The Chemical Engineering Journal, 31 (1985)
Prediction of Multicomponent Azeotrope Composition and Temperature
NADER VAHDAT
Department of Chemical Engineering, Tuskegee
GLENN A. SATHER
Department of Chemical Engineering, University
(Received May 1, 1984; in final form March
ABSTRACT
Wilson and NRTL correlations are used to
derive equations for predicting the composi-
tion and temperature of multicomponent
azeotropes from binary equilibrium data. The
equations lead to an efficient and reliable
algorithm for their solution. The model is
used successfully for ternary and quaternary
systems. The effect of the pressure on the
composition and boiling point of ternary
azeotropes was investigated, and it is shown
that if the variation of the composition of
ternary azeotropes with pressure is plotted on
a triangular diagram it produces a straight
line.
1. INTRODUCTION
Many attempts have been made to predict
the composition and temperature of ter-
nary azeotropes using equlibrium data.
Kudryavtseva and co-workers [l - 31 have
proposed a method for the calculation of
composition of multicomponent azeotropes
from data for the binary azeotropes and the
pure components. This method, however,
yields more than one result for the composi-
tion of the azeotrope (e.g. three for a ternary
system and six for a quaternary azeotrope),
of which only one is close to the actual
azeotropic composition. Therefore, the meth-
od is not very effective for predicting the
unknown composition of an azeotrope. Tamir
and Wisniak [4] have used a Redlich-Kister
expansion to calculate the boiling point, and
the composition of ternary azeotropes. But
the Redlich-Kister expansion contains binary,
ternary, quaternary, . . . , constants which
should be determined directly from experi-
0300-9467/85/$3.30
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12, 1985)
mental data on the multicomponent systems.
Such equilibrium data are not readily avail-
able. Tamir [ 51 has developed a method for
predicting the multicomponent azeotropes
using the Wilson equation. The parameters in
the Wilson equation were calculated from the
multicomponent equilibrium data. The com-
position of azeotropes is determined by
computing vapor-liquid equilibria in the
vicinity of the azeotrope. This is the approach
implemented in the process simulators such as
FLOWTRAN [ 61. An objective of this work
has been to prepare a more efficient and
reliable algorithm that calculates only the
azeotropic compositions and temperature.
In this work the composition and tempera-
ture of ternary and quatemary azeotropes are
predicted from the binary experimental data
using the Wilson and NRTL equations. The
model is shown to be more efficient and
reliable than the algorithm used in the process
simulators. The model has been tested success-
fully for sixteen ternary and two quaternary
systems, and was used to predict the existence
and/or the composition and boiling point of
ternary azeotropes for which no experimental
data are available. The influence of the
pressure on the composition and boiling point
of ternary azeotropes was investigated, and a
diagram prepared for all the systems studied.
2. SOLUTION MODEL
The boiling point of a multicomponent
mixture at low pressures [7] is given by
AGE- 5 XiTF AS:
T=
i=l
(1)
Ro-AS
0 Elsevier Sequoia/Printed in The Netherlands
84

where

(2)

T: and AS: are the boiling point and entropy of vaporization of pure component i at system
pressure respectively, and

N
AS= C xi AS: (3)
i=l

In the vicinity of the azeotrope composition o = 0, eqn. (1) is reduced to

5 XiTP
i=l
AS: - AGE
T= (4)
AS

At the azeotrope

0 (5)
lfk

If a correlation is assumed for the excess Gibbs energy, AGE, eqns. (4) and (5) can be used to
calculate the composition and temperature of a multicomponent azeotrope. The Wilson equation
[ 81 is given by

AG"fRT= -f Xi In (6)
i=l

where

(7)

Substitution of eqn. (6) into (4) yields

i=l
T= (8)
N r N 1
AS--R 2 Xi ln(lT;IXjAij]
i=l

Assuming the parameters Aij to be constant, eqn. (8) is substituted into eqn. (5) to obtain

[TRASH-TkASG] AS-R: xiln

i=1

AS,” - AS; - R
i
-f

i=’
xi Aik-AiN
$
i=l
xjAij
+ ln[zl -ln[ilXd.vi])~=
Xdkj] o
(9)
 85

where k goes from

1 to N - 1. Equations (8) and (9) are N equations with N unknowns
(Xl 9 3t2, which can be solved.
. . . , xN- 1, 2’)

The NRTL equation [9] is given by

2 TjiGjiXj
AGE/ET = 5 xi j=’
i=l

m=1
$_Grnixm
where

hji - Xii
Tji = and Gji = exp(-ojirji) (11)
RT

Substitution of eqn. (10) into (4) yields

g XiTP AS;
i=l
T=- (12)
$ TjiGjiXj
AS+R$ xij=l

i=l $, Gmixm

Assuming the parameters rir to be constant, eqn. (12) is substituted into (5) to obtain

$ TjkGjkXj
i=l
- =0
+ (13)

i-b
m=1
mkXm

As in the case of the Wilson equation, eqns. (12) and (13) are N equations with N unknowns,
which can be solved to determine the composition and temperature of the multicomponent
azeotrope.
It was found that a consistently successful method for solving eqns. (8) and (9) or (12) and
(13) is the non-linear regression method which minimizes x:=1 (fk)2, where fk = 0 is any one of
the equations. A subroutine based on this method (NREG) was used in solving these non-linear
86

equations for binary, ternary and quaternary vapor phase is neglected, the vapor-liquid
systems. This subroutine uses a modified equilibrium condition is
Marquardt and Gauss method.
Yip?
The boiling points TF and the enthalpy of Ki= yi = -
(15)
Xi P
vaporization of pure components were found
at atmospheric pressure from the literature, at the azeotrope, Ki = 1 or
and hence the entropies of vaporization AS’: P
were calculated. For systems at other pres- i= 1, 2, . . ..N (16)
sures, T,: values were found from the Antoine yi= pi*
equation, and the enthalpies of vaporization If a correlation (such as NRTL or Wilson) is
were calculated from Watson’s correlation assumed for the activity coefficient, eqn. (16)
r101, can be solved to calculate the composition and

Tc
- T,1
temperature of a multicomponent azeotrope.
AH; T, - T2 o*38
-= Equation (16) should be compared with
AH; I eqns. (8) and (9) (for Wilson) or (12) and (13)
where AH; and AH; are the enthalpy of (for NRTL), of the solution model. Equations
vaporization at temperatures T, and T2 (9) and (13) are weak functions of tempera-
respectively and T, is the critical tempera- ture (the only temperature dependent terms
ture. are the Wilson and NRTL parameters). This
The parameters in the Wilson and NRTL is shown in Fig. 1 where eqn. (13) is plotted
equations were found from the literature for the binary system of ethanol-cyclohexane
[ 11 - 143. For those binary systems for which at different temperatures. Figure 1 clearly
such parameters were not available, they were shows that at the azeotrope eqn. (13) (or 9)
calculated by fitting the activity coefficient is almost independent of temperature. There-
correlations to the experimental binary fore, when solving the system of eqns. (8) and
vapor-liquid equilibria. This was done by (9) (or 12 and 13), one can solve eqn. (9)
using the non-linear regression subroutine to (or 13) first, (by assuming a value for tem-
minimize 2% i (y ,, _, + y2, cal - 1)2, where perature) to determine the (N - 1) composi-
yi,cai and y2,cal are the calculated values of tions. The temperature is then computed
vapor mole fractions, and M is the number of from eqn. (8) (or 12). The calculated tem-
experimental data points. The parameters perature is next used along with eqn. (9) (or
used for predicting the composition and 13) to compute the compositions again. This
temperature of azeotropes are given in procedure is repeated until the answers are
Table 1. found. But as eqn. (9) (or 13) is not very
To use the Wilson equation it is necessary sensitive to temperature, usually only two
to have the liquid molar volume of the pure iterations are needed for convergence. On the
components as a function of temperature. other hand when solving the system of
Using the molar volumes of three different eqns. (16), as the vapor pressure of com-
temperatures [15 - 181, the constants in the ponent i (Pt) is present in all the equations,
quadratic equation the system of N equations should be solved
simultaneously to compute the azeotropic
Vi = ai + biT f ciT2 (14) temperature and composition. As a result the
were calculated for each component. The convergence is more difficult, and the com-
molar volume at any other temperature could putation time is higher for this method. It was
then be calculated by using eqn. (14). also found that in some cases, if the initial
guesses for temperature and compositions are
not close to the answers, the system of eqns.
(16) does not converge. This problem does
3. SOLUTION ALGORITHM not occur with eqns. (9) or (13). Therefore
the solution model given in the previous
The solution model given in the previous section is more efficient and reliable.
section should be compared with the algo- When the solution model is used for the
rithm used in the process simulators such as systems with no azeotrope, it proceeds
FLOWTRAN [6 3. If the non-ideality in the smoothly to the upper or lower bounds,
 87

TABLE 1
Parameters of Wilson and NRTL equations for binary data

Binary System (l-2) Temp. or Parameters (cal (gm mol)-‘) Ref.

Press. -
Wilson NRTL

x21 - AlI Al2 - A22 x2, - x11 Xl2 - A22 a12

Acetone-chloroform 760 mm 11 -412 107 -499 0.30 12

45 “C 55 -460 86 -500 0.30 12
55 “C 75 -480 80 -500 0.30 12
Acetone-cyclohexane 760 mm 1001 321 811 302 0.20 12
Acetone-dimethylbutane 760 mm 1250.87 228.47 721 664.13 0.47 19a
Acetone-ethanol 760 mm 205 200 540 -120 0.30 12
55 “c! 197 201 -26 414 0.30 12
Acetone-hexane 45 “C 954 376 431 665 0.20 12
55 “C 945 300 436 610 0.20 12
Acetone-methanol 760 mm -147 545 265 120 0.30 12
50 “C -254 629 139 224 0.30 12
55 “C -126 546 443 -16 0.30 12
Acetonitrile-ethanol 20 “C 916.34 167.06 810.28 428.44 0.643 23a
Acetonitrile-water 760 mm 694.08 1610.07 1639.51 859.44 0.581 11, 24a
Benzene-cyclohexane 760 mm 149 135 26 245 0.30 12
70 “C 51 240 -197 497 0.30 12
Benzene-ethanol 180 mm 150 1600 470 1160 0.47 12
Benzene-n-heptane 760 mm 99.35 292.94 -359 756 0.30 11,12
400 mm 300 100 -276 735 0.30 12
Benzene-isopropanol 500 mm 272.35 1066.93 11
760 mm 245 895 0.47 12
Benzene-propanol 75 “C 60 1240 185 1105 0.47 12
Benzene-methanol 55 “C 141 1827 690 1242 0.47 12
Chloroform-ethanol 55 “C -295 1445 -295 1375 0.30 12
Chloroform-hexane 45 “C 325 45 11 326 0.20 12
55 “c! 240 120 100.7 434.4 0.362 12,13
Chloroform-methanol 50 “C -440 1940 -205 1535 0.30 12
Chloroform-methyl acetate 50 “C -503 127 -724 412 0.30 12
Cyclohexane-ethanol 760 mm 1956 319 1401 794 0.47 12
Cyclohexane-ethyl acetate 760 mm -92.05 847.71 129.35 555.03 0.12 25
Cyclohexane-isopropanol 500 mm 223.13 1590.51 11
760 mm 220 1500 500 1150 0.47 12
Cyclohexane-methanol 55 “C 600 2700 1450 1805 0.47 12
Cyclohexane-methyl acetate 760 mm 88 1001 259 652 0.20 12
Cyclohexane-propanol 65 “C 225.84 1712.4 546.26 1378.69 0.455 26a
Dimethylbutane-methanol 760 mm 545 2715 1505 1865 0.47 12
Ethanol-ethyl acetate 760 mm 808.84 -192.04 127.68 360.40 -0.472 27a
60 “C 744.81 -52.14 11
55 “C -86.39 1203 0.307 13
Ethanol-n-heptane 760 mm 2096.5 617.57 1420 1000 0.47 12
Ethanol-n-hexane 55 “C 2144 327 1381 1001 0.47 12
Ethanol-water 760 mm 442 901 1488 -215 0.30 12
70 “C 381.76 234.07 0.279 13
Ethyl acetate-isopropanol 60 “C 45.72 488.11 11
760 mm 206.2 94.18 -0.856 2Sa
Ethyl acetate-water 760 mm 1477.53 2364.69 2ga
70 “C 2246.32 -206.94 0.104 13
n-Heptane-methanol 760 mm 753 2521 1670 1700 0.47 12
n.Hexane-methanol 45 “C 922.18 2425.94 1514.22 1531.80 0.432 13.14
Isopropanol-isopropyl ether 760 mm 1037.19 -207.81 569.30 266.35 0.54 30s
Isopropanol-water 380 mm 655.59 1311.53 1874.7 -179.7 0.234 31a
Isopropyl ether-water 760 mm 2114.19 3079.6 3091.95 1999.41 0.443 30a
Methanol-methyl acetate 50 “c! 800 -89 331 338 0.30 12

aParameters were not available in the literature. They are calculated from the binary equilibrium data given in the
reference.
 composition and temperature of azeotropes
with reasonable accuracy, the computations
showed that the best result is found if the
parameters at or close to the boiling point of
the azeotrope are used in the Wilson or NRTL
equations. Table 3 shows that for all the
systems, the deviation between the experi-
mental and calculated values of the boiling
points of the ternary azeotropes is less than
1 “C!, except for the system ethanol-aceto-
nitrile-water (system 16) which is 2.11 “C
(Wilson equation) and 2.42 “C (NRTL equa-
tion). This probably is caused by the activity
coefficient parameters for the binary aceto-
nitrile-ethanol being available only at 20 “C
(Table 1) which is more than 50 “C below the
boiling point of the ternary azeotrope.
Equations (8) or (12) can be used to obtain
the isotherms in the vicinity of the azeotrope
-12000 L J composition. If these isotherms are plotted
Fig. 1. A plot of eqn. (13) us. x1 for the binary for a ternary system, the type of azeotrope
system ethanol(l)-cyclohexane(2) at different tem- (minimum< maximum or saddle point) can be
peratures. determined as shown in Figs. (2) and (3).
Using this technique, the types of all the
CXi = 1 or 0 respectively. The algorithm does sixteen ternary azeotropes were identified,
not depend on the initial guesses, and any and are given in Table 3. Figure (2) clearly
reasonable values can be used for the initial shows that the system acetone-dimethyl-
mole fractions and temperature. butane--methanol has a minimum azeotrope,
which is in contradiction to what Tamir and
co-worker had indicated (they had found this
4. RESULTS AND DISCUSSION system to have a saddle point azeotrope).
It should be noted that the accuracy of eqns.
The results of predictions for binary and (8) or (12) for computing isotherms degrades
ternary systems, along with the experimental as X moves away from the azeotropic com-
data, are given in Tables 2 and 3. As was position.
expected, the accuracy of prediction for Equations (S), (9), (12) and (13) were also
binary azeotropes is excellent for both the solved for two quaternary systems, and the
Wilson and NRTL correlations. The composi- results are given in Table 4. For the system
tions and temperatures of sixteen ternary chloroform-hexane-ethanol-acetone the
azeotropes were calculated and compared agreement between the experimental and
with the experimental data, and the results calculated results is very good. For the system
are listed in Table 3. This table shows that the methyl acetate-chloroform-methanol-
calculated values of the ternary azeotropes are benzene, calculations showed that there is no
very close to the experimental values for all quaternary azeotrope, which is in agreement
the systems. The average deviation between with the experimental result [ 52 3.
the experimental and calculated values of The model was used to predict the exis-
mole fractions for all the systems is about tence and the composition of ternary azeo-
0.02, and for the boiling points is about tropes for systems where no accurate experi-
0.5 “C. These deviations are well within the mental data were available. The results are
accuracy of experimental data. shown in Table 5. The system methyl
The parameters in Wilson and NRTL acetate(l)-methanol(2)-acetone(3) was stud-
equations are functions of temperature ied by LeCat [ 191 and Fuchs [20]. LeCat
(Table 1). Although the parameters at any found a ternary azeotrope at 53.7 “C with a
temperature can be used to predict the composition of x1 = 0.618 and IY~= 0.323. On
TABLE 2
Experimental and calculated values of the azeotropic point for binary systems

No. System Experimental Calculated

Xl t CC) Wilson equation NRTL equation

x1 t (“C) Ax1 At Xl t (“C) Ax1 At

1 Ethanol (1) 0.430 64.80 0.441 64.66 -0.011 0.14 0.436 64.65 -0.006 0.15
Cyclohexane (2) [32]
2 Ethanol (1) 0.440 67.90 0.435 67.15 0.005 0.75 0.434 67.29 0.006 0.61
Benzene (2) [ 33 ]
3 Cyclohexane (1) 0.475 77.40 0.466 77.15 0.009 0.25 0.466 77.14 0.009 0.26
Benzene (2) [34]
4 Methyl acetate (1) 0.350 64.70 0.351 65.06 -0.001 -0.36 0.354 65.02 -0.004 -0.32
Chloroform (2) [ 353
5 Methyl acetate (1) 0.672 53.80 0.665 53.88 0.007 -0.08 0.661 53.87 0.011 -0.07
Methanol (2) [36]
6 Chloroform (1) 0.650 53.50 0.668 53.49 -0.018 0.01 0.667 53.32 -0.017 0.18
Methanol (2) [37]
I Acetone (1) 0.788 55.00 0.797 55.80 -0.009 -0.80 0.797 55.82 -0.009 -0.82
Methanol (2) [ 381
8 Dimethylbutane (1) 0.610 44.50 0.611 43.85 -0.001 0.65 0.626 44.39 -0.016 0.11
Methanol (2) [ 391
9 Cyclohexane (1) 0.603 69.40 0.614 68.67 -0.011 0.73 0.611 68.91 -0.008 0.49
IsopropanoI(2) 1401
10 Lsopropanol (1) 0.398 71.74 0.397 70.85 0.001 0.89 0.384 72.03 0.013 -0.29
Benzene (2) [40]
11 Chloroform (1) 0.785 60.40 0.782 60.23 0.003 0.17 0.781 60.23 0.004 0.17
Hexane (2) [ 411
12 Chloroform (1) 0.840 59.35 0.847 59.12 -0.007 0.23 0.829 58.81 0.011 0.54
Ethanol (2) [ 421
13 Hexane (1) 0.655 58.10 0.659 58.00 -0.004 0.10 0.638 58.98 0.017 -0.88
Ethanol (2) [ 43 I
14 Chloroform (1) 0.635 64.36 0.647 64.72 -0.012 -0.36 0.639 64.74 -0.004 -0.38
Acetone (2) [44]
15 Hexane (1) 0.360 49.70 0.365 49.73 -0.005 -0.03 0.374 49.77 -0.014 -0.07
Acetone (2) [45]
(continued) g
TABLE 2 (continuedj B

No. System Experimen to1 Calculated

Xl t P3 Wilson equation NRTL equation

x1 t (“C) AXI At Xl t P-3 Ax, At

16 Cyclohexane (1) 0.759 74.69 0.753 73.77 0.006 0.92 0.746 73.29 0.013 1.40
Propanol(2) [40]
17 Benzene (1) 0.788 77.10 0.795 76.72 -0.007 0.38 0.792 76.58 -0.004 0.52
Propanol(2) [40]
18 Acetone (1) 0.751 53.00 0.744 53.47 0.007 -0.47 0.733 53.66 0.014 -0.66
Cyclohexane (2 ) [ 46 ]
19 Methyl acetate (1) 0.800 55.50 0.784 55.67 0.016 -0.17 0.777 55.42 0.023 0.08
Cyclohexane (2) [ 34 ]
20 Isopropyl ether (1) 0.780 65.60 0.802 66.06 -0.022 -0.46 0.800 66.08 -0.020 -0.48
Isopropanol (2) [ 47 ]
21 Ethyl acetate (1) 0.601 72.18 0.575 72.23 0.026 -0.05 0.537 72.20 0.064 -0.02
Ethanol (2) [48]
22 Ethanol (1) 0.638 71.00 0.628 69.83 0.010 1.17 0.622 70.94 0.016 0.06
n-Heptane (2) [49]
23 Acetone (1) 0.505 45.60 0.484 44.58 0.021 1.02 0.499 44.83 0.006 0.77
Dimethylbutane (2) [39]
24 Ethanol (1) 0.530 72.50 0.556 71.05 -0.026 1.45 0.547 70.60 -0.017 1.90
Acetonitrile (2) [ 191
25 Acetonitrile (1) 0.693 76.50 0.686 75.07 0.007 1.43 0.714 76.84 -0.021 -0.34
Water (2) [ 501

Average deviation 0.01 0.52 0.014 0.46

TABLE 3
Experimental and calculated values of the azeotropic point for ternary systems

No. System Experimental Calculated Type

of
Xl x2 t (“C) Wilson equation NRTL equation
azeo-
Xl x2 t (“c) Ax, Ax2 At x1 x2 t (“c) Ax, Ax2 At trope

1 Ethanol (1) 0.424 0.418 0.413 0.435 64.40 0.011 -0.017 0.411 0.451 64.43 0.013 -0.033 min.
Cyclohexane (2)
Benzene (3) [ 511
2 Methyl acetate (1) 0.250 0.300 56.40 0.263 0.287 56.04 -0.013 0.013 0.36 0.271 0.285 55.93 -0.021 0.015 0.47 Saddle
Chloroform (2) Pt.
Methanol (3) [52]
3 Acetone (1) 0.229 0.517 43.20 0.227 0.535 42.84 0.002 -0.018 0.36 0.247 0.526 43.44 -0.018 -0.009 -0.22 min.
Dimethylbutane (2)
Methanol (3) [39]
4 Cyclohexane (1) 0.474 0.384 69.10 0.458 0.361 68.39 0.016 0.023 0.71 0.524 0.371 68.83 -0.05 0.013 0.27 min.
Isopropanol (2)
Benzene (3) [53]
5 Chloroform (1) 0.440 0.358 0.408 0.375 56.80 0.032 -0.017 0.424 0.348 56.09 0.016 0.010 min.
Hexane (2)
Ethanol (3) [54 ]
6 Chloroform (1) 0.607 0.313 0.633 0.321 60.17 -0.026 -0.008 0.643 0.321 60.22 -0.036 -0.008 Saddle
Hexane (2) Pt.
Acetone (3) [54]
7 Cyclohexane (1) 0.494 0.276 73.75 0.529 0.265 73.11 -0.035 0.010 0.64 0.550 0.234 72.76 -0.056 0.042 0.99 min.
Benzene (2)
Propanol(3) [ 55,561
8 Acetone (1) 0.316 0.412 47.00 0.294 0.404 47.64 0.022 0.008 -0.64 0.274 0.415 47.86 0.042 -0.003 -0.86 min.
Hexane (2)
Methanol (3) [ 571
9 Acetone (1) 0.429 0.276 51.10 0.397 0.298 51.68 0.032 -0.022 -0.58 0.443 0.289 52.54 -0.014 -0.013 -0.44 min.
Cyclohexane (2)
Methanol (3) [ 211
10 Acetone (1) 0.315 0.446 57.50 0.339 0.445 57.48 -0.024 0.001 0.02 0.335 0.452 57.66 -0.02 -0.006 -0.16 Saddle
Methanol (2) Pt.
Chloroform (3) [ 58,591
11 Methanol (1) 0.345 0.407 50.80 0.364 0.364 51.22 -0.019 0.042 0.44 0.349 0.405 51.77 -0.004 0.002 0.03 min.
Methyl acetate (2)
Cyclohexane (3) [ 211

(continued) E
92
 93

0.56
r

0.61 0.62 0.63 0.64 0.65 0.66

XI Xl
Fig. 2. Isotherms in the vicinity of azeotrope for Fig. 3. Isotherms in the vicinity of azeotrope for
acetone(l)-dimethylbutane(2)-methanol(3), using chloroform( 1 )-hexane( 2)-acetone(3), using the
the Wilson equation. Wilson equation.

TABLE 4
Experimental and calculated values of the azeotropic point for quaternary systems

No. System Experimental Calculated

x t (“C) Wilson equation NRTL equation

x t (“c) Ax At x t (“c) Ax At

1 Chloroform (1) 0.340 0.323 0.017 0.303 0,037

Hexane (2 ) 0.420 55.00 0.433 54.92 -0.013 0.08 0.418 54.81 0.002 0.19
Ethanol (3) 0.220 0.229 -0.009 0.240 -0.020
Acetone (4) [62]

2 Methyl acetate (1) Non-azeotrope Non-azeotrope Non-azeotrope

Chloroform (2)
Methanol (3 )
Benzene (4) [ 52 ]

TABLE 5
Predicted values of the azeotropic point for ternary systems

No. System Wilson equation NRTL equation Type

Xl X2 t X1 X2 t

17 Methyl acetate (1) Non-azeotrope Non-azeotrope

Methanol (2)
Acetone (3)
18 Isopropanol (1) 0.316 0.145 68.59 0.329 0.147 68.56 min.
Ethyl acetate (2)
Cyclohexane (3 )
19 Ethanol (1) 0.423 0.036 64.63 0.422 0.062 64.60 min.
Ethyl acetate (2)
Cyclohexane (3)

20 Carbon tetrachloride (1) Nonazeotrope Non-azeotrope

Methyl acetate (2)
Benzene (3 )
21 n-Heptane (1) 0.111 0.273 57.09 0.104 0.285 57.15 min.
Benzene(2)
Methanol (3 )
94

the other hand Fuchs has shown that the

800
system has no ternary azeotrope. The results
of calculations confirm that no ternary
600
azeotrope exists. P
mmHg
The ternary system isopropanol( 1)-ethyl
400
acetate(2)-cyclohexane(3) has been studied
by LeCat [ 19 ] who concluded that it contains
an azeotrope boiling at 68.3 “C, but no values
were reported for the composition of the
azeotrope. The results of calculations for this x t(E)
system are given in Table 5. The compositions
Fig. 4. Variation of the composition and boiling
of the azeotrope predicted by the Wilson and point of the ternary azeotrope acetone(l))cyclo.
NRTL equations are very close, and therefore hexene(2)-methanol(3).
it is concluded that the system has a mini-
mum azeotrope boiling at 68.5 “C! with x1 =
0.32 and 3c2N 0.14.
The ternary system ethanol( 1)-ethyl of prediction is very good for both points,
acetate(2)-cyclohexane(3) was studied by which shows that the model is quite suitable
LeCat [ 191 who showed that there may be a for predicting the effect of pressure on the
ternary azeotrope at a temperature of 64.3 “C. azeotropic composition.
The results of calculations (Table 5) show It is also possible to plot the variation of
that the system contains a minimum azeotrope the composition of the ternary azeotrope
at 64.6 “C. The predicted values of the com- with pressure on a triangular diagram. This
position of the azeotrope are X, Y 0.42 and was done at pressures ranging from 200 to
X2 = 0.05. 800 mmHg, for all the systems studied in
No experimental data are available on the this work, and is shown in Fig. 5. The diagram
ternary azeotrope of carbon tetrachloride( l)- has an interesting property of giving straight
methyl acetate(2)-benzene(3) (system 20). lines for all the systems. To confirm that this
The results of calculations using both Wilson is a characteristic of ternary azeotropes, and
and NRTL correlations showed that the is not a property of the model used for
system contains no ternary azeotrope. computing the azeotropic composition, four
The last system which was studied is
n-heptane(l)-benzene(2)-methanol(3). No
experimental data are available for this
system. The results of computations (system
21) showed that this ternary system contains
a minimum azeotrope at 57.1 “C with a
composition of X, Y 0.11 and x2 N 0.28.

5. THE EFFECTS OF PRESSURE ON AZEOTROPIC

COMPOSITION

The influence of pressure on the composi-

tion and boiling point of a ternary azeotrope
can be investigated by solving eqns. (8) and
(9) or (12) and (13) at different pressures. Fig. 5. Variation of the composition of ternary azeo-
The results of computations for the system tropes with pressure from 200 to 800 mmHg. The
acetone(l)-cyclohexane(2)-methanol(3) arrows show the direction of pressure increase. (a)
Acetic acid(l)-formic acid(2)-water(3) [63]; (b)
using the Wilson equation as well as the
water(l)-hexene(2))ethanol(3) [64]; (c) water(l)-
experimental data at 760 mmHg [21] and octene(2)-butanol(3) [64]; (d) propanol(l)-water(2)
35 “C [22] are shown in Fig. 4. The accuracy -propyl acetate(3) [65].
 95

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96

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ci
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(1957) 42. Gji coefficient as defined by eqn. (11)
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42 Wade and Finnemore, J. Chem. Sot., 85 (1904) ponent i
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Ki
i
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44 K. Kojima, A. Kato, H. Sunaga and G. Hasimoto, M number of binary experimental
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45 S. K. Ogorodnikov, V. B. Kogan and M. S. N number of components
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AS;
49 K. Katz and M. Newman, Ind. Eng. Chem., 48
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Yi
56 Zieborak and Galska-Krajewska, Bull. Acad. Pol.
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Greek symbols
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62 A. N. Marinichev and M. P. Susarev, Zh. Prikl.
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63 T. M. Kushner, G. I. Tatsievskaya, V. A. Irzun,
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