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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.
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.
2)
Assuming vapor phase ideality, w e obtain the following cxprcssions for rclative volatility at three concentrations.
(alrh
(al?)l
( a l & :,
L!
...............................................................................
+ h. . . . . . . . . . . . . . . .
(c/T) + d . . . . . . . . . . . . . . . . .
(a/T)
(11)
(12)
of Chemical Engineering,
April, 1965
MOLE
FwAcTioN
waurwa
IN
Liauio
Figure 1-Vapor-liquid
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' . . . . . . . . . . . .
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)).
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
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-
7.5
1.2
1.3
3.3
2.2
1.6
2.1
<
4. Ethanol-benzene
Q
.4
YI
5. 2-Butanone-
cyclohexane
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
Y21P20
= 2*'
UIZ,
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
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).
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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).
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( 1 2 ) Swami, D. R., Kumarkrishna Rao, V. N. and Narashinga Rao, M.,
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( 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).
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(1959).
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Trans. Indian Inst. Chem. Engrs., 9, 47 (1956-57).
(1)
(2)
(3)
(4j
(5)
(6)
* * *