COMPOSITION OF VAPORS FROM BOILING

NITRIC ACID SOLUTIONS

BATTELLE MEMORIAL INSTITUTE

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 Report No. BMI-978
Chemistry-General
(M-3679, 15th E d . )

M
Contract No. W-7405-eng-92

COMPOSITION OF VAPORS FROM

BOILING NITRIC ACID SOLUTIONS

by

R. C. Crooks
R. Q. Wilson
A. E. Bearse
R. B. Filbert, Jr.

F e b r u a r y 9, 1955

BATTELLE MEMORIAL INSTITUTE

505 King Avenue
Columbus 1, Ohio
 K
TABLE OF CONTENTS

Page

ABSTRACT 1

INTRODUCTION 1

PART I. COMPOSITION OF VAPORS FROM AQUEOUS

SOLUTIONS OF NITRIC ACID BOILING AT 200 MM
MERCURY PRESSURE 2

E x p e r i m e n t a l Work 2
Results and Discussion 4
Conclusions 15

PART II. VAPORIZATION OF CHLORIDE FROM AQUEOUS

NITRIC ACID SOLUTIONS 18

E x p e r i m e n t a l Work 18
Results and Discussion 20
Conclusions . . . . . . . . . . . . . . . . . 26

PART III. PHOTOMETRIC DETERMINATION OF CHLORIDE

IN AQUEOUS NITRIC ACID SOLUTIONS 27

Apparatus and Reagents 27

Determination of Chloride 28
C h a r a c t e r i s t i c s of Silver Chloride Suspensions 30
Conclusions 33

SUMMARY 36

REFERENCES 36
 - / -
COMPOSITION OF VAPORS FROM
BOILING NITRIC ACID SOLUTIONS

R. C. Crooks, R, Q. Wilson, A. E , B e a r s e , and R. B. F i l b e r t , Jr.

The composition of vapors from aqueous nitric acid solutions

boiling at 200 mm mercury total pressure is established for solutions
containing between 0 and 67,5 tv/o nitric acid. The volatility character-
istics of low concentrations of chloride in the same concentration range
of nitric acid have been measured in solutions boiling at 200 mm mercury.
The effects of chloride concentration and pressure of boiling are evalu-
ated. A spectrophotometric method for the determination of chloride in
nitric acid solutions is described.

.-]

INTRODUCTION

The c u r r e n t technology of m a t e r i a l s p r o c e s s i n g has r e s u l t e d in i n -

c r e a s e d use of nitric acid as a solubilizing agent in the p r o c e s s i n g of n u c l e a r -
fuel m a t e r i a l s . R e c o v e r y of nitric acid for recycling to m a t e r i a l s - p r o c e s s i n g
operations has become i n c r e a s i n g l y i m p o r t a n t . The p r e s e n t investigation
was undertaken as a p a r t of the p r o g r a m of plant a s s i s t a n c e to the F e e d
M a t e r i a l s Production Center operated by the National Lead Company of Ohio.

The technology of nitric acid p r o c e s s i n g is somewhat d e t e r m i n e d by

the c o r r o s i o n r e s i s t a n c e of available m a t e r i a l s of construction. Although
the r e c o v e r e d n i t r i c acid is usually concentrated by rectification at a t m o s -
pheric p r e s s u r e , advantages of lower c o r r o s i o n r a t e s in equipment a r e found
in the lower t e m p e r a t u r e s of distillation at subatmospheric p r e s s u r e s .
Therefore, the objective of this work was to examine the existing values'^)
of the vapor composition in boiling nitric acid solutions and to extend the
e x p e r i m e n t a l data to lower concentrations of nitric acid for solutions boiling
at 200 m m of m e r c u r y total p r e s s u r e .

In the concentration of n i t r i c acid solutions which contain some chloride,

the chloride tends to accumulate in the fractionation column and s o m e t i m e s
p r e s e n t s a s e v e r e .corrosion p r o b l e m . Although s e v e r a l nickel-containing
alloys a r e p r a c t i c a l l y inert to attack by nitric acid solutions, they a r e often
rapidly c o r r o d e d by nitric acid solutions in which chloride is p r e s e n t . C h l o -
ride m a t e r i a l s tend to accumulate in fractionating equipment because hydrogen
chloride is rapidly stripped from solutions which a r e high in n i t r i c acid con-
centration, and is quickly a b s o r b e d in the reflvix liquid which is low in acid
concentration.

* References at end of this report.

 2

Haggerty and Hixon(2) have m e a s u r e d the volatility c h a r a c t e r i s t i c s of

chloride in n i t r i c acid solutions boiling at a t m o s p h e r i c p r e s s u r e . This r e -
port p r e s e n t s work on the d e t e r m i n a t i o n of c h l o r i d e - d i s t r i b u t i o n r a t i o s in
nitric acid solutions boiling at 200 mnn m e r c u r y total p r e s s u r e .

In the c o u r s e of this work, a s p e c t r o p h o t o m e t r i c p r o c e d u r e was d e v e l -

oped for the d e t e r m i n a t i o n of s m a l l concentrations of chloride in n i t r i c acid
solutions.

PART I. COMPOSITION OF VAPORS FROM AQUEOUS

SOLUTIONS OF NITRIC ACID BOILING
AT 200 MM MERCURY PRESSURE

The liquid-vapor equilibrium compositions of aqueous n i t r i c acid solu-

tions were m e a s u r e d in solutions boiling at 200 m m m e r c u r y total p r e s s u r e .
The compositions and boiling t e m p e r a t u r e s were d e t e r m i n e d in solutions
which contained between 0. 0165 and 0. 385 mole fraction HNO3. Published
d a t a ( ' ) on p a r t i a l p r e s s u r e s of n i t r i c acid over aqueous solutions show values
for nitric acid concentrations for 20 w / o (0. 0665 mole fraction) n i t r i c acid
and above. Since dilute nitric acid solutions do not follow H e n r y ' s law, the
liquid-vapor equilibrium r e l a t i o n s h i p for the m o r e dilute n i t r i c acid solutions
was u n c e r t a i n . T h e r e f o r e , the a i m s of this work were (1) to m e a s u r e the
liquid-vapor equilibrium compositions for dilute n i t r i c acid solutions, and
(2) to t e s t the e x p e r i m e n t a l data for t h e r m o d y n a m i c consistency.

The e q u i l i b r i u m - c o m p o s i t i o n values obtained in this work a r e in a g r e e -

ment with those of T a y l o r ( l ) , but slightly lower boiling t e m p e r a t u r e s were
o b s e r v e d . Both this work and T a y l o r ' s values were checked by t h e r m o d y -
namic consistency by g r a p h i c a l integration of the Gibbs-Duhem equation. .
The equilibrium r e l a t i o n s h i p s for the n i t r i c a c i d - w a t e r s y s t e m a r e r e a d i l y
extrapolated to z e r o acid concentration when the data a r e plotted as r a t i o s
of the vapor and liquid compositions. The extrapolation provides the i n f o r m a -
tion n e c e s s a r y for the construction of liquid-vapor equilibrium d i a g r a m s in
the dilute-acid region as used in the engineering design of n i t r i c acid d i s t i l l a -
tion c o l u m n s .

E x p e r i m e n t a l Work

Apparatus

The compositions of liquid and vapor f r o m nitric acid solutions boiling

at 200 m m m e r c u r y total p r e s s u r e were obtained by use of an O t h m e r - t y p e
stillw) of improved design. Vacuum was provided by a water a s p i r a t o r ; a
C a r t e s i a n manostat controlled the s y s t e m p r e s s u r e to within about 0. 5 nnm
 3

of the 200 m e r c u r y operating p r e s s u r e . A tower filled with soda lime and a

1. 5-liter flask were connected between the m a n o s t a t and the equilibrium still
to a b s o r b nitric acid v a p o r s and reduce the p r e s s u r e fluctuations in the still
s y s t e m . A c a p i l l a r y tube drawn to a v e r y fine d i a m e t e r at the tip provided
a minute s t r e a m of a i r to promote smooth boiling action at the 200 m m m e r -
c u r y p r e s s u r e . Without such a boiling aid, s e v e r e bumping was tinavoidable.
A r e s i s t a n c e wire of 25 ohms, wrapped about an e x t e r n a l r e b o i l e r U-tube at
the bottom of the still, supplied the heat for boiling. The upper s u r f a c e s of
the still unit were insulated by a s b e s t o s and a cloth wrapping.

A t h e r m o m e t e r with its bulb located in the vapor tube of the still m e a s -

u r e d the vapor t e n n p e r a t u r e . The t h e r m o m e t e r was graduated in 0. 2 C d i v i -
sions, was c a l i b r a t e d against another t h e r m o m e t e r which had been c a l i b r a t e d
by the National Bureau of Standards, and was checked in the still against the
boiling t e m p e r a t u r e of distilled water at v a r i o u s p r e s s u r e s . C o r r e c t i o n s for
the exposed t h e r m o m e t e r s t e m were applied to all r e a d i n g s . A U-tube
m e r c u r y - f i l l e d absolute m a n o m e t e r was used to m e a s u r e the absolute p r e s -
s u r e in the equilibrium s t i l l .

Analytical Method

Samples of the liquid and condensed vapor w e r e analyzed for total

acidity by t i t r a t i o n with c a r b o n a t e - f r e e 0, 1487 N NaOH to a phenolphthalein
end point. The sodiunn hydroxide solution was standardized against p o t a s -
sium acid phthalate.

Procedure

Approximately 250 m l of a solution of nitric acid in water was charged

to the still and the s y s t e m evacuated to an absolute p r e s s u r e of 200 mnn
m e r c u r y . With the d e s i r e d p r e s s u r e in the s y s t e m , the b y - p a s s stopcock
on the manostat p r e s s u r e controller was closed to maintain the p r e s s u r e at
that value. Power was then applied to the h e a t e r winding of the still to heat
the solution to boiling, and the boiling action was continued for 1.5 hr to
bring the compositions of the still liquid and vapor condensate to s t e a d y -
state v a l u e s . Steady t e m p e r a t u r e readings were obtained within 0.75 hr
after the boiling s t a r t e d . During the boiling period, approximately 5 volumes
of condensate flowed through the condensate r e c e i v e r , t h e r e b y a s s u r i n g
s t e a d y - s t a t e compositions in both the r e c e i v e r and the s t i l l .

Samples were taken f r o m the draw-off connections on the still and the
condensate r e c e i v e r d i r e c t l y into 6 0 - m l g l a s s - s t o p p e r e d dropper b o t t l e s .
Check e x p e r i m e n t s showed that no significant change in composition by s e l e c -
tive vaporization o c c u r r e d with this method of sampling.

The heating r a t e of 160 w was selected as providing the b e s t r a t e of

boiling for this p a r t i c u l a r equilibrium s t i l l . Lower heating r a t e s r e s u l t e d
 4

in some fractionation of the vapor, and higher heating r a t e s led to e n t r a i n -

ment of p a r t i c l e s of liquid in the v a p o r . The effect of heating r a t e on the
condensation t e m p e r a t u r e of the vapor while boiling a 20 w / o nitric acid
solution is shown in F i g u r e 1. The t e m p e r a t u r e curve shows that the f r a c -
tionation effect b e c o m e s negligible at heating r a t e s over 140 w.

System p r e s s u r e s were r e c o r d e d to within 0. 1 m m m e r c u r y . T e m -

p e r a t u r e readings after s t e m c o r r e c t i o n were further adjusted to a p r e s s u r e
of 200. 0 m m m e r c u r y .

R e s u l t s and D i s c u s s i o n

Liquid-Vapor E q u i l i b r i u m Data

The observed values for the liquid-vapor equilibrium compositions of

n i t r i c acid solutions boiling at 200 m m m e r c u r y p r e s s u r e a r e shown in
Table 1 and on the t e m p e r a t u r e - c o m p o s i t i o n graph for the HNO3-H2O s y s t e m
in F i g u r e 2. In the t e m p e r a t u r e - c o m p o s i t i o n d i a g r a m of F i g u r e 2, the conn-
positions of liquid and vapor obtained in this work a g r e e well with those of
Taylor, but the o b s e r v e d boiling t e m p e r a t u r e s a r e somewhat l o w e r . The
activity coefficients of n i t r i c acid v a r y over an exceedingly wide r a n g e ,
fronn a nninimunn of 0. 00272 in a dilute solution to a nnaximum of 0. 287 n e a r
the a z e o t r o p e .

The o b s e r v e d activity coefficients of n i t r i c acid and water a r e plotted

in F i g u r e 3, as

yi ^ ^ y2 p
•y1 = X
—= p « , and 72 = X— P ° >
1 1 2 2
where

-y = activity coefficient
x = mole fraction in liquid
y = mole fraction in vapor
P = total p r e s s u r e
P" = vapor p r e s s u r e of pure component
Subscript 1 = H2O
Subscript 2 = HNO3.

The p a r t i a l p r e s s u r e s for 100 per cent HNO3 f r o m Taylor were plotted

against t e m p e r a t u r e to obtain values for n i t r i c acid vapor p r e s s u r e , P2° •

Smoothed values a r e shown in Table 2 for the boiling t e m p e r a t u r e s ,

the liquid and vapor compositions, the activity coefficients, and the n i t r i c
acid distribution r a t i o . The n i t r i c acid distribution r a t i o , K = y / x , is plotted
 5

120 240
Heat Input,w

FIGURE EFFECT OF HEATING RATE ON VAPOR TEMPERATURE IN THE RE-

CIRCULATING STILL
A- I 3 6 8 8
 4
TABLE 1. EXPERIMENTAL RESULTS FOR LIQUID-VAPOR EQUILIBRIA BETWEEN
NITRIC ACID AND WATER AT 200 MM MERCURY PRESSURE

Activity Coefficient
Concentration of HNO3
Tennperature, x^. Mole F r a c t i o n y-y^ Mole F r a c t i o n for for
C in Liquid in Vapor HoO HNO3

66.46 0 0 1.000 —
67.13 0.0166 0.000095 0.986 0.00272
67.96 0.0315 0.000228 0.966 0.00338
68.76 0.0466 0.000699 0.947 0.00682
68.84 0.0488 0.000940 0.941 0.00875
69.77 0.0631 0.001061 0.922 0.00737
70.98 0.0820 0.002180 0.892 0.01119
72.69 0.1075 0.00540 0.850 0.0203
74.91 0.1374 0.01167 0.796 0.0316
76.62 0.1606 0.0201 0.755 0.0440
77.88 0.1830 0.0335 0.726 0.0621
80.88 0.2212 0.0644 0.653 0.0909
82.95 0.2554 0.1082 0.599 0.1248
84.73 0.2979 0.1831 0.542 0.1721
86.18 0. 3440 0.2928 0.475 0.228
36.38 0.3850 0.4122 0.418 0.287
 0.20 030 0.40
HNO , mole fraction

FIGURE 2. TEMPERATURE-COMPOSITION DIAGRAM FOR THE SYSTEM HNO-H 0 AT 200 MM MERCURY

' A-l 3 6 8 9
 8
\J0
p-^JCtoo4v.
\^ P<x
^ K_ H,^\ _
rS:" - 0
2

/ ^
,/=«

/
HNC'3
/
/^
f
a. a.
x" 4
II
/

c
0)

0) /
o f
o

/
o 0.010
«
41'

r
0.001
0.0 0.1 0.2 0.3 0.4
Mole Fraction HNOg in L i q u i d , x g

FIGURE 3. ACTIVITY COEFFICIENTS OF HNO3 AND

HgO IN SOLUTIONS BOILING AT 2 0 0 M M
MERCURY
A- I 3 6 9 0
 1
TABLE 2. SMOOTHED VALUES F O R LIQUID-VAPOR EQUILIBRIA B E T W E E N
N I T R I C A C I D AND W A T E R A T 200 MM M E R C U R Y P R E S S U R E

Molar
Activity Coefficient Distribution
C o n c e n t r a t i o n of HNO3 7j, 72, R a t i o , K, for
Temperature, X T . Mole F r a c t i o n y^^ Mole F r a c t i o n for for HNO^,
C in L i q u i d in V a p o r H2O HNO3 (K = y2 /X2)

66.46 0.000 0.00000 1.000 (0,00182) (0.00370)

67.4 0.020 0.000128 0.981 0.00306 0.00650
68.4 0.040 0.000433 0.956 0.00497 0.01075
69.6 0.060 0.00105 0.927 0.00776 0.0175
70.8 0.080 0.00221 0.894 0.01169 0.0276
72.2 0.100 0.00421 0.863 0.01708 0.0421
73.6 0.120 0.00752 0.829 0.02428 0.0626
75.1 0.140 0.01273 0.795 0.03351 0.0910
76.6 0.160 0.02023 0.761 0.04511 0.1268
78.0 0.180 0.03098 0.727 0.0588 0.1720
79.5 0.200 0.04529 0.693 0.0743 0.226
82.6 0.250 0.0998 0.611 0.1191 0.399
85.0 0.300 0.1881 0.534 0.1737 0.627
85.6 0.320 0.2337 0.504 0.1981 0.730
86.15 0.340 0.2841 0.475 0.2238 0.835
86.35 0.350 0.3103 0.461 0.2377 0.887
86.45 0.360 0.3393 0.448 0.2506 0.944
86.5 0.3726 0.3758 0.431 0.2678 1.009
86.4 0.380 0.3982 0.420 0.2783 1.050
86.1 0.400 0.4595 0.394 0.3069 1.149
 10

in F i g u r e 4 a s a function of n i t r i c acid concentration. The smooth curve for

the distribution r a t i o is r e a d i l y extrapolated to z e r o n i t r i c acid concentration
and should be p a r t i c u l a r l y useful in distillation calculations on dilute solu-
tions of nitric acid.

F i g u r e 5 shows the liquid-vapor equilibrium curve for solutions of

nitric acid in water at 200 m m m e r c u r y . The c u r v a t u r e of the equilibrium
curve in dilute nitric acid solutions is i l l u s t r a t e d in F i g u r e 6, which was
computed f r o m the extrapolated values for the K distribution r a t i o .

The boiling t e m p e r a t u r e s w e r e r e a d f r o m the t e m p e r a t u r e - c o m p o s i t i o n

plot. Smoothed values for the activity coefficients were taken f r o m the
activity function c u r v e s shown in F i g u r e 7. Since the activity of n i t r i c acid
v a r i e s over a l a r g e r a n g e , the data w e r e plotted in the f o r m of

log 7 ,
iSi * ^,
(l-xj)

as suggested by Darken and G u r r y , ('*) F r o m the smoothed values of j3 were

calculated the corresponding smoothed values for the activity coefficients
and the vapor compositions for the chosen liquid compositions.

Evaluation of Data

Both the equilibrium data of this work and those of Taylor were found
to be t h e r m o d y n a m i c a l l y consistent when checked by the Gibbs-Duhem e q u a -
tion. The usual f o r m of the equation.
= xi

In -Y,
7i == -- // —^—
-—- d^ in
In 72,

d e s c r i b e s the m a n n e r in which the activity coefficients of the water (sub-

s c r i p t 1) and n i t r i c acid ( s u b s c r i p t 2) a r e r e l a t e d under equilibrium condi-
t i o n s . F o r example, the Gibbs-Duhem r e l a t i o n r e q u i r e s , for equilibrium
conditions, that each i n c r e a s e in the activity coefficient of n i t r i c acid r e s u l t -
ing f r o m a change in the acid concentration be accompanied by a c o r r e s p o n d -
ing d e c r e a s e in the activity coefficient of the w a t e r . Though this equation is
s t r i c t l y t r u e only for conditions of constant p r e s s u r e and t e m p e r a t u r e , the
unavoidable e r r o r s a r e not g r e a t over s m a l l changes of p r e s s u r e or t e m p e r a -
t u r e . In a b i n a r y s y s t e m , such as nitric acid and water, boiling under c o n -
stant p r e s s u r e , the changes in composition cause changes in the boiling
temperature.

The t h e r m o d y n a m i c a l l y consistent curve for the activity coefficient of

water a s computed f r o m smoothed values of the n i t r i c acid activity
 II

10.0 1

1.0
jy ^^•"^
^|x~
II V^
f^
a
r ^

X
A^

c
o 0.1 urve from smoothe d values
/<^

CO
,y
;^
O
OJ
o
/
c
O
Z
n
oA (D Experimental v alues ~1
A Calculated fron1 values cif Taylor
X
001
yo

0.001
0.05 0.10 0.15 0.20 0.25 0.30 035 0.40
Mole Fraction HNO, In Liquid,x.

FIGURE 4. DISTRIBUTION RATIO OF HNO3 IN BOILING AQUEOUS NITRIC ACID

SOLUTIONS AT 2 0 0 MM MERCURY
A- I 3 6 9 1
 12

1.0

^ ^

k^
r^

Ol X
^
/ ^

V
_y

CM

>« /^
o
o. /
o aoi /
>
1 /
F
O
Z Curve from sm oothed v(nlues
X /
c
o
u 0.001 /
o Y/
L _^
o

0.000!
\

00000!
ao5 0.10 0.15 020 025 0.30 0.35 0.40
Mole Fraction HNO^in Liquid, Xg
FIGURE 5. VAPOR COMPOSITIONS OVER BOILING AQUEOUS NITRIC ACID SOLUTIONS
AT 2 0 0 MM MERCURY
A-13692
 13

0.0005

0.0000
0.01 0.02 0.03 0X)4
Mole Fraction HNO3 in Liquid,Xg
FIGURE 6. EQUILIBRIUM DIAGRAM FOR DILUTE SOLUTIONS OF NITRIC ACID IN
WATER AT 200 MM MERCURY
A-13693
 14

-2.8

-2.4

OJ
X
-08
o
.M

-2.0 g«
I I
II o
car •*-
c
o
X u
-1.6 c
c U.
o

3 -04- ••-
u
UL
<

-1.2
<

-02

-as

-QC-
± ± _L
0 OIO 020 030 0.40
Mole Fraction HNOjin Liquid, Xg

FIGURE 7 )S ACTIVITY FUNCTIONS FOR HgO AND HNO3

A- 1 3 6 9 4
 15

coefficient is shown in F i g u r e 8, F o r these calculations, the activity coeffi-

cients were obtained by graphically integrating the Gibbs-Duhem equation,
starting at the azeotropic composition and integrating toward the c o m p o s i -
tion pure H2O, Similar computations were made to t e s t the t h e r m o d y n a m i c
consistency of the nitric a c i d - w a t e r values compiled by Taylor, and the r e -
sults a r e shown in F i g u r e 9. Both the data of this work and the values of
Taylor conapare favorably with the computed t h e r m o d y n a m i c a l l y consistent
c u r v e s for water a c t i v i t i e s . The m a x i m u m deviation in the computed water
activity for the data of this work is 5, 8 per cent, o c c u r r i n g at 8 mole per
cent nitric acid. The s i m i l a r m a x i m u m deviation for the Taylor data is
4, 3 per cent, o c c u r r i n g at about 19 mole per cent n i t r i c acid. In both c a s e s ,
the graphical integrations f r o m the n i t r i c a c i d - w a t e r azeotrope composition
give calculated activity coefficients for p u r e water which a r e within 2 per
cent of the t r u e activity coefficient of 1 for pure w a t e r .

To facilitate the integration of the Gibbs-Duhem equation, the method

d e s c r i b e d by Darken and Gurry''*) was used. In this method, the activity
coefficient -y is i n c o r p o r a t e d in a new function a, defined as

In
\
a.-> =

Upon substituting ao in the Gibbs-Duhem equation, the activity coefficient

7 j of water was then e x p r e s s e d in the equation

/^ ^l"^ r ] f^r'
^°^\—J =-[''2 ^1 ^2 -°^i ^1 ^2 J - J x i ' °^2^^1-

In this work, the " p r i m e " quantities refer to the azeotrope composition, and
the " d o u b l e - p r i m e " quantities r e f e r to n i t r i c acid concentrations between
the azeotrope and pure w a t e r .

Conclusions

The liquid-vapor equilibrium compositions of nitric acid solutions

boiling at 2 0 0 - m m m e r c u r y p r e s s u r e have been e s t a b l i s h e d for all concentra-
tions of nitric acid between pure water and the azeotrope (37 mole per cent
HNO,), This has been done by extrapolation of the e x p e r i m e n t a l l y d e t e r -
mined distribution r a t i o s , K, for nitric acid to z e r o acid concentrations on
a semilogarithmic chart.

The data of this work and the values r e p o r t e d by Taylor a r e both

fairly consistent from a t h e r m o d y n a m i c standpoint as shown by c o m p a r i s o n
of the data with the values computed f r o m the Gibbs-Duhem equation.
 IL

1.0

^Thermodynamically consistent activity coefficient of water

w- 0.9 obtained by graphical integration of Gibbs-Duhem equation
0) from composition of azeotrope
i
0> 0.8-
o
«^
9i
O
O
>\ 07
>
u Experimental water
< activity coefficient curve a.
06 from smoothed data o

OS

0.4
0.10 0.20 030 0.40
Mole Fraction Nitric Acid in Liquid ,Xg
FIGURE 8. ACTIVITY COEFFICIENT OF HgO IN NITRIC ACID SOLUTIONS AT 2 0 0 MM MERCURY
A- 1 3 6 9 5
 I i

17

c
0)
.2 0.7 -
0)
o
O
>s
• * -

'>
• * -

U
<

0.!0 0.20 0.30 0.40

Mole Fraction Nitric Acid in L i q u i d , Xg
FIGURE 9. ACTIVITY COEFFICIENT OF HgO IN NITRIC ACID SOLUTIONS AT 200MM MERCURY,FR0M DATA
OF TAYLOR(')
A-l 3 6 9 6
 18

PART II, VAPORIZATION OF CHLORIDE

FROM AQUEOUS NITRIC ACID SOLUTIONS

Chlorides in the n i t r i c acid solution feeds to n i t r i c acid distillation

columns under c e r t a i n operating conditions sonnetimes r e s u l t in s e r i o u s
c o r r o s i o n p r o b l e m s . Chlorides tend to accumulate in the column r a t h e r
than to p a s s through in a straightforward path.

Operating conditions which favor the build-up of chloride concentration

in a column can occur when dilute n i t r i c acid is concentrated toward the
higher boiling azeotropic composition (67 w / o HNO3) and the lower boiling
water is rectified f r o m the top of the column. Under these c i r c u m s t a n c e s ,
the chloride is rapidly vaporized f r o m the solutions in the lower p a r t of the
column, and quickly a b s o r b e d by the dilute n i t r i c acid refliix in the upper
p a r t of the column. Chlorides originally p r e s e n t in low concentrations in
the feed accumulate to much higher concentrations within the column. At
this point, the p a r t i c u l a r c o r r o s i v e p r o p e r t i e s of chlorides become evident.

Aqueous solutions of strong inorganic acids a r e highly nonideal in b e -

havior, and t h e i r vaporization c h a r a c t e r i s t i c s a r e difficult to p r e d i c t . In
concentrated n i t r i c acid solutions, chloride is oxidized to free c h l o r i n e ,
Haggerty and Hixon \^) investigated the volatility of chloride in n i t r i c acid
solutions boiling under a t m o s p h e r i c p r e s s u r e . In this work, the effects of
p r e s s u r e and concentration level of chloride on the vaporization c h a r a c t e r -
i s t i c s of chloride in nitric acid solution were studied.

E x p e r i m e n t a l Work

Apparatus

A r e c i r c u l a t i o n still c o n s t r u c t e d according to the specifications of

O t h m e r w ) was used to obtain equilibrium liquid and vapor s a m p l e s of n i t r i c
acid solutions of c h l o r i d e , A C a r t e s i a n manostat in the vacuvim line was
used to control the p r e s s u r e in the s y s t e m . P a r t I of this r e p o r t gives
additional details on the construction and a r r a n g e m e n t of the a p p a r a t u s .

Analytical Methods

Chlorides were d e t e r m i n e d f r o m the absorbance of light by the silver

chloride suspensions formed upon r e a c t i o n with silver n i t r a t e , A Beckman
Model DU spectrophotometer with 1-cm-wide Corex cells was used to m e a s -
u r e the light a b s o r b a n c e of the silver chloride suspensions at a wavelength
of 450 mju. Since the silver chloride suspensions were not stable, they w e r e
p r e p a r e d and examined under controlled conditions. The suspensions w e r e
p r e p a r e d in an aqueous m e d i a which contained 25 volume p e r cent
 19

ethyl alcohol and n i t r i c acid in the range between 0, 5 and 2, 0 N HNO3,

Absorbance r e a d i n g s w e r e taken at 20 min after the silver chloride was p r e -
cipitated. Chloride concentrations in the suspensions w e r e then obtained
f r o m a calibration c u r v e .

To p r e p a r e a sample for chloride a n a l y s i s , a sample of known volume

and containing between 0, 05 and 1, 5 mg of chloride was pipetted into a
50-ml volumetric flask. Then 2, 5 m l of 13 N HNO3, 12 m l of 200-proof
ethyl alcohol, and siofficient distilled water to bring the total volume to
about 40 m l were added to the flask and the contents mixed. Following t h i s ,
2, 5 m l of 0. 05 N AgN03 was added dropwise to the flask while swirling the
contents, then distilled water was added to the 5 0 - m l m a r k and the s u s p e n -
sion thoroughly mixed, A portion of the suspension was poured d i r e c t l y
into the Corex cell, and the covered cell positioned in the s p e c t r o p h o t o m e t e r
c o m p a r t m e n t . Twenty min after the suspension was formed, the light
absorbance of the suspension at 450 naju was m e a s u r e d . Distilled water in
a s i m i l a r Corex cell was used a s a r e f e r e n c e at 100 per cent t r a n s m i s s i o n .
Additional information on the s p e c t r o p h o t o m e t r i c method for the d e t e r m i n a -
tion is p r e s e n t e d in P a r t III,

The acid contents of the liquid and vapor w e r e d e t e r m i n e d by t i t r a t i o n

with 0, 1487 N NaOH to a phenolphthalein end point. Since c o m p a r a t i v e l y
s m a l l quantities of HCl were p r e s e n t in the s a m p l e s , the total acidities w e r e
r e c o r d e d a s n i t r i c acid c o n c e n t r a t i o n s .

Procedure

Approximately 250 m l of a solution of nitric acid containing a m e a s u r e d

quantity of hydrochloric acid was charged to the equilibrium s t i l l . Known
volumes of a standardized hydrochloric acid solution provided the d e s i r e d
chloride c o n c e n t r a t i o n s . After evacuation to a s u b a t m o s p h e r i c p r e s s u r e of
200 m m m e r c u r y , the still was heated at a r a t e of 160 w to give a boiling
period of about 1 h r . During the boiling period, about t h r e e r e c e i v e r v o l -
u m e s of condensate flowed through the condensate r e c e i v e r to provide s t e a d y -
state compositions in the still pot and the r e c e i v e r . Samples w e r e taken at
a t m o s p h e r i c p r e s s u r e , f r o m draw-off connections on the still and condensate
r e c e i v e r , d i r e c t l y into 6 0 - m l g l a s s - s t o p p e r e d dropper b o t t l e s .

• Caution: Concentrated nitric acid may react with ethanol to form ethyl nitrate which is highly explosive.
 20

R e s u l t s and D i s c u s s i o n

Data on Vaporization of Chloride

The vaporization c h a r a c t e r i s t i c s of chloride in aqueous solutions con-

taining between 0 and 67, 5 w / o of nitric acid w e r e m e a s u r e d . In these solu-
t i o n s , chloride was p r e s e n t in concentrations between 17 and 2180 ppm a s
c h l o r i d e . The m e a s u r e d r e l a t i v e volatilities of chloride v a r i e d widely in
magnitude, from v e r y low values in nitric a c i d - f r e e solutions to exceedingly
high values in concentrated n i t r i c acid. F o r example, in a n i t r i c a c i d - f r e e
solution of dilute hydrochloric acid, the m e a s u r e d m o l a r distribution ratio
between the vapor and the liquid for chloride was K = 0, 0046, In a solution
containing 58 w / o nitric acid, the distribution r a t i o was K = 9 1 . 9 .

The e x p e r i m e n t a l r e s u l t s on the vaporization of chloride f r o m n i t r i c

acid solutions a r e shown in Table 3, Acidities of the liquid and vapor p h a s e s
a r e e x p r e s s e d a s total acidity in t e r m s of mole fraction of n i t r i c acid, b e -
cause the hydrochloric acid concentrations a r e c o m p a r a t i v e l y v e r y low. The
tendency for the chloride to vaporize is e x p r e s s e d as the m o l a r distribution
ratio
^ci-
K = ,
X
ci-
where

y ^_ = mole fraction of chloride (Cl~) in the vapor

Cl
x _ , - = mole fraction of chloride (CI") in the liquid.

Since the p r e s e n c e of n i t r i c acid r e s u l t e d in the loss of chloride f r o m

the distillation s y s t e m , the durations of boiling and amounts of chloride r e -
covered a r e r e p o r t e d in the data. In the solution which contained 68, 5 w / o
n i t r i c acid (Run 8), the chloride was r a p i d l y oxidized to free chlorine as
the solution was heated to its boiling t e m p e r a t u r e . Over 99 per cent of the
chloride was lost from the concentrated nitric acid solution during the 1-hr
boiling p e r i o d . The p r e s e n c e of a s m a l l quantity of free chlorine was noted
in the v a p o r s f r o m a solution containing 58, 15 w / o n i t r i c acid (Run 10), but
no free chlorine was o b s e r v e d during distillation of solutions containing l e s s
than 50 w / o n i t r i c acid.

The chloride concentrations r e p o r t e d in Table 3 r e p r e s e n t the total

chlorine content of the liquid and vapor s a m p l e s . A n a l y s e s in which sodium
nitrite was used to reduce free chlorine that m a y have been p r e s e n t gave the
same r e s u l t s as when the s a m p l e s w e r e not t r e a t e d with sodium n i t r i t e .
 al
TABLE 3 . VAPORIZATION OF CHLORIDE FROM NITRIC ACID SOLUTIONS

Total Chloride in
Distillation
Molar Apparatus Chloride
Concentration of HNO3 Concentration of Chloride Distribution Charged Found Recovered
''HNOS yHN03 ''C1-. Vci-. Ratio of Duration of Before After Per Cent of

r
Temperature, Pressure, mm Mole Fraction Mole Fraction Mole Fraction Mole Fraction _, Chloride, Boiling, Boiling, Boiling, Cl-in
Run C mercury in Liquid in Vapor in Liquid x 10^ in Vapor x 10^ mg mg Charge
\ Cl

1 66.2 199.0 0.0000 0.0000 181. 0,83 0.0046 2.2 75.0 75.7 101
2 66.9 200.0 0.0292 0.000273 193. 1.08 0.0056 1.3 78.6 79.5 101
3 68.6 198.7 0.0588 0.000945 187. 5.50 0.0294 1.0 82.3 76.9 94
4 72.3 198.5 0.1038 0.00312 198. 33.2 0.167 1.0 86.5 81.0 94
M
5 75.9 200.2 0.1528 0.01860 184. 215. 1.17 0.8 91.1 85.1 93
6 79.0 197.0 0.2020 0.0489 98.5 563. 5.72 0.9 96.0 77.2 80
7 83.6 198.0 0.283 0.1580 15.2 746. 49.1 1.0 102.0 56.2 55
8 85.6 199.0 0.362 0.394 2.6(^) 1.6(a) -- (^) 1.0 105.0 0.96 0.9
9 72.0 197.0 0.1063 0.00515 212. 32.2 0.152 0.8 86.4 84.9 98
10 83.1 199.0 0.284 0.1670 54.3 4990. 91.9 0.5 678. 347. 51
11 83.7 198.0 0.285 0.1620 6.84 312. 45.6 0.5 20.4 23.7 116 (b)
12 76.3 202.0 0.1565 0.0211 1270. 1052. 0.829 0.8 607. 550. 90
13 75.9 200,0 0.1528 0.0173 29.4 40.0 1.36 0.9 6.08 14.0 230 (b)
14 75.9 200.0 0.1510 0.0204 12.3 16.6 1.35 1.5 6.0 5.8 97
15 69.0 200.0 0.0545 0.00069 1160. 25.6 0.0222 0.8 550. 477. 87
16 66.4 .200.4 0.0011 0.000005 1110. 5.48 0.0049 0.8 507, 462, 91

(a) Chloride was rapidly oxidized to free chlorine.

(b) High chloride recovery due to presence of some chloride in the still from a previous run.
 22

Evidently the oxidation-reduction r e a c t i o n between concentrated n i t r i c acid

and the chloride, a s

3HC1 + HNO3 = CI2 + NOCl + 2H2O,

m a y have been r e v e r s e d upon dilution of the s a m p l e s for a n a l y s i s . Although

t h e r e is the possibility that the ethyl alcohol used to stabilize the silver
chloride suspension m a y have r e d u c e d some free chlorine to the chloride,
other e x p e r i m e n t s show that such a reduction was not likely. F o r example,
chloric acid, HCIO3, t e s t e d by the s a m e analytical p r o c e d u r e showed p r a c -
tically no reduction by the ethyl alcohol to the chloride, but was rapidly r e -
duced by sodium n i t r i t e .

Distribution Ratio of Chloride in Boiling

Acid Solutions

The volatility of chloride in boiling n i t r i c acid solutions was found to

depend p r i m a r i l y upon the total acidity. Values for the m o l a r - d i s t r i b u t i o n
r a t i o s for chlorides o b s e r v e d in the boiling n i t r i c acid solutions a r e plotted
as a function of the nitric acid acidity in F i g u r e 10, Over the range of c h l o -
ride concentrations investigated, the distribution r a t i o was independent of
the chloride concentration. The curve drawn on the c h a r t probably r e p r e -
sents all the data within the range of e x p e r i m e n t a l a c c u r a c y . Since some
chloride was slowly lost f r o m the distillation s y s t e m , m o s t likely through
oxidation to free chlorine by the n i t r i c acid, it was not possible to obtain a
t r u e physical equilibrium in some of the e x p e r i m e n t s .

The chloride volatility is d e t e r m i n e d p r i m a r i l y by the acidity of the

solution. To a s m a l l e r extent the chloride volatility is a l t e r e d by changes
in the chloride concentration and by the p r e s s u r e a t e m p e r a t u r e at which
boiling takes p l a c e . As seen in F i g u r e 10, the distribution r a t i o , K, for
chloride v a r i e s f r o m a value of 0, 002 in v e r y dilute acid solutions to values
over 70 in solutions containing over 0, 30 nnole fraction (60 w/o) n i t r i c acid.
Therefore a range of over 35, 000 to 1 in the value of K m a y occur in a d i s -
tillation p r o c e s s for concentrating n i t r i c acid.

When the boiling p r e s s u r e is i n c r e a s e d f r o m 200 m m m e r c u r y total

p r e s s u r e to a t m o s p h e r i c p r e s s u r e , the distribution r a t i o , K, for chloride
in boiling nitric acid solutions i n c r e a s e s by a factor of f r o m 2 to 4, The
chloride distribution r a t i o s calculated f r o m the data of Haggerty and Hixon
a r e plotted against n i t r i c acid acidity in F i g u r e 11, The smooth curve
drawn through the a t m o s p h e r i c - p r e s s u r e K values lies about 300 per cent
above the 2 0 0 - m m curve for K,

In n i t r i c acid solutions which contain l e s s than about 2 w / o of chloride,

the c h l o r i d e - d i s t r i b u t i o n r a t i o , K, is e s s e n t i a l l y independent of the chloride
concentration. F i g u r e 12 shows the K values for chloride in boiling h y d r o -
chloric acid plotted as a function of the HCl acidity, as computed f r o m
 23

o o
>»|K
II

_o
x:
O
•«-
o
o
o

3
jQ

(A

000!
0 0.05 010
Acidity, mole fraction HNO3
FIGURE 10. DISTRIBUTION RATIO OF CHLORIDE IN NITRIC ACID SOLUTIONS
BOILING AT 2 0 0 MM MERCURY
A- 1 3 6 9 7
 24

100

u o
II

<U

w
O

o
<*•
o
o
Q:

v>
O
o
o

0.001
0.05 0.10 0.15 0.20 0.25 0.30
A c i d i t y , mole fraction HNO3
FIGURE II. EFFECT OF PRESSURE ON THE DISTRIBUTION RATIO OF CHLORIDE
IN BOILING NITRIC ACID SOLUTIONS
A-l 3 6 9 6
 25

too
/ y
/
/
/
/
/
/
/
/
10 /
/

1 3 0 ^ - + ^ ^^
2,V / "^
o >^ / ***^
X X
X / / K-».|atx = l
II
/ /
^ / /
to/ /
CJ
X
••- ^ ' ! 3.127 mole fraction HCl =22.8 V o HCl.
o «r20/4?A°"0^''0P® #
o

c /c^V
o
3 # /
•-
-^/'V.S*^
.2
Q #+/^
/ Am— Curve fromFigure 10
o
o /
/
/ f
6//
0.01 / /
/ ' 1
/ /
oA + Points calculated from partial.
2 // pressure values of Zeisberg»'.
Figures indicate weight per cent
HCl in 1Iquid.

0.001
0 0.05 0. 0 0. 5 0 20 0. 25 0.30
Acidity, mole fraction HCl or HNO3
FIGURE 12. DISTRIBUTION RATIO OF CHLORIDE AS HCl IN BOILING AQUEOUS
HYDROCHLORIC ACID SOLUTIONS AT SELECTED^OILING TEMPERATURES
Boiling temperature has some value as for nitric acid solutions of equivalent
acidity and boiling under 200 mm mercury total pressure.
A-13699
 26

published v a l u e s ' ^ ' on p a r t i a l p r e s s u r e s over hydrochloric acid solutions.

In the calculation of the K v a l u e s , the boiling t e m p e r a t u r e s of the h y d r o c h l o -
r i c acid solutions were selected to m a t c h the boiling t e m p e r a t u r e s of n i t r i c
acid solutions of equivalent acidity and boiling under 200 m m nnercury total
p r e s s u r e , A c o m p a r i s o n of the values for the distribution r a t i o , K, of c h l o -
ride in hydrochloric acid solutions with the chloride K values at equivalent
acidities in n i t r i c acid solutions shows that they do not differ g r e a t l y over
a wide range of acidity. In solutions containing l e s s than 0,2 mole fraction
of HCl or HNO3, the l a r g e s t deviation is about 300 p e r cent between the
n i t r i c acid solutions and the hydrochloric acid solutions. T h e r e f o r e , the
K values for chloride should v a r y not m o r e than about plus or minus 15 per
cent in nitric acid solutions which have an HC1:HN03 mole r a t i o of l e s s than
0, 1, However, high concentrations of nitric acid no doubt would i n c r e a s e
the volatility of chloride by oxidation of the chloride to free c h l o r i n e .

The d e c r e a s e in value of the distribution r a t i o of chloride in concen-

t r a t e d hydrochloric acid solutions o c c u r s because HCl and H2O constitute a
b i n a r y s y s t e m , in which the distribution r a t i o , K, m u s t approach unity as
the s y s t e m composition a p p r o a c h e s pure HCl, In aqueous n i t r i c acid s o l u -
tions of HCl, a t e r n a r y s y s t e m HNO3-HCI-H2O is formed, t h e r e f o r e , t h e r e
is no t h e o r e t i c a l limit to the values which K m a y a s s u m e .

Conclusions

The m o l a r distribution r a t i o , K, of chloride in boiling n i t r i c acid s o l u -

tions is d e t e r m i n e d p r i m a r i l y by the total acidity of the solutions, and v a r i e s
over an e x t r e m e l y wide r a n g e . In the r a n g e between 0, 00 and 0, 30 mole
fraction (60 w/o) of HNO3, the values for K i n c r e a s e f r o m 0, 002 to 70, or
a range of 35, 000 to 1,

Lowering of the boiling p r e s s u r e r e s u l t s in a lower volatility of c h l o -

r i d e . At 200 m m m e r c u r y p r e s s u r e , the volatility of chloride is about o n e -
third that of chloride in nitric acid solutions boiling at a t m o s p h e r i c p r e s s u r e .

In dilute solutions of chloride in n i t r i c acid, the distribution r a t i o of

chloride is n e a r l y independent of the chloride concentration.

In nitric acid solutions of chloride boiling at 200 m m m e r c u r y p r e s -

s u r e , chloride is rapidly oxidized by 67, 5 w / o HNO3, but only slowly o x i -
dized by 58 w / o HNO3.
 27

PART n i . PHOTOMETRIC DETERMINATION OF CHLORIDE

IN AQUEOUS NITRIC ACID SOLUTIONS

The v e r y low solubility of silver chloride in aqueous solutions has

been for s e v e r a l y e a r s a convenient b a s i s for the d e t e r m i n a t i o n of chloride
in the p a r t s per million range of c o n c e n t r a t i o n s . By the formation of a
p r e c i p i t a t e of silver chloride under controlled conditions, the turbidity of
the resulting suspension can be m e a s u r e d by one of s e v e r a l optical
methodsV") and the chloride concentration then obtained f r o m a calibration
c u r v e . However, the silver chloride suspensions a r e not completely stable
and their stability c h a r a c t e r i s t i c s a r e often affected by interfering m a t e r i a l s
p r e s e n t in solution. In the d e t e r m i n a t i o n of s m a l l amovints of chloride in
nitric acid solutions, c o m p a r a t i v e l y l a r g e quantities of nitric acid a r e p r e s -
ent in the silver chloride suspensions and a d v e r s e l y affect the stability of
the s u s p e n s i o n s .

By adding ethanol to the sample as suggested by the work of L a m b ,

Carlton, and M e l d r t i m ' ' ) the stability of the silver chloride suspension was
g r e a t l y i n c r e a s e d . Within a c e r t a i n range of n i t r i c acid concentrations, the
optical density of silver chloride suspensions was found to be substantially
independent of the acid concentration. By using alcohol a s a stabilizing
agent, and controlling the acidity of the sample, the silver chloride s u s p e n -
sions were sufficiently stable and reproducible to p e r m i t the d e t e r m i n a t i o n
of chloride in dilute or concentrated n i t r i c acid solutions,

Kolthoff and Yutzyv°) d e s c r i b e the stabilizing action of ethanol upon

silver chloride suspensions, and d i s c u s s the effects of other f a c t o r s in the
p r e p a r a t i o n of s a m p l e s . Luce, Denice, and Akerlund(9) d e s c r i b e a t u r b i d i -
m e t r i c method for the d e t e r m i n a t i o n of chloride in which the sample is f i r s t
n e u t r a l i z e d by addition of alkali (or acid) and the suspension stabilized by
the use of ethanol.

Apparatus and Reagents

A Beckman Model DU s p e c t r o p h o t o m e t e r was used to m e a s u r e the

absorbance of the silver chloride suspension. C o r e x sample cells having a
light-path length of 1,0 cm contained the s a m p l e s of silver chloride s u s p e n -
sion and distilled water, which was used a s a r e f e r e n c e m a t e r i a l . Light at
a wavelength of 450 na/i was used in the m e a s u r e m e n t of a b s o r b a n c e for the
determination of c h l o r i d e .

The silver n i t r a t e solution was 0, 05 N AgN03 and 0, 2 N HNO3, c o n -

taining 8, 5 g of silver n i t r a t e and 12, 5 m l concentrated n i t r i c acid per l i t e r
of solution in distilled w a t e r . The n i t r i c acid r e a g e n t was 13 N HNO3, p r e -
p a r e d by dilution of concentrated n i t r i c acid with distilled w a t e r . The
 28

ethanol used in the p r e p a r a t i o n of s a m p l e s was 200 proof, A stock solution

of hydrochloric acid which contained 100 mg chloride per liter of solution
was used in the p r e p a r a t i o n of the calibration c u r v e .

Determination of Chloride

Calibration Curve

A calibration curve was p r e p a r e d by m e a s u r i n g the a b s o r b a n c i e s of

suspensions containing known quantities of c h l o r i d e . Aliquot quantities of
the hydrochloric acid stock solution to give concentrations of 1, 2, 5, 10,
20, 30, 40, and 60 mg of chloride per liter of dilution were used in the p r e p -
a r a t i o n of the calibration c u r v e . The silver chloride suspensions were p r e -
pared by the p r o c e d u r e d e s c r i b e d in the following section for the d e t e r m i n a -
tion of c h l o r i d e . The suspensions w e r e 0, 65 N HNO3, contained 25 volume
per cent ethanol, and were m e a s u r e d at 450 m/i at 20 min zifter the formation
of the silver chloride p r e c i p i t a t e .

The calibration curve in F i g u r e 13 shows the a b s o r b a n c i e s of the s u s -

pensions plotted against the chloride c o n c e n t r a t i o n s , A straight line p a s s e s
through the calibration points for chloride concentrations between 2 and 30
mg chloride per liter c o n c e n t r a t i o n s . At concentrations below 2 mg per liter
chloride the curve is no longer s t r a i g h t . Above 30 mg p e r liter chloride,
the suspensions were too unstable and e r r a t i c readings w e r e obtained.

The optical p r o p e r t i e s of the suspension deviated slightly from the

L a m b e r t - B e e r relationship, which r e q u i r e s in n o r m a l solutions that the
absorbancy be d i r e c t l y proportional to the f i r s t power of the concentration.
In the silver chloride suspensions containing between 2 and 30 mg per liter
chloride, the absorbance curve for the 1-cm light path length is d e s c r i b e d
by the equation

A 1 ^o n ^iQ /-O. 8 4 7
A = log = 0, 418 C ,

where,

A = absorbance
I = intensity of incident light (450 mjj.)
I = intensity of t r a n s m i t t e d light
C = concentration of chloride in mg per l i t e r .

The absorbance of the r e a g e n t s in the sample was v e r y s m a l l , a m o u n t -

ing to an absorbance value of 0, 004 when no chloride was added to the sample
in blank d e t e r m i n a t i o n s . Therefore the absorbance of the r e a g e n t was i n -
cluded in the values used for the calibration c u r v e , •
 29

i.O
^

/
^ i

f
/

/
/
V

/
a>
u
c /
o 0.1
ja
y^ Age of suspension 2 0 min
o(Ak.
/ 1 Concentration of ethanol 25 volume per cen1
<
Coneentrationof HNO3 0.65 N
/ L'gh f wavelength 4 5 0 m 1IL

Y ^
Slit width
Refe rence at lOOper cent
0.28rr m 1
Distille d water
^ trcmsmission

0.01
I 10 100
Concentration of Chloride, mg chloride per liter

FIGURE 13. CALIBRATION CURVE FOR CHLORIDE IN SUSPENSION OF SILVER

CHLORIDE
A-13700
 30

Analytical P r o c e d u r e

A known volunne of sample containing between 0, 05 and 1, 5 mg of

chloride was t r a n s f e r r e d to a 5 0 - m l volumetric flask by use of a p i p e t t e .
To the sample were added 2, 5 m l of 13 N HNO3, 12 m l of ethanol, and
sufficient distilled water to bring the total volume to about 40 m l , and the
contents mixed. With s a m p l e s which contained over about 20 w / o HNO^* a.
portion of the distilled water was added before the ethanol to avoid exposure
of ethanol to high concentrations of n i t r i c acid, * Then 2, 5 m l of 0, 05 N
AgN03 r e a g e n t was added dropwise to the flask while swirling the contents,
distilled water added to the 5 0 - m l m a r k , and the suspension thoroughly
mixed, A portion of the suspension was poured into the Corex sample cell,
the cell cover replaced, and the sample cell positioned in the spectrophotom-
e t e r c o m p a r t m e n t . The light a b s o r b a n c e of the suspension was m e a s u r e d
at 450 m/i at a time 20 min after the silver chloride was p r e c i p i t a t e d . D i s -
tilled water was used as a r e f e r e n c e at 100 p e r cent t r a n s m i s s i o n . The
concentration of chloride in the suspension was then r e a d f r o m the c a l i b r a -
tion curve, and the chloride concentration in the original sample calculated
from the dilution factor and density of the sample, a s

/(mg CI
^1-/1 1 \ = *—a
/kg sample) (mg C l ~ :/ l i t e r suspension)
£ L I( 50
(density of sample) \ m l sample

C h a r a c t e r i s t i c s of Silver Chloride Suspensions

Spectral Transmission

Silver chloride suspensions in water have t h e i r g r e a t e s t light a b s o r b -

ancies at the lower wavelengths. F i g u r e 14 shows that t h e r e a r e no peaks
in a s p e c t r a l - a b s o r b a n c e curve between 350 and 900 m/Li, but the a b s o r b a n c e
d e c r e a s e s rapidly a s the wavelength is i n c r e a s e d . The absorbance of the
silver chloride suspension is probably m o r e a c h a r a c t e r i s t i c of the size of
p a r t i c l e s r a t h e r than the s p e c t r a l color of the individual p a r t i c l e s .

Stability of Silver Chloride Suspensions

In Aqueous Nitric Acid Solutions, Suspensions of s i l v e r chloride w e r e

found to be much m o r e stable in e x t r e m e l y dilute or v e r y concentrated solu-
tions of n i t r i c acid than they w e r e in acid solutions of i n t e r m e d i a t e concentra-
tion. F i g u r e 15 shows the effect of n i t r i c acid concentration upon the s t a b i l -
ity of the silver chloride s u s p e n s i o n s . The stability is seen to be at a
m i n i m u m at an acid concentration of 0,20 N HNO3, However, the stability

* Caution: Concentrated nitric acid may react with ethanol to form ethyl nitrate which is highly explosive.
 31

04

0.3

Chloride, 9-6 mg per liter

Acidity, 0.0064 NHNO3

u
c
o 0.2
o
«A

<

0.1

0.0 ± ± ± ± _L ±
300 400 500 600 700 800 900
Wavelength, m/i
FIGURE 14. EFFECT OF WAVELENGTH UPON ABSORBANCE OF A SILVER
CHLORIDE SUSPENSION
A - I 3701
 32

0.60

aoo3 N

0.50

Chloride content, 10 mg per liter

Wavelength, 375 m/i,

0)
u
c
o a4o
o

030 -
o 0.003 N HNO3
o 0.10 N HNO3
< 0 2 0 N HNO3
n 0.50 N HNO3
> 2.0 N HNO3
A 5.0 N HNO3
V 11.7 N HNO3

0.20 J. J.
10 20 30 40 50
Time After Precipitation of Silver Chloride,min

FIGURE 15. EFFECT OF NITRIC ACID CONCENTRATION UPON THE AGING CHARAC-
TERISTICS OF SILVER CHLORIDE SUSPENSIONS IN AQUEOUS NITRIC
ACID SOLUTIONS
A- 1 3 7 0 2
 33

of the silver chloride suspension was r e l a t i v e l y independent of the actual

acid concentration in the range between about 0,20 and 2, 0 N HNO3,

The s i m i l a r i t y of stability c h a r a c t e r i s t i c over a c o m p a r a t i v e l y wide

range of acid concentrations b e c o m e s a useful feature in a nnethod for the
determination of chloride in nitric acid solutions. By adjusting the n i t r i c
acid concentration to within a suitable r a n g e , by either dilution with water
or addition of concentrated n i t r i c acid, it was possible to f o r m silver c h l o -
ride p r e c i p i t a t e s of reproducible stability c h a r a c t e r i s t i c s .

During the formation of the precipitate the p a r t i c l e s f i r s t grow in size

and number, and the optical absorbance of the suspension i n c r e a s e s . Upon
aging, the individual p a r t i c l e s tend to a g g l o m e r a t e and settle out of s u s p e n -
sion. E i t h e r action r e s u l t s in lower a b s o r b a n c e .

In Alcoholic Nitric Acid Solutions, Ethanol in the suspending m e d i u m

was quite effective in stabilizing the silver chloride suspensions for a short
period of t i m e . In aqueous solutions containing n i t r i c acid, the optical a b s o r b -
ance of the suspension d e c r e a s e d rapidly with t i m e from the e a r l i e s t reading,
which was about 4 min after the silver chloride was p r e c i p i t a t e d . The p r e s -
ence of ethanol r e s u l t e d in a gradual initial i n c r e a s e in the a b s o r b a n c e , which
r e a c h e d a m a x i m u m within 20 to 30 min after the suspension was f o r m e d .
F i g u r e 16 shows the effect of ethanol upon the stability of the suspension in
solutions with 0, 50 N and 0, 65 N HNO3 a c i d i t i e s . Lower initial optical
a b s o r b a n c i e s were obtained with suspensions in which ethanol was p r e s e n t .

The p r e s e n c e of ethanol g r e a t l y improved the stability of the silver

chloride suspensions in the p r e s e n c e of nitric a c i d . F i g u r e 17 shows that
suspensions which contained 25 volume per cent ethanol gradually i n c r e a s e d
to a m a x i m u m in a b s o r b a n c e . F o r the acidity range between 0, 65 and 2, 5 N
HNO3, it is seen that a variation in acidity would r e s u l t in no m o r e than a
4 per cent change in the optical a b s o r b a n c y . The stabilization effect of
ethanol and the v e r y s m a l l v a r i a t i o n in a b s o r b a n c e over a range of n i t r i c
acid acidity provided a b a s i s for s p e c t r o p h o t o m e t r i c d e t e r m i n a t i o n of c h l o -
ride in nitric acid solutions.

Conclusions

By using ethanol to stabilize the silver chloride suspension and c o n -

trolling the n i t r i c acid acidity, low concentrations of chloride in n i t r i c acid
solutions can r e a d i l y be d e t e r m i n e d by a s p e c t r o p h o t o m e t r i c p r o c e d u r e .
 34

050

O Ovoiume percent ethyl alcohol,

0 5 0 N HN03,375m/i
25volume percent ethyl alcohol,
0.65 N HN03,450m/x
50 volume percent ethyl alcohol,
a65NHN03, 4 5 0 m/I
0.40
Chloride content, 10 mg per liter

0*
0 percent alcohol
u
c
o
o
w
<
0.30

0.20'--
10 20 30 40
Time After Precipitation of Silver Chloride,min
FIGURE 16. EFFECT OF ETHYL ALCOHOL UPON THE AGING CHARACTERISTICS
OF SILVER CHLORIDE SUSPENSIONS IN DILUTE NITRIC ACID
SOLUTIONS
A-l 3 703
 36

aeo
Chloride content,20 mg per liter
Ethanol, 25 volume per cent
4 5 0 m^

0.1 N HNO3
u
c 0.65JiHN03
0)
•^ 0.50 2.5 N HNO3
o
M

<
5.ONHNO3

0.40 ± ± I ±
0 10 20 30 40
Time After Precipitation of Silver Chloride, min
FIGURE 17 EFFECT OF NITRIC ACID CONCENTRATION UPON THE AGING
CHARACTERISTICS OF SILVER CHLORIDE SUSPENSIONS IN
DILUTE ETHYL ALCOHOL SOLUTIONS
A - I 3 704
 36

SUMMARY

The compositions of liquid and vapor in aqueous solutions of nitric

acid boiling at 200 m m m e r c u r y total p r e s s u r e have been e s t a b l i s h e d for
the range of concentrations between pure water and the the n i t r i c a c i d - w a t e r
azeotrope (67, 5 w / o HNO3), The m o l a r distribution r a t i o of nitric acid con-
centrations in the vapor and liquid p h a s e s r e a c h e s a m i n i m u m of about 0,004
in v e r y dilute solutions of nitric acid.

The liquid-vapor equilibrium m e a s u r e m e n t s a r e in a g r e e m e n t with

p a r t i a l - p r e s s u r e data published for nitric acid concentrations over 20 w / o .
The t h e r m o d y n a m i c activities of the water component a r e shown to be
t h e r m o d y n a m i c a l l y consistent with the n i t r i c acid a c t i v i t i e s , using the G i b b s -
Duhem equation as a c r i t e r i o n .

The vaporization c h a r a c t e r i s t i c s of chloride in boiling n i t r i c acid

solutions v a r y over a wide range and a r e d e t e r m i n e d p r i m a r i l y by the total
acidity of the solutions. Over a n i t r i c acid concentration range between 0
and 60 w / o HNO3, the chloride m o l a r distribution r a t i o i n c r e a s e s f r o m 0, 002
to 70, a range of 35, 000 to 1, in n i t r i c acid solutions boiling at 200 m m
m e r c u r y . The data of Haggerty and Hixon indicate that the relative volatility
of chloride is about 300 per cent g r e a t e r in s i m i l a r solutions at a t m o s p h e r i c
p r e s s u r e . In n i t r i c acid solutions which contain l e s s than about 2 or 3 p e r
cent of chloride, the chloride distribution r a t i o is p r a c t i c a l l y independent of
the chloride concentration.

Chloride in a 58 w / o n i t r i c acid solution boiling at 2 0 0 - m m m e r c u r y

is slowly oxidized to free chlorine, and rapidly oxidized in a 67, 5 w / o n i t r i c
acid solution.

Chloride concentrations a s low a s 1 p a r t p e r million were d e t e r m i n e d

in nitric acid solutions by m e a s u r e m e n t of the light absorbance of silver
chloride suspensions at 450 m/i. The suspensions w e r e stabilized by the
addition of ethanol to the diluted n i t r i c acid solutions p r i o r to the addition
of a silver n i t r a t e r e a g e n t . Consistent m e a s u r e m e n t s were obtained by
adjusting the acidity and reading the light a b s o r b a n c e of the suspensions at
a definite time after p r e c i p i t a t i o n .

REFERENCES

(1) International C r i t i c a l Tables, Vol. Ill, (G. B. Taylor), McGraw-Hill

Book Company, New York (1928), 304,

(2) Haggerty, P . F , , and Hixon, A, N , , P r i v a t e Communication, January,

1953, University of Pennsylvania, Philadelphia, Pennsylvania,
 ^y 37 and 38

(3) Othmer, D, F . , Analytical C h e m i s t r y , ^ , 763 (1948).

(4) Darken, L, S , , and G u r r y , R, W., P h y s i c a l C h e m i s t r y of Metals,

pp, 262 to 266, McGraw-Hill Book Company, New York (1953).

(5) International C r i t i c a l Tables, Vol, III, p , 301 ( F r e d C, Z e i s b e r g ) ,

McGraw-Hill Book Company, New York (1928).

(6) Wells, P , V , , Chemical Reviews, 3, 331 (1927).

(7) L a m b , A. B . , Carlton, P . W., and Meldrum, W. B . , J. A m . Chem.

S o c , 42, 251 (1920).

(8) Kolthoff, I. M . , and Yutzy, H . , J. A m . Chem, S o c , ^ , 1915 (1933).

(9) Luce, E , N , , Denice, E , C , , and Akerlund, F , E . , Ind, Eng. C h e m , ,

Anal. E d , , 15, 365 (1943),

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 J-JI RNJ
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