Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

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Journal of the Taiwan Institute of Chemical Engineers

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Isothermal vaporliquid equilibria for binary mixtures of hexane, heptane, octane,

nonane and cyclohexane at 333.15 K, 343.15 K and 353.15 K
Kun-Jung Lee a, Wei-Kuan Chen a, Jing-Wei Ko b, Liang-Sun Lee c, Chieh-Ming J. Chang a,*
a

National Chung Hsing University, Department of Chemical Engineering, 250 Kuokuang Road, Taichung 402, Taiwan
Process Research Department, Rening & Manufacturing Research Institute, Chiayi 600, Taiwan
c
Department of Chemical and Materials Engineering, National Central University, Chung-li 32001, Taiwan
b

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 7 January 2009
Received in revised form 5 March 2009
Accepted 6 March 2009

Isothermal vaporliquid equilibria at 333.15 K, 343.15 K and 353.15 K for four binary mixtures of
hexane + heptane, heptane + octane, cyclohexane + octane and cyclohexane + nonane have been
obtained at pressures ranged from 0 to 101.3 kPa. The NRTL, UNIQUAC and Wilson activity coefcient
models have been employed to correlate experimental pressures and liquid mole fractions. The nonideal behavior of the vapor phase has been considered by using the SoaveRedlichKwong equation of
state in calculating the vapor mole fraction. Liquid and vapor densities were also measured by using two
vibrating tube densitometers. Phase behaviors of the Pxy diagrams indicate that three mixtures of
hexane + heptane, heptane + octane, cyclohexane + octane were close to the ideal solution. However, the
cyclohexane + nonane mixture presents a large positive deviation from the ideal solution. Only the
cyclohexane + octane mixture is negative in the excess Gibbs energy indicates that it is an exothermic
system.
2009 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords:
Vaporliquid equilibrium
Hexane
Heptane
Octane
Nonane
Cyclohexane
Density
Excess Gibbs energy

1. Introduction
Vaporliquid equilibrium (VLE) data are essential for engineering design of separation processes and unit operations. It is
useful for an extension of a few thermodynamic models
commonly applied for designing petrochemical related processes. Such information can be obtained experimentally or
adopted from generalized methods to calculate properties of
multi-component mixtures. Most liquid systems of industrial
interest deviate from an ideal behavior. Usually, densities of
vapor and liquid phases are important to give a proper size in the
process design of many separation equipments. This study is
aimed to obtain binary vaporliquid equilibrium data of
aromatics and straight-chain solvents, and then to obtain binary
interactional parameters in liquid phase models by using a
gammaphi relationship in order to increase separation efciencies of these distillation towers.
A few commonly used liquid phase activity coefcient models
have been described with detailed (Raal and Muhlbauer, 1998).
The VLE data of the hexane + heptane mixture from 339.5 to

* Corresponding author. Tel.: +886 4 2285 2592; fax: +886 4 2286 0231.
E-mail address: cmchang@dragon.nchu.edu.tw (C.-M. J. Chang).

369.0 K and the heptane + octane mixture from 368.55 to 395.95 K

have been respectively measured at 94 kPa by Wisniak et al.
(1997a,b). Chen et al. (1996) successfully obtain their isobaric VLE
data of the cyclohexane + octane mixture from 353.87 to 398.76 K
at 101.3 kPa. In their studies, binary interaction parameters of
mixtures were obtained to predict phase behavior by examining
experimental data for thermodynamic consistency. Isothermal
density and compressibility of the cyclohexane + nonane mixture
have been measured at 298.15 K, 308.15 K, 318.15 K and 333.15 K
by Alcart et al. (1980). To our knowledge, no isothermal VLE data
from 0 to 101.3 kPa for the mixture of cyclohexane + nonane have
been presented in literature.
In this study, experimental Px data were measured at 333.15 K
and 353.15 K under pressure ranged from 0 to 101.3 kPa for four
binary mixtures of hexane + heptane, heptane + octane, cyclohexane + octane and cyclohexane + nonane by using the isothermal
bubble-point pressure method. These experimental data were then
used to obtain vapor mole fraction (yi), activity coefcient (gi) and
the system excess molar Gibbs free energies (GE). Finally, the phase
equilibrium calculation was carried out by adopting the Soave
RedlichKwong (SRK) equation of state (Soave, 1972) for the vapor
phase and the Wilson, NRTL and UNIQUAC activity coefcient
models (Abrams and Prausnitz, 1975; Orye and Prausnitz, 1965;
Wilson, 1964) for the liquid phase.

1876-1070/$ see front matter 2009 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jtice.2009.03.002

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

574

Nomenclature
a
A12, A21
b
GE
n
N
P
Pc
R
T
Tc
Tr

v
Vi
xi
yi

energy related parameter (m6/mol2)

parameters of the liquid models (K)
volume related parameter (m3/mol)
excess molar Gibbs energies (J/mol)
number of experiments
number of component
pressure (kPa)
critical temperature (kPa)
gas constant (J/mol K)
temperature (K)
critical temperature (K)
reduced temperature
molar volume (m3/mol)
mole volume of pure component i (m3/mol)
liquid mole fraction of component i
vapor mole fraction of component i

Greek symbols
difference
acentric factor
objective function
density (g/cm3)
fugacity coefcient of component i
activity coefcient of component i

d
v
P
r
fi
gi

Superscripts
cal
calculated data
exp
experimental data
L
liquid phase
sat
saturated state
V
vapor phase
Subscript
m
mixture

2. Experimental
2.1. Chemicals
De-ionized water was prepared using a milli-Q purication
system and 99.99% nitrogen was obtained from Air Product Co.
(Taiwan). Both are used for calibration of pressure and temperature related constants for two densitometers. All the chemicals
were standard-grade reagents and purchased from a local supplier,
such as, hexane (SigmaAldrich, 399% pure), heptane (Sigma
Aldrich, 399% pure), octane (Alfa Aesar, 398% pure), cyclohexane
(SigmaAldrich, 399.9% pure) and nonane (Alfa Aesar, 399% pure)
used without further purication.
2.2. Apparatus and procedures
The apparatus used was described by Chang et al. (2005). The
system employed mainly consists of a vacuum pump, a vapor
liquid equilibrium cell equipped with a side-view glass window, a
data acquisition set, and two densitometers, shown in Fig. 1. Two
magnetic circulation pumps (Micropump, 1805R-346) were used
to speed up the achievement of the vaporliquid equilibrium
within 2 h, which is a mixed device of static and dynamic methods.
The equilibrium cell possesses a specic volume of approximately

Fig. 1. Schematic ow diagram of an experimental set-up for vaporliquid phase

equilibrium measurement.

80 mL. Temperature studied at 333.15 K and 353.15 K and

corresponding vapor pressure ranged from 0 to 101.3 kPa. In each
experiment, the equilibrium cell was charged with 50 mL of a pure
liquid or a binary mixture with a certain composition at a xed
temperature. The equilibrium cell was heated and the temperature
was controlled within 0.01 K. Equilibrium was usually reached
after 2 h, when the readings of temperatures, pressures and the
vibration period of the liquid and vapor phases were constant and
unchanged. After the equilibrium, the readings of the bubble pressure
of the system and the density of two phases were recorded. Vibration
periods of vapor and liquid phases were measured by two
densitometers (Anton-Paar, DMA512 and DMA512P) and a digital
data processor (DMA60), and densities of two phases can be obtained
from individual calibration equation described by Kao et al. (2007).
The temperature in the vibrating tube housing of the cell was
thermally controlled by a high-precision circulator (Julabo, F10-HC)
at the same temperature of the equilibrium cell. The temperature in
the circulator was determined using a standard thermometer (Hart
Scientic, model 1506). At a VL equilibrium, the experimental liquid
phase composition (x) was obtained by using a corresponding
equation of x = ar + b from the measured density (r) at known liquid
phase composition. The regression coefcients of these straight lines
all attain 0.999. The correction of liquid phase composition shows
Table 1
Comparison of our experimental densities with literature data at 333.15 K and mole
fraction purity (x) of the liquids.
Liquid

Cyclohexane
n-Hexane
n-Heptane
n-Octane
n-Nonane
a

Source

SigmaAldrich
SigmaAldrich
SigmaAldrich
Alfa Aesar
Alfa Aesar

Reference: Alcart et al. (1980).

102x

99.9
99
99
98
99

r (g/cm3)
Exp.

Lit.a

333.15 K

333.15 K

0.7415
0.6218
0.6499
0.6696
0.6933

0.74036
0.62221
0.64931
0.66938
0.68633

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579
Table 2
Experimental VLE data of hexane(1) + heptane(2) mixture at 333.15 K and 343.15 K.
P (kPa)

x1

rV (103 g/cm3)

T = 333.15 K
27.5
33.3
37.8
42.8
48.1
52.8
57.0
62.0
66.1
71.8
77.1

0.000
0.102
0.199
0.298
0.400
0.497
0.596
0.697
0.796
0.897
1.000

1.017
1.303
1.419
1.574
1.706
1.841
1.927
2.069
2.272
2.326
2.465

T = 343.15 K
39.8
47.1
54.6
60.8
67.0
72.6
79.9
85.4
91.9
97.7
105.4

0.000
0.099
0.211
0.298
0.401
0.495
0.605
0.697
0.811
0.905
1.000

1.380
1.513
1.855
1.998
2.231
2.311
2.569
2.769
2.947
2.986
3.255

rL (g/cm3)

575

Table 4
Experimental VLE data of cyclohexane(1) + octane(2) mixture at 333.15 K and
353.15 K.
P (kPa)

x1

rV (103 g/cm3)

rL (g/cm3)

0.6499
0.6463
0.6430
0.6398
0.6367
0.6339
0.6312
0.6286
0.6262
0.6239
0.6218

T = 333.15 K
10.3
14.2
18.8
22.3
26.0
30.7
34.5
38.9
43.1
48.2
53.0

0.000
0.108
0.208
0.306
0.408
0.503
0.595
0.707
0.796
0.899
1.000

0.422
0.559
0.694
0.779
0.850
1.016
1.113
1.274
1.323
1.481
1.640

0.6696
0.6738
0.6784
0.6837
0.6900
0.6965
0.7034
0.7127
0.7208
0.7309
0.7415

0.6332
0.6296
0.6259
0.6230
0.6199
0.6172
0.6142
0.6119
0.6091
0.6071
0.6051

T = 353.15 K
23.8
29.9
36.8
44.5
52.7
60.5
67.9
75.6
84.4
91.3
99.6

0.000
0.104
0.197
0.302
0.401
0.503
0.593
0.707
0.799
0.896
1.000

0.927
1.068
1.167
1.475
1.752
1.923
2.116
2.371
2.536
2.702
2.979

0.6527
0.6568
0.6611
0.6667
0.6727
0.6797
0.6865
0.6959
0.7043
0.7137
0.7246

that the deviation between the experimental and the prepared liquid
composition is less than 0.001.
The densitometer has a repeatability of about 5(10)5 g/cm3,
the electronic balance has the minimum reading about 1(10)5 g,
the variation of the temperature was found to be less than 0.01 K,
the accuracy of the pressure reading was within 0.1% for the full
scale, and the liquid mole fraction of each component (xi) was
estimated to be deviated within 0.001.
3. Results and discussion

mole fraction.
Pexp P exp

yi

(1)

A classical VLE relationship between the activity coefcient (gi)

and fugacity coefcient (fi) was substituted into the above
equation to result in Eq. (2).

Pexp

 L


2
sat
X
g i xi Pisat fsat
=RT
i exp Vi P  Pi

(2)

fi

i1

3.1. Experimental Pxy and density data

At equilibrium under a given temperature (T), experimental
pressure (Pexp) can be given by Eq. (1), while the yi is the vapor
Table 3
Experimental VLE data of heptane(1) + octane(2) mixture at 333.15 K and 353.15 K.
P (kPa)

x1

rV (103 g/cm3)

rL (g/cm3)

T = 333.15 K
10.3
12.4
14.4
16.0
17.8
19.7
21.5
22.9
24.4
26.0
27.6

0.000
0.116
0.198
0.297
0.399
0.503
0.599
0.696
0.799
0.898
1.000

0.398
0.424
0.496
0.558
0.615
0.656
0.692
0.733
0.785
0.836
0.862

0.6696
0.6667
0.6644
0.6619
0.6597
0.6576
0.6559
0.6539
0.6525
0.6512
0.6499

T = 353.15 K
24.1
27.5
30.4
34.1
37.4
41.4
44.0
47.1
50.4
53.9
56.9

0.000
0.105
0.203
0.299
0.395
0.503
0.604
0.695
0.797
0.897
1.000

0.751
0.852
0.978
1.129
1.255
1.357
1.458
1.559
1.660
1.761
1.862

0.6528
0.6500
0.6475
0.6452
0.6431
0.6409
0.6390
0.6374
0.6358
0.6344
0.6332

where fisat is the fugacity coefcient of pure component i in its

saturated state, the saturated vapor pressure is denoted by P i sat ,
and V i L is the saturated liquid molar volume of pure component i.
The Ponyting pressure correction was considered to be unity in this
study. Then, the gi can be calculated by giving experimental bubble
pressure (Pexp) and liquid mole fraction (xi). The gi was individually
obtained by NRTL, UNIQUAC, or Wilson model. The fi and fisat

Table 5
Experimental VLE data of cyclohexane(1) + nonane(2) mixture at 333.15 K and
353.15 K.
P (kPa)

x1

rV (103 g/cm3)

rL (g/cm3)

T = 333.15 K
3.7
11.8
23.1
32.5
39.8
48.7
53.0

0.000
0.103
0.312
0.519
0.718
0.899
1.000

0.168
0.321
0.688
0.985
1.228
1.511
1.600

0.6933
0.6957
0.7008
0.7090
0.7200
0.7326
0.7415

T = 353.15 K
9.5
24.1
45.1
62.0
76.7
92.2
99.1

0.000
0.104
0.308
0.498
0.701
0.901
1.000

0.425
0.829
1.333
1.933
2.242
2.768
2.964

0.6765
0.6788
0.6837
0.6914
0.7022
0.7160
0.7246

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

576

Table 6
Calculated VLE data of hexane(1) + heptane(2) mixture using NRTL, UNIQUAC and
Wilson models at 333.15 K and 343.15 K.

Table 8
Calculated VLE data of cyclohexane(1) + octane(2) mixture using NRTL, UNIQUAC
and Wilson model at 333.15 K and 353.15 K.

P (kPa)

P (kPa)

x1

SRK/NRTL
Pcal
(kPa)

y1cal

SRK/UNIQUAC

SRK/Wilson

Pcal
(kPa)

Pcal
(kPa)

y1cal

x1

y1cal

SRK/NRTL

SRK/UNIQUAC

SRK/Wilson

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

T = 333.15 K
27.5
0.000
33.3
0.102
37.8
0.199
42.8
0.298
48.1
0.398
52.8
0.497
57.0
0.596
62.0
0.697
66.1
0.796
71.8
0.897
77.1
1.000

28.0
33.2
38.0
42.9
47.8
52.4
57.1
61.9
66.6
71.4
76.3

0.000
0.239
0.405
0.535
0.641
0.724
0.795
0.856
0.909
0.957
1.000

28.0
33.2
38.0
42.9
47.8
52.4
57.1
61.9
66.6
71.4
76.3

0.000
0.239
0.405
0.535
0.641
0.724
0.795
0.856
0.909
0.957
1.000

28.0
33.2
38.0
42.9
47.8
52.4
57.1
61.9
66.6
71.4
76.3

0.000
0.239
0.405
0.535
0.641
0.724
0.795
0.856
0.909
0.957
1.000

T = 333.15 K
10.3
0.000
14.2
0.108
18.8
0.208
22.3
0.306
26.0
0.408
30.7
0.503
34.5
0.595
38.9
0.707
43.1
0.796
48.2
0.897
53.0
1.000

10.4
14.4
18.3
22.2
26.4
30.4
34.3
39.2
43.0
47.5
51.9

0.000
0.353
0.546
0.673
0.766
0.830
0.878
0.923
0.952
0.979
1.000

10.4
14.5
18.4
22.3
26.4
30.4
34.3
39.1
43.0
47.5
51.9

0.000
0.355
0.547
0.673
0.765
0.829
0.877
0.923
0.951
0.979
1.000

10.4
14.4
18.3
22.2
26.4
30.4
34.3
39.2
43.0
47.5
51.9

0.000
0.353
0.546
0.673
0.766
0.830
0.878
0.923
0.952
0.979
1.000

T = 343.15 K
40.0
0.000
47.1
0.099
54.6
0.211
60.8
0.298
67.0
0.401
72.6
0.495
79.9
0.605
85.4
0.697
91.9
0.811
97.7
0.905
105.4
1.000

40.7
47.3
54.7
60.4
66.9
72.7
79.6
85.2
92.2
98.0
103.9

0.000
0.222
0.407
0.521
0.626
0.708
0.789
0.847
0.911
0.957
1.000

40.7
47.3
54.7
60.4
66.9
72.7
79.6
85.2
92.2
98.0
103.9

0.000
0.222
0.407
0.521
0.626
0.708
0.789
0.847
0.911
0.957
1.000

40.7
47.3
54.7
60.4
66.9
72.7
79.6
85.2
92.2
98.0
103.9

0.000
0.222
0.407
0.521
0.626
0.708
0.789
0.847
0.911
0.957
1.000

T = 353.15 K
23.8
0.000
29.9
0.104
36.8
0.197
44.5
0.302
52.7
0.401
60.5
0.503
67.9
0.593
75.6
0.707
84.4
0.799
91.3
0.896
99.6
1.000

23.3
30.5
37.2
44.9
52.4
60.2
67.1
76.0
83.3
90.9
99.1

0.000
0.313
0.494
0.635
0.731
0.806
0.857
0.909
0.943
0.973
1.000

23.3
30.6
37.3
45.1
52.5
60.2
67.2
76.0
83.3
90.9
99.1

0.000
0.316
0.495
0.635
0.730
0.805
0.857
0.909
0.943
0.973
1.000

23.3
30.3
36.9
44.7
52.2
60.3
67.5
76.6
83.9
91.3
99.1

0.000
0.309
0.490
0.634
0.732
0.808
0.860
0.912
0.944
0.973
1.000

were calculated by the SRK equation of state, shown in Eq. (3).

P

RT

vb

(6)

aaT
vv b

(3)

The simple van der Waals mixing rule was used to evaluate the
mixture parameters.

R2 Tc2
Pc

(4)

am

RT c
Pc

(5)

a 0:42748

b 0:08664

x1

N X
N
X
x i x j ai j

(7)

i1 j1

bm

N X
N
X
xi x j bi j

(8)

i1 j1

Table 7
Calculated VLE data of heptane(1) + octane(2) mixture using NRTL, UNIQUAC and
Wilson model at 333.15 K and 353.15 K.
P (kPa)

aT 1 0:48 1:574v  0:176v2 1  Tr0:5 

SRK/NRTL

SRK/UNIQUAC

SRK/Wilson

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

T = 333.15 K
10.3
0.000
12.4
0.116
14.4
0.198
16.0
0.297
17.8
0.399
19.7
0.503
21.5
0.598
22.9
0.696
24.4
0.799
26.0
0.898
27.6
1.000

10.4
12.6
14.2
16.0
17.8
19.6
21.2
22.9
24.6
26.3
28.0

0.000
0.268
0.405
0.534
0.640
0.727
0.796
0.854
0.909
0.956
1.000

10.4
12.6
14.2
16.0
17.8
19.6
21.2
22.9
24.6
26.3
28.0

0.000
0.268
0.405
0.534
0.640
0.727
0.796
0.854
0.909
0.956
1.000

10.4
12.6
14.2
16.0
17.8
19.6
21.2
22.9
24.6
26.3
28.0

0.000
0.268
0.405
0.534
0.640
0.727
0.796
0.854
0.909
0.956
1.000

T = 353.15 K
24.1
0.000
27.5
0.105
30.4
0.203
34.1
0.299
37.4
0.395
41.4
0.503
44.0
0.604
47.1
0.695
50.4
0.797
53.9
0.897
56.9
1.000

23.3
27.2
30.7
34.1
37.3
40.9
44.2
47.2
50.4
53.8
57.0

0.000
0.230
0.390
0.513
0.613
0.707
0.782
0.841
0.899
0.953
1.000

23.3
27.2
30.7
34.1
37.3
40.9
44.2
47.2
50.4
53.8
57.0

0.000
0.230
0.390
0.513
0.613
0.707
0.782
0.841
0.899
0.953
1.000

23.3
27.2
30.7
34.1
37.3
40.9
44.2
47.2
50.4
53.8
57.0

0.000
0.230
0.390
0.513
0.613
0.707
0.782
0.841
0.899
0.953
1.000

For the measurement of the density, two pressure-dependent

calibration constants of the vapor and the liquid densitometer
were determined at constant temperature, using water and
nitrogen as calibrated uids for all investigated pressures, then,
the density of each phase was obtained. Table 1 lists a comparison
Table 9
Calculated VLE data of cyclohexane(1) + nonane(2) mixture using NRTL, UNIQUAC
and Wilson model at 333.15 K and 353.15 K.
P (kPa)

x1

SRK/NRTL

SRK/UNIQUAC

SRK/Wilson

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

Pcal
(kPa)

y1cal

T = 333.15 K
3.7
0.000
11.8
0.103
23.1
0.312
32.5
0.519
39.8
0.718
48.7
0.899
53.0
1.000

3.4
11.5
23.4
32.3
40.0
47.4
51.9

0.000
0.725
0.889
0.937
0.966
0.987
1.000

3.4
11.4
23.4
32.3
40.0
47.4
51.9

0.000
0.723
0.889
0.937
0.966
0.987
1.000

3.4
11.5
23.4
32.3
40.0
47.4
51.9

0.000
0.725
0.889
0.937
0.966
0.987
1.000

T = 353.15 K
9.5
0.000
24.1
0.104
45.1
0.308
62.0
0.499
76.7
0.701
92.2
0.901
99.1
1.000

8.5
23.3
45.8
61.9
76.4
91.1
99.0

0.000
0.667
0.861
0.918
0.953
0.984
1.000

8.5
23.3
45.8
61.9
76.5
91.1
99.0

0.000
0.667
0.861
0.918
0.953
0.984
1.000

8.5
23.3
45.8
61.9
76.5
91.1
99.0

0.000
0.667
0.860
0.918
0.953
0.984
1.000

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

577

Fig. 2. Pxy diagram of hexane(1) + heptane(2) mixture at 333.15 K and 343.15 K.

Fig. 4. Pxy diagram of cyclohexane(1) + octane(2) mixture at 333.15 K and

353.15 K.

of our experimental densities of the liquids at mole fraction purity

(x  98%) with literature data at 333.15 K. The deviations between
these densities are very small. Tables 25 present experimental
data of the liquid mole fraction of one component and the density
of each phase for four binary systems at 333.15 K and 353.15 K,
respectively. Tables 69 lists calculated data including the system
bubble pressure and the vapor mole fraction for four binary
systems at 333.15 K and 353.15 K, respectively. In this study, 11
experiments have been done at each temperature for the VL
equilibrium. Only 7 experiments were carried out at each
temperature for the cyclohexane + nonane system since the
nonane is very expensive. Fig. 2 shows Pxy diagrams of the
hexane + heptane binary mixture at 333.15 K and 343.15 K.
Figs. 35 display Pxy diagrams of the hexane + octane, cyclohexane + octane and cyclohexane + nonane mixtures at 333.15 K

and 353.15 K by using the NRTL, UNIQUAC and Wilson models,

respectively. These three models t experimental data well for all
four binary systems. No azeotrope was found for these four binary
systems. Fig. 6 displays the calculated activity coefcient (gi) using
the NRTL model at 333.15 K (a) and 353.15 K (b), respectively.
Activity coefcients (gi) approaching to the unity indicate three
symmetric systems of the hexane + heptane, heptane + octane and
cyclohexane + octane mixtures are close to an ideal solution.
However, the asymmetric system of the cyclohexane + nonane
mixture was largely deviated from the ideal solution, shown in
Fig. 6.
Usually, the order of magnitude of the Gibbs excess energy in a
binary regular mixing solution is mainly determined by that of the
excess enthalpy because of the excess entropy is small. Fig. 7
displays the calculated excess Gibbs energy (GE) using the NRTL

Fig. 3. Pxy diagram of heptane(1) + octane(2) mixture at 333.15 K and 353.15 K.

Fig. 5. Pxy diagram of cyclohexane(1) + nonane(2) mixture at 333.15 K and

353.15 K.

578

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

Fig. 6. Calculated activity coefcients for four binary mixtures at (a) 333.15 K and
(b) 353.15 K using the NRTL model.

Fig. 7. Calculated excess Gibbs energies for four binary mixtures at (a) 333.15 K and
(b) 353.15 K using the NRTL model.

model at 333.15 K (a) and 353.15 K (b), respectively. The

cyclohexane + octane mixture exhibiting a negative GE value
indicates it is an exothermic system. Other three mixtures of
the hexane + heptane, heptane + octane and cyclohexane + nonane
presenting positive GE values indicate that they belong to
endothermic systems.

function (P).

3.2. Modelling
The experimental results were then used to obtain the binary
parameters by using the SoaveRedlichKwong equation of state
(SRK-EOS) combined with various activity coefcient models of
NRTL, UNIQUAC and Wilson. The expressions of the activity
coefcients models for the NRTL (Santiago et al., 2007), UNIQUAC
(Simoni et al., 2008) and Wilson (Huang and Lee, 1996) are listed in
the literature. The optimal interaction parameters for each binary
system were obtained by minimizing the following objective

#

 n " cal
exp 
100 X
Pk  Pk 
P


2n k1  Pkexp 

(9)

The regression results are shown in Table 10. The root mean square
deviations of dP were dened as follows:
s
Pn cal
exp
k Pk  Pk
dP
n

(10)

The deviation between experimental and calculated equilibrium bubble pressures is reasonably small, and it is indicated that
these three activity coefcient models are suitable to represent the
binary experimental data. The calculated Pxy diagrams of four
binary systems are shown in Figs. 25, respectively. As expected,
nevertheless, there is little difference among three liquid activity

K.-J. Lee et al. / Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 573579

579

Table 10
Optimal binary interaction parameters in NRTL, UNIQUAC and Wilson correlations for four binary mixtures.
T (K)

NRTL
A12

Hexane(1) + heptane(2)
333.15
45.95
343.15
29.19

UNIQUAC
A21
64.95
8.724

dP

A12

Wilson
A21

dP

A12

A21

dP

0.366
0.529

51.15
27.22

60.49
34.23

0.366
0.529

78.27
38.24

60.49
17.86

0.366
0.529

34.58
86.86

10.36
57.60

0.221
0.309

Heptane(1) + octane(2)
333.15
35.46
353.15
42.85

11.09
73.14

0.221
0.310

21.44
52.93

27.97
64.17

0.221
0.310

Cyclohexane(1) + octane(2)
333.15
16.41
353.15
128.8

14.32
122.0

0.452
0.564

51.93
23.59

51.92
23.59

0.453
0.595

120.6
145.8

Cyclohexane(1) + nonane(2)
333.15
61.93
353.15
182.1

136.6
33.85

0.673
0.678

107.3
81.20

0.677
0.683

295.1
238.8

193.6
157.8

151.2
320.7

89.73
16.76

0.452
0.463

0.671
0.668

NRTL: A12 = (g12  g22)/R; A21 = (g21  g11)/R; a = 0.3.

UNIQUAC: A12 = (U12  U22)/R; A21 = (U21  U11)/R.
Wilson: A12 = (l12  l22)/R; A21 = (l21  l11)/R.
s
Pn cal
exp
k Pk  Pk
dP
.
n

coefcient models for the four binary systems studied. Figs. 6 and 7
individually show the calculated activity coefcient (gi) and excess
Gibbs energy (GE) using the NRTL model.
4. Conclusions
Vaporliquid equilibria of four binary mixtures of hexane,
heptane, octane, nonane and cyclohexane have successfully been
obtained at 333.15 K, 343.15 K and 353.15 K in this study.
Experimental data of phase densities, liquid mole fractions and
system pressures were determined using the bubble-point method
coupled with two vibration densitometers. Three activity coefcient models have been employed to correlate the experimental
data and the results are satisfactory. The calculated activity
coefcient and excess Gibbs energy values reveal that the
hexane + heptane, heptane + octane and cyclohexane + octane
systems were close to the ideal solution. However, the cyclohexane + octane system shows a high deviation from the ideal
solution. The associated binary interaction parameters between
each component for four mixtures were nally obtained from the
optimal correlation of our experimental data.
Acknowledgements
The authors would like to thank the National Science Council of
the Republic of China, Taiwan for nancially supporting this
research (NSC 97-2622-E005-011-CC1). This work is also supported in part by the ministry of Education, Taiwan, ROC under the
ATU plan and China Petroleum Company and National Chung
Hsing University project (EEA9715003).

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