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J. Chem. Eng. Data 2003, 48, 66-70

Measurement and Prediction of Quaternary Azeotropes for

Cyclohexane + 2-Propanol + Ethyl Acetate + Butanone System at
Elevated Pressures
Qi Wang,* Xin-Huan Yan, Geng-Hua Chen, and Shi-Jun Han
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China

The azeotropic data of the cyclohexane + 2-propanol + ethyl acetate + butanone quaternary system
were measured by using a stainless steel azeotrope apparatus developed by the authors at elevated
pressures of 101.3, 302.0, 502.0, 702.0, and 902.0 kPa and predicted by using the Wilson and NRTL
activity coefficient models with the paired energy parameters obtained from binary azeotropic data of
the six corresponding systems. The calculated results demonstrate that the predicted data are in good
agreement with the experimental, and the Wilson and NRTL equations are of comparable accuracy in
the prediction of azeotropes for this miscible quaternary system at elevated pressures.

Introduction
The azeotropic point is a distinctive point in vapor-liquid
equilibrium, at which the compositions and many other
properties, such as enthalpies of vaporization, enthalpies
of solvation, etc., are identical for both the vapor and liquid
phases. Investigations of the behavior of azeotropic mixtures are of keen interest to theoretical studies and are
equally important for industrial and engineering applications. Naturally, It is of great practical importance to
predict and calculate multicomponent azeotropes, including
ternary, quaternary, or higher-order ones, from readily
available binary azeotropic or vapor-liquid equilibrium
data. Therefore, many recent attempts have been made to
predict the compositions and temperature for ternary
azeotropes using vapor-liquid equilibrium data.
Kudryavtseva et al.1 proposed a method to calculate the
compositions for multicomponent azeotropes from the data
of binary azeotropes and the pure components. However,
it could not be guaranteed that unique azeotropic compositions could be obtained. Eduljee and Tiwari2 reported a
method for predicting ternary azeotropic compositions and
temperature from unlike interaction parameters of binary
azeotropic mixtures in conjunction with binary azeotropic
information according to a general classification of liquids
based on their hydrogen bonding capabilities. Tamir and
Wisniak3 employed the Redlich-Kister equation to calculate the azeotropes for ternary systems, but multicomponent (ternary) interaction parameters were required in
addition to binary ones. Later, Tamir4 developed a method
for predicting multicomponent azeotropes by using the
Wilson equation with parameters estimated from multicomponent vapor-liquid equilibrium data. Kudryavtseva
and Toome5 proposed a simple method to predict ternary
azeotropic data that was based on a topographic feature
of the ternary mixtures and only required information on
binary azeotropes and pure components. Recently, Vahdat
and Sather6 used the Wilson and NRTL equations to derive
equations that predict the compositions and temperature
of multicomponent azeotropes from binary equilibrium
data. This model was successfully used for ternary and
* To whom correspondence should be addressed. E-mail: qiwang@
css.zju.edu.cn.

quaternary systems, but entropy data of vaporization were

required in the calculations. Lan and Mansoori7 developed
a hard sphere expansion conformal solution theory, based
on statistical mechanics and the molecular theory of fluid
mixtures, to predict the vapor-liquid equilibrium properties of multicomponent mixtures, and an equation of state
for multicomponent fluid was developed. The vapor-liquid
equilibria as well as azeotropic properties of several binary
and ternary nonpolar mixtures were predicted. The proposed approach provides a detailed insight into the peculiar
behavior of the azeotropic mixtures. However, all of these
prediction methods were mainly proposed and used at
normal and lower pressures, but no models and algorithms
have been tested and confirmed at elevated pressures. One
of the objectives of this work is to provide a more reliable
and efficient algorithm, which can predict azeotropic points
for multicomponent systems, including ternary, quaternary, and higher-order ones, at elevated pressures from
binary azeotropic or vapor-liquid equilibrium data.
The azeotropic and vapor-liquid equilibrium data of the
cyclohexane + 2-propanol + ethyl acetate + butanone
quaternary system at elevated pressures are not reported
in the literature. The azeotropic data for this system were
determined at elevated pressures up to 902 kPa in this
work.
Experimental Section
Chemicals. All of the chemicals, cyclohexane, 2-propanol, ethyl acetate, and butanone, were of analytical grade
and were further purified by rectifying and collecting the
fraction with constant boiling temperature and refractive
index. All of the pure chemicals were confirmed by gas
chromatography analysis, and the purities were estimated
to be higher than 99.9%. The physical properties of the
chemicals used in these measurements were compared to
literature data and presented in the previous work.8
Apparatus. The stainless steel azeotrope apparatus
described in the previous work7 was employed for the
determining of quaternary azeotrope. The high-performance rectifying column was packed with high-efficient
stainless steel round packing materials and wrapped with
rock wool to minimize heat losses. A pressure control unit

10.1021/je020091a CCC: $25.00 2003 American Chemical Society

Published on Web 11/21/2002


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Journal of Chemical and Engineering Data, Vol. 48, No. 1, 2003 67

Table 1. Experimental Tests of Composition Analysis of

Prepared Mixtures for the Quaternary System
Cyclohexane (1) + 2-Propanol (2) + Ethyl Acetate (3) +
Butanone (4)
prepared

deviations

x1

x2

x3

x4

x1

x2

x3

x4

0.4256
0.4098
0.3924
0.2630
0.2515
0.3515
0.5107
0.5547
0.4448

0.2982
0.4746
0.5816
0.6735
0.7109
0.6003
0.2104
0.1874
0.2017

0.1054
0.0459
0.0174
0.0109
0.0203
0.0311
0.1109
0.0837
0.2617

0.1697
0.0696
0.0236
0.0524
0.0181
0.0171
0.1680
0.1742
0.0918

0.0042
-0.0058
-0.0049
0.0038
0.0014
-0.0018
0.0047
0.0029
-0.0038

0.0011
0.0042
0.0037
-0.0049
-0.0028
0.0030
-0.0009
0.0019
-0.0012

-0.0005
0.0005
0.0006
0.0001
0.0008
-0.0009
-0.0018
-0.0011
0.0041

-0.0048
0.0011
0.0006
0.0010
0.0006
-0.0003
-0.0020
-0.0038
0.0009

0.0037

0.0026

0.0012

0.0017

with a digital pressure transducer was designed to control

and measure the system pressure with an accuracy of (0.1
kPa. The thermometer well is located at the top of the
column, and a secondary standard platinum resistance
thermometer, accompanied with a 5-1/2 digital multimeter, was used for the temperature measurement. The
accuracy of measured resistance is (0.001, which is
equivalent to (0.01 K for the azeotropic temperature.
Composition Analysis. The compositions of the quaternary mixtures were analyzed and determined by a
Shimazu gas chromatograph equipped with a thermal
conductivity detector. The chromatograph column was
packed with Porapak-Q packing materials (Waters Associates, Inc.). The flow rate of the carrier gas, H2, was 60
mLmin-1. The column temperature was maintained around
443.15 K. The compositions were determined by the relative area method whose accuracy was estimated to be 0.003
mole fraction for quaternary mixtures. Some test results
for prepared mixtures are given in Table 1. The prepared
samples were analyzed three times independently, and
every final result was taken from the average of the values
of these three measurements.
Test of Quaternary Azeotropic Compositions. As to
the quaternary systems, the variation of boiling temperature is not notable, but that of the composition is too
sensitive in the vicinity of the azeotrope. Sometimes the
change in a quaternary composition will amount to 0.1 mole
fraction even though the temperature change is less than
only 0.05 K. Thus, it is imperative to propose a reliability
test for quaternary azeotropic compositions before working
on measurements at elevated pressures. Because quaternary azeotropic data for this system at normal and elevated
pressures are not available in the literatures, the azeotropic
temperature and composition for this system were determined at 101.3 kPa with different prepared starting
compositions. Each of them was distilled seven times at
the same reflux ratio. The light fraction was collected up
to about one-half of the starting volume, and the remnant

mixtures in the boiler were replaced by the collected light

fractions for further distillation. The temperature was
measured, and the composition was analyzed in each cycle.
The test results of the last four cycles are presented in
Table 2 with first three cycles omitted. It demonstrates that
the temperature and composition tend to a certain value
after six cycles, and the final azeotropic temperature and
composition was almost uniform, even when starting from
different prepared compositions. It also indicates that the
quaternary azeotropic data measured by this apparatus are
accurate and reliable.
Results and Discussion
Determination of Quaternary Azeotropic Data. As
discussed above, it is more difficult to determine a quaternary azeotrope than a binary one because especially
large deviations probably occur in the azeotropic compositions. The prepared starting mixtures should be distilled
with all of the light fractions returned to the rectifying
column for longer than 1 h, and a larger reflux ratio should
be maintained during the entire measuring procedure. The
compositions should also be sampled and analyzed for every
circulation. If the amount of the remnant liquid mixture
is too small to continue measuring after several cycles, the
liquid mixture should be prepared again according to the
last analyzed composition, and then continue rectifying
until both the temperature and composition remain unchanged. In this way, the azeotropic temperatures and
compositions for the cyclohexane + 2-propanol + ethyl
acetate + butanone quaternary system were determined
at elevated pressures up to 902 kPa. They are presented
in Table 3 and in Figures 1 and 2.
Ordinarily, because the requirements to form a quaternary azeotrope are very sensitive to changes and complicated, it is not easy to form a quaternary azeotrope. The
quaternary azeotrope probably degenerates into a ternary
azeotrope, or even to a binary one, when the system
pressure changes even slightly. In this study, the quaternary azeotrope of the cyclohexane + 2-propanol + ethyl
acetate + butanone system degenerated into a ternary
azeotrope at 502 kPa and into a binary one at pressures
higher than 702 kPa.
Prediction of Quaternary Azeotropic Data. In this
work, quaternary azeotropic data were predicted by using
an activity coefficient method as discussed for ternary
azeotropic temperatures and compositions at normal and
lower pressures.9 According to the vapor-liquid equilibrium criterion, the fugacities of the vapor and the liquid
phases should be equal when equilibrium is achieved:

ziPyi ) ip0i xi

(i ) 1-4)

(1)

where x and y are the mole fractions for the liquid and the

Table 2. Measurements of Quaternary Azeotropic Compositions at 101.3 kPa for System Cyclohexane (1) + 2-Propanol
(2) + Ethyl Acetate (3) + Butanone (4)
starting
composition

fourth
cycle

fifth
cycle

sixth
cycle

seventh
cycle

T/K

T/K

T/K

T/K

x1
x2
x3
x4

0.5016
0.2011
0.2178
0.0795

341.84

0.4901
0.2519
0.1715
0.0863

341.70

0.4914
0.2662
0.1607
0.0817

341.68

0.4862
0.2793
0.1507
0.0842

341.68

0.4881
0.2864
0.1500
0.0815

x1
x2
x3
x4

0.4088
0.3142
0.1203
0.1567

341.73

0.4743
0.2811
0.1403
0.1043

341.69

0.4824
0.2737
0.1511
0.0910

341.68

0.4853
0.2704
0.1590
0.0853

341.68

0.4894
0.2739
0.1573
0.0794


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68 Journal of Chemical and Engineering Data, Vol. 48, No. 1, 2003

the Antoine equation with the constants taken from

Stephenson and Malanowski.11 The activity coefficients in
eq 1 were calculated from the multicomponent Wilson
equation reformulated by Orye and Prausnitz:12
4

ln i ) 1 - ln

Gijxj

Gjixj -

j)1

j)1

(3)

kjxk

k)1

where

Gji )

vLi

exp -

vLj

gji - gii
RT

(4)

( )

and the multicomponent NRTL equation13

Figure 1. Plot of the logarithm of pressure versus the reciprocal
of azeotropic temperature for the quaternary system: O, experimental, quaternary azeotrope; [, ternary azeotrope; b, binary
azeotrope; -, Wilson equation; , NRTL equation; - - -, extrapolated from quaternary.

ln i )

jiGjixj

j)1

j)1

kixk

k)1

Gijxj
4

kjxk

k)1

G x
lj

ij -

lj l

l)1
4

(5)

kjxk

k)1

where

ji )

gji - gii
RT

Gji ) exp(-Rjiji)

Figure 2. Plot of the quaternary azeotropic compositions versus

the azeotropic temperature: 9 experimental, x1; O, x2; 0, x3; b, x4;
-, Wilson equation; , NRTL equation.
Table 3. Experimental Azeotropic Temperatures and
Compositions of the Quaternary System Cyclohexane (1)
+ 2-Propanol (2) + Ethyl Acetate (3) + Butanone (4)
P/kPa

T/K

x1

x2

x3

x4

101.3
302.0
502.0
702.0
902.0

341.68
376.82
395.09
408.90
420.03

0.4887
0.4706
0.4221
0.3736
0.3422

0.2771
0.4710
0.5548
0.6264
0.6578

0.1536
0.0495
0.0230
0
0

0.0804
0.0089
0
0
0

vapor phases, respectively, P is the total pressure, p0 is

the saturated vapor pressure of the pure component, is
the activity coefficient for the liquid phase, and z is the
nonideal correction factor for the vapor phase. By using a
virial equation of state truncated after the B term, the
correction factor could be reduced if the effect of pressure
on molar volume of the pure component liquid is neglected,
thus

zi ) exp

(Bii - vLi )(P - p0i )

RT

(2)

where the second virial coefficients Bii were calculated by

the Tsonopoulos10 method, vLi is the molar volume of the
pure liquid, and the vapor pressures p0i were calculated by

(6)
(7)

where gji-gii and gij-gjj are the Wilson and NRTL paired
energy parameters.
Furthermore, the predictive calculations were made for
multicomponent azeotropic points from the corresponding
binary azeotropic temperatures and compositions by using
the Wilson and NRTL activity coefficient models. A prediction of a multicomponent azeotrope is done by searching a
set of compositions of equilibrium vapor that equal those
of the coexisting liquid phase. At the azeotropic point, the
vapor-liquid equilibrium relationship eq 1 becomes eq 8
because of the identical composition for the vapor and
liquid phases:

i )

z iP
p0i

(i ) 1-4)

(8)

Hence, two paired activity coefficients could be calculated

more accurately from the azeotropic temperatures and
pressures by using this equation than from the measurement of equilibrium compositions. The activity coefficients
calculated with this equation and the compositions were
then substituted into the two-component Wilson14 or NRTL
equations (Rij ) 0.47) for each coupled system, and two
paired energy parameters were calculated by an iteration
algorithm. Thus, six pairs of energy parameters for calculating the activity coefficients of the quaternary systems
could be obtained from the azeotropic data of the six
corresponding binary systems. In this calculation, the
azeotropic data of the related binary systems were taken
from the correlation equations with the pressures reported
previously.8 The obtained Wilson and NRTL paired energy
parameters are tabulated in Table 4.
A dual iterative technique was employed in the calculation of the azeotropic temperature and compositions for the
quaternary system at a given total pressure, until the


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Journal of Chemical and Engineering Data, Vol. 48, No. 1, 2003 69

Table 4. Wilson and NRTL Paired Energy Parameters for Systems Involving Cyclohexane (1), 2-Propanol (2), Ethyl
Acetate (3), and Butanone (4) in eqs 4 and 6 in Jmol-1
P/kPa

g21-g11

g12-g22

g31-g11

g13-g33

g41-g11

101.3
302.0
502.0
702.0
902.0

1310.18
195.28
-275.92
-571.17
-774.65

5461.46
5252.00
5223.85
5191.03
5133.61

344.01
714.62
819.58
792.45
663.14

2755.93
1889.83
1520.85
1349.87
1312.15

101.3
302.0
502.0
702.0
902.0

2534.55
1714.36
1411.34
1240.39
1137.35

4060.40
3590.93
3409.07
3264.52
3119.38

639.55
1041.16
1208.33
1251.59
1194.64

2406.12
1542.57
1117.67
879.40
771.38

g14-g44

g32-g22

Wilson Equation
2921.11 1109.39
2694.46 1584.65
2497.08 3488.51
2378.44 5310.58
2329.25 5421.83

g23-g33

g42-g22

g24-g44

g43-g33

g34-g44

1084.89
-426.52
-2057.85
-2934.44
-2963.46

1702.20
-0.42
1298.06 -165.05
1418.28 -396.61
-1691.95 4815.17
nonazeotrope

483.45
-1969.40
-2040.72
-1431.44
6267.15

14.61
3386.09
3388.32
2186.05
-2699.60

NRTL Equation (Rij ) 0.47)

1122.05 2335.42
201.87
1953.32
1152.95 2080.33
405.76
748.71
1076.94 1867.50 2087.32
-720.14
955.81 1736.28 3262.95 -1321.80
798.97 1677.14 3273.88 -1276.15

1017.69
675.59
356.99
772.57
336.45
682.19
-3169.94 6386.25
nonazeotrope

742.81
-1756.93
-1878.13
-1322.34
4052.22

-248.16
3111.02
3171.35
2068.87
-2195.90

585.71
573.83
473.68
334.66
164.50

Table 5. Predicted Azeotropic Temperatures and Compositions of the Quaternary System Cyclohexane (1) + 2-Propanol
(2) + Ethyl Acetate (3) + Butanone (4)
predicted
P/kPa

T/K

x1

x2

deviations
x3

x4

Wilson Equation
0.0484
0.42
0.0030
0.50
0
0.93
0
0.53
0
0.05

x1

x2

x3

x4

101.3
302.0
502.0
702.0
902.0

342.10
377.32
396.02
409.43
420.08

0.4973
0.4736
0.4152
0.3726
0.3386

0.3068
0.5212
0.5831
0.6264
0.6604

0.1475
0.0022
0.0013
0
0

0.0086
0.0030
-0.0069
-0.0010
-0.0036

0.0297
0.0502
0.0283
0.0000
0.0026

-0.0061
-0.0473
-0.0217
0
0

-0.0320
-0.0059
0
0
0

101.3
302.0
502.0
702.0
902.0

342.15
377.32
396.01
409.43
420.08

0.4985
0.4738
0.4152
0.3726
0.3385

0.3063
0.5216
0.5832
0.6264
0.6604

NRTL Equation (Rij ) 0.47)

0.1396
0.0556
0.47
0.0098
0.0020
0.0026
0.50
0.0032
0.0013
0
0.92
-0.0069
0
0
0.53
-0.0010
0
0
0.05
-0.0037

0.0292
0.0506
0.0284
0.0000
0.0026

-0.0140
-0.0475
-0.0217
0
0

-0.0248
-0.0063
0
0
0

101.3
302.0
502.0
702.0
902.0

342.93
377.14
395.35
408.48
418.95

0.4945
0.4627
0.4163
0.3780
0.3493

0.2644
0.5099
0.5816
0.6208
0.6497

0.0281
0.0249
0.0020
0
0

-0.0127
0.0389
0.0268
-0.0056
-0.0081

-0.1255
-0.0246
-0.0210
0
0

0.1325
-0.0064
0
0
0

UNIFAC
0.2129
1.25
0.0025
0.32
0
0.26
0
-0.42
0
-1.08

calculated equilibrium vapor composition was equal to the

liquid one within a tolerance level. That is

y i| e  1

(9)

i)1

|xi - yi| e 2

virial coefficient was calculated by the Tsonopoulos10 method. The predicted results are also presented in Table 5.
Conclusions

|1 -

0.0058
-0.0079
-0.0058
0.0044
0.0071

(i ) 1-4)

(10)

where 1 ) 0.00001 and 2 ) 0.0001 are the mole fraction

tolerances in this calculation. In this way, quaternary
azeotropic points for this system were predicted with the
Wilson and NRTL equations and compared with the
experimental results. The calculated temperatures and
compositions and their deviations from the experimental
data are presented in Table 5 and are represented in
Figures 1 and 2 by the solid lines for the Wilson equation
and the dotted lines for the NRTL equation. Because the
quaternary azeotropes degenerate into ternary azeotrope
at 502 kPa, and into binary ones at the pressures of 702
and 902 kPa, the azeotropic temperatures deviate slightly
from the extrapolation of the quaternary azeotropic temperatures.
Prediction of Quaternary Azeotropic Points by
UNIFAC. The quaternary, ternary, and binary azeotropic
temperatures and compositions were predicted by using the
UNIFAC group contribution method15,16 to calculate the activity coefficients in the liquid phase, and using the B-truncated virial equation to calculate the fugacity coefficients
in the vapor phase. The coordination number was calculated by the Skjold-Jorgensen17 method, and the second

The experimental investigation demonstrates that the

cyclohexane + 2-propanol + ethyl acetate + butanone
quaternary system exhibits a minimum boiling azeotrope,
and the azeotropic temperatures and compositions for this
system were determined by using a stainless steel azeotrope apparatus at normal and elevated pressures of 101.3,
302.0, 502.0, 702.0, and 902.0 kPa. However, in this
observation, the quaternary azeotrope degenerates into a
ternary azeotrope at 502 kPa and into a binary one at
pressures higher than 702 kPa. It also makes it clear that
it is difficult to form a quaternary azeotrope because of the
sensitivity of the quaternary compositions and also difficult
to accurately determine the quaternary azeotropic compositions because the quaternary temperature-compositions
surface is too complanated in the vicinity of the azeotrope.
The variation of azeotropic compositions for multicomponent systems with pressures is usually more complicated
than that of binary systems. In general, the relationship
of binary azeotropic compositions to azeotropic temperature
is linear, but this trend does not always hold for multicomponent systems, especially at elevated pressures. Sometimes it turns around and behaves as a curve as observed
in this work (Figure 2) and in the previous work for the
ternary system of benzene + n-heptane + ethanol. However, the relationship of the logarithm of pressure versus
the reciprocal of azeotropic temperature is essentially
linear for binary, ternary, and quaternary azeotropes


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70 Journal of Chemical and Engineering Data, Vol. 48, No. 1, 2003

(Figure 1), which has been confirmed by many experimental observations.
From the azeotropic temperatures and compositions of
the corresponding binary systems, the quaternary azeotropes were predicted with the Wilson and NRTL activity
coefficient models in this work. The calculations satisfactorily agree with the experimental results. It shows that
the Wilson and NRTL equations could be satisfactorily used
to predict quaternary azeotropes from the binary azeotropes at elevated pressures, and that the Wilson and
NRTL equations are of comparable accuracy in the prediction of azeotropes for miscible quaternary systems at
elevated pressures. This means that vapor-liquid equilibrium behavior at elevated pressures for quaternary systems
could also be predicted from the azeotropic data of corresponding binary systems. The quaternary azeotropic azeotropes were also predicted with the UNIFAC group contribution method, but the calculation results suggest that
the deviations are larger than those with the Wilson and
NRTL models.
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(2) Eduljee, G. H.; Tiwari, K. K. Prediction of Ternary Azeotropes.
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(3) Tamir, A.; Wisniak, J. Correlation and Prediction of Boiling
Temperatures and Azeotropic Conditions in Multicomponent
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(4) Tamir, A. New Correlations for Fitting Multicomponent VaporLiquid Equilibria Data and Prediction of Azeotropic Behaviour.
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Received for review May 10, 2002. Revised October 3, 2002.
Accepted October 10, 2002. The financial supports of the National
Natural Science Foundation of China (through the Grant 20176048)
and of the Zhejiang Provincial Natural Science Foundation of China
(Grant No. 299035) are gratefully acknowledged.

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