Prediction of Vapor.

Liquid Equilibrium Data

of Binary Systems'
ISAMU NAGATAZ

This paper presents a method of predicting vaporliquid equilibria of binary systems at reduced or higher
pressures if vapor-liquid equilibria of the systems concerned arc available at atmospheric pressure. The method
is based upon Prahl's threeeonstant equation which expresses vapor-liquid composition relationships directly.
Experimental data and those calculated by the proposed
method are compared for five typical nonideal binary
systems.

On prdsente une mdthode, basde sur I'dquation de Prahl,

pour pridire I'dquilibre vapeur-liquide de systemes binaires
pour diverses pressions lorsque I'on connait l'dquilibre
vapeur-liquide ii la pression atmosphgrique. Les donndes
expdrimentales et cellcs obtenues par ealculs i I'aide de la
mdthode proposde sont compardes pour cinq syst&mes
binaires non-iddals.

equations, bccausc in general the van Laar equations have been

found to fit experimental activity cocficicnt data sonica.hat
better than the 5largulcs

ethods which permit the extension of vapor-liquid q u i l i b riuni data available at one condition to other conditions
arc needed from an engineering standpoint. A few methods
* * their
~ ) , use is limited
have been proposed in the l i t ~ r a t u r c ( ~ ~but
only to nonazeotropic systems. T h e present investigation
prcscnts an cmpirical nicthod which is applicablc to both
azcotropie and nonlzeotropic systems.

Proposed Method
T h e method is based on Prahl's equation'" given by
air =

ylsz
-.

XI

~ 2 . ~ 1 .Yzhlz

+ s?a12 . . .
+
.

(1)

xIc~?

where uI2.I),? and rlyarc binary constants and are connected with
relative volatility at infinitc dilutions and equimolal composition.

'l'hc evaluation of A and H from the whole experimental data

at atmospheric prcssure is usually an acccptatilc procedure.
T h e van 1,aar constants change with temperature and the magnitude of the variation of A is not always equal to that of H .
I t is assumed that A and H arc dependent upon temperature
as follows.
A = A * ( T ? * / I - ~ r~j , = B * ( T ~ * / T ~ ) * . , . . ( 1 0 )
, .

2)

Assuming vapor phase ideality, w e obtain the following cxprcssions for rclative volatility at three concentrations.
(alrh

(al?)l

( a l & :,

I.:xaiiiination of the van I a r constants of a nuinticr of ttinary

organic systems, which should tend to bccoine niorc idcal with
increasing temperature, revealed that in many caws rhc exponents m and n range approximately from 2 to 3 . In the present
investigation the exponents 'rn and n were assumed to bc equal
to 2. Given experimental data at more than one pressure, it
is possible to calculate cmpirical values for 711 and ti in I.;quation
( 1 0) so as to fit the data.
Another relation bctwecn the van Laar constants and thc
tcmpcraturc may tic expressed by nieans of the equatim'61

(pIo/pso)r,. ( y l h = ( p l o / p ? o ) 7 , ~ *. ...x. ~. .~. ~( $ 1

( p l o / p r O h.l 1/(y2I1= (p,o/p?o),le-2.s3H..

. .
(6)
.
.
.
.
.
.
(p~"/p2"i~*(rl/y~)~~
....
(7)

L!

where A and B arc referred to as the terminal valucs of thc

logarithm of the activity coefficients and are calculated by using
the van Laar equations instead of the t a w c o n s t a n t Margules

...............................................................................

'Manuscript received March 24; accepted July 7, 1964.

'Department of Chemical Engineering, Kanuzawa University, Kanuzawn,
Jnpan.
Present address: Department of Chemical Engineering, William Marsh
Rice Unioersity, Houston, Texas, U.S.A.

+ h. . . . . . . . . . . . . . . .
(c/T) + d . . . . . . . . . . . . . . . . .
(a/T)

(11)

(12)

i t ' i t h the aid o f thcsc relations it is possible to extrapolate and

interpolate for equilibrium data as in the proposed method but
with incrcased accuracy. T h e variation of the van Laar constants
with temperature is not so simple for aqueous solutions as for
mixtures of organic liquids. Over a short range of temperature
the van Laar constants of aqueous mixtures are approximately
regarded as to be independent of temperature('). It is difficult
to estimate the variation of the van Laar constants over a wide
range of temperature and one should have access to the literature.
The Canadian Journal

of Chemical Engineering,

April, 1965

MOLE

FwAcTioN

waurwa

IN

Liauio

Figure 1-Vapor-liquid

eomporitionr for n-butanolethylbenzene"'.

experimental data at 100 mm. of Hg, -predicted

Prediction Procedure
( I ) Obtain from the literature the accurate vapor pressure data
and representation of the pure components, for example,
constants of the Antoine equation.
(2) Calculate the activity coefficients of components by the
following equations

y , = - - y'
P1

XI

MOLL f R A C l I O N

=Y
y* = p20x2' . . . . . . . . . . . .

Figure LVapor-liquid comporitionsfor p-cymeneaniline"O'

0 experimental data at 100 mm. of Hg, -predicted

(3) Evaluate A and B using the whole experimental activity

coefficients.
(4) Calculate the vapor pressure ratios of pure components at

their boiling points, Tt' and TI' under system pressure ofd.
( 5 ) Estimate A ' at TZ' and B' at TI' in accordance with Equation
(10) (if possible, use Equations (1 1) and (12)).

(6) Calculate (a12)o and (a12)1 by substituting (pl0/p2")r,', A',

( p ~ " / p Pr1'
) and B' into Equations (5) and (6), respectively.

UCTUANOL I N L l O U l O

Figure 3
Vapor-liquid eomporitionr for methanol-water
0 experimental data at 200 mm. of Hg'='.
-predicted
experimental data at 4.22
experimental data at 11.93 atma
The Canadian Journal of Che.mical Enginaering, April, 1965

M Q L CRACTION P-CVMCNL IN L I Q U I 0

MOLL

fRACTlON

Figure &Vapor-liquid

ETHANOL I N L I Q U I D

eompoeitiom for ethanol-benzene""

experimental data at 180 mm. of Hg, -predicted

0 experimental data at 400 mm. of l i g

85

TABLE1
COMPARISoN OF PREDICTED WITH EXPERIMENTAL
DATA

-__

Predicted
Condition

Sya tem
Q

Aymar.

AYWS.

-~
-

>

(mole :mole

07
10)

1 .s

1. n-Butanol-

Y
z

ethylbenzene

<

ir;

2. p-Cynieneanilinr
3. Methanol-water

0
I-

100 mni. Hg.!'O)

7.5

1.2

200 nun. Hg.(ll) 5.5

4.22 atm.(I2)
15.9
11.93 atm.(I2)
7.1

1.3
3.3

180 mm. Hg.c15) 6.4

4.0

2.2
1.6

2.1

<

4. Ethanol-benzene

Q
.4

YI

5. 2-Butanone-

cyclohexane

400 mni. Hg.('b)

4.54 atm.(lB)
12.72 atm.(16)

4.7
3.2

1.1

0.7

___
__
/

0.2

0.4

MOLE

I
0.0

FRACTION

PBUTANONE

0.8
IN

1.0

Figure &Vapor-liquid

compositions for Z-butanone-cyclohexanen''

experimental data at 4.54 atm.
-predicted
experimental data at 12.72 atm.

(7) T h e following method is used to estimate (a,2)0.6under 77'.

Assume an equilibrium temperature, then evaluate the vapor
pressures of pure components at this temperature and
estimate activity coefficients according to Equations (8),
(9) and (10) (or Equations (11) and (12)). If the assumed
temperature is suitable, the following equation holds
Yl'Pl"

Y21P20

= 2*'

If necessary, repeat the above calculation at another assumed

temperature.
after the equation is satisfied.
Calculate (a12)0.5
(8) Calculate

UIZ,

612and clZ by means of Equations (2) to (4).

(9) Use uI2, 612and CIZ to calculate vapor-liquid equilibrium data.

Results
T h e proposed method has been tested for five systems at
five reduced and at four higher pressures. T h e fugacities of
the components were used at higher pressures and, where
possible, the vapor pressure and fugacity data for the pure
components were taken from the same source as vapor-liquid
equilibrium data and the published source^(*^^). Figures 1 to 5
show a comparison of experimental and calculated results and
the maximum and the average deviations from experimental
data are given in Table I . These results seem to indicate the
present empirical method to be satisfactory for azeotropic
systems. In the methanol-water system the equilibrium data
at atmospheric pressure and 7.80 atm. were assumed to be given
and A and B were considered to be independent of temperature.
In the 2- butanone-cyclohexane system basic information was
taken at two conditions. T h e variation of A and B with temperature as expressed by means of Equations (1 1) and (I 2).

86

Nomenclature

LIQUID

A,B
a,b,c,d

=
=

a12,b12,~12
=
m,n

=
=
=

a12

(al&

=
=
=
=
=

(a12)o5

(a1&
Y
77

constants of Equations (S), (6), (8) and (9)

constants of Equations (11) and (12)
constants of Equation (1)
exponents of Equation (10)
vapor pressure of pure component
absolute temperature
mole fraction in liquid phase
mole fraction in vapor phase
relative volatility of component 1 with respect to
component 2
limiting value of a12at x1 = 0
value of a l 2a t equimolal composition
limiting value of a I 2a t YI = 1
activity coefficient
pressure of system

Superscripts
#

=
=

predicted
basic

Subscripts

1,2

components

References
Ho, J. C. K. and Lu, B. C.-Y., Ind. Eng. Chem., 53, 384 (1961).
Lu, B. C.-Y., A.1.Ch.E. Journal, 2, 525 (1956).
Tamura. M. and Nanata. I.. Ib?d.. 8, 161 (1962).
Prahl, W. H., Ind. Ekg.'Cbem., 43, i767 ( i g s i j .
Carlson, H. C. and Colhurn, A. P., Ibid., 34, 581 (1942).
Yu, K . T. and Coull, J.. Chem. Eng. Prom. Symposium Ser.. 48,
No. 2, 38 (1952).
( 7 ) Black, C., Ind. Eng. Chem.. 51, 211 (1959).
( 8 ) Mfg. Chemists' Assoc., Reesarch Project, Data Sheets. Chemical
Thermodyanmic Properties Center, A. and M. College of Texas,
College Station, T :xas.
( 9 ) Timmermans, J., "Physico-chemical Constants of Pure Organic
Compounds", Elsevier New York 1950.
(10) Ellis, S. R. M. and'Razavipod, M., Chem. Eng. Sci., 11, 99
(1959).
( 1 1 ) Othmer, D . F. and Benenati, R. F., Ind. Eng. Chem., 37, 299
(1945).
( 1 2 ) Swami, D. R., Kumarkrishna Rao, V. N. and Narashinga Rao, M.,
Trans. Indian Inst. Chem. Engrs., 9, 32 (1956-57).
( 1 3 ) Ellis, S. R. M., Trans. Inst. Chem. Engn. (London), 30, 58
(1952.
( 1 4 ) Landwehr, J. C., Yerazunis, S . and Steinhauser, H. H. Jr., J.
Chem. Eng. Data, 3, 231 (1958).
( 1 5 ) Nielsen, R. L. and Weber, J. H., J. Chem. Eng. Data, 4, 145
(1959).
( 1 6 ) Swami, D. R., Kumarkrishna Rao, V. N. and Narashinga Rao, M.,
Trans. Indian Inst. Chem. Engrs., 9, 47 (1956-57).
(1)
(2)
(3)
(4j
(5)
(6)

* * *

The Canadian Journal of Chemical Engineering, April, 1965