Journal of Chemical Engineering of Japan, Advance Publication

doi: 10.1252/jcej.12we159; published online on July 25, 2012

Prediction of Vapor-Liquid Equilibria of Alcohol + Hydrocarbon Binary

Systems by Using Wilson Equation with Parameters Estimated from
Pure – Component Properties
Shigetoshi KOBUCHI1, Kenji ISHIGE1, Kei TAKAKURA1
Setsuko YONEZAWA 2, Kenji FUKUCHI3 and Yasuhiko ARAI2*
1
Department of Environmental Science and Engineering, Graduate School of Science and Engineering,
Yamaguchi University, 2-16-1 Tokiwadai, Ube-shi, Yamaguchi 755-8611, Japan
2
Department of Chemical Engineering, Faculty of Engineering, Kyushu University, 744 Motooka,
Nishi-ku, Fukuoka-shi, Fukuoka 819-0395, Japan
3
Department of Chemical and Biological Engineering, Ube National College of Technology,
2-14-1 Tokiwadai, Ube-shi,Yamaguchi 755-8555, Japan

Keywords: Wilson Parameter, Vapor-Liquid Equilibrium, Binary System, Alcohol, Hydrocarbon,

Solubility Parameter, Molar Volume, Pure-Component Property

The coefficients of estimation equations required to obtain the interaction parameters between unlike
molecules from pure-component properties are reported for alcohol + hydrocarbon binary systems. By using the
equations, the Wilson parameters can be estimated and the VLE of the mixtures can be predicted on the basis of
the method previously proposed.

In a previous paper (Kobuchi et al., 2011a), a simple
approach to estimate the Wilson parameters (Wilson, 1964)
has been proposed based on the molecular structures and by
using pure-component properties alone of the constituent
components to predict vapor-liquid equilibria (VLE) with no
VLE data of the mixtures concerned. Briefly, the Wilson
parameters 12 and 21 can be estimated as follows:
vj  ij  ii 
ij  exp   (Kobuchi et al., 2010, 2012b). By using the vapor-liquid
vi  RT 
where
ij  1  ij vi v j  0.5  i j
12 = a12+ b12t b, 1+ c12t b, 2+ d12 25, 12+ e12 25, 22
21 = a21+ b21t b, 1+ c21t b, 2+ d21 25, 12+ e21 25, 22
The molar volume v and the solubility parameter at a given
temperature can be easily obtained on the basis of the
group-contribution methods. The interaction parameters
between unlike molecules 12 and 21 can be approximated by
Eqs. (3) and (4) which are essentially empirical. It is
considered that the cohesive energy density 252 may express
the polarity of a molecule and the normal boiling point tb is
effective to distinguish isomers. The coefficients of Eqs. (3)
and (4) required have been determined for various binary
* Professor Emeritus of Kyushu University
Received on , 2012. Correspondence concerning this
article should be addressed to S. Kobuchi (E-mail address:
kobuchi@yamaguchi-u.ac.jp).
systems consisting of non-polar and polar molecules
(Kobuchi et al., 2011a, 2011b, 2012a, 2012b).
However, those of alcohol + hydrocarbon binary
systems are limited to only ethanol as a typical alcohol. As a
continuation, therefore, the coefficients of other alcohol +
hydrocarbon binary systems have been evaluated in this
communication. The physical properties of ethylbenzene are
presented in Table 1. Those of other alcohols and
(1) hydrocarbons have been reported in previous papers
equilibrium (VLE) data available in the literature for
methanol, propanol, or butanol + hydrocarbon binary
systems, the interaction parameters 12 and 21 have been
determined and presented in Table 2 with the correlation
(2) performances. The average deviations are y1=1.6% and
t=0.3℃ which show good correlation results. A typical
(3) illustration is shown in Figure 1. The VLE studied for
methanol mixtures are quite limited because VLE with
homogeneous liquid phase have been considered. The
(4) coefficients 12 and 21 obtained were then attempted to be
approximated by Eqs. (3) and (4). First, all alcohol +
hydrocarbon binary systems including ethanol binary
systems previously studied (Kobuchi et al., 2011a) were
examined and the coefficients of Eqs. (3) and (4) were
determined. As a result, the averaged deviations are found to
be large especially for methanol and ethanol binary systems
(methanol binary systems: avg.y1=3.4% and t=1.2℃;
ethanol binary systems: avg.y1=3.6% and t=0.9 ℃ ).
Further, ethanol, propanol, and butanol binary systems,
except methanol binary systems, were examined and the
coefficients were re-evaluated. However, the averaged
deviations for ethanol binary systems seem to be still large
(avg.y1=3.9% and t=0.8℃) while avg.y1=1.7% and
t=0.4℃ for ethanol + hydrocarbon six binary systems as
examined in the previous paper (Kobuchi et al., 2011a).

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 Journal of Chemical Engineering of Japan, Advance Publication
doi: 10.1252/jcej.12we159; published online on July 25, 2012

Table 1 Physical properties of pure substances

v25 vb 25 tb a Constants of Antoine’s equation*, a

Substance
[cm ･mol1] [cm3･mol1]
3 3 0.5
[ (J･cm ) ] [℃] A B C
Ethylbenzene 121.0 140.4 18.5 136.186 6.07850 1421.653 60.274

* log p [kPa]  A  B /(T [K]  C )

a
Boublik et al. (1984)

Table 2 Interaction parameters and correlation (prediction) performances for VLE of alcohol (1) + hydrocarbon (2)
binary systems at 101.3 kPa

Interaction parameters Deviations*

Binary system (1) + (2) Ref. N
12  21 y1 t
a
Methanol+Benzene c 18 0.2206 0.0290 1.2 0.2
Methanol+Toluene a c 14 0.2880 0.0247 1.1 0.3
1-Propanol+Benzene a
c 50 0.0406 0.1759 3.3 (3.4) b
0.6 (0.8)b
a b
1-Propanol+Toluene c 12 0.0037 0.1209 0.6 (2.0) 0.3 (0.4)b
1-Propanol+Ethylbenzene c 13 0.0559 0.0679 1.2 (2.4)b 0.2 (0.9)b
1-Propanol+Cyclohexane a
c 6 0.0061 0.1911 2.3 (2.7) b
0.3 (0.4)b
1-Propanol+Heptane a d 19 0.0394 0.1524 1.3 (2.3)b 0.6 (0.4)b
a b
1-Propanol+Octane e 18 0.1075 0.0962 0.7 (0.7) 0.2 (0.4)b
2-Propanol+Benzene a f 43 0.0383 0.1627 2.2 (2.2)b 0.1 (0.1)b
a b
2-Propanol+Toluene g 35 0.0235 0.1047 1.4 (1.4) 0.3 (0.3)b
2-Propanol+Ethylbenzene g 33 0.0691 0.0549 0.9 (1.4)b 0.3 (0.5)b
2-Propanol+Cyclohexane a f 11 0.0389 0.1675 1.4 (3.4)b 0.3 (0.8)b
2-Propanol+Hexane a
f 14 0.0218 0.2001 2.3 (3.8) b
0.5 (0.3)b
2-Propanol+Heptane a g 18 0.0608 0.1340 1.7 (1.5)b 0.4 (0.6)b
a b
2-Propanol+Octane h 17 0.1224 0.0649 0.5 (0.8) 0.2 (0.2)b
1-Butanol+Benzene f 21 0.1378 0.2069 1.9 (5.5)b 0.3 (0.5)b
1-Butanol+Toluene a
i 16 0.0871 0.1620 0.9 (2.6) b
0.3 (0.2)b
1-Butanol+Ethylbenzene a f 20 0.0202 0.1066 1.4 (1.3)b 0.2 (0.4)b
1-Butanol+Cyclohexane a
i 15 0.0664 0.2094 2.2 (2.7) b
0.3 (0.5)b
1-Butanol+Hexane i 21 0.0931 0.2442 2.8 (2.9)b 0.4 (0.4)b
1-Butanol+Heptane a f 8 0.0372 0.1829 1.1 (1.2)b 0.3 (0.3)b
a b
1-Butanol+Octane i 25 0.0273 0.1254 0.5 (1.7) 0.2 (0.8)b
2-Butanol+Benzene a j 16 0.1184 0.1924 2.1 (2.3)b 0.2 (0.3)b
2-Butanol+Cyclohexane a
k 24 0.0781 0.1965 3.5 (4.0) b
0.8 (1.0)b
2-Butanol+Hexane a l 15 0.0985 0.2207 2.9 (4.2)b 0.2 (0.5)b
a b
2-Butanol+Octane m 19 0.0321 0.0963 0.6 (0.9) 0.2 (0.1)b
t-Butanol+Benzene a f 16 0.0848 0.1612 1.4 (1.4)b 0.6 (0.9)b
t-Butanol+Cyclohexane a
j 22 0.0170 0.1571 0.7 (3.6) b
0.2 (0.7)b
t-Butanol+Hexane a f 24 0.0901 0.1943 1.8 (7.6)b 0.5 (0.4)b
t-Butanol+Heptane a
g 21 0.0031 0.1290 1.3 (2.2) b
0.3 (0.1)b
Avg. 1.6 (2.6)b 0.3 (0.5)b
100 N y1, calc  y1, exp
N
1
*  y1[%] 
N
 y ,  t [℃] 
N
 t calc  t exp , N = number of data points
1, exp

a
Minimum azeotropic mixture, b Values in parentheses are obtained by Eqs. (3) and (4), c Gmehling et al. (1977), d idem (1988), e Hiaki et al.
(1995), f Gmehling et al. (1978), g idem (1990), h idem (2007), i idem (2008), j idem (1982), k Feng et al. (1998), l Domínguez et al. (2002),
m
Góral et al. (1998)

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 Journal of Chemical Engineering of Japan, Advance Publication
doi: 10.1252/jcej.12we159; published online on July 25, 2012

Table 3 Coefficients of Eqs. (3) and (4) for alcohol (1) + hydrocarbon (2) binary systems

a12 b12 c12 d12 e12

Binary system (1) + (2) a21 b21 c 21 d 21 e 21
C3, C4 alcohol* + Hydrocarbon 0.3488 2.13×103 2.02×103 8.82×104 4.85×104
0.2225 1.45×103 2.04×103 4.42×10 4.31×105

* C3 alcohol = 1- or 2-propanol and C4 alcohol = 1-, 2- or t-butanol

Therefore, finally, the coefficients for propanol or butanol + 1.0

hydrocarbon binary systems have been determined and are
presented Table 3. As shown in Table 2, the averaged 0.8
deviations are y1=2.6% and t=0.5℃ which show fairly

[ ]
good prediction results. A graphical presentation is given in 0.6

y (Benzene)
Figure 1 with the dashed line.
0.4

Literature Cited 0.2

Boublik, T., V. Fried and E. Hála; The Vapour Pressures of Pure
Substances, 2nd ed., Elsevier, Amsterdam, The Netherlands
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Domínguez, M., S. Martín, H. Artigas, M. C. López and F. M. Royo; x (Benzene) [ ]

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and (4)
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