COMPUTATION OF VAPOR-LIQUID

EQUILIBRIUM DATA FROM SOLUTION VAPOR

PRESSURE MEASUREMENTS
F

. 0 . h1 I X 0 N ,

Research Triangle Institute, Durham, N . C.

B0 G DA N GU M0 W S

K I AND B

. H. CA RP ENT E R ,

Union Carbide Gorp., South Charleston, W. Va.

Downloaded by QINGDAO UNIV SCIENCE AND TECHNOLOGY on September 12, 2015 | http://pubs.acs.org
Publication Date: November 1, 1965 | doi: 10.1021/i160016a017

A new method for computing vapor-liquid equilibrium data from solution vapor pressure measurements for
systems of any number of components involves determination of the excess Gibbs free energy by successive
approximatioris to the solution vapor pressure surface, with activity coefficients obtained b y differentiation
of the free energy function. Results are given for the chloroform-ethanol and acetone-chloroform-methanol
systems.

HE usual technique for obtaining vapor-liquid equilibrium

T d a t a is by direct measurement-Le., equilibrium is established, and phases are Isampled and analyzed. Normally in
the operation of equilibrium stills, the experimental technique
must be rather delicate in order to ensure meaningful results.
This fact, coupled with the necessity for much analytical work,
tends to enhance interrst in methods for the determination
of equilibrium data that do not involve sampling and analysis of
the vapor phase. I t has long been realized, in the case of
binary solutions a t least, that the behavior of one component is
coupled to that of the other through the Gibbs-Duhem equation and that the gross behavior of the solution (vapor pressure
us. composition or equilibrium temperature us. composition)
is thus uniquely dependent on the behavior of only one of its
components. This dependency then suggests the possibility
of inferring, within the framework of classical thermodynamics,
the behavior of one component of a binary solution from a
knowledge of the behavior of the solution itself. More specifically, it is possible to determine vapor-liquid equilibrium data
from experimental measurements of solution vapor pressure
over the composition range.
Several methods have been employed for the calculation of
component behavior frclm gross solution behavior. Ljunglin
and Van Ness (4) have suggested the classification of these
methods into two categories, direct and indirect methods.
The direct methods involve calculation of vapor compositions
by integration of the coexistence equation, a first-order differential equation derived from the Gibbs-Duhem equation
relating phase compositions a t equilibrium. Hala, Pick, Fried,
and Vilim (3)have given a detailed discussion of the basic direct
method, and Ljunglin and Van Ness (4) have discussed techniques for handling nonconstant temperature or pressure conditions as well as nonideal vapor phase behavior.
The indirect methods involve first the calculation, by some
appropriate means, of thLe liquid phase activity coefficients and
subsequent calculation of vapor compositions therefrom.
These methods usually involve ascertaining which of selected
solution equations to the Gibbs-Duhem equation lead to the
best fit to the experimental vapor pressure data, and of the
determination of the pal-ametric values producing the best fit.
Barker (7), for example, has developed a procedure based on
the assumption that the excess free energy can be represented
as a polynomial function of composition. This assumption is,
of course, equivalent to assuming that the Margules equations
relate the activity coefficients to composition.

There is a basic difference in the degree of rigor associated

with the direct method and the indirect method of Barker.
In the former, one makes no assumptions about the solution
behavior-Le., the nature of molecular interactions. Solution
behavior is determined directly from the experimental vapor
pressure data. The Barker method necessitates the assumption
of a particular model and the estimation of its parameters,
This deficiency in the method of Barker has been recognized
by Tao (7), who has presented another indirect method in
which the necessity for the a priori assumption of a particular
functional form for the excess free energy has been removed.
Taos procedure involves calculation of the activity coefficienu
essentially by integration of an equation resembling the coexistence equation. His procedure, though indirect, retains
the rigor usually associated with the direct method.
Virtually all of the methods for calculating vapor phase
compositions from solution vapor pressure measurements have
been applied only to binary systems. Apart from numerical
complexities, however, there is no reason why such calculations
cannot be made for ternary and higher ordered systems. If one
considers the application of the direct method to ternary
systems, one finds that the problem increases in complexity
from the solution of one first-order ordinary differential equation to the simultaneous solution of two first-order partial
differential equations. Not only are two independent variables
involved (the two independent liquid phase compositions) but
also two dependent variables (the two independent vapor
phase compositions). I t is easy to see that generalization of
the direct method to higher ordered systems will be limited by
the availability of computing machinery capable of handling
the required dimensionality.
An indirect method such as that of Barker is readily and
easily generalized to ternary and higher ordered systems, but
this method retains the disadvantage of lacking rigor as compared with the direct method. The method of Tao appears
specific to binary systems and does not seem to be easily
generalized.
This paper presents an indirect method that retains the same
degree of rigor that characterizes Taos method and integration
of the coexistence equations. The a priori assumption of a
functional form for the excess free energy is not necessary, and
the method is comparatively easy to generalize to ternary and
higher ordered systems. Basically, an expression is written for
the solution vapor pressure in terms of the excess free energy and
its composition derivatives. The expression is inverted to
VOL. 4

NO. 4

NOVEMBER 1 9 6 5

455

give the excess free energy function that produces the observed
vapor pressure behavior, and activity coefficients are then deduced from the excess free energy function.
Thermodynamic Formulation

Assuming ideal vapor phase behavior, the total pressure for a

system of N components is given by
1v-

where the correction terms, g(n)( E ) , are determined so that

P c n + l ) ( ~will
) be a closer approximation to P ( E ) than P ( % ) ( E ) .
If the excess free energy values are incremented according to
Equation 6, the corresponding pressure change will be given
to within the locally linear approximation by the Taylor expansion of Equation 5 to linear terms in g ( n ) ( ~ about
)
G(')(?i). That is,

(7)

Downloaded by QINGDAO UNIV SCIENCE AND TECHNOLOGY on September 12, 2015 | http://pubs.acs.org
Publication Date: November 1, 1965 | doi: 10.1021/i160016a017

k=1

Equation 1 can be approximated by its finite difference representation in the following manner. The 1%' - 1 independent
composition coordinates are regarded as orthogonal coordinates in N - 1 dimensional space and further regarded as
being discretized with lattice interval A , so that
xi = aiA for integral ai

(2)

With this representation, both the pressure and the excess free
energy have values for all lattice points and can be regarded
as entries in A: - 1 dimensional arrays, designated as P(a1,
a2, . . ., as-l) and G(a1, (YZ, . . ., aAv--l).
If, furthermore,
i k is the N - 1 dimensional elementary vector with unity in the
kth position and zeros elsewhere,
i k = (0,0, . . ., 1, 0,. . .)

G(E

+ i k ) - G ( E - Zk)

bxl,

Direct calculation of the partial derivatives from Equation 5

and substitution into Equation 9 yield, after some rearrangement,

(3)

then the finite difference representation for the partial derivatives can be written as

bG _

where the partial derivatives are calculated from Equation 5

and are evaluated at G(')(E) and where the sum is to range
over all admissible values of 8. One would like to determine
the correction terms, g ( n ) ( E ) , from Equation 7 in such a
)
identical with the experimanner that P ( n + l ) ( ~becomes
mental pressure, P ( E ) . Substitution of this requirement into
Equation 7 results in

(4)

2A

Then the finite difference representation of Equation 1 becomes

Equation 9, repeated for all lattice points, provides a linear set

of equations in the correction terms g(E) that can be solved by
relaxation techniques-Le., by either block or point relaxation,
as preferred. I n this study, block relaxation techniques were'
used for binary calculations, and point relaxation was used for
the ternary calculation.
Binary Calculations, Block Relaxation

N-1

i-1

G(E
a4

+ pi)

G ( E - ii)

2A

For a binary system, Equation 9 becomes

I+

p1W - p l i d
2A

Equation 5 shows the explicit dependence of the pressure, P , a t

the lattice point represented by E on the free energy a t lattice
point 8 and the neighboring lattice points. The computational
problem is that of finding values of the excess free energy function a t all lattice points that will reproduce the experimentally
observed pressures according to Equation 5 .

g(.

+ 1) = P(a) - P'"'(a)

(10)

If Equation 10 is then repeated for all lattice points, there results, in matrix-vector form,

Computational Procedure

The computational procedure for solving Equation 5 is a

combination of Newton's method with either block or point
relaxation techniques. Assume that one has available the
nth estimates of the free energy values, W ) ( E ) , a t the lattice
points. Corresponding to these estimates of the free energy
will be estimated values for the solution vapor pressure, P ( n )( E ) ,
where P ( n ) ( ~is) calculated from Equation 5 with the nth
estimates of the free energy appropriately substituted. In
general,
(a)will differ from P(E),the experimental solution vapor pressure, and G ( " ) ( E ) must be incremented to
G(%+l)(~)-i.e.,

G(n+l)(a)= G ( ' ~ ( E+
) g(")(&)
456

I&EC FUNDAMENTALS

(6)

P(1)
P(2)
P(3)

&l

- P'"'(4)
- P'"'(2)
- P'"'(3)

.AM):

(11)

Table 1. Calculated Results for Chloroform-Ethanol System at

55" c.

The set of equations represented by Equation 11 can be solved

very efficiently utilizing a method described by Bruce et al. ( 2 ) .
The procedure is as follows:
C(1)

A.

Set w(1) = B ( 1 ) , b(1) = -,f(l)

B.

Compute
W(.)

Downloaded by QINGDAO UNIV SCIENCE AND TECHNOLOGY on September 12, 2015 | http://pubs.acs.org
Publication Date: November 1, 1965 | doi: 10.1021/i160016a017

41)

B(.)

- A(a)b(a -

1)

(1 6)

AGE/RT
y,
YZ
0
1.0000
279.69
321.73 0.0290
1.8205 0.9990
365.95
0,0596
1.8572 0,9975
409.58 0.0908
1.8589 0.9974
450.64
0.1216
1.8334 1 , 0 0 0 4
487.83 0.1511
1.7876 I 0079
520.44 0.1786
i17274
1.0212
548.24 0.2035
1.6577 1.0417
571.38 0.2249
1.5831 1.0710
590.29 0.2423 1.5069 1.1109
605.58 0.2552
1.4322 1.1632
617.95 0.2630
1.3613
1 2305
628.05
0.2652
1.2958 1.3155
636.43 0.2614
1.2369 1.4218
643.39 0.2511
1.1846 1.5553
648.91 0.2339
1.1385 1.7275
652.54 0.2090
1.0960 1.9706
653.31 0.1734
1.0434 2.4976
649.60
0.1247
1.0979 2.9663
639.05
0.0667
1.0043 3.5001
1.0000
1 .o
618.49
0
a Pressure calculated f r o m following polynominal:
P = 279.69 f
796.10~1 1751.98~1~
- 5506.50~1~ 6603.88~1~
- 2706.66~1~.
y~

x1

P,"Mrn.Hg

0
0.1750
0.3139
0.4211
0.5033
0.5666
0.6158
0.6546
0.6854
0.7105
0.7314
0,7494
0.7657
0.7813
0.7972
0.8139
0.8311
0.8396
0.8723
0.9234

0
0.0500
0.1000
0.1500
0.2000
0.2500
0.3000
0.3500
0.4000
0.4500
0.5000
0.5500
0.6000
0.6500
0.7000
0.7500
0.8000
0.8500
0.9000
0.9500
1 .o

Results

Starting with the initial approximation

G(a) = 0

(21)

iteration of the above procedure to a value of n of around 6 to 10

yields the excess free energy function producing the desired
solution vapor pressure. Activity coefficients are then calculated as indicated by Equation l , and vapor phase compositions by the usual equations.

The proposed method has been tested on several binary

systems and on one ternary system. I n all cases, polynomials,
fitted to the experimental pressure data by least squares, have
been used for smoothing the experimental data and for interpolation.
For the chloroform-ethanol system at 55" C., the solution
vapor pressure data of Scatchard and Raymond ( 5 ) Ivere fitted
by the polynomial

= 279.69

Ternary Calculations, Point Relaxation

Because of difficulties in programming block relaxation calculations over the triangular composition diagram, point
relaxation was used in preference to the more efficient block
relaxation methods. Clne simply computes a new value of
g a t each lattice point from the old values ofg a t the neighboring
lattice points as indicated by Equation 9. When convergence
is obtained on g, the free energy values are incremented according to Equation 6. New coefficients for the g values in
Equation 9 are calculated, and the calculation is repeated until
convergence to the experimental pressure is obtained. Again,
activity coefficients are calculated as indicated by Equation 1,
and vapor phase compositions by the usual equations.

1.0

+ 7 9 6 . 1 0 ~ 1+ 1 1 5 1 . 9 8 ~ 1-~
5 5 0 6 . 5 0 ~ 1+
~ 6 6 0 3 . 8 8 ~ 1~ 2 7 0 6 . 6 6 ~ 1 ~(22)

This equation fits the experimental data to within u limits of

2.18 mm. of Hg.
Vapor phase compositions for this system have been calculated both by the present method and by integration of the
coexistence equation as described by Hala et al. ( 3 ) . Both
methods produce identical results; these results are summarized in Table I and are shown graphically in Figures 1 and
L.

The calculated values of the vapor composition are higher by

approximately 0.005 mole fraction of chloroform than the reported values over the entire composition range. This syste-

7001

bLCULbTED RESUL

'

Figure 1 .

'

bNO RbYHOND

02

' '

C'8
a , . MOL FRACTION
CHLOROFORM I N LICIUID

0.4

0.6

1.0

2ooi

0.2
0.4 0.6 0.8
I!O
x , - M O L FRACTION
CHLOROFORM IN LIQUID

Chloroform-ethanol at 55" C.

A. Vopor-liquid equilibrium curve

6. Solution vapor pressure-liquid composition curve

X I - M O L FRACTION
CHLOROFORM IN LIQUID

Figure 2.
A.

6.

Chloroform-ethanol at 55" C.
Excess free energy os a function of liquid composition
Activity coefficients as o function of liquid composition

VOL. 4

NO. 4

NOVEMBER 1 9 6 5

457

Experimental (6) and Calculated Results for Acetone-Chloroform-Methanol System at 50' C.

Table II.

Liquid Composition, Mole

&fao

Xl

Downloaded by QINGDAO UNIV SCIENCE AND TECHNOLOGY on September 12, 2015 | http://pubs.acs.org
Publication Date: November 1, 1965 | doi: 10.1021/i160016a017

Vapor Composition, Mole

Y1
Y2

x3

E
0,051
0.904
C
0,050
0.900
E
0.200
0.590
C
0,200
0.600
E
0.453
0,047
C
0.450
0.050
E
0.045
0.053
C
0.050
0.050
E
0.195
0.188
C
0,200
0.200
E
0.896
0.052
C
0.900
0.050
E
0.401
0.140
C
0.400
0.150
a E.
Exjerimental data.
C.

X2

0.045
0.050
0.211
0.200
0.500
0.500
0.902
0.900
0.622
0.600
0.052
0.050
0.459
0.450

0.023
0.023
0.119
0.126
0.550
0.529
0.081
0.098
0.218
0.216
0.914
0.914
0.422
0.437

0 837
0.834
0.571
0.548
0.035
0.041
0.119
0.125
0.252
0.253
0.026
0.024
0.120
0.137

PI3

P23

+
XZPZO
+

x1Plo

x3P3O
x3P3O

+
+

x1x3[a31x1

+
+

a l m

X ~ X ~ [ ~ ~ Z aX Zm

- ~ U X I X ~ ] (24)
- d 2 3 x m I (25)

For the ternary system :

=

XlPlO

+
+
+
+

x2P20

xm[a21x1
xlx3[@1x1

x3P30

+ + + + +
am2

~IZXIXZ]

am?

d l m x ~ ]

X ~ X ~ [ ~ ~ Z a23x3
X Z

xmxz[a21

013

d 2 3 ~ ~ ~ 3 1

023

-c

m - czxz

- ~2x31

(26)

This particular representation of the pressure data was

chosen for the following reasons :
Equation 26 reduces to 23, 24, or 25 for x3, x 2 , or x1 equal to
zero, respectively.
The binary parameters can be estimated from vapor pressure data on the binary systems alone, leaving only the c values
to be estimated from ternary pressure data.
For the system tested, this particular form fits the experimental pressure data to within an average deviation of about
1% of the total pressure.
Vapor phase compositions have been calculated for the
acetone-chloroform-methanol system using the proposed
method. Computed results a t selected points are compared
with the experimental data in Table 11. Though there is some
458

Y3

0.140
0.143
0.311
0,327
0.415
0.429
0.800
0,777
0.529
0.531
0.061
0.062
0.408
0.426

Activity Coefficients

Y1

YZ

Y3

0.424
0.414
0.571
0.594
1.170
1.117
1.400
1.543
1.010
0.984
1.010
1.002
1.110
1.011

1.010
1.001
1.080
1.032
0.814
0.940
1.990
2.387
1.400
1.374
0.568
0.574
0.935
1.010

4.190
3.818
2.010
2.260
1.140
1.208
0.997
1.010
1.100
1.192
1.640
1.790
1.190
1.298

Pressure,
Mm. H g

577
555
586
580
588
583
47 3
485
552
558
604
605
575
568

Calculated datn.

matic discrepancy is the result of a slight overestimation of the

activity coefficient of chloroform, as shown in Figure 2B.
The computed values of the excess free energy are somewhat
lower than the results derived from Scatchard and Raymond's
data. This systematic discrepancy is apparently the result of
failure to correct for vapor phase nonideality. Torgeson has
reported a better fit to the experimental data when provisions
for vapor phase nonideality are included in a procedure based
on numerical integration of a coexistence equation (8). The
fact that the present method and the coexistence equation produce identical results for the ideal vapor approximation suggests that inclusion of vapor phase nonideality into the
present method would remove the systematic discrepancy
between the experimental data and the calculated results.
For the acetone-chloroform-methanol system, the solution
vapor pressure data of Severns et al. (6) were fitted by the
following form :
For the binary pairs:

l&EC FUNDAMENTALS

discrepancy, the agreement is satisfactory. Part of the discrepancy between calculated and experimental results can be
attributed to slight differences in the liquid compositions a t the
chosen points. Also, Severns et al. used compressibility factors
to account for the nonideality in the vapor phase. As with
binaries, no corrections for vapor phase nonideality were made
in the present work.
Discussion

The present method for computing vapor compositions from

solution vapor pressure measurements has several advantages
over previous methods. For example, integration of some
form of the coexistence equation for binaries, as pointed out by
Hala et al. ( 3 ) ,requires special attention to the regions at the
ends of the concentration range and at the azeotrope, if one
exists. The coexistence equation reduces to an indeterminate
form at these points, and an alternate formulation must be
applied. The present method requires no such special attention at any point along the entire composition range.
The present method is successful and calculations proceed
smoothly for some cases in which the coexistence equation
method meets with difficulty. For example, we have been
unable to obtain a realistic numerical integration of this equation for the acetone-chloroform system, which exhibits a strong
No difficulty was
negative departure from ideality.
experienced with the method described herein for this or any
other system tested. The difficulty in integrating the coexistence equation seems to result from the fact that the experimental vapor pressure data must somehow be differentiated as
part of the procedure. Our method for doing this was to obtain a least squares polynomial fit to the data and then to differentiate the polynomial. However, even though such
polynomials can fit the vapor pressure data very well, there can
also be local oscillations of the polynomial function slightly
above and below the data. If such is the case, errors resulting
from differentiation of the smoothed data can apparently cause
difficulty in subsequent integration of the coexistence equation.
No doubt such difficulties can be avoided by special treatment
of the raw data to ensure sufficient smoothness in the derivatives, but the computational procedure presented in this paper
completely avoids the problem. Differentiation of the data is
not required, and the results are much more insensitive than
those from the coexistence equation method to the particular
technique chosen for smoothing the data.

Downloaded by QINGDAO UNIV SCIENCE AND TECHNOLOGY on September 12, 2015 | http://pubs.acs.org
Publication Date: November 1, 1965 | doi: 10.1021/i160016a017

If one considers the extension of the coexistence equation

method to ternary systems, one is faced with two partial differential equations involving two independent variables (liquid
phase compositions) aind two dependent variables (vapor
compositions or partial pressures). I n the present formulation,
one has a single partial differential equation in a single dependent variable (the excess free energy). The latter is somewhat more convenient from a computational point of view, and
certainly becomes more attractive as one considers solutions
with more components.
Of the methods reported in the past for calculation of vapor
compositions from solution vapor pressure data, only that of
Barker ( 7 ) seems easily generalized to ternary and higher
ordered systems. Barker's method involves assuming a
polynomial form for the excess free energy and then using
statistical techniques to estimate the parameters therein so as
to get the best fit to the experimental pressure data. The
present method has an advantage over Barker's method in that
it is not necessary a t the outset to select a model. Though we
used polynomials for data smoothing and interpolation, this is
not necessary. I n principle, the method can be applied to
graphically smoothed data or, if sufficient data are available,
to the raw data themselves. Thus, the present method is
not limited to the a priori choice of a particular excess free
energy functionality.
If deviations from ideality in the vapor phase are significant,
these deviations can be taken into account rather easily. One
first computes vapor phase compositions under the assumption
that ideality holds, then uses these compositions to estimate
vapor phase activity coefficients by the usual methods. With
Equation 1 replaced by

the entire procedure is repeated for the final relaxation. The

effect will be to change the coefficients in Equation 9 slightly
by the introduction of the gas law correction terms.

Nomenclature

quantity defined by Equation 12

parameter in vapor pressure function, Equations
23 to 26
b
= quantity defined by Equation 17
B
= quantity defined by Equation 13
c
= parameter in vapor pressure function
C
= quantity defined by Equation 14
d
= parameter in vapor pressure function
f
= quantity defined by Equation 18
g @ ) ( n ) = nth estimate of correction to G ( ~ ) ( E )
G
= GE/RT
GE
= excess Gibbs free energy of mixing
G ( " ) ( E )= nth estimate of value of G at lattice point designated
by E
= number of comDonents in solution
= nth estimate of partial pressure of kth component,
=
=

XkYi;(")Pk0

=
=
=

=
W

xi

Yk

=
=
=

ak

6k

partial pressure of kth component in an ideal solution, xkPko

solution vapor pressure
vapor pressure of kth component
nth estimate of solution vapor pressure at lattice
point designated by E
quantity defined by Equation 16
mole fraction of ith component in liquid
vector of lattice indices
liquid phase activity coefficient of kth component
lattice interval
elementary vector defined by Equation 3
vapor phase activity coefficient of kth component

literature Cited
(1) Barker, J. A , Australian J . Chem. 6 , 207 (1953).
(2) Bruce, G. H., et al., Trans. Am. Inst. Mining, Met. Petrol. Engrr.
198. 79 (1953).
(3) Hala, 'E., Pick, J., Fried, V., Vilim, O., "Vapor-Liquid
Equilibrium," Pergamon, New York, 1958.
(4) Ljunglin, J. J., Van Ness, H. C., Chem. Eng. Sci. 17, 531 (1962).
(5) Scatchard, G., Raymond, C. L., J . Am. Chem. Soc. 60, 1278

(1938).
(6)' Sevkrns, \Y. H., ef ai., '4.I.Ch.E. J . 1, 401 (1955).
(7) Tao, L. C.. Ind. Eng. Chem. 53, 307 (1961).
(8) Torgeson, R. L., "Calculation of Vapor-Liquid Equilibria at
Constant Temperature," M.S. thesis, bniver&ty of -Delaware,
1965.
RECEIVED
for review November 9, 1964
ACCEPTED
July 20, 1965

GROUP CONTRIBUTIONS T O ACTIVITY

COEFFICIIENTS
The CH, and OH Groups
W I LL IA M A

SC H ELL

E R , The Unnrersity o f x e b r a s k a , Lincoln, A'eb.

The group contribution work reported by Wilson and Deal i s modified and extended. The theory i s developed in terms of thermodynamic instead of empirical quantities. Extensive data for the CH2 and O H
group contribultions to the residual partial molal energy of mixing are reported over a CH2 concentration
range of 3.0 tlo 99.9%. A method for calculating the standard state group contributions needed for applying the method is presented. Additional information for using the method with diols and triols is provided.
Logarithms of activity coefficients for eight binary systems near 50" C. were calculated from group contributions with an absolute average deviation from the experimental values of less than 10%.

FOR

process evaluation and design calculations it is highly

desirable to account for solution nonidealities because of
their effect on equilibrhm composition and equipment requirements. However, it is not always feasible to determine
activity coefficients experimentally for this purpose. As a
result attempts have been made to develop generalized methods

for predicting activity coefficients, especially for solutions of

nonelectrolytes.
Hildebrand's method (5) for regular solutions requires the
use of solubility parameters. These can be calculated from
heats of vaporization. In the method described by Pierotti,
Deal, and Derr ( 7 7 ) , activity coefficients at infinite dilution
VOL. 4

NO. 4

NOVEMBER 1 9 6 5

459