroxyl in cellulose acetate is determined by reaction
stopper, and cool in a desiccator. (An oven with mechanical with phenyl isocyanate in pyridine solution under anhydrous
circulation is to be preferred over a convection-type oven). conditions to form the carbanilate derivative. The derivative is
25.2 Weigh the bottle containing the sample to the nearest then analyzed for its carbanilate content by ultraviolet absorp-
0.001 g, transfer the sample to a 250-mL Erlenmeyer flask, and tion.
weigh the bottle again to the nearest 0.001 g. Handle the bottle 28.2 The acetyl content of cellulose acetates may be calcu-
with either tongs or a clean dry cloth during these manipula- lated provided that the degree of polymerization is not exces-
tions. Add 40 mL of ethyl alcohol (75 %) to each sample. sively low.
Include a blank determination with each set of samples and
carry the blank determination through the complete procedure, 29. Significance and Use
including the back titration. 29.1 Hydroxyl content is a measure of the free hydroxyl on
25.3 Heat the flasks, loosely stoppered, for 30 min at 50 to the cellulose backbone of the polymer. Hydroxyl content has a
60°C. Add 40 mL of 0.5 N NaOH solution to each flask and strong effect on the polymer’s solubility and physical proper-
heat again at 50 to 60°C for 15 min. Stopper the flasks tightly ties. Hydroxyl content also impacts the propensity for this
and allow to stand at room temperature for about 48 h. If the polymer to crosslink with various crosslinking agents.
acetyl content of the sample is over 43 %, or if the sample is
hard and horny, allow to stand for about 72 h. At the end of this 30. Apparatus
time back titrate the excess NaOH with 0.5 N HCl, using 30.1 Spectrophotometer, complete with hydrogen light
phenolphthalein as the indicator. Add an excess of about 1 mL source and a set of four 1.00-cm quartz cells, or an equally
of 0.5 N HCl and allow the NaOH to diffuse from the suitable apparatus. The wavelength calibration, as checked
regenerated cellulose for several hours, or, preferably over- against a mercury lamp, shall be within the manufacturer’s
night. The disappearance of the pink color indicates the tolerances. As a further check, measure the absorbance of a
complete neutralization of the NaOH. Titrate the small excess potassium chromate (K2CrO4) solution prepared as follows:
4
D 871
Dissolve 0.0400 g of K2CrO4 or 0.0303 g of potassium 31. Reagents
dichromate K2Cr2O7 in 0.05 N potassium hydroxide (KOH) 31.1 Acetone.
solution and dilute to 1 litre in a volumetric flask with 0.05 N 31.2 Ethyl Alcohol, denatured, Formula 2B, 3A, or 30.
KOH solution. Using the hydrogen lamp, measure the absor- 31.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9
bance at 280 nm of a silica cell filled with the K2CrO4 solution parts by weight of methylene chloride with 1 part of methyl
and also of the same cell filled with water. The absorbance of alcohol. This mixture should have an absorbance of less than
the solution minus that of the blank shall be 0.723 6 0.023. 0.2 at 280 nm in a 1.00-cm silica cell measured against air.
30.2 Bottles, 4-oz, with screw caps, for washing the Pure methylene chloride has an absorbance of about 0.05, but
samples. the commercial product may have an absorbance as high as
30.3 Special Reflux Tubes for the carbanilation, constructed 1.00. The methylene chloride and methanol should be selected
as follows (see Fig. 1): Make a test tube approximately 20 by to have low absorbance; otherwise, they should be redistilled.
150 mm from the outer part of a 24/40 standard-taper ground 31.4 Phenyl Isocyanate.
glass joint by closing the open end in a blast lamp. Draw the 31.5 Pyridine, redistilled, low water content, preferably less
tubing on the inner joint to a constriction just above the joint. than 0.05 %.
Cut the glass at that point and seal on a short length of 8-mm
tubing to provide a bearing for a glass stirrer. Make a stirrer of 32. Procedure
4-mm glass rod with a semicircle at right angles to the shaft at
the bottom and small enough to fit into the test tube. When 32.1 In the following procedure the phenyl isocyanate
properly constructed this unit acts as an air condenser, thus reagent shall be used under anhydrous conditions. Therefore,
preventing the loss of solvent by evaporation. the sample, containers, pipet, and all other equipment shall be
30.4 Pipet, serological-type, 5-mL capacity, graduated in thoroughly dried.
0.1-mL divisions. 32.2 Place a 0.5-g sample in a special reflux tube and dry in
30.5 Büchner Funnel, of a size accommodating 90-mm an electric oven at 105°C for 2 h. Remove the tube from the
filter paper. oven, add 5 mL of pyridine, assemble the reflux apparatus
30.6 Automatic Shaker, with speed regulator mechanism. complete with glass stirring rod, and place in the 115 to 120°C
30.7 Electric Oven, maintained at 105 6 3°C. oil bath. Stir occasionally until the sample is completely
30.8 Oil Bath, equipped with a rack to hold several of the dissolved. Add 0.5 mL of phenyl isocyanate, stir thoroughly,
special reflux tubes. This bath shall be kept between 115 and and reflux in the oil bath for 1⁄2 h to complete the reaction. Use
120°C. 0.1 mL of phenyl isocyanate for each percent of estimated
hydroxyl content, but never less than 0.5 mL.
32.3 At the end of the reaction time, remove the sample and
dilute it with acetone to the proper viscosity for precipitation.
The amount of acetone used to thin the solution is a critical
factor in acquiring a good precipitate. Samples having low
viscosity require little, if any, dilution. The average sample
requires the addition of about an equal volume of acetone.
Precipitate the carbanilate by pouring the solution into about
200 mL of ethyl alcohol. The precipitate should be fluffy and
white. Sticky precipitates indicate too little dilution. Stir the
alcohol vigorously during precipitation. Filter off the precipi-
tate, using paper on a Büchner funnel, with suction applied
only as long as is necessary to remove the bulk of the solvent;
prolonged suction may cause undesirable clumping together of
the precipitate.
32.4 Wash by transferring the precipitate to a 4-oz screw cap
bottle containing 75 mL of ethyl alcohol, capping securely, and
shaking for 1⁄2 h on an automatic shaker at medium speed.
Filter the precipitate on the Büchner funnel, pressing out as
much liquid as possible with a glass stopper. Repeat the
washing and filtering operations twice more. Allow the pre-
cipitate to air-dry 1 to 2 h at room temperature with good
ventilation or preferably overnight to ensure complete removal
of the alcohol. (Samples wet with alcohol may sinter and stick
to paper or glass when dried at 105°C.) Dry the sample at
105°C in the oven for 1 h and cool in a desiccator. Small
manila envelopes are convenient for drying and cooling the
samples.
32.5 Weigh 0.1231 g of the dry precipitate into a 100-mL
FIG. 1 Special Reflux Tube for Carbanilation volumetric flask fitted with a ground-glass stopper. Add 60 to
5
D 871
80 mL of the methylene chloride-methyl alcohol mixture, and 37.2 Place a 0.5-g sample in the test tube of the special
shake occasionally until complete solution occurs. Dilute to reflux apparatus and dry for 2 h at 105 6 3°C. Add 5 mL of
100 mL and mix thoroughly. Using the spectrophotometer with pyridine, insert the top of the reflux apparatus and the stirrer
a 1-cm silica cell measure the absorbance of the solution at 280 and heat with stirring in a 115 to 120°C oil bath. After the
nm against the solvent mixture as a reference. sample has dissolved, add 0.5 g of trityl chloride. If the total
hydroxyl content exceeds 3 %, use an additional 0.075 g of
33. Calculation trityl chloride for each additional 1 % hydroxyl. Stir the
33.1 Calculate the percentage of carbanilate, c, for a sample mixture thoroughly and reflux in the oil bath for exactly 2 h at
weight of 0.1231 g as follows:5 115 to 120°C. Remove the tube and cool.
Carbanilate, % 5 A 3 17.1 (4) 37.3 Dilute the sample with acetone to the proper viscosity
for precipitation. The amount of acetone used to thin the
where: solution is a critical factor in obtaining a good precipitate.
A 5 absorbance. Samples having low viscosity require little, if any, dilution. The
33.2 Calculate the percentage of hydroxyl as follows: average sample requires the addition of about an equal volume
Hydroxyl, % 5 14.3c/~100 2 c! of acetone. Precipitate the trityl derivative by pouring the
33.3 Calculate the percentage of acetyl as follows: solution into about 200 mL of ethyl alcohol with vigorous
stirring. The precipitate should be fluffy and white. Sticky
Acetyl, % 5 ~4480 2 65.1c! / ~100 2 c! precipitates indicate too little dilution. Separate the precipitate
NOTE 5—The calculation for acetyl content assumes exactly three by filtering through paper on a Büchner funnel, with suction
hydroxyls per anhydroglucose unit and applies to cellulose acetates only. applied only as long as necessary to remove the bulk of the
solvent; prolonged suction may evaporate the alcohol and
PRIMARY HYDROXYL CONTENT cause the precipitate to partially redissolve in the remaining
34. Summary of Test Method pyridine.
37.4 Wash the precipitate by transferring it to a 4-oz screw
34.1 The primary hydroxyl content of cellulose acetate is
cap bottle containing 75 mL of ethyl alcohol, capping securely,
determined by formation of the triphenylmethyl (trityl) ether
and shaking for 1⁄2 h on a shaker at medium speed. Again
and measurement of the trityl group by ultraviolet absorbance.5
collect the precipitate on a Büchner funnel, pressing out as
Trityl chloride reacts preferentially with primary hydroxyls.
much liquid as possible with a glass stopper. Repeat this
Since there is also a slight reaction with secondary hydroxyls,
washing and filtering operation twice more, or until the
standardized reaction conditions are important.6
absorbance of the filtrate at 259 nm is about the same as that of
35. Apparatus an alcohol blank. Allow the precipitate to air-dry on the filter
paper for 1⁄2 h at room temperature with good ventilation, or
35.1 See Section 30.
preferably overnight, to remove most of the alcohol. (Samples
36. Reagents wet with alcohol may sinter or stick to paper or glass when
36.1 Acetone. dried at 105°C.) Transfer the sample to a manila envelope, dry
36.2 Ethyl Alcohol, denatured, Formula 2B, 3A, or 30. it for 1 h at 105°C, and cool in a desiccator.
36.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9 37.5 Weigh 0.1231 g of the dry trityl ether derivative into a
parts by weight of methylene chloride with 1 part of methyl 100-mL volumetric flask fitted with a ground-glass stopper,
alcohol. This mixture should have an absorbance of less than and dissolve in the methylene chloride-methyl alcohol mixture.
0.2 at 259 nm in a 1-cm silica cell measured against air; Dilute to 100 mL and mix thoroughly. Measure the absorbance
otherwise the solvents should be redistilled. of this solution in a 1-cm silica cell using a spectrophotometer
36.4 Pyridine, redistilled to a water content less than at 259 nm against the solvent as a reference.
0.05 %. The water content may be reduced further by storing 38. Calculation
over a suitable drying agent, such as a molecular sieve, Type
4A. 38.1 Calculate the trityl content, t, for this concentration of
36.5 Trityl Chloride (Chlorotriphenylmethane or Triphenyl- 0.1 g/100 g and with a correction of 0.015 for the absorbance
methyl Chloride), reagent grade. of the cellulose acetate as follows:7
Trityl, % 5 25.25 ~A 2 0.015! (5)
37. Procedure
37.1 The reagents shall be used under anhydrous conditions. where:
It is imperative that the sample and all equipment be thor- A 5 absorbance.
oughly dry. 38.2 Calculate the weight percentage of primary hydroxyl in
cellulose acetate as follows:
Primary hydroxyl, % 5 7.02t / ~100.4 2 t! (6)
5
Malm, C. J., Tanghe, L. J., Laird, B. C., and Smith, G. C., “Determination of
Total and Primary Hydroxyl in Cellulose Esters by Ultraviolet Absorption Meth-
ods,” Analytical Chemistry, ANCHA, Vol 26, 1954, p. 189.
6 7
Malm, C. J., Tanghe, L. J., and Laird, B. C., “Primary Hydroxyl Groups in Wagner, R. H., and Russell, John, “Capillary Tube Viscometer for Routine
Hydrolyzed Cellulose Acetate,” Journal of the American Chemical Society, JACSA, Measurement of Dilute High Polymer Solutions,” Analytical Chemistry, ANCHA,
Vol 72, 1950, p. 2674. Vol 20, 1948, pp. 151–157.
6
D 871
38.3 Calculate the percentage primary hydroxyl of the total 43.9 Silver Nitrate Solution (50 g/L)—Dissolve 50 g of
hydroxyl as follows: silver nitrate (AgNO3) in water and dilute to 1 L.
Primary hydroxyl of total hydroxyl, % 5 ~B/C! 3 100 (7) 43.10 Sodium Carbonate (Na2CO3).
43.11 Sodium Hydroxide Solution (400 g/L)—Dissolve 400
where: g of sodium hydroxide (NaOH) in water and dilute to 1 L.
B 5 value of primary hydroxyl as determined in 38.2, and
44. Procedure
C 5 value of total hydroxyl as determined in 33.2.
44.1 Treatment Prior to Analysis—Remove uncombined
39. Precision and Bias sulfur as follows (Note 6): Dissolve 25 g of sample in
39.1 No statement on bias can be made as no reference approximately 300 mL of acetone, depending on the viscosity.
material is available as a standard. If the sample is of too high acetyl content to be directly soluble
SULFUR OR SULFATE CONTENT in acetone, cool in a dry ice cabinet overnight; then allow to
come to room temperature while tumbling or stirring. Filter the
40. Summary of Test Method solution, if necessary, through felt or a coarse sintered-glass
40.1 The sulfur or sulfate content of cellulose acetate is crucible. Precipitate with rapid stirring into a beaker or pail
measured by oxidizing the sample in a nitric acid-perchloric containing 2 to 3 L of acetic acid (1+49). Filter through a cloth
acid mixture and determining gravimetrically as barium sul- bag or a Büchner funnel and give two 15-min washes with
fate. To determine combined sulfur the sample must first be water using mechanical agitation. A little Na2CO3 may be
reprecipitated into dilute acid to remove noncombined sulfur added to the last wash to stabilize samples of high sulfur
compounds. content. Filter and dry overnight at 60°C.
40.2 The sulfur or sulfate content may also be determined NOTE 6—To analyze for total sulfur content omit this treatment.
by Test Method D 2929. In this case the X-ray method shall be
calibrated against the chemical method following in Sections 44.2 Decomposition:
42 to 45, and the sample shall be treated in accordance with 44.2.1 Weigh 10 6 0.1 g of cellulose acetate and transfer to
Section 44 if combined sulfur is to be determined. a clean, wide-mouth, 500-mL Erlenmeyer flask. Add 50 mL of
the HNO3-HClO4 mixture to the flask, and swirl the flask
41. Significance and Use gently to wet the sample thoroughly. Place the modified funnel
41.1 Sulfur and sulfate content indicates the amount of in the mouth of the flask and heat the flask carefully on a hot
sulfur in the cellulose ester either as inorganic salts (usually plate in a fume hood.
sulfates) or as organic sulfate (usually as sulfate ester com- NOTE 7—Precaution: Use the utmost care in handling the HNO3-
bined to the cellulose backbone). The presence of high levels of HClO4 mixture. If a spill occurs, wash down with plenty of water. Wear
sulfur and sulfate can be detrimental to the melt stability of the safety glasses or a face shield.
ester. 44.2.2 After the mixture becomes hot and less viscous,
42. Apparatus increase the heat of the hot plate. Continue the digestion until
42.1 Funnel, modified by cutting the stem off at the apex of all the sample has been oxidized and the thick reddish-brown
the funnel and fire polishing. fumes of nitrogen dioxide (NO2) have been expelled. At this
42.2 Crucibles, 30-mL, extra-fine porosity. point, white fumes will appear and a rather vigorous reaction
42.3 Oven, controlled at 120 to 125°C. will occur that is caused by the last traces of organic material
42.4 Muffle Furnace, controlled at 800 6 50°C. being oxidized and the HNO3 fuming off.
44.2.3 When this reaction starts, remove the flask from the
43. Reagents hot plate, swirl gently for a few seconds, and set it on the shelf
43.1 Acetone. in front of the hood until the reaction is complete. Place the
43.2 Acetic Acid (1+49)—Mix 1 volume of glacial acetic flask back on the hot plate and continue the digestion until the
acid with 49 volumes of water. HClO4 refluxes about half way up the side of the Erlenmeyer
43.3 Barium Chloride Solution (100 g/L)—Dissolve 100 g flask and about 5 mL is left in the flask. The HNO3-HClO4
of barium chloride (BaCl·2H2O) in water and dilute to 1 L. mixture should be clear and colorless. If it is not, set the flask
43.4 Hydrochloric Acid (1+1)—Mix 1 volume of concen- off the hot plate to cool and then add 3 to 5 mL of HNO3 (sp
trated hydrochloric acid (HCl, sp gr 1.19) with 1 volume of gr 1.42). Replace the flask on the hot plate and continue heating
water. until the HClO4 refluxes half way up the flask. Remove the
43.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid flask from the hot plate and allow the flask and its contents to
(HNO3). cool.
43.6 Nitric Acid (2+3)—Mix 2 volumes of concentrated 44.3 Determination of Barium Sulfate:
HNO3 (sp gr 1.42) with 3 volumes of water. 44.3.1 Wash the modified funnel top thoroughly with water,
43.7 Nitric Acid-Perchloric Acid Mixture—Mix 5 volumes collecting the rinsings in the flask. Add 50 ml of water. Swirl
of concentrated HNO3 with 1 volume of concentrated perchlo- the flask to mix the solution thoroughly. Add 2 drops of
ric acid (HClO4, 70 %). phenolphthalein indicator solution and neutralize the acid with
43.8 Phenolphthalein Indicator Solution (1 g/100 mL)— the NaOH solution to a faint pink. Acidify immediately with
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol HCl (1+1), dropwise, until the solution is just acid to phenol-
(95 %). phthalein; then add 2 mL of HCl (1+1).
7
D 871
44.3.2 Filter through a 12.5-cm fine-porosity paper into a A 5 weight of sample, g,
clean 400-mL beaker. Wash the flask thoroughly with water, B 5 weight of crucible for sample, g,
filtering the washings through the paper. Finally wash the paper C 5 weight of crucible and BaSO4 for sample, g,
thoroughly with ten portions of hot water. Dilute the filtrate to C−B 5 weight of BaSO4 for sample,
approximately 200 mL. Place the beaker on the hot plate and D 5 weight of crucible for blank, g,
heat almost to boiling. Slowly add 10 mL of BaCl2 solution E 5 weight of crucible and BaSO4 for blank, g, and
from a pipet, stirring the solution during the addition. Do not E−D 5 weight of BaSO4 for blank, g.
add the BaCl2 solution rapidly, as from a graduate, since the
rapid addition will produce an impure precipitate. Remove the 46. Precision and Bias
stirring rod from the beaker and wash it with a stream of water 46.1 No statement on bias can be made as no reference
from the wash bottle, collecting the washings in the beaker. material is available as a standard.
Cover the beaker with a watch glass and keep the mixture near
the boiling temperature of 6 h or overnight. Do not allow the HEAT STABILITY
liquid to evaporate to dryness. 47. Summary of Test Method
44.3.3 Using suction, decant the supernatant liquid through
an extra-fine porosity porcelain filter crucible that has been 47.1 The heat stability of cellulose acetate is one indication
previously rinsed with acetone, ignited, and weighed to the of its quality. It is measured by heating the sample for a
nearest 0.1 mg. Transfer the precipitate with the aid of a stream specified time and temperature, observing it for amount and
of hot water. Always use a stirring rod in this transfer. Scrub the uniformity of color developed, and possibly also measuring the
sides and bottom of the beaker with a rubber policeman to loss of viscosity as a result of heating. Suggested times of
remove any adhering precipitate. The crucibles may be used to heating are 8 h at 180°C or 2 h at 190°C. The time and
collect several precipitates one on top of the other. Close temperature of heating, method of grading, and limits are
control of temperature and time of heating and cooling are matters for agreement between purchaser and the supplier.
necessary. Cleaning with hot water is generally sufficient; 48. Significance and Use
drastic attack with cleaning solution should be avoided.
44.3.4 Wash the precipitate on the filter until free of 48.1 The heat stability of a cellulose ester is one indication
chlorides by the following test: To 5 mL of wash water, of its quality.
collected in a separate test tube or on a watch glass, add 1 mL
49. Apparatus
of HNO3 (2+3) and 1 mL of AgNO3 solution. The appearance
of a milky white precipitate indicates the presence of chlorides, 49.1 Heater Block—A metal block of suitable size is heated
and the washing should therefore continue until the test is electrically and maintained at the specified temperature
negative. Do not attempt to get a completely negative test for within6 1°C. This is best accomplished by providing continu-
chloride. Discontinue washing when no more than a faint ous heat to hold the temperature a few degrees below the
opalescence is produced in the test. specified temperature, and providing intermittent additional
44.3.5 Finally pour a few millilitres of pure acetone through heat thermostatically controlled. Holes are drilled in the top of
the filter and suck it dry. Place the crucible in a larger crucible the block to hold test tubes, a thermoregulator, and a thermom-
or in a metal tray with perforated sides and bottom for eter. The block should be insulated.
protection and place it in an oven at 120 to 125°C for 1 h. Do 49.2 Test Tubes, either 18 by 150 mm or 20 by 150 mm,
not handle the crucibles with the fingers between ignition and fitted with corks. The corks shall be fitted with glass tubes the
the completion of weighing; use forceps. length of the cork and 4 mm in inside diameter or shall have a
44.3.6 Remove the crucible from the oven and ignite it for small V-shaped notch of equivalent cross-section cut in a
10 min in a muffle furnace at 800 6 50°C. Cool in a desiccator vertical position.
for 75 6 15 min and weigh to the nearest 0.0001 g. It is
50. Solvent
permissible to return the crucible to the oven for at least 15 min
before transferring to the desiccator. 50.1 Methylene Chloride-Methanol Mixture—Mix 9 parts
44.3.7 From time to time, and especially when using new by weight of methylene chloride with 1 part of methyl alcohol.
reagents, run a blank in duplicate in the reagents. If the weight
51. Heat Treatment
of the precipitate exceeds 0.0005 g, investigate and eliminate
the cause. This is equivalent to an error of 0.002 % on a 10-g 51.1 Place the sample, ground to pass a No. 20 (850-µm)
sample. sieve, in a clean dry test tube and pack it firmly and uniformly.
Stopper with a cork having a notch or tube as described in 49.2.
45. Calculation Heat the tube and contents for 8 h at 180°C or as otherwise
45.1 Calculate the percentage of sulfur and sulfate as specified.
follows: 52. Dry Color Evaluation
Sulfur, % 5 ~@~C 2 B! 2 ~E 2 D!# 3 0.1374 3 100! / A (8) 52.1 Examine the heated sample for uniformity of color and
Sulfate, % 5 ~@~C 2 B! 2 ~E 2 D!# 3 0.4115 3 100 / A (9) for the presence of charred or decomposed spots. Compare the
color of the material at the bottom of the tube with standards
where: prepared as follows: Heat portions of a check batch of similar
8
D 871
particle size, representative quality and stability, and accepted
by mutual agreement between the purchaser and the seller.
Pack portions of this check batch firmly in each of twelve
clean, dry test tubes and stopper with corks as described in
49.2. Heat the tubes at 180°C, or as otherwise specified,
remove one tube each 2 h, and mark the time of heating in
hours on each tube. This set of numbered tubes serves as the
color standards. They should be checked and renewed if
necessary every 6 months.
53. Solution Color Using Platinum - Cobalt Standards
53.1 Heat a 1-g sample for the specified time and tempera-
ture and, after cooling, examine for charred or decomposed
spots. Dissolve the heated sample in 15 mL of the methylene
chloride-methanol mixture. Compare the color of the solution
(viewing transversely) with test tubes of platinum-cobalt color
standards, prepared as described in Section 70. (It may be
necessary to prepare standards having as much as 2000 ppm of
platinum for this purpose or to dilute the sample solution
before grading.)
54. Solution Color by Spectrophotometer
FIG. 2 Wagner Capillary Tube Viscometer7
54.1 The color of the solution prepared as described in
Section 53 may also be measured spectrophotometrically.
Measure the absorbance at 400 nm against the solvent, using a 59.2 Water Bath—A constant-temperature water bath con-
suitable spectrophotometer with a 1-cm silica cell. trolled at 25.0 6 0.1°C and with a pump for circulating the
water through the viscometer jacket or tank.
55. Viscosity Change 59.3 Stop Clock or Watch, calibrated in tenths of a second.
55.1 Measure the intrinsic viscosity of the heated sample
and of an unheated sample as described in Sections 57 to 61 of 60. Procedure
this test method. The percentage loss of viscosity as the result 60.1 Sample Preparation—Dry about 0.26 g of sample in a
of heating is a measure of heat stability. weighing bottle at 105 6 3°C for 2 h, stopper, and cool in a
desiccator. Weigh the bottle containing the sample to the
56. Precision and Bias nearest 0.001 g, transfer the sample to a 250-mL flask, and
56.1 No statement on bias can be made as no reference reweigh the bottle. Pipet into the flask 100 mL of solvent at 25
material is available as a standard. 6 0.1°C. The solvent used should be mutually agreed upon by
the purchaser and the supplier. Suitable solvents are listed in
INTRINSIC VISCOSITY Table 1. After the sample is completely dissolved, place it in
the constant-temperature bath at 25°C along with a portion of
57. Summary of Test Method the solvent used, and allow sufficient time for both to come to
57.1 Intrinsic viscosity, expressed in decilitres of solution
per gram of solute, is determined by measuring the flow times TABLE 1 Solvents for Intrinsic Viscosity Determination
of a solution of known concentration and also of the solvent
Value of k for
used and making a calculation by means of the modified SolventA Ingredients, weight % Calculation
Baker-Philippoff equation. (see 61.2)
A 90 % acetoneB 10
NOTE 8—By expressing concentration in grams per millilitre rather
10 % ethyl alcoholC
than grams per decilitre, the result will be limiting viscosity number B acetoneB 10
instead of intrinsic viscosity, and will be 100 times greater. C or D 90 % methylene chlorideD 3
10 % ethyl alcoholC
58. Significance and Use E 96 % acetoneB 10
4 % water
58.1 Intrinisic viscosity number can be used to estimate the F 90 % methylene chlorideD 3
molecular weight of a cellulose ester by using the Mark- 10 % methanolE
Houwink equation and constants measured for the solvent, A
Solvent designations conform to those used in Table 2 for viscosity determi-
temperature, and ester of concern. nations.
B
alcohol.
59. Apparatus C
Ethyl alcohol (95 volume %). Formula 2B or 3A denatured ethyl alcohol may be
59.1 Capillary Viscometer, such as the Wagner apparatus used.
D
Methylene chloride having a boiling range of 39.2 to 40.0 C and less than
(Fig. 2) or an Ostwald-Fenske-Cannon pipet, that will give a 0.001 % acidity calculated as HCl.
flow time for the solvent of not less than 70 s. E
Methyl alcohol (sp gr 20/20°C 5 0.785 to 0.795).
9
D 871
temperature before making the viscosity measurements. Dur- TABLE 2 Solutions for Viscosity Determination
ing this conditioning period, water at 25°C should be circulat- Formula
ing through the water jacket of the viscometer to allow ample A B C D E F
time for the pipet to reach temperature equilibrium. Ingredients, weight %
60.2 Viscosity Measurements—Rinse the reservoir and the Cellulose acetate 20A 20A 20B 15C 20A 10C
outside of the capillary tube thoroughly with solvent. Rinse the AcetoneD 72 80 ... ... ... ...
inside of the capillary tube twice by alternately applying Acetone, 96 % ... ... ... ... ... ...
Water, 4 %
pressure at points B and A (Fig. 2). Discard the wash portion of Ethyl alcoholE 8 ... 8 8.5 ... ...
the solvent. Pour more solvent into the reservoir and allow Methyl alcoholF ... ... ... ... ... 9
several minutes for complete drainage and thermal equilibrium Methylene chlorideG ... ... 72 76.5 ... 81
to be obtained. Adjust the outer meniscus to a reference point, Typical Solution Densities, g/mL at 25 C
D, that will give a flow time between 70 and 100 s. Apply air 0.84 0.86 1.25 1.23 0.86 1.24
pressure at B to force the solvent up through the capillary past A
Acetyl content 40.5 %, max.
the upper timing mark, C, on the measuring bulb, E. Record the B
Acetyl content 40.5 to 42.7 %.
C
time in seconds required for the meniscus to fall between the Acetyl content 42.7 to 44.8 %.
D
timing marks, C and F. Take a minimum of two readings. alcohol.
Repeat these operations, substituting the solution for the E
Ethyl alcohol (95 volume %). Formula 2B or 3A denatured ethyl alcohol may be
solvent. used.
F
Methyl alcohol (sp gr 20/20 C 5 0.785 to 0.795).
G
61. Calculation 0.001 % acidity calculated as HCl.
61.1 Calculate the relative viscosity, hrel, as follows:
hrel 5 t1/t2 (10) material is available as a standard.
where: COLOR AND HAZE
t1 5 flow time of solution, and
t2 5 flow time of solvent. 67. Summary of Test Method
61.2 Calculate the intrinsic viscosity, [h], as follows: 67.1 Color and haze determinations on cellulose ester solu-
@h# 5 ~k/c! @antilog~log hrel/k! 2 1# (11) tions are made by comparison with standards. Simultaneous
measurement of these properties is desirable because haze
where: reduces the amount of color observed.
k 5 values from Table 1, and
c 5 concentration in grams per decilitre (Note 8 in Section 68. Significance and Use
57). 68.1 Solution color and haze of a cellulose ester is a
62. Precision and Bias measurement of the optical properties of cellulose esters when
dissolved in a specific solvent.
material is available as a standard. 69. Apparatus
VISCOSITY 69.1 Light Box—A suitable light box (Fig. 3 and Fig. 4) is
described as follows. The light source consists of a mercury
63. Significance and Use vapor bulb, which requires an auto transformer for the current
63.1 A measurement of viscosity is of great practical utility source. The bulb is mounted horizontally across the lower front
in determining the proper processing equipment and process
concentrations for cellulose esters.
64. Procedure
64.1 Solution—Dry the sample for 1 to 2 h at 105 6 3°C
and cool in a desiccator. Prepare a solution of the dried sample
in a solvent and at a concentration mutually agreed upon by the
purchaser and the seller. Suitable solutions are listed in Table 2.
64.2 Viscosity Determination—Prepare the solution and
measure the viscosity in accordance with Test Method D 1343,
(Note 10 in Section 71 of these methods).
65. Report
65.1 Report the results in poises, unless otherwise specified.
The viscosity values shall be prefixed with the letter A, B, C,
etc., corresponding to the formula of the solution employed.
66.1 No statement on bias can be made as no reference FIG. 3 Color and Haze Apparatus
10
D 871
Metric Equivalents
in. mm in. mm in. mm in. mm in. mm
⁄
18 3.2 1⁄
34 44.4 3⁄
34 95.2 6⁄
14 158.8 8⁄
12 215.9
⁄
12 12.7 21⁄2 63.5 43⁄4 120.6 71⁄2 190.5 13 330.2
13 16⁄ 20.6 3 76.2 5 127.0 81⁄4 209.6 171⁄2 444.5
1 25.4 31⁄4 82.6 6 152.4 83⁄8 212.7 201⁄2 520.7
FIG. 4 Color and Haze Apparatus (Details)
part of a plywood box 350-mm wide, 430-mm high, and 70. Reference Standards
330-mm deep. This box is lined with a heat resistant board and 70.1 Color Standards—A color standard containing 500
is painted black inside, except that the inside back surface ppm of platinum may be purchased or the solution may also be
toward the viewer is white. A bottle holder large enough to hold prepared as follows: Dissolve 1.245 g of potassium platinum
four bottles is built onto the front of the light box, and a 63.5 chloride (K2PtCl6), containing 0.500 g of platinum, and 1.000
by 152.4-mm horizontal viewing hole is cut through the front g of crystallized cobalt chloride (CoCl2·6H2O), containing
of the box. This opening is covered with clear glass, and a 0.248 g of cobalt, in water, add 100 mL of HCl (sp gr 1.19), and
6.4-mm strip of black tape is fastened to the glass horizontally dilute to 1 L with water. Prepare standards containing 50, 60,
to aid in judging haze in the solution. Holes are cut in the 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400 and 500
bottom and top of the box for cooling by air convection. For ppm of platinum by diluting suitable aliquots of the standard
continuous use, forced circulation of air would be desirable. A solution to 500 mL with water. Place these standards in the
black metal baffle over the bulb prevents direct light on the special bottles (see 69.2), taking care to select bottles with
viewing glass. good clarity and free of flaws. Label and cap tightly.
69.2 Sample Bottles—The bottles used for the sample solu- 70.2 Haze Standards—Prepare haze standards by diluting a
tions are French square bottles, 16-oz, with screw caps. These stock solution having a turbidity of 1000 ppm. Prepare bottles
same bottles may be used for the color and haze standards. containing 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,
NOTE 9—These bottles may also be used for determination of viscosity, 175, 200, and 400 ppm of turbidity, label, and cap tightly.
as described in 64.2. NOTE 10—The previously recommended stock solution for preparing
69.3 Cap Liners—Cap liners shall be of a composition not these standards was made from fuller’s earth, water, and hydrochloric
acid. This solution is no longer available. A comparable stock solution can
affected by the solvents used. Liners of fiber board covered be made using a diatomaceous earth. To obtain haze levels equivalent to
with cellophane or aluminum foil are usually satisfactory, but the fuller’s earth standard, 1.1 parts diatomaceous should be used in place
vinyl resin or waxed liners may cause interference with of 1.0 parts of fuller’s earth in preparing the aqueous suspension. No
viscosity, color, or haze measurements. hydrochloric acid is needed.
11
D 871
71. Procedure NOTE 11—When viscosity, color, and haze determinations, and an
observation of general appearance are to be made on a cellulose ester
71.1 Prepare the solution to be graded by dissolving the sample, a considerable saving in time can be made by using one solution
cellulose ester in the specified amount and kind of solvent, in in a square bottle for all three determinations. Dry the cellulose ester as
one of the square bottles. See Table 2 for suitable solutions. At required for the viscosity determination, prepare the solution carefully,
least 350 mL are required. Tumble until a uniform solution is and allow the bottle to stand long enough to form a thick solution before
obtained. Allow the solution to stand until it is free of bubbles tumbling, to avoid solvent loss around the cap. Use a large enough sample
before grading it for color and haze: to provide at least 350 mL of solution in the bottle. Measure the viscosity
as described in Test Method D 1343, and then rate the color and haze.
71.2 Place the bottle containing the solution to be graded at
the front of the shelf on the apparatus and place a similar bottle 72. Precision and Bias
containing water behind it. Place the freshly shaken haze
standard at the front of the shelf beside the bottle containing the 72.1 No statement on bias can be made as no reference
solution to be tested and place the color standard behind it. material is available as a standard.
Determine the amount of color and haze in the solution by
changing the color and haze standards until as good a match as 73. Keywords
possible has been obtained. The haze standards settle out 73.1 apparent acetyl; ash; cellulose acetate; cellulose ester;
quickly so they must be reshaken at short intervals. Report color; free acidity; haze; hydroxyl; intrinsic viscosity; sulfate
results in parts per million for both color and haze. content
12

Volatile Oil in Rosin1
1. Scope connections with the flask and condenser, in order to avoid

1.1 This test method covers the determination of the volatile vapor loss.
oil content of rosin or similar material. The oil may consist of NOTE 1—This trap is a modification of the original Clevenger trap used
naturally occurring terpene oil, such as heavy fractions of to recover oils lighter than water. In that trap the oil and water condensate
turpentine, resulting from incomplete distillation in the pro- drop directly into the graduated part of the trap. Due to the viscous
cessing of the rosin, or of foreign nonterpene oil resulting from character, density, and surface tension of the oils recovered from rosin,
incomplete removal of mineral or coal-tar solvent used to cylindrical columns of oil were formed below the surface of the water in
the graduated section of the trap, which were not penetrated by the water
extract the rosin from wood or still wastes. In certain cases the condensed immediately thereafter. This resulted in alternate columns of oil
volatile oil could consist of decarboxylated rosin formed and water in the graduated section. These were returned to the distilling
during the processing of the rosin. flask in the same order as they occurred, through the side arm of the trap.
1.2 This standard does not purport to address all of the As this condition continued indefinitely, it was impossible to completely
safety concerns, if any, associated with its use. It is the remove all the oil from the rosin. By raising the opening of the side arm
responsibility of the user of this standard to establish appro- of the trap to the position shown, to bring the surface of the liquid into the
wide part of the trap above the narrow graduated section, the oil is
collected in a thinner film that can be penetrated readily by the droplets of
bility of regulatory limitations prior to use. water falling from the end of the condenser, and only the water is thus
collected in the narrow graduated section. At the end of the test, the oil is
2. Referenced Documents slowly brought down into the graduated section and its volume read. The
2.1 ASTM Standards: system or apparatus loss amounts to not more than 0.1 mL of oil.
D 233 Test Methods of Sampling and Testing Turpentine2 4.3 Condenser, straight-tube, 300-mm, water-jacketed re-
E 1 Specification for ASTM Thermometers3 flux type, with a 24/40 standard-taper ground joint for connec-
3. Significance and Use tion with the trap.
4.4 Heat Source—An oil bath containing high-temperature-
3.1 Rosin and similar materials such as rosin derivatives resistant oil, or an electric heater of the mantle type in which
often contain volatile material derived from the raw material the heating elements are encased in a glass cloth mantle of such
used or formed as a result of the processing of the rosin. This shape as to partially or completely surround the flask being
volatile material can have a significant effect on the physical heated.
and chemical properties of the rosin and so a standard method 4.5 Thermometer, having a range from 30 to 200 °C, ASTM
for its determination is required. 16C or equivalent (see Specification E 1).
4. Apparatus 4.6 Glass Beads.
4.1 Flask, 500-mL round-bottom having a thermometer well 5. Procedure
and a 24/40 standard-taper ground joint for connection with the 5.1 Place 50 g of the crushed sample in the flask, add 125
trap (see Fig. 1). mL of a glycerin-water solution (4 + 1), add a few glass beads,
4.2 Trap (Fig. 2), designed so as to overcome the tendency insert an ebullition tube, and connect the flask with the trap.
for droplets of oil to remain below the surface of the water, due Fill the trap (Fig. 2) with water through the top opening until
to the greater viscosity of the volatile oils recovered from rosin, the water level is even with the bottom of the seal of the small
and thus be returned to the flask (Note 1). The trap shall be return tube to the side arm. Insert the thermometer, and connect
fitted with 24/40 standard-taper ground joints to provide tight the condenser.
5.2 Regulate the applied heat until the liquid in the flask is
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint brought to a boil and distillation continues at a constant
and Related Coatings, Materials, and Applications and is the direct responsibility of temperature, which will be about 125°C at the start. At this
Subcommittee D01.34 on Naval Stores. stage, open the stopcock slightly and withdraw the water from
Current edition approved Dec. 10, 1999. Published February 2000. Originally
published as D 889 – 46. Last previous edition D 889 – 93. the trap into a small graduated cylinder at the rate of 1 drop to
2
Annual Book of ASTM Standards, Vol 06.03. 5 drops off the lower end of the condenser. Control the reflux
3
1
D 889
FIG. 1 Flask
FIG. 2 Trap
rate so that no uncondensed vapors escape from the top of the NOTE 2—The contents of the flask should be poured out while still
condenser. The withdrawal of water from the system should be warm, before the rosin has become viscous or solid, to facilitate cleaning
at the rate of about 1 mL/min. Increase the heat from time to and avoid strain on the glass when the rosin becomes cold.
time to maintain uniform continuous operation with slowly
6. Report
rising temperature. Discontinue the distillation when the tem-
perature reaches 180°C. 6.1 Properly made rosin yields not more than 0.5 mL of
5.3 Remove the source of heat and allow the distillation to residual volatile oil per 50 g of sample. If the recovered oil is
subside (Note 2). Draw off water until all the oil is brought into within such limit, report the rosin as free of excess volatile oil.
the graduated section of the trap and note the volume. The If more than 0.5 mL of oil is recovered, report the total volume
density of the oil is usually very close to 1.00. obtained.
2
D 889
NOTE 3—The volatile oil recovered from gum rosin consists primarily and determine the refractive index. For further information on
of high-boiling terpene components of the crude gum, most of which the nature of the oil, volume permitting, make a polymerization
under proper distillation will have been recovered as turpentine by the
test according to the procedure given in Test Methods D 233.
time the rosin is drawn from the still. Faulty distillation or premature
withdrawal may yield a rosin giving a higher than normal recovery of oil,
with a refractive index below 1.483. The polymerization residue should 8. Precision and Bias
have a refractive index not lower than 1.500. In the case of wood rosins,
generally obtained by extraction from stumpwood with a petroleum or 8.1 This test method is not oftern used for the determination
naphtha solvent, any recovered oil would probably consist of unrecovered of volatile oil in rosin and so it is not practical to measure its
solvent. The refractive index of both the recovered oil and the polymer- precision and bias.
ization residue therefrom would be well under the above figures for gum
rosin. 9. Keywords
7. Additional Examination of Oil 9.1 rosin; volatile oil
7.1 Drain off the water, transfer the oil to a small glass
container, stopper, and allow to settle until clear. Note the odor
3

Water in Liquid Naval Stores1
1. Scope 2. Referenced Documents

1.1 These test methods cover the quantitative determination 2.1 ASTM Standards:
of dissolved or occluded water present in any proportion in D 803 Test Methods for Tall Oil3
liquid naval stores, such as turpentine, pinene, dipentene, pine D 1364 Test Method for Water in Volatile Solvents (Fischer
oil, tall oil, and tall oil fatty acids. Three methods of moisture Reagent Titration Method)4
testing are included. The Karl Fisher titration method is the
preferred method for testing tall oil, Test Methods D 803. 3. Significance and Use
1.1.1 The Karl Fischer Titration method is based on the 3.1 Many naval stores products contain water as a result of
reaction between water and a complex reagent2 consisting of the processes used for their production. Typically refined
iodine, sulfur dioxide, pyridine, and methanol, whereby the products such as terpenes, pine oil, tall oil fatty acids, and
iodine is converted to a colorless compound. The appearance distilled tall oil contain only traces of water, but crude tall oil
of a persistent iodine color in the reaction mixture indicates the might contain 0.5 to 2.5 % of water. Although the Karl Fischer
complete removal of free water by reaction with the reagent, and coulometric methods are most applicable to low levels of
and the endpoint may be measured colorimetrically. Automatic moisture, these can be and are used at higher levels. The
titrators find this endpoint by the restoration of a current azeotropic distillation method is generally used at higher
strength when the resistance provided by the presence of water levels.
is eliminated. Amperometric automatic titrators find this end-
point by detecting the current flow that occurs once water is Moisture By Karl Fischer Titration
eliminated. (Preferred method)
1.1.2 The coulometric titration method determines water 4. Apparatus
content by electronic integration of a current sufficient to
generate the precise amount of iodine from the required reagent 4.1 Titration Vessel, preferably closed, with stirring capa-
to react with the water in the sample. bilities,
1.1.3 The azeotropic method utilizes the relatively low 4.2 Buret, capable of being read at 0.1 mL divisions, or
boiling point of water, as compared with other sample con- automatic buret, or
stituents, in a toluene or xylene matrix so that water is collected 4.3 Automatic Karl Fischer titrator.
in a trap and measured. 4.4 Balance, capable of weighing to the nearest 0.0001 g.
1.2 This standard does not purport to address all of the 5. Reagents
5.1 Karl Fischer Reagent, or Other Suitable Reagent, such
as Pyridine-free Adaptations of Karl Fischer Reagent. Re-
agents vary in strength (titer). This test method is written
assuming a titer of 5 mg water/mL reagent. Recommended
additions of water in this test method may need to be adjusted
depending on the titer of the reagent.
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 5.2 Methanol—ACS grade.
Subcommittee D01.34 on Naval Stores. 6. Standardization of Iodine Reagent
published as D 890-1946. Last previous edition D 890-93.
6.1 Add methanol to the titration vessel, and titrate with
2
This procedure has been adapted from the method of Karl Fischer published in reagent until the lemon-yellow color just changes to a red-
Zeitschrift für Angewandte Chemie, Vol 48, 1935, p. 395; Chemical Abstracts, Vol brown color, or, if an automatic titrator is used, until the
29, 1935, p. 6532; as modified by Smith, Bryant, and Mitchell, Journal, Am. readings indicate no free water present. The titration vessel is
Chemical Soc., Vol. 61, 1939, p. 2407; and further modified by Axel Johansson,
Svensk Papperstidning, Vol 50, No. 11B, 1947, p. 124; see also Publication 19 of the now ready for titrating, and is considered conditioned.
Swedish Wood Research Institute, Wood Chemistry and Paper Technique (Stock-
holm) (1947). Karl Fischer reagent is available from various laboratory supplies. 3
Pyridine-free adaptations of the Karl Fischer reagent are available commercially. Annual Book of ASTM Standards, Vol 06.03.
4
1
D 890
6.2 Add a drop of water, weighed to the nearest 0.0001 g, to 12. Instrument Preparation
the titration vessel by use of a transfer pipet, or a weighing 12.1 Prepare and calibrate the instrument according to the
pipet, weighing the pipet before and after the addition. Each manufacturer’s operating instructions. This generally includes:
drop will weigh approximately 0.03 g and will require roughly 12.1.1 Clean and assemble the titration chamber.
6 mL of titrant having a titer of 5 mg/mL. Alternatively, a 12.1.2 Pour titration solution into the chamber.
25-µL, or other volume syringe may be used to introduce exact 12.1.3 Add the iodine generator solution to the generator
volumes. assembly.
6.3 Titrate with reagent until the lemon-yellow color just 12.1.4 Put the instrument in the STANDBY position.
changes to a red-brown color, or, if an automatic titrator is 12.1.5 Slowly add water, or a solution containing water,
used, until the readings indicate no free water present. Record (normally by injection with a syringe).
the mL of titrant used. 12.1.6 Continue the addition until the instrument indicates
6.4 Calculate the water equivalent of the iodine reagent, in that excess water is present, usually by a light or liquid crystal
milligrams of water per millilitre of reagent, as follows: display (LCD) reading.
W 3 1000 12.1.7 Stop the addition of water.
T5 (1)
V 12.1.8 Let the instrument stabilize for 1 h in the STANDBY
position.
where: 12.2 Verify the instrument by injecting a known amount of
T 5 water equivalent of the iodine reagent, mg/mL,
water, usually 1 µL to 5 µL, below the surface of the titration
W 5 weighed water added, in g, and
V 5 iodine reagent, mL. solution.
12.3 Put the instrument in the TITRATE or RUN position
7. Procedure and record the reading when the END light comes on or a
7.1 Condition the titration vessel, as described in 6.1. message appears that the titration is complete.
7.2 Add an amount of sample which will contain 50 mg or 12.4 Record the reading. This reading is usually in
less water to the titration vessel. micrograms or milligrams of water and should be within 6
7.3 Titrate to a red-brown color end point, as with previous 5 % of the amount of water added. Example: for 5 µL of water
titrations, or, if an automatic titrator is used, titrate according to the reading should be 5000 µg6 250 µg.
the instrument’s operating instructions.
13. Procedure
8. Calculation
13.1 Some coulometric titrators require that the sample be
8.1 Calculate the percentage of water as follows: injected through a septum. If this is the case proceed as follows
V3T (for instruments that do not require through-septum injections,
Water, % 5 W 3 10 (2)
go to 13.2):
13.1.1 Draw approximately 0.5 mL of sample into a 1-cc
where:
V 5 iodine reagent required for the titration of the sample, disposable syringe. Wipe the needle clean with a dry paper
in mL, towel.
T 5 (titer), water equivalent of the iodine reagent, and 13.1.2 Weigh the syringe with the sample to the nearest
W 5 sample used, g. 0.0001 g. Record this weight.
8.2 Report to the nearest 0.01 %. 13.1.3 Inject about 0.1 to 0.2 mL of the sample into the
titrator. Withdraw the syringe.
9. Precision and Bias 13.1.4 Weigh the syringe to the nearest 0.0001 g and record
9.1 The precision and bias of this test method for measuring this weight.
water content of the most highly refined naval stores products 13.1.5 Proceed to 13.6.
are essentially as specified in Test Method D 1364. It is not 13.2 Add approximately 4 mL of sample in a small sample
practical to measure the precision for moisture content of vial. Do not allow the sample to touch the outside of the vial.
Naval Stores products, since these test methods are applicable 13.3 Put a medicine dropper into the vial, and weigh the
to many of these products that vary widely in purity, and the vial, sample, and medicine dropper together on an analytical
precision would vary with the purity of each product. balance to the nearest 0.0001 g. Record this weight.
Moisture By Coulometric Titration 13.4 Using the medicine dropper, introduce one to two
drops of sample into the coulometric titrator.
10. Apparatus 13.5 Put the medicine dropper back in the vial, and weigh to
10.1 Coulometric Karl Fischer Titrator. the nearest 0.0001 g. Record this weight.
10.2 Sample Vials, 8-mL or 4-dram 13.6 Begin the titration.
10.3 Medicine Dropper.
10.4 Disposable Plastic Syringes, 1-cc with 16, 18 or 20 14. Calculation
gage needles. 14.1 Calculate the percentage of water as follows:
10.5 Syringe, 10 µL Water, µg
Water, % 5 Sample Weight, g 3 10 000 (3)
11. Reagents
11.1 See 5.1. 14.2 Report to the nearest 0.01 %.
2
D 890
15. Precision and Bias 18.3 Heat gently until the solvent begins to reflux. Continue
15.1 It is not possible to specify the precision of this vigorous refluxing for 2 h. Wash the condenser down with
coulometric titration procedure for measuring the water content 5-mL portions of solvent from time to time during the reflux
of naval stores products because the procedure is not widely period, and with four 5-mL portions of solvent at the end. A
used and insufficient data could be generated to develop a drop of water on the condenser may be dislodged with a fine
meaningful precision and bias statement. wire or a stirring rod wet with methanol.
18.4 Record the volume of water in the trap.
Moisture By Azeotropic Distillation
19. Calculation
16. Apparatus 19.1 Calculate the percentage of water as follows:
16.1 Flask, 1-L, short-neck, round-bottom glass flask or V
Erlenmeyer flask. Use of smaller flasks should be accompanied Water, % 5 W 3 100 (4)
by reductions in sample size and solvent.
16.2 Electric Mantle, with variable-resistance controller. where:
16.3 Condenser, connected to the flask and discharging into V 5 volume of water, mL
a trap. W 5 weight of sample, g.
16.4 Trap, 5-mL, subdivided into 0.1 mL divisions, with 19.2 Report to the nearest 0.1 %.
each 1 mL line numbered.
17. Reagents 20.1 It is not possible to specify the precision of this
17.1 Toluene or Xylene—Reagent grade, moisture free. azeotropic distillation procedure for measuring the water
content of naval stores products because this procedure is no
18. Procedure longer widely used and insufficient data could be generated to
18.1 Weigh 100 g of sample into the flask. Add a few develop a meaningful precision and bias statement.
boiling stones. Fit the flask with a moisture trap and a reflux
condenser. 21. Keywords
18.2 Add 150 mL of toluene or xylene to the flask and fill 21.1 azeotropic; coulometric, Karl Fischer; moisture; naval
the moisture trap with the solvent. stores; pine oil; tall oil; terpenes; turpentine; water
3

Cuprous Oxide for Use in Antifouling Paints1
1. Scope Coarse particles (total residue retained on a No. 325 (45-µm) 0.5
sieve), max, %
1.1 This specification covers cuprous oxide for use in Total nitric acid insoluble residue on a No. 200 (75-µm) sieve, 0.1
antifouling paints. max, %

D 185 Test Methods for Coarse Particles in Pigments, packages from each lot, batch, day’s pack, or other unit of
Pastes, and Paints2 production in a shipment. When no markings distinguishing
D 283 Test Methods for Chemical Analysis of Cuprous between units of production appear, samples shall be taken
Oxide and Copper Pigments2 from different packages in the ratio of two samples for each
3. Composition 10 000 lb two samples shall be taken. At the option of the
3.1 The pigment shall consist essentially of finely divided purchaser, the samples may be tested separately or after
cuprous oxide and shall conform to the following require- blending in equal quantities the samples from the same
ments: production unit to form a composite sample.
Cuprous oxide, min, % 97
Total copper, calculated as Cu, min, % 86 5. Test Methods
Total reducing power as Cu2O, min, % 97
Metals other than copper, max, % 0.5
Combined chlorides, calculated as Cl, and sulfates, calculated 0.5 ing ASTM test methods. Test procedures not covered by ASTM
as SO4, max, % test methods shall be mutually agreed upon between the
Acetone-soluble matter, max, % 0.5
Stability: decrease in total reducing power after stability test, 2.0
max, % 5.2 Coarse Particles—Test Methods D 185.
5.3 Cuprous Oxide Content, Total Copper, Reducing Power,
Other Metals, Chlorides, Sulfates, Acetone, Soluble Matter,
1
and Stability—Methods D 283.
Current edition approved Oct. 30, 1981. Published December 1981. Originally 6.1 antifouling paints; copper; cuprous oxide
2
1

Ethylcellulose1
1. Scope specifications are available.7 Where such specifications have

1.1 These test methods cover the testing of ethylcellulose. not been established, reagents of the best grade available shall
1.2 The test procedures appear in the following order: be used. References to water shall be understood to mean
Sections
distilled water.
Moisture 4 to 6
Sulfated Ash 7 to 11 MOISTURE
Chlorides (as Sodium Chloride) 12 to 16
Ethoxyl Content 20 to 24 4. Scope
Viscosity 25 to 39
4.1 This test method covers the determination of the volatile
1.3 This standard may involve hazardous materials, opera- content of ethylcellulose.
tions, and equipment. This standard does not purport to
address all of the safety concerns, if any, associated with its 5. Significance and Use
use. It is the responsibility of the user of this standard to 5.1 The results of this test are used for calculating the total
establish appropriate safety and health practices and deter- solids in the sample and, by common usage, all materials
mine the applicability of regulatory limitations prior to use. volatile at this test temperature are designated as moisture.
5.2 Moisture analysis (along with sulfated ash) is used to
calculate the amount of active polymer in the material and shall
2.1 ASTM Standards: be considered when determining the amount of ethylcellulose
D 362 Specification for Industrial Grade Toluene2 in various functions.
D 446 Specifications and Operating Instructions for Glass
Capillary Kinematic Viscometers3 6. Apparatus
D 841 Specification for Nitration Grade Toluene4 6.1 Oven, gravity convection, capable of maintaining a
D 4794 Test Method for Determination of Ethoxyl or Hy- temperature of 105 6 3°C.
droxyethoxyl Substitution in Cellulose Ether Products by 6.2 Weighing Bottles.
Gas Chromatography5 6.3 Analytical Balance.
7. Procedure
3. Purity of Reagents and Materials 7.1 Weigh accurately 2 to 5 g of the sample to the nearest
3.1 Reagent grade chemicals shall be used in all tests. 0.001 g into a tared dish (fitted with a lid) and dry for 2 h in an
Unless otherwise indicated, all of the reagents used shall oven at 100 to 105°C. Remove the dish from the oven, cover
conform to the specifications of the Committee on Analytical with a lid, cool in a desiccator, and weigh.
8. Calculation
8.1 Calculate the percent moisture, M as follows:
1
These test methods are under the jurisdiction of ASTM Committee D01 on
M 5 ~A/B! 3 100 (1)
Paint and Related Coatings, Materials, and Applications, and are the direct
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. where:
Current edition approved Nov. 10, 2000. Published January 2001. Originally A = mass loss on heating, g, and
2
Discontinued 1989; see 1988 Annual Book of ASTM Standards, Vol 06.03.
3
4
Annual Book of ASTM Standards, Vol 06.04. 7
5
6
MD.
1
D 914
B = sample used, g. chloride content of ethylcellulose.

9. Precision and Bias 18. Significance and Use
9.1 Precision—Statistical analysis of intralaboratory (re- 18.1 Sodium chloride is a major by-product of the ethylcel-
peatability) test results indicates a precision of 65 % at the lulose manufacturing process. This test is a measure of the
95 % confidence level. purity of ethylcellulose. Chlorides may also affect solution
9.2 Bias—No statement of bias can be made as no suitable properties.
reference material is available as a standard. 19. Apparatus
SULFATED ASH 19.1 Titration pH Meter.
19.2 Mercury-Mercurous Sulfate Reference Electrode—The
10. Scope
electrode uses a potassium sulfate electrolyte to avoid chloride
10.1 This test method covers the determination of the contamination from a chloride electrolyte.
residue on ignition of ethylcellulose after a specimen has been 19.3 Silver-Silver Chloride Electrode—The electrode is
treated with sulfuric acid. coated with silver chloride periodically. Prepare the electrode
11. Significance and Use by polishing with fine steel wool, briefly soaking it in 5 %
potassium cyanide solution, and rinsing it with water. Coat the
11.1 This test method (along with moisture) is used to
electrode with silver chloride by electrodeposition from 0.1 N
calculate the active polymer in the material. It shall be used
potassium chloride solution using a 3-V dry cell and a platinum
when testing ethylcellulose in United States government regu-
wire electrode. Connect the silver electrode to the positive pole
lated applications. Excessive ash may also affect solution
of the battery and electrolyze for 20 s; then reverse the
clarity and film properties.
connections for 5 s. Repeat these operations twice, and finally,
12. Apparatus chloridize the silver electrode for 20 s at the positive terminal.
12.1 Muffle Furnace. Store the silver electrode in 0.1 N potassium chloride solution.
12.2 Crucibles, either porcelain, Coors No. 1, or platinum. Rinse the electrode with water and wipe it with a soft tissue
before each titration.
13. Reagent 19.4 Salt Bridge for Reference Electrode—Fig. 1 shows one
13.1 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid configuration in use. Exact dimensions are not important. The
(H2SO4). salt bridge is used to keep the reference electrode from
plugging with the ethylcellulose slurry.
14. Procedure
19.5 Air-Driven Stirrer.
14.1 Ignite a crucible for 10 to 15 min at 800 6 25°C, cool
in a desiccator, and weigh to the nearest 0.001 g. 20. Reagents
14.2 Weigh about 5 g of sample to the nearest 0.001 g 20.1 Ethanol (95 volume %), undenatured or specially
(previously dried for 3 h at 105°C) into the crucible. Burn off
the bulk of the carbonaceous material directly over a flame.
After cooling, add 1 mL of H2SO4 in such a way as to moisten
the entire ash; then cautiously heat with the burner to dense
white fumes. Ignite in a muffle furnace at 800 6 25°C until all
signs of carbon are gone. Cool in a desiccator and reweigh to
the nearest 0.001 g.
15. Calculation
15.1 Calculate the percent ash (as sulfate), C, as follows:
C 5 ~A/B! 3 100 (2)
where:
A = ash, g, and
B = sample used, g.
16.1 Precision—Statistical analysis of interlaboratory (re-
producibility) test results indicates a precision of 610 % at the
95 % confidence level.
16.2 Bias—No statement of bias can be made as no suitable
reference material is available as a standard.
in. 1⁄32 1⁄8 5⁄16 3⁄8 1⁄2 7⁄8 11⁄2 3 6
CHLORIDES (as Sodium Chloride) mm 0.8 3.2 7.9 9.5 12.7 22.2 38 76 152
17. Scope FIG. 1 Salt Bridge and Reference Electrode for Chloride
17.1 This test method covers the determination of the Determination
2
D 914
denatured conforming to Formula 2B of the U.S. Bureau of producibility) test results indicates a precision of 65 % at the
Internal Revenue. 95 % confidence level.
20.2 Ethanol-Distilled Water Solvent Mixture (80 + 20)— 23.2 Bias—No statement of bias can be made as no suitable
Mix 800 g of 2B ethanol with 200 g of water. Add 7.5 g of reference material is available as a standard.
aerosol OT 100 % surface-active agent per 3000 g of ethanol-
water mixture. ETHOXYL CONTENT
20.3 Potassium Nitrate (KNO3) Solution (saturated) for salt 24. Scope
bridge (Fig. 1).
20.4 Silver Nitrate, Standard Solution (0.02 N)—Dissolve 24.1 This test method covers the determination of the
3.4 g of silver nitrate (AgNO3) in water, dilute to 1 L with ethoxyl content of ethylcellulose.
water in a volumetric flask, and mix. Weigh exactly 0.5845 g of 24.2 For an alternative method see Test Method D 4794.
dry, primary standard sodium chloride (NaCl), dissolve in 25 25. Significance and Use
mL of water, and dilute to 1 L with water in a volumetric flask.
25.1 This test method determines the amount of substituent
Add 10 mL of H2SO4 (1 + 16) to each aliquot before titrating.
groups added to the cellulose backbone. The level can greatly
Titrate aliquots of this solution potentiometrically with the
affect solution properties, rheology, solubility parameters, and
AgNO3 solution. Calculate the normality, N, of the AgNO3
film properties.
solution as follows:
N 5 ~A/B! 3 0.01 (3) 26. Apparatus
26.1 Distillation Apparatus, as illustrated in Fig. 2, consist-
where:
ing of a boiling flask with a side arm for admission of carbon
A = 0.01 N NaCl solution added, mL, and
B = AgNO3 solution required for the titration, mL. dioxide (CO2) or nitrogen, an air condenser with a trap, and a
receiver.
20.5 Sulfuric Acid (1 + 16)—Add 1 volume of concentrated
26.2 Oil Bath, equipped with a heating device, preferably
sulfuric acid (H2SO4, sp gr 1.84) slowly with stirring into 16
electrical, so that the bath can be maintained at 145 to 150°C.
volumes of water.
20.6 Toluene, meeting the requirements of Specification 27. Reagents
D 362.
27.1 Bromine Solution—Dissolve 5 mL of bromine in 145
20.7 Toluene-Ethanol Solvent Mixture (90 + 10)—Mix 900
mL of the potassium acetate (KC2H3O 2) solution. Prepare the
g of toluene with 100 g of ethanol.
21. Procedure
21.1 Weigh accurately 10 g of sample to the nearest 0.001 g
(previously dried for 2 h at 100 to 105°C) and transfer to a
600-mL beaker containing 200 mL of the toluene-ethanol
solvent mixture. Stir with an air-driven stirrer until solution is
complete.
21.2 Add 200 mL of the ethanol-water mixture and agitate
for 5 min to form a uniform emulsion. Immerse the electrodes
in the emulsion using an air-driven stirrer for mixing. Add 10
mL of H2SO 4 (1 + 16) and agitate for 3 to 4 min to allow the
system to reach equilibrium.
21.3 Titrate slowly with the 0.02 N AgNO3 solution. Make
intermittent additions of 0.1 mL. It is advisable to allow longer
periods of time between additions of titrant as the end point is
approached to avoid passing the equivalence point. Run a
blank by the same procedure.
22. Calculation
22.1 Calculate parts per million of chlorides as NaCl, C, as
follows:
C 5 @~VN 3 0.05845!/W# 3 1 000 000 (4)
where:
V = AgNO3 solution, mL,
N = normality of AgNO3 solution,
W = sample used, g, and
0.05845 = milliequivalent mass of NaCl.
23.1 Precision—Statistical analysis of interlaboratory (re- FIG. 2 Distillation Apparatus for Ethoxyl Determination
3
D 914
bromine solution fresh daily in a hood to remove bromine of Standards and Technology Standard Sample No. 136) in
vapors. water and diluting to 1 L in a volumetric flask. By means of a
27.2 Carbon Dioxide—Pass the CO 2 through a bubble buret, measure accurately 35 to 45 mL of the K2Cr2O7 solution
counter and a dry trap, and then through a pressure regulator into a 250-mL Erlenmeyer flask. Add 2 g of KI and 50 mL of
consisting of a glass tee whose vertical arm extends almost to sulfuric acid (H2SO4, 1 + 9) and allow to stand for about 5 min.
the bottom of a 10-in. (254-mm) column of water. A screw Titrate the liberated iodine with the Na2S 2O3 solution, using
clamp shall be attached to the thin-walled rubber tubing starch indicator solution near the end point. At the end point,
connecting the horizontal arm of the tee with the boiling flask. the blue color of the starch indicator will be destroyed, leaving
This arrangement permits regulation of the flow of gas and the pale green color of the chromate ion. The normality of the
allows any excess gas to escape. Nitrogen may be used in place Na 2S2O3, solution should be checked at least once a week.
of CO2. Calculate the normality, N, of the Na 2S2O3 solution as follows:
27.3 Formic Acid (90 %). N 5 ~A/B! 3 0.1 (5)
27.4 Gelatin Capsules—Gelatin capsules of a suitable size
to hold from 50 to 60 mg of the dried sample will be required. where:
27.5 Hydriodic Acid (sp gr 1.70)8—Hydriodic acid (HI) A = 0.1000 N K2Cr2O7 solution added, mL, and
forms with water a constant-boiling mixture (boiling point 126 B = Na2S 2O3 solution required for the titration, mL.
to 127°C) that contains 57 % HI. The concentration of HI in the As an alternative procedure, the Na2S2O3 solution may be
reagent used should be not less than 56.5 %. The blank standardized against 0.1 N iodine that has been standardized in
determination, which is affected primarily by free iodine in the turn against arsenic trioxide (As2O 3) (National Institute of
reagent, should require no more than 0.5 mL of 0.1 N sodium Standards and Technology Standard Sample No. 83) or potas-
thiosulfate (Na 2S2O3) standard solution. If necessary, the acid sium iodate (KIO3).
may be purified by adding to it a small amount of red 27.11 Starch Indicator Solution.
phosphorus and boiling for 20 to 30 min in a hood while 27.12 Sulfuric Acid (1 + 9)—slowly add with stirring 1
passing a stream of CO2 into the liquid. Distillation is then volume of concentrated H 2SO4 (sp gr 1.84) to 9 volumes of
carried out behind a safety-glass shield in a hood, using an water.
all-glass apparatus with a slow stream of CO2 running through
the receiver. Under some conditions, the poisonous gas phos- 28. Procedure
phine (PH 3) is formed during distillation, and this may unite 28.1 Dry the sample at 105°C for at least 30 min. Through
with molecular iodine to form phosphorus triiodide (PI3) which the condenser, add to the trap in the distillation apparatus (Fig.
may explode on contact with air. It is, therefore, advisable to 2) enough of the phosphorus slurry to make the trap about half
keep the current of CO 2 going after the distillation is ended full. Add 19 to 20 mL of the bromine solution to the receiver.
and until the apparatus has cooled; this will prevent air from Accurately weigh from 50 to 60 mg of the dry sample into a
being sucked into the apparatus. Put the purified HI in small, gelatin capsule and drop it into the boiling flask. (The weighing
brown, glass-stoppered bottles, previously swept out with CO2, should be done as rapidly as possible without sacrificing
and seal the stoppers with molten paraffin. Store in a dark accuracy because dry ethyl-cellulose picks up moisture rap-
place. To minimize decomposition of HI due to contact with idly.)
air, run CO2 into the bottle while withdrawing portions of the 28.2 Add a few small glass beads or chips of clay plate and
acid for use. then 6 mL of HI. Attach the boiling flask at once to the
27.6 Phosphorus Slurry (0.06 g/100 mL)—Add about 0.06 condenser, using a few drops of HI to moisten the ground-glass
g of red phosphorus to 100 mL of water. Shake well before joint, and then connect the side arm of the flask to the source
using. of CO2. Pass a current of CO 2 into the apparatus at the rate of
27.7 Potassium Acetate Solution (100 g/L)—Dissolve 100 g about 2 bubbles per second. Immerse the flask in the oil bath,
of anhydrous potassium acetate (KC2H3O2) crystal in 1 L of a maintained at 150°C, and heat for 40 min.
solution containing 900 mL of glacial acetic acid and 100 mL 28.3 Add 10 mL of sodium acetate solution to a 500-mL
of acetic anhydride. Erlenmeyer flask and wash into it the contents of the receiver;
27.8 Potassium Iodide (KI). dilute to 125 mL with water. Add formic acid dropwise, with
27.9 Sodium Acetate Solution (220 g/L)—Dissolve 220 g of swirling, until the brown color of bromine is discharged, and
anhydrous sodium acetate in water and dilute to 1 L. then add about 6 drops more. A total of 12 to 15 drops is
27.10 Sodium Thiosulfate, Standard Solution (0.1 N)— usually required. After about 3 min, add 3 g of KI and 15 mL
Dissolve 25 g of sodium thiosulfate (Na2S2O3·5H 2O) in 200 of H2SO4 (1 + 9) and titrate immediately with 0.1 N Na2S2O3
mL of water and dilute to 1 L. Use freshly boiled and cooled solution to a light straw color. Add a little starch solution and
water. It is preferable to allow the solution to stand for a few continue the titration to the disappearance of the blue color.
days before standardization. Standardize the solution against 28.4 Blank—Make a blank determination, using the same
0.1000 N potassium dichromate (K2Cr2O7) solution prepared amounts of reagents and the same procedures as for the
by dissolving exactly 4.9037 g of K2Cr2O 7 (National Institute specimen. (Usually, about 0.1 mL of 0.1 N Na2S 2O3 solution is
required.)
8
Hydriodic acid suitable for ethoxyl determination may also be prepared by the 29. Calculation
method of Samsel, E. P., and McHard, J. A., Industrial and Engineering Chemistry,
Analytical Edition, Vol 14, 1942, p. 750. 29.1 Calculate the percent ethoxyl, E, as follows:
4
D 914
E 5 ~@~A 2 B!N 3 0.00751#/W! 3 100 (6) or metal baseboard large enough to support its entire length.
The board is in turn hinged at one end to a larger board and is
where: provided with a movable-support arm to hold it at a 45° angle
A = Na2S2O3 solution required for titration of the sample,
with the base. The bottom board should have adjustable legs so
mL,
that it can be leveled. The board that supports the capillary tube
B = Na2S 2O3 solution required for titration of the blank,
is equipped with a spirit level. Care must be taken in mounting
mL,
N = normality of the Na2S2O3 solution, and the tube to see that the capillary is exactly parallel to the board
W = sample used, g. holding the spirit level. The water running through the jacket
should come from a constant-temperature bath maintained at
30. Precision and Bias 25.06 0.1°C.
30.1 Precision—Statistical analysis of intralaboratory (re- 33.2 Shaker, Bottle.
peatability) test results indicates a precision of 61 % absolute 33.3 Timer, calculated in 0.1-s units.
at the 95 % confidence level.
30.2 Bias—No statement of bias can be made as no suitable 34. Reagents
reference material is available as a standard. 34.1 Standard Calibrating Liquid, 100 cP and 25 C.
34.2 Ethanol (95 volume %)—Undenatured or specially
VISCOSITY denatured conforming to Formula 2B of the U.S. Bureau of
Internal Revenue.
31. Scope 34.3 Mixed Solvent (80 + 20 toluene ethanol by mass)—
31.1 Ethylcellulose viscosity is arbitrarily measured on a Prepare by weighing proportional amounts of toluene and
5 % solution in a specific solvent system. The viscosity ethanol described in 34.1 and 34.2. Mix thoroughly.
normally ranges from 7 to 200 cP at 25°C. 34.4 Toluene, meeting the requirements of Specification
31.2 Two test methods for measuring ethylcellulose viscos- D 362.
ity are given below. One test method specifies use of the
Hercules Horizontal Capillary Viscometer and a solvent system 35. Calibration
of 80 + 20 toluene-ethanol while the other specifies the Dow 35.1 Make a mark on the capillary tube about 10 cm from
Modified Ubbelohde viscometer and solvent systems of the point where the capillary is attached to the reservoir. Mount
80 + 20 toluene-ethanol for product with an ethoxyl content the tube in a water jacket, adjust the temperature, elevate the
above 47 % and 60 + 40 toluene-ethanol for ethoxyl content board holding the tube to the 45° position, and fill the reservoir
below 47 %. to the etched mark with the standard liquid. Lower the board
31.3 The two test methods given below do not give the same holding the tube to the baseboard and level the instrument
resultant viscosity. Therefore, they should be used only in a while holding one finger over the end of the capillary tube.
relative sense and not interchangeably. Remove the finger when ready and the liquid will start to flow
31.4 Neither test method is intended to be a referee method. through the capillary. Start the timer when the liquid reaches
the etched mark. Determine the place where the second mark is
to be placed by noting the distance the liquid has traveled when
32.1 This test method determines the relative ability of the the elapsed time, in seconds, is equal to the viscosity of the oil
polymer to thicken organic solvents and is therefore related to in centipoises. It is advisable to use a movable mark, such as a
the concentration required in various formulations to achieve small rubber band, until the exact position of the mark has been
the desired finished product viscosity. It can also affect film rechecked quite carefully; then an etched line can be made.
properties such as tensile strength, flexibility, elongation, and
brittleness. 36. Procedure
HERCULES HORIZONTAL CAPILLARY VISCOSITY 36.1 Dry a portion of the sample at 100 to 105°C for 1 h.
Weigh 5 g of the sample to the nearest 0.01 g into an 8-oz
33. Apparatus (250-mL) widemouth bottle. Add 95.00 g of the mixed solvent,
33.1 Hercules Horizontal Capillary Viscometer9 (Fig. 3)— cover the neck of the bottle with a sheet of cellophane, and
The tube is surrounded by a glass tube that acts as a water screw on the cap.
jacket and is connected with it by rubber stoppers at both ends 36.2 Agitate on a bottle shaker until the solution is complete
which have proper holes to provide for water inlet and outlet by visual inspection. After the solution is complete, place the
and for insertion of a thermometer. For convenient use, it is bottle of the solution in a constant-temperature bath maintained
desirable to cut the openings in the stopper at the end next to at 25 6 0.1°C for 1 h.
the reservoir bulb. One of the thermostated water lines should 36.3 Remove the bottle of solution from the bath and check
extend inside the jacket, nearly to the opposite end, to provide to be sure it is free of air bubbles. Fill the viscometer reservoir
good circulation. The tube and its jacket are attached to a wood to the etched mark, while vertical, with the solution to be
tested. Place a finger over the end of the capillary, release the
brace, lower the tube, and level.
9
Detailed drawings of the complete installation can be obtained from Hercules 36.4 Release the finger and determine the time for the liquid
Incorporated, Wilmington, DE as Drawings No. 2173U and 2174U. to flow from the first mark to the second.
5
D 914
FIG. 3 Hercules Horizontal Capillary Viscometer
37. Calculation alcohol described in 41.1 and 41.2. Mix thoroughly.

37.1 Calculate the viscosity as follows:
42. Calibration
N 5 td/D (7)
42.1 Select viscosity-calibrating liquids that will yield a
where: minimum efflux time of 200 s in the viscometers to be
N = viscosity, cP, standardized at 256 0.1°C. See Specification D 446.
t = time of flow for the sample, s, 42.2 Calibrate one viscometer of each capillary size to be
d = density of the sample solution at 25°C (0.859), and
used in the viscosity test work using the calibrating liquid that
D = density of the oil used for calibration of the viscom-
is indicated in Table 1.
eter.
42.3 Charge the Ubbelohde viscometer selected with the
38. Report appropriate viscometer calibrating liquid by pouring the liquid
38.1 Report the viscosity in centipoises, the solution con- into the large tube to a level in line with the bottom of the
centration, and the test method (Hercules Horizontal Capil- vent-tube entrance. Charge the viscometer in such a manner so
lary). that the U-tube at the bottom fills completely without trapping
air.
39. Precision and Bias 42.4 Place the viscometer in a constant-temperature water
39.1 Precision—Statistical analysis of intralaboratory (re- bath at 25 6 0.1°C, immersing the viscometer to cover the
peatability) test results indicates a precision of 65 % at the functioning areas. Allow the liquid to reach the required
95 % confidence level. temperature. Determine the temperature by placing the ther-
39.2 Bias—No statement of bias can be made as no suitable mometer into the liquid. Remove the thermometer. Place a
reference material is available as a standard. suction bulb over the end of the calibrated flow tube and your
finger over the end of the vent tube; then apply suction on the
DOW MODIFIED UBBELOHDE VISCOSITY calibrated tube until the liquid level is drawn half way up into
40. Apparatus the upper bulb of the calibrated tube. Release the suction and
finger from the viscometer.
40.1 Constant-Temperature Bath, capable of maintaining a
42.5 Time the flow in seconds between the upper and lower
temperature of 25 6 0.1°C.
calibration lines to the nearest 0.10 s with a timer. If the time
40.2 Shaker, Bottle.
in seconds is less than 200, select a viscometer with a smaller
40.3 Timer, calibrated in 0.1-s units.
capillary and repeat the operation.
40.4 Viscometers, modified Ubbelohde (Fig. 4).
40.5 Thermometer—ASTM Kinematic Viscosity Thermom- 42.6 Without recharging the viscometer, make check deter-
eter, having a range from 74.5 to 79.5 F and conforming to the minations by repeating the procedures five times. Determine
requirements for Thermometer 45F as prescribed in Specifica- the efflux time by averaging the five values. The range of the
tion E 1. individual values should not exceed 0.5 s.
42.7 Calculate the standard viscometer constant, F, for
41. Reagents ethylcellulose solutions as follows:
41.1 Ethanol (95 volume %), undenatured or specially F 5 ~V 3 d e! / ~d0 /t! (8)
denatured conforming to Formula 2B of the U.S. Bureau of
Internal Revenue. where:
41.2 Toluene, meeting the requirements of Specification V = absolute viscosity of the calibrating liquid at 25°C,
D 841. d0 = density of the calibrating liquid at 25°C,
41.3 Standard Calibrating Liquids (see 42.2). de = density of the sample solution at 25°C (use 0.861 for
41.4 Mixed Solvents (80 + 20 and 60 + 40 toluene-ethanol 80 + 20 and 0.845 for 60 + 40 toluene-ethanol), and
t = flow time, s.
by mass)—Mix proportional amounts of toluene and ethyl
6
D 914
FIG. 4 Dow Modified Ubbelohde Viscometer
TABLE 1 Solutions for Viscosity Determination thermometer. Charge the viscometer by placing a suction bulb
Capillary
Approximate Cannon over the end of the calibrated flow tube and then, with a finger
Dow Approximate D 446 Standard over the opening of the vent tube, apply suction on the
Bore
Viscometer Viscosity, Design Viscometer
Designation
Diameter,
cP at 25 C Ubbelohde Calibrating calibrated tube until the liquid level is drawn half-way up into
mm
Viscometers Liquid the upper half of the calibrated tube. Release suction and finger
P 1.10 ... 2 S-60 from the tubes.
Q 1.49 10 2C S-200 43.5 Time the flow between the upper and lower calibration
R 1.77 20 2B S-200
S 2.51 80 3C S-600
lines to the nearest 0.1 s.
T 3.15 150 3B S-600 43.6 Repeat the above procedure and average the two efflux
U 4.40 ... 4C S-8000 times. If the time range exceeds 1 s, repeat the operation a third
time and average the two values that deviate the least.
43. Procedure
44. Calculation
43.1 Weigh 57 6 0.02 g of the solvent solution into an 8-oz
44.1 Calculate viscosity, V in centipoises as follows:
(250-mL) jar. Weigh 3.0 6 0.01 g of dry sample and add to the 1
solvent in the jar. Close the jar with a lined screw cap and V1 5 F 3 T (9)
shake to wet and disperse the sample. Continue to shake for where:
about 15 min on the shaker, or until the sample is completely F = viscometer constant (see 42.7); and
dissolved. T = efflux time, s, from 43.6.
43.2 Select a Ubbelohde viscometer based on the approxi-
mate viscosity range (see 42.2). Add sample solution to the 45. Report
large tube to a level in line with the bottom of the vent tube 45.1 Report viscosity in centipoises, solution concentration,
entrance. and the test method (Dow Modified Ubbelohde).
43.3 Place the viscometer in the 25 6 0.1°C constant-
temperature bath. (Immerse the viscometer to cover the func- 46. Precision and Bias
tioning areas.) 46.1 Precision—Statistical analysis of intralaboratory (re-
43.4 Place a thermometer in the viscometer (see 42.4). After peatability) test results indicates a precision of 65 % at the
the liquid has reached the required temperature, remove the 95 % confidence level.
7
D 914
46.2 Bias—No statement of bias can be made as no suitable 47. Keywords
reference material is available as a standard. 47.1 chlorides; ethoxyl content; ethylcellulose; moisture;
sulfated ash; viscosity
8

Raw Castor Oil1
1. Scope TABLE 1 Properties of Castor Oil

ASTM Test
1.1 This specification covers castor oil suitable for use in Property Requirement
Method
resins and protective coatings, including lacquers. This is
generally known in the trade as No. 1 castor oil . Clarity clear D 2090
Color (Gardner), max 2 D 1544
2. Referenced Documents Hydroxyl value 160 to 168 D 1957
Loss on heating, max, % 0.3 D 1960
2.1 ASTM Standards: Refractive index, 25°C 1.4764 to 1.4778 ...
D 555 Guide for Testing Drying Oils2 Saponification value 176 to 184 D 1962
Solubility in alcoholA complete ...
D 1466 Test Method for Sampling Liquid Oils and Fatty Specific gravity, 25/25°C 0.957 to 0.961 D 1963
Acids Commonly Used in Paints, Varnishes, and Related Unsaponifiable, max, % 0.7 D 1965
Viscosity, St 6.3 to 8.9 D 1545
Materials2 Iodine value 83 to 88 D 1959
D 1544 Test Method for Color of Transparent Liquids A
Castor oil shall be completely soluble without turbidity at 20°C in two volumes
(Gardner Color Scale)3 of specifically denatured alcohol (95 %) conforming to Formula 3A of U. S. Bureau
D 1545 Test Method for Viscosity of Transparent Liquids of Alcohol, Tobacco, and Firearms.
by Bubble Time Method2 D 2090 Test Method for Clarity and Cleanness of Paint and
D 1639 Test Method for Acid Value of Organic Coating Ink Liquids2
Materials2
D 1957 Test Method for Hydroxyl Value of Fatty Oils and 3. Properties
Acids2 3.1 Castor oil shall conform to the requirements given in
D 1959 Test Method for Iodine Value of Drying Oils and Table 1.
Fatty Acids2
D 1960 Test Method for Loss on Heating of Drying Oils2 4. Test Methods
D 1962 Test Method for Saponification Value of Drying 4.1 The properties enumerated in this specification shall be
Oils, Fatty Acids, and Polymerized Fatty Acids2 determined in accordance with the ASTM test methods listed in
D 1963 Test Method for Specific Gravity of Drying Oils, Table 1.
D 1965 Test Method for Unsaponifiable Matter in Drying 5. Sampling
Oils, Fatty Acids, and Polymerized Fatty Acids2 5.1 Sampling shall be conducted in accordance with Test
Method D 1466.
1
and Related Coatings, Materials, and Applications and is the direct responsibility of 6.1 The significance of the test methods enumerated under
Subcommittee D01.32 on Drying Oils. Section 2 of this specification is discussed in Guide D 555.
Current edition approved Oct. 29, 1979. Published January 1980. Originally
published as D 960 – 63 T. Last previous edition D 960 – 73. 7. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 7.1 castor oil; non-drying oils
1

Dehydrated Castor Oil1
1. Scope D 1962 Test Method for Saponification Value of Drying

1.1 This specification covers a drying oil made from castor Oils, Fatty Acids, and Polymerized Fatty Acids3
oil that has been treated to remove the elements of water. Two D 1963 Test Method for Specific Gravity of Drying Oils,
types of dehydrated castor oil are covered: unbodied and Z-3 Varnishes, Resins, and Related Materials at 25/25°C3
bodied. D 2090 Test Method for Clarity and Cleanness of Paint and
Ink Liquids3
NOTE 1—Other types of bodied dehydrated castor oil are commercially E 1 Specification for ASTM Thermometers5
available but are not covered by this specification.
3. Properties
3.1 Dehydrated castor oil shall conform to the requirements
2.1 ASTM Standards:
prescribed in Table 1.
D 445 Test Method for Kinematic Viscosity of Transparent
and Opaque Liquids (and the Calculation of Dynamic 4. Test Methods
Viscosity)2
D 555 Guide for Testing Drying Oils3
determined in accordance with the appropriate methods given
D 1475 Test Method for Density of Paint, Varnish, Lacquer,
in Table 1 with the following exceptions:
4.1.1 Gel Time—Determine the gel time in accordance with
Test Method D 1955 but with the following changes:
(Gardner Color Scale)4
4.1.1.1 Use an ASTM Partial Immersion Thermometer hav-
D 1545 Test Method for Viscosity of Transparent Liquids
ing a range from 20 to 760°F and conforming to the require-
by Bubble Time Method3
ments for Thermometer 3F as prescribed in Specification E 1.
4.1.1.2 Heat the bath to 600 6 1°F (315 6 0.5°C), insert the
Materials3
tubes containing the oil in the bath, maintain the bath at 600 6
D 1640 Test Methods for Drying, Curing, or Film Forma-
1°F for the duration of the test, and
4.1.1.3 Raise the glass rods a fraction of an inch at 1-min
D 1955 Test Method for Gel Time of Drying Oils3
intervals after 125 min in the case of the unbodied oil or after
25 min in the case of the bodied oil.
Fatty Acids3
4.1.2 Iodine Value—Use the procedure described in Method
D 1959, to determine the iodine value, except that the speci-
men weights shall be 0.11 to 0.13 g of oil.
1
4.2 The significance of and comments on the referenced
and Related Coatings, Materials, and Applications, and is the direct responsibility of methods are discussed in Guide D 555.
Subcommittee D 01.32 on Drying Oils.
Current edition approved March 27, 1986. Published May 1986. Originally 5. Keywords
2 5.1 castor oil; dehydrated; dehydrated castor oil
3
4 5
1
D 961
TABLE 1 Requirements for Dehydrated Castor Oil
Unbodied Bodied ASTM Method
Viscosity at 25°C F to I Z2 to Z4 D 1545, D 445
Specific gravity, 25/25°C 0.926 to 0.937 0.944 to 0.966 D 1963, D 1475
Acid value, max 6 6 D 1639
Saponification value 188 to 195 188 to 195 D 1962
Iodine value (Wijs) 125 to 145 100 min D 1959
Color No. (Gardner), max 6 7 D 1544
Gel time at 600°F (315°C), min 145, approximately 63, approximately D 1955
Set-to-touch time, h 2.5, approximately 1.4, approximately D 1640
Refractive index at 25°C 1.4805 to 1.4825 1.4860 to 1.4890 ...
Clarity clear and transparent clear and transparent D 2090
at 25°C at 25°C
2

Aluminum Powder and Paste Pigments for Paints1
1. Scope No. 325 (45-µm) sieve.

1.1 This specification covers four types and three classes of 3.4.3 Class C, Coarse—Maximum of 11.0 % retained on a
aluminum pigments for use in paints. No. 325 (45-µm) sieve.
NOTE 1—The particle size characteristics of the Type 3 and Type 4
2. Referenced Documents pigments of the same class do not correspond with each other; in the case
2.1 ASTM Standards: of Types 1 and 2 they do.
D 480 Test Methods for Sampling and Testing of Flaked
Aluminum Powders and Pastes2 4. Composition and Properties
E 34 Test Methods for Chemical Analysis of Aluminum and 4.1 Aluminum Pigment Powder (Type 1, Leafing and Type
Aluminum Base Alloys3 3, Nonleafing)—The aluminum pigment powder shall consist
of commercially pure aluminum in the form of fine, polished
3. Classification flakes, and a suitable fatty lubricant. It shall contain no filler or
3.1 Type I—Leafing Aluminum Pigment Powder: extender pigments.
3.1.1 Class A, Fine—Maximum of 0.1 % retained on a No. 4.2 Aluminum Pigment Paste (Type 2, Leafing and Type 4,
325 (45-µm) sieve. Nonleafing)—The aluminum pigment paste shall consist of
3.1.2 Class B, Medium—Maximum of 1.5 % retained on a commercially pure aluminum in the form of fine, polished
No. 325 (45-µm) sieve. flakes, and a suitable fatty lubricant combined with a volatile
3.1.3 Class C, Coarse—Maximum of 20 % retained on a thinner. It shall contain no filler or extender pigments.
No. 325 (45-µm) sieve. 4.3 The aluminum pigments, powder, and paste of both
3.2 Type II—Leafing Aluminum Pigment Paste: leafing and nonleafing types shall conform to the requirements
3.2.1 Class A, Fine—Maximum of 0.1 % retained on a No. given in Table 1.
325 (45-µm) sieve. 4.4 The paint made from the powder or paste shall be
3.2.2 Class B, Medium—Maximum of 1.0 % retained on a free-flowing and shall give a continuous coating at least equal
No. 325 (45-µm) sieve. in smoothness, luster, and general appearance to that of a
3.2.3 Class C, Coarse—Maximum of 15 % retained on a reference sample mutually agreed upon by the purchaser and
No. 325 (45-µm) sieve. the seller.
3.3 Type III—Nonleafing Aluminum Pigment Powder 4.5 The aluminum pigments, powder and paste of both
(Note): leafing and nonleafing types, stored in unopened original
3.3.1 Class A, Fine—Maximum of 1.5 % retained on a No. packages within 6 months after shipment shall pass all tests
325 (45-µm) sieve. applicable to the respective type and class as described in Test
3.3.2 Class B, Medium—Maximum of 6.0 % retained on a Methods D 480.
No. 325 (45-µm) sieve.
3.3.3 Class C, Coarse—Maximum of 20 % retained on a 5. Test Methods and Sampling
No. 325 (45-µm) sieve. 5.1 Sampling and tests shall be conducted in accordance
3.4 Type IV—Nonleafing Aluminum Pigment Paste (Note 1): with Test Methods D 480. Since several of the methods are
3.4.1 Class A, Fine—Maximum of 0.1 % retained on a No. empirical and the results are affected by the method, the
325 (45-µm) sieve. specified procedures should be closely followed.
3.4.2 Class B, Medium—Maximum of 1.0 % retained on a
6. Packaging
6.1 Aluminum paste should be packaged in a polyvent
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint container that can be safely vented in case of pressure build-up.
published as D962 – 48 T. Last previous edition D962 – 66 (1973). 7.1 aluminum powder; flake; leafing; nonleafing; paste;
2
Annual Book of ASTM Standards, Vol 06.03. polishing lubricant
3
1
D 962
TABLE 1 Requirements for Aluminum Pigments
Leafing Nonleafing
Type 1 Type 2 Type 3 Type 4
(Powder) (Paste) (Powder) (Paste)
Nonvolatile matter at 105 to 110°C, min, % 99 65 99 65
Easily extracted fatty and oily matter (polishing lubricant), max,%A 4.0 3.0 4.0 3.0
Total impurities other than fatty and oily matter, max, %A 1.0 0.7 1.0 1.25
Coarse particles, max, %:
Class A (total residue retained on a No. 325 (45-µm) sieve) 0.1 0.1 1.5 0.1
Class B (total residue retained on a No. 325 (45-µm) sieve) 1.5 1.0 6.0 1.0
Class C (total residue retained on:
No. 100 (150-µm) sieve 0.5 0.5 0.5 0.5
No. 325 (45-µm) sieve) 20.0 15.0 20.0 11.0
Leafing, min, %:
Class A 50 55 absent absent
Class B 50 50 absent absent
Class C 50 50 absent absent
A
Nonleafing pigments may contain metal compounds as dispersants. If required, a complete analysis may be made in accordance with Test Method E 34.
2

Copper Powder for Use in Antifouling Paints1
1. Scope Coarse particles, max, % 1.0

1.1 This specification covers copper powder for use in 4. Sampling
antifouling paints.
2. Referenced Documents packages from each lot, batch, day’s pack, or other unit of
2.1 ASTM Standards: production in a shipment. When no markings distinguishing
D 185 Test Methods for Coarse Particles in Pigments, between units of production appear, samples shall be taken
Pastes, and Paints2 from different packages in the ratio of two samples for each
D 283 Test Methods for Chemical Analysis of Cuprous 10 000 lb (5000 kg), except that for shipments of less than
Oxide and Copper Pigments2 10 000 lb two samples shall be taken. At the option of the
3. Composition blending in equal quantities the samples from the same
3.1 The pigment shall consist essentially of finely divided production unit to form a composite sample.
copper metal and shall conform to the following requirements: 5. Test Methods
Copper, min, % 99
ing ASTM test methods:
5.1.1 Copper—Test Methods D 283.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.2 Coarse Particles—Test Methods D 185.
published as D 964 – 48. Last previous edition D 964 – 55. 6.1 antifouling paint; copper pigment; copper powder; cu-
2
Annual Book of ASTM Standards, Vol 06.03. prous oxide
1

Para Red and Toluidine Red Pigments1
1. Scope where such specifications are available.5 Other grades may be

1.1 These test methods cover para red and toluidine red used, provided it is first ascertained that the reagent is of
pigments (toners) in the dry form commercially known as sufficiently high purity to permit its use without lessening the
“pure.” accuracy of the determination.
1.2 This standard does not purport to address all of the 4.2 Purity of Water—Unless otherwise indicated, references
safety concerns, if any, associated with its use. It is the to water shall be understood to mean water conforming to Type
responsibility of the user of this standard to establish appro- II of Specification D 1193.
priate safety and health practices and determine the applica- 4.3 Chloroform.
bility of regulatory limitations prior to use. 4.4 Hydrochloric Acid (1+1)—Mix equal volumes of con-
centrated hydrochloric acid (HCl, sp gr 1.19) and water.
2. Referenced Documents 4.5 Nitric Acid (3+5)—Mix 3 volumes of concentrated
2.1 ASTM Standards: nitric acid (HNO3, sp gr 1.42) with 5 volumes of water.
D 185 Test Methods for Coarse Particles in Pigments, 4.6 Potassium Hydroxide, Alcoholic Solution—Dissolve 10
Pastes, and Paints2 g of potassium hydroxide (KOH) in 90 mL of ethyl alcohol
D 280 Test Methods for Hygroscopic Moisture (and Other (95 %).
Matter Volatile Under the Test Conditions) in Pigments2 4.7 Sodium Hydroxide (100 g/L)—Dissolve 100 g of so-
D 387 Test Method for Color and Strength of Color Pig- dium hydroxide (NaOH) in water and dilute to 1 L.
5. Solubility in Chloroform
D 3335 Test Method for Low Concentrations of Lead, 5.1 Place about 0.05 g of the dry pigment in a 50-mL
Cadmium, and Cobalt in Paint by Atomic Absorption Nessler tube, add 40 mL of chloroform, and warm slightly,
Spectroscopy3 stirring with a glass rod. Compare this solution with a similarly
D 3624 Test Method for Low Concentrations of Mercury in prepared solution of a standard sample of known purity.
Paint by Atomic Absorption Spectroscopy3 Complete solubility of the pigment in chloroform is indicated
if a clear orange red solution is obtained.
NOTE 1—Any turbidity indicating an impurity may be separated con-
3.1 These test methods are used to determine the purity and veniently by extracting 5 g of the pigment in a soxhlet extractor, using
some physical properties of para red and toluidine red pig- chloroform as the solvent. The residue may then be examined and
ments. This information is significant to pigment producers and estimated.
to coatings manufacturers.
6. Qualitative Test for Identity and Purity
4. Reagents 6.1 To 10 mL of the chloroform solution (5.1) add 2 mL of
4.1 Purity of Reagents—Reagent grade chemicals shall be alcoholic potassium hydroxide (KOH) solution. An intense
used in all tests. Unless otherwise indicated, it is intended that violet coloration indicates the presence of para red toner, (1-(
all reagents shall conform to the specifications of the Commit- p-nitro-phenylazo)-2-naphthol). A wine red coloration indi-
tee on Analytical Reagents of the American Chemical Society, cates the presence of toluidine red toner (1-(2-nitro-p-tolyl-
azo)-2-naphthol). It is well to make side-by-side comparisons,
using a standard pigment as control.
1
5
Current edition approved Sept. 26, 1986. Published November 1986. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 970 – 48. Last previous edition D 970 – 73 (1979) e1. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
1
D 970
NOTE 2—Infrared spectrophotometry may also be employed for this (1+1). Repeat using NaOH solution (100 g/L), omitting the
purpose if equipment is available and suitable reference spectra have been filtration.
agreed upon by purchaser and seller.
9. Moisture and Other Volatile Matter
7. Ash
9.1 Determine the percent moisture and other volatile matter
7.1 Transfer about 2 g of the sample (weighed to 0.1 mg) to in accordance with Test Methods D 280.
a tared porcelain or platinum crucible and heat at red heat until
all organic matter is destroyed. Cool and weigh. 10. Coarse Particles
10.1 Determine the percent of coarse particles in accordance
NOTE 3—For examination for low concentrations of lead and mercury,
refer to Test Methods D 3335 and D 3624. with Test Methods D 185.
7.2 Calculate the percent of ash present as follows: 11. Mass Color and Character of Tint
Ash, % 5 ~R/S! 3 100 11.1 Determine the mass color and character of tint in
accordance with Test Method D 387.
where:
R 5 residue, g, and 12. Precision and Bias
S 5 sample used, g. 12.1 Data are not available to determine the precision and
8. Resistance to Acids and Alkalis bias of these test methods. There are no plans at present to
obtain such data. The methods have been in use for several
8.1 Place about 0.5 g of the dry pigment in a 50-mL beaker years and are considered acceptable.
and add about 40 mL of HNO3 (3+5). Stir well and allow the
pigment to settle. Decant the liquid and filter it. The filtrate 13. Keywords
should show no more color than a reference pigment mutually 13.1 para red pigment; analysis of; pigment; toluidine red
agreed upon by the purchaser and the seller. Repeat using HCl pigment; analysis of; toner; para red and toluidine red
2

sec-Butyl Alcohol1,2
1. Scope * 3. Properties
1.1 This specification covers sec-butyl alcohol for use in 3.1 sec-Butyl alcohol shall conform to the following re-
paint, varnish, lacquer, and related products. quirements:
1.2 For hazard information and guidance, see the supplier’s Apparent specific gravity:
Material Safety Data Sheet. 20/20°C 0.807 to 0.809
25/25°C 0.804 to 0.806
2. Referenced Documents Distillation range, 760 mmHg, °C as:
2.1 ASTM Standards: Initial boiling point, min 98.0
D 268 Guide for Sampling and Testing Volatile Solvents Nonvolatile matter, max, mg/100 mL 5
and Chemical Intermediates for Use in Paint and Related Water, max, weight % 0.5
Coatings and Materials3 Acidity, as acetic acid, max, weight % 0.002A
__________
D 1078 Test Method for Distillation Range of Volatile A
Organic Liquids3
D 1209 Test Method for Color of Clear Liquids (Platinum- 4. Sampling
Cobalt Scale)3 4.1 The material shall be sampled in accordance with
D 1353 Test Method for Nonvolatile Matter in Volatile Practice E 300.
Solvents for Use in Paint, Varnish, Lacquer, and Related
Products3 5. Test Methods
D 1364 Test Method for Water in Volatile Solvents (Karl 5.1 The properties enumerated in this specification shall be
Fischer Reagent Titration Method)3 determined in accordance with the following ASTM methods:
D 1613 Test Method for Acidity in Volatile Solvents and 5.1.1 Apparent Specific Gravity—Determine the apparent
Chemical Intermediates Used in Paint, Varnish, Lacquer, specific gravity at 20 or 25°C by a convenient method that is
and Related Products3 accurate to the third decimal place. See Guide D 268 or Test
D 4052 Test Method for Density and Relative Density of Method D 4052.
Liquids by Digital Density Meter4 5.1.2 Color—Test Method D 1209.
E 1 Specification for ASTM Thermometers5 5.1.3 Distillation Range—Test Method D 1078 using an
E 300 Practice for Sampling Industrial Chemicals6 ASTM Solvents Distillation Thermometer 40C, having a range
2.2 U.S. Federal Specification: from 72 to 126°C and conforming to the requirements in
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging Specification E 1.
of 7 5.1.4 Nonvolatile Matter—Test Method D 1353.
5.1.5 Water—Test Methods D 1364 .
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 6. Packaging and Package Marking
and Related Coatings, Materials, and Applications and is the direct responsibility
D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 6.1 Package size shall be agreed upon between the pur-
Current edition approved Jan. 10, 2000. Published March 2000. Originally chaser and the supplier.
published as D 1007 – 49 T. Last previous edition D 1007 – 95. 6.2 Packaging shall conform to applicable carrier rules and
2
This compound is also known under the names 2-butanol and secondary
butanol. regulations or when specified shall conform to Fed. Spec.
3
4
5
6
7
Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700 7.1 methyl ethyl carbinol; sec-butyl alcohol; 2–hydroxybu-
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. tane

1
D 1007
SUMMARY OF CHANGES
(1) Added hazard caveat. (3) Added Summary of Changes section.

(2) Deleted Test Method D 1476.
2

Determining Total Nitrogen in Resins and Plastics1
1. Scope that no loss of volatile constituents will be sustained during the

1.1 This test method covers the determination of total weighing operation.
nitrogen in nitrogen-containing plastics, resins, and resin 5. Reagents
solutions. This test method is not applicable for use on
materials containing nitro-groups. 5.1 Purity of Reagents—Reagent grade chemicals shall be
1.2 This standard does not purport to address all of the used in all tests. Unless otherwise indicated, it is intended that
safety concerns, if any, associated with its use. It is the all reagents shall conform to the specifications of the Commit-
responsibility of the user of this standard to establish appro- tee on Analytical Reagents of the American Chemical Society,
priate safety and health practices and determine the applica- where such specifications are available.3 Other grades may be
bility of regulatory limitations prior to use. used, provided it is first ascertained that the reagent is of
2. Referenced Documents accuracy of the determination.
2.1 ASTM Standards: 5.2 Purity of Water—Unless otherwise indicated, reference
D 1193 Specification for Reagent Water2 to water shall be understood to mean reagent water conforming
to Type II of Specification D 1193.
3. Significance and Use 5.3 Hydrochloric or Sulfuric Acid, (standard 0.5 N)—Dilute
3.1 Total nitrogen content gives an indication of the level or 43 mL of HCl (sp gr 1.19) or 14 mL of H2SO4 (sp gr 1.84) to
purity of a nitrogen-containing material such as an amine resin. 1 L with water. Standardize against the 0.5 N NaOH solution
It is important for the quality control of amine resins and is (3.7), using the same indicator as will be used in titration of the
often used to determine whether the proper amounts of many specimen (4.4).
types of nitrogen-containing materials are present in formu- 5.4 Metallic Mercury or Mercuric Oxide.
lated products. 5.5 Methyl Purple Indicator Solution.
NOTE 1—Methyl purple has recently met with considerable favor, and
4. Apparatus is to be recommended because of the abruptness of its color change in the
4.1 Kjeldahl Flasks, for digestion and distillation, 800-mL presence of ammonium salts. This indicator may be purchased in solution
capacity, moderately heavy wall, and made of hard glass. form ready for use.
4.2 Connecting Bulbs, of the Davisson type, or a bulb 5.6 Methyl Red Indicator Solution—Dissolve 0.2 g of me-
equally effective in preventing mechanical carry-over of the thyl red in 100 mL of methanol, ethanol, or isopropanol.
contents of the distillation flask to the condenser. 5.7 Potassium Sulfate.
4.3 Digestion and Distillation Equipment—A suitable 5.8 Sodium Hydroxide Solution (760 g/L)—Dissolve 1000 g
Kjeldahl digestion and distillation apparatus, such as any of the of technical grade NaOH in 1 L of water.
well-known commercial units for multiple work. The units 5.9 Sodium Hydroxide, Standard Solution (0.5 N)—Prepare
may be heated either electrically or by gas burner. a 0.5 N NaOH solution free of carbonates, using reagent grade
4.4 Connecting Tubes made of moderately heavy-wall glass NaOH, and standardize against the National Bureau of Stan-
tubing, 6 to 8 in. (150 to 200 mm) in length, for conducting the dards standard reference material No. 84 of potassium acid
distillate from the condenser to the receiver. phthalate, using phenolphthalein indicator. Protect the solution
4.5 Weighing Tube (for Liquid Resins)—Any convenient against CO2 absorption.
device for weighing a few grams of sample in a matter such 5.10 Sulfide or Thiosulfate Solution—Dissolve 40 g of K2S
1 3
Subcommittee D01.33 on Polymers and Resins. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved April 15, 1993. Published June 1993. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 1013 – 49. Last previous edition D 1013 – 88. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
1
D 1013
or Na2S, or 80 g of Na2S2O3·5H2O, in water and dilute to 1 L. 6.5 Add 5 to 7 drops of methyl red or methyl purple
5.11 Sulfuric Acid (sp gr 1.84). indicator solution and titrate the excess acid with 0.5 N NaOH
solution.
6. Procedure 6.6 Blank—Make a blank determination, following the
6.1 Transfer a portion of the sample, weighed to 1 mg, to a same procedure and using the same amounts of all reagents.
Kjeldahl flask, using a weighing tube if the material is a liquid.
The quantity of sample taken should be an amount that will 7. Calculation
contain from 150 to 250 mg of nitrogen. Add from 0.5 to 0.75 7.1 Calculate the percent nitrogen A as follows:
g of metallic mercury or the equivalent weight of HgO, 10 g of A 5 @~~B 2 V!N 3 0.014!/S# 3 100 (1)
K2SO4, and 25 to 35 mL of H2SO4 (sp gr 1.84). If the material
under test is a urethane resin or polymer the amount of H2SO4 where:
(sp gr 1.84) should be increased to 60 mL. If preferred, H2SO4 B 5 NaOH solution required for titration of the blank, mL,
(1 + 1) may be used for digestion in place of H2SO4 (sp gr V 5 NaOH solution required for titration of the specimen,
1.84) in which case the number of millilitres used should be mL,
doubled. N 5 normality of the NaOH solution, and
6.2 Mix the contents of the flask thoroughly, place on the S 5 specimen weight used, g.
digestion rack, and heat slowly at first until frothing subsides.
Increase the heat until the acid boils briskly then continue the 8. Precision and Bias
digestion for 2 h after the solution becomes colorless or nearly 8.1 On the basis of an interlaboratory test of this test method
so. in which operators in five laboratories analyzed six materials,
6.3 After allowing the flask to cool, add about 500 mL of the following criteria should be used for judging the
water and a little granular zinc or a few boiling aids to prevent acceptability of results at the 95 % confidence level:
bumping. Add an excess (25 to 30 mL) of K2S, Na2S, or 8.1.1 Repeatability—Two results, each the mean of
Na2S2O3 solution. If Na2S2O3 solution is used, it should be duplicate determinations, obtained by the same analyst should
mixed with the NaOH solution (760 g/L) so that both are added be considered suspect if they differ by more than 0.25 %
together. Add an excess (80 to 90 mL) of NaOH solution (760 absolute.
g/L), pouring it slowly down the side of the flask so that it does 8.1.2 Reproducibility—Two results, each the mean of
not mix at once with the acid solution. Immediately connect the duplicate determinations, obtained by analysts in different
flask to the connecting bulb and condenser, and mix the laboratories, should be considered suspect if they differ by
contents of the flask thoroughly. more than 0.5% absolute.
6.4 Distill the solution into 50 mL of 0.5 N HCl or H2SO4, 8.2 Bias—No bias can be determined since no standard
making certain that the connecting tube from the condenser determining nitrogen containing plastics or resin is available.
extends below the surface of the acid in the receiver. Continue
the distillation until the ammonia has been collected in the 9. Keywords
receiver (about 300 mL of distillate). 9.1 methyl purple; plastic; resins; thiosulfate; total nitrogen
2

Iron in Rosin Tall Oil Fatty Acids and Other Related
Products1
1. Scope tee on Analytical Reagents of the American Chemical Society,

1.1 These test methods cover colorimetric procedures for where such specifications are available.2 Other grades may be
the determination of iron in rosin tall oil fatty acids and other used, provided it is first ascertained that the reagent is of
related products. Both spectrophotometric and visual methods sufficiently high purity to permit its use without lessening the
are covered. accuracy of the determination.
1.2 This standard does not purport to address all of the 3.2 Unless otherwise indicated, references to water shall be
safety concerns, if any, associated with its use. It is the understood to mean deionized or distilled water.
responsibility of the user of this standard to establish appro- SPECTROPHOTOMETRIC METHOD
bility of regulatory limitations prior to use. 4. Summary of Test Method
2. Significance and Use 4.1 Ferrous iron, in a dilute hydrochloric acid solution,
forms a red-colored complex with 1,10-phenanthroline. The
2.1 Iron is a possible contaminant in naval stores products, intensity of the color is measured at approximately 505 nm by
being introduced into these products during their production means of a spectrophotometer.
from various raw material sources. Gum rosin in particular is
prone to iron contamination as the equipment used for its 5. Apparatus
collection and processing is often made from iron containing 5.1 Photometer—Any spectrophotometer or filter photom-
metals. eter that will measure accurately the transmittance of the
2.2 Iron is a troublesome contaminant in rosin and fatty solutions in the range from 500 to 520 nm.
acids, as even trace quantities will catalyze the oxidation and a 5.2 Dishes, high-silica glass,3 silica, or porcelain, 50 and
subsequent darkening of these products. 100-mL capacity.
2.3 The test methods described in this standard were devel-
oped many years ago and to a large extent have been replaced NOTE 1—Platinum or platinum-rhodium dishes are not recommended
by modern instrumental methods such as atomic absorbance as they sometimes cause a color interference with the phenanthroline
reagent.
and inductively coupled plasma spectroscopies. The test meth-
ods described in this standard are subject to interferences from 5.3 Watch Glasses, to cover the dishes described in 5.2.
other species in the sample being tested. However, the test 5.4 Pipets—One 100-mL, two 10-mL, three 5-mL, and two
methods described here are acceptable if approximate or trend 2-mL pipets.
values are required and if appropriate analytical instrumenta- 5.5 Measuring Pipet, Mohr-type, 10-mL.
tion is not available. 5.6 Volumetric Flasks, 1-L and 50-mL capacities.
5.7 Absorption Cells, having a capacity of at least 25 mL.
3. Reagents
3.1 Purity of Reagents—Reagent grade chemicals shall be 2
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
all reagents shall conform to the specifications of the Commit- listed by the American Chemical Society, see Analar Standards for Laboratory
and National Formulary, U.S. Pharmacopoeial Convention, Inc. (USPC), Rockville,
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint MD.
3
and Related Coatings, Materials, and Applications and are the direct responsibility The sole source of supply of the high-silica glass known to the committee at
of Subcommittee D01.34 on Naval Stores. this time is Vycor. If you are aware of alternative suppliers, please provide this
Current edition approved June 10, 1997. Published September 1997. Originally information to ASTM Headquarters. Your comments will receive careful consider-
published as D 1064 – 49. Last previous edition D 1064 – 93. ation at a meeting of the responsible technical committee,1 which you may attend.
1
D 1064
Smaller cells may be used when the color is developed in a 2). When the iron content is too high to be read from the
flask or beaker. calibration curve, take a smaller aliquot and dilute to 10 mL
with water. Add 2 mL of hydroxylamine hydrochloride or
6. Reagents hydroquinone solution, 5 mL of 1,10-phenanthroline solution,
6.1 Hydrochloric Acid (1 + 19)—Dilute 1 volume of A.C.S. and 5 mL of sodium acetate solution, using volumetric pipets.
grade HCl (sp gr 1.18) with 19 volumes of water. Mix thoroughly after each addition.
6.2 Iron Solution, Standard (1 mL 5 0.1 mg Fe)—Dissolve
NOTE 2—When 25-mL absorption cells are not available for the
0.1000 g of pure iron wire (99.85 % iron) in 10 mL of H2SO4 spectrophotometer, develop color as described in 7.4, but in a flask,
(1 + 9) and 3 mL of HNO3 (sp gr 1.42). Dilute with water to 1 beaker, or large test tube, and transfer an aliquot of the solution to a
L in a volumetric flask. suitable absorption cell.
6.3 Iron Solution, Standard (1 mL 5 0.01 mg Fe)—Pipet 8.5 Blank—Run a blank along with the sample to be sure
100 mL of standard iron solution (1 mL 5 0.1 mg Fe) into a none of the reagents have become contaminated (Note 3) and
1-L volumetric flask and dilute to the mark with HCl (1 + 19). for a reference solution against which the transmittance of the
6.4 Hydroxylamine Hydrochloride Solution—Dissolve 10 g sample is measured. Measure the transmittance of the blank
of (c.p.) hydroxylamine hydrochloride in 190 mL of water. with the spectrophotometer adjusted to read 100 % transmit-
This reagent is stable at room temperature. tance, or zero percent absorbance at a wavelength of 505 nm
6.5 Hydroquinone Solution—Dissolve 2.5 g of hydro- when the absorption cell contains water.
quinone, reagent or photographic grade, in 100 mL of HCl
(1 + 200). Keep in a refrigerator at about 10°C when not in use. NOTE 3—When the reagents contain more than 0.002 or 0.003 mg of
6.6 1,10-Phenanthroline Solution—Dissolve 0.5 g of 1,10- iron, prepare new reagents and look for the source of contamination.
phenanthroline in 500 mL of water. 8.6 Measure the transmittance of the sample solution at 505
6.7 Sodium Acetate Solution—Dissolve 100 g of A.C.S. nm with the spectrophotometer adjusted to read 100 % for the
grade NaC2H3O2·3H2O in 400 mL of water. blank. Read the iron content of the sample solution in milli-
grams from the calibration curve.
7. Preparation of Calibration Curve 8.7 Calculation—Calculate the iron content of the sample in
7.1 Pipet 0.5, 1.0, 2.0, 3.0, 4.0, and 5.0-mL aliquots of parts per million as follows:
standard iron solution (1 mL 5 0.01 mg Fe) into absorption Iron, ppm 5 ~A/B! 3 1000 (1)
cells and dilute to 10 mL with HCl (1 + 19) measured with a
Mohr-type pipet. Add 10 mL of HCl (1 + 19) to an additional where:
absorption cell and carry through as a reagent blank. A 5 milligrams of iron found, and
7.2 Develop color in the solutions as described in 8.4. B 5 grams of sample represented in the aliquot used.
7.3 Measure the transmittance or absorbance of the solution 8.8 Check Determination—Make a single determination
at 505 nm with the spectrophotometer adjusted to read 100 % daily using 1 to 5 mL of standard iron solution (1 mL 5 0.01
transmittance or zero percent absorbance for the reagent blank. mg Fe) and proceeding as described in 7.1 and 7.2. If the
7.4 Using semilogarithmic paper, plot the percentage trans- determined and known values do not agree within the limits of
mittance of the solutions against milligrams of iron present. Or, experimental error (61 % transmittance) repeat the test. If the
plot the percentage absorbance on rectalinear graph paper second results do not agree, prepare a new standard solution. If
against the milligrams of iron present. determined and known values do not check after preparing a
new standard, investigate for errors in technique and reagents,
8. Procedure and if none can be found, prepare a new calibration curve. This
8.1 Weigh 5.00 g of the sample into a high-silica glass, should not be necessary, and be sure to thoroughly investigate
silica, or porcelain dish. If the iron content is less than 5 ppm, all other factors before doing this.
use a weight of sample such that the solution on which the
spectrophotometer reading is made will contain from 0.05 to VISUAL METHOD
0.050 mg of iron.
8.2 Place the dish in an electrically heated muffle furnace 9. Summary of Test Method
and raise the temperature slowly until the sample is completely 9.1 Ferrous iron, in a dilute hydrochloric acid solution,
charred. Then raise the temperature to 500°C and maintain at forms a red-colored complex with 1,10-phenanthroline. The
500 to 550°C until the sample is greyish white. This usually intensity of the color is compared visually in matched Nessler
required 4 to 6 h, but no harm will be done if the sample is tubes against reference color standards containing known
allowed to remain in the muffle overnight. Remove the dish amounts of iron, in which color has been developed in the same
from the muffle furnace, cool to room temperature, and add 5 manner.
mL of HCl (1 + 1) in such a manner that any ash on the sides
of the dish is washed to the bottom. Cover the dish with a 10. Apparatus
watch glass and heat just to boiling. 10.1 Nessler Tubes—For visual comparison of colors,
8.3 Transfer the sample to a 50-mL volumetric flask, using matched 50-mL Nessler tubes shall be used.
water to wash the last trace from the dish and watch glass.
Dilute to the mark with water and mix thoroughly. 11. Reagents
8.4 Pipet 10 mL of the solution into an absorption cell (Note 11.1 See Section 3.
2
D 1064
12. Preparation of Reference Color Standards 13.2 Pipet 10 mL of the solution into a 50-mL Nessler tube.
12.1 Pipet 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0-mL aliquots of When the iron content is too high for accurate visual compari-
standard iron solution (1 mL 5 0.01 mg Fe) into 50-mL son, reduce the size of the aliquot. Add 2 mL of hydroxylamine
matched Nessler tubes. Dilute to 10 mL with HCl (1 + 19) hydrochloride or hydroquinone solution, 5 mL of 1,10-
measured with a Mohr-type pipet. Add 10 mL of HCl (1 + 19) phenanthroline solution, and 5 mL of sodium acetate solution,
to an additional 50-mL Nessler tube and carry through as a using volumetric pipets. Mix thoroughly after each addition.
reagent blank. Dilute to 50 mL with water and mix thoroughly.
12.2 Develop the iron color as directed in 13.2. A set of 13.3 Compare the resultant color with standards prepared as
standards may be kept for 2 to 3 weeks if the Nessler tubes are directed in Section 12. Estimate the iron content to the nearest
stoppered. During this period the standards shall be checked milligram and calculate the iron present as described in 8.7.
daily, or whenever tests are made, by preparing a single fresh
standard and comparing it with the one of the same concen- 14. Precision and Bias
tration in the series. Use a different concentration of iron each 14.1 These test methods are no longer widely used for the
time the standards are checked. When these do not check, a determination of iron in rosin and so it is not practical to
new series of standards shall be prepared. measure their precision and bias.

13.1 Proceed as directed in 8.1 through 8.3. 15.1 iron; rosin; tall oil; tall oil fatty acids
3

Unsaponifiable Matter in Naval Stores, Including Rosin, Tall
Oil, and Related Products1
1. Scope 4. Apparatus
1.1 This test method covers the determination of the per- 4.1 Erlenmeyer or Other Flat-Bottom Flask, of 125-mL to
centage of material in Naval Stores products as defined in 250-mL capacity, with standard-taper 24/40 joint.
Terminology D 8042 including rosin, tall oil and related prod- 4.2 Erlenmeyer Flask, of 250-mL to 300-mL capacity, with
ucts, other than insoluble dirt or similar visible foreign matter wide mouth.
that does not yield a water-soluble soap when the sample is 4.3 Separatory Funnels, of 300-mL to 500-mL capacity,
saponified with potassium hydroxide. with glass or polytetrafluoroethylene (PFTE) stoppers.
1.2 This standard does not purport to address all of the 4.4 Graduated Cylinder, one of 10 to 25-mL and one of 50
safety concerns, if any, associated with its use. It is the to 100-mL capacity.
responsibility of the user of this standard to establish appro- 4.5 Beaker, of up to 250-mL capacity.
bility of regulatory limitations prior to use. 5. Reagents
2. Referenced Documents used in all tests. Unless otherwise indicated, it is intended that
2.1 ASTM Standards: all reagents shall conform to the specifications of the Commit-
D 509 Test Methods of Sampling and Grading Rosin2 tee on Analytical Reagents of the American Chemical Society,
D 803 Test Methods of Testing Tall Oil2 where such specifications are available.4 Other grades may be
D 804 Terminology Relating to Naval Stores and Related used, provided it is first ascertained that the reagent is of
Products2 sufficiently high purity to permit use without lessening the
E 177 Practice for Use of the Terms Precision and Bias in accuracy of the determination.
ASTM Test Methods3 5.2 Purity of Water—Unless otherwise indicated, references
E 691 Practice for Conducting an Interlaboratory Study to to water shall be understood to mean distilled, or deionized
Determine the Precision of a Test Method3 water.
3. Significance and Use 6. Preparation of Sample
3.1 This test method is designed to broaden the scope of the 6.1 Procurement and handling of samples will vary depend-
previous edition of the test method by the inclusion of tall oil ing upon the physical state of the material. In all instances, the
and tall oil derived from products as test materials. Test sampling should conform to accepted sampling techniques
Methods, D803 currently includes a method for the determi- which ensure the sample is representative of the material being
nation of unsaponifiable matter. sampled.
3.2 The amount of unsaponifiable matter in tall oil and other 6.2 Uniform liquid material should be mixed well and an
related products is important in characterizing such products as aliquot removed for analysis. Titer in fatty acid samples should
it indicates the level of nonacidic material, both free and be resolubilized by gentle heating and agitation. Rosin crystal-
combined, present in the test material. The unsaponifiable in lization in liquid samples, such as distilled tall oil (DTO),
naval stores products is primarily composed of higher molecu- should be resolubilized by heating to 160°C with periodic
lar weight alcohols, sterols, and hydrocarbons. agitation. Homogeneous representative samples are impera-
tive.
6.3 Solids that melt at relatively low temperature (that is,
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
4
and Related Coatings, Materials, and Applications and is the direct responsibility of Reagent Chemicals, American Chemical Society Specifications, American
Subcommittee D01.34 on Naval Stores. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Dec. 10, 1996. Published February 1997. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1065 – 49 T. Last previous edition D 1065 – 92. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1065
tall oil pitch) should be warmed to liquification to facilitate funnel into the original saponification flask again, and add the
mixing and pouring. Homogeneous representative samples are ether layer to the first funnel as before, thereby combining it
imperative. with the two previous extracts. Now drain off, and add to the
6.4 Solids that melt at relatively high temperatures (that is, soap solution already in the original saponification flask, all but
rosin) should be fractured and chipped if possible, (see Test a few drops of aqueous soap solution that has collected at the
Methods D 509). The sample taken for analysis shall consist of bottom of the first separatory funnel below the combined ether
small pieces of rosin chipped from a freshly exposed part of a extract layers. Add 2 mL of water to the first separatory funnel
lump of lumps, and thereafter crushed to facilitate weighing and drain off all but a few drops, combining it in the
and solution. The sample shall be prepared the same day on saponification flask.
which the test is begun in order to avoid changes in properties 8.3 Again pour the combined aqueous soap layers from the
due to surface oxidation that is very pronounced on ground original saponification flask into the second separatory funnel,
rosin having a large surface area exposed to the air. add 30 mL ether, and extract for the fourth time. After
separation of the layers, discard the aqueous soap layer (lower
7. Reagents
layer) from the second separatory funnel and add the ether
7.1 Alkali (titrant), Standard Alcoholic Solution (0.1 N)— layer to the combined ether extracts in the first separatory
Dissolve 6.6 g KOH or 5.2 g NaOH, preferably in pellet form, funnel. Carefully drain off any remaining aqueous soap layer
in 1 L of methanol (99.5 %) or ethanol (95 %) denatured by that may have collected above the stopcock under the ether
Formula No. 3A or No. 30 of the U.S. Bureau of Internal extracts in the first separatory funnel. Add 2 mL of water, swirl
Revenue. Standardize this solution to 6 0.001 N using potas- the separatory funnel gently, allow the water to settle, and then
sium acid phthalate, or another accepted primary standard for drain off and discard the water layer (lower). Repeat this
alkaline titrant, according to accepted quantitative practice. washing once with 5 mL of water, followed by three washes
7.2 Ethyl Ether (diethyl ether). with 30 mL of water. Drain a portion of the third 30-mL water
7.3 Isopropyl Alcohol (Isopropanol) (91 to 99 %)—If not wash into a beaker, add 2 drops of phenolphthalein solution,
neutral, make neutral to phenolphthalein by adding 0.1 N alkali and examine for any pink color. If pink color is observed, wash
solution dropwise. once more with 30-mL water. The absence of pink color
7.4 Phenolphthalein Solution—Dissolve 1.0 g of phenol- indicates the wash is neutral to phenolphthalein.
phthalein in 100 mL of alcohol conforming to 6.1. 8.4 Drain the neutral washed, combined ether extracts into a
7.5 Potassium Hydroxide, Ethanolic (Saponification) Solu- dry, tared (to 0.001 g or 0.0001 g), wide-mouth Erlenmeyer
tion (132 g KOH/L)—Dissolve 132 g of KOH (preferably flask, rinse the separatory funnel with 15 mL ether and add this
pellets) in 150 mL of water and dilute to 1 L with ethanol to the tared Erlenmeyer flask. Evaporate the ether from the
(95 %) denatured by Formula No. 3A or No. 30 of the U.S. flask using a steam bath. If any water droplets collect in the
Bureau of Internal Revenue. flask, add a few millilitres of acetone, and continue to
7.6 Thymol Blue Indicator Solution—Dissolve 0.1 g of evaporate on the steam bath until a clean, dry residue is
thymol blue in 100 mL methanol (99.5 %). obtained. Place the flask in a forced convection drying oven at
8. Procedure 100 to 105°C for 15 to 30 min. Inspect for solvent vapor, if
none, cool in a desiccator, and weigh (to 0.001 g or 0.0001 g).
8.1 Weigh 5.0 6 0.1 g (to 0.01 g) of the sample into the
8.5 Dissolve the contents of the flask with 50 mL of
125-mL (250-mL) Erlenmeyer or other flat-bottom flask, using
isopropyl alcohol conforming to 6.3, add 4 or 5 drops of
the 10 or 25-mL graduated cylinder add 15 mL of the ethanolic
thymol blue or phenolphthalein indicator solution, and titrate
KOH solution (132 g KOH/L), attach to the condenser, and
with the standardized 0.1 N alkali solution in 6.1. When the
heat to reflux and maintain for 1.5 h. Remove the flask, add 30
solution is too colored to detect with certainty the endpoint
mL water, transfer to a separatory funnel, and rinse the flask
internally, titrate until a faint color change is noted. Then
with an additional 20 mL of water that is added to the
withdraw approximately 0.5 mL of the solution to a porcelain
separatory funnel. Rinse the flask with 40 mL of ethyl ether,
spot plate, and to the portion on the spot plate add 1 drop of the
adding the ether rinse to the separatory funnel. Stopper and
indicator solution. Continue titrating with 0.1-mL increments
shake the separatory funnel, then allow to stand until the ether
of titrant, followed by testing on the spot plate, until a definite
layer separates from the water/soap layer. Drain the aqueous
color change that persists for at least one minute is obtained.
soap layer (lower layer) into a second separatory funnel,
allowing a few drops of the aqueous layer to remain above the
9. Calculation and Report
stopcock to prevent loss of ether extract by creepage through
the stopcock joint. 9.1 Calculate the percentage of unsaponifiable matter in the
8.2 To the aqueous soap layer in the second funnel, add 30 sample as follows, and report the results to the nearest 0.1 %:
mL ether and extract as before. Drain the aqueous soap layer Unsaponifiable matter, % 5 @~A 2 ~CN 3 0.302!! / B# 3 100 (1)
into the original saponification flask. Add the ether layer from
the second separatory funnel to the first separatory funnel, where:
thereby combining the extracts. Pour the aqueous soap layer A 5 dried residue, g,
from the original saponification flask into the second separa- B 5 sample used (dry basis), g,
tory funnel, add 30 mL ether and extract for the third time. C 5 alkali titrant solution used, mL, and
N 5 normality of the alkali titrant solution.
Drain the aqueous soap layer from the second separatory
2
D 1065
10. Precision and Bias 5 10.2.1 Repeatability Limit, 95 % (within labora-
10.1 Precision—Interlaboratory Test Program: An inter- tory) 5 0.3 %.
laboratory study of the unsaponifiable matter content of three 10.2.2 Reproducibility Limit, 95 % (between labora-
substances, tall oil fatty acids, distilled tall oil, and rosin, were tory) 5 1.1 %.
run in 1994. Results for determinations for tall oil fatty acids 10.3 These terms (repeatability limit and reproducibility
were reported for 17 laboratories, determinations for distilled limit) are used as specified in Practice E 177. The respective
tall oil for 16 laboratories and determinations for rosin from 6 standard deviations among test results, related to the above
laboratories. The design of the experiment, similar to that of numbers by the factor of 2.8 are as follows:
Practice E 691 and a within-between analysis of the data are
10.3.1 Repeatability standard deviation 5 0.1 %.
given in Research Report No. D01-1102.
10.2 Test Results—The precision information given below 10.3.2 Reproducibility standard deviation 5 0.4 %.
for the unsaponifiable matter content of naval stores products is 10.4 Bias—This test method has no bias because unsaponi-
for a comparison of two test results, each of which is the fiable matter content is defined only in terms of this test
average of three test determinations as follows: method.
5
11. Keywords
Supporting data are available from ASTM Headquarters. Request RR:D01-
1102. 11.1 rosin; tall oil; tall oil fatty acids; unsaponifiable matter
3
Designation: 195/81

Distillation Range of Volatile Organic Liquids1
1. Scope * sate leaves the condenser tube.

1.1 This test method covers the determination of the distil- 3.1.2 dry point—the temperature indicated at the instant the
lation range of liquids boiling between 30 and 350°C, that are last drop of liquid evaporates from the lowest point in the
chemically stable during the distillation process, by manual or distillation flask, disregarding any liquid on the side of the
automatic distillation procedures. flask.
1.2 This test method is applicable to organic liquids such as 3.1.3 decomposition point—the thermometer reading that
hydrocarbons, oxygenated compounds, chemical intermedi- coincides with the first indications of thermal decomposition of
ates, and blends thereof. the liquid in the flask.
1.3 For hazard information and guidance, see the supplier’s 3.2 Definitions of Terms Specific to This Standard:
Material Safety Data Sheet. 3.2.1 final boiling point—the maximum thermometer read-
1.4 This standard does not purport to address all of the ing obtained during the test.
safety concerns, if any, associated with its use. It is the 3.2.1.1 Discussion—This usually occurs after the evapora-
responsibility of the user of this standard to establish appro- tion of all liquid from the bottom of the flask. The term
priate safety and health practices and determine the applica- “maximum temperature” is a frequently used synonym.
bility of regulatory limitations prior to use. Specific hazard 3.2.2 end point 5 minutes—the thermometer reading ob-
statements are given in Section 7. tained 5 min after the 95 % distillation point if no dry or final
boiling point occurs.
2.1 ASTM Standards:
D 86 Test Method for Distillation of Petroleum Products at 4.1 A 100-mL specimen is distilled under conditions equiva-
Atmospheric Pressure2 lent to a simple batch differential distillation. The temperature
E 1 Specification for ASTM Thermometers3 of the mercury in the thermometer is equilibrated with that of
E 133 Specification for Distillation Equipment4 the refluxing liquid before the distillate is taken over. Boiling
E 299 Test Method for Trace Amounts of Peroxides in temperatures observed on a partial immersion thermometer are
Organic Solvents5 corrected to standard atmospheric pressure to give true boiling
E 691 Practice for Conducting an Interlaboratory Study to temperatures.
Determine the Precision of a Test Method4
3. Terminology 5.1 This test method provides a method of measurement of
3.1 Definitions: distillation range of volatile organic liquids. The relative
3.1.1 initial boiling point—the temperature indicated by the volatility of organic liquids can be used with other tests for
distillation thermometer at the instant the first drop of conden- identification and measurement of quality. Therefore, this test
method provides a test procedure for assessing compliance
1
with a specification.
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 5.2 This test method also provides an empirical value of
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. residue, solvent recovery capacity, and loss (or non-recovery)
Current edition approved July 10, 1999. Published September 1999. Originally on heating. Organic liquids are used as solvents in many
published as D 1078 – 49 T. Last previous edition D 1078 – 97. chemical processes. As the relative volatility, residual matter
2
3
and recovery capability affect the efficiency of these processes,
4
Annual Book of ASTM Standards, Vol 14.02. this test method is useful in manufacturing control.
5

1
D 1078
6. Apparatus and accuracy as the appropriate and calibrated mercury-in-
6.1 Distillation Apparatus—See Condenser and Cooling glass thermometer. Confirmation of the calibration of these
Bath section, Figs. 1 and Figs. 2, and Metal Shield or Enclosure temperature sensors shall be done at regular intervals. This can
for Flask section of Specification E 133. be accomplished potentiometrically by the use of standard
6.2 Distillation Flasks, 200-mL of borosilicate glass com- precision resistance, depending on the type of probe. Another
plying with the specifications given in Distillation Flask technique is to distill pure toluene (99.9 + % purity) and
section, Fig. 3, and Flask C of Specification E 133. compare the temperature indicated by the thermocouple or
resistance thermometer with that shown by the mercury-in-
NOTE 1—Liquid superheating in a new flask may be prevented by glass thermometer.
depositing a small amount of carbon in the bottom of the flask. This may
be accomplished by heating and decomposing a pinch of tartaric acid in NOTE 2—Toluene is shown in reference manuals as boiling at 110.6°C
the bottom of the flask. The flask is then prepared for use by washing with (corrected for barometric pressure) under the conditions of a manual
water, rinsing with acetone, and drying. D 1078 distillation that uses a partial immersion thermometer.
6.3 Source of Heat—An adjustable gas burner or electric 7. Hazards
heater so constructed that sufficient heat can be obtained to 7.1 Precaution—Certain solvents and chemical intermedi-
distill the product at the uniform rate specified in Section 8. For ates, particularly, but not only ethers and unsaturated com-
narrow-range (less than 2°C) liquids, an electric heater may be pounds, may form peroxides during storage. These peroxides
used only if it has been proven to give results comparable to may present a violent explosion hazard when the chemical is
those obtained when using gas heat. (See Section 9 for factors distilled, especially as the dry point is approached. When
that cause superheating, and Appendix X1 for a discussion on peroxide formation is likely because of chemical type or length
the use of electric heaters.) of storage, the material should be analyzed for peroxides (See
6.4 Distillation Receiver: Test Method E 299.) and if they exist in hazardous concentra-
6.4.1 Manual Distillation Receiver—A 100-mL cylinder tions, appropriate precautions should be taken such as destroy-
graduated in 1 mL subdivision and having an overall height of ing the peroxide before distillation, shielding, or destroying the
250 to 260 mm. sample and not running the test.
6.4.2 Automatic Distillation Receiver—A receiver to be 7.2 Most organic solvents and chemical intermediates will
used with automatic distillation in accordance with the instru- burn. In the operation of the distillation apparatus, use a
ment manufacturer’s instructions, conforming to the dimen- suitable catch pan and shielding to contain spilled liquid in the
sions given in 6.4.1, with the exception of the graduations. event of accidental breakage of the distillation flask.
6.4.2.1 Automatic Distillation Level Follower—The level 7.3 Provide adequate ventilation to maintain solvent vapor
follower/recording mechanism of the automatic apparatus shall concentrations below the lower explosive limit in the immedi-
have a resolution of 0.1 mL with an accuracy of 6 1 mL. ate vicinity of the distillation apparatus, and below the thresh-
6.5 Temperature Measurement Devices: old limit value in the general work area.
6.5.1 Manual Distillation Thermometers—Partial immer-
sion thermometers as listed in Table 1, conforming to Specifi- 8. Preparation of Apparatus
cation E 1. Both bore corrections and either ice or steam 8.1 Manual Distillation Apparatus:
standardization corrections are recommended. 8.1.1 Clean and dry the condenser tube by swabbing with a
6.5.2 Automatic Distillation Temperature Sensors— piece of soft lint-free cloth attached to a wire or cord, or by any
Temperature measurement systems using thermocouples or other suitable means.
resistance thermometers shall exhibit the same temperature lag 8.1.2 Use the thermometer listed in the material specifica-
tion for the product under study. If no thermometer is specified,
select one from Table 1 with the smallest graduations that will
TABLE 1 Thermometers
cover the entire distillation range of the material. Center the
ASTM Sub-
Thermometer IP Range, °C division,
thermometer into the neck of the flask through a tight-fitting
Number °C cork stopper so that the upper end of the contraction chamber
2CA 62CA −5 to + 300 1.0 (or bulb if Thermometer 2C or IP thermometer 62C is used) is
3CA 73CA −5 to + 400 B level with the lower side of the vapor tube at its junction with
14C ... 38 to 82 0.1 the neck of the flask. (See Fig. 1 of Test Method D 86.)
37C 77C −2 to + 52 0.2
38C 78C 24 to 78 0.2 NOTE 3—It is far more important that the greatest volume of mercury
39C 79C 48 to 102 0.2 be immersed in the refluxing zone than that the immersion mark on the
40C 80C 72 to 126 0.2
41C 81C 98 to 152 0.2
thermometer be placed at any specific point.
42CA 82CA 95 to 255 0.5 8.1.3 Position the correct heat shield (see 9.1.3.1 and
102C 83C 123 to 177 0.2
103C 84C 148 to 202 0.2
9.1.3.2).
104C 85C 173 to 227 0.2
NOTE 4—For low-boiling materials, cool the apparatus to room tem-
105C 86C 198 to 252 0.2
106C 87C 223 to 277 0.2 perature before starting the test.
107C 88C 248 to 302 0.2 8.1.4 Fill the condenser bath with water of the appropriate
A
These thermometers have more temperature lag than the other thermometers temperature shown in Table 2.
listed herein and are not satisfactory for use with narrow-boiling range liquids.
B
1 to 301°C; 1.5°C above 301°C. NOTE 5—When distilling pure compounds always ensure that the
2
D 1078
TABLE 2 Temperatures collection of the first drop of distillate within 15 min of the start
Initial Boiling Condenser, Sample, of heating.
Point,° C °C °C 9.1.4 Adjust the heat input so that the distillation proceeds at
Below 50 0 to 3 0 to 3 a rate of 4 to 5 mL/min (approximately 2 drops per second),
50 to 70 0 to 10 10 to 20
70 to 150 25 to 30 20 to 30
and move the receiving cylinder so that the tip of the condenser
Above 150 35 to 50 20 to 30 tube touches one side of the cylinder after the first drop falls
(initial boiling point). Record the readings of the distillation
thermometer after collecting 5, 10, 20, 30, 40, 50, 60, 70, 80,
condenser bath temperature is above the crystallizing point of the 90, and 95 mL of distillate.
compound. 9.1.5 Without changing the heater setting, continue distilla-
8.1.5 Adjust the temperature of the appropriate portion of tion beyond the 95 % point until the dry point is observed.
the sample to the applicable temperature shown in Table 2. Record the temperature at this point as the dry point (Section
8.2 Automatic Distillation Apparatus—For assembly of au- 3). If a dry point is not obtained (that is, if active decomposi-
tomatic distillation apparatus, consult instrument manufactur- tion should occur before the dry point is reached, as evidenced
er’s operating manual. by a rapid evolution of vapor or heavy fumes; or if there is
liquid remaining on the bottom of the flask when the maximum
9. Procedure temperature is observed on the distillation thermometer),
record this fact.
9.1 Manual Distillation Procedure:
9.1.6 When a dry point cannot be obtained, report as the end
9.1.1 Using the graduated receiver measure 100 6 0.5 mL
point the maximum temperature observed on the distillation
of the temperature-adjusted sample. Remove the flask from the
thermometer or final boiling point (Section 3). When active
apparatus and transfer the fresh specimen directly to the flask,
decomposition is encountered, the rapid evolution of vapor and
allowing the graduate to drain for 15 to 20 s.
heavy fumes is usually followed by a gradual decrease in the
NOTE 6—For viscous liquids, a longer drainage period may be neces- distillation temperature. Record the temperature and report as
sary to complete the transfer of the specimen to the flask, but the drainage the decomposition point (Section 3). If the expected drop in
time should not exceed 5 min. Do not allow any of the specimen to enter temperature does not occur, record the maximum temperature
the vapor tube.
observed on the distillation thermometer 5 min after the 95 %
9.1.2 Connect the flask to the condenser by inserting the point has been reached, and report as “end point, 5 min.” This
vapor tube of the flask into the condenser, making a tight notation shows that a true end point could not be reached
connection with a well-rolled cork or similar material. Adjust within the given time limit. In any event, the end point should
the position of the heat shield so that the neck of the flask is not exceed 5 min after the 95 % point.
vertical and the vapor tube extends into the condenser tube a 9.1.7 Read and record the barometric pressure.
distance of 25 to 50 mm. Have the bottom of the flask resting 9.1.8 After the condenser tube has drained, read the total
firmly in the hole of the heat shield. Insert the thermometer as volume of distillate and record it as recovery. The total yield of
described in 8.1.2. Place the receiver, without drying, at the distillate from a material having a distillation range of 10°C or
outlet of the condenser tube in such a position that the less should be not less than 97 % for nonviscous liquids. For
condenser tube extends into the graduate at least 25 mm but viscous liquids and materials having a wider distillation range
does not extend below the 100-mL mark. If the initial boiling than 10°C, a yield of 95 volume % is satisfactory. If yields are
point of the material is below 70°C, immerse the cylinder in a not obtained within these limits, repeat the test.
transparent bath and maintain at a temperature of 10 to 20°C 9.1.9 If any residue is present, cool to room temperature and
throughout the distillation. Place a flat cover on the top of the pour into a small cylinder graduated in 0.1-mL subdivisions.
graduate to prevent condensed moisture from entering the Measure the volume and record it as residue. Record the
graduate. difference between 100 and the sum of the residue plus
9.1.3 A certain amount of judgment is necessary in choosing recovery as distillation loss.
the best operating conditions to get acceptable accuracy and 9.2 Automatic Distillation Procedure:
precision for materials having different distilling temperatures. 9.2.1 Using the automatic distillation receiver measure 100
As a general guide, it is recommended that: 6 0.5 mL of the temperature-adjusted sample. Transfer the
9.1.3.1 For materials having an initial boiling point below fresh specimen directly to the flask, allowing the receiver to
150°C, the following conditions be established: drain for 15 to 20 s (see Note 6).
(a) Heat Shield—Hole size, 32-mm diameter. 9.2.2 Connect the distillation flask to the condenser and fit
(b) Heating Rate—Time from application of heat to first the temperature measuring device to the flask according to the
drop of distillate, 5 to 10 min, and time of rise of vapor column instrument manufacturer’s instruction.
in neck of flask to side arm, 21⁄2 to 31⁄2min. 9.2.3 Start the distillation following the instrument manu-
9.1.3.2 For materials having an initial boiling point above facturer’s instruction.
150°C, the following conditions should be established:
(a) Heat Shield—Hole size, 38-mm diameter. 10. Factors Causing Superheating
(b) Heating Rate—Time from application of heat to first 10.1 In general, any condition whereby the temperature
drop of distillate, 10 to 15 min, and time of rise of vapor surrounding the vapor exceeds the temperature of the vapor in
column in neck of flask to side arm, sufficiently rapid to permit equilibrium with the liquid will cause superheating. Specific
3
D 1078
factors conducive to superheating are as follows, and should be 11.1.3 Barometer Pressure Correction—After applying the
avoided: corrections for thermometer error, correct each reading for
10.2 Flame in Contact with the Flask— The applied gas deviation of the barometric pressure from normal by adding
flame should be prevented from contacting more than the algebraically the correction calculated as follows:
specified portion of the flask by the following procedures: 11.1.3.1 For values of K in degrees Celsius per millimetre of
10.2.1 Maintain the correct overall dimensions and speci- mercury
fied hole diameter of the asbestos cement board. The hole must Correction 5 K~760 2 P! (1)
be perfectly circular, with no irregularities.
10.2.2 Use a board that is free of cracks and checks. where:
10.2.3 Set the flask snugly in the hole in the upper insulating K 5 rate of change of boiling point with pressure, in
board. degrees Celsius per millimetre, as given in Table 3
10.3 Application of Heat—Attention should be given to (Note 7), and
burner placement, position, and character of flame, as follows: P 5 barometric pressure in millimetres of mercury at
10.3.1 Apply the source of heat directly beneath the flask. standard temperature.
Any variation would result in heating a larger portion of 11.1.3.2 For values of K in degrees Celsius per millibar:
surrounding air to a higher temperature than that of the flask. Correction 5 K~1013 2 P! (2)
10.3.2 The flame should not have a larger cross section than
is necessary, and should be nonluminous.
10.3.3 Place the burner at a level such that the complete TABLE 3 Change of Boiling Point with Pressure
combustion area of a nonluminous flame is approximately 3⁄4 Value of K, °C K, °C per Boiling Point
in. (20 mm) below the board. Compound per mm Hg at mbar at at 760 mm Hg,
10.4 Extraneous Heat Source—An extraneous source of Boiling Point Boiling Point °C
heat such as sunlight falling directly on the flask can cause Acetone 0.039 0.029 56.1
superheating. n-Amyl alcohol 0.041 0.031 138.0
n-Amyl acetate 0.048 0.036 149.5
10.5 Condition of Equipment—Observe caution in employ- Aromatic solvent naphtha 0.049 0.037 ...
ing the apparatus for immediate reuse. For low-boiling mate-
rials, cool the heating unit to room temperature before starting Benzene 0.043 0.032 80.1
Isobutyl acetate 0.045 0.035 117.3
the test. n-Butyl acetate 0.045 0.035 126.1
10.6 Use of Electric Heaters—Electric heaters generally sec-Butyl acetate 0.045 0.034 112.4
cause superheating. These should be used only after they have Isobutyl alcohol 0.036 0.027 107.9
n-Butyl alcohol 0.037 0.028 117.7
been proven to give results comparable to those obtained when sec-Butyl alcohol 0.035 0.026 99.5
using gas heat. The superheating effect obtained from electric
heaters may be minimized, but not completely eliminated, by Diacetone alcohol 0.050 0.037 ...
Diethylene glycol 0.050 0.037 245.0
selecting a heater that, by its design, concentrates the heating Dipropylene glycol 0.051 0.038 232.8
elements to a minimum area, and contains a minimum amount
of ceramic material in its overall construction. The fulfillment Ethyl acetate 0.041 0.030 77.2
Ethyl alcohol 0.033 0.025 78.3
of these requirements will reduce, but not completely elimi- Ethylene glycol 0.045 0.033 197.6
nate, the amount of extraneous heat radiating around the 2-Butoxyethanol 0.047 0.035 171.2
perimeter of the asbestos-cement board on which the distilla- 2-Ethoxyethanol 0.044 0.033 135.1
2-Ethoxyethyl acetate 0.046 0.035 156.3
tion flask is placed.6 (See Appendix X1 for a more complete
discussion of the problems encountered in the use of electric Hexylene glycol 0.045 0.033 197.1
n-Hexyl acetate 0.050 0.037 171.6
heaters.)
11. Calculations Isophorone 0.057 0.043 215.3
11.1 Manual Distillation Calculations: Methyl alcohol 0.033 0.025 64.5

11.1.1 Thermometer Bore Correction—Apply the correc- Methyl ethyl ketone 0.043 0.032 79.6
Methyl isoamyl acetate 0.048 0.036 146.2
tions for any variations in the bore of the thermometer as given Methyl isoamyl ketone 0.048 0.036 144.9
by the calibration. Methyl isobutyl carbinol 0.041 0.030 131.8
11.1.2 Thermometer Bulb Shrinkage Correction—Apply the Methyl isobutyl ketone 0.046 0.035 116.2
correction for shrinkage of the mercury bulb of the thermom- Perchloroethylene 0.048 0.036 121.2
eter as determined by any change in its ice or steam point Isopropyl alcohol 0.033 0.025 82.3
where applicable. Other means can be employed, such as the Isopropyl acetate 0.041 0.030 88.5
Propylene glycol 0.043 0.032 187.6
use of a platinum-resistance thermometer or a National Bureau Pyridine 0.046 0.035 115.4
of Standards thermometer.
Toluene 0.046 0.035 110.6
Trichloroethylene 0.043 0.032 87.1
6
The sole source of supply of the Lo-Cap heater known to the committee at this
time is Precision Scientific Co., Chicago, IL. If you are aware of alternative Vinyl acetate 0.040 0.030 72.7
suppliers, please provide this information to ASTM Headquarters. Your comments
will receive careful consideration at a meeting of the responsible technical Xylene (mixed isomers) 0.049 0.037 ...
committee,1 which you may attend.
4
D 1078
where: general, the precision improves with increasing purity and

K 5 rate of change of boiling point with pressure, in decreasing boiling point of the material being tested, while it is
degrees Celsius per millibar, as given in Table 3 (Note poorest for mixtures that have a wide boiling range at elevated
7), and temperatures. The values shown for the different solvents may
P 5 barometric pressure in millibars at standard tempera- be used as examples of the precision obtainable with this test
ture and pressure. method at the 95 % confidence level. For a better estimate of
precision for a particular case, a cooperative study should be
NOTE 7—For other pure compounds not listed in Table 3, the value K
should be obtained from the literature. For narrow-boiling hydrocarbon
made on the compound or product of interest.
materials, the value of K may be assumed as 0.00012 times the normal 13.1.1.1 Repeatability—Two results, each the mean of two
boiling point on the absolute temperature scale. runs, obtained by the same operator should be considered
11.1.4 If the overall distillation range of the sample does not suspect if they differ by more than the values shown in Table
exceed 2°C, combined thermometer (bore irregularities and 4 for a material with similar boiling range and 50 % point.
bulb shrinkage) and barometric corrections may be made on 13.1.1.2 Reproducibility—Two results, each the mean of
the basis of the difference between the observed 50 % boiling two runs, obtained by operators in different laboratories should
point and the true boiling point at 760 mm as given in Table 3. be considered suspect if they differ by more than values shown
11.2 Automatic Distillation Calculations—Barometric cor- in Table 4 for a material with a similar boiling range and 50 %
rection shall be done according to 11.1.3 and 11.1.4. point.
13.2 Automatic Distillation Precision:
12. Report 13.2.1 A preliminary measure of the precision of this test
12.1 Report the results in a manner conforming with the method done by automatic distillation is based on replicate
specifications of the material tested. If no definite manner of analyses of a narrow boiling range solvent by one laboratory
reporting is specified, report the corrected temperatures at each and four solvents of different boiling ranges by another
observed volume, and report the volume percentages of resi- laboratory. The standard deviation for these various solvents
due, recovery, and distillation loss. are given in Table 58. An interlaboratory study on the precision
of automatic D 1078 distillation following Practice E 691
13. Precision guidelines will be conducted within the next five years to
13.1 Manual Distillation Precision7: determine repeatability and reproducibility values at 95 %
13.1.1 The precision of this test method done by manual confidence level.
distillation is based on three interlaboratory studies involving 13.3 Bias:
ten laboratories and several solvents. It was established that, in 13.3.1 Absolute Bias—Since the temperature measuring
devices specified by this test method are calibrated against the
7 8
Supporting data are available from ASTM Headquarters. Request RR: D01- Supporting data are available from ASTM Headquarters: Request RR:D01-
1051. 1114.
TABLE 4 Summary of Manual Distillation PrecisionA

Acetate Ester of
Diethylene Xylene-Pseudo-
AcetoneB Glycol Mixture Mineral Spirits
Glycol Mono- cumene
ethyl Ether
Initial Boiling Point, °C
Mean Value 55.87 6 0.09 215.33 6 0.31 190.70 6 0.42 141.03 6 0.52 163.68 6 0.35
Checking Limits 0.10 0.77 0.76 0.50 1.13
Repeatability 0.09 0.87 0.51 0.34 2.13
Reproducibility 0.42 1.53 1.92 2.36 2.19
50-mL Point,° C
Mean Value 56.03 6 0.07 218.24 6 0.24 192.83 6 0.35 146.18 6 0.37 175.02 6 0.26
Checking Limits 0.07 0.21 0.40 0.56 0.93
Repeatability 0.15 0.58 0.34 0.81 0.48
Dry Point,° C
Mean Value 56.36 6 0.11 220.03 6 0.29 202.51 6 0.74 168.75 6 0.57 200.35 6 0.77
Checking Limits 0.27 0.46 0.57 0.80 1.22
Repeatability 0.24 0.57 0.77 1.20 0.80
Distillation Range, °C
Mean Dp—Average Ibp 0.49 4.7 11.8 27.8 36.7
Checking Limits 0.29 0.90 0.95 0.95 1.67
Repeatability 0.26 1.04 0.93 1.25 2.28
A
All values are at the 95 % confidence level and were calculated in accordance with Practice E 180.
B
ASTM thermometer 39C was used.
5
D 1078
TABLE 5 Summary of Automatic Distillation Precision and Relative Bias of Automatic and Manual D 1078 Distillation (A-M) in °C
Methyl Ethyl Commercial Light Naphtha Naphtha Mineral
Ketone Nonene Solvent Solvent Spirits
Number of Replicates 49 15 16 16 24
Manual Automatic Manual Automatic Manual Automatic Manual Automatic Manual Automatic
Initial Boiling Point
Mean 79.4 79.3 136.3 136.6 78.8 78.2 116.4 116.8 158.2 160.1
Standard Deviation 0.08 0.09 0.21 0.07 0.45 0.24 0.54 0.23 0.50 0.38
Relative Bias (A-M) −0.1 0.3 −0.5 0.4 1.9
50 %
Mean 138.4 137.9 86.3 86.2 126.4 126.5 172.2 172.4
Standard Deviation 0.11 0.07 0.45 0.08 0.31 0.11 0.34 0.22
Relative Bias (A-M) −0.5 −0.1 0.1 0.2
Dry Point
Mean 79.8 79.9 143.0 142.7 98.1 97.3 144.9 146.2 193.2 193.4
Relative Bias (A-M) 0.1 −0.3 −0.7 1.3 0.2
Range
Mean 0.4 0.6 6.7 6.1 19.3 19.1 28.5 29.4 35.0 33.3
normal boiling point of toluene (99.9 + % purity), this test are only for the solvents studied and may not be necessarily
method has no bias with respect to pure toluene as a reference applicable to other solvents.
material.
13.3.2 Relative Bias Between Manual and Automatic NOTE 8—In cases of dispute, the parties involved may agree to
designate either the manual or the automatic method to be the referee test
Distillation—A preliminary measure of the relative bias be-
method. If an agreement on which method to designate cannot be made,
tween manual and automatic distillation is based on the manual the referee test method will be the manual method.
and automatic D 1078 results of a narrow boiling solvent by
one laboratory and four solvents of different boiling ranges by 14. Keywords
another laboratory. The data for the relative bias on these
solvents are summarized in Table 58. The observed bias (if any) 14.1 distillation range; solvents
APPENDIX
X1. DISCUSSION ON THE USE OF ELECTRIC HEATERS WHEN APPLYING TEST METHOD D1078/IP 195 TO THE
DETERMINATION OF THE DISTILLATION RANGE OF NARROW RANGE (<2°C) PURE COMPOUNDS
X1.1 Test Method D 1078/IP 195, in the hands of a TABLE X1.1 Comparison of Gas Versus Electric Heat
competent operator using properly designed equipment, has Gas Heat
Electric
been found over the years to be a valuable tool in detecting the Heater5
presence of low-boiling and high-boiling impurities in rela- Range Range

tively pure compounds. Determination 1:
Initial boiling point 64.5 0.3 64.5 1.5
Dry point 64.8 66.0
X1.2 In recent years many laboratories, for reasons of Determination 2:
safety and convenience, have eliminated the availability of Initial boiling point 64.5 0.4 64.5 1.9
Dry point 64.9 66.4
natural or artifical gas, with the resulting trend toward the Mean range ... 0.35 ... 1.7
exclusive use of electric heaters in place of gas burners. The
use of electricity instead of gas as the source of heat, coupled
with the application of this test method to materials of X1.3 The higher dry point obtained with the electric heater
extremely high purity and narrow distillation ranges (2°C or is due to the large amount of extraneous heat radiating around
less), has resulted in the distortion of the dry point. This the distillation flask which in turn is due to the relatively large
distortion effect can be illustrated by comparing the distillation area of the distillation board exposed to the heating elements of
range results using gas and electric heat on a sample of the electric heater. For example, the heating elements of the
high-purity methanol (Table X1.1). The purity of the methanol electric heater5 cover an area of 63.5 by 76 mm whereas the
employed was established by gas chromatography and other flame of a properly adjusted gas burner can be concentrated to
instrumental procedures. an area no larger than the 32-mm hole of the supporting
6
D 1078
asbestos cement (or ceramic) board. This means that when the glowing electric heating elements. This assumption has been
heating elements of the electric heater are brought up to supported by the following experimental evidence: The bottom
sufficient temperature to effect the proper distillation rate of the of a standard 200-mL distillation flask was coated with a
methanol, a relatively large area of the board also is exposed to 38-mm diameter circle of black ceramic marking ink. The
the heat of these elements so that as the end of the distillation black ink was in turn fired into the glass by heating the bottom
is approached, a considerable amount of heat is being radiated of the flask to a dull-red heat with a gas-oxygen glass
from the board to the air surrounding the distillation flask. This blowtorch. The presence of this black coating on the bottom of
hot air surrounding the flask is sufficient to cause a distortion of the flask would absorb any infrared radiation emanating from
the dry point as the last drop of liquid is vaporized from the the electrical heating elements, thus preventing it from affect-
bottom of the flask. Conversely, the ability to concentrate the ing the bulb of the thermometer at the end of the distillation.
gas flame to only the 32-mm exposed area of the flask Distillation ranges were then determined on the same methanol
minimizes the extent of the extraneous heat radiating from the as used in the previous experiments following Test Method
board, which, in turn, eliminates the distortion of the dry point D 1078/IP 195, except that in one case a standard 200-mL flask
from this cause. This conclusion was substantiated by results was used with an electric heater plus the “water-cooled board,”
from the following experiment: The board with the 32-mm and in the other case, the specially prepared “black bottom”
hole was replaced by a 190.7 by 190.7-mm stainless steel plate 200-mL flask was employed. Both of these special conditions
in which a 32-mm hole had been cut. Four turns of 6.4-mm were compared to the standard procedure using gas heat. The
copper tubing with sufficient inlet and outlet leads were results of this experiment, given in Table X1.3, show that the
silver-soldered to the underside of the plate so that water could use of the “black-bottom flask” in conjunction with the electric
be circulated through the tubing during the course of the heater and “water-cooled board” causes a significant lowering
distillation. With this “water-cooled board” substituted for the of the dry point which confirms the theory that infrared
standard board, only the heat from the electrical elements radiation emanating from the electric heating elements causes
immediately under the 32-mm outlet could reach the distilla- a slight distortion of the dry point.
tion flask. The heat emanating from the outer perimeter of the X1.6 The above discussion and experimental evidence are
heater was dissipated by the water circulating through the presented to show how and why the use of electric heater
tubing on the underside of the board, as evidenced by the causes a distortion of the dry point when carrying out the
ability to hold one’s finger on top of the“ water-cooled board” procedure as specified in Test Method D 1078/IP 195. Al-
during the course of the distillation. Using the same high-purity though this distortion is of a minor nature, and therefore of
methanol employed in the previous experiment, distillation little importance when applying this test method to compounds
ranges were determined using gas heat, electric heat, and or mixtures which have distillation ranges of 5°C or more, the
electric heat with the “water-cooled board” substituted for the effect becomes significant when the method is applied to
standard board. These results are given in Table X1.1. narrow range (2°C or less) pure compounds. It is the further
objective of this discussion to suggest to those laboratories
X1.4 The results from the above experiment demonstrate
equipped with only electricity, a technique whereby the distil-
the effect the extraneous radiant heat from the electric heater
lation range results obtained with electric heaters may be made
had on the dry point, and also suggest a means whereby this
equivalent to those obtained with gas heat.
effect could be greatly reduced.
X1.7 The sponsoring subcommittee of this test method has
X1.5 Despite the fact that the use of a “water-cooled board” not had the opportunity to apply this technique to a sufficiently
in conjunction with an electric heater eliminated the extraneous large number of compounds over a wide range of boiling
radiant heat surrounding the distillation flask, it is evident from temperatures to warrant including it as a part of Test Method
the results in Table X1.2 that the dry point obtained when using D 1078/IP 195; and is, therefore, presenting it for information
the electric heater and “water-cooled board” was still signifi- purposes only. Comments are solicited from those attempting
cantly higher than the dry point obtained when using gas heat. to employ the suggestions contained in this report as well as
The assumption was made that this “residual” interference to other ideas that might be employed to equate the use of electric
the dry point was caused by infrared radiation from the heat with gas heat.
TABLE X1.2 Comparison of Electric Heat Plus Water-Cooled Board to Gas Heat
Electric Heat5 plus
Gas Heat Electric Heat5
Water-Cooled Board
Range Range Range
Determination 1:
Initial boiling point 64.5 0.3 64.5 1.6 64.5 0.5
Dry point 64.8 66.1 65.0
Determination 2:
Dry point 64.9 65.9 65.1
Mean range ... 0.3 ... 1.5 ... 0.55
7
D 1078
TABLE X1.3 Effect of Infrared Radiation on Dry Point
Electric Heater5 with Water-Cooled Electric Heater5 with Water-Cooled
Gas Heat
Board and Standard Flask Board and Black-Bottom Flash
Range Range Range
Determination 1:
Dry point 64.8 65.1 64.8
Determination 2:
Dry point 64.9 65.2 64.9
Mean range ... 0.35 ... 0.6 ... 0.25
SUMMARY OF CHANGES
Committee D1 has identified the location of selected changes to this standard since the last date of issue that
(1) Revised 1.1 to include automatic D 1078 distillation. (5) Revised Section 11 to include calculations as they apply to
(2) Revised 6.4 and 6.5 to include automatic D 1078 distilla- automatic D 1078 distillation.
tion apparatus and accessories. (6) Revised Section 13 to include preliminary precision and
(3) Revised Section 8 to include prepatation of automatic relative bias of automatic D 1078 distillation. A New Table 5
D 1078 distillation apparatus. was added.
(4) Revised Section 9 to include procedure for automatic
(7) Added Summary of Changes
D 1078 distillation.
8

Rosin Oils1
1. Scope commerce and standard methods are required to ensure that

1.1 These test methods are intended for use in determining products meet established specifications.
whether a rosin oil conforms with the specifications and 4. Appearance
requirements usually applied to ensure its suitability for a
particular use. In general, not all of the tests will be required to 4.1 Examine a sample of the oil in a clear glass tube by
determine the fitness of an oil for a specific use. The term transmitted light, to ascertain whether any separated water,
“rosin oil” includes the oils obtained by dry destructive crystals, or insoluble foreign matter are present.
distillation of rosin, with or without subsequent redistillation, 5. Specific Gravity
and also certain compounded oils prepared from a rosin oil
base. It has no relationship to the product formerly known as 5.1 Determine the specific gravity of the oil at 15.5°C
liquid rosin, for which the term “tall oil” has been adopted. (60°F) by means of any suitable apparatus that has been
1.2 This standard does not purport to address all of the calibrated at 15.5°C (60°F). Report the specific gravity to the
safety concerns, if any, associated with its use. It is the third decimal as:
responsibility of the user of this standard to establish Specific gravity, 15.5/15.5°C ~60/60°F! (1)
appropriate safety and health practices and determine the Such observed specific gravity may be converted to the
applicability of regulatory limitations prior to use. 25/25°C (77/77°F) basis by multiplying the observed reading
by the factor 1.002.
2.1 ASTM Standards: NOTE 1—If a pycnometer is used, the weight of water contained by the
pycnometer at 25°C shall be determined, in which case the ratio of oil to
D 88 Test Method for Saybolt Viscosity2
water will be the specific gravity at 25/25°C. To convert this to the
D 93 Test Methods for Flash Point by Pensky-Martens 25/15.5°C (77/60°F) basis, multiply by the factor 0.998.
Closed Tester3
D 95 Test Method for Water in Petroleum Products and 6. Viscosity
Bituminous Materials By Distillation3 6.1 Determine the viscosity of the oil at 25°C using Test
D 803 Methods of Testing Tall Oil4 Method D 1545.
D 1545 Test Method for Viscosity of Transparent Liquids 6.2 Determine the viscosity of the oil at 100°F (37.8°C),
by Bubble Time Method4 130°F (54.4°C), or 210°F (98.9°C), using a Saybolt Universal
D 2196 Test Methods for Rheological Properties of Non- Viscometer in accordance with Test Method D 88. Report the
Newtonian Materials by Rotational (Brookfield) viscosity in Saybolt Universal seconds.
Viscometer5 6.3 Determine the viscosity of the oil in centipoise at 25°C
D 3278 Test Methods for Flash Points of Liquids by using Test Method D 2196.
Setaflash Closed Cup Apparatus5
7. Flash Point
7.1 Determine the flash point of the oil either in accordance
3.1 Rosin oil, made by the decarboxylation of rosin, has with Test Methods D 3278 or in accordance with Test Method
been a commercial product for many years. Although less D 93. Report the method used.
widely used at the present time, it is still a significant item of
8. Acid Number
1
These methods are under the jurisdiction of ASTM Committee D-1 on Paint 8.1 Weigh 4.95 to 5.05 g, to the nearest 0.01 g, of the sample
and Related Coatings, Materials, and Applications and are the direct responsibility into a 300-mL Erlenmeyer flask. Add 100 mL of a solvent
of Subcommittee D01.34 on Naval Stores. containing equal parts of acetone and either 95 % ethyl alcohol
published as D 1131 – 50 T. Last previous edition D 1131– 93.
(Formula No. 3A or No. 30 denatured) or methyl alcohol. Place
2
Annual Book of ASTM Standards, Vol 04.04. on a steam bath and dissolve the oil in the solvent, connecting
3
4
Annual Book of ASTM Standards, Vol 05.01. in air-tube condenser to the neck of the flask and heating for
Annual Book of ASTM Standards, Vol 06.03. not more than 15 min, if necessary. Cool, and
5
1
D 1131
potentiometrically titrate with either aqueous or alcoholic 0.2 N 10. Precision and Bias
standard alkali solution. Calculate the acid number, in
10.1 Where the test method listed in this standard references
milligrams of KOH per gram of sample, as follows:
another ASTM standard method, that method should be studied
Acid number 5 ~V 3 N3 56.1!/W (2) to determine the precision and bias. Other methods listed are
where: well established and determination of precision and bias is not
N 5 normality of the standard alkali solution, practical.
V 5 millilitres of alkali solution, and
W 5 weight of sample. 11. Keywords
11.1 rosin oil
9. Moisture
9.1 Determine the moisture in rosin oil on a 200-mL sample
in accordance with Test Method D 95, using xylene as the
solvent.
2

Kauri-Butanol Value of Hydrocarbon Solvents1
1. Scope against toluene, which has an assigned value of 105, and a

1.1 This test method covers the determination of the relative mixture of 75 % n-heptane and 25 % toluene on a volume
solvent power of hydrocarbon solvents used in paint and basis, which has an assigned value of 40.
lacquer formulations. This test method is suitable for use with 4. Significance and Use
solvents having an initial boiling point over 40°C and a dry
point under 300°C when determined in accordance with the 4.1 The kauri-butanol value is used as a measure of solvent
procedures in Note 1. power of hydrocarbon solvents. High kauri-butanol values
indicate relatively strong solvency.
NOTE 1—Test Method D 86 is used to determine the initial boiling point
and dry point for mineral spirits and similar petroleum solvents. Test 5. Apparatus
Method D 1078 is used for pure compounds and narrow boiling range
cuts.
5.1 Water Bath, a clear-glass vessel, maintained at 25 6
1°C. Alternatively, a room maintained at 25 6 1°C may be
1.2 This standard does not purport to address all of the used.
safety concerns, if any, associated with its use. It is the 5.2 Volumetric Flask, 200-mL capacity.
responsibility of the user of this standard to establish appro- 5.3 Erlenmeyer Flask, 250-mL capacity.
priate safety and health practices and determine the applica- 5.4 Buret, 50-mL capacity.
bility of regulatory limitations prior to use. 5.5 Print Specimen—A sheet of white paper having on it
1.3 For specific hazard information and guidance, consult black 10 or 12 point print, No. 31 Bruce old style type.
the supplier’s Material Safety Data Sheet.
NOTE 2—Text in this published standard is satisfactory to use as print
2. Referenced Documents specimen.
2.1 ASTM Standards: 6. Reagents
D 86 Test Method for Distillation of Petroleum Products2
D 304 Specification for n-Butyl Alcohol (Butanol)3 6.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests unless otherwise specified. Unless otherwise
D 611 Test Methods for Aniline Point and Mixed Aniline
indicated, it is intended that all reagents shall conform to the
Point of Petroleum Products and Hydrocarbon Solvents2
D 841 Specification for Nitration Grade Toluene3 specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are
available.4 Other grades may be used, provided it is first
Organic Liquids3
ascertained that the reagent is of sufficiently high purity to
3. Terminology permit its use without lessening the accuracy of the determi-
3.1 Definitions: nation.
3.1.1 kauri-butanol value—of a solvent, the volume in 6.2 Kauri-Butanol Solution5—Place in a 3-L flask 400 g of
millilitres at 25°C of the solvent, corrected to a defined clean, pale, bold kauri resin of Grade XXXX, XXX, or XX
standard, required to produce a defined degree of turbidity ground to pea-size or smaller. Add, while agitating vigorously,
when added to 20 g of a standard solution of kauri resin in
normal butyl alcohol. 4
3.1.1.1 Discussion—The kauri resin solution is standardized Chemical Society, Washington, DC. For suggestions on the testing of reagents not
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
and Related Coatings, Materials, and Applications and is the direct responsibility of MD.
5
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. The sole source of supply of prepared kauri-butanol solutions known to the
Current edition approved Nov. 10, 1997. Published August 1998. Originally committee at this time is the Chemical Service Laboratories, 5543 Dyer St., Dallas,
published as D 1133 – 50 T. Last previous edition D 1133 – 94. TX 75206. If you are aware of alternative suppliers, please provide this information
2
Annual Book of ASTM Standards, Vol 05.01. to ASTM Headquarters. Your comments will receive careful consideration at a
3
Annual Book of ASTM Standards, Vol 06.04. meeting of the responsible technical committee,1 which you may attend.
1
D 1133
2000 g of n-butyl alcohol, (conforming to Specification solution to age before initial standardization and, in any case, the
D 304). Shake on a mechanical shaker until the resin goes into standardization should be rechecked on successive days until the toluene
solution, warming to about 55°C, if necessary to aid solution. factor and blend factor remain constant.
If a mechanical shaker is not available, fit the flask with a 8. Procedure
reflux condenser and heat on a steam bath until all of the kauri
resin is dissolved. Permit the solution to stand 48 h and then 8.1 Weigh 20 6 0.10 g of the adjusted kauri-butanol
clarify by filtering through a Büchner funnel with suction, solution into a 250-mL Erlenmeyer flask. Place the flask in the
using double filter paper and changing as frequently as water bath at 25 6 1°C. Fill the 50-mL buret with the solvent
necessary. being tested and titrate the solvent into the Erlenmeyer flask
6.3 Standard Toluene conforming to Specification D 841 with constant swirling while maintaining the mixture in the
for use as a high-solvency standard. flask at 25°C. Gradually reduce the successive amounts of
6.4 Heptane-Toluene Blend consisting of 25 6 0.1 % tolu- solvent added as the end point is approached. The end point is
ene and 75 6 0.1 % n-heptane on a volume basis, for use as a reached when the sharp outlines of 10-point print (see 5.5)
low-solvency standard. The heptane shall conform to the placed directly beneath the water bath and observed through
requirements for knock test grade n-heptane prescribed in the liquid are obscured or blurred, but not to the point where
Table 1 of Test Methods D 611. the print becomes illegible. Check the temperature in the flask
immediately after the end point has been reached and if over
NOTE 3—The blend of 25 6 0.1 % toluene and 75 6 0.1 % heptane can 26°C or under 24°C, repeat the titration. Designate the volume
be prepared in any way that will give the desired accuracy. The following of solvent, in millilitres, to produce turbidity as C.
technique is adequate: Bring the toluene and heptane and a calibrated
200-mL volumetric flask to the same temperature, preferably in a 9. Calculation
constant-temperature room or thermostat. Run 50 mL of toluene into the
200-mL volumetric flask, using a buret or pipet calibrated to deliver 50 mL 9.1 Calculate the kauri-butanol value, V, as follows:
of toluene at the chosen temperature (preferably 25°C). Fill the volumetric V 5 @65~C 2 B!/~A 2 B!# 1 40 (1)
flask to slightly below the calibration line with n-heptane, insert the
ground-glass stopper of the volumetric flask, and mix carefully by where:
repeatedly inverting the flask. Allow to stand for a few minutes; then bring A 5 toluene required to titrate 20 g of kauri-butanol
to the 200-mL calibration mark with heptane and again carefully mix. solution (7.2), mL,
B 5 heptane-toluene blend required to titrate 20 g of
7. Standardization kauri-butanol solution (7.3), mL, and
7.1 Weigh out 20 6 0.10 g of kauri-butanol solution in a C 5 solvent under test required to titrate 20 g of kauri-
250-mL Erlenmeyer flask and place in the water bath at 25°C. butanol solution (Section 8), mL.
Titrate with the standard toluene into the flask, with constant 9.2 If the buret is maintained at a temperature other than 25
swirling, while maintaining the mixture in the flask at 25 6 6 1°C, correct the volume of solvent used, S, in millilitres, to
1°C. Gradually reduce the successive amounts of toluene standard temperature as follows:
added as the end point is approached. The end point is reached S 5 C~25 2 T! 3 0.0009 (2)
when the sharp outlines of 10-point print placed directly
beneath the water bath and observed through the liquid are where:
obscured or blurred, but not to the point where the print C 5 solvent used in the titration, mL, and
becomes illegible. Check the temperature in the flask immedi- T 5 temperature of the solvent in the buret, °C.
ately after the end point has been reached, and if over 26°C or
under 24°C, repeat the titration. 10. Precision and Bias
7.2 The volume of toluene used, in millilitres, represents the 10.1 The following criteria should be used for judging the
actual titer for the particular kauri-butanol solution at hand. acceptability of the results in the range from 30 to 90 at the
This value should lie reasonably close to 105 mL, but not over 95 % confidence level.
110 nor under 100 mL. If these limits are exceeded, adjust the 10.1.1 Repeatability—Two results, each the mean of
concentration of the kauri-butanol solution to bring the total duplicates, obtained by the same operator on different days
volume of toluene within them. Designate the final value using should be considered suspect if they differ by more than 0.01
toluene as A. K − 0.1, where K 5 mean kauri-butanol value.
7.3 Weigh out 20 6 0.10 g of the kauri-butanol solution 10.1.2 Reproducibility—Two results, each the mean of
(adjusted as described in 7.2) in a 250-mL Erlenmeyer flask duplicates, obtained by two laboratories should not be
and place in the water bath. Titrate with the heptane-toluene considered suspect unless they differ by more than 0.03 K
blend in the same manner as described in 7.1. Designate the + 1.0 where K 5 mean kauri-butanol value.
volume, in millilitres, of the blend used in this titration as B. 10.2 Bias—Test bias can result if the kauri-butanol solution
is not carefully standardized and adjusted (see 7.2 and 7.3). The
NOTE 4—If the composition of the blend is known to differ from 25 6
test method has no definitive bias statement because the value
1.0 % toluene, but is within the range from 22 to 28 % toluene, the
constant in the blend factor equation will differ from 40.0 by 0.60 units for of the test result is defined only in terms of the test method.
each 1 % toluene. For example, at 28 % toluene, the constant is 41.8
11. Keywords
instead of 40.0.
NOTE 5—Freshly prepared kauri-butanol solution may change in stan- 11.1 kauri-butanol value; hydrocarbon solvents; solvency
dardization from day to day. It is, therefore, desirable to permit the power
2
D 1133
3

Chemical Analysis of Blue Pigments1
1. Scope Matter Volatile Under the Test Conditions) in Pigments2

1.1 These test methods cover procedures for the chemical D 1193 Specification for Reagent Water3
analysis of blue pigments known commercially as iron blue, D 1208 Test Methods for Common Properties of Certain
copper phthalocyanine blue, and ultramarine blue. Pigments2
1.2 The analytical procedures appear in the following order: D 2448 Test Method for Water-Soluble Salts in Pigments by
Sections
Measuring the Specific Resistance of the Leachate of the
Pigment2
IRON BLUE PIGMENTS E 11 Specification for Wire-Cloth Sieves for Testing Pur-
Identification 6
poses4
Moisture by the Brabender Moisture Tester 7 and 8
Moisture by Toluene Distillation 9 3. Significance and Use
Water-Soluble Matter by Extraction 10
Water-Soluble Salts by Electrical Conductivity 11
3.1 These test methods are suitable for determining if
Detection of Acid-Insoluble Extenders 1213 impurities are present and establishing that the required pig-
Detection of Acid-Soluble Extenders 14 to 17 ments are present. These test methods may be used for
Detection of Organic Colors and Lakes 18
manufacturing quality control.
COPPER PHTHALOCYANINE BLUE PIGMENTS
4. Purity of Reagents and Water
Identification 19
4.1 Purity of Reagents—Unless otherwise indicated, it is
Detection of Basic Dye Derivatives 21 intended that all reagents shall conform to the specifications of
Detection of Other Organic Coloring Matter 22 the Committee on Analytical Reagents of the American Chemi-
Detection of Ultramarine Blue 23
Detection of Iron Blue 24
cal Society, where such specifications are available.5 Other
grades may be used, provided it is first ascertained that the
ULTRAMARINE BLUE reagent is of sufficiently high purity to permit its use without
Identification 25
Moisture and Other Volatile Matter 26 4.2 Purity of Water—Unless otherwise indicated, references
Water-Soluble Matter 27 to water shall be understood to mean reagent water conforming
Detection of Basic Dye Derivatives 28
Detection of Other Organic Coloring Matter 29
1.3 This standard does not purport to address the safety 5. Preparation of Sample
concerns associated with its use. It is the responsibility of the 5.1 Mix the sample thoroughly and take a representative
user of this standard to establish appropriate safety and health portion for analysis. Reduce any lumps or coarse particles to a
practices and determine the applicability of regulatory limita- fine powder by grinding.
tions prior to use. 5.2 Grind extracted pigments to pass a No. 80 (180-µm)
3
D 280 Test Methods for Hygroscopic Moisture (and Other 4
5
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint listed by the American Chemical Society, see Analar Standards for Laboratory
and Related Coatings, Materials, and Applications and are the direct responsibility Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
of Subcommittee D01.31 on Pigment Specifications. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Current edition approved March 27, 1986. Published May 1986. Originally MD.
1
D 1135
sieve.6 Discard any skins that do not pass through the sieve.
Mix the finely ground pigment thoroughly.
IRON BLUE
(Prussian Blue, Chinese Blue, Milori Blue)
IDENTIFICATION with HCl (1+1), and add approximately 2 mL of a ferric salt solution
(ferric sulfate or ferric alum (20 g/L)). The formation of a blue precipitate
6. Procedure established the pigment as consisting, at least in part, of iron blue.
6.1 To approximately 0.1 g of pigment in a 50-mL beaker, MOISTURE BY THE BRABENDER MOISTURE
add 15 mL of NaOH solution (50 g/L). Heat to boiling. In a few TESTER
minutes the blue color should be completely destroyed, giving
in its place the characteristic reddish brown precipitate of ferric 7. Apparatus
hydroxide. Add HCl (1+1) until faintly acid to litmus. The iron 7.1 Brabender Moisture Tester—The Brabender moisture
blue should be reformed, yielding again the characteristic blue tester (Fig. 1) consists of a constant-temperature oven with
color. weighing apparatus attached. Specimens placed in the oven
NOTE 1—If the NaOH treatment does not completely destroy the blue may be weighed without opening the oven door or removing
color, the evidence is strong that a foreign pigment is present. If this the specimen from the oven, as the balance scale is calibrated
occurs, it is best to filter the alkaline solution, weakly acidify the filtrate to read directly in percent of moisture.
FIG. 1 Brabender Moisture Tester
2
D 1135
8. Procedure denatured with methyl alcohol (Formula No. 3A) has been found suitable.
8.1 Set the temperature control at 160°C and allow the oven 10.3 Let settle, filter through a dry filter paper, and discard
to reach this temperature before checking or making any the first 20 mL of the filtrate. Transfer 100 mL of the clear
weighing. Check the scale by placing a sample dish containing filtrate to a weighed dish, and evaporate to dryness on a steam
9.200 g standard analytical balance weights in the oven. The bath. Dry for 1 h in an oven at 105 6 2°C, cool, and weigh.
apparatus should read 8.0 % moisture. If it does not, adjust to 10.4 Calculation—Calculate the percent of water-soluble
a reading of 8.0 % by turning either the right hand or left hand matter as follows:
foot screw. Water2soluble matter, % 5 grams of residue 3 100
8.2 Weight 10.000 g of the sample in the aluminum dish and
WATER-SOLUBLE SALTS BY ELECTRICAL
place in the oven. For a series of specimens, all should be
CONDUCTIVITY
placed in the oven at as nearly the same time as possible. No
specimen should occupy the position directly in front of the 11. Procedure
door. Weigh the specimen at the end of each hour for 5 h. After 11.1 Determine water soluble salt content in accordance
each weighing, return the specimen to its original place in the with Test Method D 2448.
oven.
DETECTION OF ACID-INSOLUBLE EXTENDERS
NOTE 2—The dried pigment is very hygroscopic. In order to obtain
12. Scope
consistent results, the specimen position must not be changed and the oven
door must not be opened. 12.1 Acid-insoluble extenders include barium sulfate, silica,
8.3 Calculation and Report—Plot time against percent loss and silicates. Alumina may also be found, in part, with this
in weight on rectilinear cross-section paper. Extrapolate the group.
linear portion of the curve to zero time. That portion beyond 13. Procedure
about 2 h will be essentially linear. Report the percent loss in 13.1 Ignite about 1 g (weighed to 0.1 mg) of the sample at
weight at the extrapolated zero time as the percent moisture in a low temperature, just enough to decompose the last trace of
the pigment. pigment but not high enough to render the iron difficultly
NOTE 3—The pigment undergoes a slight loss in weight due to soluble in HCl (Note 5). Cool, and add 15 mL of HCl (sp gr
decomposition during the heating. The method of plotting and extrapola- 1.19) and a few drops of bromine. Cover with a watch glass
tion corrects for this loss. An approximate value for moisture content may and evaporate to a sirup. Add about 15 mL of water, and boil.
be obtained by taking the reading at the end of the first hour’s heating. An It may be necessary to add a drop or two of HCl to effect
occasional pigment may decompose rapidly at the oven temperature. In complete solution of the ferric iron residue. Filter and wash
such cases, determine moisture by the toluene distillation method (Section
with hot water. Save the filtrate for the determination of
9).
alumina hydrate (Section 16).
MOISTURE BY TOLUENE DISTILLATION NOTE 5—The ignition can conveniently be carried out in a 250-mL
beaker or a porcelain dish over a free flame. Oxidation of the specimen is
9. Procedure
evidenced by a dull glowing. While being heated, it is advisable to roll the
9.1 Determine the moisture content in accordance with specimen around in the beaker or dish exposing all of the surface to the
Sections 7 and 8 of Test Method D 1208, but using 25 g of oxygen of the air. A moderately low flame should be used and the ignition
pigment and 200 mL of toluene and adjusting the calculation is complete when the specimen ceases to glow and acquires a uniform
accordingly. brown color.
13.2 A residue of less than 3 mg that appears as small black
WATER-SOLUBLE MATTER BY EXTRACTION specks can be neglected, since quite frequently a small amount
10. Procedure of iron is rendered insoluble or a small amount of blue pigment
escapes destruction. Ignite the residue and weigh. If apprecia-
10.1 Determine whether or not the pigment is easily wet by
bly more than 3 mg are present, extenders should be suspected,
water at room temperature by adding a little to some water in
and if it is required to know which extenders are present,
a beaker. If it tends to float on top of the water with very little,
analyze the residue for silica, barium sulfate, and alumina.
if any, tendency to sink to the bottom or disperse throughout
the solution, even after agitation, it contains a hydrophobic NOTE 6—If alumina is present, it may appear both with the acid-
treating agent. insoluble and acid-soluble extenders. As a rule, most of it will appear with
the acid-soluble extenders.
10.2 Weigh to 1 mg about 2.5 g of the pigment into a
250-mL volumetric flask. If the pigment is hydrophobic as DETECTION OF ACID-SOLUBLE EXTENDERS
tested above, moisten thoroughly with a few mL of ethyl
14. Scope
alcohol (Note 4). If the pigment is easily wet with water, no
alcohol is necessary. Fill the flask about half full with water 14.1 Acid-soluble extenders include the alkaline earth car-
and shake to disperse the pigment thoroughly. Fill to the mark bonates or sulfates, magnesium carbonate, and alumina hy-
and again shake. Allow to remain at room temperature for not drate.
less than 15 h, shaking from time to time, preferably with an 15. Reagents
automatic shaking device. 15.1 Ammonium Oxalate Solution—Dissolve 40 g of am-
NOTE 4—Ethyl alcohol denatured with acetone (Formula No. 23A) or monium oxalate monohydrate in warm water and dilute to 1 L.
3
D 1135
15.2 Ammonium Phosphate Solution—Dissolve 100 g of glass rod to initiate crystallization. A white microcrystalline
(NH4)2HPO4 in water and dilute to 1 L. precipitate indicates the presence of magnesium salts and
possibly some alkaline earth salts as well.
16. Procedure for Alumina Hydrate 17.3 To the other portion of the filtrate, add 5 mL of
16.1 To the filtrate from 13.1, add NaOH solution (50 g/L) ammonium oxalate solution. Make slightly alkaline with
until just alkaline; then add 5 mL excess. Boil for about 2 min NH4OH (sp gr 0.90). If no precipitate forms immediately,
and let stand in a warm place until the hydrous iron oxide is warm on a hot plate and let stand for a short time. A white
coagulated. Filter through a rapid filter paper, wash a few times microcrystalline precipitate indicates the presence of alkaline
with hot water, and discard the precipitate. earth salts. If it is required to know specifically which acid
16.2 To the filtrate add 7 mL of HCl (1+1). Add NH 4OH soluble extenders are present, any of the established tests for
(1+4) until just ammoniacal. Boil about 2 min. If no precipitate these metal salts may be employed.
is apparent, allow to stand about 1⁄2 h. If the solution is still
clear, no alumina hydrate is present. A white gelatinous DETECTION OF ORGANIC COLORS AND LAKES
precipitate indicates alumina hydrate. Filter and save the 18. Procedure
filtrate for the detection of alkaline earth and magnesium salts
(Section 17). 18.1 Boil 2 g of the sample for 2 min with 25 mL of water.
16.3 If a rough estimate of the amount of alumina hydrate is Let settle and decant the supernatant liquid. Similarly, boil the
desired, the residue may be washed, dried, ignited, and residue with 25 mL of denatured ethyl alcohol (95 %) and
weighed as Al 2O3. decant as before. Likewise boil with 25 mL of chloroform and
again decant. If any one of the above solutions is colored,
17. Procedure for Alkaline Earth and Magnesium Salts organic colors are present. If all solutions remain colorless,
17.1 To the filtrate from Section 16, add HCl (1+1) until disregarding a slight yellowish cast, organic colors are presum-
faintly acid. Divide the filtrate into two portions. ably absent. The presence of organic colors resistant to the
17.2 To one portion of the filtrate, add 15 mL of (NH above reagents is unlikely, but may be tested by reference to
4)2HPO4 solution and neutralize with NH4OH (sp gr 0.90). Add
procedures given in standard reference works.6
10 mL excess NH4OH. If no precipitate forms immediately, let
stand for a short time in a cool place with occasional vigorous 6
Reference may be made to the following: Payne, H. F., “Organic Coatings
stirring. Rub the inside of the beaker from time to time with a Technology,” Vol II, John Wiley & Sons, Inc., New York, NY, 1961.
COPPER PHTHALOCYANINE BLUE
IDENTIFICATION DETECTION OF BASIC DYE DERIVATIVES

19.1 To about 0.05 g of the sample in a 50-mL beaker, add 21.1 Add to 1 g of the sample, 50 mL of a mixture of equal
30 mL of H2SO4 (sp gr 1.84). Stir occasionally for 15 min; the parts of NH4OH (sp gr 0.90) and denatured ethyl alcohol
sample should dissolve, forming a dark greenish yellow (95 %). Warm gently and filter. Neutralize the filtrate with
solution (color best seen on the side of the beaker). Pour the tartaric acid solution (200 g/L) until slightly acid to litmus. If
solution into 250 mL of water and stir. The copper phthalo- the solution is colorless, discounting a slight yellow tinge, no
cyanine should immediately precipitate as a brilliant blue basic dye is present.
flocculent mass. 21.2 If the solution is colored beyond a slight yellow tinge,
19.2 Filter off the precipitate, washing once or twice with add about 5 mL of 0.1 N TiCl3 solution (Note 8). If a basic dye
water. Scrape a small amount of the precipitate off the filter, is present, the color will lighten significantly. If no basic dye is
place on a clean platinum wire moistened with HCl, and present, no significant color change will occur.
subject it to the low flame of a bunsen burner. As the precipitate
NOTE 8—Titanium trichloride is marketed as a 16 % solution in HCl.
burns, a light blue-green flame should be clearly evident. This
Mix 7 mL of this solution with 90 mL of HCl (1+2) to obtain a reagent
indicates organically combined copper. approximately 0.1 N. Protect from oxidation.
NOTE 7—Characteristic spectrophotometric absorption spectra in the
near infrared range (700 to 900 nm) are exhibited by dilute solutions of DETECTION OF OTHER ORGANIC COLORING
copper phthalocyanine blue pigments in H2SO4 (sp gr 1.84) (2 to 50 MATTER
mg/L). The absorption maxima are so sharp and well defined that they
may be used for positive qualitative identification of the various phthalo- 22. Procedure
cyanine pigments. 22.1 Weigh about 0.05 g of the sample into each of two
MOISTURE AND OTHER VOLATILE MATTER 50-mL beakers. Add 25 mL (at room temperature) of denatured
ethyl alcohol (95 %) to one beaker and about 25 mL of acetone
20. Procedure to the other. Stir each well for a few minutes, and let stand for
20.1 Determine moisture in accordance with Method A of about 2 h. Filter through two thicknesses of medium-texture,
Test Methods D 280. qualitative filter paper. If neither filtrate possesses more than an
4
D 1135
extremely slight pink, yellow, or blue cast, organic colors are DETECTION OF IRON BLUE
presumably absent, but may be tested for by procedures given 24. Procedure
in standard reference works.7
24.1 To 1 g of the sample in a 100-mL beaker, add 25 mL
DETECTION OF ULTRAMARINE BLUE of NaOH solution (50 g/L). Boil for about 1 min. Dilute to
approximately 40 mL and filter.
23. Procedure 24.2 Add HCl (1+1) to the filtrate until faintly acid to
23.1 Warm gently about 1 g of the sample with HCl (1+1). litmus. Add 2 mL of a ferric iron solution (ferric sulfate or
Decomposition of the ultramarine blue takes place with evo- ferric alum (20 g/L)). The development of a blue color reveals
lution of H 2S. This may be detected by either its odor or a the presence of ferrocyanide, and hence iron blue in the
brown coloration appearing on a strip of moistened lead acetate original pigment. For amounts around 0.05 % iron blue, the
paper. color may take 2 to 3 h to develop.
ULTRAMARINE BLUE
IDENTIFICATION 27.3 Cool and transfer to a 250-mL volumetric flask. Dilute

to the mark with wash water from the beaker; complete transfer
25. Procedure of the pigment to the flask is not necessary. After thorough
25.1 Warm gently approximately 0.1 g pigment with HCl shaking, allow to settle somewhat and filter the supernatant
(1+1). If the pigment is ultramarine blue, the color will be liquid through a dry paper, discarding the first 20 mL.
completely destroyed with the liberation of sulfur and H2S, Evaporate 100 mL of the clear filtrate to dryness in a weighed
which may be detected by its characteristic odor or by a brown dish. Heat for 1 h at 105 6 2°C, cool, and weigh.
coloration appearing on a strip of moistened lead acetate paper 27.4 Calculation—Calculate the percent of water-soluble
when held above the beaker. Quite frequently warming is not matter as follows:
necessary, the destruction taking place at room temperature. Water2soluble matter, % 5 grams of residue 3 100
NOTE 9—If any color remains after this treatment, it can be construed
as evidence that a foreign pigment is present. DETECTION OF BASIC DYE DERIVATIVES
MOISTURE AND OTHER VOLATILE MATTER 28. Procedure

28.1 Determine basic dye derivatives in accordance with
26. Procedure Section 21.
26.1 Determine moisture in accordance with Method A of
Test Methods D 280. DETECTION OF OTHER ORGANIC COLORING
MATTER
WATER-SOLUBLE MATTER
29. Procedure
27. Procedure 29.1 Determine other organic coloring matter in accordance
27.1 Establish whether or not the pigment is easily wet by with Section 22.
water by adding a little to some water in a beaker. If it tends to
float on top with little tendency to sink to the bottom or 30. Precision and Bias
disperse through the solution it contains a hydrophobic treating 30.1 Precision and Bias have not been determined.
agent.
27.2 Transfer 2.5 g (weighed to 1 mg) of the sample to a 31. Keywords
400-mL beaker. If the pigment is hydrophobic as tested above, 31.1 blue pigment, chemical analysis of; Brabender mois-
moisten thoroughly with a few millilitres of ethyl alcohol (Note ture tester; copper phthalocyanine blue, identification of; mois-
4). If the pigment is easily wet with water, the alcohol is not ture, Brabender tester; moisture, toluene distillation; pigment,
necessary. Add 250 mL of water and boil for 5 min with good acid soluble extenders; ultramarine blue pigment, identification
agitation. of
5
D 1135
6

Methanol (Methyl Alcohol)1
1. Scope Apparent specific

gravity:
1.1 This specification covers methanol (99.85 % grade). 20/20°C 0.7920 to 0.7930
1.2 This standard does not purport to address all of the 25/25°C 0.7883 to 0.7893
safety concerns, if any, associated with its use. It is the Color, Pt-Co, max 10
Distillation range, °C, max 1.0 (to include 64.6 6 0.1)
responsibility of the user of this standard to establish appro- Nonvolatile matter, mg/100 5
priate safety and health practices and determine the applica- mL, max
bility of regulatory limitations prior to use. Odor (see Note 1) nonresidual
Water, weight %, max 0.10
1.3 For specific hazard information and guidance, see the Acidity (free acid as acetic 0.003, equivalent to 0.028 mg KOH per gram
supplier’s Material Safety Data Sheet for materials listed in this acid), weight %, max of material
specification. Acetone, weight %, max 0.003
Hydrocarbons to pass test
Sulfuric acid wash test 50
2. Referenced Documents (carbonizable impurities)
2.1 ASTM Standards: Color, Pt-Co, max
Permanganate time, min 50
D 1296 Test Method for Odor of Volatile Solvents and
Diluents2 NOTE 1—Optional: Test for odor only when agreed upon as necessary
D 1353 Test Method for Nonvolatile Matter in Volatile between the purchaser and the supplier.
Products2
E 300 Practice for Sampling Industrial Chemicals3 4.1 Sample the material in accordance with Practice E 300.
E 346 Test Methods for Analysis of Methanol3 5. Test Methods
2.2 U.S. Fed. Specification:
PPP-C-2020 Federal Specification Packaging of Chemicals,
determined in accordance with Method E 346 and the follow-
Liquid, Dry, and Paste4
ing methods:
3. Properties 5.1.1 Nonvolatile Matter—Test Method D 1353.
3.1 Methanol (99.85 % grade) shall conform to the follow- 5.1.2 Odor—Test Method D 1296.
ing requirements: 6. Packaging and Package Marking
6.1 Package size shall be agreed upon between the pur-
chaser and the supplier.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 6.2 Packaging shall conform to applicable carrier rules and
Subcommittee D01.35 on Solvents, Plasticizers and Chemical Intermediates. regulations or when specified shall conform to U.S. Fed. Spec.
Current edition approved Dec. 10, 1997. Published August 1998. Originally PPP-C-2020.
published as D 1152 – 31. Last previous edition D 1152 – 89 (l993)e1.
2
3
4
Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700 7.1 methanol; methyl alcohol
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.
1

Methyl Isobutyl Ketone1,2

1.1 This specification covers methyl isobutyl ketone of7
(99.0 % grade).
3. Properties
1.2 For specific hazard information and guidance, see the
supplier’s Material Safety Data Sheet for materials listed in this 3.1 Methyl isobutyl ketone (99.0 % grade) shall conform to
specification. the following requirements:
Methyl isobutyl ketone wt %, min 99.0
2. Referenced Documents Apparent specific gravity:
20/20°C 0.800 to 0.803
2.1 ASTM Standards: 25/25°C 0.796 to 0.799
D 268 Guide for Sampling and Testing Volatile Solvents Color, Pt-Co units, max 15
Distillation, °C
and Chemical Intermediates for Use in Paint Related Initial boiling point, min 114.0
Coatings and Materials3 Dry point, max 117.0
D 1078 Test Method for Distillation Range of Volatile Nonvolatile matter, mg/100 mL, max 5
OdorA nonresidual
Organic Liquids3 Water, wt %, maxB 0.1
D 1209 Test Method for Color of Clear Liquids (Platinum- Acidity (free acid as acetic acid), wt % , max 0.01
Cobalt Scale)3 Methyl isobutyl carbinol, wt %, max 0.3
______________
D 1296 Test Method for Odor of Volatile Solvents and A
Optional: Test for odor only when agreed upon as necessary by the purchaser
Diluents3 and the supplier.
D 1353 Test Method for Nonvolatile Matter in Volatile B
Solvents for Use in Paint, Varnish, Lacquer, and Related turbidity with 19 volumes of 99 % heptane at 20°C.
Products3
4. Sampling
D 1364 Test Method for Water in Volatile Solvents (Fischer
Reagent Titration Method)3 4.1 The material shall be sampled in accordance with
D 1476 Test Method for Heptane Miscibility of Lacquer Practice E 300.
Chemical Intermediates Used in Paint, Varnish, Lacquer, 5.1 The properties enumerated in this application shall be
and Related Products3 determined in accordance with the following ASTM test
D 3329 Test Method for Purity of Methyl Isobutyl Ketone Methods:
by Gas Chromatography3 5.1.1 Apparent Specific Gravity—Determine the apparent
D 4052 Test Method for Density and Relative Density of specific gravity by any convenient method that is accurate to
Liquids by Digital Density Meter4 the third decimal place, the temperature of both specimen and
E 1 Specification for ASTM Thermometers5 water being 20 or 25°C. See Guide D 268 or Test Method
E 300 Practice for Sampling Industrial Chemicals6 D 4052.
2.2 U.S. Federal Specification: 5.1.2 Color—Test Method D 1209.
5.1.3 Distillation Range—Test Method D 1078 using an
1
ASTM Solvents Distillation Thermometer having a range from
98 to 152°C and conforming to the requirements for Thermom-
Subcommittee D 01.35 on Solvents, Plasticizers, and Chemical Intermediates. eter 41C as prescribed in Specification E 1.
Current edition approved April 15, 1994. Published June 1994. Originally 5.1.4 Nonvolatile Matter—Test Method D 1353.
published as D 1153 – 51 T. Last previous edition D 1153 – 90. 5.1.5 Odor—Test Method D 1296.
2
This compound is also known under the name of 2-methyl -4-pentanone.
3
4
5 7
6
1
D 1153
5.1.6 Water—Test Method D 1364 or D 1476. 6.2 Packaging shall conform to applicable carrier rules and
5.1.7 Acidity—Test Method D 1613. regulations or when specified shall conform to Fed. Spec.
5.1.8 Alcohol and Purity—Method D 3329. PPP-C-2020.
6. Packaging and Package Marking 7. Keywords
6.1 Package site shall be agreed upon by the purchaser and 7.1 ketones; methyl isobutyl ketone (MIBK); solvents;2-
the supplier. methyl-4-pentanone
2

Solvent Tolerance of Amine Resins1
1.1 This test method covers the determination of the 6.1 Decahydronaphthalene, (decalin) having a boiling range
quantity of hydrocarbon solvent that an amine resin will between 188 and 195°C and a density, at 25°C, between 0.885
tolerate at 77°F (25°C). and 0.890 g/mL.
1.2 This standard does not purport to address all of the 6.2 Isooctane (2,2,4-trimethylpentane), having a purity of at
safety concerns, if any, associated with its use. It is the least 99 mol %.
responsibility of the user of this standard to establish 6.3 Toluene, conforming to Specification D 362.
appropriate safety and health practices and determine the 6.4 Solvent Mixture:
applicability of regulatory limitations prior to use. 6.4.1 Blend the above three hydrocarbons in the proportions
indicated below and determine the density at 25°C in
2. Referenced Documents accordance with Test Methods D 891.
2.1 ASTM Standards: Parts by Weight
D 362 Specification for Industrial Grade Toluene2 Isooctane 84
Decahydronaphthalene 8
D 891 Test Methods for Specific Gravity of Liquid Toluene 8
Industrial Chemicals3
6.4.2 Standardize the solvent by titration against 206 0.1 g
3. Summary of Test Method of mineral-spirits-standardized kauri-butanol solution. The
3.1 A standard solvent prepared from three relatively pure volume of solvent necessary to reach the end point described in
hydrocarbons is employed to titrate a specimen of the resin to 7.3 should be between 31 and 32 mL. If the volume of solvent
a defined degree of turbidity and the solvent tolerance is is not between 31 and 32 mL make an adjustment by varying
calculated from the volume of solvent added. the concentration of decahydronaphthalene. If the titrant
volume is low add more decahydronaphthalene, if high add
4. Significance and Use 84 + 8 isooctane-toluene mixture. Determine the density of the
4.1 This test method gives an indication of the solubility of final mixture at 25°C.
an amine resin. This property is important in determining the NOTE 1—Although similar in certain respects to commercial products
utility of the resin in new paint formulations and in ensuring its identified as mineral spirits, the solvent possesses an advantage for this
compatibility with existing paint formulations. This test determination in that it is a mixture of known constant composition.
method is thus useful for evaluation and quality control of
amine resins. 7. Procedure
7.1 Adjust the temperature of the solvent and the sample to
5. Apparatus 77 6 1°F (25 6 0.5°C), and conduct the determination at this
5.1 Erlenmeyer Flask, wide-mouth, 250-mL capacity. temperature.
5.2 Buret, 50-mL capacity, graduated in 0.1-mL divisions. 7.2 Weigh the Erlenmeyer flask on a suitable balance to 10
5.3 Print Specimen—A sheet of paper having on it printing mg. Transfer approximately 10 g of resin to the flask and again
in a black ink from 10-point, No. 31 old style type, including weigh to 10 mg to obtain the weight of the specimen.
a double quotation mark (lower case letters approximately 1⁄16 7.3 Fill the buret with the solvent, and titrate the specimen
in. (1.5 mm) high) with normal spacing, upper and lower case while swirling the flask constantly. Add the solvent rapidly, but
with no italicized or bold letters. at a rate such that precipitation caused by local excess of
solvent is kept to a minimum, until about 90 % of the required
1
amount has been added. As the end point is approached, add
the solvent in small increments. The end point is reached when
Subcommittee D 01.33 on Polymers and Resins. the 10-point print placed beneath the flask becomes illegible.
Current edition approved April 15, 1993. Published June 1993. Originally Alternatively the end point may be taken as the point where a
published as D 1198 – 52. Last previous edition D 1198 – 88. double quotation mark can no longer be resolved. Record the
2
Discontinued; See 1989 Annual Book of ASTM Standards, Vol 06.03.
3
volume of solvent added.
1
D 1198
8. Calculation 48 determinations. The results do not include the component of
8.1 Calculate the solvent tolerance T, expressed as grams of variation due to difference in solvent since the same solvent
solvent tolerated by 100 g of resin, as follows: was used by all participants. The within-laboratory coefficient
of variation was found to be 0.65 % with 11 degrees of
T 5 ~VD/S! 3 100 (1)
freedom and the between-laboratory coefficient of variation
where: was found to be 1.67 % with 5 degrees of freedom. Based on
V 5 solvent used in the titration, mL, these coefficients the following criteria should be used for
D 5 density of solvent, and judging the acceptability of results at the 95 % confidence
S 5 specimen weight used, g. limit:
NOTE 2—If preferred, instead of determining the density of the solvent
10.1.1 Repeatability—Two results, each the mean of
the flask may be weighed again after completing the titration, thus duplicate determinations, obtained by the same operator on
obtaining directly the weight of solvent required. different days should be considered suspect if they differ by
more than 2.9 % relative.
9. Report
10.1.2 Reproducibility—Two results, each the mean of
9.1 Report the grams of solvent tolerated by 100 g of sample duplicate determinations, obtained by operators in different
to 1 g. Duplicate runs that agree within 2.7 % relative are laboratories should be considered suspect if they differ by more
acceptable for averaging (95 % confidence level). than 6.1 % relative.
10. Precision and Bias 10.2 Bias—No bias can be determined since no standard
10.1 The precision estimates are based on an interlaboratory amine resin is available.
study of this test method on one sample each of a modified
urea-formaldehyde resin and a butylated melamine- 11. Keywords
formaldehyde resin. Six laboratories analyzed each sample in 11.1 amine resin; decahydronaphthalene; hydrocarbon
duplicate and repeated the analysis on another day for a total of solvent; isooctane; solvent tolerance; toluene
2

Calcium Carbonate Pigments1
1. Scope TABLE 1 Composition of Calcium Carbonate Pigments
1.1 This specification covers two types of high-content Type PC Type GC
calcium carbonate pigments, as follows: Moisture and other volatile matter, max, % 0.7 0.2
Calcium reported as carbonate, moisture-free, 96.5A ...
1.1.1 Type PC—Calcium carbonate precipitate, prepared min, %
either by complete solution or by carbonation of lime. Total calcium and magnesium reported as ... 94
1.1.2 Type GC—Ground mineral product. carbonates, moisture-free, min, %
Magnesium as carbonate, max, % ... ...
1.2 Six grades of pigments, based on particle size (see 3.3)
A
are covered. Does not apply to specialty calcium carbonate.
2. Referenced Documents 3.3.1 Grade I (Fine Paint Grade)—This grade possesses

2.1 ASTM Standards: substantial amounts of material in the fine sizes, and is in
C 25 Test Methods for Chemical Analysis of Limestone, general essentially below 15 to 20 µm maximum size. Coarse
Quicklime, and Hydrated Lime2 particles retained on the No. 325 (45-µm) sieve shall be less
D 280 Test Methods for Hygroscopic Moisture (and Other than 0.05 %. The maximum Specific Surface Diameter (SSD)
Matter Volatile Under the Test Conditions) in Pigments3 shall be 2.5 µm.
D 281 Test Method for Oil Absorption of Pigments by 3.3.2 Grade II (Coarse Paint Grade)—This grade is char-
Spatula Rub-Out4 acterized by substantial amounts in the 5- to 45-µm range, and
D 718 Test Methods for Analysis of Aluminum Silicate is lower in pigment value than Grade I. Coarse particles
Pigment3 retained on the No. 325 (45-µm) sieve shall be less than 0.5 %.
D 1366 Practice for Reporting Particle Size Characteristics The maximum SSD shall be 6 µm.
of Pigments3 3.3.3 Grade III (Filler Grade)—This grade is characterized
D 3360 Test Method for Particle Size Distribution by Hy- by substantial amounts in the 10- to 45-µm range but with the
drometer of the Common White Extender Pigments3 coarse particles retained on No. 325 (45-µm) sieve less than
E 97 Test Method for Directional Reflectance Factor, 45- 25 % and a maximum SSD of 9 µm.
deg 0-deg, of Opaque Specimens by Broad-Band Filter 3.3.4 Grade IV (Putty Powder Grade)—This grade pos-
Reflectometry5 sesses less fines, and have substantial amounts of coarse
particles. The coarse particles, however, shall not exceed 30 %
3. Composition and Properties retained on the No. 200 (75-µm) sieve. The maximum SSD
3.1 The pigment may be prepared by chemical precipitation shall be 12 µm.
or by the fine grinding of natural calcium carbonate containing 3.3.5 Grade V (Superfine Grade)—This grade is a super-
minerals. If additional agents are used or any surface treatment fine ground natural limestone and is characterized by major
is given, their purpose shall be indicated; acceptance shall be as amounts less than 5 µm and a weight median particle size in the
agreed upon by the purchaser and the seller. range of 1 µm. The SSD is finer than 1 µm.
3.2 Composition—The pigment shall conform to the re- 3.3.5.1 Particle size methods for Grade V that are applicable
quirements for composition prescribed in Table 1. include transmission electron microscopy, scanning electron
3.3 Fineness—The pigment shall conform to the following microscopy, and the Sedigraph.6 Specific Surface Diameter can
general requirements for fineness for the grade specified: be determined by BET nitrogen absorption. The method of
measurement produces different values, therefore, the method
1
of measurement shall be agreed upon by the purchaser and the
and Related Coatings, Materials, and Applications, and is the direct responsibility of seller.
6
published as D1199 – 52 T. Last previous edition D1199 – 80. The sole source of supply of the sedigraph known to the committee at this time
2
Annual Book of ASTM Standards, Vol 04.01. is Micromeritics, 5680 Goshen Springs Rd., Norcross, GA 30093. If you are aware
3
Annual Book of ASTM Standards, Vol 06.03. of alternative suppliers, please provide this information to ASTM Headquarters.
4
Annual Book of ASTM Standards, Vol 06.01. Your comments will receive careful consideration at a meeting of the responsible
5
Discontinued; See 1992 Annual Book of ASTM Standards, Vol 06.01. technical committee,1 which you may attend.
1
D 1199
3.3.6 Grade VI (Ultrafine Grade)—This grade is an ul- 5. Test Methods
trafine precipitated calcium carbonate and is characterized by 5.1 Tests shall be conducted in accordance with the follow-
major amounts less than 2 µm and a median particle diameter ing ASTM test methods. Test procedures not covered by ASTM
determined by electron microscopy in the range of 0.05 µm. test methods shall be agreed upon by the purchaser and the
3.3.6.1 Particle size methods for Grade VI that are appli- seller.
cable include transmission electron microscopy and scanning
5.2 Calcium and Magnesium Reported as Carbonate—
electron microscopy. The Sedigraph will give weight median
Methods C 25.
particle size values aproximately 10 times greater (;0.5 µm)
than by microscopy. Since the method of measurement pro- 5.3 Moisture and Other Volatile Matter— Method A of Test
duces different values, the method of measurement shall be Methods D 280.
agreed upon by the purchaser and the seller. 5.4 Oil Absorption—Test Method D 281.
3.3.7 When closer control within a grade is required, the 5.5 Coarse Particles—Method D 718.
fineness requirements shall be as agreed upon by the purchaser 5.6 Dispersed Color—Method D 718, substituting the ref-
and the seller. erence and test samples of calcium carbonate pigment for the
3.4 Dry Brightness or Dispersed Color— The dry bright- standard extender pigment and sample respectively.
ness or dispersed color shall be equal, within agreed upon 5.7 Specific Surface Diameter—Practice D 1366.7
tolerances, to that of a reference sample agreed upon by the 5.8 Dry Brightness—The test sample and reference sample
purchaser and the seller. shall be prepared into suitable smooth, dry, packed surfaces in
3.5 Oil Absorption—Oil absorption values shall be as accordance with accepted practice and tested for reflectance
agreed upon by the purchaser and the seller. using the green filter in accordance with Test Method E 97.
4. Sampling 5.9 Particle Size—Test Method D 3360 is applicable only to
Grades I, II, III, and IV.
4.1 Two samples, each more than 1 lb (0.45 kg) shall be
taken at random from different packages from each lot, batch, NOTE 1—See 3.3.5 for other acceptable methods.
day’s pack, or other unit of production in a shipment. When no
markings distinguishing between units of production appear, 6. Keywords
samples shall be taken from different packages in the ratio of 6.1 calcium carbonate
two samples for each 10 000 lb (5000 kg), except that for
shipments of less than 10 000 lb two samples shall be taken. At
the option of the purchaser, the samples may be tested
7
separately, or after blending, in equal quantities, the samples The sole source of supply of the sub-sieve sizer known to the committee at this
time is Fisher Manufacturer. If you are aware of alternative suppliers, please provide
from the same production unit forming a composite sample. this information to ASTM Headquarters. Your comments will receive careful
Before testing, each of the samples shall be split, and one half consideration at a meeting of the responsible technical committee,1 which you may
of each may be sealed for referee testing. attend.
2

Common Properties of Certain Pigments1
1. Scope LOSS ON IGNITION AND ASH

1.1 These test methods cover procedures for determining 4. Procedure
certain properties of pigments. The procedures appear in the
following order: 4.1 Dry about 5 g of the sample at 105 6 2°C for 2 h.
Dry Pigments Sections
Transfer about 1 g of the dried pigment, weighed to 0.1 mg, to
a previously ignited, weighed porcelain crucible, and ignite at
Loss on Ignition and Ash 4 900 to 1000°C for 20 min. Cool in a desiccator and weigh. Heat
Hydrogen Ion Concentration (pH 6
again for 10 min at 900 to 1000°C to check the loss in weight.
Value) 4.2 Calculation—Calculate the percent of loss on ignition,
Alkalinity or Acidity by Titration 7 and 8 L, and of ash, A, as follows:
Water Content (Distillation Method) 9 and 10
Lw
Pigment Pastes in Oil L 5 S 3 100 (1)
1
Water Content (Distillation Method)

Pigment Content of Paste in Oil
9 and 10
11 S Wa
A 5 S 3 100
1
D
Total Volatile Matter in Paste in Oil 12
where:
Lw 5 loss in weight on ignition, g,
safety concerns, if any, associated with its use. It is the A 5 ash, %,
responsibility of the user of this standard to establish appro- Wa 5 weight of ash, g, and
priate safety and health practices and determine the applica- S1 5 specimen weight, g.
2. Referenced Documents MATTER SOLUBLE IN WATER
2.1 ASTM Standards: 5. Procedure (Note 1)
D 95 Test Method for Water in Petroleum Products and 5.1 Weigh about 10 g of the sample to 1 mg, and place in a
Bituminous Materials by Distillation2 400-mL beaker. Add 100 mL of water (Note 2), boil for 5 min
D 280 Test Methods for Hygroscopic Moisture (and Other cool, and transfer quantitatively to a 250-mL volumetric flask.
Matter Volatile Under the Test Conditions) in Pigments3 Dilute with water to 250 mL, mix, and allow to settle. Filter the
D 1135 Test Methods for Chemical Analysis of Blue Pig- supernatant liquid through a dry paper (Note 3) and discard the
ments3 first 25 mL. Evaporate 100 mL of the clear filtrate to dryness
E 70 Test Method for pH of Aqueous Solutions with the in a weighed flatbottom dish, preferably in an oven at 105 6
Glass Electrode4 2°C. Cool and weigh.
3. Significance and Use NOTE 1—This test method is not suitable for use with iron blue
3.1 This collection of test methods is used by pigment pigment. Use the conductivity method given in Test Methods D 1135.
NOTE 2—If the pigment is found to be strongly water-repellent, wet the
producers and paint manufacturers for process control, for
sample with a small amount of alcohol or carry out a preliminary washing
product acceptance, and for research and development. with chloroform.
NOTE 3—Water-dispersible pigments must be filtered with a suitable
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint filter pad or the method may not be applicable.
of Subcommittee D01.31 on Pigment Specifications. 5.2 Calculation—Calculate the percent of matter soluble in
Current edition approved Nov. 10, 1996. Published January 1997. Originally water, M, as follows:
published as D 1208 – 52 T. Last previous edition D 1208 – 84 (1989)e1.
2
Annual Book of ASTM Standards, Vol 05.01. R1 3 2.5
3
M5 S2 3 100 (2)
4
1
D 1208
where: 10. Procedure (Note 5 and Note 6)

R1 5 residue weight, g, and 10.1 Place 50 g of the sample in the flask and add 100 mL
S2 5 specimen weight, g. of toluene or of petroleum solvent having a boiling point
between 110 and 120°C. Mix well. Add more solvent, if
HYDROGEN ION CONCENTRATION (pH VALUE)
necessary, to cover the pigment.
6. Procedure 10.2 Rinse the inner tube of the condenser with a little
toluene or petroleum solvent just before starting the distilla-
6.1 Determine hydrogen ion concentration in accordance
tion, so as to wet the inner surface completely. Distill at a
with either of the following methods:
moderate rate until the volume of condensed water no longer
6.1.1 Electrometric Method (Preferred Procedure)—Weigh
increases (about 3 h). If any water is lodged in the condenser
about 5 g of the sample to 10 mg, place in a 150-mL beaker,
tube at the end of the test, wash it down with solvent or with
and add 50 g of warm distilled water, freshly boiled to remove
a brush wetted with solvent.
carbon dioxide. Mix well by means of a glass rod and cool to
10.3 Calculation—Calculate the weight percent of water,
25°C. Measure the pH of the mixture in accordance with Test
W, as follows (assuming that 1 mL of water weighs 1 g):
Method E 70.
6.1.2 Colorimetric Method—Weigh about 10 g of the Wc
W 5 50 3 100 (4)
sample to the nearest 10 mg, place in a 250-mL glass-stoppered
Erlenmeyer flask, and add 150 g of warm distilled water, where Wc 5 water collected, mL.
freshly boiled to remove carbon dioxide. Stopper the flask and
NOTE 5—This test method is not suitable for pigments that release
shake vigorously for about 1 min. Cool to 25°C. Let stand 1 h combined water under the conditions of the test.
to allow the pigment to settle. Decant the clear liquid and NOTE 6—Test methods especially adapted for the determination of
determine its pH at once by means of a suitable indicator, using moisture in iron blue pigments are given in Test Methods D 1135.
a block comparator or similar colorimetric method. NOTE 7—Test Methods designed for the determination of free water (as
opposed to water of crystallization) in dry pigments are given in Test
NOTE 4—A block comparator or equivalent device is necessary in order
Methods D 280.
to compensate for the color of the extract.
6.2 Report—In reporting test results, state the particular PIGMENT CONTENT OF PASTE IN OIL
method used.
11. Procedure
ALKALINITY OR ACIDITY BY TITRATION 11.1 Select a portion of the well-mixed sample that is free of
7. Reagents skins. Weigh to 10 mg, about 15 g of the sample in a weighed
60-mL centrifuge tube. Add about 30 mL of petroleum ether,
7.1 Methyl Orange Indicator Solution—Dissolve 1 g of mix thoroughly with a glass rod, and wash the rod with more
methyl orange in 1 L of reagent water. petroleum ether (Note 8). Centrifuge at a moderate speed until
7.2 Sodium Hydroxide, Standard Solution (0.02 N). well settled. Decant the clear supernatant liquid, and repeat the
7.3 Sulfuric Acid, Standard Solution (0.02 N). extraction twice with 40 mL of petroleum ether and once with
8. Procedure 40 mL of ethyl ether. After decanting the ether, set the tube on
top of a warm oven for 10 min and then in an oven at 105 6
8.1 Shake 20 g of the dry pigment with 200 mL of distilled
2°C for 2 h. Cool and weigh.
water for 5 min, let settle, and filter through a dry filter paper
into a dry beaker, discarding the first 10 mL of the filtrate. NOTE 8—Other solvents or solvent mixtures may be used, provided that
Transfer 100 mL of the clear filtrate to a flask, add 3 drops of they leave no residue on evaporation.
methyl orange indicator solution, and titrate to the end point 11.2 Calculation—Calculate the percent pigment content,
with 0.02 N sulfuric acid (H2SO4), if alkaline, or 0.02 N P, as follows:
sodium hydroxide (NaOH) solution, if acid. R2
8.2 Calculation—Calculate the acidity or alkalinity, ex- P 5 S 3 100 (5)
3
pressed as milligrams of NaOH equivalent to 1 g of the sample,
as follows (1 mL of 0.020 N NaOH solution is equivalent to 0.8 where:
mg of NaOH): R2 5 residue weight in centrifuge tube, g and
Alkalinity or acidity 5 mL of NaOH or H2SO4 3 0.8 (3)
S3 5 specimen weight, g.
WATER CONTENT TOTAL VOLATILE MATTER IN PASTE IN OIL
9. Apparatus 12. Procedure

9.1 Distillation Apparatus—A water distillation apparatus 12.1 Weigh to 1 mg a flatbottom dish about 80 mm in
consisting of a 250-mL roundbottom flask, a straight-tube diameter containing a piece of stiff wire 100 mm long. Leave
reflux condenser, and a graduated receiving trap similar to Fig. the wire in the dish throughout the test. Place about 4 g of the
1 of Test Method D 95. sample, weighed to 1 mg in the dish. Spread the specimen over
9.2 Heat Source consisting of a gas burner and oil bath, or the bottom by means of the wire and heat for 21⁄2 h in an oven
an electric heater of the enclosed element type. at 105 6 2°C. If a skin forms, break it up at intervals during the
2
D 1208
heating by means of the wire. Cool the dish and contents in a PRECISION AND BIAS
desiccator and weigh. Heat again for 30 min to check the loss
in weight. 13. Precision and Bias
12.2 Calculation—Calculate the percent volatile matter in 13.1 Precision data are not available at this time. When they
the sample, V, as follows: are available the appropriate statements will be added.
L 13.2 Bias—No bias has been determined for this test
V 5 S 3 100 (6) method.
4
where: 14. Keywords

L 5 loss in weight on heating, g, and 14.1 analytical; ash; common products; loss on ignition;
S4 5 specimen weight, g. pigments; volatile water; water content; water solubility ph
3

Color of Clear Liquids (Platinum-Cobalt Scale)1
1. Scope color that can be tolerated being dependent on the color

1.1 This test method describes a procedure for the visual characteristics of the material in which it is used. The paint,
measurement of the color of essentially light colored liquids varnish, and lacquer solvents, or diluents commercially avail-
(Note 1). It is applicable only to materials in which the able on today’s market normally have little or no color. The
color-producing bodies present have light absorption charac- presence or absence of color in such material is an indication
teristics nearly identical with those of the platinum-cobalt color of the degree of refinement to which the solvent has been
standards used. subjected or of the cleanliness of the shipping or storage
container in which it is handled, or both.
NOTE 1—A procedure for estimating color of darker liquids, described 3.2 For a number of years the term “water-white” was
for soluble nitrocellulose base solutions, is given in Methods D 365.
considered sufficient as a measurement of solvent color.
1.2 This standard does not purport to address all of the Several expressions for defining “water-white” gradually ap-
safety concerns, if any, associated with its use. It is the peared and it became evident that a more precise color standard
responsibility of the user of this standard to establish appro- was needed. This was accomplished in 1952 with the adoption
priate safety and health practices and determine the applica- of Test Method D 1209 using the platinum-cobalt scale. This
bility of regulatory limitations prior to use. For specific hazard test method is similar to the description given in Standard
statements see Section 6. Methods for the Examination of Water and Waste Water7 and is
1.3 For specific hazard information, see the Material Safety referred to by many as “APHA Color.” The preparation of these
Data Sheet. platinum-cobalt color standards was originally described by A.
Hazen in the American Chemical Journal8 in which he
2. Referenced Documents assigned the number 5 (parts per ten thousand) to his platinum-
2.1 ASTM Standards: cobalt stock solution. Subsequently, in their first edition (1905)
D 156 Test Method for Saybolt Color of Petroleum Prod- of Standard Methods for the Examination of Water, the
ucts (Saybolt Chromometer Method)2 American Public Health Association, using exactly the same
D 365 Test Methods for Soluble Nitrocellulose Base Solu- concentration of reagents, assigned the color designation 500
tions3 (parts per million) which is the same ratio. The parts per
D 1193 Specification for Reagent Water4 million nomenclature is not used since color is not referred
D 1209 Test Method for Color of Clear Liquids (Platinum- directly to a weight relationship. It is therefore recommended
Cobalt Scale)5 that the incorrect term “Hazen Color” should not be used. Also,
E 202 Test Methods for Analysis of Ethylene Glycols and because it refers primarily to water, the term“ APHA Color” is
Propylene Glycols6 undesirable. The recommended nomenclature for referring to
E 346 Test Methods for Analysis of Methanol6 the color of organic liquids is “Platinum-Cobalt Color, Test
Method D 1209.”
3.3 The petroleum industry uses the Saybolt colorimeter
3.1 The property of color of a solvent varies in importance Test Method D 156 for measuring and defining the color of
with the application for which it is intended, the amount of hydrocarbon solvents; however, this system of color measure-
ment is not commonly employed outside of the petroleum
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint industry. It has been reported by various sources that a Saybolt
and Related Coatings, Materials, and Applications and is the direct responsibility of color of +25 is equivalent to 25 in the platinum-cobalt system
or to colors produced by masses of potassium dichromate
2
3 7
Annual Book of ASTM Standards, Vol 06.02. Standard Methods for the Examination of Water and Waste Water, M. Franson,
4
Annual Book of ASTM Standards, Vol 11.01. Ed., American Public Health Assoc., 14th ed., 1975, p. 65.
5 8
Annual Book of ASTM Standards, Vol 06.04. Hazen, A., “New Color Standard for Natural Waters,” American Chemical
6
Annual Book of ASTM Standards, Vol 15.05. Journal, Vol XIV, 1892, p. 300–310.
1
D 1209
TABLE 1 Absorbance Tolerance Limits For No. 500 Platinum- dinal axes. The comparator should be constructed so that white
Cobalt Stock Solution light is passed through or reflected off a white glass plate and
Wavelength, nm Absorbance directed with equal intensity through the tubes, and should be
430 0.110 to 0.120 shielded so that no light enters the tubes from the side.10
455 0.130 to 0.145
480 0.105 to 0.120
510 0.055 to 0.065
5. Reagents
TABLE 2 Platinum-Cobalt Color Standards all reagents shall conform to the specifications of the Commit-
Color Standard Stock Solution, Color Standard Stock Solution, tee on Analytical Reagents of the American Chemical Society,
Number mL Number mL where such specifications are available.11 Other grades may be
5 1 70 14 used, provided it is first ascertained that the reagent is of
10 2 100 20
15 3 150 30
20 4 200 40 accuracy of the determination.
25 5 250 50 5.2 Purity of Water—Unless otherwise indicated, references
30 6 300 60
35 7 350 70
40 8 400 80 to Type IV of Specification D 1193.
50 10 450 90 5.3 Cobalt Chloride (CoCl2·6H2O).
60 12 500 100A
5.4 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
A
This is platinum-cobalt color No. 10 in Methods D 365.
chloric acid (HCl).
5.5 Potassium Chloroplatinate (K2PtCl6).
TABLE 3 Platinum-Cobalt Color Standards for Very Light Colors
Color Standard Stock Solution, Color Standard Stock Solution, 6. Platinum-Cobalt Reference Standards
Number mL Number mL
6.1 Platinum-Cobalt Stock Solution— Dissolve 1.245 g of
1 0.20 9 1.80
2 0.40 10 2.00
potassium chloroplatinate (K2PtCl6) and 1.00 g of cobalt
3 0.60 11 2.20 chloride (CoCl2·6H2O) in water. Carefully add 100 mL of
4 0.80 12 2.40 hydrochloric acid (HCl, sp gr 1.19) and dilute to 1 L with
5 1.00 13 2.60
6 1.20 14 2.80
water. The absorbance of the 500 platinum-cobalt stock solu-
7 1.40 15 3.00 tion in a cell having a 10-mm light path, with reagent water in
8 1.60 a matched cell as the reference solution,12 must fall within the
limits given in Table 1.
NOTE 3—This stock solution is commercially available from reputable
ranging between 4.8 and 5.6 mg dissolved in 1 L of distilled chemical suppliers.
water. Because of the differences in the spectral characteristics
6.2 Platinum-Cobalt Standards—From the stock solution,
of the several color systems being compared and the subjective
prepare color standards in accordance with Table 2 by diluting
manner in which the measurements are made, exact equivalen-
the required volumes to 100 mL with water in the Nessler
cies are difficult to obtain.
tubes. Cap the tubes and seal the caps with shellac or a
4. Apparatus waterproof cement. When properly sealed and stored, these
standards are stable for at least 1 year and do not degrade
4.1 Spectrophotometer, equipped for liquid samples and for
markedly for 2 years.13
measurements in the visible region.
6.2.1 For a more precise measurement of light colors below
NOTE 2—The spectrophotometer used must be clean and in first-class 15 platinum-cobalt, prepare color standards from the stock
operating condition. The instrument should be calibrated in accordance solution in accordance with Table 3 by diluting the required
with the instructions given in the Standards for Checking the Calibration
of Spectrophotometers (200 to 1000 nm).9
4.2 Spectrophotometer Cells, matched having a 10-mm light 10
The sole source of supply of the unit known to the committee at this time is
path. Scientific Glass and Instruments, Inc., P.O. Box 6, Houston, TX 77001. If you are
4.3 Color Comparison Tubes—Matched 100-mL, tall-form aware of alternative suppliers, please provide this information to ASTM Headquar-
Nessler tubes, provided with ground-on, optically clear, glass ters. Your comments will receive careful consideration at a meeting of the
responsible technical committee,1 which you may attend.
caps. Tubes should be selected so that the height of the 100-mL 11
graduation mark is 275 to 295 mm above the bottom of the Chemical Society, Washington, DC. For suggestions on the testing of reagents not
tube. listed by the American Chemical Society, see Analar Standards for Laboratory
4.4 Color Comparator—A color comparator constructed to and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
permit visual comparison of light transmitted through tall- MD.
form, 100-mL Nessler tubes in the direction of their longitu- 12
See the manufacturer’s instruction manual for complete details for operating
the spectrophotometer.
13
Scharf, W. W., Ferber, K. H., and White, R. G., “Stability of Platinum-Cobalt
Color Standards,” Materials Research and Standards, Vol 6, No. 6, June 1966, pp.
9
See NIST Letter Circular LC-1017. 302–304.
2
D 1209
volumes to 100 mL with water in the Nessler tubes. Use a 9.1.1.1 Repeatability—Two results, obtained by the same
semi-microburet for measuring the required amount of stock analyst should be considered suspect if they differ by more
solution. than:
r 5 0.027 (X + 92) platinum-cobalt units
7. Procedure where X is the average of the two results.
7.1 Introduce 100 mL of specimen into a Nessler tube, 9.1.1.2 Reproducibility—Two results, obtained by analysts
passing the specimen through a filter if it has any visible in different laboratories, should be considered suspect if they
turbidity. Cap the tube, place in the comparator, and compare differ by more than: R 5 0.087 ( X + 92) platinum-cobalt units
with the standards. where X is the average of the two results.
9.1.1.3 Table 4 shows precision values for samples with
8. Report Pt-Co Color of greater than 25.
9.2 Color Samples with Pt-Co Color Less than 2515:
8.1 Report as the color the number of the standard that most
9.2.1 The results of two interlaboratory studies were pooled
nearly matches the specimen. In the event that the color lies
to give precision values calculated according to RR-D02-1007.
midway between two standards, report the darker of the two.
One study of glycols included 4 samples and 7 laboratories; the
8.2 If, owing to differences in hue between the specimen
other study included 5 samples and 6 laboratories. Based on the
and the standards, a definite match cannot be obtained, report
pooled repeatability and reproducibility standard deviations,
the range over which an apparent match is obtained, and report
the following criteria should be used for judging, at the 95 %
the material as “off-hue.”
confidence level, the acceptability of results obtained on
samples with less than 25 Pt-Co Color.
9. Precision
9.2.1.1 Reapeatability—Two results, each the mean of du-
9.1 Color Samples with Pt-Co Color Greater than 2514: plicates, obtained by the same operator on different days
9.1.1 These precision statements are based upon an inter- should be considered suspect if they differ by more than two
laboratory study in which six platinum-cobalt standards having platinum-colbalt units.
values of 25, 75, 170, 265, 385, and 475 were prepared in 9.2.1.2 Reproducibility—Two results, each the mean of
accordance with the instructions given in Section 6 of this test duplicates, obatined by operators in different laboratories,
method and were given coded labels. These solutions were should be considered suspect of they differ by more than seven
tested by one analyst in each of ten different laboratories platinum-cobalt units.
making a single observation on one day and then repeating the 9.3 Bias—The test procedure has no bias because the value
observation on a second day. The analysts were requested to of the test result is defined only in terms of of the test method.
estimate the color to the nearest one unit for solutions below 40
10. Keywords
platinum-cobalt, to the nearest five units for solutions between
40 and 100 platinum-cobalt and to the nearest ten units for 10.1 clear liquids; color; platinum-cobalt color scale
solutions above 100 platinum-cobalt. Based on the results of 15
These precision statements are based on interlaboratory studies conducted by
this interlaboratory study, the following criteria, calculated Committee E-15 on Industrial Chemicals on samples of ethylene glycol and
methanol as reported in Test Methods E 202, E 346, and research reports RR:
according to RR-D02-1007, should be used for judging the E15-28, and D01-1108.
acceptability of results at the 95 % confidence level when the
results are obtained under optimum conditions where the hue TABLE 4 Precision Values for Greater than 25 Pt-Co Color
of the sample matches exactly the hue of the standards. Poor
Color (Pt-Co units) Repeatability, r Reproducibility, R
precision will be obtained in varying degrees as the hue of the
25 3 10
sample departs from that of the standards. 75 5 15
165 7 22
265 10 31
385 13 41
14
Supporting data are available from ASTM Headquarters. Request RR: D01- 475 16 49
1024 and RR: D02-1007.
3

Rosin Acids Content of Naval Stores, Including Rosin, Tall
1. Scope much early work is based on this test method, it is included

1.1 These test methods cover the determination of rosin here for reference.
acids in tall oil, tall oil fatty acid, tall oil rosin, and other naval 4.1.1 For materials containing less than 15 % rosin, the
stores products. modified Glidden procedure has gained acceptance as the
1.2 These test methods may not be applicable to adducts or method of choice over the Herrlinger-Compeau. For materials
derivatives of rosin, fatty acid, or other naval stores products. containing more than 15 % rosin the modified Wolfe Method,
1.3 This standard does not purport to address all of the once part of Test Methods D 1585, is preferred. The modified
safety concerns, if any, associated with its use. It is the Wolfe and modified Glidden procedures differ only in their
responsibility of the user of this standard to establish appro- details. Both methods have been combined here into a single
priate safety and health practices and determine the applica- procedure.
bility of regulatory limitations prior to use. 4.2 Rosin and tall oil are composed primarily of rosin acids
and fatty acids, and, therefore, the measurement of these
2. Referenced Documents components is important in establishing the composition of
2.1 ASTM Standards: these materials.
D 1585 Test Methods for Fatty Acids Content of Naval
5. Reagents
Stores, Including Rosin, Tall Oil, and Related Products2
E 70 Test Method for pH of Aqueous Solutions with the 5.1 Purity of Reagents—Reagent grade chemicals shall be
Glass Electrode3 used in all tests. Unless otherwise indicated, it is intended that
E 177 Practice for the Use of the Terms Precision and Bias all reagents shall conform to the specifications of the Commit-
in ASTM Test Methods4 tee on Analytical Reagents of the American Chemical Society
E 691 Practice for Conducting an Interlaboratory Study to where such specifications are available.5 Other grades may be
Determine the Precision of a Test Method4 used, provided it is first ascertained that the reagent is of
3. Summary of Test Method accuracy of the determination.
3.1 The rosin acids content is determined using either the 5.2 Unless otherwise indicated, references to water shall be
potentiometric method or the indicator method described in understood to mean deionized or distilled water.
Sections 6 to 17. Rosin acids are calculated as abietic acid.
6. Preparation of Sample
4. Significance and Use 6.1 Homogeneous liquid materials may be used without
4.1 This is a major revision of Test Methods D 1240. The further preparation.
old refereed version, the Herrlinger-Compeau Method, em- 6.2 Nonhomogeneous liquid materials should be heated
ployed a sodium sulfate solution extraction. It is limited in until they are homogeneous, then a portion taken for analysis.
application to materials containing less than 15 % rosin, 6.3 Solid samples are subject to surface oxidation which
principally fatty acids. It is used little in the industry, but since may affect the results. Prepare the sample for analysis by
chipping small pieces from a freshly exposed surface of a lump
or lumps and crush to a coarse powder to facilitate weighing
and solution. Prepare fresh on the same day, prior to weighing,
1
5
of Subcommittee D01.34 on Naval Stores. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Jan. 10, 1996. Published March 1996. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
3
Annual Book of ASTM Standards, Vol 15.05. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
4
1
D 1240
in order to avoid changes due to surface oxidation of crushed 10.4 Methyl Sulfuric Acid Solution—Slowly pour 100 g of
rosin on exposure to the air. concentrated sulfuric acid (H2SO4 sp gr 1.82 to 1.84), while
stirring constantly, into 400 g of methanol. Extreme caution
ROSIN ACIDS CONTENT BY THE should be taken while preparing the methyl sulfuric acid.
POTENTIOMETRIC METHOD Adding sulfuric acid too rapidly may cause the methanol to
(Referee Method) flash out of its container. Store the methyl sulfuric acid in a
glass-stoppered bottle.
7. Scope
10.5 Toluene.
7.1 This test method covers the determination of rosin acids
content of tall oil rosin, tall oil fatty acid, and other naval stores 11. Procedure
products, where the most reproducible results are desired. By 11.1 Weigh the sample to the nearest 0.001 g in a 250-mL
using the potentiometric inflection end points, the error due to flask. Choose the amount of sample so that the second titration
colorimetric end points is avoided. will consume between 10 and 30 mL of KOH solution. For
8. Summary of Test Method rosin acids, this will be about 5 g of material. For fatty acids
containing less than 15 % rosin, this will be about 40 g of
8.1 A sample is refluxed with methyl sulfuric acid to esterify material. For fatty acids containing less than 3 % rosin acids
the fatty acids. The rosin acids and sulfuric acid are then titrating with 0.1 N KOH may give superior results. Table 1
titrated potentiometrically, and the rosin acids content calcu- gives suggested amounts of material to use.
lated from the difference between the two inflection points 11.2 Dissolve the sample in 100 mL of methanol in a
obtained. 250-mL flask. If the sample has a high rosin content it may be
helpful first to dissolve it in 25 mL of toluene before adding the
9. Apparatus
methanol. For material believed to contain less than 15 % fatty
9.1 pH Meter—An indicating potentiometer having a limit acid, add 5 mL of methyl sulfuric acid, connect the flask
of error not greater than 60.1 pH over a range from pH 1 to pH assembly, and reflux the solution for 2 min. (Solid samples
13, using an alkali-resistant glass electrode and a saturated must be in solution before beginning reflux.) For materials
calomel half-cell. The pH meter shall conform to the require- believed to contain concentrations of fatty acid higher than
ments of Test Method E 70. Alternatively, an automatic poten- 15 % use 10 mL of methyl sulfuric and reflux for 20 min.
tiometric titrator may be used. Measure reflux time from the moment the first drop of solvent
9.2 Stirrer, magnetic, equipped with returns to the flask from the condenser. Cool and transfer to a
poly(tetrafluoroethylene)-coated stir bar. 400-mL beaker, using a total of 100 mL of methanol (Note 1)
9.3 Buret, 50-mL capacity, with 0.1-mL divisions. The in three successive rinsings.
so-called automatic buret is preferable as its use minimizes
errors due to evaporation. The automatic buret should be NOTE 1—Ethanol is preferable when an automatic titrator is used.
guarded with soda-lime tubes against the absorption of CO2 11.3 Turn the pH meter on and allow a few minutes for it to
from the air. come to equilibrium. Balance the meter using a standard buffer
9.4 Erlenmeyer Flask, 250-mL or larger of a chemically solution as described in Test Method E 70; then rinse the
resistant glass with a standard-taper 24/40 joint. electrodes thoroughly with water and then with alcohol.
9.5 Condenser, water-cooled, equipped with a joint fitting 11.4 Adjust the beaker containing the solution of the sample
the flask described in accordance with 9.4. so that the buret tip is close to the surface of the solution.
Adjust the electrodes so the lower half of each is immersed.
10. Reagents Start the stirrer slowly; then adjust its speed for vigorous
10.1 Alcoholic Alkali, Standard Solution (0.5 N)—Dissolve stirring without spattering. Record the initial pH if it is on the
33 g of potassium hydroxide (KOH), preferably in pellet form, scale. Add suitable small portions of the KOH solution, and,
in methanol (CH3OH) and dilute to 1 L with methanol. waiting after each addition until an unchanging potential has
Standardize to 60.001 N with potassium acid phthalate been established, record the pH and buret readings. Add 5-mL
(C6H4COOKCOOH) in 60 mL of water followed by 40 mL of portions of KOH solution until a pH solution until a pH of 1.0
methanol; 2.553 g of potassium acid phthalate will be neutral- to 1.5 is reached; then add 1-mL portions until the change in
ized by 25.00 mL of 0.5 N KOH solution. Protect the pH per portion added, exceeds 0.3 pH unit. Continue to add the
standardized solution against evaporation and absorption of KOH solution in 0.1-mL or smaller portions until the first end
carbon dioxide (CO2) from the air. Restandardize the solution point has been passed, as indicated by a significant decrease in
frequently, either potentiometrically or colorimetrically, using pH change per unit volume added. Thereafter, add 1 to 2-mL
phenolphthalein as the indicator.
10.1.1 For fatty acids containing low concentrations of rosin TABLE 1 Sample Size and Titrant
acids, 0.1 N alcoholic potassium hydroxide may give superior
Sample Size, Reflux Time, KOH
results. Material g min Normality,
10.2 Ethanol (95 %)—Denatured alcohol conforming to N
Formula No. 3A or No. 30 of the U.S. Bureau of Internal Rosin 5 2 0.5
Revenue, neutralized by the addition of KOH. Fatty acid, <15 % rosin 40 20 0.5
Fatty acid, <3 % rosin 40 20 0.1
10.3 Methanol (99.5 %).
2
D 1240
portions until the pH change per portion added again exceeds 15. Apparatus
0.3 pH unit. Again add 0.1-mL or smaller portions until the 15.1 The apparatus for the esterification and titration of the
second end point has been passed as indicated by significant sample shall consist of the flask, condenser, and buret de-
decrease in pH change per unit volume of KOH solution added. scribed in Section 9.
After the pH change is less than 0.1 pH unit per 0.1 mL of
KOH solution added, the increments may be increased to 1.0 16. Reagents
mL. End the titration at pH 12 or above. 16.1 Alcoholic Alkali, Standard Solution—See 10.1.
11.5 Determine the inflection points (points of maximum 16.2 Methanol—See 10.4
change in pH per 0.1 mL of 0.5 N KOH solution) to the nearest 16.3 Methyl Sulfuric Acid Solution—See 10.5.
0.1 mL. They may be found by inspection of a plot of pH 16.4 Thymol Blue Indicator Solution (1 g/L)—Dissolve 0.1
against millilitres of KOH solution added, or by plotting the g of thymol blue in 1000 mL of methanol.
change in pH per millilitre of KOH solution against the pH 16.5 Toluene.
reading. The inflection points shall be taken as the end points 17. Procedure
of the titration. If an automatic titrator is used, the end points
shall be taken at the inflection points or at the fixed pH of 4.0 17.1 Weigh the sample to the nearest 0.001 g in a 250-mL
and 10.8. flask. Choose the amount of sample so that the titration will
consume between 10 and 30 mL of 0.5 N KOH. For rosin acids,
12. Calculation this will be about 5 g of material. For fatty acids containing less
than 15 % rosin, this will be about 40 g of material. For fatty
12.1 Calculate the percentage of rosin acids as follows: acids containing less than 3 % rosin acids, titrating with 0.1 N
12.1.1 For materials containing less than 15 % rosin: KOH may give superior results. Table 1 gives suggested
Rosin acids, % 5 @~AN/B! 3 30.24# 2 1.1 (1) amounts of material to use.
17.2 Dissolve the sample in 100 mL of methanol in a
where:
250-mL flask. If the sample has a high-rosin content it may be
A 5 KOH solution required for titration between the
helpful first to dissolve it in 25 mL of toluene before adding the
first and second end points, mL,
N 5 normality of the KOH solution, methanol. For material believed to contain less than 15 % fatty
B 5 sample used, g, and acid, add 5 mL of methyl sulfuric acid, connect the flask
30.24 5 (mol weight of abietic acid 3 100)/1000 assembly, and reflux the solution for 2 min. (Solid samples
12.1.2 For materials containing greater than 15 % rosin: must be in solution before beginning reflux.) For materials
believed to contain concentrations of fatty acid higher than
Rosin acids, % 5 ~AN/B! 3 30.24 (2)
15 %, use 10 mL of methyl sulfuric and reflux for 20 min.
where: Measure reflux time from the moment the first drop of solvent
A 5 KOH solution required for titration between the returns to the flask from the condenser. Cool, add 1 mL of
first and second end points, mL, thymol blue indicator.
N 5 normality of the KOH solution, 17.3 Titrate with the KOH solution to the first end point,
B 5 sample used, g, and about pH 4.0, when the solution changes color from red to
30.24 5 (mol wt of abietic acid 3 100)/1000 yellow. Record the reading or refill the buret. Continue the
12.2 Report the percentage of rosin acids calculated by titration to the second end point, about pH 10.8, when the
either 12.1.1 or 12.1.2 to the first decimal place. solution changes color from yellow to blue. Record to the
nearest 0.1 mL the millilitres of KOH solution required for
ROSIN ACIDS CONTENT BY THE INTERNAL titration between the two end points.
INDICATOR METHOD
NOTE 2—These end points approximate the inflection points under the
(Alternative Method) nonaqueous conditions employed.
13. Scope 18. Calculation

13.1 This test method covers the determination of rosin 18.1 Calculate the percentage of rosin acids as described in
acids content of tall oil rosin, tall oil fatty acid, and other naval 12.1.
stores products, using an internal indicator for the determina- 18.2 Report the percentage of rosin acids to the first decimal
tion of the end point. It gives good results when routinely place.
applied by a skilled analyst. However, where most reproduc-
ROSIN ACIDS IN FATTY ACIDS
ible results by different analysts and laboratories are desired,
(Herrlinger-Compeau Method)
the referee method (Sections 6 to 11) should be used.
19. Scope
14. Summary of Test Method 19.1 The Herrlinger-Compeau Method given here has been
14.1 A sample is refluxed with methyl sulfuric acid to largely superseded by the methods described in Sections 1
esterify the fatty acids. The rosin acids and sulfuric acid are through 18.
then titrated in the presence of thymol blue indicator. The rosin 19.2 This test method covers the determination of rosin
acids content is then calculated from the difference between the acids in fatty acids when the rosin acids content does not
two color end points obtained. exceed 15 %.
3
D 1240
20. Summary of Test Method and complete the quantitative transfer of the flask contents with
20.1 The rosin acids are determined by titration, after 100 mL of ether. Thoroughly shake the mixture in the funnel.
esterification of the fatty acids with methanol in the presence of Allow to settle, draw off the salt layer, and discard. Wash the
sulfuric acid as a catalyst, followed by separation of the acids. contents of the funnel twice again with 250-mL portions of
This test method requires use of an experimentally determined Na2SO4 solution. The last washing should not react pink to
correction factor dependent upon the amount of rosin acids methyl orange indicator.
present.6 23.3 After removing the last wash, drain the contents of the
separatory funnel into a 500-mL Erlenmeyer flask. Rinse the
21. Apparatus funnel with 20 mL of ether and add the rinsings to the flask.
21.1 Flask, 250-mL flat-bottom, of chemically resistant Add 20 mL of ethyl alcohol and 1 mL of the phenolphthalein
glass with a standard-taper 24/40 neck. indicator solution. Titrate to the appearance of the pink-red
21.2 Condenser, water-cooled, with a joint fitting the flask color using 0.2-N alcoholic KOH solution if the rosin acids is
described in 21.1 less than 5 % or 0.5 N if more than 5 %.
21.3 Separatory Funnel, 500-mL, pear-shaped, fitted with a
glass stopper. 24. Calculation
21.4 Buret, 50-mL capacity, with 0.1-mL divisions. 24.1 Calculate the percentage of rosin acids as follows:
Rosin acids, % 5 ~1.031 3 AN3 30.2!/S 2 0.74 (3)
22. Reagents
22.1 Alcohol—Neutral methanol, neutral isopropanol (91 to where:
99 %), neutral 95 % ethanol, or neutral denatured alcohol A 5 KOH solution used for titration of the sample, mL,
conforming to formula No. 30 or No. 3A of the U.S. Bureau of N 5 normality of KOH solution,
Internal Revenue. S 5 sample used, g, and
22.2 Ethyl Ether. 0.74 5 correlation factor6 for a rosin acids content not over
22.3 Methanol (99.5 %). 15 %.
22.4 Methyl Orange Indicator Solution—Dissolve 0.1 g of 25. Precision and Bias
methyl orange in 100 mL of water.
22.5 Phenolphthalein Indicator Solution—Dissolve 1 g of 25.1 Interlaboratory Test Program—An interlaboratory
phenolphthalein in 100 mL of methanol. study of the rosin acid content of three substances, tall oil fatty
22.6 Potassium Hydroxide Standard Alcoholic Solu- acids, distilled tall oil, and rosin, was run in 1994. Each of 14
tion (0.2 or 0.5 N)—Dissolve 13.3 g of KOH (preferably in laboratories tested each of the three materials. The design of
pellet form) for a 0.2-N solution or 33.3 g for a 0.5-N solution the experiment, similar to that of Practice E 691 and a
(see 23.3) in methanol (99.5 %) and dilute to 1 L with within-between analysis of the data are given in ASTM
methanol. Standardize to 60.001 N. The standardized solution Research Report.7
should be protected against evaporation and the absorption of 25.2 Test Result—The precision information given below
CO2 from the air, and should be restandardized frequently. for the rosin acid content of naval stores products is for the
22.7 Sodium Sulfate Solution—Dissolve 100 g Na2SO4 in comparison of two test results, each of which is the average of
water and dilute to 1 L. The resulting solution should have a pH three test determinations as follows:
of 7.2 6 0.4 (Note 2). 25.2.1 Repeatability Limit, 95 % (within labora-
tory) 5 0.6 %.
NOTE 3—A suitable pH adjustment may be made by adding dilute (5 %) 25.2.2 Reproducibility Limit, 95 % (between laborato-
NaOH solution to a faint pink-red phenolphthalein color, then adding
ries) 5 1.4 %.
dilute sulfuric acid (5 %) solution until the color is discharged.
22.8 Sulfuric Acid (sp gr 1.84). limit) are used as specified in Practice E 177. The respective
23. Procedure standard deviations among test results, related to the above
23.1 Dissolve 40 6 0.1 g of the sample in 100 ml of 25.3.1 Repeatability standard deviation 5 0.2 %.
methanol in a 250-mL flat-bottomed flask. Twirl the flask to 25.3.2 Reproducibility standard deviation 5 0.5 %.
dissolve the oil and add a clean boiling chip. Add slowly t mL 25.4 Bias—These test methods have no bias because rosin
of H2SO4, while swirling the flask vigorously. Connect the acid content is defined only in terms of these test methods.
flask to the condenser, apply heat, and reflux the contents for
10 min. Cool the flask to room temperature with cold water. 26. Keywords
23.2 Add 250 mL of the Na2SO4 solution to a 500-mL 26.1 fatty acids; Glidden method; Herrlinger-Compeau
separatory funnel. Pour the contents of the flask into the funnel method; rosin; tall oil; tall oil fatty acid; tall oil rosin; Wolfe
Method
6
For information on the development of this test method and the establishment
of the correction factor, see Herrlinger, R., and Compeau, G. M., “The Determina-
7
tion of Rosin in Fatty Acids.” Journal of the American Oil Chemists’ Society, Supporting data are available from ASTM Headquarters. Request RR:D01–
August 1952, pp. 342–344. 1087.
4
D 1240
5

High-Gravity Glycerin1,2
1.1 This specification covers high-gravity glycerin (98.7 3.1 The glycerin shall conform to the following require-
weight %, minimum) for use in the manufacture of alkyd and ments:
other synthetic resins. Apparent specific gravity, min:
15.6/15.6°C (60/60°F) 1.2620
supplier’s Material Safety Data Sheet for materials listed in this 25/25°C 1.2587
specification. Color, Pt-Co scale, max 20
Sulfate ash, max, weight % 0.1
2. Referenced Documents Acid value, max, mg KOH per g of 0.3
material
2.1 ASTM Standards:
D 1258 Test Method for High-Gravity Glycerin3 4. Test Methods and Sampling
2.2 U.S. Federal Standard: 4.1 The material shall be sampled and the properties enu-
PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging merated in this specification determined in accordance with
of4 Test Method D 1258.
5.1 Package size to be agreed upon between the purchaser
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint and supplier.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 5.2 Packaging shall conform to applicable carrier rules and
Current edition approved May 25, 1990. Published July 1990. Originally regulations or when specified shall conform to Fed. Spec.
published as D 1257 – 79. Last previous edition D 1257 – 84. PPP-C-2020.
2
Also known as 1,2,3-propanetriol and glycerol.
3
4
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS. 6.1 high-gravity glycerins
1

High-Gravity Glycerin1,2
1. Scope 5. Procedure
1.1 These test methods cover the procedures for the sam- 5.1 Apparent Specific Gravity—Determine the apparent spe-
pling and testing of glycerin (1,2,3-propanetriol) for use in the cific gravity by a pycnometer method that is accurate to 0.0002,
manufacture of alkyd resins and other synthetic resins. such as in Test Methods D 891 or D 4052.
1.2 This standard does not purport to address all of the 5.2 Color—Determine the color in accordance with Test
safety concerns, if any, associated with its use. It is the Method D 1209.
responsibility of the user of this standard to establish appro- 5.3 Sulfate Ash—Weigh to the nearest 0.001 g, 50 g of
priate safety and health practices and determine the applica- glycerin sample, into an open, shallow dish of porcelain,
bility of regulatory limitations prior to use. platinum, or other suitable material. Heat the dish carefully
1.3 For hazard information and guidance, see the supplier’s until the contents can be ignited with a flame and allow it to
Material Safety Data Sheet. burn without further application of heat in a place free of
drafts. When burning ceases, allow the dish to cool to room
2. Referenced Documents temperature and then moisten the residue with 0.5 mL of
2.1 ASTM Standards: concentrated sulfuric acid. Cautiously heat the dish until fumes
D 891 Test Methods for Specific Gravity, Apparent, of are no longer evolved and the carbon is completely consumed.
Liquid Industrial Chemicals3 Ignite, cool in a desiccator, and weigh to 1 mg. Repeat until
D 1209 Test Method for Color of Clear Liquids (Platinum- weight is constant within 1 mg. Calculate the percent of sulfate
Cobalt Scale)4 ash, A, as follows:
D 1613 Test Method for Acidity in Volatile Solvents and A 5 ~R/S! 3 100 (1)
Chemical Intermediates Used in Paint, Varnish, Lacquer
and Related Products4 where:
D 4052 Test Method for Density and Relative Density of R 5 sulfate ash, g, and
Liquids by Digital Density Meter5 S 5 specimen used, g.
NOTE 1—The sulfate ash procedure is equivalent to the “Residue on
3. Significance and Use Ignition” determination for glycerin in the Pharmacopeia of the United
States, nineteenth revision.
3.1 These test methods provide a measurement of purity of
high-gravity glycerin. The results of these measurements can 5.4 Acid Value—Determine the percent acid in accordance
be used for specification acceptance. with Test Method D 1613.
4. Sampling 6. Precision and Bias

4.1 Sample the material in accordance with Practice E 300. 6.1 Precision—The precisions of the test procedures pre-
sented in these test methods have not been determined.
6.2 Bias—The biases of the test procedure presented in this
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint standard have not been determined because no material having
an accepted value is available.
Current edition approved Feb. 15, 1995. Published April 1995. Originally
2
Also known as 1,2,3-propanetriol and glycerol. 7.1 glycerine; glycerol; high-gravity glycerin; 1;2;3-
3
4
propunetriol; trihydroxy propane
5
6
1
D 1258
2

Odor of Volatile Solvents and Diluents1
1. Scope 4. Hazards
1.1 This test method covers a comparative procedure for 4.1 Many solvents and diluents, such as some aromatic and
observing the characteristic and residual odors of volatile aliphatic hydrocarbons, are hazardous or toxic. Take special
organic solvents and diluents to determine their odor accept- precautions while determining the odor of these products.
ability in a solvent system. Make the tests only as frequently as is necessary for control
1.2 It is not intended that this test method be employed to and base the evaluations on short sniffs, inhaling as little vapor
determine subtle odor differences between materials or to as possible.
determine odor intensity. 4.2 Provide adequate ventilation to maintain solvent or
1.3 It is recommended that this test method not be employed diluent concentration below the personnel exposure limit value
to determine the residual odor of a liquid if its time for established for the general work area as given in the MSDS.
evaporation to dryness at room temperature exceeds 30 min or 4.3 Other hazards may also be present. These may be, but
as agreed upon. are not limited to, flammable, combustible, corrosive, or
1.4 This standard does not purport to address all of the explosive (monomers) hazards.
responsibility of the user of this standard to establish appro- 5. Procedures
priate safety and health practices and determine the applica- 5.1 Characteristic Odor—Dip 25 by 75-mm strips of rapid
bility of regulatory limitations prior to use. For specific hazard qualititive paper, free of foreign odor, to a depth of 50 mm into
statements, see Section 4. the specimen and the reference standard, each contained in a
1.5 For specific hazard information, see the supplier’s Ma- beaker or other suitable container. Make an immediate com-
terial Safety Data Sheet (MSDS). parison between the odor of the two materials on the filter
papers.
2. Reference Standards 5.2 Residual Odor—Dip 25 by 75-mm strips of a rapid
2.1 Samples of the particular products being tested, having qualitative paper, free of foreign odor, to a depth of 50 mm into
odor characteristics satisfactory to purchaser and manufacturer, the specimen under test and the reference sample, each
are required. contained in a beaker or other suitable container. Permit the
papers to dry in air at room temperature and examine them at
3. Significance and Use suitable intervals for differences in odor (see 1.3). The evapo-
3.1 The comparative odor characteristics can be used, com- ration step may be omitted if only the“ characteristic” odor of
bined with other tests, for product identification and assessing the material is to be determined.
compliance with a specification.
3.2 The residual odor characteristics can be used to judge 6. Report
the presence of relatively nonvolatile materials that may be 6.1 Characteristic Odor—Report the odor as “characteris-
associated with manufacture or contamination during distribu- tic” if, upon immediate examination, the odor of the wet filter
tion. Since volatile solvents and diluents are used in a wide paper containing the specimen is similar to the odor of the filter
variety of chemical processes and residual materials may affect paper containing the standard. However, report the odor as
the efficiency of such processes, this test method provides a “noncharacteristic” if the odor of the specimen, compared with
comparative test for manufacturing control and assessing the standard, is unsuitable for its intended solvent use.
compliance with a specification. 6.2 Residual Odor—Report the odor as“ nonresidual” if no
odor is detectable on the sample paper after both the standard
and sample papers appear dry. It is assumed that the standard,
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint which is acceptable to both consumer and producer, has no
detectable residual odor. Report the odor as “residual” if an
1
D 1296
odor persists on the sample paper after none is detectable on component. In either case, the accuracy of odor measurements
the standard paper. should be considered suspect. In case of differing results
between purchaser and supplier, it may be helpful to employ an
odor panel consisting of no less than three persons. Consider-
7.1 Precision—Since the result of the test is merely a ation should be given to the qualifications of the panelists, such
subjective judgment of whether there is comparative similarity as the following: familiarity with odor determinations, length
with the reference standard specified in the procedure, no of time exposed to either the main or suspected minor
statement is made about the precision of assessing either component, and the environment in which the test is to be
characteristic or residual odor. conducted.
7.2 Bias—No statement is made about the bias of either the
characteristic or residual odor. Some analysts have little
8. Keywords
olfactory sensitivity to some materials, while other analysts
have extreme sensitivity to either the main or (if any) minor 8.1 odor; solvent
2

Chemical Analysis of White Lead Pigments1
1. Scope D 185 Test Methods for Coarse Particles in Pigments,

1.1 These test methods cover procedures for the chemical Pastes, and Paints3
analysis of basic carbonate white lead and basic sulfate white D 215 Practice for Chemical Analysis of White Linseed Oil
lead. Paints3
NOTE 1—If it is necessary to separate these pigments from others, refer Matter Volatile Under the Test Conditions) in Pigments3
to Test Methods D 215.
1.2 The analytical procedures appear in the following order: D 2371 Test Method for Pigment Content of Solvent-
Section Reducible Paints5
D 2372 Practice for Separation of Vehicle from Solvent-
Preparation of Sample 6
Basic Carbonate White Lead: Reducible Paints5
Small Amounts of Iron 7 D 3280 Test Methods for Analysis of White Zinc Pigments3
Total Lead 8
E 11 Specification for Wire-Cloth Sieves for Testing Pur-
Carbon Dioxide (Evolution Method) 10 poses6
Carbon Dioxide and Combined Water (Combustion Method) 11
Lead Carbonate 12 3. Significance and Use
Total Matter Insoluble in Acetic Acid 13
Total Matter Insoluble in Acid Ammonium Acetate 14 3.1 These test methods are suitable for determining the level
Total Impurities Other Than Moisture 15 of purity and for determining the levels of various impurities.
Coarse Particles 16 They may be used to establish compliance with specification
Basic Sulfate White Lead:
Small Amounts of Iron 17 requirements.
Total Lead
Moisture and Other Volatile Matter 19 4. Reagents
Total Sulfate 20
Zinc Oxide 21 4.1 Purity of Reagents—Reagent grade chemicals shall be
Basic Lead Oxide 22 used in all tests. Unless otherwise indicated, it is intended that
Total Impurities 23 all reagents shall conform to specifications of the Committee
Coarse Particles 24
on Analytical Reagents of the American Chemical Society,
1.3 This standard does not purport to address the safety where such specifications are available.7 Other grades may be
concerns, if any, associated with its use. It is the responsibility used, provided it is first ascertained that the reagent is of
of the user of this standard to establish appropriate safety and sufficiently high purity to permit its use without lessening the
health practices and determine the applicability of regulatory accuracy of the determination.
limitations prior to use. 4.2 Purity of Water—Unless otherwise indicated, references
2.1 ASTM Standards: 4.3 Concentration of Reagents:
C 25 Test Methods for Chemical Analysis of Limestone,
Quicklime, and Hydrated Lime2
3
4
5
6
1 7
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint Reagent Chemicals, American Chemical Society Specifications, American
and Related Coatings, Materials, and Applications and are the direct responsibility Chemical Society, Washington, DC. For suggestions on the testing of reagents not
of Subcommittee D01.31 on Pigment Specifications. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved Feb. 22, 1991. Published April 1991. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
1
D 1301
4.3.1 Concentrated Acids and Ammonium Hydroxide— dilute to about 200 mL with water. If insoluble matter remains
When acids and ammonium hydroxide are specified by name following treatment with HNO3 and dilution, filter and wash
or chemical formula only, it shall be understood that concen- the residue with hot water until lead free. Evaporate the filtrate
trated reagents of the following specific gravities or concen- and washings to about 200 mL. Add 20 mL of H2SO4 (1 + 1)
trations are intended: to precipitate the bulk of the lead (it is unnecessary to
Acetic acid, CH3COOH 99.5 % evaporate down). Cool, filter, and wash with diluted H2SO4
Hydrochloric acid, HCl sp gr 1.19 (1 + 99). Save the precipitate for determination of total lead
Hydrofluoric acid, HF 48 %
Nitric acid, HNO3 sp gr 1.42
(Section 8).
Sulfuric acid, H2SO4 sp gr 1.84 7.2.2 Ignite the HNO3-insoluble matter and treat with HF
Ammonium hydroxide, NH4OH sp gr 0.90 and H2SO4. Bring into solution, filter (any precipitate is
The desired specific gravities or concentrations of all other probably BaSO4), and add to the PbSO4 filtrate.
concentrated acids are stated whenever they are specified. 7.2.3 Colorimetrically determine iron in the combined fil-
Warning—See Section 5. trates by the thiocyanate method,8 using the same amounts of
4.3.2 Diluted Acids and Ammonium Hydroxide— reagents in preparing the reference standards. If copper is
Concentrations of diluted acids and ammonium hydroxide, present in the filtrate, as shown by the characteristic blue-green
except when standardized, are specified as a ratio stating the or yellow color, remove it by precipitating the iron with
number of volumes of concentrated reagent to be diluted with NH4OH, filtering, washing, redissolving the Fe(OH)3 in 10 mL
a given number of volumes of water, as in the following of HNO3(1 + 1), and diluting to about 200 mL before proceed-
example: HCl (1 + 99) means 1 volume of concentrated HCl ing with the thiocyanate method.
(sp gr 1.19) diluted with 99 volumes of water.
8. Total Lead
5. Hazards 8.1 Apparatus:
5.1 The concentrated acids bases and other reagents used in 8.1.1 Gooch Crucible, prepared prior to use.
these test methods can be dangerous. Check their Material 8.2 Reagents:
Safety Data Sheets, (MSDS) before use. 8.2.1 Acetic Acid (glacial)—Warning—See 5.1.
8.2.2 Ammonium Hydroxide (sp gr 0.90)—Warning—See
6. Preparation of Sample 5.1.
6.1 Grind dry pigments, if lumpy or not finely ground, to a 8.2.3 Ethyl Alcohol (95 volume %)—Warning—See 5.1.
fine powder for analysis. Large samples may be thoroughly 8.2.4 Potassium Dichromate Solution (100 g K2Cr2O7/L)—
mixed and a representative portion taken and powdered if Warning—See 5.1.
lumpy or not finely ground. Mix the sample in all cases 8.3 Procedure:
thoroughly and comminute before taking specimens for analy- 8.3.1 Ignite the PbSO4 precipitate and filter paper from 7.2.1
sis. at or below 1020°F (550°C), and transfer the residue to a
6.2 In cases of pastes in oil, extract the oil from the pigment 400-mL beaker. (If preferred, a new 1-g specimen of pigment
as described in Test Methods D 2371 or D 2372, but without may be weighed to 10 mg into a 400-mL beaker. Proceed to
straining. 8.3.2.)
6.3 Dry pigments separated from paints or pastes in oil in an 8.3.2 Moisten with water and add 5 mL of glacial acetic
oven at 203 to 210°F (95 to 98°C) for 2 h, grind to a fine acid. Warm to dissolve the material and dilute to about 200 mL
powder, pass through a No. 80 (180-µm) sieve (Note 2) to with water. Neutralize the solution with NH4OH and then make
remove skins, and mix thoroughly. Such pigments, after slightly acid with acetic acid, adding about 3 mL excess. Filter
weighing, should be moistened with a little ethyl alcohol off any insoluble residue and wash thoroughly with hot water.
(95 %) before adding reagents for analysis. 8.3.3 Unite the filtrate and washings, heat to boiling, and
add 15 mL of K2Cr2O7 solution. Stir and heat until the yellow
NOTE 2—Detailed requirements for this sieve are given in Specification precipitate assumes an orange color. Let settle and filter on a
E 11. weighed Gooch crucible. Wash by decantation with hot water
6.4 Preserve all samples in stoppered bottles or containers. until the washings are colorless. Finally transfer all the
precipitate from the beaker to the crucible and wash with ethyl
BASIC CARBONATE WHITE LEAD alcohol (95 %). Dry at 220 6 4°F (105 6 2°C) for 1 h. Cool
in a desiccator and weigh as PbCrO4.
7. Small Amounts of Iron 8.4 Calculation:
7.1 Reagents: PbO, % 5 ~P 3 0.691 / S! 3 100
7.1.1 Ammonium Hydroxide (sp gr 0.90). Warning—See
5.1. where:
7.1.2 Hydrofluoric Acid (48 %). Warning—See 5.1. P 5 PbCrO4 precipitate, g,
7.1.3 Nitric Acid (sp gr 1.42). Warning—See 5.1. S 5 specimen, g, and
7.1.4 Sulfuric Acid (sp gr 1.84). Warning—See 5.1.
7.2 Procedure:
7.2.1 Weigh to 10 mg about 1 g of specimen into a 400-mL 8
Described in Scott, Standard Methods of Chemical Analysis, Fifth Edition, D.
beaker. Treat the sample with 10 mL of HNO3 (1 + 1) and Van Nostrand Co., New York, NY, 1939, p. 486.
2
D 1301
0.691 5 PbO/PbCrO4 5 223.19/323.18. absorption bulbs from the combustion tube, after closing all
stopcocks, place in a desiccator to cool, and then weigh.
9. Moisture and Other Volatile Matter 11.3 Calculation:
9.1 Procedure—Determine moisture and other volatile mat- Carbon dioxide, % 5 100 3 C1
ter in accordance with Method A of Test Methods D 280. Combined water, % 5 100 W1 2 M
10. Carbon Dioxide (Evolution Method) Combined water as Pb~OH!2, % 5 ~100 W1 2 M! 3 13.39
10.1 Apparatus—Knorr type of CO 2 evolution apparatus where:

with dropping funnel, condenser, and suitable purifying train. C1 5 CO2, g,
NOTE 3—A description of a suitable purifying train, is found in the
W1 5 total water, g,
Carbon Dioxide Standard Method section of Test Methods C 25. M 5 free moisture, %, and
13.39 5 Pb(OH)2/H 2O 5 241.20/18.015.
10.2 Reagent:
10.2.1 Nitric Acid (1 + 19). 12. Lead Carbonate
10.3 Procedure—Transfer about 2 g of the sample, weighed
to 10 mg, to a clean, dry evolution flask. Connect the evolution 12.1 Calculation—Calculate the percent of PbCO3 from the
flask to the absorption train, which previously has been flushed CO2 content, as follows:
free of any CO2, and add 100 mL of HNO3, (1 + 19) through PbCO3, % 5 C 1 3 6.071/S2 3 100
a separatory funnel. When all of the HNO3 has been introduced
where:
into the flask, close the stopcock from the separatory funnel.
C1 5 CO2(10.4 or 11.3), g,
Heat the solution in the flask to gentle boiling and boil for 5 S2 5 specimen weight used in the CO2 determination, g,
min. Turn off the heat and aspirate CO2 free air through the and
system for 20 min. Remove the absorbing tube from the 6.071 5 PbCO3/CO2 5 267.20/44.01.
system, seal, cool in a desiccator, and weigh. The increase in
weight is CO2. 13. Total Matter Insoluble in Acetic Acid
10.4 Calculation—Calculate the percent of carbon dioxide
as follows: 13.1 Apparatus—Gooch Crucible, prepared and weighed
prior to use.
CO 2, % 5 ~C1/S1! 3 100
13.2 Reagent—Acetic Acid (3 + 2).
where: 13.3 Procedure—Transfer 10 g of the sample, weighed to
C1 5 CO2, g, and 10 mg, to a 250-mL beaker and add 40 mL of acetic acid
S1 5 specimen, g. (2 + 3). Heat until solution is complete and filter through a
previously prepared and weighed Gooch crucible. Wash thor-
11. Carbon Dioxide and Combined Water (Combustion oughly with hot water, dry at 220 6 4°F (105 6 2°C) for 1 h,
Method) cool, and weigh.
11.1 Apparatus—Combustion Train, consisting of the fol- 13.4 Calculation—Calculate the percent of total matter
lowing parts connected in the order specified; tank of purified insoluble in acetic acid as:
compressed nitrogen, purifying jars including a CO2 absorp-
~R/S3! 3 100
tion jar, drying tube, combustion tube, tube furnace provided
with suitable controls to maintain the temperature from 840 to where:
1020°F (450 to 550°C), absorption bulb for water, and an R 5 residue, g, and
absorption bulb for CO2. S3 5 specimen, g.
11.2 Procedure:
11.2.1 Heat the furnace, without the combustion tube, from 14. Total Matter Insoluble in Acid Ammonium Acetate
840 to 1022°F (450 to 550°C). Connect the combustion tube 14.1 Apparatus—Gooch Crucible, prepared and weighed
beside the furnace, connect the absorption tubes to the nitrogen prior to use.
supply, and pass a slow stream of nitrogen (about 30 mL/min)
14.2 Reagent—Acid Ammonium Acetate Solution—Mix 150
through them, to clear out any residual moisture and CO2.
mL of acetic acid (3 + 2) with 100 mL of water and then with
Accurately weigh the absorption bulbs and reconnect them in
95 mL of NH4OH (sp gr 0.90).
the train. Transfer 1 g of the specimen, weighed to 10 mg, to a
combustion boat that has been previously ignited and cooled. 14.3 Procedure—Transfer about 10 g of the sample,
11.2.2 With the nitrogen still flowing, disconnect the train weighed to 10 mg, to a 250-mL beaker. Add 40 mL of acid
and place the boat containing the specimen in the middle of the ammonium acetate solution and heat until solution is complete.
tube with the aid of a hooked wire. Flush the combustion tube Filter through a previously prepared and weighed Gooch
thoroughly with nitrogen and reconnect with the train. Place crucible and wash thoroughly with hot water. Dry at 105 to
the tube in the furnace. 110°C for 1 h, cool, and weigh.
11.2.3 Continue the combustion for 30 min, or until the 14.4 Calculation—Calculate the percent of total matter
water that condenses in the inlet arm of the first absorption bulb insoluble in acid ammonium acetate as:
has been completely swept into the bulb. Disconnect the ~R/S4! 3 100
3
D 1301
where: discarding the first 15 to 20 mL of filtrate. Measure exactly 200

R 1 5 residue, g, and mL in a volumetric flask and transfer to a 600-mL beaker. The
S4 5 specimen, g. test solution will now be equivalent to 0.5 g of the original
specimen.
15. Total Impurities Other Than Moisture 20.3.2 Carefully add HCl (sp gr 1.19) from a pipet to the
15.1 Calculations: alkaline solution until the solution is neutral, and add 0.4 mL
15.1.1 Calculate the percent of total impurities other than excess for each 100 mL of solution. Bring to boiling to expel
moisture as: the CO2 and then add to the boiling solution, drop by drop, 20
100 2 ~L 1 C 1 H 1 M!
to 25 mL of a BaCl 2 solution. Allow to stand in a warm place
for at least 2 h. Filter on a previously ignited and weighed
where: Gooch crucible or a fine-textured filter paper and wash with hot
L 5 PbO % (8.4), water. Dry and ignite. Cool, and weigh as BaSO 4.
C 5 CO2 % (10.4 or 11.3), 20.4 Calculations:
H 5 combined water, % (11.3), and Total sulfate as SO3 % 5 68.6 3 P
M 5 free moisture, % (9.1).
15.1.2 In the case of extracted pigments where direct Total sulfate as PbSO4 % 5 259.8 3 P
determination of combined water cannot be made conve- where:
niently, calculate the impurities other than moisture as: 100 P 5 BaSO4 precipitate, g.
(L + 1.205 D + M) where L, D, are as defined in 15.1.1 and 68.6 5 SO3/BaSO4 3 100/0.5 5 80.06/233.40 3 200
1.025 5 2 CO2 + H2O/2 CO2 5 106.035/88.02. 259.8 5 PbSO 4/BaSO4 3 100/0.5 5 303.25/233.40
16. Coarse Particles 21. Zinc Oxide
16.1 Procedure—Determine coarse particles in accordance 21.1 Procedure—Determine zinc oxide in accordance with
with Test Methods D 185. Methods D 3280.
BASIC SULFATE WHITE LEAD 22. Basic Lead Oxide
22.1 Calculation—Calculate the percent of basic lead oxide
17. Small Amounts of Iron as follows:
17.1 Procedure—Determine small amounts of iron in ac-
Basic PbO, % 5 L 5 Su 1~0.736!
cordance with Section 7.
where:
18. Total Lead L 5 total lead as PbO, % (Section 18),
18.1 Procedure—Determine total lead in accordance with Su1 5 total sulfate as PbSO4, % (20.4), and
Section 88. 0.736 5 PbO/PbSO4 5 233.19/303.25.
19. Moisture and Other Volatile Matter 23. Total Impurities

19.1 Procedure—Determine moisture and other volatile 23.1 Calculation—Calculate the percent of total impurities
matter in accordance with Method A of Test Methods D 280. as follows:
Total impurities, % 5 100 2 ~L 1 Su 2 1 Z!
20. Total Sulfate
20.1 Apparatus—Gooch Crucible, ignited and weighed where:
prior to use. L 5 total lead as PbO, % (Section 18),
Su2 5 total sulfate as SO3, % (20.4), and
20.2 Reagents:
Z 5 zinc oxide, % (Section 21).
20.2.1 Barium Chloride Solution (100 g BaCl2/L)—
Dissolve 117 g of BaCl2·2H 2O in water and dilute to 1 L). 24. Coarse Particles
20.2.2 Bromine Water (saturated).
24.1 Procedure—Determine coarse particles in accordance
20.2.3 Hydrochloric Acid (1+1).
20.2.4 Sodium Chloride.
20.2.5 Sodium Carbonate Solution (saturated). PRECISION
20.3 Procedure:
20.3.1 Transfer 0.625 g of the sample to a 400-mL beaker. 25. Precision
Add 2 g of NaCl, 3 to 4 mL of bromine water, and 25 mL of 25.1 Data are not available to determine the precision of
HCl (1+1), and heat over a low flame until solution is these test methods. There are no plans at present to obtain such
complete. Dilute to 75 mL with water and bring to boiling to data. The test methods have been in use for many years and are
expel the bromine. Cool somewhat, but not enough for the considered acceptable.
PbCl2 to separate, and then cautiously add, by means of a pipet,
Na2CO3 solution until decidedly alkaline. Bring to boiling and 26. Keywords
transfer to a 250-mL volumetric flask. Cool to room tempera- 26.1 ammonium acetate soluble; pigment; basic carbonate;
ture, dilute to the mark, and mix. Filter through a dry paper, white lead; basic lead oxide pigment; basic sulfate white lead;
4
D 1301
carbon dioxide; pigment; chemical analysis; white lead pig-
ment; lead carbonate pigment
5

Phthalic Anhydride Content of Alkyd Resins and Esters
Containing Other Dibasic Acids (Gravimetric)1
1. Scope fitted with an air-cooled glass reflux condenser 30 in. (760 mm)
1.1 This test method covers the gravimetric determination in length. The connection between the flask and condenser
of phthalic anhydride in alkyd resins and esters that contain shall be a standard-taper 24/40 ground-glass joint.
dibasic acids such as maleic, fumaric, adipic, and sebacic, 5.2 Water Bath.
which would interfere if Test Method D 563 was used. 5.3 Guard Tube, filled with soda lime.
1.2 This standard does not purport to address all of the 5.4 Fritted-Glass Filter Crucible, medium porosity, of
safety concerns, if any, associated with its use. It is the 30-mL capacity.
responsibility of the user of this standard to establish appro- 5.5 Filter Flasks, suction-type.
priate safety and health practices and determine the applica- 5.6 Crucible Holder.
bility of regulatory limitations prior to use. 5.7 Oven, of gravity convection type.
5.8 Desiccator, containing concentrated H2SO4 (sp gr 1.84)
2. Referenced Documents as the desiccant.
2.1 ASTM Standards: 5.9 Flash Filtrator.
D 563 Test Method for Phthalic Anhydride Content of 5.10 pH Test Assembly.
Alkyd Resins and Resin Solutions2 5.11 Volumetric Flask, 100-mL.
D 1193 Specification for Reagent Water3 5.12 Erlenmeyer Flask, 250-mL, wide-mouth, with glass
stopper not smaller than a No. 27.
3. Summary of Test Method 5.13 Delivery Pipet, 2-mL.
3.1 The specimen is saponified with alcoholic potassium
6. Reagents
hydroxide and benzene to precipitate quantitatively the potas-
sium salt of phthalic acid as C6H4(COOH)2·C2H5OH. Interfer- 6.1 Purity of Reagent—Reagent grade chemicals shall be
ing substances are eliminated by dissolving the precipitate in used in all tests. Unless otherwise indicated, it is intended that
water, adjusting the pH of the solution to 2.5 with nitric acid, all reagents shall conform to the specifications of the Commit-
and filtering. Phthalic acid is then precipitated as nonstoichio- tee on Analytical Reagents of the American Chemical Society,
metric lead phthalate and calculated to phthalic anhydride, where such specifications are available.4 Other grades may be
using a factor obtained when compositions of known purity used, provided it is first ascertained that the reagent is of
were analyzed similarly. sufficiently high purity to permit its use without lessening the
4. Significance and Use 6.2 Purity of Water—Unless otherwise indicated, references
4.1 The phthalic anhydride content of alkyd resins controls to water shall be understood to mean reagent water as defined
the properties of the final film. by Type II of Specification D 1193.
6.3 Acetic Acid, Glacial.
5. Apparatus 6.4 Alcohol-Benzene Wash Solution—Mix 1 volume of
5.1 Flask and Condenser—A 500-mL Erlenmeyer flask absolute ethyl alcohol (Note 1) with 3 volumes of benzene.
1
4
and Related Coatings, Materials, and Applications, and is the direct responsibility of Reagent Chemicals, American Chemical Society Specifications, American
Subcommittee D01.33 on Polymers and Resins. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved May 27, 1988. Published October 1988. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1306 –54 T. Last previous edition D 1306 – 80. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1306
NOTE 1—The alcohol may be denatured Formula 2-B, but must be 7.5 Dissolve the contents of the crucible in 70 mL of water,
anhydrous. using a filtrator so as to collect the washings in a 250-mL
6.5 Benzene (anhydrous). beaker. Adjust the pH of the specimen to 2.5, using HNO3
6.6 Ether (anhydrous). (1 + 3) and a pH test assembly. After the specimen has stood 30
6.7 Lead Acetate Solution—Dissolve 25 g of lead acetate min or longer, filter through double thicknesses of the finest
trihydrate in glacial acetic acid and dilute to 100-mL volume paper directly into a 100-mL volumetric flask (Note 3). Dilute
with acetic acid. to volume with water, simultaneously using the water to wash
6.8 Methanol (anhydrous). the beaker and filter paper; mix thoroughly.
6.9 Nitric Acid (1 + 3)—Mix 1 volume of concentrated
NOTE 3—If the solution does not cloud when acidified, it may be
nitric acid (HNO3) (sp gr 1.42) with 3 volumes of water.
diluted to volume at once and the filtering omitted.
6.10 Potassium Hydroxide Alcoholic, Solution (66 g/L)—
Dissolve 66 g of potassium hydroxide (KOH) in 1 L of 7.6 Withdraw an aliquot containing not less than 60 nor
absolute ethyl alcohol (Note 1). Allow the solution to stand more than 90 mg of the dissolved salts. Transfer this aliquot
overnight protected against carbon dioxide (CO2) absorption. into the 250-mL Erlenmeyer flask. Dry the contents of the flask
Filter just before use. in the oven at 60°C. Add 5 mL of glacial acetic acid, vent the
stopper by inserting a paper strip under one side, and heat in
7. Procedure the oven at 60°C for 1 h. Add 100 mL of anhydrous methanol
7.1 Weigh by difference, from a closed container into the and continue heating in the oven with occasional agitation until
500-mL Erlenmeyer flask, a sample of resin or resin solution the material is completely dissolved. To the hot solution, add
sufficient to yield from 0.8 to 1.2 g of potassium alcohol slowly, by pipet, 2.0 mL of lead acetate solution. Agitate the
phthalate. Add 150 mL of benzene, warming slightly on the solution during the addition of this reagent. Return the flask to
steam bath if necessary, to effect solution. Add 60 mL of the 60°C oven for 1 h. Remove and stopper tightly after 30
alcoholic KOH solution, and attach the condenser. Place the min. Allow to stand 12 h or longer. Filter the solution through
flask in a water bath to a depth approximately equal to that of a dry tared fritted-glass crucible of medium porosity, to which
the contents of the flask. Warm the bath, maintaining a additional mats of coarse and fine asbestos have been added.
temperature of 40°C for 1 h, then gradually raise the tempera- Agitate the solution just before filtering. Wash the flask
ture until the alcoholic solution boils gently. Reflux for 11⁄2 h. thoroughly, using anhydrous methanol. Examine the filtrate
7.2 Remove the flask from the bath and wash down the carefully before discarding and, if cloudy, filter again through
inside of the condenser with a few millilitres of alcohol- the same crucible. Dry the crucible for 1 h at 105°C, cool in a
benzene wash solution. Remove the condenser, cap the flask desiccator, and weigh.
with the soda-lime guard tube, and cool by means of running
water or an ice bath. 8. Calculation
7.3 When cool, filter immediately and as rapidly as possible,
8.1 Calculate the percent of phthalic anhydride A in the
through a fritted-glass crucible that previously has been tared,
specimen as follows:
using the alcohol-benzene wash solution for transferring the
precipitate and washing the reaction flask. Wash the precipitate A 5 @~P 3 0.323!/S# 3 100 (1)
with successive portions of alcohol-benzene wash solution
where:
until a few millilitres of washings collected in a second suction P 5 lead precipitate, g, and
flask are no longer alkaline to phenolphthalein. (Normally S 5 specimen represented in the aliquot used, g.
about 75 mL of wash solution are sufficient.) Do not allow air
to be drawn through the crystals as they are hygroscopic. 9. Precision
Finally, pour 25 mL of ether into the crucible and draw through
the precipitate with the aid of suction. 9.1 Two results obtained by operators should be considered
7.4 Wipe the outer surface of the crucible with a clean cloth suspect if they differ by more than 1 % absolute.
and place in a gravity convection oven at 60°C for 1 h. Cool to
room temperature in a desiccator, and weigh. 10. Keywords
NOTE 2—The crucible weighings are for determining aliquot size and 10.1 alkyd resins; dibasic acids; esters; gravimetric; phthalic
need be weighed to the nearest 10 mg only. anhydride
2

Apparent Free Phenols in Synthetic Phenolic Resins or
Solutions Used for Coating Purposes1
1. Scope ISOLATION OF FREE PHENOLS

1.1 These test methods cover the determination of the 4. Apparatus
amount of apparent free phenol in synthetic phenolic resins or
solutions used for coating purposes. The test method for 4.1 Steam Generator.
isolation of the free phenol applies to all the commonly used 4.2 Distillation Flask—A 500-mL Kjeldahl flask.
resins except those containing p-phenyl-phenol. Test Method A 4.3 Condenser.
applies to the simpler phenols up to and including the xylenols; 5. Reagents
Test Method B applies to the common alkylated phenols.
1.2 This standard does not purport to address all of the 5.1 Sodium Hydroxide Solution (100 g NaOH/L)—
safety concerns, if any, associated with its use. It is the Dissolve 100 g of NaOH [Caution] in water and dilute to 1 L.
responsibility of the user of this standard to establish 6. Procedure
appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use. 6.1 Transfer 1 to 2 g of the sample, weighed to the nearest
0.01 g, to a 500-mL Kjeldahl flask. Add 50 mL of water. Lead
2. Referenced Documents steam from a steam generator through a T-trap and then
2.1 ASTM Standards: through a tube extending to the bottom of the flask. Take off the
D 1193 Specification for Reagent Water2 distillate through a second bent tube that extends just through
the stopper of the flask and is attached to the top of an inclined
3. Purity of Reagents long condenser. Using a 1000-mL volumetric flask as a
3.1 Reagent grade chemicals shall be used in all tests. receiver, collect 900 mL of the distillate. A small flame may be
Unless otherwise indicated, it is intended that all reagents shall applied to the bottom of the Kjeldahl flask during distillation to
conform to the specifications of the Committee on Analytical maintain the volume of water constant. If the distillate is clear,
Reagents of the American Chemical Society, where such dilute to 1000 mL; if not, add several millilitres of NaOH
specifications are available.3 Other grades may be used, solution to dissolve the insoluble phenols. Determine the
provided it is first ascertained that the reagent is of sufficiently apparent free phenol in accordance with Method A or B, as
high purity to permit its use without lessening the accuracy of required.
the determination. NOTE 1—p-Phenylphenol is not completely isolated by this procedure.
understood to mean reagent water conforming to Type III of TEST METHOD A—SIMPLER PHENOLS
7.1 Free phenols are isolated by steam distillation, reacted
1 with a measured excess of bromine, and the excess back-
and Related Coatings, Materials, and Applications and are the direct responsibility titrated with standard sodium thiosulfate solution.
of Subcommittee D01.33 on Polymers and Resins.
Current edition approved April 15, 1993. Published June 1993. Originally 8. Apparatus
2
8.1 Iodine Flasks, 500-mL, glass-stoppered.
3
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 9. Reagents
listed by the American Chemical Society, see Analar Standards for Laboratory 9.1 Bromide-Bromate Solution—Dissolve 2.784 g of KBrO3
and 10 g of KBr in 1 L of water.
MD. 9.2 Potassium Iodide Solution (100 g KI/L)—Dissolve 100
1
D 1312
g of KI in water and dilute to 1 L. 15. Reagents
9.3 Sodium Thiosulfate, Standard Solution (0.1 N)— 15.1 Iodine Solution—Dissolve 4.2 g of iodine in 15 g of a
Dissolve 25 g of Na2S2O3·5H2O in 1 L of water. Standardize saturated aqueous KI solution and dilute to 1 L.
against iodine. 15.2 Sodium Bicarbonate Solution (84 g NaHCO3/L)—
9.4 Starch Indicator Solution—Dissolve 1 g of soluble Dissolve 84 g of NaHCO3 in water and dilute to 1 L.
starch in 100 mL of boiling water and cool. 15.3 Sodium Hydroxide Solution (100 g NaOH/L)—
Dissolve 100 g of NaOH in water and dilute to 1 L.
10. Procedure
15.4 Sodium Thiosulfate, Standard Solution (0.1 N)—See
10.1 Pipet a 25-mL (or larger) aliquot of the distillate into a 7.3.
500-mL iodine flask. Add 25 mL of KBr - KBrO3 solution, 15.5 Starch Indicator Solution—See 9.4.
shake, and add 10 mL of HCl (sp gr 1.19). Stopper quickly, 15.6 Sulfuric Acid (1+19)—Add slowly, while stirring, 1
shake to mix thoroughly, and fill the gutter with water. Let volume of concentrated H2SO4 [Caution] (sp gr 1.84) to 19
stand 15 min. (If the bromine color disappears during the volumes of water.
shaking, take a fresh aliquot, add double the amount of bromate
solution, and proceed as described.) Raise the stopper carefully 16. Procedure
and add 10 mL of the KI solution. Shake, and wash down the 16.1 Add 15 mL of NaOH solution to the steam distillate
stopper and walls of the flask. Titrate with 0.1 N Na2S2O3, and dilute to 1 L. Add 100 mL of water to a 500-mL iodine
solution using 1 mL of starch indicator at the end. flask. Pipet a 10-mL (or larger) aliquot of distillate into the
10.2 Blank—Run a blank in exactly the same manner, flask (Note 3) and add 30 mL of the iodine solution. Stopper
except to omit the test material. and shake continuously for 5 min. Add 50 mL of H2SO4
(1 + 19) to the flask and titrate with 0.1 N Na2S2O3 solution to
11. Calculation a colorless end point, using 1 mL of starch solution as the
11.1 Calculate the percentage of apparent free phenols indicator.
(Note 2), as follows: NOTE 3—If the sample is pure p-phenylphenol, add 50 mL of the
Phenols, % 5 @~T1 2 T! N 3 1.567#/ W (1) NaHCO3 solution to the flask before the sample is added to prevent the
formation of color that interferes with the titration end point.
where: 16.2 Blank—Run a blank in exactly the same manner,
T1 5 Na2S2O3 solution required for titration of the blank, except omit the sample.
mL,
T 5 Na2S2O3 solution required for titration of the sample, 17. Calculation
mL, 17.1 Calculate the percentage of apparent free alkylphenols
N 5 normality of the Na2S2O3 solution, and (Note 4) as follows:
W 5 sample represented in the aliquot used, g.
Phenols, % 5 @~B 2 V! N 3 F#/ S (2)
NOTE 2—The cresols (CH3C6H4OH) and xylenols (CH3)2C6H3OH
have one or two reactive positions on the ring, depending on the isomer, where:
but their tendency to add more bromine as an addition product that is not B 5 Na2S2O3 solution required for titration of the blank,
later removed by KI renders the exact extent of reaction uncertain. Since mL,
those materials are ordinarily used as mixtures in a resin-forming reaction, V 5 Na2S2O3 solution required for titration of the sample,
it is convenient and sufficiently informative to express the amount found mL,
as primary phenol. N 5 normality of the Na2S2O3 solution,
F 5 conversion factor
12. Precision
5 3.755 for p-tertiary-butyl phenol
12.1 The individual test results should not differ from the 5 4.106 for p-tertiary-amyl phenol
mean by more than 60.5 %. 5 4.255 for p-phenyl phenol, and
S 5 sample represented in the aliquot used, g.
TEST METHOD B—COMMON ALKYLATED
PHENOLS NOTE 4—The alkyl phenols form normal di-iodo compounds.

18.1 The individual test results should not differ from the
13.1 Free phenols are isolated by steam distillation, reacted
mean by more than 60.5 %.
with a measured excess of iodine, and the excess back-titrated
18.2 Bias—No bias can be determined since no standard
with standard sodium thiosulfate solution.
phenolic resin is available.
14. Apparatus 19. Keywords
14.1 Iodine Flasks, 500-mL, glass stoppered. 19.1 free phenol; iodine solution; phenolic resin
2
D 1312
3

Viscosity of Cellulose Derivatives by Ball-Drop Method1
1. Scope D 871 Test Methods of Testing Cellulose Acetate3

1.1 This test method describes the apparatus and general E 691 Practice for Conducting an Introlaboratory Study to
procedure for making ball-drop viscosity measurements on Determine the Precision of a Test Method5
solutions of various cellulose derivatives. Instructions for 3. Summary of Test Method
sample preparation, solution concentration, and other details
are discussed in the ASTM methods for the respective cellulose 3.1 A solution of the cellulose derivative is made in a
derivatives. suitable solvent and allowed to equilibrate at a chosen tem-
1.2 This test method is applicable to solutions of various perature. A stainless steel or aluminum ball is dropped into the
cellulose derivatives having viscosities greater than 10 P, by solution, and the time required for it to cover a measured
using balls of various diameters and densities. Viscosity results distance in its fall is recorded. The viscosity of the solution can
are expressed preferably in poises. then be calculated in poise or recorded in seconds.
1.3 In commercial practice, viscosities are often expressed NOTE 1—The choice of solvent has significant influence on viscosity.
in seconds using 2.38–mm (3⁄32-in.) stainless steel balls.2 When
the viscosity is outside the practical range for these balls (75 to 4. Significance and Use
300 P), the measurement can be made using a calibrated pipet 4.1 This test provides an easy method of determining the
viscometer or a different ball and calculating the observed viscosity of cellulose derivatives in a given solvent. The
viscosity to the corresponding time for a 2.38-mm (3⁄32-in.) answers are in units commonly used in industrial practice.
ball, even though it is a small fraction of a second. Such information is needed for cellulose derivatives that are to
1.4 The values stated in SI units are to be regarded as the be extruded, molded, sprayed, or brushed as is or in solution.
only. 5. Apparatus
safety concerns, if any, associated with its use. It is the TABLE 1 Bottles
responsibility of the user of this standard to establish appro- Bottle Round Square
priate safety and health practices and determine the applica- Capacity, oz 16 16
bility of regulatory limitations prior to use. Weight, oz 12 12
Height, in. 6.7 7
2. Referenced Documents Inside diameter, cm 6.4
Side to side, cm ... 6.0
2.1 ASTM Standards: Corner to corner, cm ... 7.2
D 301 Test Methods for Soluble Cellulose Nitrate3
D 445 Test Method for Kinematic Viscosity of Transparent
and Opaque Liquids 4 5.1 Constant-Temperature Water Bath, glass-walled.
D 817 Test Methods of Testing Cellulose Acetate Propi- 5.1.1 For routine testing, an aquarium viscometer is recom-
onate and Cellulose Acetate Butyrate3 mended. This viscometer is a rectangular glass enclosure with
front and rear walls that have etched horizontal parallel lines
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 50.8 mm (2.00 6 0.02 in.) apart. The bottles containing the
and Related Coatings, Materials, and Applications and is the direct responsibility of samples solutions are set inside the viscometer at a level such
Subcommittee D01.36 on Cellulose and Cellulose Derivatives. that the upper etched line of the viscometer is at least 12.7 mm
Current edition approved Nov. 10, 1995. Published January 1996. Originally
(1⁄2 in.) below the upper surface of the solution in the bottle,
2
When a 3⁄32-in. stainless steel ball is used, the viscosities in seconds should be and the lower etched line of the viscometer is at least 12.7 mm
practically the same as those obtained using the apparatus described in Section 11 (1⁄2 in.) above the bottom of the sample bottle. Suitable lighting
of Test Methods D 871 – 48, and in Section 10 of Specifications D 301 – 50, which
last appeared in the 1952 Annual Book of ASTM Standards, Part 4.
3
4 5
1
D 1343
is provided to enable the observer to sight across the parallel 7. Procedure
etched lines, through the sample bottle and solution, avoiding 7.1 Preparation of Solution—Dry the sample and prepare a
in this manner parallax errors. With this viscometer no timing solution as specified for the particular material. Such instruc-
markers need to be provided on the bottles. tions are given in the viscosity sections of Test Methods D 301,
5.2 Bottles and Caps: D 871, and D 817. Weigh into the bottle an appropriate amount
5.2.1 Bottles, round or square, conforming to the dimen- of dry sample and specified solvent, accurate to 0.1 g, to make
sional requirements shown in Table 1, shall be used. Screw about 350 mL of solution. The accurate and precise make up of
caps of metal or phenolic plastic in sizes to fit the bottles and the solution is a necessity (example: 60.00 g of cellulose
having aluminum foil or cardboard and cellophane liners may acetate and 240.00 g solvent). Close the bottle tightly. Allow to
be used to close the bottles. Alternatively, rubber stoppers stand a short time for the solvent to penetrate the sample. Then
covered with aluminum or tin foil, may also be used as tumble or shake until a uniform solution is obtained. For some
closures. In this latter case, solvent loss during measurement of samples this may require several days. Transfer to the water
viscosity can be minimized by removing the stopper, leaving bath at 25 6 0.1°C, and allow the solution to come to
the foil in place, and making a small hole in the center of the temperature. A practical method to determine possible solvent
foil through which the balls may be dropped.
TABLE 2 Balls
Typical Data
Viscosity Range,
Ball Apparatus
P Diameter, cm Weight, g Density, g/cm3, a
Constant, K
⁄ -in. (1.59-mm) (aluminum)
1 16 10 to 50 0.256 0.1588 0.00591 2.82
⁄ -in. (1.59-mm) (stainless steel)

1 16 35 to 150 0.256 0.1588 0.01605 7.66
⁄ -in. (2.38-mm)
3 32 75 to 300 0.560 0.2380 0.0542 7.68
⁄ -in. (3.18-mm)
18 125 to 600 0.965 0.3170 0.1277 7.68
7⁄32-in. (5.56-mm) 350 to 1800 2.70 0.5556 0.6897 7.68
5.2.2 Timing marks shall be provided around each bottle or loss during this time involves weighing the bottle immediately
on the front and back of the glass-walled constant-temperature after adding the components, and again before performing the
water bath, to avoid parallax errors. The lower timing mark ball drop.
shall be at least 13 mm ( 0.5 in.) above the base of the bottle, 7.2 Viscosity Determination—Drop a 2.38-mm (3⁄32-in.)
and the upper mark shall be 50.8 6 0.5 mm (2.00 6 0.02 in. stainless steel ball through the center of the column of solution
) above the lower mark. A practical means of marking consists and time its fall through the marked 50.8-mm (2-in.) distance,
of wrapping a 50.8 mm (2-in.) strip of transparent sheeting
using a stop watch and taking precautions to avoid parallax
around the water bath at the proper location. The edges of the
errors. If the observed time is less than 15 s or greater than 100
sheeting may be darkened with crayon. A light located back of
s repeat the measurement, unless directed otherwise, using a
the water bath aids in observing the ball during its fall.
different ball (see Table 2) which has a time of fall within these
5.3 Balls—Unless specifically directed otherwise, balls of
limits. If the solution is known to be thixotropic in nature or if
varying size and density shall be used, depending on the
the times of fall for successive balls vary significantly, use
viscosity of the solution. Table 2 gives the useful ranges,
freshly prepared solutions for duplicate measurements or
approximate apparatus constants, and dimensions of several
such balls. The exact diameter, weight, and density shall be measurements with balls of other sizes.
determined accurately for each lot of balls used. 7.3 Determination of Lower Viscosities— If the viscosity of
5.4 Stop Watch—A stop watch reading to 0.2 s. the solution is too low to measure satisfactorily using one of
the balls, use a calibrated pipet as described in Test Method
6. Calibration D 445, or other instrument of suitable range. Calculate the
result in poises. Convert poises to equivalent ball-drop seconds
6.1 Calculate the apparatus constant, K, using the following as shown in 8.2.
equation and exact dimensions of the bottle and balls used:
K 5 2gr 2@1 2 2.104~d/D! 1 2.09~d/D! 3#/9L 8. Calculation
where: 8.1 Ball-Drop Viscosities—Calculate the viscosity in poises
g 5 acceleration of gravity in cgs units as follows:
r 5 ball radius, cm, h 5 K~a 2 b!t
d 5 ball diameter, cm,
D 5 bottle diameter, cm (in the case of square bottles the where:
average of the side to side and corner to corner h 5 viscosity at the specified temperature, P,
diameters shall be used), and K 5 apparatus constant,6
L 5 distance of ball drop, cm. a 5 ball density6, in g/cm3,
2
D 1343
b 5 solution density, given in referenced documents Test

Methods D 817 and D 871, g/cm3, and
t 5 time of fall, s.
In the case of a ball of stated diameter and density, this
calculation can be simplified to:6
h 5 F 3 t,
where:
F 5 K(a − b).
This factor varies with solution density, b. Approximate factors
for the various balls can be read from Fig. 1. Exact factors can
be calculated from the exact measurements of the viscometer
and balls.
8.2 Poises to Seconds—Poises may be converted to equiva-
lent ball-drop seconds, t, as follows:
t ~for 3/322in. ball! 5 h/K~a 2 b!
where:
h 5 observed viscosity, P,
K 5 apparatus constant for the 3⁄32 in. stainless steel ball,
a 5 ball density for the 3⁄32-in. stainless steel ball, and
b 5 solution density for the solution being tested.
9. Report
FIG. 1 Factors for Converting Viscosities in Seconds to Poises
9.1 Results shall be reported in poises, or in seconds, for a
3⁄32-in. stainless steel ball.
h5F3t
10. Precision and Bias ability standard deviation (Sr) and reproducibility standard
10.1 Precision—Table 3 is based on a round robin con- deviation (SR) have been calculated from a large enough body
TABLE 3 Precision Statistics from Round Robin Study According to Practice E 691
Laboratory Repeatability Reproducibility
Material Average Standard Standard Standard Repeatability Reproducibility
Deviation Deviation Deviation
CAB-381-20 20.35 0.823 0.458 0.942 1.28 2.64
CA-394-60 57.13 2.661 1.755 3.187 4.91 8.92
ducted in 1991 in accordance with Practice E 691, involving of data, and for test results that are averages of four ball drops
two materials (cellulose acetate and cellulose acetate butyrate), per dope, the information in 10.2.1 through 10.2.3 applies.
tested by eight laboratories.7 Both materials were prepared at 10.2.1 Repeatability, (r), is used for comparing two test
one source, which also provided the sample bottles and the results for the same material by the same operator using the
stainless steel balls. Each test result was the average of four same equipment. The two test results should be judged not
ball drops on one prepared dope. Each laboratory obtained equivalent if they differ by more than the r value for that
three test results (one test result was obtained each week). material.
NOTE 2—The following explanations of r and R (10.2 through 10.2.3) 10.2.2 Reproducibility, (R) is used for comparing two test
are only intended to present a meaningful way of considering the results for the same material, obtained by different operators
approximate precision of this test method. The data in Table 3 should not using different equipment. The two test results should be
be rigorously applied to acceptance or rejection of material, as those data judged not equivalent if they differ by more than the R value
are specific to the round robin and may not be representative of other lots, for that material.
conditions, materials, or laboratories. Users of this test method should
apply the principles outlined in Practice E 691 to generate data specific to
10.2.3 Any judgement in accordance with 10.2.1 or 10.2.2
their laboratory and materials, or between specific laboratories. The would have an approximate 95 % (0.95) probability of being
principles of 10.2 through 10.2.3, would then be valid for such data. correct.
10.2 Concept of Repeatability/Reproducbility—If repeat- 10.3 Bias—There are no recognized standards by which to
estimate bias of this test method.
6
See Table 2 for approximate values. 11. Keywords
7
Supporting data are available from ASTM Headquarters. Request RR:D 01-
1074. 11.1 ball drop; cellulose esters; viscosity
3
D 1343
4

Methylcellulose1
1. Scope high purity to permit its use without lessening the accuracy of
1.1 These test methods cover the testing of methylcellulose. the determination.
1.2 The test methods appear in the following order: 3.2 Unless otherwise indicated, references to water shall be
Sections
understood to mean distilled water.
Moisture 4 and 5
Ash—as Sulfate 6-8 MOISTURE
Chlorides—as Sodium Chloride 9-11
Alkalinity—as Na2CO3 12-14 4. Procedure
Iron 15-19
Heavy Metals 20-22 4.1 Transfer 2 to 5 g of the sample, weighed to the nearest
Methoxyl Content 23-26 0.01 g, to a tared dish (fitted with a lid) and dry it for 3 h in an
Viscosity:
Water-Soluble Methylcellulose 27-29
oven at 105 6 3°C. Remove the dish from the oven, cover it
Alkali-Soluble Methylcellulose 30 and 31 with a lid, cool in a desiccator, and weigh.
pH 32
Solids 33 and 34 5. Calculation
Density 35-39
5.1 Calculate the percent moisture, M, as follows:
1.3 This standard does not purport to address the safety
M 5 ~A/B! 3 100 (1)
concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and where:
health practices and determine the applicability of regulatory A 5 mass loss on heating, g, and
limitations prior to use. For a specific hazard statement, see B 5 sample used, g.
Note 1.
ASH—AS SULFATE
2.1 ASTM Standards: 6. Reagent
D 96 Test Methods for Water and Sediment in Crude Oil by 6.1 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
Centrifuge Method (Field Procedure)2 (H2SO4).
3. Purity of Reagents 7. Procedure
3.1 Reagent grade chemicals shall be used in all tests. 7.1 Weigh, to the nearest 0.01 g, about 2 g of the sample
Unless otherwise indicated, it is intended that all reagents shall (previously dried for 1⁄2 h at 105°C) and transfer it to a tared
conform to the specifications of the Committee on Analytical platinum crucible. Place it in a muffle furnace at 575 6 25°C
Reagents of the American Chemical Society, where such for approximately 1⁄2 h, to char the organic material.
specifications are available.3 Other grades may be used, pro- 7.2 Cool the crucible and add 1 mL of H2SO4 so that it
vided it is first ascertained that the reagent is of sufficiently completely wets the charred residue. Then cautiously heat it
over a small flame to dense white fumes. Place the crucible in
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint a muffle furnace at 575 6 25°C and leave it there until all signs
and Related Coatings, Materials, and Applications, and are the direct responsibility of carbon are gone (approximately 1 h). Transfer the specimen
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. to a desiccator until cool, then weigh.
Current edition approved Feb. 9, 1972. Published March 1972. Originally
2
8. Calculation
3
Reagent Chemicals, American Chemical Society Specifications, American 8.1 Calculate the percent of ash, C, as follows:
listed by the American Chemical Society, see Analar Standards for Laboratory C 5 ~A/B! 3 100 (2)
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, where:
MD.
1
D 1347
A 5 ash, g, and 13. Procedure

B 5 sample used, g. 13.1 Weigh, to the nearest 0.01 g, about 1.0 g of the sample
(previously dried for 1⁄2 h at 100 to 105°C) and transfer it to a
CHLORIDES—AS SODIUM CHLORIDE 500-mL wide-mouth Erlenmeyer flask. Add 250 mL of hot
9. Reagents water to the flask and swirl it for a few minutes, then cool to
dissolve.
9.1 Ferric Alum Indicator Solution—Add 100 g of ferric
13.2 Add 4 drops of methyl purple indicator to the flask
aluminum sulfate (Fe2SO4)3·(NH4)2SO4· 24H2O) to 250 mL of
solution and titrate to a blue-gray end point with 0.01 N H2SO4.
water. Heat it to boiling and add HNO3 (sp gr 1.42) slowly until
the red color is removed. This will usually require about 6 to 15 14. Calculation
mL of HNO3. Filter the solution and store it in a glass bottle.
14.1 Calculate the percent of alkalinity, D, as anhydrous
9.2 Potassium Thiocyanate, Solution, Standard (0.1 N)—
sodium carbonate (Na2CO3) as follows:
Dissolve 10 g of potassium thioagonate (KCNS) in 1 L of
water. By means of a pipet, measure 25 mL of 0.1000 N D 5 @~AB 3 0.053!/C# 3 100 (5)
AgNO3 solution into a 400-mL beaker. Add 100 mL of water,
where:
10 mL of nitric acid (NHO3, sp gr 1.42) and 5 mL of ferric A 5 H2SO4 required for titration of the sample, mL,
alum indicator solution. Titrate with the KCNS solution, while B 5 normality of the H2SO4, and
stirring, until a faint persistent red color is produced. Calculate C 5 sample used, g.
the normality of the KCNS solution, N, as follows:
N 5 ~A/B! 3 0.1 (3) IRON
where: 15. Apparatus

A 5 0.100 N AgNO3 solution added, mL, and 15.1 Photometer—Any photoelectric filter photometer or
B 5 KCNS solution required for the titration, mL. spectrophotometer suitable for measurements at 430 nm.
9.3 Silver Nitrate, Solution, Standard (0.1 N)—Grind silver 15.2 Kjeldahl Flasks, calibrated to contain 30 mL, and made
nitrate (AgNO3) crystals fine enough to pass through a 850-µm of heat- and chemical-resistant glass.
(No. 20) sieve, and then dry for 2 h at 110°C. Prepare a 0.1000
N solution by dissolving 16.989 g of dry AgNO3 in chloride- 16. Reagents
free water and diluting it to 1 L in a volumetric flask. 16.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
10. Procedure monium hydroxide (NH4OH).
16.2 Buffer Solution—Dissolve 20 g of sodium bicarbonate
10.1 Weigh, to the nearest 0.01 g, about 1.0 g of the sample (NaHCO3) and 10 g of sodium carbonate (Na2CO3) in water
(previously dried for 1⁄2 h at 100 to 105°C) and transfer to a and dilute to 1 L.
500-mL wide-mouth Erlenmeyer flask. Add 250 mL of hot 16.3 Disodium-1,2-Dihydroxybenzene-3,5-Disulfonate
water to the flask and swirl it for a few minutes, then cool to Solution4—Prepare an aqueous solution containing 25 g/L.
dissolve. 16.4 Hydrogen Peroxide (30 %)—Concentrated hydrogen
10.2 Add 5 mL of 0.1000 N AgNO3 solution and 5 mL of peroxide (H2O2).
ferric alum indicator solution, and then back-titrate with 0.1 N 16.5 Iron, Solution, Standard (0.0001 g Fe/mL)—Dissolve
KCNS solution to the first appearance of a faint pink color. 0.01 g of iron powder containing not less than 99.9 % Fe in
11. Calculation hydrochloric acid (HCl, sp gr 1.19). Oxidize the solution with
bromine water and expel the excess by boiling. Dilute to 1 L in
11.1 Calculate the percent of chlorides, C, as sodium
a volumetric flask.
chloride (NaCl) as follows:
16.6 Phenolphthalein Indicator Solution.
C 5 ~@~AB 2 CD! 3 0.0585#/E! 3 100 (4) 16.7 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H2SO4).
where:
A 5 AgNO3 solution added, mL, 16.8 Sulfuric Acid (1 + 4)—Carefully mix 1 volume of
B 5 normality of the AgNO3 solution, H2SO4 (sp gr 1.84) with 4 volumes of water, adding the H2SO4
C 5 KCNS solution required to back-titrate the excess gradually while mixing.
AgNO3, mL,
D 5 normality of the KCNS solution, and 17. Preparation of Calibration Curve
E 5 sample used, g. 17.1 Following the procedure given in Section 18, and using
varied amounts of the standard iron solution prepared in
ALKALINITY—AS SODIUM CARBONATE, accordance with 16.1, prepare a calibration curve showing iron
ANHYDROUS content in parts per million and the corresponding photometer
readings.
12. Reagents
12.1 Methyl Purple Indicator Solution.
12.2 Sulfuric Acid, Standard (0.01 N)—Prepare and stan- 4
A suitable prepared solution of this reagent, known as Tiron, is available from
dardize a 0.01 N solution of sulfuric acid (H2SO4). the La Motte Chemical Products Co., Chestertown, MD.
2
D 1347
18. Procedure tions 6 and 7). Digest the residue by slowly boiling for a few
18.1 Weigh approximately 2 g of the sample of methylcel- minutes over a small flame. Transfer the contents of the
lulose to the nearest 0.01 g, and transfer by means of a funnel crucible to a 50-mL volumetric flask, using about 25 mL of
to a Kjeldahl flask. Place the flask at a 20° angle in a furnace water to rinse the crucible. Neutralize with NH4OH (1 + 5) to
at 600°C, or on a microdigestion rack equipped with electric a phenolphthalein end point and dilute to 50 mL.
heating elements, and heat until some charring of the methyl- 22.2 Transfer a 25-mL aliquot of the solution to a 50-mL
cellulose has taken place. (Care must be taken not to char too Nessler tube, and add 2 mL of acetic acid (6 + 94) and 10 mL
much.) Remove and allow to cool. of a saturated solution of H2S. Mix, allow to stand for 10 min,
18.2 Add 3 mL of concentrated H2SO4 to the flask. Place the and compare with a standard lead solution to which H2S has
flask on the digestion rack and digest. Cool, and add H2O2 been added.
dropwise until the solution is clear. Heat over a Meker burner 22.3 Report the lead content in parts per million.
to a volume of 2 mL. Cool, and wash the sides of the flask with
METHOXYL CONTENT
water. Add 3 drops of phenolphthalein indicator solution. Add
NH4OH to a red end point. Wash the neck of the flask. The 23. Apparatus
solution should be clear and not greater than 20 mL in volume.
18.3 Add 2 mL of the color-forming solution described in 23.1 Distillation Apparatus (Fig. 1), consisting of a boiling
16.3 and mix. Dilute to near the mark with buffer solution and flask with a side arm for admission of carbon dioxide (CO2) or
mix thoroughly. Adjust the solution to a pH of 7 by adding nitrogen, an air condenser with a trap, and a receiver.
NH4OH or H2SO4 (1 + 4), and then dilute to the mark. Transfer 23.2 Oil Bath, equipped with a heating device, preferably
a small portion to an absorption cell and determine the electrical, so that the bath can be maintained at 145 to 150°C.
photometer reading at 430 nm. 24. Reagents and Materials
19. Calculation 24.1 Bromine Solution—Dissolve 5 mL of bromine in 145
19.1 Read the iron content, in parts per million, directly mL of the potassium acetate solution. Prepare the bromine
from the calibration curve (Section 17). solution fresh daily in a hood to remove bromine vapors.
24.2 Carbon Dioxide—This may be obtained by the inter-
HEAVY METALS action of marble and HCl (1 + 1) in a Kipp generator or,
20. Apparatus preferably, from a cylinder of the gas equipped with a suitable
20.1 Nessler Tubes, 50-mL. needle valve. The CO2 shall be passed through a bubble
20.2 Volumetric Flasks, 50-mL.
21. Reagents
21.1 Acetic Acid (6 + 94)—Mix 6 volumes of glacial acetic
acid with 94 volumes of water.
21.2 Ammonium Hydroxide (1 + 5)—Mix 1 volume of con-
centrated ammonium hydroxide (NH4OH, sp gr 0.90) with 5
volumes of water.
21.3 Hydrochloric Acid (1 + 3)—Mix 1 volume of concen-
trated hydrochloric acid (HCl, sp gr 1.19) with 3 volumes of
water.
21.4 Hydrogen Sulfide Solution (Saturated)—Saturate cold
water with hydrogen sulfide (H2S).
21.5 Lead, Solution, Standard (1 mL 5 0.1 mg Pb)—
Dissolve 0.1598 g of lead nitrate (Pb(NO3)2) in 100 mL of
water to which has been added 1 mL of concentrated nitric acid
(HNO3, sp gr 1.42). Dilute to 1000 mL with water.
21.6 Lead, Solution, Standard (1 mL 5 0.01 mg Pb)—
Dilute 10.0 mL of Pb(NO3)2 solution (1 mL 5 0.1 mg Pb) to
100 mL with water. This solution must be freshly prepared.
When 0.1 mL of this standard lead solution is employed to
prepare the standard to be compared with a solution of 1 g of
the substance being tested, the comparison solution thus
prepared contains the equivalent of one part of lead per million
parts of the substance tested.
21.7 Phenolphthalein Indicator Solution.
22. Procedure
22.1 Add 5 mL of HCl (1 + 3) to the residue in the platinum
crucible that was used in the sulfate ash determination (Sec- FIG. 1 Distillation Apparatus for Methoxyl Determination
3
D 1347
counter and a dry trap, and then through a pressure regulator using starch indicator solution near the end point. At the end
consisting of a glass tee whose vertical arm extends almost to point, the blue color of the starch indicator will be destroyed,
the bottom of a 254-mm column of water. A screw clamp is leaving the pale green color of the chromate ion. The normality
attached to the thin-walled rubber tubing connecting the of the Na2S2O3 solution should be checked at least once a
horizontal arm of the tee with the boiling flask. This arrange- week. Calculate the normality of the Na2S2O3 solution, N, as
ment permits regulation of the flow of gas and allows any follows:
excess gas to escape. Nitrogen may be used in place of CO2. N 5 ~A/B! 3 0.1 (6)
24.3 Formic Acid (HCOOH, 90 %).
24.4 Gelatin Capsules—Gelatin capsules of a suitable size where:
to hold 50 to 60 mg of the dried specimen will be required. A 5 0.1000 N K2Cr2O7 solution added, mL, and
24.5 Hydriodic Acid (57 %, sp gr 1.70)—Hydriodic acid B 5 Na2S2O3 solution required for the titration, mL.
(HI) forms with water a constant-boiling mixture (boiling point As an alternative procedure, the Na2S2O3 solution may be
126 to 127°C) which contains 57 % HI. The concentration of standardized against 0.1 N iodine solution that has been
HI in the reagent used should be not less than 56.5 %. The standardized in turn against arsenic trioxide (As2O3, National
blank determination, which is affected primarily by free iodine Institute of Standards and Technology Standard Sample No.
in the reagent, should require not more than 0.5 mL of 0.1 N 83) or potassium iodate (KIO3).
sodium thiosulfate (Na2S2O3) solution.5 If necessary, the acid 24.10 Starch Indicator Solution.
may be purified by adding to it a small amount of red 24.11 Sulfuric Acid (1 + 9)—Carefully mix 1 volume of
phosphorus and boiling for 20 to 30 min in a hood, while concentrated sulfuric acid (H2SO4, sp gr 1.84) with 9 volumes
passing a stream of CO2 into the liquid. Distillation shall then of water, adding the H2SO4 gradually while mixing.
be carried out behind a safety glass shield in a hood, using an
all-glass apparatus with a slow stream of CO2 running through 25. Procedure
the receiver.
25.1 Dry the sample at 105°C for at least 30 min. Through
NOTE 1—Warning: Under some conditions, the poisonous gas phos- the condenser, add to the trap in the distillation apparatus (Fig.
phine (PH3) is formed during distillation and this may unite with 1) enough distilled water to make the trap about half full. Add
molecular iodine to form phosphorus triiodide (PI3), which may explode
on contact with air. It is, therefore, advisable to keep the current of CO2
8 to 9 mL of bromine solution to the receiver. Weigh 50 to 60
going after the distillation is ended and until the apparatus has cooled; this mg of the dry sample, to the nearest 0.1 mg, into a gelatin
will prevent air from being sucked into the apparatus. Put the purified HI capsule and drop it into the boiling flask. (The weighing should
in small, brown, glass-stoppered bottles, previously swept out with CO2 be done as rapidly as possible without sacrificing accuracy,
and seal the stoppers with molten paraffin. Store in a dark place. To since dry methylcellulose picks up moisture rapidly.)
minimize decomposition of HI due to contact with air, run CO2 into the
25.2 Add a few small glass beads or chips of clay plate and
bottle while withdrawing portions of the acid for use.
then 6 mL of HI. Attach the boiling flask at once to the
24.6 Potassium Acetate Solution—Dissolve 100 g of anhy- condenser, using a few drops of HI to moisten the ground-glass
drous potassium acetate crystals in 1 L of a solution containing joint, and then connect the side arm of the flask to the source
900 mL of glacial acetic acid and 100 mL of acetic anhydride. of CO2. Pass a current of CO2 into the apparatus at the rate of
24.7 Potassium Iodide (KI). about 2 bubbles/s. Immerse the flask in the oil bath, maintained
24.8 Sodium Acetate Solution (220 g/L)—Dissolve 220 g of at 150°C, and heat for 50 min.
anhydrous sodium acetate in water and dilute to 1 L. 25.3 Add 10 mL of sodium acetate solution to a 500-mL
24.9 Sodium Thiosulfate Solution, Standard (0.1 N)— Erlenmeyer flask and wash into it the contents of the receiver;
Dissolve 25 g of sodium thiosulfate (Na2S2O3 · 5H2O) in 200 dilute to 125 mL with water. Add HCOOH dropwise, with
mL of water and dilute to 1 L. Use freshly boiled and cooled swirling, until the brown color of bromine is discharged, and
water. It is preferable to allow the solution to stand for a few then add about 6 drops more. A total of 12 to 15 drops is
days before standardization. Standardize the solution against usually required. After about 3 min add 3 g of KI and 15 mL
0.1000 N potassium dichromate (K2Cr2O7) solution prepared of H2SO4 (1 + 9) and titrate immediately with 0.1 N Na2S2O3
by dissolving exactly 4.9037 g of K2Cr2O7 (National Institute solution to a light straw color. Add a little starch solution and
of Standards and Technology Standard Sample No. 136) in continue the titration to the disappearance of the blue color.
water and diluting to 1 L in a volumetric flask. By means of a
25.4 Blank—Make a blank determination, using the same
buret, measure accurately 35 to 45 mL of the K2Cr2O7 solution
amounts of reagents and the same procedure as for the sample.
into a 250-mL Erlenmeyer flask. Add 2 g of KI and 50 mL of
(Usually, about 0.1 mL of 0.1 N Na2S2O3 solution is required.)
H2SO4 (1 + 9) and allow to stand for about 5 min. The flask
should be stoppered during the standing period to avoid loss of
26. Calculation
iodine. Titrate the liberated iodine with the Na2S2O3 solution,
26.1 Calculate the percent of methoxyl, M, as follows:
M 5 @~~A – B!C 3 0.00517!/D# 3 100 (7)
5
Hydriodic acid suitable for methoxyl determination may be prepared by the
method of Samsel, E. P., and McHard, J. A., Industrial and Engineering Chemistry, where:
Analytical Edition, Vol 14, 1942, p. 750. Hydriodic acid available from Merck & A 5 Na2S2O3 solution required for titration of the sample,
Co., WBC 220, P.O. Box 2000, Rahway, NJ 07065 under the designation “For
Methoxyl Determination” has been found satisfactory for this purpose.
mL,
4
D 1347
B 5 Na2S2O3 solution required for titration of the blank, 5 @100/~100– moisture content, %!# 3 2
mL, 28.3 Place the sample in an 8-oz (250-cm3) wide-mouth
C 5 normality of the Na2S2O3 solution, and bottle. This weighing step is critical in obtaining good checks
D 5 sample used, g. and should be done on a good balance sensitive to 1 mg.
Weights to the nearest 0.01 g will be sufficiently accurate.
VISCOSITY OF WATER-SOLUBLE
28.4 Add 98.0 g of hot water (85 to 90°C) to the 8-oz bottle
METHYLCELLULOSE
containing the 2-g specimen of methylcellulose.
27. Apparatus 28.5 Agitate with a mechanical stirrer for 10 min, then place
the bottle in an ice bath (0 to 5°C) until solution is complete.
27.1 Viscometer, Fig. 2(a) or (b).
Equip the stirrer assembly with a one-hole stopper or bottle cap
NOTE 2—If a viscometer has been repaired, it should be recalibrated so that no water vapor is lost during agitation. For precision, it
before it is used again. Even minor repairs can cause significant changes is preferable to deair the solution by some means such as
in the K value. centrifuging.
27.2 Mechanical Stirrer. 28.6 When solution is complete, as evidenced by the ab-
sence of partially swollen or undispersed particles, determine
28. Procedure the viscosity in a methylcellulose viscometer at 20 6 0.1°C.
28.1 Determine the moisture content of a portion of the Observe two precautions at this point: (1) the solution shall be
sample. Since cellulose and its water-soluble derivatives are essentially free of air bubbles, and (2) the temperature of the
hygroscopic, exposure of the sample to the atmosphere should material in the tube shall be checked to make certain that it is
be kept to a minimum. Changes in moisture content can actually at the bath temperature.
introduce large errors into the accuracy of the determination 28.7 The methylcellulose viscosity tube (Fig. 2) consists of
and this step should never be omitted if precise results are three parts: (1) a large filling tube with a reservoir at its lower
desired. extremity, A; (2) the orifice tube, B; and (3) an air vent to the
28.2 Correcting for the moisture content, weigh out enough reservoir, C. When B is filled, close C to prevent the sucking of
of the sample of undried methylcellulose to give 2.000 g of air bubbles into the orifice tube.
solids, calculated as follows: 28.8 Before the specimen is allowed to flow through the
Weight of specimen, g (8) orifice for the viscosity determination, open the vent, C, so that
FIG. 2 Methylcellulose Viscometers
5
D 1347
the column of solution in B will flow into the reservoir against 34. Procedure
atmospheric pressure. Failure to open C before running will 34.1 Add 1.50 g of bone-dry methylcellulose to 148.5 g of
cause false values in the viscosity results. 90°C water in a 21⁄4 by 6-in. (32 by 152-mm) bottle and agitate
vigorously for about 15 min, or until the material has become
29. Calculation
finely divided. Place an ice bath around the bottle and agitate
29.1 Calculate the viscosity as follows: the mixture until the solution is effected. (This usually requires
V 5 Kdt (9) about 15 min.)
34.2 Place 100 mL of this 1 % solution in an oil tube, cool
where: to 10°C, and centrifuge at 725 times gravity for 5 min. The
V 5 viscosity, cP, solution temperature shall be below 20°C when finished. Read
K 5 viscometer constant (Note 2),
the volume percent of solids from the graduations on the tube.
d 5 density of the methylcellulose solution at 20/20°C
(Note 3), and DENSITY
t 5 time for the solution to pass from the upper to the 35. Scope
lower mark of the viscometer, s.
35.1 This test method covers the determination of the bulk
NOTE 3—The viscometer constant is determined by passing a standard density of methylcellulose.
oil of known viscosity through the tube and determining the time of flow.
The above equation can then be solved for K. 36. Summary of Test Method
NOTE 4—For routine work, the density of solutions of methylcellulose 36.1 A weighed amount of methylcellulose is transferred to
may be assumed to be 1.00. a 250-mL graduated cylinder and the graduate vibrated to settle
VISCOSITY OF ALKALI-SOLUBLE the powder.
METHYLCELLULOSE 37. Apparatus
30. Reagents 37.1 Vibrator—A magnetic-type electric vibrator attached
to the vertical support rod of a ring stand approximately 1 ft
30.1 Sodium Hydroxide Solution (40 g NaOH/L)—Dissolve (0.3 m) above the base. A condenser clamp of sufficient size to
40 g of sodium hydroxide (NaOH) in carbon dioxide (CO2)- hold a 250-mL graduated cylinder also shall be attached to the
free water and dilute to 1 L. above rod. The base of the stand should be weighted.
31.1 Proceed as directed in Sections 28 and 29, except add 38.1 Place 50.0 g of methylcellulose in a 250-mL graduated
98.0 g of the NaOH solution to the sample, instead of adding cylinder and place the cylinder in the condenser clamp. Turn on
hot water in accordance with 28.3. the vibrator and allow the cylinder to vibrate for 3 min. Record
the level (in millilitres) to which the specimen has compacted.
pH 38.2 Alternatively, the specimen may be compacted manu-
ally. Tap it on a hard surface by dropping the cylinder
32. Procedure
repeatedly from a height of about 1 in. (25 mm), until the
32.1 Determine the pH of the viscosity solution from volume of the specimen remains constant. In order to prevent
Section 28, using any suitable pH meter. cylinder breakage, cover the tapping surface with a 1⁄8 to 1⁄4-in.
(3 to 6-mm) thick rubber sheet, or use a plastic graduated
SOLIDS cylinder.
33. Apparatus 39. Calculation
33.1 Oil Tubes, graduated, 100-mL, tapered, conforming to 39.1 Calculate the density, D, in grams per millilitre as
the requirements prescribed in 3.2 and Fig. 1 of Test Methods follows:
D 96. D 5 50/observed reading, mL (10)
33.2 Centrifuge, capable of whirling filled centrifuge tubes
at a speed that will produce a centrifugal force of 725 times 40. Keywords
gravity. 40.1 ball drop; cellulose esters; viscosity
6

Moisture in Cellulose1
1. Scope 3.1.2 Except for those samples taken in an atmosphere with

1.1 These test methods cover the determination of moisture which the sample is in equilibrium, the moisture content of the
in cellulose using two oven-drying procedures and one Karl sample will begin to change immediately after it is removed
Fischer procedure. from its original surroundings. This change can be reduced by
1.2 The test procedures appear in the following order: taking extra layers of sheeted material and discarding a few
Sections
layers from the top and bottom before weighing, folding, or
Test Method A—Specimen Weighed in Oven 4-10 rolling the sample to reduce the exposed area, and by placing
Test Method B—Specimen Weighed Outside of Oven 11-17 small samples in cans or bottles and protecting larger samples
Test Method C—Karl Fischer Method 18-25
by wrapping in rubber sheets, moistureproof cellophane, or
1.3 The values stated in SI units are to be regarded as the other protective wrappings. These means do not provide
standard. The values given in parentheses are for information continuous protection, and the test samples should be weighed
only. as soon as possible.
1.4 This standard does not purport to address all of the 3.1.3 When possible, bulk samples should be taken. These
safety concerns, if any, associated with its use. It is the samples should weigh from 100 to 300 g (3.5 to 10.5 oz), the
responsibility of the user of this standard to establish appro- larger samples being taken when the moisture content is low or
priate safety and health practices and determine the applica- variable. Following the initial weighing, the bulk samples
bility of regulatory limitations prior to use. should be cut up or torn into small pieces and then mixed and
allowed to stand overnight or longer in a sealed container to
2. Significance and Use obtain moisture equilibrium before weighing out test speci-
2.1 These test methods determine the amount of moisture mens; or the sample may be allowed to come to approximate
contained in a cellulose sample which determines the amount equilibrium with the laboratory air and reweighed to determine
of bone dry cellulose present in a sample. The actual amount of moisture change before weighing test specimens. The latter
cellulose in a sample is an essential entity when using cellulose procedure is recommended since it permits routine weighing of
as a starting material for the production of cellulose deriva- samples without the use of special weighing bottles or boxes,
tives. and a series of accumulated samples can be weighed simulta-
neously. Predrying is very desirable on samples with a high
3. Sampling moisture content (more than 5 % above equilibrium value).
3.1 Cellulose in a variety of forms is sampled for moisture, When samples have been predried, calculate the moisture lost,
and no single set of directions can be given that is applicable as follows:
to all types of cellulose material. The following general R 5 @M – A/A# 3 100 (1)
considerations should be borne in mind.
3.1.1 Cellulose, either in compact form, such as wood, where:
sheeted pulp or paper, baled cotton or baled staple rayon, or in R 5 moisture, air-dry sample basis, %,
loose form such as sawdust or chips, may have an appreciably M 5 original mass of the sample, g, and
different moisture content in sections lying relatively close A 5 air-dry mass of sample, g.
together. In order to secure representative samples, therefore, a 3.1.4 The apparent moisture subsequently observed when
bulk sample should be made up of small portions taken from testing a predried sample must be calculated on the basis of the
various parts of the lot and having the proper proportion of original sample mass in order to get the original moisture
edge and center material. content. Calculate the original mass of the air-dried sample as
follows:
Original sample mass, g 5 @A 3 ~100 1 R!#/100 (2)
1
NOTE 1—Example—If 1000 g (35 oz) of bulk (wet) sample on exposure
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. to air lose 200 g (7 oz) of water, the apparent moisture content is 20 % and
Current edition approved Oct. 15, 1994. Published December 1994. Originally equivalent regain is 25 %. If an 8-g (0.28-oz) specimen of the air-dry
1
D 1348
material is taken for drying in the oven, the original mass is 8 3 1.25 5 10 7.2 Dry the specimen for 2 h at 105 6 3°C, passing a
g (0.35 oz). current of dry air into the bottom of the oven during the drying
period. (If dry air is not forced through the oven, dry for 4 h.)
TEST METHOD A—SPECIMEN WEIGHED IN OVEN
NOTE 4—Reproducible but less accurate values (under unfavorable
4. Scope conditions the absolute error may be as high as 1 %) will be obtained if the
4.1 This test method for moisture determination is appli- current of predried air is omitted. Since the error will be identical for all
cable to a variety of cellulose types and can be used in most similar samples in the oven at one time, the results obtained in these cases
will be comparable. The magnitude of error will vary directly with the
cases where a sample does not contain nonaqueous material relative humidity of the air entering the oven and with the equilibrium
volatile at 105°C. The test method can be used for samples moisture content of samples at low relative humidity. Thus, the error will
having either high or low moisture content. be higher on regenerated cellulose than on wood pulp or cotton, but it still
would not usually be greater than 0.2 %, absolute.
7.3 At the end of the specified period, cut off the flow of air
5.1 The specimen is heated to constant mass at 105°C in a and weigh the specimen without removing it from the oven.
ventilated gravity-convection oven, in a current of dry air, for Continue drying for ½ h longer, with the normal air flow, and
a period of 2 h. If no dry air is used, the specimen is heated for reweigh the specimen. Repeat the drying and weighing until
4 h. the mass loss between successive weighings is not more than
6. Apparatus 0.005 g, or until the specimen shows a gain in mass. Designate
this mass as D.
6.1 Oven with Built-In Weighing Equipment—Such an oven
7.4 Additional specimens should not be placed in the oven
employs a system of tared containers mounted on a table or
until the first specimens have attained constant mass.
track that can be rotated to bring specimens to a specific point
in the oven, where the specimen and container can be placed on 8. Calculation
a hook or a tray connected to an outside balance. The oven 8.1 Calculate moisture, as measured in the oven, as follows:
must be capable of maintaining a constant temperature of 105
6 3°C, with an average temperature of 105°C; continuous Moisture content, % 5 @~M – D/M# 3 100 (3)
operation below 105°C is not satisfactory. Moisture, dry basis ~regain!, % 5 @~M – D!/D# 3 100 (4)
NOTE 2—In ovens having heating elements at the bottom only, and no where:
cross circulation, the temperature of the lower shelves should be checked M 5 original mass of specimen, and .
before they are used. D 5 mass of oven-dry specimen.
6.2 Dry Air Stream—Air, dried by passing through silica
gel, aluminum oxide, concentrated sulfuric acid, or other 9. Report
suitable drying agent, should be passed through the oven at a 9.1 Report the moisture in the cellulose on either or both of
rate sufficient to effect a complete change once every 2 min. If the following bases:
the air is dried by means of concentrated sulfuric acid, 9.1.1 On the basis of the original sample, when it is termed
adequate traps must be provided. The use of sulfuric acid “moisture content,” “moisture as received,” or “moisture as is”
followed by perchloric drying agents should be avoided. basis.
6.3 Shallow Glass Weighing Bottles—Bottles with ground 9.1.2 On the basis of the oven-dry cellulose, when it is
glass stoppers, measuring 30 mm high, and having a capacity termed “moisture, dry basis” or “moisture regain.”
of 30 mL. 9.2 In order to avoid confusion always use the appropriate
6.4 Seamless Metal Weighing Boxes, having a wall height, term.
when open, preferably not over 25.4 mm (1 in.).
7. Procedure 10.1 Precision:
7.1 Remove the basket, shallow pan, or other container 10.1.1 Statistical analysis of intralaboratory (repeatability)
supplied for use with the oven (Note 3). Weigh the container test results on samples containing 5 to 15 % moisture indicates
and place in it a specimen of 10 to 50 g (0.35 to 1.75 oz) a precision of 60.14 % at the 95 % confidence level.
weighed to the nearest 0.005 g. Designate this mass as M. Place 10.1.2 Statistical analysis of interlaboratory (reproducibil-
the specimen in a tared container in the oven in such a manner ity) test results on samples containing 5 to 15 % moisture
that it can be reweighed without removal from the oven. indicates a precision of 60.2 % at the 95 % confidence level.
10.2 Bias—No justifiable statement can be made on the bias
NOTE 3—Experience has shown that when yarn and fiber specimens are of the procedure for measuring moisture in cellulose because
left in comparatively deep weighing bottles in the oven, relatively
discordant results are obtained and the drying period is unnecessarily long.
no suitable reference material exists.
To avoid these difficulties specimens should be dried in containers that TEST METHOD B—SPECIMEN WEIGHED OUTSIDE
give the cellulose free access to the air. For fibrous or bulky materials to
be weighed in an oven, use containers such as open wire grills or baskets.
OF OVEN
For small specimens to be weighed out of the oven, use wire screen 11. Scope
baskets that will fit in weighing bottles, but if the specimen is powdery or
tends to shed lint or fine short fibers, use a small weighing bottle or metal 11.1 The scope and application of this test method are the
boxes. same as those of Test Method A (see Section 4).
2
D 1348
12. Summary of Test Method 15. Calculation
12.1 See Test Method A (Section 5). 15.1 Calculate moisture, as measured outside of the oven, as
follows:
13. Apparatus
Moisture content, % @~M – D!/~M – T!# 3 100 (5)
13.1 Oven Without Built-In Weighing Equipment—Any
Moisture, dry basis, ~regain!, % 5 @~M – D!/~D – T!# 3 100 (6)
ventilated oven capable of maintaining a constant temperature
of 105 6 3°C, with an average temperature of 105°C; where:
continuous operation below 105°C is not satisfactory. M 5 original mass of the specimen (plus basket) and
NOTE 5—In ovens having heating elements at the bottom only, and no weighing bottle,
cross circulation, the temperature of the lower shelves should be checked D 5 oven-dry mass of the specimen (plus basket), and
before they are used. T 5 mass of the empty weighing bottle (plus basket).
13.2 Dry Air Stream—See 6.2. 16. Report
13.3 Shallow Glass Weighing Bottles—See 6.3. 16.1 Report the moisture in the cellulose as directed in
13.4 Seamless Metal Weighing Boxes—See 6.4. Section 9.
13.5 Weighing Bottles, glass with ground-glass stoppers,
approximately 40 mm wide and 80 mm high. 17. Precision and Bias
13.6 Wire Baskets—Fitted baskets for weighing bottles 17.1 See Section 10.
made from approximately 15-mesh stainless steel, Monel, or
other suitable screen. The height and depth of the basket will be TEST METHOD C—KARL FISCHER METHOD
determined by the weighing bottle used; the basket must slide 18. Scope
into and out of the bottle without binding. The basket should
18.1 This test method covers the determination of moisture
have a solid bottom, but no top is required.
in cellulose by titration with Karl Fischer reagent. The test
14. Procedure method is applicable to all types and forms of cellulose. It is
especially useful with samples containing nonaqueous material
14.1 If the sample is free of lint, dust, or short fibers, place volatile at 110°C, since such substances interfere in the
approximately 10 g (0.35 oz) of the sample into a previously oven-drying methods. Anhydrides, alkalies, and large amounts
dried and desiccated wire basket (Note 2) contained in a dry of aldehydes and ketones interfere.
weighing bottle. Stopper the weighing bottle, and weigh to the 18.2 The Karl Fischer titration method is especially valu-
nearest 0.001 g. Designate this mass as M. Remove the basket able where only small amounts of samples are available. The
containing the specimen from the weighing bottle and place the procedure lends itself to multiple determinations.
basket, weighing bottle, and stopper in the oven. If the 18.3 It is essential that the Karl Fischer reagent, standard
specimen includes powder-like material, transfer the specimen water solution, and anhydrous methanol be protected from
directly into a small weighing bottle or can. Stopper the bottle atmospheric moisture at all times. During the titration a stream
and weigh to the nearest 0.001 g (M). Remove the stopper from of dry air or nitrogen will protect the contents of the titration
the bottle and place the bottle containing the specimen and the flask from atmospheric moisture pick-up.
stopper in the oven.
14.2 Dry for 2 h at 105 6 3°C, passing a current of dry air 19. Summary of Test Method
into the bottom of the oven during the drying period. (If dry air 19.1 An excess of Karl Fischer reagent is added to the
is not forced through the oven, dry for 4 h.) specimen suspended in anhydrous methanol. After shaking for
14.3 At the end of the specified period, quickly place the 15 to 20 min to extract the moisture, the excess is back-titrated
basket and specimen in the weighing bottle again and stopper with standard water solution. It is also permissible to titrate
it (or stopper directly). Remove the weighing bottle from the directly to the end point with Karl Fischer reagent. The end
oven and place it in a desiccator containing an efficient point is best detected electrometrically, but, with practice, it
desiccant, such as anhydrous calcium sulfate. Allow it to cool may be satisfactorily determined visually.
for 1 h, momentarily open the weighing bottle to equalize the
NOTE 6—To determine the moisture content of certain plastic materials
pressure, and weigh to the nearest 0.001 g.
the following solvents or solvent combinations may be used: chloroform,
14.4 Return the specimen to the oven, exposing it as m-cresol, pyridine, o-dichlorobenzene-methanol, dioxane-methanol;
directed above, and dry for at least 1 h more. Place it in a dioxane-pyridine, methylene chloride-methanol (1 + 1), pyridine-
desiccator to cool and weigh in accordance with 14.3. Repeat methanol, and toluene-methanol.
the drying and weighing until the mass loss between two
successive weighings is not more than 0.005 g (or until the 20. Apparatus
specimen shows a gain in mass). Designate the lowest ob- 20.1 Buret, automatic, 25 or 50 mL (0.85 or 1.7 oz),
served mass as D. attached to an amber glass reservoir so that any air entering the
14.5 When constant mass has been obtained, discard the system must pass through an efficient absorber containing
specimen and weigh the weighing bottle (plus basket) or can. anhydrous calcium sulfate (Drierite) and soda-asbestos (Ascar-
Designate this mass as T. ite).
14.6 Do not place additional specimens in the oven until the 20.2 Pipets, automatic or transfer, 50- and 100-mL (1.70-
first specimens have attained constant mass. and 3.40-oz).
3
D 1348
20.3 Flasks, or bottles, glass-stoppered, 125-mL or 250-mL all-glass apparatus. Standardize daily as described in Section
(4.25- or 8.50-oz), for visual end point, or suitable enclosed 22.
reaction vessel for electrometrically determined end point. 21.4 Methanol, anhydrous, water content less than 0.05%.
20.4 Bottle, dropping, or equivalent, for weighing water for 21.5 Water Solution, for use if back-titration is desired.
standardization of reagent. Prepare by adding 1.0 mL (0.034 oz) of water to 1 L (0.26 gal)
20.5 Electrode and Meter System, with provision for ad- of anhydrous methanol. Mix well and store in an all-glass
equate stirring, and flasks or containers adapted to the assem- assembly protected from contamination by atmospheric mois-
bly if the end point is to be determined electrometrically. ture. Standardize as described in Section 22.
20.6 Filter, sintered glass, coarse porosity, 30-mL (1.02-oz).
20.7 Bottle, weighing, low-form, 45 by 65 mm (1.8 by 2.6 22. Standardization of Reagents
in.) for drying wet pulp. 22.1 Back-Titration—Standardize the Karl Fischer reagent
and water solution daily. It is important that the same technique
21. Reagents
and end point be used both in the standardization and in
21.1 Purity of Reagents—Reagent grade chemicals shall be subsequent analyses. The following directions apply to the
used in all tests. Unless otherwise indicated, it is intended that visual detection of the end point, but with obvious modifica-
all reagents shall conform to the specifications of the Commit- tion, depending upon the particular apparatus used, they may
tee on Analytical Reagents of the American Chemical Society, be followed for instrumental end point detection.
where such specifications are available.2 Other grades may be 22.1.1 Pass a stream of dry air or nitrogen through the flasks
used, provided it is first ascertained that the reagent is of during all additions and titrations unless the titration assembly
sufficiently high purity to permit its use without lessening the provides protection from atmospheric moisture.
accuracy of the determination. 22.1.2 Add Karl Fischer reagent to 50 mL (1.7 oz) of
21.2 Air or Nitrogen, under a pressure of 152.4 to 304.8 mm anhydrous methanol contained in a dry 250-mL (8.5-oz)
(6 to 12 in.) of water (1.5 to 3.0 kPa) and dried by passing Erlenmeyer flask until a dark brown color has been reached
through concentrated sulfuric acid (H2SO4, sp gr 1.84) fol- (AF). Back-titrate with water solution until the end point
lowed by indicating grade anhydrous calcium sulfate or other described in Section 23 has been reached (AW). Reserve this
suitable indicating desiccant. If the titration assembly provides solution, refill burets, and accurately measure approximately
adequate protection from atmospheric moisture, this will not be 15 mL (0.51 oz) of Karl Fischer reagent into this same flask
required. (WF). Back-titrate with water solution as described above
21.3 Karl Fischer Reagent—Suitable reagent may be pur- (WW).
chased from laboratory supply houses or prepared as follows: 22.1.3 Weigh to the nearest 0.0001 g (0.0028 oz), by
21.3.1 Place 530 6 5 mL (18.02 6 0.17 oz) of dry methanol difference (conveniently from a Sattler weighing pipet), from
(CH3OH) in a clean, dry, 9-L (2.34-gal) chemical-resistant 0.15 to 0.20 g (4.2 to 5.6 oz) of water (G) (Note 6) into a dry
glass carboy. Add 2025 6 25 mL (68.85 6 0.85 oz) of 250-mL Erlenmeyer flask containing 50 mL of anhydrous
pyridine. Add 1270 6 1 g (43.18 6 0.034 oz) of iodine crystals methanol. Titrate with Fischer reagent to a dark brown color
and shake the carboy until the iodine is completely dissolved. (SF), indicating an excess of 2 to 5 mL (0.068 to 0.17 oz) of the
Place the carboy in a cracked ice bath and allow to stand about reagent. Back-titrate with water solution to the end point (SW).
1 h. If the end point should be passed, more Fischer reagent may be
21.3.2 Weigh on a platform scale to 25 g (0.05 lb) a cylinder added and the titration with water solution continued until the
of sulfur dioxide (SO2) with chemical-resistant glass tubing exact end point has been reached.
attached to the outlet with polyethylene tubing. Tilt the
NOTE 7—If desired, standard Rochelle salts or other material with
cylinder with the outlet down.
known water of hydration, may be used instead of weighing the water
21.3.3 Open the cylinder valve and allow the sulfur dioxide directly.
to run into the solution in the carboy. Use the chemical-
resistant glass tubing, through which the SO2 flows, to stir the 22.1.4 Calculate the water equivalent, T, of the Karl Fischer
solution. When 955 6 5 g (2.1 6 0.05 lb), as determined by reagent as follows:
difference in scale mass reading, have run in, stopper the bottle A 5 WF/WW (7)
tightly.
21.3.4 Add about 4300 mL (146.2 oz) of methylene chloride where:
(CH2Cl2) and mix well. If desired, the methylene chloride may A 5 millilitres of Karl Fischer reagent equivalent to 1
be omitted and a total of 6375 mL (216.75 oz) of pyridine used. mL of water solution,
WF 5 millilitres of Karl Fischer reagent measured into
Allow the solution to stand 24 h before use. Protect from
the titrated methanol, and
contamination by atmospheric moisture by storing in an
WW 5 millilitres of water solution required to titrate the
excess Karl Fischer reagent.
2
Reagent Chemicals, American Chemical Society Specifications, American B 5 AF – ~ A 3 AW ! (8)
listed by the American Chemical Society, see Analar Standards for Laboratory where:
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia B 5 millilitres of Karl Fischer reagent required by 50
mL of methanol,
MD.
4
D 1348
AF 5 millilitres of Karl Fischer reagent added to 50 mL of more Karl Fischer reagent. Record the amount of reagent
methanol, and added.
AW 5 millilitres of water solution required to titrate the 23.4 Pass a stream of dry air or nitrogen through the flask
excess Karl Fischer reagent in 50 mL of methanol. and titrate with water solution until the end point has been
reached, as shown by an instrument or indicated visually. In the
T 5 G/@SF – ~SW 3 A! – B# (9)
latter case, the titrated solution will have a yellow color with
just a trace of brown at this point. If the end point should be
where: overtitrated, add more Karl Fischer reagent dropwise to the
T 5 water equivalent of the Karl Fischer reagent, g/mL, first appearance of the brown color.
G 5 grams of water added (21.1.3), 23.5 Alternatively, titrate directly to the end point with Karl
SF 5 millilitres of Karl Fischer reagent added to the Fischer reagent. The visual end point is a color change from
weighed water, and light brown to dark reddish-brown.
SW 5 millilitres of water solution required to titrate the
NOTE 8—An excellent visual standard of comparison is an 0.016 N
excess Karl Fischer reagent.
iodine solution (prepared by mixing 15 mL (0.51 oz) of 0.1 N iodine
22.2 Direct Titration: solution and 75 mL (2.55 oz) of water). The end point is best observed by
22.2.1 Alternatively, add from an automatic pipet or from an examining the solution by transmitted light from a 15-W fluorescent tube.
oven-dried pipet, 50 mL of methanol to each of four oven-dried It is essential to titrate to the same end point in the standardization and the
titrating flasks or bottles. Weigh by difference to the nearest 0.1 same titration.
mg, 0.10 to 0.25 g (0.035 to 0.00875 oz) of distilled water from 23.6 Run a blank on 50 mL (1.7 oz) of the methanol by
a weighing bottle fitted with a dropper, into each of two of the titrating as described in 23.3 and 23.4 or 23.5. The titrated
flasks. Titrate the solvent-water standards directly to the end alcohol may be stoppered and used as an end point color
point with Karl Fischer reagent (T1). Titrate the solvent blanks standard when the end point is detected visually.
to the same end point as for the standards (T2). 23.7 If calculation on the dry mass basis is desired, transfer
22.2.2 Calculate the water equivalent of the Karl Fischer the cellulose specimen to a coarse, fritted-glass crucible
reagent as follows: previously washed with methanol or with alcohol conforming
T 5 A/~T1 – T2! (10) to Formula 30 of the U. S. Bureau of Internal Revenue, dried
at 120°C, and weighed to the nearest 1 mg. Wash, using
where: suction, with about 15 mL of methanol or Formula 30 alcohol.
T 5 water equivalent of the Karl Fischer reagent, g/mL,
Suck as dry as possible to remove all alcohol vapors.
A 5 grams of water added (22.2.1),
T2 5 millilitres of Karl Fischer reagent required for titra- 23.8 Place the crucible on a hot plate or steam bath (be sure
tion of solvent blank, and the surface is clean) for 3 to 5 min to flash off any remaining
T1 5 millilitres of Karl Fischer reagent required for titra- alcohol, and then place it in an oven at 120°C to dry for 30 min.
tion of solvent and water. Cool the crucible containing the cellulose in a desiccator and
22.2.3 Average the duplicate results and round off the weigh to the nearest 1 mg. Determine the mass of the dry pulp
average to three significant figures. Duplicate values of T by difference.
should agree within 0.0001.
24. Calculation
23. Procedure 24.1 Calculate the percent moisture as follows:
23.1 Weigh to the nearest 0.0001 g an amount of sample 24.1.1 For Back-Titration Method:
estimated to contain from 0.10 to 0.15 g (0.0035 to 0.00525 oz) P 5 ~@C – DA – B!3 T 3 R#/W! 3 100 (11)
of water. For samples containing from 4 to 6 % water, a test 24.1.2 For Direct Titration Method:
specimen weighing from 2.5 to 3.0 g (0.0875 to 0.105 oz) is
P 5 ~@C – B! 3 T3 R#/W! 3 100 (12)
satisfactory. Transfer the weighed specimen to a dry, 250-mL
Erlenmeyer flask with minimum exposure to the atmosphere and,
and add 100 mL (3.4 oz) of anhydrous methanol. Stopper the Moisture, dry basis, ~regain!, % 5 @P/~100 – P! 3 100 (13)
flask and shake slowly for 15 to 20 min, or allow the stoppered 5 @~W – Z!/Z# 3 100
flask to stand for 1 h with occasional shaking.
23.2 With an oven-dried pipet, transfer 50 mL (1.7 oz) of where:
the supernatant liquid to a 125-mL (4.25-oz) oven-dried, P 5 moisture content, %,
glass-stoppered bottle. Exposure to the atmosphere may be C 5 millilitres of Karl Fischer reagent required for titra-
minimized by covering all flask openings with rubber sheeting tion of the sample,
during transfer and titration operations. Pipets and buret tips D 5 millilitres of water solution added (23.4),
may be inserted through a small slit in the rubber sheeting. A 5 millilitres of Karl Fischer reagent equivalent to 1 mL
23.3 Titrate with Karl Fischer reagent to the same end point of the water solution,
as in the standardization. If back-titration is to be used, rapidly B 5 millilitres of Karl Fischer reagent required for titra-
titrate with Karl Fischer reagent until the solution has a dark tion of 50 mL of methanol (23.6),
brown color. Stopper the flask and allow to stand for 15 min. T 5 grams of water equivalent to 1 mL of the Karl Fischer
If the brown color should fade during the standing period, add reagent,
5
D 1348
W 5 grams of sample used, 25.2 Bias—No justifiable statement can be made on the bias
R 5 aliquot factor (Note 8), and of the procedure for measuring moisture in cellulose because
Z 5 grams of dried cellulose. no suitable reference material exists.
26. Keywords
NOTE 9—The aliquot factor is 2 when 100 mL of methanol is taken to
extract the water from the cellulose and 50 mL is titrated. 26.1 electrochemical detection; Karl Fisher; moisture; oven;
predrying; rayon
peatability) test results indicates a precision of 60.82 % at the
95 % confidence level.
6

Nonvolatile Matter in Volatile Solvents for Use in Paint,
Varnish, Lacquer, and Related Products1
e1 NOTE—Editorial changes were made throughout in May 2000.
1. Scope 4.2 Dish, evaporating, platinum, 125-mL. A platinum

1.1 This test method covers the determination of the non- evaporating dish is preferred. Alternatively, an aluminum or
volatile matter in volatile solvents for use in paint, varnish, porcelain dish may be used (see Note 1).
lacquer, and related products. NOTE 1—Precision data were determined utilizing only platinum
1.2 This standard does not purport to address all of the dishes.
safety concerns, if any, associated with its use. It is the 4.3 Cylinder, graduated, 100-mL.
responsibility of the user of this standard to establish appro- 4.4 Analytical Balance, precision to 60.1 mg.
bility of regulatory limitations prior to use. For specific hazard 5. Hazards
statements, see Section 5. 5.1 Warning—Certain solvents and chemical intermedi-
1.3 For hazard information and guidance, see the supplier’s ates, particularly, but not only ethers and unsaturated com-
Material Safety Data Sheet for materials listed in this test pounds, may form peroxides during storage. These peroxides
method. may present a violent explosion hazard when the chemicals are
2. Referenced Documents evaporated. When peroxide formation is likely because of
chemical type or length of storage time, analyze the material
2.1 ASTM Standards: for peroxides (see Test Method E 299). If they exist in
E 180 Practice for Determining the Precision Data of hazardous concentrations, take appropriate precautions such as
ASTM Methods for Analysis and Testing of Industrial and destroying the peroxides before evaporation, shielding, or
Specialty Chemicals2 disposal of the sample and not running the test.
E 299 Test Method for Trace Amounts of Peroxide in
Organic Solvents2 6. Procedure
3. Significance and Use 6.1 Dry a 125-mL platinum evaporating dish in an oven at
105 6 5°C and cool in a desiccator. Repeat until the weight is
3.1 This test method describes the analytical measurement within 0.1 mg of the previous weighing.
of residual matter in solvents that are intended to be 100 % 6.2 With the graduated cylinder, measure 100 mL of sample
volatile at 105 6 5°C. Volatile solvents are used in the at room temperature into the conditioned platinum evaporating
manufacture of paint, varnish, lacquer, and other related dish, place on a steam bath and evaporate the specimen to
products, and the presence of any residue may affect the dryness. Dry the outside of the dish with a clean, lint-free cloth
product quality or efficiency of the process. This test method is and heat in an oven at 105 6 5°C for approximately 1 h. Cool
useful in manufacturing control and assessing compliance with in a desiccator and weigh the evaporating dish and contents to
specifications. 0.1 mg.
4. Apparatus 6.3 Return the dish and contents to the oven for 15 to 30
min, cool, and reweigh. Repeat, if necessary, until the weight is
4.1 Oven, thermostatically controlled at 105 6 5°C. constant to within 0.1 mg of the previous weighing.
1
7. Report
and Related Coatings, Materials, and Applications and is the direct responsibility of 7.1 Report as nonvolatile matter the residue obtained from
Subcommittee D 01.35 on Solvents, Plasticizers, and Chemical Intermediates.
2
1
D 1353
the specimen as milligrams of nonvolatile residue/100 mL. standard deviation 0.71 mg/100 mL. Based upon these standard
deviations, the following criteria should be used for judging the
8. Precision and Bias 3 acceptability of results at the 95 % confidence level:
8.1 Precision—The precision statements are based upon an 8.1.1 Repeatability—Two results, each the mean of dupli-
interlaboratory study in which one operator in each of eight cates, obtained by the same operator on different days should
different laboratories analyzed one sample of methyl ethyl be considered suspect if they differ by more than 0.9 mg/100
ketone in duplicate on two different days. This sample was mL.
prepared by adding 0.006 % of a nonvolatile resin to commer- 8.1.2 Reproducibility—Two results, each the mean of dupli-
cial methyl ethyl ketone. Platinum evaporating dishes were cates, obtained by operators in different laboratories should be
used in this study. The results were analyzed in accordance considered suspect if they differ by more than 2.4 mg/100 mL.
with Practice E 180. The within-laboratory standard deviation 8.2 Bias—Bias can not be determined because there is no
was found to be 0.26 mg/100 mL, and the between-laboratories available material having an accepted reference value.
3
9. Keywords
Supporting data are available from ASTM Headquarters. Request RR:
D01 – 1044. 9.1 nonvolatile matter; solvents; volatile solvents
2

Spectrophotometric Diene Value of Dehydrated Castor Oil
and Its Derivatives1
e1 NOTE—Unit of measurement statement and Keywords were added editorially in May 1995.
1. Scope photometer,2 covering a spectral range from 200 to 350 nm,

1.1 This test method covers the determination of the spec- with a wavelength scale readable to 0.1 nm, and equipped with
trophotometric diene value as a measure of the content of an absorption cell compartment3 for holding 10.00-mm cells.
conjugated dienoic acids in dehydrated castor oil and its 4.2 Absorption Cells, quartz, matched pairs of lengths 10.00
derivatives. Due to the high linoleic acid content in dehydrated 6 0.05 mm. The cells in a pair, when filled with water or
castor oil and its derivatives, the absolute conjugated dienoic isooctane, shall match within 0.01 absorbancy unit (Note 1).
acid content cannot be determined by this test method. The cells may be the 10.00-mm nondemountable type made of
1.2 The values stated in SI units are to be regarded as the quartz, or the demountable type consisting of a chemically
standard. The values given in parentheses are for information resistant glass4 cell body of outside diameter of about 22 mm
only. with centered-ground glass stopper, threaded metal caps, pol-
1.3 This standard does not purport to address all of the ished crystalline quartz windows, and cork gaskets.
safety concerns, if any, associated with its use. It is the NOTE 1—If the cells do not match within 0.01 absorbancy unit, they
responsibility of the user of this standard to establish appro- may be filled with water or isooctane and calibrated against each other at
priate safety and health practices and determine the applica- the specified wavelength. The necessary correction in absorbancy units is
bility of regulatory limitations prior to use. Specific hazard then applied where necessary. Highest precision is obtained by the method
statements are given in Section 6. of reversing cells. The absorbancy of the solution is read against the
solvent blank. The cells are then cleaned and the solvent blank put in the
2. Terminology cell previously used for the solution and the solution in the cell previously
used for the blank and the absorbancy measured. The two absorbancies are
2.1 Description of Term Specific to This Standard: then averaged to obtain As, the observed absorbancy. The cells should be
2.1.1 spectrophotometric diene value—under the conditions rinsed with solvent, water, concentrated nitric acid, water, and solvent, in
of this test method, the percent of conjugated dienoic acids. that sequence, before each reading.
4.3 Filter Tube, 810 by 45 mm (32 by 13⁄4 in.).
4.4 Cork Stopper covered with aluminum foil to fit loosely
3.1 In the process of dehydrating castor oil, a double bond in the top of the filter tube.
is formed in the ricinoleic acid to make either conjugated 4.5 Dropping Bottle, stoppered, for weighing the samples.
linoleic or normal linoleic fatty acid segments in the oil. This 4.6 Volumetric Flasks, glass-stoppered, having capacities of
test method attempts to measure the amount of conjugated 100 mL, 50 mL, and 25 mL.
unsaturation by means of the absorbance at a specific wave- 4.7 Volumetric Pipets, precision grade, assorted sizes, for
length which is in the ultraviolet range. Since some absorption making dilutions when required.
is due to linoleic acid, a correction factor is included in the
calculation. This test method is only applicable to dehydrated 5. Reagents and Materials
castor oil products. 5.1 Silica Gel, 28 to 200-mesh.5
4. Apparatus
2
4.1 Spectrophotometer—Ultraviolet photoelectric spectro- The Beckman Model DU photoelectric quartz spectrophotometer, Catalog No.
2500 DU, Beckman Laboratories, S. Pasadena, CA, has been found satis-
factory for this purpose.
3
The cell compartment assembly, as Catalog No. 2510, and the ultraviolet
accessory set, as Catalog No. 2501, that includes the No. 2230 hydrogen discharge
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint lamp, the No. 2511 adapter, No. 23-10-10-89 cells, and No. 2504 cover, both
and Related Coatings, Materials, and Applications, and is the direct responsibility of available from Beckman Laboratories, S. Pasadena, CA, have been found satis-
Subcommittee D01.32 on Drying Oils. factory for this purpose.
4
Current edition approved March 27, 1986. Published May 1986. Originally Borosilicate glass has been found satisfactory for this purpose.
5
published as D 1358 – 55 T. Last previous edition D 1358 – 58 (1984)e1. Silica gel available from Davison Chemical Co., Baltimore, MD, as Code
11-08, or the equivalent, has been found satisfactory for this purpose.
1
D 1358
5.2 Glass Wool. and allow to stand at least 15 min to attain temperature
5.3 Isooctane (2,2,4 Trimethylpentane)—Pure or spectro- equilibrium. Dilute to volume with purified solvent and mix
scopic grades of isooctane are satisfactory. Check the absor- thoroughly.
bancy of a 10-mm layer of the isooctane against distilled water 8.3 Make necessary dilutions, in no greater than ten-fold
at 233 nm. The absorbancy compared with distilled water set at steps, to give a final concentration of about 0.01 g of the
zero absorbancy shall not be more than 0.070 at 233 nm. If the sample per litre. Measure the absorbancy of the solution at 233
isooctane does not meet these requirements, purify it as nm (Note 2). Use a matched cell containing purified solvent
follows: Place about 90 mm (31⁄2 in.) of glass wool above the only for the blank cell. Take several readings and calculate the
lower end of the filter tube. Add about 500 mm (20 in.) of silica mean. The observed absorbancy readings should lie between
gel and about 50 mm (2 in.) of glass wool. Fasten the tube 0.35 and 0.55; otherwise change the weight or the dilution to
vertically to a ring stand and place a funnel and 2-L amber give the required reading.
bottle under the tube. Pour the isooctane slowly into the tube,
NOTE 2—For highest precision, when making dilutions, allow sufficient
filling about three-fourths full, and allow the isooctane to filter time for the solutions to reach room temperature.
through the silica gel. Renew the silica gel in the tube as often
as necessary to yield isooctane conforming to the transmission 9. Calculation and Report
limit given above. A constant flow can be maintained by
9.1 Calculate the percent of conjugated dienoic acids, C2, as
feeding the isooctane from a 500-mL glass-stoppered separa-
follows:
tory funnel, the tip of which is below the surface of the
isooctane in the filter tube. The 2-L amber bottle used for C2, % 5 8.4 @~As/bc!2ao#
storing the purified isooctane should be rinsed with a little of
where:
the first eluate from the column, and the rinse should be ao 5 0.07 for esters,
discarded. An aluminum-lined screw cap should be used to 5 0.03 for acid,
close the bottle for storage. As 5 observed absorbancy at 233 nm,
b 5 cell length, mm, and
6. Hazards
c 5 sample per litre of the final dilution used for the
6.1 Isooctane is an extremely flammable solvent with a absorption measurement, g.
flash point of − 10°C (10°F). Keep away from heat and open 9.2 Report the percent of conjugated dienoic acids to three
flame. Can react vigorously with reducing materials. See significant figures.
supplier’s Material Safety Data Sheet for further information.
10. Precision
7. Calibration of Spectrophotometer
10.1 Repeatability—Two results obtained by the same op-
7.1 Operational instructions for spectrophotometers vary
erator on the same apparatus should not differ from the mean
with different models. Consult the manufacturer’s literature for
by more than 60.39.
establishing optimum conditions for the specific instrument
used. 10.2 Reproducibility—Two results obtained by operators in
different laboratories should not differ from the mean by more
8. Procedure than 61.26.
8.1 Weigh by difference into a 100-mL volumetric flask, to 10.3 Bias—Bias has not been determined.
0.1 mg, 90 to 130 mg of the sample. Add about 75 mL of
purified isooctane. 11. Keywords
8.2 Rotate the flask and warm the contents, if necessary, to 11.1 dehydrated caster oil; diene value; UV—ultra violet
dissolve the specimen completely. Cool to room temperature, absorption
2

Permanganate Time of Acetone and Methanol1
1. Scope 4.2 Many chemical processes that use acetone or methanol,

1.1 This test method covers the detection in acetone and or both, involve catalyst, metals, or ligand complexes that are
methanol of the presence of impurities that reduce potassium sensitive to oxidation. Since oxidizable contaminants may
permanganate. affect the efficiency of these processes, this test method
1.2 This standard does not purport to address all of the provides a comparative test for manufacturing control and
safety concerns, if any, associated with its use. It is the assessing compliance with a specification.
responsibility of the user of this standard to establish appro- 5. Apparatus
bility of regulatory limitations prior to use. 5.1 Color Comparison Tubes—Matched 50-mL, tall form
1.3 For specific hazard information and guidance, consult Nessler tubes, provided with ground on, optically clear, glass
the supplier’s Material Safety Data Sheet. caps.
5.2 Constant-Temperature Bath, capable of maintaining a
2. Referenced Documents temperature of 15.0 6 0.5°C or of 25.0 6 0.5°C. It is important
2.1 ASTM Standards: that the constant-temperature bath be protected from direct
D 329 Specification for Acetone2 light. If a glass constant-temperature bath is employed, it
D 1152 Specification for Methanol (Methyl Alcohol)2 should be wrapped or coated with an opaque material.
D 1193 Specification for Reagent Water3 5.3 Pipet, capable of delivering 2.0 mL of solution.
D 1209 Test Method for Color of Clear Liquids (Platinum- 5.4 Interval Timer and Clock, capable of measuring a time
Cobalt Scale)2 interval of 120 min or more. An alarm arrangement may be
E 180 Practice for Determining the Precision of ASTM desirable.
Methods for Analysis and Testing of Industrial Chemicals4 6. Reagents
E 346 Test Method for Analysis of Methanol4
6.1 Reagent-grade chemicals shall be used in all tests.
3. Summary of Test Method Unless otherwise indicated, it is intended that all reagents shall
3.1 Substances reacting with potassium permanganate in conform to the specifications of the Committee on Analytical
neutral solutions reduce it to manganese dioxide which colors Reagents of the American Chemical Society, where such
the solution yellow. In the permanganate test the time required specifications are available.5 Other grades may be used, pro-
for the color of the test solution to change to that of a standard vided it is first ascertained that the reagent is of sufficiently
solution is measured. The color of the test solution changes high purity to permit its use without lessening the accuracy of
from pink-orange to yellow-orange. the determination.
4. Significance and Use understood to mean reagent water conforming to Type IV of
4.1 The permanganate time can be used to judge the Specification D 1193.
presence of oxidizable materials that may be associated with 6.3 Potassium Permanganate Solution (0.200 g/L)—
manufacture or contamination during distribution and to assess Dissolve 0.200 g of potassium permanganate (KMnO4) and
compliance with a specification. dilute to 1 L with freshly boiled water. Clean glassware is
essential to the stability of this solution. The solution should be
stored in brown bottles and be prepared every week needed.
1
5
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Reagent Chemicals, American Chemical Society Specifications, American
published as D1363 – 55 T. Last previous edition D1363 – 88 (1992)e1. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
1
D 1363
6.4 Cobaltous Chloride-Platinum Cobalt Standard 8.1.1 If the residual pink color of the specimen is greater
Solution—Weigh on analytical balance 175 mg of cobaltous than the standard, report the permanganate time as “greater
chloride (CoCl2·6H2O) and add 21.4 mL of 500 Pt-Co standard than X minutes.” If the residual pink color of the specimen is
(Note 1). Transfer to a 50-mL volumetric flask, dilute to the equal to that of the standard, report the permanganate time as
mark, and mix thoroughly. This standard solution represents “X minutes.” If the residual pink color of the specimen is less
the color of the end point to which the sample solution fades in than the standard, report as “less than X minutes,” where “X
the KMnO4 test. The solution is stable and should be kept in a minutes” is the minimum time specified for the material being
50-mL glass-stoppered Nessler tube exactly the same as those tested (see 7.1).
in which the test is run. 8.1.2 An estimate of the actual permanganate time may be
NOTE 1—The preparation of the 500 Pt-Co standard is covered in Test made by closely observing the sample and reporting to the
Method D 1209. nearest minute the time when the color of the specimen
matches that of the standard. Duplicate determinations that
7. Procedure agree within 3.0 % are suitable for averaging (see Section 9).
7.1 Employ the following time and temperature conditions
6
during the test: 9. Precision and Bias
Temperature Permanganate 9.1 Precision—These precision statements are based on an
of Test, °C Time, min
interlaboratory study in which three samples of methanol
Acetone 25 30 having average permanganate times of 60, 73, and 95 min were
Methanol 15 50 each analyzed by fourteen different laboratories in duplicate on
two different days. In this interlaboratory study, the within-
NOTE 2—It is advisable to check specifications D329, D1152 and Test
Method E 346 for possible changes in acetone and methanol specifications
laboratory coefficient of variation was found to be 2.35 % with
and permanganate time test conditions. 40 df and the between-laboratories coefficient of variation
NOTE 3—Clean test cylinders and permanganate storage and handling 8.20 % with 12 df. Based upon these coefficients calculated in
equipment with concentrated hydrochloric acid (HCl, sp gr 1.19) to accordance with Practice E 180, the following criteria should
remove residual manganese dioxide (MnO2) which catalyzes reduction of be used for judging the acceptability of results at the 95 %
KMnO4. Remove the acid with not less than ten rinsings with reagent confidence level:
water.
9.2 Repeatability—Two results, each the mean of dupli-
7.2 Fill a 50-mL Nessler tube beyond the mark with the cates, obtained by the same operator on different days should
sample under test and place in the constant-temperature bath. be considered suspect if they differ by more than 6.7 %.
Maintain the water level in the bath approximately 25 mm (1 9.3 Reproducibility—Two results, each the mean of dupli-
in.) below the top of the tube. When the specimen has reached cates, obtained by operators in different laboratories should be
the specified temperature, bring the level to the 50-mL mark. considered suspect if they differ by more than 25.2 %.
With a pipet, add 2 mL of the KMnO4 solution. Stopper the 9.4 Bias—Bias cannot be determined because there is no
tube, invert once to mix the contents, return to the bath and available material having an accepted reference value.
note the time. At the end of the minimum time specified for the
material being tested, remove the tube and compare it to the 10. Keywords
color standard by viewing downward through the tube against
a white background from which diffused white light is re- 10.1 acetone; methanol; permanganate time
flected.
8. Report 6
8.1 Report the following information: 1033.
2

Water in Volatile Solvents (Karl Fischer Reagent Titration
Method)1
1. Scope NOTE 2—View the color by transmitted daylight or by transmitted light

from an artificial daylight lamp, such as the one that complies with the
1.1 This test method covers the determination of water in specifications given in Test Method D 1500.
volatile solvents and chemical intermediates used in paint,
varnish, lacquer, and related products. 4. Summary of Test Method
1.2 This test method is not applicable in the presence of 4.1 This test method is based essentially upon the reduction
mercaptans, peroxides, or appreciable quantities of aldehydes of iodine by sulfur dioxide in the presence of water. This
or amines. reaction can be used quantitatively only when pyridine and an
1.3 This standard does not purport to address all of the alcohol are present to react with the sulfur trioxide and
safety concerns, if any, associated with its use. It is the hydriodic acid produced according to the following reactions:
H2O 1 I2 1 SO2 1 3C5H5N → 2C5H5N·HI 1 C5H5N·SO3
priate safety and health practices and determine the applica- C5H5N·SO3 1 ROH → C5H5N·HSO4R
bility of regulatory limitations prior to use. (1)
1.4 For hazard information and guidance, see the supplier’s
Material Safety Data sheet. 4.2 To determine water, Karl Fischer reagent (a solution of
iodine, pyridine, and sulfur dioxide, in the molar ratio of
2. Referenced Documents 1 + 10 + 3) dissolved in anhydrous 2-methoxyethanol is added
2.1 ASTM Standards: to a solution of the sample in anhydrous pyridine-ethylene
D 1500 Test Method for ASTM Color of Petroleum Prod- glycol (1 + 4) until all water present has been consumed. This
ucts (ASTM Color Scale)2 is evidenced by the persistence of the orange-red end-point
color; or alternatively by an indication on a galvanometer or
3. Terminology similar current-indicating device which records the depolariza-
3.1 Definitions of Terms Specific to This Standard: tion of a pair of noble-metal electrodes. The reagent is
3.1.1 instrumental end point—that point in the titration standardized by titration of water.
when two small platinum electrodes, upon which a potential of 5. Significance and Use
20 to 50 mV has been impressed, are depolarized by the
addition of 0.05 mL of Karl Fischer reagent (6 mg of H2O per 5.1 Volatile solvents are used in a variety of chemical
mL), causing a change of current flow of 10 to 20 µA that processes which may be affected by water. Therefore, this test
persists for at least 30 s. method provides a test procedure for assessing compliance
with a specification.
NOTE 1—This end point is sometimes incorrectly called the “dead stop”
which is the reverse of the above. 6. Apparatus
3.1.2 color end point—During the titration, the solution first 6.1 Titration Vessel—For color end point titrations, use a
turns yellow, then later deepens towards the end of the titration; 100 or 250-mL volumetric flask, which need not be calibrated;
the end point is indicated by the change from yellow to a 250-mL flask fitted with interchangeable electrodes (Fig. 1)3
orange-red which is quite sharp and easily repeated. The may also be used for the instrumental end point and is
orange-red color must persist for at least 30 s in order to particularly suitable for titrations at ice temperatures. For
indicate an end point. permanently mounted assemblies, the vessel should have a
capacity about equal to that of a 300-mL tall-form beaker; and
1
3
and Related Coatings, Materials, and Applications and is the direct responsibility of The sole source of supply of flasks known to the committee at this time is the
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Rankin Glass Blowing Co., 3920 Franklin Canyon Road, Martinez, CA. If you are
Current edition approved April 15, 1995. Published June 1995. Originally aware of alternative suuppliers, please provide this information to ASTM Head-
published as D 1364 – 55 T. Last previous edition D 1364 – 90. quarters. Your comments will receive careful consideration at a meeting of the
2
Annual Book of ASTM Standards, Vol 05.01. responsibile technical committee,1 which you may attend.
1
D 1364
7. Reagents
tee on Analytical Reagents of the American Chemical Society,
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without decreasing the
7.1.1 Karl Fischer Reagent (equivalent to 6 mg of H2O per
mL)7—For each liter of solution, dissolve 133 6 1 g of I2 in
4256 2 mL of anhydrous (less than 0.1 % H2O) pyridine in a
dry glass-stoppered bottle. Add 425 6 2 mL of anhydrous (less
than 0.1 % H2O) 2-methoxyethanol. Cool to below 4°C in an
ice bath and add gaseous SO2, dried by bubbling through
concentrated H2SO4(sp gr 1.84); determine the amount of SO2
added by measuring the change in weight of the SO2 cylinder
(102 6 1 g) or the increase in volume (70 6 1 mL) of the
reagent mixture. Alternatively, add 70 mL of freshly drawn
liquid SO2 in small increments.
7.1.2 Solvent Mixture—Mix 1 volume of anhydrous (less
NOTE 1—All dimensions in millimetres.
than 0.1 % H2O) pyridine with 4 volumes of anhydrous (less
FIG. 1 Titration Flask Assembly
than 0.1 % H2O) ethylene glycol.
be provided with a tight-fitting closure to protect the sample NOTE 3—Pyridine, ethylene glycol, and 2-methoxyethanol, each con-
and reagent from atmospheric moisture, a stirrer, and a means taining less than 0.1 % water, are available and should be used.
of adding sample and reagents and removing spent reaction NOTE 4—If adequately dry reagents cannot be procured, they can each
mixture. It is desirable to have a means for cooling the titration be dried by distillation through a multiple-plate column, discarding the
vessel to ice temperature. first 5 % of material distilling overhead and using the 95 % remaining.
Drying may also be accomplished by the addition of 1 volume of toluene
6.2 Instrument Electrodes—Platinum with a surface equiva- or cyclohexane to 19 volumes of the pyridine-glycol, or of the pyridine
lent to two No. 26 wires 5 mm long. The wires should be 3 to ethylene glycol monomethyl ether mixture, followed by distillation; the
8 mm apart and so inserted in the vessel that 25 mL of liquid first 5 % distilled is discarded and the residual 95 % is used.
will cover them.
6.3 Instrument Depolarization Indicator, having an internal 8. Sampling
resistance of less than 5000 V and consisting of a means of 8.1 Hygroscopic Solvents, including for example, ketones,
impressing and showing a voltage of 20 to 50 mV across the acetates, alcohols, and glycol ethers, absorb ambient moisture.
electrodes and capable of indicating a current flow of 10 to 20 It is essential to avoid changes in the water content of these
µA by means of a galvanometer or radiotuning eye circuit.4 materials during sampling operations. Errors from this source
6.4 Buret Assembly for Karl Fischer reagent, consisting of a are particularly significant in the analysis of materials having
25 or 50-mL buret connected by means of glass (not rubber) low water content. When analyzing materials that absorb
connectors to a source of reagent; several types of automatic ambient water readily, limit as much as possible contact with
dispensing burets5 may be used. Since the reagent loses air in transferring the specimen into the titration vessel. Avoid
strength when exposed to moist air, all vents must be protected intermediate sample containers, if possible.
against atmospheric moisture by adequate drying tubes con-
taining indicating calcium sulfate drying agent. All stopcocks 9. Standardization of Reagent
and joints should be lubricated with a lubricant not particularly 9.1 Standardize the Karl Fischer reagent each day used by
reactive with the reagent. either the color or instrument end point (Section 3) method
6.5 Weighing Bottle, of the Lunge or Grethen Type, or using the same procedure as used for titrating the sample.
equivalent.
4 6
The sole source of supply of instrument depolarization indicator known to the Reagent Chemicals, American Chemical Society Specifications, American
committee at this time is Fisher Scientific Co. (need address). If you are aware of Chemical Society, Washington, DC. For suggestions on the testing of reagents not
alternative suuppliers, please provide this information to ASTM Headquarters. Your listed by the American Chemical Society, see Analar Standards for Laboratory
comments will receive careful consideration at a meeting of the responsibile Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
technical committee,1 which you may attend. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
5
The sole source of supply of automatice dispensing burets, No. J-821, known MD.
7
to the committee at this time is Scientifice glass Apparatus Co., Bloomfield NJ. If Karl Fischer Reagent is available from various laboratory suppliers. Pyridine-
you are aware of alternative suuppliers, please provide this information to ASTM free adaptations are available and may be used if precision can be established. If you
Headquarters. Your comments will receive careful consideration at a meeting of the are aware of alternative suppliers, please provide this information to ASTM
responsibile technical committee,1 which you may attend. These specifically Headquarters. Your comments will receive careful consideration at a meeting of the
designed burets present the minimum contact of reagent with stopcock lubricant. responsibile technical committee,1 which you may attend.
2
D 1364
9.1.1 Add to each flask 25 mL of ethylene glycol-pyridene 11. Calculation
mixture, and titrate this as described in Section 10. Add to the 11.1 Calculate the water content of the specimen as follows:
solvent thus titrated, in place of the sample, 0.15 to 0.18 g of
Water, %, by weight 5 ~V 3 W!/~10 3 S! (3)
water from a weighing bottle or weighing pipet, weighed to the
nearest 0.1 mg. Complete titration with Karl Fischer reagent as where:
described in Section 10. V 5 volume of Karl Fischer reagent required for titrating
9.1.2 Calculate the equivalency factor, W, of the reagent in by the specimen, mL,
terms of water content per millilitre by means of the following W 5 equivalency factor for Karl Fischer reagent, water per
equation: millilitre of reagent, mg, and
W 5 A/V (2) S 5 specimen weight used, g.
NOTE 8—If specimen was added volumetrically by means of a cali-
where: brated volumetric pipet, then S 5 volume of specimen 3 density of
W 5 equivalency factor, mg of water per mL, specimen, g.
A 5 weight of water used in the standardization, mg, and
V 5 volume of Karl Fischer reagent required, mL. 12. Report
10. Procedure 12.1 For water concentrations below 0.5 %, report all re-
sults to 0.001 %. Two determinations which agree within
10.1 Introduce 10 to 25 mL of the anhydrous solvent 0.008 %, absolute, are acceptable for averaging (95 % confi-
mixture (pyridine-glycol, 1 + 4) into the titration vessel, mak- dence level).
ing sure, if an instrument end point apparatus is used, that the
electrodes are covered by this amount of solvent. If the color 13. Precision and Bias
end point is to be determined, make up a second flask as well. 13.1 Precision for Water 0.100 to 0.500 % by Weight—On
10.2 Adjust the stirrer, if any, to provide adequate mixing the basis of an interlaboratory study in which one operator
without splashing. Titrate the mixture to the instrumental end made duplicate determinations in each of eight different
point (see 3.1), or the color end point (see section 3.2 ), with laboratories, on two days, on samples of acetone containing
Karl Fischer reagent. If the color end point is to be observed, 0.118 and 0.406 % water and of methyl ethyl ketone containing
titrate one flask to the orange-red end point and the second to 0.050 and 0.176 % water, the following criteria should be used
match the first. Set aside the first flask as a comparison for judging at the 95 % confidence level the acceptability of
standard for titrating the specimen. results on samples containing less than 0.5 % water:
10.3 To the titration mixture thus prepared, add an amount NOTE 9—Supporting documentation for this interlaboratory study is not
of specimen as indicated in Table 1. Exercise care when the available from ASTM Headquarters.
specimen is transferred so that water is not absorbed from the 13.1.1 Repeatability—Two results, each the mean of dupli-
air, particularly under conditions of high humidity. Again, cate determinations, obtained by the same operator should be
titrate the mixture with Karl Fischer reagent to the same considered suspect if they differ by more than 0.015 %
instrumental or color end point previously employed. Record absolute.
the amount of reagent used to titrate the water in the specimen. 13.1.2 Reproducibility—Two results, each the mean of du-
NOTE 5—(a) Ketones—In titrating ketones when greatest precision is plicate determinations, obtained by operator in different labo-
required, cool the reaction mixture in ice water during the addition of Karl ratories should be considered suspect if they differ by more
Fischer reagent. than 0.027 % absolute.
(b) Organic Acids—Cool the reaction mixture in ice water prior to the
13.2 Precision for Water 0.010 to 0.100 % by Weight8—In
addition of Karl Fischer reagent.
NOTE 6—When using the volumetric flask type titration vessel in humid another interlaboratory study, one operator in each of seven
climates, place a piece of thin sheet rubber over the mouth of the vessel; different laboratories, on two different days, made duplicate
provide a small hole for introducing the buret tip. In less humid climates determinations on five randomly coded samples of hexyl
it is sufficient to lower the tip of the buret deeply into the long neck of the acetate containing 0.015, 0.034, 0.052, 0.071, and 0.098 %
titration flask. water. One of the seven laboratories used three different
NOTE 7—In titrating with the volumetric flask type titration vessel, equipment or procedural variations, or both, thereby making
avoid wetting the stopper and upper end of the flask with either the reagent
this, in effect, a nine interlaboratory study. The statistically
or the sample solvent. Each time the titration is interrupted, touch the buret
tip to the neck of the flask to remove droplets which, if not removed, designed study covered a variety of equipment, analytical
would absorb moisture from the atmosphere. When the flask is removed methods, and reagents using the Karl Fischer chemistry.
from under the buret tip, wipe the tip with a clean dry cloth in a downward 13.2.1 Repeatability—Two results, each the mean of dupli-
motion. cate determinations, obtained by the same analyst should be
considered suspect if they differ by more than 0.030 = x̄ %
TABLE 1 Recommended Specimen Sizes absolute, where x̄ is the average of two determininations.
Water
Specimen Size
Manner Specimen 13.2.2 Reproducibility—Two results, each the mean of du-
Content, % Taken
plicate determinations, obtained by analysts in different labo-
2.5 to 10 weight containing 0.15 to weighing pipet ratories should be considered suspect if they differ by more
0.18 g of H2O
0.5 to 2.5 10 mL calibrated volumetric pipet
8
Below 0.5 25 mL same as for 0.5 to 2.5 Supporting data is available from ASTM Headquarters. Request RR:
D01 – 1049.
3
D 1364
than 0.060 = x̄ % absolute, where x̄ is the average of two factors that might influence test bias.
determinations.
13.3 Bias—Bias cannot be determined for this test method 14. Keywords
because there is no available material having an accepted 14.1 Karl Fisher method; solvents; water content
reference value. Refer to 8.1 and Note 5, Note 6, and Note 7 for
4
Standard Practice for

Reporting Particle Size Characteristics of Pigments1
1. Scope where:
1.1 This practice for reporting the fineness characteristics of SSD 5 specific surface diameter, µm,
pigments is designed to apply in most cases where well-known d 5 mean class size, µm, and
methods for determining these particle size characteristics in f 5 frequency.
the subsieve range are employed, such as microscopic, sedi- Therefore the SSD is the diameter of a sphere having the
mentation, and turbidimetric methods; and partially to absorp- specific surface characteristic of the pigment. The true specific
tion and permeability methods. surface of all pigments involves a shape factor. Report SSD
1.2 Laminar, plate-like pigments and composite pigments whether or not the effect of shape has been considered in the
having a definite bimodal distribution are not considered within calculations. Presumably, as the effect of shape is better
the scope of this practice. understood, it will figure more and more in calculations
1.3 Parameters—The fineness characteristics are reported involving particle size, but in the meantime it will of necessity
in the following three parameters: be ignored in many cases.
1.3.1 Particle Size Parameter. 3.1.2 coarseness parameter (CP)—that diameter, expressed
1.3.2 Coarseness Parameter—A parameter descriptive of in micrometres, below which 99.5 % of the pigment falls.
the coarseness character of the pigment, making use of a 3.1.3 dispersion parameter (DP)—the ratio of the
limiting value in the subsieve range similar to that used in the micrometre size within which 50 % of the pigment lies, to the
sieve ranges. specific surface diameter, SSD. The larger the DP number, the
1.3.3 Dispersion Parameter—A parameter descriptive of greater the dispersion parameter and the lower the uniformity.
the uniformity of the particle size distribution. Report the dispersion parameter in all cases when a distribution
1.4 This standard does not purport to address the safety curve can be prepared from the original data. The dispersion
problems, if any, associated with its use. It is the responsibility parameter cannot be calculated from data obtained by
of the user of this standard to establish appropriate safety and absorption or permeability methods. Determine as follows:
health practices and determine the applicability of regulatory 3.1.3.1 Prepare a cumulative-size distribution curve on
limitations prior to use. 3-phase log paper, using the vertical axis for the percent falling
below the size indicated, and the horizontal axis (log scale) for
2. Referenced Documents diameter in micrometres. Use the upper class limit
2.1 ASTM Standards: corresponding to the cumulative weight percentage. Subtract
E 20 Practice for Particle-Size Analysis of Particulate Sub- the micrometre size at 25 % cumulative weight from the
stances in the Range of 0.2 to 75 µm by Optical Micros- micrometre size at 75 %, and multiply the difference by 100 4
copy2 SSD, as follows:
DP 5 ~µm at 75 % 2 µm at 25 %!/~SSD! 3 100 (2)
3. Terminology
3.1 Definitions: 4. Significance and Use
3.1.1 particle size parameter (specific surface diameter, 4.1 This practice is of value (1) to the producer of fine
SSD)—diameter d3 used elsewhere in ASTM test methods. particles as a means of reporting particle characteristics with
This parameter is the same as that frequently reported as respect to quality control and (2) to the buyer to assure that the
“Average Particle Size by Surface Mean,” and “Specific particle size and particle size distribution meet his
Particle Size,” and is defined as follows: requirements.
SSD 5 (d3f/(d 2f (1) 5. Procedure
5.1 Particle Size by Microscopical Methods—Procedures
1
This practice is under the jurisdiction of ASTM Committee D-1 on Paint and for determining particle size by microscopical methods are
Related Coatings, Materials, and Applications, and is the direct responsibility of described in Practice E 20. When microscopical methods are
employed, report the data in tabular form similar to that shown
published as D 1366 – 55 T. Last previous edition D 1366 – 65 (1981)e1. in Table 1 .
2
Annual Book of ASTM Standards, Vol 14.02. 5.2 Particle Size by Sedimentation Methods—
1
D 1366
TABLE 1 Example of Data Sheet for Microscopic Method
Class Limits, µm Mean Class Cumulative
2 3 2
Frequency, f d f d f d f, %
Lower Upper Size, d Weight, %
0.25 0.75 0.5 71.4 17.8 8.9 0.007 0.007

0.75 1.25 1.0 50.9 50.9 50.9 0.040 0.047
1.25 1.75 1.5 57.9 130.2 195.4 0.154 0.191
1.75 2.25 2.0 36.9 147.5 295.0 0.233 0.424
2.25 2.75 2.5 41.1 256.8 641.9 0.506 0.93
2.75 3.25 3.0 34.5 310.9 932.7 0.736 1.69
3.25 3.75 3.5 34.5 423.2 1 481.2 1.17 2.86
3.75 4.25 4.0 21.0 336.1 1 344.5 1.06 3.92
4.25 4.75 4.5 42.0 850.8 3 828.8 3.02 6.94
4.75 5.25 5.0 81.2 2 030.8 10 154.0 8.02 14.96
5.25 5.75 5.5 283.8 8 586.3 47 225.0 37.25 52.21
5.75 6.25 6.0 155.9 5 613.4 33 680.0 26.60 78.81
6.25 6.75 6.5 71.0 2 998.1 19 487.9 15.38 94.19
6.75 7.25 7.0 7.9 388.9 2 722.4 2.15 96.34
7.25 7.75 7.5 5.1 288.8 2 166.3 1.71 98.05
7.75 8.25 8.0 4.2 268.9 2 151.4 1.71 99.76
3.25 8.75 8.5 0.5 33.7 286.8 0.23 99.99
Totals 999.8 22 733.1 126 653.1
Sedimentation methods provide data from which may be In the second case, where S equals square metres per gram
calculated the mean class size and percentage by weight for (Note), the equation is as follows:
each of these class sizes. Table 2 presents in the second and SSD 5 6/~sp gr 3 s! (4)
third columns data normally obtained by sedimentation
methods. Column 3 of Table 2, which gives the distribution by NOTE 1—Example—Channel black has a specific gravity of 2.0. If the
specific surface in square metres per gram is reported as 94.0, then:
weight of the class sizes, is identical with the function d 3f.
Therefore, the d3f function in Column 4 equals d3f/d. The fifth SSD 5 6/~2 3 94! 5 0.032 (5)
column, cumulative weight, percent, is obtained from the 6. Calculation and Report
values in Column 3.
6.1 To determine the coarseness and dispersion parameters
5.3 Particle Size by Turbidimetric Methods—Like the
from the microscopical data of Table 1, draw Curve I of Fig. 1
sedimentation method, the turbidimetric methods provide class
, using the cumulative weight percentage and the upper class
sizes and a percentage by weight for each class size, and the
size units of Table 1. From this curve, read the CP at the point
calculation is the same as that in Table 2. However, frequently
where the curve crosses the 99.5 % line, that is, 8.7, and obtain
a weight distribution curve is obtained from data not directly
the DP from the sizes where the curve crosses the 25 and 75 %
convertible into the class-size distribution table. In such cases,
lines; then calculate as follows:
reconstruct the size-weight distribution table from the
distribution by weight curve. SSD 5 126 653.1/22 733.1 5 5.57 µm (6)
5.4 Particle Size by Absorption and Permeability p1 5 d75 % 2 d25 % 5 0.70 µm
Methods—The absorption and permeability methods, and a DP 5 100 p1/SSD 5 ~100 3 0.70!/5.57 5 12.6
few others, provide no means of making a distribution curve.
CP 5 8.7 µm
Therefore, obtain specific surface either as square metres per
cubic centimetre, or as square metres per gram of material. In 6.2 To determine the coarseness and dispersion parameters
the first case, where s equals square metres per cubic from the sedimentation data of Table 2, draw Curve II of Fig.
centimetre, the equation is as follows: 1, using the cumulative weight percentage and upper class size
units of Table 2. From this curve, determine the coarseness and
SSD 5 6/s (3)
dispersion parameters as described in 5.1, as follows:
TABLE 2 Example of Data Sheet for Sedimentation Method SSD 5 (d3f/(d 2f 5 100.0/84.47 5 1.183 µm (7)
Diameter Class Size Limits Class Size DP 5 17.0 µm
Weight %, 2 Cumulative
Diameter, d f
Lower Upper d, µm
d3f Weight, % p2 5 5.30 2 1.18 5 4.12 µm
0.0 0.5 0.25 11.0 44.00 11.0 DP 5 100 p2/SSD 5 348.0
0.5 1.0 0.75 10.0 13.33 21.0 CP 5 17.0 µm
1.0 1.5 1.25 10.0 8.00 31.0
1.5 2.0 1.75 9.0 5.14 40.0 6.3 While theoretically the size of pigment particles is
2.0 3.0 2.50 15.0 6.00 55.0
3.0 4.0 3.50 9.5 2.71 64.5
independent of the method of determination used, it is
4.0 5.0 4.50 8.5 1.89 73.0 recognized that various methods of determining subsieve
5.0 7.5 6.25 12.5 2.00 85.5 particle size distribution give somewhat different results,
7.5 10.0 8.75 8.0 0.91 93.5
10.0 15.0 12.50 5.3 0.42 98.8
depending on the assumption made in the particle method. It is
15.0 20.0 17.50 1.2 0.07 100.0 recommended, therefore, that the method of determination
20.0 30.0 25.00 0.0 0.00 always be made a part of the report of the size distribution
Totals 100.0 84.47
determined under this practice.
2
D 1366
FIG. 1 Curves for Obtaining Coarseness and Dispersion Parameters
7. Keywords permeability absorption

7.1 microscopic; pigments; sedimentation; turbidimetric
3

Safflower Oil1
1. Scope TABLE 1 Physical Properties
1.1 This specification covers a safflower oil suitable for use Property Requirement ASTM Method
in protective coatings. Specific gravity, 25/25°C 0.922 to 0.927 D 1963, D1475

Refractive index, 25°C 1.4740 to 1.4750 ...
Iodine value 140 to 150 D 1541, D1959
2. Referenced Documents Acid value, max 3.0 D 1639
2.1 ASTM Standards: Saponification value 189 to 195 D 1962
D 555 Guide for Testing Drying Oils2 110°C, max, %
D 1475 Test Method for Density of Paint, Varnish, Lacquer, Break, max, % 0.003 D 1952
and Related Products3 Clarity clear and D 2090
transpar-
D 1541 Test Method for Total Iodine Value of Drying Oils ent at 65°C
and Their Derivatives2 Color (Gardner), max 12 D 1544
D 1544 Test Method for Color of Transparent Liquids Color after heating, max 5 D 1967
Materials2 D 2090 Test Method for Clarity and Cleanness of Paint and
D 1952 Test Method for Quantitative Determination of Ink Liquids2
Break in Drying Oils2
D 1959 Test Method for Iodine Value of Drying Oils and 3. Properties
Fatty Acids2 3.1 Safflower Oil shall be the oil obtained solely from
D 1960 Test Method for Loss on Heating of Drying Oils2 safflower seed, shall be free of dirt or other contamination, and
D 1962 Test Method for Saponification Value of Drying shall conform to the requirements in Table 1.
Varnishes, Resins, and Related Materials at 25/25°C2 4.1 Sampling—Sampling shall be conducted in accordance
D 1967 Test Method for Measuring Color After Heating of with Test Method D 1466.
Drying Oils2 4.2 The properties enumerated in this specification shall be
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint methods listed in Table 1. The significance of the methods of
and Related Coatings, Materials, and Applications, and is the direct responsibility of testing enumerated under properties in this specification is
Subcommittee D01.32 on Drying Oils. discussed in Guide D 555.
2
3
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; safflower oil
1

Chemical Analysis of White Titanium Pigments1

1.1 These test methods cover procedures for the chemical used, provided it is first ascertained that the reagent is of
analysis of white titanium dioxide pigments. sufficiently high purity to permit its use without lessening the
1.2 The analytical procedures appear in the following order: accuracy of the determination.
Sections
Preparation of Sample 4 understood to mean reagent water conforming to Type IV of
Qualitative Analysis 5 and 6 Specification D 1193.
Moisture 7
Total Titanium:
Jones Reductor Method 8-12
Aluminum Reduction Method 13-17 4.1 The sample shall, in all cases, be thoroughly mixed and
Aluminum Oxide 18-22
Silica 23-29
comminuted before taking portions for analysis.
1.3 This standard does not purport to address all of the QUALITATIVE ANALYSIS
responsibility of the user of this standard to establish appro- 5. Reagents
priate safety and health practices and determine the applica- 5.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
bility of regulatory limitations prior to use. A specific hazard monium hydroxide (NH4OH).
statement is given in Section 19. 5.2 Ammonium Sulfate—((NH4) 2SO4).
2. Referenced Documents chloric acid (HCl).
2.1 ASTM Standards: 5.4 Hydrogen Peroxide (30 %)—Concentrated hydrogen
D 280 Test Methods for Hygroscopic Moisture (and Other peroxide (H2O2).
Matter Volatile Under the Test Conditions) in Pigments2 5.5 Hydrogen Sulfide (H2S).
D 1193 Specification for Reagent Water3 5.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
E 50 Practices for Apparatus, Reagents, and Safety Precau- (H2SO 4).
tions for Chemical Analysis of Metals4 5.7 Sulfuric Acid (1+19)—Carefully mix 1 volume of
H2SO4 (sp gr 1.84) with 19 volumes of water.
3. Reagents 5.8 Tartaric Acid.
3.1 Purity of Reagent—Reagent grade chemicals shall be 5.9 Tin or Zinc Metal.
all reagents shall conform to the specifications of the Commit- 6. Procedure
tee on Analytical Reagents of the American Chemical Society, 6.1 Place about 0.5 g of the sample in a 250-mL glass
beaker,6 and add 20 mL of H2SO4 (sp gr 1.84) and 7 to 8 g of
(NH4)2SO4. Mix well and boil for a few minutes. The sample
should go completely into solution; a residue denotes the
1
These test methods are under the jurisdiction of ASTM Committee D-1 on presence of silicon dioxide (SiO2) or siliceous matter. Cool the
Paints and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.31 on Pigment Specifications.
solution, dilute with 100 mL of water, heat to boiling, let settle,
Current edition approved June 25, 1976. Published August 1976. Originally filter, wash with hot H2SO4 (1+19) until free of titanium, and
2
5
3
Annual Book of ASTM Standards, Vol 11.01. Reagent Chemicals, American Chemical Society Specifications, American
4
MD.
6
Borosilicate glass has been found satisfactory for this purpose.
1
D 1394
test the residue for lead, etc.
6.2 Test the filtrate for calcium, zinc, iron, chromium, etc.,
by the regular methods of qualitative analysis.7 For the iron
determination add to a portion of the filtrate 5 g of tartaric acid,
render slightly ammoniacal, pass in H2S in excess, and digest
on a steam bath. No precipitate after 30 min indicates the
absence of iron, nickel, cobalt, lead, copper, etc. A black
precipitate readily soluble in dilute HCl denotes iron. For
titanium, test a small portion of the original filtrate with H2O2
(a clear yellow-orange color should result) and another portion
with metallic tin or zinc (a pale blue to violet coloration should
result). Negative results should be shown for sulfide, carbon-
ate, or appreciable water-soluble matter.
MOISTURE
7. Procedure
7.1 Determine moisture and other volatile matter in accor-
dance with Test Method A of Test Methods D 280.
TOTAL TITANIUM BY THE JONES REDUCTOR

METHOD
8. Scope
8.1 This method gives results similar to those obtained with
the Aluminum Reduction Method, Sections 13-17.
9. Apparatus
9.1 Jones Reductor 8 having a zinc column at least 450 mm
in length, and 19 mm in diameter (Fig. 1 and Fig. 2). The FIG. 1 Jones Reduction
filtering pad must be tight enough to hold all the particles of
amalgamated zinc resting on it, and may be made of asbestos H2SO4, and heat to dense white fumes. Cool, dilute with water
or, preferably, glass-wool supported by platinum gauze or a to 1 L, digest on a steam bath until sulfates are dissolved, and
perforated porcelain plate. Use the least amount (0.1 to 1.0 %) filter if necessary. To oxidize any ferrous iron that may be
of mercury that will enable satisfactory control of hydrogen present, add 0.1 N KMnO4 solution until a faint pink color
evolution, since heavy amalgamation tends to reduce the rate persists for 5 min. Ferric ammonium sulfate (FeNH4(SO4)2 ·
of reaction. Prepare the amalgam by washing 20-mesh zinc for 12H2O) may also be used to prepare this solution (See 15.4).
1 min in enough 1 N HCl to cover it, adding the proper amount 10.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
of 0.25 M mercuric nitrate or chloride solution, and stirring chloric acid (HCl).
rapidly for 3 min. Decant the solution and wash the amalgam 10.6 Iron or Carbon Steel—Pure iron or plain carbon steel.
with water and store under water to which a few drops of HCl 10.7 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
have been added. After using, keep the reductor filled with (HNO3).
water when not in use, in order that basic salts will not be 10.8 Sodium Oxalate—National Institute of Standards and
formed and clog it. Technology standard reference material No. 40 of sodium
oxalate (Na2C2O4).
10. Reagents 10.9 Potassium Permanganate, Standard Reference Mate-
10.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- rial (0.1 N, 1 mL 5 0.008 g TiO2)—Dissolve 3.16 g of KMnO4
monium hydroxide (NH4OH). in water and dilute to 1 L. Let stand 8 to 14 days, siphon off the
10.2 Ammonium Sulfate ((NH4)2SO4). clear solution (or filter through sintered glass, medium poros-
10.3 Carbon Steel or Iron—Pure iron or plain carbon steel. ity), and standardize against the National Bureau of Standards
10.4 Ferric Sulfate Solution (1 mL 5 0.02 g Fe)—Dissolve standard sample No. 40 of sodium oxalate (Na2C 2O4) as
20 g of iron or carbon steel in a slight excess of HCl, oxidize follows: In a 400-mL beaker dissolve 250 to 300 mg Na2C2O4
with approximately 12 mL of HNO3, add about 80 mL of in 250 mL of hot water (80 to 90°C) and add 15 mL of H2SO4
(1+1). Titrate at once with the KMnO4 solution, stirring the
liquid vigorously and continuously. The KMnO4 solution must
7
Treadwell, F. P., and Hall, William T., Qualitative Analysis, John Wiley & Sons, not be added more rapidly than 10 to 15 mL/min, and the last
Inc., New York, NY, Vol. 1, Ninth English Ed., 1937.
8 0.5 to 1 mL must be added dropwise with particular care to
Directions for preparing a Jones Reductor may be found in Hillebrand, W. F.,
et al., Applied Inorganic Analysis, John Wiley & Sons, Inc., New York, NY, Second allow each drop to be fully decolorized before the next is
Ed., 1953, p. 108. introduced. The solution shall not be below 60°C by the time
2
D 1394
weigh as rapidly as possible. Calculate the dry weight of the
specimen and use in the actual calculation.
11.3 Transfer the dried specimen to a dry 250 mL chemical-
and heat-resistant glass beaker,6 add 20 mL of H2SO 4 (sp gr
1.84) and 7 to 8 g of (NH4)2SO4. Mix well and heat on a hot
plate until dense white fumes are evolved, and then continue
the heating over a strong flame until solution is complete
(usually requires not over 5 min of boiling) or it is apparent that
the residue is composed of SiO2 or siliceous matter. Caution
should be observed in visually examining this hot solution.
Cool the solution, dilute with 100 mL of water, stir, heat
carefully to boiling while stirring, let settle, filter through
paper, and transfer the precipitate completely to the paper.
11.4 Wash the insoluble residue with cold H2SO 4 (1+19)
until titanium is removed. Dilute the filtrate to 200 mL and add
about 5 mL of NH4OH to lower the acidity to approximately 10
to 15 % H2SO4 (by volume). Wash out the Jones reductor with
H2SO4 (1+19) and water, leaving sufficient water in the
reductor to fill to the upper level of the zinc. (These washings
should require not more than one or two drops of 0.1 N KMnO4
solution to obtain a pink color.) Empty the receiver, and put in
it 25 mL of ferric sulfate solution. Reduce the prepared
titanium solution as follows:
11.4.1 Run 50 mL of H2SO4 (1+19) through the reductor at
such a uniform rate as to require 5 to 10 min for passage.
11.4.2 Follow this with the titanium solution at such a
uniform rate as to require 10 min to pass through the reductor.
11.4.3 Wash out with 100 mL of H2SO4 (1+19).
11.4.4 Finally run through about 100 mL of water. Take care
that the reductor is always filled with solution or water to the
upper level of the zinc.
FIG. 2 Jones Reductor, Assembled 11.5 Gradually release the suction, wash thoroughly the
glass tube that was immersed in the ferric sulfate solution,
the end point has been reached. (More rapid cooling may be remove the receiver, and titrate immediately with 0.1 N KMnO
prevented by allowing the beaker to stand on a small hot plate 4 solution. Run a blank determination, using the same reagents
during the titration. The use of a small type thermometer as a and washing the reductor as in the above determination.
stirring rod is most convenient.) Keep the KMnO 4 solution in
12. Calculation
a glass-stoppered bottle painted black to keep out light or in a
brown glass bottle stored in a dark place. Calculate the TiO 2 12.1 Calculate the percent of TiO2 as follows:
equivalent in grams of TiO2 per millilitre of the KMnO 4 ~ V1 2 B ! 3 T
solution as follows: TiO2, % 5 S 3 100
TiO2 equivalent 5 ~W 3 1.192!/V

where:
where: V 1 5 KMnO4 solution required for titration of specimen,
W 5 Na2C2O4 used, g, and mL
V 5 KMnO4 solution required for the titration, mL. B 5 KMnO 4 solution required for titration of the blank,
10.10 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid mL
(H2SO4). T 5 TiO2 equivalent of the KMnO4 solution, g/mL, and
10.11 Sulfuric Acid (1+1)—Carefully mix 1 volume of S 5 dried specimen, g.
H2SO4 (sp gr 1.84) into 1 volume of water with rapid stirring. 12.2 The results calculated in accordance with 12.1 will
10.12 Sulfuric Acid (1+19)—Carefully mix 1 volume of include iron, chromium, arsenic, and any other substance that
H2SO4 into 19 volumes of water with rapid stirring. is reduced by zinc and acid. However, appreciable quantities of
interfering materials are not likely to be encountered in normal,
11. Procedure white titanium pigments.
11.1 Determine the dry weight of a weighing bottle and cap TOTAL TITANIUM BY THE ALUMINUM
to 0.1 mg. Weight to 0.1 mg 300 to 350 mg of the sample to be REDUCTION METHOD
analyzed into the weighing bottle.
11.2 Dry the specimen in the opened weighing bottle for 2 13. Scope
h at 105 to 110°C. Cool in a desiccator, cap the bottle, and 13.1 This method gives results similar to those obtained
3
D 1394
with the Jones Reductor Method (Sections 8-12). fumes are evolved, and continue the heating over a strong
flame until solution is complete (usually requires not over 5
14. Apparatus min of boiling) or it is apparent that the residue is composed of
14.1 Delivery Tube, made of about 4-mm inside diameter SiO2 or siliceous matter. Cool and, with caution, add 120 mL
glass tubing bent so that there is a horizontal run of about 6 in. of water and 20 mL of HCl. Bring to a boil and remove from
(152 mm) and a vertical drop of about 3 in. (76 mm) at one end, heat.
and a vertical drop of about 6 in. at the other end. 16.4 Insert the short end of the delivery tube into one hole
14.2 Weighing Bottle, wide-mouth, with an external-fitting of a two-hole rubber stopper suitable for the Erlenmeyer flask.
cap, and no larger than necessary for the required amount of Insert a glass rod with a slight hook or collar at the bottom end
sample. into the other hole of the stopper in such a way that the bottom
end will be near the bottom of the flask when the stopper is
15. Reagents inserted into the flask. Attach approximately 1 g of aluminum
15.1 Aluminum Metal Foil, electrolytic grade. foil to the bottom end of the rod by crumpling or coiling the
15.2 Ammonium Sulfate—((NH4) 2SO4). foil around the rod. It may be possible to use a thermometer
15.3 Ammonium Thiocyanate Indicator Solution—Dissolve instead of a collared glass rod and, if one ranging from 0 to
24.5 g of ammonium thiocyanate (NH4CNS) in 80 mL of hot 150°C is used, it can be used for determining temperature later.
water, filter, bring to room temperature, and dilute to 100 mL. Insert the stopper, carrying the rod with the foil and the
Keep in a well-stoppered, dark-colored bottle. delivery tube, into the flask in such a way that the foil will be
15.4 Ferric Ammonium Sulfate Solution (1 mL 5 0.005 g near the bottom of the flask at the same time that the long end
TiO2)—Dissolve 30.16 g of fresh ferric ammonium sulfate of the delivery tube will be near the bottom of a 250-mL beaker
(FeNH4(SO4) 2 · 12H2O) in 800 mL of water containing 15 mL containing about 150 mL of NaHCO3 solution.
of H2SO4(sp gr 1.84). Add 5 mL of 3 % H2O 2 and boil for at 16.5 As soon as dissolution of the aluminum is complete,
least 15 min then cool to room temperature. Dilute to exactly heat the flask to gentle boiling for 3 to 5 min without removing
1 L and mix well. Filter if cloudy. Standardize using 190 to 210 the delivery tube from the NaHCO3 solution. Cool to about
mg of NBS standard reference material No. 154 of titanium 60°C, preferably by partial immersion of the flask in a vessel of
dioxide and proceeding as directed in Section 16. Calculate the water. The NaHCO3 solution should siphon into the flask
TiO2 equivalent of the solution in grams of TiO2 per millilitre during this cooling, giving an atmosphere of CO2 over the
of solution, as follows: reduced titanium solution. Withdraw the stopper, but rinse the
TiO 2 equivalent 5 ~W1 3 P!/~V 2 3 100! glass rod attached to it with a little water, catching the rinse
water in the flask before removing the stopper, rod, and
where: delivery tube completely.
W 1 5 National Bureau of Standards standard sample of 16.6 Add 2 mL of NH4CNS indicator solution and titrate
TiO2 used, g, immediately with ferric ammonium sulfate solution (15.4) to a
P 5 percent TiO2 in National Bureau of Standards
straw-colored end point. It is best to add the bulk of the ferric
standard sample, and
ammonium sulfate solution at once, shake well, and finish the
V2 5 ferric ammonium sulfate solution required for the
titration drop by drop.
titration, mL.
17. Calculations
chloric acid (HCl).
15.6 Hydrogen Peroxide—3 %. 17.1 Calculate the percent of TiO2 as follows:
15.7 Sodium Bicarbonate Solution—Make up a saturated TiO2, % 5 ~V 3 3 T1 3 100!/S
solution at the time of analysis. About 10 g of sodium
bicarbonate (NaHCO3) to 90 g of water is required. where:
15.8 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid V 3 5 ferric ammonium sulfate solution required for titra-
(H2SO4). tion of specimen, mL
15.9 Titanium Dioxide (TiO2)—National Bureau of Stan- T 1 5 TiO2 equivalent of the ferric ammonium sulfate
dards standard sample No. 154 of titanium dioxide. solution, g/mL, and
S 5 dried specimen, g.
16. Procedure 17.2 The results calculated in accordance with 17.1 will
16.1 Determine the dry weight of the weighing bottle and include chromium, arsenic, and any other substance which is
cap. Weigh to the nearest 0.1 mg, 190 to 210 mg of the sample reduced by aluminum and subsequently oxidized by ferric ion.
to be analyzed into the weighing bottle. However, appreciable quantities of interfering materials are not
16.2 Dry the specimen in the open weighing bottle for 2 h at likely to be encountered in normal, white titanium pigments.
105 to 110°C. Cool in a desiccator, cap the bottle, and weigh as
rapidly as possible. Calculate the dry weight of the specimen ALUMINUM OXIDE
and use in the actual calculation.
16.3 Transfer the dry specimen to a 500-mL dry, wide- 18. Scope
mouth Erlenmeyer flask. Add 7 to 9 g of (NH4)2SO4 and 20 mL 18.1 This method covers the determination of aluminum
of H2SO4. Mix well, heat on a hot plate until dense white oxide in titanium dioxide pigments.
4
D 1394
19. Reagents the EDTA titration. Heat on a hot plate starting at low heat,
NOTE 1—Precaution: All solutions should be stored in polyethylene
then gradually raise the heat until full heat is reached. When the
bottles. spattering has stopped and light fumes of SO 3 appear, heat the
flask in the full flame of a Meker burner, with the flask tilted so
19.1 Acetic Acid, glacial. that the fusion is concentrated at one end of the flask. Swirl
19.2 Ammonium Acetate Solution (Buffer Solution)— constantly until the melt is clear. Avoid prolonged heating to
Dissolve 77 g of ammonium acetate in water, add 10 mL of prevent precipitation of titanium dioxide. Cool and add 25 mL
glacial acetic acid and dilute with water to 1 L.
of H2SO4 (1+1). Heat until the mass has dissolved, and a clear
19.3 Ammonium Hydroxide (1+4)—Dilute 1 volume of
solution results. (If silica is present, a little insoluble silica may
concentrated ammonium hydroxide (sp gr 0.90) with 4 vol-
remain.) Cool and add 120 mL of water.
umes of water.
19.4 Ammonium Phosphate, Dibasic Solution—Dissolve 20.2 Measure out 200 mL of 6.25 M NaOH solution. Add 65
150 g of (NH4)2HPO4 in 700 mL of water. Adjust pH to 5.5 mL of this NaOH solution to the sample solution while stirring
with HCl (1+1). Dilute with water to 1 L. constantly with a magnetic stirrer. Pour the remaining NaOH
19.5 EDTA Solution (0.02 M)—Dissolve 7.45 g of diso- solution into a 500-mL volumetric flask. Slowly, and with
dium ethylenediamine tetraacetate dihydrate in water and constant stirring, add the sample solution to the NaOH solu-
dilute to 1 L. tion. Police with water, cool, and dilute to volume. (If the
19.6 Hydrochloric Acid (1+1)—Dilute 1 volume of concen- procedure is delayed at this point for more than 2 h, transfer the
trated hydrochloric acid (sp gr 1.19) with 1 volume of water. contents of the volumetric flask to a polyethylene bottle.)
19.7 Methyl Orange Indicator Solution— Dissolve 0.1 g of Either centrifuge for 5 min, or allow most of the precipitate to
methyl orange in 100 mL of water, in accordance with settle out, then filter the supernatant liquid through a very fine
Practices E 50. filter paper until a little more than 100 mL have been collected.
19.8 Sodium Bisulfate Monohydrate — (NaHSO4 · H2O). 20.3 Place a 100-mL aliquot of the above solution in a
19.9 Sodium Fluoride (NaF). 500-mL Erlenmeyer flask, add 1 drop of methyl orange
19.10 Sodium Hydroxide Solution (6.25 M)—Dissolve 500 indicator solution and acidify with HCl (1+1) until the color
g of sodium hydroxide (NaOH) in water and dilute to 2 L. changes to red; add approximately 3 mL in excess.
19.11 Sulfuric Acid (1+1)—To 1 volume of water add 20.4 Add 25 mL of EDTA solution. (If the approximate
slowly with stirring 1 volume of concentrated H2SO4. alumina level is known, use the following mathematical
19.12 Xylenol Orange Indicator Solution—Dissolve 0.2 g formula for determining the amount of EDTA to add for best
of xylenol orange tetrasodium salt in 100 mL of water. Renew results: 4 3 % Al 2O3 + 5 5 mL of 0.02 M EDTA.) Add,
solutions weekly. dropwise, NH4OH (1+4) until the solution color is just com-
19.13 Zinc Sulfate, Standard Solution (0.01 M)—Dissolve pletely changed from red to orange-yellow. Add 10 mL of
2.90 g of zinc sulfate (ZnSO4 · 7H2O) in water and dilute to 1 buffer solution and 10 mL of (NH4)2 · HPO4 solution, boil for
L. Standardize as follows: 5 min, and cool quickly to room temperature in running water.
19.13.1 Dissolve with the aid of heat 0.50 g of high-purity Add 3 drops of xylenol orange indicator solution. If the
(99.8 %) aluminum wire, weighed to 0.1 mg, in 20 mL of solution is purple, yellow-brown, or pink, bring the pH to
concentrated HCl. Transfer to a 1-L volumetric flask and dilute 5.3-5.7 with acetic acid. If the pH is correct, a pink color
to volume with water. indicates insufficient EDTA; repeat with a new aliquot, starting
19.13.2 Place a 10-mL aliquot of this solution into a 500-mL with 20.3 and using 50 mL of EDTA solution in 20.4.
Erlenmeyer flask containing approximately 90 mL of water and 20.5 Titrate with ZnSO4 solution to a yellow-brown or pink
3 mL of HCl. Add 1 drop of methyl orange indicator solution. end point. This titration should be performed quickly near the
Continue with step 20.4. end point by rapidly adding 0.2-mL increments until the first
19.13.3 Calculate the titre of the ZnSO4 solution as follows: color change occurs. This color will fade in 5 or 10 s, but is the
A 5 ~18.8955 3 W 1!/V4 true end point. This step is critical, and failure to observe the
first color change will result in an incorrect value. The fading
where: end point does not occur in the second titration. This first
A 5 Al2O3 per millilitre of ZnSO4 solution, mL titration must be greater than 8 mL of ZnSO4 solution. For
W1 5 weight of aluminum wire dissolved in 19.13.2, g,
most accurate work this first titration should require 10 to 15
V4 5 ZnSO4 solution consumed in the second titration,
mL of ZnSO4 solution.
mL, and
20.6 Add 2 g of NaF, boil for 2 to 5 min, and cool in running
mol weight of Al2O3 3 10
18.8955 5 water. Titrate the EDTA, released from its aluminum complex
2 3 mol weight of Al
by the fluoride, with ZnSO4 solution to the same end point as
20. Procedure in 20.5.
20.1 Fuse about 1 g of pigment weighed to 0.1 mg with 10 21. Calculation

g of NaHSO4 · H2O in a 250-mL Erlenmeyer flask until the
melt is clear. Use a 250-mL high-silica glass Erlenmeyer flask 21.1 Calculate the aluminum oxide content of the pigment
to prevent cracking. Do not use more sodium bisulfate than sample as follows:
specified since excess concentrations of salt will interfere with A 5 ~Z 3 T!/~2 3 S! (1)
5
D 1394
where: 27.2 Heat over a Meker burner, frequently swirling the flask
A 5 percent Al2O3, until decomposition and fusion is complete and clear (except
Z 5 ZnSO4 solution consumed in the second titration, mL for SiO 2). Be careful of overheating at start and of spattering
T 5 Al2O3 per millilitre of ZnSO 4 solution, g, and of the fusion.
S 5 specimen used, g. 27.3 Allow to cool and to the cold melt, add 25 mL of
H2SO4 (1+1), and heat very carefully and very slowly until the
22. Precision fusion is dissolved. Carefully evaporate to fumes of H2SO 4.
22.1 Based on interlaboratory studies the following criteria 27.4 Cool and carefully add 150 mL of water. Pour very
should be used for judging the acceptability of results at the small amounts of water down the sides of the flask with
95 % confidence level: frequent swirling of the contents to avoid overheating and
22.1.1 Repeatability—Two results obtained by the same spattering. Let cool and filter through fine ashless filter paper,
operator on the same sample should be considered suspect if using a 60° gravity funnel.
they differ by more than 0.22 % relative. 27.5 Wash out all silica from the flask onto the filter paper
22.1.2 Reproducibility—Two results, each the mean of du- with H2SO4 (1+9). Police the flask carefully.
plicates obtained by operators in different laboratories should 27.6 Place the filter paper in a platinum crucible and dry in
be considered suspect if they differ by more than 0.62 % a 120°C oven. Heat the partly covered crucible over a bunsen
relative. burner. Avoid flaming the filter paper by heating first the cover
from above and then the crucible from below. When the filter
SILICA paper is consumed, heat at 1000°C for 30 min in a muffle
23. Scope furnace. Cool in a desiccator and weigh the crucible.
27.7 Add 2 drops of H2SO4 (1+1) and 5 mL of HF (sp gr
23.1 This method covers the determination of silica in
1.15). Carefully evaporate to dryness, first on a low heat hot
titanium dioxide (TiO2) pigments.
plate to remove the HF and then over a bunsen burner to
24. Summary of Method remove the H2SO4. Avoid spattering, especially after removal
of the HF.
24.1 The fusion of TiO2 pigment with sodium bisulfate
27.8 Ignite at 1000°C for 10 min. Cool in a desiccator and
leaves only the silica insoluble when the melt is dissolved in
weigh the crucible again. The difference in weight is silica.
sulfuric acid. To assure no loss of the silica the sulfuric acid is
taken to fuming to dehydrate the silica. The silica content is 28. Calculation
determined by volatilizing the silica in the weighed filtration 28.1 Calculate the silica content as follows:
residue with hydrofluoric acid.
SiO2, % 5 ~W 2/S3! 3 100
25. Apparatus
where:
25.1 Erlenmeyer Flask, 250-mL, high silica. W 2 5 SiO2 found, g, and
25.2 Filter Paper, very fine, ashless, acid washed. S3 5 specimen used, g.
25.3 Platinum Crucible and Cover.
25.4 Oven, controlled at 120°C. 29. Precision
25.5 Muffle Furnace, controlled at 1000 6 25°C. 29.1 On the basis of an interlaboratory test of this test
method in which six laboratories tested, in duplicate, five
26. Reagents samples of titanium dioxide ranging in silica content from 1.5
26.1 Hydrofluoric Acid (sp gr 1.15)—Concentrated hydrof- to 8.2 %, within-laboratory standard deviation was found to be
luoric acid (HF). 1.79 % and between-laboratories standard deviation was found
26.2 Sodium Bisulfate—(NaHSO4 · H2O). to be 3.44 %. Based on this, the following criteria should be
26.3 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid used for judging the precision of results at the 95 % confidence
(H2SO4). level:
26.4 Sulfuric Acid (1+1)—To 1 volume of water add slowly 29.1.1 Repeatability—Two results obtained by the same
with stirring 1 volume of concentrated H2SO4. operator should be considered suspect if they differ by more
26.5 Sulfuric Acid (1+9)—To 9 volumes of water add than 5.1% relative.
slowly with stirring 1 volume of concentrated H2SO4. 29.1.2 Reproducibility—Two results, each the mean of du-
plicates, obtained by operators in different laboratories should
27. Procedure be considered suspect if they differ by more than 9.7 %
27.1 Transfer 1 g of pigment weighed to 0.1 mg to a 250-mL relative.
high silica Erlenmeyer flask containing 10 g of NaHSO4 · H2O.
If an SiO2 content in excess of 5 % is expected a 0.5-g 30. Keywords
specimen of pigment may be used to facilitate complete fusion 30.1 aluminum oxide; aluminum reduction; Jones Reductor;
with 10 g of NaHSO4 · H2O. titanium pigment; chemical analysis
6
D 1394
7

Chemical Analysis of Poly(Vinyl Butyral)1
1. Scope 4.1.2 Phenolphthalein Indicator Solution (10 g/L)—

1.1 These methods cover procedures for the determination Dissolve 1 g of phenolphthalein in 100 mL of ethanol (95 %),
of poly(vinyl alcohol), poly(vinyl acetate), and butyraldehyde methanol, or isopropanol.
in poly(vinyl butyral). 4.1.3 Potassium Hydroxide, Standard Alcoholic
1.2 The procedures appear in the following order: Solution (0.5 N)—Dissolve 33 g of KOH in methanol and
Sections
dilute to 1 L. Standardize against potassium acid phthalate
Poly(vinyl alcohol) 4 using phenolphthalein indicator solution.
Poly(vinyl acetate) 5 4.1.4 Pyridine Acetic Anhydride Reagent—Mix slowly
Butyraldehyde 6
1000 mL of pyridine and 87 mL of acetic anhydride. Make only
1.3 This standard does not purport to address all of the about a week’s supply, and keep it in a brown bottle.
safety concerns, if any, associated with its use. It is the 4.2 Procedure:
responsibility of the user of this standard to establish 4.2.1 Transfer 2.2 g of the dry sample to a clean, dry,
appropriate safety and health practices and determine the 500-mL glass-stoppered flask. Add 25.0 mL of pyridine-acetic
applicability of regulatory limitations prior to use. anhydride reagent. Insert the stopper, and heat the flask on a
sand or steam bath below the boiling point for 51⁄2 h. Swirl
2. Referenced Documents gently until the sample is completely dissolved. Vent the flask
2.1 ASTM Standards: occasionally during the first part of the heating period to
D 1193 Specification for Reagent Water2 prevent the stopper from blowing out.
4.2.2 At the end of the 51⁄2-h period, add 25 mL of ethylene
3. Reagents dichloride and shake well. Add 100 mL of water, and shake
3.1 Purity of Reagents—Reagent grade chemicals shall be vigorously immediately after adding the water. Let the flask
used in all tests. Unless otherwise indicated, it is intended that stand for 1⁄2 h.
all reagents shall conform to the specifications of the 4.2.3 Add a few drops of phenolphthalein solution and
Committee on Analytical Reagents of the American Chemical titrate with 0.5 N alcoholic KOH solution. Shake vigorously
Society, where such specifications are available.3 Other grades during the titration.
may be used, provided it is first ascertained that the reagent is 4.2.4 Blank—Run a blank determination on the reagents,
of sufficiently high purity to permit its use without lessening following the same procedure as for the sample.
the accuracy of the determination. 4.3 Calculation—Calculate the percentage of poly(vinyl
3.2 Purity of Water—Unless otherwise indicated, references alcohol) as follows:
to water shall be understood to mean reagent water conforming Poly~vinyl alcohol!, % 5 ~@B 2 V! N 3 4.4#/ S (1)
to Specification D 1193.
where:
4. Poly(Vinyl Alcohol) B 5 KOH solution required for titration of the blank, mL,
4.1 Reagents: V 5 KOH solution required for titration of the sample, mL,
4.1.1 Ethylene Dichloride, technical grade. N 5 normality of the KOH solution, and
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint 5. Poly(Vinyl Acetate)
of Subcommittee D01.33 on Polymers and Resins. 5.1 Apparatus:
Current edition approved May 15, 1992. Published July 1992. Originally 5.1.1 Flask, Wide-Mouth, 500-mL capacity, equipped with a
published as D 1396 – 56 T. Last previous edition D 1396 – 73 (1987)e1. metal reflux condenser.
2
3
Reagent Chemicals, American Chemical Society Specifications, American 5.2 Reagents:
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 5.2.1 Hydrochloric Acid Standard Alcoholic Solution (0.5
listed by the American Chemical Society, see Analar Standards for Laboratory N).
5.2.2 Methanol:
MD. 5.2.3 Phenolphthalein Solution (10 g/L)—See 4.1.2.
1
D 1396
5.2.4 Potassium Hydroxide Alcoholic Solution (28 g KOH/ NOTE 2—The pH value of the blank and sample vary with temperature;
L)—Dissolve 33 g of potassium hydroxide (85 % KOH in if the temperature is raised the green end point will turn yellow and if the
ethyl alcohol and dilute to 1 L with methanol. This solution is temperature is lowered the green end point will turn blue. The pH value
of the blank changes more quickly than the pH of the sample solution for
approximately 0.5 N so standardized solution (4.1.3) may be a given change in temperature. Therefore, the blank is titrated and kept at
used if desired. 24 6 2°C and the sample is titrated at the same temperature.
5.3 Procedure: NOTE 3—The color change of the indicator will be a gradual one from
5.3.1 Transfer 2.15 g of the dry sample to the 500-mL flask. yellow to green to blue. No sharp transition point will be found. Choose
Add 200 mL of methanol, measured in a graduate. Measure a point of yellow green to green coloration. A buffer solution containing
from a buret 25.0 mL of KOH solution (4.2.3). Reflux on a 2.05 g of potassium acid phthalate 24 mL of 0.1 N H2SO4, and 50 mL of
methanol gives a color matching a blank titrated with 6.85 mL of 0.0938
sand or water bath for 2 h.
N NaOH solution. The color in the buffer solution will fade out but the
5.3.2 Rinse down the condenser and flask with a small regular blank may be kept as a standard for the determination.
amount of water, add a few drops of phenolphthalein solution,
and backtitrate, using 0.5 N alcoholic HCl. 6.3 Procedure for Analysis of Sample:
5.3.3 Blank—Run a blank determination on the reagents, 6.3.1 Transfer 2 g of the dry sample, weighed to the nearest
following the same procedure as for the sample. 0.1 mg, to the 500-mL Erlenmeyer flask. Add 50 mL of
5.4 Calculation—Calculate the percentage of poly(vinyl n-butanol and 50 mL of hydroxylamine hydrochloride solution,
acetate) as follows: and attach the 12-in. (305-mm) reflux condenser. Be sure the
ground-glass joint is dry. Add a boiling chip, and reflux for 2
Poly~vinyl acetate!, % 5 @~B 2 V!N 3 8.6#/S (2) h.
where: NOTE 4—The resin gradually forms a milky emulsion. At this point, the
B 5 HCl required for back-titration of the blank, mL, reaction tends to bump and must be watched. After approximately 1.5 h
V 5 HCl required for back-titration of the sample, mL, the bumping lessens considerably and the mixture clears.
N 5 normality of the HCl, and 6.3.2 Cool, add 5 drops of bromphenol blue solution and
S 5 sample used, g.
titrate with 0.5 N NaOH solution until at least two-thirds of the
expected requirement has been run in. Add 50 mL of methanol.
6. Total Butyraldehyde
At the first appearance of a green tinge, bring the flask to 24 6
6.1 Reagents: 2°C (Note 5). Titrate to the same color as the blank (Note 6).
6.1.1 Bromphenol Blue Indicator Solution—Dissolve 0.2 g
of bromphenol blue indicator solution in 100-mL of methanol, NOTE 5—The heat of neutralization changes the temperature during the
titration.
ethanol, or isopropanol. NOTE 6—The blank may be diluted to give the same intensity of color
6.1.2 n-Butanol. as in the analysis of the sample if the percentage of butyraldehyde in all
NOTE 1—The same lot of n-butanol should be used for all determinations is fairly constant. Otherwise, adjust the intensity of color
determinations that are to be compared. by the amount of indicator present.
6.4 Calculation—Calculate the percent of total
6.1.3 Hydroxylamine Hydrochloride Solution (0.5 N).
butyraldehyde as follows:
6.1.4 Methanol.
6.1.5 Sodium Hydroxide Standard Solution (0.5 N)— Butyraldehyde, % 5 @~V 2 B!N 3 7.2#/S (3)
Dissolve 20 g of NaOH in water and dilute to 1 L. Standardize
where:
against potassium acid phthalate.
V 5 NaOH solution required for titration of the specimen,
6.2 Blank Determination:
mL,
6.2.1 Place 50 mL of n-butanol and 50 mL of the B 5 NaOH solution required for titration of the blank, mL,
hydroxylamine hydrochloride solution in a 500-mL N 5 normality of the NaOH solution, and
Erlenmeyer flask, and fit by means of the ground-glass joint to S 5 specimen weight, g.
a 12-in. (305-mm) reflux condenser. Be sure the ground-glass
joint is dry. Add a porous plate boiling chip, and reflux for 2 h 7. Precision and Bias
on a hot plate. Cool to 24 6 2°C. 7.1 The precision of the three determinations has not been
6.2.2 Add exactly 5 drops of bromphenol blue indicator determined.
solution and 50 mL of methanol to the solution and titrate with 7.2 Bias cannot be determined as no standards are available.
0.5 N NaOH solution to a green end point (Note 2). Run at least
two blank determinations checking to within 0.5 mL of each 8. Keywords
other, titrating to the same end point at 24 6 2°C (Note 3). 8.1 poly(vinyl acetate); poly(vinyl butyral)
2

Unsaponifiable Matter in Alkyd Resins and Resin Solutions1
1. Scope 5. Reagents and Materials

1.1 This test method covers the determination of unsaponi- 5.1 Reagent grade chemicals shall be used in all tests.
fiable matter in alkyd resins and resin solutions. This test Unless otherwise indicated, it is intended that all reagents shall
method is not applicable to alkyd resins containing modifying conform to the specifications of the Committee on Analytical
agents such as urea, melamine, phenols, rosin, and styrene. Reagents of the American Chemical Society, where such
1.2 This standard does not purport to address all of the specifications are available.4 Other grades may be used, pro-
safety concerns, if any, associated with its use. It is the vided it is first ascertained that the reagent is of sufficiently
responsibility of the user of this standard to establish appro- high purity to permit its use without lessening the accuracy of
priate safety and health practices and determine the applica- the determination.
bility of regulatory limitations prior to use. For a specific 5.2 Unless otherwise indicated references to water shall be
hazard statement, see Note 4. understood to mean reagent water as defined by Type II of
2. Referenced Documents 5.3 Benzene.
2.1 ASTM Standards: 5.4 Benzene–Alcohol Mixture—Mix equal volumes of ben-
D 1193 Specification for Reagent Water2 zene and ethyl alcohol, add 2 drops of phenolphthalein
indicator solution, and neutralize with 0.02 N sodium hydrox-
3. Significance and Use ide (NaOH) solution to a persistent faint pink color.
3.1 The unsaponifiable matter in alkyd resins controls the 5.5 Ethyl Alcohol (95 volume %)—Pure ethyl alcohol or
properties of the final film. denatured alcohol conforming to Formula No. 2B of the U. S.
Bureau of Internal Revenue.
4. Apparatus 5.6 Ethyl Ether.
4.1 Aluminum Beaker, having a capacity of 125 mL.3 5.7 Phenolphthalein Indicator Solution (10 g/L)—Dissolve
4.2 Flask and Condenser—A 200-mL Erlenmeyer flask 1 g of phenolphthalein in ethyl alcohol (95 %) and dilute to 100
fitted with a water-cooled glass reflux condenser. The connec- mL with ethyl alcohol.
tion between the flask and condenser shall be a standard 24/40 5.8 pH Indicator Paper, universal type.
taper ground-glass joint. 5.9 Sodium Hydroxide Solution (50 %)—Dissolve sodium
4.3 Separatory Funnels—Three 500-mL capacity fitted with hydroxide (NaOH) in an equal weight of water.
standard-taper, ground-glass stoppers and stopcocks. Stop- 5.10 Sodium Hydroxide, Standard Solution (0.02 N)—
cocks should be lubricated sparingly with ether-insoluble Prepare and accurately standardize a 0.02 N aqueous NaOH
stopcock grease. Alternatively, funnels fitted with tetrafluoro- solution.
ethylene (TFE-fluorocarbon) stopcocks may be used.
4.4 Steam Bath. 6. Procedure
4.5 Vacuum Drying Oven—A small, laboratory-size vacuum 6.1 Weigh by difference, from a closed container into the
oven, thermostatically controlled to operate at 80 6 5°C. A 200-mL Erlenmeyer flask, a portion of resin or resin solution
water aspirator vacuum source is satisfactory. containing from 0.05 to 0.2 g of unsaponifiable matter (Note 1)
(8 to 10 g of resin solution usually is sufficient).
NOTE 1—The maximum specimen size is limited to 10 g of nonvolatile
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint matter; otherwise saponification or separation difficulties may arise. The
4
Current edition approved April 15, 1993. Published June 1993. Originally Reagent Chemicals, American Chemical Society Specifications, American
published as D 1397 – 56 T. Last previous edition D 1397 – 88. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
3
Aluminum beakers, Catalog No. 2100, manufactured by the A. H. Thomas Co., Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
W. Washington Square, Philadelphia, PA 19105, have been found satisfactory for and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
this purpose. MD.
1
D 1397
specimen should be weighed to the nearest milligram. 0.02 N NaOH solution to the same persistent faint pink color as
6.2 Add 10 mL of benzene, and warm to dissolve the in the neutralization of the benzene-alcohol mixture (see 5.3).
sample. Add 50 mL of alcohol, swirl gently to mix, and then
add slowly 5 mL of the NaOH solution (50 %), whileswirling 7. Calculation and Report
gently. Add 5 mL of water, attach to the condenser, and allow 7.1 Calculate the unsaponifiable matter as follows, and
to reflux gently on the steam bath for 2 h. report the results to the nearest 0.1 %:
6.3 Remove from the heat source, cool to room temperature, F 5 VN 3 0.280 (1)
and wash down the condenser and joint with a few millilitres
of water from a wash bottle. Transfer the contents of the flask where:
to a 500-mL separatory funnel with the aid of water from the F 5 fatty acids in extract, g,
wash bottle. Finally, rinse the flask with three 25-mL portions V 5 NaOH solution required for titration of the residue,
of ether, adding the ether washes to the sample in the mL,
separatory funnel. Add sufficient water to bring the volume of N 5 normality of the NaOH solution, and
the lower aqueous layer to 300 mL, and add 10 mL of alcohol. 0.280 5 the factor used for normal 18-carbon atom fatty
6.4 Stopper the separatory funnel, shake gently, and allow acids. If coconut, lauric, pelargonic, or other short
the layers to separate. Draw off the lower aqueous layer into chain fatty acids are suspected or known to be
the second separatory funnel (Note 2). Continue the extraction present, use the arbitrary factor 0.216 in the above
of the aqueous layer with successive 20-mL portions (not less equation.
than three) until a colorless ether extract is obtained, U 5 @~R 2 F!/S# 3 100
combining the ether extracts in the first funnel, and using the (2)
second and third funnels for the successive extractions.
where:
NOTE 2—If the layers do not separate easily, carefully draw off the U 5 unsaponifiable matter,% ,
lower, clear, aqueous layer and add 2 to 3 mL of alcohol, by means of a R 5 residue, g, and
pipet, to the ether-emulsion phases in the separatory funnel. Swirl gently S 5 specimen, g.
to break the emulsion, and continue to draw off the lower layer. This
procedure for breaking the emulsion may be repeated on subsequent
extractions, if necessary.
6.5 Wash the final combined ether extracts with 25-mL 8.1 On the basis of an interlaboratory study of this test
portions of water until the washings are neutral when tested method in which the within-laboratory standard deviation was
with the indicator paper or solution. Transfer the final ether found to be 0.08 % absolute and the between-laboratory
extract portion-wise into the 125-mL beaker containing a small standard deviation was found to be 0.11 % absolute the
boiling stone and previously weighed to the nearest 1 mg, following criteria should be used for judging the acceptability
evaporating the ether from each portion on the steam bath of results at the 95 % confidence level:
(Note 3). (Precaution—See Note 4.) Finally, rinse the 8.1.1 Repeatability—Two results, each the mean of
separatory funnel with a few successive millilitres of ether, duplicate determinations, obtained by the same operator,
adding these washes to the extract in the beaker. should be considered suspect if they differ by more than 0.25 %
absolute.
NOTE 3—The metal top of the steam bath should be covered with clean
8.1.2 Reproducibility—Two results, each the mean of
aluminum foil to prevent corrosion of the aluminum beaker during the
evaporation. duplicate determinations, obtained by operators in different
NOTE 4—Precaution: In addition to other precautions, be sure to use a laboratories, should be considered suspect if they differ by
hood. more than 0.33 % absolute.
6.6 Evaporate the final portion of ether; then transfer the 8.2 Bias—No bias can be determined for this test method
beaker and its contents to the vacuum oven, previously heated since no standard alkyd resin exists.
to 80°C. Heat to constant weight, allowing to cool to room
temperature in a desiccator before weighing. 9. Keywords
6.7 After weighing, take up the residue in 50 mL of warm 9.1 alcohol benzene solution; alkyd resin; alkyd resin
(approximately 50°C) benzene-alcohol mixture. Titrate with solution; coconut acid; lauric acid; pelargonic acid
2

Fatty Acid Content of Alkyd Resins and Alkyd Resin
Solutions1
1. Scope 4.5 Flask, 250-mL, flat-bottom, with standard taper open-

1.1 This test method covers the gravimetric determination ing.
of the total fatty acids in alkyd resins and alkyd resin solutions. 4.6 Nitrogen Gas Supply.
The test method is not applicable to alkyd resins containing 4.7 Separatory Funnels, three 500-mL capacity glass-
modifying agents such as urea, melamine, phenols, rosin, and stoppered, fitted with standard-taper ground-glass stoppers and
styrene. stopcocks.
1.2 This standard does not purport to address all of the 4.8 Steam Bath.
safety concerns, if any, associated with its use. It is the 4.9 Water Bath.
responsibility of whoever uses this standard to consult and 4.10 Vacuum Drying Oven, small, laboratory-size, thermo-
establish appropriate safety and health practices and deter- statically controlled to operate at 606 2°C. A water-aspirator
mine the applicability of regulatory limitations prior to use. vacuum source is satisfactory.
4.11 Cotton, absorbent, USP.
5. Reagents and Materials
2.1 ASTM Standards:
D 563 Test Method for Phthalic Anhydride Content of 5.1 Purity of Reagents—Reagent grade chemicals shall be
Alkyd Resins and Resin Solutions2 used in all tests. Unless otherwise indicated, it is intended that
D 1193 Specification for Reagent Water3 all reagents shall conform to the specifications of the Commit-
D 1615 Test Methods for Glycerol, Ethylene Glycol, and tee on Analytical Reagents of the American Chemical Society,
Pentaerythritol in Alkyd Resins2 where such specifications are available.5 Other grades may be
D 2245 Test Method for Identification of Oils and Oil Acids used, provided it is first ascertained that the reagent is of
in Solvent-Reducible Paints4 sufficiently high purity to permit its use without lessening the
3. Significance 5.2 Purity of Water—Unless otherwise indicated, references
3.1 This test method is used to determine total fatty acid to water shall be understood to mean reagent water conforming
content of alkyl resins and this solution, in the absence of to Type IV of Specification D 1193.
interfering compounds, as a means whereby the relative 5.3 Ether, anhydrous.
applicability of the alkyd resin to the particular end use may be 5.4 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
estimated by buyer and seller. chloric acid (HCl).
5.5 Indicator Paper, universal-type.
4. Apparatus 5.6 Sodium Sulfate (Na2SO4), anhydrous.
4.1 Beakers, having capacities of 150 and 400 mL.
6. Procedure
4.2 Desiccator,
4.3 Filter Paper, rapid, low-ash filter paper, to fit the 6.1 Saponify a portion of resin or resin solution in accor-
filtering funnel. dance with Test Method D 563. After filtering the potassium
4.4 Filtering Funnel, 75-mm diameter, long-stem. phthalate alcoholate (6.3), transfer the combined filtrate and
washings to the 400-mL beaker with the aid of 25 mL of water
from a wash bottle. Concentrate to a volume of approximately
1
5
Subcommittee D01.33 on Polymers and Resins. Reagent Chemicals, American Chemical Society Specifications, American
published as D 1398 – 56. Last previous edition D 1398 – 84. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
1
D 1398
25 mL on the steam bath under a blanket of nitrogen to prevent NOTE 4—A small brass screw soldered to the end of a stiff brass wire
oxidation of the fatty acids. (Caution—Be sure to use a hood.) will serve for this purpose.
Transfer to a 500-mL separatory funnel with the aid of water 6.7.3 Insert a clean plug of cotton moistened with ether into
from a wash bottle, dilute with water to approximately 300 mL, the funnel stem and filter the ether solution through the cotton
and add 10 mL of alcohol. plug into the appropriate receiver.
6.2 Extract the unsaponifiable and volatile thinners with
successive 50-mL portions of ether (not less than three, or until NOTE 5—Experience will show how tightly packed the cotton must be
to hold back the Na2SO4 and still allow a sufficient flow of ether extract.
a colorless ether extract is obtained), combining the ether
extracts in the first separatory funnel and using the other two 6.8 Evaporate the ether portionwise from the beaker or
funnels for the successive extractions (Note 1). Finally, wash distill it from the flask on the steam bath, in a hood. Apply a
the combined ether extracts with three 15-mL portions of blanket of nitrogen over the beaker during evaporation.
water, adding the water washes to the main aqueous phase. Remove the last portions of fatty acids from the Na2SO4 in the
Discard the combined ether extracts. funnel by washing with successive small portions of ether until
NOTE 1—If the layers do not separate easily, carefully draw off the
a colorless extract is obtained. Remove the final traces of fatty
lower, clear aqueous layer and add 2 to 3 mL of alcohol, by means of a acids from the filter paper or cotton plug by using several
pipet, to the ether emulsion phases in the separatory funnel. Swirl gently successive small portions of ether.
to break the emulsion and continue to draw off the lower layer. This 6.9 If a gas chromatographic analysis of the separated fatty
procedure for breaking the emulsion may be repeated on subsequent acids is to be performed, observe the precautions given in 7.2
extractions, if necessary. of Test Method D 2245.
6.3 Acidify the aqueous phase to a pH of approximately 2 6.10 Complete the evaporation of the fatty acid-ether
by slowly adding HCl, cooling under running tap water. When solution on the steam bath, while maintaining a nitrogen
the mixture has cooled to room temperature, extract the fatty atmosphere over the acids. Remove the final traces of ether by
acids with successive 25-mL portions (not less than three) of heating for successive 20-min periods in a vacuum oven at
ether until a colorless ether extract is obtained, combining the 60°C until minimum weight is obtained. After each heating
ether extracts in the first separatory funnel and using the other period, allow the beaker and contents to cool in a desiccator
two funnels for the successive extractions. Wash the combined and then weigh to 1 mg.
ether extracts with successive 10-mL portions of water until
free of mineral acid when tested with an indicator paper. 7. Calculation and Report
Discard the aqueous phase (unless Test Method D 1615 is 7.1 Calculate the percent total fatty acids content, T, as
being followed). follows, and report the results to 0.1 %:
6.4 Dry the combined ether extracts in the separatory funnel
by the addition of successive small quantities of anhydrous A2B
T5 S 3 100 (1)
Na2SO4.
NOTE 2—The free water has been removed when, by the addition of a where:
small quantity of Na2SO4 and gentle swirling, the excess Na2SO4 is seen A 5 weight of beaker plus residue,
to disperse as a freely moving powder. B 5 weight of beaker, and
6.5 By either of the following methods, filter the ether S 5 specimen weight taken for analysis.
extract portionwise into a tared (to 1 mg) 250-mL standard-
taper flat-bottom flask or 150-mL beaker, containing a small 8. Precision and Bias
boiling aid. 8.1 On the basis of an interlaboratory study of this test
6.6 Method A—Filter the dried ether extract, portionwise method, the within-laboratory standard deviation was found to
through a rapid, low-ash paper by decanting from the top be 0.31 and the between-laboratories standard deviation was
opening of the separatory funnel into the appropriate receiver. found to be 0.50. Based on these standard deviations, the
Cover the filter funnel with a watch glass between each following criteria should be used for judging the acceptability
filtration step. of results at the 95 % confidence level:
6.7 Method B: 8.1.1 Repeatability—Two results obtained by same operator
6.7.1 Invert the separatory funnel and open the stopcock, should be considered suspect if they differ by more than 0.9 %
allowing any water in the bore of the stopcock to run back into absolute.
the funnel. 8.1.2 Reproducibility—Two results, each the mean of
NOTE 3—A small amount of ether applied to and evaporated from the duplicates, obtained by operators in different laboratories
outside of the funnel before the cock is opened will assure that the water should be considered suspect if they differ by more than 1.5 %
will drain back into the funnel. absolute.
6.7.2 Close the cock and then shake the contents of the 8.2 Bias— No bias can be determined for this test method
funnel sufficiently for the Na2SO4 to absorb all the water. If since no standard alkyd resin exists.
needed, add more Na2SO4 and gently swirl the funnel and
contents. Swab out the stem of the funnel with a piece of cotton 9. Keywords
attached to a stiff wire. 9.1 alkyd resin; fatty acid; fatty acid content
2
D 1398
3

Unsaponifiable Contents of Tricresyl Phosphate1
1. Scope 5.3 Evaporating Dish, porcelain or glass, having a capacity

1.1 This test method covers the determination of the amount of 120 mL.
of unsaponifiable impurities in tricresyl phosphate. 5.4 Steam Bath.
1.2 This standard does not purport to address all of the 5.5 Drying Oven, thermostatically controlled, at a tempera-
safety concerns, if any, associated with its use. It is the ture of 75 6 5°C.
responsibility of the user of this standard to establish appro- 6. Reagents
bility of regulatory limitations prior to use. For specific hazard 6.1 Purity of Reagents—Unless otherwise indicated, it is
statements, see Section 7. intended that all reagents shall conform to the specifications of
1.3 For hazard information and guidance, see the supplier’s the Committee on Analytical Reagents of the American Chemi-
Material Safety Data Sheet. cal Society, where such specifications are available.3 Other-
wise, the best available grade shall be used.
2. Referenced Documents 6.2 Purity of Water—References to water shall be under-
2.1 ASTM Standards: stood to mean reagent water conforming to Type IV of
D 1193 Specification for Reagent Water2 Specification D 1193.
6.3 Petroleum Ether, having a boiling range from 30 to
3. Summary of Test Method 65°C.
3.1 The specimen is refluxed in the presence of an aqueous 6.4 Sodium Hydroxide (NaOH) Pellets.
solution of sodium hydroxide which converts the phosphate
7. Hazards
ester to water-soluble salts. The saponified material is extracted
with petroleum ether which dissolves any unsaponifiable or 7.1 Tricresyl phosphate is hazardous through inhalation or
water-insoluble material. The combined extracts are evapo- skin absorption. Care should be taken in handling the material.
rated in a tared evaporating dish, and the residual nonvolatile 7.2 Ortho-isomer of tricresyl phosphate is considered toxic.
material is determined. Trace amounts may be present in tricresyl phosphate speci-
mens.
8. Procedure
4.1 This test method determines the amount of unsaponifi-
able impurities in tricresyl phosphate remaining after manu- 8.1 Place approximately 30 mL of water in the 250-mL
facture or that may be introduced during handling and storage. Erlenmeyer flask and to this carefully add approximately 10 g
4.2 Water-insoluble materials, which do not evaporate on a of NaOH pellets. Carefully swirl the flask to dissolve the
steam bath or in a drying oven operated at 75 6 5°C for 1 h, NaOH, and cool the solution to room temperature.
will be included as unsaponifiable material. 8.2 By means of a weighing pipet, transfer a 10-g specimen,
weighed to 1 mg, to the flask. Add several boiling-stones,
5. Apparatus connect the flask to the reflux condenser, and reflux for 1 h.
5.1 Reflux Apparatus, consisting of a 250-mL Erlenmeyer (Warning—See 7.1 and 7.2.)
flask equipped with a 24/40 standard-taper joint attached to an 8.3 At the end of the refluxing period remove the flask from
Allihn-type reflux condenser similarly equipped with a 24/40 the heat and wash the condenser down with 50 mL of water.
standard-taper joint. 8.4 Cool the flask to room temperature and transfer its
5.2 Separatory Funnel, having a capacity of 250 mL. content to the 250-mL separatory funnel. Extract the saponified
1 3
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved Aug. 15, 1995. Published October 1995. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
1
D 1399
material three times with 25-mL portions of petroleum ether. S 5 specimen weight, g.
Exercise particular care in separating the two phases so that
none of the aqueous phase is occluded in the ether phase. 10. Precision and Bias
8.5 Combine the ether extract and place in the 120-mL
evaporating dish, weighed to 1 mg. Place on the steam bath and 10.1 Precision—Results should not differ from the mean by
carefully evaporate to dryness. Dry the bottom of the evapo- more than the following amounts:
rating dish with a clean lint-free cloth and place in the drying Repeatability Reproducibility
(One operator (Different operators
oven set at 75 6 5°C for 1 h. Cool in a desiccator and weigh and apparatus) and apparatus)
the evaporating dish and its contents to 1 mg.
Unsaponifiable content, weight % 0.05 0.1
absolute
9. Calculation
9.1 Calculate in weight percent the unsaponifiable content, 10.2 Bias—Bias cannot be determined because there is no
U, of the specimen as follows: available material having an accepted reference value.
U 5 ~R/S! 3 100 (1)
11. Keywords
where:
R 5 residue weight from evaporation, g, and 11.1 tricresyl phosphate; unsaponifiable content
2

Sodium Carboxymethylcellulose1
1. Scope provided it is first ascertained that the reagent is of sufficiently

1.1 These test methods cover the testing of sodium high purity to permit its use without lessening the accuracy of
carboxymethylcellulose. the determination.
1.2 The test procedures appear in the following order: 3.2 Unless otherwise indicated, references to water shall be
Sections
understood to mean distilled water.
Moisture 4-9
Degree of Etherification: MOISTURE
Test Method A—Acid Wash 10-17
Test Method B—Nonaqueous Titration 10, 11, 18-23 4. Scope
Viscosity 24-30
Purity 31-38 4.1 This test method covers the determination of the volatile
Sodium Glycolate 39-47 content of sodium carboxymethylcellulose.
Sodium Chloride 48-55
Density 56-62
4.2 The results of this test are used for calculating the total
solids in the sample; and, by common usage, all materials
1.3 The values stated in inch-pound units are to be regarded volatile at this test temperature are designated as moisture.
information only. 5. Significance and Use
1.4 This standard does not purport to address all of the 5.1 Moisture analysis (along with purity) is used to calculate
safety concerns, if any, associated with its use. It is the the amount of active polymer in the material and must be
responsibility of the user of this standard to establish considered when determining the amount of sodium
appropriate safety and health practices and determine the carboxymethylcellulose to use in various formulations.
applicability of regulatory limitations prior to use. For specific
hazard statements, see Note 1 and Note 2. 6. Apparatus
6.1 Oven—Gravity convection oven, capable of
maintaining a temperature of 105 6 3°C.
2.1 ASTM Standards: 6.2 Weighing Bottles, low-form, 50-mm inside diameter by
D 1347 Test Methods for Methylcellulose2 30-mm height, or equivalent.
E 1 Specification for ASTM Thermometers3 6.3 Analytical Balance.
3. Purity of Reagents 7. Procedure
3.1 Reagent grade chemicals shall be used in all tests. 7.1 Weigh 3 to 5 g of the sample to the nearest 0.001 g in a
Unless otherwise indicated, it is intended that all reagents shall tared and covered weighing bottle.
conform to the specifications of the Committee on Analytical 7.2 Place the bottle in an oven at 105°C for 2 h with the
Reagents of the American Chemical Society4, where such cover removed. Cool the bottle in a desiccator, replace the
specifications are available. Other grades may be used, cover, and weigh.
7.3 Replace the sample in the oven for 30 min, cool, and
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint reweigh.
and Related Coatings, Materials, and Applications and are the direct responsibility 7.4 Continue this procedure to a mass loss of not more than
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. 5 mg for 30 min drying time.
Current edition approved Nov. 10, 1997. Published July 1998. Originally
2
8. Calculation
3
Annual Book of ASTM Standards, Vol 14.03. 8.1 Calculate the percent moisture, M, as follows:
4
Chemical Society, Washington, DC. For suggestions on the testing of reagents not M 5 ~A/B! 3 100 (1)
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia where:
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, A 5 mass loss on heating, g, and
MD.
1
D 1439
B 5 sample used, g. 14.6 Nitric Acid (sp gr 1.42)—Concentrated nitric acid

(HNO3).
9. Precision and Bias 14.7 Sodium Hydroxide, Standard Solution (0.3 to 0.5 N)—
9.1 Precision—Statistical analysis of interlaboratory Prepare and standardize a 0.3 to 0.5 N solution of sodium
reproducibility test results on samples containing 2 to 10 % hydroxide (NaOH).
moisture indicates a precision of 60.2 % absolute at the 95 % 14.8 Sulfuric Acid (9 + 2)—Carefully mix 9 volumes H2SO4
confidence level. with 2 volumes of water.
9.2 Bias—No justifiable statement can be made on the bias 15. Procedure
of the procedure for measuring moisture because no suitable
reference material exists. 15.1 Weigh approximately 4 g of the sample into a 250-mL
beaker and add 75 mL of ethyl alcohol (95 %). Stir the mixture
DEGREE OF ETHERIFICATION with an air–driven stirrer until a good slurry is obtained. Add 5
mL of HNO3, while agitating, and continue agitation for 1 to 2
10. Scope min. Heat the slurry and boil for 5 min. (Warning—See Note
10.1 These test methods cover the determination of the 1.) Remove the heat and continue agitation for 10 to 15 min.
degree of etherification (D.E.) of sodium NOTE 1—Warning: Exercise care to avoid fire.
carboxymethylcellulose.
10.2 Two test methods are included as follows: 15.2 Decant the supernatant liquid through the filter and
10.2.1 Test Method A (Acid Wash), for crude grades of transfer the precipitate to the filter with 50 to 100 mL of ethyl
sodium carboxymethylcellulose with degrees of etherification alcohol (95 %). Wash the precipitate with ethyl alcohol (80 %)
up to 0.85. Above 0.85 degree of etherification, slightly low that has been heated to 60°C, until all of the acid has been
results may be obtained. removed.
10.2.2 Test Method B (Nonaqueous Titration), for purified 15.3 Test for the removal of acid and salts (ash) by mixing
grades of sodium carboxymethylcellulose of all degrees of a drop of the acid carboxymethylcellulose slurry from the filter
etherification. It is not applicable to the crude grades. with a drop of diphenylamine reagent on a white spot plate. A
Test Method A—Acid Wash blue color indicates the presence of nitrate and the necessity for
further washing. If the first drop of reagent does not produce a
11. Summary of Test Method blue color, further drops should be added until an excess of
11.1 The water-soluble sodium carboxymethylcellulose is reagent is known to be present, noting the color after each drop.
converted to the insoluble acid form, purified by washing, Four to six washings will usually suffice to give a negative test
dried, and then a weighed sample is reconverted to the sodium for nitrate.
salt with a measured excess of sodium hydroxide. 15.4 Finally, wash the precipitate with a small amount of
anhydrous methanol and draw air through it until the alcohol is
12. Significance and Use completely removed. Transfer the precipitate to a glass or
12.1 These test methods determine the amount of aluminum weighing dish provided with a cover. Heat the
substituent groups added to the cellulose backbone. The level uncovered dish on a steam bath until the odor of alcohol can no
can greatly affect solution properties, rheology, viscosity, longer be detected (in order to avoid fires due to methanol
hygroscopicity, salt tolerance, and many other properties of the fumes in the oven), then dry the dish and contents, uncovered
polymer. for 3 h at 105°C. Place the cover on the dish and cool to room
temperature in a desiccator.
13. Apparatus 15.5 The sulfate ash content of the sample at this point
13.1 Stirrer, air-driven. should be less than 0.5 % when determined on 0.5 g of the
13.2 Buchner Funnel, 75-mm, fitted with a 70-mm fine- sample by the procedure given in the Ash as Sulfate section of
texture, heavy-duty filter paper. A60-mm medium-porosity, Test Methods D 1347. If the ash content is greater than 0.5 %,
fritted glass funnel may also be used. rewash the sample with ethyl alcohol (80 %). If necessary,
13.3 Drying Oven, maintained at 105°C. repeat the procedure described in 13.1-13.3 to 13.4.
15.6 Weigh, to the nearest 0.01 g, about 1 to 1.5 g of the
14. Reagents dried acid carboxymethylcellulose (depending on the
14.1 Diphenylamine Reagent—Dissolve 0.5 g of normality of the acid and base to be used) into a 500-mL
diphenylamine in 120 mL of sulfuric acid (H2SO4, 9 + 2). The Erlenmeyer flask. Add 100 mL of water and 25.00 mL of 0.3 to
reagent should be essentially water-white. It will give a deep 0.5 N NaOH solution, while stirring. Heat the solution to
blue coloration with traces of nitrate or other oxidizing agents. boiling, and boil for 15 to 30 min.
14.2 Ethyl Alcohol (95 volume %)—Denatured ethyl 15.7 Titrate the excess NaOH, while the solution is hot, with
alcohol conforming to either Formula 2B, 3A, or 30 of the U. the 0.3 to 0.5 N HCl to a phenolphthalein end point.
S. Bureau of Internal Revenue. 16. Calculation
14.3 Ethyl Alcohol (80 % by volume)—Dilute 840 mL of
16.1 Calculate the degree of etherification, G, as follows:
Formula 2B, 3A, or 30 denatured alcohol to 1 L with water.
14.4 Hydrochloric Acid, Standard (HCl, 0.3 to 0.5 N). A 5 ~BC – DE!/F (2)
14.5 Methanol, anhydrous. G 5 0.162A/~1– 0.0584A! (3)
2
D 1439
where: acid, shake to dissolve, and then make up to volume and mix
A 5 milliequivalents of acid consumed per gram of thoroughly. Pipet 10 mL into a 100-mL beaker and add 50 mL
sample, of acetic acid. Place on a magnetic stirrer and insert the
B 5 NaOH solution added, mL, electrodes of the pH meter. Add nearly the required amount of
C 5 normality of the NaOH solution, HClO4 from a buret, then decrease the increments to 0.05 mL
D 5 HCl required for titration of the excess NaOH, mL, as the end point is approached. Record the millilitres of titrant
E 5 normality of the HCl, versus millivolts, and continue the titration a few millilitres
F 5 acid carboxymethylcellulose used, g, beyond the end point. Plot the titration curve and read the
162 5 gram molecular mass of the anhydroglucose unit of volume of titrant at the inflection point. Calculate the
cellulose, and normality, N, as follows:
58 5 net increase in molecular mass of anhydroglucose
unit for each carboxymethyl group substituted. N 5 ~A 3 10 3 1000!/~B 3 204.22 3 250! (4)
where:
17. Precision and Bias A 5 potassium acid phthalate used, g,
17.1 Precision—Statistical analysis of intralaboratory B 5 HClO4 added, mL,
(repeatability) test results indicates a precision of 60.04 D.E. 204.22 5 gram molecular mass of potassium acid
units at the 95 % confidence level. phthalate,
17.2 Bias—No justifiable statement can be made on the bias 10 5 potassium acid phthalate solution added, mL,
of the procedure for measuring degree of etherification because and
no suitable reference material exists. 250 5 glacial acetic acid used to dissolve potassium
Test Method B—Nonaqueous Titration acid phthalate, mL.
20.5 Potassium Acid Phthalate, primary standard, National
18. Summary of Test Methods Institute of Standards and Technology Standard Sample No.
18.1 This measurement is based upon a nonaqueous acid- 84.
base titration. The sample is refluxed with glacial acetic acid, 21. Procedure
and the resulting sodium acetate is titrated with a standard 21.1 Weigh 0.2 g of the sample, to the nearest 0.0001 g, into
solution of perchloric acid in dioxane, to a potentiometric end a 250-mL Erlenmeyer flask with ground-glass joint. Add 75
point. Impurities containing alkaline sodium will also be mL of acetic acid, connect to a water-cooled condenser, and
titrated under these conditions. Sodium chloride does not reflux gently on a hot plate for 2 h.
interfere. 21.2 Cool, and transfer the solution to a 250-mL beaker with
the aid of 50 mL of acetic acid. Place on the magnetic stirrer
19. Apparatus
and titrate to a potentiometric end point with 0.1 N HClO4 in
19.1 pH Meter, equipped with a standard glass electrode and accordance with 20.4.
a calomel electrode modified as follows:
19.1.1 Discard the aqueous potassium chloride solution, 22. Calculation
then rinse and fill with the calomel electrode solution as 22.1 Calculate the degree of etherification, H, as follows
described in 20.2. (Note 3):
19.1.2 Add a few crystals of potassium chloride and silver M 5 ~AN 3 100!/~G 3 ~100 2 B!! (5)
chloride or silver oxide to the electrode.
H 5 0.162 M/~1.000– ~0.080 M!! (6)
19.2 Buret, micro, 10-mL capacity.
where:
20. Reagents M 5 milliequivalents of acid consumed per gram of
20.1 Acetic Acid, glacial. sample,
20.2 Calomel Electrode Solution—Add 2 g of potassium A 5 HClO4 added, mL,
chloride (KCl) and 2 g of silver chloride (AgCl) or silver oxide N 5 normality of HClO4,
(Ag2O) to 100 mL of methanol and shake thoroughly to G 5 sample used, g,
saturate. Use the supernatant liquid. B 5 percent moisture, determined on a separate sample,
20.3 1,4-Dioxane. in accordance with Sections 4-7,
20.4 Perchloric Acid (0.1 N)—Add 9 mL of concentrated 162 5 gram molecular mass of an anhydroglucose unit of
perchloric acid (HClO4, 70 % to 1 L of dioxane, with stirring cellulose, and
80 5 net increase in molecular mass of an
(Warning—See Note 2). Store in an amber glass bottle. Any
anhydroglucose unit for each sodium
slight discoloration that appears on standing may be
carboxymethyl group added.
disregarded.
NOTE 3—The result calculated in accordance with Section 18 includes
NOTE 2—Warning: The solution of perchloric acid in dioxane should
the alkaline sodium from sodium glycolate; however, if the latter is less
never be heated or allowed to evaporate.
than 0.5 %, the interference is negligible.
20.4.1 Standardize the solution as follows: Dry potassium
acid phthalate for 2 h at 120°C. Weigh 2.5 g to the nearest 23. Precision and Bias
0.0001 g into a 250-mL volumetric flask. Add glacial acetic 23.1 Precision—Statistical analysis of interlaboratory test
3
D 1439
results indicates the precision of this test method as shown
below:
Approximate Precision, D.E. Units
D.E. Level (95 % Confidence Level)
0.40 60.010
0.80 60.012
1.35 60.038

of the procedure for measuring degree of etherification because
no suitable reference material exists.
VISCOSITY
24. Scope
24.1 This is an arbitrary test method for determining the
viscosity of aqueous solutions of sodium
carboxymethylcellulose in the viscosity range from 10 to
10 000 cP at 25°C.
24.2 The concentration to be used for the test should be
agreed upon between the purchaser and the seller. It should be
such that the viscosity of the solution will fall within the range
of this test.
24.3 The results for the viscosity of sodium
carboxymethylcellulose by this test method will not necessarily
check with results from other types of instruments used for
viscosity measurements.
24.4 The determinations are run on a calculated dry basis;
that is, the amount of sodium carboxymethylcellulose required
for the desired concentration on a dry basis is calculated from
the known moisture content.
24.5 This test method is intended for referee purposes. The FIG. 1 Stirrer
Brookfield spindles and speeds given in Table 1 are
recommended for this purpose, but slight derivations from the 26.5 Water Bath, constant-temperature, set at 25°C and
table may occasionally be found convenient for individual capable of maintaining that temperature within 60.2°C.
application. 26.6 Thermometer—ASTM Saybolt Viscosity
Thermometer having a range from 19 to 27°C and conforming
to the requirements for Thermometer 17C, as prescribed in
25.1 This test method determines the relative ability of the Specification E 1.
polymer to thicken water. This is the primary function of
sodium carboxymethylcellulose. 27. Procedure
26. Apparatus 27.1 Determine moisture in accordance with Sections 4-9.
27.2 Calculate the dry-basis sample mass, M, in grams
26.1 Viscometer, Brookfield type. necessary to make 240 g of test solution as follows:
26.2 Container—Glass jar, approximately 21⁄2-in. (64-mm)
in diameter and 6 in. (152 mm) deep, unconstricted at the top, M 5 100A/~100 2 B! (7)
capacity 12 oz (340 g). where:
26.3 Analytical Balance. A 5 desired dry mass of sample, g, and
26.4 Mechanical Stirrer—Stirrer constructed of either B 5 moisture in the sample as received, %.
stainless steel or glass (Fig. 1) attached to a variable speed 27.3 Calculate the quantity of distilled water required as
motor capable of operating at 900 6 100 rpm under varying follows:
load conditions.
V 5 240 2 S (8)
TABLE 1 Viscometer Spindles Required for Given Speeds where:
Viscosity
Spindle Speed,
V 5 volume of distilled water, mL, and
Range,
No. rpm
Scale Factor S 5 mass of sample, g.
cP
27.4 Add the calculated quantity of water to the jar. Position
10 to 100 1 60 100 1
100 to 200 1 30 100 2
the stirrer in the jar allowing minimum clearance between the
200 to 1000 2 30 100 10 stirrer and the bottom of the container.
1000 to 4000 3 30 100 40 27.5 Begin stirring and slowly add the sodium
4000 to 10000 4 30 100 200
carboxymethylcellulose specimen. Adjust the stirring speed to
4
D 1439
approximately 900 6 100 r/min and mix for exactly 2 h. Do 33. Significance and Use
not allow the stirring speed to exceed 1200 r/min since higher 33.1 This test method is intended for use in testing sodium
speeds tend to affect viscosity on certain grades of sodium carboxymethylcellulose for applications in which purity is not
carboxymethylcellulose. a critical property. If purity greater than 98 % is required,
NOTE 4—If the specimen is added too rapidly, agglomeration will analysis for individual impurities (sodium chloride and sodium
occur. This may prevent complete dissolution within the required mixing glycolate) is essential.
time.
34. Apparatus
27.6 Remove the stirrer and transfer the specimen container
to the constant-temperature bath for 1 h. Check the specimen 34.1 Filtering Crucible, fritted glass, medium-porosity,
temperature with a thermometer at the end of 1 h to ensure that 50-mL capacity.
the test temperature has been reached. 34.2 Mechanical Stirring Motor, electric or air-driven, with
27.7 Remove the specimen container from the bath and any convenient stirrer of appropriate size.
shake vigorously for 10 s. Measure the viscosity with the 34.3 Water Bath, constant-temperature, maintained at 60 to
Brookfield viscometer, selecting the proper spindle and speed 65°C.
from Table 1. Allow the spindle to rotate for three min before 34.4 Cover—A lid to keep a 400-mL beaker substantially
taking the reading. covered during mechanical stirring in bath. A flanged lid,
preferably of stainless steel, with a slot, wide enough to pass
28. Calculation the shaft of the mechanical stirrer, cut from the rim to the
28.1 Calculate the viscosity, V, in centipoises as follows: center, has been found satisfactory. The center should be cut
V 5 reading 3 factor (9) out somewhat larger than the shaft of the stirrer to permit free
rotation of the stirrer. Such a lid serves to weight down the
29. Report beaker as well as to minimize the evaporation losses during
29.1 Report the results as Brookfield viscosity at 25 C, leaching.
stating the solution concentration and the spindle and speed
used. 35. Reagents
35.1 Ethanol (95 volume %)—Undenatured or specially
denatured ethanol conforming to Formula 2B (Note 5) of the
30.1 Precision—Statistical analysis of interlaboratory U. S. Bureau of Internal Revenue.
(reproducibility) test results indicates a precision of 610 % at
the 95 % confidence level. NOTE 5—Other grades of denatured alcohol, such as Formula 3A, are
not satisfactory for this purpose.
of the procedure for measuring viscosity because no suitable 35.2 Ethanol (80 volume %)—Dilute 840 mL of 95 %
reference material exists. ethanol (30.1) to 1 L with water. The specific gravity should be
0.8576 0.001 at 25/25°C. If necessary, add water or ethanol
PURITY OF CRUDE SODIUM
until the specific gravity is within the specified limits.
CARBOXYMETHYLCELLULOSE
35.3 Ethyl Ether, anhydrous, ethanol-free.
31. Scope
36. Procedure
31.1 This test method covers the determination of purity or
percent of active ingredient in crude sodium 36.1 Weigh 3 to 5 g of the sample into a tared low-form,
carboxymethylcellulose containing no phosphate. The test 65-mm diameter glass weighing dish fitted with a cover. Dry to
method has been standardized on materials having a degree of constant mass at 105 6 1°C in either a gravity or a mechanical
etherification of about 0.85 or less. convection oven. Weigh at the end of an initial 2-h heating
31.2 For determination of purity of refined sodium period, then continue with 30-min heating periods until the
carboxymethylcellulose (purity approximately 98 % or change in mass during a 30-min heating period is not more than
higher), analysis for individual or combined impurities and 0.10 %. If there is an increase in mass of the sample during one
calculation of purity by difference will give more reliable or more drying periods, record the lowest mass observed as the
results. mass for use in the calculation of moisture content. Calculate
the loss in mass as the percent of moisture in the sample.
32. Summary of Test Method 36.2 Weigh 3 6 0.1 g of the sample, in the “as-received”
32.1 A 3-g sample is stirred mechanically in a beaker for 15 condition, to the nearest 0.001 g and transfer to a 400-mL
min with each of two 150-mL portions of ethanol (80 % by beaker.
volume) at a temperature of 60 to 65°C. The supernatant liquid 36.3 Add 150 mL of ethanol (80 %) that has been heated to
is decanted through a tared filtering crucible after each between 60 and 65°C, and immediately place the beaker in a
treatment. The undissolved matter is transferred quantitatively constant-temperature water bath maintained at 60 to 65°C. The
to the crucible, dried, weighed, and calculated as percent of level of the water in the bath should be somewhat higher than
sodium carboxymethylcellulose. The temperature of the the level of the liquid in the beaker. Cover the beaker as
ethanol during the leaching need not be closely controlled, but completely as possible with a lid that will permit mechanical
the concentration of the ethanol must be closely controlled (sp stirring. Lower a mechanical stirrer almost to the bottom of the
gr within 0.001). beaker, and stir for 10 min at a rate suitable to provide good
5
D 1439
agitation without spattering material on the walls of the beaker of the procedure for measuring purity of crude sodium
above the liquid level. carboxymethylcellulose because no suitable reference material
36.4 Stop the stirrer. Allow the undissolved matter to settle exists.
with the beaker still in the bath, and then decant the hot
supernatant liquid as completely as possible through a tared, SODIUM GLYCOLATE
fritted-glass filtering crucible. 39. Scope
36.5 Add 150 mL of ethanol (80 %), at 60 to 65°C to the
beaker and proceed in accordance with 32.3 and 32.4.
sodium glycolate content of purified sodium
36.6 After decanting the supernatant liquid as completely as
carboxymethylcellulose containing not more than 2.0 %
possible, transfer the insoluble matter to the crucible with the
sodium glycolate.
aid of ethanol (80 %) at 60 to 65°C in a wash bottle, being
careful to scrape all insoluble matter from the lid, the stirrer, 40. Summary of Test Method
and the beaker. A total of about 250 mL of ethanol (80 %) will 40.1 The sodium carboxymethylcellulose is dissolved in
normally be required to transfer the insoluble matter to the acetic acid (50 %), precipitated with acetone and sodium
crucible and to further wash the insoluble matter in the sulfate and the insoluble material filtered off. The filtrate
crucible. During the operations prescribed in this paragraph, containing the sodium glycolate (as glycolic acid) is treated to
apply suction only while filtration is in progress. Make every remove the acetone and reacted with 2,7-dihydroxy
effort to avoid drying-out of the filter cake. If fines appear to naphthalene. The resulting color is measured at 540 nm with a
pass through the filter, use only gentle suction. spectrophotometer calibrated with known solutions.
36.7 Wash the residue in the crucible with 50 mL of ethanol
(95 %) at room temperature, and finally with several portions 41. Significance and Use
of ether at room temperature (Note 6). Without permitting 41.1 This test method (along with moisture and sodium
suction to continue longer than necessary, place the crucible in chloride) is used to calculate the amount of active polymer in
a beaker or weighing bottle on the steam bath until no odor of the material. It must be used when analyzing highly purified
ether can be detected. (>98 %) grades of sodium carboxymethylcellulose, especially
NOTE 6—Thorough washing with ether is necessary to remove ethanol in government-regulated applications (that is, food,
completely from the insoluble matter. If ethanol is not completely pharmaceuticals, cosmetics, etc.).
removed before oven drying, it may not be completely removed during the
oven drying. 42. Apparatus
36.8 Place the crucible in an oven at 105 6 1°C for 1 h. Stir 42.1 Spectrophotometer or Filter Photometer, suitable for
the contents of the crucible with a dissecting needle or thin rod measuring absorbance at 540 nm.
(preferably of smooth-surfaced metal) to break up the cake and 42.2 Absorption Cells, for spectrophotometer, 1-cm light
facilitate complete drying. Again, dry at 105 6 1°C for 1 h. path.
Place the crucible in a desiccator. Cover it with a flat glass 42.3 Aluminum Foil—Cut to approximately 2-in. (51-mm)
plate, weighing bottle cover, or other suitable cover to squares.
minimize absorption of moisture from the atmosphere in the 43. Reagents
desiccator; and cool to room temperature (at least 30 min).
Weigh the uncovered crucible as rapidly as possible. 43.1 Acetic Acid, glacial.
36.9 Dry the crucible for additional 1-h periods until the 43.2 Acetone.
change in mass during a 1-h drying period does not exceed 43.3 Dihydroxy Naphthalene Reagent (0.100 g/L)—
0.003 g. If increases in mass are observed after such additional Dissolve 0.100 g of 2,7-dihydroxy naphthalene in 1 L of
drying periods, record the lowest mass observed as the mass of sulfuric acid (H2SO4). Before using, allow the solution to stand
the crucible plus dry sodium carboxymethylcellulose. until the initial yellow color disappears. If the solution is very
dark, discard it and prepare a new solution from a different
37. Calculation supply of H2SO4. This solution is stable for approximately 1
37.1 Calculate the percent sodium carboxymethylcellulose, month if stored in a dark bottle.
S, on the dry basis as follows: 43.4 Glycolic Acid, Standard Solution (1 mg glycolic acid/
mL)—Dry several grams of glycolic acid in a desiccator at
S 5 ~A 3 10 000!/~B ~100 2 C!! (10)
room temperature overnight. Accurately weigh 0.100 g of the
where: dried material, dissolve in water, and make up to volume in a
A 5 mass of dried residue, g, 100-mL volumetric flask. This solution will contain 1 mg of
B 5 mass of specimen used, g, and glycolic acid/mL. The solution is stable for approximately 1
C 5 moisture in the specimen as received, %. month.
43.5 Sodium Chloride (NaCl).
38. Precision and Bias 43.6 Sulfuric Acid (sp gr 1.84)—Concentrated H2SO4.
38.1 Precision—Statistical analysis of interlaboratory
(reproducibility) test results indicate a precision of 60.6 % 44. Preparation of Calibration Curve
absolute at the 95 % confidence level. 44.1 Into a series of five 100-mL volumetric flasks
38.2 Bias—No justifiable statement can be made on the bias accurately introduce 1, 2, 3, and 4-mL aliquots of the standard
6
D 1439
glycolic acid solution, reserving the fifth flask for a blank. Add sodium glycolate indicate a precision of 60.03 % absolute at
sufficient water to each flask to give a total volume of 5 mL. the 95 % confidence level.
Add 5 mL of glacial acetic acid, make up to volume with 47.2 Bias—No justifiable statement can be made on the bias
acetone and mix. These solutions will contain 0, 1, 2, 3 and 4 of the procedure for measuring sodium glycolate because no
mg of glycolic acid, respectively. suitable reference material exists.
44.2 Pipet 2 mL of each of these solutions into individual
25-mL volumetric flasks. Place the uncovered flasks upright in SODIUM CHLORIDE
a boiling water bath for exactly 20 min to remove the acetone. 48. Scope
Remove the flasks from the bath and cool.
44.3 To each flask add 20 mL of 2,7-dihydroxy naphthalene
sodium chloride content of purified sodium
reagent as follows: Add 5 mL of reagent initially, mix
carboxymethylcellulose.
thoroughly, then add the remaining 15 mL of reagent and mix.
Cover the mouth of the flasks with a small piece of aluminum 49. Summary of Test Method
foil and place upright in the boiling water bath for 20 min.
49.1 The sodium carboxymethylcellulose is dissolved in
Remove from the bath, cool, and make up to volume with
water and titrated with a standard solution of silver nitrate to a
H2SO4.
potentiometric end point. Hydrogen peroxide is added to
44.4 Measure the absorbance of each solution at 540 nm
reduce the viscosity of the solution.
against the blank solution. Plot the milligrams of glycolic acid
in the original 100 mL of solution against absorbance to give a 50. Significance and Use
calibration curve. 50.1 This test method (along with moisture and sodium
45. Procedure glycolate) is used to calculate the amount of active polymer in
45.1 Weigh about 0.5 g of the sample (0.2 g for semirefined the material. It must be used when analyzing highly purified
grades) to the nearest 0.001 g and transfer to a 100-mL beaker. (>98 %) grades of sodium carboxymethylcellulose, especially
Moisten the specimen thoroughly with 5 mL of acetic acid in government-regulated applications (that is, food,
followed by 5 mL of water, and stir with a glass rod until pharmaceuticals, cosmetics, etc.).
solution is complete (usually about 15 min is required). Slowly 51. Apparatus
add 50 mL of acetone, stirring during addition, followed by
51.1 pH Meter, equipped with a silver electrode and a
approximately 1 g of NaCl. Stir several minutes to ensure
mercurous sulfate-potassium sulfate electrode.
complete precipitation of the carboxymethylcellulose.
51.2 Buret, micro, 10-mL capacity.
45.2 Filter through a soft, open-texture paper, previously
wetted with a small amount of acetone, and collect the filtrate 52. Reagents
in a 100-mL volumetric flask. Use an additional 30 mL of
52.1 Hydrogen Peroxide (30 mass %)—Concentrated
acetone to facilitate transfer of the solids and to wash the filter
hydrogen peroxide (H2O2).
cake. Make up to volume with acetone and mix.
52.2 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
45.3 Prepare a blank solution containing 5 mL of water and
(HNO3).
5 mL of glacial acetic acid in another 100-mL volumetric flask.
52.3 Silver Nitrate, Standard Solution (0.1 N)—Dissolve
Make up to the mark with acetone and mix.
17.0 g of silver nitrate (AgNO3) in 1 L of water. Store in an
45.4 Pipet 2 mL of the solution from the specimen and 2 mL
amber glass bottle. Standardize the solution as follows:
of the blank solution into separate 25-mL volumetric flasks.
52.3.1 Dry the sodium chloride (NaCl) for 2 h at 120°C.
Develop the color and measure the absorbance in accordance
Weigh 0.65 g to the nearest 0.0001 g, into a 250-mL beaker and
with 39.2 to 39.4.
add 100 mL of water. Place on a magnetic stirrer, add 10 mL
45.5 Using the observed absorbance, refer to the calibration
of HNO3, and insert the electrodes of the pH meter. Add nearly
curve and read the corresponding milligrams of glycolic acid.
the required amount of AgNO3 solution from a buret, then
46. Calculation decrease the increments to 0.05 mL as the end point is
46.1 Calculate the percent sodium glycolate content, C, as approached. Record the millilitres of titrant versus millivolts,
follows: and continue the titration a few millilitres beyond the end
point. Plot the titration curve and read the volume of titrant at
C 5 ~B 3 12.9!/@W 3 ~100 2 A!# (11)
the inflection point. Calculate the normality, N, as follows:
where: N 5 ~A 3 1000!/~B 3 58.45! (12)
B 5 glycolic acid, read from the calibration curve, mg,
W 5 sample used, g, where:
A 5 moisture in the sample as received, %, and A 5 NaCl used, g,
12.9 5 (gram molecular mass of sodium glycolate per B 5 AgNO3 solution added, mL, and
gram molecular mass of glycolic acid) 3 10. 58.45 5 gram molecular mass of NaCl.
52.4 Sodium Chloride (NaCl).
47.1 Precision—Statistical analysis of intralaboratory 53. Procedure
(repeatability) data on material containing less than 0.50 % 53.1 Weigh 5 g of the sample, to the nearest 0.0001 g, into
7
D 1439
a 250-mL beaker. Add 50 mL of water and 5 mL of 59. Apparatus
H2O2(30 %). Place the beaker on a steam bath, stirring
59.1 Vibrator—A magnetic-type electric vibrator attached
occasionally to achieve a nonviscous solution. If solution is not
to the vertical support rod of a ring stand approximately 1 ft
complete after 20 min, add 5 mL more of H2O2 and heat until
(0.3 m) above the base. A condenser clamp of sufficient size to
solution is complete.
53.2 Cool the beaker, add 100 mL of water and 10 mL of hold a 100-mL graduated cylinder also shall be attached to the
HNO3. Place it on the magnetic stirrer and titrate to a above rod. The base of the stand should be weighted.
potentiometric end point with 0.1 N AgNO3 solution in 46.3.
60. Procedure
54. Calculation
60.1 Place 50.0 g of sodium carboxymethylcellulose in a
54.1 Calculate the percent sodium chloride content, C, as 100-mL graduated cylinder and place it in the condenser
follows: clamp. Turn on the vibrator and allow the cylinder to vibrate
C 5 ~AN 3 584.5!/@G 3 ~100 2 B!# (13) for 3 min. Record the level (in millilitres) to which the
specimen has compacted.
where:
A 5
AgNO3 solution added, mL, 60.2 Alternatively, the specimen may be compacted
N 5
normality of AgNO3 solution, manually. Tap it on a hard surface by dropping the cylinder
G 5
sample used, g, repeatedly from a height of about 1 in. (25 mm) until the
B 5
moisture, determined on a separate sample, %, in volume of the specimen remains constant. In order to prevent
accordance with Sections 4-7, and cylinder breakage, cover the tapping surface with a 1⁄8 to 1⁄4-in.
584.5 5 gram molecular mass of NaCl 3 10. (3 to 6-mm) thick rubber sheet or use a plastic graduated
cylinder.
55.1 Precision—The precision of this test method is 61. Calculation
estimated to be 60.05 % absolute for material containing less
than 0.50 % sodium chloride and 60.10 % absolute for 61.1 Calculate the density, D, in grams per millilitre as
material containing greater than 0.59 % sodium chloride. follows:
55.2 Bias—No justifiable statement can be made on the bias D 5 50/r (14)
of the procedure for measuring sodium chloride because no
suitable reference material exists. where:
r 5 observed reading, mL.
DENSITY
56. Scope
62.1 Precision—Statistical analysis of intralaboratory
56.1 This test method covers the determination of the bulk
(repeatability) test results indicates a precision of 60.04 g/mL
density of sodium carboxymethylcellulose.
at the 95 % confidence level.
57. Summary of Test Method 62.2 Bias—No justifiable statement can be made on the bias
57.1 A weighed amount of sodium carboxymethylcellulose of the procedure for measuring density because no suitable
is transferred to a 100-mL graduated cylinder and the graduate reference material exists.
vibrated to settle the powder.
63. Keywords
63.1 degree of etherification; density; moisture; purity;
58.1 The density of the material can relate to dry flow sodium carboxymethylcellulose; sodium chloride; sodium
properties, rate of dissolution, lumping, and package and
glycolate; viscosity
storage space requirements.
8

Refined Soybean Oil1
1. Scope TABLE 1 Physical Properties
1.1 This specification covers refined soybean oil suitable for Property Requirements ASTM Method
use in the paint and varnish industry. Specific gravity, 25/25°C 0.917 to 0.924 D 1963, D 1475
Saponification value 189 to 195 D 1962
2. Referenced Documents Unsaponifiable matter, max, % 1.5 D 1965
2.1 ASTM Standards: Iodine value (Wijs), min 126 D 1959
D 445 Test Method for Kinematic Viscosity of Transparent 110°C, max, %
and Opaque Liquids 2 Clarity clear and trans- D 2090
D 555 Guide for Testing Drying Oils3 parent at 65°C
Color (Gardner), max 6 D 1544
D 1475 Test Method for Density of Paint, Varnish, Lacquer, Color (after heating), max 4 D 1967
and Related Products4 Break, max, % 0.02 D 1952
D 1544 Test Method for Color of Transparent Liquids Viscosity, approximate stokes 0.32 to 0.50 D 1545, D 445
D 1545 Test Method for Viscosity of Transparent Liquids
by Bubble Time Method3 Oils, Fatty Acids, and Polymerized Fatty Acids3
D 1639 Test Method for Acid Value of Organic Coating D 1967 Test Method for Measuring Color After Heating of
Materials3 Drying Oils3
D 1952 Test Method for Quantitative Determination of D 2090 Test Method for Clarity and Cleanness of Paint and
Break in Drying Oils3 Ink Liquids3
Fatty Acids3 3. Properties
D 1960 Test Method for Loss on Heating of Drying Oils3 3.1 Refined soybean oil shall conform to the requirements in
D 1962 Test Method for Saponification Value of Drying Table 1.
Varnishes, Resins, and Related Materials at 25/25°C3 4.1 Sampling—Sampling shall be conducted in accordance
D 1965 Test Method for Unsaponifiable Matter in Drying with Test Method D 1466.
1
and Related Coatings, Materials, and Applications and is the direct responsibility of methods listed in Table 1. The significance of the test methods
Subcommittee D01.32 on Drying Oils. enumerated under properties in this specification is discussed
Current edition approved March 15, 1992. Published May 1992. Originally in Guide D 555.
2
3
4
Annual Book of ASTM Standards, Vol 06.01. 5.1 drying oils; refined soybean oil; soybean oil
1

Sampling Liquid Oils and Fatty Acids Commonly Used in
Paints, Varnishes, and Related Materials1
1. Scope 4.1.1 Liquid Oils and Fatty Acids—A glass tube, 9.5 to 12.7
1.1 This test method covers procedures for obtaining repre- mm (3⁄9 to 1⁄2 in.) in internal diameter and approximately 1 m
sentative samples of oils, fatty acids, and polymerized fatty (40 in.) in length. One end shall be constricted by a short taper
acids that are commonly used in paints, varnishes, and related to approximately 6 mm (1⁄4 in.), and the other end shall be
materials, and that are in a liquid state when sampled. constricted sufficiently so that it can be used as a finger valve.
1.2 The values stated in SI units are to be regarded as the This thief is used for sampling casks, drums, etc.
standard. The values given in parentheses are for information 4.1.2 Polymerized Fatty Acids—A glass tube, 20 to 25 mm
only. (3⁄4 to 1 in.) in internal diameter, and approximately 1 m (40
1.3 This standard does not purport to address all of the in.) in length. One end shall be constricted so it can be used as
safety concerns, if any, associated with its use. It is the a finger valve. This thief shall be used for sampling casks,
responsibility of whoever uses this standard to consult and drums, etc.
establish appropriate safety and health practices and deter- 4.2 Zone Sampler, 305-mm (12-in.) oil thief,2 consisting of
mine the applicability of regulatory limitations prior to use. a graduated glass tube with either aluminum or cadmium-
plated brass fittings.
2. Summary of Test Method 4.3 Compositing Pail, noncorrosive compositing pail, made
2.1 Samples of drying oils, fatty acids, and polymerized of stainless steel, aluminum, enamelware, polyethylene, or
fatty acids are subjected to various test methods for determin- comparable material.
ing physical and chemical characteristics. It is necessary to 4.4 Graduated Cylinders:
obtain a sample or a composite of several samples in such 4.5 Sample Containers, clear glass or brown glass bottles, or
manner and from such locations in the container, that the cans (for other than fatty acids and polymerized fatty acids).
sample or composite will be truly representative of the product. The clear glass bottles are advantageous because they may be
The precautions required to assure such a representative examined visually for cleanliness, sediment, etc. The brown
sample are numerous, depending on the type of product, the glass bottles afford some protection from light. Only cans that
container, the cleanliness of the sample container, and the do not have any solder flux on the interior are permissible for
sampling procedure that is to be used. storing oils. Cans shall not be used for fatty acids or polymer-
ized fatty acids.
3. Significance and Use 4.5.1 The closure for the glass bottles may be good quality
3.1 Because precipitated saturated acids or oils containing a corks, with or without tin or aluminum foil. Screw caps may be
high proportion of saturated acids, foots, or other insoluble used for both bottles and cans.
matter may not be homogeneous, the sampling procedure must 4.5.2 All sample containers shall be clean and free of water,
be designed so that the sample obtained is representative of the lint, dirt, washing compounds, solvents, flux or acids, rust, oil,
overall composition of the material. Different sampling proce- etc.
dures are presented such that a representative sample may be
5. Samples
obtained from material stored in different types of containers.
5.1 The size of the sample should be kept to a minimum. In
4. Apparatus most instances, 0.9 L (1 qt) of material should suffice.
4.1 Oil Thief: However, in many tests, a minimum of 11 L (3 gal) is
required—3.8 L (1 gal) for the purchaser, 3.8 L (1 gal) for the
1
seller, and 3.8 L (1 gal) in reserve for a possible arbitration
D01.32 on Drying Oils.
2
Current edition approved March 27, 1986. Published May 1986. Originally Samples manufactured by the W. H. Curtin Co., Houston, TX, has been found
published as D 1466 – 57. Last previous edition D 1466 – 67 (1984)e1. suitable for this purpose.
1
D 1466
umpire test. If refining or bleaching tests are required, the portions of the tank car in that order. If no water or solids are
minimum quantity is approximately 3.8 L (1 gal). noted, make a composite by blending one part of the top, two
5.2 The oil shall be completely liquid for proper sampling. parts of the middle, and one part of the bottom sample.
The temperature during melting should not exceed the melting 6.3 Sampling Tank Cars When Suspended Solids Are
point by more than 15°C. If the oil is completely liquid, it Present—With the zone sampler (see 4.2), sample the top,
should have a minimum temperature of 10°C. Polymerized middle, and bottom portions of the tank car in that order. If the
fatty acids should be heated to a temperature only sufficiently bottom zone sample shows the presence of water or suspended
warm to facilitate flow. solids, note the depth of the foots layer to the nearest 1⁄2 in.
5.3 Oil drums shall be placed in a warm place for several (12.5 mm). Transfer the entire contents of the 12-in. (305-mm)
hours or longer prior to sampling, so that their contents will zone sampler to a clean, dry container marked“ bottom
completely liquefy. sample,” and report the depth of foots in the sampler. Also
5.4 Tank cars, if equipped with heater coils in proper report the capacity of the car in gallons. Composite the footy
condition, may be slowly heated to 15°C above the melting oil with the upper oil in the laboratory or under the direct
point of the oil, keeping in mind that prolonged heating might supervision of the laboratory as follows:
discolor the product, particularly fatty acids and polymerized 6.3.1 Blend one part of the top sample with two parts of the
fatty acids. middle sample.
5.5 Labels shall be so affixed to the containers that the 6.3.2 Using the depth of suspended solids and the capacity
adhesion is of a permanent nature and the labeling does not of the car reported, determine from Table 1 the number of parts
smear. of well-mixed bottom sample to be blended with the one part
5.6 The labels shall identify the sample as to material, date top and two parts middle sample blended in accordance with
received, date sampled, shipper, car number, container size, 6.3.1.
number of containers, temperature and volume in containers, 6.3.3 Measure in a graduated cylinder the correct amount of
receiving slip number, and batch number. well-mixed bottom sample determined from Table 1. Pour it
5.7 On agreement between the purchaser and the seller, into the one part top and two parts middle sample blended in
samples shall be stored in a cupboard or storeroom out of the accordance with 6.3.1. Rinse the remaining suspended solids
direct rays of the sun and for no longer than 6 months. adhering to the walls of the graduated cylinder with some of
the composite just prepared, and then return the rinsings to the
6. Procedure composite sample.
6.1 Sampling Drums or Casks—Mix the contents of the 6.3.4 Stir vigorously until the foots have been uniformly
drum or cask by rolling it through a few complete revolutions; distributed; then subdivide into several identical portions
up-end the drum or cask, introduce the oil thief through the (usually three, of about 3 L (3⁄4 gal) each) in appropriate
bung opening, and slowly lower it to the bottom. Close the end containers and mark clearly so as to define the contents, or as
opening of the thief with a finger and remove quickly. Place the may be designated by trading rules or regulations governing
contents of the thief in a container and repeat the sampling until the transaction represented.
sufficient material has been obtained. When sampling of each 7. Precision and Bias
drum or cask is not feasible, sample a minimum of 10 % of the
7.1 Precision and bias are not applicable to this test method.
containers to form the composite sample.
6.2 Sampling Tank Cars When No Solids Are Present—With 8. Keywords
the zone sampler (see 4.2), sample the top, middle, and bottom 8.1 fatty acids; sampling; oils; drying—sampling
TABLE 1 Parts of Bottom Sample to Be Blended with Top and Middle Sample (see 6.3)
Depth of Stratified 4000-gal (15 100-L) 6000-gal (22 700-L) 8000-gal (30 000-L) 10 000-gal (37 800-L) 12 000-gal (45 400-L)
Matter in Oil Car, approximately Car, approximately Car, approximately Car, approximately Car, approximately
Thief, in. (mm) 60-in. (1.5-m) dia 72-in (1.8-m) dia 78-in. (2-m) dia 87-in. (2.2-m) dia 92-in. (2.3-m) dia
1 (25) 0.35 0.24 0.23 0.20 0.19
2 (50) 0.34 0.24 0.22 0.19 0.18
3 (75) 0.36 0.26 0.24 0.20 0.19
4 (100) 0.38 0.27 0.26 0.21 0.20
5 (125) 0.40 0.29 0.27 0.22 0.21
6 (150) 0.43 0.31 0.28 0.24 0.22
7 (180) 0.45 0.32 0.30 0.25 0.23
8 (200) 0.47 0.34 0.31 0.26 0.24
9 (230) 0.49 0.36 0.32 0.27 0.25
10 (250) 0.51 0.37 0.34 0.28 0.26
11 (280) 0.53 0.38 0.35 0.29 0.27
12 (300) 0.55 0.40 0.36 0.30 0.28
2
D 1466
3
Standard Guide for Testing

Fatty Acids Used in Protective Coatings1
1. Scope Acids Commonly Used in Paints, Varnishes, and Related

1.1 This guide covers the selection and application of Materials3
procedures for testing fatty acids such as cottonseed, linseed, D 1541 Test Method for Total Iodine Value of Drying Oils
soybean, dehydrated castor, tall oil, etc. used in protective and Their Derivatives3
coatings. D 1544 Test Method for Color of Transparent Liquids
1.2 The test methods included are listed as follows: (Gardner Color Scale)4
ASTM
D 1951 Test Method for Ash in Drying Oils and Fatty
Test Method Section Test Method Acids3
Acid Value 4 D 1980 D 1957 Test Method for Hydroxyl Value of Fatty Oils and
Appearance 13 D 1544
Ash 9 D 1951
Acids3
Clarity 13 D 2090 D 1959 Test Method for Iodine Value of Drying Oils and
Color: Fatty Acids3
Gardner 14 D 1544
Platinum-Cobalt 14 D 1209 D 1962 Test Method for Saponification Value of Drying
Color Change After Heating 6 D 1981 Oils, Fatty Acids, and Polymerized Fatty Acids3
Fatty Acid Composition 12 D 1983 D 1965 Test Method for Unsaponifiable Matter in Drying
Hydroxyl Value 10 D 1957
Rosin Acids 11 D 1240 Oils, Fatty Acids and Polymerized Fatty Acids3
Sampling 3 D 1466 D 1980 Test Method for Acid Value of Fatty Acids and
Saponification Value 7 D 1962 Polymerized Fatty Acids3
Titer 15 D 1982
Unsaponifiable Matter 8 D 1965 D 1981 Test Method for Measuring Color After Heating of
Unsaturation: Fatty Acids3
Diene Value 5 D 1358 D 1982 Test Method for Titer of Fatty Acids3
Iodine Value 5 D 1959
D 1983 Test Method for Fatty Acid Composition by Gas-
1.3 This standard does not purport to address all of the Liquid Chromatography of Methyl Esters3
safety concerns, if any, associated with its use. It is the D 2090 Test Method for Clarity and Cleanness of Paint and
responsibility of the user of this standard to establish appro- Ink Liquids3
priate safety and health practices and determine the applica- D 3457 Test Method for Preparation of Methyl Esters from
bility of regulatory limitations prior to use. Fatty Acids for Determination of Fatty Acid Composition
by Gas-Liquid Chromatography3
2. Referenced Documents 2.2 American Oil Chemists’ Society (AOCS) Methods:5
2.1 ASTM Standards: Tj-1a Polyunsaturated Acids
D 1209 Test Method for Color of Clear Liquids (Platinum- Cc-13b Color, Wesson Method (Lovibond)
Cobalt Scale)2 Td-2a Photometric Index
D 1240 Test Method for Rosin Acids Content of Naval
Stores, Including Rosin, Tall Oil and Related Products3 3. Sampling
D 1358 Test Methods for Spectrophotometric Diene Value 3.1 Sample the material in accordance with Test Method
of Dehydrated Castor Oil and Its Derivatives3 D 1466.
D 1466 Test Method for Sampling Liquid Oils and Fatty 3.2 Fatty acids are frequently solid at room temperature and
shall be completely liquified and blended prior to testing.
1
These methods are under the jurisdiction of ASTM Committee D-1 on Paint
Temperatures during liquefying of the fatty acids should not
and Related Coatings, Materials, and Applications and are the direct responsibility exceed 10 to 15°C above the melting point of the sample.
of Subcommittee D01.32 on Drying Oils.
published as D 1467 – 57 T. Last previous edition D 1467 – 72 (1981)e1. 4
2 5
Annual Book of ASTM Standards, Vol 06.04. Available from American Oil Chemists Society, 508 S. 6th St., Champlain, IL
3
Annual Book of ASTM Standards, Vol 06.03. 61820.
1
D 1467
3.3 Samples should be stored preferably in the dark, in full groups in fatty acids and is expressed as the number of
glass containers. Partially filled containers should be filled with milligrams of potassium hydroxide that will react with 1 g of
inert gas or carbon dioxide to prevent oxidation. sample. The saponification value on a good grade of vegetable
4. Acid Value fatty acids is normally only 1 or 2 points above the acid value
as determined in accordance with Test Method D 1980. The
4.1 Acid value is a measure of the quantity of free fatty difference between the saponification value and the acid value
acids and is defined as the number of milligrams of potassium is frequently referred to as the ester value. Saponification value
hydroxide required to neutralize the fatty acids in 1 g of can be used to calculate the average molecular weight of the
sample. Acid value determination is useful in establishing the fatty acid.
identity and purity of a fatty acid. 7.2 Determine the saponification value in accordance with
4.2 Determine the acid value in accordance with Test Test Method D 1962.
Method D 1980 which is the referee method. Other solvents
should be checked out carefully before using for control 8. Unsaponifiable Matter
purposes. 8.1 The term unsaponifiable matter includes all of those
5. Unsaturation substances that are not saponified by alkali and that are soluble
in the ordinary fat solvents. Included are the higher aliphatic
5.1 Iodine value is a convenient test for expressing the
alcohols, sterols, and hydrocarbons.
degree of unsaturation of a fatty acid. Iodine value is the
8.2 Determine unsaponifiable matter in accordance with
weight percent of iodine absorbed.
Test Method D 1965. Normal fatty acids contain small amounts
5.2 Determine the iodine value in accordance with Test
of unsaponifiable matter, usually under 2 %. When excessive
Method D 1959 which gives fairly good accuracy and preci-
amounts of unsaponifiable matter are found, low quality is
sion (Note 1) when applied to normal fatty acids. When Test
indicated.
Method D 1959 is applied to fatty acids containing conjugated
double bonds such as dehydrated castor or tung an empirical 9. Ash
figure is obtained giving only a relative measure of the total 9.1 The ash in fatty acids is determined by igniting the acids
unsaturation. Refer to Test Method D 1541 for a more accurate under specified conditions and determining the amounts of
procedure for the determination of the total unsaturation of noncombustible material. Carry out this procedure in accor-
tung oil acids. When Test Method D 1959 is used for dehy- dance with Test Method D 1951. The ash content of normal
drated castor acids, a specimen weight of 0.11 to 0.13 g of fatty fatty acids should be very small.
acids must be used to get comparative results between labora-
tories. 10. Hydroxyl Value
NOTE 1—The analyst is cautioned to follow the test method exactly as 10.1 Hydroxyl value is defined as the number of milligrams
written since small deviations in sample size, reagents, and time of of potassium hydroxide equivalent to the hydroxyl (OH)
reaction will definitely affect the accuracy and precision of the test content of 1 g of sample. Hydroxystearic acid is the only
method. common fatty acid to which this test is applicable.
5.3 When Test Methods D 1358 is applied to dehydrated 10.2 Determine the hydroxyl value in accordance with Test
castor acids an empirical value is also obtained due to the high Method D 1957.
linoleic acid content. In this method the conjugated diene 11. Rosin Acids
content is derived from spectrophotometric measurements.
Determine the amount of conjugated diene content of fatty 11.1 Fatty acids derived from tall oils will normally contain
acids in accordance with Test Methods D 1358, noting the varying amounts of rosin acids. When the amount of the rosin
empirical nature of the result for dehydrated castor acids. acids does not exceed 15 %, determine their content in accor-
5.4 The iodine value of tall oil fatty acids containing dance with Test Method D 1240.
appreciable amounts of rosin acids is not a reliable measure of 11.2 In Test Method D 1240 the rosin acids are determined
the fatty acid unsaturation because of the unsaturation of the by titration after esterification of the fatty acids with methanol
rosin acids. in the presence of sulfuric acid as a catalyst, followed by
separation of the acids. The test method requires use of an
6. Color Change After Heating experimentally determined correction factor, dependent upon
6.1 The color stability of fatty acids when subjected to the amount of rosin acids present.
elevated temperatures is of importance to many commercial
users of fatty acids. The conditions under which the color 12. Fatty Acid Composition
stability is determined such as temperature, time of heating, 12.1 Fatty acid composition can be determined in accor-
time of upheat, exposure to air, etc, all affect the final results. dance with Test Method D 1983 after esterification of the fatty
6.2 Measure the color of fatty acids after heating by Test acids in accordance with Test Method D 3457.
Method D 1981, which is applicable to all normal fatty acids. NOTE 2—The types and amounts of polyunsaturated acids in a sample
It has been shown to have good precision within and between of fatty acids may also be determined by use of an ultraviolet spectro-
laboratories and should be used as the referee test method. photometer. By using this test method the percent of conjugated diene,
triene, tetraene, and pentaene acids, and of linoleic, linolenic, arachidonic,
7. Saponification Value and pentaenoic acids can be calculated. This test method is time-
7.1 Saponification value is a measure of the alkali-reactive consuming and the techniques required do not lend themselves to good
2
D 1467
accuracy or precision. The ultraviolet spectrophotometric method is not 14.2 Where extremely light colored fatty acids are encoun-
included in the ASTM methods, and reference should be made to AOCS tered, use Test Method D 1209.
Method Tj-1a.
NOTE 3—No accurate correlation between Test Methods D 1209 and
13. Appearance D 1544 has been possible.
13.1 Observations for appearance of fatty acids should be 14.3 Lovibond glasses (AOCS Official Method Cc-13b) and
made on the liquefied sample. Transfer the sample to a spectrophotometric measurements (AOCS Method Id-2a) are
viscosity tube as described in Test Method D 1544 and check occasionally used to measure fatty acid colors.
for haze, dirt, skins, or other materials that might indicate
NOTE 4—No correlation has been established between these methods
contamination of the material. and Test Method D 1544 when used for fatty acids.
13.2 Determine the clarity in accordance with Test Method
D 2090. 15. Titer
15.1 Titer is the solidification point of fatty acids under
14. Color
specified conditions. Determine titer in accordance with Test
14.1 The color reference standards described in Test Method Method D 1982. The titer value can be correlated with the
D 1544 provide a rapid and sufficiently accurate means for degree of unsaturation of a fatty acid and is useful in
determining color on most fatty acids (Note 3). Where the hue determining the identity and purity of a fatty acid.
of the fatty acids sample does not exactly match that of the
reference sample, it is suggested that the intensity of color be 16. Keywords
matched rather than attempting to match hue. 16.1 fatty acids; protective coatings
3

Volatile Matter in Tricresyl Phosphate1
1. Scope Trace amounts may be present in tricresyl phosphate speci-

1.1 This test method covers a procedure for determining the mens.
volatile matter in tricresyl phosphate. 5. Procedure
safety concerns, if any, associated with its use. It is the 5.1 Place a flat aluminum, glass, or porcelain dish in an
responsibility of the user of this standard to establish appro- oven at 1056 5°C for 1 h. Cool in a desiccator and weigh to 10
priate safety and health practices and determine the applica- mg. Spread evenly over the bottom of the dish approximately
bility of regulatory limitations prior to use. For specific hazard 25 g of the sample. Weigh the dish and the specimen to 10 mg
statements, see Section 4. and place in an oven at 105 6 5°C for 3 h. Cool the dish and
1.3 For hazard information and guidance, see the supplier’s specimen in a desiccator, and reweigh to 10 mg.
Material Safety Data Sheet. 6. Calculation
2. Significance and Use 6.1 Calculate the volatile matter in tricresyl phosphate as
2.1 This test method provides a measurement of volatile follows:
matter in tricresyl phosphate. The results of this measurement Volatile matter, % 5 @~S 2 R!/S# 3 100 (1)
can be used for specification acceptance and determining
performance in plasticizer use. where:
S 5 weight of specimen used, g, and
3. Apparatus R 5 weight of specimen after heating, g.
3.1 Oven, thermostatically controlled at 105 6 5°C. 7. Precision and Bias
3.2 Petri Dish, 100-mm diameter, or equivalent.
7.1 Precision—Results should not differ from the mean by
4. Hazards more than the following amounts:
Within Between
4.1 Tricresyl phosphate is hazardous through inhalation or laboratory laboratories
skin absorption. Take care in handling the material.
4.2 Ortho-isomer of tricresyl phosphate is considered toxic. Volatile matter, weight % 0.05 0.1
7.2 Bias—Bias has not been determined for this test

1
method.
and Related Coatings, Materials, and Applicationsand is the direct responsibility of
Subcommittee D01.35on Solvents, Plasticizers, and Chemical Intermediates.
8. Keywords
Current edition approved Oct. 15, 1993. Published December 1993. Originally 8.1 tricresyl phosphate; volatile matter
published as D 1468 – 57 T. Last previous edition D 1468 – 84 (1988)e1
1

Total Rosin Acids Content of Coating Vehicles1
1. Scope 3.4 Moisture Collection Trap, Bidwell-Sterling, 5–mL ca-

1.1 This test method covers the determination of the rosin pacity, with 24/40 joints. Wrap with insulating tape.
acids content of rosin, unmodified by such materials as maleic 3.5 Dispensing Pipet, 50-mL capacity, repeatability or re-
or fumaric acid, or phenols. Rosin acids determined by this test producibility of # 0.1 %.
method include free rosin. 4. Reagents and Materials
1.2 The values stated in SI units are to be regarded as the
standard. The values given in parentheses are for information 4.1 Purity of Reagents—Reagent grade chemicals shall be
only. used in all tests. Unless otherwise indicated, it is intended that
1.3 This standard does not purport to address all of the all reagents shall conform to the specifications of the Commit-
safety concerns, if any, associated with its use. It is the tee on Analytical Reagents of the American Chemical Society,
responsibility of the user of this standard to establish appro- where such specifications are available.3 Other grades may be
priate safety and health practices and determine the applica- used, provided it is first ascertained that the reagent is of
bility of regulatory limitations prior to use. sufficiently high purity to permit its use without lessening the
2. Summary of Test Method 4.2 Cyclohexane.
2.1 The rosin acids content of tall oil rosin and related 4.3 n-Butyl Alcohol.
products is determined from a titration of the residual acidity of 4.4 Butyl Alcohol-Sulfuric Acid Esterification Reagent—
a specimen after first selectively esterifying any fatty acids, Add 500 mL of n-butyl alcohol, 500 mL of cyclohexane, and
which may be present. 3.3 mL (6 g) of concentrated sulfuric acid (H2SO4) to a 2-L
2.2 The specimen is refluxed in a solution of cyclohexane round-bottom flask with ground joint, connect to a moisture
and butylsulfuric acid, with continuous removal of the water of trap and condenser; then reflux on a hot plate for 30 min to
esterification. The residual acidity, which consists of the rosin distill out the water and to form butyl-sulfuric acid. Cool and
acids and the butyl sulfuric acid catalyst, is then titrated; a store in a glass-stoppered bottle.
reagent blank is treated in the same manner and titrated to 4.5 Potassium Hydroxide, Alcoholic Standard Solution, 0.5
determne the amount of acid catalyst. The percent rosin acids N (13.3 g/L)— Dissolve 13.3 g of KOH pellets in 1 L of ethyl
is calculated as the difference between the two titrations2. alcohol. Standardize against potassium acid phthalate primary
2.3 This test method is applicable over the entire range of standard.
rosin acids-fatty acids concentrations. 4.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H2SO4).
3. Apparatus 4.7 Thymol Blue Indicator Solution (10 g/L)—Mix 1 g of
3.1 Air Condenser, 760 mm (30 in.), with a 24/40 standard- thymol blue indicator with 100 mL of ethyl alcohol.
taper joint.
5. Procedure
3.2 Buret, self-zeroing, Class A, having a capacity of 25 mL,
for the standard potassium hydroxide solution, fitted with 5.1 Transfer to a 250-mL Erlenmeyer flask 1.0 to 1.2 g of
soda-lime traps to protect against absorption of atmospheric sample, weighed to the nearest 0.0001 g.
carbon dioxide (CO2). 5.2 Using a dispensing pipet, accurately measure 50 mL of
3.3 Erlenmeyer Flasks, 250-mL capacity, with 24/40 ground the esterification reagent into the flask. Connect the flask to the
joint. moisture collection trap and condenser, place on a hot plate,
heat to boiling, and reflux for 20 min AFTER the first drop of
1
This test method is under the jurisdiction of ASTM Committee D01 on Paint
3
Subcommittee D01.34 on Naval Stores. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D1469 – 57 T. Last previous edition D1469 – 93. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Linder, A., and Persson, V., “Determination of Rosin Acids in Mixtures with and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Fatty Acids,” Journal, Am. Oil Chemists’ Soc., Vol XXXIV, No. 1, 1957, pp. 24−27. MD.
1
D 1469
liquid falls from the condenser tip. At the end of the heating 1.0184 = experimentally determined factor to correct for
period, allow the flask to cool somewhat, then remove the flask the slight esterification of rosin acids, and
from the condenser and cool to room temperature. Discard the 0.30 = experimentally determined factor to correct for
water collected in the trap. unesterified fatty acids.
5.3 Add 0.5 mL of thymol blue indicator solution. Titrate 6.2 Report the results to one decimal place.
with the standardized alcoholic KOH solution, recording the
volume of titrant at the second end point-yellow to blue, at 7. Precision and Bias
about pH 10 to 11.
5.4 Make a blank titration on 50 mL of the esterification 7.1 Precision-The within-laboratory standard deviation of
solution, after refluxing it in the same manner. this test method was found to be 0.29 % absolute, at the 83.6
% rosin acid level. Duplicate determinations from a single
6. Calculation laboratory should agree within 0.81 %. Such values are suitable
6.1 Calculate the percent of rosin acids Y, as follows: for averaging.
Y 5 @~A 2 B!N 3 30.244 3 1.0184#/S 2 0.30 (1) 7.1.1 The between-laboratory standard deviation was found
to be 0.43 %, ablsolute Single determinations from two
where: laboratories should agree within 1.2 %.
A = alcoholic KOH solution required for titration of 7.2 Bias—No bias can be determined since no standard
the sample, mL,
naval stores products are available.
B = alcoholic KOH solution required for titration of
blank, mL,
N = normality of the KOH solution used, 8. Keywords
S = sample, g, 8.1 fatty acids; rosin; rosin acid
30.244 = molecular weight of abietic acid multiplied by
100 and divided by 1000,
2

Heptane Miscibility of Lacquer Solvents1
1. Scope provides a qualitative indication of the presence or absence of

1.1 This test method covers determination of the miscibility moisture in these solvents (often esters and ketones). The
of lacquer solvents with heptane. It may also be used to detect results of these measurements may be used for specification
qualitatively the presence of moisture in esters and ketones. acceptance.
NOTE 1—For the quantitative determination of water content, see Test 4. Reagents
Method D 1364.
4.1 Heptane, containing not less than 99 % n-heptane.
NOTE 2—Detailed requirements for 99 % n-heptane are specified in
safety concerns, if any, associated with its use. It is the Table 1 of Test Method D 611.
priate safety and health practices and determine the applica- 5. Procedure
bility of regulatory limitations prior to use. 5.1 Both the specimen and the heptane shall be at a
1.3 For hazard information and guidance, see the supplier’s temperature of 206 1°C. Transfer 5 mL of the specimen to a
Material Safety Data Sheet. 100-mL glass-stoppered (graduated) cylinder and add 5-mL
2. Referenced Documents increments of heptane until the total specified volume has been
added, shaking well after each addition. A clear solution
2.1 ASTM Standards: indicates miscibility and a turbid solution indicates immisci-
D 611 Test Methods for Aniline Point and Mixed Aniline bility or the presence of water in the specimen, or both.
Point of Petroleum Products and Hydrocarbon Solvents2
D 1364 Test Method for Water in Volatile Solvents (Karl 6. Report
Fischer Reagent Titration Method)3 6.1 If the solution remains clear after the addition of the
3. Significance and Use specified amount of heptane, report the specimen as passing
this test.
3.1 Water in a solvent may interfere with many uses of the
solvent. This test method provides a measure of the miscibility 7. Precision and Bias
of lacquer solvents with a nonpolar medium-heptane. It also 7.1 Because of the pass-fail nature of this test procedure, no
precision or bias statement is presented.
1
and Related Coatings, Materials, and Applications and is the responsibility of 8. Keywords
8.1 heptane miscibility test; lacquer solvents; water content;
published as D 1476 – 57 T. Last previous edition D 1476 – 84. qualitative
2
3
1

Bromine Index of Aromatic Hydrocarbons by Coulometric
Titration1
1. Scope D 2710 Test Method for Bromine Index of Petroleum Hy-

1.1 This test method covers the determination of the amount drocarbons by Electrometric Titration6
of bromine-reactive material in aromatic hydrocarbons. It is D 3437 Practice for Sampling and Handling Liquid Cyclic
usually applied to materials having bromine indexes below Products7
500. D 3505 Test Method for Density or Relative Density of
Pure Liquid Chemicals7
NOTE 1—Other test methods for determining bromine-reactive material D 4052 Test Method for Density and Relative Density of
are Test Methods D 1159, D 1491, D 2710, and D 5776.
1.2 This test method has been found applicable to aromatic D 5776 Test Method for Bromine Index of Aromatic Hy-
hydrocarbons containing no more than trace amounts of olefins drocarbons by Electrometric Titration7
and that are substantially free from material lighter than E 29 Practice for Using Significant Digits in Test Data to
isobutane and have a distillation end point under 288°C. Determine Conformance with Specifications8
1.3 The following applies to all specified limits in this test 2.2 Other Document:
method: For purposes of determining conformance with this OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
test method, an observed value or a calculated value shall be 1910.12009
used in expressing the specification limit, in accordance with 3. Terminology
the rounding-off method of Practice E 29. 3.1 Definition:
1.4 This standard does not purport to address all of the 3.1.1 bromine index—the number of milligrams of bromine
safety concerns, if any, associated with its use. It is the consumed by 100 g of sample under given conditions.
priate safety and health practices and determine the applica- 4. Summary of Test Method
bility of regulatory limitations prior to use. For a specific 4.1 The specimen is added to a solvent and titrated with
hazard statement see Section 8. electrolytically generated bromine at room temperature. The
end point is determined by a dead-stop method. The time of
2. Referenced Documents titration is proportional to the bromine added to the specimen.
2.1 ASTM Standards:
D 891 Test Methods for Specific Gravity, Apparent, of 5. Significance and Use
Liquid Industrial Chemicals2 5.1 This test method is useful for setting specification, for
D 1159 Test Method for Bromine Number of Petroleum use as an internal quality control tool, and for use in develop-
Distillates and Commercial Aliphatic Olefins by Electro- ment or research work on industrial aromatic hydrocarbons and
metric Titration3 related materials. This test method gives a broad indication of
D 1193 Specification for Reagent Water4 olefinic content. It will not differentiate between the types of
D 1491 Test Method for Bromine Index of Aromatic Hy- aliphatic unsaturation.
drocarbons by Potentiometric Titration5
6. Apparatus
1
This test method is under the jurisdiction of ASTM Committee D-16 on 6.1 Amperometric-Coulometric Apparatus, automatic, suit-
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of able for bromine index titrations with variable generator
6
2 7
3 8
4 9
5
Discontinued; see 1985 Annual Book of ASTM Standards, Vol 06.03. Office, Washington, DC 20402.
1
D 1492
FIG. 1 Automatic Amperometric-Coulometric Titrator Circuit
current and timer. A typical circuit diagram of suitable equip- 7.3 Electrolyte—To make 1 L, mix 600 mL of glacial acetic
ment is shown in Fig. 1.10 acid, 260 mL of absolute methanol, and 140 mL of KBr
6.2 Syringe, 2 mL with needle and rubber cap seal. solution (119 g/L). Dissolve 2 g of Mercury II acetate in this
6.3 Stirrer, magnetic. mixture.
7.4 Potassium Bromide Solution (119 g/L)—Dissolve 119 g
7. Reagents of potassium bromide (KBr) in water and dilute to 1 L.
7.1 Purity of Reagent—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 8. Hazards
all reagents shall conform to the specifications of the Commit- 8.1 Consult current OSHA regulations, supplier’s Material
tee on Analytical Reagents of the American Chemical Society, Safety Data Sheets, and local regulations for all materials used
where such specifications are available.11 Other grades may be in this test method.
sufficiently high purity to permit its use without lessening the 9. Sampling
accuracy of the determination. 9.1 Sample the material in accordance with Practice
7.2 Purity of Water—Unless otherwise indicated, references D 3437.
to Type IV of Specification D 1193. 10. Procedure
10.1 Place 50 mL of electrolyte in a clean, dry titration cell,
insert the electrodes, and begin stirring. Apply the generation
10
The sole source of supply of the apparatus known to the committee at this time current in accordance with Table 1.
is Refinery Supply Co., 6901 E12th St. Tulsa, OK 74112. If you are aware of
alternative suppliers, please provide this information to ASTM Headquarters. Your
comments will receive careful consideration at a meeting of the responsible TABLE 1 Specimen Size and Generation Current
technical committee,1 which you may attend. Estimated Specimen Weight, Generation
11
“Reagent Chemicals, American Chemical Society Specifications,” Am. Chem. Bromine Index g Current, mA
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
American Chemical Society, see “Reagent Chemicals and Standards,” by Joseph 0 to 20 1.000 1.0
20 to 200 0.600 5.0
Rosin, D. Van Nostrand Co., Inc., New York, NY, and the “United States
200 to 2000 0.060 5.0
Pharmacopeia.”
2
D 1492
10.2 Before introducing the specimen and immediately I 5 generation current, mA, and
before each determination, bring the coulometer to equilib- W 5 weight of specimen, g.
rium.
10.3 Draw into the syringe the amount of sample prescribed 12. Report
in Table 1 corresponding to the estimated bromine index. Wipe 12.1 Report the following information:
the needle with a clean cloth, attach a rubber cap seal to the 12.1.1 Report bromine index to the nearest unit.
needle, and weigh on the analytical balance. Remove the seal,
add the specimen to the electrolyte, and set the timer to zero. 13. Precision and Bias
Replace the seal, reweigh the syringe, and calculate the
13.1 Precision data were generated using titrators from
specimen weight.
Central Scientific Co. The precision obtained using titrators
NOTE 2—If the density or specific gravity of the specimen is known from other suppliers has not been determined.
(Test Methods D 891, D 3505, or D 4052 can be used), the specimen can 13.2 Precision—The following data should be used for
be added by means of a pipet or microburet and the weight calculated.
judging the acceptability of results (95 % probability) for
10.4 Begin titration of the specimen. As the titration pro- bromine indexes from 0 to 50:
ceeds, keep the generation current at the selected value. The 13.2.1 Intermediate Precision (formerly called
generation of bromine will continue as long as it is consumed Repeatability)—The standard deviation is 0.39. Duplicate
by the sample. At the end point an incremental increase in results by the same operator should be considered suspect if
bromine concentration causes the titrator and timer to stop results differ by more than 1.15.
automatically. Forty seconds after the titrator has shut off, NOTE 3—Number of data used, 91; number of degrees of freedom, 61;
continue the titration. If the titrator cuts off, immediately, the number of cooperating laboratories, 4.
end point has been reached and the titration may be considered
complete. Otherwise, it may be necessary to continue the 13.2.2 Reproducibility—The standard deviation is 1.43. The
titration in steps, waiting about 40 s between steps, until the results submitted by two laboratories should be considered
titration time increment is 4 s or less. Note the total titration suspect if they differ by more than 4.1.
time and generation current. NOTE 4—Number of data used, 41; number of degrees of freedom, 30;
number of cooperating laboratories, 4.
11. Calculation 13.3 Bias—The procedure in this test method has no bias
11.1 Calculate the bromine index, B, as follows: because the value of bromine index can be defined only in
TI 3 79.9 terms of a test method.
B5 965W (1)
14. Keywords
where: 14.1 aromatic hydrocarbons; bromine index; bromine-
T 5 titration time, s, reactive; coulometric titration; titration
3

Solidification Point of Industrial Organic Chemicals1
1. Scope D 3437 Practice for Sampling and Handling Liquid Cyclic

1.1 This test method covers a general procedure for deter- Products2
mining the solidification point of most organic chemicals D 3438 Practice for Sampling and Handling Naphthalene,
having appreciable heats of fusion and solidification points Maleic Anhydride, and Phthalic Anhydride2
between −20 and +150°C. D 3852 Practice for Sampling and Handling Phenol and
1.2 This test method is applicable only to relatively pure Cresyl Acid2
compounds. Values obtained for grossly impure compounds E 1 Specification for ASTM Thermometers4
can be low because of the freezing out of one component E 29 Practice for Using Significant Digit in Test Data to
during the determination. Determine Conformance with Specifications5
1.3 In order that the test method may be used on many E 77 Test Method for Inspection and Verification of Ther-
materials, a choice of certain alternatives and a selection of mometers4
apparatus are permitted. The report (Section 12) requires that 2.2 Other Document:
the selected alternatives must be stated. Materials to which the OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
test method is applicable in particular detail include phenol, 1910.12006
naphthalene, phthalic anhydride, and maleic anhydride. 3. Terminology
1.4 The following applies to all specified limits in this test
method: for purposes of determining conformance with this 3.1 Definitions:
test method, an observed value or a calculated value shall be 3.1.1 solidification point—an empirical constant defined as
rounded off “to the nearest unit” in the right-hand digit used in the temperature at which the liquid phase of a substance is in
expressing the specification limit, in accordance with the approximate equilibrium with a relatively small amount of the
rounding-off method of Practice E 29. same substance in its solid phase.
3.1.1.1 Discussion—Solidification point is distinguished
NOTE 1—A companion test method is Test Method D 852. from freezing point, which is described in Test Method D 1015.
1.5 This standard does not purport to address all of the An interpretation of mole percent purity in terms of freezing
safety concerns, if any, associated with its use. It is the point is given in Test Method D 1016.
priate safety and health practices and determine the applica- 4. Summary of Test Method
bility of regulatory limitations prior to use. For specific hazard 4.1 Solidification point is measured by noting the maximum
statements, see Section 8. temperature reached during a controlled cooling cycle after the
appearance of a solid phase in a liquid sample.
2.1 ASTM Standards: 5. Significance and Use
D 850 Test Method for Distillation of Industrial Aromatic 5.1 This test method is suitable for setting specifications on
Hydrocarbons and Related Materials2 compounds of the type described in Section 1. It is also suitable
D 852 Test Method for Solidification Point of Benzene2 for use as an intense quality-control tool and in development
D 1015 Test Method for Freezing Points of High Purity and research work involving these compounds.
Hydrocarbons3
D 1016 Test Method for Purity of Hydrocarbons from 6. Apparatus
Freezing Points3 6.1 Thermometer—An etched-stem liquid-in-glass ther-
mometer having a range of no more than 30°C shall be used. It
1
shall be graduated in subdivisions no greater than 0.1°C.
4
Current edition approved Feb. 10, 1997. Published September 1997. Originally Annual Book of ASTM Standards, Vol 14.03.
5
2 6
3
1
D 1493
Unless otherwise specified, it shall be calibrated, for 76-mm than 150 mm, and shall pass through an off-center hole in a
immersion, at no fewer than three points. These shall include two-hole cork stopper, the center hole of which holds the
the approximate solidification point of the material being tested thermometer. The upper end of the shaft may be attached to a
and two other points, respectively, about 5°C above and below reciprocating device for mechanical stirring, or may be formed
the solidification point. A total immersion thermometer can be into a loop to facilitate lifting it for stirring by hand.
used if it is specified for testing a particular material, as, for 6.4 Flasks:
example, benzene. (See Test Method D 852.) The thermometer 6.4.1 A 200-mL, side-tube, heat-resistant glass distillation
shall conform to Specification E 1. It should be so chosen that flask as described in Test Method D 850 and
the graduation at which the solidification point is to be 6.4.2 Two narrow-neck, heat-resistant glass Erlenmeyer
observed is not hidden from view when the thermometer is flasks, 400-mL capacity each.
inserted in the sample container. Suitable thermometers are 6.5 Heaters:
ASTM Thermometers 89C to 96C, inclusive. Table 1 lists 6.5.1 A hot plate, and
several of these thermometers and the materials for which, 6.5.2 An electric heater that is fully adjustable as described
respectively, they are useful in particular in accordance with in Test Method D 850, or a bunsen or similar gas burner (see
this test method. A thermometer, for example ASTM Ther- Section 9.2), or both.
mometer 17C, 18C, or 91C, is needed when the average 6.6 Insulation Board—A sheet of hard insulation board 3 to
temperature of the emergent mercury column of the 6-mm thick and 15 cm square, with a circular hole 50 mm in
solidification-point thermometer is measured. diameter in the center of it, is needed if the drying procedure
TABLE 1 ASTM Thermometers for Solidification Point

Selected Standardization Average Temperature of Emergent
ASTM Number Range of Temperature, °C Material for Test
Temperature,° C Mercury Column, °C
91C 20 to 50 40 25 phenol
92C 40 to 70 52 25 maleic anhydride
93C 60 to 90 80 30 naphthalene
96C 120 to 150 130 35 phthalic anhydride
6.2 Specimen Container—A standard heat-resistant glass given in 9.2 is used.

test tube with lip shall be used. The test tube shall measure 25 NOTE 2—Items described in 6.7, 6.8, and 6.9, are not essential for
mm in outside diameter and 150 mm in length. routinely testing materials that have solidification points substantially
6.3 Stirrer (see Fig. 1)—The stirrer shall consist of a 1-mm above room temperature, for example above 30°C; but, for referee testing,
diameter (B&S gage 18), corrosion-resistant wire bent into a these items shall be used always, regardless of the solidification points of
series of three circular loops about 25 mm apart at right angles the materials being tested.
to the shaft, the circle of each loop being about 20 mm in 6.7 Air Jacket—A standard heat-resistant glass tube with
diameter, so that the stirrer can move freely in the annular lip, 38 mm in outside diameter and 200 mm in length, shall be
space between the inner wall of the specimen container and the fitted with a cork stopper bored with a hole of 25 to 26-mm
thermometer stem when the latter is inserted in the container. diameter and into which the specimen container is to be
The shaft of the stirrer may be of any convenient length not less inserted up to its lip.
6.8 Cooling Bath—A 2-L beaker or similar suitable con-
tainer having an effective depth of at least 175 mm shall be
filled with a cooling medium, which shall be glycerin for
operating at temperatures between 145 and 25°C, water and ice
between 25 and 0°C, and alcohol and dry ice between 0
and −25°C. A thermostatically controlled agitated bath may be
used optionally. (See Fig. 2 for assembly of apparatus.)
6.9 Clamp and Ring Stand—A clamp, attached to a stand,
holds the air jacket rigidly just below its lip when it is
immersed in the cooling bath to a depth between 160 and 200
mm.
NOTE 3—Items listed in 6.10-6.15 inclusive, are required only for
checking the accuracy of the thermometer at the solidification point of the
material being tested. This check is desirable to detect changes that occur
in a thermometer with time and use and to minimize errors generally.7
6.10 Thermometric Cell—A sealed glass cell made from
standard-wall glass tubing, 38 mm in outside diameter, and
7
Enagonio, D. P., Pearson, E. G., and Saylor, C. P. Temperature—Its Measure-
ment and Control in Science and Industry, Reinhold Publishing Corp., New York,
FIG. 1 Stirrer NY, Vol 3, Part 1, 1962, pp. 219–230.
2
D 1493
FIG. 4 Reference Cell in Vacuum Flask
FIG. 2 Apparatus for Determining Solidification Point

6.12 Oven—An electrically heated oven, preferably with
about 140 mm in length, has a thermometer well, 120-mm internal circulation of air, shall be used if the crystallizable
deep, formed as an integral part lengthwise in it. The cell compound described in 6.9 is solid at room temperature. The
contains a relatively pure crystallizable compound of known oven must be thermostatically controlled over the temperature
freezing point that fills it to a level about 10 mm above the range of 60 to 200°C with tolerance of 610°C at any setting in
height of the 76-mm immersion mark of a partial immersion this range. Its chamber must be large enough to hold the items
thermometer when the latter is inserted in the well down to the described in 6.10, 6.11, 6.12 and 6.13 at the same time. A
bottom. The well shall be made from 10-mm tubing, about 8 chamber of satisfactory size shall be cubic, 500 mm to a side.
mm in inside diameter. (See Fig. 3.) For a total immersion A thermometer shall be inserted at the top with its bulb about
thermometer, the lengths of the cell and the well shall be 125 mm below the ceiling of the chamber.
increased to fit. The cell shall have a calibration temperature, 6.13 Cradle—Two pieces of fireproof, 6.4-mm board are
Tc, determined with a platinum resistance thermometer and needed to support the thermometric cell in the oven. The
assigned to it for use as a thermometric standard. (See Section dimensions of each piece shall be about 120 mm in length, 70
10.) mm in width, and between 6 and 12 mm in thickness.
6.11 Vacuum Flask—An open-mouthed Dewar-type of 6.14 Safety Items—For personal protection when handling
vacuum-jacketed flask is needed. Its capacity shall be nomi- fragile cells with contents of a molten compound that is a
nally 500-mL in size. It shall be provided with a base to hold skin-irritant or that has a melting point above 60°C, the
it upright. (See Fig. 4.) operator will need a pair of heat-resistant gloves, a long rubber
apron, and a transparent visor.
6.15 Magnifying Glass—For accurately reading the tem-
perature indicated by the thermometer, it is advantangeous to
use a magnifying glass, provided with an eyepiece and a
cross-hair, and mounted on a friction-slide that fits over the
thermometer stem.
7.1 Cork Stoppers—Suitable corks to be used as described
in 6.2, 6.3, and 6.4.
7.2 Cooling Medium—Technical grade glycerin, technical
grade methanol or denatured alcohol, water, ice, and dry ice for
use with the cooling bath.
7.3 Drying Agents—A molecular sieve zeolite with 4A size
of pores shall be used for drying liquid hydrocarbons and
phenol. The zeolite may be in the form of a powder or of
cylindrical granules about 3 mm in diameter. The granules are
preferred. The pore size is critical, because pores larger than
4A will absorb some hydrocarbons preferentially. Sodium
FIG. 3 Thermometric Reference Cell hydroxide pellets can be used for drying liquid hydrocarbons
3
D 1493
and other nonacidic compounds. Anhydrous calcium sulfate condense in the neck of the flask. If considerable water is
granules, free of dust, can also be used. present, it will distill out of the side tube of the flask and it
7.4 Packing Materials—Cotton wadding, cloth wipers, and should be collected in a receiver and then discarded. This
glass wool for packing around glass cells of hot, molten method shall not be used for materials that have initial boiling
compounds. Thin aluminum foil, light duty wrap, will also be points below 80°C or above 260°C. Allow the dry condensed
needed as described in 10.10. liquid to rise in the neck of the flask by further heating, for not
more than 1 min, until the liquid just reaches the side tube.
8. Hazards Remove the source of heat and the stopper. Let the sample cool
8.1 Consult current OSHA regulations, supplier’s Material for 1 min. Then warm the neck of the flask above the side tube
Safety Data Sheets, and local regulations for all materials used with a very small flame of the bunsen burner to drive off any
in this test method. condensed moisture. Then stopper the flask with a dry cork. Let
the sample cool until it can be poured conveniently and safely;
9. Sampling and Handling while its temperature is still at least 10°C above its solidifica-
9.1 Sample the material in accordance with Practices tion point, swirl it in the flask to ensure homogeneity, and pour
D 3432, D 3438, and D 3852. enough of it into the specimen container to reach a depth of
about 100 mm. Then proceed as described in 11.1.
10.5 If the sample is not to be fired but is to be tested as
10.1 If a sample is a solid mass at room temperature, melt received, pour it in liquid form into the specimen container to
the entire sample by heating it at about 10°C above its a depth of about 100 mm. If it is not liquid at room
solidification point and swirl it for homogeneity before pouring temperature, heat about 100 g of it in a 400-mL Erlenmeyer
the portion, as specified below, for drying and analysis, or both. flask to a temperature about 10°C above its melting point and
10.2 If the sample is to be dried before being tested, place swirl it for homogeneity before pouring it into the specimen
about 100 g of the material in a 400-mL Erlenmeyer flask and container. Use this procedure in the testing of refined naphtha-
add about 50 g of drying agent, for example, anhydrous lene. Then proceed as described in 11.1.
calcium sulfate or sodium hydroxide pellets. Liquids shall be 10.6 If the sample is a water-immiscible substance, for
dried at room temperature and solids on a hot plate at about example a liquid hydrocarbon, and is specified to be tested
10°C above their solidification point. If the sample is hygro- after saturation with water, proceed as described in 10.6 to
scopic, place a very loosely fitting stopper in the flask. After 15 introduce the sample into the sample container. Then add one
min, decant the sample to another flask and repeat the drying drop, about 0.06 g, of water; stopper the specimen container,
step with occasional stirring. Pour sufficient sample into the and shake it vigorously. Then proceed as described in 11.1.
sample container to fill it to a depth of approximately 100 mm.
Then proceed as described in 10.1. 11. Procedure
10.3 Highly hygroscopic materials, or materials like refined
phenol of which the solidification point is very sensitive to 11.1 The cooling bath temperature shall be 5 to 10°C below
moisture, shall be dried as follows: Add 15 g of 4A molecular the expected solidification point. When the solidification point
sieve to 100 g of the molten material in a 400-mL Erlenmeyer of the material under test is sensitive to cooling conditions, it
flask; stopper the flask very loosely and place it on a hot plate is desirable to keep the bath at the 5°C differential. Refined
at a temperature at least 10°C above the solidification point of naphthalene and phenol are two such materials. For naphtha-
the sample, but not hot enough to cause the sample to boil or lene the cooling bath shall be held at 70 to 75°C, and for phenol
to decompose. For example, a sample of phenol shall be heated at 30 to 35°C, the higher temperature being preferable in each
at 60°C. Heat the sample for 20 min with agitation by swirling range. Fit the sample container up to its lip into the cork
at 5-min intervals. This method of drying is satisfactory for stopper of the air-jacket. Fit the thermometer and the stirrer
phenol containing as much as 2 % water. Quickly transfer the into the two-hole stopper of the specimen container. Adjust the
dried sample, including any entrained drying agent, to the partial-immersion thermometer so that it is immersed up to its
specimen container to a depth of about 100 mm. The layer of 76-mm calibration mark in the specimen. The bottom of the
entrained drying agent, after it has settled in the specimen thermometer bulb will then be about 24 mm above the bottom
container, must not exceed a depth of 15 mm. If there is any of the specimen container. Use this procedure exactly when
doubt as to the completeness of drying, decant the molten naphthalene, phenol, phthalic anhydride, or maleic anhydride
sample from the drying agent and repeat the procedure with is being tested.
fresh drying agent on the same sample. After drying the 11.2 Clamp the assembly, described in 10.1 and illustrated
sample, proceed as described in 10.1. in Fig. 2, to the ring stand and place it so that the air jacket is
10.4 In an alternative method, when specified, dry the immersed vertically in the cooling bath to a depth at which at
sample by heating it to its initial boiling point. Support the least 100 mm of length of the specimen container is below the
distillation flask on the asbestos board over the bunsen burner surface of the cooling medium.
or the electric heater by means of the ring stand. Attach the 11.3 Allow the specimen to cool while stirring it at the rate
clamp to the lower part of the neck of the flask. Transfer about of about 60 strokes per minute. A mechanical reciprocating
100 g of the sample to the flask and place a solid cork stopper device that will simulate hand stirring is permissible. The
in the neck. Heat the flask slowly and allow the sample to melt stirrer should not touch the thermometer or the wall of the
and then to boil gently. Any water present in the sample will sample container. Discontinue stirring after an appreciable
4
D 1493
amount of crystals has formed but while the specimen is still magnifying glass, to make sure that there are no minute cracks
mainly liquid. in the bulb and no air bubbles in the thread or column of
11.4 Observe and record the thermometer readings at regu- mercury. If air bubbles are noted, remove them by cooling the
lar intervals, estimating degrees to the nearest 0.01°C until the thermometer in dry ice and tapping it gently. Place the
temperature rises from minimum, due to supercooling, to a thermometer down to its immersion mark in the cooling bath at
maximum and finally begins to drop. The true maximum the temperature at which the bath will be held for determining
temperature is the solidification point. As the temperature the solidification point of a sample of the compound in the
approaches this point on the rise, thermometer readings should thermometric cell, and hold the thermometer there for at least
be taken at 10-s intervals in order to make sure that the 1⁄2 h. For example, Thermometer 96C shall be conditioned thus
temperature has reached its maximum, and at least three more at about 126°C for use in testing phthalic anhydride.
readings should therefore then be taken at the maximum level, 11.8 If the compound in the thermometric cell is solid, it
until the first drop in temperature is noted. This will ensure must be melted in the oven under controlled conditions at a
against mistaking a temporary plateau of temperature level for temperature above its melting point by 40 to 60°C. An
the true maximum temperature. If there is any doubt about the increment of 60°C is preferred. For example, phthalic anhy-
trend of the readings, plotting a graph of temperature versus dride is melted at 190°C, oven temperature. First, prepare a
time on linear graph paper will help in interpreting the data cradle to hold the cell, by placing the two pieces of fireproof
clearly. Note the experimental maximum temperature, te. (See board about 20 mm apart on the oven shelf, laying them flat
Section 12 for temperature corrections to be added to te.) with their long sides parallel. Place the thermometric cell lying
NOTE 4—The accuracy of the thermometer readings can be increased down lengthwise in the groove thus formed by the boards and
by using a magnifying glass that assures a reading on a line of sight with the nipple, where the glass was sealed in the manufacture
perpendicular to the stem of the thermometer. This should be done in the of the cell, facing upward. Place the vacuum flask on the oven
testing of refined naphthalene and phthalic anhydride. Also, for the record, floor at the same time for conditioning. If the vacuum flask is
the average temperature, t0, of the emergent mercury column should be one that is set in its base with uintaite cement, do not heat it
taken. (See 11.1-11.4.)
above 120°C. If the compound in the thermometric cell is
NOTE 5—If the temperature rise after initial crystallization exceeds
0.5°C, remelt the specimen by warming it gently in the specimen container
normally liquid or if its solidification point is below 45°C, the
and repeat the test. Seed with two or three small crystals of the sample conditioning of the cell and the vacuum flask shall be carried
when the temperature is 0.2 to 0.3°C below the expected solidification out at an appropriate temperature in the cooling bath instead of
point. When the sample is a liquid, these crystals may be obtained by the oven, in a way similar to that used for the thermometer
freezing a small quantity of the liquid in a test tube immersed directly in described in 11.7. For example, a cell containing benzene shall
the cooling bath. Some compounds have more than one solidification be conditioned in cold water at 4.5 to 5.0°C, and a cell
point due to the occurrence of metastable phases. Therefore it is essential
containing phenol shall be conditioned in hot water at 70 to
to select, for the seeding, crystals known to be of the desired stable phase
as found by a previous determinination of solidification point. As an 80°C. An alternative way to condition the vacuum flask is to
alternative to induce crystallization, a chilled wire may be substituted in store within it, for 1⁄2 h, a thermometric cell, for example a
place of small crystals of the sample. duplicate or a dummy, which itself has been conditioned at the
NOTE 6—The procedure described in 10.5 to 10.10 inclusive, is appropriate temperature.
required only for checking the accuracy of the thermometer at the 11.9 Close the oven door and leave it closed for 10 min.
solidification point of the material being tested.
Then open the door and rotate the cell one complete turn in the
11.5 When the accuracy of the thermometer is to be groove of the cradle before reclosing the door. Repeat this
checked, as indicated in Note 3 and Note 6, make the check by turning every 2 min until the crystals in the cell have melted
means of a thermometric cell. Check immediately before completely. For phthalic anhydride, repeat this turning four or
determining the solidification point of the sample. To make five times; the crystals will be completely molten in about 20
sure that the temperature of the emergent mercury column in min. This melting procedure is fairly critical in order to avoid
the stem of the thermometer is the same during the check as breakage of cells containing crystals that melt at about 80°C or
during the determination of solidification point, carry out both higher and that are fused together in a lump in the cell. Using
operations at the same spot. heat-insulating gloves, take the vacuum flask out and set it on
11.6 The thermometric cell contains a crystallizable com- its stand. Then wrap the hot cell in cotton wadding or in several
pound. This shall be preferably a pure sample of the same layers of cloth wipers, with both ends of the cell exposed. With
compound as the sample of which the solidification point is to due precaution against burns, grasp the bundled cell and shake
be determined with the thermometer that is being checked. The it vigorously, end to end in the direction of its long axis, until
solidification point of the material in the cell shall be certified a slurry or mush of fine crystals appears in it. This fairly dense
by a referee from the measurement made with an accurate mush should appear practically all at once. Its occurrence can
platinum-resistant thermometer in the well of the cell. Repeat be promoted by directing a gentle jet of air at the top of the cell
the measurement under comparable conditions with the ther- or by touching the top with a lump of dry ice. Then continue
mometer of unknown accuracy. The difference between the two the shaking for 5.0 s longer and, with a layer of cloth wipers or
measurements is a correction for the test thermometer at the cotton wadding about the cell to provide a snug fit in the
temperature of the solidification point of the test sample. (See vacuum flask, insert the cell right side up in the conditioned
12.4-12.8.) vacuum flask; lay additional wadding or glass wool over it, as
11.7 Inspect the thermometer very closely, preferably with a shown in Fig. 4, sufficiently loose to allow the thermometer
5
D 1493
later to be inserted in the well of the cell. procedure without using the air jacket; then, after observing te,
11.10 Insert the thermometer, which has been conditioned in let the specimen remain in the apparatus for 20 min more,
accordance with 10.7, into the well of the cell. The fit must be measure to again, and take the temperature of the cooling bath
snug, to ensure good heat transfer through the wall of the well for the value of tb in the term (tb − ts).
to the bulb of the thermometer. If the fit is loose, either wrap a 12.3 The emergent stem correction is algebraically additive.
turn of aluminum foil around the bulb only, or pour into the Its value for a mercury-in-glass thermometer graduated in
well about 0.5 mL of glycerin preheated to just slightly below degrees Celsius is calculated by the formula 0.00016 N
the solidification point of the material in the cell, in order to (tb − to), where N is the number of degrees emergent from the
improve heat transfer. Adjust the top wadding about the stem of bath.
the thermometer so as not to obscure the mercury thread from 12.4 Report the corrected temperature as follows:
sight. After 5 min read the temperature to the nearest 0.01°C,
tn 5 ts 1 0.00016 n ~ts 2 to! for a partial immersion thermometer
using a magnifying glass to aid in visual estimation of (1)
hundredths of a degree. Read the temperature at regular,
frequent intervals and note its maximum value, the uncorrected or
temperature, Tu. The time to attain the maximum, and then to t8n 5 ts 1 0.00016 N ~tb 2 to! for a total immersion thermometer
reveal a distinct drop in temperature, varies for different (2)
materials. It must be not less than 10 min. The intervals at If the thermometer scale was certified to be accurate within
which temperature readings are taken shall be every 2 min after 0.02°C when the test was made, report tn or t8n as the
the first reading until the sixth reading; if the maximum reading solidification point.
is not attained after 15 min total elapsed time, readings shall 12.5 For referee tests, either the thermometer shall be
then be made at 5-min intervals. After the first 15 min, take the stipulated to be accurate within 0.02°C of scale at the level of
average temperature, To, of the emergent stem of the thermom- ts, or the thermometer shall be checked for accuracy, immedi-
eter with another thermometer placed alongside with its bulb at ately prior to the measurement of ts. (See Section 10.6 and
a level about half way along the length of the emergent 10.10.) In this check the apparent scalar error is measured. It is
mercury column. Do not hold the thermometer that is being the difference, (Te − Tu), between Te, the certified calibration
checked, because the warmth of one’s fingers can affect the temperature assigned to the thermometric cell, and Tu, the
value Tu as much as 0.03°C. uncorrected temperature observed with the test thermometer at
11.11 Platinum resistance or quartz thermometers may be the solidification point of the reference compound in the cell. If
used to calibrate the liquid in glass thermometers used in this this difference is a number between +0.02 and −0.02°C, it shall
test method. be disregarded as being indistinguishable from zero by this
12. Temperature Corrections measurement. If the difference is either a positive or a negative
number outside of the range from +0.02 to −0.02°C, inclusive,
12.1 If a thermometer other than one of those listed in Table it shall be applied as an algebraically additive scalar correction.
1 was used in this test method, calculate and report a
12.6 If the thermometer was selected in accordance with
temperature correction to be added to te. This correction is
Table 1 and used in accordance with 10.10, and in general
called the emergent stem correction. In a partial immersion
whenever the emergent stem temperature is the same in the
thermometer, this correction compensates for the difference,
checking procedure for accuracy as in the testing procedure for
(ts − to), between ts, the stem temperature at which the scale of
solidification point, that is, whenever T0 5 to, report solidifi-
the thermometer was standardized, and to, the observed aver-
cation point as follows:
age temperature of the emergent column of mercury. (See Test
Method E 77.) See Note 6 for reference to to. For ts, see the tp 5 ts 1 Kn~ts 2 to! 1 ~Tc 2 Tu! 5 tn 1 ~Tc 2 Tu! (3)
Selected Standardization Temperature in Table 1 or see Table 2 12.7 If a partial immersion thermometer other than one
of Specification E 1. The correction is algebraically additive. listed in Table 1 is used, and whenever To 5 to, report
Its value is calculated by the formula Kn(ts − to), where K is the solidification point as follows:
differential coefficient of expansion between the liquid in the tq 5 tm 1 ~Tc 2 Tu! 2 Km~Te 2 To! (4)
thermometer and the glass of which the thermometer is made.
For mercury-in-glass thermometers graduated in degrees Cel- where m is the number of degrees on the scale between Tu
sius, K 5 0.00016; and n is the number of degrees Celsius and the start of the scale.
between the start of the scale on a partial immersion thermom- 12.8 If a total immersion thermometer is used, report
eter and te, the experimental maximum temperature. solidification point as follows:
12.2 In a total immersion thermometer, the emergent stem t8q t8n 1 ~Tc 2 Tu! 2 KM~Tc 2 Tc! (5)
correction is calculated differently and is needed only when the
thermometer is used at partial immersion. This correction where M is the number of degrees on the scale between Tu
compensates for the difference, (tb − to), between tb, the tem- and the level of the surface of the molten reference compound
perature of the bulk of the thermometer, and to, the observed in the cell.
average temperature of the emergent column of mercury. One
way to assign a numerical value to tb is to measure te with a 13. Report
thermometer of which the scale is certified to be accurate 13.1 For completeness of record and for referee tests, report
within 0.02°C and to take tb 5 te. Another way is to repeat the the following information:
6
D 1493
13.1.1 Whether the sample was tested dry or water-saturated 13.4.6 That scale error was stipulated to be negligible if it is
or as received, neglected, and
13.1.2 Which method of drying, if any, was used, 13.4.7 The value of tp, if, under 13.4.6, the report does not
13.1.3 Which drying agent, if any, was used, state that scale error was stipulated to be negligible.
13.1.4 Whether the air-jacket and cooling bath were used, 13.5 When the sample is tested water-saturated and a
13.1.5 Temperature of the cooling-bath, if it was used, standard correction for the effect of the moisture is specified, as
13.1.6 ASTM thermometer that was used, for benzene as described in Test Method D 852, add the
13.1.7 te, the experimental maximum temperature, as the correction and report the corrected solidification point.
average of at least three readings of the maximum value, to the
nearest 0.01°C (see 10.4), and 14. Precision and Bias
13.1.8 If one of the thermometers listed in Table 1 was used 14.1 For the materials reported respectively in accordance
and if its scale was stipulated to be accurate within 0.02°C with 13.2, 13.3, and 13.4, the precision of the solidification
when the test was made, report te as the solidification point. point at the level of 95 % confidence is as follows:
NOTE 7—See Section 11 for calculations to be made if a thermometer Refined Material Repeatability, °C Reproducibility, °C
other than one of those listed in Table 1 was used or if a temperature Phenol 0.03 0.07
correction must be added to te. Naphthalene 0.05 0.10
Phthalic anhydride 0.05 0.11
13.2 For referee tests of refined phenol, the report shall
confirm that the following requirements have been met: 14.2 For a measure of precision in the checking procedure
13.2.1 The sample was tested dry, described in 10.10, the standard deviation of Tu has been found
13.2.2 The drying method described in 13.1 was used, to be no greater than 0.005°C in repeatability. Tu is the
13.2.3 The drying agent used was molecular sieve 4A in uncorrected temperature observed with a partial immersion
granular form, thermometer at the solidification point of the reference com-
13.2.4 The air jacket and cooling bath were used, pound in a thermometric cell.
13.2.5 The temperature of the cooling bath was between 30 14.3 For a measure of the accuracy that is attainable in the
and 35°C, and checking procedure described in 10.10, the difference
13.2.6 ASTM Thermometer 91C was used. The report shall (Tc − T8u) has been taken. Tc is the certified temperature
also include the following: assigned to a thermometric cell for the solidification point of
13.2.7 The value of te, the reference compound in it. T8u is a special value of Tu: in the
13.2.8 That scale error was stipulated to be negligible if it is special case in which Tu is observed with an accurate ther-
neglected, and mometer requiring no scalar correction, Tu 5 T8u. The follow-
13.2.9 The value of tp, if, under 13.2.8, the report does not ing limits have been found for the value of (Tc − T8u):
state that scale error was stipulated to be negligible. Numerical Limits of the
Value of (Tc − T8u)
13.3 For referee tests of refined naphthalene, the report shall Reference Compound in Minimum Value, Maximum Value,
conform that the following requirements have been met: Thermometric Cell deg°C deg°C
13.3.1 The sample was tested as received, Phenol −0.012 −0.022
Naphthalene +0.020 −0.031
13.3.2 The air jacket and cooling bath were used, Phthalic anhydride −0.095 −0.112
13.3.3 The temperature of the cooling bath was between 70
and 75°C, and 14.4 The following criteria should be used for judging the
13.3.4 ASTM Thermometer 93C was used. The report shall acceptability of results for maleic anhydride:
also include the following: 14.4.1 Intermediate Precision (formerly called
13.3.5 The value of te, Repeatability)—The standard deviation of results (each the
13.3.6 That scale error was stipulated to be negligible if it is average of duplicates), obtained by the same analyst on
neglected, and different days, has been estimated to be 0.012°C at 10 dP. Two
13.3.7 The value of tp, if, under 13.3.6, the report does not such values should be considered suspect (95 % confidence
state that scale error was stipulated to be negligible. level) if they differ by more than 0.05°C.
13.4 For referee tests of phthalic anhydride, the report shall 14.4.2 Reproducibility (Multilaboratory)—The standard de-
confirm that the following requirements have been met: viation of results (each the average of duplicates), obtained by
13.4.1 The sample was tested as received, analysis in different laboratories, has been estimated to be
13.4.2 The air jacket and cooling bath were used, 0.077°C at 9 dP. Two such values should be considered suspect
13.4.3 The temperature of the cooling bath was between (95 % confidence level) if they differ by more than 0.25°C.
121 and 126°C, and
13.4.4 ASTM Thermometer 96C was used. The report shall 15. Keywords
also include the following: 15.1 heat of fusion; heat of solidification; solidification
13.4.5 The value of te, point
7
D 1493
8

Distilled Soybean Fatty Acids1

1.1 This specification covers distilled acids derived from the Oils, Fatty Acids, and Polymerized Fatty Acids2
distillation of soybean oil. Three types are covered, as follows D 1965 Test Method for Unsaponifiable Matter in Drying
: Oils, Fatty Acids, and Polymerized Fatty Acids2
1.1.1 Type I—Usually produced from degummed soybean D 1980 Test Method for Acid Value of Fatty Acids and
oil and referred to as water white soybean fatty acids. Polymerized Fatty Acids2
1.1.2 Types II and III—Usually produced from recovered D 1982 Test Method for Titer of Fatty Acids2
soybean oil.
3. Properties
3.1 Distilled soybean fatty acids shall conform to the
2.1 ASTM Standards: requirements in Table 1.
D 1467 Guide for Testing Fatty Acids Used in Protective
Coatings2
4. Test Methods
(Gardner Color Scale)3 4.1 The properties enumerated in this specification shall be
D 1959 Test Method for Iodine Value of Drying Oils and determined in accordance with Methods D 1467.
Fatty Acids2
5. Keywords
1
5.1 soybean fatty acids; soybean oil
Current edition approved Sept. 19, 1960. Originally issued 1958. Replaces
D 1537 – 58 T.
2 3
1
D 1537
TABLE 1 Requirements for Distilled Soybean Fatty Acids
ASTM Test Methods Type I Type II Type III
Acid value D 1980 197 to 204 195 to 205 195 to 205
Saponification value D 1962 197 to 204 197 to 207 197 to 207
Unsaponifiable matter, max, % D 1965 1.0 2.0 2.0
Iodine value, min D 1959 133 125 120
Color, Gardner, max D 1544 2 4 6
Titer, °C D 1982 21 to 24 23 to 29 23 to 29
2

Distilled Linseed Fatty Acids1

1.1 This specification covers distilled acids derived from the Oils, Fatty Acids, and Polymerized Fatty Acids2
distillation of linseed oil. Two types are covered as follows: D 1965 Test Method for Unsaponifiable Matter in Drying
1.1.1 Type I—Usually produced from degummed linseed oil Oils, Fatty Acids, and Polymerized Fatty Acids2
and referred to as water white linseed fatty acids. D 1980 Test Method for Acid Value of Fatty Acids and
Polymerized Fatty Acids2
1.1.2 Type II—Usually produced from recovered linseed oil
D 1982 Test Method for Titer of Fatty Acids2
and referred to as regular distilled linseed fatty acids.
3. Properties
3.1 Distilled linseed fatty acids shall conform to the follow-
2.1 ASTM Standards: ing requirements:
D 1467 Guide for Testing Fatty Acids Used in Protective ASTM
Coatings2 Test
D 1544 Test Method for Color of Transparent Liquids Methods Type I Type II
(Gardner Color Scale)3 Acid value D 1980 197 to 204 195 to 202
D 1959 Test Method for Iodine Value of Drying Oils and Saponification value D 1962 197 to 204 195 to 202
Fatty Acids2 Unsaponifiable matter, D 1965 1.0 2.0
max, %
Iodine value, min D 1959 179 155
Color, Gardner, max D 1544 3 7
Titer, °C D 1982 17 to 20 19 to 25
1
and Related Coatings, Materials, and Applicationsand is the direct responsibility of 4. Test Methods
Subcommittee D01.32on Drying Oils.
Current edition approved Sept. 19, 1960. Originally issued 1958. Replaces 4.1 The properties enumerated in this specification shall be
D 1538 – 58 T. determined in accordance with Methods D 1467.
2
3
5.1 linseed fatty acids; linseed oil
1

Dehydrated Castor Acids1
1. Scope TABLE 1 Requirements for Dehydrated Castor Acids
1.1 This specification covers acids produced from dehy- ASTM

Test Type I Type II
drated castor oil. Two types are covered as follows: Method
1.1.1 Type I—Distilled dehydrated castor acids. Acid value D 1980 195 to 200 187 to 195
1.1.2 Type II—Undistilled dehydrated castor acids. Saponification value D 1962 195 to 200 193 to 199
Iodine value D 1959 150 to 156 138 to 143
2. Referenced Documents Color, Gardner D 1544 1 max 5 to 8
Spectrophotometric diene value D 1358 28 to 35 25 to 32
2.1 ASTM Standards:
D 1358 Test Method for Spectrophotometric Diene Value of D 1962 Test Method for Saponification Value of Drying
Dehydrated Castor Oil and Its Derivatives2 Oils, Fatty Acids, and Polymerized Fatty Acids2
D 1467 Guide for Testing Fatty Acids Used in Protective D 1980 Test Method for Acid Value of Fatty Acids and
Coatings2 Polymerized Fatty Acids2
D 1544 Test Method for Color of Transparent Liquids 3. Properties
D 1959 Test Method for Iodine Value of Drying Oils and 3.1 Dehydrated castor acids shall conform to the following
Fatty Acids2 requirements given in Table 1.
4. Test Methods
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint determined in accordance with Methods D 1467, except that
and Related Coatings, Materials, and Applications and is the direct responsibility of the spectrophotometric diene value shall be determined in
Current edition approved Sept. 19, 1960. Originally issued 1958. Replaces accordance with Test Method D 1358.
D 1539 – 58 T. 5. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 5.1 castor fatty acids; castor oil; dehydrated castor acids
1

Total Iodine Value of Drying Oils and Their Derivatives1
1. Scope in a catalyzed bromine solution to the double bonds. The

1.1 This test method2 covers the determination of total amount of bromine absorbed is determined by back titration of
iodine value. the excess bromine, and then compared to a blank determina-
1.2 This test method is applicable to oils, fatty acids, and tion. This test method is preferred over Test Method D 1959 for
bodied oils. While this test method is applicable to all oils and products containing conjugated unsaturation.
fatty acids and bodied oils, it is particularly useful for those 5. Apparatus
drying oils or derivatives that have conjugated unsaturation.
1.3 This standard does not purport to address all of the 5.1 Iodine Flasks, glass-stoppered, of 250-mL capacity.
safety concerns, if any, associated with its use. It is the NOTE 2—The test may be run either in a photographic-type darkroom
responsibility of whoever uses this standard to consult and under red safelight illumination5 or in a darkened laboratory in which the
establish appropriate safety and health practices and deter- light intensity is adjusted to 0.5 footcandle (5.4 1x) or less. The darkroom
mine the applicability of regulatory limitations prior to use. with red safelights permits the use of clear flasks. If the test shall be run
in a darkened laboratory, low-actinic (amber) flasks, or clear flasks
Specific hazard statements are given in Sections 6 and 7.
protected from light by covering as described below, must be used.
2. Referenced Documents Alternative modes of using clear flasks in a darkened laboratory are
described as follows. The type of covering is left to the discretion of the
2.1 ASTM Standards: analyst:
D 1193 Specification for Reagent Water3 (1) Place the clear iodine flask in a suitable metal can so that the neck
D 1959 Test Method for Iodine Value of Drying Oils and of the flask is level with the can rim. Over the top of the can, place a piece
Fatty Acids4 of heavy cardboard, with a hole precut in the center to just fit over the neck
of the flask; the top of the flask should just protrude out of the hole in the
3. Terminology cardboard cover. Then run the analysis as usual in a darkened laboratory.
(2) Wrap heavy aluminum foil around the iodine flasks so as to cover
3.1 Definitions: all but the top rim. The foil can be then removed at the latter stage of
3.1.1 total iodine value—a measure of the total unsaturation titration. Run the analysis in a darkened laboratory.
present in fats and oils (Note 1), expressed as the number of (3) Place the flask in an opaque bag that has a drawstring neck. The rim
centigrams of iodine equivalent to the unsaturation present in 1 of the iodine flask should just protrude from the bag to allow addition of
g of sample (weight percent of absorbed iodine). reagent.
NOTE 1—When the total iodine value is determined on oils having

5.2 Graduates, 5, 25, and 50-mL capacity.
conjugated systems, the result is a measure of the total unsaturation. This 5.3 Volumetric Pipets, 10, 20, and 50-mL capacity.
is in contrast to the iodine value method described in Test Method D 1959 NOTE 3—The bulb of the 50-mL pipet should be covered with alumi-
which determines only part of the total unsaturation of conjugated num foil.
systems.
5.4 Buret, 50-mL capacity graduated in 0.1-mL divisions.
4. Significance and Use 5.5 Weighing Device for Sample—A small, wide-mouth
4.1 This test method measures the total amount of unsatura- vial, fitted with a cork stopper and medicine dropper, may be
tion including conjugated unsaturation by addition of bromine used to weigh the sample by difference. Alternatively, the
sample may be weighed directly into a 1-mL microbeaker, and
1
carefully dropped into the iodine flask.
and Related Coatings and Materialsand is the direct responsibility of Subcommittee 5.6 Photoelectric Light Meter—Any suitable meter for mea-
D01.32on Drying Oils. suring room illumination in footcandles. If a darkroom and red
Current edition approved Aug. 10, 1997. Published October 1997. Originally safelight illumination are to be used, a meter is not required.
2
This procedure is essentially identical with that of Planck, R. W., Pack, F. C.,
and Goldblatt, L. A., as published in the Journal, Am. Oil Chemists’ Soc., Vol 30,
5
1953, p. 417, using the Rosenmund-Kuhnhenn reagent. Previously Benham, G. H., The sole source of supply of the red safelights Wratten No. 1 known to the
and Klee, L. J., published data on the use of this reagent for determining committee at this time is Eastman Kodak Co., 343 State St. Rochester, NY 14650.
unsaturation in the Journal, Am. Oil Chemists’ Soc., Vol 27, 1950, pp. 127–130. If you are aware of alternative suppliers, please provide this information to ASTM
3
Annual Book of ASTM Standards, Vol 11.01. Headquarters. Your comments will receive careful consideration at a meeting of the
4
Annual Book of ASTM Standards, Vol 06.03. responsible technical committee,1 which you may attend.
1
D 1541
5.7 Erlenmeyer Flasks, three, 250-mL. of sodium carbonate (Na2CO3) and a few drops of chloroform,
5.8 Volumetric Flasks, four, 1-L, glass-stoppered. as a preservative. Standardize against potassium iodate (KIO3)
5.9 Bottle, Amber, one, 4-L, glass-stoppered. primary standard as follows: Weigh, to the nearest 0.1 mg, into
a 250-mL Erlenmeyer flask about 0.12 to 0.17 g of the KIO3
6. Reagents and dissolve in 50 mL of water. Add 2 g of KI, and as soon as
6.1 Purity of Reagents—Reagent grade chemicals shall be this is dissolved, 1 mL of concentrated hydrochloric acid (HCl,
used in all tests. Unless otherwise indicated, it is intended that sp gr 1.19) diluted to 10 mL. Titrate the liberated iodine
all reagents shall conform to the specifications of the Commit- immediately with the Na2S2O3 solution, using starch indicator
tee on Analytical Reagents of the American Chemical Society, near the end point. Calculate the normality of the Na2S2O3
where such specifications are available.6 Other grades may be solution as follows:
used, provided it is first ascertained that the reagent is of Normality 5 W/~0.03567 3 V! (1)
accuracy of the determination. where:
6.2 Purity of Water—Unless otherwise indicated, references W = KIO3 used, g, and
to water shall be understood to mean reagent water conforming V = Na2S2O3 solution required for titration of the KIO3,
to Type I of Specification D 1193. mL.
6.3 Solvents: isooctane or fresh cyclohexane to replace long NOTE 5—The Na2S2O3 may be standardized against potassium dichro-
used carbon tetrachloride now banned as hazardous mate (K2Cr2O7), if desired, as described in Test Method D 1959.
(Precaution—See 7.1).
6.4 Carbon Tetrachloride (CCl4)—(Precaution—See 7.1) 6.9 Starch Indicator Solution—Make a paste with 10 g of
6.5 Mercuric Acetate Solution—Dissolve 25 g of mercuric starch in cold water. Add to this 1 L of boiling water, stir
acetate (Hg(C2H3O2)2) (Precaution—See 7.2) in glacial acetic rapidly, and cool. Salicylic acid (1.25 g/L) may be added as a
acid (CH3COOH) and dilute to 1 L with glacial acetic acid. preservative. If long storage is required, keep the solution in a
(Precaution—See 7.3) refrigerator at 40 to 50°F (4 to 10°C). Prepare fresh indicator
6.6 Potassium Iodide Solution (150 g/L)—Dissolve 150 g of when the end point of the titration from blue to colorless fails
potassium iodide (KI) in water and dilute to 1 L. to be sharp.
6.7 Rosenmund-Kuhnhenn Reagent—Place 40 mL of gla-
cial acetic acid (CH3COOH) in each of three 250-mL Erlen- 7. Hazards
meyer flasks. To the first, add slowly 28.4 6 0.2 g of pyridine, 7.1 Carbon Tetrachloride is a very hazardous liquid. It is
(Precaution—See 7.4) with cooling in an ice bath. To the absorbed by the skin. Its vapor is hazardous through inhalation.
second flask, add slowly 35.5 6 0.2 g of concentrated sulfuric It is an irritant to skin and eyes; avoid breathing (TLV-10 ppm).
acid (H2SO4, sp gr 1.84) with cooling as above. When cool, It causes liver and kidney damage and has cumulative effects.
add the contents of the second flask to the contents of the first Use with adequate ventilation (in a hood) and wear rubber
flask, with further cooling. To the third flask, add the contents gloves. See supplier’s Material Safety Data Sheet.
of a 1-oz (28.4-g) bottle (or ampule) of bromine. Add the 7.2 Mercuric Acetate—Mercuric acetate and other organic
bromine solution to the mixture of the first two solutions. mercury compounds are poisonous by oral ingestion and can be
Transfer to a 1-L volumetric flask with the aid of glacial acetic absorbed by the skin. Overheating results in decomposition. Do
acid, and make up to 1 L with glacial acetic acid. Mix not flush mercuric acetate and its solutions down a drain but
thoroughly and transfer to a 4-L, amber, glass-stoppered bottle. disposed of as hazardous wastes. See supplier’s Material
Add an additional 2.5 L of glacial acetic acid, making a total of Safety Data Sheet.
3.5 L of reagent. In this way, the weighing or measuring of 7.3 Acetic Acid, Glacial, is corrosive and may cause burns
bromine is eliminated. The reagent is approximately 0.1 N with to the skin and eyes. See supplier’s Material Safety Data Sheet.
respect to bromine. Fresh reagent should be prepared if the 7.4 Pyridine is a flammable liquid and hazardous by inha-
bromine concentration drops below 0.99 N. The normality of lation. It is an eye, skin and respiratory irritant (TLV-5 ppm).
the reagent can be checked by running a reagent blank titration May cause liver and kidney damage. Use with adequate
as described in 8.4, but eliminating the 1-h standing time. ventilation; perform all operations in a hood. See supplier’s
Material Safety Data Sheet.
NOTE 4—The stock bottle containing the Rosenmund-Kuhnhenn re-
agent should be kept stoppered when it is not in use to minimize loss of 7.5 Sulfuric Acid is corrosive to skin, eyes, and mucous
bromine. membranes in form of liquid, mist or fumes. It causes severe
burn. Take care to prevent the contact of the acid with eyes,
6.8 Sodium Thiosulfate, Standard Solution (0.1 N)
skin, or on clothing. In making dilute solutions, always add the
(Precaution—See 7.1-7.7)—Dissolve 24.8 g of sodium thio-
acid to water with care. See supplier’s Material Safety Data
sulfate (Na2S2O3·5H2O) in water and dilute to 1 L. Add 0.5 g
Sheet.
7.6 Bromine is a powerful oxidizer and may cause fire on
6
Reagent Chemicals, American Chemical Society Specifications, American contact with organic matter. Liquid and vapor may cause
Chemical Society, Washington, DC. For suggestions on the testing of reagents not severe burns. The gas is toxic (TLV-0.1 ppm) and, as such, is
a serious respiratory irritant. Use with adequate ventilation (in
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, a hood); avoid contact with skin and eyes. Handle bromine
MD. with rubber gloves. See supplier’s Material Safety Data Sheet.
2
D 1541
7.7 Chloroform is a hazardous liquid that can be absorbed darkened laboratory (or darkroom under red safelight), add
through the skin. Its vapor is hazardous through inhalation. It 20.0 mL of KI solution by pipet, swirl two or three times, add
is a narcotic. Use only with adequate ventilation (in a hood). It 20 mL of water, swirl again, stopper the flask, and allow it to
is also extremely flammable. See supplier’s Material Safety stand for 1 min. Then, using normal illumination, rinse the
Data Sheet. stopper and neck of the flask with about 10 mL of water.
8.4 Titrate the released iodine with Na2S2O3 solution by
8. Procedure adding rapidly from the 50-mL buret, with continuous agita-
8.1 To a 250-mL glass-stoppered iodine flask (Note 2), add tion, about 25 to 30 mL (all but 5 to 10 mL) of the required
5 mL of solvent. In this dissolve the specimen, weighed to 0.1 Na2S2O3 solution. Then, if low-actinic flasks are being used,
mg, using the weight of specimen prescribed in Table 1. transfer the contents to a colorless flask, rinsing three times
with a total of about 30 mL of water, and complete the titration
NOTE 6—The specimen weight is so chosen as to result in a 200 to
250 % excess of reagent of the amount absorbed. After running the in the usual manner using starch indicator when near the end
analysis, use the following calculation to determine whether the proper point. If clear flasks are used, there is no need to transfer.
specimen size has been used: Simply add 30 mL of water and complete the titration as
E, % 5 @V1/~B 2 V!# 3 100 (2) described, using starch indicator solution when near the end
point.
where: 8.5 With each group of samples, conduct at least two blank
E = excess reagent, determinations following the same procedure as described in
V1 = Na2S2O3 solution required for titration of the specimen, mL,
8.1-8.4, except that no sample is added. In the titration, run into
and
B = Na2S2O3 solution required for titration of the blank, mL. the flask about 40 to 45 mL of Na2S2O3 solution before
If the reagent excess falls outside these limits, the analysis must be completing the titration as described.
repeated using the proper specimen size. 9. Calculation and Report
8.2 Make sure that the specimen is completely dissolved, 9.1 Calculate the total iodine value, T, as follows:
and then in a darkened room of light intensity preferably less
T 5 @~B 2 V! 3 N 3 12.69#/S (3)
than 0.5 footcandle (5.4 lx), as measured with a light meter, or
in a darkroom under red safelight illumination, pipet into the where:
flask 10.0 mL of the Hg(C2H3O2)2 solution. Swirl the flask two B = Na2S2O3 solution required for titration of the blank,
or three times, add 50.0 mL of the Rosenmund-Kuhnhenn mL,
reagent, and note the time. Stopper the flask, add a small V = Na2S2O3 solution required for titration of the speci-
amount of KI solution to the well of the flask to seal it, swirl men, mL,
until the contents are well mixed (2 or 3 s), and place the flask N = normality of the Na2S2O3 solution, and
in a dark place at a temperature of 23 to 27°C. S = specimen used, g.
8.3 Exactly 1 h after the addition of the Rosenmund- 9.2 Report the total iodine value to the first decimal place.
Kuhnhenn reagent to the specimen, bring the flask out into the 10. Precision and Bias
10.1 Repeatability—Two results obtained by the same op-
TABLE 1 Iodine Value in Relation to Weight of Specimen
erator should be considered suspect, at the 95 % confidence
Total Iodine Weight of Specimen, g
Value
level, if they differ by more than 3.6 in iodine level (3.6 %
200 % Excess 250 % Excess absolute).
100 0.212 0.182 10.2 Reproducibility—Two results, each the mean of two
125 0.169 0.145
150 0.141 0.121
determinations, obtained by operators in different laboratories
175 0.121 0.104 should be considered suspect, at the 95 % confidence level, if
200 0.106 0.091 they differ by more than 6.1 in iodine value (6.1 % absolute).
225 0.094 0.081
250 0.085 0.073
10.3 Bias—Bias has not been determined.
275 0.073 0.066 11. Keywords
300 0.071 0.061
11.1 drying oils; iodine value; iodine value—drying oils
3

Viscosity of Transparent Liquids by Bubble Time Method1
1. Scope 3.3 Reference Standards—A series of standard viscosity

1.1 This test method covers the determination of the viscos- tubes (3.2) filled with transparent liquids having predetermined
ity in bubble seconds by timing. The bubble seconds are viscosities in stokes and bubble seconds and spaced in loga-
approximately equal to stokes for most liquids. rithmically even increments of about 26 % (log
1.2 The test method is applicable to transparent liquids that 1.260 5 0.100), as listed in Table 1. The standards shall be
are free from crystalline or gel particles. marked alphabetically or numerically as shown in Table 1
1.3 This standard does not purport to address all of the without reference to stokes or bubble time (Note 2). Also listed
safety concerns, if any, associated with its use. It is the in Table 1, for general and historical reference only, is the long
responsibility of the user of this standard to establish appro- established series of Gardner-Holdt letter standards, in tubes
priate safety and health practices and determine the applica- that do not have the three lines and are shorter than the standard
bility of regulatory limitations prior to use. viscosity tubes described in 3.2.
NOTE 2—For convenience, the reference standards can be divided in
2. Terminology three series: light series, 15 tubes marked 0.22 to 8.0; heavy series, 14
2.1 Definitions: tubes marked 10 to 200; and very heavy series, 7 tubes, marked 250 to
2.1.1 viscosity—the resistance experienced by one portion 1000.
of a liquid moving over another portion of the liquid. The 3.4 Timing Device—Stopwatch or electric stop clock ca-
absolute unit of viscosity in the cgs system is the poise which pable of being read to a precision of 0.1 s.
is expressed as dyne-seconds per square centimetre. Stokes are 3.5 Tube Racks, capable of inverting one or more viscosity
equal to poises divided by density. The absolute SI viscosity tubes 180° to within 1° of a vertical position while rack and
unit is the pascal-second. tubes are immersed in the constant temperature bath.
3.6 Viscosity Tube Corks, No. 2 short.
3. Apparatus
3.1 Constant-Temperature Bath—Any suitable bath capable 4. Procedure
of maintaining temperature at 25 6 0.1°C with water as the 4.1 Fill a standard viscosity tube with the material to be
bath medium. tested to approximately level with the 108-mm line.
3.2 Standard Viscosity Tubes,2 of clear glass and with flat 4.2 Transfer the tube to a constant 25°C temperature bath
bottoms, 10.65 6 0.025 mm in inside diameter; 114 6 1 mm with the cork loosely inserted. Hold at this temperature for 10
in outside length. Plainly legible lines shall be located as min.
follows (Note 1):
NOTE 3—Adequate control of the temperature bath is essential. A
27 6 0.5 mm
variation of 0.1°C in the temperature of the bath will cause a 1 % variation
100 6 0.5 mm in the timed bubble travel.
108 6 0.5 mm
The distance between the first and second lines shall be 73 6 4.3 At the end of 10 min adjust the level of the liquid so that
0.5 mm. the bottom meniscus will be level with the 100-mm line. Insert
the cork so that the bottom of the cork is on the level with the
NOTE 1—All distances shall be measured from the outside bottom of 108-mm line. This will ensure a bubble of suitable and uniform
the tube. size.
4.4 Insert the tube in the rack and immerse in the 25°C
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint water bath. Allow the tube(s) to stand with cork down in the
and Related Coatings, Materials, and Applications and is the direct responsibility of bath a minimum of 20 min before determining the viscosity.
Current edition approved Oct. 10, 1998. Published December 1998. Originally NOTE 4—For viscosities of liquids that have a timed bubble travel of 4
published as D 1545 – 58 T. Last previous edition D 1545 – 89(1993)e1. s or less, more precise results can be obtained by comparison against
2
Empty standard viscosity tubes are available from the R. P. Cargille Labora- reference standards having a predetermined viscosity or timed bubble
tories, Inc., 55 Commerce Rd., Cedar Grove, NJ, 07009, or Byk-Gardner Inc., travel.
Gardner Laboratory, 2435 Linden Lane, Silver Spring, MD 20910.
1
D 1545
TABLE 1 Recommended Numerical Standards for Comparator the time in seconds start the timing device when the top of the
Viscosity TubesA bubble becomes tangent to the 27-mm line on the tube. Stop
Bubble the timing when the top of the bubble becomes tangent with the
Gardner- SecondsB Gardner-
Bubble TubeC 100-mm line. This gives a 73-mm timed bubble travel. All
Stokes Holdt and Stokes Holdt
SecondsB Number
Letter TubeC Letter timings shall be made with the tube in an exact vertical
Number
position.
– 0.10– 10–– 10–
–W NOTE 5—Positioning of the tube in a vertical position is mandatory. A
– 0.13– 13–– 13––X
tube one radius off the vertical will give an error of approximately 10 %
–A3
– 0.16– 16–– 16– in the time of bubble travel.
–Y
– 0.20– 20–– 20– 5. Report
0.75–— 0.22– –A2
–Z 5.1 Report the following information:
– 0.25– 25–– 25–
–Z1 5.1.1 The viscosity obtained by the timing method ex-
– 0.32––A1 32–– 32– pressed as “bubble seconds” or “approximate stokes.”
0.81–– 0.34–
–Z2
NOTE 6—The time in seconds or “bubble seconds” is an approximate
– 0.40– 40–– 40–
–Z3 measurement of stokes when the bubble time method is applied to most
0.90–– 0.50–– 0.50––A 50–– 50– raw materials and finished products encountered by the paint, varnish, and
– 0.63– 63–– 63– lacquer industries. This relationship does not hold for silicones or water
–B –Z4 dispersions of gums or similar materials. Viscosity results by this test
1.00–– 0.68–
– 0.80– 80–– 80–
method are influenced by non-Newtonian behavior and by surface tension.
–C Other variations on bubble-tube viscometers are described in ASTM STP
1.15–– 0.92– 500, Section 3.2.9.3
–Z5
– 1.00––D 100–– 100–
1.30–– 1.15–
– 1.25––E 125–– 125–
–F
6.1 Precision—On the basis of an interlaboratory study4 of
1.55–– †1.45– –Z6 this test method in which ten laboratories tested liquids ranging
– 1.60– 160–– 160– in viscosity from 4.5 to 440 St, the following criteria should be
–G
1.85–– 1.80– used for judging the acceptability of results at the 95 %
– 2.00––H 200–– 200– confidence level:
2.20–– 2.15–
–I 6.1.1 Two results obtained by the same operator should be
– 2.50––J 250–– 250– considered suspect if they differ by more than 4.9 % relative.
2.65D–– 2.65D–
–K 6.1.2 Two results, each the mean of duplicates, obtained by
–L operators in different laboratories should be considered suspect
3.20–– 3.20–– 3.20––M 320–– 320–
–N
if they differ by more than 9.0 % relative.
–O 6.2 Bias—No information can be presented on the bias of
–Z7
4.00–– 4.00–– 4.00––P 400–– 400–
this test method because no materials having an accepted
–Q reference value is available.
–R
5.00–– 5.00–– 5.00––S 500–– 500–
–T 7. Keywords
–Z8
6.30–– 6.30–– 6.30––U 630–– 630– 7.1 Gardner-Holdt; GH viscosity; viscosity
8.00–– 8.00–– 8.00– 800–– 800–
–Z9
–V
10.0–– 10.0–– 10.0– 1000–– 1000–
–Z10
A
Arranged to show relationship between stokes, bubble seconds, and Gardner-
Holdt letters. Stokes are shown in logarithmic progression.
B
The bubble time, in seconds, of the numerical tubes under 4 s was determined
by a technique employing a movie camera.
C
For reference purposes only. Numbered tubes are no longer commercially
available.
D
Above 2.65 the bubble seconds as measured by the kinematic method are
approximately equivalent for most products. Below 2.65 this relationship does not
hold.
† Editorially corrected. 3
Paint Testing Manual, ASTM STP 500, ASTM, 1972.
4
See Holt, K. E., Proceedings, ASTM, Vol 57, 1957, pp. 297–300, and Offıcial
4.5 To read, invert the tube quickly and determine the time Digest, Federation of Societies for Paint Technology, Vol 30, May 1958, pp.
required for the bubble to rise in seconds. When determining 540–543.
2
D 1545
3

Calculation of Volume and Weight of Industrial Aromatic
Hydrocarbons1
1. Scope TABLE 1 Relative Density and Density Data
1.1 These tables are for use in calculating the weight and Relative Density Density in Air at 60°F lb
Product
60°F/60°F per U.S. Gallon
volume of benzene, toluene, mixed xylenes, styrene, ortho-
Benzene 0.8844 7.365
xylene, meta-xylene, para-xylene, cumene, ethylbenzene, 300 Cumene 0.8663 7.214
to 350°F aromatic hydrocarbons, 350° to 400°F aromatic Cyclohexane 0.7834 6.522
hydrocarbons and cyclohexane. A method is given for calcu- Ethylbenzene 0.8718 7.259
m-Xylene 0.8687 7.234
lating the volume at 60°F from an observed volume at t°F. o-Xylene 0.8848 7.367
Table 1 lists the density in pounds per gallon at 60°F for high p-Xylene 0.8657 7.209
purity chemicals. Styrene 0.9110 7.586
Toluene 0.8718 7.260
1.2 A procedure for the calculation of density in pounds per
gallon at 60°F of materials of lower purity is provided.
NOTE 1—The purchaser and the seller should agree on a reasonable D 1250 Guide for Petroleum Measurement Tables2
policy in regard to rounding of final numbers in all computations. D 3505 Test Method for Density or Relative Density of
Rounding the final weight or volume to not more than five significant Pure Liquid Chemicals3
digits is, in most cases, consistent with the experimental reliability of the D 4052 Test Method for Density and Relative Density of
data. Liquids by Digital Density Meter4
NOTE 2—An alternative method is Test Method D 4052.
E 29 Practice for Using Significant Digits in Test Data to
1.3 The following applies to all specified limits in this test Determine Conformance with Specifications5
method: for purposes of determining conformance with this 2.2 Other Document:
test method, an observed value or calculated value shall be American Petroleum Institute Research Project 446
used in expressing the specification limit, in accordance with 3. Significance and Use
the rounding-off method of Practice E 29. 3.1 This test method is suitable for use in calculating
1.4 This standard does not purport to address all of the weights and volumes of products outlined in Section 1. The
safety concerns, if any, associated with its use. It is the information gained from this method can be used for deter-
responsibility of the user of this standard to establish appro- mining quantities of stated aromatic hydrocarbons in tanks,
priate safety and health practices and determine the applica- shipping containers, etc.
4. Basic Data
2. Referenced Documents 4.1 All calculations are derived from densities furnished by
2.1 ASTM Standards: the American Petroleum Institute Research Project 44. The
D 941 Test Method for Density and Relative Density (Spe- tables are based on data for compounds of the highest purity,
cific Gravity) of Liquids by Lipkin Bicapillary Pycnom- but can be used for materials in the range indicated in Table 2.
eter2 4.2 The basic data and conversion factors used are given in
D 1217 Test Method for Density and Relative Density the Appendix to the 1963 Annual Report7 of ASTM Committee
(Specific Gravity) of Liquids by Bingham Pycnometer2
3
4
1 5
This method is under the jurisdiction of ASTM Committee D-16 on Aromatic Annual Book of ASTM Standards, Vol 14.02.
6
Hydrocarbons and Related Chemicals and is the direct responsibility of Subcom- “Selected Values of Properties of Hydrocarbons and Related Compounds,”
mittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their Derivatives. prepared by American Petroleum Institute Research Project 44 at the Chemical
Current edition approved Sept. 15, 1995. Published November 1995. Originally Thermodynamic Center, Department of Chemistry, Agriculture and Mechanical
published as D 1555 – 57. Last previous edition D 1555 – 92. College Station, TX.
2 7
Annual Book of ASTM Standards, Vol 05.01. Proceedings, ASTM, Vol 63, 1963.
1
D 1555
TABLE 2 Application Range of Table 3 D-16. Densities listed in Table 1 are given in ASTM Data
Commercial Product Series Publications.8
Benzene 95 to 100 %
Toluene 95 to 100 % 5. Tables
Mixed xylene all proportions
Styrene 95 to 100 % 5.1 Table 3 contains 12 columns as follows:
o-Xylene 95 to 100 %
m-Xylene 95 to 100 %
p-Xylene 94 to 100 %
Cyclohexane 90 to 100 %
300–350°F Aromatic Hydrocarbons all proportions
350–400°F Aromatic Hydrocarbons all proportions
Cumene 95 to 100 %
Ethylbenzene 95 to 100 %
8
“Physical Constants of Hydrocarbons C1 to C10,” ASTM Data Service Publi-
cation DS4A, ASTM, 1971.
TABLE 3 Volume Corrections
Volume Corrections to 60°FA

300 to 350 to
Temperature, m-Xylene
350°F 400°F
°F and Cyclo- Ethyl-
Benzene Toluene Styrene o-Xylene p-Xylene CumeneB Aromatic Aromatic
Mixed hexaneB benzeneB
Hydro- Hydro-
Xylene
carbons carbons
−5 ... 1.0383 ... ... ... ... ... ... ... ... ...
−4 ... 1.0377 ... ... ... ... ... ... ... ... ...
−3 ... 1.0371 ... ... ... ... ... ... ... ... ...
−2 ... 1.0365 ... ... ... ... ... ... ... ... ...
−1 ... 1.0359 ... ... ... ... ... ... ... ... ...
0 ... 1.0353 ... ... ... ... ... ... ... ... ...
1 ... 1.0347 ... ... ... ... ... ... ... ... ...
2 ... 1.0341 ... ... ... ... ... ... ... ... ...
3 ... 1.0336 ... ... ... ... ... ... ... ... ...
4 ... 1.0330 ... ... ... ... ... ... ... ... ...
5 ... 1.0324 1.0293 ... 1.0288 ... ... 1.0306 1.0297 1.0286 1.0266
6 ... 1.0318 1.0287 ... 1.0283 ... ... 1.0300 1.0292 1.0280 1.0262
7 ... 1.0312 1.0282 ... 1.0278 ... ... 1.0295 1.0287 1.0275 1.0257
8 ... 1.0306 1.0277 ... 1.0273 ... ... 1.0289 1.0281 1.0270 1.0252
9 ... 1.0300 1.0272 ... 1.0267 ... ... 1.0284 1.0276 1.0265 1.0248
10 ... 1.0294 1.0266 ... 1.0262 ... ... 1.0278 1.0270 1.0260 1.0243
11 ... 1.0288 1.0261 ... 1.0257 ... ... 1.0273 1.0265 1.0254 1.0238
12 ... 1.0283 1.0256 ... 1.0252 ... ... 1.0267 1.0260 1.0249 1.0233
13 ... 1.0277 1.0251 ... 1.0246 ... ... 1.0262 1.0254 1.0244 1.0228
14 ... 1.0271 1.0245 ... 1.0241 ... ... 1.0256 1.0249 1.0239 1.0223
15 ... 1.0265 1.0240 1.0242 1.0236 ... ... 1.0251 1.0244 1.0234 1.0218
16 ... 1.0259 1.0235 1.0237 1.0231 ... ... 1.0245 1.0238 1.0228 1.0214
17 ... 1.0253 1.0230 1.0231 1.0225 ... ... 1.0239 1.0233 1.0223 1.0209
18 ... 1.0247 1.0224 1.0226 1.0220 ... ... 1.0234 1.0228 1.0218 1.0203
19 ... 1.0241 1.0219 1.0221 1.0215 ... ... 1.0228 1.0222 1.0213 1.0199
20 ... 1.0235 1.0214 1.0215 1.0210 ... ... 1.0223 1.0217 1.0208 1.0194
21 ... 1.0230 1.0208 1.0210 1.0204 ... ... 1.0217 1.0211 1.0203 1.0189
22 ... 1.0224 1.0203 1.0204 1.0199 ... ... 1.0212 1.0206 1.0197 1.0184
23 ... 1.0218 1.0198 1.0199 1.0194 ... ... 1.0206 1.0201 1.0192 1.0180
24 ... 1.0212 1.0193 1.0194 1.0189 ... ... 1.0201 1.0195 1.0187 1.0175
25 ... 1.0206 1.0187 1.0188 1.0184 ... ... 1.0195 1.0190 1.0182 1.0170
26 ... 1.0200 1.0182 1.0183 1.0178 ... ... 1.0190 1.0184 1.0177 1.0165
27 ... 1.0194 1.0177 1.0178 1.0173 ... ... 1.0184 1.0179 1.0172 1.0160
28 ... 1.0188 1.0171 1.0172 1.0168 ... ... 1.0179 1.0174 1.0166 1.0155
29 ... 1.0182 1.0166 1.0167 1.0163 ... ... 1.0173 1.0168 1.0161 1.0151
30 ... 1.0177 1.0161 1.0162 1.0157 ... ... 1.0167 1.0163 1.0156 1.0146
31 ... 1.0171 1.0155 1.0156 1.0152 ... ... 1.0162 1.0157 1.0151 1.0141
32 ... 1.0165 1.0150 1.0151 1.0147 ... ... 1.0156 1.0152 1.0145 1.0136
2
D 1555
TABLE 3 Continued
300 to 350 to
350°F 400°F
°F and Cyclo- Ethyl- B
Benzene Toluene Styrene o-Xylene p-Xylene Cumene Aromatic Aromatic
Hydro- Hydro-
Xylene
carbons carbons
33 ... 1.0159 1.0145 1.0145 1.0142 ... ... 1.0151 1.0147 1.0140 1.0131
34 ... 1.0153 1.0139 1.0140 1.0136 ... ... 1.0145 1.0141 1.0135 1.0126
35 ... 1.0147 1.0134 1.0135 1.0131 ... ... 1.0140 1.0136 1.0130 1.0122
36 ... 1.0141 1.0129 1.0129 1.0126 ... ... 1.0134 1.0130 1.0125 1.0116
37 ... 1.0135 1.0123 1.0124 1.0121 ... ... 1.0129 1.0125 1.0120 1.0112
38 ... 1.0130 1.0118 1.0119 1.0115 ... ... 1.0123 1.0120 1.0114 1.0107
39 ... 1.0124 1.0113 1.0113 1.0110 ... ... 1.0117 1.0114 1.0109 1.0102
40 1.0130 1.0118 1.0107 1.0108 1.0105 ... 1.0132 1.0112 1.0109 1.0104 1.0097
41 1.0124 1.0112 1.0102 1.0102 1.0100 ... 1.0126 1.0106 1.0103 1.0099 1.0092
42 1.0117 1.0106 1.0097 1.0097 1.0094 ... 1.0119 1.0101 1.0098 1.0094 1.0087
43 1.0111 1.0100 1.0091 1.0092 1.0089 ... 1.0112 1.0095 1.0092 1.0088 1.0082
44 1.0104 1.0094 1.0086 1.0086 1.0084 ... 1.0106 1.0090 1.0087 1.0083 1.0078
45 1.0098 1.0088 1.0081 1.0081 1.0079 ... 1.0099 1.0084 1.0082 1.0078 1.0073
46 1.0091 1.0082 1.0075 1.0075 1.0074 ... 1.0093 1.0078 1.0076 1.0073 1.0068
47 1.0085 1.0077 1.0070 1.0070 1.0068 ... 1.0085 1.0073 1.0071 1.0068 1.0063
48 1.0078 1.0071 1.0065 1.0065 1.0063 ... 1.0079 1.0067 1.0065 1.0063 1.0058
49 1.0072 1.0065 1.0059 1.0059 1.0058 ... 1.0073 1.0062 1.0060 1.0057 1.0054
50 1.0065 1.0059 1.0054 1.0054 1.0053 ... 1.0066 1.0056 1.0054 1.0052 1.0048
51 1.0059 1.0053 1.0048 1.0049 1.0047 ... 1.0060 1.0050 1.0049 1.0047 1.0044
52 1.0052 1.0047 1.0043 1.0043 1.0042 ... 1.0053 1.0045 1.0044 1.0042 1.0039
53 1.0046 1.0041 1.0038 1.0038 1.0037 ... 1.0046 1.0039 1.0038 1.0037 1.0034
54 1.0039 1.0035 1.0032 1.0032 1.0032 ... 1.0040 1.0034 1.0033 1.0032 1.0029
55 1.0033 1.0029 1.0027 1.0027 1.0026 1.0027 1.0033 1.0028 1.0027 1.0026 1.0024
56 1.0026 1.0024 1.0022 1.0022 1.0021 1.0022 1.0027 1.0022 1.0022 1.0021 1.0019
57 1.0020 1.0018 1.0016 1.0016 1.0016 1.0016 1.0020 1.0017 1.0016 1.0016 1.0014
58 1.0013 1.0012 1.0011 1.0011 1.0011 1.0011 1.0013 1.0011 1.0011 1.0012 1.0011
59 1.0007 1.0006 1.0005 1.0005 1.0005 1.0005 1.0007 1.0006 1.0005 1.0006 1.0005
60 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
61 0.9993 0.9994 0.9995 0.9995 0.9995 0.9994 0.9993 0.9994 0.9995 0.9995 0.9995
62 0.9987 0.9988 0.9989 0.9989 0.9989 0.9989 0.9987 0.9989 0.9989 0.9990 0.9990
63 0.9980 0.9982 0.9984 0.9984 0.9984 0.9983 0.9980 0.9983 0.9984 0.9984 0.9986
64 0.9974 0.9976 0.9978 0.9978 0.9979 0.9978 0.9973 0.9978 0.9978 0.9980 0.9980
65 0.9967 0.9971 0.9973 0.9973 0.9974 0.9972 0.9967 0.9972 0.9973 0.9974 0.9976
66 0.9961 0.9965 0.9968 0.9968 0.9968 0.9967 0.9960 0.9966 0.9967 0.9969 0.9971
67 0.9954 0.9959 0.9962 0.9962 0.9963 0.9961 0.9953 0.9961 0.9962 0.9964 0.9966
68 0.9947 0.9953 0.9957 0.9957 0.9958 0.9956 0.9947 0.9955 0.9956 0.9959 0.9961
69 0.9941 0.9947 0.9951 0.9951 0.9953 0.9950 0.9940 0.9949 0.9951 0.9954 0.9956
70 0.9934 0.9941 0.9946 0.9946 0.9947 0.9945 0.9934 0.9944 0.9945 0.9948 0.9951
71 0.9928 0.9935 0.9940 0.9941 0.9942 0.9939 0.9927 0.9938 0.9940 0.9943 0.9946
72 0.9921 0.9929 0.9935 0.9935 0.9937 0.9934 0.9920 0.9933 0.9934 0.9938 0.9941
73 0.9914 0.9923 0.9930 0.9930 0.9932 0.9928 0.9914 0.9927 0.9929 0.9933 0.9936
74 0.9908 0.9918 0.9924 0.9924 0.9926 0.9923 0.9907 0.9921 0.9923 0.9928 0.9932
75 0.9901 0.9912 0.9919 0.9919 0.9921 0.9917 0.9900 0.9916 0.9918 0.9922 0.9927
76 0.9894 0.9905 0.9913 0.9914 0.9916 0.9912 0.9893 0.9910 0.9912 0.9917 0.9922
77 0.9888 0.9900 0.9908 0.9908 0.9911 0.9906 0.9887 0.9904 0.9907 0.9912 0.9917
78 0.9881 0.9894 0.9902 0.9903 0.9905 0.9901 0.9880 0.9899 0.9902 0.9907 0.9912
79 0.9874 0.9888 0.9897 0.9897 0.9900 0.9895 0.9873 0.9893 0.9896 0.9902 0.9907
80 0.9868 0.9882 0.9891 0.9892 0.9895 0.9890 0.9867 0.9887 0.9891 0.9897 0.9902
81 0.9861 0.9876 0.9886 0.9886 0.9889 0.9884 0.9860 0.9882 0.9885 0.9892 0.9898
82 0.9854 0.9870 0.9880 0.9881 0.9884 0.9878 0.9853 0.9876 0.9880 0.9886 0.9893
83 0.9848 0.9865 0.9875 0.9876 0.9879 0.9873 0.9847 0.9870 0.9874 0.9881 0.9888
84 0.9841 0.9859 0.9869 0.9870 0.9874 0.9867 0.9840 0.9865 0.9869 0.9876 0.9883
85 0.9834 0.9853 0.9864 0.9865 0.9868 0.9862 0.9833 0.9859 0.9863 0.9870 0.9878
86 0.9828 0.9847 0.9859 0.9859 0.9863 0.9856 0.9827 0.9853 0.9858 0.9865 0.9873
87 0.9821 0.9841 0.9853 0.9854 0.9858 0.9851 0.9820 0.9848 0.9852 0.9860 0.9868
88 0.9814 0.9835 0.9848 0.9849 0.9852 0.9845 0.9813 0.9842 0.9847 0.9855 0.9863
89 0.9808 0.9829 0.9842 0.9843 0.9847 0.9840 0.9806 0.9836 0.9841 0.9850 0.9858
3
D 1555
TABLE 3 Continued
300 to 350 to
350°F 400°F
Hydro- Hydro-
Xylene
carbons carbons
90 0.9801 0.9823 0.9837 0.9838 0.9842 0.9834 0.9800 0.9831 0.9836 0.9844 0.9853
91 0.9794 0.9818 0.9831 0.9832 0.9837 0.9828 0.9793 0.9825 0.9830 0.9839 0.9848
92 0.9787 0.9812 0.9826 0.9827 0.9831 0.9823 0.9786 0.9819 0.9825 0.9834 0.9844
93 0.9781 0.9806 0.9820 0.9821 0.9826 0.9817 0.9780 0.9814 0.9819 0.9829 0.9839
94 0.9774 0.9800 0.9815 0.9816 0.9821 0.9812 0.9773 0.9808 0.9813 0.9824 0.9834
95 0.9767 0.9794 0.9809 0.9811 0.9815 0.9806 0.9766 0.9802 0.9808 0.9819 0.9829
96 0.9761 0.9788 0.9804 0.9805 0.9810 0.9801 0.9759 0.9797 0.9802 0.9813 0.9824
97 0.9754 0.9782 0.9798 0.9800 0.9805 0.9795 0.9753 0.9791 0.9797 0.9808 0.9819
98 0.9747 0.9776 0.9793 0.9794 0.9800 0.9789 0.9746 0.9785 0.9791 0.9803 0.9814
99 0.9740 0.9770 0.9787 0.9789 0.9794 0.9784 0.9739 0.9780 0.9786 0.9798 0.9810
100 0.9734 0.9765 0.9782 0.9783 0.9789 0.9778 0.9733 0.9774 0.9780 0.9793 0.9805
101 0.9727 0.9759 0.9776 0.9778 0.9784 0.9773 0.9726 0.9768 0.9775 0.9787 0.9800
102 0.9720 0.9753 0.9771 0.9773 0.9778 0.9767 0.9719 0.9763 0.9769 0.9782 0.9795
103 0.9713 0.9747 0.9765 0.9767 0.9773 0.9761 0.9712 0.9757 0.9764 0.9777 0.9790
104 0.9706 0.9741 0.9759 0.9762 0.9768 0.9756 0.9706 0.9751 0.9758 0.9772 0.9785
105 0.9700 0.9735 0.9754 0.9756 0.9762 0.9750 0.9689 0.9746 0.9753 0.9766 0.9780
106 0.9693 0.9729 0.9748 0.9751 0.9757 0.9745 0.9692 0.9740 0.9747 0.9762 0.9775
107 0.9686 0.9723 0.9743 0.9745 0.9752 0.9739 0.9685 0.9734 0.9742 0.9756 0.9770
108 0.9679 0.9717 0.9737 0.9740 0.9746 0.9733 0.9679 0.9729 0.9736 0.9751 0.9766
109 0.9672 0.9712 0.9732 0.9734 0.9741 0.9728 0.9672 0.9723 0.9731 0.9746 0.9760
110 0.9666 0.9706 0.9726 0.9729 0.9736 0.9722 0.9665 0.9717 0.9725 0.9741 0.9756
111 0.9659 0.9700 0.9721 0.9724 0.9731 0.9716 0.9658 0.9711 0.9720 ... ...
112 0.9652 0.9694 0.9714 0.9718 0.9725 0.9711 0.9652 0.9706 0.9714 ... ...
113 0.9645 0.9688 0.9710 0.9713 0.9720 0.9705 0.9645 0.9700 0.9708 ... ...
114 0.9638 0.9682 0.9704 0.9707 0.9715 0.9700 0.9638 0.9694 0.9703 ... ...
115 0.9632 0.9676 0.9698 0.9702 0.9709 0.9694 0.9631 0.9689 0.9697 ... ...
116 0.9625 0.9670 0.9693 0.9696 0.9704 0.9688 0.9625 0.9683 0.9692 ... ...
117 0.9618 0.9664 0.9687 0.9691 0.9699 0.9683 0.9618 0.9677 0.9686 ... ...
118 0.9611 0.9659 0.9682 0.9685 0.9693 0.9677 0.9611 0.9672 0.9681 ... ...
119 0.9604 0.9653 0.9676 0.9680 0.9688 0.9671 0.9604 0.9666 0.9675 ... ...
120 0.9597 0.9647 0.9671 0.9675 0.9683 0.9666 0.9597 0.9660 0.9670 ... ...
121 ... ... ... ... ... 0.9660 ... ... ... ... ...
122 ... ... ... ... ... 0.9655 ... ... ... ... ...
123 ... ... ... ... ... 0.9649 ... ... ... ... ...
124 ... ... ... ... ... 0.9643 ... ... ... ... ...
125 ... ... ... ... ... 0.9638 ... ... ... ... ...
126 ... ... ... ... ... 0.9632 ... ... ... ... ...
127 ... ... ... ... ... 0.9626 ... ... ... ... ...
128 ... ... ... ... ... 0.9621 ... ... ... ... ...
129 ... ... ... ... ... 0.9615 ... ... ... ... ...
130 ... ... ... ... ... 0.9609 ... ... ... ... ...
131 ... ... ... ... ... 0.9604 ... ... ... ... ...
132 ... ... ... ... ... 0.9598 ... ... ... ... ...
133 ... ... ... ... ... 0.9592 ... ... ... ... ...
134 ... ... ... ... ... 0.9587 ... ... ... ... ...
135 ... ... ... ... ... 0.9581 ... ... ... ... ...
136 ... ... ... ... ... 0.9575 ... ... ... ... ...
137 ... ... ... ... ... 0.9570 ... ... ... ... ...
138 ... ... ... ... ... 0.9564 ... ... ... ... ...
139 ... ... ... ... ... 0.9558 ... ... ... ... ...
140 ... ... ... ... ... 0.9553 ... ... ... ... ...
141 ... ... ... ... ... 0.9547 ... ... ... ... ...
142 ... ... ... ... ... 0.9541 ... ... ... ... ...
143 ... ... ... ... ... 0.9535 ... ... ... ... ...
144 ... ... ... ... ... 0.9530 ... ... ... ... ...
145 ... ... ... ... ... 0.9524 ... ... ... ... ...
146 ... ... ... ... ... 0.9518 ... ... ... ... ...
147 ... ... ... ... ... 0.9513 ... ... ... ... ...
4
D 1555
TABLE 3 Continued
300 to 350 to
350°F 400°F
Hydro- Hydro-
Xylene
carbons carbons
148 ... ... ... ... ... 0.9507 ... ... ... ... ...
149 ... ... ... ... ... 0.9500 ... ... ... ... ...
150 ... ... ... ... ... 0.9496 ... ... ... ... ...
A
Based on API Project 44 data—essentially correct for all purities above 95 %.
B
Based on API Project 44 data and non-linear regression analysis of those data using this equation:
RHO 5 EXP@2ALPHT 3 ~TEMP 2 60! 3 ~1 1 0.8 3 ALPHT 3 ~TEMP 2 60!!# 3 RHOT
where:
RHO 5 the density of the material in kg/m3 at the observed temperature
ALPHT 5 the coefficient of expansion of the material at 60°F
TEMP 5 the observed temperature in° F, and
RHOT 5 the density of the material in kg/m3 at 60°F.
5.1.1 Column 1—Observed temperature in degrees Fahren- TABLE 4 Converting to Densities in Standard Air
heit. Density at 60°F, Correction Factor,
in Vacuum, g/mL A, g/mL
5.1.2 Columns 2 to 12, Inclusive—Multiplying factors for
the reduction to 60°F, specifically the ratio of the volume at 0.82 0.001098
0.83 0.001097
60°F to the volume at t°F. 0.84 0.001095
0.85 0.001094
0.86 0.001092
6. Use of Tables
0.87 0.001091
6.1 Volume Reduction to 60°F—Enter the appropriate Col- 0.88 0.001090
0.89 0.001088
umn of Table 3, selecting that temperature to the nearest degree 0.90 0.001087
Fahrenheit at which the bulk volume was measured (tempera-
ture t), and select the corresponding volume reduction factor
(ratio) in Columns 2 to 12. Multiply the bulk volume measure- Example 3—What is the weight (in air) of the contents of a tank car of mixed
ment at temperature, t, by the factor selected from the table (see xylenes having a calculated density (Section 7) of 0.87638 g/mL (in vacuum),
Note 1). whose volume was measured to be 9280 U.S. gal at a mean temperature of
88.7°F?
Example 1—What is the volume at 60°F of a tank care of para-xylene whose Enter Table 3 at 89°F and note that the “Factor for Reducing Volume to 60°F” is
volume was measured to be 9280 U.S. gal at a mean temperature of 88.7°F? 0.9842. The volume at 60°F is 9280 3 0.9842 5 9133.4 U.S. gal. From Eq 1:
Enter Table 3, Column 7, at 89.0°F and note that the “volume ratio” is 0.9840. (0.87638–0.001090) (8.34522) 5 7.30449 lb per U.S. gal. The weight of mixed
The volume at 60°F is 9280 3 0.9840 5 9131.5 U.S. gal. xylenes in the tank car is then 9133.4 3 7.30449 5 66 715 lb.
6.2 Converting Volume to Weight for Chemicals other than 7. Density Calculation
Mixed Xylenes Listed in Table 1—Multiply the volume in
gallons at 60°F (5 digits) by the density in pounds per gallon at 7.1 Density determinations may be carried out by any
60°F (see Table 1). procedure known to be reliable to four digits. Test Methods
D 941, D 4052 and D 1217 are suitable and are written to give
Example 2—What is the weight of para-xylene whose volume is 9280 U.S. gal
at 88.7°F? density completely in vacuum (corrected) which is required for
See Example 1. The weight is 9131.5 3 7.209 5 65 829 lb. the computation described herein.
7.2 If the methods described in Test Methods D 3505 are
6.3 Converting Volume to Weight for Mixed Xylenes—
used, relative density in air is first converted to density in
Correct the measured bulk volume to 60°F as described in 6.1.
grams per millilitre in air by use of the factors given in Table
Determine the density (all weights in vacuum) at 60°F in grams
5.
per millilitre as described in Section 7. Obtain the value for
pounds per U.S. gallon in standard air at 60°F, by means of the NOTE 3—“Relative density in air” means that all weighings were in air,
following equation, and round to five digits: and no air buoyancy correction was applied. “Apparent density” for the
purposes of this test is defined as the density calculated when the apparent
a 5 ~b 2 A! 3 8.34522 (1)
where: TABLE 5 Factors for Converting from Relative Density in Air to

a 5 pounds per U.S. gallon in standard air at 60°F, Apparent Density in Air in Grams per Millilitre (Note 3)
b 5 grams per millilitre in vacuum at 60°F, and Measurement Temperature
Multiply Relative Density in Air by this
A 5 correction factor as given in Table 4. Number to Get Apparent Density
Multiply the corrected volume by the calculated pounds per 60/60°F or 15.56/15.56°C 0.99904 at 60°F
68/68°F or 20/20°C 0.99823 at 68°F
U.S. gallon at 60°F value in order to obtain the weight in 77/77°F or 25/25°C 0.99708 at 77°F
pounds in air (see Note 1).
5
D 1555
volume of the pycnometer is calibrated with water, weighed in air, and TABLE 6 Vacuum Corrections, Apparent Density to Density in
when the sample is weighed in air, and no air buoyancy correction is used Vacuum
for either weighing, even though the density in vacuum of water is used Apparent Density, Correction,A Apparent Density Correction,A
in calculating the apparent volume of the pycnometer. “Density in air” for W/V plus W/V plus
the purpose of this method is the weight per unit volume in vacuum minus 0.70 0.00036 0.85 0.00018
the weight of a volume of air equal to the difference between the volume 0.71 0.00035 0.86 0.00017
of the sample and the volume of brass weights equivalent to the weight in 0.72 0.00033 0.87 0.00016
0.73 0.00032 0.88 0.00014
vacuum of the sample. If it is desired to make a direct experimental
0.74 0.00031 0.89 0.00013
determination of “density in air” using a pycnometer, apply the air
buoyancy correction to the water weight, calculate the true volume of the 0.75 0.00030 0.90 0.00012
pycnometer from the weight of water in vacuum, and then fill the 0.76 0.00029 0.91 0.00011
pycnometer with sample, weigh in air, subtract the weight of the 0.77 0.00028 0.92 0.00010
0.78 0.00026 0.93 0.00009
pycnometer in air, and apply no air buoyancy correction. This sample 0.79 0.00025 0.94 0.00007
weight in air, divided by the true volume in millilitres is the “density in
air” at the experimental temperatures. Densities given in Tables D 1250 0.80 0.00024 0.95 0.00006
are on this basis. 0.81 0.00023 0.96 0.00005
0.82 0.00022 0.97 0.00004
7.3 Convert apparent density in grams per millilitre in air to 0.83 0.00020 0.98 0.00003
0.84 0.00019 0.99 0.00001
density in vacuum by use of Table 6. A
This table applies for all air density values between 0.0011 and 0.0013 g/mL.
7.4 Convert density in vacuum at t degrees to density at For air densities outside this range, the vacuum correction, C, should be calculated
60°F (15.56°C) using the multipliers given in Table 7 on as follows:
C 5 da/0.99823 3 @0.99823 2 ~W/V!#
interpolated values.
Example 4—The density in vacuum of a mixed xylenes sample was determined where:
at 25°C and found to be 0.87095. The coefficient from the table is 1.00931. The C 5 vacuum correction,
density in vacuum at 60°F is 0.87095 3 1.00931 5 0.87905. da 5 density of air in the balance case, g/mL,
W 5 weight of sample in pycnometer,
7.5 Calculate pounds per U.S. gallon in air in accordance V 5 volume of sample in pycnometer, and
W/V 5 apparent density (Note 3).
with 6.3.

8.1 Since this is a calculation method, no precision and bias
statement is required.
9. Keywords
9.1 benzene; calculation; conversion; cumene; density; eth-
ylbenzene; m-xylene; mixed xylene; o-xylene; p-xylene; spe-
cific gravity; styrene; 300 to 350°F aromatic hydrocarbons;
350 to 400°F aromatic hydrocarbons; toluene; volume; weight
TABLE 7 Multipliers to Convert From Density in Vacuum at t

Degrees to Density at 60°F (15.56°C) in Vacuum
Multiplier for Temperature
Product 59°F 68°F 77°F 86°F
(15°C) (20°C) (25°C) (30°C)
Benzene 0.99934 1.00529 1.01136 1.01753
Toluene 0.99941 1.00473 1.01011 1.01554
Mixed xylenes 0.99946 1.00435 1.00931 1.01435
Styrene 0.99946 1.00434 1.00927 1.01426
m-Xylene 0.99946 1.00435 1.00931 1.01435
o-Xylene 0.99919 1.00693 1.01573 1.02575
p-Xylene 0.99945 1.00443 1.00947 1.01459
Cyclohexane 0.99935 1.00528 1.01133 1.01750
Cumene 0.99946 1.00435 1.00931 1.01435
Ethylbenzene 0.99946 1.00435 1.00931 1.01435
6
D 1555
7
Designation: D 1555M – 00
METRIC

Calculation of Volume and Weight of Industrial Aromatic
Hydrocarbons [Metric]1
This standard is issued under the fixed designation D 1555M; the number immediately following the designation indicates the year of
1. Scope TABLE 1 Density Data
1.1 The tables in this test method cover calculating the Density in Vacuum at Density in Air at 15°C,
Product
15.0°C, g/mL kg/L
weight and volume of benzene, toluene, mixed xylenes, sty-
Benzene 0.8842 0.8831
rene, o-xylene, m-xylene, p-xylene, cumene, ethylbenzene, Cumene 0.8660 0.8649
148.9 to 176.7°C (300 to 350°F) aromatic hydrocarbons, 176.7 Cyclohexane 0.7832 0.7821
to 204.4°C (350 to 400°F) aromatic hydrocarbons, and cyclo- Ethylbenzene 0.8714 0.8703
m-Xylene 0.8684 0.8673
hexane. A procedure is given for calculating the volume at o-Xylene 0.8843 0.8832
15.0°C from an observed volume at t°C. Table 1 lists the p-Xylene 0.8654 0.8643
density in kilograms per litre at 15.0°C for high purity Styrene 0.9106 0.9095
Toluene 0.8716 0.8705
chemicals.
1.2 A procedure for the calculation of density in kilograms
per litre at 15.0°C of materials of lower purity is provided.
NOTE 1—The purchaser and the seller should agree on a reasonable cific Gravity) of Liquids by Lipkin Bicapillary Pycnom-
policy in regard to rounding of final numbers in all computations. eter2
Rounding the final weight or volume to not more than five significant D 1217 Test Method for Density and Relative Density
digits is, in most cases, consistent with the experimental reliability of the (Specific Gravity) of Liquids by Bingham Pycnometer2
data. D 1555 Test Method for Calculation of Volume and Weight
NOTE 2—An alternative test method is Test Method D 4052.
of Industrial Aromatic Hydrocarbons3
1.3 This test method is the SI companion of Test Method D 3505 Test Method for Density or Relative Density of
D 1555. Pure Liquid Chemicals3
1.4 The following applies to all specified limits in this test D 4052 Test Method for Density and Relative Density of
method: for purpose of determining conformance with this test Liquids by Digital Density Meter4
method, an observed value or calculated value shall be rounded E 29 Practice for Using Significant Digits in Test Data to
off “to the nearest unit” in the last right-hand digit used on Determine Conformance with Specifications5
expressing the specification limit, in accordance with the E 201 Test Method for Calculation of Volume and Weight of
rounding-off method of Practice E 29. Industrial Chemical Liquids6
1.5 This standard does not purport to address all of the E 380 Practice for Use of the International System of Units
safety concerns, if any, associated with its use. It is the (SI) (the Modernized Metric System)7
priate safety and health practices and determine the applica- 3. Significance and Use
bility of regulatory limitations prior to use. 3.1 This test method is suitable for use in calculating
weights and volumes of products outlined in Section 1. The
2. Referenced Documents information gained from this test method can be used for
2.1 ASTM Standards: determining quantities of stated aromatic hydrocarbons in
D 941 Test Method for Density and Relative Density (Spe- tanks, shipping containers, etc.
2
1
This test method is under the jurisdiction of ASTM Committee D-16 on Annual Book of ASTM Standards, Vol 05.01.
3
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of Annual Book of ASTM Standards, Vol 06.04.
4
Subcommittee D16.0A on Benzene, Toluene, Xylenes, Cyclohexane, and Their Annual Book of ASTM Standards, Vol 05.02.
5
Derivatives. Annual Book of ASTM Standards, Vol 14.02.
6
Current edition approved Jan. 10, 2000. Published March 2000. Originally Annual Book of ASTM Standards, Vol 15.05.
7
published as D 1555M – 93. Last previous edition D 1555M – 97. Discontinued 1997. Replaced by IEEE/SI 10. Available from ASTM Headquar-
ters.
1
D 1555M
TABLE 2 Application Range of Table 3 at a mean temperature of 31.4°C? Enter Table 3, Column 7, at
Commercial Product % 31.5°C and note that the “volume ratio” is 0.9836. The volume
Benzene 95 to 100 at 15.0°C is 35 130 3 0.9836 5 34 554 L.
Toluene 95 to 100 6.2 Converting Volume to Weight for Chemicals Other Than
Mixed xylenes all proportions
Styrene 95 to 100
Mixed Xylenes Listed in Table 1—Multiple the volume in litres
o-Xylene 95 to 100 at 15.0°C (five digits) by the density in air in kilograms per litre
m-Xylene 95 to 100 at 15.0°C (see Table 1).
p-Xylene 94 to 100
Cyclohexane 90 to 100
6.2.1 Example 2—What is the weight of para-xylene whose
148.9° to 176.7°C aromatic hydrocarbons all proportions volume is 35 130 L at 31.4°C? See Example 1. The weight is
176.7° to 204.4°C aromatic hydrocarbons all proportions 34 554 3 0.8643 5 29 865 kg.
Cumene 95 to 100
Ethylbenzene 95 to 100
6.3 Converting Volume to Weight for Mixed Xylenes—
Correct the measured bulk volume to 15.0°C as described in
6.1. Determine the density (all weights in vacuum) at 15.0°C in
4. Basic Data grams per millitre as described in Section 7. Obtain the value
for kilograms per litre in standard air at 15.0°C by means of the
4.1 This test method is a companion test method for Test
following equation, and round to five digits:
Method D 1555 and is intended to be the metric equivalent of
Test Method D 1555. All of the tables in this test method were a 5 ~b 2 A! (1)
derived from the tables in Test Method D 1555, with some where:
information from other standards. When other standards or a 5 kilograms per litre in standard air at 15.0°C,
extended calculations were used, references are made in the b 5 grams per millilitre (also kg/L) in vacuum at 15.0°C,
appendix. Tables 5 and 6 in Test Method D 1555 were deleted A 5 correction factor as given in Table Table 4.
from this test method as they were deemed unnecessary in 6.3.1 Multiply the corrected volume by the calculated kilo-
countries where the metric system is used. grams per litre at 15.0°C value in order to obtain the weight in
4.2 All calculations in Test Method D 1555 are derived from kilograms in air (see Note 1).
the densities furnished by the American Petroleum Institute 6.3.1.1 Example 3—What is the weight (in air) of the
Research Project 44.8 The tables in Test Method D 1555 are contents of a tank car of mixed xylenes having a calculated
based on data for compounds of the highest purity, but can be density (see Section 7) of 0.87638 g/mL (in vacuum), whose
used for materials in the range indicated in Table 2. volume was measured to be 35 130 L at a mean temperature of
4.3 The basic data and conversion factors used are given in 31.4°C? Enter Table 3 at 31.5°C and note the “factor for
the appendix of Committee D-16’s 1963 Annual Report.9 reducing volume to 15.0°C” is 0.9840. The volume at 15.0°C
Densities listed in Table 1 are given in ASTM Data Series is 35 130 3 0.9840 5 34 568 L. From Eq 1:
Publications.10 0.87368 − 0.001090 5 0.87529 kg/L. The weight of mixed
xylenes in the tank car is then 34 568 3 0.87529 5 30 257 kg.
5. Tables
5.1 Table 3 contains twelve columns as follows: 7. Calculation
5.1.1 Column 1—Observed temperature in degrees centi- 7.1 Density determination may be carried out by any pro-
grade, and cedure known to be reliable to four digits. Test Methods D 941,
5.1.2 Columns 2 through 12, Inclusive— Multiplying fac- D 4052 and D 1217 are suitable and are written to give density
tors for the reduction to 15.0°C, specifically the ratio of the completely in vacuum (corrected) that is required for the
volume at 15.0°C to the volume at t°C. computation described herein.
6. Procedure 7.2 If the methods described in Test Method D 3505 are
used, the density in grams per millilitre in vacuum at 20.0°C
6.1 Volume Reduction to 15.0°C— Enter the appropriate should be determined.
column of Table 3, selecting that temperature to the nearest 7.3 Convert density in vacuum at t degrees to density at
0.5°C at which the bulk volume was measured (temperature t), 15.0°C using the multipliers given in Table 4 on interpolated
and select the corresponding volume reduction factor (ratio) in values.
Columns 2 through 12. Multiply the bulk volume measurement 7.3.1 Example 4—The density in vacuum of a mixed
at temperature, t, by the factor selected from the table (see Note xylenes sample was determined at 25°C and found to be
1). 0.87095. The coefficient from the table is 1.00986. The density
6.1.1 Example 1—What is the volume at 15.0°C of a tank in vacuum at 15.0°C is 0.87095 3 1.00986 5 0.87954.
car of para-xylene whose volume was measured to be 35 130 L 7.4 Convert the density at 15.0°C in vacuum to density in
air at 15.0°C by use of Table 5.
8
“Selected Values of Properties of Hydrocarbons and Related Compounds,”
7.5 Calculate kilograms per litre in air in accordance with
prepared by American Petroleum Institute Research Project 44 at the Chemical 6.3.
Thermodynamic Center, Department of Chemistry, Agriculture and Mechanical,
College Station, TX.
9
Proceedings, ASTM, Vol 63, 1963.
10
“Physical Constants of Hydrocarbons C1 to C10.” ASTM Data Service 8.1 Since this is a calculation method, no precision and bias
Publication DS4A, ASTM, 1971. statement is required.
2
D 1555M
9. Keywords aromatic hydrocarbons; m-xylene; mixed xylene; o-xylene;
9.1 aromatic hydrocarbons; benzene; calculation; conver- p-xylene; specific gravity; styrene; toluene; volume; weight
sion; cumene; cyclohexane; density; ethylbenzene; industrial
TABLE 3 Volume Corrections to 15°C
148.9 to 176.7 to
m-Xylene 176.7°C 204.4°C
Temperature Cyclo- Ethyl-
Benzene Toluene and Mixed Styrene o-Xylene p-Xylene Cumene Aromatic Aromatic
°C hexane benzene
Xylenes Hydro- Hydro-
carbons carbons
−20.5 ... 1.0376 ... ... ... ... ... ... ... ... ...
−20.0 ... 1.0371 ... ... ... ... ... ... ... ... ...
−19.5 ... 1.0366 ... ... ... ... ... ... ... ... ...
−19.0 ... 1.0361 ... ... ... ... ... ... ... ... ...
−18.5 ... 1.0355 ... ... ... ... ... ... ... ... ...
−18.0 ... 1.0350 ... ... ... ... ... ... ... ... ...
−17.5 ... 1.0345 ... ... ... ... ... ... ... ... ...
−17.0 ... 1.0339 ... ... ... ... ... ... ... ... ...
−16.5 ... 1.0334 ... ... ... ... ... ... ... ... ...
−16.0 ... 1.0329 ... ... ... ... ... ... ... ... ...
−15.5 ... 1.0323 ... ... ... ... ... ... ... ... ...
−15.0 ... 1.0318 1.0289 ... 1.0285 ... ... 1.0300 1.0293 1.0278 1.0262
−14.5 ... 1.0313 1.0284 ... 1.0280 ... ... 1.0295 1.0288 1.0274 1.0258
−14.0 ... 1.0308 1.0280 ... 1.0275 ... ... 1.0290 1.0283 1.0269 1.0253
−13.5 ... 1.0302 1.0275 ... 1.0270 ... ... 1.0285 1.0278 1.0265 1.0249
−13.0 ... 1.0297 1.0270 ... 1.0266 ... ... 1.0280 1.0274 1.0260 1.0245
−12.5 ... 1.0292 1.0265 ... 1.0261 ... ... 1.0275 1.0269 1.0255 1.0240
−12.0 ... 1.0286 1.0260 ... 1.0256 ... ... 1.0270 1.0264 1.0251 1.0236
−11.5 ... 1.0281 1.0256 ... 1.0251 ... ... 1.0265 1.0259 1.0246 1.0232
−11.0 ... 1.0276 1.0251 ... 1.0247 ... ... 1.0260 1.0254 1.0241 1.0227
−10.5 ... 1.0270 1.0246 ... 1.0242 ... ... 1.0255 1.0249 1.0237 1.0223
−10.0 ... 1.0265 1.0241 ... 1.0237 ... ... 1.0250 1.0244 1.0232 1.0218
−9.5 ... 1.0260 1.0236 1.0237 1.0232 ... ... 1.0245 1.0240 1.0228 1.0214
−9.0 ... 1.0254 1.0232 1.0232 1.0228 ... ... 1.0240 1.0235 1.0223 1.0210
−8.5 ... 1.0249 1.0227 1.0227 1.0223 ... ... 1.0235 1.0230 1.0218 1.0205
−8.0 ... 1.0244 1.0222 1.0222 1.0218 ... ... 1.0230 1.0225 1.0214 1.0201
−7.5 ... 1.0239 1.0217 1.0217 1.0214 ... ... 1.0225 1.0220 1.0209 1.0197
−7.0 ... 1.0233 1.0213 1.0212 1.0209 ... ... 1.0220 1.0215 1.0204 1.0192
−6.5 ... 1.0228 1.0208 1.0208 1.0204 ... ... 1.0216 1.0210 1.0200 1.0188
−6.0 ... 1.0223 1.0203 1.0203 1.0199 ... ... 1.0211 1.0205 1.0195 1.0184
−5.5 ... 1.0217 1.0198 1.0198 1.0195 ... ... 1.0206 1.0201 1.0191 1.0179
−5.0 ... 1.0212 1.0193 1.0193 1.0190 ... ... 1.0201 1.0196 1.0186 1.0175
−4.5 ... 1.0207 1.0188 1.0188 1.0185 ... ... 1.0196 1.0191 1.0181 1.0171
−4.0 ... 1.0201 1.0184 1.0184 1.0180 ... ... 1.0191 1.0186 1.0177 1.0166
−3.5 ... 1.0196 1.0179 1.0179 1.0176 ... ... 1.0186 1.0181 1.0172 1.0162
−3.0 ... 1.0191 1.0174 1.0174 1.0171 ... ... 1.0181 1.0176 1.0167 1.0157
−2.5 ... 1.0186 1.0169 1.0169 1.0166 ... ... 1.0176 1.0171 1.0163 1.0153
−2.0 ... 1.0180 1.0164 1.0164 1.0161 ... ... 1.0171 1.0166 1.0158 1.0149
−1.5 ... 1.0175 1.0160 1.0159 1.0157 ... ... 1.0166 1.0162 1.0153 1.0144
−1.0 ... 1.0170 1.0155 1.0155 1.0152 ... ... 1.0161 1.0157 1.0149 1.0140
−0.5 ... 1.0164 1.0150 1.0150 1.0147 ... ... 1.0156 1.0152 1.0144 1.0136
0.0 ... 1.0159 1.0145 1.0145 1.0142 ... ... 1.0151 1.0147 1.0140 1.0131
0.5 ... 1.0154 1.0140 1.0140 1.0138 ... ... 1.0146 1.0142 1.0135 1.0127
1.0 ... 1.0148 1.0136 1.0135 1.0133 ... ... 1.0141 1.0137 1.0130 1.0123
1.5 ... 1.0143 1.0131 1.0131 1.0128 ... ... 1.0136 1.0132 1.0126 1.0118
2.0 ... 1.0138 1.0126 1.0126 1.0123 ... ... 1.0131 1.0127 1.0121 1.0114
2.5 ... 1.0133 1.0121 1.0121 1.0119 ... ... 1.0126 1.0122 1.0116 1.0109
3.0 ... 1.0127 1.0116 1.0116 1.0114 ... ... 1.0121 1.0118 1.0112 1.0105
3.5 ... 1.0122 1.0111 1.0111 1.0109 ... ... 1.0116 1.0113 1.0107 1.0101
4.0 ... 1.0117 1.0107 1.0106 1.0104 ... ... 1.0111 1.0108 1.0102 1.0096
4.5 1.0123 1.0111 1.0102 1.0102 1.0100 ... 1.0126 1.0106 1.0103 1.0098 1.0092
5.0 1.0118 1.0106 1.0097 1.0097 1.0095 ... 1.0120 1.0101 1.0098 1.0093 1.0088
5.5 1.0112 1.0101 1.0092 1.0092 1.0090 ... 1.0114 1.0096 1.0093 1.0088 1.0083
6.0 1.0106 1.0095 1.0087 1.0087 1.0085 ... 1.0108 1.0091 1.0088 1.0084 1.0079
6.5 1.0100 1.0090 1.0082 1.0082 1.0081 ... 1.0102 1.0086 1.0083 1.0079 1.0074
7.0 1.0094 1.0085 1.0078 1.0077 1.0076 ... 1.0096 1.0081 1.0078 1.0074 1.0070
7.5 1.0088 1.0080 1.0073 1.0073 1.0071 ... 1.0090 1.0076 1.0074 1.0070 1.0066
8.0 1.0083 1.0074 1.0068 1.0068 1.0066 ... 1.0084 1.0071 1.0069 1.0065 1.0061
8.5 1.0077 1.0069 1.0063 1.0063 1.0062 ... 1.0078 1.0066 1.0064 1.0061 1.0057
9.0 1.0071 1.0064 1.0058 1.0058 1.0057 ... 1.0072 1.0061 1.0059 1.0056 1.0053
9.5 1.0065 1.0058 1.0053 1.0053 1.0052 ... 1.0066 1.0056 1.0054 1.0051 1.0048
10.0 1.0059 1.0053 1.0049 1.0048 1.0047 ... 1.0060 1.0050 1.0049 1.0047 1.0044
10.5 1.0053 1.0048 1.0044 1.0044 1.0043 ... 1.0054 1.0045 1.0044 1.0042 1.0039
11.0 1.0047 1.0042 1.0039 1.0039 1.0038 ... 1.0048 1.0040 1.0039 1.0037 1.0035
3
D 1555M
TABLE 3 Continued
148.9 to 176.7 to
m-Xylene 176.7°C 204.4°C
°C hexane benzene
carbons carbons
11.5 1.0041 1.0037 1.0034 1.0034 1.0033 ... 1.0042 1.0035 1.0034 1.0033 1.0031
12.0 1.0036 1.0032 1.0029 1.0029 1.0028 ... 1.0036 1.0030 1.0029 1.0028 1.0026
12.5 1.0030 1.0027 1.0024 1.0024 1.0024 1.0025 1.0030 1.0025 1.0025 1.0023 1.0022
13.0 1.0024 1.0021 1.0019 1.0019 1.0019 1.0020 1.0024 1.0020 1.0020 1.0019 1.0018
13.5 1.0018 1.0016 1.0015 1.0015 1.0014 1.0015 1.0018 1.0015 1.0015 1.0014 1.0013
14.0 1.0012 1.0011 1.0010 1.0010 1.0009 1.0010 1.0012 1.0010 1.0010 1.0009 1.0009
14.5 1.0006 1.0005 1.0005 1.0005 1.0005 1.0005 1.0006 1.0005 1.0005 1.0005 1.0004
15.0 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
15.5 0.9994 0.9995 0.9995 0.9995 0.9995 0.9995 0.9994 0.9995 0.9995 0.9995 0.9996
16.0 0.9988 0.9989 0.9990 0.9990 0.9991 0.9990 0.9988 0.9990 0.9990 0.9991 0.9991
16.5 0.9982 0.9984 0.9985 0.9985 0.9986 0.9985 0.9982 0.9985 0.9985 0.9986 0.9987
17.0 0.9977 0.9979 0.9981 0.9981 0.9981 0.9980 0.9976 0.9980 0.9980 0.9981 0.9982
17.5 0.9971 0.9973 0.9976 0.9976 0.9976 0.9975 0.9970 0.9975 0.9975 0.9977 0.9978
18.0 0.9965 0.9968 0.9971 0.9971 0.9972 0.9970 0.9964 0.9970 0.9971 0.9972 0.9974
18.5 0.9959 0.9963 0.9966 0.9966 0.9967 0.9965 0.9958 0.9965 0.9966 0.9967 0.9969
19.0 0.9953 0.9958 0.9961 0.9961 0.9962 0.9961 0.9952 0.9959 0.9961 0.9963 0.9965
19.5 0.9947 0.9952 0.9956 0.9956 0.9957 0.9956 0.9946 0.9954 0.9956 0.9958 0.9961
20.0 0.9941 0.9947 0.9951 0.9952 0.9953 0.9951 0.9940 0.9949 0.9951 0.9953 0.9956
20.5 0.9935 0.9942 0.9946 0.9947 0.9948 0.9946 0.9934 0.9944 0.9946 0.9949 0.9952
21.0 0.9929 0.9936 0.9942 0.9942 0.9943 0.9941 0.9928 0.9939 0.9941 0.9944 0.9947
21.5 0.9923 0.9931 0.9937 0.9937 0.9938 0.9936 0.9922 0.9934 0.9936 0.9939 0.9943
22.0 0.9917 0.9926 0.9932 0.9932 0.9934 0.9931 0.9916 0.9929 0.9931 0.9935 0.9939
22.5 0.9911 0.9920 0.9927 0.9927 0.9929 0.9926 0.9910 0.9924 0.9926 0.9930 0.9934
23.0 0.9905 0.9915 0.9922 0.9922 0.9924 0.9921 0.9904 0.9919 0.9921 0.9925 0.9930
23.5 0.9899 0.9910 0.9917 0.9918 0.9919 0.9916 0.9898 0.9914 0.9916 0.9921 0.9925
24.0 0.9893 0.9905 0.9912 0.9913 0.9915 0.9911 0.9892 0.9909 0.9912 0.9916 0.9921
24.5 0.9887 0.9899 0.9907 0.9908 0.9910 0.9906 0.9886 0.9904 0.9907 0.9911 0.9917
25.0 0.9881 0.9894 0.9902 0.9903 0.9905 0.9901 0.9880 0.9898 0.9902 0.9907 0.9912
25.5 0.9875 0.9889 0.9898 0.9898 0.9900 0.9896 0.9874 0.9893 0.9897 0.9902 0.9908
26.0 0.9869 0.9883 0.9893 0.9893 0.9896 0.9891 0.9868 0.9888 0.9892 0.9897 0.9903
26.5 0.9863 0.9878 0.9888 0.9888 0.9891 0.9886 0.9862 0.9883 0.9887 0.9893 0.9899
27.0 0.9857 0.9873 0.9883 0.9884 0.9886 0.9881 0.9856 0.9878 0.9882 0.9888 0.9895
27.5 0.9851 0.9867 0.9878 0.9879 0.9881 0.9876 0.9850 0.9873 0.9877 0.9883 0.9890
28.0 0.9845 0.9862 0.9873 0.9874 0.9877 0.9871 0.9844 0.9868 0.9872 0.9879 0.9886
28.5 0.9839 0.9857 0.9868 0.9869 0.9872 0.9866 0.9838 0.9863 0.9867 0.9874 0.9881
29.0 0.9833 0.9852 0.9863 0.9864 0.9867 0.9861 0.9832 0.9858 0.9862 0.9869 0.9877
29.5 0.9827 0.9846 0.9858 0.9859 0.9862 0.9856 0.9826 0.9852 0.9857 0.9865 0.9873
30.0 0.9821 0.9841 0.9854 0.9854 0.9858 0.9851 0.9820 0.9847 0.9853 0.9860 0.9868
30.5 0.9815 0.9836 0.9849 0.9850 0.9853 0.9846 0.9814 0.9842 0.9848 0.9855 0.9864
31.0 0.9809 0.9830 0.9844 0.9845 0.9848 0.9841 0.9808 0.9837 0.9843 0.9851 0.9859
31.5 0.9803 0.9825 0.9839 0.9840 0.9843 0.9836 0.9802 0.9832 0.9838 0.9846 0.9855
32.0 0.9797 0.9820 0.9834 0.9835 0.9839 0.9831 0.9796 0.9827 0.9833 0.9841 0.9851
32.5 0.9791 0.9814 0.9829 0.9830 0.9834 0.9826 0.9790 0.9822 0.9828 0.9837 0.9846
33.0 0.9785 0.9809 0.9824 0.9825 0.9829 0.9821 0.9784 0.9817 0.9823 0.9832 0.9842
33.5 0.9779 0.9804 0.9819 0.9820 0.9824 0.9816 0.9778 0.9811 0.9818 0.9827 0.9837
34.0 0.9773 0.9799 0.9814 0.9815 0.9820 0.9811 0.9772 0.9806 0.9813 0.9822 0.9833
34.5 0.9767 0.9793 0.9809 0.9811 0.9815 0.9806 0.9766 0.9801 0.9808 0.9818 0.9828
35.0 0.9761 0.9788 0.9804 0.9806 0.9810 0.9801 0.9760 0.9796 0.9803 0.9813 0.9824
35.5 0.9755 0.9783 0.9799 0.9801 0.9805 0.9796 0.9754 0.9791 0.9798 0.9808 0.9820
36.0 0.9749 0.9777 0.9795 0.9796 0.9801 0.9791 0.9748 0.9786 0.9793 0.9804 0.9815
36.5 0.9743 0.9772 0.9790 0.9791 0.9796 0.9786 0.9742 0.9780 0.9788 0.9799 0.9811
37.0 0.9737 0.9767 0.9785 0.9786 0.9791 0.9781 0.9736 0.9775 0.9783 0.9794 0.9806
37.5 0.9731 0.9761 0.9780 0.9781 0.9786 0.9776 0.9730 0.9770 0.9779 0.9790 0.9802
38.0 0.9724 0.9756 0.9775 0.9776 0.9782 0.9771 0.9724 0.9765 0.9774 0.9785 0.9798
38.5 0.9718 0.9751 0.9770 0.9772 0.9777 0.9766 0.9717 0.9760 0.9769 0.9780 0.9793
39.0 0.9712 0.9746 0.9765 0.9767 0.9772 0.9761 0.9711 0.9755 0.9764 0.9776 0.9789
39.5 0.9706 0.9740 0.9760 0.9762 0.9768 0.9756 0.9705 0.9750 0.9759 0.9771 0.9784
40.0 0.9700 0.9735 0.9755 0.9757 0.9763 0.9751 0.9699 0.9744 0.9754 0.9766 0.9780
40.5 0.9694 0.9730 0.9750 0.9752 0.9758 0.9746 0.9693 0.9739 0.9749 0.9762 0.9776
41.0 0.9688 0.9724 0.9745 0.9747 0.9753 0.9741 0.9687 0.9734 0.9744 0.9757 0.9771
41.5 0.9682 0.9719 0.9740 0.9742 0.9749 0.9736 0.9681 0.9729 0.9739 0.9752 0.9767
42.0 0.9676 0.9714 0.9735 0.9737 0.9744 0.9731 0.9675 0.9724 0.9734 0.9747 0.9762
42.5 0.9670 0.9708 0.9730 0.9733 0.9739 0.9726 0.9669 0.9719 0.9729 0.9743 0.9758
43.0 0.9663 0.9703 0.9726 0.9728 0.9734 0.9721 0.9663 0.9713 0.9724 0.9738 0.9753
43.5 0.9657 0.9698 0.9721 0.9723 0.9730 0.9716 0.9657 0.9708 0.9719 0.9733 0.9749
44.0 0.9651 0.9692 0.9716 0.9718 0.9725 0.9711 0.9651 0.9703 0.9714 0.9729 0.9745
44.5 0.9645 0.9687 0.9711 0.9713 0.9720 0.9706 0.9645 0.9698 0.9709 ... ...
45.0 0.9639 0.9682 0.9706 0.9708 0.9715 0.9701 0.9639 0.9693 0.9704 ... ...
45.5 0.9633 0.9677 0.9701 0.9703 0.9711 0.9696 0.9633 0.9687 0.9699 ... ...
46.0 0.9627 0.9671 0.9696 0.9698 0.9706 0.9691 0.9627 0.9682 0.9694 ... ...
4
D 1555M
TABLE 3 Continued
148.9 to 176.7 to
m-Xylene 176.7°C 204.4°C
°C hexane benzene
carbons carbons
46.5 0.9620 0.9666 0.9691 0.9693 0.9701 0.9686 0.9621 0.9677 0.9690 ... ...
47.0 0.9614 0.9661 0.9686 0.9689 0.9696 0.9681 0.9615 0.9672 0.9685 ... ...
47.5 0.9608 0.9655 0.9681 0.9684 0.9692 0.9676 0.9609 0.9667 0.9680 ... ...
48.0 0.9602 0.9650 0.9676 0.9679 0.9687 0.9670 0.9603 0.9661 0.9675 ... ...
48.5 0.9596 0.9645 0.9671 0.9674 0.9682 0.9665 0.9597 0.9656 0.9670 ... ...
49.0 0.9590 0.9639 0.9666 0.9669 0.9677 0.9660 0.9591 0.9651 0.9665 ... ...
49.5 0.9583 0.9634 0.9661 0.9664 0.9673 0.9655 0.9585 0.9646 0.9660 ... ...
50.0 ... ... ... ... ... 0.9650 ... ... ... ... ...
50.5 ... ... ... ... ... 0.9645 ... ... ... ... ...
51.0 ... ... ... ... ... 0.9640 ... ... ... ... ...
51.5 ... ... ... ... ... 0.9635 ... ... ... ... ...
52.0 ... ... ... ... ... 0.9630 ... ... ... ... ...
52.5 ... ... ... ... ... 0.9625 ... ... ... ... ...
53.0 ... ... ... ... ... 0.9620 ... ... ... ... ...
53.5 ... ... ... ... ... 0.9615 ... ... ... ... ...
54.0 ... ... ... ... ... 0.9610 ... ... ... ... ...
54.5 ... ... ... ... ... 0.9604 ... ... ... ... ...
55.0 ... ... ... ... ... 0.9599 ... ... ... ... ...
55.5 ... ... ... ... ... 0.9594 ... ... ... ... ...
56.0 ... ... ... ... ... 0.9589 ... ... ... ... ...
56.5 ... ... ... ... ... 0.9584 ... ... ... ... ...
57.0 ... ... ... ... ... 0.9579 ... ... ... ... ...
57.5 ... ... ... ... ... 0.9574 ... ... ... ... ...
58.0 ... ... ... ... ... 0.9569 ... ... ... ... ...
58.5 ... ... ... ... ... 0.9564 ... ... ... ... ...
59.0 ... ... ... ... ... 0.9559 ... ... ... ... ...
59.5 ... ... ... ... ... 0.9553 ... ... ... ... ...
60.0 ... ... ... ... ... 0.9548 ... ... ... ... ...
60.5 ... ... ... ... ... 0.9543 ... ... ... ... ...
61.0 ... ... ... ... ... 0.9538 ... ... ... ... ...
61.5 ... ... ... ... ... 0.9533 ... ... ... ... ...
62.0 ... ... ... ... ... 0.9528 ... ... ... ... ...
62.5 ... ... ... ... ... 0.9523 ... ... ... ... ...
63.0 ... ... ... ... ... 0.9518 ... ... ... ... ...
63.5 ... ... ... ... ... 0.9512 ... ... ... ... ...
64.0 ... ... ... ... ... 0.9507 ... ... ... ... ...
64.5 ... ... ... ... ... 0.9502 ... ... ... ... ...
65.0 ... ... ... ... ... 0.9497 ... ... ... ... ...
65.5 ... ... ... ... ... 0.9492 ... ... ... ... ...
TABLE 4 Multipliers to Convert From Density in Vacuum at t

Degrees to Density at 15.0°C in Vacuum
Multiplier for Temperature
Product
20°C 25°C 30°C
Benzene 1.00595 1.01203 1.01820
Toluene 1.00532 1.01071 1.01614
Mixed xylenes 1.00489 1.00986 1.01490
Styrene 1.00488 1.00982 1.01481
m-Xyelene 1.00489 1.00986 1.01490
o-Xylene 1.00775 1.01655 1.02658
p-Xylene 1.00498 1.01003 1.01515
Cyclohexane 1.00593 1.01199 1.01816
Cumene 1.00489 1.00986 1.01490
Ethylbenzene 1.00489 1.00986 1.01490
5
D 1555M
TABLE 5 Converting to Densities in Standard Air
Density at 15.0°C,
Correction Factor, A,
in Vacuum,
g/mL
g/mL
0.82 0.001098
0.83 0.001097
0.84 0.001095
0.85 0.001094
0.86 0.001092
0.87 0.001091
0.88 0.001090
0.89 0.001088
0.90 0.001087
APPENDIX
X1. TABLE DATA DERIVATION DETAILS
X1.1 Introduction adding 0.0011 to the data in Column 3 (see X1.2.3 and Table
X1.1.1 Test Method D 1555 is widely used in commerce. 5).
Products are generally bought and sold by weight or volume at X1.2.3 Column 3, lb/gal at 60°F to kg/L at 15.0°C (see Eq
a specified temperature. In the United States the normal X1.2 and Practice E 380):
reference temperature has been 60°F. Recent movement to the ~lb/gal 60°F! 3 F 15~59! 5 lb/gal 15.0°C (X1.3)
metric system required for international trade was accom- kg/L 5 lb/gal 3 0.4535924 kg/lb 3 0.2641729 gal/L
plished by simply changing to 15.56°C as the reference. This
temperature is not convenient to use in many cases and a new X1.3 Table 2 of Test Method D 1555 Conversion to Table
standard at a more meaningful temperature was desired. For 2 of This Test Method
simplicity 15.0°C was chosen as the reference temperature for X1.3.1 Table contained no reference to temperature and was
this test method. The conversions done to Test Method D 1555 left unchanged.
tables were simple algebraic in nature and resulted in differ-
X1.4 Table 3 of Test Method D 1555 Conversion to Table
ences no greater than 0.0002 in any case. Hence, they are
3 of This Test Method
considered to be equivalent. The general algebraic equations
used in the conversions are as follows from Tables 1 and 3 of X1.4.1 Column 1, 1°F increments changed to 0.5°C.
Test Method D 1555: X1.4.2 Columns 2 Through 10, Inclusive—Table 3 contains
multiplying factors that are ratios of one volume to another (or
Dp60 5 W 4 V60 and V60 5 @V15~59!# 3 @F 15~59!# (X1.1)
one density to another). As explained in the research report for
and W remains constant: Test Method E 201 this volume versus temperature curve can
Dp15~59! 5 W 4 V15~59! be represented by different equations. It was found that the
5 W4 @V60 1 F15~59!# quadratic equation would fit well. The conversion to degrees
Celsius was done by getting three densities (using density at
5 @W4 V60# 3 F15~59! 60°F from Table 1 in Test Method D 1555, and the multiplying
5 D p60 3 F15~59! (X1.2) factors from Table 1 of Test Method D 1555). Then one would
use those three densities to calculate constants for the quadratic
where: equation, and then for calculating the ratios. This procedure
Dp 60 5 density of product at 60°F (15.56°C), Table 1, would also be suitable for determining a curve for any product
W 5 weight or mass of product, that three densities could be analyzed. More detail of the steps
V60 5 volume of product at 60°F (15.56°C), are as follows:
V15(59) 5 volume of product at 15.0°C (59°F), and X1.4.2.1 Pick three temperatures (t1, t2, and t3) so that t1 >
F15(59) 5 multiplying factor for product at 59°F, from t2 > t3 and t1 − t2 5 t2 − t3. It is important that the three
Table 3. temperatures represent the range of temperatures to be encoun-
tered with a product. Then calculate three densities at t1, t2, t3
by Dt 5 Dp60 3 Ft (see Eq X1.2). The density at any tempera-
ture, by the quadratic equation, is Dt 5 Dtc + a (t − tc) + b
X1.2.1 Column 1, the product names remained unchanged. (t − tc)2(from the research report for Test Method E 201), by
X1.2.2 Column 2, relative density was not required in substituting t1, t2, t3 in two equations a and b can be solved
countries where the metric system is used and was replaced for, a 5 (Dt1 − Dt3)/[2( t1 − t2)] and b 5 (Dt1 − 2Dt2 + Dt3)/[2(
with density in vacuum. Calculation of the data was done by t1 − t2)2], then the multiplying factor for any product for any
6
D 1555M
temperature t equals Dt/D15. The density at 15°C was calcu- X1.5 Table 4 of Test Method D 1555 Conversion to Table
lated by Eq X1.2 and Table 1 of Test Method D 1555. Values 4 of This Test Method
used for the calculation were: X1.5.1 The reference temperature changed to 15.0°C. Cal-
t1 t2 t3 a b culations were done to correct the values listed in Column 2.
Benzene 5 25 45 −0.0010650 −0.000000700
Toluene −5 15 35 −0.0009250 −0.000000000 These resulted in changes in the eighth decimal place. Hence
m-Xylene −5 15 35 −0.0008450 −0.000000250 (when rounded off to six places), the values appear to be
Styrene −5 15 35 −0.0008825 −0.000000125 unchanged, but are the corrected data.
o-Xylene −5 15 35 −0.0008400 −0.000000000
p-Xylene 15 35 55 −0.0008675 −0.000000375
Cyclohexane 5 25 45 −0.0009425 −0.000000125 X1.6 Table 5 and 6 Deletion of Test Method D 1555
Ethylbenzene −5 15 35 −0.0008825 −0.000000375
Cumene −5 15 35 −0.0008700 −0.000000125 X1.6.1 Relative density and apparent density were not of
interest to countries where the metric system is used and were
X1.4.3 Columns 11 and 12—Columns 2 through 10 were
deleted from this standard.
done by using an equation to represent the change in density
with temperature and the densities came from Table 1 in Test
Method D 1555. There is no fixed density for aromatic hydro-
carbons, so an alternate method was used. Algebraically,
working through the calculations with Dp60 3 Ft instead of D X1.7.1 Reference temperature in title was changed to
t, the density will eventually drop out of the equation and a 15.0°C. Column 2 was deleted as meaningless. Columns 3
quadratic formula can be generated with the multiplying through 5 were calculated by the following:
factors only. This worked well and equivalent curves were density 60°F 5 density t 3 multiplier for t,
density 15°C 3 multiplier for 15°C 5 density 60°F,
produced. Values used in the calculation are: density 15°C 5 density 60°F 4 multiplier for 15°C,
t1 t2 t3 a b density 15°C 5 (density t 3 multiplier for t) 4 multiplier for 15°C,
159-177 AH −5 15 35 −0.0009325 −0.000000125 density 15°C 5 density t 3 (multiplier for t 4 multiplier for 15°C), and
177-204 AH −5 15 35 −0.0008775 −0.000000125 multiplier for t 4 multiplier for 15°C 5 the new multiplier listed.
7

Fatty Acids Content of Naval Stores, Including Rosin, Tall
1. Scope 3.4 The fatty acids are calculated by two methods.

1.1 These test methods cover the determination of the fatty 3.4.1 For materials with a fatty acid content less than 5 %,
acids of naval stores, including rosin, tall oil, and related fatty acid content is calculated from the rosin acids content and
products. the acid number.
1.2 These test methods may not be applicable to adducts or 3.4.2 For materials with a fatty acid content greater than
derivatives of rosin or other naval stores products. 5 %, fatty acid content is calculated from the rosin acids and
1.3 This standard does not purport to address all of the unsaponifiables content.
safety concerns, if any, associated with its use. It is the 3.5 The same method for end point detection, either poten-
responsibility of the user of this standard to establish appro- tiometric or indicator, should be used for acid number, unsa-
priate safety and health practices and determine the applica- ponifiables, and rosin acids content determination, in order to
bility of regulatory limitations prior to use. avoid slight variables that might occur.
3.6 Since the fatty acids remaining in tall oil rosin, tall oil,
2. Referenced Documents and other naval stores products consist of oleic acid with
2.1 ASTM Standards: varying amounts of other saturated and unsaturated acids, it has
D 465 Test Methods for Acid Number of Naval Stores become customary to calculate and report the fatty acid content
Products Including Tall Oil and Other Related Products2 as oleic acid.
D 803 Test Methods for Testing Tall Oil2
D 890 Test Method for Water in Liquid Naval Stores2
D 1065 Test Methods for Unsaponifiable Matter in Naval 4.1 These test methods are designed to broaden the scope of
Stores, Including Rosin, Tall Oil, and Related Products2 the previous edition of these test methods by the inclusion of
D 1240 Test Methods for Rosin Acids Content of Naval tall oil as a test material. Test Methods D 803 currently
Stores Including Rosin, Tall Oil, and Related Products2 includes methods for the determination of the rosin acid and
E 177 Practice for the Use of the Terms Precision and Bias fatty acid content of crude tall oil. Test Methods D 803
in ASTM Test Methods3 references Test Method D 1585.
E 691 Practice for Conducting an Interlaboratory Study to 4.2 Rosin and tall oil are composed primarily of rosin acids
Determine the Precision of a Test Method3 and fatty acids, and the measurement of these components is
important in establishing the composition of these materials.
3.1 The rosin acids content is determined using either the
modified potentiometric Wolfe Method or the modified indica- 5.1 Reagent grade chemicals shall be used in all tests.
tor Wolfe Method described in Test Methods D 1240. Rosin Unless otherwise indicated, it is intended that all reagents shall
acids are calculated as abietic acid. conform to the specifications of the Committee on Analytical
3.2 The acid number is determined by either the potentio- Reagents of the American Chemical Society, where such
metric or the indicator method in accordance with Test Meth- specifications are available.4 Other grades may be used, pro-
ods D 465. vided it is first ascertained that the reagent is of sufficiently
3.3 The unsaponifiable matter is determined in accordance high purity to permit its use without lessening the accuracy of
with the methods described in Test Methods D 1065. the determination.
1
4
of Subcommittee D01.34 on Naval Stores. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Jan. 10, 1996. Published March 1996. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1585 – 58T. Last previous edition D 1585 – 93. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1585
understood to mean deionized or distilled water. A 5 acid number of original sample,
R 5 rosin acids, %,
6. Preparation of Sample 1.855 5 (56.1 3 1000)/(302.4 3 100) (factor to convert
6.1 Homogeneous liquid materials may be used without the percentage of rosin acids to acid number), and
further preparation. 1.986 5 (56.1 3 1000)/(282.4 3 100) (factor to convert
6.2 Heat nonhomogeneous liquid materials until they are acid number to percentage of oleic acid).
homogeneous, then take a portion for analysis. 11.2 For materials containing equal to or greater than 5 %
6.3 Solid samples are subject to surface oxidation which fatty acid, calculate the percent fatty acid from the percent
may affect the results. Prepare the sample for analysis by rosin acids and unsaponifiables as follows:
chipping small pieces from a freshly exposed surface of a lump Fatty Acids, % 5 100 2 R 2 U 2 W (2)
or lumps and crush to a coarse powder to facilitate weighing
and solution. Prepare fresh on the same day, prior to weighing, where:
in order to avoid changes due to surface oxidation of crushed R 5 rosin acids, %,
rosin on exposure to the air. U 5 unsaponifiable matter, %,
W 5 water, %.
PERCENT ROSIN ACID 11.3 Report the percentage of fatty acids determined in 11.1
or 11.2 to one decimal place.
7. Procedure
7.1 Determine the percent rosin acid of the sample by the 12. Precision and Bias
potentiometric or the indicator modified Wolfe Method in 12.1 Interlaboratory Test Program—An interlaboratory
accordance with Test Methods D 1240. study of the fatty acid content of three substances, tall oil fatty
ACID NUMBER acids, distilled tall oil, and rosin, was run in 1994. Each of 14
laboratories tested each of the three materials. The design of
8. Procedure the experiment, similar to that of Practice E 691 and a
8.1 Determine the acid number by either the potentiometric within-between analysis of the data are given in ASTM
or the indicator modification in accordance with Test Methods Research Report.5
D 465. 12.2 Test Result—The precision information given below
for the fatty acid content of naval stores products is for the
UNSAPONIFIABLE MATTER comparison of two test results, each of which is the average of
three test determinations as follows:
9. Procedure 12.2.1 Repeatability Limit, 95 % (within labora-
9.1 Determine the percentage of unsaponifiable matter by tory) 5 0.6 %.
either the potentiometric or the indicator modification in 12.2.2 Reproducibility Limit, 95 % (between laborato-
accordance with Test Methods D 1065. ries) 5 1.9 %.
WATER limit) are used as specified in Practice E 177. The respective
standard deviations among test results, related to the above
10. Procedure
10.1 Determine the percent water in the sample by the 12.3.1 Repeatability standard deviation 5 0.2 %.
Karl-Fischer Method in accordance with Test Method D 890. 12.3.2 Reproducibility standard deviation 5 0.7 %.
FATTY ACIDS 12.4 Bias—These test methods have no bias because fatty
acid content is defined only in terms of these test methods.
11. Calculation
11.1 For materials containing less than 5 % fatty acid, 13. Keywords
calculate the percentage of fatty acids from the acid number 13.1 rosin; tall oil; tall oil fatty acids; tall oil rosin; Wolfe
and the percentage of rosin acids as follows: Method.
Fatty acids as oleic acid, % 5 @A 2 ~R 3 1.855!#/1.986 (1)
where: 5
Support data are available from ASTM Headquarters. Request RR:D01– 1088.
2
D 1585
3

Acetone in Methanol1
1. Scope Reagents of the American Chemical Society, where such

1.1 This test method covers a procedure for detecting the specifications are available.3 Other grades may be used, pro-
presence of acetone in methanol in amounts greater than 0.003 vided it is first ascertained that the reagent is of sufficiently
weight %. high purity to permit its use without lessening the accuracy of
1.2 This standard does not purport to address all of the the determination.
safety concerns, if any, associated with its use. It is the 6.2 Unless otherwise indicated, references to water shall be
responsibility of the user of this standard to establish appro- understood to mean reagent water conforming to Type IV of
priate safety and health practices and determine the applica- Specification D 1193. It is essential that the reagent water be
bility of regulatory limitations prior to use. free of ammonia.
1.3 For hazard information and guidance, see the supplier’s 6.3 Acetone Standard—Pipet 6.0 mL of acetone into a 1-L
Material Safety Data Sheet. volumetric flask and dilute with water to the 1-L mark. Take
1.0 mL of the resulting solution and make up to 1 L with water
2. Referenced Documents in a volumetric flask. Five millilitres of this solution contain
2.1 ASTM Standards: 0.024 mg of acetone. Under conditions outlined for this test
D 1193 Specification for Reagent Water2 method, the standard made up for comparison is equivalent to
a methanol specimen containing 0.003 weight % of acetone.
3. Summary of Test Method 6.4 Nessler’s Reagent:
3.1 The specimen is reacted with Nessler’s reagent and the 6.4.1 Solution A—Dissolve 270 g of sodium hydroxide
turbidity that is produced is compared to a standard containing (NaOH) pellets in water and dilute to 1 L.
the equivalent of 0.003 weight % of acetone. 6.4.2 Solution B—Dissolve 36 g of potassium iodide (KI)
crystals and 13.6 g of mercuric chloride (HgCl2) powder in
4. Significance and Use water and dilute to 500 mL. To prepare the Nessler’s reagent,
4.1 This test method can be used to detect residual amounts mix three parts of Solution A with 5 parts of Solution B and
of carbonyl compounds in synthetic and natural methanol. The allow to stand until clear before using.
carbonyl compounds are quantified by comparison to a known
7. Procedure
standard of acetone solution.
4.2 Carbonyl compounds may be present as a result of 7.1 Carefully pipet 1 mL of the sample and 4 mL of water
contamination during storage, distribution, or manufacture. into one of the matched test tubes and mix thoroughly.
This test method may be used in assessing compliance with a Carefully pipet 5 mL of the acetone standard into a second
specification. matched test tube. Pipet 5 mL of the Nessler’s reagent into each
of the tubes containing the specimen and the acetone standard.
5. Apparatus Quickly mix the contents of each tube and allow both to stand
5.1 Volumetric Pipets, 1, 4, and 5-mL capacity. for 5 min. At the end of the 5-min standing period, compare the
5.2 Test Tubes, matched for color, 1.5 by 15 cm. turbidity of the specimen to the turbidity of the acetone
standard.
6. Reagents
6.1 Reagent grade chemicals shall be used in all tests. 8. Report
Unless otherwise indicated, it is intended that all reagents shall 8.1 If the turbidity of the specimen is less than that of the
conform to the specifications of the Committee on Analytical acetone standard, report the acetone content is “less than 0.003
1 3
Current edition approved Feb. 15, 1995. Published April 1995. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
1
D 1612
weight %.” If the turbidity of the specimen is greater than that 9.2.1 The results are reported “less than” or “greater than”
of the acetone standard, report the acetone content as “greater as acetone. Since various ketones or other carbonyl compounds
than 0.003 weight %.” may be present, the actual level of acetone may be different.
10. Keywords
9.1 Precision—Because of the “pass-fail” nature of this
procedure, there is no precision statement. 10.1 methanol; methanol—acetone content; methyl alcohol;
9.2 Bias—Any material or contaminant that will react with wood alcohol
Nessler’s reagent will affect the results.
2

Acidity in Volatile Solvents and Chemical Intermediates
Used in Paint, Varnish, Lacquer, and Related Products1
1. Scope decomposition during storage or distribution, or manufacture.

1.1 This test method covers the determination of total This test method may be used in assessing compliance with a
acidity as acetic acid, in concentrations below 0.05 %, in specification.
organic compounds and hydrocarbon mixtures used in paint, 5. Apparatus
varnish, and lacquer solvents and diluents. It is known to be
applicable to such mixtures as low molecular weight saturated 5.1 Buret, 10-mL, graduated in 0.05-mL subdivisions.
and unsaturated alcohols, ketones, ethers, esters, hydrocarbon 5.2 Erlenmeyer Flask, 250-mL capacity.
diluents, naphtha, and other light distillate petroleum fractions. 6. Purity of Reagents
concerns, if any, associated with its use. It is the responsibility 6.1 Reagent grade chemicals shall be used in all tests.
of whoever uses this standard to consult and establish appro- Unless otherwise indicated, it is intended that all reagents shall
priate safety and health practices and determine the applica- conform to the specifications of the Committee on Analytical
bility of regulatory limitations prior to use. Reagents of the American Chemical Society, where such
1.3 For specific hazard information and guidance consult specifications are available.5 Other grades may be used pro-
supplier’s Material Safety Data Sheet. vided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of
2. Referenced Documents the determination.
2.1 ASTM Standards: 6.2 Unless otherwise indicated, references to water shall be
D 770 Specification for Isopropyl Alcohol2 understood to mean reagent water conforming to Type IV of
D 1193 Specification for Reagent Water3 Specification D 1193.
E 200 Practice for Preparation, Standardization, and Stor- 7. Reagents
age of Standard and Reagent Solutions for Chemical
Analysis4 7.1 Alcohols, refined, ethyl or isopropyl.
NOTE 1—Isopropyl alcohol (99 % grade) conforming to Specification
3. Summary of Test Method D 770, or 190 proof ethyl alcohol conforming to formula No. 3A of the
3.1 The specimen is mixed with either an equal volume of U.S. Bureau of Internal Revenue is suitable for use as the solvent. The use
water or an equal volume of alcohol, and titrated with aqueous of methyl alcohol is not recommended.
sodium hydroxide solution to the phenolphthalein end point. 7.2 Phenolphthalein Indicator Solution, (10 g/L)—Dissolve
1 g of phenolphthalein in ethyl or isopropyl alcohol (see Note
4. Significance and Use 1) and dilute to 100 mL with the alcohol.
4.1 This test method is useful for determining low levels of 7.3 Sodium Hydroxide, Standard Solution (0.05 N)—
acidity, below 0.05 %, in organic compounds and hydrocarbon Prepare and standardize a 0.05 N sodium hydroxide (NaOH)
mixtures. The total acidity is calculated as acetic acid or solution (Note 2) in accordance with Sections 12 to 17 of
milligrams of sodium hydroxide per gram of sample. Practice E 200.
4.2 Acidity may be present as a result of contamination,
NOTE 2—Alternatively, KOH solution may be used.
1
5
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved May 10, 1996. Published July 1996. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
3
4
1
D 1613
8. Procedure 11. Precision and Bias 6
8.1 Measure into a 250-mL Erlenmeyer flask 50 mL of 11.1 Precision:
water, if the sample is completely water-soluble, or 50 mL of 11.1.1 The following criteria should be used for judging the
alcohol, if the sample is not completely water-soluble. acceptability of results at the 95 % confidence level:
11.1.1.1 Repeatability—The normal range between two re-
8.2 Add 0.5 mL of phenolphthalein indicator solution.
sults, each the mean of duplicate determinations, obtained by
Titrate the water or alcohol with 0.05 N NaOH solution to the
the same analyst on different days, is estimated to be 0.0003 %,
first perceptible pink color. absolute. Two such values should be considered suspect if they
8.3 Pipet 50 mL of the sample into the flask. Titrate with the differ by more than 0.0008 %, absolute.
0.05 N NaOH solution to the same first perceptible pink color 11.1.1.2 Reproducibility—The normal range between two
originally obtained. results, each the mean of duplicate determinations obtained by
analysts in different laboratories, is estimated to be 0.0005 %,
9. Calculations absolute. Two such values should be considered suspect if they
differ by more than 0.0014 %, absolute.
9.1 Calculate the acidity of the sample as follows:
Acidity as acetic acid, weight % 5 ~VN3 0.12!/D (1) NOTE 3—The above precision estimates are based on an interlaboratory
study on two samples each of n-butyl acetate, n-butyl alcohol, and methyl
or, ethyl ketone containing 0.0058, 0.0112, 0.0007, 0.0046, 0.0026, and
0.0067 % acetic acid, respectively. Each of four laboratories analyzed all
Acidity as mg KOH per g of sample 5 ~VN 3 1.12!/D (2) six samples, with two analysts in each laboratory performing duplicate
determinations using both 99 % isopropyl alcohol and formula 3A ethanol
where: as solvents, and repeating on a second day, for a total of 384 determina-
V 5 NaOH solution required for titration of the sample, tions.
mL,
N 5 normality of the NaOH solution, and 11.2 Bias—The bias of this test method has not been
D 5 sp gr of the specimen at the test temperature. determined because there is no available material with an
accepted reference value.
10. Report 12. Keywords
10.1 Report the percent of acetic acid to the nearest 12.1 solvents; acidity; total acidity as acetic acid
0.0001 %. Duplicate runs that agree within 0.0005 %, absolute,
are acceptable for averaging (95 % confidence level). 6
Supporting data are available from ASTM Headquarters. Request RR: D01-
1041.
2

Alkalinity in Acetone1
1. Scope all reagents shall conform to the specifications of the Commit-

1.1 This test method covers the determination in acetone of tee on Analytical Reagents of the American Chem-ical Society,
alkalinity calculated as ammonia (NH3). where such specifications are available.4 Other grades may be
1.2 This standard does not purport to address the safety used, provided it is first ascertained that the reagent is of
concerns, if any, associated with its use. It is the responsibility sufficiently high purity to permit its use without lessening the
of whoever uses this standard to consult and establish appro- accuracy of the determination.
priate safety and health practices and determine the applica- 6.2 Purity of Water—Unless otherwise indicated, references
bility of regulatory limitations prior to use. Specific hazard to water shall be understood to mean reagent water conforming
statements are given in Section 7. to Type IV of Specification D 1193.
1.3 For specific hazard information and guidance, consult 6.3 Methyl Red Indicator Solution (1 g/L)—Dissolve 0.2 g
the supplier’s Material Safety Data Sheet. of methyl red in 100 mL of methanol, ethanol, or isopropanol.
Prepare a fresh solution at least once a month as needed.
2. Referenced Documents 6.4 Sodium Hydroxide, Standard Solution (0.05 N)—
2.1 ASTM Standards: Prepare and standardize a 0.05 N sodium hydroxide (NaOH)
D 1193 Specification for Reagent Water2 solution (Note) in accordance with Sections 12 to 17 of
E 200 Practice for Preparation, Standardization, and Stor- Practice E 200.
age of Standard and Reagent Solutions for Chemical NOTE 1—Alternatively, potassium hydroxide (KOH) solution may be
Analysis3 used.
3. Summary of Test Method 6.5 Sulfuric Acid, Standard Solution (0.05 N)—Prepare and
standardize a 0.05 N sulfuric acid (H2SO4) solution.
3.1 The specimen is added to water previously neutralized
to the methyl red end point. If alkalinity is detected, it is titrated 7. Hazards
with 0.05 N H2SO4 and reported as weight percent of NH3. 7.1 Acetone is a highly flammable liquid.
4. Significance and Use 7.2 The reagents sulfuric acid and sodium hydroxide are
hazardous as they can cause severe burns of the skin or eyes.
4.1 This test method provides a measurement of alkalinity
in acetone. The results of this measurement can be used for 8. Procedure
specification acceptance. 8.1 To a 250-mL Erlenmeyer flask, add 50 mL of water and
5. Apparatus 3 drops of methyl red indicator solution. If the water is basic,
neutralize to the first faint pink coloration with 0.05 N H2SO4.
5.1 Buret, 10-mL, graduated in 0.05-mL subdivisions. If acidic, neutralize to the first yellow coloration with 0.05 N
5.2 Erlenmeyer Flask, 250-mL capacity. NaOH solution and then to the first faint pink coloration with
6. Reagents and Materials 0.05 N H2SO4 solution. Now add 50 mL of sample to the
neutralized water. If there is no change in the color of the
solution, the sample may be considered free of alkalinity. If,
however, the solution turns yellow, titrate it with 0.05 N H2SO4
1
4
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 1614 – 58. Last previous edition D 1614 – 91. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1614
to the first pink coloration. 11. Precision and Bias 5
11.1 Precision:
9. Calculation 11.1.1 On the basis of an interlaboratory study of this test
method in which operators in eleven laboratories analyzed one
9.1 When it is necessary to titrate the solution with the 0.05 sample of acetone with a mean alkalinity of 0.0009 %, the
N H2SO4 calculate the percent of alkalinity as ammonia (NH3) within-laboratory standard deviation was found to be
as follows: 0.00002 % absolute with nine degrees of freedom and the
between-laboratories standard deviation 0.00007 % absolute
NH3, % 5 ~VN3 0.034!/D (1)
with eight degrees of freedom. Based on these standard
where: deviations, the following criteria should be used for judging the
V 5 H2SO4 required for titration of the specimen, mL, acceptability of results at the 95 % confidence level:
N 5 normality of the H2SO4, and 11.1.1.1 Repeatability—Two results, each the mean of du-
D 5 specific gravity of the specimen at the test temperature. plicates, obtained by the same operator on different days
should be considered suspect if they differ by more than
0.0001 % absolute.
10. Report 11.1.1.2 Reproducibility—Two results, each the mean of
duplicates, obtained by operators in different laboratories
10.1 If the solution does not turn yellow, report alkalinity as should be considered suspect if they differ by more than
zero. 0.0002 % absolute.
11.2 Bias—Bias cannot be determined for this test method
10.2 If the solution is alkaline, report the percent of ammo- because there is no available material having an accepted
nia to the nearest 0.0001 %. Duplicate runs that agree within reference value.
0.00007 % absolute are acceptable for averaging (95 % confi-
12. Keywords
dence level).
12.1 acetone; alkalinity test; alkalinity test; acetone
5
1020.
2

Glycerol, Ethylene Glycol, and Pentaerythritol in Alkyd Resins1
e1 NOTE—Keywords were added editorially and editorial changes made throughout in May 1995.
1. Scope Unless otherwise indicated, it is intended that all reagents shall

1.1 These test methods cover the determination of glycerol, conform to the specifications of the Committee on Analytical
ethylene glycol, and pentaerythritol in alkyd resins and resin Reagents of the American Chemical Society, where such
solutions. Other polyhydric alcohols that can be oxidized by specifications are available.4 Other grades may be used, pro-
periodic acid to formaldehyde or formic acid, or both, will vided it is first ascertained that the reagent is of sufficiently
interfere with the determination of glycerol and ethylene glycol high purity to permit its use without lessening the accuracy of
(see Test Methods D 2456 or D 2998). Urea, melamine, or the determination.
phenolic resins interfere and render this procedure inappli- 3.2 Unless otherwise indicated, references to water shall be
cable. understood to mean reagent water conforming to Specification
1.2 This standard does not purport to address all of the D 1193.3
safety concerns, if any, associated with its use. It is the NOTE 1—The reagents and samples used in these methods may, under
responsibility of the user of this standard to establish appro- some conditions, be hazardous. Refer to the manufacturer’s Material
priate safety and health practices and determine the applica- Safety Data Sheets for specific handling and safety precautions. Safe
bility of regulatory limitations prior to use. laboratory handling procedures and all applicable OSHA regulations are to
be followed.
GLYCEROL AND ETHYLENE GLYCOL
2.1 ASTM Standards:
D 563 Test Method for Phthalic Anhydride Content of 4. Summary of Test Method
Alkyd Resins and Resin Solutions2 4.1 The primary hydroxyl groups of ethylene glycol and
D 1193 Specification for Reagent Water3 glycerol are oxidized to formaldehyde by periodic acid; the
D 1398 Test Method for Fatty Acid Content of Alkyd secondary hydroxyl group of glycerol is oxidized to formic
Resins and Alkyd Resin Solutions2 acid. By acidimetric and iodometric titration, the proportions of
D 2456 Test Method for Identification of Polyhydric Alco- formic acid and formaldehyde can be determined respectively,
hols in Alkyd Resins2 and calculated to glycerol and ethylene glycol by algebraic
D 2998 Test Method for Polyhydric Alcohols in Alkyd equations. The equations for the oxidation of the polyhydric
Resins2 alcohols are as follows:
1
4
of Subcommittee D01.33 on Polymers and Resins. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Sept. 19, 1960. Originally issued 1958. Replaces listed by the American Chemical Society, see Analar Standards for Laboratory
D 1615 – 58 T. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1615
C3H8O3 + 2H5I06 source of heat. Keep the beaker covered with a watch glass6
glycerol periodic during boiling.
acid
↓ 7.2.2 Cool to room temperature, and filter through a rapid
2HCHO + HCOOH + 2HIO3 + 5H2O paper into a 100-mL volumetric flask. (Take the sample for
formal- formic iodic water pentaerythritol determination from this same volumetric flask.)
dehyde acid acid
C2H6O2 + H5I06 Fill to the mark and agitate.
ethylene periodic 7.2.3 Pipet 20 mL (1⁄5 aliquot) (Note 2) into a 1-L Erlenm-
glycol acid eyer, glass-stoppered flask. Add 2 drops of methyl purple
↓
2HCHO + HIO3 + 3H2O indicator solution and neutralize with NaOH. Pipet into the 1-L
formal- iodic water flask also 50 mL of HIO4 solution, stopper, and swirl to mix
dehyde acid thoroughly.
With pentaerythritol, there is no reaction. NOTE 2—The aliquot should be so chosen, if possible, that 15 to 20 %
5. Apparatus of the periodic acid is consumed during the oxidation. Considerable
excess of periodic acid is required to complete the oxidation, and in case
5.1 Burets, 50 and 100-mL capacity. more than 20 % is consumed the results should be disregarded and a
5.2 Pipets, 20 and 50-mL capacity. smaller aliquot taken. On the other hand, too small an aliquot is not
5.3 Beakers, two of 400-mL capacity. advisable, for in such a situation the difference between titration and blank
5.4 Erlenmeyer Flasks, four of 1000-mL capacity, glass- is small and any titration errors are magnified.
stoppered. 7.3 Simultaneously prepare two blanks containing 20 mL of
5.5 Volumetric Flasks, two of 100-mL capacity. water. Allow to stand 50 to 70 min at room temperature.
5.6 Graduated Cylinder, 10-mL capacity. 7.4 To the aliquot of the sample (7.2.3) and the blank, add
5.7 Filter Paper, fast, qualitative grade. 100 mL of water and 3 drops of methyl purple indicator and
5.8 Watch Glass. titrate with 0.1 N NaOH solution to neutrality. Use the 50-mL
6. Reagents buret and record the volume to the nearest 0.01 mL.
7.5 To the solution that has just been titrated, add 150 mL of
6.1 Methyl Purple Indicator Solution. 5 water, 30 mL of KI solution, and 25 mL of H2SO4 (1+5).
6.2 Periodic Acid (11 g/L)—Dissolve 11 g of periodic acid Titrate with 0.2 N Na2S2O3 solution to faint iodine color, add
(HIO4) in water and dilute to 1 L. Prepare fresh daily and store 10 mL of starch indicator and titrate to the disappearance of the
in a brown bottle. blue color.
6.3 Potassium Iodide Solution (200 g/L)—Dissolve 200 g of
potassium iodide (KI) in water and dilute to 1 L. NOTE 3—If the end point is not stable, as indicated by return of the blue
6.4 Sodium Hydroxide, Standard Solution (0.1 N)—Prepare color in the stoppered flask in 5 min, add water and titrate to a stable end
point. Use the 100-mL buret and record the volume to the nearest
and standardize a 0.1 N aqueous sodium hydroxide (NaOH)
estimated 0.05 mL.
solution.
6.5 Sodium Thiosulfate, Standard Solution (0.2 N)— 8. Calculations
Prepare and standardize a 0.2 N aqueous sodium thiosulfate
(Na2S2O3) solution. 8.1 Calculate the percentage of glycerol, G, as follows:
6.6 Starch Indicator Solution—Dissolve 5 g of soluble G 5 @~A 2 B!N 3 0.09206!/WF# 3 100
starch in water and dilute to 1 L. Preserve the solution with 1
where:
g of salicyclic acid.
A 5 millilitres of NaOH solution required for titra-
6.7 Sulfuric Acid (1+5)—Carefully mix 1 volume of con-
tion of the sample,
centrated sulfuric acid (H2SO4, sp gr 1.84) with 5 volumes of B 5 millilitres of NaOH solution required for titra-
water. tion of the blank,
7. Procedure N 5 normality of the NaOH solution,
0.09206 5 grams of glycerol equivalent to 1 mL of 1 N
7.1 Determine the phthalic anhydride in accordance with NaOH solution (acidimetric),
Test Method D 563. Following this, extract the fatty acids in W 5 grams of sample used, and
accordance with 5.6 through 7 of Test Method D 1398, except F 5 aliquot fraction 5 1⁄5.
do not discard the aqueous phase. 8.2 Calculate the percentage of glycerol and ethylene gly-
7.2 Test the remaining water solution containing the poly- col, T, as a percentage of glycerol as follows:
alcohols for glycerol and ethylene glycol in the following
manner: ~T 5 @~B8 2 A8!N 3 0.023015!/WF# 3 100
7.2.1 Transfer the solution to a 400-mL beaker and evapo- where:
rate to about 60-mL volume, using an electric hot plate as A8 5 millilitres of Na2S2O3 solution required for
titration of the sample,
5
Methyl purple indicator manufactured by the Fleisher Chemical Co., Benjamin
Franklin Station, Washington 4, D.C., U.S. Patent No. 2,416,619, has been found
satisfactory for this purpose.
6
The Speedyvap watch glass has been found satisfactory for this purpose.
2
D 1615
B8 5 millilitres of Na2S2O3 solution required for zaldehyde,7 add 100 mL of technical grade anhydrous metha-
titration of the blank, nol (CH3OH).
0.023015 5 grams of glycerol equivalent to 1 mL of 1 N 12.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
Na2S2O3 solution (iodometric), chloric acid (HCl).
N 5 normality of the Na2S2O3 solution, 12.3 Methanol-Water Wash Solution (1 + 1)—Mix equal
W 5 grams of sample used, and volumes of technical anhydrous CH3OH and water. (Because
F 5 aliquot fraction 5 1⁄5. of heat of solution, prepare this solution in advance.) One
8.3 If E is the percentage of ethylene glycol, then fourth of the wash solution is to be stored in a refrigerator and
E 5 1.348~T 2 G! used cold; the remainder is kept at room temperature.
When E 5 O, the sample is free of ethylene glycol. 13. Procedure
NOTE 4—In practice, samples containing no ethylene glycol have given 13.1 Transfer an aliquot of the 100-mL of sample solution
calculated E values of up to 1 %. Therefore, samples with E values of 1 % (7.2.2) containing 0.15 to 0.55 g of pentaerythritol to a 100-mL
or less should be considered as containing no ethylene glycol, and samples beaker. Evaporate on a steam bath to a volume of approxi-
with higher E values may be corrected by 1 % at the discretion of the
mately 5 mL. To the hot solution (incipient boiling) add 15 mL
analyst.
of benzaldehyde-methanol reagent and 12 mL of HCl. Swirl
9. Precision and Bias and allow to stand at room temperature 15 min, swirling
9.1 Repeatability—The average difference between dupli- occasionally during this time to prevent the precipitate from
cate runs performed by the same analyst in the same laboratory adhering to the bottom of the beaker. Place the beaker in an ice
should approximate the following values: bath, maintaining the temperature at 0 to 2°C for 1 h or more.
13.2 Remove the reaction mixture from the ice bath and
Percentage of glycerol 0.1
Percentage of glycol 0.4 immediately filter with suction through a weighed fritted-glass
crucible of medium porosity. Rinse the beaker with 25 mL of
Not more than once in twenty times would the difference be the cold (0 to 2°C) methanol wash solution and add to the
expected to exceed: crucible. Continue to transfer and wash the precipitate with 100
Percentage of glycerol 0.3
Percentage of glycol 1.0
mL of methanol-water wash solution at 20 to 25°C as follows:
13.2.1 Disconnect the vacuum line, pour a 10-mL portion of
9.2 Reproducibility: the wash solution from the beaker to the crucible, and stir the
9.2.1 The average difference between results obtained by precipitate to form a homogeneous slurry, using a short flat-end
different analysts in different laboratories, when reported as the glass rod. Connect the vacuum line and draw the wash solution
average of duplicate determinations, should approximate: through the crucible. Repeat this washing operation six times.
Percentage of glycerol 0.2 With the last 30 mL of methanol-water wash solution, rinse the
interior walls of the crucible and rinse and remove the short
9.2.2 Not more than once in twenty times should the stirring rod.
difference be expected to exceed: 13.3 Aspirate thoroughly and dry the precipitate at 105°C
Percentage of glycerol 0.6 for 2 h. Cool in a desiccator and weigh.
14. Calculations
PENTAERYTHRITOL
14.1 Calculate the percentage of monopentaerythritol, P, of
10. Summary of Test Method the resin from the precipitate obtained in accordance with 14.3
10.1 Monopentaerythritol reacts with benzaldehyde to form follows:
a dibenzal which is crystalline and can be handled gravimetri- P 5 @~W2 1 0.0269! 3 43.6#/W1F
cally.
where:
11. Apparatus W1 5 grams of sample,
11.1 Beakers, 100-mL capacity. W2 5 grams of precipitate, and
11.2 Delivery Pipets (for aliquots), 10 to 50-mL capacity. F 5 aliquot fraction.
11.3 Steam Bath. 14.2 To convert the percentage of monopentaerythritol, P,
11.4 Ice Bath. to the percentage of commercial technical monopentaerythri-
11.5 Crucible, medium porosity, fritted glass. tol, use the following arbitrary formula which is based on the
11.6 Suction Flask. assumption that the commercial grade contains 85 % mono-
11.7 Water Aspirator. pentaerythritol:
11.8 Desiccator. Commercial monopentaerythritol, % 5 P/0.85
11.9 Drying Oven, capable of maintaining a temperature of
105°C. 15. Precision and Bias
11.10 Glass Rod, flat-end. 15.1 Repeatability— The average difference in percentage
12.1 Benzaldehyde-Methanol Reagent—To 20 mL of ben- 7
Merck, N. F. grade benzaldehyde has been found satisfactory for this purpose.
3
D 1615
of monopentaerythritol found, between duplicate runs per- average of duplicate determinations should approximate 0.5.
formed by the same analyst in the same laboratory, should Not more than once in twenty times would the difference be
approximate 0.25. Not more than once in twenty times would expected to exceed 1.4.
the difference be expected to exceed 0.6.
15.2 Reproducibility—The average difference in percentage 16. Keywords
of monopentaerythritol found, between results obtained by
different analysts in different laboratories, when reported as the 16.1 alkyd resins; ethylene glycol; glycerol; pentaerythritol
4

Ester Value of Solvents and Thinners1
1. Scope lyzed by the reagent, particularly at 98°C, and are a possible

1.1 This test method covers the determination of the ester source of error. Ketones interfere only slightly with this
value of solvents and thinners used in lacquers and other procedure. Aldehydes consume some alkali, but the error
coatings. introduced by small amounts is negligible.
1.2 This standard does not purport to address all of the 6. Apparatus
responsibility of the user of this standard to establish appro- 6.1 Pressure Bottle,3 200 to 350-mL capacity, made from
priate safety and health practices and determine the applica- heat-resistant glass.
bility of regulatory limitations prior to use. For a specific 6.2 Container for Pressure Bottle—A suitable safety device
hazard statement, see Note 2. to contain the pressure bottle. A metal container with hinged
1.3 For hazard information and guidance, see the supplier’s top and perforated bottom, a strong synthetic fabric or canvas
Material Safety Data Sheet. bag, or a safety shield may be used.
6.3 Ampoule, 1 or 2-mL capacity.
2. Referenced Documents 6.4 Weighing Pipet, Lunge or similar type.
2.1 ASTM Standards: 6.5 Erlenmeyer Flasks, 250-mL glass-stoppered.
D 1193 Specification for Reagent Water2 6.6 Buret, 50-mL capacity.
6.7 Boiling Water Bath.
7. Reagents
3.1 The specimen is reacted with a measured excess of
aqueous potassium hydroxide, using isopropanol as a mutual 7.1 Purity of Reagents—Reagent grade chemicals shall be
solvent if necessary. The amount of potassium hydroxide used in all tests. Unless otherwise indicated, it is intended that
consumed, which is determined by titrating the excess with all reagents shall conform to the specifications of the Commit-
standard mineral acid, is a measure of the ester originally tee on Analytical Reagents of the American Chemical Society,
present. where such specifications are available.4 Other grades may be
3.2 Since this determination is based on an acidimetric used provided it is first ascertained that the reagent is of
titration, a suitable correction should be applied if the acidity of sufficiently high purity to permit its use without lessening the
the sample exceeds the limit of the specification. accuracy of the determination.
4. Significance and Use to water shall be understood to mean reagent water conforming
4.1 This test method is useful in determining the assay of to Type IV of Specification D 1193.
solvents and thinners which are esters or solutions of esters of 7.3 Hydrochloric Acid, Standard (0.5 N)—Prepare 0.5 N
carboxylic acid. The ester value is calculated as percent ester. hydrochloric acid (HCl) and standardize to four significant
This test method has its greatest application where the solvent figures.
or thinner is not a pure ester. This test method may be used in 7.4 Isopropyl Alcohol (99 %).
assessing compliance to specification. 7.5 Phenolphthalein Indicator Solution—Dissolve 1 g of
phenolphthalein in 100 mL of methanol, ethanol, or isopropyl
5. Interferences alcohol.
5.1 Organic chlorides, nitriles, and amides may be hydro-
3
Bottles of this type, equipped with lever-type closures, can be obtained from
Preiser Scientific, PO Box 1330, 94 Oliver St., St. Albans, WV 25177.
1 4
Current edition approved May 25, 1990. Published July 1990. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 1617 – 58 T. Last previous edition D 1617 – 85. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
2
1
D 1617
7.6 Potassium Hydroxide, Standard Solution (1.0 N)— 8.8 If a white precipitate develops in the specimen flasks or
Dissolve 66 g of potassium hydroxide (KOH) pellets in water bottles, add sufficient water to dissolve the salt. Add the same
and dilute to 1 L with water (see Note 1). amount of water to each of the blanks. Add 6 to 8 drops of the
7.7 Sulfuric Acid, Standard (0.5 N)—Prepare 0.5 N sulfuric phenolphthalein indicator solution to each flask or bottle and
acid (H2SO4) and standardize to four significant figures. titrate with 0.5 N H2SO4 just to the disappearance of the pink
color. If more than 25 mL of isopropyl alcohol were added in
8. Procedure
accordance with 8.3, titrate with 0.5 N HCl.
8.1 Prepare a sufficient number of 250-mL, glass-stoppered 8.9 Measure the temperature of the acid titrant. If the
Erlenmeyer flasks to make all blank and test determinations in temperature of the reagent at the time the ester determination is
duplicate. Use heat-resistant pressure bottles if sealed glass made is not the same as it was at the time the reagent was
ampoules are required or if the reaction is conducted at 98°C. standardized, apply a temperature correction of 0.00014/°C to
8.2 Into each of the flasks or bottles, carefully introduce 25 the normality.
mL of 1.0 N KOH solution (Note 1) by means of a suitable
transfer pipet. Use the same pipet for each transfer. 9. Calculation
9.1 Calculate the percent of ester, E, as follows:
NOTE 1—Do not substitute sodium hydroxide (NaOH) solution. The
reaction conditions given in Table 1 are valid only when 1.0 N KOH E 5 @~~B 2 V!N 3 F!/S# 3 100 (1)
solution is used.
where:
8.3 Add the amount of isopropyl alcohol prescribed in Table V 5 0.5 N H2SO4 (or HCl) required for titration of the
1 but never add more than 40 mL. Stopper and reserve two of specimen (8.8), mL
the flasks or bottles for the blank determinations. B 5 0.5 N H2SO4 (or HCl) required for titration of the
8.4 Into each of the other flasks or bottles introduce an blanks (8.8), avg, mL,
amount of sample containing not more than 0.016 mol (16 N 5 normality of the H2SO4 (or HCl) corrected for tem-
milliequivalents) of the ester. For substantially pure material, perature,
weigh the specimen to the nearest 0.1 mg, using the amount F 5 factor specified in Table 2 for the ester being deter-
and procedure specified in Table 1. Stopper the flasks after mined, and
addition of the specimen. S 5 specimen used, g.
8.5 If a sealed glass ampoule is used, add several pieces of
NOTE 3—If the acidity of the ester exceeds the limit of the specification,
fire-polished 8-mm glass rod to each bottle, stopper, and shake
it is recommended that a suitable correction be applied to the ester value.
the bottle vigorously to break the ampoule. Table 2
8.6 Reaction at 98°C (Precaution—See Note 2.)—Place
the specimens and blanks as close together as possible in a 10. Report
boiling water bath maintained at least at 98°C for the time 10.1 Report the following information:
prescribed in Table 1. Maintain sufficient water in the bath to 10.1.1 All results to the nearest 0.1 %. Duplicate determi-
just cover the liquid in the bottles. Remove the bottles from the nations that agree within 0.38 %, absolute, are acceptable for
bath and allow them to cool to room temperature. When the averaging (95 % confidence level).
bottles have cooled, remove them from the safety device and
uncap them carefully to release any pressure. Continue as 11. Precision and Bias
described in 8.8. 11.1 Precision—The precision statements are based upon an
interlaboratory study in which two analysts in each of four
NOTE 2—Precaution: Enclose each bottle securely in a suitable safety
device to restrain fragments of glass should the pressure bottle rupture. different laboratories analyzed one sample of ethyl acetate,
88 %, and one sample of dibutyl phthalate, 99 %, in duplicate
8.7 Reaction at Room Temperature—Allow the specimen to on three different days. The within-laboratory coefficient of
stand together with the blanks at room temperature for the variation was found to be 0.154 % at 40 df, and the between-
length of time specified in Table 1. laboratory coefficient of variation was found to be 0.313 % at
TABLE 1 Specimen Size and Reaction Conditions approximately 16 df. Based on these coefficients of variation,
Isopropyl Minimum Reaction the following criteria should be used in judging the acceptabil-
A
Alcohol Conditions ity of results at the 95 % confidence level.
Ester Specimen, g Added,
Time, Tempera-
mL TABLE 2 Ester Factors
min ture, °C
Ester FactorA
Amyl acetate 1.4 to 1.6 40 30 98
Dibutyl phthalate 1.4 to 2.0 30 30 98 Amyl acetate 0.1302
2-Ethoxyethyl acetate 1.3 to 2.1 0 30 25 Dibutyl phthalate 0.1392
Ethyl acetate 0.9 to 1.4B 0 30 25 2-Ethoxyethyl acetate 0.1322
Isobutyl acetate 1.2 to 1.9 25 45 25 Ethyl acetate 0.0881
Isopropyl acetate 1.0 to 1.6B 10 30 25 Isobutyl acetate 0.1162
Methyl amyl acetate 1.4 to 2.3 30 30 98 Isopropyl acetate 0.1021
Normal butyl acetate 1.2 to 1.9 25 45 25 Methyl amyl acetate 0.1442
Normal propyl acetate 1.0 to 1.6B 10 30 25 Normal butyl acetate 0.1162
sec–Butyl acetate 1.2 to 1.9 25 45 98 Normal propyl acetate 0.1021
A sec–Butyl acetate 0.1162
Use a suitable weighing pipet unless otherwise specified.
B
Use a sealed glass ampoule. A
Factor 5 molecular weight of compound/number of reacting groups 3 1000.
2
D 1617
11.1.1 Repeatability—Two results, each the mean of dupli- 11.2 Bias—Any material or contaminant (see Section 5 and
cates, obtained by the same operator on different days should Note 3) that will react with potassium hydroxide under the test
be considered suspect if they differ by more than 0.44 % conditions will affect the results.
relative.
11.1.2 Reproducibility—Two results, each the mean of du- 12. Keywords
plicates, obtained by operators in different laboratories should
be considered suspect if they differ by more than 0.94 % 12.1 ester value; solvents; thinner
relative.
3

Water in Phenol and Related Materials by the Iodine
Reagent Method1
1. Scope 3. Terminology
1.1 This test method covers the determination of water in 3.1 See Terminology D 4790 for definition of terms used in
phenol and related materials such as cresols, xylenols, naph- this test method.
thalene, pyridine, and quinoline.
1.2 This test method has been found applicable to a variety 4. Summary of Test Method
of materials varying in water content from 100 mg/kg to 4.1 When solutions of iodine in methanol and of sulfur
solutions containing a relatively high percent of water. dioxide in pyridine are mixed in the presence of water, the
1.3 The following applies to all specified limits in this following reaction occurs:
standard: for purposes of determining conformance with this I2 1 SO2 1 H2O →
← 2HI 1 SO3 (1)
standard, an observed value or a calculated value shall be
rounded off “to the nearest unit” in the last right-hand digit 4.1.1 Sufficient pyridine is present in the reagent to consume
used in expressing the specification limit in accordance with the hydriodic acid and sulfur trioxide:
the rounding-off method of Practice E 29.
bility of regulatory limitations prior to use. For specific hazard
statements, see Section 9. 4.1.2 The pyridine sulfur trioxide salt reacts with the metha-
nol, this preventing a second mole of water from being
consumed:
Fischer Reagent Titration Method)
D 3437 Practice for Sampling and Handling Liquid Cyclic
Products
D 3852 Practice for Sampling and Handling Phenol and
Cresylic Acid 4.2 When the pyridine solution contains water and the sulfur
D 4790 Terminology of Aromatic Hydrocarbons and Re- dioxide is titrated with iodine in methanol solution, the
lated Chemicals2 platinum electrodes remain polarized until all the water reacts.
E 29 Practice for Using Significant Digits in Test Data to A slight excess of iodine depolarizes the electrodes, allowing
Determine Conformance with Specifications3 current to flow through the microammeter which indicates the
2.2 Other Document:4 end point.
OSHA Regulations, 29 CFR, Paragraphs 1910.1000 and 5. Significance and Use
1910.1200
5.1 This test method is particularly useful for determining
1
small amounts of water in hygroscopic materials. This test
method is suitable for setting specifications on materials
Subcommittee D16.0C on Oxygenated Aromatics. referenced in the scope. It may also be used as an internal
Current edition approved June 10, 1999. Published August 1999. Originally quality control tool and in development or research work.
2
Annual Book of ASTM Standards, Vol 06.04. 6. Interferences
3
4
Available from Superintendent of Documents, U.S. Government Printing 6.1 This test method is not applicable in the presence of
1
D 1631
mercaptans, peroxides, or appreciable quantities of aldehydes 8.4 Pyridine Solution—Place 4000 mL of refined grade
or amines. pyridine in a 5000-mL distilling flask. Distill over and discard
6.2 If ketones are present in the sample, interference from 400 mL of forecut at atmospheric pressure. Distill off 3400 mL
them can be avoided by employing the glycol-pyridine sample of center cut and transfer to a suitable glass bottle fitted with a
solvent specified in Test Method D 1364. two-hole stopper. Through one hole of the stopper insert a
piece of glass tubing that extends almost to the bottom of the
7. Apparatus bottle; through the other hole insert a short piece of glass
7.1 The apparatus shall be assembled as shown in Fig. 1. tubing to serve as a vent. Through the long tube add 400 g of
Any suitable modification permitting equal facility and accu- refrigerant-grade sulfur dioxide (SO2) dried through concen-
racy may be used. Automatic titration equipment is commer- trated sulfuric acid (H2SO4 sp gr 1.84), and allow the solution
cially available and may be used. to cool. Fit the vent tube with a drying tube and an aspirator
bulb; connect the long tube with an adapter suitable for
8. Reagents introducing the reagent into the titration flask. For convenience
8.1 Reagent grade chemicals shall be used in all tests. in measuring, a suitable reservoir may be placed in the system.
Unless otherwise indicated, it is intended that all reagents shall NOTE 1—In place of the divided reagents described in 8.2, 8.3, and 8.4
conform to the specifications of the Committee on Analytical it is permissible to employ the single solution reagent specified in Test
Reagents of the American Chemical Society, where such Method D 1364 or commercial Karl Fischer reagents. Pyridine-free
specifications are available.5 Other grades may be used, pro- reagents are available from various laboratory suppliers and may be used
vided it is first ascertained that the reagent is of sufficiently if suitable for the material being tested.
high purity to permit its use without lessening the accuracy of 8.5 When handling Karl Fischer reagent refer to Practice
the determination. D 3437.
8.2 Iodine Solution—Dissolve 150 g of iodine (I2) crystals
in 3 L of anhydrous methanol. Place the solution in the reagent 9. Hazards
bottle connected to the buret as shown in Fig. 1. 9.1 Consult current OSHA regulations supplier’s Material
8.3 Methanol, anhydrous, containing less than 0.05 % wa- Safety Data Sheets and local regulations for all materials used
ter. in this test method.
9.2 Phenol, pyridine, and related materials are extremely
toxic when ingested and corrosive to the skin. Appropriate
5
Reagent Chemicals, American Chemical Society Specifications, American precaution must be exercised when handling them.
listed by the American Chemical Society, see Analar Standards for Laboratory 10. Sampling
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 10.1 Sample in accordance with Practice D 3852 for proper
MD. sampling and handling of phenol and related materials ana-
lyzed by this test method (see 9.1 and 9.2.).
10.2 Precautions must be taken in sampling to preclude any
possibility of contamination with atmospheric moisture adher-
ing to the walls of the pipet.
10.3 The sample size recommended, on the basis of water
content expected is as follows:
Expected Water Content, % Size of Specimen, g
0.01 to 0.03 50
0.03 to 0.3 25
0.3 to 0.6 10
0.6 to 1.0 5
1.0 to 5.0 2
5.0 to 10.0 1
10.0 to 20.0 0.5
11. Standardization of Sulfur Dioxide–Iodine Reagent

11.1 By means of pressure from the aspirator bulb, transfer
sufficient pyridine solution (Warning—see 9.2) to the titration
flask to cover the electrodes. If an automatic titration apparatus
is used, a small amount of methanol may be added to the
pyridine to improve the response of the titrator. Turn on the
magnetic stirrer and turn the “zero-set” knob until a reading of
70 µA is obtained on the ammeter. Add the iodine solution
dropwise from the buret until the ammeter reads a maximum
value, about 130 µA. Remove the drying tube from the sidearm
and quickly introduce an amount of distilled water, or water of
FIG. 1 Titration Assembly equivalent purity, at least equal to that to be determined,
2
D 1631
weighed to the nearest 0.1 mg by means of a suitable weighing specimens. Washing should be followed by an alcohol or acetone rinse and
pipet. Immediately replace the drying tube. drying in a ventilated oven at 100 to 130°C for several hours. The clean
11.2 Titrate with the iodine solution, approaching the end flask may be cooled in a desiccator or attached to the buret to cool with
the openings closed with drying tubes. If a series of specimens is to be
point dropwise until the maximum value, about 130 µA, is tested, it is preferable to continue additions of specimens and titration (and
obtained on the ammeter. The standardization should be addition of pyridine if necessary) until the volume of liquid in the flask is
repeated daily. If desired, a suitable accurately weighed amount too great for further titration.
of sodium tartrate dihydrate reagent may be used in place of NOTE 3—Visual observation of the end point may be used in place of
water as follows: Accurately weigh a small aluminum weigh- the more precise electrometric method described if the solution is very
ing dish containing about 0.20 to 0.22 g of powdered sodium lightcolored. During the titration the solution turns yellow after the
addition of the first few millilitres of the reagent. This color change must
tartrate dihydrate (Na2C4H4O6·2H2O) to the nearest 0.1 mg.
not be confused with the true end point, which is brown. The transition
Remove the stopper from the titration flask and introduce the from yellow to brown is quite sharp and easily reproducible.
tartrate by inserting the spout into the opening and gently
tapping so that the powder falls freely into the liquid without 13. Calculation
contacting the side walls. Do not brush out the dish: accurately 13.1 Calculate the amount of water in the specimen as
reweigh it and calculate the weight of tartrate used by follows:
difference. Quickly reseal the flask, turn on the stirrer, and
Water, weight % 5 CF/D (4)
titrate to the end point. Record the volume of reagent and
weight of tartrate used. where:
11.3 Calculate the water equivalent of the sulfur dioxide- C 5 sulfur dioxide-iodine reagent required for titration of
iodine reagent as follows: the specimen, mL, and
F 5 100A/B (2) D 5 weight of specimen used, g.
where:
F 5 water equivalent of the reagent, g/100 mL,
A 5 water added, g, and 14.1 Intermediate Precision (formerly called
B 5 volume of reagent used for the titration, mL. Repeatability)—Duplicate results should be considered suspect
if they differ by more than the following:
If sodium tartrate dihydrate is used in place of water for
Intermediate Precision Reproducibility
standardizing: Range, %
(By Same Operator) (By Two Different Laboratories)
F 5 15.66S/B (3) 0.01 to 0.12 0.0035 0.021
where S 5 tartrate used, g. 14.1.1 Data on which these precision values are based are
given in the 1959 Report of Committee D-16, Proceedings,
12. Procedure
ASTM, Vol 59, 1959.
12.1 Repeat the procedure described in Section 11 adding, 14.2 Bias—Since there is no accepted reference material
instead of water, an amount of specimen selected according to suitable for determining the bias in this test method, bias has
Section 10. Record all weighings to the nearest 0.1 mg. As long not been determined.
as an excess of pyridine remains in the titration flask, further
additions of specimen and titration may be made. (Warning— 15. Keywords
See 9.2.) 15.1 cresols; iodine; Karl Fischer method; naphthalene;
NOTE 2—The titration flask may be removed and cleaned between phenol; pyridine; quinoline; water; xylenols
3

Acid Value of Organic Coating Materials1
1. Scope relative applicability of the varnish, oil, resin, or paint vehicle

1.1 This test method covers the measurement of the free to the particular end use may be estimated by the buyer and the
acidity present in the nonvolatile portion of varnishes, oils, seller.
certain resins, and paint vehicles, by the reaction with standard 4.2 This test method also provides a convenient method of
alkali solution. process control for the manufacture of certain resins and paint
1.2 If carboxylic anhydrides are present, only one half of the vehicles designed to meet particular requirements of the buyer
reactive groups will be titrated and indicated by this test and the seller.
method. 5. Reagents and Solvents
concerns, if any, associated with its use. It is the responsibility 5.1 Purity of Reagents—Reagent grade chemicals shall be
of the user of this standard to establish appropriate safety and used in all tests. Unless otherwise indicated, it is intended that
health practices and determine the applicability of regulatory all reagents shall conform to the specifications of the Commit-
limitations prior to use. tee on Analytical Reagents of the American Chemical Society,
2. Referenced Documents used, provided it is first ascertained that the reagent is of
2.1 ASTM Standards: sufficiently high purity to permit its use without lessening the
D 362 Specification for Industrial Grade Toluene2 accuracy of the determination.
D 770 Specification for Isopropyl Alcohol3 5.2 Phenolphthalein Indicator Solution (10 g/L)—Dissolve
D 1259 Test Methods for Nonvolatile Content of Resin 1 g of phenolphthalein in 100 mL of methanol, ethanol, or
Solutions4 isopropranol.
D 1644 Test Methods for Nonvolatile Content of Varnishes4 5.3 Potassium Hydroxide, Methyl Alcohol (Methanol) Solu-
D 1960 Test Method for Loss on Heating of Drying Oils5 tion (1 mL 5 5.6 mg KOH)—Dissolve 6.6 g of potassium
hydroxide (KOH) in 1 L of methyl alcohol. Standardize against
3. Terminology National Institute of Standards and Technology standard po-
3.1 Definitions: tassium hydrogen phthalate Standard Reference No. 84, using
3.1.1 acid value—the number of milligrams of potassium phenolphthalein as the indicator (5.2). Do not adjust the
hydroxide (KOH) required to neutralize the alkali-reactive concentration of the solution, but calculate the milligrams of
groups in 1 g of material under the conditions of test (see 6.4). KOH per litre of solution, K. (See Note.)
NOTE 1—At the discretion of the purchaser and the seller, an aqueous
4. Significance and Use solution of potassium hydroxide of 0.1 N or 0.5 N may be used.
4.1 This test method is used to determine the free acidity NOTE 2—Potassium hydroxide, methyl alcohol (methanol) solution
present in the nonvolatile portion of varnishes, oils, certain may be purchased from most major laboratory chemical supplier houses.
resins, and paint vehicles by the reaction with a standard alkali This material should be standardized as just indicated.
solution. Use of this test method provides a means whereby the 5.4 Neutral Solvent Mixture—Mix equal parts by volume of
isopropyl alcohol (isopropanol) (see Specification D 770) and
1
industrial toluene (see Specification D 362). Neutralize the
6
Current edition approved Oct. 26, 1990. Published December 1990. Originally Reagent Chemicals, American Chemical Society Specifications, American
published as D 1639 – 51. Last previous edition D 1639 – 89. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
Discontinued; See 1989 Annual Book of ASTM Standards, Vol 06.03. listed by the American Chemical Society, see Analar Standards for Laboratory
3
4
5
1
D 1639
mixture using 0.1 N KOH solution (4.3) and phenolphthalein where:
indicator solution (5.2) until the pink color persists for 1 min. V 5 volume of KOH solution required for titration of the
6. Procedure specimen, mL,
K 5 weight of KOH per millilitre of KOH solution, mg,
6.1 Weigh or transfer into a 250-mL Erlenmeyer flask the S 5 specimen weight, g, and
specimen mass, S, prescribed in Table 1. N 5 nonvolatile content of the material expressed as a
6.2 Add 100 mL of neutral solvent. Mix until all material is decimal fraction.
dissolved, warming if necessary. Cool to room temperature,
7.2 Calculate the mean of the two runs.
about 77°F (25°C), before titrating. Add 1 mL of phenolphtha-
lein indicator solution and titrate with the 0.1 N KOH solution
(5.3) to the end point, which is a pink color persisting for 30 s 8. Report
(V). 8.1 Report the acid value of the nonvolatile matter to the
6.3 Repeat with a second specimen. nearest decimal (0.1).
6.4 In the case of materials containing a solvent, determine
the nonvolatile content in accordance with Test Methods 9. Precision
D 1259, D 1644, D 1960 or other applicable method agreed
upon between the purchaser and the seller. 9.1 Because of the many types of material covered by this
test method, the precision is not as good as might be expected
7. Calculation
of a quantitative analytical method. The following criteria
7.1 Calculate the acid value A as follows: should be used for judging the acceptability of results:
VK 9.1.1 Repeatability—Duplicate results obtained by the same
A 5S3N
operator should be considered suspect if they differ by more
TABLE 1 Specimen Size
than 10 % of the mean acid value.
Accuracy of 9.1.2 Reproducibility—Two results obtained by operators in
Approximate
Expected Acid Value Specimen
weighing, different laboratories should be considered suspect if they
plus or mi-
Mass, g
nus, mg
differ by more than 20 % of the mean acid value.
0 to 5 20 50
Over 5 to 15 10 50 10. Keywords
Over 15 to 30 5 50
Over 30 to 100 2.5 1 10.1 free acidity; nonvolatile; oils; organic coating materi-
Over 100 1 1 als; resins; varnishes
2

Resistance of Dried Films of Varnishes to Water and Alkali1
e1 NOTE—Keywords and the unit measurement statement were added editorially in October 1996.
1. Scope two factors which tend to break down this protective coating.
1.1 These test methods cover the determination of the This test method can be used as a comparison basis between
resistance of dried varnish films to immersion in water and manufacturer and consumer to determine the ability of the
dilute alkali at room temperature. varnish to resist water and dilute alkali.
1.2 The values stated in inch-pound units are to be regarded 5. Reagents
information only. 5.1 Purity of Reagents—Reagent grade chemicals shall be
1.3 This standard does not purport to address all of the used in all tests. Unless otherwise indicated, it is intended that
safety concerns, if any, associated with its use. It is the all reagents conform to the specifications of the Committee on
responsibility of the user of this standard to establish appro- Analytical Reagents of the American Chemical Society, where
priate safety and health practices and determine the applica- such specifications are available.4
bility of regulatory limitations prior to use. 5.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water as defined
2. Referenced Documents by Type IV of Specification D 1193.
2.1 ASTM Standards: TEST METHOD A—WATER RESISTANCE OF DRIED
D 609 Practice for Preparation of Cold-Rolled Steel Panels FILMS
for Testing Paint, Varnish, Conversion Coatings, and
Related Coating Products2 6. Apparatus and Materials
D 1193 Specification for Reagent Water3 6.1 Beaker, glass, 600 mL or larger.
D 3924 Specification for Standard Environment for Condi- 6.2 Tinplate Panels, 3 by 5 in. (75 by 125 mm) cut from
tioning and Testing Paint, Varnish, Lacquers, and Related commercial No. 31 gage (0.225-mm) bright tin plate, weighing
Materials2 0.4 to 0.5 lb/ft2 (1.90 to 2.50 kg/m2) and carefully cleaned and
3. Summary of Test Methods dried before use in accordance with Methods B or C of Practice
D 609.
3.1 Test Method A—The material under test is flowed onto
tinplate panels and dried for 48 h. The panels are then 7. Procedure
immersed to half their length in reagent water for 18 h, or other 7.1 Flow the varnish onto the tin panels, allow to drain in a
agreed upon time, removed, and examined visually. nearly vertical position, and dry for 48 h in the standard
3.2 Test Method B—The material under test is applied to atmosphere described in Specification D 3924.
glass test tubes by dipping and dried for 72 h. The tubes are 7.2 Place the panels in a beaker containing about 2.5 in. (65
then suspended in dilute sodium hydroxide for periods ranging mm) of water at room temperature, immersing the ends that
from 1 to 24 h, removed, rinsed, and after drying for 30 min, were uppermost during drying, and allow to remain in the
examined visually. water for 18 h, or other suitable period as agreed upon between
4. Significance and Use the purchaser and the seller.
7.3 Remove the panels from the water, wipe carefully, and
4.1 Dried Varnish Films are a source of primary protection
allow to dry at room temperature. Note the time required for
for surfaces. Exposure to water and dilute alkali solutions are whitening, if any, to disappear. Blooming, which sometimes
1
4
Current edition approved April 28, 1989. Published June 1989. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
1
D 1647
occurs on immersion, is considered a type of whitening.
8. Report
8.1 Report the results of the water test as follows:
8.1.1 Not visibly affected,
8.1.2 Whitening disappears within 20 min,
8.1.3 Whitening does not disappear within 20 min, but
disappears within 2 h,
8.1.4 Whitening does not disappear within 2 h, but disap-
pears within 24 h, or
8.1.5 Whitening does not disappear within 24 h.
TEST METHOD B—DILUTE ALKALI RESISTANCE

OF DRIED FILMS
9. Reagent
9.1 Sodium Hydroxide Solution (30 g/L)—Dissolve 30 g of
sodium hydroxide (NaOH) in water and dilute to 1 L.
10. Procedure
10.1 Thoroughly clean and dry twenty 1 by 6-in. (25 by
150-mm) test tubes in toluene. Dip the tubes into the varnish NOTE 1—1 in. 5 25.4 mm.
under test, remove immediately, invert the tubes, and allow the FIG. 1 Apparatus for Alkali Resistance Test
varnish to dry for 726 1 h in the standard atmosphere
described in Specification D 3924. A suggested test schedule to the dowels and the corks fitting into the tubes and the cover
fit into normal working hours is shown in Table 1. plate fitting the beaker as tightly as possible. Maintain the
10.2 Into each of ten 1000-mL, tall-form lipless, chemically NaOH solution at a temperature of 23 6 2°C.
resistant plastic or glass beakers, place 300 mL of the NaOH 10.3 Remove a set of two varnish-coated tubes after immer-
solution. Suspend a set of two varnish-coated tubes in each sion for each of the following time periods: 1, 2, 3, 4, 5, 6, 7,
beaker so that the tubes do not touch the bottom or sides of the 8, 16, and 24 h. Rinse the tubes under a gentle stream of water,
beaker and are immersed for a distance of approximately 2 in. allow to air-dry for 30 min, and examine for film whitening,
(50 mm). As a suspending device (see Fig. 1), use a wooden blistering, or removal. The end point of the test is the number
cover plate and two dowels, and two one-hole cork stoppers, of hours immersion at which the first signs of film whitening,
blistering, or removal are noted on the vertical sides of the
TABLE 1 Suggested Test Schedule tubes or on the spherical bottom portion of the tube. The results
Day Hour Operation
may be compared with those from materials known to give
acceptable performance. For referee work, the test on materials
Monday 8:30 a.m. coat 16 tubes
4:00 p.m. coat 4 tubes
known to be acceptable should be made simultaneously.
dry tubes for 72 h
Thursday 8:30 a.m. start alkali immersion on first 16 tubes 11. Report
9:30 a.m. and each hour remove one set of tubes from alkali, 11.1 Report the results of the alkali test as follows:
thereafter to 4:30 p.m. rinse, and air-dry for 30 min
10:00 a.m. and each examine varnish film on set of tubes 11.1.1 Type of varnish, and
hour thereafter to 5:00 removed 1⁄2 h earlier 11.1.2 End point of the test, h.
p.m.
4:00 p.m. start alkali immersion on last 4 tubes 12. Precision
Friday 8:00 a.m. remove one set of tubes from alkali,
rinse, and air dry for 30 min 12.1 Precision has not been determined due to the multi-
8:30 a.m. examine varnish film on set of tubes plicity of ambient test conditions.
removed and rinsed 1⁄2 h earlier
4:00 p.m. remove last set of tubes, rinse, and
air-dry for 30 min
13. Keywords
4:30 p.m. examine varnish film on last set of 13.1 dilute alkali; dried varnish films; varnishes; water
tubes
resistance
2

Basic Lead Silicochromate Pigment1
1. Scope TABLE 1 Requirements for Pigments
1.1 This specification covers two types of pigment commer- Weight %
cially known as basic lead silicochromate. Type 1 Type 2

Regular Particle Size Fine Particle Size
2. Referenced Documents Min Max Min Max
2.1 ASTM Standards: Lead oxide (PbO) 46.0 49.0 42.5 46.0
Chromium trioxide (CrO3) 5.1 5.7 6.3 7.2
D 1208 Test Methods for Common Properties of Certain Silica (SiO2) 45.5 48.5 47.5 50.5
Pigments2 Moisture and other volatile mat- ... 0.2 ... 0.2
D 1366 Practice for Reporting Particle Size Characteristics ter, % ... 0.2 ... 0.2
Ignition loss at 450 to
of Pigments2 550°C, %
D 1844 Test Methods for Chemical Analysis of Basic Lead
Silicochromate2
E 20 Practice for Particle Size Analysis of Particulate Sub-
stances in the Range of 0.2 to 75 µm by Optical Micros- fineness requirements shall be as agreed upon by the purchaser
copy3 and the seller.
3. Composition and Properties 4. Sampling

3.1 Both types of pigment shall consist of silica coated with 4.1 Two samples shall be taken at random from different
lead silicates and lead chromates and shall conform to the packages from each lot, batch, day’s pack, or other unit of
requirements in Table 1. production in a shipment. When no markings distinguishing
3.2 The mass color and character of the tint obtained by between units of a production appear, samples shall be taken
mixing the pigment with a white pigment shall be the same as from different packages, in the ratio of two samples for each
that of a reference sample mutually agreed upon by the 10 000 lb (5000 kg), except that for shipments of less than
purchaser and the seller. 10 000 lb two samples shall be taken. At the option of the
3.3 The oil absorption shall be equal, within agreed upon purchaser, the samples may be tested separately or after
tolerances, to that of a reference sample agreed upon by the blending in equal quantities the samples from the same
purchaser and the seller. production unit to form a composite sample.
3.4 Particle Size:
5. Test Methods
3.4.1 Type 1—This grade is characterized by major amounts
of particles in the 6.5- to 28-µm range. Coarse particles 5.1 Tests shall be conducted in accordance with the follow-
retained on a 45-µm (No. 325) sieve shall be less than 0.3 %. ing ASTM test methods. Test procedures not covered by ASTM
The maximum specific surface diameter (SSD) shall be 8.5 µm. test methods shall be mutually agreed upon by the purchaser
3.4.2 Type 2—This grade is characterized by major amounts and the seller.
of fine-sized particles. In general, the maximum size is 5.2 Chemical Analysis—Test Methods D 1844.
essentially below 1.0 to 2.5 µm. Coarse particles retained on a 5.3 Ignition Loss—Determine the loss on ignition in accor-
45-µm (No. 325) sieve shall be less than 0.1 %. The maximum dance with the section on Procedure of Test Methods D 1208,
Specific Surface Diameter (SSD) shall be 2.0 µm. but using an ignition temperature of 450 to 550°C.
3.4.3 Where closer control within a grade is required, the 5.4 Particle Size by Microscopic Methods—Procedures for
determining particle size by microscopic methods are de-
scribed in Practice E 20.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.5 Specific Surface Diameter—Practice D 1366.
published as D1648 – 59 T. Last previous edition D1648 – 81.
6.1 basic lead silicochromate (BLSC); chrominium in
2
Annual Book of ASTM Standards, Vol 06.03. BLSC; lead chromate; lead in BLSC; lead oxide; pigment;
3
Annual Book of ASTM Standards, Vol 14.02. silica in BLSC
1
D 1648
2

Strontium Chromate Pigment1
1. Scope percent
1.1 This specification covers the pigment commercially Strontium as SrO, min 48
known as strontium chromate which is suitable for use in the Chromium as CrO3, min 47
manufacture of protective or decorative coatings. Chloride as Cl, max 0.1
Sulfate as SO3, max 0.2
Water content, max 0.2
2. Referenced Documents Coarse particles (total residue retained on No. 1.0
2.1 ASTM Standards: 325 (45-µm) sieve), max
D 387 Test Method for Color and Strength of Color Pig- 3.2 The mass color and character of the tint and tinting
ments with a Mechanical Muller2 strength formed by a mixture with a white pigment shall be
D 1208 Test Methods for Common Properties of Certain within mutually agreed upon limits of a standard acceptable to
Pigments3 both the purchaser and the seller when tested in accordance
D 1845 Test Methods for Chemical Analysis of Strontium with Test Method D 387.
Chromate Pigment3
4. Sampling
3.1 Dry Pigment—The pigment shall be commercially pure packages from each lot, batch, day’s pack, or other unit of
strontium chromate-free of extenders and organic material, production in a shipment. When no markings distinguishing
except for materials introduced to improve those properties for between units of production appear, samples shall be taken
which the pigment is used. The pigment shall conform to the from different packages in the ratio of two samples for each 5
following requirements: tons (inch-pound or SI), except that for shipments of less than
5. Test Methods
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1 Tests shall be conducted in accordance with the appro-
and Related Coatings, Materials, and Applications and is the direct responsibility of priate ASTM test methods. Test procedures not covered by
Subcommittee D01.31 on Pigment Specifications. ASTM test methods shall be mutually agreed upon between the
2
Annual Book of ASTM Standards, Vol 06.01. 5.1.1 Chemical Analysis—Test Methods D 1845.
3
Annual Book of ASTM Standards, Vol 06.03. 5.1.2 Water Content—Test Methods D 1208.
1

Epoxy Content of Epoxy Resins1
1. Scope confirm the stated epoxy content of purchased epoxy resins.

1.1 These test methods cover the quantitative determination 5. Reagents
of the epoxy content of epoxy resins.
1.2 This standard does not purport to address all of the 5.1 Purity of Reagents—Reagent grade chemicals shall be
safety concerns, if any, associated with its use. It is the used in all tests. Unless otherwise indicated, it is intended that
responsibility of the user of this standard to establish appro- all reagents shall conform to the specifications of the Commit-
priate safety and health practices and determine the applica- tee on Analytical Reagents of the American Chemical Society,
bility of regulatory limitations prior to use. For specific hazard where such specifications are available.4 Other grades may be
statements, see Section 6. used, provided it is first ascertained that the reagent is of
2. Referenced Documents accuracy of the determination.
2.1 ASTM Standards: 5.2 Purity of Water—Unless otherwise indicated, references
D 1193 Specification for Reagent Water2 to water shall be understood to mean reagent water as defined
E 200 Practice for Preparation, Standardization, and Stor- by Type II of Specification D 1193.
age of Standard Solutions for Chemical Analysis3
6. Hazards
3. Summary of Test Method 6.1 Hydrogen bromide and glacial acetic acid are corrosive.
3.1 The resin is dissolved in a suitable solvent and the Chlorobenzene and chloroform are considered hazardous. In
resulting solution is titrated with hydrogen bromide either addition to other precautions, take care to avoid inhalation and
directly or in situ. The hydrogen bromide reacts stoichiometri- skin or eye contact with these chemicals. Use goggles or a face
cally with epoxy groups to form bromohydrins; therefore, the shield, or both. Protect skin by use of suitable protective
quantity of acid consumed is a measure of the epoxy content. clothing. All specimen preparations shall be done in a well
3.1.1 In Test Method A, the titration is direct with a standard ventilated area, such as a fume hood.
solution of hydrogen bromide in glacial acetic acid.
TEST METHOD A
3.1.2 In Test Method B, the titration is with standard
perchloric acid in the presence of an excess of tetraethylam- 7. Apparatus
monium bromide. Hydrogen bromide generated in situ by the 7.1 Buret, closed-reservoir type. The buret tip should be
addition of perchloric acid to the quaternary ammonium halide fitted with a rubber stopper of proper size to fit the neck of the
rapidly opens the oxirane ring. Erlenmeyer flask and the stopper should have an additional
4. Significance and Use small hole to permit escape of replaced air during titration.
7.2 Magnetic Stirrer, adjustable speed.
4.1 The epoxy content of epoxy resins is an important
7.3 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE)
variable in determining their reactivity and the properties of
coated.
coatings made from them. These test methods may be used to
determine the epoxy content of manufactured epoxy resins and 8. Reagents and Materials
8.1 Chlorobenzene (Warning—See Section 6).
1
4
Current edition approved June 10, 1997. Published October 1997. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1652 – 59 T. Last previous edition D 1652 – 90 (1996). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1652
8.2 Chloroform-Chlorobenzene Mixture (1+1) (Warning— B 5 HBr solution used for titration of the blank, mL, and
See Section 6). W 5 specimen used, g.
8.3 Crystal Violet Indicator Solution—Prepare a 0.1 % so- 10.3 Calculate the percent of oxirane oxygen, O, as follows:
lution of crystal violet in glacial acetic acid. O 5 1.6N~V – B!/W (3)
8.4 Glacial Acetic Acid (Warning—See Section 6).
8.5 Hydrogen Bromide (HBr), anhydrous (Warning—See 10.4 Calculate the weight per epoxy equivalent, WPE, that
Section 6). is, grams of resin containing 1 g equivalent of epoxy groups, as
8.6 Potassium Acid Phthalate (KHC8H4O4)—Primary Stan- follows:
dard grade. WPE 5 1000W/N~V– B! (4)
8.7 Hydrogen Bromide in Acetic Acid, Standard Solu- 11. Precision
tion (0.1 N) (Warning—See Section 6)—Prepare by bubbling
anhydrous HBr at a slow rate through glacial acetic acid until 11.1 Repeatability—The difference between two results ob-
the desired normality is attained (approximately 8 g of HBr/L). tained by the same analyst will approximate 0.7 % of the epoxy
Standardize each day used against 0.4 g of potassium acid content of the resin tested. Two such values should be
phthalate (KHC8H4O4) accurately weighed and dissolved by considered suspect if they differ by more than 2 % absolute.
gently heating in 10 mL of glacial acetic acid. 11.2 Reproducibility—The difference between two results,
each the mean of two determinations, obtained by analysts in
NOTE 1—Reagent of 0.1 N concentration has been specified. As different laboratories, will approximate 2 % of the epoxy
solutions exceed this concentration they became progressively less stable
content of the resin tested. Two such values should be
(for further information see Practice E 200).
considered suspect if they differ by more than 6 % absolute.
9. Procedure TEST METHOD B
9.1 Use a quantity of specimen that contains 0.001 to
0.002-g equivalents of epoxy groups. Weigh the appropriate 12. Apparatus
amount, to within 1 mg, into an Erlenmeyer flask. Use a 50-mL 12.1 Buret, closed-reservoir type, bottom filling, 25 mL with
1⁄10-mL division, or potentiometric automatic titrator.
flask for low-molecular-weight resins (liquid grades) and a
125-mL flask for high-molecular-weight resins (solid grades). 12.2 Erlenmeyer Flasks, 100-mL, 250-mL, and 500-mL.
9.2 Dissolve the specimen in a solvent at room temperature. 12.3 Magnetic Stirrer, adjustable speed.
Use 10 mL of chlorobenzene for liquid grade resins or 25 mL 12.4 Magnetic Stirring Bars, polytetrafluoroethylene
of a 1+1 mixture of chloroform and chlorobenzene for solid (PTFE) coated.
grade resins. Place a magnetic stirring bar into the flask and 12.5 Pipets:
mix on the magnetic stirrer to dissolve. 12.5.1 Measuring Pipet, 25-mL.
9.3 Add 4 to 6 drops of crystal violet indicator solution and 12.5.2 Volumetric Pipet, 50-mL.
attach the flask to the rubber stopper on the buret tip. Lower the 12.6 Volumetric Flask, 1 L.
buret tip to a point just above the solution and titrate with the 12.7 Bottle, 2 oz wide-mouth, or 100-mL disposable beaker,
hydrogen bromide in acetic acid solution to a blue-green end or equivalent.
point with the magnetic stirrer rotating at a moderate speed to 13. Reagents
avoid splashing. Slow down the titration near the end point to
allow ample time for the reaction to take place. Titrate, as 13.1 Glacial Acetic Acid (Warning—See Section 6).
nearly as possible, to the same color at the end point as that 13.2 Tetraethylammonium Bromide, anhydrous crystals.
obtained during standardization of the reagent. 13.3 Perchloric Acid (HClO4), 60 % (Warning—See Sec-
9.4 Make a blank determination on the reagents in an tion 6).
identical manner. 13.4 Acetic Anhydride (Warning—See Section 6).
13.5 Methylene Chloride (Warning—See Section 6).
10. Calculation 13.6 Crystal Violet Indicator, crystals.
13.7 Potassium Acid Phthalate—(KHC8H4O4) primary
10.1 Calculate the normality, N, of the HBr acetic acid as standard grade.
follows: 13.8 Diglycidyl Ether of Bisphenol-A.
N 5 ~W 3 1000!/~204.2 3 V! (1)
14. Reagent Preparation
where: 14.1 Perchloric Acid (0.1 N Solution in Glacial Acetic
W 5 KHC8H4O4 used, g, and Acid) (Warning—See Section 6)—Prepare in the following
V 5 HBr solution used, mL. manner and sequence in order to avoid an excessive rise in
10.2 Calculate the epoxy content, E, in gram equivalents of temperature.
epoxy groups per 100 g of resin as follows: 14.1.1 Place approximately 250 mL of glacial acetic acid
E 5 N~V – B!/10 3 W (2) into a 1 L volumetric flask. Add 13 mL of 60 % perchloric acid
and mix. Add 50 mL of acetic anhydride, dilute to the mark
where: with glacial acetic acid, and mix thoroughly.
N 5 normality of the HBr in acetic acid, 14.1.2 Allow to stand at least 8 h for completion of reaction
V 5 HBr solution used for titration of the specimen, mL,
between the acetic anhydride and water. A shorter time period
2
D 1652
may be used if completion of the reaction is analytically 16. Procedure
verified. 16.1 Weigh the required amount of specimen into a 2-oz
14.2 Tetraethylammonium Bromide Solution in Glacial Ace- disposable glass bottle or plastic beaker. The amount ofspeci-
tic Acid (Warning—See Section 6): men weight used is dependent on the expected epoxide
14.2.1 Dissolve, with agitation at room temperature, 100 g equivalent weight (EEW) as follows:
of tetraethylammonium bromide in 400 mL of glacial acetic EEW Approximate Specimen Size, g
acid. 170–375 0.4
375–600 0.6
14.3 Crystal Violet Indicator Solution—Prepare 0.1 % solu-
600–1000 0.8
tion of crystal violet indicator in glacial acetic acid 1000–1500 1.3
(Warnings—See Section 6). 1500–2000 1.8
2000–2500 2.3
2500–5000 2.8
15. Standardization of 0.1 N Perchloric Acid Reagent
16.2 Add 10 to 15 mL of methylene chloride to the
15.1 Procedure A—Standardization with Potassium Acid
specimen. Insert a clean stirring bar and adjust the magnetic
Phthalate:
stirrer to effect solution. Continue agitation through the titra-
15.1.1 Dissolve, by gentle heating, 0.4 g of potassium acid
tion procedure.
phthalate, weighed accurately to the nearest milligram, in 50
16.3 Add 10 mL of tetraethylammonium bromide reagent
mL of glacial acetic acid, and add 6 to 8 drops of crystal violet
and 6 to 8 drops of crystal violet indicator solution. Titrate with
indicator solution. Insert a clean stirring bar into the sample,
0.1 N perchloric acid reagent to a sharp blue to green end point
and adjust the magnetic stirrer to effect solution. Continue
which is stable for at least 30 s. Record the volume of
agitation throughout the titration procedure. Titrate with per-
perchloric acid reagent used to titrate the specimen.
chloric acid reagent solution to the end point which is a sharp
change in color from blue to green, stablilize for at least 2 min. 17. Calculation
15.1.2 Calculate and record the perchloric acid reagent
17.1 If 15.1 is used for standardization, calculate weight
normality as follows:
percent epoxide, E, as follows:
N 5 ~W 3 1000!/~204.23 V! (5)
E 5 4.3 3 V 3 N/W (7)
where: 17.2 If 15.2 is used for standardization, calculate weight
N 5 normality of perchloric acid reagent, percent epoxide, E, as follows:
W 5 potassium acid phthalate used, g, and
E 5 F 3 V/We (8)
V 5 volume of perchloric acid reagent required to titrate
the standard, mL. where:
15.2 Procedure B—Standardization with Diglycidyl Ether of We 5 weight of epoxy resin specimen used, g.
Bisphenol-A (DGEBA): 17.3 Calculate the epoxy equivalent weight, WEEW, as
15.2.1 Dissolve 0.25 to 0.40 g of the DGEBA accurately follows:
weighed to the nearest milligram into a 2 oz wide-mouth bottle WEEW 5 43 3 100/E (9)
or 100 mL disposable beaker. Add 10 to 15 mL of methylene
chloride. Insert a clean stirring bar into the sample and adjust where 43 5 mol weight of the epoxy ring.
the magnetic stirrer to effect solution. Continue agitation 17.4 Calculate weight percent of oxirane oxygen, O, as
throughout the titration procedure. follows:
15.2.2 Add 10 mL of tetraethylammonium bromide reagent O 5 16/43 3 E 5 1.6 3 V 3 N/W (10)
and 6 to 8 drops of crystal violet indicator solution and titrate
18. Precision
to a sharp blue-to-green end point with the perchloric acid
reagent solution. The end point should be stable for at least 30 18.1 A liquid epoxy resin sample with approximately
s. 24.1 % epoxide was tested by seven laboratories where ten
15.2.3 Calculate and record the perchloric acid reagent analysts obtained the following results:
factor, F, as follows: 18.1.1 Repeatability—The difference between two results
obtained by the same analyst should not vary by more than
F 5 ~Wd 3 E!/V (6)
1.22 % relative.
where: 18.1.2 Reproducibility—The difference between two re-
Wd 5 diglycidyl ether of bisphenol-A standard used, g, sults, each the mean of two determinations obtained by
E 5 epoxide of the standard used (normally 25.19), analysts in different laboratories should not vary by more than
weight % 2.97 % relative.
The perchloric acid should be standardized initially by
Procedure A and thereafter at least twice per week by Proce- 19. Keywords
dure A or B. Temperature of the reagent solution must be kept 19.1 epoxide equivalent weight (EEW); liquid epoxy resin;
at 25 6 2°C (77 6 3°F). (For further information see Practice oxirane; weight percent epoxide; weight per epoxy equivalent
E 200.) (WPE)
3
D 1652
4

Traces of Thiophene in Benzene by Spectrophotometry1
1. Scope * 2.2 Other Document:

1.1 This test method covers the determination of thiophene OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
in benzene in which the thiophene concentration is between 0.1 1910.12005
and 250 mg/kg.
3. Terminology
1.2 Contaminating materials that are darkened by sulfuric
acid interfere and must be compensated for by a sample blank 3.1 Definitions:
determination. Neither carbon disulfide in concentrations as 3.1.1 For definition of terms used in this test method see
high as 100 mg/kg nor water as high as the level of saturation Terminology D 4790.
will interfere. 4. Summary of Test Method
1.3 Contaminating materials may occasionally cause the
color development in this test method to be time dependent and 4.1 Thiophene is reacted with isatin, under prescribed con-
may also contribute to spectral interferences at 589 nm. ditions, to form a colored compound. The compound is
Consequently, test results indicating substantial thiophene, that extracted into sulfuric acid, and the intensity of the color is
cannot be verified by total sulfur analysis, should be considered measured spectrophotometrically. Thiophene concentration is
suspect. obtained by correlation with knowns.
1.4 The following applies to all specified limits in this test 5. Significance and Use
method: for purposes of determining conformance with this
test method, an observed value or a calculated value shall be 5.1 This test method is suitable for setting specifications on
round off “to the nearest unit” in the last right-hand digit used benzene and for use as an internal quality control tool where
in expressing the specification limit, in accordance with the benzene is either produced or used in a manufacturing process.
round-off method of Practice E 29. It may also be used in development or research work involving
1.5 This standard does not purport to address all of the benzene.
safety concerns, if any, associated with its use. It is the 6. Apparatus
priate safety and health practices and determine the applica- 6.1 Separatory Funnels, 50, 250, 500, and 1000-mL, with
bility of regulatory limitations prior to use. For specific hazard glass stoppers.
statements, see Note 1, 8.1, and 9.1. 6.2 Spectrophotometer—Any spectrophotometer may be
used that is capable of repeatability of 0.005 absorbance units
2. Referenced Documents in the range from 0.1 to 1.4 absorbance and repeatability of
2.1 ASTM Standards: wavelength of 1 nm in the region from 400 to 700 nm.
D 1193 Specification for Reagent Water2 6.3 Absorption Cells, 1-cm, matched, glass or silica.
D 3437 Practice for Sampling and Handling Liquid Cyclic 6.4 Analytical Balance.
Products3 6.5 Pipets, 1, 2, 5, and 10-mL.
D 4790 Terminology of Aromatic Hydrocarbons and Re- 6.6 Graduated Cylinders, 250 and 1000-mL.
lated Chemicals3 6.7 Volumetric Flasks, glass-stoppered, 50, 100, 250, and
E 29 Practice for Using Significant Digits in Test Data to 1000-mL.
Determine Conformance with Specifications4 6.8 Filter Paper, medium filter6 and rapid hardened.7
7. Reagents
1
This test method is under the jurisdiction of ASTM Committee D-16 on 7.1 Purity of Reagents—Reagent grade chemicals shall be
Subcommittee D16.0A on Benzene, Toluene, Xylene, Cyclohexane, and Their
Derivatives.
5
published as D 1685 – 58 T. Last previous edition D 1685 – 95. Available from Superintendent of Documents, U.S. Government Printing
2
3 6
Annual Book of ASTM Standards, Vol 06.04. This method is based on the use of Whatman 1.
4 7
Annual Book of ASTM Standards, Vol 14.02. This method is based on the use of Whatman 54.

1
D 1685
all reagents shall conform to the specifications of the Commit- adhere to all safety precautions as outlined in the latest OSHA
tee on Analytical Reagents of the American Chemical Society, regulations. Refer to Practice D 3437 for proper sampling and
where such specifications are available.8 Other grades may be handling of benzene.
sufficiently high purity to permit its use without lessening the 10. Preparation of Reagent Blanks and Sample Blank
accuracy of the determination. 10.1 Reagent Blank 1—To a 50-mL separatory funnel pipet
7.2 Purity of Water—Unless otherwise indicated, references 5 mL of isatin solution and 10 mL of ferric sulfate-sulfuric acid
to water shall be understood to mean Type IV reagent water solution. Stopper and shake for 2 min 6 15 s. The shaking is
conforming to Specification D 1193. accomplished by wrist action in a rocking motion through a
7.3 Cadmium Chloride Solution (20 g/L)—Dissolve 20 g of 180° arc roughly once each second. Allow the two phases to
anhydrous cadmium chloride (CdCl 2) or 25 g of cadmium separate and draw off the lower H2SO 4 layer into a 50-mL
chloride hydrate (CdCl2·2|n$ H2O) in 200 mL of water and volumetric flask. Add 10 mL of H2SO 4 to the separatory
dilute to 1 L. funnel, stopper, and shake for 30 6 5 s. Again draw off the
7.4 Sulfuric Acid (sp gr 1.84)—Concentrated H2SO4. lower H2SO4 layer into the 50-mL volumetric flask containing
7.5 Benzene, Thiophene-Free: the first extract. Dilute to volume with H 2SO4 and mix. This
7.5.1 Wash 700 mL of benzene in a 1000-mL separatory blank is stable for 8 h and need not be repeated with each
funnel with successive 100-mL portions of concentrated sul- analysis during this period.
furic acid (H 2SO4) to which has been added 5 mL of isatin 10.2 Reagent Blank 2—Into a 50-mL volumetric flask, pipet
solution, until the H2SO4 layer is light yellow or colorless. 10 mL of ferric sulfate-sulfuric acid solution and dilute to
Wash the benzene with 100 mL of water and then twice with volume with H2SO4. Stopper and mix. This blank is stable for
100 mL of cadmium chloride solution (CdCl2). Finally, wash 8 h and need not be repeated with each analysis during this
with another 100-mL portion of water. Filter the benzene period.
through medium filter paper into a storage bottle and tightly 10.3 Sample Blank—Take a 100-mL portion of the CdCl2
stopper. washed and filtered benzene sample (prepared in accordance
7.5.2 Prepare 1400 mL of thiophene-free benzene. Measure with the procedure in 12.1). Transfer to a 250-mL separatory
the absorbance of this material by the procedure outlined in funnel. Add 10 mL of ferric sulfate-sulfuric acid solution,
11.2 and 12.2. The absorbance should be no greater than 0.01. stopper, and shake for 2 min 6 15 s. Allow the two phases to
7.6 Ferric Sulfate, Sulfuric Acid Solution—Add 0.2 g of separate and draw off the lower H2SO4 layer into a 50-mL
ferric sulfate (Fe2(SO4)3·9H 2O) together with 38 mL of water volumetric flask. Add 10 mL of H2SO4 to the separatory funnel
to a 1-L volumetric flask. Swirl to dissolve. Cautiously add and shake for 30 6 5 s. Again draw off the lower H2SO4 layer
about 100 mL of H2SO4 and swirl. Allow time for the heat of into the 50-mL volumetric flask containing the first extract.
reaction to subside and dilute to volume with H 2SO4. Dilute to volume and mix. Repeat with each specimen.
NOTE 1—Precaution: Protective clothing and goggles should be worn 11. Preparation of Calibration Curves
whenever H2SO 4 is used.
11.1 Add approximately 0.2 g of thiophene, weighed to the
7.7 Isatin, Chloroform, Benzene Solution—Add 0.5 g of nearest 0.0002 g to a 100-mL volumetric flask containing about
isatin to 200 mL of chloroform. Heat, in a fume hood, to a 50 mL of thiophene-free benzene. Dilute to volume with
temperature just below the boiling point (61°C) of chloroform thiophene-free benzene and mix. This is Solution 1. Pipet 1 mL
and maintain for 5 min with stirring. Filter into a 250-mL of Solution 1 into a 100-mL volumetric flask, dilute to volume
volumetric flask through hardened rapid filter paper. Wash the with thiophene-free benzene, stopper, and mix. This is Solution
filter paper with two 20-mL portions of thiophene-free benzene 2 and will contain approximately 20 µg of thiophene per
(from 7.5) eluting the washings into the volumetric flask. millilitre.
Dilute to volume with thiophene-free benzene. 11.2 Pipet 0, 1, 2, 5, 7, and 10-mL of Solution 2 into 100-mL
7.8 Thiophene.9 volumetric flasks and dilute to volume with thiophene-free
8. Hazards benzene. Transfer to 500-mL separatory funnels and follow the
procedure in 12.2 and 12.3 for each concentration. Plot
8.1 Consult current OSHA regulations and supplier’s Mate-
absorbance versus concentration in micrograms per millilitre.
rial Safety Data Sheets for all materials used in this test
11.3 Prepare Solution 3 containing approximately 40 µg of
method.
thiophene per millilitre by pipetting 2 mL of Solution 1 into a
9. Sampling 100-mL volumetric flask and diluting to volume with
9.1 Sampling of benzene should follow safe rules in order to thiophene-free benzene. Follow the procedure in 11.2 to obtain
the calibration curve for 50-mL specimens.
8
Reagent Chemicals, American Chemical Society Specifications, American 12. Procedure
listed by the American Chemical Society, see Analar Standards for Laboratory 12.1 To a 500-mL separatory funnel, add 250 mL of sample
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and 40 mL of cadmium chloride solution. Stopper and shake
MD.
for approximately 30 s. Allow to settle and discard the aqueous
9
Thiophene such as Eastman Catalog No. 1860 or equivalent has been found layer. Filter the benzene layer through medium filter paper into
satisfactory for this purpose. a 250-mL graduated cylinder. Part of the filtered benzene is to
2
D 1685
TABLE 1 Calculation Factors
Designation of Cell Solutions
Equation of
Section 12 Solution of Sample Versus Solution of Reference
A H2SO4·Fe2(SO4)3; isatin after contact with sample, reagent blank 1 (see 10.1)
(see 12.2)
B sample blank (see 10.3) reagent blank 2 (see 10.2)
be used for the sample blank. Proceed with preparation of the B 5 apparent thiophene determined for sample blank from
sample blank as described in 10.3. From the remaining filtered appropriate calibration curve (see Table 1), µg/mL,
benzene, transfer 100 mL to 250-mL separatory funnel. F 5 dilution factor of sample, and
12.2 To the separatory funnel add 5 mL of isatin solution d 5 density of benzene at the temperature of the sample.
and 10 mL of ferric sulfate-sulfuric acid solution. Stopper and
shake for 2 min 6 15 s. Allow the phases to separate and draw 14. Precision and Bias
off the lower H 2SO4 layer into a 50-mL volumetric flask. Add 14.1 The data given in Table 2 should be used for judging
10 mL of H 2SO4 to the separatory funnel, stopper, and shake the acceptability of results (95 % probability).
for 306 5 s. Again draw off the lower H2SO4 layer into the
50-mL volumetric flask containing the first extract. Dilute to NOTE 2—The precision limits given in Table 2 are based on data
published as Appendix III to Report of Committee D-16, ASTM Proceed-
volume with H2SO4 and mix. ings, Am. Soc. Testing Mats., Vol 59, 1959, p. 514.
12.3 Measure the absorbance of this material at 589 nm in a
1-cm cell versus Reagent Blank 1 (10.1) in a matched 1-cm
cell. Instrument conditions should be identical with those TABLE 2 Precision Limits
employed during calibration. Thiophene
Repeatability, Reproducibility,
12.4 Determine the concentration of thiophene from the Concentration,
Percent of Value Percent of Value
Range, mg/kg
calibration curve (Section 11). If the absorbance is greater than
1.5, repeat the procedure using a 50-mL specimen instead of 100 to 250 11.4 15
20 to 100 12.3 19
100 mL. If the 50-mL specimen still gives absorbance above 2 to 20 13.8 21
1.5, then the specimen must be diluted with thiophene-free 0.4 to 2 14.0 25
benzene before proceeding. less than 0.4 less than 0.06 mg/kg less than 0.15 mg/kg
12.5 Determine the absorbance of the sample blank (10.3) at

589 nm using Reagent Blank 2 (10.2) as reference. Determine
the apparent concentration of thiophene in the sample blank. 14.2 Repeatability is based on test results obtained by
repetitive testing of a homogeneous sample by a single
13. Calculation operator. Reproducibility is based on test results obtained by
13.1 Calculate the thiophene content of the sample in repetitive testing of different samples in different laboratories
milligrams per kilogram as follows: and different operators.
Thiophene, mg/kg 5 ~A 2 B!F/d 14.3 Bias—The bias of this test method has not been
determined.
where:
A 5 thiophene for sample determined from appropriate 15. Keywords
calibration curve (see Table 1), µg/mL,
15.1 benzene; spectrophotometry; thiophene
SUMMARY OF CHANGES
(1) Terminology D 4790 was added to Referenced Documents (2) Added section on Terminology.
section.
3
D 1685
4

Color of Solid Aromatic Hydrocarbons and Related Materials
in the Molten State (Platinum-Cobalt Scale)1
1. Scope This test method is suitable for setting specifications and for
1.1 This test method covers the visual measurement of the use as an internal quality control tool.
color of thermally stable solids melting below 150°C. It is 4. Apparatus
applicable only to materials in which the color-producing
bodies present have light absorption characteristics quite simi- 4.1 Color Comparison Tubes—Matched 100-mL, tall-form
lar to those of the standards used. Nessler tubes, provided with ground-on, optically clear, glass
1.2 The following applies to all specified limits in this test caps. Tubes should be selected so that the height of the 100-mL
method: for purposes of determining conformance with this graduation mark is 300 6 3 mm above the bottom of the tube.
test method, an observed value or a calculated value shall be The use of heat-resistant tubes is preferred for safety reasons.
rounded off “to the nearest unit” in the last right-hand digit 4.2 Color Comparator—A color comparator constructed to
used in expressing the specification limit, in accordance with permit visual comparison of light transmitted through tall-
the rounding-off method of Practice E 29. form, 100-mL Nessler tubes in the direction of their longitu-
1.3 This standard does not purport to address all of the dinal axes. The comparator should be constructed so that white
safety concerns, if any, associated with its use. It is the light is reflected off a white plate and directed with equal
responsibility of the user of this standard to establish appro- intensity through the tubes, and should be shielded so that no
priate safety and health practices and determine the applica- light enters the tubes from the side.
bility of regulatory limitations prior to use. For specific hazard 4.3 Oven—An oven, preferably of the forced draft type and
statements see Sections 7 and 9. capable of maintaining a constant temperature 61°C in the
range up to 150°C. Alternatively, the use of an aluminum
2. Referenced Documents heating block provided with proper temperature control or
2.1 ASTM Standards: other similar equipment is permissible.
D 1193 Specification for Reagent Water2 5. Reagents
D 3438 Practice for Sampling and Handling Naphthalene,
Maleic Anhydride, and Phthalic Anhydride3 5.1 Purity of Reagents—Reagent grade chemicals shall be
D 3852 Practice for Sampling and Handling Phenol and used in all tests. Unless otherwise indicated, it is intended that
Cresylic Acid3 all reagents shall conform to the specifications of the Commit-
E 29 Practice for Using Significant Digits in Test Data to tee on Analytical Reagents of the American Chemical Society,
Determine Conformance with Specifications4 where such specifications are available.6 Other grades may be
2.2 Other Document: used, provided it is first ascertained that the reagent is of
OSHA Regulations, 29 CFR, paragraphs 1910.1000 and sufficiently high purity to permit its use without lessening the
1910.12005 accuracy of the determination.
3. Significance and Use to water shall be understood to mean Type IV reagent water
3.1 Color by this test method is a measure of color- conforming to Specification D 1193.
producing impurities present in the thermally stable solids. 5.3 Cobalt Chloride (CoCl2·6H2O).
1
chloric acid (HCl).
This test method is under the jurisdiction of ASTM Committee D16 on
5.5 Potassium Chloroplatinate (K2PtCl6).
Subcommittee D16.0C on Oxygenated Aromatics.
Current edition approved Jan. 10, 1996. Published March 1996. Originally
6
published as D 1686 – 59 T. Last previous edition D 1686 – 95. Reagent Chemicals, American Chemical Society Specifications, American
2
3
4
5
Available from Superintendent of Documents, U.S. Government Printing and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Office, Washington, DC 20402. MD.
1
D 1686
6. Standards and cap the tube. Place the tube in the comparator and
6.1 Platinum-Cobalt Stock Solution— Dissolve 1.245 g of immediately compare with the standards.
K2PtCl6 and 1.000 g of CoCl 2·6H2O in water. Add 100 mL of NOTE 1—A variation of more than 2 to 3 mm in depth can affect the test
HCl and dilute to 1 L with water. This solution has a color of results.
500.7 9.3 When measuring the color of solids that sublime, some
difficulty may be encountered due to condensation of solid on
TABLE 1 Platinum-Cobalt Color StandardsA the cap. In such a case, the Nessler tube may be reheated in the
Color Stock Color Stock oven after first loosening the cap, or, the color may be
Standard Solution, Standard Solution, measured using an open Nessler tube without a cap (Warning,
No. mL No. mL see 9.3.1). In this latter case the caps should also be removed
5 1 35 7 from the standards.
10 2 40 8
15 3 50 10
9.3.1 Warning: Make sure to provide adequate ventilation
20 4 60 12 if open tubes are used.
25 5 70 14 9.4 In no case shall this test method be applied if the molten
30 6 100 20
sample contains any visible turbidity.
A
Other color standards may be prepared by proportional dilution.
10. Report
10.1 Report as the color, the number of the standard that
6.2 Platinum-Cobalt Standards8—From the stock solution,
most nearly matches the sample. In the event that the color lies
prepare color standards, as given in Table 1, by diluting the
midway between two standards, report the darker of the two.
required volumes to 100 mL with water in the Nessler tubes. If
10.2 If, owing to small differences in hue between the
desired, these standards may be made permanent by sealing on
sample and the standards, an exact match cannot be obtained,
the caps with a suitable colorless cement.
but an estimate is possible, report the range over which an
7. Hazards approximate match is obtained, and report the sample as “off
hue.”
7.1 Consult OSHA regulations, supplier’s Material Safety
10.3 If, owing to large differences in hue between the
Data Sheets, and local regulations for all materials used in this
sample and the standards, no estimate is possible, report the
test method.
sample as “no match.”
7.2 Warning: When handling molten solids in open tubes,
adequate ventilation must be provided and proper protection 11. Precision and Bias
should be used to prevent thermal burns. 11.1 Intermediate Precision (formerly called
Repeatability)—Results in the same laboratory should not be
8. Sampling considered suspect unless they differ by more than the follow-
8.1 Sample the material in accordance with Practices ing amounts:
D 3438 or D 3852. Platinum-Cobalt Color Intermediate Precision
9. Procedure Under No. 50 2.5

No. 50 to No. 100 5
9.1 Melt approximately 150 g of the sample and simulta- Over No. 100 10
neously preheat a Nessler tube and cap in an oven maintained 11.2 Reproducibility—Results submitted by two laborato-
at constant temperature at 10 to 20°C above the solidification ries should not be considered suspect unless they differ by
point of the sample. The sample must not be heated to more more than the following amounts:
than 20°C above its solidification point.
Platinum-Cobalt Color Reproducibility
9.2 As soon as the sample is completely liquid, mix by
stirring with a clean dry glass rod, then quickly fill the Under No. 50 5
preheated Nessler tube to the 100-mL mark with the sample No. 50 to No. 100 10
Over No. 100 15
11.3 Bias—Since there is no accepted reference material

7
The stock solution with color No. 500 may be purchased as such from chemical suitable for determining the bias for the procedure in this test
supply firms. Use of the purchased standard is satisfactory.
8
method, bias has not been determined.
The preparation of these platinum-cobalt standards was originally described by
A. Hazen, American Chemical Journal, Vol 14, p. 300 (1892). The description given 12. Keywords
in Test Method D 1686 is identical with that given in the “Standard Methods for the
Examination of Water and Sewage,” American Public Health Assn., Tenth Edition,
12.1 color; cresylic acid; maleic anhydride; naphthalene;
1955, p. 88. A description is also given by W. W. Scott, “Standard Methods of phenol; phthalic anhydride; platinum-cobalt; solid aromatic
Chemical Analysis,” D. Van Nostrand Co., Inc., Fifth Ed., Vol 2, p. 2048. hydrocarbons
2
D 1686
3
Standard Terminology of
Cellulose and Cellulose Derivatives1
1. Scope arabinomethylglucuronoxylan—a hemicellulose containing

1.1 This terminology standard contains terms, definition of arabinose, 4-O-methylglucuronic acid, and xylose groups in
terms, descriptions of terms, nomenclature, and explanations of its structure.
acronyms and symbols specifically associated with standards beta-cellulose—(1) Historically, a term used to indicate impu-
under the jurisdiction of ASTM Committee D-1 on Paint and rities of moderate chain lengths found in pulps, predomi-
Related Coatings, Materials, and Applications; Subcommittee nately degraded cellulose. (2) Beta-cellulose content, as
D01.36 on Cellulose and Cellulose Derivatives. measured by TAPPI Method T 203 om-93, is the pulp
1.2 This terminology is divided into three classes as fol- fraction soluble in caustic, which precipitates upon acidifi-
lows: cation.
Section
carbohydrates not cellulose—the noncellulosic carbohy-
Cellulosic Materials and Constituents 3 drates of a cellulosic material.
Chemical Modifications and Derivatives of Cellulose 4 cellophane pulps—pulps used in the manufacture of cello-
Properties of Cellulose and Associated Concepts that are
applicable to both Sections 3 and 4 5
phane, and subject to various specifications by the manufac-
turers, including those of purity, moisture content, sheet
2. Referenced Documents properties, and viscosity.
2.1 The numerous ASTM Standards to which this standard cellulose—(1) the main solid constituent of woody plants; it
applies are found in the Annual Book of ASTM Standards, Vol occurs widely elsewhere in the vegetable kingdom, and to a
06.03. small extent in the animal kingdom. (2) chemically, cellulose
2.2 TAPPI Method T 203 om-932 is b-1-4 glucan of high degree of polymerization. It is
desirable to apply “cellulose” to this material only and to
3. Cellulosic Materials and Constituents designate the predominantly cellulosic residue obtained by
acetylation pulps—pulps used in the manufacture of cellulose subjecting woody tissues to various pulping processes as
acetate or other esters, and subject to various specifications “cellulosic residues,” “cellulosic pulps,” or the like.
by the manufacturers, including those of purity, moisture cellulose I—the crystalline modification of cellulose that
content, sheet properties, and viscosity. normally occurs in nature.
alpha-cellulose—(1) Historically, a term used to indicate the cellulose II—the crystalline modification of cellulose that is
pure, relative undegraded cellulose found in pulps. (2) found in mercerized cellulose, in regenerated cellulose, and
Alpha-cellulose content is often measured by TAPPI Method in cellulose produced by the hydrolysis of various cellulose
T 203 om-93 where alpha-cellulose is that portion of the derivatives.
pulp which does not dissolve under the test conditions. cellulose III—a crystalline modification of cellulose produced
alpha pulps—see chemical cellulose. by treatment, under certain conditions, with ammonia or
araban—a pentosan yielding essentially only arabinose on sometimes by amines. The method of removing the reagent
hydrolysis. determines the modification produced.
arabinogalactan—a polysaccharide consisting of arabinose cellulose IV—a crystalline modification of cellulose produced
and galactose units, like the water-soluble polysaccharide of by heat treatment of cellulose II.
larch. cellulose X—a crystalline modification of cellulose produced
arabinose—a pentose that occurs as one of the sugar units in by treatment of cellulose with strong hydrochloric acid or
some hemicelluloses. phosphoric acid.
cellulose, purified cotton—see cotton cellulose, purified.
1
cellulose, purified wood—see wood cellulose, purified.
This terminology is under the jurisdiction of ASTM Committee D-1 on Paint
chemical cellulose—a chemically purified cellulosic material
Subcommittee D01.36 on Cellulose and Cellulose Derivatives. that is intended for chemical treatment to produce deriva-
Current edition approved Nov. 10, 1996. Published Janury 1997. Originally tives.
published as D 1695 – 59 T. Last previous edition D 1695 – 77 (1989)e1. chemical cotton—chemical cellulose prepared from cotton;
2
Technical Association of Pulp and Paper Industry, Technology Park/Atlanta
P.O. Box 105113, Atlanta, GA 30348. generally, but not necessarily, cotton linters.
1
D 1695
chemical pulps—in the paper industry, pulps produced by to a limited extent as a fibrous raw material for special
chemical processes, as contrasted to those produced by papers. The principal use, however, is for chemical cellulose,
mechanical processes. (see also chemical wood pulp). that is, as the raw material for the manufacture of cellulose
chemical wood pulp—a term used in the paper industry for derivatives.
pulps obtained by digestion of wood with solutions of mannan—strictly, a polysaccharide composed entirely of
various chemicals. mannose units, but used conventionally to distinguish the
DISCUSSION—This term, which refers to pulp produced and purified
hexosan wood hemicelluloses from the pentosans (xylan).
by chemical processes, should not be confused with chemical cellulose (see also galactoglucomannan and glucomannan)
which refers to pulp that is to be used in chemical processes. mannogalactan—see galactomannan.
methylglucuronoxylan—the main hemicellulose of hardwood
cotton cellulose, purified—chemical cellulose from cotton pulps; a polysaccharide containing xylose and 4-O-
fiber or linters. (see also chemical cotton) methylglucuronic acid groups. In the wood it is partially
cotton linters—see linters. acetylated.
dissolving pulps—see pulps, dissolving. nitrating pulps—pulps used for the manufacture of cellulose
extractives—compounds occurring in plant materials, but not nitrate and subject to various specifications by the manufac-
forming part of the structural elements, that are removed turers, including those of alpha-cellulose content and viscos-
with neutral solvents such as ether, alcohol, and water. ity.
galactan—a polysaccharide composed essentially of galactose oligosaccharides—polymeric carbohydrates containing rela-
units. (see also arabinogalactan) tively few (compared to the polysaccharides) sugar units
galactoglucomannan—one of the hemicelluloses of soft- connected by glycosidal linkages. Two to nine units has been
woods, containing three types of sugar units—galactose, suggested as a suitable range. For longer chains the polymers
glucose, and mannose. cannot be readily separated into individual molecular spe-
galactomannan—a polysaccharide containing galactose and cies.
mannose units. Galactomannans usually have a long chain of pectic substrates—complex polysaccharides containing a
mannose units with galactose side chains and are found in large proportion of galacturonic acid units.
seed gums (guar, locust bean). pectins—colorless, amorphous, water-soluble polysaccharides
gamma-cellulose—(1) Historically, a term used to indicate occurring in plant tissues that yield pectic acid and methanol
impurities of short chain lengths found in pulps, predomi- on hydrolysis.
nately hemicelluloses. (2) Gama-cellulose content, as mea- pentosans—one of the groups of amorphous carbohydrates
sured by TAPPI Method T 203 om-93, is the pulp fraction included under the general term “hemicellulose.” Pentosans
soluble in caustic, which remains in solution upon acidifi- yield principally pentoses on acid hydrolysis. The principal
cation. pentosan in wood is xylan.
glucan—a macromolecular substance that can be hydrolyzed polyuronides—polysaccharides containing uronic acid
to give almost exclusively glucose. groups.
glucomannan—a hemicellulose consisting essentially of glu- pulps, dissolving—chemical cellulose from wood pulp.
cose and mannose. pulps for chemical conversion—chemical cellulose from
glucuronoxylan—a common designation for the xylose- wood pulp.
containing hardwood hemicelluloses. (see also methylglu- pulps for manufacture of cellulose derivatives—chemical
curonoxylan) cellulose from wood pulp.
hemicellulose—any of a number of cell-wall polysaccharides purified cotton cellulose—see cotton cellulose, purified.
that are removable by extraction with aqueous alkali and that purified wood cellulose—see wood cellulose, purified.
may be hydrolyzed by boiling with dilute acids to give R10—the portion of a cellulose pulp that is insoluble in 10 %
constituent monosaccharide units; any of the noncellulosic sodium hydroxide using Test Method D 16963 or its equiva-
cell-wall polysaccharides. lent.
hexosan—frequently used in contradistinction to pentosan, for
a polysaccharide consisting mainly of hexose units. DISCUSSION—R10 indicates the pure, relatively undegraded cellulose
holocellulose—the total polysaccharide fraction of extractive- content of pulps, and as such may be compared to alpha-cellulose,
although they are determined by different test procedures.
free wood. The method of isolation or of determination
should always be given. rayon pulps—pulps used in the manufacture of rayon, and
kraft pulp—pulp cooked by the alkaline liquor consisting subject to various specifications by the manufacturers, in-
essentially of a mixture of caustic soda and sodium sulfide. cluding those of purity, moisture content, sheet properties,
The make-up chemical is traditionally sodium sulfate, which and viscosity.
is reduced to the sulfide in the chemical recovery process; S10—the portion of a cellulose pulp that is soluble in 10 %
hence the alternative designation, sulfate pulp. sodium hydroxide using Test Method D 1696, or its equiva-
lignin—that part of plant material which is not saccharified by lent.
the action of 72 % sulfuric acid or 42 % hydrochloric acid, DISCUSSION—S10 is considered to contain both hemicellulose and
after the resins, waxes, and tannins have been removed.
linters—the short fibrous material adhering to cotton seed after
the ginning operation. After removal from the seed it is used 3
2
D 1695
degraded, short chain length cellulose (see R10). cellulose xanthates—the salts of cellulose xanthic acid. Com-
S18—the portion of a cellulose pulp that is soluble in 18 % monly, cellulose xanthate refers to sodium cellulose xan-
sodium hydroxide using Test Method D 1696, or its equiva- thate, the essential constituent of the viscose solution, from
lent. which viscose rayon is spun.
dope—a composition, usually a cellulose lacquer, for applica-
DISCUSSION—S18 is considered to be mainly hemicelluloses, and may tion on textiles and leathers. Also a very viscous crude
be compared to gamma-cellulose, although they are determined by reaction product, as acetylation dope.
different test procedures.
ethylcellulose—any of several ethyl ethers of cellulose. The
S10–S18—an estimate of the portion of degraded cellulose in a one most generally used in industry has sufficient substitu-
pulp obtained by subtracting S18 from S10. tion to be soluble in organic solvents.
DISCUSSION—Some workers use S10 to S18 as an estimate of the hydrocelluloses—water-insoluble products of the hydrolysis
hemicellulose content of pulps, and may be compared to gamma- of cellulose with acids. They are molecularly heterogeneous
cellulose, although they are determined by different test procedures. in the sense that they are composed of molecules varying in
degree of polymerization. The average degree of polymer-
sulfate pulp—see kraft pulp.
ization (DP) and the DP distribution depend on the nature of
sulfite pulp—wood pulp produced by cooking with a sulfite
the acid treatment and of the original cellulose. The term
liquor made by dissolving sulfur dioxide in an aqueous base.
may also be applied to any insoluble polysaccharide so
wood cellulose, purified—chemical cellulose from wood.
formed and separated as a more or less homogeneous
xylan—a pentosan giving almost exclusively xylose on hy-
fraction from the mixture of products, but the singular form“
drolysis.
hydrocellulose” should not be used without an article, to
4. Chemical Modifications and Derivatives of Cellulose avoid the implication of a molecularly homogeneous spe-
carboxymethylcellulose, CMC—the common name for a cies.
cellulose ether of glycolic acid. It is usually marketed as a (2-hydroxyethyl)cellulose—any of several cellulose ethers in
water-soluble sodium salt, more properly called sodium which some of the hydroxyl groups have been substituted
carboxymethylcellulose. In the early literature, it is some- with hydroxyethyl groups. Hydroxyethyl cellulose, except at
times called cellulose glycolate or cellulose glycolic acid. very low degrees of substitution, is water-soluble.
cellulose acetate—in the broad sense, any of several esters of (2-hydroxyethyl)ethylcellulose—a mixed ether of cellulose
cellulose and acetic acid. (see also cellulose triacetate) containing both hydroxyethyl and ethyl groups.
cellulose acetate butyrate—a mixed ester of cellulose con- (2-hydroxyethyl)methylcellulose—a mixed ether of cellulose
taining both acetate and butyrate groups. containing both hydroxyethyl and methyl groups.
cellulose acetate phthalate—a mixed ester of cellulose con- (2-hydroxypropyl)methylcellulose—a mixed ether of cellu-
taining both acetate and phthalate groups. lose containing both hydroxypropyl and methyl groups.
cellulose acetate propionate—a mixed ester of cellulose ionic cellulose ethers—those water-soluble cellulose ethers
containing both acetate and propionate groups. which contain ionizable groups, in more than trace amounts.
cellulose derivative—a substance derived from cellulose by Sodium carboxymethyl cellulose is an example.
substitution of one or more of the hydroxyl groups with lacquer—see cellulose lacquer.
some other radical. Most derivatives are ethers or esters. methylcellulose—any of several methyl ethers of cellulose.
cellulose esters—derivatives of cellulose in which one or more Commercially, the water-soluble ether (degree of substitu-
of the hydroxyl hydrogens have been replaced acyl groups. tion approximately 1.5 to 2.0).
cellulose ethers—derivatives of cellulose in which one or methylethylcellulose—a cellulose ether containing both me-
more of the hydroxyl hydrogens have been replaced by alkyl thyl and ethyl groups.
groups. microcrystalline cellulose—a commercial name for cellulose
cellulose lacquer—a liquid coating composition containing as that has been hydrolyzed to the limiting DP and that consists
the basic film-forming ingredient a cellulose ester or ether essentially of microcrystals.
and plasticizers with or without resins or pigments. nitrocellulose—see cellulose nitrate.
cellulose mixed ester—a cellulose ester containing more than nonionic cellulose ethers—that class of cellulose ethers which
one type of acyl group. does not contain any ionizable groups.
cellulose nitrate—any of various nitrate esters of cellulose.
oxycelluloses—water-insoluble substances formed by the ac-
DISCUSSION—Cellulose nitrate is often and erroneously called “nitro- tion of oxidizing agents on cellulose. The chemical nature of
cellulose.” oxycelluloses varies with the oxidant used, and the type is
cellulose plastics—plastics based on cellulose compounds, indicated by attaching the name of the oxidant adjectivally to
such as esters (cellulose acetate) and ethers (ethylcellulose). “oxycelluloses” as in “hypochlorite oxycelluloses.” Any
cellulose propionate—any ester of cellulose with propionic such mixture is “an oxycellulose” and the word should not
acid. be used in the singular without either the definite or
cellulose sodium glycolate—see carboxymethyl cellulose. indefinite article. In many respects, the phrases “oxidized
cellulose triacetate—that form of cellulose acetate in which cellulose” or “partially oxidized cellulose” are preferable.
the degree of substitution approaches 3 sufficiently that the propylene glycol ether of methylcellulose—see (2-
product is not soluble in acetone. hydroxypropyl)methylcellulose.
3
D 1695
regenerated cellulose—cellulose regenerated from a solution amorphous regions—those regions within a cellulosic mate-
of cellulose or from a cellulose derivative. rial which, on the basis of X-ray diffraction or other suitable
sodium carboxymethylcellulose—see carboxymethylcellu- technique, do not show any evidence of crystalline structure.
lose. The technique should be specified.
viscose—a solution of sodium cellulose xanthate prepared by anhydroglucose units—the repeating unit of many polysac-
dissolving the reaction product formed by the interaction of charides, including cellulose; since the glucose molecules
carbon disulfide and alkali cellulose in an aqueous solution have combined with elimination of water, the unit is called
of sodium hydroxide. Viscose is used mainly in the manu- “anhydroglucose” rather than “glucose.”
facture of rayon or cellophane, where it is extruded through ash—the inorganic residue obtained by igniting a specimen of
fine openings of the proper shape into a coagulating bath. pulp, paper, or other cellulosic material in such a way that all
combustible and volatile compounds are removed. Condi-
5. Properties of Cellulose and Associated Concepts
tions of ashing should be specified.
accessibility—the fraction of total cellulose present that is bleachability—the capacity of a pulp to bleach to a given
accessible to certain reagents under certain specified condi- whiteness. This is approximately and indirectly related to
tions. The conditions of determination should always be lignin content.
indicated. bone-dry—see oven-dry.
acetylation—substitution of an acetyl radical for an active brightness—as commonly used in the paper industry, the
hydrogen. Specifically, formation of cellulose acetate from reflectivity of a sheet of pulp or paper for blue light
cellulose. measured under standardized conditions on a particular
acetyl groups—the characteristic groups of acetic acid; instrument designed and calibrated specifically for the pur-
CH3CO—. pose.
acyl groups—radicals derived from carboxylic acids by re-
carbonyl group—the bivalent radical,— CO—, especially as
moval of the hydroxyl group.
it occurs in aldehydes or ketones.
acid groups—functional groups having the properties of acids.
carboxyl group—the radical —COOH characteristic of most
In cellulose and its derivatives, these are usually carboxyl
organic acids.
groups.
CED (cupriethylenediamine) viscosity—see viscosity, cupri-
aging—in general, the change of properties with the passage of
ethylenediamine.
time. Specifically, the changes occurring in shredded alkali
cellulose when allowed to stand exposed to air. chain length distribution—in a linear polymer like cellulose,
air-dry—a condition applied to paper or pulp whereby its the frequency distribution of molecular size, usually ex-
moisture content is in equilibrium with the atmospheric pressed in units of degree of polymerization.
conditions to which it is exposed. According to trade custom, chlorine number—the number of grams of chlorine gas or of
pulps are generally understood to be air dry when they bleaching powder (expressed as its equivalent in chlorine)
contain 10 % of moisture, for example, a pound of air-dry that is consumed by 100 g of ovendry pulp in a definite time
pulp contains 0.9 lb of oven-dry pulp and 0.1 lb of moisture under certain specified conditions. The chlorine number is an
(see STP 60-B). indication of the bleach requirement of the pulp and an
alcohol-benzene solubility—solubility of a cellulosic pulp in indirect estimate of the lignin content.
a mixture of ethanol and benzene. The term is without color reversion—a process common to almost all bleached
precise meaning unless complete specification of an analyti- cellulose pulps in which the color darkens to a greater or
cal procedure is attached explicitly or implicitly. lesser extent on standing.
aldehyde groups—carbonyl groups to which a hydrogen atom commercial moisture regain—see moisture regain, commer-
is attached; the first oxidation stage of an alcohol;— CHO. cial.
alkali resistance—for a cellulosic pulp, the fraction insoluble copper number—the number of grams of copper in the
in alkali, usually sodium hydroxide, of a fixed concentration cuprous oxide reduced from a cupric compound by 100 g of
under specified conditions. The term is without precise pulp or paper (after deduction of moisture, ash, and sizing
meaning unless complete specification of an analytical materials) treated under specified conditions with an excess
procedure is attached explicitly or implicitly. (see also alkali of cupric solution. The copper number is an indication of the
solubility) relative number of reducing groups in the pulp or paper.
alkali solubility—for a cellulosic pulp, the fraction in alkali of cross linking—the reaction of a difunctional molecule with
a fixed concentration under specified conditions. This term is each of two molecules of a polymer. This change of the
without precise meaning unless complete specification of an polymer from linearity produces profound changes in the
analytical procedure is attached explicitly or implicitly. physical properties.
Some related terms imply at least a partial specification, for crystalline regions—see crystallinity.
example, “ten percent potassium hydroxide solubility” or crystallinity—a regular arrangement of the atoms of a solid in
“nondilution alkali solubility.” space. In most polymers, including cellulose, this state is
alkali staining—discoloration caused by the presence of an usually imperfectly achieved. The crystalline regions (or-
alkali. dered regions) are submicroscopic volumes in which there is
alkyl groups—monovalent aliphatic radicals derived from more or less regularity of arrangement of the component
aliphatic hydrocarbons by removal of a hydrogen. molecules. In these regions there is sufficient geometric
4
D 1695
order to enable definite X-ray diffraction patterns to be seldom important. One end group is reducing (probably a
obtained. (see also degree of crystallinity; degree of order) hemiacetal) and one nonreducing (a free hydroxyl in the
crystallinity index—a number used to represent the state of 4-position).
crystallinity of cellulose as a whole. Unfortunately, it has equilibrium moisture content—the percentage mass of mois-
been differently defined by different investigators and should ture in a material when it has attained equilibrium with water
not be used unless it is clearly stated which crystallinity vapor at a specified pressure or partial pressure. It is
index is meant. (see also crystallinity) determined by successive weighings of the sample, either on
crystallite—a single crystalline region. (see also crystallinity) the adsorption or desorption curve, and plotting moisture
cuam viscosity—see viscosity, cuprammonium. content against the logarithm of time. It should be designated
cuene viscosity—see viscosity, cupriethylenediamine. as adsorption equilibrium or desorption equilibrium.
cuprammonium process—a process for making rayon by exchange capacity—see ion-exchange capacity.
dissolving cellulose in an ammoniacal copper solution and fiber—the unit cell of vegetable growth, which is many times
spinning the resulting solution into an acid bath, thereby longer than its diameter and which consists largely of
regenerating the cellulose as fibers. cellulose. It is the basic unit of pulps and papers.
cuprammonium viscosity—see viscosity, cuprammonium. fiber length—when applied to a pulp, this applies to the mean
cupriethylenediamine viscosity (cuene or CED)—see viscosity, fiber length and both the experimental details and the
cupriethylenediamine. calculations must be specified.
degradation—in general chemical use, the conversion of a fiber length distribution—the frequency distribution of the
complex compound to a simpler. Specifically for cellulose, individual fiber lengths in a material about the mean fiber
the breakdown of the polymer chain, usually by hydrolysis length.
or oxidation. Degradation is usually applied to changes in fiber saturation point—the moisture content in the absorption
chemical structure. (see also deterioration) of water by cellulose when the cell walls are saturated, but
degree of crystallinity—the fraction by mass of a cellulose virtually no free water is present in the grosser capillary
sample occurring in crystalline regions. The method of structure. The concept is based on the hypothesis that a
determining crystallinity must be stated. (see also crystal- discontinuity occurs in the sorption curve at this point. Some
linity) careful studies of the region have failed to show a disconti-
degree of lateral order—the relative degree of molecular nuity, but it is still possible to define “fiber saturation point”
alignment. As for degree of crystallinity, quantitative values as an extrapolation of the adsorption curve. In any case, it
must be defined in terms of the experimental measurements. should only be used with reference to the method of
(see also crystallinity) determination.
degree of polymerization, DP—in general, the average num- fiber structure—the morphological structure of a fiber at the
ber of base units, or of monomeric units per molecule in visual or microscopic level. (see also fine structure)
linear polymers. Specifically, the average number of anhy- fibril—a fiberlike bundle of molecules, oriented in one direc-
droglucose units (or derivative units) per molecule of cellu- tion either with the fiber axis or spirally around it. It makes
lose (or cellulose derivative). The type of average obtained up the fibrous structural unit of the single fiber. The cellulose
depends upon the method used for the determination. Hence, fibrils are crystalline as shown by X-ray diffraction.
the method must always be specified. film—sheeting, including that composed of cellulose or its
degree of substitution, DS—in a cellulose derivative, the derivatives, having nominal thickness not greater than 10
average number of hydroxyl groups substituted per anhydro- mils. (see also films)
glucose unit. DS varies from zero to about 3. films—transparent sheeting. If this is used as a generic term,
density—the mass per unit volume at a specified temperature. regardless of sheet thickness, the plural should be used and
density, apparent—the mass per unit volume of a sheet of the singular restricted to a specified size. (see also film)
pulp or paper. It is commonly calculated by dividing the fine structure—a generic term denoting the submicroscopic
basis weight by the caliper, although it must be recognized structure that depends on molecular arrangement.
that the numerical value thus obtained is dependent upon the fluidity—the reciprocal of viscosity.
definition of the ream. gamma number—degree of substitution (DS) 3 100. This
density, bulk—the mass of a cellulosic material that will fill a term is of widespread use in the cellulose xanthate field.
unit volume of a container under specified conditions. gloss—the geometrically selective reflectance of a surface
deterioration—a permanent impairment of the physical prop- responsible for its shiny or lustrous appearance. Surface
erties. (see also degradation) reflectance is commonly at a maximum in or near the
dry weight—a term is usually applied to the mass of the geometric directions in which a mirror would reflect light.
ovendry material, but it is ambiguous unless the method of hardness—a term referring to the degree of cooking of a pulp.
drying is specified. A hard pulp is one in which the residual lignin content is
end groups—the functional groups at either end of the relatively high.
cellulose molecule. It is frequently used for the terminal haze—the turbidity produced by the material in some cellulose
glucose units that contain these groups. It is usually clear derivatives that is not completely soluble in the medium.
from the context which is meant, and the differentiation is This turbidity may refer to solutions or to the solid plastic.
5
D 1695
hemiacetal groups—functional groups derived from carbonyl “gloss” or “sheen.” (see also gloss)
groups by addition of one molecule of an alcohol, of the mercerization—the process of subjecting a vegetable fiber to
general structure: the action of a fairly concentrated aqueous solution of a
strong base so as to produce great swelling with resultant
changes in fine structure, dimensions, morphology, and
mechanical properties.
mesomorphous cellulose—those portions of cellulose in
which the segments of the individual molecules have some
hornification—the behavior of certain forms of cellulose and regularity of arrangement, but not enough to permit strict
related materials on drying, which results in a lowered lattice order to give a distinct X-ray diffraction pattern.
reactivity. This is apparently caused by the formation of new methoxyl group—the monovalent group —OCH3, character-
hydrogen bonds with a corresponding decrease in accessi- istic of methyl alcohol and its esters or ethers.
bility. moisture content—the moisture present in a cellulosic mate-
hydrodynamic specific surface—the specific surface of a rial, as determined by prescribed methods, conventionally
fibrous material as measured by the filtration resistance of a expressed as a percentage of the total mass of the “wet”
compacted pad formed from a fiber suspension under speci- material.
fied conditions. moisture equilibrium—the condition reached by a sample
hydrophilic—having an affinity for water. when it no longer takes up moisture from, or gives up
hydrophobic—having an antagonism to water. moisture to the surrounding air.
hydroxyl groups—the monovalent group —OH, characteristic moisture equilibrium for preconditioning—the moisture
of hydroxides and alcohols. equilibrium condition reached by a sample after free expo-
inherent viscosity—see viscosity, inherent. sure to air controlled at the standard condition for precon-
intrinsic viscosity—see viscosity, intrinsic. ditioning.
ion exchange—a reversible process by which ions are inter- moisture equilibrium for testing—the equilibrium moisture
changed between a solid and a liquid with no substantial condition reached by a sample after free exposure to moving
structural changes in the solid. air controlled at standard conditions.
ion-exchange capacity—for cellulosic ion-exchange materi- moisture regain—the moisture present in a cellulosic material,
als, the number of milliequivalents of ions that can be as determined by prescribed methods, expressed as a per-
exchanged by 1 g of the ion-exchange material. centage of the ovendry mass.
ion-exchange materials—insoluble solid materials with the moisture regain, commercial—an arbitrary figure formally
ability to exchange reversibly certain ions, in the structure or adopted as the regain to be used in calculating the commer-
attached to the surface as functional groups, with ions in a cial or legal mass of shipments or deliveries of any specific
surrounding medium. material.
iron-sodium tartrate, EWNN or FeTNa—a complex tartaric moisture regain, standard—the moisture regain of sample
acid salt of sodium and ferric iron. Solutions in aqueous brought from a lower moisture regain into equilibrium with
sodium hydroxide will dissolve cellulose. Both the German the standard atmosphere.
abbreviation, EWNN, and the English, FeTNa, are to be moles of substituent combined, MS—in a cellulose deriva-
found in English articles. The details of preparation of the tive, the average number of substituent molecules per
solution should always be given. glucose unit. For most derivatives, MS 5 DS, but for a few,
iron-sodium tartrate viscosity—the viscosity of a solution or such as hydroxyethylcellulose, the substituted group may
dispersion of cellulose or pulp under standardized condition also be reactive and MS may be greater than DS.
when dissolved in the iron-sodium tartrate solvent. (see also nonreducing end groups—those terminal glucose units of
iron -sodium tartrate) cellulose or its derivatives which contain a free hydroxyl in
kappa number—the number of millilitres of 0.1 N potassium the 4-position and do not reduce Fehling’s solution or similar
permanganate solution consumed by 1 g of ovendry pulp reagents.
under specified conditions. It is an indication of the hardness oleoresins—nonaqueous secretions of resin acids dissolved in
or bleachability of a pulp. An indirect estimate of lignin terpenic hydrocarbons that are produced or exuded from the
content. intercellular resin ducts of living trees, especially the coni-
lateral order—the degree of regularity of arrangement of fers, and accumulated, together with oxidation products, in
atoms and atomic groups in the direction normal to the the wood of weathered limbs or stumps.
molecular chain axes in linear polymers. Quantitative evalu- order distribution—see lateral order.
ation is impossible without further specification and without orientation—the angle made by the crystallites of the cellulose
description of the particular experimental technique. with the fiber axis. This is approximately the same angle as
leveling-off degree of polymerization, LODP—the nearly that made by the molecules or the fibrils.
constant degree of polymerization of cellulose reached after overdry—the state of a cellulosic material that has been dried
very prolonged mild hydrolysis or short drastic hydrolysis. to constant mass at a temperature of 100 to 105°C.
limiting viscosity number—see viscosity, intrinsic. percent hydrolysis-resistant cellulose—the residue after
luster—in the pulp and paper industry, synonymous with treatment of cellulose with acid under specified conditions,
6
D 1695
expressed as a percentage of the original. substance for this purpose is water; the value obtained with
permanganate number—the number of millilitres of 0.1 N water is close to the potential maximum surface that can be
potassium permanganate solution that is consumed by 1 g of developed without disruption of the crystalline structure.
ovendry pulp under certain specified and carefully controlled unit cell—a parallelepiped element of crystal structure, con-
conditions. It is an indication of the hardness or bleachability taining a certain number of atoms, the repetition of which
of a pulp. It also is an indirect estimate of lignin content. through space will build up the complete crystal.
plastic—(1) capable of being deformed continuously and uronic acids—oxidation products of the sugars in which a
permanently in any direction without rupture, under a stress primary alcohol group has been oxidized to a carboxyl
exceeding the yield value. (2) made of, consisting of or without changing the reducing functional group.
pertaining to plastics. (3) a material containing as an viscosity—in general, the resistance of a fluid to flow or
essential ingredient an organic substance of large molecular motion within itself. As applied to cellulose or its deriva-
mass, which is solid in its finished state and, at some stage tives, the viscosity of a solution of the substance.
in its manufacture or in its processing into finished articles, viscosity, cuprammonium—the viscosity of a solution or
can be shaped by flow. dispersion of cellulose or pulp in cuprammonium hydroxide
porosity—the existence in a material of connected air voids. It under standardized conditions.
is frequently expressed as the ratio of void volume to total viscosity, cupriethylenediamine—the viscosity of a solution
volume. or dispersion of cellulose or pulp under standard conditions
reactivity—the ability to react. For proper use of the term, the when dissolved in a solution of copper hydroxide in ethyl-
reaction in question and the conditions should be stated and enediamine.
the parameter used in measuring reactivity indicated, such as viscosity in absolute units, CGS poises—the force in dynes
rate, uniformity, or the like. required to move, at a velocity of 1 cm/s, one surface having
reduced viscosity—see viscosity, reduced. an area of 1 cm2 past another parallel-like surface 1 cm away,
reducing end groups—those terminal glucose units in cellu- overcoming the resistance to shear of the material filling the
lose or its derivatives in which the 1-position is not substi- space between.
tuted or involved in a glycosidic linkage. These end groups viscosity index—the ratio of the viscosity of a highly concen-
will reduce Fehling’s solution or similar reagents. trated solution to that of a dilute solution. It is a measure of
regain—see moisture regain. solvent power and, in derivatives, of uniformity of substitu-
relative viscosity—see viscosity, relative. tion.
reversion—in general, the tendency of pulp or paper proper- viscosity, inherent—the quotient of the natural logarithm of
ties to return to those of the material at some other stage. It relative viscosity by the concentration, that is, ln hrel/c. The
is frequently specifically applied to the loss of brightness concentration should be specified.
with time, after bleaching has produced a high brightness. viscosity, intrinsic—the limiting value of reduced viscosity,
ripening—in the manufacture of viscose rayon, that stage hsp/c, as c (concentration) approaches zero. In the cellulosic
where the cellulose xanthate solution is stored several days field the concentration is generally expressed as grams per
under controlled conditions to reach a state from which decilitre. The IUPAC Committee of Nomenclature has rec-
coagulation is easier. ommended the expression “Limiting viscosity number” for
sliver—a continuous strand of loosely assembled fibers that is this and the concentration is generally expressed as grams
approximately uniform in cross-sectional area and without per millilitre.
twist. viscosity number—see viscosity, reduced.
specific gravity—the ratio of the mass of a specimen to the viscosity ratio—see viscosity, relative.
mass of an equal volume of water, both at the same specified viscosity, reduced—the specific viscosity divided by the
temperature. Generally, density is more useful. (see also concentration. In the cellulosic field the concentration is
density) generally expressed as grams per decilitre. The IUPAC
specific surface—the surface per unit mass (or less frequently Committee on Nomenclature has recommended the expres-
per unit volume) of a moisture-free sample. The specific sion “viscosity number” for this, in which case the preferred
external surface is used as a measure of the degree of expression of concentration is grams per millilitre.
fineness of fibrillation. viscosity, relative—the ratio of the viscosity of a solution to
specific viscosity—see viscosity, specific. that of the pure solvent. The IUPAC Committee on Nomen-
standard moisture regain—see moisture regain, standard. clature has recommended the expression “Viscosity ratio”
surface area—the total area of the surface. As usually used for for this.
reactive pulps, this applies not to external surface, but to the viscosity, specific—the difference between the viscosity of a
internal surface as well, the total surface available to gases or solution and that of a solvent, divided by the latter.
penetrating liquids. It is useful to express this as specific viscosity, xanthate—for a cellulosic pulp, the viscosity of the
surface, area per gram. viscose that will be obtained as a result of a specified series
swelling—increase in volume and dimensions caused by of processes.
penetration of a liquid. viscous flow—flow, usually at low velocity, in which fluid
total internal surface—the surface of a cellulosic material elements flow in a straight line parallel to the direction of
available for absorption of a given substance. A useful flow of the liquid in the absence of turbulence.
7
D 1695
water vapor permeability—the rate of water vapor transmis- xanthate viscosity—see viscosity, xanthate.
sion per unit of thickness and per unit of vapor pressure
differential. Test conditions must be specified. 6. Keywords
whiteness—the degree of approach of the color of a substance
6.1 cellulose; cellulose derivatives; definitions; glossary;
to that of the ideal white, commonly represented by a
standardized preparation of magnesium oxide. terminology
8

Solubility of Cellulose in Sodium Hydroxide1
1. Scope cellulose must not be applied to any test values obtained by this
1.1 This test method2 is intended for application to procedure since they are defined only by the method of their
dissolving-type cellulose pulps prepared from cotton or wood. determination.
The procedure is not directly applicable to unrefined pulps for 3.3 The essential feature of the method is to prepare sodium
use in chemical conversion processes because solubility equi- hydroxide extracts and oxidize the soluble material with
librium may not be attained within the specified extraction dichromate as described. Alternative methods of estimating
time. dichromate by titration with ferrous ammonium sulfate and
1.2 TThis standard does not purport to address all of the sodium thiosulfate are described.
safety concerns, if any, associated with its use. It is the 4. Significance and Use
responsibility of the user of this standard to consult and
establish appropriate safety and health practices and deter- 4.1 The measurement of soluble oxidizable components of
mine the applicability of regulatory limitations prior to use. cellulose in sodium hydroxide is indicative of the purity of the
cellulose sample, since pure cellulose is insoluble in sodium
2. Referenced Documents hydroxide. The extracted components are typically hemicellu-
2.1 ASTM Standards: loses, which are naturally present in the wood. Differences in
D 1193 Specification for Reagent Water3 pulp purity can have a dramatic impact on the processing and
D 1347 Test Methods for Methylcellulose4 properties of the cellulose derivatives produced from the pulp.
D 1348 Test Methods for Moisture in Cellulose4 5. Apparatus
2.2 TAPPI Standard:
T 429 Method for Alpha-Cellulose in Paper5 5.1 Constant-Temperature Bath—A water bath maintained
at 20 6 0.2°C.
3. Summary of Test Method 5.2 Stirrer—Mechanical stirrer as shown in Fig. 1. All parts
3.1 Pulp is steeped in a sodium hydroxide solution of a in contact with solutions must be of stainless steel. The stirrer
specified concentration for 1 h at 20°C. The soluble fraction is motor shall be a variable speed laboratory motor with 1500
estimated by dichromate oxidation of the filtered steeping rpm max speed.
alkali. The concentration of sodium hydroxide used in the pulp 5.3 Fritted-Glass Filter Crucible— A fritted-glass filter
extraction process must be reported as part of the analytical crucible, coarse porosity (pore size 40 to 60 µm), of 30-mL
result. Sodium hydroxide concentrations of 10, 18, and 21.5 % capacity.
are most frequently used. Data are reported as percent of dry 5.4 Electrometric Titration Apparatus— For estimation of
sample weight. dichromate by titration with ferrous ammonium sulfate. An
3.2 The extraction procedure avoids dilution sequences, and indicator may be used as described in 8.6, but for rapid,
therefore, the results are not comparable to data obtained by the accurate analysis an electrometric apparatus is recommended.
alpha, beta, gamma methods of pulp fractionation (see TAPPI 6. Purity of Reagents
Method T 429). The terms “alpha-,” “beta-,” or“gamma-”
1
Unless otherwise indicated, it is intended that all reagents shall
Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Reagents of the American Chemical Society,6 where such
Current edition approved Sept. 15, 1995. Published November 1995. Originally specifications are available. Other grades may be used, pro-
published as D 1696 – 59. Last previous edition D 1696 – 90. vided it is first ascertained that the reagent is of sufficiently
2
This test method is an adaptation of the method designated CCA 8:55 by the
Analysis Committee of the Central Committee of the Cellulose Industry of the
6
Swedish Association of Pulp and Paper Engineers. This test method is also Reagent Chemicals, American Chemical Society Specifications, American
comparable with the TAPPI Tentative Standard T 235 m-58, Solubility of Pulp in Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Cold Sodium Hydroxide. listed by the American Chemical Society, see Analar Standards for Laboratory
3
4
5
Available from TAPPI P. O. Box 105113, Atlanta, GA 30348. MD.
1
D 1696
Metric Equivalents
in. ⁄
18 ⁄
14 ⁄
12 3⁄4 1 31⁄4 61⁄2 85⁄8
mm 3.2 6.4 12.7 19.0 25.4 82.6 165.1 219.1
FIG. 1 Design Details of Mechanical Stirrer
high purity to permit its use without lessening the accuracy of 7.4 Potassium Iodide (KI).7
the determination. 7.5 Sodium Hydroxide Solution—Dissolve solid sodium
6.2 Unless otherwise indicated, references to water shall be hydroxide (NaOH) in an equal weight of water. Cover and
understood to mean reagent water conforming to Specification allow to stand about one week to permit settling of sodium
D 1193. carbonate (Na2CO 3). Prepare the dilute NaOH solutions listed
below by approximate addition of freshly boiled water to
7. Reagents portions of the concentrated stock solution. Use a siphon to
7.1 Ferroin (0.025 M)—Dissolve 1.48 g of orthophenan- withdraw the required volume of 50 % NaOH solution from
throline monohydrate (or 1.624 g of the hydrochloride) with the stock bottle; do not disturb the Na2CO3 precipitate. The
0.695 g of ferrous sulfate (FeSO4) in water and dilute to 100 Na2CO3 content of the dilute solutions should not exceed 1
mL. g/L. Standardize the final dilute solutions by titration with
7.2 Ferrous Ammonium Sulfate Solution (0.1 N)—Dissolve standard acid.
40 to 41 g of ferrous ammonium sulfate (FeSO4(NH4)2-SO 7.5.1 Sodium Hydroxide Solution (10 %)—Prepare a solu-
4·6H2O) in water containing 10 mL of H2SO 4 and dilute to 1 tion containing 10.0 6 0.1 g NaOH per 100 g of solution.
litre in a volumetric flask. Standardize the solution daily Specific gravity at 20/4°C is 1.1089. This solution is 2.77 N.
against potassium permanganate (KMnO4). 7.5.2 Sodium Hydroxide Solution (18 %)—Prepare a solu-
7.3 Potassium Dichromate Solution (20 g/L)—Weigh 20.0 g tion containing 18.0 6 0.1 g NaOH per 100 g of solution.
of potassium dichromate (K 2Cr2O7), transfer to a 2-L beaker,
and dissolve in approximately 700 mL of water. Add, with 7
This reagent is required only for the iodometric method for measuring
constant stirring, 150 mL of H 2SO4. Allow to cool to room dichromate (see section 9.7). Thyodene, supplied by Fisher Scientific Co., Pitts-
temperature. Dilute to 1 L with water. burgh, PA is an acceptable substitute.
2
D 1696
Specific gravity at 20/4°C is 1.1972. This solution is 5.39 N. a coarse fritted-glass filter. Apply suction but do not pull air
7.5.3 Sodium Hydroxide Solution (21.5 %)—Prepare a so- through the cellulose mat on the filter. Discard the first 10 mL
lution containing 21.5 6 0.1 g NaOH per 100 g of solution. of filtrate. If suspended fibers are noted in the filtrate, recycle
Specific gravity at 20/4°C is 1.2356. This solution is 6.64 N. the filtrate through the cellulose mat to clarify. Retain the
7.6 Sodium Thiosulfate Solution (0.1 N)6—Prepare and filtrate in a stoppered Erlenmeyer flask.
standardize 0.1 N sodium thiosulfate (Na 2S2O3) solution as 9.4 Transfer 10-mL aliquots of the NaOH filtrates to
directed in 23.11 of Test Methods D 1347. 250-mL Erlenmeyer flasks. Add 10 mL K2Cr2O7 solution to
7.7 Starch Solution (5 g/L). each flask; then carefully add 30 mL of H2SO4 to each flask.
7.8 Sulfuric Acid (sp gr 184)—Concentrated sulfuric acid After 10 min (Note 2), cool to room temperature. Include a
(H2SO4). blank test with the original NaOH extraction solution in this
operation.
8. Preparation of Samples
NOTE 2—It is suggested that heat be applied to maintain a temperature
8.1 Condition the air-dry pulp samples to obtain moisture in the range of 125 to 130°C for the entire 10-min period. A reflux system
equilibrium by exposing them to the atmosphere for 24 h in the is highly satisfactory.
room where the portions of this sample will be weighed for
9.5 The 10-mL aliquot of the NaOH filtrates specified in 9.4
moisture and solubility analysis.
is generally suitable for dissolving-type pulps; however, if the
8.2 If the pulp is in sheeted form, tear it into pieces about 10
alkali solubility is greater than 16 %, reduce the volume of
mm square. Do not use cut edges. Weigh a portion for moisture
filtrate to 5 mL and the volume of H2SO4 to 25 mL. For pulps
analysis and immediately also weigh, to the nearest 1 mg,
with alkali solubility less than 5 %, use 20 mL of filtrate and 45
about 1.6 g of the air-dry sample for the solubility determina-
mL of H2SO4.
tion.
9.6 After dichromate oxidation, add 50 mL of water to each
8.3 Determine the moisture content of the air-dry sample in
sample and the blank. Cool again to room temperature. Titrate
accordance with Test Methods D 1348. Calculate the oven-dry
the excess K2Cr2O7 with 0.1 N ferrous ammonium sulfate
weight of the sample for the solubility determination.
solution. An electrometric titrimeter is preferred for this
9. Procedure operation. If this equipment is not available, ferroin indicator
9.1 Precool the NaOH solutions to 20°C. Pulp solubility in may be used to detect the end point.
18 and 21.5 % NaOH solutions is not affected by a few degrees 9.7 An acceptable alternative for measuring dichromate
variation in temperature. Hence, temperatures of 20 6 2°C are concentration is to use iodometric methods. In this case,
satisfactory in this case. However, pulp solubility in 10 % transfer the cooled solution with about 500 mL of water to a
NaOH solution is very sensitive to temperature variation. The 1-L Erlenmeyer flask. Add about 2 g of Kl and after 5 min
operator must control temperature to 20 6 0.2°C in all phases titrate the solution to a visual end point with 0.1 N Na2S2O3
of pulp extraction with 10 % NaOH solution. solution, using starch as the indicator. Make a blank test on the
9.2 With a pipet or buret, transfer 100 mL of the NaOH original NaOH extraction solution in the same manner.
solution of the desired concentration (10, 18, or 21.5 %) into a 10. Calculations
250-mL beaker. Add the 1.6 g air-dry pulp sample to the 10.1 Calculate the results, when obtained by titration with
solution. Allow the pulp to swell for 2 min; then introduce the ferrous ammonium sulfate, as follows:
stirring apparatus into the beaker so that the surface of the
Alkali solubility, % 5 @~b 2 a!N3 68.5#/mw (1)
liquid coincides with the draft tube top. Disintegrate the pulp
by stirring for 3 min (Note 1). Adjust the stirring speed to where:
prevent addition of air to the slurry (about 1500 rpm). Remove a = ferrous ammonium sulfate solution required for
the stirrer. Carefully clean the stirring apparatus and walls of titration of the sample, mL,
the beaker with a glass rod so that all pulp fibers are retained b = ferrous ammonium sulfate solution required for
in the alkali. Cover the beaker with a watch glass and leave in titration of the blank, mL,
the 20°C bath until a total of 60 min have elapsed from the time N = normality of the ferrous ammonium sulfate solu-
of addition of NaOH to the sample. For solubility determination,
tions in 10 % NaOH solution, all extraction operations must be 68.5 = cellulose equivalent to 1 milliequivalent of
performed with the sample container in the constant- K2Cr2O7, times 10 (Note 3), mg,
temperature water bath. In work with 18 or 21.5 % NaOH, the m = filtrate used for oxidation, mL, and
sample container may be removed from the bath for the w = oven-dry weight of sample used, g.
disintegration process. NOTE 3—The factor 68.5 is the experimental value recommended in
NOTE 1—Most pulps are completely disintegrated after 3 min. A method CCA 8:55.2 As an alternative, the problem of standardization of
reasonable increase in the time of disintegration does not sensibly affect ferrous ammonium sulfate can be handled in terms of oxidation of a
the solubility. On the other hand, low values are obtained if the reference cellulose solution prepared at each occasion for analysis as
disintegration is not complete. The stirrer should, therefore, be run until follows: Dissolve 200 mg (oven-dry weight) of high-quality cotton linters
complete disintegration is obtained, even if the time required exceeds 3 pulp in H2SO 4 (3 + 1) (prepared by mixing 3 volumes of H2SO 4 (sp gr.
min. 1.84) with 1 volume of water) and dilute to 100 mL with H 2SO4 (3 + 1).
Do not use heat in the preparation of this solution. Immediately after
9.3 At the end of the 1-h total extraction time, remove the preparation, oxidize 2-mL aliquots of this solution in the procedure
beaker from the bath and immediately filter the slurry through described in Section 8 for blank and sample treatment. Compare the
3
D 1696
cellulose solution and blank to express the concentration of ferrous 11. Report
ammonium sulfate solution in terms of milligrams of cellulose per
millilitre of solution. The calculation then becomes:
11.1 Report the alkali solubility as a percentage of oven-dry
pulp to one decimal place. Use the symbol S for alkali
Alkali solubility, % 5 @10 C~b 2 a!#/mw (2) solubility. Denote the strength of the sodium hydroxide solu-
where: tion by a numerical suffix, for example, designate the solubility
C = concentration of ferrous ammonium sulfate solution in terms of in 10 % NaOH solution by the symbol S10.
milligrams of cellulose per millilitre, and 11.2 If it is of interest to report the insoluble fraction,
b, a, m, w are defined as in 10.1. subtract the S value from 100. Use the symbol R, with the
appropriate subscript, to report this value. For example:
10.2 Calculate the results, when obtained by titration with
R10 = 100 − S10.
Na2S2O3 solution, as follows:
Alkali solubility, % 5 @~V 1 2 V2!N 3 68.5#mw (3) 12. Precision and Bias
12.1 Precision—Statistical analysis indicates a precision of
where: no less than 68 % at the 95 % confidence level for all
V 1 = Na2S2O3 solution required for titration of the
concentrations of sodium hydroxide.
sample, mL,
12.2 Bias—No statement of bias can be made as no suitable
V2 = Na2S2O 3 solution required for titration of the blank,
reference material exists for determining bias.
mL, and
N = normality of the Na2S2O 3 solution, and m and w are 13. Keywords
defined as in 10.1.
13.1 cellulose; sodium hydroxide solubility
4

Isobutyl Acetate (95 % Grade)1

1.1 This specification covers isobutyl acetate (95 % grade). of6
3. Properties
supplier’s Material Safety Data Sheet for material listed in this
specification. 3.1 Isobutyl acetate shall conform to the following require-
ments:7
2. Referenced Documents Apparent specific gravity:
20/20°C 0.868 to 0.873
2.1 ASTM Standards: 25/25°C 0.864 to 0.869
D 268 Guide for Sampling and Testing Volatile Solvents Color Pt-Co units, max 10
and Chemical Intermediates for Use in Paint and Related Distillation, °C at 760 mmHg
Initial boiling point, min 112.0
Coatings and Materials2 Dry point, max 119.0
D 1078 Test Method for Distillation Range of Volatile Nonvolatile matter mg/100 mL, max 5
Organic Liquids2 Water, wt %, max7 0.1
Acidity (free acid as acetic), wt %, max 0.01
D 1209 Test Method for Color of Clear Liquids (Platinum- Purity, wt %, min 95
Cobalt Scale)2
Products2 4.1 The material shall be sampled in accordance with
D 1364 Test Method for Water in Volatile Solvents (Karl Practice E 300.
5. Test Method
D 1476 Test Method for Heptane Miscibility of Laquer
Solvents2 5.1 The properties enumerated in this specification shall be
D 1613 Test Method for Acidity in Volatile Solvents and determined in accordance with the following ASTM methods:
Chemical Intermediates Used in Paint, Varnish, Lacquer, 5.1.1 Apparent Specific Gravity—Determine the apparent
and Related Products2 specific gravity by any convenient method that is accurate to
D 3545 Test Method for Alcohol Content and Purity of the third decimal place, the temperature of both specimen and
Acetate Esters by Gas Chromatography2 water being 20°C. See Guide D 268 or Test Method D 4052.
Liquids by Digital Density Meter3 5.1.3 Distillation Range—Test Method D 1078, using an
E 1 Specification for ASTM Thermometers4 ASTM Solvents Distillation thermometer having a range from
E 300 Practice for Sampling Industrial Chemicals5 98 to 152°C, and conforming to the requirements for thermom-
2.2 U.S. Federal Specification: eter 41C, as prescribed in Specification E 1.
5.1.4 Nonvolatile Matter—Test Method D 1353.
5.1.5 Water—Test Method D 1364 and Method D 1476.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.7 Purity—Test Method D 3545.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 6. Packaging and Package Marking
published as D 1718 – 60 T. Last previous edition D 1718 – 90(1994){1. 6.1 Package size shall be agreed upon between the pur-
2
3
Annual Book of ASTM Standards, Vol 06.04. chaser and the supplier.
4
5 6
Robbins Ave., Philadelphia, PA 19111-5094.
7
turbidity with 19 volumes of 99 % heptane at 20°C.
1
D 1718
6.2 Packaging shall conform to applicable carrier rules and 7. Keywords
regulations or when specified shall conform to Fed. Spec.
7.1 ester; isobutyl acetate
PPP-C-2020.
2

Isobutyl Alcohol1,2

1.1 This specification covers isobutyl alcohol for use in of7
paint, varnish, lacquer, and related products.
3. Properties
supplier’s Material Safety Data Sheets for materials listed in 3.1 Isobutyl alcohol shall conform to the following require-
this specification. ments:
Apparent specific gravity:
25/25°C 0.794 to 0.801
2.1 ASTM Standards: Color, Pt-Co Scale, max 10
A
D 268 Guide for Sampling and Testing Volatile Solvents Distillation range
Nonvolatile matter, max, g/100 mL 0.005
and Chemical Intermediates for Use in Paint and Related Water, max, weight % 0.2B
Coatings and Materials3 Acidity (free acid as acetic), max, 0.003C
D 1078 Test Method for Distillation Range of Volatile weight %
______________
Organic Liquids3 A
Shall distill entirely within a 2°C range which shall include 107.9°C.
D 1209 Test Method for Color of Clear Liquids (Platinum- B
Cobalt Scale)3 turbidity with 19 volumes of 99 % heptane at 20°C.
C
Products3
4.1 This material shall be sampled in accordance with
Practice E 300.
D 1476 Test Method for Heptane Miscibility of Lacquer 5. Test Methods
Solvents3
determined in accordance with the following ASTM methods.
Chemical Intermediates Used in Paint, Varnish, Lacquer,
5.1.1 Apparent Specific Gravity—Determine the apparent
specific gravity by any convenient method that is accurate to
D 4052 Test Method for Density and Relative Density of
the third decimal place, the temperature of both material and
water being 20 or 25°C. See Guide D 268 or Test Method
D 4052.
5.1.2 Color—Test Method D 1209.
2.2 U.S. Federal Specification:
5.1.3 Distillation Range—Test Method D 1078, using an
ASTM Solvents Distillation Thermometer 40C having a range
from 72 to 126°C and conforming to the requirements in
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint Specification E 1.
and Related Coatings, Materials, and Applications and is the direct responsibility of 5.1.4 Nonvolatile Matter—Test Method D 1353.
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. 5.1.5 Water—Test Methods D 1364 and D 1476.
2
This compound is also known under the names 2-methyl-1-propanol and
isobutanol. 6. Packaging and Package Marking
3
Annual Book of ASTM Standards, Vol 06.04. 6.1 Package size shall be agreed upon between the pur-
4
5
chaser and the supplier.
6
7
Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.
1
D 1719
6.2 Packaging shall conform to applicable carrier rules and 7. Keywords
regulations, or when specified, shall conform to Fed. Spec.
7.1 isobutanol; isobutyl alcohol; 2–methyl–1–propanol
PPP-C-2020.
2

Dilution Ratio of Active Solvents in Cellulose Nitrate
Solutions1
1. Scope two of the three components, namely, oxygenated solvent,

1.1 This test method covers the determination of the volume diluent, or cellulose nitrate, the effect of different batches or
ratio of hydrocarbon diluent to active solvent required to cause different types of the third component can be determined.
persistent heterogeneity (precipitation) in a solution of cellu- 4.2 This test method is applicable for the determination of
lose nitrate. the following:
1.2 This standard does not purport to address all of the 4.2.1 The dilution ratio of toluene as the standard diluent to
safety concerns, if any, associated with its use. It is the an oxygenated solvent under test, using as the solute standard
responsibility of the user of this standard to establish appro- cellulose nitrate as defined in 5.2.
priate safety and health practices and determine the applica- 4.2.2 The dilution ratio of a hydrocarbon diluent under test
bility of regulatory limitations prior to use. For specific hazard to n-butyl acetate as the standard solvent, using as a solute
statements, see Section 6. standard cellulose nitrate as defined in 5.2.
1.3 For hazard information and guidance, see the supplier’s 4.2.3 The dilution ratio of toluene, as the standard diluent, to
Material Safety Data Sheet. n-butyl acetate as the standard solvent, using as the solute
cellulose nitrate of varying solubility characteristics.
5. Materials
2.1 ASTM Standards:
D 301 Test Methods for Soluble Cellulose Nitrate2 5.1 n-Butyl Acetate (90 to 92 %), conforming to Specifi-
D 841 Specification for Nitration Grade Toluene3 cation D 4615.
D 4615 Specification for n-Butyl Acetate (All Grades)3 NOTE 2—This grade of n-butyl acetate contains 8 to 10 % n-butyl
alcohol.
3. Terminology
5.2 Cellulose Nitrate, conforming to the Sampling section
3.1 Definitions of Terms Specific to This Standard: (Appearance, Ash, and Stability requirements) of Test Methods
3.1.1 dilution ratio—the maximum number of unit volumes D 301 and of such quality that, when used in determining the
of a diluent that can be added to a unit volume of solvent to toluene dilution ratios of n-butyl acetate and methyl n-propyl
cause the first persistent heterogeneity (precipitation) in the ketone, it will give results between the following limits:
solution at a concentration of 8 g cellulose nitrate per 100 mL
Toluene Dilution Ratio
of combined solvent plus diluent and at a temperature of 25 6
3°C. n-butyl acetate 2.73 to 2.83
methyl n-propyl ketone 3.80 to 3.90
NOTE 1—The dilution ratio decreases as the cellulose nitrate concen-
tration at the end point increases. It is, therefore, necessary to set an 5.3 Toluene (Toluol), conforming to Specification D 841.
arbitrary concentration of cellulose nitrate as part of the dilution ratio
term. For this purpose 8.0 g of cellulose nitrate per 100 mL of solvent plus 6. Hazards
diluent has been adopted. 6.1 Soluble cellulose nitrate is a flammable material, the
degree of flammability varying with the extent and nature of
the wetting medium. Cellulose nitrate is always wet with water
4.1 By use of standard or reference grade materials for any or alcohol in commercial handling, shipping, and storage, in
which condition it presents no unusual hazard. Dry cellulose
1
nitrate, if ignited by fire, spark, or static electricity, burns very
and Related Coatings, Materials, and Applications and is the direct responsibility of rapidly. Do not store samples of dry cellulose nitrate at any
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. time. Dry only that portion required for immediate test. Wear a
Current edition approved Nov. 10, 1996. Published January 1997. Originally face shield when the oven is opened after samples have been
2
Annual Book of ASTM Standards, Vol 06.03. heated. Wet excess material and the samples left after testing
3
Annual Book of ASTM Standards, Vol 06.04. with water and dispose of properly.
1
D 1720
7. Drying Cellulose Nitrate TABLE 1 Volume of Solvent Required to Dissolve Cellulose
Nitrate
7.1 Dry not more than 20 g of cellulose nitrate at a time by
Probable Dilution Ratio, volume of mL of Solvent per 5 g of Cellulose
spreading in a thin layer on a tray at room temperature for 12 diluent:volume of solvent Nitrate at 25°C
to 16 h, or on top of a 100°C oven where the temperature is 35
1 25.0
to 40°C for about 8 h (Warning, see 6.1). Alternatively, use a 2 16.7
steam or hot water-heated oven maintained at 45 to 50°C to dry 3 12.5
4 10.0
specimens in about 8 h. For safety reasons, the oven should 5 8.3
have the latch removed.
7.2 Another simple way to dry small quantities of cellulose
nitrate is to use a drier assembled from common laboratory concentration of cellulose nitrate in solvent is required, disper-
apparatus. The assembled drier is shown in Fig. 1. Hot air from sion may be more quickly accomplished by adding a measured
a laboratory electric oven is drawn through wet cellulose portion of the diluent to the flask. This reduces the solids
nitrate contained in a brass tube hooked up through a thistle concentration and thus lowers the viscosity of the solution,
tube, or small funnel, and suction flask to a water aspirator or making it easier to dissolve the cellulose nitrate.
other vacuum source. The brass pipe should be about 40 mm in 9. Procedure
diameter and 200 mm long, these relative dimensions having
9.1 Add the diluent, maintained at 25 6 3.0°C, to the flask
been found to give efficient results. Such a tube will hold about
from a buret in small additions. Five-millilitre increments may
25 g, dry weight, of wet cellulose nitrate. The pipe is insulated
be added at first, but these shall be decreased to about 0.5 mL
to conserve heat. The suction flask end of the brass tube is fitted
as the end point is approached. After each addition, stopper the
with a thistle tube, or a small funnel, over the mouth of which
flask and swirl vigorously to disperse any gel or precipitate
is tied a silk cloth screen. An indentation made in the funnel
thrown down by local overconcentration of diluent (Note 4).
edge allows insertion of the thermometer. The funnel and
When precipitation persists after at least 2 min of vigorous
thermometer are held in place by means of a rubber stopper.
swirling, the initial end point has been reached, as indicated by
When using an oven temperature of 85°C and vacuum supplied
the presence of gel particles in the solution or on the sides of
by a water aspirator or other vacuum source, the alcohol-wet
the flask (Note 5). Determine the total volume of diluent added
cellulose nitrate will be dried in about 4 h.
to the flask at this point.
7.3 If larger quantities of cellulose nitrate are required, the
drying equipment described in the Procedure section of Drying NOTE 4—Take care to prevent loss of volatile components by evapo-
Samples of Test Methods D 301 may be used. ration. Avoid contact of the solution with the stopper.
NOTE 5—Presence of a uniform fine haze that is usually formed when
8. Preparation of Solution aliphatic hydrocarbons are used as diluents must not be confused with the
gel end point.
8.1 When testing either a solvent or diluent, first estimate
the probable dilution ratio for the unknown component in 9.2 Determine a second end point using the same solution.
relation to the other to determine the amount of solvent This requires addition of solvent to redissolve the cellulose
required to dissolve the cellulose nitrate (Table 1). This volume nitrate. The amount of solvent to add depends upon the amount
of solvent should be such that there will be approximately 10 g of diluent used in the initial titration. The volume of solvent to
of cellulose nitrate present per 100 mL of solvent plus diluent be added is obtained directly from Fig. 2 and the volume of
at the end point. diluent used to reach the initial end point.
9.3 After addition of the required volume of solvent, swirl
NOTE 3—Reference to published data on similar types of solvents or the flask to redisperse the cellulose nitrate. Then, continue the
diluents will provide a good approximation of the amount of solvent titration with diluent to the second end point, at which point
required. If data are not available, several solutions with varying amounts
of solvents may be required to arrive at a suitable volume to use.
there should be approximately 8 g of cellulose nitrate present
per 100 mL of solvent plus diluent.
8.2 On an analytical balance, weigh 5 6 0.01 g of the
cellulose nitrate into a 125-mL cork-stoppered, preweighed 10. Calculation
Erlenmeyer flask, or other suitable container. From a buret add 10.1 Calculate the dilution ratio and cellulose nitrate con-
the volume of solvent indicated in Table 1. Swirl the flask until centration at both the initial and the second end points as
the cellulose nitrate is completely dissolved. When a high follows:
FIG. 1 Assembled Drier
2
D 1720
the relationship between the dilution ratio and cellulose nitrate
concentration is not necessarily a straight line, the error made
by interpolating or extrapolating from the straight line connect-
ing the two points is negligible in the proximity of 8 6 1 g/100
mL of volatile matter.
NOTE 6—Example: Assuming a probable dilution ratio of approxi-
mately 3, the following results are obtained:
Solvent
Initial Added Second
End (from End
Point Fig. 2) Point
Cellulose nitrate, g 5.00 ... 5.00

Solvent, mL 12.5 3 15.5
FIG. 2 Volume of Solvent to Be Added to Complete Titration Diluent, mL 35.0 ... 49.6
versus Volume of Diluent Used to Reach Initial End Point Solvent plus diluent, mL 47.5 ... 65.1
Dilution ratio 35/12.5 = 2.8 ... 49.6/15.5
= 3.2
Cellulose nitrate per 100 mL of 10.5 ... 7.7
Dilution ratio 5 A/B (1) volatile matter, g
From Fig. 3 the dilution ratio at 8.0 g of cellulose nitrate = 3.16
Cellulose nitrate concentration per 100 mL of volatile matter 5
C/~A 1 B! 11. Report
where: 11.1 When testing solvents, report the ratio of the volume of
A = diluent for the titration, mL, toluene to the volume of solvent at 8 g of cellulose nitrate per
B = solvent used, mL, and 100 mL of volatile matter.
C = cellulose nitrate used, g. 11.2 When testing diluents, report the ratio of the volume of
10.2 Construct a graph for dilution ratio versus cellulose diluent to the volume of n-butyl acetate at 8 g of cellulose
nitrate concentration. Plot as two points on the graph (Fig. 3) nitrate per 100 mL of volatile matter.
the two sets of values calculated as described in 10.1. One of 11.3 When testing cellulose nitrate, report the ratio of the
the points will be very close to 8 g/100 mL of volatile matter. volume of toluene to the volume of n-butyl acetate at 8 g of
The correct value at exactly 8 g/100 mL of volatile matter may cellulose nitrate per 100 mL of volatile matter.
be interpolated by drawing a straight line connecting the two 12. Precision and Bias
experimentally determined points. While the curve showing 12.1 Precision—The following criteria should be used for
judging the acceptability of results at the 95 % confidence
level.
12.1.1 Repeatability—Two results obtained by the same
operator should be considered suspect if they differ by more
than 0.1.
12.1.2 Reproducibility—Two results obtained by operators
in different laboratories should be considered suspect if they
differ by more than 0.2.
12.2 Bias—This test method has no bias because the value
of the test result is defined only in terms of the test method.
13. Keywords
FIG. 3 Grams of Cellulose Nitrate per 100 mL of Volatile Matter 13.1 active solvents; cellulose nitrate solutions; dilution
versus Dilution Ratio ratio; hydrocarbon diluent
3

Permanganate Time of Tricresyl Phosphate1

1.1 This test method covers the detection in tricresyl phos- used, provided it is first ascertained that the reagent is of
phate of the presence of impurities that reduce potassium sufficiently high purity to permit its use without lessening the
permanganate. accuracy of the determination.
1.2 This standard does not purport to address all of the 5.2 Purity of Water—Unless otherwise indicated, references
safety concerns, if any, associated with its use. It is the to water shall be understood to mean reagent water conforming
responsibility of the user of this standard to establish appro- to Type IV of Specification D 1193.
priate safety and health practices and determine the applica- 5.3 Potassium Permanganate Solution (0.316 g/L)—
bility of regulatory limitations prior to use. For specific hazard Dissolve 0.316 g of potassium permanganate (KMnO4) in
statements, see Section 6. water and dilute to 1 L with freshly boiled water (Note). The
1.3 For hazard information and guidance, see the supplier’s solution should be stored in brown bottles and be freshly
Material Safety Data Sheet. prepared weekly as required.
NOTE 1—Clean glassware is essential to the stability of the KMnO4
2. Referenced Documents solution. Clean graduated cylinders and permanganate storage and han-
2.1 ASTM Standards: dling equipment with concentrated hydrochloric acid (HCl, sp gr 1.19) to
D 1193 Specification for Reagent Water2 remove residual manganese oxide (MnO2) which catalyzes reduction of
KMnO4. Remove the acid with not less than ten rinsings with water.
6. Hazards
3.1 Impurities such as phenols, if present in tricresyl phos-
phate, will react with potassium permanganate, reducing it to 6.1 Tricresyl phosphate is hazardous through inhalation or
manganese dioxide. In the permanganate test, the color of the skin absorption. Take care in handling the material. Avoid eye
test solution is observed at the end of a 30-min period, and if and skin contact and inhalation of vapors.
the pink color is still present, the sample is considered 6.2 Ortho–isomer of tricresyl phosphate is considered toxic.
substantially free of oxidizable impurities. Trace amounts may be present in tricresyl phosphate speci-
3.2 The results of this measurement can be used for specimens.
fication acceptance. 7. Procedure
4. Apparatus 7.1 Weigh 10 6 0.1 g of the sample to be tested into a
4.1 Graduated Cylinders, glass-stoppered, 100-mL capac- 100-mL glass-stoppered graduated cylinder. To this, add 50 mL
ity. of the KMnO4 solution. Vigorously shake the mixture for 2
min, noting the time when the shaking begins. Allow the test to
5. Reagents stand for a period of 28 min following the shaking period and
5.1 Purity of Reagents—Reagent grade chemicals shall be observe the color.
used in all tests. Unless otherwise indicated, it is intended that 8. Report
tee on Analytical Reagents of the American Chemical Society, 8.1 If the color of the permanganate solution is still pink,
report the sample as “passing.” If no pink color is present,
report the sample as “not passing.”
1 3
This test method is under the jurisdiction of ASTM Committee D-1 on Paint “Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-
and Related Coatings, Materials, and Applications and is the direct responsibility of cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates. the American Chemical Society, see “Analar Standards for Laboratory U.K.,
Current edition approved Nov. 10, 1997. Published August 1998. Originally Chemicals,” BDH Ltd., Poole, Dorset, U.K., and the“United States Pharmacopeia,
published as D 1721 – 60 T. Last previous edition D 1721 – 93. and National Formulary,” U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
1
D 1721
9. Precision and Bias because there is no available material having an accepted
9.1 Precision—No statement is made about the precision of reference value.
assessing this test method, since the results of the test method
are pass-fail. 10. Keywords
9.2 Bias—Bias cannot be determined for this test method 10.1 permanganate time; tricresyl phosphate
2

Water Miscibility of Water-Soluble Solvents1
1. Scope to be completely water miscible may interfere with many uses

1.1 This test method covers the determination of the misci- of the solvent. This test method provides a measure of the
bility of water-soluble solvents with water. While written miscibility of water-soluble solvents with a polar medium-
specifically for testing acetone, isopropyl alcohol (isopro- water. It also provides a qualitative indication of the presence
panol), and methyl alcohol (methanol), the method is suitable or absence of water-immiscible contaminants.
for testing most water-soluble solvents. 4.2 The results of this test method may be used in assessing
1.2 This test method serves to detect water-immiscible compliance with a specification. Prior to agreeing to this test
contaminants qualitatively; the level of detection of these method as the basis of a specification requirement, it may be
impurities varies widely with both the type of solvent and the desirable that the interpretation of what constitutes cloudiness
type of impurity. or turbidity be agreed upon between the supplier and the
1.3 The level of detection of water-insoluble materials purchaser.
depends upon the solvent tested and the type of impurity or 5. Apparatus
impurities present, that is paraffin, olefin, aromatic, high
molecular weight alcohol, or ketone, etc. There is, therefore, no 5.1 Cylinder, graduated, glass-stoppered, 250-mL.
specific level of impurity detected by this procedure. 6. Reagent
NOTE 1—This test method is normally performed at ambient, but other 6.1 Water—References to water shall be understood to
temperatures may be used as specified by the consumer and supplier. mean reagent water conforming to Type IV of Specification
1.4 This standard does not purport to address all of the D 1193.
responsibility of the user of this standard to establish appro- 7. Procedure
priate safety and health practices and determine the applica- 7.1 Transfer 25 mL of the sample to one of two clean
bility of regulatory limitations prior to use. 250-mL graduated cylinders, dilute to the 250–mL mark with
1.5 For specific hazard information and guidance, consult water, and mix thoroughly. Allow any bubbles to rise to the
the supplier’s Material Safety Data Sheet for materials listed in surface.
this test method. 7.2 Add 250 mL of water to the second cylinder and reserve
as a blank.
2. Referenced Documents 7.3 Compare the specimen solution with the water blank by
2.1 ASTM Standards: viewing through the length of the column of liquid toward a
D 1193 Specification for Reagent Water2 dark background. When an artificial light source is used,
position the light so that it passes transversely through the
3. Summary of Method cylinders.
3.1 The specimen is diluted to 10 volumes with water and
the resulting mixture examined for cloudiness or turbidity. 8. Report
8.1 If the specimen-water mixture is as free of cloudiness or
4. Significance and Use turbidity as the blank, report the sample as “passes test.” If any
4.1 Water-insoluble materials present in a solvent expected cloudiness or turbidity is detected after 30 min, report as “fails
test.”
1
This test method is under the jurisdiction of Committee D-1 on Paint and 9. Precision and Bias
Subcommittee D 01.35 on Solvents, Plasticizers, and Chemical Intermediates. 9.1 No information is presented about either precision or
Current edition approved Dec. 00, 1998. Published February 1999. Originally bias of this test method for water miscibility of water-soluble
published as D 1722 – 60. Last previous edition D 1722 – 90(1994).
2
1
D 1722
solvents since the test result is nonquantitative and is reported 10. Keywords
as pass or fail. 10.1 solvents; water miscibility test
2

Viscosity of Resin Solutions1
e1 NOTE—Editorial changes were made throughout in November 1996.
1. Scope should be checked with a small level and T-square to make

1.1 This test method covers the measurement of the viscos- certain it holds the tubes in an exact vertical position after
ity of resin solutions. being placed in the constant-temperature bath.
1.2 The values stated in inch-pound units are to be regarded 4.6 Bottle Shaker, preferably one which will give end-over-
as the standard. The values given in parentheses are for end agitation.
information only. 4.7 Timing Device, such as a stopwatch or electric stop
1.3 This standard does not purport to address all of the clock capable of being read to a precision of 0.1 s.
safety concerns, if any, associated with its use. It is the 4.8 Viscosity Tubes, of clear glass and flat bottoms, having
responsibility of the user of this standard to establish appro- 10.65 6 0.025-mm inside diameter and 114 6 1-mm outside
priate safety and health practices and determine the applica- length. Plainly legible lines shall be located on the tubes as
bility of regulatory limitations prior to use. follows:
27 6 0.5 mm
2. Referenced Documents 100 6 0.5 mm
108 6 0.5 mm
2.1 ASTM Standards:
D 154 Guide for Testing Varnishes2 All distances shall be measured from the bottom outside of
D 1545 Test Method for Viscosity of Transparent Liquids the tube. The distance between the first and second lines shall
by Bubble Time Method3 be 73 6 0.5 mm.
3. Summary of Test Method 5. Solvent

3.1 Solid resins are dissolved in organic solvents by cold- 5.1 The solvent used should be mutually agreed upon
cut or hot-cut methods in the laboratory. The viscosity of such between the purchaser and the manufacturer. Toluene, xylene,
prepared solutions, or of commercial solutions of resins is then mineral spirits, alcohols, etc., are used for the preparation of
determined by the bubble time method (Test Method D 1545). solutions of resins. For a given resin, the viscosity obtained
The bubble seconds are approximately equal to stokes. will depend on the solvent used. In case of dispute, both
laboratories should use portions of the same batch of solvent.
4. Apparatus
6. Preparation of Resin Solutions
4.1 Bath, constant-temperature, consisting of a cylindrical
glass jar of about 5-gal capacity, or an aquarium tank with 6.1 The procedure employed for dissolving solid resins will
controls capable of maintaining the temperature at 25 6 0.1°C be dependent upon the chemical nature of the resin under test.
with water as the bath medium. Some resins will dissolve readily in cold solvent with moderate
4.2 Bottles, 8-oz (225-mL), wide-mouth, screw cap. agitation, while others must be hot-cut in order to effect
4.3 Cellophane, sheet, cut into 4 or 5-in. (102 or 127- mm) solution. The method of solution shall be agreed upon mutually
squares. between the purchaser and the seller since there may be
4.4 Corks, No. 2 short taper, to fit viscosity tubes. differences in solubility or viscosity between solutions pre-
4.5 Holder for Viscosity Tubes, preferably a mechanical pared with and without heat. The solvent concentration may
holder with rack and pinion for inverting the tubes. The holder vary from 30 to 90 % and is generally selected to give a
solution having a viscosity between 5 and 300 s. With hard
resin use only material taken from freshly broken lumps. Do
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint not use crushed or powdered material from the resin sample
Subcommittee D01.33 on Polymers and Resins. container.
Current edition accepted Sept. 28, 1962. Originally issued 1960. Replaces 6.2 Cold-Cut Solutions—Because it is not easy to tell when
D 1725 – 60 T.
2
solution of the resin is complete, proceed exactly in accordance
3
A suitable mechanical holder is available from the Gardner Laboratory, Inc.,
with the following directions, unless experience has shown that
5521 Landy Lane, Washington, DC, Item 660. short cuts can be safely taken:
1
D 1725
6.2.1 Prepare 100 g of solution as follows: Weigh an 8-oz content, use a solvent or solvent combination suitable for use
(225-mL), screw-cap bottle, cap, and cellophane sheet to the with resin under test, as agreed upon between the manufacturer
nearest 0.05 g. Weigh into the bottle to the nearest 0.05 g the and the purchaser.
appropriate amount of solvent (40 g for a 60 % solution).
7. Procedure
6.2.2 Weigh into a beaker to the nearest 0.05 g the correct
amount (60 g for a 60 % solution) of the freshly crushed resin, 7.1 Determine the viscosity of the resin solution in accor-
passing a No. 10 (2000-µm) sieve. dance with Test Method D 1545, repeating the timing determi-
6.2.3 Pour the resin slowly into the bottle containing the nation until three readings are obtained that agree within 10 s
solvent, swirling gently so as to wet the resin as thoroughly as or 3 % relative, whichever is larger.
possible as it is added. Place the cellophane sheet over the 7.2 For viscosities of solutions which have a timed bubble
mouth of the bottle and screw on the cap tightly. travel of 5 s or less, more precise results can be obtained by
6.2.4 Immediately shake vigorously by hand and place on a comparison against reference standards having predetermined
shaker to give end-over-end agitation for an overnight period. viscosity (Test Method D 154) or timed bubble travel (Guide
6.2.5 Check the weight of the bottle and solution to make D 1545).
certain that none was lost during the mixing. If appreciable loss 8. Report
has occurred, discard the solution and prepare a fresh one. 8.1 Report the following information:
6.3 Hot-Cut Solutions: 8.1.1 The mean bubble travel time, in seconds, as the
6.3.1 Prepare 100 g of solution as follows: Weigh a 250-mL viscosity at 25°C, including:
Erlenmeyer flask with a ground joint to the nearest 0.05 g. 8.1.1.1 Solution concentration,
Weigh into the flask to the nearest 0.05 g the appropriate 8.1.1.2 Solvent used, and
amount of solvent (40 g for a 60 % solution). 8.1.1.3 Whether cold- or hot-cut solutions were used.
6.3.2 Weigh into the flask to the nearest 0.05 g the correct
amount (60 g for a 60 % solution) of the freshly crushed resin 9. Precision
passing a No. 10 (2000-µm) sieve. Connect the flask to a 9.1 Repeatability and Reproducibility—Two results, each
suitable air or water condenser and warm gently on a hot plate the mean of three readings, should be considered suspect if
with swirling as necessary to prevent any charring or scorching they differ by more than 7 % relative (95 % confidence level).
of the resin. Usually, the solution will be complete in 15 or 20
NOTE 1—This estimate of precision is based on an interlaboratory
min. study.4 Because the data showed no significant difference for between
6.3.3 When the solution is complete, cool the flask, discon- laboratory and within laboratory variances, the precision estimates for
nect, and weigh. If over 0.1 g of solvent has been lost, add the repeatability and reproducibility were pooled and a single value reported.
necessary amount and swirl to mix.
6.3.4 If any air bubbles are present, allow the solution to 10. Keywords
stand until they disappear. 10.1 bubble time; resin solutions; viscosity
6.4 Resins Supplied in Solution—These resins ordinarily
can be tested for viscosity as received. However, if modifica- 4
For the results of the interlaboratory study, see Report of Committee D-1,
tion is necessary, such as a reduction to a specified solids Proceedings, ASTM, Vol 60, 1960.
2

Hydrolyzable Chloride Content of Liquid Epoxy Resins1
1. Scope chloride content of purchased epoxy resins.

1.1 These test methods cover the determination of the easily 5. Apparatus
hydrolyzable chloride content of liquid epoxy resins which are
defined as the reaction product of a chlorohydrin and a di- or 5.1 Reflux Apparatus, consisting of a 250-mL Erlenmeyer
polyfunctional phenolic compound. flask attached to a reflux condenser and a hot plate with
1.1.1 In Test Method A, the easily hydrolyzable chloride is variable heat control.
saponified with potassium hydroxide and directly titrated with 6. Purity of Reagents
hydrochloric acid. This test method can be used for concen-
trations of 1 weight % and below. 6.1 Purity of Reagents—Reagent grade chemicals shall be
1.1.2 In Test Method B, the easily hydrolyzable chloride is used in all tests. Unless otherwise indicated, it is intended that
again saponified with potassium hydroxide, then titrated po- all reagents shall conform to the specifications of the Commit-
tentiometrically with silver nitrate. This test method can be tee on Analytical Reagents of the American Chemical Society,4
used for concentrations of 5 to 2500 ppm hydrolyzable where such specifications are available. Other grades may be
chloride. used, provided it is first ascertained that the reagent is of
1.2 This standard does not purport to address all of the sufficiently high purity to permit its use without lessening the
safety concerns, if any, associated with its use. It is the accuracy of the determination.
responsibility of the user of this standard to establish appro- 6.2 Purity of Water—Unless otherwise indicated, references
priate safety and health practices and determine the applica- to water shall be understood to mean reagent water conforming
bility of regulatory limitations prior to use. For specific hazard to Type II of Specification D 1193.
statements see Sections 8 and 14. TEST METHOD A
2. Referenced Documents 7. Reagents and Materials
2.1 ASTM Standards: 7.1 Hydrochloric Acid, Standard (0.1 N)—Dilute 9 mL of
D 841 Specification for Nitration Grade Toluene2 concentrated hydrochloric acid (HCl, sp gr 1.19) to 1 L with
D 1193 Specification for Reagent Water3 water. Standardize against 0.25 g of sodium carbonate
3. Summary of Test Method (Na2CO3) accurately weighed and dissolved in 75 to 100 mL of
water.
3.1 The sample is refluxed in the presence of a known 7.2 Methyl Ethyl Ketone.
amount of 0.1 N alcoholic potassium hydroxide. The amount of 7.3 Phenolphthalein Indicator Solution—Dissolve 1 g of
potassium hydroxide consumed in the hydrolysis is a measure phenolphthalein in 100 mL of methanol, ethanol, or isopro-
of the hydrolyzable chloride content of the resin. panol.
4. Significance and Use 7.4 Potassium Hydroxide, Alcohol Solution (0.1 N)—
Dissolve 5.5 to 6.0 g of potassium hydroxide (KOH) in 1 L of
4.1 The hydrolyzable chloride content of liquid epoxy resins
methanol (99 %) or ethanol conforming to Formula No. SD-30
is an important variable in determining their reactivity and the
of the U.S. Bureau of Internal Revenue. No standardization of
properties of coatings made from them. These test methods
the solution is necessary.
may be used to determine the hydrolyzable chloride content of
7.5 Toluene (Warning—See Section 8.), conforming to
manufactured epoxy resins and confirm the stated hydrolyzable
1
4
and Related Coatings, Materials, and Applicationsand is the direct responsibility of Reagent Chemicals, American Chemical Society Specifications, American
Subcommittee D01.33on Polymers and Resins. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved May 25, 1990. Published July 1990. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
1
D 1726
8. Hazards 12.3 Magnetic Stirrer, with polytetrafluoroethylene (PTFE)-
8.1 Hydrochloric acid and potassium hydroxide are corro- coated stirring bar.
sive. Toluene and methyl ethyl ketone are flammable and their 12.4 Buret or Automatic Titrator.
vapors can be harmful. Precautions should be taken to avoid 12.5 Silver Electrode or equivalent.
inhalation and skin or eye contact with these chemicals. All 12.6 Boiling Chips.
sample preparations should be done in a well ventilated area, 13. Reagents and Material
such as a fume hood.
13.1 Acetone.
9. Procedure 13.2 Bromcresol Green Indicator Solution (0.1 %)—
Dissolve 0.1 g of bromcresol green in 100 mL of water.
9.1 Weigh to the nearest 1 mg, 6 to 8 g of neutral specimen
13.3 Nitric acid, (HNO3) (1 + 1), diluted with water.
into a 250-mL glass-stoppered Erlenmeyer flask. By means of
13.4 Potassium Hydroxide, alcohol solution (0.1 N)—
a pipet, transfer 50.0 mL of 0.1 N alcoholic KOH solution into
Dissolve 5.6 g of potassium hydroxide (KOH) in 1 mL of
the flask and add 15 mL of toluene. Stopper the flask and swirl
methanol (99 %) or ethanol conforming to Formula No. SD-30
to mix. Add a few boiling aids and attach to the reflux
of the US Bureau of Internal Revenue. No standardization of
condenser on the hot plate.
the solution is necessary.
9.2 Allow the solution to reflux gently for 15 6 1 min. At
13.5 Silver Nitrate, alcohol solution (0.0025 N)—Dissolve
the end of the reflux period, remove the flask from the hot plate
0.425 g of silver nitrate (AgNO3), weighed to the nearest 1 mg,
and cool to room temperature with the condenser in place.
in 1 L of methanol (99 %) or ethanol conforming to Formula
9.3 Remove the condenser, add 3 drops of phenolphthalein
No. SD-30 of the US Bureau of Internal Revenue. Standardize
indicator solution to the specimen, and titrate with 0.1 N HCl.
against hydrochloric acid or sodium chloride solution (with
The end point is taken when 1 drop changes the solution from
traceability to an NIST standard).
pink to colorless.
13.6 Toluene.
NOTE 1—Add 100 mL of methyl ketone to the specimen if required to
ensure a homogeneous solution during titration of the excess KOH 14. Hazards
solution. 14.1 Nitric acid, potassium hydroxide, and silver nitrate are
9.4 Make a blank determination on the reagents following corrosive. Acetone and toluene are flammable and their vapors
the same procedure but omitting the specimen. can be harmful. Precautions should be taken to avoid inhalation
and skin or eye contact with these chemicals. All sample
10. Calculation preparations should be done in a well ventilated area, such as
10.1 Calculate the weight percent hydrolyzable chloride a fume hood.
content, H, of the specimen as follows: 15. Procedure
H 5 @~V 2 B!N 3 3.55#/W (1) 15.1 Weigh 2 to 3 g of specimen, to the nearest 0.005 g, into
where: a 250-mL Erlenmeyer flask. Add 20 mL of toluene, 20 mL of
B 5 HCl required for titration of the blank, mL, acetone, and 50 mL of 0.1 N alcoholic KOH. Swirl or mix until
V 5 HCl required for titration of the hydrolyzed speci- dissolution is complete.
men, mL, 15.2 Add several boiling chips, connect the flask to the
N 5 normality of the HCl, reflux condenser, and gently reflux for 15 6 1 min on a hot
3.55 5 grams of chlorine per milliequivalent multiplied by plate.
the percentage factor of 100, and 15.3 Remove the hot plate from under the flask and allow
W 5 specimen weight, g. the flask and contents to cool to room temperature. Rinse down
the condenser with acetone then remove from the flask.
11. Precision 15.4 Quantitatively transfer the contents of the flask to a
11.1 The following criteria should be used for judging the 250-mL beaker using acetone as wash solution. Dilute the
acceptability of results at the 95 % confidence level: solution to about 125 mL with acetone, insert a stirring bar, and
11.1.1 Repeatability—Two results obtained by the same place on a magnetic stirrer.
operator should be considered suspect if they differ by more 15.5 Add five drops of bromcresol green indicator. While
than 0.02 % absolute. stirring add 1 + 1 nitric acid dropwise just until the permanent
11.1.2 Reproducibility—Two results obtained by operators color changes from blue to yellow.
in different laboratories should be considered suspect if they NOTE 2—Caution—Do not add excess nitric acid. Do not acidify the
differ by more than 0.05 weight %. solution until ready to begin the titration. Make certain that the solution is
at room temperature before acidifying. These cautions are necessary to
TEST METHOD B prevent the chloride results from being low due to recombination with the
resin.
12. Apparatus 15.6 Titrate with 0.0025 N silver nitrate using the combina-
12.1 Reflux Apparatus, consisting of a 250-mL Erlenmeyer tion silver electrode and the automatic titrator or buret.
flask attached to a reflux condensor. 15.7 Reflux a blank, which includes all components except
12.2 Hot Plate, with variable heat control. the sample, and titrate with 0.0025 N silver nitrate.
2
D 1726
16. Calculation lyzable chloride was sampled to five laboratories and seven
16.1 Calculate the parts per million hydrolyzable chloride analysts obtained the following results.
content, H, of the specimen as follows: 17.1.1 Repeatability—The difference between two results
H 5 @~V 2 B!N 3 35.5 3 103#/W
obtained by the same analyst should not vary by more than
8.32 % at the 95 % confidence level.
where: 17.1.2 Reproducibility—The difference between two re-
B 5 AgNO3 required for the titration of the blank, sults, each the mean of two determinations, obtained by
mL, analysts in different laboratories should not vary by more than
V 5 AgNO3 required for the titration of the hy-
15.88 % relative at the 95 % confidence level.
drolyzed specimen, mL,
N 5 Normality of the AgNO3,
35.5 3 103 5 grams of chlorine per milliequivalent multi- 18. Keywords
plied by the ppm conversion of 1 3 106, and 18.1 hydrolyzable chloride; liquid epoxy resin; saponifiable
W 5 specimen weight, g. chloride
17. Precision
17.1 A liquid epoxy resin of approximately 150 ppm hydro-
3

Intrinsic Viscosity of Cellulose1

1.1 This test method covers the determination of the intrin- 4.1 This test is a sensitive measure of the degradation of
sic viscosity of purified celluloses such as bleached wood cellulose resulting from the action of heat, light, acids, alkalies,
pulps, cotton linters, and regenerated cellulose. It is applicable oxidizing and reducing agents, and the like, used in its
to all cellulose samples with an intrinsic viscosity of 15 dl/g or processing or purification. The intrinsic viscosity value may be
less. Most native (unpurified) celluloses have intrinsic viscos- converted to degree of polymerization (DP) or to intrinsic
ity values too high for measurement by this test method. fluidity, if desired.
4.2 Solutions of cellulose are not Newtonian liquids; that is,
NOTE 1—The use of cuprammonium hydroxide solution for regular
viscosity determination is described in Test Methods D 539, Method their viscosity depends upon the rate-of-shear or velocity
T 206 m-55 of the Technical Association of Pulp and Paper Industry on gradient during measurement. This effect is smaller for samples
“Cuprammonium Disperse Viscosity of Pulp,” and Joint Army-Navy of low molecular mass (DP) and at low concentrations than for
Specifications JAN-C-206. high-DP samples and at high concentrations. For the celluloses
1.2 This standard does not purport to address all of the and concentrations included within the limits set forth in this
safety concerns, if any, associated with its use. It is the test method, the effect of rate-of-shear is assumed to be
responsibility of the user of this standard to establish appro- negligible for referee purposes. For other conditions and for
priate safety and health practices and determine the applica- research purposes this assumption may be invalid, but to
bility of regulatory limitations prior to use. discuss ways of accounting for this effect is beyond the scope
of the present test method.
5. Apparatus
2.1 ASTM Standards:
D 445 Test Method for Kinematic Viscosity of Transparent 5.1 Viscometer, Glass, Capillary Type— The Cannon-
and Opaque Liquids (and the Calculation of Dynamic Fenske, Ubbelohde, or similar capillary type instrument as
Viscosity)2 described in Test Method D 445 is recommended. Viscometers
D 539 Test Methods for Apparent Fluidity of Dispersions of described in Test Methods D 539 are also suitable. In order to
Cellulose Fibers3 avoid correction for the kinetic energy effect, choose a viscom-
D 629 Test Methods for Quantitative Analysis of Textiles4 eter with a small enough capillary to give an outflow time of 80
E 1 Specification for ASTM Thermometers5 s or more for the Cannon-Fenske type. (A size 100 viscometer
is normally used for the sample solution and a size 50 for the
3. Summary of Test Method solvent.)
3.1 A weighed sample of the material is dissolved in a 0.5 M 5.2 Thermometer—ASTM Kinematic Viscosity Thermom-
cupriethylenediamine hydroxide solution. The viscosity of this eter for use at 25°C, having a range from 19 to 27°C and
solution, and also that of the solvent, is determined at 25°C by conforming to the requirement for Thermometer 17C as
means of a calibrated glass capillary-type viscometer. The prescribed in Specification E 1.
relative viscosity is calculated and the corresponding intrinsic 5.3 Bath—A constant-temperature bath at 25°C suitable for
viscosity is read from a table. immersion of the viscometer so that the reservoir or the top of
the capillary, whichever is uppermost, is immersed at least 50
mm, and with provision for visibility of the instrument and the
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint thermometer. Firm supports for the viscometer shall be pro-
and Related Coatings, Materials, and Applications and is the direct responsibility of vided; or the viscometer may be sealed in as an integral part of
Subcommittee D01.36 on Cellulose and Cellulose Derivatives.
the bath. Either a liquid bath with thermostatic regulation and
published as D 1795 – 60. Last previous edition D 1795 – 94. a stirrer or a vapor bath with pressure regulation is permissible.
2
Annual Book of ASTM Standards, Vol 05.01. The efficiency of the stirring and the balance between heat
3
Discontinued, see 1973 Annual Book of ASTM Standards, Part 24. losses and heat input must be such that the temperature of the
4
5
bath medium does not vary by more than 60.1°C over the
1
D 1795
length of the viscometer, or from viscometer to viscometer in NOTE 4—Calibration of the viscometers may be avoided if both solvent
the various bath positions. If a vapor bath is used, there must and solution are measured in the same instrument. Then the relative
be no temperature gradient over the length of the viscometer viscosity is nearly the ratio of outflow times for solution and solvent,
respectively. This simplification involves two assumptions. The first, that
greater than that permitted in a liquid bath. the densities of solution and solvent are equal, holds very well for the
5.4 Timer—A stop watch or other spring-activated timing dilute solutions used in these tests. The second, that the kinetic energy
device or electrical timing device shall be used, graduated in correction is zero, depends upon the choice of viscometer. If the one used
divisions of 0.2 s or less, and accurate to within 0.05 % when gives convenient outflow times for the solution of less than 150 s, then it
tested over not less than a 10-min period. Such electrical will be too fast for the solvent. The kinetic energy correction is zero,
timing devices shall be used only on electrical circuits of depending upon flow. On the other hand, if one is chosen so that the
outflow time for the solvent is large enough (80 s or more), then the times
continuously controlled frequency. Frequency-controlled de-
for the solutions will in most cases be inconveniently long. For some
vices of suitable capacity for laboratory purposes, accurate to work, however, it may be desirable to make some sacrifice in accuracy or
within 1 part in 10 000 should be used. Errors exceeding in convenience during measurement in order to avoid calibration and
0.05 % of a 10-min interval may occur in timing devices using two sizes of viscometers.
actuated by electrical synchronous motors driven by most 8.2 By means of a pipet, add 7.0 mL of the calibrating liquid
public power systems, which are intermittently and not con- to the viscometer, in a constant-temperature bath at 25 6 0.1°C
tinuously controlled. (or fill as described in Test Method D 445, Appendix A).
6. Reagent 8.3 When the liquid has reached temperature equilibrium
with the bath (in about 5 min), determine the outflow time t by
6.1 Cupriethylenediamine Hydroxide Solution (1.00 6 0.01
drawing the top meniscus of the liquid above the mark between
M), in copper, with the molar ratio of ethylenediamine to
the two bulbs and measuring the time required for the meniscus
copper of 2 6 0.1 to 1. This solvent may be prepared in the
to pass from this mark to the mark below the lower bulb. Take
laboratory as described in Test Methods D 539. It is also
the average of two or more observations, which should differ
commercially available.6
by not more than 0.2 s.
7. Reference Materials 8.4 Determine the viscometer constant C by the equation:
7.1 Viscosity Oil Standards—Calibrating oils in the speci- C 5 h/dt (1)
fied ranges of viscosity.6 Aqueous solutions of glycerol may be
used instead of standardized oils; the compositions for various where:
h = viscosity of the calibrating liquid, cP,
viscosities are given in chemical handbooks. The applicable
d = density, g/mL, and
viscosity oil standards (Note 2) are listed in Table 1. t = time, s.
TABLE 1 Viscosity Oil Standards 9. Preparation of Sample
Viscometer Viscosity Oil Standard 9.1 To avoid undesirable effects from long heating at high
Approximate
Absolute Viscosity temperature, samples should be air-dried and the moisture
Size Designation Absolute Viscosity
Range, cPA
at 77°F (25°C), cP content determined on a portion that is not used for measure-
50 0.9 to 3.5 S-3 3.3
100 3.3 to 13.3 S-6 7.7
ment of viscosity. The mass of air-dried samples is then
A
corrected for moisture to obtain the mass of oven-dried
For solution with density of 0.9.
cellulose used to calculate concentration.
9.2 Soft, sheeted pulp should be picked apart with tweezers
NOTE 2—The viscosity oil standards are available only as 1-pt (4.7- m
3) samples. More than 1 pt of any given oil (for example, duplicate or scraped with a dull knife. Hard-pressed or harsh pulp should
samples) are supplied only when it is established that 1 pt is inadequate.6 be slurried in water, formed into thin sheets on a Büchner
funnel, and dried at a temperature below 100°C (preferably
8. Calibration of Viscometer room temperature). Loose pulp should be picked apart by hand
8.1 The following directions apply to the Cannon-Fenske to break up any lumps. Slurried or slush pulps should be
viscometer (Note 3). They should be modified according to the formed into thin sheets and dried. Yarn and staple should be
operating instructions for other types of viscometers. The washed in warm water containing a little detergent to remove
viscometers shall be calibrated (Note 4) by means of liquids the finish, rinsed thoroughly, dried (at low temperature), and
having known viscosities approximately equal to those of the fluffed. (It will be found helpful to cut yarn and long staple into
solvent and cellulose solutions respectively (1.2 and 12 cP, short lengths, say 1⁄2 in. (13 mm), before washing.) Fabrics
approximately). should be cut into small pieces, desized (see Test Methods
D 629, Section 8), thoroughly washed, and dried. Raveling will
NOTE 3—Detailed specifications and directions for filling, calibrating,
and measurement with types of capillary viscometers most used are given
be helpful before dissolving samples that tend to get in the
in Test Method D 445. solvent. Materials containing a considerable amount of non-
cellulosic matter must first be purified; such treatments lie
outside the scope of this test method.
6
The sole source of supply of the viscosity oil standards known to the committee
at this time is Cannon Instrument Co., P. O. Box 16, State College, PA 16801. If you 10. Preparation of Solution
are aware of alternative suppliers, please provide this information to ASTM
Headquarters. Your comments will receive careful consideration at a meeting of the 10.1 The sample size is dependent upon the nature of the
responsible technical committee,1 which you may attend. material, smaller masses of high-viscosity celluloses and larger
2
D 1795
TABLE 2 Intrinsic Viscosities of Typical Samples on fritted-glass filters have been observed to give erratic results. Inad-
Intrinsic Approximate equate dispersion of the sample is apparently the cause, and two
Type of Material Viscosity, Concentration, modifications in procedure have been recommended in such cases. One is
dL/g g/dL to add about 0.04 % wetting agent to the water used to wet out the
Regenerated cellulose (rayons) 2 to 3 1 sample.7 The other requires use of cupriethylenediamine solutions of two
Dissolving pulps: concentrations: The sample is wetted out with one solution that is 0.167 M
Low viscosity 3 to 4 1 in copper and dispersion is completed by adding the second solution,
Regular viscosity 4 to 7 0.5 1.000 M in copper, in such volume as to make the final copper
High viscosity 7 to 10 0.3 concentration 0.500 M (see Section 14 of Test Methods D 539).
Cotton linters, for rayon and acetate 6 to 9 0.4
Paper (wood) pulps 3 to 8 0.4
Native cellulosesA 15 to 30 0.1 to 0.2
11. Measurement of Viscosity
A
Serious error may be introduced when this test method, which neglects effects 11.1 Transfer 7.0 mL of the solution by means of a syringe
of rate of shear upon viscosity, is used for native celluloses of high intrinsic or pipet to a viscometer previously placed in the bath at 25°C
viscosity.
and flushed with nitrogen (or fill as described in Test Method
D 445, Appendix A). Allow at least 5 min for the solution to
masses of low-viscosity celluloses being used in order to keep reach bath temperature.
the viscosity of the solutions within rather narrow limits. 11.2 By applying either pressure (with nitrogen) or suction,
(Working at nearly constant viscosity reduces the effect of rate draw the solution into the lower bulb of the viscometer until the
of shear upon the measurements.) The concentration for each top meniscus is a little above the mark between the two bulbs.
sample is chosen according to the rule: Measure the time t required for the meniscus to pass from this
@h#c 5 3.09 6 0.5 (2) mark to the mark below the lower bulb. Repeat at least twice
and average the observations, which should not differ by more
where: than 0.3 %.
[h] = intrinsic viscosity, dL/g, and 11.3 In the same way, measure the outflow time t0 for the
c = cellulose concentration, g/dL.
solvent. This of course must be determined not for the 1.00 M
Obviously, use of this rule requires knowledge of the
solvent as prepared or purchased, but for this solvent diluted
approximate intrinsic viscosity of the sample before the con-
with an equal volume of water.
centration can be estimated. In routine control work, such
information is available. If it is not, Table 2 will serve as an 12. Calculations
approximate guide.
10.2 Make up a preliminary solution of about the indicated 12.1 Calculate the viscosity, h, in centipoises, as follows:
concentration, and determine the viscosity as described in h 5 Ctd (3)
Sections 11 and 12. From the relative viscosity thus obtained,
where:
find the approximate value of the intrinsic viscosity by means C = viscometer constant (Section 8),
of Table 3. From this determine the concentration needed to t = outflow time, s, and
give: [h] c = 3.0. If this preliminary solution does not give a d = density, g/mL.
value of [h]c of 3.0 6 0.5, prepare a second solution of the Calculate the relative viscosity, hrel, as follows:
indicated concentration for the final viscosity measurement.
hrel 5 h/h 0
10.3 Alkaline solutions of cellulose are known to be sensi-
tive to oxidation. Hence it is usually necessary to exclude air where h0 is the viscosity of the solvent. Since the densities
during solution of the sample; several ways of doing this are of solvent and solution are practically the same, they cancel in
described in the literature, but the following is simple and determining relative viscosity. Hence a little work may be
adequate: Weigh out the calculated amount of air-dried cellu- saved by determining the kinematic viscosity, e, in centistokes,
lose (corrected to oven-dry mass) and transfer quantitatively to for solution and solvent:
a suitable glass or polyethylene container (capacity somewhat e 5 Ct (4)
more than 50 mL) that can be tightly closed by a stopper or
and then
screw cap. Add 25.0 mL of distilled water from a pipet or buret,
insert the stopper or cap, and shake in order to wet out and h rel 5 e/e0 (5)
disperse the sample. Sweep the air from the vessel with a If both solution and solvent are measured in the same
stream of nitrogen and, with the nitrogen still flowing, add 25.0 viscometer (see Note 4), relative viscosity may be obtained
mL of solvent. Stopper or cap tightly and shake vigorously by directly from the ratio of outflow times:
hand or in a mechanical shaker until the cellulose is completely hrel 5 t/t0 (6)
dissolved.
12.2 By means of Table 3, determine the product [h]c
NOTE 5—Most work pulp and regenerated celluloses dissolve within 5 corresponding to the value of the relative viscosity. From this
min. Mercerized celluloses do not dissolve as easily in cupriethylenedi- value and the concentration, calculate the intrinsic viscosity in
amine as in cuprammonium solvent and require longer times (up to 1 h).
decilitres per gram.
Some operators report difficulty in dissolving native celluloses including
cotton linters with degree of polymerization (DP) as low as that of wood
pulps. The difficulty shows up by much poorer precision of results than the
1 to 2 % that is normally obtained between measurements made with two 7
Lindsley, C. H., “Rapid Dispersion of Cellulose in Cupriethylenediamine,”
or more solutions of the same sample. Even solutions that leave no residue Textile Research Journal, Vol 21, 1951, p. 286.
3
D 1795
TABLE 3 Intrinsic Viscosity, [h]c , at Different Values of Relative Viscosity, h re l
A,B
[h]c
hrel
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
1.1 0.098 0.106 0.115 0.125 0.134 0.143 0.152 0.161 0.170 0.180
1.2 0.189 0.198 0.207 0.216 0.225 0.233 0.242 0.250 0.259 0.268
1.3 0.276 0.285 0.293 0.302 0.310 0.318 0.326 0.334 0.342 0.350
1.4 0.358 0.367 0.375 0.383 0.391 0.399 0.407 0.414 0.422 0.430
1.5 0.437 0.445 0.453 0.460 0.468 0.476 0.484 0.491 0.499 0.507
1.6 0.515 0.522 0.529 0.536 0.544 0.551 0.558 0.566 0.573 0.580
1.7 0.587 0.595 0.602 0.608 0.615 0.622 0.629 0.636 0.642 0.649
1.8 0.656 0.663 0.670 0.677 0.683 0.690 0.697 0.704 0.710 0.717
1.9 0.723 0.730 0.736 0.743 0.749 0.756 0.762 0.769 0.775 0.782
2.0 0.788 0.795 0.802 0.809 0.815 0.821 0.827 0.833 0.840 0.846
2.1 0.852 0.858 0.864 0.870 0.876 0.882 0.888 0.894 0.900 0.906
2.2 0.912 0.918 0.924 0.929 0.935 0.941 0.948 0.953 0.959 0.965
2.3 0.971 0.976 0.983 0.988 0.994 1.000 1.006 1.011 1.017 1.022
2.4 1.028 1.033 1.039 1.044 1.050 1.056 1.061 1.067 1.072 1.078
2.5 1.083 1.089 1.094 1.100 1.105 1.111 1.116 1.121 1.126 1.131
2.6 1.137 1.142 1.147 1.153 1.158 1.163 1.169 1.174 1.179 1.184
2.7 1.190 1.195 1.200 1.205 1.210 1.215 1.220 1.225 1.230 1.235
2.8 1.240 1.245 1.250 1.255 1.260 1.265 1.270 1.275 1.280 1.285
2.9 1.290 1.295 1.300 1.305 1.310 1.314 1.319 1.324 1.329 1.333
3.0 1.338 1.343 1.348 1.352 1.357 1.362 1.367 1.371 1.376 1.381
3.1 1.386 1.390 1.395 1.400 1.405 1.409 1.414 1.418 1.423 1.427
3.2 1.432 1.436 1.441 1.446 1.450 1.455 1.459 1.464 1.468 1.473
3.3 1.477 1.482 1.486 1.491 1.496 1.500 1.504 1.508 1.513 1.517
3.4 1.521 1.525 1.529 1.533 1.537 1.542 1.546 1.550 1.554 1.558
3.5 1.562 1.566 1.570 1.575 1.579 1.583 1.587 1.591 1.595 1.600
3.6 1.604 1.608 1.612 1.617 1.621 1.625 1.629 1.633 1.637 1.642
3.7 1.646 1.650 1.654 1.658 1.662 1.666 1.671 1.675 1.679 1.683
3.8 1.687 1.691 1.695 1.700 1.704 1.708 1.712 1.715 1.719 1.723
3.9 1.727 1.731 1.735 1.739 1.742 1.746 1.750 1.754 1.758 1.762
4.0 1.765 1.769 1.773 1.777 1.781 1.785 1.789 1.792 1.796 1.800
4.1 1.804 1.808 1.811 1.815 1.819 1.822 1.826 1.830 1.833 1.837
4.2 1.841 1.845 1.848 1.852 1.856 1.859 1.863 1.867 1.870 1.874
4.3 1.878 1.882 1.885 1.889 1.893 1.896 1.900 1.904 1.907 1.911
4.4 1.914 1.918 1.921 1.925 1.929 1.932 1.936 1.939 1.943 1.946
4.5 1.950 1.954 1.957 1.961 1.964 1.968 1.971 1.975 1.979 1.982
4.6 1.986 1.989 1.993 1.996 2.000 2.003 2.007 2.010 2.013 2.017
4.7 2.020 2.023 2.027 2.030 2.033 2.037 2.040 2.043 2.047 2.050
4.8 2.053 2.057 2.060 2.063 2.067 2.070 2.073 2.077 2.080 2.083
4.9 2.087 2.090 2.093 2.097 2.100 2.103 2.107 2.110 2.113 2.116
5.0 2.119 2.122 2.125 2.129 2.132 2.135 2.139 2.142 2.145 2.148
5.1 2.151 2.154 2.158 2.160 2.164 2.167 2.170 2.173 2.176 2.180
5.2 2.183 2.186 2.190 2.192 2.195 2.197 2.200 2.203 2.206 2.209
5.3 2.212 2.215 2.218 2.221 2.224 2.227 2.230 2.233 2.236 2.240
5.4 2.243 2.246 2.249 2.252 2.255 2.258 2.261 2.264 2.267 2.270
5.5 2.273 2.276 2.279 2.282 2.285 2.288 2.291 2.294 2.297 2.300
5.6 2.303 2.306 2.309 2.312 2.315 2.318 2.320 2.324 2.326 2.329
5.7 2.332 2.335 2.338 2.341 2.344 2.347 2.350 2.353 2.355 2.358
5.8 2.361 2.364 2.367 2.370 2.373 2.376 2.379 2.382 2.384 2.387
5.9 2.390 2.393 2.396 2.400 2.403 2.405 2.408 2.411 2.414 2.417
6.0 2.419 2.422 2.425 2.428 2.431 2.433 2.436 2.439 2.442 2.444
6.1 2.447 2.450 2.453 2.456 2.458 2.461 2.464 2.467 2.470 2.472
6.2 2.475 2.478 2.481 2.483 2.486 2.489 2.492 2.494 2.497 2.500
6.3 2.503 2.505 2.508 2.511 2.513 2.516 2.518 2.521 2.524 2.526
6.4 2.529 2.532 2.534 2.537 2.540 2.542 2.545 2.547 2.550 2.553
6.5 2.555 2.558 2.561 2.563 2.566 2.568 2.571 2.574 2.576 2.579
6.6 2.581 2.584 2.587 2.590 2.592 2.595 2.597 2.600 2.603 2.605
6.7 2.608 2.610 2.613 2.615 2.618 2.620 2.623 2.625 2.627 2.630
6.8 2.633 2.635 2.637 2.640 2.643 2.645 2.648 2.650 2.653 2.655
6.9 2.658 2.660 2.663 2.665 2.668 2.670 2.673 2.675 2.678 2.680
7.0 2.683 2.685 2.687 2.690 2.693 2.695 2.698 2.700 2.702 2.705
7.1 2.707 2.710 2.712 2.714 2.717 2.719 2.721 2.724 2.726 2.729
7.2 2.731 2.733 2.736 2.738 2.740 2.743 2.745 2.748 2.750 2.752
7.3 2.755 2.757 2.760 2.762 2.764 2.767 2.769 2.771 2.774 2.776
7.4 2.779 2.781 2.783 2.786 2.788 2.790 2.793 2.795 2.798 2.800
7.5 2.802 2.805 2.807 2.809 2.812 2.814 2.816 2.819 2.821 2.823
7.6 2.826 2.828 2.830 2.833 2.835 2.837 2.840 2.842 2.844 2.847
4
D 1795
TABLE 3 Continued
[h]c
hrel
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
7.7 2.849 2.851 2.854 2.856 2.858 2.860 2.863 2.865 2.868 2.870
7.8 2.873 2.875 2.877 2.879 2.881 2.884 2.887 2.889 2.891 2.893
7.9 2.895 2.898 2.900 2.902 2.905 2.907 2.909 2.911 2.913 2.915
8.0 2.918 2.920 2.922 2.924 2.926 2.928 2.931 2.933 2.935 2.937
8.1 2.939 2.942 2.944 2.946 2.948 2.950 2.952 2.955 2.957 2.959
8.2 2.961 2.963 2.966 2.968 2.970 2.972 2.974 2.976 2.979 2.981
8.3 2.983 2.985 2.987 2.990 2.992 2.994 2.996 2.998 3.000 3.002
8.4 3.004 3.006 3.008 3.010 3.012 3.015 3.017 3.019 3.021 3.023
8.5 3.025 3.027 3.029 3.031 3.033 3.035 3.037 3.040 3.042 3.044
8.6 3.046 3.048 3.050 3.052 3.054 3.056 3.058 3.060 3.062 3.064
8.7 3.067 3.069 3.071 3.073 3.075 3.077 3.079 3.081 3.083 3.085
8.8 3.087 3.089 3.092 3.094 3.096 3.098 3.100 3.102 3.104 3.106
8.9 3.108 3.110 3.112 3.114 3.116 3.118 3.120 3.122 3.124 3.126
9.0 3.128 3.130 3.132 3.134 3.136 3.138 3.140 3.142 3.144 3.146
9.1 3.148 3.150 3.152 3.154 3.156 3.158 3.160 3.162 3.164 3.166
9.2 3.168 3.170 3.172 3.174 3.176 3.178 3.180 3.182 3.184 3.186
9.3 3.188 3.190 3.192 3.194 3.196 3.198 3.200 3.202 3.204 3.206
9.4 3.208 3.210 3.212 3.214 3.215 3.217 3.219 3.221 3.223 3.225
9.5 3.227 3.229 3.231 3.233 3.235 3.237 3.239 3.241 3.242 3.244
9.6 3.246 3.248 3.250 3.252 3.254 3.256 3.258 3.260 3.262 3.264
9.7 3.266 3.268 3.269 3.271 3.273 3.275 3.277 3.279 3.281 3.283
9.8 3.285 3.287 3.289 3.291 3.293 3.295 3.297 3.298 3.300 3.302
9.9 3.304 3.305 3.307 3.309 3.311 3.313 3.316 3.318 3.320 3.321
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
10 3.32 3.34 3.36 3.37 3.39 3.41 3.43 3.45 3.46 3.48
11 3.50 3.52 3.53 3.55 3.56 3.58 3.60 3.61 3.63 3.64
12 3.66 3.68 3.69 3.71 3.72 3.74 3.76 3.77 3.79 3.80
13 3.80 3.83 3.85 3.86 3.88 3.89 3.90 3.92 3.93 3.95
14 3.96 3.97 3.99 4.00 4.02 4.03 4.04 4.06 4.07 4.09
15 4.10 4.11 4.13 4.14 4.15 4.17 4.18 4.19 4.20 4.22
16 4.23 4.24 4.25 4.27 4.28 4.29 4.30 4.31 4.33 4.34
17 4.35 4.36 4.37 4.38 4.39 4.41 4.42 4.43 4.44 4.45
18 4.46 4.47 4.48 4.49 4.50 4.52 4.53 4.54 4.55 4.56
19 4.57 4.58 4.59 4.60 4.61 4.62 4.63 4.64 4.65 4.66
A
Swedish Method CCA 27:57, Karin Wilson, Svensk Papperstidning, Vol 60, 1957, pp. 513 to 521.
B
Derived from the equation:
hrel 2 1 5 h sp 5 @h#cek·@h#c (7)
where: k8 = 0.30.
NOTE 6—Table 3 gives values of [h]c for the indicated values of h rel 12.4 The concept of fluidity is used by large numbers of
determined by the Martin equation: operators in place of viscosity. These two quantities are
log@~hrel 2 1!/c# 5 log@h# 1 k@h#c (8) reciprocals of one another. Intrinsic fluidity, the reciprocal of
intrinsic viscosity, is useful because it is a nearly linear
where k = 0.13. More precise values of [h] can be obtained by finding hrel function of yarn or fiber strength; its unit is grams per decilitre.
for three or more concentrations, plotting log [(hrel− 1)/ c] against c and
extrapolating the straight line through the points to c = 0. The intercept 13. Precision and Bias
gives log [h].
13.1 Precision—Based on interlaboratory testing, the repro-
12.3 For some purposes it is desirable to express results as ducibility is within 3 % of each other.
degree of polymerization, since this concept is easily under- 13.2 Bias—No statement of bias can be made, as no suitable
stood by nontechnical people who must interpret technical reference material exists for determining bias.
data. A reasonably good approximation to degree of polymer-
ization is obtained by multiplying intrinsic viscosity by 190, 14. Keywords
but values so obtained have relative not absolute significance. 14.1 cellulose; intrinsic viscosity
5
D 1795
6

Commercial Hexanes1
1. Scope * Liquid Petroleum Hydrocarbons by Oxidative Microcou-

1.1 This specification covers the range of products com- lometry4
monly referred to as hexanes, which find uses in the prepara- D 4367 Test Method for Benzene in Hydrocarbon Solvents
tion of adhesives, coatings, and printing inks, as raw materials By Gas Chromatography3
in chemical synthesis operations, and as solvents in various E 1 Specification for ASTM Thermometers5
kinds of extraction operations. E 300 Practice for Sampling Industrial Chemicals6
1.2 This standard does not purport to address all of the 2.2 U.S. Federal Specification:
safety concerns, if any, associated with its use. It is the PPP-C-2020 Chemicals, Liquid, Dry, and Paste: Packaging
responsibility of the user of this standard to establish appro- of7
priate safety and health practices and determine the applica- 3. Properties
1.3 For specific hazard information and guidance consult 3.1 Commercial hexanes shall conform to the following
supplier’s Material Safety Data Sheet. requirements:
Aniline point, min 57°C
2. Referenced Documents Apparent specific gravity
15.6/15.6°C 0.660–0.686
2.1 ASTM Standards: Bromine index, max 100
D 156 Test Method for Saybolt Color of Petroleum Prod- Color not darker than + 28 on the Saybolt
Scale or 10 on the Pt-Co Scale
ucts (Saybolt Chromometer Method)2 Distillation range:
D 268 Guide for Sampling and Testing Volatile Solvents Initial boiling point, min 63°C
and Chemical Intermediates for Use in Paint, and Related Dry point, max 71°C
Kauri-butanol value, max 33
Coatings and Materials3 Nonvolatile matter, mg/100 mL, max 1
D 611 Test Methods for Aniline Point and Mixed Anilene Odor nonresidual
Point of Petroleum Products and Hydrocarbon Solvents2 Sulfur, ppm, max 5
Benzene content, weight %, max 0.1
Organic Liquids3 4. Sampling
D 1133 Test Method for Kauri-Butanol Value of Hydrocar- 4.1 The material shall be sampled in accordance with
bon Solvents3 Practice E 300.
Cobalt Scale)3 5. Test Methods
D 1296 Test Method for Odor of Volatile Solvents and 5.1 The properties enumerated in this specification shall be
Diluents3 determined in accordance with the following ASTM test
D 1353 Test Method for Nonvolatile Matter in Volatile methods:
Solvents for Use in Paint, Varnish, Lacquer, and Related 5.1.1 Aniline Point—Test Method D 611.
Products3 5.1.2 Apparent Specific Gravity—Determine apparent spe-
D 2710 Test Method for Bromine Index of Petroleum Hy- cific gravity by any method that is accurate to the third decimal
drocarbons by Electrometric Titration4 place, the temperature of both specimen and water being
D 3120 Test Method for Trace Quantities of Sulfur in Light 15.6°C. See Guide D 268. If measurement is by hydrometer,
the instrument must be calibrated at the test temperature.
5.1.3 Benzene Content—Test Method D 4367.
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.4 Bromine Index—Test Method D 2710. Bromine index
and Related Coatings, Materials, and Applications and is the direct responsibility of is defined as the number of milligrams of bromine which will
5
2 6
3 7
Annual Book of ASTM Standards, Vol 06.04. Available from Standardization Documents, Order Desk, Bldg. 4 Section D,
4
Annual Book of ASTM Standards, Vol 05.02. 700 Robbins Ave., Philadelphia, PA 19111-5094, ATTN: NPODS.

1
D 1836
react with a 100–g sample under test conditions. 5.1.10 Sulfur—Test Method D 3120.
5.1.5 Color—Test Method D 156 or D 1209. In case of
dispute, Test Method D 156 shall be the referee method. 6. Packaging and Package Marking
5.1.6 Distillation—Test Method D 1078, using an ASTM
6.1 Package size shall be agreed upon by the purchaser and
Solvents Distillation Thermometer 39C having a range from 48
to 102°C and conforming to the requirements in Specification the supplier.
E 1. 6.2 Packaging shall conform to applicable carrier rules and
5.1.7 Kauri-Butanol Value—Test Method D 1133. regulations or when specified shall conform to Fed. Spec.
5.1.8 Nonvolatile Matter—Test Method D 1353. PPP-C-2020.
5.1.9 Odor—Test Method D 1296. Samples of particular
types of products being tested, having odor characteristics 7. Keywords
satisfactory to consumer and producer, are to be used as
7.1 commercial hexanes; hexanes; solvents
reference standards for comparison.
SUMMARY OF CHANGES
Committee D-1 has identified the location of the change to this standard since the last date of issue that my
impact the use of this standard.
(1) The definition and units of bromine index have been added
to 5.1.4 for information and to differentiate bromine index from
bromine number to avoid possible confusion.
2

Distilled Coconut Fatty Acids1
1. Scope D 1980 Test Method for Acid Value of Fatty Acids and
1.1 This specification covers distilled fatty acids derived Polymerized Fatty Acids2
from coconut oil. Two types are covered as follows: D 1982 Test Method for Titer of Fatty Acids2
1.1.1 Type I—Usually produced from raw coconut oil.
1.1.2 Type II—Usually produced from recovered coconut 3. Properties
oil. 3.1 Distilled coconut fatty acids shall conform to the re-
quirements in Table 1 .
2.1 ASTM Standards:
TABLE 1 Requirements for Distilled Coconut Fatty Acids
ASTM
Coatings2 Test Type I Type II
D 1544 Test Method for Color of Transparent Liquids Method
(Gardner Color Scale)3 Acid value D 1980 258 to 268 255 to 266
D 1959 Test Method for Iodine Value of Drying Oils and Saponification value D 1962 260 to 272 257 to 268
Fatty Acids2 Unsaponifiable matter, D 1965 1.00 1.00
max, %
D 1962 Test Method for Saponification Value of Drying Iodine value D 1959 8 to 15 8 to 15
Oils, Fatty Acids, and Polymerized Fatty Acids2 Color, Gardner, max D 1544 3 5
Titer, ° C D 1982 22 to 26 22 to 28
D 1965 Test Method for Unsaponifiable Matter in Drying
1
4. Test Method
and Related Coatings, Materials, and Applications and is the direct responsibility of 4.1 The properties enumerated in this specification shall be
Subcommittee D01.32 on Drying Oils. determined in accordance with Methods D 1467.
Current edition accepted Sept. 30, 1963. Originally issued 1961. Replaces
D 1841 – 61 T. 5. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 5.1 coconut fatty acids; coconut oil; fatty acids
1

Distilled Corn Fatty Acids1
1. Scope D 1980 Test Method for Acid Value of Fatty Acids and
1.1 This specification covers distilled fatty acids derived Polymerized Fatty Acids2
from corn oil; recovered corn oil usually is used. D 1982 Test Method for Titer of Fatty Acids2
2. Referenced Documents 3. Properties

2.1 ASTM Standards: 3.1 Distilled corn fatty acids shall conform to the require-
D 1467 Guide for Testing Fatty Acids Used in Protective ments in Table 1 .
Coatings2 TABLE 1 Requirements for Distilled Corn Fatty Acids
ASTM
(Gardner Color Scale)3 Test
D 1959 Test Method for Iodine Value of Drying Oils and Method
Fatty Acids2 Acid value D 1980 195 to 205
D 1962 Test Method for Saponification Value of Drying Saponification value D 1962 197 to 207
Unsaponifiable matter, max, % D 1965 1.50
Oils, Fatty Acids, and Polymerized Fatty Acids2 Iodine value, min D 1959 110
D 1965 Test Method for Unsaponifiable Matter in Drying Color, Gardner, max D 1544 8
Oils, Fatty Acids, and Polymerized Fatty Acids2 Titer, ° C D 1982 26 to 32
1
This specification is under the jurisdiction of ASTM Committee D-1 on Paint 4. Test Method
and Related Coatings, Materials, and Applications and is the direct responsibility of 4.1 The properties enumerated in this specification shall be
Current edition accepted Sept. 30, 1963. Originally issued 1961. Replaced
determined in accordance with Methods D 1467.
D 1842 – 61 T. 5. Keywords
2
3
Annual Book of ASTM Standards, Vol 06.01. 5.1 corn fatty acids; corn oil; fatty acids
1

Fractionated and Distilled Cottonseed Fatty Acids1

1.1 This specification covers distilled acids derived from Oils, Fatty Acids, and Polymerized Fatty Acids2
cottonseed oil. Three types are covered as follows: D 1965 Test Method for Unsaponifiable Matter in Drying
1.1.1 Type I—Highly fractionated fatty acids usually pro- Oils, Fatty Acids, and Polymerized Fatty Acids2
duced from recovered cottonseed oil. D 1980 Test Method for Acid Value of Fatty Acids and
1.1.2 Type II—Fractionated fatty acids usually produced Polymerized Fatty Acids2
from recovered cottonseed oil. D 1982 Test Method for Titer of Fatty Acids2
1.1.3 Type III—Usually produced from recovered cotton-
seed oil. 3. Properties
2. Referenced Documents 3.1 Fractionated and distilled cottonseed fatty acids shall
conform to the requirements in Table 1.
2.1 ASTM Standards:
4. Test Methods
Coatings2
D 1544 Test Method for Color of Transparent Liquids 4.1 The properties enumerated in this specification shall be
(Gardner Color Scale)3 determined in accordance with Methods D 1467.
Fatty Acids2 5. Keywords
1
5.1 cottonseed oil; fatty acids
Current edition accepted Sept. 30, 1963. Originally issued 1961. Replaces
D 1843 – 61 T.
2 3
1
D 1843
TABLE 1 Requirements for Distilled Cottonseed Fatty Acids
ASTM Test Method Type I Type II Type III
Acid value D 1980 195 to 201 106 to 204 199 to 205
Saponification value D 1962 197 to 203 198 to 206 201 to 207
Unsaponifiable matter, max, % D 1965 1.00 1.50 1.50
Iodine value D 1959 140 to 145 120 to 130 95 to 110
Color, Gardner, max D 1544 2 5 8
Titer, °C D 1982 5 max 25 max 32 to 38
2

Chemical Analysis of Basic Lead Silicochromate1
1. Scope D 2371 Test Method for Pigment Content of Solvent-

1.1 These test methods cover the chemical analysis of the Reducible Paints3
pigment commercially known as basic lead silicochromate and
are applicable to pigment supplied by the manufacturer and to
pigment, but not mixed pigments, separated from liquid 3.1 These test methods may be used to confirm the stated
coatings. The presence of basic lead silicochromate species lead oxide, chromium trioxide and silica content of basic lead
shall be confirmed by X-ray diffraction analysis (see Specifi- silicochromate and is useful for quality control.
cation D 1648). 4. Purity of Reagents
1.2 For liquid coatings the pigment must first be separated
from the vehicle before conducting the analysis. 4.1 Reagent grade chemicals shall be used in all tests.
1.3 The analytical procedures appear in the following order: Unless otherwise indicated, it is intended that all reagents shall
Sections
Lead oxide 6 to 14 specifications are available.5 Other grades may be used, pro-
Chromium trioxide 15 to 23
Silica 24 to 27
Moisture and other volatile matter 28 high purity to permit its use without lessening the accuracy of
Coarse particles 29 the determination.
Oil absorption 30
Mass color and tinting strength 31
understood to mean reagent water conforming to Type II of
1.4 This standard does not purport to address the safety Specification D 1193.
concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and 5. Preparation of Sample
health practices and determine the applicability of regulatory 5.1 Thoroughly mix liquid coatings and separate in accor-
limitations prior to use. dance with Test Method D 2371 sufficient pigment to enable
the required analyses to be carried out.
5.2 Thoroughly mix pigment supplied as such and grind
2.1 ASTM Standards: separated pigment to a fine powder in a mortar and pestle
D 185 Test Methods for Coarse Particles in Pigments, before taking portions for analysis.
Pastes, and Paints2
D 280 Test Methods for Hygroscopic Moisture (and Other TOTAL LEAD AS LEAD OXIDE-GRAVIMETRIC
Matter Volatile Under the Test Conditions) in Pigments2 METHOD
D 281 Test Method for Oil Absorption of Pigments by
Spatula Rub-Out3 6. Apparatus
D 387 Test Method for Color and Strength of Color Pig- 6.1 Glass Filtering Crucible (medium-porosity fritted
ments with a Mechanical Muller3 disk), dried to constant weight before use.
D 1193 Specification for Reagent Water4 6.2 Platinum Dish.
D 1648 Specification for Basic Lead Silicochromate Pig-
ment2 7. Reagents
7.1 Acetic Acid (Glacial).
1
5
of Subcommittee D01.31 on Pigments Specifications. Reagent Chemicals, American Chemical Society Specifications, American
2
3
Annual Book of ASTM Standards, Vol 06.01. and National Formulary, U.S. Pharmacopeial Convention, Inc., (USPC), Rockville,
4
1
D 1844
7.2 Ammonium Hydroxide (sp gr 0.90)—Concentrated am- 9. Calculation
monium hydroxide (NH4OH). 9.1 Calculate the percent of total lead as lead oxide (PbO) as
7.3 Ammonium Acetate, Acid Solution— To 300 mL of follows:
water add an equal volume of NH4OH. Neutralize with glacial
PbO, % 5 ~P3 69.06!/S
acetic acid and add 20 mL in excess.
7.4 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- where:
chloric acid (HCl). P 5 lead chromate (PbCrO4) precipitate, g,
7.5 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric S 5 sample used, g, and
acid (HF). molecular weight ~PbO!
7.6 Hydrogen Sulfide (H2S)—Handle and use H2S in hood. molecular weight ~PbCrO4 5
7.7 Isopropyl Alcohol (50 and 98 %). 223.21
7.8 Nitric Acid (sp gr 1.42)—Concentrated nitric acid 323.21 5 0.6906 3 100 ~for percent! 5 69.06
(HNO3) (see 7.4.1). 69.06 represents the gravimetric factor to convert grams of
7.9 Potassium Dichromate Solution (saturated)—Prepare a PbCrO 4 to grams of PbO.
saturated solution of potassium dichromate (K2Cr2O7) in water. This gravimetric factor has led to high results due to the
7.10 Sulfuric Acid (1 + 1)—Carefully mix 1 volume of presence of mixed lead chromates and an empirical factor can
concentrated sulfuric acid (H2SO4, sp gr 1.84) with 1 volume be used to compensate:
of water (see 7.4.1). Empirical factor 5 69.06 3 0.9944 5 68.67
8. Procedure ALTERNATIVE METHOD FOR TOTAL LEAD AS

LEAD OXIDE—TITRIMETRIC METHOD
8.1 Weigh accurately (to 0.1 mg) 1 g of the sample into a
platinum dish. Add 5 mL of HNO3 and 10 mL of HF. 10. Apparatus
Cautiously evaporate to dryness on a steam bath. Repeat the 10.1 Platinum Dish.
addition of HNO3 and HF and again cautiously evaporate to 10.2 Filter Paper, ashless, medium texture, or paper pulp.
dryness. Wash the sides of the dish with a little water and
evaporate to dryness. Wet the residue with 5 mL of HNO3, 11. Reagents
warm gently, and transfer the residue to a 400-mL beaker using 11.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
a policeman. Neutralize with NH4OH, and then make the monium hydroxide (NH4OH).
solution just acid with HCl, adding 5 mL in excess. Dilute to 11.2 Glacial Acetic Acid (min 99.7 %)—Concentrated gla-
200 mL and heat to just below the boiling point until solution cial acetic acid (CH3COOH).
is complete. 11.3 Acid Ammonium Acetate Buffer—Mix 400 mL of
8.2 Pass H2S through the solution for about 20 min. Filter, distilled water and 400 mL of ammonium hydroxide (sp gr
using paper pulp. Wash the precipitate five to six times with 0.90). Add 375 mL of reagent grade glacial acetic acid slowly
water just acid with HCl and saturated with H2S. Transfer the while stirring.
paper and precipitate to the original beaker, add 25 mL of 11.4 Cupric Sulfate Solution (0.1 M)—Dissolve 25 g of
HNO3, boil until the residue is white, then add 10 mL of H2SO4 CuSO 4·5H2O in distilled water and dilute to 1 L.
(1 + 1). Destroy the organic material by evaporating the 11.5 Disodium Ethylenediaminetetracetate Dihydrate (0.05
solution to dense white fumes, making further additions of M) (EDTA solution)6—Dissolve 18.6 g of the salt in distilled
HNO3 until there is no charring. water and dilute to 1 L. Standardize the solution as follows:
8.3 Cool the solution, add 10 mL of water, and evaporate to Transfer 25 mL of lead standard (11.14) to a 400-mL beaker.
fumes. Repeat the addition of water and the evaporation. Cool Add concentrated ammonium hydroxide (11.1) dropwise until
the solution, add 40 mL of water, and bring the solution to a permanent precipitate just forms. Add 25 mL of acid
boiling. Cool the solution and add 50 mL of isopropyl alcohol ammonium acetate (11.3), dilute to 200 mL, heat to boiling,
(98 %), stir, and allow the solution to stand cold for at least 4 add 4 drops of copper EDTA (11.7) and 12 drops of PAN
h. Filter, using paper pulp, and wash once with cold isopropyl (11.13) and titrate with the EDTA to a clear yellow.
alcohol (50 %) containing 10 mL of H2SO 4 (sp gr 1.84)/100 1 mL Na2 EDTA 5 0.2790/V g PbO
mL.
8.4 Transfer the precipitate to the original beaker with 150 where:
mL of water, add 50 mL of the ammonium acetate solution, and V 5 EDTA required for titration, mL
boil the solution until the lead sulfate dissolves. Filter while hot g 5 lead oxide, g, and
through the original paper and wash well (6 to 8 washes) with 0.05 M 3 0.22321 5 0.01116 g PbO in 1 mL of lead
hot water. To the filtrate add 5 mL of glacial acetic acid, heat standard (10.14) (25 mL) (0.05 M) (0.22321) 5 0.2790 g PbO
the solution to boiling, and add 20 mL of saturated K2Cr2O7 in 25 mL of lead standard (10.14).
solution. Boil the solution until the precipitate turns orange, 11.6 Murexide Indicator Tablets—Ammonium salt of pur-
and allow to stand on a warm plate for at least 2 h. Filter puric acid.
through a glass filtering crucible (medium-porosity fritted
disk), wash three times with hot water, and finally once with 6
The standardized solution may also be purchased from Corco Chemical Corp.
alcohol. Dry in an oven at 105°C for 2 h, cool, and weigh. Catalog No.—Special.
2
D 1844
11.7 Copper-EDTA Solution—Mix equivalent amounts of cate determinations obtained by the same operator should be
cupric sulfate solution (11.4) and EDTA solution (11.5) and considered suspect if they differ by more than the following:
store in a dropping bottle. The cupric sulfate EDTA equiva- Percent Absolute PbO
lence may be determined as follows: Pipet 10 mL of cupric 28 % 0.20
45 % 0.30
sulfate into a beaker, add concentrated ammonium hydroxide
dropwise until the precipitate which forms just redissolves. 14.1.2 Reproducibility—A realistic range could not be es-
Dilute to 200 mL with water, add two Murexide indicator tablished for results between laboratories because of the
tablets, and titrate immediately with EDTA to a color change limited number of participating laboratories.
from yellow to purple. 14.1.3 Bias—A bias statement could not be established
11.8 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- because of the limited number of participating laboratories.
chloric acid (HCl) (see 7.4.1).
11.9 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric CHROMIUM TRIOXIDE
acid (HF).
11.10 Hydrogen Sulfide (H2S)—Cylinder. Handle and use in 15. Interference
a hood. 15.1 Soluble Fe+3 will cause high results. See Section 20
11.11 Hydrogen Sulfide Wash Solution— Add 10 mL of HCl .
(sp gr 1.19) to 1 L of water and saturate with H2S.
11.12 Nitric Acid (sp gr 1.42)—Concentrated nitric acid 16. Reagents
(HNO3). 16.1 Potassium Dichromate, Standard Solution (0.1 N)—
11.13 Pan Indicator (1-(2-pyridylazo)-2-naphthol)— Weigh 4.904 g of dried potassium dichromate (K2Cr2O7),
Dissolve 0.1 g in 100 mL of ethanol. dissolve it in water, and dilute to 1 L with water in a volumetric
11.14 Primary Standard (0.05 M lead nitrate)—Dissolve flask.
16.5615 g of reagent grade lead nitrate in distilled water and 16.2 Potassium Iodide Solution (150 g/L)—Dissolve 150 g
dilute to 1 L. of potassium iodide (KI) in water and dilute to 1 L.
1 mL 5 0.01116 g PbO 16.3 Hydrochloric Acid Mixture—Saturate water with NaCl
(about 350 g/L). To each litre of this solution add 150 mL of
11.15 Sulfuric Acid (1 + 1)—Carefully mix 1 volume of water and 100 mL of concentrated HCl (sp gr 1.19).
concentrated sulfuric acid (H2SO4, sp gr 1.84) with 1 volume 16.4 Sodium Thiosulfate Solution (0.1 N)—Dissolve 24.8 g
of water. of reagent grade Na2S2O3·5H2O in recently boiled water and
12. Procedure dilute to 1 L with additional recently boiled water. To stan-
dardize, pipet 25 mL of the standard potassium dichromate
12.1 Dissolve 1 g of pigment in accordance with 8.1 and
solution (exactly 0.1000 N) into a 250-mL Erlenmeyer flask.
8.2.
Add 100 mL of water, 15 mL of potassium iodide solution, and
12.2 Cool, so that the addition of 25 mL of water does not
15 mL of concentrated hydrochloric acid (sp gr 1.19). Titrate
cause excessive splattering of the sulfuric acid; the solution at
the liberated iodine with sodium thiosulfate solution until the
this point should be water white. Add ammonium hydroxide
reddish-brown color becomes quite faint. Add 5 mL of starch
(sp gr 0.90) until the pH of the solution is 5 to 5.5 (as indicated
solution and continue the titration dropwise until the blue color
by pH paper). Add 50 mL of acid ammonium acetate (11.3),
changes to a pale green. Calculate the normality of the sodium
boil 5 min, dilute to 200 mL with water, heat to boiling, add 4
thiosulfate solution as follows:
drops of copper-EDTA (11.7) and 12 drops of PAN
(11.1311.13) and titrate while hot with standard EDTA to a 2.5000
N 5 M
clear yellow.
13. Calculation where:
N 5 normality, and
13.1 Calculate the percent lead oxide as follows: M 5 sodium thiosulfate solution, mL,
V 3 L 3 100 16.5 Starch Indicator Solution—Make a homogeneous
PbO, % 5 S paste of 10 g of soluble starch in cold water. Add to this 1 L of
where: boiling water, stir rapidly, and cool. Salicylic acid (1.25 g/L)
V 5 EDTA required for titration, mL, may be added to preserve the indicator. If long storage is
L 5 lead equivalent of EDTA solution, and required, the solution should be kept in a refrigerator at 4 to
S 5 specimen weight, g. 10°C (40 to 50°F). Prepare fresh indicator when the end point
of the titration from blue to colorless or blue to light green fails
14. Precision and Bias to be sharp.
14.1 On the basis of an interlaboratory study of the method
in which operators in three laboratories analyzed two paints 17. Procedure
containing basic lead silicochromate with iron oxide the 17.1 Weigh to 0.1 mg about 1 g of sample into a 500-mL
following criteria should be used for judging the acceptability Erlenmeyer flask. Add 100 mL of NaCl-HCl solution and
of the results at the 95 % confidence level: dissolve the sample without heat, keeping the solution cold.
14.1.1 Repeatability—Two results, each the mean of dupli- (Silica will not dissolve, but it does not interfere with the
3
D 1844
analysis.) Add 10 mL of KI solution and titrate with 0.1 N 21. Procedure
sodium thiosulfate solution until the reddish-brown color is 21.1 Transfer 0.5 g of pigment to a 500-mL high-silica
almost gone. Add 5 mL of starch solution and titrate slowly, Erlenmeyer flask.7 Add 10 mL of nitric acid (sp gr 1.42), and
dropwise, until the blue color changes to a light green. 10 mL of perchloric acid (sp gr 1.67) and cover with a watch
glass. Evaporate to fumes (flask will fill with white vapor) of
18. Calculation
perchloric acid, cool, add 15 mL of water, and evaporate to
18.1 Calculate the percent of chromium trioxide (CrO 3) as fumes. Continue fuming for 15–20 min (the specimen should
follows: be red-orange color). Cool immediately by placing the flask in
CrO3, % 5 @~V1N 3 0.03334!/S 2# 3 100 a cold water bath.
21.2 Wash down the cover glass and sides of the flask with
where: water. Add 50 mL of HCl mixture and 50 mL of 0.05 M EDTA
V 1 5 sodium thiosulfate solution required for titration of solution. Adjust to pH 8 (determined with pH paper) with
the specimen, mL ammonium hydroxide (sp gr 0.90) and add 50 mL of HCl
N 5 normality of the sodium thiosulfate solution,
mixture (16.3). Cool the flask to 20 to 25°C, add 10 mL of
S 1 5 sample used, g, and
potassium iodide solution, 10 mL of starch solution, and titrate
16 immediately with standard sodium thiosulfate solution to a
CrO3 → Cr13 sharp change in the starch indicator. (The final solution color
milliequivalent weight may be lavender or green depending on the composition of the
molecular weight ~CrO3
sample).
5 1000 3 3 ~valence! 21.3 Add 2 to 3 mL of HF, (20.4) stir for 1⁄2 min and if the
indicator changes color titrate to the endpoint.
99.99
5 1000 3 3 22. Calculation
5 0.03334 (1) 22.1 Calculate the percent chromium trioxide (CrO 3) as
follows:
ALTERNATIVE METHOD FOR CHROMIUM
TRIOXIDE CrO3, % 5 @~V2N1 3 0.03334!/S 3# 3 100
19. Scope where:

V 2 5 sodium thiosulfate solution required for titration of
19.1 This test method determines total chromium as chro- the specimen, g,
mium trioxide. Iron oxide interference is masked by the use of N1 5 normality of the sodium thiosulfate solution, and
EDTA. This procedure is not applicable when chromium oxide S3 5 sample used, g.
green (Cr2O3) is present. This test method is limited to basic
lead silicochromate pigments with or without iron oxide. 23. Precision and Bias
19.2 The perchloric acid is employed as an oxidizing agent 23.1 On the basis of an interlaboratory study of this test
to ensure complete oxidation of any reduced chromium. When method in which operators in three laboratories analyzed two
perchloric acid is used, concentrated nitric acid must also be paints containing basic lead silicochromate with iron oxide the
used. The use of a perchloric acid hood is optional since the following criteria should be used for judging the acceptability
specimen is covered with a watch glass and is being oxidized, of the results at the 95 % confidence level.
not wet ashed. 23.1.1 Repeatability—Two results, each the mean of dupli-
20. Reagents cate determinations, obtained by the same operator should be
considered suspect if they differ by more than the following:
20.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
Percent Absolute
monium hydroxide (NH4OH). CrO3
20.2 Disodium Ethylenediaminetetracetate Dihydrate 3 % CrO3 0.15
5 % CrO3 0.40
(0.05 M) (EDTA)— Dissolve 18.6 g of the reagent grade salt in
distilled water and dilute to 1 L. See 11.5 for standardization. 23.1.2 Reproducibility—A realistic range could not be es-
20.3 Hydrochloric Acid Mixture—See 16.3. tablished for results between laboratories because of the
20.4 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric limited number of participating laboratories.
acid (HF). 23.1.3 Bias—A bias statement could not be established
20.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid because of the limited number of participating laboratories.
(HNO3).
20.6 Perchloric Acid (sp gr 1.67)—Concentrated perchloric SILICA
acid (HClO4).
20.7 Potassium Dichromate, Standard Solution (0.1 N)— 24. Apparatus
See 16.1. 24.1 Platinum Crucible.
20.8 Potassium Iodide Solution (150 g/Litre)—See 16.2.
20.9 Sodium Thiosulfate Solution (0.1 N)—See 16.4.
20.10 Starch Indicator Solution—See 16.5. 7
Vycor has been found suitable for this purpose.
4
D 1844
25. Reagents W 1 5 weight of crucible and contents before HF treat-
25.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- ment, g,
chloric acid (HCl). W2 5 weight of crucible and contents after HF treatment,
25.2 Hydrofluoric Acid (47 %)—Concentrated hydrofluoric g, and
acid (HF). S4 5 weight of sample used, g.
25.3 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
(HNO3). MOISTURE AND OTHER VOLATILE MATTER
25.4 Nitric Acid (1 + 19)—Mix 1 volume of concentrated
HNO3(sp gr 1.42) with 19 volumes of water. 28. Procedure
25.5 Perchloric Acid (sp gr 1.67)—Concentrated perchloric 28.1 Determine moisture and other volatile matter in accor-
acid (HClO4). dance with Method A of Test Method D 280.
25.6 Sulfuric Acid (1 + 4)—Carefully mix 1 volume of
concentrated sulfuric acid (H2SO4, sp gr 1.84)6 with 4 volumes COARSE PARTICLES
of water.
29. Procedure
26. Procedure 29.1 Determine the percent coarse particles in the pigment
26.1 Weigh 0.5 g of pigment and transfer to a 400-mL as received in accordance with Test Methods D 185.
beaker. Add 10 mL each of HCl (sp gr 1.19) and HNO3(sp gr
1.42). Warm slightly, if necessary, to dissolve the chromate. OIL ABSORPTION
Add 50 mL of HClO 4 and fume for 15 to 20 min. Wash the
sides of the beaker down with 30 to 40 mL of water, evaporate, 30. Procedure
and fume for 10 min. Cool and dilute to 200 mL with water. 30.1 Determine the oil absorption of the pigment in accor-
Filter through a double acid-washed quantitative paper and dance with Test Method D 281.
wash eight times with hot water, once with HNO3 (1 + 19) and
finally again with hot water. MASS COLOR AND TINTING STRENGTH
26.2 Dry and ignite the paper and precipitate in a platinum
crucible. Cool in a desiccator and weigh the crucible and 31. Procedure
contents. To the crucible add 2 drops of H2SO4 (1 + 4) and 15 31.1 Determine the mass color and tinting strength in
mL of HF. Evaporate cautiously on a hot plate and ignite at accordance with Test Method D 387.
1000°C for approximately 5 min. Cool in a desiccator and
weigh to constant weight. 32. Precision and Bias
32.1 Precision and bias have not been determined.
27. Calculation
27.1 Calculate the percent of silica (SiO2) as follows: 33. Keywords
SiO 2, % 5 @~W1 2 W2!/S 4# 3 100 33.1 basic lead silicochromate; chromium in basic lead
silicochromate; lead in basic lead silicochromate; lead oxide;
where: pigment; silica in basic lead silicochromate
5

Chemical Analysis of Strontium Chromate Pigment1

1.1 These test methods cover the chemical analysis of 5.1 Reagent grade chemicals shall be used in all tests.
strontium chromate pigment. Unless otherwise indicated, it is intended that all reagents shall
1.2 The analytical procedures appear in the following order: conform to the specifications of the Committee on Analytical
Sections Reagents of the American Chemical Society, where such
specifications are available.5 Other grades may be used, pro-
Strontium by the Strontium Sulfate Method 7to10
Chromium by the Thiosulfate Method 11to14
Chloride Content 15 high purity to permit its use, without lessening the accuracy of
Sulfate Content 16 the determination.
Coarse Particles 18
Mass Color and Tinting Strength 19 understood to mean Type II of Specification D 1193.
1.3 This standard does not purport to address the safety 6. Preparation of Sample
concerns associated with its use. It is the responsibility of the
6.1 Mix the sample thoroughly. Take a sufficient quantity
user of this standard to establish appropriate safety and health
for chemical analysis and pass it through a No. 325 (4-µm)
practices and determine the applicability of regulatory limita-
sieve.
tions prior to use.
STRONTIUM BY THE STRONTIUM SULFATE
METHOD
2.1 ASTM Standards:
D 185 Test Methods for Coarse Particles in Pigments, 7. Reagents
Pastes, and Paints2 7.1 Acetic Acid (glacial).
D 280 Test Methods for Hygroscopic Moisture (and Other 7.2 Ammonium Hydroxide (1+3)—Mix 1 volume of concen-
Matter Volatile Under the Test Conditions) in Pigments2 trated ammonium hydroxide (NH4OH, sp gr 0.90) with 3
D 387 Test Method for Color and Strength of Color Pig- volumes of water.
ments with a Mechanical Muller3 7.3 Ethyl Alcohol, conforming to Formula No. 2B or No. 30
D 444 Test Methods for Chemical Analysis of Zinc Yellow of the U.S. Bureau of Alcohol, Tobacco, and Firearms.
Pigment (Zinc Chromate Yellow)2 7.4 Hydrochloric Acid (1+1)—Mix equal volumes of con-
D 1193 Specification for Reagent Water4 centrated hydrochloric acid (HCl, sp gr 1.19) and water.
7.5 Sulfuric Acid (1+19)—Mix 1 volume of concentrated
sulfuric acid (H2SO4, sp gr 1.84) with 19 volumes of water.
3.1 These test methods may be used to confirm the stated
strontium oxide and chromium oxide content of strontium 8. Procedure
chromate. 8.1 Weigh to 0.1 mg about 0.5 g of the sample into a
400-mL beaker. Add 40 mL of HCl (1+1) and heat the solution
4. Apparatus
to dissolve the pigment. Add 40 mL of ethyl alcohol until the
4.1 Gooch crucible. chromium is reduced, as this is indicated by a dark coloration
4.2 Electric Furnace, capable of 800°C. of the solution. Add to the solution 100 mL of water and
sufficient NH4OH (1+3) to form a slight persistent precipitate.
1
and Related Coatings, Materials, and Applications and are under the jurisdiction of
5
Subcommittee D01.31 on Pigment Specifications. Reagent Chemicals, American Chemical Society Specifications, American
published as D 1845 – 61 T. Last previous edition D 1845– 65 (1979)e2. listed by the American Chemical Society, see Analar Standards for Laboratory
2
3
4
1
D 1845
8.2 Add HCl dropwise until the precipitate just redissolves where:
(Note 1). Heat the solution to just under boiling and add 20 mL N 5 normality, and
of H2SO4(1+19). Add 100 mL of ethyl alcohol and allow the M 5 sodium thiosulfate solution, g.
precipitate to settle for several hours or overnight. 11.4 Starch Indicator Solution—Make a homogenous paste
NOTE 1—For a cleaner precipitate, add HCl until a pH of 2.0 is reached, of 10 g of soluble starch in cold water. Add to this 1 L of
instead of adding HCl dropwise until the precipitate is just dissolved. Then boiling water, stir rapidly, and cool. Salicylic acid (1.25 g/L)
add 25 mL of acetic acid to minimize the tendency of the sulfate to form may be added to preserve the indicator. If long storage is
a complex with trivalent chromium. Finally, heat the solution, and add required, the solution should be kept in a refrigerator at 4 to
H2SO 4 (1 + 19). 10°C (40 to 50°F). Prepare fresh indicator when the end point
8.3 Filter the precipitate through a Gooch crucible that has of the titration from blue to colorless or blue to light green fails
been previously dried to constant weight. Wash the precipitate to be sharp.
several times with a solution of equal volumes of ethyl alcohol,
water, and H 2SO4 (1+19). Dry the crucible in an oven and then 12. Procedure
ignite for 1⁄2 h at 800°C or until constant weight is attained 12.1 Weigh accurately approximately 0.2 g of the sample
(weight loss less than 0.1 mg). Cool and weigh the crucible. into a 250-mL iodine flask. Add 50 mL of water and 50 mL of
HCl (1 + 5); swirl the flask to complete solution. Add 20 mL of
9. Calculation KI solution and allow the solution to stand for several minutes.
9.1 Calculate the percent of strontium oxide (SrO) as 12.2 Titrate the liberated iodine with 0.1 N Na2S2O3 solu-
follows: tion until the reddish brown iodine color becomes faint. Add 1
SrO, % 5 @~P 3 0.56416!/S# 3 100 mL of starch solution and continue the titration cautiously to
the end point which is easily discernible when the color
where: changes from blue to a light green with no blue tinge.
P 5 SrSO4 precipitate, g, and
S 5 pigment specimen, g. 13. Calculation
molecular weight of SrO 103.63 13.1 Calculate the percent of chromium as chromic oxide
0.56416 5 molecular weight of SrSO 5 163.70
4 (CrO3) as follows:
10. Precision CrO3, % 5 @~VN 3 0.03334!/S# 3 100
10.1 Within Laboratory—The usual difference between du- where:

plicate runs performed by the same analyst is approximately V 5 Na2S2O3 solution required for titration of specimen,
0.2 % of the SrO content of the pigment tested. mL,
10.2 Between Laboratories—The average difference be- N 5 normality of the Na 2S2O3 solution, and
tween two determinations performed by different analysts in S 5 sample used, g.
different laboratories is approximately 0.5 % of the SrO
content of the pigment tested. 14. Precision and Bias
14.1 Within Laboratories—The usual difference between
CHROMIUM BY THE THIOSULFATE METHOD duplicate runs performed by the same analyst is approximately
0.3 % of the CrO3 content of the pigment tested.
11. Reagents
14.2 Between Laboratories—The average difference be-
11.1 Hydrochloric Acid (1+5)—Mix 1 volume of concen- tween two determinations performed by different analysts in
trated hydrochloric acid (HCl, sp gr 1.19) with 5 volumes of different laboratories is approximately 0.5 % of the CrO3
water. content of the pigment tested.
11.2 Potassium Iodide Solution (150 g per L)—Dissolve
molecular weight CrO2 99.99
150 g of potassium iodide (KI) in water and dilute to 1 L. 0.0334 5 5 1000 3 3
1000 3 3 ~volume!
11.3 Sodium Thiosulfate Standard Solution (0.1 N)—
Dissolve 24.8 g of reagent grade Na2S2O3·5H2O in recently 5 milliequivalent weight
boiled water and dilute to 1 L with additional recently boiled
water. To standardize, pipet 25 mL of the standard potassium CHLORIDE CONTENT
dichromate solution (exactly 0.1000 N) into a 250-mL Erlen-
meyer flask. Add 100 mL of water, 15 mL of potassium iodide 15. Procedure
solution, and 15 mL of concentrated hydrochloric acid (sp gr 15.1 Determine the chloride content in accordance with Test
1.19). Titrate the liberated iodine with sodium thiosulfate Methods D 444.
solution until the reddish-brown color becomes quite faint. Add
5 mL of starch solution and continue the titration dropwise SULFATE CONTENT
until the blue color changes to a pale green. Calculate the
normality of the sodium thiosulfate solution as follows: 16. Procedure
2.5000 16.1 Determine the sulfate content in accordance with the
N5 M Test Methods D 444.
2
D 1845
MOISTURE AND OTHER VOLATILE MATTER MASS COLOR AND TINTING STRENGTH
17.1 Determine moisture and other volatile matter in accor-
dance with Method A of Test Methods D 280. 19.1 Determine mass color and tinting strength in accor-
dance with Test Method D 387.
COARSE PARTICLES
20. Keywords
18. Procedure
20.1 chromium; thiosulfate method; strontium chromate
18.1 Determine the percentage of coarse particles in the
pigment as received in accordance with Test Methods D 185. pigment
3

Total Chlorine Content of Epoxy Resins1

1.1 These test methods cover the determination of the total 5.1 Reagent grade chemicals shall be used in all tests.
chlorine content, in concentrations below 1 weight percent, of Unless otherwise indicated, it is intended that all reagents shall
epoxy resins. Both organic and inorganic chlorine compounds conform to the specifications of the Committee on Analytical
contained in the resin are determined. Epoxy resin is defined as Reagents of the American Chemical Society, where such
the reaction product of a chlorohydrin and a di- or polyfunc- specifications are available.3 Other grades may be used, pro-
tional phenolic compound. vided it is first ascertained that the reagent is of sufficiently
1.2 Two alternative test methods for determining chloride high purity to permit its use without lessening the accuracy of
ion concentration resulting from combustion of the sample are the determination.
included as follows: 5.2 Unless otherwise indicated, references to water shall be
Sections understood to mean reagent water conforming to Type II of
Test Method A—Potentiometric Titration 6-10 Specification D 1193.
Test Method B—Gravimetric Determination 11-15
1.3 This standard does not purport to address all of the TEST METHOD A—POTENTIOMETRIC TITRATION
6. Apparatus
priate safety and health practices and determine the applica- 6.1 Combustion Apparatus—An oxygen bomb4 apparatus
bility of regulatory limitations prior to use. for combustion of the sample.
6.2 Titration Apparatus—A suitable pH meter equipped
2. Referenced Documents with a glass-silver electrode system and titration stand, stirrer,
2.1 ASTM Standards: beakers, and 10-mL buret.
7. Reagents
3. Summary of Test Method 7.1 Methyl Red Indicator (0.2 % alcohol solution)—
3.1 The resin is oxidized by combustion in a bomb contain- Dissolve 0.2 g of methyl red in 100 mL of methanol, ethanol or
ing oxygen under pressure. The chlorine compounds thus isopropanol.
liberated are absorbed in a sodium carbonate solution. In Test 7.2 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
Method A the amount of chlorine present is determined by (HNO3).
potentiometric titration with standard silver nitrate solution. In 7.3 Oxygen, free of combustible materials and halogen
Test Method B the amount of chlorine present is determined compounds, available at a pressure of 40 atm.
gravimetrically by precipitation as silver chloride. 7.4 Silver Nitrate, Standard Solution (0.01 N)—Dissolve in
water 1.70 6 0.01 g of crystalline silver nitrate (AgNO3) which
4. Significance and Use previously has been pulverized, dried at 150°C for 1 h, and
4.1 The total chlorine content of epoxy resins is an impor- stored in a glass-stoppered bottle, and dilute to 1 L. Standardize
tant variable in determining reactivity of epoxy resins and
performance of coatings prepared from them. These test 3
methods may be used to determine the total chlorine content of Chemical Society, Washington, DC. For suggestions on the testing of reagents not
manufactured epoxy resins to confirm specification limits. listed by the American Chemical Society, see Analar Standards for Laboratory
MD.
4
The sole source of supply of the double-valve, self-sealing oxygen bomb
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint equipped with a safety-relief-type oxygen filling connection, ignition circuit, fuse
and Related Coatings, Materials, and Applications and are the direct responsibility wire, sample cups, and water bath, known to the committee at this time is Parr
of Subcommittee D 01.33 on Polymers and Resins. Instrument Co., 209 53rd St., Moline, IL 61265. If you are aware of alternative
Current edition approved April 15, 1993. Published June 1993. Originally suppliers, please provide this information to ASTM Headquarters. Your comments
published as D 1847 – 61 T. Last previous edition D 1847 – 87. will receive careful consideration at a meeting of the responsible technical
2
Annual Book of ASTM Standards, Vol 11.01. committee,1 which you may attend.
1
D 1847
against an accurately weighed amount of sodium chloride 8.2.4 Continue the titration until the rate of change of cell
(NaCl) dissolved in 75 to 100 mL of water. potential is less than 2 mV per 0.1 mL of AgNO3 solution.
7.5 Sodium Carbonate Solution (20 g/L)—Dissolve 20 g of Remove the titrated solution, rinse the electrodes well with
sodium carbonate (Na2CO3) in water and dilute to 1 L. water, wipe with a dry cloth, and burnish the silver electrode
lightly with a fine emery cloth. Between determinations,
8. Procedure immerse the electrodes in water.
8.1 Combustion of Specimen: 8.2.5 Plot the cumulative volumes of 0.1 N AgNO3 solution
8.1.1 Place 25 mL of Na2CO3 solution in the bottom of the added against the corresponding cell potentials. Select as the
bomb. Incline the bomb and rotate it in such a manner that the end point the midway point on the steepest portion of the
interior surface is moistened by the solution. inflection curve.
8.1.2 Weigh to 1 mg 0.8 to 1.2 g of sample into the metal 8.2.6 Make a blank determination in accordance with 8.2.1-
sample cup. Grind solid resins to pass a No. 60 (250-µm) sieve 8.2.4, but omit the specimen. This procedure will give a
and moisten with a few drops of acetone before combustion. measure of the chlorine in the reagents used.
8.1.3 Insert the cup containing the sample in the loop
electrode and attach the fuse wire so that it hangs slightly 9. Calculation
above the specimen. Assemble the bomb and tighten the cover 9.1 Calculate the chlorine content of the sample as follows:
securely; however, do not use auxiliary tools to tighten the Chlorine, % 5 @~V 2 B!N 3 0.0355/S# 3 100
cover. (1)
8.1.4 Attach the filling connection to the oxygen-filling
valve and admit oxygen slowly (to avoid blowing the sample where:
from the cup) until a pressure of 35 atm is indicated on the V 5 AgNO3 solution required for titration of the specimen,
gage; then close the control valve. Open the relief valve to mL
reduce the pressure in the tube and in the connection to B 5 AgNO3 solution required for titration of the blank, mL
atmospheric pressure. Detach the filling connection from the N 5 normality of the AgNO3 solution, and
bomb and replace with the bomb thumb nut. Tighten the thumb S 5 specimen weight used, g.
nut with finger pressure. 10. Precision
8.1.5 Immerse the bomb in the water bath, then connect the
terminals to the electrical circuit. Ignite the charge within the 10.1 The following criteria should be used for judging the
bomb by closing the switch for not more than 5 s, or until the acceptability of results at the 95 % confidence level.
pilot light goes out. Allow the bomb to stand in the water bath 10.1.1 Repeatability—Two results obtained by the same
for 10 min while cooling. operator should be considered suspect if they differ by more
8.1.6 Remove the bomb from the water bath, and invert and than 0.02 weight %.
rotate it so that maximum washing of the inside surface is 10.1.2 Reproducibility—The results, each the mean of two
achieved. Release the pressure at a uniform rate over a period determinations, obtained by operators in different laboratories
of not less than 1 min. should be considered suspect if they differ by more than 0.05
8.2 Titration: weight %.
8.2.1 Transfer the absorbing solution from the combustion TEST METHOD B—GRAVIMETRIC
of the sample to a 250-mL tall-form titration beaker. Wash all DETERMINATION
the inside surfaces of the bomb with a fine stream of water and
transfer the washings to the beaker. Adjust the volume of the 11. Apparatus
solution to 150 to 200 mL with water. Add three drops of 11.1 Combustion Apparatus—See 6.1.
methyl red indicator solution and neutralize with HNO3; then 11.2 Fritted-Glass, medium porosity.
add 6 drops in excess.
8.2.2 Place the beaker on the titration stand and adjust its 12. Reagents
position so that the electrodes are about half immersed. Fill the 12.1 Warning—Nitric Acid (sp gr 1.42)—Concentrated
buret with 0.01 N AgNO3 solution, and place the buret in nitric acid (HNO3).
position on the titration assembly so that the tip extends 12.2 Caution—Nitric Acid (1 + 99)—Mix 1 volume of
approximately 25 mm below the surface of the liquid in the HNO3(sp gr 1.42) with 99 volumes of water.
beaker. Adjust the speed of the stirrer to give vigorous stirring 12.3 Oxygen—See 7.3.
without splattering. Record the initial buret and meter (cell 12.4 Potassium Iodide Solution (300 g/litre)—Dissolve 300
potential) readings. g of potassium iodide (KI) in water and dilute to 1 L.
8.2.3 Add small portions of 0.01 N AgNO3 solution and, 12.5 Silver Nitrate Solution (100 g/L)—Dissolve 100 g of
after waiting until a constant potential has been established, silver nitrate (AgNO3) in water and dilute to 1 L.
record the buret and meter readings. In regions between 12.6 Silver Nitrate, Standard Solution (0.01 N)—See 7.4.
inflections where the potential change is small for each 12.7 Sodium Carbonate Solution (20 g/L)—See 7.5.
increment of AgNO3 solution, add volumes as large as 0.5 mL.
When the rate of change of cell potential becomes greater than 13. Procedure
5 mV per 0.1 mL, use 0.1-mL increments of 0.01 N AgNO3 13.1 Oxidize the specimen by combustion in accordance
solution. with 8.1.1-8.1.6.
2
D 1847
13.2 Transfer the absorbing solution from the combustion of Chlorine, % 5 @~P 2 B! 3 0.2474/S# 3 100 (2)
the specimen to a 250-mL beaker. Wash all the inside surfaces
of the bomb with a fine stream of water and transfer the where:
P 5 AgCl precipitate from the specimen, g,
washings to the beaker. Add 1 mL of HNO3(sp gr 1.42) to the
B 5 AgCl found in the blank, g, and
solution; then, with stirring, add 1 mL of AgNO3 solution (100 S 5 specimen used, g.
g/L). Heat the solution to boiling as rapidly as possible. Allow
the mixture to cool in a dark cabinet for at least 1 h.
13.3 Filter the precipitate by suction on a clean, fritted-glass
filter funnel. Wash the silver chloride (AgCl) precipitate 15.1 The following criteria should be used for judging the
thoroughly with HNO3(1 + 99). Dry the filter and precipitate at acceptability of results at the 95% confidence level.
110°C for 1 h. Cool in a desiccator and weigh accurately to 0.1 15.1.1 Repeatability—Two results obtained by the same
mg. operator should be considered suspect if they differ by more
13.4 Dissolve the AgCl from the filter, using KI solution. than 0.05 weight percent.
Wash the filter thoroughly with HNO3 (1 + 99). Dry the filter at
15.1.2 Reproducibility—Two results, each the mean of two
110°C for 1 h, cool in a desiccator, and reweigh. The weight of
AgCl obtained from the sample is the difference between the determinations, obtained by operators in different laboratories
weight of the filter funnel containing the precipitate and the should be considered suspect if they differ by more than 0.05
weight of the filter funnel obtained at this time. weight percent.
13.5 Make a blank determination in accordance with 13.2 15.2 Bias—No bias can be determined since no standard
and 13.4, but omit the specimen. This procedure will give a epoxy resin exists.
measure of the chlorine in the reagents used.
16. Keywords
14. Calculation
16.1 chlorine; chlorine content; epoxy; oxygen bomb; total
14.1 Calculate the chlorine content of the specimen as
follows: chlorine
3

Carboxyl Content of Cellulose1
1. Scope Reagents of the American Chemical Society, where such

1.1 These test methods cover the determination of the specifications are available.4 Other grades may be used, pro-
carboxyl content, or ion-exchange capacity, of cellulose from vided it is first ascertained that the reagent is of sufficiently
any source. Two test methods are described, the sodium high purity to permit its use without lessening the accuracy of
chloride-sodium bicarbonate method (1)2 and the methylene the determination.
blue method (2). The test methods must be used within their 4.2 Unless otherwise indicated, references to water shall be
limitations, and it must be recognized that there is no way of understood to mean reagent water conforming to Specification
determining the accuracy of any method for the determination D 1193.
of carboxyl. The precision of the sodium chloride-sodium
SODIUM CHLORIDE-SODIUM BICARBONATE
bicarbonate method is low in the lower range of carboxyl
METHOD
values. The methylene blue method can be used over the whole
range of carboxyl values; it is especially useful in the low 5. Summary of Test Method
range. It is not applicable to the determination of carboxyl in 5.1 In the sodium chloride-sodium bicarbonate method the
soluble carbohydrate material. Although these test methods specimen is deashed with hydrochloric acid, washed, soaked in
may be used to determine the ion-exchange capacity of sodium chloride-sodium bicarbonate solution, filtered, and an
unbleached pulps, the residual lignin will cause an undeter- aliquot of the filtrate titrated with 0.01 N hydrochloric acid to
mined error, especially the sulfonic acid groups in unbleached a methyl red end point. The difference between the concentra-
sulfite pulps (3). tion of the filtrate and of the sodium chloride-sodium bicar-
1.2 This standard does not purport to address all of the bonate solution is a measure of the ion-exchange capacity of
safety concerns, if any, associated with its use. It is the the cellulose.
priate safety and health practices and determine the applica- 6. Reagents
bility of regulatory limitations prior to use. 6.1 Hydrochloric Acid, Standard (0.01 N)—Prepare and
2. Referenced Documents standardize a 0.01 N solution of hydrochloric acid (HCl).
6.2 Hydrochloric Acid (1 + 99)—Dilute 1 volume of con-
2.1 ASTM Standards: centrated HCl (sp gr 1.19) with 99 volumes of water.
D 1193 Specification for Reagent Water3 6.3 Methyl Red Indicator Solution.
3. Significance and Use 6.4 Sodium Chloride-Sodium Bicarbonate Solution—
Dissolve 5.85 g of sodium chloride (NaCl) and 0.84 g of
3.1 These test methods measure the amount of carboxyl
sodium bicarbonate (NaHCO3) in water and dilute to 1 L.
groups present in wood or cotton linter pulp. Carboxyl groups 6.5 Sodium Hydroxide Solution (0.4 g/L)—Dissolve 0.4 g of
are indicative of the surface charge of the pulp which is a very sodium hydroxide (NaOH) in water and dilute to 1 L.
important quantity for use in the papermaking industry.
7. Procedure
7.1 Condition the specimen in the atmosphere near the
4.1 Reagent-grade chemicals shall be used in all tests. balance for at least 20 min before weighing duplicate portions
Unless otherwise indicated, it is intended that all reagents shall of 2.5 6 0.01 g. At the same time, weigh specimens for the
conform to the specifications of the Committee on Analytical determination of moisture. Disintegrate the specimen in water,
1
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct
4
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Nov. 10, 2000. Published January 2001. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
published as D 1926 – 61. Last previous edition D 1926 – 95. listed by the American Chemical Society, see Analar Standards for Laboratory
2
The boldface numbers in parentheses refer to the list of references at the end of Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
these test methods. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
3
1
D 1926
filter through fritted glass, and disperse to about 1 % consis- with diethylbarbituric acid (barbital). The decrease in methyl-
tency in HCl (1 + 99) at room temperature. After 2 h collect the ene blue concentration, measured photometrically, is a function
specimen on a fritted-glass filter funnel and wash with water of the ion-exchange capacity of the cellulose.
saturated with carbon dioxide (CO2). Continue the washing
until the filtrate, after boiling, does not require more than 1 or 12. Apparatus
2 drops of NaOH solution to give an alkaline color with methyl
red. 12.1 Spectrophotometer or Filter Photometer, capable of
7.2 Weigh the wet pulp pad, transfer it immediately to a measuring absorbance near 620 mm.
250-mL glass-stoppered Erlenmeyer flask, add 50 mL of the 12.2 Shaker or Mixer for agitating the specimens in the
NaCl-NaHCO 3 solution with a pipet, and shake to obtain a methylene blue solution. A wheel or rod, to which the specimen
homogeneous slurry (Note 1). Allow the mixture to stand for 1 vials can be attached, that rotates at about 15 r/min, has proven
h at room temperature. Filter through a clean, dry, frittedglass satisfactory.
funnel, pipet a 25-mL aliquot of the filtrate into an Erlenmeyer 12.3 Centrifuge, capable of settling the cellulose from the
flask, and titrate with 0.01 N HCl, using methyl red solution as methylene blue solution.
an indicator. When the first change in color occurs, boil the
solution for about 1 min to expel the carbon dioxide and 13. Reagents
continue the titration to a sharp end point.
13.1 Buffer, Stock Solution—Dissolve 1.151 g of diethylbar-
NOTE 1—If the cation-exchange capacity is very low, use a solution bituric acid (barbital) in water, add the equivalent of 0.16 g of
containing about 5.85 g of NaCl and 0.42 g of NaHCO3 per litre. It is sodium hydroxide using a standard solution and buret, and
important that the excess of NaHCO3 be large enough that the pH does not
fall below 7.0.
dilute with water to 1 L in a volumetric flask.
13.2 Hydrochloric Acid (1 + 99)—Dilute 1 volume of con-
7.3 Pipet 25 mL of the NaCl-NaHCO3 solution into an
centrated hydrochloric acid (HCl, sp gr 1.19) with 99 volumes
Erlenmeyer flask and titrate as described in 7.2.
of water.
8. Calculation 13.3 Methylene Blue, Stock Solution (0.002 M)—Dissolve
8.1 Calculate the cation-exchange capacity, c, of the speci- 0.640 g of methylene blue in water, making allowance for
men in milliequivalents per 100 g as follows: moisture, and dilute to 1 L in a volumetric flask.
c5 S D
av 2
b 2 a 2 50 G (1) NOTE 2—Information on the determination of the purity of methylene
blue is given in the literature (5).
where: 13.4 Methylene Blue—Buffer Solution (0.0002 M)—Mix 1
G = weight of oven-dry specimen, g, volume of methylene blue stock solution with 1 volume of
v = weight of water in the wet pulp pad, g, buffer stock solution and dilute to a total of 10 volumes in a
a = millilitres of 0.01 N HCl consumed by 25 mL of volumetric flask. The volume of solution to be prepared will
filtrate, and vary with the requirements. For example, pipet 10 mL of each
b = millilitres of 0.01 N HCl consumed by 25 mL of the solution into a 100-mL volumetric flask, dilute to the mark with
NaCl-NaHCO 3 solution.
water, and mix thoroughly. Prepare a fresh solution for each
9. Report determination.
9.1 Until more data are obtained on the precision of this test
method, it is suggested that the ion-exchange capacity be 14. Preparation of Calibration Curve for Ordinary Size
reported to 0.01 milliequivalent/100 g of pulp. Specimens
10. Precision and Bias 14.1 In order to prepare a calibration curve, make up a series
of methylene blue buffer solutions containing the same amount
10.1 Work sponsored by ASTM, TAPPI, ACS, and ICCA of buffer but different amounts of methylene blue, to cover the
(see Ref 4) found that precision decreased with decreasing desired range. Add 50 mL of the stock solution of buffer to
carboxyl content. For pulps varying in carboxyl content from each of nine 500-mL volumetric flasks. Add to these flasks 10,
5.75 to 0.40 mmol/100 g pulp, the repeatability (intralabora- 15, 20, 25, 30, 35, 40, 45, and 50 mL, respectively, of the 0.002
tory) expressed as a percent coefficient of variance was 2.2 to M stock solution of methylene blue. Dilute each solution to the
8.1 %, respectively. Interlaboratory results based on different mark with water and mix thoroughly.
materials and various test methods gave percent coefficient of
variance of 9.0 to 33 % for these same materials. NOTE 3—The concentrations suggested for preparing calibration curves
10.2 No statement on bias can be made as no suitable need not be followed exactly as long as enough points are obtained to
reference material exists for determining bias. allow construction of an acceptable calibration curve.
METHYLENE BLUE METHOD 14.2 Pipet 10 mL of each solution into 100-mL volumetric
flasks, add 10 mL of HCl (1 + 99), dilute to the mark with
11. Summary of Test Method water, and mix (Note 4). Measure the absorbance of the
11.1 In the methylene blue method the specimen is treated solutions and prepare a plot of absorbance at 620 nm against
with 0.0002 M methylene blue solution buffered to a pH of 8 concentration (Note 5).
2
D 1926
NOTE 4—The procedure described for the colorimetric determination of specimens (Section 16). Weigh the specimens into glass-
methylene blue is based on the use of the Beckman DU spectrophotometer stoppered weighing bottles of about 10-mL capacity and add 5
with 1-cm absorption cells. The dilution procedure may have to be mL of 0.0002 M methylene blue-buffer solution. After over-
modified for use with filter photometers or for cells with a longer light
path.
night agitation, centrifuge the solutions, remove a 1-mL aliquot
NOTE 5—It has been reported (5) that Beer’s law is obeyed at 620 nm, with an automatic pipet, and transfer to a 10-mL volumetric
and it is recommended that measurements be made at this wavelength. flask. Add about 1 mL of HCl (1 + 99), dilute to the mark, and
Measurements may also be made at 675 nm, which is close to the measure the absorbance at 620 nm. Determine the specimen
absorption peak, but Beer’s law is not obeyed at this wavelength. size that gives 50 % exhaustion of the methylene blue solution
as described in 16.4.
15. Preparation of Calibration Curve for Small
Specimens
18. Calculations
15.1 In order to prepare a calibration curve, pipet 1 mL of
each of the nine solutions mentioned in Section 14 into 10-mL 18.1 Ordinary Size Specimens—The size specimen that
volumetric flasks, add 1 mL of HCl (1 + 99), dilute to the mark, gives 50 % exhaustion of 50 mL of 0.0002 M methylene blue
mix, and measure the absorbance at 620 nm. If the volumetric solution has used 0.005 millimole of methylene blue in ion
apparatus is sufficiently precise, this calibration curve should exchange with carboxyl groups. Therefore the millimoles of
be identical with the one described in Section 14. Obviously, carboxyl per 100 g of cellulose, M1, is calculated as follows:
any specific procedure that gives solutions in the right concen- M1 5 ~0.005/W! 3 100 (2)
tration range for the colorimetric measurements should be where W = specimen to give 50 % exhaustion of 50 mL of
satisfactory. 0.0002 M methylene blue solution, g.
16. Procedure for Ordinary Size Specimens 18.2 Small Specimens—The size specimen that gives 50 %
16.1 Determine the approximate carboxyl content in a exhaustion of 5 mL of 0.0002 M methylene blue solution has
preliminary experiment. Weigh out three specimens, one esti- used 0.0005 millimole of methylene blue in ion exchange with
mated to give 50 % exhaustion of the dye solution, one 10 to carboxyl groups. Therefore the millimoles of carboxyl per 100
15 % smaller, and one 10 to 15 % larger, making allowance for g of cellulose, M2, is calculated as follows:
the moisture content. Weigh the specimens into 125-mL M2 5 ~0.0005/W! 3 100 (3)
glass-stoppered flasks (any other convenient size flask may be where W = specimen to give 50 % exhaustion of 5 mL of
used), and add 50 mL of 0.0002 M methylene blue-buffer 0.0002 M methylene blue solution, g.
solution from a pipet. Lubricate the stoppers with a little
petroleum jelly and secure them with rubber bands. Place the 19. Report
flasks on a device that will turn them end over end or otherwise
agitate the solutions. 19.1 Until more data are obtained on the precision of this
16.2 After overnight agitation, centrifuge the solutions and test method, it is suggested that the ion-exchange capacity be
pipet a 10-mL aliquot of the supernatant liquid into a 100-mL reported to 0.01 meq/100 g of pulp.
volumetric flask. Add 10 mL of HCl (1 + 99), and fill the flask
to the mark with water. Measure the absorbance of the 20. Precision and Bias
solutions at 620 nm. 20.1 Work sponsored by ASTM, TAPPI, ACS, and ICCA
16.3 Using the observed absorbances, refer to the calibra- (see Ref 4) found that precision decreased with decreasing
tion curve and read the concentration of methylene blue present carboxyl content. For pulps varying in carboxyl content from
for each of the three portions of specimen. 5.75 to 0.40 mmol/100 g pulp, the repeatability (intralabora-
16.4 Plot the specimen size against the concentration of tory) expressed as a percent coefficient of variance was 2.2 to
methylene blue in the supernatant liquid, and read from the plot 8.1 %, respectively. Interlaboratory results based on different
the specimen size that gives 50 % exhaustion of the dye materials and various test methods gave percent coefficient of
solution. variance of 9.0 to 33 % for these same materials.
NOTE 6—It is not absolutely necessary to plot the specimen size against 20.2 No statement of bias can be made as no suitable
methylene blue concentration in order to calculate dye absorption. The dye reference material exists for determining bias.
absorption may be calculated from two slightly different weights of
cellulose that will give approximately 50 % exhaustion, and the mean of 21. Keywords
the two results taken.
21.1 carboxyl content; cellulose; ion exchange capacity;
17. Procedure for Small Specimens methylene blue method; sodium chloride/sodium bicarbonate
17.1 The general procedure is the same as for ordinary size method
3
D 1926
REFERENCES
(1) Wilson, K., “Bestämming av Karboxylgrupper i Cellulosa,” Svensk (4) Wilson, W. K., and Mandel, J., “Determination of Carboxyl in
Papperstidn, Vol 51, 1948, p. 45. Cellulose; Comparison of Various Methods, Report of TAPPI-ACS-
(2) Davidson, G. F., “The Absorption of Methylene Blue,” Journal, ICCA Subcommittee on Carboxyl,” Tappi, Vol 44, 1961, p. 131.
Textile Institute, Vol 39, 1948, p. T65. (5) Davidson, G. F., “The Determination of Methylene Blue,” Journal,
(3) Jayme, G., and Neuschäffer, K., “Uber die Bestimmung des Carboxy- Textile Institute, Vol 38, 1947, p. T408.
lgruppengehaltes von Zellstoffen,” Das Papier, Vol 9, 1955, p. 143.
4

Acetone Tolerance of Heat-Bodied Drying Oils1
1. Scope sample, the two probably have been produced by the same
1.1 This test method covers the determination of the acetone technique.
tolerance of heat-bodied drying oils when no nonfatty material 4. Apparatus
is present.
1.2 The values stated in SI units are to be regarded as the 4.1 Balance, capable of weighing to an accuracy of 0.5 mg.
standard. The values given in parentheses are for information 4.2 Erlenmeyer Flasks, 250-mL, glass-stoppered.
only. 4.3 Bath Clamp.
1.3 This standard does not purport to address all of the 4.4 Ringstand, approximately 4 ft (1.2 m) high.
safety concerns, if any, associated with its use. It is the 4.5 Buret, with a capacity of 50 mL, fitted at the top with a
responsibility of whoever uses this standard to consult and suitable drying tube.
establish appropriate safety and health practices and deter- 4.6 Water Jacket Assembly for Buret, as shown in Fig. 1.
mine the applicability of regulatory limitations prior to use. 4.7 Water Bath—A constant-temperature water bath capable
Specific hazard statements are given in Section 6. of maintaining a temperature of 25 6 0.1°C. The bath shall be
fitted with a water pump for circulating water through the bath
2. Terminology and the water jacket as shown in Fig. 1.
2.1 Definitions of Terms Specific to This Standard: NOTE 1—Details for the thermostatic control unit and heating element
2.1.1 acetone tolerance—of a drying oil, the number of have been omitted from the drawing in Fig. 1, since the proper selection
grams of acetone required to produce a persistent cloudiness in and construction of this unit may be left to the discretion of the analyst.
100 g of the oil at 25°C, under the conditions prescribed in this 4.8 Volumetric Flask, 25-mL, glass-stoppered, for use as a
test method. specific gravity bottle.
4.9 Glass Beads, approximately 1.5 to 3 mm (1⁄16 to 1⁄8 in.)
in diameter.
3.1 Unbodied drying oils are miscible with acetone. As
drying oils are heat-bodied, higher molecular weight species 5. Reagents and Materials
are formed that are acetone insoluble. Therefore, addition of 5.1 Acetone (Warning—See 6.1):
acetone to a drying oil can be used as an indication of the 5.1.1 Place a suitable quantity of acetone in a round-bottom,
degree of polymerization present in the oil. Since solubility of glass-stoppered flask and to it add 25 % of its weight of
a polymer is extremely temperature-dependent, the tempera- anydrous cupric sulfate (CuSO4). Stopper the flask and allow
ture must be precisely controlled. This test method is appli- the mixture to stand for at least 3 days. At the end of this
cable to heat-bodied oils only when no other nonfatty material period, attach the flask and its contents to an all-glass distilla-
is present. tion apparatus that previously has been thoroughly dried and
3.2 There is no correlation between the acetone tolerance distill the acetone directly from the drying agent, using a steam
and the usefulness of an oil, but, if acetone tolerance and other bath for heating. Discard the first 10 % and the last 10 % of the
properties of an oil are the same as those of an accepted distillate. During the distillation, protect the apparatus from
atmospheric moisture by means of a trap containing anydrous
CuSO4. Collect and store the acetone in the same receiving
bottle, fitted with a similar moisture trap.
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 5.1.2 Determine the specific gravity at 25/25°C and the
Subcommittee D01.32 on Drying Oils. percent of moisture in the acetone. The acetone shall be
Current edition approved March 27, 1986. Published May 1986. Originally considered suitable for use if the specific gravity is between
published as Sections 43–47 of Test Method D 555 – 58. Last previous edition
D 1950 – 68 (1984).
1
D 1950
above the level of the specimen. Clamp the flask into position
by means of the bath clamp. Fill the buret with acetone and
attach the drying tube. Bring the flask and its contents, and the
acetone, to 25 6 0.1°C by allowing them to stand for at least
10 min.
7.3 Disconnect the flask from the clamp, remove the stop-
per, and run in the acetone from the buret. Add the acetone in
small portions, while keeping the flask immersed in the water
bath. After the addition of each portion of acetone, stopper the
flask and swirl it gently to dissolve the contents properly. If it
should become necessary to remove the flask from the bath to
facilitate mixing, reimmerse the stoppered flask in the bath and
allow to stand for at least 5 min before continuing with the
titration. Take care not to splash the contents over the upper
part of the flask during the titration. Each addition of acetone
produces a dense cloudiness that will be discharged by agitat-
ing the mixture. As the end point is neared, the cloudiness will
persist for longer periods of time. At this point, add the reagent
dropwise until the addition of 1 drop of the reagent produces a
persistent dense cloudiness. Stopper the flask immediately and
wipe dry with a clean cloth.
NOTE 2—A suitable magnetic stirring apparatus may be used instead of
the beads.
7.4 Weigh the flask and its contents to 0.1 mg. Record the
FIG. 1 Apparatus for Acetone Tolerance Test weight of acetone by difference.
8. Calculation
0.7864 and 0.7872, equivalent to a water content of 0.00 to
0.24 %. 8.1 Calculate the acetone tolerance, T, as follows:
5.2 Cupric Sulfate, Anhydrous—Technical grade, anhy- T 5 ~A/S! 3 100
drous, powdered cupric sulfate (CuSO4).
where:
6. Hazards A 5 acetone required for titration of the specimen, g, and
6.1 Acetone is a flammable liquid. It is harmful if inhaled, S 5 specimen used, g.
use only with adequate ventilation. Avoid prolonged contact
with skin or any contact with the eyes. See supplier’s Material 9. Precision and Bias
Safety Data Sheet.
9.1 Precision and bias data were not established at the time
7. Procedure this test method was written. An effort is being made to obtain
7.1 Weigh the glass-stoppered Erlenmeyer flask, containing the precision and, if obtainable, will be published in future
three or four glass beads, to 0.1 mg. Transfer about 30 g of the revisions. This test method has been in use for many years, and
sample of the Erlenmeyer flask and weigh the flask and its usefulness has been well established.
contents to 0.1 mg. Record the weight of the specimen by
difference. 10. Keywords
7.2 Immerse the flask and its contents in the constant- 10.1 acetone tolerance of drying oils; drying oils; heat
temperature bath so that the level of the water in the bath is bodies
2

Ash in Drying Oils and Fatty Acids1
1. Scope NOTE 2—Platinum is not recommended. Boiled oils or oils contami-

nated with driers containing lead may ruin platinum by alloy formation.
1.1 This test method covers the determination of the residue
or ash resulting from ignition, under prescribed conditions, of 3.2 Electric Muffle Furnace.
all natural and synthetic drying oils and their fatty acids. This 3.3 Desiccator, containing an efficient desiccant. Anhydrous
test method is not applicable to boiled oils. calcium sulfate (CaSO4), phosphorus pentoxide (P2O5)
(Warning—see 4.1) or concentrated sulfuric acid (Warning—
NOTE 1—Boiled oils do not give reproducible results. Lead driers are
see 4.2) (H2SO4, sp gr 1.84) are satisfactory.
partially reduced by the carbon to give metallic lead and oxides of variable
composition, and zinc oxide is relatively volatile at the muffle furnace NOTE 3—Magnesium Perchlorate and Barium Perchlorate are also
temperature. Ash determinations on boiled oils consequently are empirical efficient desiccators and were previously listed in this section. However
and not highly reproducible. because of their explosive danger, and the availability of other safer
1.2 The values stated in SI units are to be regarded as the materials, the recommendation for their use has been discontinued.
standard. The values given in parentheses are for information 3.4 Oil Sample Bottle, 120-mL (4-oz).
only. 3.5 Triangle, Nichrome or clay.
safety concerns, if any, associated with its use. It is the 4. Hazards
responsibility of whoever uses this standard to consult and 4.1 Phosphorus Pentoxide is a strong oxidizer and reacts
establish appropriate safety and health practices and deter- violently with water, reducing agents and organic matter.
mine the applicability of regulatory limitations prior to use. Causes burns. Avoid contact with skin or eyes, or clothing, or
Specific hazard statements are given in Section 4. inhalation as dust. Refer to supplier’s Material Safety Data
Sheet.
2. Significance and Use 4.2 Sulfuric Acid is corrosive to skin, eyes and mucous
2.1 Most natural and processed oils contain small amounts membranes in form of liquid, mist or fumes. It causes severe
of ash, but the amount is insignificant. Certain, synthetic drying burns. Take care to prevent the contact of the acid with eyes,
oils may contain residual catalyst or other materials, thus skin or on clothing. In making dilute solutions, always add the
giving larger amounts of ash. Although the ash and metal acid to water with care. See supplier’s Material Safety Data
content of boiled oils may be specified, the trend with new and Sheet.
improved driers is toward the specification of drying time,
allowing the manufacturer to obtain this in any way desired. 5. Procedure
2.2 In this test method, ash is determined by igniting the 5.1 Ignite the crucible in the muffle furnace at 550 to 650°C.
specimen under specified conditions and weighing the residue. Cool slightly, place in a desiccator for 1 h, and weigh to 0.1
Due to the volatility or the reduction of certain metal oxides, mg.
some inaccuracies may result. Wet ashing or extraction meth- 5.2 Fill a 120-mL (4-oz) sample bottle with the sample and
ods may give more accurate results. weigh to 0.05 g. Pour about 20 g of the sample from the bottle
into the crucible supported on a triangle, using care so that no
3. Apparatus oil runs down the outside of the crucible or bottle.
3.1 Crucible, porcelain or high-silica glass (Note 2), 50-mL 5.3 Heat gently by moving a flame on the bottom and sides
capacity. of the crucible until the oil ignites. Reduce the size of the flame
until the heat is just sufficient to keep the sample burning.
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint When the first batch of oil has burned out, add about 20 g more
and Related Coatings, Materials, and Applications and is the direct responsibility of of the sample and continue in the same manner until all of the
Subcommittee D01.32 on Drying Oils. oil in the 20-mL bottle has been added. Reweigh the sample
bottle to obtain the total weight of sample used, which will be
1
D 1951
somewhat over 100 g. R 5 residue (5.4), g, and
5.4 Continue heating the crucible until the oil is oxidized to S 5 sample used, g.
a black char and transfer to a muffle furnace. Heat at 550 to
650°C for 1 h. Remove from the furnace, cool slightly, place in 7. Precision and Bias
a desiccator, and cool to room temperature. Weigh and repeat
heating in the furnace to constant weight (within 0.1 mg). 7.1 Precision and bias were not established at the time this
test method was written. An effort is being made to obtain the
6. Calculation precision and, if obtainable, it will be published in future
revisions. This method has been in use for many years, and its
6.1 Calculate the ash content, A, of the sample as follows:
usefulness has been well established.
A, % 5 ~R/S! 3 100
or, 8. Keywords
A, ppm 5 ~R/S! 3 1 000 000 8.1 ash; drying oils; fatty acids
where:
2

Quantitative Determination of Break in Drying Oils1
1. Scope heating to a specified temperature. Since the temperature must

1.1 This test method covers the quantitative determination be specified, the results are empirical.
of break in drying oils. This test method is applicable to raw 6. Apparatus
and refined drying or fatty oils that have not been substantially
polymerized, oxidized, or chemically modified. 6.1 Beaker, 100-mL capacity, tall-form.
1.2 This standard does not purport to address all of the 6.2 Thermometer—An ASTM Open Flash Thermometer
safety concerns, if any, associated with its use. It is the having a range from −6 to +400°C and conforming to the
responsibility of whoever uses this standard to consult and requirements for Thermometer 11C as prescribed in Specifica-
establish appropriate safety and health practices and deter- tion E 1.
mine the applicability of regulatory limitations prior to use. 6.3 Filtering Crucible, porcelain bitumen-type, with top
Specific hazard statements are given in Section 8. diameter of 44 mm and depth of 25 mm prepared by matting
with medium fiber asbestos (Precaution—See 8.1), drying to
2. Referenced Documents constant weight (within 0.1 mg) at 105°C, and cooling in a
2.1 ASTM Standards: desiccator.
E 1 Specification for ASTM Thermometers2 7. Reagents and Materials
3. Terminology 7.1 Purity of Reagents—Reagent grade chemicals shall be
3.1 Description of Term Specific to This Standard: used in all tests. Unless otherwise indicated, it is intended that
3.1.1 break—in drying oils, that material rendered insoluble all reagents shall conform to the specifications of the Commit-
when an oil is heated to polymerization or varnish-making tee on Analytical Reagents of the American Chemical Society,
temperatures. where such specifications are available.3 Other grades may be
4. Summary of Test Method sufficiently high purity to permit its use without lessening the
4.1 The oil under test is treated with hydrochloric acid accuracy of the determination.
heated to 290°C, allowed to cool, diluted with carbon tetra- 7.2 Carbon Tetrachloride (CCl4) (Precaution—See 8.3).
chloride, and the resulting insoluble break is separated and 7.3 Filter Aid—Diatomaceous silica4 dried at 105°C and
weighed. stored in a desiccator.
5. Significance and Use chloric acid (HCl) (Precaution—See 8.2).
5.1 This test method provides a quantitative determination
8. Hazards
of the amount of non-oil material that will become insoluble
when the oil is heated. Break is not significant except in oils 8.1 Asbestos—Inhalation of asbestos fiber or dust has been
that are to be heated, as in manufacture of varnishes and alkyd found to be a cause of asbestosis and lung cancer. Handle dry
resins. This test method is not applicable to polymerized, asbestos in a suitable hood. Prewetting of asbestos with water
oxidized, or chemically modified oils. The break is rendered or solvent can help reduce the concentration of airborne
insoluble in the oil by the addition of hydrochloric acid and
3
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint listed by the American Chemical Society, see Analar Standards for Laboratory
and Related Coatings, Materials, and Applications and is the direct responsibility of Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Subcommittee D01.32 on Drying Oils. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Current edition approved March 27, 1986. Published May 1986. Originally MD.
published as D 1952 – 61. Last previous edition D 1952 – 61 (1984)e1. 4
Hyflo Super-Cel, produced by Johns-Manville Corp., has been found satisfac-
2
Annual Book of ASTM Standards, Vol 14.03. tory for this purpose.
1
D 1952
particles. Use of a particulate filter face mask is recommended. 9.3 Filter, with the aid of vacuum, through the porcelain
See supplier’s Material Safety Data Sheet for proper handling crucible previously prepared and weighed to 0.1 mg. Wash the
procedures. residue with four 15-mL portions of CCl4, using a policeman to
8.2 Hydrochloric Acid—Concentrated hydrochloric acid is remove any traces of solids from the beaker, and adding each
corrosive and may cause burns to the skin and eyes; the vapor portion as soon as the previous one has drained.
is irritating to mucous membranes. Avoid contact with skin and 9.4 Dry the crucible and its contents at 105°C to constant
eyes. Wash clothing before reuse. See supplier’s Material weight (within 0.1 mg), allowing it to cool in a desiccator prior
Safety Data Sheet. to weighing.
8.3 Carbon Tetrachloride is a very hazardous liquid. It is
absorbed by the skin. Its vapor is hazardous through inhalation. 10. Calculation
It is an irritant to skin and eyes; avoid breathing (TLV-10 10.1 Calculate the percent of break, B, as follows:
PPM). It causes liver and kidney damage and has cumulative
B, % 5 @~A 2 C 2 W!/S# 3 100 (1)
effects. Use with adequate ventilation (in a hood) and wear
rubber gloves. See supplier’s Material Safety Data Sheet. where:
A 5 total weight of dried crucible and its contents, g,
9. Procedure C 5 filter aid added, g
9.1 Weigh, to 0.1 g, 25 g of the well-mixed sample into the W 5 weight of crucible and asbestos mat, g, and
beaker on an analytical balance. Add 0.15 mL of HCl from a S 5 specimen weight, g.
measuring pipet and stir thoroughly with the thermometer.
Suspend the thermometer in the center of the mixture so that 11. Report
the bulb is completely immersed in the liquid but not touching 11.1 Report the results to the second decimal place.
the bottom of the beaker. Apply heat (Warning, Note 1) so that
the temperature rises to 290°C in 3 to 3.5 min. After heating to 12. Precision and Bias
290°C, withdraw the flame.
12.1 Precision—Cooperative results indicate that the repro-
NOTE 1—Warning: Do not stir the specimen after heating has begun. ducibility of this test method is approximately 0.02 % relative.
9.2 Cool to room temperature; then add, while stirring, 50 12.2 Bias—Bias has not been determined.
mL of CCl4 followed by 0.2 g of diatomaceous filter aid
weighed to 0.1 mg. Allow to stand for 1 h, stirring at 15-min 13. Keywords
intervals. 13.1 break; drying oils; drying oils
2

Foots in Raw Linseed Oil (Volumetric Method)1
1. Scope 4. Summary of Test Method

1.1 This test method covers the determination of foots in 4.1 The oil to be tested is treated by mixing under defined
raw linseed oil. conditions with an acid-calcium chloride solution and acetone.
This mixture is allowed to settle in a graduated tube and the
NOTE 1—Test Method D 1966, is a more reproducible method and can
be used in place of Test Method D 1954 upon mutual agreement between foots content is determined volumetrically.
the purchaser and the seller.
1.2 The values stated in SI units are to be regarded as the
5.1 This test method provides an empirical measure of the
amount of solid impurities present in raw linseed oil. The
only.
impurities are usually suspended in the oil. Addition of the
reagents stratifies the impurities in a layer that is measured
volumetrically. After addition of the reagents, a period of time
responsibility of whoever uses this standard to consult and
is provided to allow the impurities to stratify. The test method
establish appropriate safety and health practices and deter-
is empirical since the volume of the impurity stratum will
mine the applicability of regulatory limitations prior to use.
increase over a period of time due to the hydration of the
Specific hazard statements are given in Section 8.
impurities.
2. Referenced Documents 5.2 After heating a sample of the oil to 65°C, it is divided
into two parts. One part is cooled to about 25°C and the other
2.1 ASTM Standards:
to 0°C before the test is run. The test results run on the two
samples are known as the heated foots and chilled foots
D 1966 Test Method for Foots in Raw Linseed Oil (Gravi-
respectively.
metric Method)3
E 1 Specification for ASTM Thermometers4 6. Apparatus
3. Terminology 6.1 Beakers, 150-mL, made of chemically resistant glass.
6.2 Thermometer—An ASTM Partial Immersion Thermom-
3.1 Definitions:
eter having a range from − 20 to + 150°C and conforming to
3.1.1 foots—a term that originally was used to describe
the requirements for Thermometer 1C as prescribed in Speci-
those solid impurities that precipitate from raw linseed oil
fication E 1.
during storage and then settle to the bottom or “foot” of a
6.3 Sample Bottles, 60-mL (2-oz).
storage tank.
6.4 Graduated Cylinders, 10 and 25-mL.
3.2 Definitions of Terms Specific to This Standard:
6.5 Graduated Tube—A buret or color comparison tube,
3.2.1 foots—a material insoluble in a mixture of equal parts
having an internal diameter of 10 to 15 mm, and a capacity of
of acetone and the oil under test, and insoluble in calcium
not less than 70 mL. The graduations in 0.1-mL should extend
chloride solution, under specific conditions of the test.
at least from 10 to 50 mL above the bottom of the tube.
1
6.6 Water Bath, capable of being maintained at 25 6 0.5°C.
and Related Coatings, Materials, and Applications and is the direct responsibility of 7. Reagents
Current edition approved March 27, 1986. Published May 1986. Originally 7.1 Purity of Reagents—Reagent grade chemicals shall be
2
3
4
Annual Book of ASTM Standards, Vol 14.03. tee on Analytical Reagents of the American Chemical Society,
1
D 1954
where such specifications are available.5 Other grades may be prepared oil into a graduate and at the same time measure out
used, provided it is first ascertained that the reagent is of 25 mL of acetone and 10 mL of the acid-CaCl2 solution. All
sufficiently high purity to permit its use without lessening the materials should be at 20 to 27°C. Pour the oil into the
accuracy of the determination. graduated tube. Rinse the graduate used for oil measurement
7.2 Purity of Water—Unless otherwise indicated, references with the acetone. Transfer the acetone rinses and the acid-
to water shall be understood to mean reagent water conforming CaCl2 solution into the graduated tube. Stopper the tube. Mix
to Type I of Specification D 1193. for 1 min by completely inverting and reinverting the tube ten
7.3 Acetone. (Precaution—See 8.1) to twelve times. Clamp the tube in a vertical position and allow
7.4 Acid-Calcium Chloride Solution—Dissolve 600 g of to stand 24 h at 25 6 0.5°C. Determine the volume of the
calcium chloride (CaCl2) or 800 g of CaCl2·2H2O in a mixture stratum lying between the clear CaCl2 solution and the clear
of 80 mL of concentrated hydrochloric acid (HCl, sp gr 1.19) acetone and oil mixture to 0.1 mL.
(Precaution—see 8.2) and 500 mL of water. Dilute to 1 L and 10.2 Determination of Chilled Foots—Place the 60-mL
mix. Filter if not clear. (2-oz) bottle in an ice water bath (0°C) for 2 h. Then place it
in a constant-temperature bath at 25 6 0.5°C for 30 min.
8. Hazards Continue as described in 10.1.
8.1 Acetone is a flammable liquid. Harmful if inhaled, use
only with adequate ventilation. Avoid prolonged contact with 11. Calculation
skin or any contact with the eyes. See supplier’s Material 11.1 Multiply the volume of the intermediate strata (10.1
Safety Data Sheet. and 10.2) by four to obtain the percent of heated and chilled
8.2 Hydrochloric Acid—Concentrated hydrochloric acid is foots.
corrosive and may cause burns to the skin and eyes; the vapor
is irritating to mucous membranes. Avoid contact with skin and 12. Report
eyes. Wash clothing before reuse. See supplier’s Material 12.1 Report the results to the first decimal place.
Safety Data Sheet.
9. Preparation of Oil 13. Precision

9.1 Place 75 g of the oil in a 150-mL beaker, heat to 65°C, 13.1 The precision of the heated foots and chilled foots test
and maintain at 65 6 1°C for 10 min. At the end of the 10-min methods has never been formally adopted from a statistical
period, divide it into two equal portions by pouring one half analysis of historical cooperative tests by ASTM members.
into a clean, dry, 60-mL (2-oz) bottle. Stopper the 2-oz bottle A1961 examination of ASTM results published in 1927 shows:
and cool immediately as described in 10.2. (1) Heated foots: 66 % coefficient of variation between
observers, and
10. Procedure (2) Chilled foots: 35 % coefficient of variation between
10.1 Determination of Heated Foots—Allow the oil in the observers.
beaker (Section 9) to cool to a temperature of 20 to 27°C and 13.2 These very wide coefficients were calculated from
maintain at this temperature for 30 min. Measure 25 mL of the single observations by seven observers on each of six samples
of oil. Values reported ranged from 0.0 to 0.2 % heated foots
and 0.4 to 2.6 chilled foots in the cleanest sample, to 3.3 to
5
Reagent Chemicals, American Chemical Society Specifications, American 17.2 % heated foots and 9.6 to 20.0 % chilled foots in the
Chemical Society, Washington, DC. For suggestions on the testing of reagents not dirtiest sample of oil.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 14. Keywords
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD. 14.1 foots; linseed oil; linseed oil
2

Gel Time of Drying Oils1
1. Scope
1.1 This test method covers the determination of the gel
time of tung oil, oiticica oil, and, with modification of
temperature, other oils having gelling characteristics.
2.1 ASTM Standards:
3. Terminology
3.1 Definition:
3.1.1 gel time, of a drying oil—the time required for the oil
to form a solid gel under specified conditions of temperature.
4.1 The gel time of an oil at elevated temperature is an
indication of its drying characteristics. Oils that have a high
degree of unsaturation are classed as drying oils. Oils in which
a high percentage of this unsaturation is conjugated dry the A— 1000-mL, tall-form beaker, 90 mm in diameter by 190 mm in height
fastest. B— support plate about 65 mm in width, made of monel metal, aluminum, or
4.2 At elevated temperatures, the conjugated oils will form stainless steel
C— test tubes, 150 mm by 16 mm, with cork stoppers
a gel; therefore this test method can be used to detect D— 5 mL of reference standard oil
adulteration in highly conjugated oils such as tung and oiticica E— thermometer, range 90 to 370°C
oil, whereas unconjugated oils do not show a sharp gel point. F— glass rods 3 mm in diameter
G— guide to prevent cover from slipping
The method is empirical in nature since the gel time must be
FIG. 1 Apparatus for Gel Time Test
compared to a known standard.
5. Apparatus The beaker shall be covered with a Monel, aluminum, or
stainless steel support plate for test tubes and thermometer.
5.1 The apparatus shall be assembled as shown in Fig. 1 and
5.1.2 Glass Rods, approximately 170 mm in length.
shall consist of the following:
5.1.3 Test Tubes, 150 by 16 mm with a mark to designate the
5.1.1 Bath—A 1000-mL, tall-form beaker, containing a
5-mL level. Each tube shall be closed with a cork having a hole
hydrogenated oil or other suitable liquid to a depth of 110 mm.
through which a 3-mm glass rod can move freely.
5.1.4 Thermometer—An ASTM Pensky-Martens High-
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint Range Thermometer having a range from 90 to 370°C and
and Related Coatings, Materials, and Applications and is the direct responsibility of conforming to the requirements for Thermometer 10C as
Subcommittee D01.32 on Drying Oils. prescribed in Specification E 1.
published as D 1955 – 58 to replace Sections 45–51 of D 555 – 58. Last previous 6. Procedure
edition D 1955 – 61 (1984).
2
Annual Book of ASTM Standards, Vol 14.03. 6.1 Heat the bath to 300 6 1°C (Note 1 and Note 2). When
1
D 1955
the bath temperature is 300°C and rising slowly, insert the tube firmly set. This is the point when the oil becomes stiff enough
containing 5 mL of the oil to be tested and another tube that the entire tube and contents may be raised by the rod.
containing 5 mL of an oil of known behavior. Note the time. Record the elapsed time for the test oil and the standard. If the
Within 2 min the bath temperature will have fallen to 288 6 standard deviates more than 30 s from the assigned value, the
1°C (Note 3), at which point it should be maintained as closely test should be repeated with closer temperature control.
as possible for the duration of the test.
NOTE 1—The recent change in immersion and running temperature for 7. Report
this test was made to compensate for the change made in the type of
7.1 Report the mean of two tests, differing by no more than
thermometer used. It is particularly important to use the specified ASTM
Thermometer 10C. 30 s, as the gel time.
NOTE 2—No stirrer shall be used in the bath. A screen around the bath
enables the temperature to be reached and maintained more easily. When 8. Precision and Bias
the bath becomes discolored and viscous it should be renewed, as heating
becomes irregular when a tarry and viscid state is reached. 8.1 Precision—Within laboratory standard deviation was 5
NOTE 3—The test may be run at a higher temperature for use with s, and between laboratories, 25 s.
dehydrated castor oil and other gelling oils where the gel times at 288°C 8.2 Bias—Bias has not been determined.
are excessively long. Include the temperature of the test in the report in
these cases.
9. Keywords
6.2 When the tubes have been in the bath 9 min, raise the
glass rods at intervals of 15 s. Note the time when the oil is 9.1 drying oils; gel time
2

Hydroxyl Value of Fatty Oils and Acids1
1. Scope 4.2 Condensers, straight-tube, Liebig type, having standard

1.1 This test method covers the determination of the hy- ground-glass joints.
droxyl content of castor oil, dehydrated castor oil, and their 5. Reagents
derivatives. This test method may also be used for other fatty
products such as fatty alcohols, mono- and diglycerides, and 5.1 Purity of Reagents—Reagent grade chemicals shall be
hydroxystearic acid, but the precision will not necessarily be as used in all tests. Unless otherwise indicated, it is intended that
indicated. all reagents shall conform to the Specifications of the Com-
1.2 This standard does not purport to address all of the mittee on Analytical Reagents of the American Chemical
safety concerns, if any, associated with its use. It is the Society, where such specifications are available.3 Other grades
responsibility of whoever uses this standard to consult and may be used provided it is first ascertained that the reagent is
establish appropriate safety and health practices and deter- of sufficiently high purity to permit its use without lessening
mine the applicability of regulatory limitations prior to use. the accuracy of the determination.
Specific hazard statements are given in Section 6. 5.2 Purity of Water—Unless otherwise indicated, references
2. Referenced Documents to Type I of Specification D 1193.
2.1 ASTM Standards: 5.3 Acetic Anhydride, (Warning—See 6.5) fresh.
D 1193 Specification for Reagent Water2 5.4 n-Butyl Alcohol (Warning—See 6.1), neutralized with
0.5 N alcoholic potassium hydroxide (KOH) solution to a faint
3. Significance and Use pink phenolphthalein end point.
3.1 Hydroxyl value is important in establishing reactivity 5.5 Ethyl Alcohol or Denatured Alcohol, conforming to
with acids and isocyanates. It is also a measure of the degree of Formula No. 3A or 30 of the U. S. Bureau of Alcohol, Tobacco,
dehydration of castor oil. and Firearms. Formula No. 3A is a mixture of 100 parts by
3.2 This test method determines the total amount of residual volume of ethanol to 5 parts by volume of methanol. Formula
hydroxyl groups present in oils and other fatty acid-containing 30 is 100 parts by volume of ethanol and 10 parts by volume
materials, reported as hydroxyl value. of methanol.
3.3 This test method involves the acetylation of hydroxyl- 5.6 Phenolphthalein Indicator Solution (10 g/L)—Dissolve
containing fatty oils and acids using pyridine as solvent. Other 1 g of phenolphthalein in methanol, ethanol, or isopropanol,
groups that will react with acetic anhydride such as primary and dilute to 100 mL.
and secondary amines under the conditions of the method will 5.7 Potassium Hydroxide, Alcoholic Solution (0.5 N)
be reported as hydroxyl. The hydroxyl value is expressed as (Warning—See 6.3)—Prepare and standardize a 0.5 N solu-
milligrams of potassium hydroxide equivalent to the hydroxyl tion of potassium hydroxide (KOH) in ethanol. The strength
content of 1 g of the oil. A correction is applied for acid groups should be not less than 0.5 N in order that the blank titrations
present. will take less than 50 mL to avoid refilling the buret.
5.8 Pyridine (Warning—See 6.4), distilled at 114 to
4. Apparatus 115°C.
4.1 Erlenmeyer Flask, 250-mL, standard ground-glass- 5.9 Pyridine-Acetic Anhydride Solution (3 + 1)—Mix 3 vol-
stoppered. umes of pyridine with 1 volume of acetic anhydride. Prepare
fresh before using.
1 3
Subcommittee D01.32 on Drying Oils. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved March 27, 1986. Published May 1986. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 1957 – 61 T. Last previous edition D 1957 – 63 (1984). and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
2
1
D 1957
6. Hazards h. By this method of heating only slight, if any, refluxing will
6.1 n-Butyl Alcohol is a flammable liquid. The liquid and occur.
vapor are irritants to the eyes, skin and mucous membranes. 7.5 Add 10 mL of water through the condensers to the
Use with adequate ventilation (hood), (TLV-100 PPM). See flasks. Heat on the steam bath for an additional 10 min with
supplier’s Material Safety Data Sheet. reflux condensers attached. Allow the flasks to cool to room
6.2 Ethyl Alcohol (denatured) is a flammable liquid. Liquid temperature with condensers still attached.
and vapor are harmful, the severity depending upon the 7.6 Add 25 mL of neutralized n-butyl alcohol to each flask
concentration of the alcohol and the nature and concentration in the following manner. About half should be added through
of the denaturant. Do not use denatured alcohol containing the condenser, the condenser removed, and the remaining
benzene. Do not swallow. Avoid breathing vapor and contact alcohol used to wash down the sides of the flasks. Add 1 mL of
with skin and eyes. See supplier’s Material Safety Data Sheet. phenolphthalein indicator solution to each flask and titrate to a
6.3 Potassium Hydroxide and its strong solutions are caus- faint pink end point with 0.5 N alcoholic KOH solution.
tic to the skin and eyes. Avoid all contact with skin and eyes.
Remove contaminated clothing and wash before reuse. See 8. Calculation and Report
supplier’s Material Safety Data Sheet. 8.1 Calculate the hydroxyl value as the number of milli-
6.4 Pyridine is a flammable liquid and hazardous by inha- grams of potassium hydroxide equivalent to the hydroxyl
lation. It is an eye, skin, and respiratory irritant (TLV-5 PPM). content of 1 g of sample as follows:
May cause liver and kidney damage. Use with adequate B 1 ~SA/C! 2 V
ventilation; perform all operations in a hood. See supplier’s Hydroxyl value 5 S N 3 56.1
Material Safety Data Sheet.
6.5 Acetic Anhydride is corrosive and may cause burns to where:
the skin and eyes; the vapor is irritating to mucous membranes. A 5 KOH solution required for titration of the acid value,
Use in a hood. Remove contaminated clothing and wash before mL,
reuse. See supplier’s Material Safety Data Sheet. B 5 KOH solution required for titration of the reagent
blank, mL,
7. Procedure C 5 sample used for the acid value, g,
7.1 Weigh, to 0.1 mg into a 250-mL Erlenmeyer flask, the V 5 KOH solution required for titration of the acetylated
correct amount of sample for acetylation determined as fol- specimen, mL, and
lows: S 5 sample used for acetylation, g.
Hydroxyl Value Specimen Weight, g 8.2 Report the results to the first decimal place.
0 to 20 10
20 to 50 5 NOTE 1—For routine analysis, the ethanol acid value may be substituted
50 to 100 3 in most cases for the pyridine acid value, and the calculation altered
100 to 200 2
accordingly.
7.2 Weigh 9.0 to 11.0 g of the sample into another flask for 9. Precision and Bias
the acid value. If the test method is being used for fatty acids,
such as hydroxystearic acid, the weight should be 0.9 to 1.1 g. 9.1 The following criteria should be used for judging the
7.3 Pipet 5.0 mL of the pyridine-acetic anhydride solution acceptability of results at the 95 % confidence level:
into the flask containing the specimen for acetylation. For 9.1.1 Repeatability—Duplicate results by the same operator
samples having 0 to 20 hydroxyl value, add an additional 5 mL should be considered suspect if they differ by more than 2.4.
of pyridine to the flask. Thoroughly mix the contents by gentle 9.1.2 Reproducibility—Two results, each the mean of dupli-
swirling. Pipet another 5.0 mL of pyridine-acetic anhydride cate determinations, obtained by operators in different labora-
solution into an empty flask for the reagent. Add 10 mL of tories should be considered suspect if they differ by more than
pyridine, neutralized to phenolphthalein, to the specimen for 3.0.
the acid value blank. Thoroughly mix the contents by gentle 9.2 Bias—Bias has not been determined.
swirling.
7.4 Insert reflux condensers into the Erlenmeyer flasks. 10. Keywords
Place the flasks on an opening of a steam bath and heat for 1 10.1 drying oils; hydroxyl value; fatty acids; hydroxyl value
2

Chloroform Insoluble Matter in Oiticica Oil1
1. Scope For further information, see supplier’s Material Safety Data

1.1 This test method covers the determination of the matter Sheet.
in oiticica oil that is insoluble in chloroform. It may also be 5. Procedure
used for other drying oils.
1.2 This standard does not purport to address all of the 5.1 Dissolve 10 g of the sample in sufficient chloroform to
safety concerns, if any, associated with its use. It is the obtain a fluid solution. Filter through a dried and weighed
responsibility of whoever uses this standard to consult and Gooch crucible, wash with chloroform until the oil is removed.
establish appropriate safety and health practices and deter- Heat the crucible and residue, if present, at 105 6 2°C, cool,
mine the applicability of regulatory limitations prior to use. A and weigh. Repeat the heating and weighing until the weight is
specific hazard statement is given in Section 4. constant to 0.1 mg.
2. Significance and Use 6. Calculation

2.1 Mineral contamination in oiticica or other drying oils is 6.1 Calculate the percent of insoluble matter, I, in chloro-
insoluble in chloroform while the natural components of the oil form as follows:
are soluble. This test method provides a means to determine the I 5 ~R/S! 3 100
degree of contamination by mineral matter.
where:
3. Reagent R 5 residue, g, and
S 5 sample used, g.
3.1 Chloroform (CHCl3) (Precaution—See 4.1).
4. Hazards 7. Precision and Bias
4.1 Chloroform is a hazardous liquid that can be absorbed 7.1 Precision and bias data were not established at the time
through the skin. Its vapor is hazardous through inhalation. It this test method was written. An effort is being made to obtain
is a narcotic. Use only with adequate ventilation (in a hood). the precision and, if obtainable, will be published in future
revisions. This test method has been in use for many years, and
its usefulness has been well established.
1
8. Keywords
Subcommittee D01.32 on Drying Oils. 8.1 chloroform insoluble matter; oiticica oil
Current edition approved August 29, 1986. Published October 1986. Originally
1

Iodine Value of Drying Oils and Fatty Acids1
1. Scope 3.1.1 iodine value—a measure of the unsaturation of oils

1.1 This test method covers the Wijs procedure for deter- and fatty acids and is expressed in terms of the number of
mination of unsaturation (iodine value) in drying oils. It is centigrams of iodine per gram of sample (weight percent of
applicable to all natural and synthetic drying oils and their fatty absorbed iodine).
acids. 3.1.1.1 Discussion—Total unsaturation of conjugated sys-
1.2 When the iodine value is determined on oils or fatty tems may be measured in accordance with Test Method
acids having conjugated systems, the result is not a measure of D 1541. The Wijs iodine value method is not reliable for tall oil
total unsaturation, but rather is an empirical value that affords fatty acids containing an appreciable quantity of rosin acids.
a comparison of total unsaturation. 4. Summary of Test Method
1.3 To obtain the total iodine value on conjugated samples,
use Test Method D 1541. 4.1 The determination of the iodine value of oils containing
isolated double bonds is based on the absorption of halogen
NOTE 1—This test method is essentially equivalent to Test Methods under conditions selected to promote stoichiometrical results.
D 2075 and D 2078.
1.4 This standard may involve hazardous materials, opera- 5. Significance and Use
tions, and equipment. This standard does not purport to 5.1 This test method measures the unsaturation as iodine
address all of the safety problems associated with its use. It is value by addition of an iodine/chlorine reagent. The amount of
the responsibility of the user of this standard to establish reagent absorbed is determined by back titrating the excess
appropriate safety and health practices and determine the reagent and comparing it to a blank determination.
applicability of regulatory limitations prior to use. For specific 5.2 In samples containing conjugated double bonds, the
hazard statements, see Section 8. iodine value obtained is empirical since the reagent does not
react stoichiometrically with conjugated unsaturation. Where
2. Referenced Documents no conjugation is present, the iodine value obtained is a
2.1 ASTM Standards: measure of the total unsaturation. By using proper specimen
D 1193 Specification for Reagent Water2 weights, the empirical values obtained are useful for compara-
D 1541 Test Method for Total Iodine Value of Drying Oils tive purposes.
and Their Derivatives3
D 2075 Test Method for Iodine Value of Fatty Amines, 6. Apparatus
Amidoamines, and Diamines3 6.1 Bottles—Glass-stoppered bottles or wide-mouth (Note
D 2078 Test Method for Iodine Value of Fatty Quarternary 2) Erlenmeyer flasks of 500-mL capacity.
Ammonium Chlorides3
NOTE 2—Wide-mouth bottles or flasks are essential if stirring is done
D 5768 Test Method for Iodine Value of Tall Oil Fatty by mechanical means.
Acids3
6.2 Pipets, 20 and 25-mL capacity.
3. Terminology
7. Reagents
3.1 Definitions:
used in all tests unless otherwise specified. Unless otherwise
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint indicated, it is intended that all reagents shall conform to the
and Related Coatings, Materials, and Applications and is the direct responsibility of Specifications of the Committee on Analytical Reagents of the
Subcommittee D 01.32 on Drying Oils.
2
3
1
D 1959
American Chemical Society, where such specifications are where:
available.4 Other grades may be used provided it is first A 5 K2Cr2O7 used, g, and
ascertained that the reagent is of sufficiently high purity to C 5 Na2S2O3 solution required for titration of the K2Cr2O7,
permit its use without lessening the accuracy of the determi- mL.
nation. 7.9 Starch Indicator Solution:
7.2 Purity of Water—Unless otherwise indicated, references 7.9.1 Use soluble starch that will pass the following test for
to water shall be understood to mean reagent water conforming sensitivity: Make a paste with 1 g of starch and a small amount
to Type I of Specification D 1193. of cold water. Add, while stirring, 200 mL of boiling water.
7.3 Acetic Acid (Glacial) (Caution—see 8.1)—Verify the Dilute 5 mL of this solution with 100 mL of water and add 0.05
absence of substances reducing permanganate as follows: mL of 0.1 N iodine solution. The deep blue color produced
Dilute 2 mL of the acid with 10 mL of water and add 0.1 mL must be discharged by 0.05 mL of 0.1 N Na2S2O3 solution.
of 0.1 N potassium permanganate (KMnO4) solution. The pink 7.9.2 Make a homogeneous paste of 10 g of soluble starch
color should not be entirely discharged at the end of 2 h.5 in cold water. Add to this 1 L of boiling water, stir rapidly, and
7.4 Solvent: isooctane or fresh cyclohexane to replace long cool. Salicylic acid (1.25 g/L) may be added to preserve the
used carbon tetrachloride, now banned as too hazardous indicator. If long storage is required, keep the solution in a
(Caution—See 8.2). refrigerator at 4 to 10°C (40 to 50°F). Prepare fresh indicator
7.5 Carbon Tetrachloride (CCl4) (Caution—See 8.2). when the end point of the titration from blue to colorless fails
to be sharp.
7.6 Chlorine (99.8% Cl ) (Caution—see 8.3)—Commercial
7.10 Wijs Solution (Caution—see 8.4) (Note 3)—Dissolve
grades of chlorine available in cylinders may be used, provided
13.0 g of iodine in 1 L of acetic acid. Gentle heat may be
the gas is dried by passing through concentrated sulfuric acid
necessary to promote solution. Cool and remove a small
(H2SO4, sp gr 1.84) before passing it into the iodine solution
quantity (100 to 200 mL) and set aside in a cool place for future
(see 7.10). Alternatively, the chlorine may be prepared by
use. Pass dry chlorine gas into the iodine solution until the
allowing concentrated hydrochloric acid (HCl, sp gr 1.19) to
original titration is not quite doubled. A characteristic color
drop onto potassium permanganate (KMnO4) or onto a mixture
change takes place in the Wijs solution when the desired
of KMnO4 and manganese dioxide (MnO2). Dry the gas thus
amount of chlorine has been added; this may be used to assist
generated by passing it through concentrated H2SO4.
in judging the end point. A convenient procedure is to add a
7.7 Potassium Iodide Solution (150 g/L)—Dissolve 150 g of
small excess of chlorine and bring back to the desired titration
potassium iodide (KI) in water and dilute to 1 L.
by addition of some of the original iodine solution that was
7.8 Sodium Thiosulfate, Standard Solution (0.1 N)— taken out at the beginning. Determine the strength of the
Dissolve 24.8 g of sodium thiosulfate (Na2S2O3·5H2O) in original iodine solution and the finished Wijs solution by
water and dilute to 1 L. Standardize against potassium dichro- titration against 0.1 N Na2S2O3 solution, as directed in .
mate (K2Cr2O7)6 as follows: Weigh to 0.1 mg, by difference
from a weighing bottle, 0.16 to 0.22 g of K2Cr2O7 that has been NOTE 3—Iodine monochloride (Wijs solution) can be purchased com-
finely ground and then dried to constant weight at 105 to 110°C mercially from various laboratory supply houses. The halogen ratio should
be checked prior to use.
prior to use. Place the K2Cr2O7 in a 500-mL flask or bottle and The halogen ratio, that is, the ratio of iodine to chlorine, can be
dissolve in 25 mL of water. Add 5 mL of concentrated determined by the Graupner-Aluise method,7 as follows:
hydrochloric acid (HCl, sp gr 1.19) and 20 mL of KI solution, Reagents:
and rotate to mix. Allow to stand for 5 min and then add 100 (1) Potassium Iodate Solution (0.04 N)—Dry potassium iodate (KIO3)
mL of water. Titrate with the Na2S2O3 solution, while shaking for 1 h at 105 to 110°C. Weigh 2.1402 g of the dried salt, dissolve in water,
constantly, until the yellow color has almost disappeared. Add dilute to 1 L in a volumetric flask, and mix.
(2) Hydrochloric Acid (1+1)—Dilute concentrated HCl (sp gr 1.19)
1 to 2 mL of starch indicator solution and continue the titration,
with an equal volume of water.
adding the Na2S2O3 solution slowly until the blue color has (3) Potassium Iodide Solution (150 g/L) (See 7.6).
just disappeared. Calculate the normality, N, of the Na2S2O3 as Procedure:
follows: (1) Measure 50 mL of HCl (1+1) and 50 mL of CCl4 into a 500-mL
N 5 ~A 3 20.39!/C iodine flask. By means of a pipet, transfer 25.00 mL of the Wijs solution
to the flask, and shake. Titrate the free iodine in the violet-colored CCl4
layer with the KIO3 solution to a colorless end point using vigorous
shaking.
4
Reagent Chemicals, American Chemical Society Specifications, American (2) On a second 25.00-mL portion of the Wijs solution, determine the
Chemical Society, Washington, DC. For suggestions on the testing of reagents not total halogen by adding 150 mL of water, 15 mL of KI solution, and
listed by the American Chemical Society, see Analar Standards for Laboratory titrating with standard Na2S2O3 solution to a starch end point.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Calculation—Calculate the iodine to chlorine ratio, R, as follows:
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, R 5 ~V1N1 1 V2N2!/~V1N1 – V2N2!
MD.
5
“Analytical Reagents, ACS Specifications,” Am. Chemical Soc., Washington,
DC (1960).
6 7
National Institute of Standards and Technology Standard Reference Material Graupner, A. J., and Aluise, V. A., “A New Rapid Titration Method for
No. 136 of potassium dichromate is recommended for this purpose, and should be Determining the Halogen Ratio of Wijs Solution and of Iodine Monochloride,”
treated as directed in the certificate of analysis accompanying the standard sample. Journal, Am. Oil Chemists’ Soc., February 1966, p. 81.
2
D 1959
where: TABLE 1 Specimen Weights
V1 5 Na2S2O3 solution required for total halogen, mL, Normal Oils and Fatty Acids, Conjugated Oils and
N1 5 normality of Na2S2O3 solution, Iodine Value 100 to 150 % Excess of Fatty Acids, 115 to 135 %
V2 5 KIO3 solution required for fre iodine, mL, and Reagent, g Excess of Reagent, g
N2 5 normality of the KIO3 solution Less than 3 10 ...
3 8.46 to 10.57 ...
8. Hazards 5 5.08 to 6.35 ...
10 2.54 to 3.17 ...
8.1 Acetic Acid, Glacial is corrosive and may cause burns to 20 0.85 to 1.59 ...
the skin and eyes. Wash clothing before reusing. See suppliers’ 40 0.64 to 0.79 ...
60 0.42 to 0.53 ...
Material Safety Data Sheet for further information. 80 0.32 to 0.40 0.34 to 0.37
8.2 Carbon Tetrachloride is a very hazardous liquid. It is 90 0.28 to 0.35 0.30 to 0.33
absorbed by the skin. Its vapor is hazardous through inhalation. 100 0.25 to 0.32 0.27 to 0.30
110 0.23 to 0.29 0.245 to 0.27
It is an irritant to the skin and eyes; avoid breathing (TLV-10 120 0.21 to 0.26 0.225 to 0.25
PPM). It causes liver and kidney damage and has cumulative 130 0.20 to 0.24 0.21 to 0.23
effects. Use with adequate ventilation (in a hood) and wear 140 0.18 to 0.23 0.19 to 0.21
150 0.17 to 0.21 0.18 to 0.20
rubber gloves. See suppliers’ Material Safety Data Sheet. 160 0.16 to 0.20 0.17 to 0.18
8.3 Chlorine is a poisonous, strongly irritating gas. Exer- 170 0.15 to 0.19 0.16 to 0.17
cise care in dispensing chlorine from a cylinder or in manu- 180 0.14 to 0.18 0.15 to 0.16
190 0.13 to 0.17 0.14 to 0.16
facture of chlorine by the action of hydrochloric acid on 200 0.12 to 0.16 0.135 to 0.15
potassium permanganate. Wijs and other similar solutions 210 0.12 to 0.15 0.13 to 0.14
should be prepared in a hood. For further information, see the 220 0.12 to 0.14 0.12 to 0.135
Chlorine Manual of the Chlorine Institute8 or suppliers’ Ma-

terial Safety Data Sheet.
8.4 Wijs Solution, iodine monochloride dissolved in glacial of 25 6 5°C. For conjugated oils or fatty acids such as tung,
acetic acid, is corrosive and may cause burns to the skin and oiticica, and dehydrated castor, allow the absorption to proceed
eyes. Wash clothing before reusing. Wijs solution should not be for 1 h at 25 6 1°C.
heated above 30°C as it may liberate chlorine, which is a
strong, irritating gas. Wijs solution can be purchased commer- 9.4 Remove the flasks from storage and add 20 mL of KI
cially or prepared in a hood. solution and 100 mL of water. Titrate with Na2S2O3 solution,
adding it gradually and with constant and vigorous shaking
9. Procedure (Note 5). Continue the titration until the yellow color has
9.1 Melt the sample if it is not already liquid (the tempera- almost disappeared. Add 1 to 2 mL of starch indicator solution
ture during melting and filtering should not exceed 10 to 15°C and continue the titration until the blue color has just disap-
above the melting point of the sample) and filter (drying oils of peared.
high viscosity should not be filtered) through filter paper to
NOTE 5—Mechanical stirring is very satisfactory for agitating during
remove any solid impurities and the last traces of moisture. The the addition of the Na2S2O3 solution.
sample must be absolutely dry.
9.1.1 All glassware used in this test must be absolutely clean 10. Calculation
and completely dry.
9.2 Place in a 500-mL flask or bottle, to which has been 10.1 Calculate the iodine value, I, as follows:
added 20 mL of solvent, an amount of sample such that there I 5 @~B 2 V!N3 12.69#/S
will be an excess of Wijs solution of 125 6 10 % for
conjugated oils or fatty acids and 125 6 25 % for normal or where:
nonconjugated oils or fatty acids. Specimen weights meeting V 5 Na2S2O3 solution required for titration of the speci-
this requirement are shown in Table 1. men, mL,
B 5 Na2S2O3 solution required for titration of the blank,
NOTE 4—For dehydrated castor oil and fatty acids use a specimen mL,
weight between 0.11 to 0.13 g. N 5 normality of the Na2S2O3 solution, and
9.3 Pipet 25 mL of Wijs solution into the flask containing S 5 sample used, g.
the specimen and also into each of at least two additional flasks
to be carried through as blanks. Stopper the flasks, and swirl 11. Precision and Bias
the flask containing the specimen to ensure an intimate 11.1 Precision and bias have not been determined.
mixture. Store the flask in a dark place for 1 h at a temperature
12. Keywords
8
Available from Chlorine Institute, 342 Madison Ave., New York, NY 10173. 12.1 drying oils; fatty acids; iodine value
3
D 1959
4

Loss on Heating of Drying Oils1
e1 NOTE—Keywords and an update statement on precision and bias were added editorially in May 1995.
1. Scope 4.2 Desiccator, containing efficient desiccant.

1.1 This test method covers the determination of moisture 4.3 Carbon Dioxide or Nitrogen Gas, (Warning—see 5.1)
and any other material that is volatile under the conditions of under pressure in cylinders.
the test. It is applicable to all natural drying oils. 5. Hazards
NOTE 1—For solutions of drying oils in volatile organic solvents it is 5.1 Carbon Dioxide and Nitrogen Gas—Gas supplied in
recommended that Test Methods D 1259 or D 1644 be used.
cylinders is dangerous because of its extremely high pressure.
1.2 This standard does not purport to address all of the Take care to prevent damage to cylinders, valves, and pressure
safety concerns, if any, associated with its use. It is the regulators. Consult supplier’s Material Safety Data Sheet.
priate safety and health practices and determine the applica- 6. Procedure
bility of regulatory limitations prior to use. Specific hazard 6.1 Weigh 10 g of sample to 0.1 mg, into a tared 50-mL
statements are given in Section 5. flask. Heat in an air oven at 105 6 2°C for 30 min, while
passing a gentle stream of carbon dioxide or nitrogen into the
2. Referenced Documents neck of the flask.
2.1 ASTM Standards:
NOTE 2—Care must be taken to keep the surface of the oil blanketed
D 1259 Test Methods for Nonvolatile Content of Resin with inert gas throughout the test to prevent oxidation of the oil.
Solutions2
D 1644 Test Methods for Nonvolatile Content of Varnishes2 6.2 Remove the flask from the oven, cool in a desiccator,
and weigh to 0.1 mg.
7. Calculation
3.1 Drying oils may contain small amounts of residual
extraction solvent, moisture or other volatile adulterants that 7.1 Calculate the percent loss on heating, L, as follows:
might interfere with their use. This test method provides a S2R
L5 S 3 100
means to measure the amount of volatile components at 105°C.
Oxidation of the oil could cause a weight gain at this
where:
temperature, and this is minimized by blanketing the specimen
S 5 specimen weight before heating, g, and
with inert gas. R 5 residue weight after heating, g.
4. Apparatus and Materials
4.1 Air Oven, maintained at 105 6 2°C.
8.1 Precision and bias have not been determined. This
method has been in use for many years, and its usefulness has
1
been well established.
Subcommittee D01.32 on Drying Oils. 9. Keywords
Current edition approved March 27, 1986. Published May 1986. Originally 9.1 drying oils; drying oils; loss in heating; drying oils;
2
volatiles
1
D 1960
2

Saponification Value of Drying Oils, Fatty Acids, and
1. Scope times longer than 1 h for complete reaction.

1.1 This test method covers the determination of the saponi- 5. Apparatus
fication value of drying oils, bodied oils, fatty acids, and
polymerized fatty acids. 5.1 Erlenmeyer Flasks, wide-mouth, alkali-resistant, 250 or
1.2 This standard does not purport to address all of the 300-mL capacity.
safety concerns, if any, associated with its use. It is the 5.2 Condenser Loop.
responsibility of the user of this standard to establish appro- NOTE 1—Suitable condenser loops are shown in Figs. 1 and 2 of Test
priate safety and health practices and determine the applica- Method D 305.
bility of regulatory limitations prior to use. For specific hazard 5.3 Steam Bath.
statements, see Section 7.
6. Reagents
2.1 ASTM Standards: used in all tests. Unless otherwise indicated, it is intended that
D 305 Test Method for Solvent-Extractable Material in all reagents shall conform to the Specifications of the Com-
Black Pigments2 mittee on Analytical Reagents of the American Chemical
D 1193 Specification for Reagent Water3 Society, where such specifications are available.4 Other grades
3. Terminology may be used, provided it is first ascertained that the reagent is
of sufficiently high purity to permit its use without lessening
3.1 Definitions: the accuracy of the determination.
3.1.1 saponification value—a measure of the alkali reactive 6.2 Purity of Water—Unless otherwise indicated, references
groups in oils and fatty acids and is expressed as the number of to water shall be understood to mean reagent water conforming
milligrams of potassium hydroxide that react with 1 g of to Type I of Specification D 1193.
sample. 6.3 Phenolphthalein Indicator Solution—Dissolve 1 g of
4. Significance and Use phenolphthalein in 100 mL of ethanol (95 %), methanol or
isopropanol.
4.1 The saponification value of oils and fatty acids is a
measure of the content of ester linkages. For an oil, provided it NOTE 2—A “masked phenolphthalein indicator” may be used with
is not significantly oxidized, the number of ester linkages per off-color materials. Prepare by dissolving 1.6 g of phenolphthalein and 2.7
g of methylene blue in 500 mL of alcohol. Adjust the pH with sodium
molecule (for example, three in a triglyceride), can be used to hydroxide (NaOH) or KOH solution so that the greenish blue color is
calculate the molecular weight of the oil. faintly tinged with purple. The color change is from green to purple when
4.2 A saponification value higher than normal indicates that going from acid to alkali.
the oil has been oxidized (blown) or chemically modified, for
6.4 Potassium Hydroxide, Alcoholic Solution—Place 5 to
example, with other acids such as maleic, fumaric, or phthalic.
10 g of potassium hydroxide (KOH) (Caution—see 7.1) in a
4.3 Saponification value alone is not a measure of the
2-L flask and add 1 to 1.5 L of ethyl alcohol (95 %) or
quality of the oil.
denatured alcohol conforming to Formula No. 30 or 3A of the
4.4 Chemically modified oils may require saponification
U. S. Bureau of Alcohol, Tobacco and Firearms. Boil on a
1
4
and Related Coatings, Materials, and Applications, and is the direct responsibility of Reagent Chemicals, American Chemical Society Specifications, American
Subcommittee D01.32 on Drying Oils. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved May 31, 1985. Published July 1985. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1962 – 61. Last previous edition D 1962 – 67 (1984). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1962
water bath under a reflux condenser for 30 to 60 min. Distill 8. Procedure
and collect the alcohol. Dissolve 40 g of KOH in 1 L of the 8.1 To an Erlenmeyer flask, transfer a specimen weight of
distilled alcohol, keeping the temperature below 15°C while such size, weighed to 1 mg, that the back titration is 45 to 55 %
the alkali is being dissolved. This solution should remain clear. of the blank. Add 25 mL of alcoholic KOH solution to the flask
6.5 Sulfuric or Hydrochloric Acid, Standard (0.5 N)—Add and to one or more additional flasks to be carried through as
about 15 mL of concentrated sulfuric acid (H2SO4, sp gr 1.84) blanks. Place a condenser loop inside the neck of each flask
(Precaution—see 7.2) or 45 mL of concentrated hydrochloric and heat on the steam bath for 1 h.
acid (HCl, sp gr 1.19) (Precaution—see 7.3) to about 900 mL
of water, cool, and dilute to 1 L. Standardize against freshly NOTE 3—Certain synthetic oils are not completely saponified in 1 h.
Run chemically modified drying oils in duplicate, using 1 and 2-h heating
standardized sodium hydroxide (NaOH) solution or by any
periods to establish completeness of saponification. If the 2-h heating
other accurate method. gives appreciably higher results than the 1-h run, additional determina-
tions using 4 and 6-h heating periods should be run to establish the time
7. Hazards required for complete reaction.
7.1 Potassium Hydroxide and its strong solutions are caus-
8.2 Cool the solution, add phenolphthalein indicator (Note
tic to the skin and eyes. Avoid all contact with skin and eyes.
2), and titrate with 0.5 N H2SO4 or HCl until the pink color has
In case of contact, immediately flush eyes for 15 min and wash
just disappeared.
hands with plenty of cold water. Call a physician. Remove
contaminated clothing and wash before reuse. See suppliers’
9. Calculation
Material Safety Data Sheet for further information.
7.2 Sulfuric Acid is corrosive to skin, eyes and mucous 9.1 Calculate the saponification number, P, as follows:
membranes in the form of liquid, mist, or fumes. It causes P 5 @~B 2 V!N 3 56.1#/S
severe burns. Take care to prevent the contact of the acid with
eyes, skin or on clothing. In making dilute solutions, always where:
add the acid to water with care. In case of contact, immediately V 5 H2SO4 or HCl required for titration of the specimen,
flush eyes with copious amounts of water for 15 min; flush skin mL,
with water (use shower if available); wash contaminated B 5 H2SO4 or HCl required for titration of the blank, mL,
N 5 normality of the H2SO4 or HCl, and
clothing before reuse. Immediately call a physician. See
suppliers’ Material Safety Data Sheet.
7.3 Concentrated Hydrochloric Acid is corrosive and may
cause burns to the skin and eyes; the vapor is irritating to
mucous membranes. Avoid contact with skin and eyes. In case 10.1 Precision and Bias have not been determined.
of contact, wash skin and flush eyes with cold water for 15 min.
Remove contaminated clothing. Call a physician. Wash cloth- 11. Keywords
ing before reuse. See suppliers’ Material Safety Data Sheet. 11.1 drying oils; fatty acids; saponification value
2

Specific Gravity of Drying Oils, Varnishes, Resins, and
Related Materials at 25/25°C1
1. Scope Petroleum Products by Hydrometer Method2

1.1 This test method covers the determination of the specific D 1475 Test Method for Density of Paint, Varnish, Lacquer,
gravity of drying oils, varnishes, alkyd resins, fatty acids, and and Related Products3
related materials. E 100 Specification for ASTM Hydrometers4
1.2 This test method is recommended where precision is 3. Terminology
required in the determination of specific gravity, such as
establishing specifications or referee work. 3.1 Definition:
1.2.1 For materials with a kinematic viscosity of 40 stokes 3.1.1 specific gravity, of drying oils and varnishes—the
or less, use the Leach type pycnometer. ratio of the mass of a given volume of material at 25°C to that
1.2.2 For materials with a viscosity in excess of 40 stokes, of an equal volume of water at 25°C, expressed as follows:
use the Hubbard-type pycnometer. Specific gravity at 25/25°C___ .
1.2.3 For materials that are solid or semisolid at 25°C but 4. Significance and Use
liquid at slightly higher temperatures, use the Hubbard-type
pycnometer. 4.1 Specific gravity is a useful measure, since conversion
from volume to weight, or vice versa, is often required. For this
NOTE 1—The weight per gallon cup method is satisfactory for most reason it should be determined with care.
routine laboratory work although the precision does not equal that of the 4.2 Specific gravity is very sensitive to temperature, and the
pycnometer method. The test method described herein for use with the
Hubbard-type pycnometer is applicable to the weight per gallon cup
temperature of measurement must be controlled, or at least
method, or Test Method D 1475 may be used. known, with high precision. If the specific gravity at some
temperature other than the standard is required, temperature
NOTE 2—Hydrometers also provide a rapid method for checking correction factors for this purpose are provided. These factors
specific gravity and are generally satisfactory for routine control work. may also be used to correct the specific gravity from some
However, the precision of the hydrometer method is not adequate where other temperature to the standard 25/25°C.
accurate results are required. Test Method D 1298 covers the use of the
4.3 In addition, various procedures are outlined in this test
hydrometer in the determination of specific gravity.
Most ASTM Hydrometers (See Specification E 100) are calibrated to method so that specific gravities of materials with widely
read specific gravity at 15.5/15.5°C (60/60°F). Information on sources of varying viscosities can be accurately measured.
hydrometers calibrated at 25/25°C is available at ASTM Headquarters. 4.4 Specific gravity is not a measure of the quality of the oil,
1.3 This standard does not purport to address all of the and an oil that deviates slightly from the specified limits, but
safety concerns, if any, associated with its use. It is the otherwise conforms, is usually completely satisfactory. Spe-
responsibility of the user of this standard to establish appro- cific gravity increases with polymerization or oxidation in a
priate safety and health practices and determine the applica- regular manner, and for every bodied or blown oil of a given
bility of regulatory limitations prior to use. For specific hazard viscosity there is an appropriate specific gravity.
statements, see Section 6. 4.5 Determine the specific gravity in accordance with this
test method, which is capable of high precision and is the
2. Referenced Documents referee method. If less accurate results (3 significant figures)
2.1 ASTM Standards: are adequate, “weight-per-gallon” cups as described in Test
D 1298 Test Method for Density, Relative Density (Specific Method D 1475 may be used.
Gravity) or API Gravity of Crude Petroleum and Liquid 5. Apparatus
1
5.1 Leach-Type Pycnometer—A glass pycnometer, conical
in shape and vented by a side arm that has a cap with a
Current edition approved Nov. 29, 1985. Published January 1986. Originally 2
published as D 1963 – 61. Last previous edition D 1963 –74 (1984). 3
4
1
D 1963
standard-taper No. 5/12 joint. A thermometer shall be sealed in at a temperature of approximately 20°C. Insert the stopper,
the neck by a standard-taper No. 10/18 interchangeable joint. taking care that no air bubbles are entrapped.
The thermometer shall have a range from 12 to 38°C in 0.2°C 8.3 Immerse in the water bath at 25 6 0.1°C to a level of 1⁄16
divisions. Either 25 or 50-mL capacity is satisfactory. Weld to 1⁄8 in. (1.5 to 3.2 mm) above the water until constant
pycnometers have also been found suitable. temperature is reached (approximately 1 h).
5.2 Hubbard-Type Pycnometer—A glass pycnometer, coni- 8.4 Seat the stopper firmly in the pycnometer and blot the
cal or cylindrical in shape, and fitted with a ground glass water from the surface so that the level in the bore is flush with
stopper 22 to 26 mm in diameter. The stopper shall have a 1.0 the surface. Remove the pycnometer from the bath, wipe dry
to 2.0-mm vertical hole in the center. The top of the stopper with a clean cloth, and weigh immediately, recording the mass
shall be a plane, smooth surface. The under surface of the as B. (The pycnometer may be cooled slightly before weighing
stopper shall be concave (approximately 5 mm at the center) to to prevent loss of water through the capillary.) Calibrate until
let the air escape when it is inserted. The capacity shall be consistent results are obtained.
about 25 to 30 mL and the weight not more than 40 g.
5.3 Water Bath, capable of being maintained at 25 6 0.1°C. 9. Procedure Using Leach-Type Pycnometer
9.1 Fill a clean, dry pycnometer with the material to be
6. Hazards
tested at a temperature of approximately 20°C, in the same
6.1 Chromic Acid Cleaning Solution is based on concen- manner as described in 7.2. If necessary, centrifuge the
trated sulfuric acid that is corrosive to skin, eyes and mucous material to remove air bubbles either before or after filling the
membranes in the form of liquid, mist, or fumes. It causes pycnometer.
severe burns. Take care to prevent contact of the acid with 9.2 Bring the material to a temperature of 25°C, dry with
eyes, skin, or clothing. In making dilute solutions, always add absorbent material moistened with toluene, and weigh as
the acid to water with care. In case of contact, immediately described in 7.3 and 7.4. Record the weight as C.
flush eyes with copious amounts of water for 15 min; flush skin
with water (use shower if available); wash contaminated NOTE 3—When using the Leach-type pycnometer for routine work it is
not necessary to bring the flask and contents to exactly 25°C. The
clothing before reuse. Immediately call a physician. Like
thermometer temperature can be read when the vent cap is put in place and
sulfuric acid, chromic acid cleaning solution is a strong a temperature correction applied to the calculated specific gravity.
oxidizer and should not be brought into contact with organic or
reducing agents as a fire or explosion can result. Consult 10. Procedure Using Hubbard-Type Pycnometer
supplier’s Material Safety Data Sheets. 10.1 When determining specific gravity on materials that
7. Calibration of Leach-Type Pycnometer are very viscous, semisolid, or solid at 25°C, use the following
procedure:
7.1 Carefully clean the pycnometer by first soaking all parts
10.1.1 Fill a clean, dry pycnometer one half full of the
in potassium dichromate (K2Cr2O7) dissolved in concentrated
material to be tested.
sulfuric acid (H2SO4) (Precaution—see 6.1) and then washing
thoroughly with water. Dry the pycnometer thoroughly and NOTE 4—Precautions must be taken to keep the material from touching
place it with all its parts in a desiccator for at least 1 h before the sides of the flask above the final level and to prevent the inclusion of
air bubbles. It is advisable to warm the bottle before filling.
weighing. Weigh the pycnometer with all its parts to 0.1 mg.
Record this weight as A. 10.1.2 Permit the bottle with its contents to cool to room
7.2 Fill the pycnometer to overflowing (by holding on its temperature and then weigh with the stopper. Record the
side in such a manner as to prevent the entrapment of air weight as C.
bubbles) with cooled, just previously boiled, distilled water at 10.1.3 Remove the pycnometer from the balance and fill it
a temperature of 20°C. Insert the thermometer by holding the with freshly boiled distilled water of approximately 20°C.
bottle 45° from the horizontal, being careful no air bubbles are Insert the stopper and place the pycnometer in the constant
included. temperature bath for at least 30 min. At the end of this time
7.3 Transfer the pycnometer to a 25°C bath so that the water firmly seat the stopper and then carefully blot the top of the
in the bath will be 1⁄16 in. (1.5 mm) lower than the top of the stopper, being careful not to draw water from the stopper
capillary vent tube and hold it in the bath for approximately 1 opening.
h or until the pycnometer-thermometer has reached 25°C.
NOTE 5—When difficulty with bubble release is encountered in making
7.4 Carefully remove excess water from the capillary with the determination, refer to a procedure in which water is replaced with
absorbent materials, and cap immediately. Remove the pyc- odorless mineral spirits.5
nometer from the bath. Dry the outside of the pycnometer by
wiping dry with an absorbent material. Take care not to handle 10.1.4 Remove the pycnometer from the bath and partially
the pycnometer so as to raise the temperature markedly or immerse it in cold distilled water until the contents recede from
leave fingerprints. Immediately weigh to 0.1 mg and record the the stopper opening. Wipe dry and weigh at once to 0.1 mg.
weight as B. Record this weight as D.
8. Calibration of Hubbard-Type Pycnometer

8.1 Clean and weigh the pycnometer as described in 7.1. 5
Ashton, H. E., “Measuring Specific Gravity of Viscous Materials,” Materials,
8.2 Fill the pycnometer with freshly boiled, distilled water Research and Standards, Vol 1, No. 7, July 1961.
2
D 1963
11. Calculation S 5 ~C 2 A!/@~B 2 A! 2 ~D 2 C!# (3)
11.1 Calculate the specific gravity, S, determined as de- where:

scribed in Sections 7-9, where the pycnometer is completely A 5 weight of empty pycnometer, g,
filled with the material to be tested as follows: B 5 weight of pycnometer plus water, g, and
S 5 ~C 2 A!/~B 2 A! (1)
C 5 weight of pycnometer plus material plus water, g.
11.4 Using 0.00068 as the thermal coefficient of drying oils
where: approximate corrections to other temperatures can be made as
A 5 weight of pycnometer, g, follows:
B 5 weight of pycnometer plus water, g, To correct from 25/25°C to 25/15.5°C, subtract 0.0018.
C 5 weight of pycnometer plus material, g. To correct from 25/25°C to 15.5/15.5°C, add 0.0047.
11.2 When the Leach pycnometer is used and the tempera- 12. Precision and Bias
ture of the pycnometer plus material, C, is not exactly 25°C, a
12.1 Precision—Fourteen laboratories participating in the
correction must be made using the thermal coefficient of the
AOCS Smalley check series reported single results on six oils
material tested. For most vegetable oils this is approximately for a total of 84 results and a calculated standard deviation of
0.00068/°C: 0.0049.
SC 5 X 1 0.00068 Y (2) 12.2 Repeatability—(95 % confidence level) Duplicate re-
sults by the same operator should be considered suspect if they
where:
differ by more than 0.0011.
SC 5 corrected specific gravity,
X 5 uncorrected specific gravity, and 12.3 Reproducibility—Single determinations made in two
Y 5 temperature difference, plus or minus, °C. different laboratories should not differ by more than 0.0013.
12.4 Bias—Bias has not been determined.
11.3 Calculate the specific gravity, S, determined as de-
scribed in 11.1, where the pycnometer is only partially filled 13. Keywords
with the material to be tested, as follows: 13.1 drying oils; resins; specific gravity; varnishes
3

Tung Oil Quality1
e1 NOTE—Unit of measurement statement was added editorially in May 1995.
1. Scope 4.2 Tripod, wide-flange, with a 75-mm (3-in.) opening.

1.1 This test method covers the determination of the quality NOTE 1—The object of the flange is to prevent superheating of the sides
of tung oil by distinguishing between pure and adulterated oil. of the casserole.
The test method is not applicable to oils other than tung oil. 4.3 Thermometer—An ASTM Low Distillation Thermom-
1.2 The values stated in SI units are to be regarded as the eter having a range from − 2 to 300°C and conforming to the
standard. The values given in parentheses are for information requirements for Thermometer 7C as prescribed in Specifica-
only. tion E 1.
safety concerns, if any, associated with its use. It is the 5. Procedure
responsibility of the user of this standard to establish appro- 5.1 Weigh 150 g of the oil into the casserole and heat so that
priate safety and health practices and determine the applica- the temperature reaches 282°C in 4 min 6 30 s while stirring
bility of regulatory limitations prior to use. with the thermometer. Turn down the flame and maintain the
2. Referenced Documents temperature at 282 6 1°C. Stir with the thermometer until, on
lifting the thermometer, the oil drops with a pronounced string,
2.1 ASTM Standards: showing that polymerization has started. The time required
E 1 Specification for ASTM Thermometers2 after reaching 282 6 1°C until the string is noted is the time of
3. Significance and Use the heat test. For pure tung oils this will not exceed 8 min.
5.2 As soon as the oil strings, turn off the flame and remove
3.1 Since tung oil contains a high degree of conjugated the thermometer. Stir with a stiff spatula until the oil is solid.
unsaturation, it will form a dry gel when subjected to elevated After stringing, a pure tung oil will require not over 40 s to
temperatures for a relatively short time. This test method is become solid.
designed to detect adulteration of tung oil with less conjugated 5.3 When the oil has solidified, allow to stand exactly 1 min.
oils, since an adulterated tung oil will require a longer gel time Turn out upside down on clean paper and cut at once with a
and will give a gel that is soft and sticky. clean spatula. Pure tung oil gives a gel that is dry, not adhering
3.2 This test method is extremely temperature sensitive and to the spatula when cut. It is firm, crumbling under pressure of
therefore the temperature must be accurately controlled. the spatula, without sticking. The crumbs should have an
4. Apparatus appearance like dry bread crumbs. Adulterated tung oil gives a
gel that is soft and sticky and does not crumble.
4.1 Casserole—An ordinary vitreous-enameled iron casse-
role having a bottom diameter of 75 mm (3 in.). 6. Precision and Bias
6.1 Precision and bias data were not established at the time
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint this test method was written. This test method has been in use
and Related Coatings, Materials, and Applications, and is the direct responsibility of for many years and its usefulness has been well established.
published as D 1964 – 61 to replace Sections 52–55 of D 555–58. Last previous
7. Keywords
edition D 1964 – 61 (1984).
2
7.1 tung oil
1
D 1964
2

Unsaponifiable Matter in Drying Oils, Fatty Acids, and
1. Scope soluble soaps. This test method determines the amount of

1.1 This test method covers the determination of the unsa- material present that is soluble in the oil but is not saponifiable.
ponifiable matter present in all natural and synthetic drying oils Under conditions of this test method, this material is not
and their fatty acids and any other fatty acids or polymerized converted to a water-soluble soap and is extracted from the
fatty acids used in protective coatings. saponification mixture with petroleum ether.
1.2 This standard does not purport to address all of the 4.2 A small amount of unsaponifiable material is character-
safety concerns, if any, associated with its use. It is the istic of drying oils and fatty acids however a large amount
responsibility of the user of this standard to establish appro- indicates contamination with hydrocarbon materials such as
priate safety and health practices and determine the applica- mineral oils or hydrocarbon resins.
bility of regulatory limitations prior to use. 4.3 This test method is the referee method for unsaponifi-
able content. The exact amount of unsaponifiable matter
2. Referenced Documents obtained is governed by the partition coefficient of the matter
2.1 ASTM Standards: between the soap solution and the solvent. Different results will
D 460 Test Methods for Sampling and Chemical Analysis be obtained if some other solvent, such as ethyl ether, is used.
of Soaps and Soap Products2 NOTE 1—See relevant specifications for appropriate numeric ranges of
D 1193 Specification for Reagent Water3 unsaponifiable matter in specific drying oils or fatty acids.
D 1466 Test Method for Sampling Liquid Oils and Fatty
Acids Commonly Used in Paints, Varnishes, and Related 5. Apparatus
Materials4 5.1 Glass-Stoppered Extraction Cylinder, graduated at 40,
2.2 AOSC Standard: 80, and 130 mL, about 300 mm in height and 35 mm in
Specification H 2-415 diameter.
5.2 Erlenmeyer or Soxhlet Flasks, 100 to 200-mL capacity.
3. Terminology
5.3 Separatory Funnels, 500-mL capacity.
3.1 Definitions: 5.4 Glass Siphon.
3.1.1 unsaponifiable matter—substances frequently found
dissolved in fatty acids that cannot be saponified by sodium 6. Reagents
hydroxide or potassium hydroxide under the conditions pre- 6.1 Purity of Reagents—Reagent grade chemicals shall be
scribed but are soluble in the ordinary fat solvents. Included are used in all tests unless otherwise specified. Unless otherwise
the higher aliphatic alcohols, sterols, pigments, and hydrocar- indicated, it is intended that all reagents shall conform to the
bons. Specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are
available.6 Other grades may be used provided it is first
4.1 The major components of drying oils and fatty acids can ascertained that the reagent is of sufficiently high purity to
be saponified by reaction with alkali and converted to water- permit its use without lessening the accuracy of the determi-
nation.
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 6.2 Purity of Water—Unless otherwise indicated, references
and Related Coatings, Materials, and Applications, and is the direct responsibility of to water shall be understood to mean reagent water conforming
6
published as D 1965 – 61. Last previous edition D 1965 – 85. Reagent Chemicals, American Chemical Society Specifications, American
2
3
4
5
Available from American Oil Chemists’ Society, 508 S. Sixth St., Champaign, and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
IL 61820. MD.
1
D 1965
to Type II of Specification D 1193. 8.4 Draw the petroleum ether fraction into a 500-mL
6.3 Ethyl Alcohol, Neutral (95 %)—Use 95 % ethyl alcohol separatory funnel containing 5 mL of ethyl alcohol (1 + 9) in
or neutral denatured alcohol conforming to Formula No. 30 or order to minimize the possibility of leakage of petroleum ether.
3A of the U. S. Bureau of Alcohol, Tobacco and Firearms. Boil 8.5 Repeat the extraction at least six more times using
and neutralize to the phenolphthalein end point with alkali just 50-mL portions of petroleum ether each time, and, shaking
before using. vigorously with each extraction.
6.4 Ethyl Alcohol (1 + 9)—Mix 1 volume of alcohol NOTE 4—There are some cases in which seven extractions may not be
conforming to 5.3 with 9 volumes of water. sufficient. This is best judged by making another extraction and
6.5 Phenolphthalein Indicator Solution (10 g/L) (Note 2)— evaporating this separately. Extraction should be discontinued when a
Dissolve 1 g of phenolphthalein in 100 mL ethanol (6.3), single extraction shows less than 5 mg of residue.
methanol, or isopropanol. 8.6 Wash the combined extracts in a separatory funnel with
NOTE 2—A “masked phenolphthalein indicator” may be used with 25-mL portions of alcohol (1 + 9), shaking vigorously and
off-color materials. Prepare by dissolving 1.6 g of phenolphthalein and 2.7 drawing off the alcohol layer after each wash. Discontinue
g of methylene blue in 500 mL of denatured alcohol conforming to 5.3. washing when the wash solution is neutral to phenolphthalein.
Adjust the pH with sodium hydroxide (NaOH) or potassium hydroxide Be careful not to remove any of the ether layer.
(KOH) solution so that the greenish-blue color is faintly tinted with
purple. The color change is from green to purple when going from acid to
8.7 Transfer the ether extract to a tared beaker and evaporate
alkaline. to dryness on a water bath under a gentle stream of clean, dry
air. Complete the drying to a weight constant to 1 mg,
6.6 Petroleum Ether conforming to the requirements given preferably in a vacuum oven at 75 to 80°C and an internal
in Test Methods D 460. pressure of not more than 200 mm of mercury, or in an air oven
NOTE 3—Petroleum ether conforming to the requirements of AOCS at 105°C for 15-min intervals. Cool in a desiccator and weigh.
Specification H 2-41 also meets these requirements. 8.8 After weighing, take up the residue in 50 mL of warm
6.7 Potassium Hydroxide Solution(50 %)—Dissolve (about 50°C) ethyl alcohol (95 %) containing approximately 1
potassium hydroxide (KOH) in an equal weight of water. mL of indicator solution and previously neutralized to a faint
6.8 Sodium Hydroxide, Standard Solution (0.02 N)— pink color. Titrate with 0.02 N NaOH solution to the same
Transfer 40 mL of 0.5 N sodium hydroxide (NaOH) solution to color.
a 1-L volumetric flask. Adjust to volume with recently boiled
and cooled water. Standardize by titrating against potassium 9. Calculation
acid phthalate, using phenolphthalein indicator solution. 9.1 Calculate the percent of unsaponifiable matter, M, as
follows:
7. Sampling A 5 VN 3 0.282 (1)
7.1 The sampling of the material and sample preparation M, % 5 @~R 2 A!/S# 3 100 (2)
and handling shall be in accordance with Test Method D 1466.
where:
8. Procedure A 5 fatty acids in the extract, g,
8.1 Transfer about 5 g of the well-mixed sample, weighed to V 5 volume of NaOH solution required for titration of the
10 mg, to an Erlenmeyer or Soxhlet flask. Add 30 mL of fatty acids (see 8.8), mL,
alcohol and 5 mL of KOH solution. Boil gently but steadily N 5 normality of the NaOH solution,
under a reflux condenser for a minimum of 1 h and until R 5 residue (see 8.7), g, and
completely saponified. Complete saponification is essential. S 5 specimen weight, g.
8.2 Transfer to the extraction cylinder and wash to the
40-mL mark with alcohol. Complete the transfer with warm 10. Precision and Bias
and then cold water until the total volume is 80 mL. Wash out 10.1 Precision and bias were not established at the time this
the flask with a little petroleum ether and add to the cylinder. test method was written. An effort is being made to assemble
Cool the cylinder and contents to room temperature (20 to this information and if obtainable it will be published in future
25°C) and then add 50 mL of petroleum ether. revisions. This test method has been in use for many years and
8.3 Insert the stopper and shake vigorously for at least 1 min its usefulness has been well established.
and allow to settle until both layers are clear. Use a glass
siphon to remove the upper layer as completely as possible 11. Keywords
without including any of the lower portion. 11.1 drying oils; fatty acids; unsaponifiable matter
2

Foots in Raw Linseed Oil (Gravimetric Method)1
1. Scope shaft shall be rotated mechanically by any means desired that

1.1 This method covers the determination of foots in raw allows one to choose either of two fixed speeds; a slow speed
linseed oil by the gravimetric method. The procedure is of 16 6 2 rpm and a fast speed of 32 6 2 rpm.
commonly known in Europe as the PAT foots method. 5.3 Centrifuge Tube, pear-shaped conforming to dimensions
1.2 This standard does not purport to address all of the given in Fig. 1, and made of thoroughly annealed glass. The
safety concerns, if any, associated with its use. It is the graduations, numbered as shown in Fig. 1, shall be clear and
responsibility of the user of this standard to establish appro- distinct and the mouth shall be constricted in shape for closure
priate safety and health practices and determine the applica- with a stopper.
bility of regulatory limitations prior to use. 5.4 Centrifuge—Capable of whirling two or more filled
tubes at a speed that can be controlled to give a relative
2. Referenced Documents centrifugal force of between 500 to 800 g at the tip of the tubes.
2.1 ASTM Standards: Calculate the speed of the rotating head as follows:
D 1193 Specification for Reagent Water2 rpm 5 265 =rcf/d (1)
3. Terminology where:
3.1 Definition: rcf 5 relative centrifugal force, g, and
3.1.1 foots—those solid impurities that precipitate from raw d 5 diameter of swing, in., measured between tips of
linseed oil during storage and which then settle to the bottom opposite tubes when in rotating position.
or“ foot” of a storage tank. 5.4.1 If d is given in millimetres, use the following equa-
3.2 Definition of Term Specific to This Standard: tion:
3.2.1 foots—in this method, the material that is precipitated rpm 5 1346 =rcf/d (2)
from the oil by phosphoric acid and which is insoluble in
NOTE 1—A list of applicable rotational speeds is given in Table 1.
acetone under the specific conditions of the test.
5.5 Pipet, 1-mL measuring type graduated in 0.01-mL
4. Summary of Test Method subdivisions.
4.1 The oil to be tested is refined with 85 % phosphoric 5.6 Desiccator, containing an efficient desiccant. Anhydrous
acid. The precipitated material is settled by centrifuging and is calcium sulfate is satisfactory.
washed free of oil with acetone. It is dried and weighed to
determine the foots content gravimetrically. 6. Reagents
5. Apparatus used in all tests. Unless otherwise indicated, it is intended that
5.1 Fritted Glass Filtering Crucibles, having a medium all reagents shall conform to the specifications of the Commit-
porosity (10 to 15 µm) and a capacity of 30 mL. tee on Analytical Reagents of the American Chemical Society,
5.2 Agitator—The agitator shall consist of a horizontal shaft where such specifications are available.3 Other grades may be
suitably supported and fitted with clamps or a clamping device used, provided it is first ascertained that the reagent is of
for holding pear-shaped centrifuge tubes. The tubes shall be sufficiently high purity to permit its use without lessening the
held in such fashion that when the shaft rotates, the tubes will accuracy of the determination.
be tipped end over end, thus allowing the liquid content of the 6.2 Purity of Water—Unless otherwise indicated, references
tube to mix as it flows from one end of tube to the other. The to water shall be understood to mean reagent water conforming
1 3
and Related Coatings, Materials, and Applications, and is the direct responsibility of Chemical Society, Washington, DC. For suggestions on the testing of reagents not
D01.32 on Drying Oils. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition effective Oct. 3, 1969. Originally issued 1964. Replaces Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
D 1966 – 64 T. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
1
D 1966
9.2 Stopper the tube and tilt it so that the acid runs out of the
tip and into the oil. Shake vigorously for a few seconds. Repeat
the tilting and shaking twice more.
9.3 Place the tube on the agitator and mix for 5 min at such
a speed that the acid disperses completely throughout the oil
and the tip of the tube empties of oil at each revolution. A speed
of 16 r/m is adequate when using the above agitator. Adjust the
speed of the agitator so that intimate mixing without separation
takes place; 32 rpm is satisfactory. Mix at this rate for 25 min.
9.4 Place the tube in the centrifuge and spin for 1 h with a
relative centrifugal force of at least 500 g at the tip or until the
deposit stays in position as a compact mass when the tube is
inverted. The temperature should be maintained at approxi-
mately 25°C. This may be accomplished by admitting air to the
centrifuge casing.
9.5 Decant or siphon the supernatant oil as completely as
FIG. 1 Pear-Shaped Centrifuge Tube
possible into a clean centrifuge tube and allow time for
drainage. If the foots layer is liquid, extra care must be taken
TABLE 1 Rotational Speeds Applicable for Centrifuges of
Various Diameters of Swing to remove the oil without disturbing the foots layer. A modified
siphon can be used to advantage.
Diameter in. (mm) rpm at 500 rcf rpm at 800 rcf
9.6 Add 25 mL of acetone to the precipitate in the first tube
12(305) 1710 2160
13(330) 1650 2080 and mix until the gummy material is dispersed. Use a wire to
14(356) 1590 2000 loosen them from the tip of the tube if necessary. Dilute to 100
15(381) 1530 1930 mL with more acetone and shake.
16(407) 1480 1870
17(432) 1440 1820 9.7 Prepare fritted glass crucibles as follows: Add 0.3 to 0.6
18(458) 1400 1770 g of diatomaceous silica to the empty crucible. With experience
19(483) 1360 1720
20(508) 1330 1680
this can roughly be measured on the tip of a spatula. Slurry
21(533) 1300 1640 with approximately 15 mL of acetone. Remove the acetone by
22(560) 1270 1600 applying a vacuum to the filter. Dry the crucible in an oven at
23(584) 1240 1560
24(610) 1210 1530
100 6 5°C for 1 h or to constant weight (0.01 mg). Cool for 1
h in a desiccator and weigh to the fourth decimal place. Store
prepared crucibles in a desiccator until they are to be used.
6.3 Acetone. 9.8 Filter the mixture prepared in accordance with 9.6
6.4 Filter Aid, diatomaceous silica.4 through a weighed, fritted glass crucible. Use a moderate
6.5 Phosphoric Acid (85 %) (H3PO4). vacuum and always maintain some acetone in the crucible.
7. Hazard Thoroughly wash the centrifuge tube and precipitate on the
filter with four, 15-mL portions of acetone. Since oil tends to
7.1 This standard may involve the use of hazardous mate- creep up the sides of the crucible care must be exercised. A
rials, operations, and equipment. It is the responsibility of wash bottle containing acetone should be used to ensure
whoever uses this standard to establish appropriate safety thorough washing of the centrifuge tube and crucible. After the
practices to determine the applicability of regulatory limita- crucible is exhausted of acetone, dry it at 100°C, cool to room
tions prior to use. temperature in the desiccator, and weigh to nearest 0.1 mg.
8. Preparation of Sample NOTE 2—The fritted glass filters must be cleaned periodically with
8.1 Allow the sample to come to room temperature (256 cleaning solution. It is well to test the filtration rate of each crucible with
1°C) and shake or mix thoroughly. Be sure that all sediment pure acetone and then to discard any that cannot be cleaned to give
satisfactory rates.
has been thoroughly dispersed. If the oil is damp, dry by
heating at 100°C under vacuum or by sparging with dry carbon 9.9 Treat the supernatant oil obtained in 9.5 with a second
dioxide or nitrogen at 100°C, cool the oil to 25°C, and proceed portion of phosphoric acid in accordance with 9.1 to 9.8.
with test.
10. Calculation
9. Procedure
10.1 Calculate the percent of gravimetric foots as follows:
9.1 Weigh into the centrifuge tube 50.0 6 0.01 g of the
Gravimetric foots, % 5 2~A 1 B!
sample and then add 0.5 6 0.05 mL of phosphoric acid (85 %)
(3)
with a pipet.
where:
4
A 5 weight of sediment from 50 g of original oil on first
Hyflo Super-Cel, produced by Johns-Manville Corp. has been found satisfac-
phosphoric treatment, g, and
tory for this purpose.
2
D 1966
B 5 weight of sediment from 50 g of supernatant oil on samelaboratory should not differ by more than 0.017 %. Assays
second phosphoric treatment, g. run in two different laboratories, each of which is the mean of
two determinations, should not differ by more than 0.026 %.
11. Report
13. Keywords
11.1 Report the results to the second decimal place.
13.1 foots; linseed oil
12. Precision
12.1 At the 95 % confidence level, assays run in the
3

Measuring Color After Heating of Drying Oils1
1. Scope 4. Apparatus
1.1 This test method covers the measurement of the color of 4.1 Heater4—A high-temperature gas burner or other suit-
drying oils after heating under specified conditions. able gas burner.
1.2 The values stated in SI units are to be regarded as the 4.2 Thermometer—An ASTM Partial Immersion Thermom-
standard. The values given in parentheses are for information eter having a range from −5 to +400°C (20 to 760°F) and
only. conforming to the requirements for Thermometer 3F (3C) as
1.3 This standard does not purport to address all of the prescribed in Specification E 1.
safety concerns, if any, associated with its use. It is the 4.3 Color Standards—A set of permanent color standards as
responsibility of whoever uses this standard to consult and described in Test Method D 1544.
establish appropriate safety and health practices and deter-
mine the applicability of regulatory limitations prior to use. 5. Procedure
5.1 Place 100 mL of the oil sample in a 250-mL heat-
2. Referenced Documents resistant Griffin low-form beaker on a ring stand with an
2.1 ASTM Standards: asbestos wire pad. Immerse the thermometer in the center of
D 1544 Test Method for Color of Transparent Liquids the oil so that the end of the bulb is from 1⁄4 to 5⁄16 in. (6 to 8
(Gardner Color Scale)2 mm) from the bottom of the beaker. Heat to 550°F (288°C) in
E 1 Specification for ASTM Thermometers3 5 to 10 min, and hold at this temperature 65°F (63°C) for 5
min. Remove the beaker from the stand and allow to cool to
3. Significance and Use room temperature. Determine the color of the sample in
3.1 When oil is heated to polymerization temperature, some accordance with Test Method D 1544.
darkening may occur rendering the oil unsuitable for use where
light color is essential. Excessive darkening may be an indica- 6. Precision and Bias
tion of residual soap content from the alkali refining process 6.1 Precision—The following criteria should be used for
rendering the oil unsuitable for use where light color is judging the acceptability of results at the 95 % confidence
essential. level.
3.2 Some oils that are low in soap content may actually 6.1.1 Repeatability—Duplicate results by the same operator
bleach when heated to polymerization temperature, which is should be considered suspect if they differ by more than
beneficial. one-third color unit.
3.3 This test method is indicative of the color developed 6.1.2 Reproducibility—Two results obtained in different
when the oil is heated to polymerization temperatures. laboratories should be considered suspect if they differ by more
than two-thirds color unit.
NOTE 1—These precision statements are based on results obtained in a
collaborative study involving six laboratories with two operators in each
laboratory and four samples of drying oils.
1
This test method is under the jurisdiction of ASTM Committee D-1 on Paint 6.2 Bias—Bias has not been determined.
Subcommittee D01.32 on Drying Oils. 7. Keywords
7.1 color after heating; drying oil color
2
3 4
Annual Book of ASTM Standards, Vol 14.03. The Fisher heater has been found satisfactory for this purpose.
1
D 1967
2

2-Ethylhexanol (Synthetic)1
e1 NOTE—Editorial changes made throughout in January 1996.
1. Scope TABLE 1 Physical and Chemical Properties of 2-Ethylhexanol
1.1 This specification covers regular and monomer grade Grade Monomer Grade Regular
2-ethylhexanol. Acidity (free acid as acetic acid, max, 0.01A 0.01A

weight %)
1.2 For specific hazard information and guidance, see the Apparent specific gravity
supplier’s Material Safety Data Sheet for materials listed in this 20/20°C 0.8325 to 0.8325 to
specification. 0.8345 0.8345
25/25°C 0.8298 to 0.8298 to
0.8318 0.8318
2. Referenced Documents Assay, weight %, min 99.6 99.0
2.1 ASTM Standards: Color, Pt-Co scale, max 5 5
Carbonyl (as 2-ethylhexanal), max, weight % 0.06 0.1
D 1078 Test Method for Distillation Range of Volatile Distillation range 760 mm Hg, °C as
Organic Liquids2 Initial boiling point, min. 182 182
D 2119 Test Method for Aldehydes in Styrene Monomer2 Dry point, max. 186 186
Distillation range entirely within a NA
D 4052 Test Method for Density and Relative Density of 2°C range
Liquids by Digital Density Meter3 Ethyl methyl pentanol, max, weight % 0.4 0.5
D 5008 Test Method for Ethyl Methyl Pentanol Content and Sulfuric acid color, Pt-Co scale, max 20 30
Water, max, weight % 0.10 0.10
Purity Value of 2-Ethylhexanol by Gas Chromatography2
A
E 852 Test Methods for C4-C13 Plasticizer Grade Alcohols5 determined in accordance with the following ASTM methods:
2.2 U.S. Federal Specifications: 5.1.1 Acidity—Test Methods E 852.
PPP-C-2020 Chemicals, Liquid, Dry and Paste: Packaging 5.1.2 Apparent Specific Gravity—Test Methods E 852 or
of6 Test Method D 4052.
5.1.3 Assay—Test Method D 5008.
3. Properties
5.1.4 Color—Test Methods E 852.
3.1 The physical and chemical properties of 2-ethylhexanol 5.1.5 Carbonyl—Test Method D 2119. Calculate the per-
shall conform to the requirements specified in Table 1. cent aldehyde as 2-ethylhexanal in Reagent Section 6 by using
0.128 in place of 0.106. “C” is the density of specimen used.
4. Sampling
5.1.6 Distillation Range—Test Method D 1078. Use ASTM
4.1 The material shall be sampled in accordance with Thermometer No. 104C (see specification E 1).
Practice E 300. 5.1.7 Ethyl Methyl Pentanol—Test Method D 5008.
5.1.8 Sulfuric Acid Color—Test Methods E 852.
5. Test Methods:
5.1.9 Water—Test Methods E 852.
1
This specification is under the jurisdiction of ASTM Committee D-01 on Paint 6.1 Package size shall be agreed upon by the purchaser and
and Related Coatings, Materials, and Applications and is the direct responsibility of the supplier.
Current edition approved May 15, 1991. Published July 1991. 6.2 Packaging shall conform to applicable carrier rules and
2
Annual Book of ASTM Standards, Vol 06.04. regulations or when specified shall conform to Fed. Spec.
3
4
5
6
Robbins Ave., Philadelphia, PA 19111-5094, ATTN: NPODS. 7.1 2-ethylhexanol; 2-ethylhexyl alcohol;2-ethyl-1-hexanol
1
D 1969
2

Free Formaldehyde Content of Amino Resins1
1. Scope above threshold amounts may produce objectionable odors and

1.1 This test method covers the determination of free irritant effects. This test method can be useful for evaluating
formaldehyde in amino resins and their aqueous and non- suppliers’ products and for quality control.
aqueous solutions. Amino resin-free formaldehyde levels from 5. Apparatus
about 0.02 to 5.0 % can be determined by this test method. The
applicability of this test method to other matrices is unknown. 5.1 Analytical Balance, 60.1 mg.
1.2 This standard does not purport to address all of the 5.2 Magnetic Stirrer and Stir Bar—A “heavy duty” mag-
safety concerns, if any, associated with its use. It is the netic stirrer is necessary.
responsibility of the user of this standard to establish appro- 5.3 Buret, 50 mL manual or electronic. Manual burets
priate safety and health practices and determine the applica- should be of the type designed to minimize the exposure of
bility of regulatory limitations prior to use. reagent to air. Electronic burets are preferred.
5.4 Beakers, glass, 100 mL, 600 mL, and 1500 mL.
2. Referenced Documents 5.5 Stopwatch or Timer.
2.1 ASTM Standards: 5.6 Graduated Cylinders, glass, 50 mL and 250 mL.
D 1193 Specification for Reagent Water2 5.7 Glass Pipet, 2 mL.
D 1959 Test Method for Iodine Value of Drying Oils and 5.8 Thermometer, subdivision 1°C.
Fatty Acids3 6. Reagents
3. Summary of Test Method 6.1 Purity of Reagents—Reagent grade chemicals shall be
3.1 Specimens are mixed with borate buffer solution and ice used in all tests. Unless otherwise indicated it is intended that
water, then kept cool in an ice bath. Excess sodium sulfite is all reagents conform to the specifications of the Committee on
added to consume free formaldehyde as follows: Analytical Reagents of the American Chemical Society where
such specifications are available.4 Other grades may be used,
CH2O 1 Na2SO3 1 H2O → HOCH2SO3Na 1 NaOH (1)
provided it is first ascertained that the reagent is of sufficient
3.2 The excess sodium sulfite is removed by titration with high purity to permit its use without lessening the accuracy of
iodine using starch as the indicator as follows: the determination.
Na2SO3 1 I2 1 H2O → Na2SO4 1 2 HI (2) 6.2 Purity of Water—Unless otherwise indicated, references
3.3 The sodium sulfite-formaldehyde complex is then de- to water shall be understood to mean reagent water as defined
composed with sodium carbonate to quantitatively regenerate by Type II of Specification D 1193.
sodium sulfite and formaldehyde as follows: 6.3 Acetic Acid Solution (1.0 M)—Dissolve 60 mL of
glacial acetic acid (CH3CO2H) in water and dilute to 1 L.
HOCH2SO3Na 1 Na2CO3 → CH2O 1 Na2SO3 1 NaHCO3 (3) 6.4 Boric Acid Buffer Solution—Prepare a sodium hydrox-
3.4 The liberated sodium sulfite is titrated with iodine (Eq 2) ide solution (1.0 M) by dissolving 40 g of sodium hydroxide
and free formaldehyde is calculated from this second iodine (NaOH) in water and diluting to 1 L. Dissolve 12.39 g of boric
titration. acid (H3BO3) in 100 mL of 1.0 M NaOH, then dilute to 1 L.
Maintain temperature at 0°C in an ice bath. The pH at 0°C
4. Significance and Use should be 9.4 (glass electrode).
4.1 The amount of free formaldehyde in amino resins may 6.5 Ice, finely crushed.
be of concern to both producer and user, as its presence in air 6.6 Iodine Solution (0.1 N)—Dissolve 40 g of iodate free
potassium iodide in 25 mL of water in a 100-mL beaker. Weigh
1
4
Subcommittee D01.33 on Polymers and Resins. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Nov. 10, 1997. Published June 1998.Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1979 - 91. Last previous edition D 1979 - 91(l997). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
3
1
D 1979
out 12.6905 g of dry re-sublimed iodine and add to the beaker. 7.6 Continue stirring for 15 min.
Stir until the iodine is dissolved and dilute to 1 L with water. 7.7 Add 10 mL of 1.0 M acetic acid solution and 10 mL of
Store iodine titrant in the dark. This reagent can be purchased the starch solution.
as a standardized solution or must be standardized against 7.8 Titrate the excess sodium sulfite with 0.1 N iodine
sodium thiosulfate. solution to a green-blue color that persists for 10 s. Re-zero the
6.7 Methylene Chloride (CH2Cl2)—Cool to 0°C in an ice buret.
bath. 7.9 Add 30 mL of 1.0 M sodium carbonate solution.
6.8 Sodium Carbonate Solution (1.0 M)—Dissolve 106 g 7.10 Titrate the liberated sodium sulfite with 0.1 N iodine
of sodium carbonate (Na2CO3) in water and dilute to 1 L. solution to a constant blue color that persists for 1 min. The
6.9 Sodium Sulfite Solution (1.0 M)—Dissolve 126 g of shade of blue varies with the sample under test and may appear
sodium sulfite (Na2SO3) in water and dilute to 1 L. This slightly different in emulsions when compared to the blank.
reagent is unstable and must be prepared fresh daily. Record the volume of the iodine solution used in this step for
6.10 Starch—0.2 % aqueous (weight/volume) or 1.0 % use in the calculation, Section 8.
aqueous (weight/volume). This indicator can be purchased as a
stabilized solution or prepared in accordance with Test Method 8. Calculation
D 1959. Store in a cool, dark place. 8.1 Calculate the weight percent free formaldehyde in the
6.11 Water (H2O)—Cool Type II water to 0°C in an ice bath. sample as follows:
~A 2 B! 3 3
7. Procedure Formaldehyde, % 5 W 3 20 (4)
7.1 A blank determination is run following this procedure,
omitting 7.2 (addition of sample). where:
7.2 Taking the appropriate specimen size from Table 1, A 5 volume of iodine solution for specimen titration
weigh the specimen to the nearest mg into a 600-mL beaker. (7.10), mL,
7.3 Place the beaker into the ice bath that rests upon a B 5 volume of iodine solution for blank titration (7.10),
heavy-duty magnetic stirrer. mL, and
7.4 Place a stirring bar in the beaker and immediately W 5 sample weight, g.
dissolve the specimen as described in 7.4.1 (for aqueous 9. Precision and Bias
specimens) or 7.4.2 (for non-aqueous specimens). Maintain the
9.1 Precision—The precision statements are based upon an
temperature of the specimen solution at 0°C by adding ice. The
interlaboratory study in which one analyst in each of five
temperature must not rise above 2°C during subsequent steps.
different laboratories analyzed three samples of commercial
Note that boric acid buffer (6.4), methylene chloride (6.7) and
melamine resins with free formaldehyde contents between 0.2
water (6.11) should be pre-cooled to 0°C.
and 2.7 % in duplicate on two different days. The within-
7.4.1 Aqueous Specimens—Rapidly mix the specimen with
laboratory coefficient of variation was found to be 4.07 % at 12
150 mL of ice water and 25 mL of boric acid buffer solution.
df, and the between-laboratories coefficient of variation was
7.4.2 Non-aqueous Specimens—Rapidly mix the specimen
found to be 13.69 % at 9 df. Based on these coefficients of
with 50 mL of methylene chloride cooled to 0°C. Stir to
variation, the following criteria should be used in judging the
dissolve specimen. Add 150 mL of ice water and 25 mL of
acceptability of results at the 95 % confidence level.
boric acid buffer. Continue extraction for 5 min. Uninterrupted
9.1.1 Repeatability—Two results, each the means of dupli-
stirring must be maintained through 7.5-7.10.
cates, obtained by the same operator on different days should
7.5 While constantly stirring the specimen solution, pipet 2
be considered suspect if they differ by more than 12.5 %
mL of 1.0 M sodium sulfite solution into the beaker.
relative.
9.1.2 Reproducibility—Two results, each the means of du-
TABLE 1 Specimen Size According to Expected Formaldehyde plicates, obtained by operators in different laboratories should
Content
be considered suspect if they differ by more than 43.8 %
Free Formaldehyde, Specimen Weight,
weight, % g
relative.
9.2 Bias—No bias can be determined for this test method
0.2–0.5 3.0
0.5–1.0 1.5
since no standard resin exists.
1.0–2.0 1.0
2.0–3.0 0.5 10. Keywords
3.0–5.0 0.25
10.1 amino resins; formaldehyde; sodium sulfite
2

Acid Value of Fatty Acids and Polymerized Fatty Acids1
1. Scope Society, where such specifications are available.3 Other grades

1.1 This test method covers the determination of acid value may be used, provided it is first ascertained that the reagent is
(a measure of the acidity or amount of free fatty acids) and is of sufficiently high purity to permit its use without lessening
applicable to all fatty acids and polymerized fatty acids. the accuracy of the determination.
to water shall be understood to mean water conforming to Type
II of Specification D 1193.
5.3 Ethyl Alcohol, Neutral (95 %)—Use 95 % ethyl alcohol
or neutral denatured alcohol conforming to Formula No. 30 or
No. 3A of the U.S. Bureau of Alcohol, Tobacco, and Firearms.
Boil and neutralize to the phenolphthalein end point with alkali
just before using.
2.1 ASTM Standards: 5.4 Phenolphthalein Indicator Solution (10 g/L) (Note 1)—
D 1193 Specification for Reagent Water2 Dissolve 1 g of phenolphthalein in 100 mL of ethanol (95 %),
methanol, or isopropanol.
3. Terminology
NOTE 1—A “masked phenolphthalein indicator” may be used with
3.1 Definitions: off-color materials. Prepare by dissolving 1.6 g of phenolphthalein and 2.7
3.1.1 acid value—the number of milligrams of potassium g of methylene blue in 500 mL of alcohol conforming to 5.3. Adjust the
hydroxide required to neutralize the fatty acids in 1 g of pH with sodium hydroxide (NaOH) or potassium hydroxide (KOH)
solution so that the greenish-blue color is faintly tinted with purple. The
sample.
color change is from green to purple when going from acid to alkaline.
4. Significance and Use 5.5 Potassium Hydroxide or Sodium Hydroxide, Standard

Solution (0.5 N): Prepare a stock concentrated solution by
4.1 Drying oils are composed primarily of triglycerides of dissolving 560 g of potassium hydroxide (KOH) or 425 g of
fatty acids, and normally contain low amounts of free fatty sodium hydroxide (NaOH) in 1 L of water.
acids. However they can be saponified to produce essentially 5.5.1 Allow this solution to cool and settle in a stoppered
only fatty acids. This test method is used to determine the bottle for several days. Decant the clear liquid from the
acidity (acid value) of the fatty acids and is therefore indicative carbonate precipitate into another clean bottle. Add clear
of the amount of free fatty acids in a sample. barium hydroxide (Ba(OH)2) solution until no further precipi-
4.2 This test method is not to be used as a quality require- tate forms. Again allow to settle until clear. Draw off about 875
ment since it measures all acidic components and does not mL and dilute to 10 L with freshly boiled reagent water.
distinguish between fatty acids of different composition. Preserve in a stock bottle provided with a large drying tube
filled with soda-lime.
5. Reagents 5.5.2 Standardize by titrating against potassium acid phtha-
5.1 Purity of Reagents—Reagent grade chemicals shall be late (National Bureau of Standards Acid Potassium Phthalate
used in all tests. Unless otherwise indicated, it is intended that No. 84), using phenolphthalein as indicator. This solution is
all reagents shall conform to the Specifications of the Com- approximately 0.5 N but instead of adjusting it to a specific
mittee on Analytical Reagents of the American Chemical value, determine the exact normality and use in the calcula-
tions.
1 3
Subcommittee D01.32 on Drying Oils. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved June 26, 1987. Published August 1987. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 1980 – 61. Last previous edition D 1980 – 85. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
2
1
D 1980
6. Procedure 8. Precision
6.1 Transfer about 5 g of the sample, weighed to 1 mg to a 8.1 On the basis of an interlaboratory test of this test method
500-mL Erlenmeyer flask and add 75 to 100 mL of hot, ethyl in which two operators in four laboratories tested three samples
alcohol. Agitation and further heating may be necessary to of fatty acids the following criteria should be used for judging
bring the fatty acids into complete solution. the acceptability of results at the 95 % confidence level:
6.2 Add 0.5 mL of the phenolphthalein indicator solution
8.1.1 Repeatability—Two results by a single operator
and titrate immediately, while shaking, with 0.5 N KOH or
NaOH solution to the first pink color that persists for 30 s. should be considered suspect if they differ by more than 2.3 in
acid value.
7. Calculation 8.1.2 Reproducibility—Two results, each the mean of two
7.1 Calculate the acid value as follows: determinations, obtained by operators in different laboratories
Acid value 5 ~VN 3 56.1!/S (1) should be considered suspect if they differ by more than 2.4.
where: 9. Keywords
V 5 KOH or NaOH solution required for the titration, mL,
N 5 normality of the KOH or NaOH solution, and 9.1 acid value; fatty acids
2

Measuring Color After Heating of Fatty Acids1
1. Scope temperature and the recovery time to reach 205°C does not
1.1 This test method covers the measurement of the color of exceed 5 min.
normal fatty acids after heating under the conditions specified 4.3 Thermometer—An ASTM Partial Immersion Thermom-
in the test and is applicable to all normal fatty acids. eter, having a range from 95 to 255°C, and conforming to the
1.2 The values stated in SI units are to be regarded as the requirements for Thermometer 42C as prescribed in Specifi-
standard. The values given in parentheses are for information cation E 1.
only. 4.4 Tubes, 25 mm (1 in.) in diameter, 240 mm (91⁄2 in.) in
1.3 This standard does not purport to address all of the length with ground-glass joints4 (Fig. 1).
safety concerns, if any, associated with its use. It is the 4.5 Test Tube Holder (Fig. 2).
responsibility of the user of this standard to establish appro- 4.6 Timer, capable of registering up to 120 min.
priate safety and health practices and determine the applica- 4.7 Nitrogen—A source of nitrogen capable of being regu-
bility of regulatory limitations prior to use. lated to a pressure of 7 to 14 kPa (1 to 2 psi).
2. Referenced Documents 5. Procedure

2.1 ASTM Standards: 5.1 Adjust the oil level so that the tubes will be immersed to
D 1544 Test Method for Color of Transparent Liquids a depth of 140 mm (51⁄2 in.). Bring the bath to a temperature of
(Gardner Color Scale)2 205 6 2°C and maintain the temperature within the specified
E 1 Specification for ASTM Thermometer3 range.
5.2 If the sample to be tested is not liquid at room
3. Significance and Use temperature, liquefy by heating on a water bath to a tempera-
3.1 The color of a fatty acid is readily affected by heat and ture not more than 20°C above the melting point of the sample.
oxidization. Variations in degree of heat, time of heat, and Fill a clean, dry tube to a depth of 127 mm (5.0 in.) with the
exposure to atmosphere during heating have a marked effect on sample and place it in the oil bath.
the color obtained; therefore, conformity to the equipment and 5.3 Place a fitted stopper in each tube and adjust the flow of
procedure outlined in this test method is essential to accuracy nitrogen so that the surface of the specimen is blanketed by
and precision. inert gas at all times. Set the timer for 60 min if the sample has
an iodine value greater than 15, or for 120 min if the sample
4. Apparatus and Materials has an iodine value of 15 or less. At the end of the applicable
4.1 Oil Bath—A 5-L stainless steel beaker equipped with a time remove the tubes from the bath and read the color
mechanical stirrer and containing any light-colored alkali- immediately in accordance with Test Method D 1544.
refined oil such as hydrogenated cottonseed oil.
4.2 Heat Source—Either three Tirrill burners or electric
immersion heaters with suitable thermostatic control may be 6.1 Precision and bias were not established at the time this
used. Burners or heaters shall be of sufficient capacity so that test method was written. An effort is being made to obtain the
when placing several tubes in the bath, the bath temperature precision and, if obtainable, will be published in future
does not drop more than 5°C below the minimum bath revisions. This test method has been in use for many years and
its usefulness has been well established.
7. Keywords
1
and Related Coatings, Materials, and Applications and is the direct responsibility of 7.1 color after heating; fatty acid color
2 4
Annual Book of ASTM Standards, Vol 06.01. Joints from Lab-Crest Scientific Glass Co., Div. of Fischer & Porter, East
3
Annual Book of ASTM Standards, Vol 14.03. County Line Rd., Warminster, PA 18974 have been found suitable for this purpose.
1
D 1981
NOTE 1—1 in. 5 25.4 mm.

FIG. 1 Details of Color-After-Heating Tube
NOTE 1—1 in. 5 25.4 mm.

FIG. 2 Tube Holder (Aluminum or Stainless Steel) for Color-After-Heating Test

Control Calidad Componentes Pinturas Ambos01

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Control Calidad Componentes Pinturas Ambos01

Caricato da

Copyright:

Formati disponibili

TOMO IV.

José Miguel Rando Cardalda

Rubén Rafael González Rivero

4. TOMO IV. CONTROL DE CALIDAD DE LOS COMPONENTES DE LAS PINTURAS.............Página

4.2. Determinaciones generales. 3

4.2.2. Puntos de fusión y de solidificación

4.2.3. Temperaturas de ebullición y de destilación

4.2.4. Determinación del índice de refracción

4.2.5. Dosificado de las sustancias

4.2.5.1. Procedimientos de volumetría. Soluciones normales

4.2.5.2. Procedimientos de gravimetría. Análisis de una barita

4.3.1. Color básico

4.3.2. Poder colorante de los pigmentos coloreados

4.3.3. Tonos secundarios de los pigmentos coloreados

4.3.4. Poder colorante de los pigmentos blancos

4.3.5. Absorción de aceite

4.3.6. Peso específico

4.3.8. Distribución del tamaño de las partículas

4.3.8.1. Método de estudio

4.3.8.2. Ejemplos prácticos de calculo teórico de densidades

4.3.11. Determinación de la humedad y de la pérdida por calcinación

4.3.12. Valoración de un blanco de zinc

4.3.13. Análisis de un litopón

4.3.14. Determinaciones del hierro, del aluminio y del titano

4.3.15. Determinación del anhídrido carbónico

4.3.16. Determinación del cobre y del arsénico

4.3.17. Valoración del cromato de plomo y del verde de zinc

4.3.18. Coloración de perlas de bórax

4.3.19. Método Kappelmeier

4.3.20. Ensayo de los pigmentos negros y de las lacas

4.3.21. Especificaciones sobre pigmentos

4.3.21.1. Pigmentos blancos

4.3.21.2. Pigmentos amarillos, ocres o pardos

4.3.21.3. Pigmentos rojos

4.3.21.4. Pigmentos verdes

4.3.21.5. Pigmentos azules

4.3.21.6. Pigmentos negros

4.4. Formadores de película. 77

4.4.2. Temperatura de reblandecimiento de sólidos

4.4.3. Peso por litro y densidad

4.4.4. Contenido total de no volátiles

4.4.5. Viscosidad de los líquidos

4.4.6. Determinación del grado de acidez

4.4.7. Determinación del índice de saponificación

4.4.8. Determinación del índice de yodo

4.4.9. Determinación del índice de Maumené

4.4.10. Determinación de los ácidos grasos

4.4.11. Determinación de los bromocompuestos

4.4.12. Determinación de la glicerina

4.4.13. Comportamiento con el ácido nitroso

4.4.14. Investigación de aceites minerales

4.4.15. Diferenciación de los aceites animales y vegetales

4.4.16. Determinación del poder secante

4.4.17. Índice de dienos

4.4.18. Índice de rodán

4.4.19. Punto de precipitación

4.4.20. Especificaciones de formadores de película

4.4.20.2. Aceites, diluentes, aparejos y secativos

4.5. Disolventes. 121

4.5.3. Peso específico

4.5.5. Intervalo de destilación

4.5.6. Velocidad de evaporación

4.5.7. Punto de inflamación