1 SM

Afinidad
TOMO LXVII N 549 SEPTIEMBRE - OCTUBRE 2010 AFINAE 67 (548) 333 - 404 (2010) ISSN 0001 - 9704
REVISTA DE QUMICA TERICA Y APLICADA
SECCIONES
Legislacin
333
Artculos Generales
335
Informacin General
401
Novedades Tcnicas
403
Notcias de Empresas
404
N 549
Un sector que responde:

ciencia e industria en accin.
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En esta nueva edicin, EXPOQUIMIA concentrar los congresos y
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EDITA
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SP - ISSN 0001 - 9704
Afinidad LXVII, 549, Septiembre - Octubre 2010
D.L.B. 460 - 1958

del Instituto Qumico de Sarri, 1973
PERIODICIDAD
6 nmeros ao
PRECIOS SUSCRIPCIN
ANUAL (2011)
Espaa: 41,50 + 4% IVA
Pases miembros de la UE
con NOI*: 41,50
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Nmero suelto (ordinario): 16,50
/ 21 $ USA + 4% IVA
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329
SUMARIO
Legislacin Espaola y Comunitaria, publicada en el B.O.E., y en el D.O.U.E.
de Junio a Agosto de 2010, por D.B. Snchez de Rojas.
333-334
Reologa de zumos de grosella, por Ibarz A., Falguera V., Garza S. y Garvn, A.
335-341
Gestin de residuos a lo largo del ciclo de vida de un automvil, por B. Amante,

A. Lacayo, M. Piqu y V. Lpez-Grimau
342-348
Efecto del tiempo de residencia sobre la eficacia de la eliminacin de NOx en

dos reactores diferentes de descarga de barrera dielctrica, por E. Len del
Villar, Julio Pedraza G, Ivan Rodriguez R, Elena Rosa D y Nancy Lopez B
349-354
Remediacin electrodialtica de suelo contaminado con cobre, por Claudia

Gutirrez, Henrik K. Hansen y Catalina Gonzalez

Reaccin de descomposicin trmica del triperxido cclico de acetona en
alcoholes alifticos, por Gladys N. Eyler, Elida E. Alvarez, Celedonio Minellono y
Adriana I. Caizo
355-361
362-366
Utilidad del cido 4-(4-acetoaminofenil)-4-oxo-but-2-enoico en la preparacin

de derivados de Pirano y Piridina como unidades estructurales para la Sntesis de Heterociclos, por M. A. El-Hashash, M. H. A. Soliman, I. I. Abd El-Gwad, S.
S. El-Sakka y M. A. Morsy
Comparacin de la eficacia de los parmetros de proceso en la extraccin de
pectina a partir de pulpa de manzana, por Hasan Ziari, Farzin Zokaee Ashtiani y
Mahdy Mohtashamy
374-379
Equilibrio isobrico lquido-vapor para el sistema binario Diisopropileter + isopropanol a 95 kPa, por Ahmad T. Shawaqfeh
380-385
Eliminacin de contaminantes orgnicos en efluentes de molinos olivareros

por nanopartculas de TiO2 utilizando la tcnica de oxidacin cataltica con
aire hmedo (CWAO), por M. I. Badawy, M.Y Ghaly, M. F. Zawrah, M.E.M. Ali y F.
El Gohary
386-392
Sntesis inducida por microondas de algunos derivados fundidos como

tiazoloquinazolina en condiciones de ausencia de disolventes y utilizando
LiBr como catalizador, por Chetna Ameta, Rakshit Ametaa, Urvashi Tiwari, P. B.
Punjabi y Suresh C. Ameta
393-400
Informacin General
Novedades Tcnicas
Noticias de Empresas
330
367-373
401-402
403
404
SUMMARY
Spanish and EU Law published at B.O.E. and D.O.U.E. from June to August
2010, by D.B. Snchez de Rojas
333-334
Rheology of redcurrant juices, by B. Amante, A. Lacayo, M. Piqu and V. LpezGrimau
335-361
Management of residues life cycle services of an automobile, by Oscar OrtizRodriguez, Cecilia Makishi Colodel, Matthias Fischer, Francesc Castells and Guido
Sonnemann
342-348
Residence time effects on the NOx removal efficiency in two different Dielectric barrier discharge cell, by E. Len del Villar, Julio Pedraza G, Ivan Rodriguez
R, Elena Rosa D and Nancy Lopez B
349-354
Electrodialytic remediation of soil contaminated with copper, by Claudia Gutirrez, Henrik K. Hansen and Catalina Gonzalez
355-361
Thermal decomposition reaction of acetone cyclic triperoxide in aliphatic alcohols, by Gladys N. Eyler, Elida E. Alvarez, Celedonio Minellono and Adriana I.
Caizo
362-366
Utility of 4-(4-acetoaminophenyl)-4-oxo-but-2-enoic acid to prepare Pyran

and Pyridine derivatives as building blocks in Heterocyclic Synthesis, by M. A.
El-Hashash, M. H. A. Soliman, I. I. Abd El-Gwad, S. S. El-Sakka and M. A. Morsy
367-373
Comparing the effectiveness of processing parameters in pectin extraction

from apple pomace, by Hasan Ziari, Farzin Zokaee Ashtiani and Mahdy Mohtashamy
374-379
Isobaric Vaporliquid equilibrium for the binary system Diisopropylether + Isopropanol at 95 kPa, by Ahmad T. Shawaqfeh
380-385
Abatement of organic pollutants from olive mill effluent by TiO2 nano-particles using Catalytic Wet Air Oxidation (CWAO) technique, by M. I. Badawy, M.Y
Ghaly, M. F. Zawrah, M.E.M. Ali and F. El Gohary
386-392
Microwave induced synthesis of some fused thiazoloquinazoline derivatives

under solvent free conditions using LiBr as a catalyst, by Chetna Ameta, Rakshit Ameta, Urvashi Tiwari, P. B. Punjabi and Suresh C. Ameta
393-400
General Information
News techniques
News Enterprises

401-402
403
404
331
SUMARI
Legislaci Espanyola i Comunitria publicada al B.O.E. i D.O.U.E. de Juny a
Agost de 2010, per D.B. Snchez de Rojas
Reologia de sucs de grosella, per Ibarz A., Falguera V., Garza S. i Garvn, A.
335-341
Gesti de residus al llarg del cicle de vida dun autombil, per B. Amante, A.
Lacayo, M. Piqu i V. Lpez-Grimau
342-348
Efecte del temps de residncia sobre leficcia de leliminaci de NOx en dos

reactors diferents de descrrega de barrera dielctrica, per E. Len del Villar,
Julio Pedraza G, Ivan Rodriguez R, Elena Rosa D i Nancy Lopez B
349-354
Descontaminaci electrodialtica de sl contaminat amb coure, per Claudia

Gutirrez, Henrik K. Hansen i Catalina Gonzalez
355-361
Reacci de descomposici trmica del triperxid cclic dacetona en alcohols

aliftics, per Gladys N. Eyler, Elida E. Alvarez, Celedonio Minellono i Adriana I.
Caizo
362-366
Utilitat de lcid 4-(4-acetoaminofenil)-4-oxo-but-2-enoic en la preparaci de

derivats de Pir i Piridine com unitats estructurals per a la Sntesi de Heterocicles, per M. A. El-Hashash, M. H. A. Soliman, I. I. Abd El-Gwad, S. S. El-Sakka i
M. A. Morsy
367-373
Comparaci de leficcia dels parmetres de procs en lextracci de pectina

a partir de polpa de poma, per Hasan Ziari, Farzin Zokaee Ashtiani i Mahdy Mohtashamy
374-379
Equilibri isobric lquid-vapor per al sistema binari Diisopropilter + isopropanol a 95 kPa, per Ahmad T. Shawaqfehz
380-385
Eliminaci de contaminants orgnics en efluents de molins oliverers per nanopartcules de TiO2 utilitzant la tcnica doxidaci cataltica amb aire humit
(CWAO), per M. I. Badawy, M.Y Ghaly, M. F. Zawrah, M.E.M. Ali i F. El Gohary
386-392
Sntesi induda per microones dalguns derivats fosos de tiazoloquinazolina

en condicions dabsncia de dissolvents i utilitzant LiBr com a catalitzador,
per Chetna Ameta, Rakshit Ameta, Urvashi Tiwari, P. B. Punjabi i Suresh C. Ameta
393-400
Informaci General
Novetats Tcniques
Notcies dEmpreses
332
333-334
401-402
403
404
Legislacin Espaola y Comunitaria,

publicada en el B.O.E., y en el D.O.U.E.
de Junio a Agosto de 2010
D.B. Snchez de Rojas
Ingeniero Forestal
Spanish and EU Law published at B.O.E. and D.O.U.E. from June to August 2010
Legislaci Espanyola i Comunitria publicada al B.O.E. i D.O.U.E. de Juny a Agost de 2010
ALIMENTACIN HUMANA
DOUE L221 de 24/08/10 p. 15
Correccin de errores de la Recomendacin 2010/307/UE
de la Comisin, de 2 de junio de 2010, relativa al control de
los niveles de acrilamida en los alimentos. (2010/307/UE)
DOUE L225 de 27/08/10 p. 1012
Directiva 2010/59/UE de la Comisin, de 26 de agosto de
2010, por la que se modifica la Directiva 2009/32/CE del
Parlamento Europeo y del Consejo, relativa a la aproximacin de las legislaciones de los Estados miembros sobre
los disolventes de extraccin utilizados en la fabricacin
de productos alimenticios y de sus ingredientes.
BIOCIDAS
BOE n 170 de 14/07/10 p. 6187789
Real Decreto 830/2010, de 25 de junio, por el que se establece la normativa reguladora de la capacitacin para
realizar tratamientos con biocidas.
BOE n 183 de 29/07/10 p. 660926
Orden PRE/2046/2010, de 21 de julio, por la que se incluyen las sustancias activas flocumafn, tolilfluanida y
acrolena, en el anexo I del Real Decreto 1054/2002, de
11 de octubre, por el que se regula el proceso de evaluacin para el registro, autorizacin y comercializacin de
biocidas.
BOE n 188 de 04/08/10 p. 678928
Orden PRE/2125/2010, de 30 de julio, por la que se incluyen las sustancias activas fluoruro de sulfurilo, cumatetralilo, fenpropimorf, bromadiolona, alfacloralosa y clorofacinona en el anexo I del Real Decreto 1054/2002, de 11
de octubre, por el que se regula el proceso de evaluacin
para el registro, autorizacin y comercializacin de biocidas.
DOUE L210 de 11/08/10 p. 3032
Directiva 2010/50/UE de la Comisin, de 10 de agosto de
2010, por la que se modifica la Directiva 98/8/CE del Parlamento Europeo y del Consejo de forma que incluya el
dazomet como sustancia activa en su anexo I. (Biocidas)
DOUE L211 de 12/08/10 p. 1416

Directiva 2010/51/UE de la Comisin, de 11 de agosto
de 2010, por la que se modifica la Directiva 98/8/CE del
Parlamento Europeo y del Consejo de forma que incluya
la N,Ndietilmetatoluamida como sustancia activa en su
anexo I. (Biocidas)
BOE n 210 de 30/08/10 p. 74919
Correccin de errores del Real Decreto 830/2010, de 25
de junio, por el que se establece la normativa reguladora
de la capacitacin para realizar tratamientos con biocidas.
CLASIFICACIN, ETIQUETADO Y ENVASADO

BOE n 189 de 05/08/10 p. 681902
Real Decreto 944/2010, de 23 de julio, por el que se modifica el Real Decreto 1599/1997, de 17 de octubre, sobre
productos cosmticos para adaptarlo al Reglamento (CE)
n 1272/2008, del Parlamento Europeo y del Consejo, de
16 de diciembre de 2008, sobre clasificacin, etiquetado y
envasado de sustancias y mezclas.
CONVENIO COLECTIVO
BOE n 184 de 30/07/10 p.663778
Resolucin de 14 de julio de 2010, de la Direccin General
de Trabajo, por la que se registra y publica el texto de la
revisin salarial para el ao 2009 del Convenio colectivo
estatal de perfumera y afines. (STANPA)
DENOMINACIONES DE ORIGEN E INDICACIONES GEOGRFICAS PROTEGIDAS

DOUE L 217 de 18/08/10 p.14
Correccin de errores del Reglamento (CE) n 607/2009
de la Comisin, de 14 de julio de 2009, por el que se establecen determinadas disposiciones de aplicacin del
Reglamento (CE)
333
LMITES MXIMOS DE RESIDUOS
NORMAS UNE
DOUE L174 de 09/07/10 p. 1839

REGLAMENTO (UE) N 600/2010 DE LA COMISIN de 8
de julio de 2010 por el que se modifica el anexo I del Reglamento (CE) n 396/2005 del Parlamento Europeo y del
Consejo a fin de aadir y modificar ejemplos de variedades u otros productos relacionados a los que se aplica un
mismo LMR.
BOE n 175 de 20/07/10 p. 6393744

Resolucin de 7 de junio de 2010, de la Direccin General
de Industria, por la que se publica la relacin de normas
UNE aprobadas por AENOR durante el mes de mayo de
2010.
DOUE L220 de 21/08/10 p. 156

Reglamento (UE) n 750/2010 de la Comisin, de 7 de julio
de 2010, que modifica los anexos II y III del Reglamento
(CE) n 396/2005 del Parlamento Europeo y del Consejo
por lo que respecta a los lmites mximos de residuos de
determinados plaguicidas en determinados productos.
DOUE L 226 de 28/08/10 p.137
Reglamento (UE) n 765/2010 de la Comisin, de 25 de
agosto de 2010, que modifica los anexos II y III del Reglamento (CE) n 396/2005 del Parlamento Europeo y del
Consejo por lo que respecta a los lmites mximos de residuos de clorotalonil, clotianidina, difenoconazol, fenhexamida, flubendiamida, nicotina, espirotetramat, tiacloprid y
tiametoxam en determinados productos.
MAIZ MODIFICADO GENTICAMENTE

DOUE L197 de 29/07/10 p. 1114
Decisin de la Comisin, de 28 de julio de 2010, por la
que se renueva la autorizacin para que sigan comercializndose los productos que contengan, se compongan o
se hayan producido a partir de maz modificado genticamente Bt11 (SYNBT111), por la que se autorizan los
alimentos e ingredientes alimentarios que contengan o se
compongan de maz forrajero Bt11 (SYNBT111) con
arreglo al Reglamento (CE) n 1829/2003 del Parlamento
Europeo y del Consejo y por la que se deroga la Decisin
2004/657/CE [notificada con el nmero C(2010) 5129].
DOUE L197 de 29/07/10 p. 1518
Decisin de la Comisin, de 28 de julio de 2010, por
la que se autoriza la introduccin en el mercado de los
productos que contengan, se compongan o se hayan
producido a partir de maz modificado genticamente
MON89034xNK603
(MON89343xMON636),
con arreglo al Reglamento (CE) n 1829/2003 del Parlamento Europeo y del Consejo [notificada con el nmero
C(2010) 5133].
NORMAS DE FACTURACIN
DOUE L189 de 22/07/10 p. 18
DIRECTIVA 2010/45/UE DEL CONSEJO de 13 de julio de
2010 por la que se modifica la Directiva 2006/112/CE relativa al sistema comn del impuesto sobre el valor aadido,
en lo que respecta a las normas de facturacin.
334
OBLIGACIONES DE DOCUMENTACIN DE
LAS OPERACIONES VINCULADAS
BOE n 167 de 10/07/10 p. 606558
Real Decreto 897/2010, de 9 de julio, por el que se modifica el Reglamento del Impuesto sobre Sociedades,
aprobado por el Real Decreto 1777/2004, de 30 de julio,
en materia de las obligaciones de documentacin de las
operaciones vinculadas.
PRODUCTOS COSMTICOS
BOE n 184 de 30/07/10 p. 662168
Orden SAS/2061/2010, de 23 de julio, por la que se modifica el anexo III del Real Decreto 1599/1997, de 17 de
octubre, sobre productos cosmticos.
PRODUCTOS VITCOLAS
DOUE L 219 de 20/08/10 p. 23
Correccin de errores del Reglamento (CE) n 606/2009
de la Comisin, de 10 de julio de 2009, que fija determinadas disposiciones de aplicacin del Reglamento (CE) n
479/2008 del Consejo en lo relativo a las categoras de
productos vitcolas, las prcticas enolgicas y las restricciones aplicables. (Diario Oficial de la Unin Europea L 193
de 24 de julio de 2009).
PROTECCIN DE ESPECIES DE LA FAUNA Y

FLORA
DOUE L212 de 13/08/10 p. 159
Reglamento (UE) n 709/2010 de la Comisin, de 22 de julio de 2010, que modifica el Reglamento (CE) n 338/97 del
Consejo, relativo a la proteccin de especies de la fauna y
flora silvestres mediante el control de su comercio.
REGLAMENTO DE LOS IMPUESTOS ESPECIALES

BOE n 166 de 09/07/10 p. 6028691
Resolucin de 1 de julio de 2010, del Departamento de
Aduanas e Impuestos Especiales de la Agencia Estatal de
Administracin Tributaria, por la que se aprueba el modelo
522 Parte trimestral de productos a que se refiere el artculo 108 ter del Reglamento de los Impuestos Especiales
y se establecen el plazo y el procedimiento para su presentacin.
Rheology of redcurrant juices

Ibarz A., Falguera V., Garza S. and Garvn, A.*
Departament de Tecnologia dAliments UP-XaRTA
(Universitat de Lleida) Av. Rovira Roure, 191, CP 25198 Lleida-Espaa
Reologa de zumos de grosella

Reologia de sucs de grosella
Recibido: 6 de septiembre de 2010; revisado: 7 de noviembre de 2010; aceptado: 1 de diciembre de 2010
Resumen
Resum
Se ha estudiado el comportamiento reolgico de dos zumos diferentes de grosella. El zumo con contenido en pectinas exhibi comportamiento no newtoniano. El zumo al
que se le han extrado las pectinas exhibi comportamiento newtoniano. El modelo de la ley de la potencia describi
la relacin entre el esfuerzo cortante y el gradiente de velocidad para el primer tipo de zumo y el modelo newtoniano
describi el comportamiento del segundo tipo de zumo. El
efecto de la temperatura en la viscosidad aparente a 100
s-1 queda descrito por la ecuacin de Arrhenius.
Sha estudiat el comportament reolgic de dos sucs diferents de grosella. El suc amb contingut en pectines va
exhibir comportament no newtoni. El suc al que se li van
extreure les pectines va mostrar un comportament newtoni. El model de la llei de la potncia va descriure la relaci
entre el esfor tallant i el gradient de velocitat pel primer
tipus de suc i el model newtoni va descriure el comportament del segon tipus de suc. Lefecte de la temperatura en
la viscositat aparent a 100 s-1 es pot descriure per lequaci dArrhenius.
Palabras clave: Reologa, grosella, zumo, viscosidad
Paraules clau: Reologia, grosella, suc, viscositat
Abstract
The rheological behaviour of two different redcurrant
juices was studied. Juices containing pectins exhibited
non-Newtonian behavior. Juices from which pectins were
removed exhibited Newtonian behavior. The power law
model described the relationship between shear stress
and shear rate for the first type of juice, and the Newtonian
model described the second type. The effect of temperature on the apparent viscosity at 100 s-1 was described by
Arrhenius equation.
Keywords: Rheology, redcurrant, juices, viscosity
*Corresponding authors: aibarz@tecal.udl.cat,

vfalguera@tecal.udl.cat,
garza@tecal.udl.cat, garvin@tecal.udl.cat*
335
INTRODUCTION
The redcurrant (ribes rubrum) is original of Western Europe. These fruits can be consumed freshly, although its
concentrated juice is often used in the elaboration of jams,
jellies, liquors, syrups and sauces. It contributes to acidify
the products due to its high content in organic acids, and
to improve their consistency because of its high content
in pectins.
The flow behavior of fruit juices and their fluid derivatives
is strongly affected by both juice and fruit characteristics.
The presence of pulp solids, as in the dispersed phase of
fruit juice, contributes to their non-Newtonian nature (Ramos & Ibarz 2006, Falguera et al 2010). Clarified and depectinated juices usually show a rheological behavior that
may be described either by Newtons viscosity equation
or by power-law equation. Juices with pectins and pulp in
suspension usually show yield stress, and their rheological
behavior may be described by Herschel-Bulkleys model.
In non-Newtonian fluids the quotient between shear stress
and shear rate is not a constant as it occurs with Newtonian fluids. Therefore, the concept of apparent viscosity
( ) is used at a given shear rate, which for fluids which
follow the power-law equation will be expressed according
to the following equation:
(1)
and fluids which follow the Herschel-Bulkley model will be

expressed according to this one:
(2)
The main purpose of this work has been to analyze the

rheological behavior of redcurrant juices studying its flow
response as a function of the temperature and soluble solids concentration. Although there are many studies with
similar fuits: raspberry, strawberry and blackberry (Alvarez
et al 2006, Haminiuk et al 2006, 2007, 2009, Ramaswamy
and Basak 1992, Sousa et al 2006) and blackcurrant (Ibarz
et al 1992b), the rheology of redcurrant juices has not been
studied yet.
MATERIALS AND METHODS

Obtaining Samples
The redcurrant juices were obtained in the laboratory from
natural fruits purchased in a local market in Lleida (Spain).
The juice was obtained by squeezing the fruits and filtering the liquor obtained. The obtained paste was clarified
by centrifugation at 3600 rpm for 20 minutes (Medifriger,
Selecta, Abrera, Spain). The clarified juice had no pulp in
suspension, but it did have pectins. Approximately half the
juice without pulp was subjected to an enzymatic clarification in order to eliminate the pectins, using Pectinex and
Ultrazym 100-C (Novo). The enzymes were left to act for
two hours at 25C, and the juice was then vacuum filtered.
Two types of juices were therefore obtained, the first one
clarified and depectinated (type I) and the other one clarified with pectins (type II).
From these two types of juices, different samples with different soluble solids contents were obtained by evaporation at approximately 25C, temperature that corresponds
336
to a pressure of 24 mm Hg (Labo-rota C-311, Resonatechnics, Buchs, Switzerland).

Samples were extracted during the time of the concentration process, which allowed obtaining juices with different
soluble solids contents: 68, 65, 60, 55, 50, 45 and 40Brix
for type I, and 63, 58, 53, 44 and 38Brix for type II.
All experiments and analysis were carried out by triplicate.
Physical and Chemical Analysis
The physicochemical analysis carried out to the redcurrant juices were:
Soluble solids. These were determined using a digital
refractometer at 20C (Atago RX-1000, Tokyo, Japan).
Density. A picnometer was used at 20C (PROTON,
Barcelona, Spain).
Total acidity. This was determined by titrating the juice
with NaOH 0.1 N, using phenolphthalein as indicator.
pH. It was determined by using a pH-meter (MicropH2001, Crison Instruments, Alella, Spain).
L-malic acid. This was determined by using the enzyme L-malate dehydrogenase. The absorbance was
measured at 340 nm (Boehringer Mannheim 1984)
using a spectrophotometer (PU 8720 UV/VIS, Philips,
Eindhoven, Netherlands).
Citric acid. This was determined by using the enzymes citrate lyase, malate dehydrogenase and Lmalate dehydrogenase. The absorbance was measured at 340 nm (Boehringer Mannheim 1984).
Ascorbic acid. This was determined by using the enzyme ascorbate oxidase. The absorbance was measured at 578 nm (Boehringer Mannheim 1984).
Glucose, fructose and sucrose. These were determined by using the enzymes hexokinase and glucose-6-phosphate dehydrogenase. The absorbance
was measured at 340 nm.
Pectins. This content was determined by degradation
in sulphuric acid medium. The absorbance was measured at 525 nm (De Giorgi et al 1985) and the result
was expressed as g of galacturonic acid (AGA) per
kg of juice.
Rheological measurements.
The rheological measurements of the different samples
were carried out on a concentric cylinder viscometer (Rotovisco RV 12, Haake, Karlsruhe, Germany), equipped with
M-500-type measurement attachment, which can transmit a torque of 4.9 N-cm. A thermostatic bath (Digitherm
30000613, Selecta, Abrera, Spain) controls the working
temperature within the range 5-65C.
Rotor speeds were variable in the range 0.01-512 rpm.
Readings were taken at decreasing rotor speeds until a
minimum speed was reached, after which it was gradually
increased. In order to eliminate the possible effects of thixotropy, the sample was previously sheared at maximum
speed for three minutes.
The rheological behavior of the juices at different temperatures (5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 and 60C.)
was studied.
Statistical analysis
The experimental results obtained were fitted to mathematical models by using the Statgraphics Plus 5.1 software (STCSC Inc. Rockville, Md, USA) for data processing.
All the fittings and the estimates were calculated at a 95%
significant level.
RESULTS AND DISCUSSION

First of all, thixotropy was not observed.
The results of the physical and chemical analysis of redcurrant juice are shown in Table 1.
Table 1.- Characteristics of centrifuged juice
Density
pH
Soluble solids
Total acidity
L-Malic acid
Citric acid
Ascorbic acid
Glucose
Fructose
Sucrose
Pectins (Type I 68Brix)
Pectins (Type II 63Brix)
1.044
g/mL
2.64
11.2
0.41
1.2
26.8
60
10.1
13.6
0.9
2.2
6.8
Brix
eq/L
g/L
g/L
mg/L
g/L
g/L
g/L
g AGA/kg
g AGA/kg
Rheological behavior of type I juice.

Figure 1 shows the experimental results obtained for the
depectinated juice of 68 Brix at the different temperatures
tested. Similar rheograms were obtained for the other concentrations.
Table 2 shows the parameters obtained with Newton and

power-law models. Herschel-Bulkley model was discarded because the yield stress obtained for all the concentrations and temperatures was smaller than 1 Pa (Vitali and
Rao 1984).
In all cases, Newton model and power-law model show
good fits. The behavior of type I juice can be considered
as Newtonian due to its bigger simplicity. Newton model
fittings show that the viscosity decreases with temperature
and increases with soluble solids content.
Power-law model always shows a flow behavior index
smaller than the unit, but near to it. As expected, the
consistency index (k) decreases with temperature and
increases with soluble solids content. The flow behavior
index (n) is relatively constant with temperature for soluble
solids content below 60Brix, similarly to previous works
(Falguera and Ibarz 2010, Falguera et al 2010). For soluble
solids content above 65Brix, the flow behavior index (n)
show a slight decrease with temperature, as it was observed by Ibarz et al. (1993).
Rheological behavior of type II juice.

Figure 2 shows the experimental results obtained for the
concentrated sample of 63Brix at the different tested
temperatures. Similar rheograms were obtained for the
other concentrations. The rheogram shows the non-linear
fit; therefore, experimental data were fitted to the powerlaw and Herschel-Bulkley models.
Table 3 shows the parameters obtained with power-law
and Herschel-Bulkley models. The values of the apparent
viscosity at a shear rate of 100 s-1 are included for each
model.
In Table 3 it can be observed that rheological behavior of

this type of juice fits better to power-law model. The flow
behavior index is always clearly smaller than the unit, thus
the rheological behavior is pseudoplastic, and it shows an
upward trend with decreasing concentration and increasing temperature. The consistency coefficient increases as
the concentration increases and temperature decreases.
The apparent viscosity increases as the concentration
rises up, temperature decreases and the pectins content
increases. The obtained values and tendencies are similar to those described in the literature (Falguera and Ibarz
2010, Falguera et al 2010, Ibarz et al 1993, Haminiuk et al
2006, 2007, 2009, Sato and Cunha 2009, Tonon et al 2009,
Vandresen et al 2009).
Temperature effect.
The variation in apparent viscosity or viscosity with
temperature can be described by an Arrhenius-type
equation (Saravacos 1970; Rao et al 1984; Ibarz et al
1992a;1992b;1996; Falguera et al, 2010):
(3)
The parameters of the equation are shown in tables 4 and

5. The activation energy increases with the soluble solids
content; therefore, temperature had a greater effect on the
samples with higher soluble solids. For fixed soluble solids
content, the value of activation energy of flow for clarified
and depectinized juice is greater than the activation energy
for juice containing pulp and pectin.
The activation energy values obtained for the clarified
and depectinized juice were very similar to those for the
depectinated apple and grape juices (Rao et al 1984),
clarified banana juice (Khalil et al 1989), depectinized pear
juice (Ibarz et al 1987), depectinized peach juice (Ibarz et
al 1992a) and depectinized blackcurrant juice (Ibarz et al
1992b). For the juice containing pulp and pectins, the values obtained were similar to those obtained in tomato
337
Table 2.- Clarified and depectinated redcurrant juices parameters

Newton Model
T
Brix
68
5
10
15
20
25
30
35
40
45
50
55
60
1866
1116
674
406
272
177.6
124.6
93.2
72.0
57.0
45.1
43.1
15
10
8
6
3
2.0
1.5
1.0
1.0
0.9
0.7
0.7
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
2.06
1.43
0.92
0.56
0.35
0.33
0.27
0.22
0.17
0.14
0.13
0.11
0.14
0.11
0.07
0.03
0.02
0.02
0.03
0.02
0.02
0.02
0.01
0.02
0.98
0.95
0.94
0.94
0.96
0.90
0.89
0.87
0.88
0.88
0.87
0.87
0.02
0.02
0.02
0.01
0.02
0.04
0.02
0.02
0.02
0.03
0.02
0.02
0.9998
0.9999
0.9997
0.9998
0.9975
0.9997
0.9995
0.9997
0.9997
0.9996
0.9999
0.9982
65
5
10
15
20
25
30
35
40
45
50
55
60
682
396
144.4
176.6
120.3
86.9
66.1
52.6
41.2
35.2
29.6
27.1
7
4
1.3
1.6
1.4
1.0
0.7
0.6
0.5
0.4
0.3
0.3
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.9999
0.67
0.59
0.51
0.29
0.27
0.21
0.17
0.13
0.11
0.10
0.07
0.06
0.05
0.04
0.03
0.04
0.03
0.02
0.02
0.01
0.01
0.02
0.01
0.01
1.00
0.93
0.89
0.93
0.88
0.87
0.87
0.88
0.88
0.86
0.89
0.89
0.02
0.01
0.01
0.03
0.09
0.02
0.02
0.02
0.01
0.03
0.02
0.02
0.9999
0.9998
0.9996
0.9985
0.9992
0.9996
0.9991
0.9991
0.9998
0.9991
0.9993
0.9996
60
5
10
15
20
25
30
35
40
45
50
55
60
194.7
123.2
86.2
63.9
48.2
36.3
29.5
25.5
21.90
19.6
17.2
15.30
2.0
1.4
0.9
0.7
0.5
0.3
0.4
0.3
0.20
0.3
0.3
0.20
0.9999
0.9998
0.9997
0.9998
0.9999
0.9999
0.9988
0.9989
0.9974
0.9976
0.9968
0.9967
0.36
0.33
0.28
0.20
0.16
0.13
0.11
0.10
0.08
0.08
0.06
0.06
0.03
0.03
0.03
0.03
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.01
0.90
0.85
0.83
0.84
0.84
0.83
0.83
0.82
0.84
0.82
0.84
0.82
0.02
0.02
0.02
0.03
0.02
0.02
0.02
0.02
0.03
0.02
0.04
0.03
0.9998
0.9995
0.9993
0.9996
0.9997
0.9992
0.9992
0.9996
0.9999
0.9998
0.9998
0.9996
55
5
10
15
20
25
30
35
40
45
50
55
60
70.6
52.5
38.0
28.5
24.2
18.1
15.10
13.00
11.70
9.40
9.40
8.30
1.0
0.6
0.7
0.5
0.3
0.3
0.20
0.20
0.20
0.20
0.10
0.10
0.9998
0.9997
0.9997
0.9995
0.9993
0.9989
0.9986
0.9985
0.9978
0.8788
0.9975
0.9978
0.17
0.14
0.11
0.08
0.08
0.07
0.05
0.05
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.01
0.03
0.01
0.01
0.87
0.86
0.86
0.87
0.84
0.83
0.85
0.81
0.84
0.86
0.86
0.88
0.02
0.02
0.02
0.02
0.02
0.02
0.04
0.06
0.02
0.09
0.05
0.06
0.9993
0.9997
0.9997
0.9991
0.9994
0.9995
0.9999
0.9972
0.9996
0.9991
0.9982
0.9996
50
5
10
15
20
25
30
35
40
45
50
55
60
36.7
27.4
21.9
17.4
14.9
9.00
10.70
9.40
8.30
7.20
7.90
6.80
0.5
0.4
0.3
0.3
0.3
0.20
0.20
0.10
0.10
0.10
0.10
0.10
0.9998
0.9996
0.9992
0.9975
0.9975
0.9943
0.9962
0.9973
0.9978
0.9998
0.9997
0.9982
0.12
0.08
0.07
0.06
0.05
0.04
0.03
0.03
0.02
0.02
0.02
0.02
0.02
0.03
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.84
0.86
0.86
0.83
0.84
0.85
0.85
0.86
0.87
0.87
0.90
0.88
0.02
0.03
0.01
0.01
0.02
0.03
0.04
0.04
0.04
0.04
0.06
0.06
0.9992
0.9992
0.9993
0.9997
0.9993
0.9999
0.9998
0.9998
0.9992
0.9996
0.9995
0.9995
45
5
10
15
20
25
30
35
40
45
50
55
60
21.3
17.00
14.20
12.10
10.40
9.00
8.20
7.00
6.70
6.30
5.60
4.90
0.3
0.20
0.20
0.20
0.20
0.10
0.10
0.10
0.10
0.07
0.07
0.06
0.9986
0.9961
0.9942
0.9932
0.9948
0.9948
0.9956
0.9973
0.9972
0.9974
0.9948
0.9923
0.54
0.08
0.07
0.06
0.05
0.04
0.04
0.03
0.03
0.02
0.02
0.04
0.22
0.12
0.01
0.01
0.01
0.01
0.01
0.01
0.08
0.02
0.02
0.01
0.71
0.79
0.80
0.79
0.80
0.82
0.81
0.80
0.82
0.82
0.82
0.83
0.06
0.13
0.03
0.03
0.04
0.05
0.05
0.02
0.04
0.08
0.10
0.05
0.9918
0.9992
0.9993
0.9997
0.9996
0.9997
0.9997
0.9994
0.9993
0.9982
0.9996
0.9993
40
5
10
15
12.90
11.00
9.10
0.15
0.13
0.11
0.9987
0.9962
0.9965
0.04
0.04
0.04
0.01
0.03
0.02
0.87
0.85
0.83
0.05
0.05
0.05
0.9994
0.9983
0.9991
338
Power-law Model
mPas
Pasn
Table 3.- Clarified redcurrant juice parameters

Power-law Model
C
Brix
63
5
10
15
20
25
30
35
40
45
50
55
60
28.3
20.53
13.5
9.55
6.20
5.69
3.39
2.28
1.65
0.99
0.50
0.33
0.5
0.18
0.3
0.13
0.15
0.17
0.12
0.10
0.02
0.04
0.05
0.04
0.50
0.51
0.55
0.56
0.60
0.57
0.63
0.66
0.67
0.72
0.79
0.81
58
5
10
15
20
25
30
35
40
45
50
55
60
8.1
4.0
3.11
2.17
2.17
1.24
0.74
0.64
0.38
0.29
0.21
0.14
0.4
0.4
0.28
0.13
0.11
0.08
0.10
0.07
0.05
0.05
0.02
0.04
0.59
0.68
0.68
0.68
0.65
0.70
0.75
0.75
0.79
0.80
0.81
0.85
53
5
10
15
20
25
30
35
40
45
50
55
60
2.72
2.30
1.51
3.11
0.88
0.62
0.60
0.38
0.28
0.20
0.15
0.14
0.18
0.15
0.13
0.07
0.08
0.05
0.03
0.03
0.03
0.02
0.02
0.03
44
5
10
15
20
25
30
35
40
45
50
55
60
0.54
0.37
0.26
0.25
0.21
0.15
0.10
0.08
0.06
0.06
0.05
0.04
38
5
10
15
20
25
30
35
40
45
50
55
60
0.16
0.19
0.17
0.11
0.08
0.06
0.51
0.05
0.03
0.03
0.03
0.04
Herschel-Bulkley Model
r
ha(100s-1)
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.9998
0.9996
0.9994
0.9997
0.9992
0.9992
0.9998
0.9997
0.9997
0.9996
0.9989
0.9991
2808.7
2161.9
1695.6
1252.4
989.1
796.5
629.5
479.8
367.4
267.4
185.8
137.1
19.4
15.2
10.6
11.0
8.4
7.8
5.8
5.3
4.0
3.8
1.8
1.9
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
12.3
8.0
5.5
3.3
2.4
2.6
2.4
0.50
2.4
2.62
2.41
0.50
1.4
1.0
0.9
0.9
0.5
0.3
0.3
0.04
0.2
0.21
0.09
0.10
0.73
0.75
0.78
0.79
0.80
0.71
0.79
0.94
0.80
0.71
0.79
0.94
0.02
0.03
0.03
0.01
0.01
0.02
0.03
0.03
0.03
0.04
0.02
0.05
0.9997
0.9963
0.9972
0.9995
0.9991
0.9991
0.9976
0.9982
0.9983
0.9977
0.9994
0.9969
1237.8
924.0
706.1
492.6
432.7
310.7
238.6
198.7
140.3
114.7
90.3
68.8
5.8
3.0
3.6
2.6
3.3
3.0
1.9
1.6
1.4
1.0
0.9
0.6
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
3.6
2.6
1.6
0.8
0.9
0.56
0.44
0.31
0.18
0.16
0.11
0.08
1.1
0.6
0.6
0.3
0.3
0.16
0.14
0.11
0.07
0.05
0.04
0.05
0.80
0.77
0.82
0.86
0.82
0.83
0.84
0.87
0.91
0.89
0.91
0.94
0.68
0.65
0.69
0.69
0.69
0.72
0.70
0.74
0.75
0.78
0.80
0.79
0.02
0.02
0.02
0.02
0.02
0.02
0.01
0.02
0.02
0.02
0.02
0.03
0.9982
0.9997
0.9986
0.9987
0.9996
0.9991
0.9998
0.9993
0.9994
0.9995
0.9995
0.9994
619.3
467.5
355.4
753.9
216.1
169.5
148.4
114.2
90.0
72.0
58.5
52.0
3.5
3.8
2.6
2.4
2.1
2.2
2.1
1.4
1.2
0.9
0.7
0.7
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
1.76
0.9
0.69
0.62
0.43
0.28
0.23
0.19
0.43
0.28
0.23
0.19
0.21
0.3
0.24
0.15
0.13
0.09
0.07
0.05
0.05
0.04
0.03
0.05
0.22
0.05
0.05
0.03
0.02
0.03
0.02
0.02
0.03
0.02
0.01
0.01
0.71
0.74
0.76
0.74
0.74
0.76
0.80
0.81
0.81
0.79
0.81
0.83
0.06
0.03
0.04
0.02
0.02
0.03
0.03
0.04
0.06
0.05
0.02
0.05
0.9911
0.9982
0.9961
0.9996
0.9992
0.9998
0.9994
0.9994
0.9989
0.9988
0.9997
0.9997
141.7
112.6
87.0
75.1
62.9
49.1
38.3
31.3
26.8
23.8
20.3
17.4
1.9
1.5
1.0
1.4
1.1
0.6
0.4
0.4
0.4
0.4
0.3
0.3
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.24
0.17
0.12
0.09
0.10
0.09
0.05
0.05
0.15
0.04
0.03
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.02
0.02
0.01
0.01
0.02
0.01
0.85
0.75
0.75
0.78
0.81
0.82
0.82
0.82
0.84
0.83
0.82
0.85
0.02
0.03
0.03
0.01
0.01
0.02
0.03
0.03
0.03
0.04
0.02
0.05
0.9973
0.9999
0.9998
0.9996
0.9984
0.9992
0.9985
0.9986
0.9994
0.9994
0.9976
0.9986
80.6
61.7
52.7
40.1
32.2
26.2
23.8
19.6
15.6
14.2
13.7
19.5
0.9
1.5
1.0
0.6
0.4
0.4
0.4
0.3
0.2
0.3
0.3
0.2
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.06
0.12
0.07
0.06
0.04
0.03
0.03
0.02
0.43
0.28
0.23
0.19
Pasn
s0
mPas
Pa
ha(100s-1)
0.05
0.05
0.05
0.07
0.06
0.03
0.05
0.16
0.05
0.02
0.05
0.19
0.9955
0.9942
0.9926
0.9863
0.9911
0.9988
0.9956
0.9636
0.9918
0.9986
0.9951
0.9638
3697.0
2430.7
3098.0
2458.9
1631.1
1316.0
1249.3
661.9
468.2
324.9
190.9
91.5
0.09
0.06
0.09
0.08
0.08
0.06
0.06
0.07
0.07
0.06
0.06
0.10
0.9776
0.9883
0.9797
0.9805
0.9849
0.9926
0.9936
0.9907
0.9938
0.9949
0.9958
0.9888
1744.2
1002.2
801.8
518.4
492.3
344.3
241.6
193.1
138.1
110.0
84.2
60.1
0.75
0.83
0.83
0.79
0.81
0.84
0.84
0.85
0.81
0.84
0.84
0.85
0.03
0.07
0.08
0.05
0.06
0.06
0.06
0.05
0.07
0.07
0.06
0.08
0.9974
0.9858
0.9863
0.9939
0.9922
0.9928
0.9941
0.9960
0.9928
0.9922
0.9948
0.9960
685.8
551.0
384.2
296.0
226.4
184.4
159.2
113.3
86.3
67.3
54.3
44.3
0.02
0.07
0.06
0.05
0.05
0.04
0.02
0.02
0.15
0.03
0.11
0.02
0.93
0.93
0.86
0.89
0.85
0.83
0.89
0.87
0.69
0.87
0.88
0.90
0.06
0.07
0.08
0.09
0.06
0.07
0.08
0.08
0.26
0.11
0.10
0.11
0.9970
0.9928
0.9902
0.9907
0.9953
0.9943
0.9940
0.9969
0.8019
0.9932
0.9988
0.9961
322.9
146.6
73.0
71.9
61.3
45.7
32.9
27.4
34.5
21.6
18.3
14.8
0.04
0.01
0.04
0.02
0.02
0.02
0.03
0.02
0.01
0.02
0.03
0.02
0.95
0.81
0.88
0.88
0.90
0.91
0.90
0.91
0.81
0.84
0.84
0.85
0.10
0.02
0.06
0.07
0.08
0.09
0.11
0.10
0.10
0.12
0.15
0.16
0.9917
0.9990
0.9963
0.9955
0.9968
0.9952
0.9940
0.9967
0.9928
0.9929
0.9947
0.9969
54.8
72.3
50.3
36.7
28.8
23.5
20.2
17.3
14.0
12.8
12.0
9.7
Pasn
mPas
Table 4.- Parameters of Arrhenius Equation for Type I redcurrant juices

Newton Model
C
Brix
68
65
60
55
50
45
Ea
kJ/mol
54.4
43.1
34.7
30.1
23.0
20.1
h10
mPas
0.83
36.74
430.56
1346.95
13217.36
35113.56
7
Power-law Model
r
0.9902
0.9745
0.9841
0.9878
0.9580
0.9929
Ea
kJ/mol
47.7
40.2
30.1
28.9
25.1
20.5
h107
mPas
0.01
0.18
41.83
42.65
10481.07
50061.41
r
0.9903
0.9938
0.9900
0.9963
0.9938
0.9920
339
Table 5.- Parameters of Arrhenius Equation for Type II redcurrant juices

Power Law
Ea
h10
Brix
kJ/mol
mPas
63
58
53
44
38
41.42
40.17
37.66
29.71
23.85
56.15
37.75
63.54
362.50
2332.04
Herschel-Bulkley
Ea
derivates (Saravacos 1970; Ibarz et al 1988) and plum and

peach pulp (Ibarz and Lozano 1992). The h values obtained of the clarified and depectinized juice were within
the same order as those for depectinized peach, blackcurrant and banana juice above mentioned.
3.
CONCLUSION
5.
From the experimental results obtained from depectinized

and non-depectinized redcurrant juices in the temperature
range of 5-60C and soluble solids content between 38 an
68Brix, the following conclusions may be drawn:
Redcurrant juices containing pectins showed rheological
behavior which was better described by the power-law
model. Herschel-Bulkley model also fitted experimental
data.
Clarified and depectinized redcurrant juices showed rheological behavior which can be described by the Newtonian
model. The parameters obtained for power-law model also
fit well.
For both depectinized and non-depectinized redcurrant
juices, the effect of temperature in apparent viscosity at
100s-1 can be described by an exponential Arrhenius-type
equation.
NOTATION

Concentration (Brix)
Activation energy (kJ/mol)
Consistency index (Pasn)
Flow behavior index (dimensionless)
Gas constant (8.314 J/mol K)
Temperature (C or K)
Shear rate (s-1)
Viscosity (mPas)
Apparent viscosity (mPas)
Apparent viscosity at great temperatures (mPas)
Shear stress (Pa)
Yield stress (Pa)
4.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
BIBLIOGRAPHY
1.
2.
340
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temperature on rheological properties of different
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17.
mPas
56.49
44.77
38.49
31.38
27.20
0.9940
0.9986
0.9536
0.9987
0.9304
h107
kJ/mol
0.02
6.16
39.97
72.56
422.40
r
0.9819
0.9977
0.9981
0.9969
0.9834
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35:122-125
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rheological properties of jaboticaba pulp. Journal of
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341
Gestin de residuos a lo largo del

ciclo de vida de un automvil
B. Amante*, A. Lacayo, M. Piqu, V. Lpez-Grimau
Departamento de Proyectos de Ingeniera .ETSEIAT (Escuela Tcnica Superior
de Ingenieras Industrial y Aeronutica Terrassa) UPC.
Management of residues life cycle services of an automobile

Gesti de residus al llarg del cicle de vida dun autombil
Recibido: 4 de octubre de 2010; revisado: 26 de noviembre de 2010; aceptado: 29 de noviembre de 2010
RESUMEN
El estudio que se desarrolla a continuacin tiene el objetivo de analizar los sectores y procesos de reciclaje de los
residuos generados por un vehculo a lo largo de su vida
til. Se pretende detectar posibles lagunas existentes en
la actualidad y proponer mejoras organizativas segn las
carencias detectadas.
Este estudio se realiza en definitiva, analizando el sector automovilstico y el reciclaje que se lleva a cabo en el
mismo, teniendo en cuenta la aplicacin de la Directiva
Europea 2000/53 en el Estado Espaol y repasando los
procesos de reciclaje de los diferentes componentes de
un vehculo.
Mediante las carencias detectadas en dichos procesos
se propone la mejora de la gestin de los residuos en los
talleres con la creacin de un SIG (Sistema Integrado de
Gestin).
Palabras clave: Automvil, plsticos, Residuos, SIG (Sistema Integrado de Gestin)
ABSTRAT
The study we present aims at analyzing the sectors and recycling processes of the waste generated by a vehicle during its lifetime. Our objective is to find out possible lacks
in nowadays processes and propose better organization
improvements according to the detected flaws.
Therefore, in this article we analyze the automobile sector
and the recycling activity carried out in it, taking into account the application of the European Directive 2000/53
in Spain. We also review the recycling processes of the
different components of a vehicle, focusing on the garage.
Starting from the weaknesses detected in the above mentioned processes, we propose an improvement in the
waste management in such specific places as garages by
implementing a MIS (Management Integrated System)
Keywords: Automotive, Plastics, Residue, SIG (Integral
system management)
342
RESUM
Lestudi que es desenvolupa a continuaci t lobjectiu
danalitzar els sectors i processos de reciclatge dels residus generats per un vehicle al llarg de la seva vida til. Es
pretn detectar possibles mancances existents a lactualitat i proposar millores organitzatives segons les carncies
detectades.
Aquest estudi es realitza en definitiva, analitzant el sector automobilstic i el reciclatge que es porta a terme en
aquest, tenint en compte laplicaci de la Directiva Europea 2000/53 a lEstat Espanyol i repassant els processos
de reciclatge dels diferents components dun vehicle.
A partir de les carncies detectades en aquests processos
es proposa la millora de la gesti dels residus en els tallers
amb la creaci dun SIG (Sistema Integrat de Gesti).
Mots clau: Autombil, Plstics, Residus, SIG(Sistema Integrat de Gesti)
*Autor para la correspondencia: beatriz.amante@upc.edu;

tel. +34 937 39 73 16, fax +34 937 39 81 01
1. INTRODUCCIN
En la actualidad los vehculos forman parte de nuestra
vida diaria y no se podra concebir la vida tal y como la conocemos sin ellos. La utilizacin de los vehculos cada vez
es mayor y stos a su vez generan una gran cantidad de
residuos, muchos de ellos, considerados peligrosos por la
UE (Unin Europea). Por ello, cada vez es ms imprescindible conocer el estado actual en Espaa del tratamiento
y la gestin de dichos residuos, con el fin de reducir su
impacto en el medioambiente.
Espaa es el tercer productor europeo de turismos y el
primer productor de vehculos industriales en Europa. Dispone de un total de 11 marcas de fabricantes que han
instalado 18 fbricas para producir sus automviles. De
los 2,5 millones de unidades que producen al ao, casi 2
millones son turismos. Dispone de un parque de vehculos
en uso de ms de 27 millones de unidades de los cuales
22 millones son del tipo turismo (el ms abundante). Otro
dato importante es que alrededor de 1 milln de vehculos
se dan de baja cada ao [1-3].
Los principales agentes implicados en la generacin de
los residuos producidos por los automviles son: los fabricantes de materias primas, los fabricantes de componentes, los fabricantes de automviles, los usuarios, los
talleres, los Centros autorizados de tratamiento (CAT), los
gestores de residuos, los fragmentadores y las empresas
recuperadoras, recicladoras y revalorizadoras que son las
que cerraran el ciclo (ver Figura 1).
Figura 1. Anlisis de la gestin de residuos
Por tanto y para poder establecer unos buenos criterios de

recuperacin y reciclaje es necesario conocer la composicin de un vehculo de forma detallada. Tambin hay que
tener en cuenta que como consecuencia del uso, aparecen durante la vida til de los automviles ms residuos a
tratar, que provendrn de los talleres de reparacin principalmente.
Otro hecho importante a tener en cuenta sera que los
materiales utilizados para fabricar un automvil cambian
constantemente, tanto en morfologa como en composicin. Todo esto dificulta el proceso de desmantelamiento y
reciclado, a la vez que aparecen intereses contrapuestos.
Por ejemplo: la sustitucin de piezas metlicas por otras
de un material ms ligero, utilizando diferentes familias de
polmeros plsticos, que reduce el consumo de combustible y en consecuencia las emisiones atmosfricas. Por
otro lado, dificulta los procesos de separacin y clasificacin de piezas que hace ms complejo el reciclado de las
mismas. Por ello la importancia de estudiar el tratamiento
del residuo y las previsiones de futuro del mismo.
En cuanto a las alternativas de tratamiento de estos residuos se debe tener en cuenta que el Real Decreto
1383/2002, transposicin de la Directiva 2000/53/CE,
establece un orden jerrquico en la gestin de residuos:
prevenir, minimizar, reutilizar, reciclar, recuperacin energtica y finalmente su eliminacin. Reducir la generacin
de residuos, no siempre es sencillo, dado que implicara
alargar la vida del vehculo, lo que lleva implcito mayor
contaminacin y menor seguridad vial.
Anualmente, se generan 800.000 Tn de residuos tan solo
con los vehculos que se dan de baja. Actualmente, Espaa cuenta con una infraestructura de recuperacin de alta
calidad, la red de centros autorizados de tratamiento (CAT)
y fragmentadores concertada por los fabricantes e importadores de vehculos ms numerosa de toda la Unin Europea.
Adems de los residuos en el fin de vida y para hacernos
una idea del volumen de los mismos generados durante
la etapa de vida til de un vehculo, podemos analizar las
cifras de los principales residuos peligrosos generados en
talleres de Catalua. Si estimamos las cantidades generadas anualmente, nos damos cuenta de la importancia
que tiene una correcta gestin de dichos residuos, que
ascienden a ms de 75.000 toneladas al ao nicamente
en Catalua [4].
Los aceites, bateras, lquido anticongelante, neumticos,
lquido de frenos, filtros de aceite, filtros de aire y combustible usados junto con las pastillas de frenos que contengan amianto son residuos peligrosos, por lo que su gestin la debera llevar a cabo un gestor autorizado. Tambin
se considera residuo peligroso todo objeto o envase que
estuviera en algn momento en contacto con el residuo
peligroso y debe tratarse como si lo fuera.
Los residuos peligrosos deben ser almacenados en condiciones de seguridad e higiene, separados entre s y del
resto de residuos, deben estar correctamente envasados
y etiquetados.
En los ltimos aos uno de los aspectos sobre los que
ms esfuerzos se han realizado ha sido la bsqueda de
nuevas vas para aumentar los niveles de recuperacin y
poder as alcanzar los objetivos de recuperacin fijados
en la Directiva 2000/53/CE. Actualmente, Espaa est recuperando aproximadamente el 85,6% del peso medio de
los vehculos, reutilizando (comentaremos las vas para el
reaprovechamiento de dichos residuos.) un 4,6% en peso
de los vehculos lo que supone unas 40.000 toneladas
anuales, reciclando un 78,5% en peso que supone aproximadamente unas 707.000 toneladas anuales y valorizando energticamente 32.000 toneladas anuales, un 2,5%.
Si nos fijamos en la reutilizacin y reciclaje de los principales materiales constituyentes de los vehculos, los podemos resumir en la Tabla 1.
Podemos destacar que la combinacin de materiales polimricos de distintos orgenes y la incompatibilidad entre
ellos hacen casi imposible el reciclado del material plstico, acabando principalmente en las fracciones destinadas
a depsitos controlados de residuos.
343
Tabla 1 Materiales recuperados en % de un automvil

Material
% Composicin
% Recuperacin
% Absoluto
Recuperacin
Material Frrico
69,50 %
68 %
99 %
Material No Frrico
7%
6,9 %
99 %
Plsticos
8,50 %
2,80 %
33 %
Neumticos
4,00 %
3,00 %
75 %
Cristales
3,50 %
3,00 %
85 %
Por tanto y en resumen, existe un 14,4% del peso medio del vehculo no recuperado actualmente, que se destina tambin y principalmente a depsitos controlados
(121.000 toneladas anuales), correspondiente a los residuos ligeros de fragmentadora y los residuos pesados sin
metales.
En este artculo presentaremos un anlisis exhaustivo del
tratamiento de los residuos dentro del sector, explicaremos alternativas como la valorizacin energtica de materiales no reciclables o reutilizables. Por otro lado, examinaremos los procesos de gestin de residuos detectando
los posibles puntos dbiles y realizaremos propuestas de
mejora en el sistema.
paola para el Tratamiento Medioambiental de los Vehculos Fuera de Uso (SIGRAUTO) que est constituida por
los principales sectores involucrados en el tratamiento
de los vehculos fuera de uso, es decir, fabricantes e importadores de vehculos, desguazadores y fragmentadores a travs de sus respectivas asociaciones sectoriales
(ANFAC(Asociacin Espaola de Fabricantes de Automviles y Camiones), ANIACAM(Asociacin Nacional de Importadores de Automviles, Camiones, Autobuses y Motocicletas), AEDRA(Asociacin Espaola de Desguaces y
Reciclaje del Automvil) y FER(Federacin Espaola de la
Recuperacin y el Reciclaje)). El objeto de SIGRAUTO es
velar por la aplicacin de los requisitos que establece la
nueva legislacin sobre vehculos fuera de uso. Pero no
solo se crea residuo al final de la vida til de un automvil,
tambin se produce durante su fabricacin y a lo largo de
su vida, por ello se debe analizar cada una de las etapas y
ver como se estn tratando.
2. METODOLOGA
En primer lugar hemos realizado un estudio de la situacin
actual en Catalua y Espaa, sobre el tratamiento de residuos procedentes del sector de la automocin a final de
su vida til. Se han verificado que existe en este gremio
una serie de asociaciones que citaremos, que se encargan
de canalizar y tratar los residuos al final de la vida til de
los automviles.
Posteriormente, hemos ampliado el estudio, focalizndolo
en la parte de uso del ciclo de vida del automvil y hemos
detectado un problema doble en los talleres. El primero
es la falta de organizacin y gestin de los residuos peligrosos y el segundo la responsabilidad de piezas. Para
suplir estas debilidades, se ha realizado en este estudio
una propuesta para cada una de ella, que presentaremos
en detalle en los siguientes apartados.
3. MATERIALES DEL AUTOMVIL

Como ya hemos comentado anteriormente, el componente mayoritario de un automvil es la chapa (39%), seguido
del acero y la fundicin (13% cada uno de ellos). Otros
componentes que se encuentran presentes son los plsticos en sus diferentes composiciones y combinaciones
(que a veces dificultan e impiden su correcto reciclado),
cristal, caucho y materiales textiles entre otros [5]. Dicha
descomposicin en % la podemos ver en la Tabla 2.
Los fabricantes de vehculos son los responsables de la
gestin de los residuos en el final de vida til del vehculo
y dicha gestin comienza por los CAT (centros autorizados de tratamiento) que descontaminan los vehculos y
los envan a las fragmentadoras y a las plantas de medios
densos para su tratamiento.
Debido a esta responsabilidad se han creado diferentes
asociaciones entre las cuales destaca la Asociacin Es-
344
Tabla 2. Composicin media de un vehculo tipo turismo
4. GENERACIN DE RESIDUOS
4.1.- Durante el diseo y la fabricacin de los vehculos:
Las posibilidades de reciclar estn en cada una de las etapas de la vida del vehculo, los fabricantes de vehculos en
la fase de desarrollo y diseo deben intentar desarrollar
materiales fciles de reciclar y diseos que permitan un
desguace o desmontaje fcil. El reciclaje debe ser un parmetro fundamental en el diseo del producto y este proceso debe nutrirse de la informacin obtenida a lo largo de
los ltimos aos y las posibilidades de reciclabilidad que
tienen los materiales. Ejemplos claros de concienciacin
desde la etapa/fase de diseo la tenemos en la empresa
Renault [6] donde se utilizan materiales adecuados para
el reciclaje y agrupar componentes del mismo material o
materiales compatibles mediante sistemas como la soldadura de friccin en vez de utilizando tornillos o clips metlicos. Es necesario establecer un sistema de marcado
y clasificacin para identificar bien los componentes y su
composicin, al igual que unas buenas instrucciones de
desmantelamiento de los componentes, como podemos
ver en el artculo [6] para los componentes plsticos. De
este modo se reducen las operaciones de desmantela-
miento y con ello se consigue una clasificacin ms rpida

y eficaz de los materiales.
En la fase de produccin, es importante reducir el uso
de materias primas y adems reutilizar y reciclar piezas
y materiales remanentes de los procesos de produccin.
Separar para reciclar debe ser la ley bsica del cuidado
medioambiental. Esto adems viene marcado por distintas
normas como RD 106/2008, RD 679/2006, RD 1619/2005,
donde hay que reducir las emisiones nocivas y evitar derrames de productos y residuos peligrosos.
Durante la fabricacin de un vehculo se consumen ms
de 1500 litros de agua, por tanto hay esfuerzos actuales
por la reduccin de su consumo. En la actualidad el agua
es depurada para reutilizarla en el proceso o verterla depurada a la alcantarilla.
Otro de los procesos clave en el proceso productivo es
la etapa de pintura, donde se han ido cambiando el tipo
de componentes de tintura, hacia la utilizacin de pinturas
plsticas, menos contaminantes y ms fciles de tratar.
4.2.- Final de su vida til:
Como ya se ha mencionado y segn los niveles marcados
por la Directiva 2000/53/CE, los problemas del reciclaje
al final de la vida til de los vehculos se centran principalmente en la recuperacin del material polimrico, as
como la recuperacin de parte del 14,4% de fraccin final
que actualmente se est destinando a los vertederos.
-Si nos fijamos en la composicin plstica del automvil
que es del 8,5% en estos momentos, tan solo un 2,8% se
recicla en la actualidad. Esto implica que hay en la actualidad un 5,8% que equivale a una media de 37.000 toneladas anuales de material plstico no reciclado y depositado
en vertederos (slo de turismos espaoles llegados a la
finalizacin de su vida til). Por otro lado, debemos pensar
en la escasez inevitable de determinadas materias primas
procedentes del petrleo a largo plazo. Por ello, al final
de su vida til los diferentes componentes deberan ser
considerados como un nuevo recurso con alto contenido
energtico.
Las crecientes polticas y estrategias de reciclaje enfocadas en aumentar la cantidad de estos materiales en la produccin de nuevos vehculos por parte de las fbricas de
automviles en la ltima dcada ha creado una demanda
en el mercado de materiales reciclados obligando a la recuperacin. Sin embargo, la demanda supera con creces
la oferta existente de productos plsticos reciclados. Por
ejemplo, Renault ha estimado [6] unas necesidades propias de 100.000 toneladas anuales de polipropileno, que
podemos ver que son cantidades elevadas, considerando
que la oferta actual europea no excede las 180.000 toneladas anuales. Esta diferencia se debe principalmente a
que la composicin en polipropileno de un vehculo actual
no es la misma que un vehculo al final de su vida til, es
decir de un vehculo con 15 aos (media en Espaa). Adems existe la complejidad de los productos presentes al
final de la vida til y las tcnicas de clasificacin y reciclaje
disponibles actualmente.
Hay varios estudios que tratan de resolver todas esta dificultades expuestas y que elaboran modelos de reciclaje
teniendo en cuenta los lmites del proceso [7-10] con los
mtodos de desmontaje [11-12], el anlisis del ciclo de
vida y consecuencias sobre la fase de diseo [13]. Una
de las mejores soluciones existentes se basa en fichas de
diseo de piezas. Esta herramienta nos permite escoger
por ejemplo los materiales plsticos a utilizar integrando
la capacidad de la tecnologa actual, la compatibilidad de

asociacin de los plsticos y la calidad del producto final.
Esta herramienta de diseo existe actualmente, ideada por
la empresa Renault [6], enfocada en el polipropileno (PP)
debido a su alta utilizacin en la industria del automvil.
-Por otra parte, si nos fijamos en el 14,4% de los residuos
generados por un VFU que no se tratan y que pertenecen
a los residuos ligeros y pesados sin metales de fragmentadora, representan una media de 91.000 toneladas de
residuo vertido, sin recuperacin factible de ste por el
momento.
Si no es material recuperable, la alternativa inmediata sera la valorizacin energtica. Una alternativa sera Auto
Shredder Residue o fluff (ASR). Es un material slido
muy heterogneo (sin poder especificar unos niveles globales de contenido) constituido principalmente por gomas, plsticos, espumas, textiles, metales no frricos, etc.
y con altas propiedades calorficas, ligado estrechamente
a su composicin orgnica. ASR tiene un carcter ms
voltil y un mayor contenido de cenizas que el carbn. Se
empieza a quemar a 300 C, temperatura que se aproxima
a la de diferentes carbones utilizados actualmente. El poder calorfico bruto se especifica entre 11 y 30 MJ / kg, con
una media de 20 MJ / kg. Actualmente se estn desarrollando mltiples investigaciones y procesos para reciclar
esta fraccin utilizando la valorizacin energtica. Algunos
de estos estudios estn en fase de experimentacin, otros
ya implementados en el territorio, ofrecen posibilidades
viables para llegar a la recuperacin de un 10% del material producido actualmente. Existen diferentes grupos
de procesos de reciclaje de shredder y los principales los
podemos encontrar definidos en [14]. Adems, la mayora
de investigaciones apuntan a que una valorizacin energtica del producto, formando parte del combustible de
algunos procesos, es una va ms rentable que un reciclaje
mecnico. Hay que especificar que la Directiva Europea
2000/53/CE marca que slo un 10% del VFU se podr
recuperar por la va de valorizacin energtica. Por todo
eso, la Agrupacin Espaola de Fabricantes de Cemento
(OFICEMEN) lleva varios aos colaborando con Sigrauto
y sus socios fundadores en el anlisis de la posibilidad
de utilizar estos residuos, despus de una preparacin y
acondicionamiento adecuados, como combustibles alternativos en los hornos de las plantas cementeras en la produccin de clnker en sustitucin de combustibles fsiles,
obteniendo un doble ahorro: la disminucin de material
vertido proveniente del ASR as como el ahorro de extraer
y manipular los combustibles fsiles que se utilizan actualmente. El sector cementero espaol utiliz en el ao 2007
unas 350.000 toneladas de residuos como combustibles
alternativos, que supusieron tan solo el 6,4% del consumo
trmico de los hornos de clnker, lo que nos sita a la cola
de Europa en valorizacin energtica, donde aproximadamente el 70% de las plantas cementeras utilizan combustibles alternativos con unos niveles mximos del 83%
de substitucin (Holanda) y una media del 30% de substitucin [15]. La pregunta ahora sera, ambientalmente es
bueno este reciclaje del ASR por combustin? Los estudios realizados determinan que los gases de combustin
estn durante largos periodos de tiempo a temperaturas
muy altas (hasta 2.000 C) y en una atmsfera rica en oxgeno, condiciones en las que los compuestos orgnicos
que contienen los residuos son destruidos, dando lugar
a emisiones de dixido de carbono (CO2) y agua (H2O),
evitando as las emisiones de compuestos orgnicos vol-
345
tiles (COV) y dioxinas y furanos (PCDD y PCDF). Por otro

lado, los gases cidos (sulfurosos y halogenados) que se
forman en la combustin cuando los residuos contienen
cloro o azufre, se neutralizan con la materia prima alcalina,
formando sales inorgnicas que se incorporan al clnker,
con lo que evita su emisin a la atmsfera. Aqu se ve la
importancia de controlar los niveles de materiales organoclorados, como una alta fraccin de plsticos. Por este
motivo, si mejoramos el reciclaje de las piezas plsticas,
tendremos un ASR de menor fraccin organoclorada y no
supondr ningn problema los gases cidos. Adems, los
metales pesados que pueden estar contenidos en los residuos quedan retenidos en su mayor parte en el clnker, evitando la emisin a la atmsfera y las cenizas procedentes
de la quema de los residuos se incorporan al producto por
lo que no se genera ningn tipo de residuo [16].
3.- Durante la vida til de los vehculos:
Por ltimo pero ms importante, se ha realizado un estudio sobre la gestin de residuos en los talleres de reparacin de vehculos. Es una actividad que ha ido mejorando progresivamente en la ltima dcada, gracias en gran
medida, a la progresiva concienciacin de la sociedad,
una mayor regulacin y el aumento de los controles y las
sanciones. Esta gestin no es en absoluto sencilla. En un
taller de reparacin se generan aproximadamente 34 residuos distintos, de los cuales, 18 tienen la consideracin
de peligrosos, lo que implica tener un gestor para cada
uno de ellos, depsitos adecuados para los mismos, una
compleja gestin administrativa como productor de esos
residuos, etc.
Se han creado sistemas de gestin (SIGs) con la aparicin
de decretos relativos nicamente a la gestin de neumticos y aceites usados, donde la gestin de los residuos
[17-18] es rentable. De forma general, con estos SIGs, los
productos en cuestin han visto incrementado su precio y
adems ha sido necesario realizar cambios administrativos, en los procesos de gestin y en los sistemas de facturacin incorporando, entre otras cosas, un sobrecoste
en la gestin del residuo.
Se puede deducir de aqu que existen muchos otros productos que no se gestionan correctamente debido a la
falta de rentabilidad y por ello, proponemos la creacin de
un servicio integral de recogida y gestin de los residuos
de los talleres, que ayude a solucionar las deficiencias. Se
tratara de establecer un sistema voluntario que garantice
la recogida y adecuada gestin de los residuos que se generan durante la vida til del vehculo (en los talleres). De
esta forma tras la recogida del residuo del taller y su separacin selectiva en las instalaciones de almacenamiento
intermedio, se conseguir su mxima recuperacin, ya sea
mediante el retorno al fabricante, su entrega a un centro
tecnolgico (previamente homologado) o el reciclado de
materiales, asegurando una correcta gestin y tratamiento
de los componentes no valorizables y de los residuos peligrosos mediante gestor autorizado. El proceso actual de
generacin de residuos y la problemtica de responsabilidades de las piezas reutilizadas se puede ver esquematizado en la Figura 2.
346
Figura 2. Planteamiento del proceso de generacin actual de residuos y problemtica de responsabilidades de las piezas reutilizadas
En este punto se realiza una nueva propuesta de un nuevo

gestor nico cuyas caractersticas y funciones principales
seran:
Realizar el asesoramiento y la formacin medioambiental que recojan las exigencias de la normativa a
todos los niveles y las traduzca en mtodos y herramientas de trabajo prcticas para el taller.
Debera ser un servicio integral de recogida y soluciones de almacenamiento con la garanta de estar
cumpliendo debidamente la normativa vigente en
todo momento.
Gestionar la recogida de todos los residuos generados en los talleres, no nicamente los residuos que
resulten viables econmicamente.
Realizar una recogida adaptada a cada taller en cuanto a periodicidad en la recogida. Establecer los criterios a seguir para el cobro de una tasa de reciclaje en
cada una de las operaciones realizadas en los talleres
para que el coste del reciclado no repercuta nicamente en ellos.
Crear centros de seleccin de residuos adecuados y
proporcionar la logstica necesaria para cubrir todo el
territorio adems de fomentar la aplicacin de Buenas prcticas medioambientales en los talleres.
Una vez realizada la recogida, termina la responsabilidad
del taller en cuanto a dichos residuos y es el gestor autorizado (tal como se puede ver en la Figura 3), el que deber
clasificar los residuos de forma adecuada. En sus centros
de Recogida de Transferencia (CRT) se realizar la concentracin, clasificacin y pre-tratamiento de cada residuo para su reenvo a plantas autorizadas de tratamiento
final. Lo interesante es que recogera todas las tipologas
de residuos a la vez evitando los problemas que tienen los
talleres para realizar su correcta gestin [19-20].
Figura 3. Esquema de la propuesta con los agentes

implicados en la gestin de residuos del automvil
Para la creacin de una red es de gran inters el poder llegar a establecer lazos de colaboracin con las principales
asociaciones ya existentes, como por ejemplo SIGRAUTO
que est constituida por los principales sectores involucrados en el tratamiento de los vehculos (ANFAC, ANIACAM, AEDRA Y FER), SERNAUTO, FACONAUTO y los
principales gremios de talleres independientes del pas.
El segundo punto donde se ha detectado un problema ha
sido planteado a raz del real Decreto 1383/2002, sobre
Gestin de Componentes al final de su vida til y durante
la vida til del vehculo y que es la imposibilidad de establecer la trazabilidad de las piezas de recambio a efectos
de establecer la responsabilidad sobre la gestin del residuo y la distribucin de costes.
Como solucin a este conflicto de intereses, se propone
establecer un principio de reciprocidad de forma que el
productor que pone los componentes en el mercado de
reposicin se ha de hacer cargo de componentes fuera de
uso (CFU) equivalente a la cantidad puesta en el mercado
nacional de reposicin.
Segn este principio, los fabricantes de piezas y componentes seran responsables de las piezas y componentes
fuera de uso equivalentes (en tipo) a las que han puesto
en el mercado, lo que no significa que sean responsables
de las mismas piezas y componentes que fsicamente han
comercializado.
Se aplicara as el principio Vendo una pieza y retiro el
residuo generado en el cambio o reparacin.
5. CONCLUSIONES
Las normativas existentes, como por ejemplo la Directiva Europea 2000/53/CE, trasladada en Espaa al RD
1383/2002 han contribuido a las mejoras tan sorprendentes obtenidas en muy pocos aos en el tratamiento de los
Vehculos Fuera de Uso. Esta normativa tiene fuertes implicaciones en toda la cadena que va desde los fabricantes de componentes y montaje de vehculos hasta las empresas desmanteladoras, pasando por los concesionarios,
talleres y por los mismos propietarios de los vehculos.
Adems otorga a los fabricantes de vehculos una serie de
obligaciones y la responsabilidad de gestionar adecuadamente los residuos al final de la vida til de los vehculos,
que han puesto en el mercado.
Es por ello que los fabricantes de automviles junto con
importadores, desguazadores y fragmentadores, han
creado durante estos ltimos aos asociaciones, como
SIGRAUTO, que han permitido cumplir con las exigencias
que Europa peda para 2006, llegar a recuperar el 85% del

peso del vehculo en su fin de vida. En Espaa, se estn
cumpliendo stas cifras gracias a la creacin de una red
de Centros Autorizados de Tratamiento conocidos como
CATs.
Adems, los fabricantes apuestan cada vez ms por medidas proactivas intentando adelantarse al cumplimiento
de futuras normativas eliminando de sus procesos de fabricacin y ensamblaje los materiales ms nocivos para
el medioambiente. En ningn momento hay que olvidar
que Europa exige para el 2015 que se reutilice y valorice
un mnimo del 95% del peso medio por vehculo y ao.
Es por ello, son necesarias nuevas mentalidades como el
diseo pensando en el reciclado donde las posibilidades
de reciclaje de los componentes pasen a ser un valor primordial previo a la eleccin y utilizacin en la cadena de
montaje. Adems, es necesario que cada automvil pueda desmantelarse de forma rpida y sencilla gracias a la
construccin modular y a tcnicas de unin que no utilicen
elementos metlicos.
El eslabn ms irregular en la cadena de reciclado es el
sector de los talleres, en parte debido a que est formado por empresas con tipologas muy diferentes, talleres
oficiales, talleres independientes, que en muchos casos
no disponen de las instalaciones ni del personal ms adecuado para organizar adecuadamente el almacenaje y la
gestin de los residuos. Se estima que los talleres mecnicos producen en un ao cerca de 75.000 toneladas
de residuos en Catalua y unas 400.000 si tenemos en
cuenta todo el territorio espaol.
Para dar respuesta a las carencias detectadas en los talleres mecnicos es necesario crear una red de recogida de
residuos formada por un gestor nico que se ocupe simultneamente de todos los residuos del taller, que ofrezca
flexibilidad y comodidad, que asesore a sus asociados
para poder estar siempre al da en los requisitos legales
y les de soporte documental, facilitando el control de la
gestin interna del taller, a la vez que minimiza y racionaliza los costes medioambientales de stos. Es conveniente crear esta red de recogida con la participacin de
otras asociaciones como SIGRAUTO que disponen ya en
la actualidad de CATs distribuidos por todo el territorio
facilitando la rpida implantacin y reduciendo los costes
iniciales.
En cuanto a la prevencin en el diseo por parte de los
fabricantes cobra una gran importancia, un ejemplo de
sto sera el futuro de los automviles donde todo apunta
hacia un cambio de tecnologa con la expansin del coche
elctrico que conllevar a su vez a una variacin de composicin respecto a los automviles actuales, con la aparicin en grandes cantidades de nuevos residuos, como las
nuevas bateras de litio o de pila de combustible.
En cuanto a los VFUs, todava se vierten demasiados residuos (cerca de un 15%) de distinta tipologa, remarcando
los plsticos y el material fragmentado final.
Hay que centrarse tambin en la recuperacin del ASR,
ya que representan el 15% en peso de un VFU. La Directiva Europea limita la valorizacin energtica en un 10% y
destina un mximo del 5% al vertedero. El estado del arte
del reciclaje especifica varios procedimientos a seguir. Por
tanto, se deber seguir investigando en los diversos mtodos propuestos.
En Espaa, as como otros pases europeos como Italia,
Dinamarca o Reino Unido, se debe introducir y mejorar el
nivel de utilizacin del ASR a las cementeras como com-
347
bustible alternativo a los fsiles actuales, corrigiendo los

problemas (por ejemplo de organoclorados) surgidos en
algunas pruebas mejorando el reciclaje de las piezas plsticas.
Por otro lado, hay que incentivar el uso de fuentes de
energa alternativa a las cementeras con incentivos fiscales o ayudas iniciales, para aprovechar en mayor grado la
capacidad tcnica de las empresas cementeras espaolas, llegando a porcentajes de utilizacin medios del 30%.
Es de gran importancia conseguir en un futuro, gracias a
las buenas prcticas y a los avances tecnolgicos aplicados por todos los agentes implicados en el sector del
automvil, el reciclado y la recuperacin de los residuos
que se generan a partir de un vehculo. Estos deben pasar
de ser vistos como un problema a ser considerados como
una alternativa medioambiental beneficiosa adems de
convertirse en una ventaja competitiva del todo rentable
para sus gestores.
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Residence time effects on the NOx

removal efficiency in two different
Dielectric barrier discharge cell
E. Len del Villar1, Julio Pedraza G2, Ivan Rodriguez R, Elena Rosa D, Nancy Lopez B .
Universidad Central Marta Abreu de las Villas
Efecto del tiempo de residencia sobre la eficacia de la eliminacin de NOx

en dos reactores diferentes de descarga de barrera dielctrica
Efecte del temps de residncia sobre leficcia de leliminaci de NOx en
dos reactors diferents de descrrega de barrera dielctrica
Recibido: 27 de enero de 2010; revisado: 21 de febrero de 2011; aceptado: 8 de marzo de 2011
RESUMEN
Las pruebas experimentales de La eliminacin de compuestos NOx se realizaron en dos reactores de descarga
de barrera dielctrica (DBD). Se estudiaron dos geometras diferentes de estos reactores, uno circular de 11,94
cm de dimetro, y otro rectangular de 16x7 cm, ambos
con una separacin de 2.5 mm y 28.0 cm3 de volumen
de reaccin. Una mezcla de gas compuesta por 1.0 l/m
de nitrgeno molecular fue inyectada a cada reactor junto
con un flujo adicional que proporcionaba una concentracin de 90 ppm de NO a las dos celdas. La mezcla del gas
fue tratada con plasma no trmico generado por descarga
de barrera dielctrica a diversos potenciales de trabajo y
a una frecuencia de 1.75 kHz. Los productos resultantes
fueron identificados por medio de un analizador de gas
Sensonic 2000. De acuerdo con los resultados experimentales, se detect una mayor eficacia de eliminacin
en el reactor rectangular que en el circular. Esto puede
atribuirse tanto al tiempo de residencia debido a efectos
geomtricos y a un factor relacionado con los mecanismos de reaccin qumica, ya que se ha demostrado que, a
potencias ms elevadas, la eficacia de la eliminacin disminuye debido a la regeneracin del NO por mecanismo
cintico inverso. Nuestro modelo cintico demuestra que
el producto principal de la reaccin era N2O en presencia
de una atmsfera reductora.
Palabras clave: Descarga de barrera dielctrica; plasma
fro; plasma no-trmico (NTP); Descarga silenciosa, plasma de no-equilibrio
ABSTRACT
Experimental tests of the removal of NOx compounds
were carried out in two dielectric barrier discharge cells
(DBD) reactors. Two different geometries of these reactor
were studied, one circular 11.94 cm diameter, and another
rectangular, 16x7 cm, both 2.5 mm gap and 28.0 cm3 reaction volume. A gas mixture composed of 1.0 l/m of molecular nitrogen was injected to each reactor along with an
additional flow that provided a concentration of 90 ppm of

NO in both cells. The gas mixture was treated with non
thermal plasma generated by dielectric barrier discharge
at different working potentials and at a 1.75 kHz frequency.
The residual products were identified by means of a Sensonic 2000 gas analyzer. According to the experimental
results, it was identified a greater removal efficiency in the
rectangular cell than in the circular one. This might be attributed both to residence time due to geometric effects
and to a factor related with the chemical reaction mechanisms, since it has been showed that, at greater powers,
the removal efficiency diminishes due to the regeneration
of NO by inverse kinetic mechanisms. Our kinetic model
proves that the main reaction product was N2O in the presence of a reducing atmosphere.
Keywords: Dielectric Barrier Discharge; cold plasma; nonthermal plasma (NTP); Silent Discharge, Nonequilibrium
plasma
RESUM
Les proves experimentals de leliminaci de compostos
NOx es van realitzar en dos reactors de descrrega de
barrera dielctrica (DBD). Es van estudiar dues geometries diferents daquests reactors, un circular d11,94 cm de
dimetre, i un altre rectangular de 16x7 cm, tots dos amb
una separaci de 2.5 mm i 28.0 cm3 de volum de reacci. Una barreja de gas formada per 1.0 l/m de nitrogen
molecular es va injectar a cada reactor juntament amb un
flux addicional que proporcionava una concentraci de 90
ppm de NO a les dues celles. La barreja del gas va ser
tractada amb plasma no trmic generat per descrrega
de barrera dielctrica a diversos potencials de treball i a
una freqncia d1.75 kHz. Els productes resultants van
ser identificats per mitj dun analitzador de gas Sensonic 2000. Dacord amb els resultats experimentals, es va
detectar una eficcia deliminaci ms elevada en el re*Correponding author: 1eliledvi14mx@yahoo.com.mx ;
2juliop@uclv.edu.cu
349
actor rectangular que en el circular. Aix pot atribuir-se

tant al temps de residncia a causa defectes geomtrics
com a un factor relacionat amb els mecanismes de reacci qumica, ja que sha demostrat que, a potncies ms
elevades, leficcia de leliminaci disminueix a causa de
la regeneraci de NO per un mecanisme cintic invers. El
nostre model cintic demostra que el producte principal
de la reacci es N2O en presncia duna atmosfera reductora.
Paraules clau: Descrrega de barrera dielctrica; plasma fred;plasma no-trmic (NTP); Descrrega silenciosa,
plasma de no-equilibri.
1.- INTRODUCTION
Recent applications of non-thermal plasma (NTP) in processes of decontamination of gas flows are a new promising technique. The main characteristic of these degradation processes lies in not increasing the temperature of the
gas[1] while boosting its removal efficiency to values above
99% without generating polluting by-products.
The cold plasma generated by means of dielectric barrier
discharge, is carried out by a collection of short lived filaments or streamers distributed at random on the dielectric surface. It`s into the streamers that the plasma generation process is made because each channel of excited
gas molecules contains very reactive species such as high
energy electrons and free radicals[2], that interact with the
gas molecules resulting as the process of decomposition
of the polluting molecules through diverse reaction mechanisms. The generation of the free radicals is very important since the recombination of compounds of the type
NOx to low concentrations[3, 4, 5].
2. EXPERIMENTAL SETUP
The NO chemical reduction was made using N2 as a carrier
gas. The initial concentration of NO was varied between 85
and 95 ppm with a total gas flow of 1.0 l/min. The experimental diagram is presented in figure 2. The gas mixture
was directly introduced to the reactor. The initial concentration and that at the end were measured with a Sensonic
2000 gas analyzer.
Two types of reactor geometry were tested: one rectangular and a circular. Both geometries follow a flat configuration of parallel electrodes.
electrodos
del sistema de
Potencia
dielctricos
gap
al analizador
de gases
Deshidratador
al sistema de
seal electrica
Mezclador
Controladores
de flujo
Tanques de gas
Figure 2 .- Gas supply system experimental set up
In the circular geometry (fig 3) the diameter was 11.94 cm

and the gas gap 2.5 mm.
Figure 1.- Dielectric barrier discharge

Figure 3 .- Metal - water circular DBD cell
We used a lacking oxygen gas mixture system except for

that removed from the molecule of NO. Such an atmosphere is totally reducing and allows the NO to recombine
in its molecular components, N2 and O2.
NO removal experiences have been developed in gas
flows as a dielectric barrier discharge (DBD) application.
The design will be presented at the experimental part. The
main objective to use two cell configurations it was to determine which offers the best removal efficiencies and the
way in which it can taken better advantage during processes of decomposition of NOx compounds .
350
The reaction volume in it was 28 cm3 The rectangular geometry dimensions were 16 cm x 7cm, 2,5 mm gas gap
and a reaction volume of 28 cm3 too. The power was provided by a high voltage transformer which is fed by halfbridge high frequency inverter[6,7].
The electric diagnostics in the plasma generator was performed by a Tektronics oscilloscope TDS 2014. The voltage in the dielectric barrier discharge was measured with a
high voltage P601A probe from tektronics while the current
in the discharge was gauged using a 0.11.0 W, 1.0V/A,
transformer from Pearson Electronics.
The experimental power in the cell during a dielectric

barrier discharge cycle was calculated from the accumulated charge and the voltage output according to Q-V
Lissajous figure [8] [9] to determinate dielectric charge,
Qdie=Cdie*Vdie, specific energy E=P/Q [joules/l] and the
CDBD power supply P=2*Qdie*Venc*f. , where Qdie is the
dielectric charge[coulombs], Vdie is the dielectric voltage
[Volt], Venc is the ignition voltage[V], P is the consumed
DBD cell power and Q is the gas flow [l]
3. CHEMICAL KINETICS
In the absence of O2 NO was most likely chemically reduced to N2 by N atoms as described by reaction 5 and 6
of table 1. The main reactions pathways for NO removal
were generated by electron impact dissociation of N2 (reaction 1 y 2 table 1) Although the process consider more
than 15 species and 50 reactions we only include in table
1 some reactions for NO removal in order to describe the
evolution of the excitation and ionization species produced
in the N2-NO mixture.
Some of these reactions are presented in table 1. (e, O,
N, N2(X, O2, N2(A), O2(a), NO, NO2, N2O, O3, N2(D), N2(C),
Where N2(X), N2(A), and N2(C), refers to the ground level
molecules and the electronically excited molecules
and
, respectively.
(a) represents the electronically excited state.
.
The reaction rates collected from literature and the respective references are given in table 1. We assumed an initial
electron density which is a most typical value in
DBD processes.
Table 1 Main chemical reactions process NO removal in DBD cell.
Reaccin
Ref
10
e+N2 e + N2(A)
e +N2 e + N + N
10
e +O2 e + O2(a)
10
e +O2 e + O + O
10
N + NO N2 + O
11
11
N + NO2 N2 + O2
NO + NO2 N+O+NO
11
N + NO2 N2 + O + O
11
11
N + NO2 N2O + O
10
N + NO2 NO + NO
11
11
O + NO2 NO + O2
11
12
O + O3 O2 + O2
11
13
NO + O3 O2 + NO2
11
14
N + O + N2 NO + N2
11
15
N+O+O2NO+O2
11
16
O + O2 + N2 O3 + N2
11
17
O + NO + N2 NO2 + N2
11
18
O + NO + O2 NO2 + O2
11
19
O + NO + NO NO2 + NO
12
20
O + NO + NO2 NO2 + NO2
12
21
O + NO + N2O NO2 + N2O
12
22
N2(A) + O2 N2 + O + O
13
23
N2(A) + O2 N2O + O
13
14
24
N2(A) + O2 N2 + O2(a)
25
N2(A) + N2O N2 + N + NO
13
26
N2(A) + N2 N2 + N2
13
27
N2(A) + NO N2 + NO
14
28
O2(a) + O O2 + O
15
29
O2(a) + O2 O2 + O2
15
30
O2(a) + O3 O2 + O2 + O
15
31
O2(a) + N NO + O
15
32
O2(a) + N2 O2 + N2
15
33
O2(a) + NO O2 + NO
12
34
N2(A) + O N(2D) + NO
12
35
N2(D) + NO N2O
12
36
N2(D) + N2O NO + N2
12
37
N2(A) + N2(A) N2(C)+N2(X)
12
351
Some first order ordinary differentials equation set had

been developed using the Rosenbrocks algorithm which
is a trustworthy integrator for stiff differential equations
and it has been possible to trace the temporary evolution
of the species. Due the value of the concentrations is initially set to zero for all the species except for NO, where an
equal 0.01N concentration is assumed along with a 0.99N
one for N2. Here, N is the total density at the atmospheric
pressure.
4. RESULTS AND DISCUSION

4.1 Eficiency, Power, Electrical field and Specific Energy
The results of the experimental power are shown in table
2. The discharge was carried out in the N2-NO mixture at a
1.0 l/min flow rate and several voltages peak to peak from
4.25 to 5.25 kV, with a fixed frequency of 1.73 kHZ practically constant.
Figure 5 .- Metal water DBD plasma formed by filaments
4.2 NO Reduction
Calculations of the composition evolution as a function of
time were made at 170, 165, 210 y 200 Td (table 2), since
NO removal in function of the reduced electric field. In
figure 6 the NO deflection is observed at the point where
the atomic nitrogen
De-NOx Rect 16x7 Feb 21-06; 1.0 l/m N2+NOx, NO=68 y 90 ppm, 110V a 160V,
f=1.76kHZ
90
75
ppm
60
45
30
15
0
0
0,5
1,5
2,5
3,5
t en min
Circ CH 90ppm NO,120V
Rect ch 90ppm,120V
Circ ch 90ppm, 140V
rect ch 90ppm,140V
Figure 4.- Q-V Diagram 1 l/min, 90 ppm , 140V

Figure 6: Temporary variations of species
Table 2: Electric characteristics
DBD cell
Circular
Rectangular
Applied Voltage(V)
120
140
120
140
Vi (Ignition voltage volts)
4.25
4.13
5.25
5.0
E (Electrical
Field kV/cm)
17
16.5
21
20
P (Power supply J/s)
18.6
16.7
14.7
36.8
E Specific energy J/l)
0.30
0.28
0.21
0.62
Er (Reduced E td)
170
165
210
200
In figure 5, the metal-water electrodes discharge is observed during a removal of NOx. in the circular cell A white
area can be appreciated on the gas inlet.
concentration grows. The NO removal is dominated by

the reaction 8 to10 of table 1. The increment of atomic
oxygen is also observed. The radical N is formed by the
dissociation of molecular nitrogen. N+NON2+O
ki = 1.7x10-11 cm3/s to 300K
At once, the atomic oxygen will contribute to the formation of NO2, following mechanisms 17 and 18 of table 1.
Yet, this reaction will be limited by the quantity of atomic
oxygen
O+NO+N2NO2+N2 ki = 6.34x10-32 cm6/s to 300 K
O+NO+O2NO2+O2 ki = 6.34x10-32 cm6/s to 300 K
At higher energies, the nitrogen excited states of atoms
and molecules begin to be important: the N2O is diminished by the reaction 36.
N(2D) + N2O NO + N2 + ki = 3.0x10-12 cm3/s to 300 K
the NO removal is increased with the reduced electric field
We can see in table 2 the efficiency reduction on NO removal al high reduced field
352
4.3.- NO Experimental Reduction

A 1.0 l/min NO + N2 gas mixture flow was fed in a DBD cell
of parallel plates of circular and rectangular geometry and
the voltage repetition rate was 1.75 kHZ.
The evolution of the NO removal by cold plasma application is shown in figures 6 Since the gas analyzer registered
the data every 6s, it was possible to follow the temporary
evolution as closely as in figure 4 approximately for 6.0 min
sampling in detecting the concentration change. A delay
time is taken before begin the NO removal and after only
few seconds an abrupt degradation is carried out For 90
ppm 120V the NO degradation began 30s after the voltage
is started and after 75s (1.7 min) the removal efficiency
reach the maxim efficiency. For 140 V a higher efficiency
was reached faster (1 min)
Table 3. Eficiencies Denox,s
90ppm,120V, celda circular
Lect
min
Lec in
Lec out
en %
10
92
42
54.35
20
92
97.83
30
92
98.91
40
92
and the electrical energy is consumed in electrical impacts

reaction with N2 mainly via reduction by the radicals N
The N2 dissociation is function of E/N so the input electrical energy is consumed in electron impact reaction with N2.
Higher removal efficiencies were obtained in the rectangular geometry than in the circular geometry. This
might be attributed to the residence time due to geometry
of the cells and a factor related with the chemical reaction mechanisms since it has been showed that at greather
residence time the removal efficiency diminishes due the
regeneration of NO o the production of NO by NO2 dissociation. The reduction rate increase when the voltage is
applied and it is in a very sharp form but NO2 production
increase too so NOx,s removal efficiency decrease for longer treatment time. The efficiency in the circular cell never
increase upper 99% otherwise decrease with the time This
might be explained due the resident time that into de circular cell al least it is 2.0 time than into the rectangular
because the inlet flow gases is very near the outlet flow
gas so part of the treated gas remain more time and is
subjected to the DBD discharge again.
The chemical reduction allowed to determine the presence of N2O among the final compounds produced by the
decomposition of NO2. Mass spectrometry has confirmed
the presence of these species.
98.91
6. ACKNOWLEDGMENTS
90ppm,120V, celda Rectangular

Lect
min
Lec in
Lec out
en %
10
92
80
13.04
20
92
100.00
30
92
100.00
40
92
100.00
90ppm,140V, celda circular

Lect
min
Lec in
Lec out
en %
10
87
87
87
97.70
40
87
1.
97.70
30
BIBLIOGRAPHY
98.85
20
I wish to express my gratefulness to Antonio Mercado C,

Regulo Lpez C, Mireya Gonzales Colin, Raul venancio
Godoy and Cuauthmoc Gutierrez R for their technical assistance in the accomplishment of this work.
97.70
2.
90ppm,140V, celda rectangular

Lect
min
Lec in
Lec out
en %
10
93
100.00
20
93
100.00
30
93
100.00
40
93
100.00
3.
4.
Table 3 presents the removal efficiency in power function
for 1, 2, 3 and 4 min after the voltage was applied and
after the equipment detects the first NO concentration
change. These results were obtained from registered dates
and evolution graphic of figures 4
5.
5. CONCLUSIONS
6.
We have carried out these experiments using a circular
and a rectangular DBD cell For dilute amounts of NO in N2
the overall removal is determined by only a few reaction
G. Anderson, L. Bechotold, A. Greene, H. Heck, M.

Kang, R. Tennant, R. Vargas and P. Wantuck, 1992,
Two discharge silent plasma/Packed-Bed Reactor Waste Treatment Test Bed, Report to LANL Advanced Waste.
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Program
(FY92
activities
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U. Kogelschatz, 2003, Dielectric-barrier discharges:
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B. M. Penetrante, M. C. Hsiao, B. T. Merritt, G. E.
Vogtlin, P. H. Wallman, 1995, Comparison of electrical discharge techniques for nonthermal plasma
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[H. H. Kim, G. Prieto, K. Takashima, S. K. Katsura, A.
Mizuno, 2002, Performance evaluation of discharge
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Y.H. Lee, J.W. Chung, Y.R. Choi, J. S. Chung, M. H.
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137 154.
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Vol. 87 N 3, pp. 361 376.
7. O. G. Godoy-Cabrera, R Lpez-Callejas, A MercadoCabrera, S R Barocio, R Valencia, AMuoz-Castro, R
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354
Remediacin electrodialtica de
suelo contaminado con cobre
Claudia Gutirrez, Henrik K. Hansen*, Catalina Gonzalez
Departamento de Ingeniera Qumica y Ambiental,Universidad Tcnica Federico Santa Maria, Casilla 110V, Valparaso, Chile
Electrodialytic remediation of soil contaminated with copper

Descontaminaci electrodialtica de sl contaminat amb coure
Recibido: 12 de marzo de 2010; revisado: 19 de noviembre de 2010; aceptado: 3 de diciembre de 2010
Resumen
Hoy en da existe preocupacin por la gran cantidad de
desechos que genera la actividad minera, dentro de los
cuales se encuentran los metales pesados. El presente
trabajo consiste en la realizacin de un total de 6 experiencias de remediacin electrodialtica, considerando
variables operacionales como duracin del tratamiento,
intensidad de la corriente aplicada y aplicacin de pulsos
elctricos, a fin de evaluar la aplicabilidad de la tcnica de
remediacin electrodialtica en un suelo proveniente de la
Ex Minera Montecarmelo, 5 Region, Chile, que se encuentra contaminado con metales pesados.
Al comparar los resultados, se concluy que la mejor opcin para realizar un tratamiento electrodialtico al tipo de
suelo estudiado, es por medio de pulsos con un rgimen
bajo; si bien esta experiencia en este trabajo no fue la que
obtuvo la mayor remocin, fue la segunda mejor, con un
valor de remocin de cobre del 24,7 % muy cercana a la
mejor y por otro lado tubo la mejor eficiencia de corriente
elctrica, con un valor del 2,3 %.
Palabras clave: remediacin electrocintica, suelo contaminado, metales pesados, cobre, campo elctrico.
SUMARY
Nowadays there is a concern over the large amounts of
waste generated by mining activities - typically including
high heavy metal content. The present work consists of
carrying out a total of 6 electrodialytic remediation experiments, considering operational variables such as duration
of treatment, intensity of the applied current and application of electrical pulses. This is done in order to assess
the applicability of the technique when treating soil from
the former copper mining site Montecarmelo, 5th Region,
Chile, which is contaminated with heavy metals.
Comparing the obtained results, it could be concluded that

the best electrodialytic treatment option for the soil type
studied, is when applying low frequency pulses; although
in this work the experiment, which had the second highest
copper removal (24,7% of copper) could be considered as
the best experiment with respect to copper current efficiency (2,3%).
Key words: electrokinetic remediation, contaminated soil,
heavy metals, copper, electric field.
RESUM
Avui en dia, hi ha preocupaci per la gran quantitat de
deixalles que genera lactivitat minera, dins de les quals
es troben els metalls pesants. En el present treball, es
realitza un total de 6 experincies de descontaminaci
electrodialtica, considerant variables operacionals tals
com la durada del tractament, la intensitat del corrent
aplicat i laplicaci de polsos elctrics, per tal davaluar
laplicabilitat de la tcnica de descontaminaci electrodialtica en un sl provinent de la Ex Minera Montecarmelo, 5
Regi, Xile, que es troba contaminat amb metalls pesants.
En comparar els resultats, es conclou que la millor opci
per a realitzar un tractament electrodialtic al tipus de sl
estudiat s mitjanant polsos amb un rgim baix. Tot i que
en aquest treball aquesta experincia no ha estat la que ha
comportat la major descontaminaci, nha estat la segona
millor, amb un valor deliminaci de coure del 24,7%, molt
propera a la millor; a ms, ha assolit la millor eficincia de
corrent elctric, amb un valor del 2,3%.
Mots clau: descontaminaci electrocintica, sl contaminat, metalls pesants, coure, camp elctric.
* Autor de correspondencia: henrik.hansen@usm.cl; tel.
+56 322654030, Fax: +56 322654278
355
1.Introduccin
Durante dcadas, la minera del cobre ha tenido un rol importante en la economa de Chile, por ser ste uno de los
principales productores de cobre a nivel mundial [1]. Durante el procesamiento y concentracin de los minerales
sulfurados de cobre, se produce un volumen considerable
de residuos lquidos, slidos y gaseosos que contienen
metales pesados, muchos de ellos con un elevado potencial txico [2]. Los metales pesados no son ni qumica ni
biolgicamente degradables y se acumulan en el ambiente durante largos periodos de tiempo.
La remediacin de sitios contaminados con metales, puede realizarse a travs de mtodos fisicoqumicos, trmicos
y/o biolgicos. Una tcnica de remediacin de suelos contaminados con metales pesados es la electroremediacin
[3-5]. Esta tcnica se basa en la aplicacin de una corriente continua de baja intensidad a travs de dos electrodos
insertados en una celda electroqumica que contiene el
suelo a tratar. De este modo se genera un campo elctrico
que provoca el transporte (principalmente mediante electrosmosis e intercambio inico) de las especies inicas
cargadas hacia el electrodo de carga opuesta, de modo
de obtener un suelo libre de contaminantes. Una mejora
en la electro-remediacin es la denominada remediacin
electrodialtica, que combina la electro-remediacin con el
uso de membranas de intercambio inico, evitando que
los productos resultantes de las reacciones en los electrodos penetren en el suelo, mejorando de esta manera, las
eficiencias en la remocin [6,7]. Con la remediacin electrodialtica se ha removido cobre desde residuos mineros
pero utilizando reactivos qumicos para promover la disolucin de los minerales con cobre [8].
El objetivo de este trabajo es aplicar una tcnica de remediacin electrodialtica a una muestra de suelo contaminado con metales pesados, para evaluar tanto la aplicabilidad as como la eficiencia de remocin que presenta
esta tcnica en un tipo determinado de suelo. Para ello
se realizar un conjunto de experiencias de laboratorio,
considerando las siguientes variables: intensidad de corriente aplicada, tiempo de remedicin y aplicacin de pulsos elctricos. Los experimentos se llevarn a cabo sin la
adicin de compuestos qumicos al suelo para no afectar
las caractersticas del suelo tratado y as evitar el deterioro
de sus propiedades y funciones.
2. Antecedentes
La electro-remediacin es una tcnica fsico-qumico basada en un proceso electroqumico, en donde un campo
elctrico es generado por la aplicacin de una corriente
o un voltaje directo a travs de dos electrodos inertes
(nodo y ctodo) insertos en una celda electroqumica. La
aplicacin de un campo elctrico genera cambios fsicoqumicos e hidrolgicos en el suelo, induciendo el transporte de las especies contaminantes en funcin de su carga elctrica, hacia el nodo o el ctodo [4,5].
En la remediacin electrocintica los electrodos (nodo
y ctodo) son aplicados directamente en el suelo; una
mejora a este mtodo de remediacin, es la remediacin
electrodialtica que incorpora la utilizacin de membranas
de intercambio inico, para evitar que los productos generados en los electrodos entren en contacto con el suelo
durante el tratamiento [6]. De este modo, el objetivo de las
356
membranas es aislar al suelo en tratamiento, de las especies generadas en los electrodos producto de la reaccin
de electrolisis, pero permitir el paso de las especies contaminantes desde el suelo hacia las soluciones presentes
en las cmaras andicas y catdicas. La Figura 1 describe
un sistema de remediacin electrodialtica.
Por otro lado, la aplicacin de un campo elctrico externo
provoca la orientacin y distribucin de las especie qumicas en funcin del campo aplicado, crendose un dipolo
inducido, de forma que se genera un proceso de polarizacin en la misma direccin del campo externo aplicado[8]. El fenmeno de polarizacin genera que el suelo
acte como un elemento capacitor, almacenando energa
en forma de un campo elctrico. Lo anterior produce una
disminucin en el transporte de iones y por consiguiente, una disminucin en la eficiencia de remocin de contaminantes. Una manera de disminuir la polarizacin del
sistema y los efectos capacitivos del suelo, es mediante
la aplicacin de un campo elctrico en forma de pulso,
que consiste en la aplicacin de una corriente elctrica en
intervalos de tiempo [10].
En este trabajo, la remediacin electrodialtica de suelos
utiliza un nivel bajo de corriente directa, del orden de mili
amperes por centmetro cuadrado (mA cm-2) de una seccin transversal de suelo, para transportar y remover especies desde el suelo. Para poder evaluar la eficiencia de
la remediacin electrodialtica se calcularn parmetros
tales como, concentracin relativa de cobre, eficiencia de
remocin de cobre y eficiencia de corriente.
3. Materiales y Mtodos
3.1. Materia Prima
Para el desarrollo de este trabajo se utiliz una muestra de
suelo proveniente de la Ex Minera Montecarmelo, ubicada
en la comuna de Puchuncav, Regin de Valparaso, Chile.
Se extrajeron 10 [kg] de suelo desde la superficie del terreno, desde cuatro puntos diferentes, seleccionados al azar.
Posteriormente, las muestras provenientes de cada uno
de estos puntos fueron mezcladas hasta lograr una nica
muestra homognea. La muestra de suelo present una
concentracin promedio de cobre de 419 27 [mg kg-1
peso seco], valor que es superior al valor de intervencin
de 190 [mg kg-1 peso seco] indicado por el Ministerio de
Medio Ambiente de los Pases Bajos [11]. Estos valores de
intervencin se utilizan actualmente en Chile como referencia en caso de contaminacin de suelo.
3.2. Reactivos
Agua destilada, cido sulfrico (H2SO4) 95 % y cido ntrico (HNO3) 65% - grado analtico.
3.3. Equipos
El tratamiento electrodialtico del suelo contaminado con
metales pesados se llev a cabo en una celda de acrlico,
el diagrama se muestra en la Figura 1. El suelo a tratar se
introdujo en el compartimiento central, con dimensiones
de 15 [cm] de largo, 8 [cm] de dimetro interno, y 1 [cm] de
espesor. Cada extremo de la cmara contenedora se uni
mediante tornillos a una cmara de electrodo (una cmara
andica y una catdica), de 4 [cm] largo cada una.
Se utilizaron electrodos de titanio, los cuales se insertaron
en las cmaras de electrodo respectivas, sumergidos en
agua destilada. Entre el suelo y los compartimientos ca-
tdico y aninico se colocaron membranas de intercambio inico, en la zona del ctodo se utiliz una membrana
de intercambio catinico marca Ultrex modelo CMI-7000,
mientras que en la zona andica se utiliz una membrana
de intercambio aninico marca Ultrex AMI-7001.
Para poder administrar una corriente constante al circuito de la celda y registrar los datos en un computador, se
conect la celda a un adquisidor de datos modelo UT60A
y a una fuente externa de poder marca Hewlett Packard
E3612A 60/120 [V], 0.5/0.25 [A]. Cuando se trabaj con
pulsos, adems se utiliz un programador de pulsos.
3.4. Mtodos analticos
3.4.1. Anlisis granulomtrico
El anlisis granulomtrico se realiza pesando 4 muestras
de 0.5 [kg] cada una, de suelo seco; se colocan los tamices apilados y cargados con 0.5 [kg] de suelo, se agitan
los tamices durante 20 [min] y se pesan las fracciones en
los tamices. El procedimiento anterior se realiza con las 4
muestras.
3.4.2. Medicin de pH
La medicin de pH se realiz mediante el estndar SW846 Mtodo 9045 de la US-EPA que define pH en lquidos
y slidos.
3.4.3. Determinacin de cobre total
La determinacin del cobre total, se realiz segn el estndar dans N 259 que define Determinacin de Metales Pesados en aguas, lodos y sedimentos, pautas generales para la determinacin por Espectrofotomtrica de
Absorcin Atmica AAS.
3.5. Preparacin y caracterizacin final de la muestra
Se toma una muestra de suelo de entre 1400 y 1500 [g]
y se le agrega agua destilada para preparar una masa
homognea con un 20% de humedad, la que posteriormente se introduce en la celda de acrlico para llevar a
cabo el tratamiento electrodialtico. Una vez finalizado el
tratamiento, el suelo tratado es extrado de la celda y es
dividido en seis partes similares, iniciando desde la zona
catdica, tal como se muestra en la Figura 1.
Cada una de las fracciones obtenidas es llevada al horno
durante 24 [h] a 100 [C] para el secado de la muestra, una
vez seca y fra la muestra es molida para luego realizar la
medicin de pH y cobre total, segn los procedimientos
mencionados anteriormente. Todos los procedimientos
realizados durante la fase experimental de este trabajo se
realizan en duplicado.
Cmara contenedora
15 [cm]
1 [cm]
Cmara
catdica
4 [cm]
Cmara
andica
8 [cm]
4 [cm]
Ctodo
Centro
Membrana de
intercambio catinica
nodo
Membrana de
intercambio aninica
Figura 1. Esquema celda electrodialtica utilizada, se indican

las particiones realizadas al suelo luego del tratamiento.
3.6. Planificacin Experimental

En el desarrollo de este trabajo, se planificaron un total
de seis experiencias de remediacin electrodialtica. De
estas seis experiencias, cuatro se realizaron a una corriente constante y las dos ltimas se realizaron mediante la
aplicacin de un campo elctrico pulsado. La Tabla 1 presenta las condiciones experimentales utilizadas para cada
una de las experiencias realizadas durante la fase experimental de este trabajo.
4. Resultados y discusin
4.1. Anlisis Granulomtrico
Con el anlisis granulomtrico se concluy, segn el Sistema Unificado de Clasificacin de Suelos, SUCS [12]
que el suelo utilizado para este estudio, corresponde a un
suelo grueso tipo arena, que vara entre arena arcillosa o
arena limosa, dependiendo de los parmetros de lmites
de plasticidad y lmite lquido.
4.2. pH
Un factor fundamental en el tratamiento electrocintico es
el pH, debido a que este parmetro determina el grado de
adsorcin de iones por las partculas del suelo, afectando
as su solubilidad, movilidad, disponibilidad y formas inicas de un contaminante y otros constituyentes del suelo. La solubilidad de muchos contaminantes inorgnicos
cambia en funcin del pH y normalmente su movilidad
disminuye con valores altos de pH.
La Tabla 2 expone los resultados obtenidos de las mediciones de pH para cada una de las experiencias realizadas.
Se incluye el valor de pH antes y despus del tratamiento
electrodialtico aplicado, en funcin de las diferentes secciones de suelo estudiadas. La nomenclatura utilizada, es
la misma que se present en la Figura 1, donde 1 corresponde al ctodo y 6 corresponde al nodo.
De la Tabla 2, se puede observar que existe una variabilidad del pH durante el tratamiento electrocintico, observndose una acidificacin del suelo hacia la zona andica.
Esta acidificacin tiene su fundamento en la generacin de
protones en la interfase suelo membrana aninica, debido
a la deficiencia de flujo de aniones desde el suelo hacia la
superficie de la membrana aninica para transportar la corriente aplicada. Esta acidificacin del suelo es favorable
para el tratamiento aplicado, ya que facilita la desorcin
de las especies inicas presentes en el suelo. Se observa de los perfiles de pH de cada una de las experiencias
que en la zona catdica se produce un aumento del pH
con respecto al valor inicial, excepto en la experiencia 6,
donde el pH final baj levemente con respecto al original.
Debido a que en todas las experiencias se utilizaron membranas de intercambio inicas, el aumento de pH por
sobre el valor de pH inicial en las cercanas de la zona
catdica no debiera ocurrir, ya que, en teora, el uso de
una membrana intercambio catinico impide el paso de
iones OH- desde la solucin electroltica hacia la muestra
de suelo tratada, y por tanto el pH de la zona catdica
nunca debiera superar el valor de pH inicial. Esto indica,
que la corriente de lmite se sobrepas como registrado en
casos similares [13].
4.3. Concentracin de cobre
La Tabla 3 expone los resultados obtenidos de las concentraciones de Cu y masas para cada una de las partes
357
Tabla 1. Planificacin Experimental.

Parmetro
Exp 1
Exp 2
Exp 3
Exp 4
Exp 5
Duracin ensayo [das]
12
Exp 6
7
Masa suelo tratada (peso seco) [kg]
1.5
1.5
1.4
1.4
1.4
1.4
Humedad del suelo % peso
20
20
20
20
20
20
Caracterstica
CC
CC
CC
CC
CEP
CEP
Corriente [mA]
10
20
10
30
10.5
11
Tiempo con corriente (ton) [min]
100
100
Tiempo sin corriente (toff) [min]
10
Tiempo ciclo (ton+toff) [min]
105
110
Rgimen de Pulso (ton/toff)
20
10
CC equivale a Corriente Constante. CEP equivale a Campo Elctrico Pulsado. (-) No aplica
Tabla 2. Mediciones de pH en las distintas experiencias realizadas.

pH final segn parte
Experiencia
pH0
6.9
7.0
6.1
6.1
6.0
5.2
3.6
6.7
7.6
5.9
5.9
4.7
3.6
3.3
6.8
7.7
6.1
6.3
6.1
4.2
3.5
6.8
9.0
6.2
4.3
3.7
3.6
3.5
6.8
8.1
6.4
6.4
6.2
5.3
3.4
6.8
6.5
6.4
6.1
6.1
5.3
3.5
pH0 indica el pH inicial de la muestra slida antes de llevar a cabo el tratamiento.
Tabla 3. Concentraciones de cobre y masas obtenidas en cada experiencia.

Distribucin de masa final
EXP
Cu Total
Inicial
[mg kg-1]
Masa
Suelo
Inicial [g]
Ctodo
Cu Total [mg kg-1]
Centro
Masa Suelo [g]
Cu Total [mg kg-1]
nodo
Masa Suelo [g]
Cu Total [mg kg-1]
Masa Suelo [g]
Parte 1
Parte 2
Parte 1
Parte 2
Parte 3
Parte 4
Parte 3
Parte 4
Parte 5
Parte 6
Parte 5
Parte 6
428.6
1272.8
489.3
375.3
218.0
191.1
395.5
439.7
206.4
208.3
406.5
325.6
203.8
245.3
428.1
1219.1
507.2
476.3
193.5
207.6
469.4
417.8
207.0
201.6
369.7
321.5
168.7
240.8
413.1
1287.7
541.6
464.2
220.5
209.0
343.9
421.2
203.3
209.2
325.0
302.6
209.9
235.8
425.7
1248.5
519.3
490.0
233.4
211.4
392.0
326.7
192.9
198.1
316.4
307.8
178.0
234.6
409.7
1218.7
521.0
471.1
167.0
171.8
455.6
405.8
191.1
229.2
335.3
314.6
258.0
201.6
413.5
1252.8
545.0
481.4
223.5
220.9
421.2
373.1
190.7
189.2
319.8
302.6
213.4
215.1
Tabla 4. Eficiencia de remocin y de corriente.
EXP
Concentraciones ponderadas
de cobre por zona [mg kg-1]
Ctodo
Centro
Concentraciones relativas de cobre por zona
nodo
Ctodo
Centro
nodo
1.02
0.97
0.85
Eficiencia de
remocin de cobre
seccin
andica %
15.5
6032
1.50
12137
0.89
Carga
total [C]
Eficiencia de corriente
seccin andica %
436.0
417.7
362.3
491.2
443.9
341.4
1.15
1.04
0.80
20.3
503.9
383.1
313.1
1.22
0.93
0.76
24.2
10446
1.30
505.4
358.9
311.5
1.19
0.84
0.73
26.8
18207
0.79
1.21
1.05
0.80
20.4
5845
1.99
0.75
24.7
5835
2.28
495.7
428.4
326.2
513.4
397.3
311.2
358
1.24
0.96
para cada experiencia realizada. Con los resultados de la

Tabla 3, se pueden calcular las concentraciones ponderadas de cada zona, las concentraciones relativas por zona,
la eficiencia de remocin de cobre en la zona andica y la
eficiencia de la corriente, y esto se presenta en la Tabla 4.
En base a lo presentado en la Tabla 4, se puede observar
que existe una tendencia creciente de los valores de concentracin relativa a medida que se avanza hacia la seccin catdica. Esto indica que, en la zona andica, todas
las experiencias lograron una remocin de cobre, mientras
que en la zona catdica se produjo una acumulacin de
cobre proveniente de la zona central y andica.
En la Tabla 4, tambin se puede ver que las eficiencias
de corriente calculadas son bajas, esto es un indicador
de que slo una parte de la corriente aplicada al sistema
se utiliz para el transporte del in Cu+2. El resto de la corriente se pudo haber perdido debido al transporte de H+ y
otras especies qumicas presentes en el suelo, las cuales
no fueron medidas en este estudio.
4.3.1. Efecto de la intensidad de corriente
Para estudiar el efecto de la intensidad de corriente aplicada se compararn las remociones de cobre obtenidas
en las experiencias 1, 2 y 4, como se muestra en la Figura
2. Queda demostrado mediante el anlisis de la Figura 2,
que existe una relacin inequvoca entre la intensidad de
corriente y las eficiencias de remocin en la zona andica, encontrndose la mxima eficiencia de remocin en
la zona andica en la experiencia 4, donde se aplic una
corriente de 30 [mA] durante 7 das consecutivos. Por otro
lado si se observan los resultados presentados en la Tabla
4, se puedes ver que esta experiencia es la que tiene la
menor eficiencia de corriente, y la que presenta la mejor
eficiencia de corriente corresponde a la experiencia 1 en
la cual se utiliz el menor valor de corriente elctrica aplicado al sistema y se obtuvo el valor menor de eficiencia
de remocin andica.
Pese a que en todas las experiencias hubo una migracin
de cobre desde el nodo hacia el ctodo, las intensidades
de corriente aplicada no fueron suficientes para que el cobre migre en su totalidad hasta la seccin catdica.
en la seccin andica, obtenindose la mxima eficiencia

de remocin cuando la duracin de la experiencia es de
12 das. Si adems se compara las concentraciones relativas por zona, como se muestra en la Figura. 4, se nota
que en la zona catdica aumenta la acumulacin de cobre,
mientras que en la zona central y andica se produce un
aumento en la remocin de cobre a medida que aumenta
la duracin del tratamiento. Por otro lado si se observan
los resultados presentados en la Tabla 4, se puede ver que
las eficiencias de corriente son muy similares, siendo un
ligeramente mayor la eficiencia de corriente de la experiencia 1.
Figura 3. Eficiencias de remocin en seccin andica segn

la duracin del tratamiento electrodialtico aplicado.
Figura 4. Distribucin del cobre segn

la duracin del tratamiento.
Figura 2. Eficiencias de remocin en seccin andica segn la intensidad de corriente aplicada.
4.3.2. Efecto de la duracin del tratamiento

Para ver el efecto de la duracin del tratamiento se compararn las remociones de cobre obtenidas en las experiencias 1 y 3, como se muestra en la Figura 3. De la figura
se observa que existe una relacin directa entre la duracin del tratamiento y la eficiencia de remocin de cobre
4.3.3. Efecto de la duracin e intensidad del tratamiento

Para ver el efecto de la duracin e intensidad del tratamiento se compararn las remociones de cobre obtenidas
en las experiencias 2 y 3, como se muestra en la Figura 5.
De la figura, se observa una relacin entre la eficiencia de
remocin en la seccin andica y la duracin e intensidad
del tratamiento, los resultados indican que es ms eficiente, desde el punto de vista de la remocin del contaminante, realizar una tratamiento de mayor duracin pero con
una intensidad de corriente baja, ya que la mxima remocin se obtiene cuando el tratamiento aplicado tiene una
duracin de 12 [das] con una intensidad de corriente de 10
[mA]. Si se fija en los resultados de eficiencia de corriente
mostrados en la Tabla 4, adems se puede observar que
la experiencia 3 es la que presenta una mejor eficiencia en
el uso de la corriente elctrica, lo que nos reafirma la con-
359
clusin anterior de que aplicar un tratamiento de mayor

duracin con baja intensidad de corriente es mejor.
de cobre y el rgimen de pulso aplicado a las experiencias

con pulsos (experiencias 5 y 6).
Si adems se observan los resultados de eficiencia de
corriente mostrados en la Tabla 4, se puede ver que los
mejores resultados en la eficiencia de corriente elctrica,
tambin son los de la experiencia 6, lo que nos lleva a la
conclusin que realizar un tratamiento con la utilizacin de
pulsos en un rgimen bajo de stos es una buena alternativa de tratamiento.
Figura 5. Eficiencias de remocin en seccin andica

segn la duracin e intensidad del tratamiento.
4.3.4. Efecto de la aplicacin de Pulsos Elctricos.

Para ver el efecto de la aplicacin de pulsos elctricos se
compararn las remociones de cobre obtenidas en las experiencias 1, 5 y 6. La principal diferencia entre las tres experiencias es el mecanismo por el cual la corriente elctrica fue aplicada. En el caso de la experiencia 1, la corriente
fue aplicada de modo constante, sin la aplicacin de pulso
elctrico. Por otro lado, las experiencias 5 y 6 se realizaron
mediante la aplicacin de pulsos elctrico, siendo el rgimen de pulso de 20 y 10, respectivamente. Los resultados
se muestran en la Figura 6. De la Figura 6, se observa que
la mnima eficiencia de remocin en la seccin andica se
obtiene cuando el tratamiento es realizado sin la aplicacin de pulsos elctricos y al comparar las los resultados
de las experiencias realizadas con pulsos elctricos, se
observa que a medida que el rgimen de pulso disminuye, la eficiencia de remocin aumenta. Este fenmeno se
debe principalmente a que un menor rgimen de pulso indica un mayor tiempo sin la aplicacin de corriente, por lo
que el sistema tiene mayor tiempo para revertir los efectos
capacitivos y de polarizacin del sistema.
Figura 6. Eficiencias de remocin en seccin

andica segn aplicacin de pulsos elctricos.
Al graficar los resultados de las concentraciones relativas

por zona de estas experiencias, como se ve en la Figura
7; existe una mayor acumulacin de cobre total en la zona
catdica cuando el tratamiento se realiza mediante la aplicacin de pulsos elctricos. Sin embargo, no se presenta
una diferencia significativa entre la concentracin relativa
360
Figura 7. Distribucin del cobre en funcin de la aplicacin de pulsos elctricos.
4. Conclusiones
Con este trabajo se establece la capacidad de la tcnica de remediacin electrodialtica para eliminar cobre de
una muestra de suelo arenoso proveniente de la Ex minera
Montecarmelo.
En la totalidad de las experiencias realizadas se present
una remocin de cobre en la zona andica, mientras que
se produce una acumulacin de la especie contaminante
en la zona catdica.
Al analizar el efecto de remocin en la zona andica, se
observa que aumenta la remocin al aumentar la intensidad de corriente, pero por otro lado la eficiencia de corriente disminuye.
Por otro lado, al analizar el efecto de la duracin e intensidad del tratamiento, se puede concluir que es ms eficiente aplicar un tratamiento de baja intensidad pero de
mayor duracin, que un tratamiento de alta intensidad por
un periodo de tiempo menor. Tambin se observa la misma tendencia en la eficiencia de la corriente.
Al analizar el efecto de la aplicacin de pulsos elctricos,
desde el punto de vista de remocin de cobre en el nodo,
se observa una menor eficiencia cuando el tratamiento se
realiza sin la aplicacin de pulsos elctricos. Por otro lado,
a medida que disminuye el rgimen de pulso, el tratamiento se vuelve ms eficiente. Tambin se observa la misma
tendencia en la eficiencia de la corriente.
Dentro de este trabajo se puede concluir que la mejor opcin para realizar un tratamiento electrodialtico al tipo de
suelo estudiado, es por medio de pulsos con un rgimen
bajo; si bien esta experiencia en este trabajo no fue la que
obtuvo la mayor remocin, fue la segunda mejor, con un
valor de remocin de cobre de 24.7 % muy cercana a la
mejor y por otro lado tubo la mejor eficiencia de corriente
elctrica, con un valor de 2.3 %.
Pese a que en todas las experiencias hubo una migracin
de cobre desde la zona andica hacia la zona catdica,
en ninguna de las experiencias se dieron las condiciones

necesarias para bajar las concentraciones de cobre en la
zona andica por debajo de los 190 [mg kg-1 peso seco]
como lo indica la legislacin. Por lo tanto para que el tratamiento sea aplicable con concentraciones finales bajo las
normadas, se podra aumentar el tiempo de tratamiento
con la utilizacin de pulsos con un rgimen bajo. Otra alternativa sera aplicar el tratamiento utilizando los pulsos
con un rgimen bajo, luego dejar reposar el suelo por un
tiempo, de forma que el cobre presente se disuelve an
ms y aplicar el tratamiento nuevamente. Tambin sera
una alternativa aumentar la corriente aplicada, pero si bien
en este caso la remocin de cobre es buena, las eficiencias de corriente son bajas.
Bibliografa
1.
2.
3.
4.
5.
Agradecimientos
Se agradece el apoyo econmico del proyecto FONDECYT 1100440 y la ayuda de la Sra. Ana Gonzalez.
6.
7.
8.
9.
10.
11.
12.
13.
Informe tendencias del Mercado del cobre. Tercer

trimestre 2009. Direccin de Estudios y Polticas Pblicas, Comisin Chilena del Cobre (COCHILCO),
2009. www.cochilco.cl.
The World Bank Group Pollution Prevention and
Abatement Handbook, 1998; World Bank, Washington D.C., USA 1999.
Lageman R., Electroreclamation, Environmental
Science and Technology, 27 (1993) 2648-2650.
Acar, Y.B. and Alshawabkeh, A.N., Principles of electrokinetic remediation, Environmental Science and
Technology 27 (1993) 2638- 2647.
Probstein, R.F. and Hicks R.E., Removal of contaminants from soil by electric fields, Science, 260 (1993)
498-503.
Ottosen, L.M., Hansen, H.K., Laursen, S., Villumsen,
A., Electrodialytic remediation of soil polluted with
copper from wood preservation industry, Environmental Science and Technology 31 (1997) 1711-1715.
Hansen, H.K., Ottosen, L.M., Hansen, L., Kliem, B.K.,
Villumsen, A., Bech-Nielsen, G., Electrodialytic remediation of soil polluted with heavy metals - Key
parameters for optimization of the process, Trans
IChemE - Chemical Engineering Research and Design
77 (1999) 218-222.
Hansen, H.K. Rojo, A., Ottosen, L.M. Electrodialytic
remediation of copper mine tailings, Journal of Hazardous Materials, B117 (2005) 179-183.
Virkutyte, J., Sillanp, M., Latostenmaa, P., Electrokinetic soil remediation critical overview, The Science of The Total Environment, 289 (2002) 97-12.
Hansen, H.K. and Rojo, A., Testing pulsed electric
fields in electroremediation of copper mine tailings.,
Electrochimica Acta, 52 (2007) 3399-3405.
Soil Remediation Circular 2009, Ministry of Housing,
Spatial Planning and the Environment, The Netherlands (2009), http://www.vrom.nl
U.S. Bureau of Reclamation, 1974. Earth Manual;
U.S. Government Printing Office, Washington, D.C.
Ottosen. L.M., Hansen, H.K., Hansen, C., Water Splitting at Ion-Exchange Membranes and Potential Differences in Soil During Electrodialytic Soil Remediation,
Journal of Applied Electrochemistry, 30 (2000) 11991207.
361
Thermal decomposition reaction of acetone

cyclic triperoxide in aliphatic alcohols
Gladys N. Eyler*, Elida E. Alvarez, Celedonio Minellono and Adriana I. Caizo
Laboratorio de Qumica, Departamento de Ingeniera Qumica, Facultad de Ingeniera,
Universidad Nacional del Centro de la Provincia de Buenos Aires (UNCPBA) Avda. del Valle
5737 (B7400JWI) Olavarra, Provincia de Buenos Aires, Repblica Argentina.
Reaccin de descomposicin trmica del triperxido cclico de acetona en alcoholes alifticos

Reacci de descomposici trmica del triperxid cclic dacetona en alcohols aliftics
Recibido: 8 de octubre 2010; aceptado: 25 de octubre de 2010
RESUMEN
El triperxido cclico de acetona (ACTP) en su forma cristalina es considerado un sensible y poderoso explosivo
peroxdico. ACTP ha sido preparado en el laboratorio con
el objetivo de determinar su cintica y parmetros termodinmicos en algunos alcoholes alifticos (etanol, 2-butanol, 2-propanol y 1-propanol) purificados por tratamiento
con la sal disdica del cido etilen diaminotetraactico
(Na2-EDTA), para remover trazas de iones metlicos. La
reaccin fue estudiada a una concentracin inicial de 0,02
M, mostrando un comportamiento de acuerdo a una ley
cintica de pseudo-primer orden hasta al menos un 60%
de conversin de ACTP. Los parmetros cinticos han
sido correlacionados con propiedades fisicoqumicas de
los alcoholes seleccionados. La reaccin se acelera en alcoholes secundarios, pero la reactividad es an mayor en
los solventes no tratados con Na2-EDTA. Probablemente
opera un mecanismo diferente de reaccin en presencia
de iones metlicos. Los parmetros de activacin fueron
analizados a travs de una relacin isocintica.
Palabras claves: triperxido de triacetona, cintica qumica, termlisis en alcoholes.
SUMMARY
Acetone cyclic triperoxide (ACTP), in its crystalline form, is
considered a sensitive and powerful peroxide based explosive. ACTP has been prepared in the laboratory in order to calculate its kinetic and thermodynamic parameters
in some aliphatic alcohols (ethanol, 2-butanol, 2-propanol,
and 1-propanol) purified by treatment with disodium salt
of ethylene diamine tetraacetic acid to remove traces of
metallic ions. The reaction was studied at an initial concentration ca. 0.02 M showing a behavior according to a
pseudo first-order kinetic law up to at least ca. 60 % ACTP
conversion. The kinetic parameters have been correlated
with the physicochemical properties of the alcohols se-
362
lected. The reaction is accelerated in secondary alcohols

but the reactivity is still higher in solvents non-treated with
Na2-EDTA. Probably a different mechanism of reaction is
operative in the presence of metallic ions. The activation
paramethers were investigated through an isokinetic relationship.
Keywords: triacetone triperoxide, chemical kinetic, thermolysis in alcohols
RESUM
El triperxid cclic dacetona (ACTP) en la seva forma
cristallina es considerat un sensible i poders explosiu
peroxdic. Es prepara ACTP en el laboratori amb lobjetiu
de determinar la seva cintica i parmetres termodinmics
en alguns alcohols aliftics (etanol, 2-butanol, 2-propanol
i 1-propanol) purificats per tractament amb la sal disdica de lcid etilendiaminotetractic (Na2-EDTA) per eliminar traces dions metllics. Sestudia la reacci a una
concentraci inicial 0,02 M, mostrant un comportament
dacord a una llei cintica de pseudo-primer ordre fins al
menys un 60% de conversi dACTP. Es correlacionen els
parmetres cintics amb propietats fisicoqumiques dels
alcohols seleccionats. La reacci saccelera en alcohols
secundaris, per la reactivitat es encara major en les solvents no tractats amb Na2-EDTA. Probablement opera un
mecanisme diferent de reacci en presncia dions metl
lics. Sanalitzen els parmetres dactivaci mitjanant una
relaci isocintica.
Mots clau: triperxid de triacetona, cintica qumica, termlisi en alcohols.
*Corresponding author: Facultad de Ingeniera UNCPBA,

Avda. del Valle 5737 (B7400JWI) Olavarra, Provincia de
Buenos Aires, Repblica Argentina. neyler@fio.unicen.
edu.ar, Tel.: 54 2284-456175. Fax: 54 2284-450628.
Introduction
In the last few years, cyclic organic peroxides have been
regaining their lost interest due their increased use as explosive materials amongst terrorist groups. Acetone cyclic
triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane, ACTP) has a high capacity of detonation, and
the materials for its preparation are within any body reach.
ACTP and its homologue acetone diperoxide (3,3,6,6-tetramethyl-1,2,4,5-tetraoxacyclohexane, ACDP) are small
cyclic molecules considered as primary explosives. ACTP
is one of the most sensitive explosives known, a property
that allows its employment as both primary explosive and
main charge [1]. ACTP may be employed for explosive devices due to it power close to that of TNT.
There are no known industrial or military applications of
ACTP [2] due of its tendency to sublime rapidly and the
fact that its danger significantly increases if is allowed to
dry. As such, there is a great demand for an analytical
methodology capable of detecting these materials [3, 4]
and designing additives that could improve their detection possibilities. The nature of these peroxides hampers
a detailed experimental study of these initiation steps and,
thus, experimental observations on peroxide-based materials are limited to analysis of post-blast residues [4] or
thermal decomposition studies in solution [5-7].
It has been shown that radicals generated among the products derived from the ozonolysis of tetramethylene (TME)
are useful in the polymerization of vinyl monomer such as
methyl methacrylate (MMA). These products are ACDP
and ACTP plus other peroxidic species which may be
open-chain oligomers [8]. However, the polystyrene (PS)
obtained by reaction of styrene in the presence of ACTP at
423 K during three hours [9] has presented the same performance and characteristic properties if compared with
that obtained by pure thermal initiation. Those results have
shown that ACTP is not efficient as initiator of styrene polymerization. Nevertheless, in the same work, it has been
shown that diethylketone cyclic triperoxide (DEKTP) and
pinacolone cyclic diperoxide (PDP), tri and bifunctional initiators respectively, present typical multifunctional initiator
behavior, and in their presence it was possible to obtain
PS with high molecular weight at high reaction rates. On
the contrary, up to the present, DEKTP has not been found
in traces analysis of explosives, which is a very important
subject in forensic investigations.
In solution, the ACTP molecule is highly stable so its thermal decomposition reaction has been investigated over
the temperature range of 403.0 to 445.0 K in solvents of
different physicochemical properties [5]. The kinetic results demonstrated that the reaction follows a pseudo-first
order kinetic law up to a high degree of conversion. The
activation parameters of the thermolysis of ACTP in solution [5-7] have been assigned to the unimolecular homolytic reaction of this triperoxide molecule and it has been
reasonably assumed that the biradical intermediate formation is the rate determining step (Eq. 1, R1=R2= CH3). The
literature [10] has reported that the main decomposition
reaction products in solution were acetone and carbon dioxide. Quantitative analysis of acetone indicated that the
molar yield of acetone per mole of ACTP decomposed was
about 2 in the gasphase and 2.5-2.6 in condensed-phase
[10]. Other authors [6, 7, 11] have found some products
derived from methyl radical hydrogen abstraction (methane) and radical-radical reactions (ethane, 2-butanone in
acetone as solvent [7], or ethylbenzene in toluene as solvent [6]). The presence of those methyl radicals has been
explained through the decomposition of the biradical initially formed (Eq. 1) by C-C bond ruptures.
The kinetic data in solution showed that protic solvents
accelerate 2-3 times the thermal decomposition of ACTP
[5], so the objective of this study was to provide a more
complete investigation of the thermolysis of ACTP in some
alcohols solution, a subject on which no information was
found in the literature. Kinetic data of the thermal decomposition reaction of ACTP in different organic solvents
and data obtained for different cyclic organic peroxides in
some aliphatic alcohols were compared.
Materials and Methods:

Materials: ACTP was prepared by the reaction of acetone
(- 271 K) with concentrated hydrogen peroxide in concentrated sulfuric acid media. The traslucent solid obtained
was purified by twice recristallization from light petroleum
ether (p.f. 369.5 370.0 K)[7]. The solvents employed in
the reaction were purified using standard methods [12],
and they were distilled from disodium salt of ethylene
diamine tetraacetic acid (Na2-EDTA) to remove traces of
metalic ions [13]. In all cases, the suitability of the purity
for kinetic studies was checked by GC analysis. 1-octanol
was employed as internal standard in quantitative GC determinations.
Caution: ACTP must be handled with care because can
it be detonated by shock.
Kinetic methods: Pyrex glass ampoules (10 cm long x 6
mm o.d.) half filled with ACTP solution were spiked with
1-octanol as an internal standard, thoroughly degassed
under vacuum at 77 K and then sealed with a flame torch.
To perform the runs, the ampoules (6 at each temperature)
were immersed in a thermostated silicone oil-bath (0.1).
The reaction was stopped after predetermined times by
cooling them at 273 K. The concentration of ACTP remaining in the solution was determined by quantitative
GC analysis in a DB-5 capillary column (5% biphenyl-95%
dimethyl polysiloxane, 30 m x 0.32 mm I.D., 0.25 mm film
thickness) installed in a Konik 2000C gas chromatograph
with nitrogen as the carrier gas, injection port at 423 K in
split mode, and flame ionization detection (523 K). The experiments were carried out under programmed conditions
(333 K, 3 min, 5 /min, 433 K, 15 min). Retention times of
internal standard and ACTP were ca. 11.2 min and 12.5
min, respectively.
The corresponding experimental pseudo first-order rate
constant values (k1), with 5 % accuracy, were calculated
from the slope of the line obtained by plotting the values
of ln [ACTP]t against reaction time in seconds. The corresponding activation parameters were deduced from the
Eyring equation and the errors were determined using a
least- means- square data treatment [14, 15].
Results and Discussion

The thermal decomposition reactions of ACTP in different
solvents (2-butanol, 1-propanol, 2-propanol, and ethanol)
were studied at an initial concentration ca. 0.02 M, and in
the temperature range of 403.0 445.0 K. The reactions
followed a pseudo first- order kinetic law up to at least
363
60 % ACTP conversion. The corresponding rate constant

values of ACTP thermolysis (k1) in different alcohols are
shown in Table I, where some data obtained in a previous
work were included [5].
Table I: Pseudo-First-Order Rate Constant Values for the
Thermal Decomposition Reaction of ACTP (0.02 M initial concentration) in solvents with Na2-EDTA treatment.
Solvent
Temp., K
k1.10 , s
2-butanol
413.0
423.0
438.0
403.0
413.0
423.0
433.0
443.0
413.0 a
423.0b
433.0
438.0
423.0
423.0
423.0
1.50
5.30
15.0
0.14
0.90
2.40
4.70
17.9
1.12
3.25
9.02
15.5
2.50
0.78
0.91
0.999
0.999
0.995
0.999
0.998
0.997
0.999
0.999
0.990
-0.993
0.997
0.995
0.999
0.999
Ethanol
2-propanol
1-propanolc
Toluened
Acetonee
-1
) ref [5]; b) interpolated value; c) ACTP conversion : 92%; d) at 424.65 K; ref [6]; e) ref [7]
Kinetic data of the thermal decomposition reaction of

ACTP in different aliphatic alcohols demonstrated that the
investigated reactions depend directly on some solvent
properties. In general, it has been found that the rate constant values (k1) are higher in more polar solvents [6], but
in the series of alcohols studied in this work it is evident
that the cause of an increment in the reaction rate is not
only due to the alcohol polarity, reflected in their ET(30) values. Figure 1 presents the plot of ln k1 in aliphatic alcohols
with and without Na2-EDTA treatment [13] as a function of
ET(30) parameter values [16] for the ACTP thermal decomposition reaction at 423 K. In ethanol the k1 value was at
least three times higher than the k1 value in acetone [7] or
toluene [6], but it was lower than the values obtained in the
other alcohols. The alcohols in Table I may be classified as
primary and secondary, and in that sense, the results have
shown that the reaction is accelerated in the secondary
ones.
sition metal ions. These compounds have catalytic activity

and can not be eliminated by distillation. The k1 value in
2-propanol at 423 K with Na2-EDTA treatment was 2 times
lower than the value obtained in the same solvent without
Na2-EDTA treatment.
Table II: Pseudo-First-Order Rate Constant Values for the
Thermal Decomposition Reaction of ACTP (0.02 M initial concentration) in solvents without Na2-EDTA treatment.
Solvent
Temp., K
k1.105, s-1
2-propanol
413.0
423.0
438.0
413.0a
423.0b
425.0
438.0
445.0
2.19
5.60
18.0
1.48
3.47
5.21
8.00
17.3
0.992
0.990
0.995
0.980
-0.999
0.990
0.990
2-methoxyethanol
) ref [5]; b) interpolated value
The temperature effect on the k1 values evaluated according to the Arrhenius method showed a linear correlation
over a relatively large interval of temperatures (at least 25
K). These results have suggested that the calculated activation parameters (Table III) are representative of a single
process as the O-O bond homolysis (Eq. 1).
(1)
Table III: Activation Parameters for the Thermal Decomposition Reaction of ACTP in solution.
DT,
K
Solvent
2-propanol
,
kJ.mol-1
,
J.mol-1.K-1
c
,
kJ.mol-1
25.0
122.47 5.02
-30.5 7.5
76.5 23.4
0.999
2-propanolb 25.0
153.41 2.51
29.3 5.4
141.0 2.51
0.999
2-butanol
25.0
130.83 7.94
-22.2 18.8
140.2 7.94 0.990
2-methoxy32.0
ethanola, b
104.92 6.27
-84.9 13.4
140.8 6.27 0.980

143.8 7.52 0.999
Ethanol
On the other hand, when the alcohols were purified only

by distillation without a previous Na2-EDTA treatment, as
it was the case of 2-propanol and 2-methoxyethanol, the
rate constant values were higher than the expected (Table
II and Fig. 1). In these cases, the acceleration of the reaction was probably caused by trace impurities such as tran-
364
168.04 7.52
57.7 16.7
32.0
174.72 6.69
77.3 15.9
142.0 6.69 0.993
Acetonee
Figure 1: Correlation of ln k1 423 K vs. ET(30) for aliphatic

alcohols. (a-solvent without Na2-EDTA treatment).
40.0
Toluened
32.0
174.72 10.45
76.5 23.4
142.4 10.45 0.998
) Without Na2-EDTA treatment b) from ref [5] c) dethermined at 423 K, d) from ref. [6], e) from ref. [7].
A strong variation of those activation parameters values

(Table III) for the thermolysis of ACTP in different solvents
can be observed (e.g., in going from 2-methoxyethanol
to ethanol the variations are DDH = 63.12 kJ.mol-1, DDS
= 142.6 J.mol-1 K-1 and DDG = 8.2 kJ.mol-1). The linear
dependence between activation enthalpies and entropies

(Table III) may be represented through equation (2) where
the slope (448.7 K) is called the isokinetic temperature
and represents a temperature at which all reactions of the
series should proceed at the same rate.
(2)
This correlation, known as the Compensation Effect or Isokinetic Relationship (IKR), has been much discussed [17]
and widely investigated for many different physical andchemical processes [18, 19]. In Figure 2 the straight line A
(r2= 0.9888) represents a correlation between DS and DH
values in alcohols.
b (454 K) obtained with this treatment (Fig. 3) is comparable with that calculated from Eq. 2. This value is slightly
above the highest experimental temperature. In Figure 3 it
can be seen that the kinetic data in 2-propanol and 2-metoxyethanol, without Na2-EDTA treatment, are represented
by parallel dotted lines and may be excluded from the correlation because they intercept the others lines within the
interval of experimental temperatures. As a consequence
of these results, it is possible to conclude that the ACTP
thermal decomposition reaction probably proceeds by two
different mechanisms. In alcohols treated with Na2-EDTA,
the reaction goes by a stepwise mechanism, initiated by
the homolytic rupture of the O-O bond, but in those solvents where the impurities of metallic ions are present, the
O-O bond rupture may be assisted by those traces, so the
decomposition reaction would be accelerated following a
different mechanism. Probably, this latter mechanism is
comparable with that proposed for antimalarial trioxanes
for the presence of the prosthetic group, heme, or Fe+2
ions, where the initial rupture of the peroxide bond by electron transfer is considered [21].
Figure 2: The enthalpy entropy relationship for ACTP

thermal decomposition in alcohol solution (Table II).
A- plot of DS vs. DH; B- plot of DG vs. DH.
The correct interpretation of the Compensation Effect

should be that DG is approximately constant within a reaction series (Figure 2, line B) because enthalpy variations
through the series of reaction are exactly compensated by
entropy changes. In this work, the variation in DG is close
to the experimental errors and these values can be considered approximately constant in comparison with the variations of DH. Nevertheless, the verification of equation (2)
and determination of the constant b is, however, hindered
by serious statistical problems. DH and DS (Eq. 2) have
not been determined directly, these quantities are mutually dependent because both have been derived from the
original kinetic data. Petersen [20] reported that in no case
the linear DH / DS plot can be taken by itself to be an adequate demonstration of the existence of an isokinetic relationship. A statistically correct solution can be achieved by
returning to the original experimental quantities [16], thus a
different representation of the Compensation Effect can be
given in the ln k1 vs. T-1, plane (or Arrhenius plane), where
a family of straight lines with different slopes intersect at
an ordinate position of ln k1 and at an abscissa value of
T-1 which corresponds to b-1 (Fig. 3). The single point of
intersection of lines in this figure could be used for a sound
statistical test.
In Fig. 3 the solid lines represent the kinetic data obtained
in alcohols with Na2-EDTA treatment. These lines intercept
in a common point, or a zone, far from the experimental
interval of temperatures. A least-squares treatment to determine the two coordinates of this point and the slopes of
all the lines was applied in order to achieve the minimum
sum of squares of the deviations of all points. The value of
Figure 3: Arrhenius plot corresponding to the thermal decomposition reaction of ACTP in aliphatic
alcohols. Solid line: solvents with Na2-EDTA treatment: 1) ethanol; 2) 2-propanol [5]; 3) 2-butanol.
Dashed line: solvent without Na2-EDTA treatment 4) 2-methoxyethanol [5]; 5) 2-propanol.
Conclusions
The thermal decomposition reaction of ACTP in aliphatic
alcohols follows a pseudo first-order kinetic law. The rate
constant values (k1) are higher in secondary alcohols than
in the primary ones probably because the former interacts
more with the ACTP molecule favoring the biradical formation. A solute-solvent interaction mechanism through
the formation of cyclic species can be postulated. The
hydrogen atoms of the OH group and C2 in secondary
alcohols may interact with the O-O bond in the peroxide
molecule. On the other hand, the primary alcohols interact
only through the hydrogen atom in the OH group.
It was demonstrated that the presence of metallic ions as
impurities in the alcohol solution accelerate the decompo-
365
sition of ACTP. Probably, the reaction mechanism in aliphatic alcohol begins with the rupture of the O-O bond of
ACTP with participation of the metallic ions that finally lead
to the formation of the reaction products and the recovery
of the metal.
The isokinetic relationships investigated make it possible
to conclude that probably different mechanisms of reaction are operative in Na2-EDTA-treated or non-treated alcohols.
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Acknowledgements
This study was financially supported by the Facultad de
Ingeniera and the Secretara de Ciencia, Arte y Tecnologa
de la Universidad Nacional del Centro de la Provincia de
Buenos Aires (UNCPBA). A.I. Caizo is member of the
Carrera de Investigador Cientfico, CONICET.
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Utility of 4-(4-acetoaminophenyl)-4oxo-but-2-enoic acid to prepare Pyran

and Pyridine derivatives as building
blocks in Heterocyclic Synthesis
M. A. El-Hashasha, M. H. A. Solimanb, I. I. Abd El-Gwadc, S. S. El-Sakkac*
and M. A. Morsy
Faculty of Science, Ain Shams University, Cairo, Egypt.bFaculty of Science, Suez Canal
University, Ismalia, Egypt. cFaculty of Science, Suez Canal University, Suez, Egypt.
Utilidad del cido 4-(4-acetoaminofenil)-4-oxo-but-2-enoico en la preparacin de derivados

de Pirano y Piridina como unidades estructurales para la Sntesis de Heterociclos
Utilitat de lcid 4-(4-acetoaminofenil)-4-oxo-but-2-enoic en la preparaci de derivats
de Pir i Piridine com unitats estructurals per a la Sntesi de Heterocicles
Recibido: 14 de octubre de 2010; aceptado: 29 de octubre de 2010
RESUMEN
El presente trabajo est dedicado al estudio de la interaccin del derivado del cido -aroil acrlico (1) con malononitrilo en presencia de piperidina y/o acetato de amonio, y
el uso de los compuestos formados como materias primas
en la sntesis de sistemas heterocclicos condensados o
aislados. Se ha establecido que el cido -aroilacrlico (1)
reacciona con malononitrilo en DMF en presencia de piperidina como catalizador formando el derivado 4H-pirnico
(2). Cambiando el catalizador por acetato de amonio, se
obtiene el derivado de piridina (3). Cuando se hizo reaccionar el compuesto (2) con trietilortoformato se obtiene
etoximetilenamino-4H-pirano (4). El compuesto (4) se utiliz como producto de partida clave en la sntesis de algunos sistemas anulares y heterocclicos interesantes (5-8).
Del mismo modo, los derivados del cido malemico (9)
y (15) se han sintetizado va interaccin de (2) y (3) con
anhdrido malico para estudiar el comportamiento de los
derivados del cido malemico como anlogos del cido
-aroilacrlico en la obtencin de compuestos con metilenos activos en la reaccin de adicin de Michael (10-14);
(16-18).
Palabras clave: cido -aroilacrlico, adicin de Michael,
2-aminopirano, 2-aminopiridina, pirimidina y cido malemico.
summary
The present work is devoted to study the interaction of
-aroylacrylic acid derivative (1) with malononitrile in the
presence of piperidine and/or ammonium acetate, then
using the formed compounds as a starting material for
synthesizing fused and isolated heterocyclic system. It
has been established that the -aroylacrylic acid (1) react
with malononitrile in (DMF) in the presence of piperidine
as catalyst with formation of 4H-pyran derivative (2). By

changing the catalyst into ammonium acetate, pyridine
derivative (3) has been obtained. When compound (2) was
allowed to react with triethylorthoformate afforded ethoxymethyleneamino-4H-pyran (4). Compound (4) was used as
key starting material for synthesizing some interesting annulated and heterocyclic systems (5-8). Also, the maleamic acid derivatives (9) and (15) have been synthesized via
the interaction of (2) and (3) with maleic anhydride to study
the behavior of the formed maleamic acid derivatives as
analogies of -aroylacrylic towards different active methylene
compounds under Michael addition reaction (10-14); (16-18).
Keywords: -aroylacrylic acid, Michael addition, 2-aminopyran, 2-aminopyridine, pyrimidine and maleamic acid
RESUM
Aquest treball est dedicat a lestudi de la interacci
del derivat de lcid -arolacrlic (1) amb malononitril en
presncia de piperidina i/o acetat damoni, i ls dels productes formats com a matries primeres en la sntesi de
sistemes heterocclics condensats o allats. Sha establert
que lcid -arolacrlic (1) reacciona amb malononitril en
DMF en presncia de piperidina com a catalitzador formant el derivat 4H-pirnic (2). Canviant el catalitzador
per acetat damoni, sobt el derivat de piridina (3). Quan
es va fer reaccionar el producte (2) amb trietilortoformat
sobt etoximetilenamino-4H-pir (4). El producte (4) es
va utilitzar com a producte de partida clau en la sntesi
dalguns sistemes anulars i heterocclics interessants (58). De la mateixa manera, els derivats de lcid malemic
(9) i (15) shan sintetitzat via interacci de (2) i (3) amb anhdrid malic per estudiar el comportament dels derivats
*
Author to whom correspondence should be addressed;
E-mail: saharelsakka@hotmail.com.
367
de lcid malemic com a anlegs de lcid -arolacrlic en

lobtenci de compostos amb metilens actius en la reacci
daddici de Michael (10-14); (16-18).
Paraules clau: cid -arolacrlic, addici de Michael,
2-aminopir, 2-aminopiridina, pirimidina i cid malemic.
Introduction
The author aimed through this work to study the behavior of acid (1) towards some containing active methylene
compounds. Also pyran and fused 4H-pyran derivatives
have attracted a great deal of interest owing to their antimicrobial activity,1,2,3 inhibition of influenza, virus sialidases,4 mutagenic activity as antiviral,5 antiprolifer-ation
agents,6 sex pheromonesactivity,7,8 antitumor9 and antiinflammatory agent.10 Moreover, pyran derivatives are well
known for their antihistaminic activity.11
Also, pyrimidines and fused pyrimidines play an inertial
role in several biological processes and have a considerable chemical and pharmacological importance. In particular pyrimidine nucleus can be found in abroad variety
of antibacterial and antitumor agents as in agrochemical
and veterinary products12-15. This current pharmacological importance has stimulated our interest to synthesize
several new and biologically active derivatives of these
heterocyclic systems.
a base (hydrazine hydrate) underwent a Dimorth rearrangement to give the thermodynamically more stable hydrazine
derivative, which underwent ring closure and yielded the
desired product. EIMS of compound 5 exhibits m/e = 322
(M.+). Refluxing an ethanolic solution of 4 with phenylhydrazine yielded the corresponding 7-(4-acetoaminophenyl)4-imino-3-phenylamino-4-hydro-5H-pyrano[2,3-d]pyrimidine-5-carboxylic acid (6). EIMS of compound 6 showed
m/e= 416 (M.+). The reaction involves nucleophilic substitution on the carbon atom of methylidene moiety followed
by ring closure. When compound 4 was submitted to react
with primary amines namely, ethylamine and aniline led to
the formation of 7-(4-acetoaminophenyl)-3-ethyl-4-imino-4-hydro-5H-pyrano[2,3-d]pyrimidine-5-carboxylic acid
(7a) and/or 7-(4-acetoaminophenyl)-3-phenyl-4-imino4-hydro-5H-pyrano[2,3-d]pyrimidine -5-carboxylic acid
(7b). Ammonolysis of compound 4 gave 4-amino-7-(4acetoaminophenyl)-5H-pyrano[2,3-d]pyrimidine-5-carboxylic acid (8). EIMS of compound 8 showed m/e = 326
(M .+). Also, the structure of compound 8 was established
by an independent synthesis from the interaction of compound 2 with formamide. The reaction involved nucleophilic substitution on the unsaturated carbon atom followed
by ring closure to afford the desired product 8.
Result and Discussion

The interaction of 4-(4-acetoaminophenyl)-4-oxo-but2-enoic acid (1) with malononitrile in dimethylformamide
(DMF) in the presence of piperidine as catalyst afforded
2-amino-6-(4-acetoaminophenyl)-3-cyano-4H-pyran4-carboxylic acid (2) . On the other hand, when the reaction was subjected in the presence of ammonium acetate
as catalyst yielded 2-amino-6-(4-acetoaminophenyl)3-cyano-4H-pyridine-4-carboxylic acid (3) . Both 2 and 3
were used as pre key starting material for synthesis of both
fused and isolated heterocyclic system
The EIMS of compound 2 exhibits m/e = 298 (M.+, intensity

33%). EIMS of compound 3 exhibits m/e = 296 (M.+, intensity 32%). The reaction takes place via nucleophilic addition of the carbanion derived from the malononitrile to the
,-unsaturated carbonyl moiety in the acid 1 followed by
cyclisation in case of 2 and ring closure and dehydration
in case of 3. Refluxing of 2 with neat triethylorthoformate
afforded 6-(4-acetoaminophenyl)-3-cyano-ethoxymethylene-amino-4H-pyran-4-carboxylic acid (4). Compound 4
was used as key starting material for synthesizing some
interesting annulated and heterocyclic systems.
Interaction of compound 4 with hydrazine hydrate in
boiling ethanol yielded 5-(4-acetoaminophenyl)-1,2,3-trihydro-6-oxo-1,2,7,9-tetra-azaphenalen-3-one (5) without
isolation of imino derivative.16 This could be explained the
formation of imino derivative first, which in the presence of
368
The reaction products of compound 4 with phenyl hydrazine, ethyl amine and aniline can exist in one of three
conformation A, B or C, both A and B are stabilized via hydrogen bond formation, so they are more stable than C, in
case A hydrogen bond is formed by using one lone pair of
electrons on the oxygen of hydroxyl group (OH, sp3), while
in case B the formed hydrogen bond will use lone pair on
the oxygen of carbonyl moiety (C=O, sp2), so hydrogen
bond in case A is stronger than B.
The N-cyclic maleamic acid 17-19 (9) has been synthesized

via interaction of compound 2 in refluxing acetic acid with
maleic anhydride. The N-cyclic maleamic acid is constructed such that due to the ringcleaved structure of
maleic anhydride (-COCH=CHCOOH) that bonded to the

amino group (NH2) of the starting N-cyclic amine via a maleamic bond (-NH-CO-). EIMS of compound 9 showed m/e
= 384 (M .+).
In this investigation the author sought to investigate the
behavior of maleamic acid derivative 9 towards active
methylene compounds under Michael reaction conditions with the aim of obtaining more precise information
about the course of the reaction and synthesizing some
interesting heterocyclic compounds. When maleamic acid
derivative 9 was allowed to react with malononitrile in the
presence of few drops of piperidine as a catalyst it yielded
2-[5-amino-3-(carboxymethyl)-4-cyanofuran-2-ylamino]6-(4-acetoaminophenyl)-3-cyano-4H-pyran-4-carboxylic
acid (10). Compound 10 was obtained from Michael addition reaction (via ,-unsaturated acid rather than ,unsaturated amide). EIMS of compound 10 showed m/e =
463 corresponding to (M .+). Interaction of maleamic acid
derivatives 9 with acetyl acetone in the presence of piperidine as catalyst it yielded the Michael adduct 2-[3-acetyl2-(carboxymethyl)-4-oxopentanamido]-6-(-acetoamino
phenyl)-3-cyano-4H-pyran-4-carboxylic acid (11). Maleamic acid derivative 9 react with acetyl acetone under
Michael reaction condition as ,-unsaturated acid rather
than ,-unsaturated amide, this is due to the polarization
by the carbonyl group of the carboxyl outweighs the po-
larization by the carbonyl of amide group, and the carbonion derivative from acetyl acetone is more bulky [we need
more work on the bifunctional substrate to make the results
more clear]. Interaction of the maleamic acid ethyl acetoacetate in the presence of piperidine as a catalyst yielded
N-cyclic maleimide 2-[(3-acetyl-4-carboxymethyl)-2,5dioxopyrro-lidin-1-yl]-6-(4-acetoaminophenyl)
3-cyano-4H-pyran-4-carboxylic acid (12). The EIMS of
compound 12 showed m/e = 480 (M .+) such spectral
data consistent with the proposed structure. By changing
the catalyst into ammonium acetate, maleamic acid derivative 9 interacted with ethyl acetoacetate and yielded
the
6-(4-acetoaminophenyl)-3-cyano-2-[3-methyl-4,6dioxo-4,5,6,7-tetrahydro-2H-pyrrolo[3,4-c]pyridine1-ylamino]-4H-pyran-4-carboxylic acid (13). The reaction
takes place via Michael addition reaction to ,- unsaturated acid moiety followed by enolisation and amination
with ring closure to afford the desired product . Refluxing
maleamic acid derivative 9 with diethyl malonate in DMF in
the presence of ammonium acetate afforded 6 (4-acetoa
minophenyl)-3-cyano-2-[3,4,6-trioxo-3,3a,4,5,6,7-hexahy
dro-2H-pyrrolo[3,4-c]pyridine-1-ylamino-4H-pyran-4-carboxylic acid (14). The reaction takes place via Michael addition reaction followed by amination and ring closure to
give the desired product.
369
On the lights of the previous results, further investigation

at the same reaction types was carried out on N-cyclic
maleamic acid derivative 15, which has been synthesized
via the interaction of compound 3 in acetic acid with maleic anhydride. Interaction of the compound 15 with malononitrile in the presence of piperidine as catalyst afforded
2-[5-amino-3-(carboxymethl)-4-cyanofuran-2-ylamino]6-(4-acetoaminophenyl)-3-cyano-pyridine-4-carboxylic acid 16. On the other hand, refluxing compound 15
with malononitrile in the presence of ammonium acetate
yielded 2-[5-amino-3-(carboxymethyl)-4-cyano-1H-pyrrolo-2-yl-amino]-6-(4-acetoaminophen-yl)-3-cyano pyridine-4-carboxylic acid (17). The reaction takes place via
Michael addition reaction to ,- unsaturated acid moiety
followed by ring closure to give the desired product. When
compound 15 was allowed to react with acetyl acetone in
presence of piperidine as catalyst it yielded 2-[4-acetyl3-(carboxymethyl)-5-methylfuran-2-ylamino]-6-(4-acetoamino-phenyl)-3-cyanopyridine-4-carboxylic acid (18).
EIMS of compound 18 showed m/e = 475 corresponding
to (M .+).
Experimental
All melting points are uncorrected and deter ined by the
m
open capillary method using Gallen Kamp melting point
apparatus. Microanalyses were carried out by the Micro
Analytical Center at Cairo University. The IR spectra were
recorded on FT/IR-300E Jasco spectrophotometer as (KBr)
discs. Mass spectra were recorded on Shomadzu GC-MS
(QP-1000EX) instrument operating at 70eV. Homogeneity
of all compounds synthesized was checked by TLC.
6-(4-acetoaminophenyl)-2-amino-3-cyano-4H-pyran4-carboxylic acid (2) and 6-(4-acetoaminophenyl)2-amino-3-cyano-4H-pyridine-4-carboxylic acid (3)
To solution of 4-(4-acetaminophenyl)
4-oxobut-2-enoic
acid (1) (1.00 g, 4.47 mmol) and malononitrile (0.3 g, 4.47
mmol) in refluxing DMF (20 ml) few drops of piperidine or
ammonium acetate (0.34 g, 4.47 mmol) were added; the
resultng mixture was refluxed for 2 hrs. The reaction mixi
ture was allowed to cool at room temperature then poured
into water (100 ml). The precipitate formed was filtered off
370
and washed with water, then dried and crystallized from

the proper solvent to give 4H-Pyran derivative and/or
pyridine derivative respectively. Compound 2 crystallized
from EtOH/H2O as orange crystals; m.p. 170oC Elemental
analysis for C15H13N3O4 (299.29): Calcd: C, 60.2; H, 4.38; N,
14.04. Found: C, 60.35; H, 4.43; N, 14.18. IR (KBr) max (cm1
): 1640, 1700, 2211, 2862, 2937, 3187 and 3317 cm-1 due
to uC=O, uCN, uCH, uNH and uOH groups, respectively.
Compound 3 crystallized from EtOH/H2O as pale yellow
crystals; m.p. 180oC Elemental analysis for C15H12N4O3
(296.29): Calcd: C, 60.81; H, 4.08; N, 18.91. Found: C,
60.95; H, 4.43; N, 18.99. IR (KBr) max (cm-1): 1634, 1672,
1728, 2213, 2928, 3113, 3384 and 3443 cm-1 due to uC=O,
uCN, uCH, uNH and uOH groups, respectively.
6-(4-acetoaminophenyl)-3-cyano-2-ethoxy
methyleneamino-4H-pyran-4-carboxylic acid (4)
4H-Pyran derivative (1.00 g, 3.4 mmol) in triethylorthoformate (10 ml) was stirred under reflux for 5 hrs. The reaction mixture was concentrated and the obtained brown
precipitate was crystallized from ethanol/water to afford
ethoxymethyleneamino-4H-pyran as white crystals; m.p.
195oC. Elemental analysis for C18H17N3O5 (355.35): Calcd:
C, 60.84; H, 4.82; N, 11.82. Found: C, 60.95; H, 4.93; N,
11.94. IR (KBr) max (cm-1): 1640, 1680, 2208, 2863, 2936,
3310 attributable to uC=O, uCN, uCH, uNH and uOH groups, respectively.
5-(4-acetoaminophenyl)-1,2,3-trihydro-6-oxo-1,2,7,9tetraazaphenalen-3one (5) and 7-(4-acetoaminophenyl)4-imino-3-phenylamino-3,5-dihydro-4H-pyrano[2,3-d]
pyrimidine-5-carboxylic acid (6)
A mixture of ethoxymhlethyleneamino-4H-pyran (4) (3.00
g, 8.70 mmol) and hydrazine hydrate (0.30 ml, 8.70 mmol)
or phenylhydrazine (0.85 ml, 8.70 mmol) in absolute ethanol (30 ml) was refluxed for 7 hrs .The reaction mixture was
left to cool at room temperature then acidified with diluted
HCl. The formed solid was filtered off, washed with cold
water, dried and crystallized from the proper solvent to afford pyranopyrimidines (5) and/or (6). Compound 5 crystallized from EtOH/H2O as white crystals; m.p. 225oC Elemental analysis for C16H12N5O3 (322.31): Calcd: C, 59.44;
H, 4.05; N, 21.66. Found: C, 59.54; H, 4.21; N, 21.74. IR
(KBr) max (cm-1): 1660, 3400 cm-1 (broad ) attributable to

uC=O , uNH, and devoid any band for uCN. EIMS exhibits m/e = 322 (M .+). Compound 6 crystallized from EtOH/
H2O as white crystals; m.p. 150oC Elemental analysis for
C22H19N5O4 (417.43): Calcd: C, 63.3; H, 4.59; N, 16.78.
Found: C, 63.45; H, 4.62; N, 16.89. IR (KBr) max (cm-1):
1631, 1693, 2937, 3100, 3400 cm-1 attributable to uC=O,
uCH, uNH and uOH groups, respectively. EIMS showed m/e
= 416 (M .+).
7-(4-acetoaminophenyl)-3-ethyl-4-imino-3,5-dihydro-4H-pyrano[2,3-d]pyrimidine-5-carboxylic acid
(7a) and/or 7-(4-acetoaminophenyl)-3-phenyl-4-imino-3,5-dihydro-4H-pyrano [2,3-d]pyrimidine-5-carboxylic acid (7b)
A mixture of ethoxymethyleneamino-4H-pyran (4) (3.00
g, 8.70 mmol) and ethylamine (0.57 ml, 8.70 mmol) and/
or aniline (0.75 ml, 8.70 mmol) in absolute ethanol (30 ml)
was refluxed for 5 hrs. After cooling, the reaction mixture
was poured into diluted HCl; the precipitated product
was filtered off and washed several times with cold water, dried and crystallized from the proper solvent to afford
the iminopyranopyrimidines (7a) and/or (7b). Compound
7a crystallized from EtOH/H2O as white crystals; m.p.
132oC. Elemental analysis for C18H18N4O4 (354.37): Calcd:
C, 61.01; H, 5.12; N, 15.81. Found: C, 61.21; H, 5.23; N,
15.94. IR (KBr) max (cm-1): 1630-1642, 1694-1695, 2937,
3282-3285, 3340-3360 attributable to uC=O, uCH, uNH and uOH
groups, respectively. Compound 7b crystallized from EtOH/
H2O as white crystals; m.p. 150oC. Elemental analysis for
C22H18N4O4 (402.43): Calcd: C, 65.67; H, 4.51; N, 13.92.
1631-1641, 1695-1696, 2936, 3280-3286, 3340-3360 attributable to uC=O, uCN, uCH, uNH and uOH groups, respectively.
7-(4-acetoaminophenyl)-4-amino-5H-pyrano[2,3-d]
pyrimidine-5-carboxylic acid 8
To a solution of ethoxymethyleneamino-4H- yran (4) (3.00
p
g, 8.70 mmol) and absolute ethanol (30 ml), ammonia solution (0.31 ml, 8.70 mmol) was added; the resulting mixture
was refluxed for 2 hrs. After cooling, the reaction mixture
was acidi ed with diluted solution of cold HCl, the precipifi
tate formed was filtered off and washed with water, dried
then crystallized from EtOH as white crystals; m.p. 140oC
to afford the aminopyrano yrimidine (8). Elemental analyp
sis for C16H14N4O4 (326): Calcd: C, 58.89; H, 4.32; N, 17.17.
1638, 1690, 2925, 3200, 3400 attributable to uC=O, uCN,
uCH, uNH and uOH groups, respectively. EIMS showed m/e
= 326 (M .+ ).
4-[6-acetoamino-3-cyano-4-hydro-4-carboxy-pyran2-yl] amino-4-oxobut-2-enoic acid (9)
Maleic anhydride (0.33 g, 3.4 mmol) was completely dissolved at room temperature in glacial acetic acid (30 ml),
and then 4H-pyran derivative (2) (1.00 g, 3.4 mmol) was
added to the solution; the resulting mixture was stirred under reflux for 1 hr. The reaction mixture was allowed to
cool at room temperature, then poured into water (500 ml),
the precipitate formed was filtered off, washed with water, dried and crystallized from MeOH as white crystals;
m.p. 230oC to afford N-cyclic maleamic acid (9). Elemental
analysis for C19H15N3O7 (397.35): Calcd: C, 57.43; H, 3.81;
N, 10.58. Found: C, 57.52; H, 3.93; N, 10.64. IR (KBr) max
(cm-1): 1635, 1695, 2210, 2862, 2936,
3110 and 3430
cm-1 attributable to umax of amide and carbonyl group, uCN,

uCH, uNH and uOH, respectively. EIMS showed m/e = 397
(M .+).
2-[5-amino-3-(carboxymethyl)-4-cyanofuran2-ylamino]-6-(4-aceto aminophenyl)-3-cyano-4H-pyran-4-carboxylic acid (10)
To a solution of maleamic acid (9) (2.00 g, 5.15 mmol) and
malononitrile (0.34 g, 5.15 mmol) in dioxan (20 ml) few
drops of piperidine was added; the resulting mixture was
refluxed at 60C for 7 hrs. The reaction mixture was allowed to cool at room temperature then acidified with diluted acetic acid (200 ml), the solid formed was filtered off,
washed with water, crystallized from EtOH/H2O as white
crystals; m.p. 190oC. Elemental analysis for C22H21N5O7
(467.42): Calcd: C, 56.53; H, 4.53; N, 14.98. Found: C,
56.99; H, 4.48; N, 15.21. IR (KBr) max (cm-1): 1631, 1697,
2211, 2864, 2938, 3284, 3300, 3400 cm-1 attributable to
umax of two carbonyl groups, uCN, uCH, uNH and uOH, respectively. EIMS showed m/e = 467 corresponding to (M .+).
2-[3-acetyl-2-(carboxymethyl)-4-oxopentanamido]6-(-acetoaminophenyl)-3-cyano-4H-pyran-4-carboxylic acid (11)
To a solution of maleamic acid (9) (2.00 g, 5.15 mmol)
and acetylacetone (0.53 ml, 5.15 mmol) in DMF (20 ml)
few drops of piperidine was added; the resulting mixture
was refluxed at 60C for 7 hrs. The reaction mixture was
allowed to cool at room temperature then acidified with
diluted acetic acid (200 ml), the solid formed was filtered
off, washed with water, dried and crystallized from MeOH/
C24H23N3O9 (497.47): Calcd: C, 57.95; H, 4.66; N, 8.45.
1642, 1691, 2210, 2863, 2936, 3183, 3313 cm-1 attributable to uC=O, uCN, uCH, uNH and uOH, respectively.
2-[(3-acetyl-4-carboxymethyl)-2,5-dioxopyrrolidin1-yl]-6-(4-acetoaminophenyl)-3-cyano-4H-pyran4-carboxylicacid (12)
A mixture of maleamic acid (9) (2.00 g, 5.15 mmol) and
ethyl acetoacetatc (0.65 ml, 5.15 mmol) in dioxan (20 ml) in
the presence of piperidine was refluxed at 60C for10 hrs.
The reaction mixture was allowed to cool at room temperature then poured into diluted solution of acetic acid
(200 ml). The solid formed was filtered off, washed with
water, dried and crystallized from methanol/water to afford
N-cyclic maleimide (12) as white crystals; m.p. 180oC. Elemental analysis for C23H19N3O9 (481.42): Calcd: C, 57.38;
H, 3.98; N, 8.73. Found: C, 57.54; H, 4.06; N, 8.94. IR (KBr)
max (cm-1): 1631, 1697, 2210, 2864, 2938, 3283, 3400 cm-1
attributable to uC=O, uC=N, uCH, uNH and/ or uOH respectively.
EIMS showed m/e = 481 (M .+).
6-(4-acetoaminophenyl)-3-cyano-2-[3-methyl-4,6dioxo-4,5,6,7-tetrahydro-2H-pyrrolo[3,4-c]pyridine1-ylamino]-4H-pyran-4-carboxylic acid (13)
ethyl acetoacetatc (0.65 ml, 5.15 mmol) in dioxan (20 ml) in
the presence of ammonium acetate was refluxed at 60C
for 10 hrs. The reaction mixture was allowed to cool at
room temperature then poured into diluted solution of ace-
371
tic acid (200 ml). The solid formed was filtered off, washed
with water, dried and crystallized from EtOH/H2O as white
(461.44): Calcd: C, 59.87; H, 4.15; N, 15.18. Found: C,
59.99; H, 4.31; N, 15.22. IR (KBr) max (cm-1): 1644, 1695,
2205, 2864, 3280, 3421 cm-1 attributable to uC=O, uCN, uNH
and uOH, respectively.
6- acetoaminophenyl-3-cyano-2-[3,4,6-trioxo-3,3a,4
,5,6,7-hexahydro-2H-pyrrolo[3,4-c]pyridine-1-ylamino-4H-pyran-4-carboxylic acid (14)
diethyl malonate (0.78 ml, 5.15 mmol) in DMF (30 ml) in
the presence of ammonium acetate was refluxed in water
bath at 60C for 6 hrs. The reaction mixture was allowed
to cool to room temperature then poured into diluted solution of acetic acid (200 ml). The solid formed was filtered
off, washed with water, dried and crystallized from EtOH/
C22H17N5O7 (463.41): Calcd: C, 57.02; H, 3.7; N, 15.11.
1632, 1695, 2210, 2863, 2937, 3186, 3315 and 3428 cm-1
attributable to umax of carbonyl groups, uCN, uNH, and uOH
respectively.
4-[6-acetoamino-3-cyano-4-hydro-4-carboxy-pyridin2-yl]amino-4-oxo-but-2-enoic acid (15)
Maleic anhydride (0.33 gm, 3.4 mmol) was completely dissolved at room temperature in glacial acetic acid or THF
(30 ml), and then pyridine derivative (3) (1.00 g, 3.4 mmol)
was added to the solution; the resulting mixture was stirred
under reflux for l hr. The reaction mixture was allowed to
cool to room temperature, and then poured into water (500
ml), the precipitate formed was filtered off, washed with
water, dried and crystallized from MeOH/H2O as white
(394.23): Calcd: C, 57.87; H, 3.58; N, 14.21. Found: C,
57.98; H, 3.67; N, 14.41. IR (KBr) max (cm-1): 1634, 1690,
1725, 2211, 3280, 3384, 3453 cm-1 attributable to umax of
carbonyl groups, uCN, uNH, and uOH, respectively.
acidified with diluted acetic acid (200 ml), the solid formed
was filtered off, washed with water, dried and crystallized
from EtOH/H2O as white crystals; m.p. 210oC. Elemental
analysis for C22H23N7O5 (465.46): Calcd: C, 56.77; H, 4.98;
N, 21.66. Found: C, 57.21; H, 4.81; N, 21.54. IR (KBr) max
(cm-1): 1635, 1690, 1725, 2213, 2926, 3200, 3448 cm-1
due to umax of carbonyl groups, uCN, uCH, uNH and/ or uOH,
respectively. EIMS showed m/e = 465 corresponding to
(M .+).
2 - [ 4 - acety l - 3 - (carb o xy methy l )- 5 - methy l f ura n 2-ylamino]-6-(4-aceto-aminophenyl)-3-cyanopyridine4-carboxylic acid (18)
A mixture of N-cyclic maleamic acid (15) (2.00g, 5.19
mmole) and acetylacetone (0.53 ml, 5.19 mmole) in DMF
(20 ml) in the presence of piperidine was refluxed at 60oC
for 3 hrs. The reaction mixture was allowed to cool to
room temperature then poured into diluted solution of acetic acid (200 ml), the solid formed was filtered off, washed
with water, dried and crystallized from EtOH/H2O as white
(482.48): Calcd: C, 59.74; H, 5.43; N, 11.61. Found: C,
60.04; H, 5.23; N, 11.94. IR (KBr) max (cm-1): 1635, 1690,
1725, 2213, 2926, 3200, 3448 cm-1 due to umax of carbonyl groups, uCN, uCH, uNH and/or uOH, respectively. EIMS
showed m/e = 482 corresponding to (M.+).
2-[5-amino-3-(carboxymethl)-4-cyanofuran2-ylamino]-6-(4-acetoamino-phenyl)-3-cyano
-pyridine-4-carboxylic acid (16)
To a solution of N-cyclic maleamic acid (15) (2.00 g, 5.19
mmol) and malononitrile (0.34 g, 5.19mmole) in DMF (15
ml) few drops of piperidine was added, the resulting mixture was refluxed at 60oC for 5 hrs. The reaction mixture
was allowed to cool to room temperature then acidified
with diluted acetic acid (200 ml), the solid formed was filtered off, washed with water, dried and crystallized from
EtOH/H2O as white crystals; m.p. 200oC. Elemental analysis for C22H22N6O6 (466.41): Calcd: C, 56.65; H, 4.75; N,
18.02. Found: C, 57.18; H, 4.61; N, 18.34. IR (KBr) max
(cm-1): 1634, 1690, 1725, 2211, 3280, 3384, 3453 cm-1
attributable to umax of carbonyl groups, uCN, uNH, and uOH,
respectively.
2-[5-amino-3-(carboxymethyl)-4-cyano-1H-pyrrolo2-ylamino]-6-(4-acetoaminophenyl)-3-cyanopyridine-4-carboxylic acid (17)
To a solution of N-cyclic maleamic acid (15) (2.00 g, 5.19
mmol) and malononitrile (0.34 g, 5.19 mmole) in DMF (15
ml) in the presence of ammonium acetate was added, the
resulting mixture was refluxed at 60oC for 5 hrs. The reaction mixture was allowed to cool to room temperature then
372
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373
Comparing the effectiveness of

processing parameters in pectin
extraction from apple pomace
Hasan Ziari1, Farzin Zokaee Ashtiani1,2*, Mahdy Mohtashamy1
Chemical Engineering Department, Amirkabir University of Technology, No. 424, Hafez Avenue, Tehran, Iran 2Food Process
Engineering and Biotechnology Research Centre, Amirkabir University of Technology, No. 424, Hafez Avenue, Tehran, Iran
Comparacin de la eficacia de los parmetros de proceso en la

extraccin de pectina a partir de pulpa de manzana
Comparaci de leficcia dels parmetres de procs en lextracci de pectina a partir de polpa de poma
Recibido: 9 de noviembre de 2010; aceptado: 10 de marzo de 2011
RESUMEN
Se ha investigado el efecto de tres variables independientes en el proceso de extraccin de pectina, incluyendo el
tiempo de extraccin (60 y 90 min), el pH de la disolucin
de extraccin (1.5 y 2.0) y la temperatura del bao Mara
(75 y 90 C), en el rendimiento y la calidad de la pectina de
pulpa de manzana. El mximo rendimiento de pectina de
15.20%, se obtuvo a pH 1.5 extrayendo durante 90 min.
a 90C, pero la mxima calidad de la pectina se obtuvo
a pH 2.0, extrayendo durante 60 min. a 75C El anlisis
estadstico indic que las variaciones de temperatura, pH
y tiempo tienen el mximo efecto sobre el rendimiento y
calidad de la pectina, respectivamente.
Palabras clave: pulpa de manzana, extraccin de pectina, pH, calidad, temperatura, tiempo, rendimiento.
SUMMARY
The effects of three independent variables in pectin extraction process, including extraction time (60 & 90 min), pH of
extraction solution (1.5 & 2.0) and water bath temperature
(75 & 90C) on yield and quality of apple pomace pectin
were investigated. The highest pectin yield of 15.20% was
obtained at pH 1.5 for 90 min at 90C, but the highest pectin quality factors were obtained at pH 2.0 for 60 min at
75C. Statistical analysis indicated that variations of tem-
374
perature, pH and time had the strongest effects on yield

and quality of pectin, respectively.
Keywords: apple pomace. pectin extraction. pH. quality.
temperature. time. yield.
RESUM
Sha investigat lefecte de tres variables independents
en el procs dextracci de pectina, incloent el temps
dextracci (60 i 90 min), el pH de la dissoluci dextracci
(1.5 i 2.0) i la temperatura del bany Mara (75 i 90C), en
el rendiment i la qualitat de la pectina de polpa de poma.
El mxim rendiment de pectina de 15.20%, es va obtenir
a Ph 1.5, extraient durant 90 min. a 90C, per la mxima qualitat de la pectina es va obtenir a pH 2,0, extraient
durant 60 min. a 75C Lanlisi estadstica va indicar que
les variacions de temperatura, pH i temps tenen lefecte
mxim sobre el rendiment i qualitat de la pectina, respectivament.
Paraules clau: polpa de poma, extracci de pectina, pH,
qualitat, temperatura, temps, rendiment.
*Corresponding author: Tel: +98(21)64543124;

+98(21)66405847; zokaee@aut.ac.ir
Fax:
1. INTRODUCTION
Pectin is a group of complex colloidal polymeric carbohydrates, consisting largely of linear polymers of D--(14)
anhydro-galacturonic acid. Pectin was first discovered by
Vauquelin in 1790 who outlined its chemical nature, Braconnot isolated it in 1824 and gave it the name pectin (1).
Pectin is part of a very complex structure in higher plants,
which gives shape to the soft non-woody parts of the
plant.
Due to gelating and/or stabilizing properties of pectins,
they are widely used in food industry for a variety of purposes such as a gelling agent, thickener, texturiser, emulsifier and stabilizer (1,2), and have been used in various
products such as jams and jellies, fruit juice, desserts and
so on. In addition, non-food applications of pectins such
as in pharmaceutical products have also been reported (3).
Pectins can be obtained on a laboratory scale from various
sources by using different extraction methods such as hot
acidic solution, cold diluted sodium hydroxide, cold and /
or hot solutions of chelating agents (4). To produce pectin
commercially, juicing operation waste products such as
apple pomace or citrus peel are used as raw material and
pectin is extracted in an acidic solution at elevated temperature. Operational extraction parameters such as pH,
temperature and extraction time are the main factors that
affect the yield and quality of pectin (5). Besides, pectin
composition varies with the source from which it is extracted (6).
Wet apple pomace after juicing, is a source of pectin consisting of approximately 1015% pectin on a dry weight
basis (7), and is characterized in many applications by its
superior gelling properties compared to citrus pectins (8).
Extraction of pectin from fresh peach pomace at different
processing parameters such as temperature, acidity and
extraction time was studied by Pgan et al. (9). The effects
of acid volume, acid-washing time and pH variation on the
yield of dried mixed varieties of peach pomace during different stages of pectic substance extraction process, has
been investigated by Faravash and Zokaee (10). Extraction of pectin from apple pomace at laboratory-scale was
performed by Canteri-Schemin et al. (1) in order to observe
the influence of citric acid concentration and reaction time
on pectin yield. Garna et al. (11) investigated the effect of
time, temperature and pH on the yield, degree of esterification, pectin content and natural sugar content of pectin
extracted from apple pomace disregarding the washing
steps of precipitated pectin using alcohol.
The main objective of the present research was to consider
the effectiveness of time, pH and temperature on the yield,
degree of methylation, pectin content and intrinsic viscosity of pectin extracted from apple pomace using statistical
analysis . This study was accompanied by a concentration
step and common alcohol washing steps, which werent
considered before. Following, is the detailed description of
the extraction process.
2. MATERIALS AND METHODS

2.1. Materials
Hydrochloric acid, sulfuric acid and sodium hydroxide
were obtained from Merck. 96% ethanol was obtained
from a local supplier. Standard galacturonic acid sample
was purchased from CP Kelco. All pH adjustments were
done by a digital pH-meter (Metrohm 744) at room temperature.

2.2. Preparation of apple flours
Fresh apples were purchased from a local store and apple pomace was directly prepared after juicing. In order
to neutralize pectolytic enzymes, the apple pomace was
bleached in boiled water at 98C for 10 min (12) which altered the apple pomace color from brown to white. Then,
the apple pomace was immediately placed in cold water
until it cooled down to ambient temperature. Then bleaching was performed in 30C water with solid:liquid ratio
1:20 (w/v) at continuous stirring for 30 min (13). Consequently, soluble materials such as sugar were removed.
The pomace was then drained and pressed to remove
excess water. The next step was drying of pomace for 6
hours in ambient condition and then in oven at 50C, until constant weight of pomace was obtained. Then, dried
pomace was ground via a hammer mill to pass a mesh size
60. The flour was kept in -20C in a non-air environment
to be used later.
2.3. Pectin isolation
Pectin was extracted from apple flour (10g) using 0.1 N
HCl as extracting agent (1:25 w/v) in a water bath apparatus equipped with a temperature controller system and
constant stirring. The extraction was carried out at two different time periods (60 & 90 min), two different pHs (1.5 &
2.0) and two different temperatures (75 & 90C) (Table 1).
After the extraction stage, the suspension were allowed to
cool to room temperature in a water bath, and then centrifuged at 1500g for 60 min. The supernatants were collected and then concentrated at 40C in a vacuum rotary
evaporator (Bchi Co., Zurich, Switzerland) to one-fourth
of its initial volume (14). Afterwards, pH of these dispersions were adjusted to 2.0 by a solution of 0.1 N NaOH
and then pectin was precipitated by addition of 2x volume
96% ethanol to the dispersions. The resulting two-phase
system was allowed to settle for 12 hours at room temperature. The precipitate was collected by filtration and a
washing process was performed twice with 60% ethanol
and twice with 70% ethanol, respectively, prior to a final
washing with 96% ethanol. All washing steps were accompanied by stirring for 30 min to remove impurities such as
monosaccharides and disaccharides (13). Thereafter, the
pectin was pressed to remove excess alcohols and then
placed in a vacuum oven (H.Jrgens, D2800 Bremen, Germany) at 40C until its weight became constant (1). Then
the dried pectin was weighed with a digital scale, comminuted by a hammer mill and kept in -20C in a non-air
environment for further analyses.
2.4. Determination of pectin yield and quality
2.4.1. Pectin yield
Pectin yield (w/w) was expressed as the ratio of dried pectin weight obtained after extraction to the initial apple flour
weight at the start of the experiment.
2.4.2. Pectin contents
Pectin content of the sample, as a percentage of anhydrogalacturonic acid (AGA), was determined by a colorimetric
method using m-hydroxydiphenyl (15).
375
Table 1. Effects of variation in time, pH and temperature on pectin yield and quality
Extraction Conditions
Analysis Parameters
pH
Temperature (C)
Time
(min)
%Yield
(w/w)
% AGA1
% DM2
IV3 (dl/gr)
MW4 (Da)
1.5
75
60
10.750.22
80.871.87
80.000.93
5.000.11
124301
1.5
75
90
11.100.17
77.001.00
79.150.79
4.350.10
102712
1.5
90
90
15.200.20
65.001.00
66.101.00
2.700.09
53444
1.5
90
60
14.750.25
67.301.08
68.501.00
3.120.04
65000
2.0
75
90
10.300.17
79.002.00
81.000.81
4.550.09
108895
2.0
75
60
10.100.10
81.001.50
82.210.71
5.250.10
132892
2.0
90
60
13.630.19
66.321.00
73.000.90
3.340.04
71522
2.0
90
90
14.300.30
65.700.75
69.400.73
2.890.07
58661
Anhydro-galacturonic Acid content of pectin

Degree of Methylation
3
Intrinsic Viscosity
4
Viscosity average molecular weight
1
2
2.4.3. Degree of Methylation

Degree of methylation (DM) expressed as the ratio of esterified galacturonic acid groups to the total galacturonic
acid groups, was determined by a titration method (16).
2.4.4. Intrinsic Viscosity
The intrinsic viscosity (IV) of water-soluble polysaccharides extracted from the apple pomace was measured
using an Ubbelohde capillary viscometer (Size 58) as carried out by Pgan and Ibarz (17). All viscosity data was
obtained at 25C. IV values were calculated based on the
following equations:
(1)
(2)
where is the viscosity of sample solution, s is the viscosity of solvent and [] is the intrinsic viscosity.
3. RESULTS AND DISCUSSION

The mean values of three replicates for each of the experiments are presented in Table 1. Independent variables
include extraction time, pH of extraction solution, and water bath temperature. Response parameters include pectin
yield and corresponding quality factors such as AGA, DM,
IV and MW that determine the functionality of pectin
3.1. Yield of pectin
Based on the results represented in Table 1, pectin yield
varied from the lowest value of 10.10% (pH 2.0 for 60 min
at 75C) to the highest value of 15.20% (pH 1.5 for 90 min
at 90C).
Independent effects of extraction time, pH and temperature on pectin yield are shown in Fig. 1. According to Fig.
1, an increase of time increased the pectin yield slightly
(pH and temperature remaining constant). The same result
was observed by Garna et al. (11) in extraction of apple
pomace pectin, as well as by Mesbahi et al. (19) in pectin
extraction from sugar-beet pulp.
2.4.5. Viscosity Average Molecular Weight

The viscosity average molecular weight (MW) of pectin was
calculated by applying the Mark-Houwink equation (18) as
below:
(3)
where [] is the intrinsic viscosity (ml/g) and MW is the average molecular weight of viscosity (Dalton).
2.5. Statistical analysis
All statistical analyses (students t-test in significance level
of p<0.05) were performed using Minitab software (version
14, Minitab Inc.). A factorial design of experiments was
conducted and analysis of variance (ANOVA) was generated for each one of the responses, Moreover, figures
for relative comparison between independent effects of
extraction parameters on pectin yield and quality factors
were plotted. Relationship between coded values (CV) and
corresponding real values of independent parameters are
as follows:
CV
pH
Temp. (C)
Time (min)
+1
2.0 90 90
-1
1.5 75 60
376
Figure 1. Independent effect of time, pH

and temperature on pectin yield.
Since pectin extraction is a mass transfer process from

solid phase to liquid phase, it could be terminated by time
(leading to an equilibrium state). Thereafter, by extending
the extraction time, the extracted pectins may degraded
due to contact with hot acidic solution and they cannot be
precipitated by adding alcohols (20). Hence, efficient extraction time should be taken into account as an important
parameter in the extraction process. This phenomenon
has been noted by Phatak et al. (21) and De Vries et al.

(22).
According to Fig. 1, the pectin yield increased with acid
strength. According to Table 1, on average 12.95% and
12.08% (%w/w) of pectin were extracted, respectively, at
pH 1.5 and pH 2.0. Similar results were observed by Garna
et al. (11) in the extraction of apple pomace pectin, Mesbahi et al. (19) in pectin extraction from sugar-beet pulp as
well as the study by Pagn and Ibarz (17) on pectin extraction from fresh peach pomace.
Using higher extraction pH value than the pH region of this
study for hydrolyzing insoluble pectic substances is not
applicable, because higher pH values or lower acidic power is equal to lower potential for hydrolyzing non-soluble
pectic substance.
With regard to the influence of the extraction temperature,
there was an increase in the pectin yield by increasing the
temperature of extraction stage. Table 2, shows this significant effect. Mesbahi et al. (19), Garna et al. (11) and
Pagn et al. (9) reported a similar effect of the temperature
on pectin yield extracted from various sources.
showed a slight effect of time on the AGA content of apple

pectin (p>0.05).
Variations of pH showed no significant change on the AGA
content of pectin (p>0.05).
Overall, temperature, time and pH of extraction were the
most effective parameters on the AGA variations of extracted pectin, respectively (Table 3).
Table 2. ANOVA for pectin yield
Since the pectin content in this work were all higher than
65%, they could be considered as commercial pectin
products (24)
p-value
Source
DF1
SS2
MS3
F-value
pH
4.515
4.515
104.19
0.000
91.611
91.611
2113.9
Figure 2. Independent effect of time, pH and temperature on the anhydro-galacturonic acid content of pectin
0.000
time
1.046
1.046
24.13
0.000
pHT
0.122
0.122
2.81
Table 3. ANOVA for anhydro-galacturonic acid content of pectin
0.113
p-value
pHtime
0.002
0.002
0.04
0.839
Source
DF
SS
MS
F-value
Ttime
0.122
0.122
2.81
0.113
pH
1.29
1.29
0.74
0.402
0.293
1075.22
1075.22
618.05
0.000
time
28.95
28.95
16.64
0.001
pHT
2.18
2.18
1.26
0.279
pHTtime
0.051
0.051
1.18
Degrees of freedom
Sum of square
3
Mean square
1
2
3.2. AGA of pectin

The AGA content as the main component of pectin molecular chain varied from 65.00% (at pH 1.5 for 90 min at
90C) to 81.00% (at pH 2.0 for 60 min at 75C) (Table 1).
Moreover, the effect of time, pH and temperature on the
AGA of pectin is shown in Fig. 2.
Based on Table 1, increasing the temperature reduced
the AGA content of extracted pectin. On average 66.08%
and 79.47% AGA was obtained, respectively, at extraction temperature of 90C and 75C. This could be due to
degradation of pectins molecular chain to compounds
with smaller molecular weight at higher temperatures, that
would not precipitable by alcohols. Garna et al. (11) reported an increase in the AGA content of apple pomace
pectin by increasing the temperature. El-Nawawi et al. (23)
reported a bilateral effect of temperature on the AGA content of orange peel pectin. They observed that AGA content increased with the temperature increase from 50C
to 90C. However, it dropped when temperature increased
up to 110C. Table 3 shows that temperature changes had
the strongest effect on the variation of AGA (p<0.001).
Based on Table 1, on average 73.87% and 71.68% AGA
was obtained, respectively, at extraction times of 60 and
90 min. Thus, an increase of time led to an insignificant
decrease of AGA content of extracted pectin (Fig. 2). This
result was in contrast to what Garna et al. (11) reported
for apple pomace pectin extraction. Although their results
pHtime
4.72
4.72
2.71
0.119
Ttime
3.26
3.26
1.87
0.190
pHTtime
0.01
0.01
0.01
0.932
3.3. DM of pectin
The DM of extracted pectin varied from 61.10% to 82.21%
(Table 1). The highest DM was obtained at pH 2 for 60 min
at 75C. The lowest DM was obtained at pH 1.5 for 90 min
at 90C.
Figure 3. Independent effect of time, pH and temperature on degree of methylation of pectin.
Independent effects of time, pH and temperature on DM

of extracted pectin are shown in Fig.3. As can be seen, (i)
a temperature increase resulted in a significant decrease
of DM. On average, 80.59% and 69.25% of DM were
obtained, respectively, at 75C and 90C. (ii) An increase
377
of time was inversely proportional to DM but with much

slighter effect than temperature. On average, 75.93% and
73.91% of DM were obtained, respectively, for 60 and 90
minutes of extraction time. (iii) An increase of pH led to
an increase of DM, since it prevents the de-methylation of
pectin. A same result was reported by Levigne et al. (25) on
pectin extraction from fresh sugar beet as well as by Joye
and luzio (24) on the lemon peel pectin extraction.
The effects of time, pH and temperature on DM of pectin
in this study were qualitatively consistent with those reported by Garna et al. (11) on pectin extraction from apple
pomace.
ANOVA for the DM of extracted pectin is presented in Table 4. The F-value of temperature shows its notably significant effect on the DM of pectin among other terms.
Since DM values in this study were higher than 50%, the
apple pectins produced are high-methoxyl pectins.
Table 4. ANOVA for Degree of Methylation of pectin
Source
DF
SS
MS
F-value
p -value
pH
52.75
52.75
70.41
0.000
771.57
771.57
1030.00
0.000
time
24.36
24.36
32.52
0.000
pHT
5.25
5.25
7.00
0.018
pHtime
0.91
0.91
1.22
0.286
Ttime
5.82
5.82
7.77
0.013
pHTtime
0.26
0.26
0.35
0.561
3.4. IV and MW of pectin

Variation of time, pH and temperature on the IV of extracted pectin is plotted in Fig. 4. According to Table 1, the
highest IV of 5.25 dl/g was obtained in pH 2.0 for 60 min at
75C, corresponding to the softest extraction conditions.
On the other hand, the lowest IV value of 2.70 was obtained in the harshest extraction condition (pH 1.5 for 90
min at 90C).
and pH of extraction on the IV was reported by Emaga et

al. (26) on pectin extraction from banana peels as well as
by Levigne et al. (25) on pectin extraction from fresh sugar
beet using both HCl and HNO3 as extracting agents.
ANOVA for the IV of extracted pectin is presented in Table
5. Temperature variation had the strongest effect on the IV
of pectin similar to DM and AGA among other terms.
Table 5. ANOVA for Intrinsic Viscosity of pectin
p -value
Source
DF
SS
MS
F-value
pH
0.2993
0.2993
49.33
0.000
19.0817
19.0817
3145.33
0.000
time
1.9041
1.9041
313.86
0.000
pHT
0.0020
0.0020
0.33
0.572
pHtime
0.0048
0.0048
0.79
0.386
Ttime
0.0988
0.0988
16.29
0.001
pHTtime
0.0011
0.0011
0.18
0.681
4. CONCLUSIONS
Operational parameters in pectin extraction process including time, pH and temperature have had different effects on the yield and quality of pectin qualitatively and
quantitatively. Amongst them, temperature has shown the
strongest effect in all analyses.
Overall, a temperature increase gave rise to increase of
pectin yield, but AGA, DM and IV of pectin decreased as
well. An increase of time had no significant effect on pectin
yield, but decreased its AGA, DM and IV. Increasing the pH
of extraction process resulted in a decrease in pectin yield
but increased its AGA, DM and IV.
The highest pectin yield and also the lowest pectin quality
factors (AGA, DM and IV) were obtained in the most drastic
extraction conditions. It means that a higher pectin yield
is not necessarily representative of pectin quality. Garna
et al. (11) reported the same phenomenon and explained
a co-precipitation of other components with pectin which
resulted in a superficial increase in pectin yield.
It can be seen that various pectin yield and quality with
desired end use could be achieved by altering the processing parameters of pectin extraction stage. Therefore,
suitable operational conditions can be chosen based on
actual need for pectin functionality.
Figure 4. Independent effect of time, pH and temperature on the intrinsic viscosity of pectin.
Based on Table 1 and Fig. 4, (i) Increasing the temperature

decreased the IV (and MW) of pectin considerably owing to
break down of pectins molecular chains. On average, 4.79
and 3.01 (dl/gr) for IV of pectin was obtained, respectively,
at 75C and 90C. (ii) Likewise, an increase of time decreased the IV of pectin but with slighter effect than temperature. (iii) Increasing the extraction pH increased the IV,
but had the lowest independent effect.
Pagn et al. (9) showed the same influence of temperature and pH on the IV of pectin extracted from fresh peach
pomace. In addition, the same effect of time, temperature
378
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Isobaric Vaporliquid equilibrium for the binary

system Diisopropylether + Isopropanol at 95 kPa
Ahmad T. Shawaqfeh
Chemical Engineering Department, Mutah University, Mutah Box 7, Karak 61710 JORDAN
Equilibrio isobrico lquido-vapor para el sistema binario Diisopropileter + isopropanol a 95 kPa.

Equilibri isobric lquid-vapor per al sistema binari Diisopropilter + isopropanol a 95 kPa.
Recibido: 15 de septiembre de 2010; revisado: 13 de noviembre
de 2010; aceptado: 22 de noviembre de 2010
RESUMEN
RESUM
Se han determinado los datos sobre el equilibrio isobrico lquido vapor para el sistema binario compuesto por
Diisopropil ter (1) y Isopropanol (2) a 95 kPa. Para ello se
ha utilizado un aparato de destilacin totalmente de vidrio,
equipado con una bomba de circulacin Cottrell. Este
sistema se caracteriza por la formacin de un azetropo
a x1 = 0.796 al mnimo punto de ebullicin. Datos VLE
termodinmicamente coherentes correlacionan satisfactoriamente con el coeficiente de actividad de la fase lquida, utilizando los modelos NRTL, Wilson y UNIQUAC. Las
predicciones del punto de burbuja y la composicin de la
fase vapor utilizando estos modelos fueron consistentes
con las determinaciones experimentales. La desviacin
cuadrtica media para el punto de burbuja y la fraccin
molar del vapor, utilizando los modelos NRTL, Wilson y
UNIQUAC, fueron (0.6 K, 0.030), (0.5 K, 0.030), y (0.6 K,
0.028) respectivamente
Shan determinat les dades sobre lequilibri isobric lquidvapor per al sistema binari format per Diisopropil ter (1)
i Isopropanol (2) a 95 kPa. Per fer aix sha utilitzat un
aparell de destillaci totalment de vidre, equipat amb una
bomba de circulaci Cottrell. Aquest sistema es caracteritza per la formaci dun azetrop a x1 = 0.796 al mnim punt debullici. Dades VLE termodinmicament coherents correlacionen satisfactriament amb el coeficient
dactivitat de la fase lquida, utilitzant els models NRTL,
Wilson i UNIQUAC. Les prediccions del punt de bombolla i la composici de la fase vapor utilitzant aquests models van ser consistents amb les determinacions experimentals. La desviaci quadrtica mitjana per al punt de
bombolla i la fracci molar del vapor, utilitzant els models
NRTL, Wilson i UNIQUAC, van ser (0.6 K, 0.030), (0.5 K,
0.030), i (0.6 K, 0.028) respectivament.
Palabras clave: mezcla binaria, diisopropil ter (DIPE);

datos VLE isobricos; Isopropanol.
Paraules clau: mescla binria, diisopropil ter (DIPE);

dades VLE isobriques; Isopropanol.
SUMMARY
Isobaric vaporliquid equilibrium data have been measured for the binary system involved {Di-isopropyl Ether
(1) + Isopropanol (2)} at 95 kPa. An all-glass re-circulating
still equipped with a Cottrell circulation pump was used.
The formation of an azeotrope was characteristic for this
system at x1 = 0.796 at the minimum boiling point. Thermodynamically consistent VLE data have been satisfactorily correlated using the NRTL, Wilson and UNIQUAC
models for the activity coefficient of the liquid phase. The
predictions of bubble point and vapor phase compositions
using these models were close to experimental measurements. Root-Mean-Square-Deviation for bubble point and
vapor mole fraction predictions were (0.6 K, 0.030), (0.5 K,
0.030), and (0.6 K, 0.028) when using NRTL, Wilson and
UNIQUAC models, respectively.
Keywords: Binary mixture; Di-isopropyl ether (DIPE); Isobaric VLE data; Isopropanol
380
*Corresponding author: Tel: (+962)323-72380(x-6113);

Fax: (+962)323-72384; shawaqat@mutah.edu.jo
INTRODUCTION
Tertiary ethers with 5 or 6 carbons, like diisopropyl ether
(DIPE), show excellent antiknock properties besides their
less polluting effects. These compounds are becoming the
preferred oxygenates for use in gasoline in order to improve its octane rating (Heese et al., 1999; Kinfton and Dai,
1999). DIPE is obtained by a reaction of propylene with
isopropyl alcohol, which is initially produced by hydration
of propylene. The ether purification involves extraction of
alcohol with water. Information on the vaporliquid equilibrium (VLE) is essential for development and design of
equipment for separation processes. Therefore, phase
equilibrium data of oxygenated mixtures are important for
predicting the vapor phase composition in equilibrium with
hydrocarbon mixtures. In many cases, the system formed
by the ether and the homologous alcohol resulted in an
azeotropic mixture (Gmehling and Blts, 1996; Lladosa
et al., 2007). Experimental determination of VLE data involves temperature, pressure, and phase compositions.
Correlation and prediction of VLE data refer to the relationship between compositions of each component in the
coexisting phases.
Isothermal as well as isobaric vaporliquid equilibrium
data were reported in literature for binary and ternary systems involving DIPE and 2-propanol (Lladosa et al., 2007;
Miller and Bliss, 1940; Verhoeye, 1970; Chamorro et al.,
2002; Arce et al., 2003; Villaman et al., 2006; Lladosa
et al., 2006; Ku and Tu, 2006). Most of the isobaric VLE
data of this system were reported at an adjusted standard
pressure of 101.32 kPa. Different equations of state were
used to calculate the nonideality of the vapor-phase. The
thermodynamic consistency of the binary VLE data was
examined by the direct test of Van Ness (Van Ness, 1995)
and the method of Kojima et al. (Kojima et al., 1990). The
VLE data of the ternary system passed the thermodynamic
consistency test of the McDermottEllis method as modified by Wisniak and Tamir (McDermott and Ellis, 1965;
Wisniak and Tamir, 1977). Activity coefficients of both the
binary and the ternary systems were satisfactorily correlated by Wilson (Wilson, 1964), NRTL (Renon and Prausnitz, 1968), and UNIQUAC (Abrams and Prausnitz, 1975)
models.
The objective of the present study is to measure experimentally the VLE behavior of the DIPE + Isopropanol binary system; at an ambient pressure of 95 kPa. The experimental data will then be analyzed and correlated using
Wilson, NRTL and UNIQUAC models. Predictions will then
be compared with the experimental data.
EXPERIMENTAL
Chemicals
All chemicals used in this study were of high-purity grade
purchased from Aldrich. The purity of all chemicals was
greater than 99.8% as validated for each one by using gas
chromatograph. These chemicals were used without further purification.
Apparatus and Procedure
The vaporliquid equilibrium apparatus used in this work is
depicted in Figure 1. It is mainly an all-glass re-circulating
still in which both liquid and vapor phase are continuously re-circulated. It was equipped with Cottrell circulation
pump to ensure continuous and intimate contact between
liquid and vapor phases during boiling as well as their

contact with the temperature sensing element. The equilibrium temperature was measured with a Beckman thermometer with uncertainty of 0.02 K. The ambient pressure was measured using a manometer with uncertainty
of 0.3 kPa. The experimental procedure was described
elsewhere (Darwish and Al-Anbar, 1997). When equilibrium
was reached, liquid and vapor-condensed phase were
sampled and their compositions were analyzed using gas
chromatograph (Varian CP-3800, column temperature
333.2 K, injector temperature 493.2 K, detector temperature 503.2 K, flow rate 30 ml.min-1). Experimental uncertainties in liquid and vapor mole fractions were estimated
as 0.001.
Figure 1: Scheme of the experimental setup for the measurement of vapor-liquid equilibrium. 1, boiler; 2, Cottrell pump;
3, separation still; 4, thermowell; 5, spiral; 6, separation cup;
7, pressure damper; 8, heat exchanger; 9, liquid sampling;
10, vapor sampling; 11, drop counter; 12, mixing chamber.
RESULTS AND DISCUSSION

The following equation was used to calculate activity coefficient for each component using the experimental VLE
data. The nonideality of vapor phase was calculated using
the virial equation of state
(1)
381
where
is the liquid-phase activity coefficient of component i, xi and yi are the experimental values of the liquid
and vapor-phase compositions, P is the total pressure,
and
.The pure liquid molar volume
was calculated using the modified Rackett equation
(Spencer and Danner, 1972). The vapor pressures
of
pure compounds were calculated using Antoines equation. The second virial coefficient of pure materials Bii and
cross second virial coefficients Bij were calculated according to the method of Hayden and OConnell (Hayden and
OConnell, 1975).
The experimental values of liquid and vapor phases compositions, xi and yi, and equilibrium temperatures, T, for
the binary system DIPE (1) + Isopropanol (2) are presented
in Table 1. The same table shows values of activity coefficients as were calculated using Eq. (1) with the experimental values of temperatures and mole fractions.
Table 1: Experimental VLE data for Diisopropyl
Ether (1) + Isopropanol (2) system at P=95 kPa.
x1
y1
T (K)
0.000
0.000
352.8
1.042
0.0263
0.0483
351.6
1.298
1.068
0.0584
0.100
350.6
1.246
0.249
347.4
1.615
0.376
345.6
2.156
1.017
0.193
0.445
343.8
2.034
1.031
0.208
0.465
342.8
2.028
1.056
0.233
0.523
342.2
2.073
0.997
0.277
0.538
341.4
1.836
0.617
339.3
1.696
0.695
338.7
1.411
0.749
337.6
1.221
0.772
337.2
1.159
0.782
336.8
1.096
0.799
336.8
1.056
0.892
337.0
1.046
0.971
337.6
1.046
3.878
1.000
1.000
338.6
1.029
339.1
0782
The experimental data were analyzed and assessed for

thermodynamic consistency by applying the Herington
area test (Herington, 1951). According to this test the ratio of the experimental activity coefficients was plotted
against the liquid mole fraction of DIPE, x1, on a semi-logarithmic scale. The following parameters were defined as
2.769
0.986
101.3
0.796
2.299
0.922
0.906
336.9
1.972
0.823
307.3
95
(Lladosa et
al., 2007)
1.595
0.776
This work
1.406
0.716
(Lladosa et al., 2007)
1.148
0.651
30
x1
1.098
0.506
T (K)
This
work
1.060
0.366
P (kPa)
1.106
0.146
Table 2: Azeotropic compositions and temperatures for the system Diisopropyl Ether (1) + Isopropanol (2) at different pressures.
1.086
0.122
ing literature values (Lladosa et al., 2007). Azeotropic

temperature was obtained from the best polynomial fit for
T=f(x1), using the x1 values previously determined. One can
observe from Table 2 the strong dependency of azeotropic
composition and temperature on pressure as well the consistency of our results with those reported in the literature.
(2)
(3)
The azeotropic composition was determined by finding the

value of x1 that make the function f(x1)= (y1x1) equal to zero.
The composition and boiling temperature of the azeotrope
are summarized in Table 2, together with the correspond-
382
where I and II are the areas above and below the zero axis,
respectively. T1, T2, and Tmin are the boiling points of pure
1 and 2, and the lowest boiling point observed in the entire composition range, respectively (all in Kelvin). Figure
2 shows the plot of (1/2) versus x1, where D is calculated
as -3.45 and J was 6.32. Herington showed that if |D| -J <
10, the data will be consistent. Numerically, this difference
equal to -2.87 which confirms the thermodynamic consistency of the experimental data.
Figure 2: Thermodynamic consistency area test of VLE

data for the diisopropyl ether (1) + isopropanol (2) system
at P= 95 kPa as proposed Herington (Herington, 1951).
The VLE data presented by this work at 95 kPa were compared with those in the literature at atmospheric pressure
for the same system. Figures 3 and 4 show these comparisons for equilibrium compositions, and temperatures, respectively. Both figures show similar trend for the variation
with mole fraction. However, the comparison showed that

the effect of pressure was evident in lowering the equilibrium temperature and increasing the azeotropic composition. This effect was confirmed by the results presented in
Table 2.
and temperature were calculated corresponding to the

measured pressure and liquid phase compositions.
Table 3: Estimated values of binary interaction parameters A12 and A21 in the NRTL (12=0.30), Wilson, and UNIQUAC models for the system Diisopropyl Ether (1) + Isopropanol (2) at P=95 kPa.
Model
-192.2
-415.1
2474.4
UNIQUAC
The activity coefficients were correlated with the NRTL,

Wilson and UNIQUAC models. Estimation of parameters
for each model was based on maximum likelihood principles as developed by Prausnitz (Prausnitz, 1969). Regression based on this principle requires the estimated uncertainties, 2, in each measured variables. In this study, the
following uncertainties were used: 0.3 kPa in pressure, 0.1
K in temperature, 0.001 in liquid mole fraction, and 0.003
in vapor mole fraction (Walas, 1985). The effective binary
interaction parameter Aij for the models NRTL, Wilson, and
UNIQUAC are defined by Aij = (gij - gjj), Aij = (aij - aii) and Aij
= (uij - ujj), respectively. The relevant parameters obtained
from the correlation of experimental data using model
equations were presented in Table 3 for each model. These
regressed parameters were used in predicting activity coefficients. Then, the equilibrium vapor phase composition
1682.5
Wilson
Figure 4: Comparison of experimental (T, x, y) equilibrium

data for diisopropyl ether (1) in the diisopropyl ether (1) +
isopropanol (2) solution. Measurements of this work were at
P= 95 kPa, while the literature data were at P= 101.3 kPa.
A21 (Jmol-1)
NRTL, 12= 0.30
Figure 3: Comparison of experimental x,y equilibrium

data for diisopropyl ether (1) in the diisopropyl ether (1) +
isopropanol (2) solution. Measurements of this work were at
P= 95 kPa, while the literature data were at P= 101.3 kPa
A12 (Jmol-1)
3136.7
-533.8
Figures 5 and 6 show the predicted values versus the

experimentally measured values of temperature and vapor phase composition of DIPE, respectively. The results
presented in these figures indicate the ability of the three
models in describing the phase behavior of DIPE + Isopropanol system. The good agreement of the predicted results with the experimental ones was evident from Figures
7 and 8. These figures show the temperature and vapor
phase composition deviations for the three models from
the experimental ones.
Figure 5: Comparison between the calculated and measured

mole fractions of diisopropyl ether in the vapor phase for the
system diisopropyl Ether (1) + isopropanol (2) at P=95 kPa.
The root mean square deviations (RMSD) were calculated

from the difference between the experimental data and the
calculated values for each model according to the following equation:
(4)
exp
where N is the number of experimental data points, yi

and yical are the experimental and calculated vapor-phase
mole fractions, respectively. The RMSD values for the
DIPE (1) + Isopropanol (2) binary system are tabulated in
Table 4. These results show that the deviations in vapor
phase compositions and equilibrium temperatures are
reasonably small, and it is indicated that the activity coefficient for all three models are suitable to represent the
binary experimental data.
383
Table 4: Root mean square deviation (RMSD) for vapor phase

composition and bubble point temperature predictions by
the NRTL (12=0.30), Wilson, and UNIQUAC models for the
system Diisopropyl Ether (1) + Isopropanol (2) at P=95 kPa.
Models
yRMSD
TRMSD (K)
NRTL, 12= 0.30
0.030
0.63
Wilson
0.030
0.53
UNIQUAC
0.028
0.58
CONCLUSIONS
Figure 6: Comparison between the calculated and
measured bubble point temperatures for the system
diisopropyl ether (1) + isopropanol (2) at P=95 kPa.
The experimentally measured VLE data for {DIPE (1) + Isopropanol (2)} binary system were successfully correlated
using NRTL, Wilson, and UNIQUAC model equations. Results showed that the calculated parameters were fitted
adequately by these models. Deviations of predictions of
these equations were reasonably small and of similar order
of magnitude. Azeotropic conditions were consistent with
the literature findings and confirm sensitivity of these conditions to the pressure of the system. Based on these results, these models could be used equivalently to describe
the VLE for the {DIPE (1) + Isopropanol (2)} system. They
meet the need for the design and operation of separation
processes.
Acknowledgment
The enormous help and communications provided by Dr.
Zaid Al-Anbar and Dr. Fares Al Momani are appreciated as
acknowledged.
Figure 7: Deviation y1 =y(exptl.) - y(calcd.) between

the calculated and measured mole fractions of diisopropyl ether in the vapor phase for the system diisopropyl ether (1) + isopropanol (2) at P=95 kPa.
Figure 8: Deviation T/K =T(exptl.)/K - T(calcd.)/K

between the calculated and measured bubble
point temperatures for the binary system diisopropyl ether (1) + isopropanol (2) at P=95 kPa.
384
List of Symbols
Bii
second virial coefficient of component
i (m3/mol)
Bij
cross virial coefficient of components i
and j (m3/mol)
D
area ratio in Herington area test method

g
characteristic energy (J mol1)
J
boiling temperature ratio defined by

Herington area test method
system total pressure (kPa)
P

Pi s
saturation vapor pressure of the pure

liquid i (kPa)
R
gas constant (8.314 J mol-1 K-1)
T
equilibrium boiling temperature (K)
xi mole fraction of component i in the li-
quid phases
yi
mole fraction of component i in vapor
phases
Greek symbols

adjustable parameter in NRTL model
i
activity coefficient of component i in

the liquid phase
viL
molar volume of pure liquid compo
nent i (m3/mol)
Superscripts
cal
exp
L
s
Subscripts
i, j
calculated results
experimental results
Liquid
saturated
component
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385
Abatement of organic pollutants from olive

mill effluent by TiO2 nano-particles using
Catalytic Wet Air Oxidation (CWAO) technique
M. I. Badawya, M.Y Ghalyb*, M. F. Zawrahc, M.E.M. Alia, F. El Goharya
National Research Centre (NRC), El-Tahrir Street, Dokki, Cairo, Egypt.
Water Pollution Research Department bChemical Engineering and Pilot Plant Department;
Energy Group, Center of Excellence c Nano Group, Center of Excellence
Eliminacin de contaminantes orgnicos en efluentes de molinos olivareros por nanopartculas

de TiO2 utilizando la tcnica de oxidacin cataltica con aire hmedo (CWAO)
Eliminaci de contaminants orgnics en efluents de molins oliverers per nanopartcules
de TiO2 utilitzant la tcnica doxidaci cataltica amb aire humit (CWAO)
Recibido: 15 de octubre de 2009; ltima revisin: 5 de septiembre
de 2010; aceptado: 9 de marzo de 2011
RESUMEN
El objetivo de este trabajo es estudiar la aplicabilidad de
la oxidacin cataltica de aire hmedo (CWAO) para el tratamiento de aguas residuales de molinos de oliva (OMW)
utilizando nanopartculas de dixido de titanio (TiO2). Los
experimentos se realizaron utilizando un reactor de alta
presin (reactor Parr) a temperatura elevada y con una
presin parcial de oxgeno inicial de 10 bares. Se ha establecido la influencia de las variables operacionales como
temperatura de reaccin, valor de pH inicial, cantidad y
tipo de catalizador, y tiempo de retencin. Se ha observado que la mineralizacin del efluente del molino de aceite
est marcadamente afectada por la temperatura inicial de
la reaccin y el pH durante la operacin. La demanda qumica de oxgeno (DQO) y el carbono orgnico total (COT)
se redujo a 84.22 y 81.19 % respectivamente, en las condiciones operativas ptimas, es decir: pH = 6 y dosis de
TiO2 = 4 g/L durante 1 hora. Los contenidos de lignina,
fenol y compuestos polifenlicos tambin disminuyeron
un 97.58, 94.77 y 84.24 %, respectivamente, en el mismo
tiempo de reaccin. Los resultados muestran la posibilidad de utilizar la tcnica de CWAO como pretratamiento
de OMW.
Palabras clave: Oxidacin cataltica con aire hmedo
(CWAO); Efluente de Molino olivarero; Tratamiento de
aguas residuales.
SUMMARY
The objective of this work was to study the suitability of
catalytic wet air oxidation (CWAO) for the treatment of olive mill wastewater (OMW) using using prepared titanium
dioxide (TiO2 nanoparticles. Experiments were performed
)
386
using high pressure reactor (Parr reactor) at elevated temperatures and an initial oxygen partial pressure of 10 bars.
The influence of the operational variables such as reaction
temperature, initial pH value, amount and type of catalyst,
and retention time was established. It was observed that
the mineralization of oil mill effluent was markedly affected
by the initial reaction temperature and operating pH. The
chemical oxygen demand (COD) and total organic carbon
(TOC) were reduced by 84.22 and 81.19 % respectively, at
optimum operating condition, i.e. pH = 6 and TiO2 dose
= 4 g/L within 1 hour. The contents of lignin, phenol and
polyphenolic compounds were also decreased to 97.58,
94.77 and 84.24 %, respectively, within the same reaction
time. The results showed the possibility of using CWAO
technique as a pretreatment step of OMW.
Keywords: Catalytic wet air oxidation (CWAO); Olive mill
effluent; Wastewater treatment.
RESUM
Lobjectiu daquest treball s estudiar laplicabilitat de
loxidaci cataltica daire humit (CWAO) per al tractament
daiges residuals de molins doliva (OMW) utilitzant nanopartcules de dixid de titani (TiO2). Els experiments es van
realitzar utilitzant un reactor dalta pressi (reactor Parr) a
temperatura elevada i amb una pressi parcial doxigen
inicial de 10 bars. Sestableix la influncia de les variables
operacionals com la temperatura de reacci, valor de pH
inicial, quantitat i tipus de catalitzador, i temps de retenci.
Sha observat que la mineralitzaci de lefluent del mol
*Corresponding author: Associate Professor Dr. Montaser
Y. Ghaly, ghalynrc@yahoo.com, Tel: +20127982260 Fax:
+20233370931
doli est marcadament afectada per la temperatura inicial

de reacci i el pH durant loperaci. La demanda qumica
doxigen (DQO) i el carboni orgnic total (COT) es van reduir a 84.22 i 81.19 % respectivament, en les condicions
operatives ptimes, s a dir: pH = 6 i dosi de TiO2 = 4 g/L
durant 1 hora. Els continguts de lignina, fenol i compostos polifenlics tamb es reduren un 97.58, 94.77 i 84.24
%, respectivament, en el mateix temps de reacci. Els resultats de mostren la possibilitat dutilitzar la tcnica de
CWAO com a pretractament dOMW.
Paraules clau: Oxidaci cataltica amb aire humit (CWAO);
Efluent de Mol doliva; Tractament daiges residuals.
1. Introduction
In the extraction process of olive oil, a black highly polluting wastewater called olive oil mill wastewater (OMW) is
generated in the short harvesting season. The disposal of
this effluent constitutes a serious environmental concern in
countries of the Mediterranean area that produce olive oil.
OMW is difficult to treat by common biological processes
due to high COD (80200 g/L), low pH and the presence
of compounds with phytotoxic and antibacterial effects [1].
OMW contains diversity of organic compounds (including
phenols, polyphenols and polyalcohols) with low biodegradability and high toxicity, which may explain the lack of
a well-established technology for their treatment. However, recently, the Mediterranean countries faced changes in
their national legislation regarding treatment and disposal
of OMW. In the last few years, there has been a great effort
to develop efficient solutions for the treatment of OMW.
Biological treatments are ineffective in practice, but when
combined with chemical or physical processes, the reduction of the OMW pollution parameters can be drastically
improved [2]. Other solutions, such as advanced oxidation
processes and/or physico-chemical processes, have also
been developed. Some examples include Fenton treatment [3], ozonation [4], ultra-filtration and photo-peroxidation techniques [5], electrochemical oxidation [6], electrocoagulation [7] and electro-Fenton oxidation [8].
Wet air oxidation (WAO) mineralizes pollutants at elevated
temperature and pressures (220320 C, 50200 bar) using oxygen or air as the oxidizing source, having the ability
to almost completely convert various organic compounds
present in the effluent into carbon dioxide and water. WAO
has been used previously for the treatment of several types
of wastewater [9-11]. Since it can also achieve high conversion rates, the wet oxidation process typically requires
much less space and produces much less quantities of
secondary pollutants compared with more traditional technologies. Moreover, no additional sludge or concentrated
wastes are produced by the WAO process. Thus the wet
air oxidation process might be an economically feasible
alternative method practically suitable for the treatment of
high COD concentration [12-14].
Gomes et al. studied the suitability of catalytic wet air oxidation (CWAO) for the treatment of olive mill wastewater
(OMW) in a high pressure reactor at 100 and 200C under an oxygen partial pressure of 6.9 bar, using carbon
supported platinum (1 wt.% Pt) and iridium (5 wt.% Ir)
catalysts. At 100 C, refractory organic compounds persisted even after prolonged reaction time (8 h). At 200 C,
complete total organic carbon and colour removal was
obtained with the Pt/C catalyst after 8 h of reaction. The

results obtained from their work indicate that Pt/C is a
promising catalyst for the CWAO of OMW [15].
WAO implies high capital costs and safety issues, mainly
due to material corrosion, which requires the construction of WAO units with high nickel content alloys, much
more expensive than common stainless steel, and large
thickness, in order to support the high pressures involved.
In order to ease and reduce these reaction conditions to
more amenable values (125220 C, 550 bar), suitable
catalysts can be introduced to reduce the oxidation reaction activation energy. This referred to as catalytic wet air
oxidation (CWAO). Homogeneous catalysts (usually metal
ions in solution) or powder metal oxides can enhance the
oxidation and conversion rates of contaminants [16].
However, these catalysts cause secondary pollutant
problem so that further treatment is required to remove
or recover the metal ions from the water after the organic
compounds have been oxidized. Several catalysts were
studied in the last decades. Heterogeneous catalysts presenting very high activity and stability have been developed over the last years [17,18], since they can be easily
removed by filtration after the wastewater is treated, and
is available for reuse.
In this work, we focused on the preparation of highly catalytic active nanosize anatase structured TiO2. Also, prepared TiO2 catalyst was used to study the degradation of
an OMW by catalytic wet air oxidation (CWAO), because of
its previous activity and stability in the oxidation of refractory organic compound.
2. Experimental
2.1. Material Used
Analytical grade Sulfuric acids, Titanium tetrachloride, Ethyl alcohol and Ammonium hydroxide supplied by Merck
(Germany) were used. Oxygen gas was supplied in cylindrical vessels that supplied by Ayag Company for industrial gases (Egypt).
2.2. Olive mill wastewater
The olive mill wastewater (OMW) used in this work was
collected from El-Salhia Olive Mills Company, an olive oil
processing plant near Isamalia in the East of Egypt, operating with a continuous three-phase centrifugation process.
The detailed characterization of the OMW (which presents
a strong brown colour) was listed in Table[1]. Before performing wet air oxidation WAO/CWAO tests, the OMW
was filtered, diluted two times with tap water, settled for 1
hour and stored at -15 C in plastic cans. After these procedures, the OMW chemical oxygen demand was reached
to value of 117860 mg/ L. For each reaction, a new frozen
sample was used in order to avoid initial composition discrepancies between them.
Table [1] Characterization of twice diluted raw olive mill wastewater after settling 1 hour
Parameter
pH
Raw
4.7
COD (mg/L)
117860
TOC (mg/L)
44250
Oil & grease (mg/L)

Lignin (phenol Index) (mg/L)
Phenol (mg/L)
6847
19161
6294
387
2.3. Preparation and Analysis of Catalyst

Titanium dioxide (TiO2) powder was synthesized by a conventional solgel process. TiCl4 was first dissolved in an
ethanol/water (volume ratio of 4:1) solution, and ammonia
was then introduced into the solution to induce condensation until pH reached 7.5. The resulted gelatinous precipitate was filtered and washed to remove chloride and then
dried at 80 C in air. The resulted powder was then dried
band to make the catalyst. The standard calcination procedure involved heating the powder at a rate of 50 C/h to
450C, and holding the powder at 450C for 3 h, finally the
powder being furnace-cooled.
The prepared nano powder was characterized X-ray diffraction (XRD), differential thermal analysis (DTA) and infra red (IR). The x-ray diffractometer type Philips, model
Brukur D8 Advance-Germany, Target Cu K, with secondary monochromator V= 40kv, A=40mA, with Ni filter was
used to investigate the crystalline phases of the prepared
nano powder. Thermal Analysis [STERAM LabsysTM
TG-DSC1600C] apparatus with heating rate 5C/min
and Fourier transform infrared spectroscopy (FT/
IR-6300-Jasco spectroscopy) were used to confirm the
obtained phases.
2.4. Apparatus & Oxidation procedure
The catalytic wet air oxidation (CWAO) reactions were performed in a 1 L stainless steel high-pressure Parr reactor
(model 4843, Parr Instrument Co. USA) equipped with a
magnetically driven stirrer and a thermocouple. The reactor was heated by an electrical heating mantle controlled
by a temperature controller unit (model PID 4843), Parr
Instrument Co. Ltd., Illinois, USA). A schematic diagram
of the reactor used in this study is shown in Figure (1). In
a typical CWAO run, the reactor was loaded with 750 ml
of the wastewater and definite amount of prepared TiO2
catalyst. After flushing with nitrogen gas (N2) in order to
remove dissolved oxygen, the reactor was heated to the
desired reaction temperature (100 or 200 C). Pressurization with oxygen was then completed (10 bars of oxygen
partial pressure), the stirring speed was set at 1500 rpm,
and zero time of reaction was considered reaching the
desired reaction temperature. Several runs were carried
out to examine the effect of several parameters on OMW
degradation using CWAO such as catalyst loading, pH and
reaction temperature. The experiments were performed in
duplicates with a standard deviation of 0.97-0.99.
Figure (1). Schematic diagram of the experimental catalytic wet air oxidation apparatus.
388
2.5. Analytical measurements

The physical and chemical characteristics of the wastewater were analyzed according to APHA [19]. Periodically,
liquid samples of 1 ml were withdrawn from the reactor
to be further analyzed for a total organic carbon (TOC)
determination using Phoenix TOC (Model 8000). Three
reproducible runs (<2%) were considered. Determination
of polyphenolic compounds, raw and treated OMW was
extracted by ethyl acetate and evaporated under vacuum
at 40C to remove organic solvent. Chromatographic
analysis was carried out using HPLC (model Agilent 1100)
equipped with diode array detector (DAD). Reversed
phase C18 column (4.6mm x 150mm x 5mm) was used.
The mobile phase consisted of 68% de-ionized water; 2%
acetic acid (25%) and 30% methanol at a flow rate of 1.0
ml/min, mode of flow is isocratic.
3. Results and discussion

3.1. Characterization of the prepared TiO2 nanoparticles
X-ray diffraction (XRD) was used to investigate the crystalline phases (anatase or rutile) of the TiO2 powder. XRD
of the prepared TiO2 photo catalysis calcined at 450oC is
shown in Figure (2). Peaks characterizing anatase with minor amount of rutile phases are detected in the pattern.
The broadness of the peaks indicates the lack of complete
crystallinity of the obtained phases at such calcination
temperature.
Two major structural forms of titanium dioxide can exhibit
photocatalytic activity: anatase and rutile [20]. Anatase
(chains of TiO6 octahedral sharing two edges) has a wider optical band gap of 3.2 eV, and the band gap of rutile
(chains of TiO6 octahedral sharing four edges) is 3.0 eV
[21]. It is important to develop methods for the selective
preparation of TiO2, because anatase and rutile are often
formed at the same time during the formation of TiO2 and
it is desired to synthesize anatase nanoparticle TiO2 since
the anatase form has a higher photocatalytic activity than
rutile TiO2 [22]. Different preparation methods and conditions yield different particle sizes and phase compositions
of the nanostructured TiO2 that display different morphological, structural, and surface physiochemical properties,
and also give different photocatalytic activities [23,24].
These conditions include the types of precursors, the concentration and molar ratio of reactants, the polarity of the
solvent, the pH, and the temperature of the reacting solution.
Figure (2). XRD of the prepared TiO2 photo catalysis calcined at 450oC.
90
80
70
% Removal
Figure (3) shows TGA thermograph of the calcined TiO2 at

550oC. About 0.5% weight loss at 165oC was obtained due
to the loss physically adsorbed and entrapped moisture
from the surrounding medium. IR spectrum of the calcined
TiO2 is shown in Figure (4). The binding vibration H-O-H
at 1624 and weak stretching vibration O-H at 3372 cm-1
indicate the existence of a small amount of water and hydroxyl group. The absorption peak at 1405 cm-1 observed
for freshly prepared TiO2 powder by wet process. The wide
peak from 410 to 1000 cm-1 is assigned to Ti-O-Ti starching vibration.
60
50
40
30
COD (WAO)
20
TOC (WAO)
COD (CWAO)
10
TOC (CWAO)
0
0
30
60
90
120
150
180
Reaction time (min)
Figure (5). Comparison between WAO and CWAO of OMW.

[pH=4.7, TiO2=4 g/L, oxygen partial pressure=10 bars].
Figure (3). TGA of the prepared TiO2 photo catalysis calcined at 450oC.
Figure (4). IR spectra of the prepared TiO2

photo catalysis calcined at 450oC
3.2. CWAO & WAO

Firstly, the treatment of OMW by wet air oxidation without
(WAO) and antase TiO2 catalyst (CWAO) was studied. The
oxidation studies carried out with the OMW samples was
conducted at 200C. The oxygen partial pressure was kept
at 10 bars at reference temperature of 200C. The percentage of both TOC and COD removals as a function of time
is shown in Figure (5) for the non-catalytic process and in
the presence of TiO2 catalyst. The TOC or COD removal at
zero time has a finite number rather than zero. This is because the initial heating of the wastewater took one to two
hours and thus some thermal decomposition is occurred [25].
From Figure (5), it is clear that the effect of wet air oxidation of OMW cannot be neglected. As expected, TOC and
COD removals increase with oxidation time; an increase
from 10.62% to 29.8% and from 12.2% to 32.8.5% for
TOC and COD respectively is observed after 60 min of reaction and from 29.8% to 35.6% and from 32.8 to 39.8%
for TOC and COD, respectively after 120 min. The small
removal of organic matter observed in the experiments
performed without any catalyst indicates that the OMW
contains a large fraction of organic compounds which are
not easily mineralized to non-organic compounds, mainly
CO2 and H2O. However, the most recalcitrant compounds

are expected to remain in the treated solution, even after 180 min of reaction, thus requiring the use of suitable
catalysts to promote their degradation. With the introduction of 4 gm/L catalysts in the system, the TOC and COD
removals observed at the same temperature are increased
comparing with WAO values.
Taking a closer look at the TOC and COD removal curves
of Figure (5) for CWAO, they can be divided into three distinct regions, each corresponding to predominant reaction
steps (although occurring simultaneously with other reaction steps). In the first region (first 60 min of reaction), there
is a sharp TOC and COD removal (from 21.9% to 63.2%
TOC removal and from 23.8% to 66.3% COD removal),
corresponding to the decomposition of large organic molecules (maybe aromatic compounds), either directly to the
final mineralization products, CO2 and H2O, or into smaller
intermediates, some of them also easily oxidizable to CO2
and H2O. In the second region (60120 min), the rate of
removal of TOC is slight, due to degradation of refractory
compound in OMW into smaller intermediates compounds
(such as carboxylic acids), or directly to CO2 and H2O. Depending on the reaction conditions, the TOC and COD removals at this stage are increased by 5-10% (from 63.2%
to 73.8% TOC removal and from 66.3% to 75.7% COD
removal). In the third region (above 120 min of reaction),
there is a residual TOC and COD originating a plateau
due to refractory organic compounds, like low molecular
weight carboxylic acids which are not further oxidized [26,
27]. This inhibition effect is because the catalysts used are
expected to be completely inactive for carboxylic acids
degradation at this temperature [16]. These results imply
the presence of organic compounds in the wastewater
that are resistant to further oxidation since both TOC and
COD are not completely removed after 2 hours of reaction
time.
3.3. Factors influencing CWAO process
There are many factors, such as reaction temperature, initial pH value of OMW and dosage of catalyst, which can
affect the CWAO oxidation of organic materials of OMW.
3.3.1. Influence of reaction temperature
One of the most important operating variables of degradation process is the temperature. A series of experiments was conducted at five temperatures: 150C, 175C,
200C, 225C and 250C at initial partial pressure of oxy-
389
on TOC and COD removal is not very important within the

range used behind 4 g/L. Thus, catalyst loading was chosen as 4 g/L in the later experiments.
100
90
80
70
% Removal
gen of 10 bars, pH value of 4.7, over a 4 g/L TiO2 for the

treatment of OMW by CWAO. Figure (6) shows the TOC
and COD removals for the experiments performed at these
different temperatures. As expected, the removals of TOC
and COD are enhanced by raising the reaction temperature. It is apparent also in Figure (6) that both TOC and
COD removals increases sharply from 150C to 200C. At
the highest temperature of 250C, TOC and COD removals
of 76 % and 81.9 % respectively were achieved after one
hour. From 200C to 250C, both TOC and COD removals
increase smoothly. For practical purposes, it is not wise
to employ excessively high temperatures because of high
energy consumption and high capital and operating costs.
Hence, a temperature of 200C would be seemed sufficient for the present CWAO process for treatment of OMW.
60
50
40
30
COD
20
TOC
10
0
0
90
80
60
50
40
30
COD
20
TOC
10
0
150
175
200
225
250
Reaction temperature (C)
Figure (6). Influence of reaction temperature on the

CWAO of OMW. [pH=4.7, TiO2=4 g/L, oxygen partial pressure=10 bars, reaction time=2hours].
3.3.2. Influence of catalyst loading

The amount of catalyst is one of the main parameters for
the degradation. TiO2 catalyst loading experiments was
performed to determine qualitatively the catalyst effect on
degradation of OMW. In order to avoid the use of excess
catalyst it is necessary to find out the optimum loading for
efficient oxidation. Experiments were performed with no
catalyst as well as with from 1 to 5 g/L of catalyst concentration, at reaction temperature of 200C, 10 bars oxygen
partial pressure, pH of 4.7 and initial TOC and COD of the
OMW are 117860 and 44250 mg/L respectively. Figure (7)
compares the effect of TiO2 catalyst loading on both TOC
and COD removals of OMW. Catalyst loading results indicate that the presence of TiO2 increases both TOC and
COD removal. The TOC and COD removals for 1 hour reaction time increased from 39.5% and 35.6% without catalyst to 57% and 59.6% respectively with 1 g/L catalyst.
It is clearly also demonstrated that an increase in catalyst concentration considerably improves the removals of
both TOC and COD of OMW. The TOC and COD removal
reached 74.8 and 78.9% respectively within 2 hour with 4
g/L. As the concentration of catalyst was increased behind
4 g/L, both TOC and COD removal did not change very
much. For example, the TOC and COD removal for 2 h
reaction time increased from 74.8% and 78.9% for TOC
and COD respectively with 4 g/L catalyst to 75.6% and
79.6% for TOC and COD respectively with 5 g/L catalyst.
This result demonstrates that the effect of catalyst loading
3.3.4. Influence of initial pH values.

Several experiments were conducted to determine whether pH has any influence on COD removal. These experiments were performed at a temperature of 200C, oxygen
partial pressure was 10 bars, and TiO2 catalyst dosage
was 4 g/L at different pH values ranging from 4 to 10. The
results are shown in Figure (8). In all these experiments,
TOC and COD removals decreased rapidly as the pH value
increases behind pH value of 6. It was found at pH equals
6, the TOC and COD removals are 81.19 and 84.22%, respectively within reaction time of two hours, which is acceptable in practical process.
100
90
80
70
% Removal
% Removal
Figure (7). Influence of catalyst loading on the CWAO

of OMW. [pH=4.7, reaction temperature=200C, oxygen partial pressure=10 bars, reaction time= 2 hours].
70
390
Catalyst loading (g/L)
60
50
40
30
COD
20
TOC
10
0
4
10
pH value
Figure (8). Influence of pH values on the CWAO of

OMW. [TiO2=4 g/L, reaction temperature=200C, oxygen partial pressure=10 bars, reaction time= 2 hours].
3.4. Efficiency of CWAO and characterization of the

treated effluent OMW
Table [2] listed the characterization of the treated effluents
of OMW by using CWAO at optimum reaction conditions.
As shown in Table [2], the concentrations of TOC, COD,
phenols, lignin, oil and grease which found in OMW, are reduced significantly by using CWAO. Tables [3] listed the efficiency of CWAO for removal of polyphenolic compounds
which represent the major refractory organic groups found
in OMW and also hazardous pollutants. From Tables [2

and 3], the contents of lignin and polyphenolic compounds
were also decreased to 97.58 and 84.24 % respectively,
within the same optimum reaction conditions. The results
show that CWAO is a promising alternative process for
treatment OMW which contains substances with high organic load and very refractory organic compounds.
Table [2] Efficiency of CWAO for removal of organic contents of olive mill wastewater
reaction intermediates because the total TOC and COD

removals were never 100%.
This result proves that CWAO is a promising technology
to treat OMW and encourages further research studies on
this subject. Since The increase of removal of both COD,
TOC and polyphenolic compounds removal is very high,
the CWAO of olive mill wastewater seems environmentally
attractive. The low concentrations of organic compounds
in the final treated effluents allows for their reuse in the
process, leading to a more efficient process water management and better environmental impact.
Treated effluent
Parameter
mg/L
Removal %
COD
18600
84.22
TOC
8320
81.19
Oil & grease
461
93.27
Lignin
463
97.58
Phenol
329
94.77
5. Acknowledgement
This research work has been carried out within the framework of a project financed by the EU (CAT-MED PROJECT Contract ICA3-CT2002-10034).
Bibliography
1.
Table [3] Efficiency of CWAO for removal of polyphenolic compounds
Compound
Raw
2.
Treated effluent
mg/L
mg/L
Removal %
cinnamic acid
756.5
91.03
87.97
3,4-dihydroxybenzoic acid
33.8
N.D
100
3,4-dihydroxibenzaldehyde
42.06
N.D
100
3.
4-hydroxybenzaldehyde
81.54
56.21
31.07
vanillic acid
9.083
N.D
100
3,4-dihydroxycinnamic acid
N.D
100
p-coumaric acid
4.32
N.D
100
Total
934.3
147.24
84.24
4. Conclusions
The present study reports on the treatment of olive mill
wastewater (OMW) by using the catalytic wet air oxidation (CWAO). The TiO2 catalyst has good performance in
catalyzing the wet air oxidation of OMW. There are many
factors that can influence on the CWAO process for treatment of OMW. The most important factors among them
are reaction temperature, pH value of wastewater and
catalytic conditions to improve treating effects and reduce
treating costs. The TOC and COD removals were observed
to increase with an increase in both temperature and the
catalyst loading. The pH value of the wastewater can affect CWAO reaction significantly. Low pH value is beneficial for speeding the reaction, but at the same time, higher
corrosion resistance of reactor and catalysts is required. At
optimum operating degradation conditions: temperature
of 200C, oxygen partial pressure of 10 bars, pH value
of 6 and reaction time within 2 hours, the TOC, COD and
polyphenolic compounds removals are 81.19, 84.22 and
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Microwave induced synthesis of some fused

thiazoloquinazoline derivatives under solvent
free conditions using LiBr as a catalyst
Chetna Ameta, Rakshit Ametaa, Urvashi Tiwari, P. B. Punjabi and
Suresh C. Ameta*
Microwave Chemistry Laboratory, Department of Chemistry, University College of Science, Mohanlal Sukhadia University,
Udaipur - 313 001 (Raj.), India. a Department of Pure & Applied Chemistry, University of Kota, Kota 324010 (Raj.), India
Sntesis inducida por microondas de algunos derivados fundidos como tiazoloquinazolina

en condiciones de ausencia de disolventes y utilizando LiBr como catalizador
Sntesi induda per microones dalguns derivats fosos de tiazoloquinazolina en
condicions dabsncia de dissolvents i utilitzant LiBr com a catalitzador
Recibido: 19 de mayo de 2010; revisado: 24 de septiembre de 2010; aceptado: 29 de octubre de 2010
RESUMEN
RESUM
Se presentan dos mtodos rpidos y eficientes para la

preparacin de derivados fundidos de tiazoloquinazolina
por reaccin de chalconas con hidroxilamina, urea e hidrato de hidrazina en condiciones de ausencia de disolventes
y exposicin a microondas. El objetivo del presente trabajo es sustituir sustancias qumicas txicas, peligrosas, y
altamente reactivas con bloques de sntesis menos reactivos, menos nocivos pero ms selectivos que pueden activar reacciones qumicas selectivas mediante una catlisis
apropiada, as como sustituir tecnologas anticuadas por
otras nuevas caracterizadas por la reduccin de subproductos y una separacin fcil de los productos.
Es presenten dos mtodes rpids i eficients per a la preparaci de derivats fosos de tiazoloquinazolina per reacci
de calcones amb hidroxilamina, urea i hidrat dhidrazina en
condicions dabsncia de dissolvents i exposici a microones. Lobjectiu del present treball s substituir substncies qumiques txiques, perilloses i altament reactives amb
blocs de sntesi menys reactius, menys nocius per ms
selectius que poden activar reaccions qumiques selectives mitjanant una catlisi apropiada, i tamb substituir
tecnologies antiquades per altres de noves caracteritzades per la reducci de subproductes i una separaci fcil
dels productes.
Palabras clave: LiBr, condiciones de ausencia de disolventes, Chalconas, Isoxazoles, Pirazoles, Pirimidinas.
Paraules clau: LiBr, condicions dabsncia de dissolvents, Calcones, Isoxazols, Pirazols, Pirimidines.
ABSTRACT
Two rapid and efficient methods for the preparation of
fused thiazoloquinazoline derivatives by the reaction of
chalcones with hydroxylamine, urea and hydrazine hydrate
under solvent free condition and microwave exposure are
reported. The aim of present work is to substitute toxic,
dangerous, highly reactive chemicals with less reactive,
less harmful but more selective building blocks which
activate selective chemical reactions by proper catalysis
and to replace substituted old technologies to new one
characterized by the reduction of by-products and easy
separation of products.
Keywords: LiBr, Solvent free condition, Chalcones, Isoxazoles, Pyrazoles, Pyrimidines.
Corresponding author: *ameta_sc@yahoo.com
393
Introduction
Results and Discussion
Preventing pollution and minimizing waste generation will

gradually clean up sins of the past. In this environmental
conscious era, the role of chemistry and chemists1 involved
is to incorporate processes and design products, which
can eliminate or minimize the generation of associated
pollutants. The increasing environmental consciousness of
the chemical community has lead to search for alternative
non-polluting media and processes that might reduce pollution at the source for chemical and organic synthesis2.
Green chemistry3 is defined as an environmentally benign
chemical synthesis, which is the science based and economically driven approach to achieve the goal of environment protection. In recent years, a new technique that is
set to revolutionalize organic synthesis has moved to the
forefront of Green chemical research. Microwave Assisted
Organic Synthesis (MAOS) is sometimes termed as microwave induced organic reaction enhancement (MORE)
chemistry4. It can also be termed as e-chemistry because it is easy, effective, economical and eco-friendly and
is believed to be a step towards green chemistry. MORE
chemistry techniques are potentially valuable as they reduce the need of organic solvents. As a result, one can
reduce the total time for compound production as well as
reduce the total cost per compound5.
The Knoevenagel condensation has been a subject of
considerable interest and to effect this condensation efficiently, large number of catalysts have been explored6,7,
e.g. sodium acetate in glacial acetic acid, piperidinium
benzoate in refluxing toluene, zeolite, tetrabutyl ammonium bromide, refluxing reactants in toluene at 110 C
for 3 days, etc. Certainly these processes are not facile
as they require long reaction times, high temperature and
products are also obtained in low yields. LiBr can potentially replace solvents and conventional corrosive acids in
many of their applications 8-11. LiBr catalyses efficiently the
three component condensation reaction of an aldehyde,
-ketoester and urea in refluxing acetonitrile to afford the
corresponding dihydropyrimidinones in high yields. It is
an improved procedure for the Biginelli reaction12. As our
interest is to synthesize heterocyclic templates (quinazolinones) capable of bearing some potential pharmacophores which can enhance the inherent biological activity.
The systematic propagation of heterocyclic rings in quinazolinones precursors with the installation of biological
active heterocyclic units such as isoxazoles, pyrimidines
and pyrazoles. Pyrimidines are found to be endowed with
potential biological activity such as antitumor13, antiviral14,
anticancer15, antibacterial16 and antimicrobial17 and many
others. Isoxazoles are reported to have bactericidal18,
fungicidal19 and antimicrobial20 activity. Pyrazoles display
a number of antimicrobial activities like anticancer21, antidiabetic22 and antidepressants23. The quinazoline moiety
is a useful functionality for the development of biologically
interesting molecules with a wide portfolio of biological
activities24 such as hypotensive25, antimalarial and antihypertensive26 activities. Thus the coupling of this MORE
synthesis with solvent free conditions and LiBr is expected
to afford an environmentally benign synthesis of biological
active compounds.
4-(4-Substituted phenyl)-2-thioxo-1,2,3,4,7,8-hexahydro
quinazolin-5(6H)-ones 1(a-c) were synthesized by LiBr
catalyzed cycloaddition of 1,3-cyclohexanedione, substituted benzaldehydes and thiourea under solvent free condition and microwave exposure. The structure of 1(a) was
confirmed by the IR bands at 3335 cm-1 due to secondary amino group, 1700 cm-1 due to C=O group and 1515
cm-1 due to C=S stretching. It is supported by the presence of a broad singlet of 2 NH protons in the region of
9.89 9.72 ppm in 1H NMR. The compound 1(a-c) was
treated with chloroacetic acid in the presence of LiBr to
give 5-(4-substituted phenyl)-8,9-dihydro-2H-thiazolo[2,3b] quinazolin-3,6[5H,7H]-diones 2(a-c). Compound 2(a)
was confirmed by the disappearance of NH stretch in
the region of 3330 cm-1 in IR spectrum and appearance
of an additional band at 1680 cm-1 due to C=O stretch
of thiazolidinone moiety 1H NMR spectrum of 2(a) shows
the appearance of a singlet of two protons at 3.67 ppm
due to CH2 proton of thiazolidinone nucleus. Compounds
2(a-c) were easily condensed with 4-chlorobenzaldehyde
in the presence of LiBr to furnish 2-(4-chlorobenzylidine)5-(4-substituted
phenyl)-8,9-dihydro-2H-thiazolo[2,3-b]
quinazolin-3,6[5H,7H]-dione 3(a-c), due to the activity of
methylene group of compound 2(a-c).
Synthesis of 2-arylmethylene derivatives 3(a-c) were
achieved in a single step by treating 1(a-c) with chloroacetic acid and 4-chlorobenzaldehyde in the presence of
catalytic amount of LiBr. The IR spectrum of compound
3(a) shows the presence of , -unsaturated moiety by
the appearance of carbonyl stretch at 1665 cm-1 due to
conjugation rather than at 1680 cm-1 (C=O of thiazolidinone ring). Other prominent peak of C-Cl also appeared
at 751 cm-1. 1H NMR spectrum of compound was characterized by the lack of the singlet of two protons of
thiazolidinone nucleus at 3.67 ppm and appearance of a
new singlet at 6.42 ppm due to arylidine proton (=CH-Ar)
of chalcone moiety. Thiazoloquinazolines are convenient
starting material for the synthesis of fused thiazoloquinazolines due to their , -unsaturated moiety. Firstly, the
absence of carbonyl stretching frequency in the region of
1665 cm-1 confirms the formation of products. Isoxazolino derivatives 4(a-c) were synthesized by the reaction of
compound 3(a-c) with equimolar ratio of hydroxylamine
hydrochloride in the presence of LiBr. The structure of 4(a)
was confirmed by appearance of absorption band at 1093
m-1 due to C-O stretch and at 940 cm-1 due to N-O stretch
in IR spectrum. It is supported by the presence of two
doublets of two methine protons of isoxazolino moiety at
about 4.83 and 3.12 ppm in 1H NMR. Compounds 3(a-c)
treated with hydrazine hydrate in the presence of LiBr as a
catalyst yielded 3-(4-chlorobenzylidine)-10-(4-substituted
phenyl)-6,7,8-trihydro-3H,3aH,2H-pyrazolo [34:4,5]thiazolo [2,3-b]quinazoline-9[10H]-ones 5(a-c). Its structure
was confirmed by the disappearance of carbonyl stretching frequency in the region of 1665 cm-1 in IR spectrum.
The methane protons of pyrazoline ring appeared as two
doublets centered at 4.98 and 3.43 ppm in its 1H NMR
spectrum. Pyrimidino derivatives of compounds 6(a-c)
were synthesized by the reaction of compounds 3(a-c)
with equimolar ratio of urea in the presence of LiBr as a
catalyst. The IR spectrum showed a new absorption band
in the region of 1687 cm-1 was assigned to new carbonyl
group (=N-C=O) and in the region of 3327 cm-1 due to NH
394
stretch. A broad signal at 8.84 ppm was observed for the

NH proton in the 1H NMR spectrum and it confirms the
formation of the product 6(a).
Antimicrobial activity
Four compounds were screened in vitro for their antimicrobial activities against four strains of bacteria (Escherichia
coli, Bacillus subtilis, Klebsiella pneumoniae, Pseudomonas aeuroginosa) and two strains of fungi (Aspergillus fumigatus, Candida albicans) using the disc diffusion method. Commercial antibacterial ciprofloxacin and antifungal
fluconazole were also screened under similar conditions

for comparison. The results have been tabulated in the
form of inhibition zones and activity index in Table 4.
The results revealed that all tested compounds exhibit
moderate to strong activity against both fungi and E. coli.
Compounds 4(a), 5(a) and 6(a) show considerable potency
against A. fumigatus while against C. albicans, they are
moderately active. Similarly, compound 6(a) was found to
show strong activity against K. pneumonae and P. aeurogenosa. 5(a) was found to show excellent activity against
K. pneumonae while against P. aeurogenosa, it exhibited
moderate activity.
Table 1 : Physical data of synthesized compounds

a = Conventional, b = Microwave + Solvent, c = Microwave + LiBr (solvent free) under microwave irradiation
Compd.
Ar
Ar
Mol. Formula
Mol. Weight
1a
4-FC6H4
1b
1c
C14H13N2OSF
276
275
4-OCH3C6H4
C15H16N2O2S
288
270
-C6H5
C14H14N2OS
258
264
2a
4-FC6H4
C16H13N2O2SF
316
224
2b
4-OCH3C6H4
C17H16N2O3S
328
220
2c
-C6H5
C16H14N2OS
298
214
3a
4-FC6H4
4-ClC6H4
C23H16N3O2SFCl
438
230
3b
4-OCH3C6H4
4-ClC6H4
C24H19N3O3ClS
450
231
3c
-C6H5
4-ClC6H4
C23H17N2O2ClS
420
228
4a
4-FC6H4
4-ClC6H4
C23H16N3O2SFCl
452
4b
4-OCH3C6H4
4-ClC6H4
C24H19N3O3ClS
-C6H5
4-ClC6H4
C23H17N3O2ClS
434
5a
4-FC6H4
4-ClC6H4
C25H19N4O2SFCl
493
5b
4-OCH3C6H4
4-ClC6H4
C26H22N4O3ClS
505
5c
-C6H5
4-ClC6H4
C25H20N4O2ClS
475
6a
4-FC6H4
4-ClC6H4
C24H16N4O2SFCl
478
6b
4-OCH3C6H4
4-ClC6H4
C25H19N4O3ClS
490
6c
-C6H5
4-ClC6H4
C24H17N4O2ClS
251
239
464
4c
M.P. (C)
460
242
265
247
251
215
213
221
Yield a %
[Time] (hr.)
66
[16]
65
[6]
68
[6]
73
[6]
70
[6]
68
[8]
69
[8]
68
[6]
68
[8]
79
[3]
65
[3]
61
[3]
65
[14]
65
[14]
70
[14]
68
[12]
64
[12]
66
[12]
Yield b %
[Time] (min.)
69
[6]
86
[5]
72
[4.5]
75
[4.5]
76
[4.5]
72
[6]
72
[5.5]
70
[6]
70
[6]
82
[6]
80
[6]
68
[7]
70
[7]
77
[6]
76
[6]
75
[8]
70
[8]
74
[9]
Yield c%
[Time] (min.)
76
[4]
80
[3]
89
[2.5]
87
[3]
87
[3]
86
[5]
88
[4]
80
[5]
86
[5]
90
[5]
87
[5]
75
[4.5]
87
[6]
85
[6]
81
[6.5]
92
[7]
87
[7]
89
[7.5]
Table 2 : Analytical data of synthesized compounds

Compd.
Calculated / Found (%)

C
1a
60.86 / 60.84
4.71 / 4.69
10.14 / 10.00
11.59 / 11.57
1b
62.50 / 62.48
5.55 / 5.58
9.72 / 9.68
11.11 / 10.99
1c
65.11 / 65.13
5.42 / 5.38
10.85 / 10.79
12.40 / 12.38
2a
60.75 / 60.79
2.82 / 2.83
19.61 / 19.60
10.12 / 9.90
2b
62.19 / 62.01
3.91 / 3.88
8.43 / 8.40
9.75 / 9.68
2c
64.42 / 64.36
4.69 / 4.65
8.53 / 8.58
10.73 / 10.68
3a
63.01 / 62.97
3.65 / 3.61
6.39 / 6.27
7.30 / 7.27
3b
64.00 / 64.06
4.22 / 4.16
6.22 / 6.15
7.11 / 7.07
3c
65.71 / 65.67
4.04 / 3.97
6.66 / 6.61
7.61 / 7.59
4a
61.06 / 60.98
3.53 / 3.49
9.29 / 9.27
7.07 / 7.10
4b
62.06 / 62.01
4.09 / 4.11
9.05 / 8.98
6.89 / 6.81
4c
63.59 / 63.51
3.91 / 3.94
9.67 / 9.54
7.37 / 7.28
5a
60.85 / 60.78
3.85 / 3.87
11.35 / 11.31
6.49 / 6.43
5b
61.78 / 61.72
4.35 / 4.29
11.08 / 10.98
6.33 / 6.28
6.73 / 6.69
5c
63.15 / 63.05
4.21 / 4.17
11.78 / 11.72
6a
60.25 / 60.17
3.34 / 3.36
11.71 / 11.69
6.69 / 6.63
6b
61.22 / 61.18
3.87 / 3.78
11.42 / 11.29
6.53 / 6.56
6c
62.60 / 62.55
3.69 / 3.61
12.17 / 12.09
6.95 / 6.90
395
Table 3: Spectral data of synthesized compounds

Compd.
1a
Spectral Data
IR (KBr cm-1):
1
1b
H NMR d:
IR (KBr cm-1):
H NMR d:
1c
IR (KBr cm-1):
1
2a
IR (KBr cm-1):
1
2b
H NMR d:
IR (KBr cm-1):
1
3b
H NMR d:
IR (KBr cm-1):
1
3a
H NMR d:
IR (KBr cm-1):
1
2c
H NMR d:
H NMR d:
IR (KBr cm-1):
1
3c
IR (KBr cm-1):
1
4a
H NMR d:
IR (KBr cm-1):
1
4c
H NMR d:
IR (KBr cm-1):
1
4b
H NMR d:
IR (KBr cm-1):
1
5a
H NMR d:
IR (KBr cm-1):
1
396
H NMR d:
IR (KBr cm-1):
1
6c
H NMR d:
IR (KBr cm-1):
1
6b
H NMR d:
IR (KBr cm-1):
1
6a
H NMR d:
IR (KBr cm-1):
1
5c
H NMR d:
IR (KBr cm-1):
1
5b
H NMR d:
H NMR d:
3067 (C-H str., Ar-H), 3335 (NH str.), 2921, 2842 (CH str., CH2), 1700 (C=O str.), 1605, 1525 (C=C str.),
1515, 1231 (C=S amide II and amide I), 1182 (C-F str.) and 835 (Ar-H bend, 1,4-disubs.)
9.89 9.72 (s, 2H, NH), 2.86 1.62 (m, 6H, -CH2), 5.02 (s, 1H, CH-Ar) and 7.97 - 7.15 (m, 4H, Ar-H).
3062 (C-H str., Ar-H), 3328 (NH str.), 2933, 2851 (CH str., CH2), 1710 (C=O str.), 1612, 1519 (C=C str.),
1516, 1225 (C=S amide II and amide I), 1093 (C-O str.) and 843 (Ar-H bend, 1,4-disubs.)
9.95 9.62 (bs, 2H, NH), 2.90 1.63 (m, 6H, -CH2), 5.09 (s, 1H, CH-Ar) and 7.93 - 7.05 (m, 4H, Ar-H).
3055 (C-H str., Ar-H), 3337 (NH str.), 2926, 2852 (CH str., CH2), 1709 (C=O str.),
1607, 1527 (C=C str.) and 1524, 1222 (C=S amide II and amide I str.),
9.83 9.57 (bs, 2H, NH), 2.90 1.63 (m, 6H, -CH2), 5.08 (s, 1H, CH-Ar) and 7.96 - 7.03 (m, 5H, Ar-H).
3057 (C-H str., Ar-H), 2932, 2835 (CH str., CH2), 1695 (C=O str.), 1680 (C=O, thiazolidinone ring), 1610 (C=N str.),
1600, 1530 (C=C str.), 1195 (C-F str.), 1115 (C-N str.), 841(Ar-H bend, 1,4-disubs.) and 695 (C-S-C str.).
7.86 - 7.17 (m, 4H, Ar-H), 5.96 (s, 1H, CH-Ar), 3.67 (s, 2H, -CH2, thiazolidinone ring) and 2.90 1.66 (m, 6H, -CH2).
3047 (C-H str., Ar-H), 2918, 2845 (CH str., CH2), 1697 (C=O str.), 1678 (C=O, thiazolidinone ring), 1611 (C=N str.),
1618, 1539 (C=C str.), 1082 (C-O str.), 1108 (C-N str.), 835 (Ar-H bend, 1,4-disubs.) and 689 (C-S-C str.).
7.91- 7.07 (m, 4H, Ar-H), 5.93 (s, 1H, CH-Ar), 3. 55 (s, 2H, -CH2, thiazolidinone ring), 3.84 (s, 3H, -OCH3) and 2. 83 1.59 (m, 6H, -CH2).
3049 (C-H str., Ar-H), 2925, 2842 (CH str., CH2), 1699 (C=O str.), 1682 (C=O, thiazolidinone ring), 1608 (C=N str.), 1612, 1541 (C=C str.), 1101 (C-N str.) and 699 (C-S-C str.).
7.73- 7.02 (m, 5H, Ar-H), 5.90 (s, 1H, CH-Ar), 3. 61 (s, 2H, -CH2, thiazolidinone ring) and 2. 87 1.58 (m, 6H, -CH2).
3075 (C-H str., Ar-H), 2954, 2851 (CH str., CH2), 1694 (C=O str.), 1665 (C=C-C=O, chalcone carbonyl str.), 1620 (C=N str.),
1607, 1513 (C=C str.), 1175 (C-F str.), 751 (C-Cl str.), 1116 (C-N str.), 843 (Ar-H bend, 1,4-disubs.) and 681 (C-S-C str.).
7.73 - 7.01 (m, 8H, Ar-H), 6.32 (s, 1H, =CH-Ar), 5.59 (s, 1H, CH-Ar) and 2.89 1.53 (m, 6H, -CH2).
3056 (C-H str., Ar-H), 2929, 2850 (CH str., CH2), 1690 (C=O str.), 1662 (C=C-C=O, chalcone carbonyl str.), 1617 (C=N str.), 1616, 1503 (C=C str.), 1182 (C-O str.), 749 (C-Cl str.), 1115
(C-N str.), 749 (C-Cl str.), 842 (Ar-H bend, 1,4-disubs.) and 674 (C-S-C str.).
7.79 - 7.07 (m, 8H, Ar-H), 6.40 (s, 1H, =CH-Ar), 5.54 (s, 1H, CH-Ar), 3.74 (s, 3H, -OCH3) and 2.81 1.56 (m, 6H, -CH2).
3064 (C-H str., Ar-H), 2923, 2849 (CH str., CH2), 1701 (C=O str.), 1664 (C=C-C=O, chalcone carbonyl str.), 1628 (C=N str.),
1627, 1507 (C=C str.), 749 (C-Cl str.), 1114 (C-N str.), 747 (C-Cl str.), 839 (Ar-H Bend, 1,4-disubs.) and 684 (C-S-C str.).
7.83 - 7.02 (m, 9H, Ar-H), 6. 34 (s, 1H, =CH-Ar), 5.63 (s, 1H, CH-Ar) and 2.85 1. 63 (m, 6H, -CH2).
3095 (C-H str., Ar-H), 2922, 2836 (CH str., CH2), 1703 (C=O str.), 1625 (C=N str.), 1609, 1505 (C=C str.), 1162 (C-F str.),
1093 (C-O str.), 940 (N-O str.), 816 (Ar-H bend, 1,4-disubs.), 745 (C-Cl str.), 1116 (C-N str.) and 683 (C-S-C str.).
7.96 - 7.13 (m, 8H, Ar-H), 5.30 (s, 1H, CH-Ar), 4.83 (d, 1H, -CH-Ar isoxazoline ring), 3.12 (d, 1H, -CH-S) and 2.90 1.73 (m, 6H, -CH2).
3080 (C-H str., Ar-H), 2918, 2849 (CH str., CH2), 1699 (C=O str.), 1628 (C=N str.), 1617, 1510 (C=C str.), 1080
(C-O str.), 930 (N-O str.), 820 (Ar-H bend, 1,4-disubs.), 755 (C-Cl str.), 1115 (C-N str.), and 676 (C-S-C str.).
7.61 - 7.03 (m, 8H, Ar-H), 5.28 (s, 1H, CH-Ar), 4.81 (d, 1H, -CH-Ar isoxazoline ring),
3.82 (s, 3H OCH3), 3.08 (d, 1H, -CH-S) and 2.78 1.53 (m, 6H, -CH2).
3076 (C-H str., Ar-H), 2925, 2851 (-CH str., CH2), 1700 (C=O str.), 1630 (C=N str.), 1619, 1500 (C=C str.),
1091 (C-O str.), 943 (N-O str.), 810 (Ar-H bend, 1,4-disubs.), 749 (C-Cl str.) and 671 (C-S-C str.).
7.81 - 7.11 (m, 9H, Ar-H), 5.27 (s, 1H, CH-Ar), 4.80 (d, 1H, -CH-Ar isoxazoline ring), 3.08 (d, 1H, -CH-S) and 2.87 1.61 (m, 6H, -CH2).
3083 (C-H str., Ar-H), 2965, 2843 (CH str., CH2), 1700 (C=O str.), 1627 (C=N str.), 1610, 1495 (C=C str.),
1172 (C-F str.), 824 (Ar-H bend, 1,4-disubs.), 732 (C-Cl str.), 1115 (C-N str.), and 682 (C-S-C str.).
7.73 - 7.01 (m, 8H, Ar-H), 5.32 (s, 1H, CH-Ar), 4.98 (d, 1H, -CH-Ar pyrazoline ring), 3.43 (d, 1H, -CH-S) and 2.93 1.62 (m, 6H, -CH2).
3080 (C-H str., Ar-H), 2954, 2847 (CH str., CH2), 1705 (C=O str.), 1620 (C=N str.), 1611, 1505 (C=C str.),
1083 (C-O str.), 837 (Ar-H bend, 1,4-disubs.), 741 (C-Cl str.), 1114 (C-N str.), and 674 (C-S-C str.).
7.73 7.01 (m, 8H, Ar-H), 5.29 (s, 1H, CH-Ar), 5.01 (d, 1H, -CH-Ar pyrazoline ring),
3.80 (s, 3H, -OCH3), 3.37 (d, 1H, -CH-S) and 2.87 1.59 (m, 6H, -CH2).
3074 (C-H str., Ar-H), 2959, 2852 (CH str., CH2), 1703 (C=O str.), 1628 (C=N str.), 1602, 1515 (C=C
str.), 830 (Ar-H bend, 1,4-disubs.), 730 (C-Cl str.), 1115 (C-N str.) and 678 (C-S-C str.).
7.69 7.01 (m, 9H, Ar-H), 5.26 (s, 1H, CH-Ar), 4.93 (d, 1H, -CH-Ar pyrazoline ring), 3.31 (d, 1H, -CH-S) and 2.89 1.63 (m, 6H, -CH2).
3327 (NH str.), 3015 (CH str., Ar-H), 2911, 2831 (CH str. CH2), 1710, 1687 (C=O str.), 1620 (C=N str.), 1607,
1527 (C=C str.), 1182 (C-F str.), 730 (C-Cl str.), 841 (Ar-H bend, 1, 4-disubs.) and 678 (C-S-C str.)
8.94 (s, 1H, NH), 7.68-7.09 (m, 8H, Ar-H), 5.23 (s, 1H, CH-Ar) and 2.86-1.61 (m, 6H, -CH2)
3324(NH str.), 3025 (CH str., Ar-H), 2921, 2842 (CH str., CH2), 1705, 1681 (C=O str.), 1630 (C=N str.), 1603,
1499 (C=C str.), 741 (C-Cl str.), 1079 (C-O str.), 837 (Ar-H bend, 1, 4-disubs.) and 669 (C-S-C str.)
8.80 (s, 1H, NH), 7.61-7.07 (m, 8H, Ar-H), 5.25 (s, 1H, CH-Ar), 3.78 (s, 3H OCH3) and 2.81-1.53 (m, 6H, -CH2)
3327(NH str.), 3028 (CH str., Ar-H), 2925, 2837 (CH str., CH2), 1710, 1685 (C=O str.), 1628 (C=N str.),
1614, 1502 (C=C str.), 745 (C-Cl str.), 832 (Ar-H bend, 1, 4-disubs.) and 673 (C-S-C str.).
8.92 (s, 1H, NH), 7.51-7.01 (m, 8H, Ar-H), 5.19 (s, 1H, CH-Ar) and 2.82-1.61 (m, 6H, -CH2).
397
Table 4 : Antimicrobial activity of some synthesized compounds (500 ppm)
Compd.
Antifungal activity (Activity index)
Antibacterial activity
(Activity index)
A. fumigatus
C. albicans
E.coli
B.subtilis
P.aeuroginosa
K.pneumoniae
4a
20
19
(0.63)
17
(0.50)
15
(0.43)
24
(0.54)
13
(0.34)
5a
24
20
(0.66)
12
(0.35)
11
(0.31)
14
(0.32)
34
(0.89)
6a
22
23
(0.76)
17
(0.50)
16
(0.46)
27
(0.61)
28
(0.73)
C1
Nil
30
34
35
44
38
C2
a
Activity index = Inhibition area of the sample / inhibition area of the standard.
Standard: C1 = Fluconazole, C2 = Ciprofloxacin.
Experimental Section
General Procedure
All reactions were carried out in a domestic microwave
oven (Kenstar, Model No. OM-26 EGO). Melting points are
uncorrected and determined in open capillaries. Reactions
were monitored by thin layer chromatography using silica
gel-G as adsorbent using ethyl acetate : n-hexane (7 : 3)
as eluent and products were detected by iodine vapors.
IR spectra (KBr pellets) were recorded on Perkin-Elmer
1800 (FTIR) spectrometer. 1H NMR spectra (DMSO-d6)
were taken on a Bruker DRX spectrometer (300 MHz FT
NMR) using TMS as internal standard and chemical shift
were expressed in . Mass spectra were taken on a JEOL
SX-102/PA-6000 (EI) spectrometer and elemental analysis
was carried out on C, H, N analyzer (Elemental Vario Carlo
Alba 1108). The results were found to be in good agreement with the calculated values ( 0.2%). The starting
compounds were prepared according to reported method.
Microwave induced synthesis of 4-(4-substituted
phenyl)-2-thioxo-1,2,3,4,7,8-hexahydro
quinazolin5(6H)-ones 1(a - c):
A mixture of thiourea (0.01 mole), aromatic aldehydes (0.01
mole), 1,3-cyclohexadione (0.01 mole) and LiBr (10 mole
%) was mixed with a glass rod and placed in small conical
flask at room temperature. The mixture was then exposed
to microwave radiations at 80 % power for 2-3 minutes.
After completion of reaction (monitored by TLC), the reaction mixture was cooled to room temperature. 15 mL
of water was then added to reaction mixture and it was
stirred for 5 minutes. The solid thus obtained was filtered,
dried and recrystallized from ethanol.
Conventional synthesis of 4-(4-substituted phenyl)2-thioxo-1,2,3,4,7,8-hexahydro quinazolin-5(6H)-ones
1(a-c):
A mixture of thiourea (0.01 mole), aromatic aldehydes (0.01
mole), 1,3-cyclohexadione (0.01 mole), absolute alcohol
(25 mL) and 36% HCl (1 mL) was refluxed for about 5 hr on
a water bath. The solvent was removed and residue was
recrystallized from ethanol to yield compound 1(a c).
Microwave induced synthesis of 5-(4-substituted phenyl)-8, 9-dihydro-2H-thiazolo [2, 3-b] quinazolin-3,
6[5H,7H]-diones 2(a-c):
398
Compound 1(a-c) (0.01 mole), chloroacetic acid (0.01

mole) and LiBr (10 mole %) was placed in small conical
flask and mixed with a glass rod at room temperature.
The mixture was then exposed to microwave radiations
at 60 % power for 3-4 minutes. After completion of reaction (monitored by TLC), the reaction mixture was cooled
to room temperature. 15 mL of water was then added to
reaction mixture and it was stirred for 5 minutes. The solid
thus obtained was filtered, dried and recrystallized from
ethanol.
Conventional synthesis of 5-(4-substituted phenyl)-8,9dihydro-2H-thiazolo[2,3-b]quinazolin-3,6[5H,7H]-diones 2(a-c):
Compound 1(a-c) (0.01 mole), chloroacetic acid (0.01
mole) and fused CH3COONa (0.5 g) in acetic acid (10 mL)
was refluxed for about 7 hr on a heating mantle. After cooling, the reaction mixture was poured into ice cold water.
The solid separated was filtered off and recrystallized from
ethanol to obtain compounds 2(a-c).
Microwave induced synthesis of 2-(4-chlorobenzylidine)5-(4-substituted phenyl)-8,9-dihydro-2H-thiazolo[2,3b]quinazolin-3,6[5H,7H]-diones 3(a-c):
Method 1
Compound 2(a-c) (0.01 mole), 4-chlorobenzaldehyde (0.01
mole) and LiBr (10 mole %) were mixed with mortar-pestle
and placed in small conical flask at room temperature.
The mixture was then exposed to microwave radiations at
50% power for 3-3.30 minutes. After completion of reaction (monitored by TLC), the reaction mixture was cooled
ethanol.
Method 2
Compound 1(a-c) (0.01mole), chloroacetic acid (0.01
mole), 4-chlorobenzaldehyde (0.01 mole) and LiBr (10
mole %) were placed in small conical flask and mixed with
a glass rod at room temperature. The mixture was then
exposed to microwave radiations at 50% power for 6-6.30
minutes. After completion of reaction (monitored by TLC),
the reaction mixture was cooled to room temperature. 15
mL of water was then added to reaction mixture, stirred for
5 minutes. The solid thus obtained was filtered, dried and

recrystallized from ethanol to afford compounds 3(a-c).
ter and recrystallized from absolute ethanol to afford compounds 5(a-c).
Conventional synthesis of 2-(4-Chlorobenzylidine)5-(4-substituted phenyl)-8,9-dihydro-2H-thiazolo[2,3b]quinazolin-3,6[5H,7H]-diones 3(a-c):

Compound 2(a-c) (0.01 mole), 4-chlorobenzaldehyde
(0.01 mole) and 2-3 drops of glacial acetic acid in ethanol
(25 mL) was refluxed on heating mantle for about 6 hr. The
solvent was removed and residue was recrystallized from
ethanol.
Microwave induced synthesis of 4-(4-chlorophenyl)11-(4-substituted phenyl)-7,8,9-trihydro-2H-pyrimido

[45:4,5]thiazolo [2,3-b]quinazoline-2,10 [3H,11H]diones 6(a-c)
Compound 3(a-c) (0.01 mole), urea (0.01 mole) and LiBr
(10 mole %) were placed in small conical flask and mixed
with a glass rod at room temperature. The mixture was
then exposed to microwave radiations at 60% power for
7-7.30 minutes. After completion of reaction (monitored by
TLC), the reaction mixture was cooled to room temperature. 15 mL of water was then added to reaction mixture
and it was stirred for 5 minutes. The solid thus obtained
was filtered, dried and recrystallized from ethanol.
Microwave induced synthesis of 3-(4-chlorobenzylidine)10-(4-substituted phenyl)-6,7,8-trihydro-3H,3aH-isoxazolo [34:4,5]thiazolo [2,3-b]quinazoline-9[10H]-ones

4(a-c)
Compound 3(a-c) (0.01 mole), hydroxylamine hydrochloride (0.012 mole) and LiBr (10 mole %) were mixed with
mortar - pestle and placed in a small conical flask at room
temperature. The mixture was then exposed to microwave
radiations at 60% power for 5-5.30 minutes. After completion of reaction (monitored by TLC), the reaction mixture
was cooled to room temperature. 15 mL of water was then
added to reaction mixture and it was stirred for 5 minutes.
The solid thus obtained was filtered, dried and recrystallized from ethanol to afford compounds 4(a-c).
Conventional synthesis of 3-(4-chlorobenzylidinel)10-(4-substituted phenyl)-6,7,8trihydro-3H,3aH-isoxazolo [34:4,5]thiazolo [2,3-b]
quinazoline-9[10H]-ones 4(a-c)
To a mixture of compound 3(a-c) (0.01 mole) and hydroxylmine hydrochloride (0.012 mole) in absolute ethanol,
(0.01 mole), a solution of sodium acetate (0.012 mole) in
acetic acid (5 mL) was added. The reaction mixture was
refluxed on heating mantle for 12 hr. The reaction mixture
was concentrated, kept overnight and poured into ice water. The resulting solid was filtered, washed with water and
recrystallized from acetic acid.
Microwave induced synthesis of 3-(4-chlorobenzylidine)10-(4-fluorophenyl)6,7,8-trihydro-3H,3aH,2H-pyrazolo
[34:4,5]thiazolo
[2,3-b]quinazoline-9[10H]-ones 5(a-c)
Compound 3(a-c) (0.01 mole), hydrazine hydrate (0.02
mole) and LiBr (10 mole %) were placed in a small conical flask and mixed with a glass rod at room temperature.
The mixture was then exposed to microwave radiations at
60% power for 6-6.30 minutes. After completion of reaction (monitored by TLC), the reaction mixture was cooled
ethanol to afford compounds 5(a-c).
Conventional synthesis of 3-(4-chlorobenzylidine)10-(4-substituted phenyl)-6,7,8trihydro-3H,3aH,2H-pyrazolo [34:4,5]thiazolo [2,3-b]
quinazoline-9[10H]-ones 5(a-c)
A solution of compound 3(a-c) (0.01 mole) in abso lute ethanol (30 mL) was treated with hydrazine hydrate in excess
(0.02 mole) and refluxed on heating mantle in the presence
of glacial acetic acid as a catalyst for 14 hr. The reaction
mixture was concentrated, kept overnight and poured into
ice water. The resulting solid was filtered, washed with wa-
Conventional synthesis of 4-(4-Chlorophenyl)-11-phenyl-7,8,9-trihydro-2Hpyrimido[45:4,5]thiazolo

[2,3-b]quinazoline-2,10
[3H,11H]-diones 6(a-c)
A solution of compound 3(a-c) (0.01 mole) in absolute
ethanol (30 mL) was treated with urea (0.01 mole). A few
drops of conc. HCl were added and refluxed on a heating
mantle for 12 hr. The reaction mixture was concentrated, kept overnight, poured into ice water and neutralized
with 5N NaOH solution. The solid product was colleced,
washed several times with water and recrystallized from
absolute ethanol.
Acknowledgement
Authors are thankful to the Head, Department of Chemistry, M.L. Sukhadia University, Udaipur for providing laboratory facilities and to the Director, SAIF, CDRI, Lucknow, India for providing spectral and analytical data. Authors are
grateful to Antimicrobial Research Laboratory, particularly
Dr. Kanika Sharma, Department of Botany, M.L. Sukhadia
University for evaluating antimicrobial activity.
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INFORMACIN GENERAL
INFORMACION DE CURSOS, CONGRESOS,
SIMPOSIUMS
ALIMENTACIN
FOOD INGREDIENTS EUROPE & NATURAL INGREDIENTS 2011
The Global Business Platform for Food & Beverage Ingredients
From 29 November to 1 December 2011, Paris Nord Villepinte, Paris, France
For over twenty years Fi Europe has been the leading industry trade show delivering a worldwide audience of over
500,000 food professionals. Over that time, Fi Europe has
continually evolved, adapted and innovated to ensure it
continually reflects the dynamics of an ever-changing global industry.
Natural ingredients is running alongside Fi Europe and
with demand for natural and organic foods growing exponentially, food manufactures are increasingly shifting
towards natural alternatives. Natural ingredients delivers
you potential customers from every sector of the food &
beverage industry.
More information: http://fieurope.ingredientsnetwork.com
ENERGA Y MEDIoaMBIENTE
Jornada WCP
Jornada Wineries for Climate Protection
10 de Junio de 2011, Palacio Nacional de Congresos
de Montjuc, Fira de Barcelona
Organizado por la Federacin Espaola del Vino y Alimentaria, y contar con la Presidencia de Honor del Sr. Ricardo Lagos, enviado especial de la ONU para el cambio
climtico.
Jornada WCP gira en torno a dos ejes principales:
presentacin de experiencias de bodegas en la reduccin de su impacto sobre el cambio climtico
firma de un compromiso conjunto del sector por la reduccin del impacto sobre el cambio climtico
El calentamiento que est experimentando nuestro planeta constituye una de las mayores amenazas socio-ambientales a las que se debe enfrentar la humanidad en
este siglo. El aumento de la temperatura en la Tierra tiene
un impacto preocupante y significativo en la sociedad, la
economa y el medio ambiente, afectando a muchas personas y ecosistemas.
Este evento rene empresas vincolas de mbito mundial
que, as, pueden intercambiar su experiencia y dar a conocer las mejores prcticas que se han implantado en las bo-
degas para reducir las emisiones de CO2 y la consecuente

presencia de carbono.
Ms informacin: secretaria@wineriesforclimateprotection.com; info@wineriesforclimateprotection.com
Pollutec Horizons 2011
Del 29 de noviembre al 3 de diciembre de 2011, Parc
des Expositions de Paris Nord Villepinte, Paris, France
Pollutec 2011, rene durante 4 das en Lyon al conjunto de
los equipamientos, tecnologas y servicios para el tratamiento de todas las contaminaciones y ms extensamente
para la conservacin del medioambiente y la implantacin
del desarrollo sostenible.
2.400 expositores que presentarn una oferta multisectorial acorde con las evoluciones del mercado a 75.000 visitantes profesionales procedentes de la industria, las colectividades locales, la construccin y el sector terciario.
Ms informacin: www.pollutec.com
INGENIERA Y BIOINGENIERA
Tailing - Mine Waste 2011
6 9 November 2011, in The Fairmont Pacific Rim, 1038
Canada Place, Vancouver, British Columbia, Canada
Tailings and Mine Waste 11 (Tailing & Mine Waste Conference 2011) is the next of a series of symposia on mill
tailings management started at Colorado State University
in 1978. The primary purpose of the Conference is to provide a forum for members of the mining community, engineers and scientists serving the mining industry, regulatory
groups, and other interest groups concerned with environmental issues related to tailings and mine waste management. Issues of environmental science and engineering,
geochemistry, geotechnics, hydrogeology, milling, mining,
mining engineering, tailings management, and other topics
related to tailings and mine waste will be covered in focused sessions. Special sessions on Oil Sands Tailings and
Mine Wastes and Northern Issues with Tailings and Mine
Wastes will be included in this conference.
More information: www.tailingsandminewaste.org
QUIMICA
EXPOQUIMIA Saln Internacional de la Qumica
EQUIPLAST Saln Internacional del Plstico y Caucho
EUROSURFAS Saln Internacional de la Pintura y el
Tratamiento de Superficies
Del 14 al 18 de noviembre de 2011, Recinto Ferial Gran
Va, Fira de Barcelona, Espaa
401
El Recinto Ferial de Gran Va de la Fira de Barcelona acoger la Feria Expoquimia 2011 Barcelona. Con seminarios,
conferencias y jornadas tcnicas con los mejores cientficos y especialistas para dar las claves del futuro desarrollo
del sector y con todas las novedades mundiales en estos
sectores:
Industria de Qumica Base Materias Primas; Productos
Intermedios y Servicios; Qumica fina y Farmaqumica;
Nuevos Materiales; Biotecnologa; Instrumentacin; Analtica Material de laboratorio; Bienes de equipo e Ingeniera; Instrumentacin de Medida y Control; Bombas y
Vlvulas; Tecnologas y Maquinaria para el Proceso de
produccin; Logstica; Manutencin y Almacenaje; Tcnicas Medioambientales;
Universidad, Investigacin, Desarrollo e innovacin; Transferencia Tecnolgica
Seguridad Industrial y Laboral; Software; Compositech
METALURGIA, MINERA Y PROCESAMIENTO

DE MINERALES
FLOTATION 11
From 14 to 17 November 2011, Vineyard Hotel, Cape
Town, South Africa
Flotation 11 features 2 symposia.
November 14-15: Flotation Fundamentals: Physics and
Chemistry. Although now over a hundred years old, the
fundamental aspects of flotation are still being intensively
researched, and new machines developed. This two day
symposium will focus on:
Fundamental reagent and flotation chemistry; Bubbles,
froths, bubble-particle interactions; Flotation cell hydrodynamics, kinetics and scale-up.
Ms informacin: www.expoquimia.com
12 Congreso Mediterrneo de Ingeniera Qumica

Del 15 al 18 de novembre 2011, Recinto Ferial Gran Va,
Fira de Barcelona, Espaa
El 12 Congreso Mediterrneo de Ingeniera Qumica se
llevar a cabo durante la feria internacional de la EXPOQUIMIA .
Se repasar todos los aspectos y resultados relacionados
con la Ingeniera Qumica, de la aplicacin en reas como
el Desarrollo Sostenible e Ingeniera Ambiental, Ingeniera de Alimentos y Bioqumica y Procesos e Ingeniera de
Producto, y en las zonas clsicas como Tecnologas de la
Separacin, Reactores Qumicos y Procesos.
November 16-17: Flotation Applications and Plant Practic.

This two day symposium focuses on the application of flotation, and will include sessions on:
Plant Operations, particularly related to new technology,
and process mineralogy problems; Flotation Circuits, and
their modelling, simulation, control and optimization; Flotation machine developments; Metallic, non-metallic and
coal flotation; Environmental considerations.
More information: www.min-eng.com/flotation11
Ms informacin: http://www.ub.edu/congmedit
MAQUINARIA Y EQUIPAMIENTO
SIMEI
International Enological and Bottling Equipment Exhibition - 24th Edition
From 22 november 2011 to 26 november 2011, Feria
Milano Congressi, Milano, Italy
Simei, biennial, is the largest strictly specialized exhibition, which presents at the same time all kind of machinery
and equipment for oenology and for beverage production,
bottling and packaging.
More information: www.simei.it
402
NOVEDADES TECNICAS
The MEGATEX XD line extension from ROTEX global
provides high-capacity screening in a compact footprint
ROTEX Global, Inc. has introduced the line extension to
the MEGATEX XDTM Screener, a high-capacity screening
solution designed to provide greater throughput and reliability than conventional screeners in a compact footprint.
The line extension for the MEGATEX XD provides increased
capacity in a small area measuring 9 x 9 x 12, continuous
operations at high temperatures, and maximum screening
efficiency. The durable machine is ideal for a wide range
of high-volume applications with demanding screening requirements, including chemical, food, plastics, abrasives,
agriculture, and many other high volume applications.
The line extension for the MEGATEX XD provides maximum screening surface and higher capacity per square
foot of screen than machines with larger footprints. The
machine uses a stacked, multiple deck design to evenly
split and distribute the incoming flow of material to all
screen decks. The compact machine also results in lower
installation costs and reduced maintenance expense. The
stacked multi-deck configuration allows individual tray
access without the need to remove all decks. A Lift-Rail
system with non-binding stainless steel cam activation enables easy screen frame installation and removal. Single
deck screen changes can be completed in 10 minutes.
Designed to provide long-lasting service, the line extension
for the MEGATEX XD is built with several durable features,
including an easily accessible external drive that allows for
maximum product recoveries at material temperatures up
to 400F (205C). The drive is a single reaction cartridge
with two spherical roller bearings designed for long life in
severe duty environments. The MEGATEX is supported by
a shaft suspension system that is constructed of sturdy industrial U-joint bearings and no-maintenance, low-torsion
center springs. Construction is available in MS or 304SS.
For more information: http://www.rotex.com/01products/
megatexXD.aspx ; www.rotex.com,
Sistema HYDROSWAGE compacto y mvil para la expansin de tubos de intercambiadores trmicos, con
mayor facilidad de uso y mejor recoleccin de datos
Haskel International acaba de presentar un modelo actualizado del sistema HydroSwage para la expansin de tubos, que cuenta con una mayor facilidad de uso y nuevas
funciones de recoleccin de datos. El compacto sistema
Mark V ofrece una gran exactitud, velocidad y repetibilidad
al expandir los tubos de los intercambiadores trmicos en
planchas de tubos por medio de la aplicacin directa de
una alta presin hidrulica interna. Est diseado para uso
en la fabricacin de intercambiadores trmicos para generacin de vapor, condensacin y evaporacin. Las aplicaciones incluyen generacin elctrica, metalurgia, acondicionamiento de aire, procesamiento qumico, y papeleras.
El nuevo equipo Mark V incluye controles electrnicos de

pantalla tctil para configurar todas las funciones de proceso. Se almacena el historial de expansin, el cual puede
descargarse a una hoja de clculo Excel por medio de un
puerto USB.
Las ruedecillas para servicio pesado facilitan desplazar el
sistema hasta la cara de las planchas de tubos para realizar la expansin. El intensificador se monta en una gaveta
conveniente que se desliza fuera de la unidad elctrica. Un
cable opcional de 6m (20 pies) de largo permite utilizar el
intensificador a una distancia de la unidad elctrica.
Diseado para proporcionar una expansin a alta presin
en un solo paso, independientemente del grosor de las
planchas de tubos, los mandriles de expansin de HydroSwage cuentan con un sistema de apoyo patentado
de sellos segmentados que mantienen altas presiones con
una minima extrusin del sello.
Capaz de lograr presiones de expansin de hasta 50.000
PSI, el sistema acepta una alimentacin monofsica de
100 a 240 VCA y requiere una presin de entrada de aire
de entre 70 y 150 psi con un mnimo de 70 pies cuadrados por minuto. Las presiones de expansin se aplican de
manera uniforme, tubo tras tubo, brindando juntas constantes todo a lo largo de la plancha de tubos. El mtodo
se ha aplicado satisfactoriamente para expandir tubos en
planchas de tubos tan delgadas como de 19 mm () y
con grosores de hasta 84 cm (33).
Ms informacin: http://www.haskel.es/
Tapflo TX 820. Nueva bomba de membrana para aplicaciones de gran capacidad

Tapflo est aumentando la capacidad de las bombas de
metal de la serie T con el lanzamiento de la nueva TX 820,
una bomba de membrana accionada por aire comprimido
fabricada en aluminio. Esta bomba consigue una capacidad de hasta 820 litros por minuto, ha sido aprobada con
certificacin ATEX, y por lo tanto es adecuada para entornos explosivos.
La TX 820 puede bombear, tanto lquidos con valor de PH
neutro como alcoholes voltiles, como aceites y lquidos
viscosos como pinturas y colas. Los lquidos nocivos para
la salud tambin pueden manipularse de forma segura, ya
que la bomba est sellada hermticamente.
La nueva bomba Tapflo TX 820 es ideal para bombear, por
ejemplo, refrigerantes y aceites para todo tipo de industrias. La bomba tambin es adecuada para las industrias
de la pintura y el vidrio, y para tareas con aguas residuales,
por ejemplo, procesamiento de aguas residuales y productos de desecho en separadores de aceite.
Ms informacin: www.tapflo.com
403
NOTICIAS DE EMPRESAS
Severn Trent Services - Apliclor elimina el arsnico del
agua en ms de 50 puntos de la pennsula
Severn Trent Services-Apliclor, empresa lder en el suministro de soluciones para tratamiento de aguas potables
y residuales, se ha adjudicado recientemente diversos
contratos para la eliminacin del arsnico del agua. El arsnico est presente de forma natural en el agua, especialmente en aguas subterrneas que discurren por zonas
con formaciones de tipo grantico.
Con las nuevas adjudicaciones, la compaa dispone de
unas 50 plantas de eliminacin de arsnico en la Pennsula
Ibrica, en especial en las zonas de Castilla Len, norte de
Madrid, Pirineo Cataln, Galicia y, Portugal.
Desde 1993, la Organizacin Mundial de la Salud establece la concentracin mxima de arsnico en el agua de
consumo humano en 10 partes por billn (ppb), es decir
10 microgramos por litro. Este lmite es el que recoge la directiva europea relativa a la calidad de las aguas destinadas al consumo humano y la normativa espaola vigente.
Diversos estudios cientficos revelan que una exposicin
continuada al arsnico a niveles superiores que los que
permite la legislacin puede provocar cncer, as como
enfermedades en la piel, cardiovasculares o neurolgicas.
En nuestro pas, la concentracin de arsnico est bien
controlada, sin embargo es un problema especialmente
serio en pases como Bangladesh, as como en zonas de
Argentina, India o Japn, en las que se han detectado niveles elevados de arsnico en aguas de pozo destinadas
a consumo humano.
El sistema empleado por Severn Trent Services-Apliclor
para la eliminacin del arsnico, Bayoxide E33, cuenta
con ms de diez aos de xito probado en filtracin del
agua para consumo humano, y permite cumplir el lmite
de 10 g/l establecido por la normativa. Actualmente es la
mejor tecnologa disponible para la remocin de arsnico
y otros metales pesados en agua. Es un sistema eficaz,
de un funcionamiento sencillo, mnimo mantenimiento y
que permite retirar definitivamente el arsnico del ciclo del
agua.
Ms informacin: http://www.apliclor.es/
La Ctedra DOW/URV presenta el manual desarrollo

sostenible
El desarrollo sostenible y la importancia de concienciar a
las generaciones actuales y futuras para lograr el equilibrio
entre los recursos limitados y la gestin de los mismos es
el tema clave del manual.
Es sostenible nuestro desarrollo futuro? Esta es precisamente la pregunta que el manual Desarrollo Sostenible de
la Ctedra Dow/URV pretende responder de una manera
indirecta. A travs de una serie de interrogantes el libro
busca que el lector reflexione y extraiga sus propias conclusiones para responder de forma informada a esta ltima
pregunta mediante el anlisis de la informacin contenida,
que se presenta acompaada de una notable cantidad de
figuras y cuadros con datos precisos y actuales.
Durante la presentacin del libro, que tuvo lugar en Tarragona y cont con la presencia de diversas autoridades
de la Generalitat, el Ayuntamiento de Tarragona y la Universidad, la vicerrectora de Transferencia e Innovacin,
Misericordia Carles, resalt la importancia de la estrecha
colaboracin entre universidad y empresas.
Para ms informacin sobre la Ctedra Dow/URV, puede
visitar la pgina: http://www.urv.cat/catedres/catedra_
dsostenible/es_links-catedra.html
AVENEER - Construction of the first MMA production

plant slated for 2014 location to be decided on in 2011
Like the traditional ACH sulfo process, AVENEER is
based on the starting materials ammonia, methane, acetone, and methanol. It dispenses, however, with the sulfuric acid that is normally used.
Just recently, Evonik Industries demonstrated its outstanding process engineering expertise in optimizing production processes by successfully launching the worldscale methacrylate integrated production network at its
Shanghai site. The investment, worth 250 million, was
used on the familiar C4 process, which was nevertheless
significantly redeveloped for the first time. This investment
considerably broadened the technology platform in the
business unit, a strategy Evonik is systematically continuing with AVENEER.
The three-year operation of the AVENEER pilot plant at
the facility in Worms, Germany, will enter the final stage in
the next few days.
With an overall yield of 95%, the process is already intensively using the resources deployed, which ultimately
has benefits for the environment. An internal study also
showed that, in contrast to established processes, CO2
emissions from the AVENEER process are lower than
1,000 kg CO2/mt MMA, virtually half of the previous figure.
More information: http://corporate.evonik.com/
El libro, presentado oficialmente en la Universitat Rovira

i Virgili (URV) de Tarragona, ha sido escrito por los profesores scar Saladi y Josep Oliveras en el marco de la
Ctedra Dow/URV de Desarrollo Sostenible.
404
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SP - ISSN 0001 - 9704

Afinidad LXVII, 549, Septiembre - Octubre 2010

D.L.B. 460 - 1958

Gestin de residuos a lo largo del ciclo de vida de un automvil, por B. Amante,

Efecto del tiempo de residencia sobre la eficacia de la eliminacin de NOx en

Remediacin electrodialtica de suelo contaminado con cobre, por Claudia

Utilidad del cido 4-(4-acetoaminofenil)-4-oxo-but-2-enoico en la preparacin

Eliminacin de contaminantes orgnicos en efluentes de molinos olivareros

Sntesis inducida por microondas de algunos derivados fundidos como

Afinidad LXVII, 549, Septiembre - Octubre 2010

Rheology of redcurrant juices, by B. Amante, A. Lacayo, M. Piqu and V. LpezGrimau

Utility of 4-(4-acetoaminophenyl)-4-oxo-but-2-enoic acid to prepare Pyran

Comparing the effectiveness of processing parameters in pectin extraction

Microwave induced synthesis of some fused thiazoloquinazoline derivatives

Afinidad LXVII, 549, Septiembre - Octubre 2010

Efecte del temps de residncia sobre leficcia de leliminaci de NOx en dos

Descontaminaci electrodialtica de sl contaminat amb coure, per Claudia

Reacci de descomposici trmica del triperxid cclic dacetona en alcohols

Utilitat de lcid 4-(4-acetoaminofenil)-4-oxo-but-2-enoic en la preparaci de

Comparaci de leficcia dels parmetres de procs en lextracci de pectina

Sntesi induda per microones dalguns derivats fosos de tiazoloquinazolina

Afinidad LXVII, 549, Septiembre - Octubre 2010

Legislacin Espaola y Comunitaria,

Afinidad LXVII, 549, Septiembre - Octubre 2010

DOUE L211 de 12/08/10 p. 1416

CLASIFICACIN, ETIQUETADO Y ENVASADO

DENOMINACIONES DE ORIGEN E INDICACIONES GEOGRFICAS PROTEGIDAS

LMITES MXIMOS DE RESIDUOS

DOUE L174 de 09/07/10 p. 1839

BOE n 175 de 20/07/10 p. 6393744

DOUE L220 de 21/08/10 p. 156

MAIZ MODIFICADO GENTICAMENTE

PROTECCIN DE ESPECIES DE LA FAUNA Y

REGLAMENTO DE LOS IMPUESTOS ESPECIALES

Afinidad LXVII, 549, Septiembre - Octubre 2010

Rheology of redcurrant juices

Reologa de zumos de grosella

Palabras clave: Reologa, grosella, zumo, viscosidad

Paraules clau: Reologia, grosella, suc, viscositat

Afinidad LXVII, 549, Septiembre - Octubre 2010

*Corresponding authors: aibarz@tecal.udl.cat,

and fluids which follow the Herschel-Bulkley model will be

The main purpose of this work has been to analyze the

MATERIALS AND METHODS

to a pressure of 24 mm Hg (Labo-rota C-311, Resonatechnics, Buchs, Switzerland).

Afinidad LXVII, 549, Septiembre - Octubre 2010

RESULTS AND DISCUSSION

Rheological behavior of type I juice.

Table 2 shows the parameters obtained with Newton and

Afinidad LXVII, 549, Septiembre - Octubre 2010

Rheological behavior of type II juice.

In Table 3 it can be observed that rheological behavior of

The parameters of the equation are shown in tables 4 and

Table 2.- Clarified and depectinated redcurrant juices parameters

Afinidad LXVII, 549, Septiembre - Octubre 2010

Table 3.- Clarified redcurrant juice parameters

Table 4.- Parameters of Arrhenius Equation for Type I redcurrant juices

Afinidad LXVII, 549, Septiembre - Octubre 2010