324 Ind. Eng. Chem. Res.
1989,28, 324-328
Person, W. B. A Criteria for Reliability of Formation Constants of
Weak Complexes. J. Am. Chem. SOC. 1965, 87, 167.
Renon, H.; Prausnitz, J. M. On the Thermodynamics of Alcohol-
Hydrocarbon Solutions. Chem. Eng. Sci. 1967, 22, 299.
Renon, H.; Prausnitz, J. M. Local Compositions in Thermodynamic
Excess Functions for Liquid Mixtures. AIChE. J. 1968,14, 135.
Saunders, M.; Hyne, J. B. Trimer Association of &Butanol by NMR.
J. Chem. Phys. 1958a, 29, 253.
Saunders, M.; Hyne, J. B. Study of Hydrogen Bonding in Systems
of Hydroxylic Compounds in Carbon Tetrachloride through the
Use of NMR. J . Chem. Phys. 1958b, 29, 1319.
Smirnova, N. A.; Kurtynina, L. M. Thermodynamic Functions of
Mixing for a Number of Binary Alcohol-Hydrocarbon Solutions.
Zh. Fiz. Khim. 1969, 43, 1883.
Thomas, E. R.; Eckert, C. A. Prediction of Limiting Activity Coef-
ficients by a Modified Separation of Cohesive Energy Density
Model and UNIFAC. Ind. Eng. Chem. Process Des. Dev. 1984,
23, 194.
Trampe, David M. Measurement and Applications of Limiting Ac-
tivity Coefficients and Liquid-Liquid Equilibria. M.S. Thesis,
University of Illinois, Urbana, 1987a.
Trampe, David M. University of Illinois, personal communication,
1987b.
Tucker, E. E.; Becker, E. D. Alcohol Association Studies. 11. Vapor
Pressure, 220-MHz Proton Magnetic Resonance, and Infrared
Investigations of tert-Butyl Alcohol Association in Hexadecane.
J . Phys. Chem. 1973, 77, 1783.
A Simple Method for Evaluating the Wilson Constants
Alexander Apelblat and Jaime Wisniak*
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel
A simple method is proposed to determine the Wilson constants from binary vapor-liquid equilibrium
data. The method is based on a polynomial description of the variation of G E/RTwith composition
and finding the maximum value of the curve. The constants are determined by using a hand scientific
calculator or a personal computer. Prediction of vapor compositions is as good or better than that
obtained by complex optimization techniques.
Many equations have been proposed to describe the
vapor-liquid equilibrium relationships. For homogeneous
systems, the two-parameter Wilson equation (Wilson,
1964) has been shown to be very suitable. In a multicom-
ponent system, it reads
where
UjL
Ai, = exp[-(Xij - Xii)/RT] (2)
ui
To a first approximation the energy terms (Xi,- Xii) are
assumed to be independent of temperature, although it is
claimed (Nagata and Yamada, 1973) that a better fit is
obtained if a polynomial dependency is assumed:
Xij - Xii =u + bT + cT' + ... (3)
Obviously application of eq 3 carries the penalty of a larger
number of constants.
The Wilson equations are attractive because they have
a built-in effect of temperature, lacking in previous models,
and permit the calculation of multicomponent systems
from a combination of parameters A,, and AIi which are
* To whom correspondence should be addressed.
088S-5885/89/2628-0324$01.50/0
Van Geet, A. L. Calibration of the Methanol and Glycol Nuclear
Magnetic Resonance Thermometers with a Static Thermistor
Probe. Anal. Chem. 1968,40,40.
Van Geet, A. L. Calibration of Methanol Nuclear Magnetic Reso-
nance Thermometer at Low Temperature. Anal. Chem. 1970,42,
679.
Varian Associates XL-Series NMR Superconducting Spectrometer
Systems Basic Operation Manual, 1984.
Vesely, Frantisek; Uchytil, P.; Zabransky, M.; Pick, J. Heats of
Mixing of Cyclohexane with 1-Propanol and 2-Propanol. Collect.
Czech. Chem. Commun. 1979,44, 2869-2881.
Vonka, P.; Svoboda, V.; Strubl, K.; Holub, R. Liquid-Vapor Equi-
librium. System Cyclohexane-1-Butanol a t 50 "C and 70 "C.
Collect. Czech. Chem. Commun. 1971, 36, 18.
Weltner, William; Pitzer, Kenneth Methyl Alcohol: The Entropy,
Heat Capacity and Polymerization Equilibria in the Vapor, and
Potential Barrier to Internal Rotation. J. Am. Chem. SOC. 1951,
73, 2606.
Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression
for the Excess Free Energy of Mixing. J. Am. Chem. SOC.1964,
86, 127.
Zong, Z.; Yang, X.; Zheng, X. Correlation of Vapor-Liquid Equilibria
of Associated Solutions. J . Chem. Eng. Jpn. 1984, 17, 71.
Received for review May 24, 1988
Accepted September 26, 1988
derived from the pertinent binary systems.
For a binary system, the activity coefficients are
In y1 =
In y1 =
Extensive tables are available (Hudson and Van Winkle,
1970; Hirata et al., 1976; Gmehling and Onken, 1977),
reporting the values of either the energy parameters (A,,
- A,,) or the constants A, and A,[.
The most difficult problem in using Wilson's equations
is how to determine the two parameters A12and Azl from
a set of data ( y , , ~ , ) .Equations 4 and 5 are a pair of
transcendental equations that can only be solved numer-
ically. Czelej (1987) has developed a mathematical pro-
cedure to transform the Wilson equations into a polyno-
mial form that allows an easier determination of the con-
stants. Due to some serious mathematical errors present
in Czelej's equations, their use is not recommended.
Several methods have been suggested for determining
the optimum constants AIz and Azl. According to Hirata
et al. (1976), the results of the methods depend upon the
0 1989 American Chemical Society

0 XI
Figure 1. Variation of G E/RTwith composition: (A) the common
case with one extreme value, (B) one extreme value and an inflection
point, and (C)the very unusual case of two extreme values.
objective functions (O.F.) employed. For example,
Gmehling and Onken (1979) use either
0.F. = C(1 - Y ~ ~ ~ 5/ cyY ~ ~ ~ (6)
J ~
or
0.F. = C(PCa1,
- PexpJ2
5 cp
Hirata et al. (1976) compared four compoutational tech-
niques for minimizing the O.F., nonlinear least-squares,
steepest ascent, pattern search, and complex search tech-
niques, and concluded that the steepest ascent algorithm
is generally the best.
Several authors (Silverman and Tassios, 1977; Verhoeye,
1970) have shown that values of the pair of constants A12
and Azl are not unique, that they may differ substantially
one from the other, and that they still have the same
confidence limits. The actual pair found will depend on
the algorithm used and the starting values of the param-
eters.
Whichever of the above methods is selected, it requires
availability of a moderate-to-large computer. We will now
show that simpler mathematical techniques can be used
to give results as accurate as the more sophisticated ones.
Theory
We present here an alternative method for evaluation
of the Wilson parameter, based on the data from the
central concentration region, where the highest accuracy
of measurements can be achieved. The method is based
on the experimental fact that the value of G E / R T is zero
for the pure components and that the function G E / R T ( x l )
will have one or two extreme values (Figure 1).
For binary mixtures, the Wilson model expresses the
excess Gibbs energy of mixing, GE, as follows:
G E / R T = -3c1 In (xl + A12x2)- x 2 In (Azlxl + x 2 ) (8)
Denoting g E = G E / R Tand defining the parameters z1and
22
1 - A12
21 = (9)
x1 + '412%
Ind. Eng. Chem. Res., Vol. 28, No. 3, 1989 325
1 - A21
22 = (10)
1 2 + A2lXl
allows us to transform eq 8 into
The corresponding expressions for the derivatives of g E
with respect to concentration, in terms of z1and z z and
at constant pressure and temperature, are
d2gE/dx12 = 21(x121- 2) + zz(x222 - 2)
d3gE/dX13 212(3- 2X1Z1) - 22(3 - 2x222) (13)
Equations 11-13 are the starting point in the process of
evaluating the Wilson parameters A12 and Azl. Combi-
nation of 11 with eq 12 and taking into account that
dgE/dxl = In (y1/y2)allows the possibility of isolating z1
and z z
x1 In [l + x2zl] + x 2 In [l + xlz2] -gE(x1) = 0 (14)
where
If at any value of the composition, xl, the experimental
value of gE(xl)or of the activity coefficients are known,
then 14 becomes a transcendental equation, with z2 as the
single variable, that can be easily solved by ordinary nu-
(7) merical methods. Substitution of z2 into eq 15 will yield
the corresponding value of zl. Knowledge of z1and z2 will
allow immediate evaluation of the Wilson parameters from
eq 9 and 10 as follows:
1- XlZ,
As it can be seen, the proposed method is normally
based on single-point data (preferably the extreme value
of g E ) but clearly the calculations can be extended to a
number of points to produce a set of A12and Azl pairs,
which properly treated will give the best values of the
parameters with regard to the chosen objective function.
The experimental g E(xl) values in the central concen-
tration region are normally of the highest accuracy and
should be preferably used in the calculations. Location
of the extreme in the experimental gE(xl)curve is helped
by expanding the function as a polynomial of x1 as follows:
n
gE(x1) = P(xJ = Cakxlk (17)
k=O
where ao, nl, u2,...,a,, are the numerical coefficients of the
polynomial P ( x l ) . Subroutines for this purpose are
available in hand scientific calculators and should not be
a problem. Differentiating eq 17 with respect to x1 yields
n-1
dP(xl)/dxl = C k w l k - ' = In (y1/y2) (18)
k=l
Thus, the values of gE(xl)and In (y1/y2)in eq 14 and
15 can be replaced by the polynomial P ( x l ) and its first
derivative, dP(xl)/dxl, respectively. Such representation
326 Ind. Eng. Chem. Res., Vol. 28, No. 3, 1989

Table I. Comparison of Proposed Method with Steepest Ascent Results

O.P." A12 A21 AYIb AYzb O.P." A12 A21 AYlb Ayzb
Ethyl Acetate-Benzene (760 mmHg) Methanol-Diisopropyl Ether (730 mmHg)
2 0.95938 0.95945 0.0078 0.0016 2 0.41114 0.41113 0.025 0.030
3 1.16591 0.77127 0.0083 0.0015 3 0.35808 0.46404 0.023 0.023
4 1.08445 0.83942 0.0083 0.0015 4 0.34763 0.50521 0.019 0.028
5 1.29352 0.66945 0.0090 0.0016 5 0.45188 0.39944 0.022 0.025
Hiratac 0.43886 1.73284 0.0062 0.0043 Hirata 0.54736 0.35937 0.021 0.015
Ethyl Acetate-Toluene (760 mmHg) 2-Propanol-Water (95 mmHg)
2 0.94213 0.84137 0.011 0.0028 2 0.26711 0.40483 0.032 0.014
3 0.94334 0.84028 0.011 0.0028 3 0.05744 0.64666 0.032 0.0028
4 1.23697 0.61601 0.010 0.0030 4 0.03225 0.74845 0.050 0.0073
5 1.51336 0.43880 0.012 0.0037 5 0.09170 0.66909 0.022 0.0057
Hirata 0.85981 0.96565 0.0063 0.0029 Hirata 0.10855 0.59478 0.016 0.0047
Acetone-Carbon Tetrachloride (760 mmHg) Methyl Ethyl Ketone-Heptane (760 mmHg)
2 0.55328 0.64365 0.015 0.0098 2 0.49887 0.47784 0.0088 0.0045
3 0.34718 0.90022 0.011 0.0037 3 0.49627 0.48004 0.0088 0.0044
4 0.33962 0.91730 0.011 0.0035 4 0.51017 0.48153 0.0087 0.0045
5 0.36150 0.88681 0.010 0.0041 5 0.56383 0.43048 0.0099 0.0061
Hirata 0.40080 0.83437 0.010 0.0053 Hirata 0.48084 0.48129 0.0096 0.0047
2-Propanol-Carbon Tetrachloride (760 mmHg) Allyl Alcohol-Water (760 mmHg)
2 0.35513 0.35784 0.016 0.033 2 0.26993 0.24845 0.041 0.041
3 0.29742 0.42566 0.016 0.028 3 0.08460 0.78953 0.022 0.0078
4 0.31766 0.44094 0.015 0.025 4 0.07346 0.83947 0.023 0.0065
5 0.37047 0.38692 0.014 0.025 5 0.08708 0.81800 0.019 0.0062
Hirata 0.27013 0.42855 0.018 0.031 Hirata 0.11014 0.86087 0.011 0.0071
Ethyl Acetate-p-Xylene (760 mmHg) Octane-p-Cresol (760 mmHg)
2 0.77454 0.77492 0.014 0.0031 2 0.22968 0.22451 0.13 0.0099
3 0.60516 0.96566 0.015 0.0027 3 0.12556 0.33922 0.19 0.0089
4 0.62334 0.95905 0.012 0.0027 4 0.12556 0.33922 0.19 0.0089
J 0.59198 0.9998 0.013 0.0027 5 0.26993 0.24845 0.088 0.0091
Hirata 0.39981 1.30443 0.020 0.0026 Hirata 0.12012 0.36003 0.19 0.0086
Benzene-Butanol (760 mmHg) Ethanol-Hexane (760 mmHg)
2 0.62916 0.44161 0.025 0.0048 2 0.12781 0.12301 0.038 0.049
3 0.92868 0.19301 0.012 0.0032 3 0.06858 0.19342 0.034 0.027
4 1.03198 0.15147 0.0085 0.0043 4 0.06334 0.27025 0.031 0.0070
5 1.06858 0.12459 0.013 0.0052 5 0.05302 0.28407 0.032 0.0069
Hirata 0.97505 0.19305 0.0041 0.0033 Hirata 0.08938 0.20175 0.031 0.022
Methanol-Benzene (760 mmHg) Methyl Acetate-Benzene (760 mmHg)
2 0.20420 0.29941 0.011 0.022 2 0.80939 0.84744 0.017 0.0088
3 0.10458 0.41537 0.022 0.028 3 0.67684 0.99795 0.017 0.0079
4 0.10221 0.44514 0.024 0.026 4 0.68462 0.99530 0.016 0.0082
5 0.13725 0.39981 0.014 0.023 5 0.99284 0.68518 0.016 0.010
Hirata 0.12633 0.37663 0.016 0.027 Hirata 0.96830 0.67459 0.021 0.0095
Acetic Acid-Water (760 mmHg) Chloroform-Benzene (760 mmHg)
2 0.94757 0.74320 0.018 0.021 2 2.61668 0.22597 0.0021 0.0059
3 1.16440 0.56697 0.016 0.022 3 2.67133 0.20743 0.0025 0.0061
4 1.34244 0.45804 0.014 0.023 4 2.53832 0.25029 0.0022 0.0055
5 1.18277 0.56458 0.015 0.022 5 2.79618 0.16436 0.0041 0.0066
Hirata 0.24607 1.60470 0.032 0.017 Hirata 2.59312 0.20302 0.0078 0.0048
Pentane-Acetone (760 mmHg) Methanol-Methyl Ethyl Ketone (760 mmHg)
2 0.29854 0.29635 0.035 0.023 2 0.68141 0.67308 0.0064 0.0023
3 0.21333 0.39796 0.050 0.020 3 0.67986 0.67336 0.0064 0.0023
4 0.24326 0.41888 0.043 0.020 4 0.68086 0.67802 0.0065 0.0024
5 0.46022 0.20398 0.016 0.030 5 0.58400 0.78301 0.0096 0.0032
Hirata 0.15167 0.42420 0.068 0.024 Hirata 0.74636 0.59282 0.0062 0.0030
Ethylcyclohexane-2-Propanol (400 mmHg) Cyclohexane-2-Propanol (500 mmHg)
2 0.19900 0.17916 0.011 0.099 2 0.28469 0.22970 0.032 0.014
3 0.24797 0.10702 0.0088 0.16 3 0.39837 0.11871 0.023 0.022
4 0.21003 0.18044 0.011 0.093 4 0.43370 0.10554 0.019 0.024
5 0.30055 0.05830 0.011 0.093 5 0.38811 0.14392 0.016 0.0051
Hirata 0.24469 0.15930 0.0093 0.10 Hirata 0.32305 0.14811 0.032 0.018
Methanol-Ethyl Acetate (730 mmHg) 2-Propanol-Methylcyclohexane (760 mmHg)
2 0.55577 0.51108 0.021 0.018 2 0.26353 0.27747 0.024 0.016
3 0.56133 0.50419 0.022 0.018 3 0.15918 0.39504 0.014 0.0066
4 0.58271 0.49283 0.021 0.017 4 0.14758 0.44341 0.016 0.0050
5 0.51313 0.56107 0.018 0.019 5 0.14363 0.44776 0.020 0.019
Hirata 0.73176 0.51768 0.017 0.014 Hirata 0.09067 0.43978 0.020 0.013
 Ind. Eng. Chem. Res., Vol. 28, No. 3, 1989 327
Table I (Continued)
O.P." '412 '421 AYlb AYZb O.P." '412 '421 AY? AYZb
Pyridine-Tetrachloroethylene (60 "C) Hexane-1.1.1-Trichloroethane (60 "C)
2 0.44051 0.92151 0.011 0.0039 2 0.84035 ' 1.0000 0.015 0.034
3 0.54962 0.72208 0.0075 0.0054 3 0.71295 Loo00 0.0013 0.0030
4 0.56379 0.72047 0.0064 0.0050 4 0.71438 1.0000 0.0013 0.0031
5 0.59094 0.69128 0.0061 0.0056 5 0.71463 1.0000 0.0013 0.0031
Hirata 0.66066 0.56980 0.012 0.0096 Hirata 0.61607 1.0950 0.0024 0.0023
Benzene-Ethanol (25 "C) Hexane-2-Butanone (60 "C)
2 0.31130 0.23214 0.026 0.013 2 0.50355 0.47397 0.0063 0.0073
3 0.44180 0.11134 0.0066 0.0024 3 0.53748 0.43928 0.0042 0.0062
4 0.48281 0.09634 0.0047 0.0023 4 0.55323 0.43491 0.0042 0.0055
5 0.45715 0.11735 0.0040 0.0020 5 0.53500 0.45175 0.0045 0.0059
Hirata 0.46589 0.11025 0.0034 0.0018 Hirata 0.64871 0.36797 0.0057 0.0041
Octane-Dioxane (80 "C) Hexane-2-Butanol (60 "C)
2 0.50199 0.53880 0.011 0.015 2 0.41780 0.30432 0.030 0.0075
3 0.30906 0.7 6373 0.0064 0.0043 3 0.53298 0.19927 0.011 0.0051
4 0.28419 0.81372 0.0073 0.0027 4 0.67772 0.14278 0.018 0.0076
5 0.33628 0.74199 0.0070 0.0041 5 0.67697 0.14301 0.018 0.0076
Hirata 0.29778 0.72565 0.0071 0.011 Hirata 0.47709 0.20058 0.025 0.0052
Nonane-Dioxane (80 "C) 2-Propanol-Heptane (60 "C)
2 0.48403 0.54656 0.0074 0.040 2 0.23802 0.24705 0.022 0.014
3 0.21271 0.90980 0.0079 0.015 3 0.14373 0.35807 0.011 0.0069
4 0.21118 0.91371 0.0079 0.015 4 0.14600 0.40647 0.012 0.0077
5 0.38011 0.64364 0.0072 0.034 5 0.18953 0.35357 0.014 0.0075
Hirata 0.29778 0.72565 0.0067 0.032 Hirata 0.16554 0.26335 0.020 0.015
Diiaopropylamine-Water (10 "C)
2 0.23132 0.27149 0.051 0.059
3 0.09226 0.44798 0.033 0.054
4 0.05969 0.56110 0.032 0.053
5 0.11822 0.47629 0.030 0.054
Hirata 0.10306 0.42809 0.034 0.054
"O.P. = order of polynomial. bAyi = Elyi - yealcl/n.cHirata et al. (1976).

of experimental data [eq 17 and 181 has obvious advantage a volume fraction term to the excess Gibbs energy of
in computer calculations. mixing:
As shown in Figure 1, gE(xl)has always a t least one G E / R T = GE/RT(Wilson) +
extreme value (maximum or minimum), its location x1 =
xl* and the corresponding extreme value gE(xl*)= P(xl*) x1 In ( x , + + +
rx,) x 2 In ( x l / r x,) (22)
can be calculated from eq 18 by taking into account that where r denotes the ratio of the molar volumes, uZL/ulL,
at this point the derivative @(xl)/dxl is nil. In this case, of the pure components and the G E/RT(Wilson) term is
eq 14 and 15 become defined in eq 8. Equation 22 is often called the T-K-
xl* In [ l + x2*zl] + x2* In [ l + x1*z2] - P(xl*) = 0 Wilson equation. The suggested algorithm can be used
(19) to determine the corresponding new pair of A12 and A,,
parameters, if gE(xl)= GE/RT is replaced by the function
and
Q(xl) = G E / R T - x1 In ( x , + rx,) - x 2 In ( x l / r x,)+
(23)
- In (1 + x1*z2)]+ x2*z2
where
The use of eq 19 and 20 for the evaluation of A,, and Q(xl) = x1 In (1 + xzzl) + x 2 In (1 + qz,) (24)
A,, will be illustrated later for a number of binary systems. Expressing Q(xl) in the polynomial form (17) permits
When the experimental data are good enough to permit calculation of the T-K-Wilson parameters from eq 19,20,
representation of the second and third derivatives of gE(x,) and 16.
in the polynomial form (17), evaluation of the Wilson Nagata et al. (1975) modified the Wilson equation by
parameters will reduce to solving the following algebraic adding the Scatchard-Hildebrand term
equations: (6, - 6,)2u1Lu,Lx1xz
~ 1 - 221
~ + 2 '22, - d2P(XJ/dX,2 = 0
1 ~ 2~ ~ - GE/RT = GE/RT(Wilson) + (X,VlL + X,V,L) (25)

+
3z12- 2xlzl3 - 3zZ2 2x,zZ3- d3P(xl)/dxl3= 0
Once again z1 and z2 can be isolated because the first
equation in (21) is quadratic in z1 or z,. Evidently, this
equation, if accurate, can replace the logarithmic rela-
tionship between z1 and z2 in eq 15 and 20.
The Wilson equation in its original form has the sig-
nificant disadvantage that it cannot represent liquid-liquid
systems. A number of modifications have been proposed
to overcome this disadvantage. The simplest one was
introduced by Tsuboka and Katayama (1975), who added
(21) where a1 and 6, are the solubility parameters of pure
components.
Once again, the calculation procedure for eq 25 is the
same as the one described for the T-K-Wilson equation,
except that the auxiliary function is defined differently:
A more versatile treatment of partially miscible systems
can be expected if the solubility parameters in eq 25 are
328 Ind. Eng. Chem. Res., Vol. 28, No. 3, 1989
replaced by an adjustable constant b or by the strictly
regular solution term, as suggested by Novak et al. (1974):
G E / R T = GE/RT(Wilson) + b x 1 x 2 (27)
If one-point data are considered, then the three param-
eters A12, Azl, and b present in eq 25 and 27 can be
evaluated from a knowledge of G E and its first and second
derivatives. For the case where GE/RT is presented in the
polynomial form (17), the corresponding equations for the
case given in (27) become
g E + bx,x2 = P(xJ
agE/dxl + b(xl - x,) = w(xl)/dxl
d2gE/dx12- 2b = d2P(xl)/dx12 (28)
where g E and its derivatives are given by eq 11-13. The
third parameter b can be easily removed from eq 28, but
there is no possibility to isolate z1 and z2. They should be
evaluated from the pair of transcendental equations (in-
troduction of Q(xl) = gE/x1x2 + b where G E / R T =
x1x2Q(x1)leads to more complex transcendental equations)
(29)
by ordinary numerical methods.
Quite clearly, the simplest form of these equations will
occur when the composition is equimolar (xl = x2 = 0.5)
and for the extreme value of P(xl*) where dP(xl)/dxl =
0.
The case represented by eq 25 can be treated in a similar
way.
Results and Discussion
A number of systems were selected from the Hirata
(Hirata et al., 1976) collection, representing solutions with
strong positive or negative deviations from ideal behavior,
with or without azeotropes, a t isobaric or isothermal con-
ditions. The values of G E/RT were calculated and then
fitted with polynomials of different degrees (from 2 to 5).
Equations 19 and 20 were solved and the Wilson constants
were determined from relations 16. The computational
procedure was done fast and efficiently in a Mac 512
computer using the Excel spreadsheet, the Statworks
statistical package for the polynomial algorithm, and the
Eureka program for the trial and error part. Overall
computational for one complete cycle took a few minutes.
A scientific hand calculator (HP 15C) was also used for
comparison purposes.
Results for the selected systems are presented in Table
I and compared with the results of Hirata et al. Inspection
of Table I leads to the following conclusions.
1. The accuracy of the suggested method (measured by
the ability to predict the vapor composition) is normally
as good or better than the complex search techniques.
2. A third or fourth degree polynomial will usually
suffice.
3. The mathematical routine described here is very fast
and avoids the need of a medium- or large-size computer.
The required algorithms are normally available with
personal and hand scientific calculators.
4. The procedure calls for data in the central part of
the composition range, where the experimental analytical
precision is the best.
5. For a given system, significantly different pairs of
Wilson constants will have the same capability of pre-
dicting the composition of the gas phase.
An additional important observation of the data re-
ported in Table I is that the predictive ability for the vapor
composition of component 2 is normally much higher than
that for component 1. We attribute this to the fact that
component 1 is usually the most volatile one and the
pertinent Antoine equation is being extrapolated beyond
its real range.
Nomenclature
Ai. = Wilson constant
G k = excess Gibbs function
R = gas universal constant
r = ratio ulL/uZL
T = absolute temperature, K
u f = liquid molar volume of component i
x i = mole fraction of component i in the liquid phase
y i = mole fraction of component i in the vapor phase
Greek S y m b o l s
= solubility parameter of component i
yi = activity coefficient of component i
Literature Cited
Czelej, M. The Polynomial Form of the Wilson Equation for Binary
and Ternary Systems. Int. Chem. Eng. 1987,27, 535-538.
Hirata, M.; Ohe, S.; Nagahama, K. Computer Aided Data Book of
Vapor-Liquid Equilibrium. Kodansha-Elsevier: Tokyo, 1976.
Hudson, J. W.; Van Winkle, M. Multicomponent Vapor-Liquid
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Received f o r review June 10, 1988
Revised manuscript received November 1, 1988
Accepted November 7, 1988