VAPOR-LIQUID EQUILIBRIA, DENSITIES, AND REFRACTIVITIES

IN THE SYSTEM ACETIC ACID - CHLOROFORM -WATER AT 25" C

AND J. ;\I. T . RI. G I E S K E S

E. M. KARTZAIARK,
A. N. CAMPBELL,
Department of Chemistry, Uninersity of Manitoba, Winnipeg, Manitoba
Received July 26, 1962

ABSTRACT
The volume changes on mixing of the two binary mixtures acetic acid -water and acetic
acid - chloroform and of the ternary mixture acetic acid - chloroform - water have been
determined. In the system acetic acid - water a volume contraction occurs, showing a miuimum
excess molar olume a t 50 mole7',. Partial molal volume deter~ninationssuggest the formation
of a mixed association of one 11loleculeof water with one molecule of acetic acid. 1x1 the system
acetic acid -chloroform the excess molar volume function is positive over the complete concen-
tration range and this suggests the probability of a positive deviation from Raoult's law.
The refractivities of the two binary systems show t h a t the true molecular volumes of acetic
acid, water, and chloroforln are additive on mixing.
Studies of the vapor-liquid equilibria show t h a t in all three constituent binary systelns
there is positive deviation from Raoult's law b u t if the dimerization of acetic acid in the vapor
phase is taken into account the vapor pressure behavior of the system acetic acid - chloroforln
is virtually ideal. The vapor pressures in the ternary system show strong positive deviations
from Raoult's law over the complete concentration range. This shows t h a t the line of pseudo-
ideality in terms of zero excess molar volume does not really represent ideal behavior. Zero
excess molar volutne i s caused by the counteracting effects of mater and of chloroforn~mole-
cules on acetic acid molecules.
I n the two binary systems investigated the experimental data satisfy the Gibbs-Duhem-
AIargules equation. This proves t h a t treatment for dimerization of acetic acid in the vapor
phase is not merely permissible but necessary.

The system acetic acid -chlorofor~n -water is a promising subject of study for the
student of the theory of solutions. Acetic acid is highly, perhaps con~pletely,dimerized
in the pure liquid state but the addition of water and of chloroform causes the diiner to
dissociate. Water, with its high dielectric constant, has the greater effect. Chloroform has
a dielectric constant about twice that of benzene, the typical non-dissociatirq solvent,
and the effect of chloroform on the dimerization of acetic acid is not negligible, though
much less than that of water. The very low degree of miscibility in the water-chloroform
system indicates high repulsion between the molecules of these two substances. This
repulsion continues t o show itself as a relatively large two-liquid area in the three-
cornpo~lentsystem. The ternary system seemed therefore very suitable for the study of
non-ideality from the thermodynamic viewpoi~lt.
The thermodynamic implications of determinations of vapor pressure are well k n o i v ~ ~ .
111such a system as the present one, vapor pressure determinations should give a more or
less quantitative measure of the non-ideality of the system. On the other hand, accurate
determinations of density yield partial ~nolalvolurnes of the constituents, again a presumed
measure of non-ideality.
Of the component binary systen:~,the system acetic acid -water has been frequently
investigated, in respect to densities, isobaric boiling points, and isothermal vapor pressures
of mixtures of varying composition. The latest data on densities are due t o 1Yoodma11 ( I )
and to Kohner and Gressinan ( 2 ) , the latter of whom determined the refractive index a t
25' C for the helium D-line. Redlich and Xielsen (3) report the apparent nlolal volun~es
up to 4 A f acetic acid.
Isobaric studies have been carried out by numerous workers, usually a t atmospheric
pressure. Arich and Tagliavini (4) give a bibliography of the subject. Chalov and
Canadian Journal of Chemistry. Volume 41 (1963)

407
408 CAXADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

,qleksandrova (5) have investigated the boiliilg point diagram a t different constailt
pressures, and thus deduced the isotherms between 20' and 80, but the extrapolation
methods used for the lower temperature make the results doubtful. Wremsky et al. (6)
determined directly the isothermal vapor pressure curves, a t 42' and 60, by an air
displace~nentinethod essentially the saine as that used in the present work. Their results
show positive deviatioiis from Raoult's law. The same conclusion results from the work
of Arich and Tagliavini (4), who investigated the isotherms a t 69.7, 79.9, and 89.9' C.
Fredenhagen and Liebster (7), also using the air displacement method, have determined
the partial pressures of acetic acid in water a t 25' up to 2.545 N solutions while Giacalone
et (11. (8) report the partial pressures of water a t 34.45' up t o a concentration of 0.1529
mole fraction acetic acid. Campbell and Kartzmark (9) report the relative viscosities a t
25' C over the complete concentration range.
The system water-chloroform shows a large miscibility gap a t 25' C, the limits being
0.8 ~ t water7 ~and 99.4 wt% water according to Brancker, I-Iunter, and Nash (10) while
Reinders and de hIi11jer (11) give the lower limit as 0.9 wtY0 water a t 2.5' C. The latter
authors, when investigating the isobaric boiling point diagram, found a minimum boiling
point a t 56.12' and 2.8% water, under a pressure of 760 inm. There appear to be no data
on the vapor pressures or densities of the system acetic acid -chloroform.
The ternary system acetic acid -chloroform - water shows a large area of partial
miscibility a t 2Z0, as was first pointed out by 1tTright(12). The limits of the area for 25'
have been most accurately defined by Brancker et al. (10). T h e composition of the plait
point can be determined from the law of rectilinear diameters and also by a method
recently developed by Tarasenkov (13). The composition a t 25' is CHC13 = 42.3%,
CH3COOH = 42.4%, H20 = 15.3%. Tarasenkov's rule, though it lacks theoretical
justificatio~~,appears t o work in practice and is worth explaining since it has not received
the publicity it deserves. According to Tarasenkov, if the tie lines of the miscibility gap,
as represented in Fig. 1, are produced they will intersect on the extension of the base

FIG.I. The method of Tarasenkov to find the plait point in the ternary system. al,concentration of A
in I ; as, coilcentration of A in 2 ; bl, concentration of B in I ; bz, concentration of B in 2. The origin is chosen
a t C.

AC a t the point K. Slight deviations are coilsidered t o be experimental error. The tangent
from K to the binodal curve will touch the binodal curve a t P, where P is the plait point.
I t follows also that the ratio of the amouilts of the codissolving constituent B in the two
layers, for any given tie line, is given by the equation
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM - WATER 409

If the codissolving constituent is not associated in either layer, the above equation gives
the distributioll coefficient, but this condition is not complied with in the system acetic
acid - chlorofortn - water because acetic acid is largely diinerized in the chloroform
layer. Hand (14) discusses the distribution of acetic acid monomers and dimers in the
water and chloroform layers.

E X P E R I hlENTAL
The acetic acid was freed from water b y distilling with acetic anhydride, when its density and freezing
point were fourld to be those of pure anhydrous acetic acid. Commercial chloroform is liable to contain a
trace of alcohol, added as a stabilizer. T o remove this the chloroform was shaken with concentrated sulphuric
acid and distilled over calcium chloride. The chloroform so obtained had a density in good agreement with
the accepted value. Very pure chloroform is not very stable. I t may be preserved in the dark for several days
but after that decomposition becomes evident from the acrid smell. Small amounts were therefore prepared
a t frequent intervals. Distilled water having a specific conductance of 5x10-6 mhos/cm a t 25' was used.
Analysis of Mixtures
Allalyses of mixtures were made by determination of acetic acid content in conjunction with physical
properties, viz. density and refractive index. Any ternary mixture can theoretically be analyzed by the
determination of two physical properties. Calibration is first done by determining the values of each physical
property for a large nutnber of binary and ternary mixtures a t a constant temperature. The results are then
plotted as curves of "iso-values" (equal density or equal refractive index) against composition on a triangular
diagram. For accuracy, it is necessary t h a t the "iso" lines of the two physical properties should intersect a t
a n angle considerably less than 180'. Further necessary requirements are the obvious ones that the physical
properties chosen must be such t h a t they can be measured with accuracy and secondly t h a t they should
alter markedly with change of composition. In order to analyze a mixture of unknown composition i t is only
necessary to determine the values of the physical properties for the given mixture: the intersection of the
two "iso-curves" then gives the composition. The present problem was simplified by the fact that one
component, acetic acid, is readily estimated by titration with standard alkali. If the apex of the cornposition
triangle represeilts acetic acid, determination of the acetic acid content places the mixture on a line paralle1
to the base of the triangle. One physical property, e.g. refractive index, is then sufficient to determine the
pqsition of the nlixture on the horizontal. Lye measured the refractive index for the D-line (5893 A) a t 25'
with a n accuracy of +0.0001. The results of our calibration curve are shown in Fig. 2.

FIG. 2. Curves of equal refractive index a t 25' C in the system acetic acid - chloroform -water.

This accuracy enables concentrations in the binary system chloroform - acetic acid to be determined with
a n accuracy of 0.2 wt7,. In the binary system acetic acid - water the accuracy is again 0.27, up to a con-
centration of 70Yc acetic acid; a t higher acid concentrations the curve of refractive index exhibits a maximum.
For the analysis of ternary mixtures, which is carried out by determining the intersection of the refractive
index curve with the horizoiltal line representing the acetic acid content, the greatest accuracy is obtained
in the middle of the triangle but all mixtures can be brought into this area by the addition of a known
amount of acetic acid. The overall accuracy is about f0.5y0 by weight.
 410 CANADIAS JOURNAL O F CHEMISTRY. VOL. 41, 1963

Densities
The densities were determined with a n Ostwald-Sprengel type pyknometer in a thermostat controlled a t
25h0.005" C. Densities were reproducible to 1 0 . 0 0 0 2 g/ml. T h e density data were used in the calculation
of molar volume, thus:

whereas the so-called "ideal volume" results as

V a p o r Pre5sures and Vapor Conzpositions

The composition of the vapor given off by a given liquid mixture was determined by the air-bubbling
method and the total vapor pressure, manometrically: from these data the partial pressures are calculated.
Pearce and Snow (15) point out t h a t the air-bubbling method has sources of error which may be serious. The
main source of error lies in the fact t h a t i t is difficult to measure accurately and conveniently the large
volume of air required. Since, a t room temperature, the vapor pressures of acetic acid and of water are low,
about 24 hours would be necessary to attain a reasonable amount of distillate, a t a n air speed of 1 liter per
hour: this makes i t difficult to measure the volume of air exactly. \;\re therefore decided to follolv the pro-
cedure of Parks and Chaffee (16), in which the vapor pressures are measured with a manometer (static
method) and the vapor compositions by isothermal distillation using the air displacement method: this
obviates the necessity of measuring the volume of air.
Little need be said about the air saturation method except to draw attention to the design of the saturators.
We used those described by Pearce and Snow (15) and by Von Bichowski and Storch (17). The temperature
of our measurements mas always 25.00&0.05". In order to ensure saturation we made use of a presaturator
maintained a t 30.0' C. The presaturator consisted of four units of the type used in the equilibrium bath.
T h e equilibrium bath itself contained eight saturators. After leaving the last unit the air passes into a tube
leading to the trap. In order to a\-oid condensation of vapor in this tube, it is wound with resistance wire
right into the trap, as shown in Fig. 3 : the current supplied by a copper oxide rectifier maintains this tube
. a t 50-60". The trap is kept in a n acetone - dry ice mixture.

DRY
AIR

PRESATURATO-q SATURATOR
TRAP

FIG.3. The isothermal distillation apparatus. a , air inlet tube; b, slanting tube; c, outlet tube; d , hole
in slanting tube; e, filling tube (glass-stoppered).

I n the literature i t is stated t h a t air speeds up to 10 liters per hour give satisfactory results b u t me used a
speed not exceeding 2 liters per hour. Varying the speed between 0.5 and 2.0 liters per hour gave no larger
deviation than 1% by weight, which we believe to represent our experimental error.

E X P E R I M E N T A L RESULTS A N D CALCULATIONS
DENSITY
AND VOLUME
Acetic Acid - Water
Table I gives the density and molar excess volume data in terins of concentration.
The molar excess volumes have been calculated using the density data for the pure
liquids of Kohner and Gressman (2) and of Woodman (I). When VE is plotted against
mole fraction a millimuin of - 1.145 ml at 0.5 mole fraction acetic acid is observed.
The partial molal volumes were calculated from our own density data, those of Wood-
man (I), Kohner and Gressman ( 2 ) , and Redlich and Nielsen (3). These data are given
in Table 11.
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM - WATER

TABLE I
Density data for system acetic acid - water

VE, m1 mole-1
WtyGHAc Moleyo HHAc di5 s.v., ml-I (negative)

TABLE I1
Partial molal volumes in the system acetic acid -water

(V-VO)HA~,* (v-v"~,o,t
LIole fraction VHAO, ml mole-' VHZO, ml mole-'
Hhc ml mole-' (negative) ml mole-' (negative)

*Partial molal excess volume of HAc.

?Partial molal excess volume of water.

Chloroform - Acetic A c i d
Table I11 gives the concentrations of chloroform, densities, and molar excess volumes
a t 25' C. A maximu~nvalue for V E of 0.555 ml exists a t 0.45 mole fraction chloroform.
Table IV gives the partial molal volumes.
TABLE 111
Density data for the system acetic acid - chloroform

LVtC,/c CHC13 h I 0 l e 7 ~CHCl3 I . ,1 A VE, m1 mole-'

Acetic A c i d - Chloroform - W a t e r
In Table V the densities and excess molar volumes are represented with the correspond-
ing concentrations. The excess volumes were plotted as functions of the composition a t
 CANADIAN JOURXAL O F CHEMISTRY. VOL. 41. 1963

TABLE IV
Partial nlolal volumes in the system acetic acid -chloroform

Mole fraction VCECI~, (a - v 0 ) c ~ c i 3 , VHAe, (V-VO)H~,,

CHC1, ml inole-' ml mole-' ml mole-I ml mole-'

TABLE V
Density data for the system \x-ater - acetic acid - chloroform

AVE,*
No. nll mole-'
0.593
0.804
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM -WATER

TABLE V (Concluded)
Density data for the system water - acetic acid - chlorofortn

H2 0 H AC
AVE,*
No. WtY0 1Ll0le7~ Wt% i?IoIe% dgj ml mole-'

74 2 0 7 25 72 5 78 80 1 1253 +O 125
75 2 0 7 60 63 7 72 70 1 1570 +O 167
76 2 0 8 05 54 3 65 45 1 1941 +O 154
77 2 0 8 65 42 3 54 95 1 2444 +O 174
78 2 0 8 95 37 1 49 85 1 2686 +0 123
*Xegati>e, uilless stated othera~se.

the same time making use of t h e binary data. From this plot the equi-excess volume lines
of Fig. 4 were interpolated. From Fig. 4 it follo\vs t h a t from the concentratioil 100 m 0 l e 7 ~
acetic acid t o 100 rn0le7~chloroforin there must run a curve along which the excess ~ n o l a r
volume is zero.
REFRACTOMETRIC
RESULTS
-4cetic Acid - Water
Table VI contains the refractive indices and inolar refractions. T h e molar refraction
calculated from those of the pure coinponents is also given. Finally the apparent inolar
refraction of acetic acid has been calculated from the formula

where xl,XI0 are the rnole fraction and molar refraction of pure water and x2 the inole
fraction of acetic acid.
Acetic Acid - C/zloroform
Table VII contains the identical d a t a for this system as is give11 in Table VI for acetic
acid - water.
 CANADIAX JOURNAL O F CHEMISTRY. VOL. 41, 1963

ACETIC A C I D
-0.2 7
m

FIG.4. The excess volume functions in the system acetic acid -chloroform - water a t 26" C.

TABLE VI
Refractive properties of the system water - acetic acid

Acetic Acid - Chloroform - Water

Table VIII contains the refractive indices as a function of composition. When these are
plotted on a composition triangle, lines of equal refractive index are obtained.

VAPOR-LIQUIDEQUILIBRIA
Acetic Acid - Water
Table IX gives total pressure versus concentratioil of acetic acid in liquid, in weight
percent, and the results of isothermal distillation (equilibrium liquid and vapor compo-
sition expressed as weight percent acetic acid).
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORhl - WATER

TABLE VII
Refractive properties of the system acetic acid - chloroform

T.4BLE VIII
Refractive properties of the system water - acetic acid - chloroform
--

We have made use of the Gibbs-Duhem-Margules equation to prove the consistency

of the results obtained. For this purpose it is necessary to obtain information on the
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

TABLE IX
Total vapor pressures in the system water - acetic acid a t 25' C

Liquid Vapor Vapor

p, p,
W t % HA4c WtY0 HAc mm Hg

molecular state of the acetic acid in the vapor phase. This can be done by ineans of a for-
mula due to Gibbs (18) which gives the relation between vapor density, pressure, and
temperature :

where

D = experimental vapor density, and

D l = 2.073 (ideal density; air = 1.0, i.e. vapor density of n~onomer).

Wrewsky et nl. (6) tested this fornlula on the system acetic acid -water a t 42" and
60" C and found that it reproduced their results over the complete concelltratioil range.
Using the above formula i t is possible to calculate the molecular weight of the acetic
acid in the vapor phase by successive approximations. Complete dimerization is first
assumed. From this and the vapor composition data the mole fraction of acetic acid in
the vapor is calculated and from this the partial pressure of acetic acid. When this is
introduced illto the above equation D is obtained and hence a n approximate mean mole-
cular weight. This procedure is repeated until no change ~ I Ithe average molecular weight
is found. I t is thus possible t o construct the vapor pressure curves as d function of true
mole fraction.
Once the true molecular weight of the acetic acid in the vapor phase is k11omn the per-
centage dimerization can be calculated and from this again the partial pressures of single
and dimerized molecules, respectively, can be obtained. Lambert (19) points out that the
plot of log K (K = dilnerizatio~lconstant) vs. 1 / T does in actual fact yield a linear plot
from which the heats and entropies of dimerizatioil call be obtained. Entropies of diineriza-
tion usually lie between 20 and 27 cal/deg mole, b u t Lanlbert finds from RlacDougall's
d a t a (20) A H = -16 kcal/mole and A S = +51 cal/deg mole. Thus the entropy is about
twice the maxinlum hitherto observed for dimerization. RIore recently, Levy and Davis
(21) have investigated this question of the dimerization of acetic acid in the presence of
water. They find t h a t a possible equilibrium between acetic acid dimer and acetic anhy-
dride is in fact negligible, the equilibrium being between dimer and monomer molecules.
They find a somewhat smaller heat of dissociation, A H = -14.4 lical /mole, with the
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM - \V-4TER 417

corresponding A S (at the normal boiling point) of +36.8 cal/deg mole. The high entropy
of dimerization is ascribed to the dimers being held together by strong hydrogen bonds.
The equilibrium liquid and vapor conipositions expressed in weight percent acetic acid
are plotted graphically in Fig. 5 . The data of Table IX have been treated by the method
outlined above and the results are given in Table X. The corresponding vapor and liquid

FIG.5 . Liquid-vapor co~llpositionequilibrium curve for the system acetic acid -water a t 25' C.

TABLE X
Dimerization data for the system water - acetic acid

Liquid Vapor

Wt% Mole% Wt% Mole% %

FIAc Hhc HXc HAc M din~er Pt,bi* PH,O PEA, P" P' K
- - 15.7 - 15.7 - - 2.89
111.4 85.5 18.1 4.1 14.0 12.0 2.0 3.00
110.7 84.3 19.3 7.3 12.0 10.1 1.9 2.81
108.1 80.1 21.2 14.3 6.9 5.5 1.4 2.81
104.2 73.6 21.9 17.0 4.9 3.6 1.3 2.13
103.6 72.6 22.7 19.4 3.3 2.4 0.9 2.96
97.1 61.8 23.5 22.1 1.4 0.85 0.55 2.83
94.6 57.6 23.6 22.5 1.1 0.6 0.5 2.40
90.2 50.3 23.8 23.1 0.7 0.35 0.35 2.86
Average K 2.8

con~positionsare found graphically from Fig. 5. Table X gives the con~positionof the
liquid in weight and mole percent, the latter being based on the average molecular weight
418 CXYADIAN JOURNAL O F CHEMISTRY. VOL. 41. 1963

of the acetic acid in the vapor phase.* T h e composition, in weight and mole percent, of
coexisting vapor is also reported, as are the average molecular weight of acetic acid in
the vapor phase, percentage dirner of acetic acid in the vapor phase, total vapor pressure,
partial vapor pressures of water and of acetic acid, partial vapor pressure due to acetic
acid dinler P", partial vapor pressure of monomer P I , and the dimerization constant k'.

von Zaxvidzki (22) applied the Gibbs-Duhem-Margules equation to vapor pressure

relations of binary systems. fIe makes use of the exponential solutions in a modified form,
which were found for this equation by l/Iargules (23).

where P 2 = az$cu3 and p3 = - a s . For the determination of the constants cu2 and cu3 one
of the experinlental partial pressure curves is used. T h e data of Table X were treated by
the above method using approximations and smoothed total pressure data. The consta~lts
a2/2 = 0.41 and a3/3 = -0.30 are obtained for acetic acid, so t h a t it follows for water
t h a t P?/2 = -0.04 and P3/3 = $0.30. T h e results are expressed in Table XI, which
shows measured and calculated partial pressures.

TABLE XI
Partial pressures obtained with voll Zawidzki treatment
in the system water -acetic acid a t 2 5 O C

A%ceticacid Water

Pmem Pcslo Pmem Poa~c

* T h e use of the average wzolecular weight of the acetic acid i n the vapor p h a s e t r the calculation of the liquid
mole fvaction calls for some justification. I t i s realized by the authors that this mole fraction" has n o actual
physical meaning, because in the liquid phase there will be a d z y e ~ e ndegree
t of association and therefore a different
average +nolecular weight.
I n this study, however, the attenzpt i s made to prozje the consistency of the data obtained by nzeans o f t h e Gibbs-
Duhem-Margules equation. von Zawidzki ($2) points out that i n the deriaation of the Gibbs-Duhem equation n o
surface work has been taken into account, but only work o f dilution. Because o f this, the nzole fractions o f the
components i n the liquid phase have to be'referred i o the fnolecular weight in theoapor phase. w h e n , therefire, a
conzponent shows di~~zerization i n the vapor phase, the calculations ntust be based on the molecular weight of the
dimerizing component. von Zawidzki shows that there are t.wo Gibbs-Duhem equations, one for the monomer
and one for the dinzev. H e also shows that the total partial pressure of the dimerizing c~nzponentfollows a third
Gibbs-Duhem equation in which the mole fraction in the liquid phase i s calculated by means of the average nzolec-
ular weight of the dinzerizing component in the vapor phase. I n the present work, we use the latter equation.
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM - R'-ATER 419

Kanlke (24) makes use of the Gibbs-Duhem-Margules differential equation in the

following form,

where x is the mole fraction in the liquid phase of the co~nponentwith the lower boiling
point. This leads to the differential equation

where y = inole fraction in the vapor phase of the component with the lower boiling
point.
Kamke now \+-rites

and makes use of this to obtain the curve of excess free energy for a binary system.
Defining the n~olecularfree energy of mixing as
[I21 AGE = RT(x1In yl+x2 In yz),
where yl and ?/? are the appropriate activity coefficients, he obtains

which leads t o

where

is the relative volatility and

1 1 -
[16] --------
1
1+(1-2~lf(~)+~(l-~){-f~(~)j
The data of Table X have been used to calculate f(y) as defined by equation [IS], and the
relative volatility (equation [lz]). These results are reported in Table X I 1 together with
the quantity
PzO/P1" 0 = 0.6640.
In Fig. 6, f(y) is given as a function of the mole fraction of water in the vapor phase (y).
The ideal curve fideal(y)is calculated according to the formula
1
f ideal (Y) = ---
a-Y
~ ~ r h e ar e= P I " / ( P I " - P Z 0 )= 23.8/(23.8- 13.8) = 2.98. Hence
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

f (y) and relative volatility data for the system

water - acetic acid a t 25' C

* x = mole fraction Hz0 in liquid; y = mole fraction Hz0 in vapor.

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
0.1 0.2 0.3 0 4 0.5 06 0.7
MOLE FRACTION W A T E R I N V A P O R PHASE

FIG.6. f(y) for the system acetic acid - water a t 25' C.

Chloroform - -4 cetic Acid

The total vapor pressures and vapor conlpositions are given in Table XI11 : the figures
in parentheses are the rlunlber of determinations from which the average is obtained. The
data of Table XI11 have been treated for dimerizatio~lof the acetic acid in the vapor phase - -

in the same way as for the water -acetic acid system. The results are reported in Table
XIV. The calculatioil of mole fraction in the liquid is again based on the average nlolecular
TABLE XI11
Total vapor pressures in the system acetic acid -chloroform

Liquid Vapor Liquid Vapor

p, p,
Wt% CHC18 \VtC/o CHC13 inm Hg Wtyo CHCla Wt7, CHCl3 mm Hg
9 . 3 (2) 56.3 - 41.6 (3) 89.7 -
15.6 - 46.4 43.8 - 93.5
19.2 - 51.3 47.6 - 101.7
23.5 - 58.6 5 3 . 1 (4) 93.2 -
 CAMPBELL ET XL.: ACETIC ACID - CHLOROFORM - LVATER 421

weight of acetic acid in the vapor phase. The data of Table X I I I have also been treated
TABLE XIV
Dimerization data for the system acetic acid - chloroform

Liquid Vapor
-
Wt% Mole% Wt% Mole% %
KO. CHC13 CHCla CHC13 CHCl3 J!f dimer Pt,t,i* P C H C ~P~H A ~ P" P' K

1 0.0 0.0 0.0 0.0 - - 15.8 0.0 15.8 - - 2.89

2 15.6 14.8 88.6 67.2 111.7 860 46.4 31.2 15.2 13.1 2.1 2.97
3 19.2 18.2 73.9 72.5 111.2 85.2 51.3 37.2 14.1 12.0 2.1 2.72
4 23.5 22.2 79.0 77.8 111.1 85.0 58.6 45.6 13.0 11.0 2.0 2.75
5 34.3 32.5 87.1 86.2 110.3 83.6 77.4 66.7 10.7 8.9 1.8 2.75
6 43.8 41.7 90.5 89.8 109.7 82.8 93.5 83.9 9.6 7.9 1.7 2.75
7 47.6 45.5 91.6 90.9 109.6 82.5 101.7 92.5 9.2 7.6 1.6 2.91
8 68.8 66.4 96.2 95.8 107.3 78.7 141.1 135.2 5.9 4.7 1.3 2.78
9 854 83.5 98.5 98.3 103.0 71.6 173.5 170.5 3.0 2.2 0.9 2.72
10 100.0 100.0 100.0 100.0 - - 199.1 199.1 0.0 - - -
Average K 2.75
"Pressures in mm Hg.

according to the for~llulae[7] and [8]. Using smoothed data for chloroform, the constants
a2/3 = 0.155 and a313 = -0.1G are obtained. This gives for acetic acid the constants
p 2 / 2 = -0.085 and P 3 / 3 = +O.16. The final results are reported in Table XV.

TABLE XV
Partial pressures obtained with von Z a w i d ~ k itreatment in
the systenl acetic acid - chlorofornl

Chloroform Acetic acid

Yo. P,,,, Peal, Pmeas Poslc

The data of Table XI11 have been used to calculate f(y) and the relative volatility.
This quantity is tabulated in Table XVI as (Pz0/PL0)8
= 0.07948.

TABLE XVI
f(y) and relative volatility data for the system acetic
acid -chloroform

f (r)
x* v (negative) 0.0790

* x = mole fraction CHC13 inliquid; y = mole fraction CHCla in

vapor.
422 CANADIAN JOURNAL O F CHEMISTRI'. VOL. 41, 1963

Acetic A c i d - ClzLorof'orm - W a t e r
The total vapor pressures as functions of composition of liquid phase are given in Table
XVII and the compositions of vapor phase in Table XVIII. As before, the figures in
TABLE XVII
Total vapor pressures in the system acetic
acid - chloroform - water a t 25' C

Liquid composition
14't % \\'t 7" P
KO. HAc CHC13 mm Hg

TABLE XI'III
17apor-liquid equilibrium compositions in the s3stem acetic
acid - chloroforn~-water a t 25' C

Total
No. Liquid compositioll Vapor composition pressure*

83 9 wtyo HHAc 27 7 wtY0 HAc

3 5 1 wtyG CHCl3 (2) 66 8 wt% CHC13 (4) 39
11 0 wt% H20 5 6 wtyO 1320

*In mm Hg.

parentheses indicate the numher of determinations from which the average is obtained.
T h e last column of Table XVIII contains the corresponding total vapor pressures, inter-
polated from Table XVII. The accuracy of the data is about A3 mm. Table X I X contains
the dimerization data, the mole fraction being again calculated on a dimerized basis.

DISCUSSION OF RESULTS
T h e S y s t e m W a t e r - Acefic il cid
When water and acetic acid are mixed there is a contractiosl in volume. This means
that there is a negative excess molar volume function as shown in Fig. 7, in which the
CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM -WATER

-
$ om3q
id.*01d.N
q q q VOq? yc?c1
*?em o i i01d.m

a
i
g mime3 b m d.01 P--$id.

m
'?
 CASADI.4S JOURNAL O F CHEMISTRY. VOL. 41, 1963

M O L E F R A C T I O N A C E T I C ACID

FIG.7 . The excess volume functioil for the systein acetic acid - water a t 25' C. X, Kohiler and Gress-
mann; @, Woodman; 0, this research.

excess volume function is plotted against mole fraction of acetic acid. The minimuin
negative value, larger than 1 n ~ mole-l
l of mixture, occurs a t a collcentration of 50 n10le7~.
In general, dipole-dipole mixtures show a si~nilarbehavior, probably because the dipole-
dipole associations of the pure liquids are partially broken up to forin mixed associations
and this causes the volume t o decrease. We suqgest that in the present case a mixed
association of one nlolecule of acetic acid and one molecule of water may occur, due to
hydrogen bonding, thus:

I //
H-C-C
H
I \
0-H---0-H
- I
When the data of Table II are plotted, the partial molal excess volumes are perfectly
sy~nmetricalwith respect t o composition both for water and for acetic acid and this
agrees with the above view. This symmetry implies that the changes in liquid structure
on addition of water to pure acetic acid and of acetic acid to pure water have similar
effects on the structure of the liquid. This is quite contrary to the behavior of the system
water - ethyl alcohol, studied by Riitchell and Wynne-Jones (25), where hydrogen
bonding is also involved. T h e viscosities of the water - acetic acid system, as reported
by Campbell and I<artzmark (9), also show perfect symmetry, with the maxiinurn a t
50 moleyo.
From the data on molar refractions (Table VI) it follo~vsthat the influence of the mixing
process on the true voluines of acetic acid and water is very small. The slight deviations
are positive but, as an approximation, it could be said that the true volurnes are additive.
This is confirmed by the constancy of the apparent molar refraction of the acetic acid.
Table X shows that the dimerization treatment is justified, since, within the experi-
mental error, the "dimerization constant" retains a constant value over the entire con-
centration range. The anlount of diillerization decreases with addition of water.
The partial pressures, calculated from the amount of dimerization by the method of
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM - \f7.ATER 435

vo11 Zawidzl<i (Table XI), agree with the measured values fairly well, as required by the
Gibbs-Duhem-RIargules equation.
Figure 8 shows that this systeni exhibits positive deviation from Raoult's law, and that
therefore the excess free energq- of mixing, AGE, is greater than zero. There is no n~axilmum

FIG.8. Total and partial vapor pressure curves on a diinerized basis for the system acetic acid -water
a t 25' C. CD, total pressure curves; AD, partial pressures of acetic acid; BC, partial pressures of water
(the straight lines are the "ideal" curves).

on the vapor pressure curve. Figure 5 also suggests the absence of an azeotropic point,
a t which the co~llpositionsof liquid and coexisting vapor \vould be the same. Complete
separation of the components is therefore possible by an isothermal fractional distillation.
A study of the graph for f(y) (Fig. 6) leads to the conclusio~lthat the second derivative
of the excess Gibbs free energy with respect to concentration d2AGE/dx"equation 1161)
is equal to zero somewhere in the concentration region. This means that the AGE(x)
curve will show a point of inflection. T h e approximate positions of both the maximum
and the point of inflection in the AGE(x) rurve are found from the curve in Fig. 9. When
0.6640 becomes equal to unity, the corresponding coilcentrations are those of the maximum
and of the point of inflection. On a non-dimerized basis, the concentrations are 0.7 and 0.1
mole fraction of acetic acid in the liquid phase.
The heats of mixing as reported in the "International critical tables" are positive (heat
absorbed) between 15 and 93 mole% acetic acid and for other conceiltrations negative.
 C A S A D I A S JOURNAL O F CHEMISTRY. T'OL. 41, 1963

.'
LO7
LO-
O

I 0!1 0!2 0!3' o!l 0!5 '0!6 0'7

M O L E F R A C T I O N WATER I N V A P O R
d B I d9
PHASE
' I!O

FIG.9. T h e relative volatility function in the system acetic acid - water a t 25' C. .lB, ideal behavior.

From the relation between the excess entropy of illixing and the excess free energy of
mixing AGE+TASE = AH ( I ' = constant) it follows t h a t ASE most probably has a
negative sign. This seems also to be indicated by the volume contraction which occurs
upon mixing. A negative ASE may explai~lthe point of inflection which occurs around
- 10 i i ~ o l acetic
e ~ ~ acid.
byhen there is a contractioli in volume in dipole-dipole liquids, a negative heat of
mixing is to be expected. T h e fact t h a t , in the system acetic acid -water, the hedt of
mixing is positive over a large concentration range can be explained in accordance with
the ideas of Joerges and hikuradse (26). Energ>- is required to break up the individual
associations of water and of acetic acid b u t energy is set free by the new association
between the water and acetic acid. 'The "dissociation" energies may be large. Lambert (19)
finds froill LlacDougall's data (20) t h a t AH = -16 kcal/rnole. This is due to the fact
t h a t a double hydrogen bond is involved. This energy is certainly larger than t h a t required
to break up the water association. The number of mixed associations cannot be larger, and
is usually smaller, than the total number of dissociations. This means t h a t even the
case where

a positive AH of mixing can result, i.e. the energy required t o break up the associations
is larger than the energy set free by the mixed associatioi~.
T h e exact determination of the magnitude of AGE from the vapor pressure data is not
possible because when there is association in the vapor phase extra terms in addition to
those of equation [13] have to be used. These extra terms involve the secoild virial co-
efficients, which become more complicated in systems where association occurs in the
vapor phase, as has been shown by Lambert (19).
We plan an experimental investigation of the heats of mixing a t 2.5' C and a possible
application of statistical thermodynamics in order t o obtain a better understanding of
AGE function.
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM -WATER 42 7

I t is hoped that a study of the dielectric behavior of the system will throw some light
on the problem of the sign of the ASE function.
The data obtained indicate that the excess free energy function AGE is larger than zero
and shoms a point of inflection. The heat of mixing, A H , has both positive and negative
values and shows a point of inflection. The excess entropy of mixing functioil T A S E
presumably has a negative sign and possibly exhibits a point of inflection. With the aid
of these data the systein acetic acid -water a t 25O C can be classified according to the
rules proposed by Kainlie (24).
T h e System Acetic Acid - Clzloroform
This system shows an increase of volume on mixing. Although this system is a dipole-
dipole mixture, the excess volume is not negative. This indicates a tendency for the
original associations to retain their identity rather than to forill mixed associations between
acetic acid and chloroform molecules. The maximum value of A V E occurs a t 45 mole%
chloroform and the excess partial molal volume curves do not show a symmetry, unlike
the systein water - acetic acid. The data for molar refraction of illixtures (Table VII)
show that the molar refractions are approximately additive and hence that the true
molecular volunles remain practically unchanged on mixing.
Table X I I I shoms that the dimerization treatment is justified because of the constancy
within the experimental error of the "dimerization constant".
The variation in the amount of dirnerization of the acetic acid in the vapor phase with
conceiltration follows the same pattern as in the systenl acetic acid - water. Treatment
of the partial pressures calculated on the dimerized basis, according to the method of
von Zawidzlii shows that with reasonable approximations the Gibbs-Duhem-RIargules
equation is satisfied, although the values calculated for acetic acid are somewhat on the
low side.
Froin Fig. 10 it follows that the behavior of the system is practically ideal in terms of
Raoult's law; there is a very slight tendency to positive deviation. If the pressure is
plotted against mole fraction on a non-dimerized basis, the apparent deviation from
Raoult's law is very large. Froin Fig. 10 it follows that the two components can be
separated completely by means of isothermal fractional distillation.
A study of Figs. 11 and 12 provides further evidence that the behavior of the system
is nearly ideal. In an ideal system the function 0.0790 will be equal to unity for all concen-
trations. The distribution of the points around the "ideal line" shows that the apparent
deviation from ideality is probably due t o experimental error.
According to the "International critical tables" the heat of mixing is positive but only
data for extreme dilution a t both ends of the concentration region are available. Because
the excess free energy function AGE is only slightly positive a negative excess entropy
can be expected but a definite conclusion with respect t o the sign of the excess entropy
should be left in abeyance until we have made a more detailed experimental study of the
heats of mixing. For this reason classification according to the rules of Kamke is as yet
impossible.
T h e S y s t e m Acid - W a t e r - Chloroform
Figure 4 shows a line running from pure acetic acid t o pure chloroform along which
the excess volume A V E is equal to zero. This might seem to indicate that mixtures along
this curve behave ideally but, as follows from the pressure data, this pseudo-ideality is
merely a result of compensating deviations. Figure 4 also shows that the excess volume
in the system water-chloroform is negative over the whole region of concentration.
 CANADIAK JOURNAL O F CHEMISTRY. VOL. 41. 1963

M O L E F R A C T I O N CHCI3
-
FIG.10. Total and partial vapor pressure curves on a dimerized basis for the system acetic acid - chloro-
form a t 25' C. CD, total pressure curves; AD, partial pressures of chloroform; RC, partial pressures of
acetic acid (the straight lines are the "ideal" curves).

0.2 0.4 0.6 0.8 1.0

MOLE F R A C T I O N C H C I S
IN VAPOR

FIG.11. f(y) for the system acetic acid -chloroform a t 25' C.

The results presented in Table XVII show that, in the ternary system, large positive
deviations from ideality occur. These large deviations are due t o the presence of water
and chloroform molecules, which are almost completely immiscible in the binary system.
T h e total vapor pressure of this system is also larger than the sum of those of the two pure
 CAMPBELL ET AL.: ACETIC ACID - CHLOROFORM -WATER

MOLE F R A C T I O N CHLOROFORM I N VAPOR

FIG: 12. The relative volatility function for the system acetic acid - chlorofor~na t 25' C. AB, ideal
behavior.

cosnponents, in the heterogeneous region. This indicates a large positive value for the
excess Gibbs free energy AGE. If the concentrations are expressed in mole percent, only a
small part of the concentration region is covered, and for this reason it is difficult t o show
that for coilcentrations where excess ~nolalvolumes is zero, the vapor pressure behavior
is not also pseudo-ideal, but, from the general behavior of the vapor pressures, idealitjr
is not t o be expected. The heats of mixing, as given in the literature, for the three binary
systems also suggest a positive value over the complete concentration region of the ternary
systein but this has still t o be shown experimentally.
From the above discussion it seems probable that the AGE function is positive for all
collcentrations but Inore experimental information is necessary t o determine the heats
and entropies of mixing. ,4 study of the dielectric properties of the system may also throw
sonie light on the latter question. I t is therefore not as yet possible t o classify this system on
the basis of the functions AGE, A H , and TASEas proposed by Kamke and Kummerle (24).

R . 11. \TOODNAN. Chem. News, 134, 36 (1927).

H. KOHKER and hI. L. GRESSXAK~Y. Z. Physik. C h e n ~A,
. 144, 137 (1929).
D. REDLICHand L. E. KIELSCN. J. Am. Chem. Soc. 64, 761 (1942).
G. ARICHand G. TAGLIAVIXI.Ric. Sci. 28, 2493 (1958).
N. 1'. CHALOV and 0. A. XT~EKSAKDROVA. Gidroliz n. i Lesokhitn. Prom. 10, No. 1, 14 (1957).
&I. S. IVREWSKI~, K. P. ~IISESKO, and B. -4. RIURONZETT. 2.physik. Chem. 133, 362 (1934).
E U H. LIEBSTER. Z. Physik. Chem. A, 162, 449 (1932).
K. F R E D E ~ H A Gand
A. GIACALOKE, F. ACCASCIKA, and G. CARNESI. Gazz. Chitn. Ital. 72, 109 (1942).
A. N. CAMPBELL and E. hI. KARTZMARK. Can. J. Res. B, 28, i61 (1950).
-4. B. BRASCKER,T. G. HUNTER,and A. R7.NASH. J. Phys. Chem. 44, 683 (1940).
IT;. REIKDERS and C. H. D E ~ ~ I X J ERec.
R . Trav. Chim. 66, 573 (1947).
C. R. A. \&'RIGHT, C. THOMPSOX, and J. T . LEOK. Proc. Roy. Soc. (London), 49, 174 (1891).
D. N. TARASENKOX. I. Gen. Chem. USSR ( E m . Transl.). 16. 1583 11946).
D. B.HAND. J. Phy< Chem. 34, 1961 (1930). "
J . N. PEARCEand R. D. SSOTV. J. Phys. Chern. 31, 231 (1927).
G. S. PARKSand C. S. CHAFFEE. J . Phys. Chetn. 31, 439 (1927).
F. R. VONBICHOTVSKI and H. STORCH. T. r\in. Chem. Soc. 37, 2695 (1915).
W. GIBBS. Am. T. Sci. 18. 277. 372 118y9).

J. v o s ZATVIDZKI.Z. Physi
hI. RIARGULES.Sitzber. Xkad. \Viss
D. KAMKEand K. KUXMERLE.2.Physik. Chem. (Frankfurt), 16, 85 (1958).
A. G. ~IITCHELL and \V. F. I<. \I~YNNE-TOKES. . Soc. 15. 161 11953).
Disc~lssioilsFaradav
M . JOERGES and A. SIKURADSL. Z. ~a*turforsch.
59, 259 (1950).