Fluid Phase Equilibria 313 (2012) 190195

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Fluid Phase Equilibria

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Isobaric vaporliquid equilibrium for the binary mixtures of nonane with

cyclohexane, toluene, m-xylene, or p-xylene at 101.3 kPa
Bhupender S. Gupta, Ming-Jer Lee
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106-07, Taiwan

a r t i c l e

i n f o

Article history:
Received 24 August 2011
Received in revised form 11 October 2011
Accepted 12 October 2011
Available online 18 October 2011
Keywords:
Isobaric
Vaporliquid equilibrium
Nonane
Cyclohexane
Aromatics

a b s t r a c t
The isobaric vaporliquid equilibrium (VLE) data were determined, by using a recirculation type
apparatus, for the binary mixtures of nonane with cyclohexane, toluene, m-xylene, or p-xylene at
101.3 kPa. All the data passed the thermodynamic consistency test and no azeotrope was formed in
the investigated binary systems. While nonane + p-xylene were found to behave as near ideal systems,
nonane + cyclohexane, nonane + toluene, and nonane + m-xylene exhibited large deviations from ideal
behavior. The experimental results were used as a basis to check the validity of two predictive models,
the UNIFAC and the conductor-like screening model for realistic solvents (COSMO-RS) models. These new
VLE data were also correlated with the Wilson, the NRTL, and the UNIQUAC activity coefcient models.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The separation of aromatic hydrocarbons (such as benzene,
toluene, alkylbenzenes, and xylenes) from aliphatic hydrocarbons
(such as hexane, heptane, octane, nonane, and decane) mixtures is
commonly encountered in renery and petrochemical industries.
To develop the separation processes, vaporliquid equilibrium
(VLE) data of the related mixtures are fundamentally important. In
the present study, we focus on the phase equilibrium properties for
the mixtures containing nonane. Among several other studies [14]
on the physical properties of this class of mixtures, the isobaric
VLE data at 101.3 kPa for the binary systems of cyclohexane + oxylene, + p-xylene, + m-xylene and heptane + o-xylene, + p-xylene,
+ m-xylene were reported by Tojo et al. [5,6] For the binary mixtures containing nonane, Calvar et al. [7] measured the densities
of nonane + benzene at 313.15 K under atmospheric pressure and
Aicart et al. [8] reported the isothermal density and compressibility
data of the nonane + cyclohexane at temperatures from 298.15 K to
333.15 K. Using density measurements to determine liquid phase
compositions, Chen et al. [9] and Lee et al. [10] reported the isothermal P-x data of nonane + benzene and nonane + cyclohexane at
temperatures ranging from 313.15 K to 353.15 K. Since the vapor
phase compositions were not measured, thermodynamics consistency test cannot be made for those VLE data.

Corresponding author. Tel.: +886 2 2737 6626; fax: +886 2 2737 6644.
E-mail address: mjlee@mail.ntust.edu.tw (M.-J. Lee).
0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.10.009

In the present study, the isobaric VLE measurements were

conducted for the binary systems of nonane with cyclohexane,
toluene, m-xylene, or p-xylene at 101.3 kPa by using an Othmertype recirculating still. The obtained VLE data were veried with
the Herington [11] thermodynamic consistency test. These new VLE
data are used to examine the validity of two predictive activity coefcient models, the UNIFAC [12] and the conductor-like screening
model for realistic solvents (COSMO-RS) [1315]. In the VLE calculation, the fugacity coefcient of each constituent compound in
the vapor phase was estimated from the two-term virial equation
together with the Hayden-OConnell (HOC) model [16] for calculating the second virial coefcients. The new VLE data were also
correlated with three correlative models, the Wilson [17], the NRTL
[18], and the UNIQUAC [19].
2. Experimental
2.1. Materials
The purity levels and sources of the chemicals used in this study
are reported in Table 1. These all substances were checked with
gas chromatography analysis. No impurity peak was detected. The
purity of the chemicals was also assessed by comparing their measured density () and normal boiling point with literature values
[2025] as shown in Table 2, where the density data were measured
by using a digital vibrating-tube densimeter (DMA 4500, Anton
Paar, Austria) with an accuracy of 0.00005 g cm3 and the normal boiling points were measured by an Othmer-type recirculating
still with an uncertainty of 0.1 K. The tabulated values reveal that

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 313 (2012) 190195

191

Table 1
Materials description.
Chemical name

Source

Mass fraction purity

Purication method

Nonane
Benzene
Cyclohexane
Toluene
m-Xylene
p-Xylene

Aldrich, USA
Reidel-dehaen, GmbH, Germany
Acros, USA
Aldrich, USA
Acros, USA
Alfa Aeser, USA

0.9998
0.9997
0.9998
0.9996
0.9999
0.9995

None
None
None
None
None
None

Table 2
Densities () at T = 298.2 K and the normal boiling points Tb of the pure components.a
Compound

Nonane
Cyclohexane
Benzene
Toluene
m-Xylene
p-Xylene
a

/(g cm3 )

Tb /K

This work

Literature

This work

Literature

0.71407
0.77386
0.87366
0.86218
0.86007
0.81097

0.71402 [20]
0.77382 [22]
0.87360 [23]
0.86219 [23]
0.86009 [23]
0.81098 [23]

423.8
353.7
353.3
383.4
412.0
411.4

423.8 [21]
353.73 [22]
353.20 [24]
383.75 [23]
412.25 [25]
411.50 [25]

u() = 0.00005 g cm3 ; u(T) = 0.1 K

the agreement between our measurements and literature values

is satisfactorily well. All the chemicals were used without further
purication.

Table 3
Experimental VLE data for binary system of toluene (1) + benzene (2) at 101.3 kPa.a
T/K

x1

y1

353.3
355.8
358.5
358.5
362.1
362.9
366.3
366.3
369.8
373.5
378.4
380.2
383.8

0.000
0.099
0.217
0.222
0.367
0.402
0.517
0.511
0.638
0.735
0.869
0.913
1.000

0.000
0.043
0.107
0.107
0.202
0.208
0.310
0.310
0.432
0.538
0.758
0.825
1.000

u(T) = 0.1 K; u(x1 ) = 0.001; u(y1 ) = 0.001.

3. Experimental results
2.2. Apparatus and experimental procedure
To validate the experimental method, the VLE data of toluene
(1) + benzene (2) at 101.3 kPa was measured and compared with
the literature values [27,28]. The experimental data (T, x1 , and
y1 ) is listed in Table 3 and the comparison is shown in Fig. 1. As
can be seen, the agreement is satisfactorily well. The apparatus
was then employed to measure the VLE data for four binary systems of nonane with cyclohexane, toluene, m-xylene, or p-xylene
at 101.3 kPa. The VLE phase diagrams of nonane (1) + cyclohexane
(2) and nonane (1) + toluene (2) are presented in Fig. 2 and nonane
(1) + m-xylene (2) and nonane (1) + p-xylene (2) in Fig. 3. Fig. 4 is a
plot of xy for all these studied systems. Non-azeotropic behavior
was observed in any investigated binary system.

390

380

T/K

In the present study, an Othmer-type recirculating VLE still

(NGW Co., Germany) was employed to measure isobaric VLE data.
The schematic diagram of this apparatus and the detailed operating
procedure have been given by Shiah et al. [26] In each experimental run, about 100 cm3 of liquid mixture was charged into
the still and then heating up gently. To maintain the isobaric
condition (at 101.3 0.2 kPa) in the equilibrium cell during the
experimental course, the recirculating still connected to a pressure
adjustment system, which was composed of a graduated burette
with an elevation-adjustable water reservoir. The cell pressure
was kept at 101.3 0.2 kPa by adjusting the water-level difference between the burette and the water reservoir to compensate
the pressure difference between local atmospheric pressure and
101.3 kPa. The atmospheric pressure was measured by a Fortin
mercury barometer (model 453, stability = 0.1 kPa, Princo Instruments, USA). Typically cells temperature maintained at a constant
for 2 h, at least, equilibrium state was attained and equilibrium
temperature was recorded. The equilibrium temperature was measured by a digital thermometer (TES 1310 type-K) calibrated with
a high precision thermometer (Model-1560, Hart Scientic Co., USA)
to an uncertainty of 0.1 K.
Vapor and liquid samples were collected for analysis as equilibrium state was attained. Three or more replicated samples were
taken for each phase. The composition of samples was determined
by a gas chromatography (model 8700, China Chromatography, Taiwan), equipped with a thermal conductivity detector. A
stainless-steel column (model SE-30, Supelcoport, 80/100 mess,
14 1/8 , 20%) was used in this study for composition analysis.
High purity helium gas (purity: 0.9999) was used as a carrier gas. For
each binary system, the response of gas chromatography analysis
was calibrated with several standard mixtures of known composition prepared gravimetrically, over the entire composition range.
With the aid of the calibration curve, each phase composition was
determined from the average of three replications. The uncertainty
of the composition determination was estimated to within 0.001
in mole fraction.

370

360

350
0.0

0.1

0.2

0.3

0.4

0.5

x1, y1

0.6

0.7

0.8

0.9

1.0

Fig. 1. Experimental boiling points at 101.3 kPa against mole fraction of toluene for
toluene (1) + benzene (2) system: (), liquid phase and (o), vapor phase from this
work; (), vapor phase and (), liquid phase compositions from reference [27]; (),
vapor phase and (), liquid phase from reference [28].

192

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 313 (2012) 190195

1.0

420

0.9
0.8

400

0.7

390

0.6

380

y1

T/K

410

0.5
0.4

370

0.3

360

0.2

350
0.0

0.1
0.1

0.2

0.3

0.4

0.5

x1 , y1

0.6

0.7

0.8

0.9

1.0

Fig. 2. Plot of experimental boiling point temperature at 101.3 kPa against mole
fraction of nonane: (), experimental liquid phase and (o), experimental vapor phase
for nonane (1) + cyclohexane (2); (), experimental liquid phase and (), experimental vapor phase for nonane (1) + toluene (2); , calculated liquid and vapor
compositions from the NRTL model; - - - -, calculated liquid and vapor compositions from the UNIQUAC model; , calculated liquid and vapor compositions from
the Wilson model; . . .., predicted liquid and vapor compositions from the UNIFAC
model; , predicted liquid and vapor compositions from the COSMO-RS model.

The experimental results are reported in Tables 47 for the

systems containing cyclohexane, toluene, m-xylene, and p-xylene,
respectively. The tabulated activity coefcient ( i ) was calculated
from the following equation:

i =

(Bii ViL )(P Pis ) + (1 yi )2 Pij

yi P
exp
RT
xi Pis

(1)

with ij = 2Bij Bii Bjj

(2)

where xi and yi are the compositions of liquid and vapor phase,

respectively, and P is the total pressure. Pi s is the vapor pressure of
pure components which was calculated from the extended Antoine
equation. The Antoine constants for each component are listed in
Table 8. The variables Bii and Bjj are the second virial coefcient

0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

x1
Fig. 4. Plot of experimental mole fraction of vapor phase (y1 ) against mole fraction
of liquid phase (x1 ) of nonane at 101.3 kPa: (o), nonane (1) + cyclohexane (2); (),
nonane (1) + toluene (2); (), nonane (1) + m-xylene; (), nonane (1) + p-xylene (2).
Table 4
Experimental VLE data for binary system of nonane (1) + cyclohexane (2) at
101.3 kPa.a
T/K

x1

y1

1

2

353.7
354.8
357.9
364.4
369.6
376.1
382.8
389.9
399.0
401.4
410.9
416.0
420.8
423.8

0.000
0.061
0.161
0.275
0.405
0.499
0.596
0.715
0.802
0.833
0.910
0.951
0.982
1.000

0.000
0.005
0.020
0.052
0.085
0.134
0.200
0.295
0.443
0.477
0.679
0.779
0.912
1.000

0.734
0.984
1.170
1.074
1.093
1.090
1.067
1.083
1.047
1.044
1.000
1.002
1.000

1.000
1.033
1.043
0.977
1.003
0.956
0.932
0.990
0.924
0.978
0.922
1.058
1.051

u(T) = 0.1 K; u(x1 ) = 0.001; u(y1 ) = 0.001

of pure component i and j, respectively, and Bij is the cross second

virial coefcient. All the second virial coefcients were estimated
from the Hayden and OConnell (HOC) model [16] with the critical properties, acentric factors, and dipole moments tabulated in

425

T/K

420
Table 5
Experimental VLE data for binary system of nonane (1) + toluene (2) at 101.3 kPa.a

415

410

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

x1, y1
Fig. 3. Plot of experimental boiling point temperature at 101.3 kPa against mole
fraction of nonane: (), experimental liquid phase and (o), experimental vapor phase
for nonane (1) + m-xylene (2); (), experimental liquid phase and (), experimental
vapor phase for nonane (1) + p-xylene (2); , calculated liquid and vapor compositions from the NRTL model; - - - -, calculated liquid and vapor compositions from
the UNIQUAC model; , calculated liquid and vapor compositions from the Wilson model; . . .., predicted liquid and vapor compositions from the UNIFAC model;
, predicted liquid and vapor compositions from the COSMO-RS model.

T/K

x1

y1

1

2

383.4
384.5
386.1
387.7
390.5
395.4
399.1
401.1
403.8
405.0
407.5
412.7
416.4
420.7
423.8

0.000
0.078
0.156
0.222
0.336
0.484
0.581
0.629
0.680
0.707
0.765
0.858
0.918
0.973
1.000

0.000
0.033
0.064
0.093
0.151
0.240
0.321
0.359
0.425
0.456
0.520
0.673
0.782
0.916
1.000

1.300
1.197
1.161
1.140
1.082
1.080
1.052
1.066
1.063
1.044
1.045
1.029
1.018
1.000

1.000
1.030
1.043
1.050
1.070
1.087
1.091
1.107
1.079
1.084
1.124
1.126
1.197
1.277

u(T) = 0.1 K; u(x1 ) = 0.001; u(y1 ) = 0.001.

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 313 (2012) 190195
Table 6
Experimental VLE data for binary system of nonane (1) + m-xylene (2) at 101.3 kPa.a

193

Table 10
Results of the Herington thermodynamic consistency test.

T/K

x1

y1

1

2

System

DJ

412.0
412.1
412.2
412.8
413.0
413.4
414.4
415.4
416.5
417.4
418.8
420.0
422.1
423.8

0.000
0.034
0.144
0.268
0.299
0.359
0.458
0.549
0.642
0.708
0.792
0.852
0.947
1.000

0.000
0.029
0.123
0.230
0.250
0.304
0.389
0.466
0.562
0.626
0.722
0.798
0.921
1.000

1.157
1.155
1.141
1.106
1.108
1.082
1.053
1.055
1.041
1.035
1.031
1.015
1.000

1.000
1.009
1.026
1.037
1.049
1.054
1.067
1.093
1.099
1.125
1.135
1.125
1.169

Nonane + cyclohexane
Nonane + toluene
Nonane + m-xylene
Nonane + p-xylene

0.7
5.1
2.7
5.2

u(T) = 0.1 K; u(x1 ) = 0.001; u(y1 ) = 0.001.

Table 7
Experimental VLE data for binary system of nonane (1) + p-xylene (2) at 101.3 kPa.a
T/K

x1

y1

1

2

411.4
412.6
413.9
415.0
416.1
417.3
418.4
419.5
420.7
421.9
423.2
423.4
423.8

0.000
0.107
0.227
0.325
0.443
0.527
0.633
0.715
0.787
0.875
0.954
0.971
1.000

0.000
0.087
0.189
0.269
0.371
0.446
0.550
0.638
0.716
0.830
0.936
0.957
1.000

1.088
1.075
1.038
1.020
0.999
0.997
0.995
0.984
0.995
0.996
0.995
1.000

1.000
0.994
0.988
0.992
1.006
1.013
1.033
1.042
1.062
1.053
1.045
1.108

4. VLE calculation
Based on the experimental VLE data, we test the predictive capability of a group-contribution based model: UNIFAC [12] and a
quantum approach based model: COSMO-RS [1315] for VLE calculations. The results of COSMO-RS are obtained by using the software
of COSMOtherm. Figs. 2 and 3 compare graphically the predicted
results with experimental values. For nonane + cyclohexane and
nonane + toluene, the predictions from both models generally agree
well with the experimental values. As seen from Fig. 3, the predictive capability of the UNIFAC model is also acceptable for
nonane + m-xylene, but not a case of the COSMO-RS model for this
system and it appears that both two models fail to quantitatively
predict the VLE properties for nonane + p-xylene.
The experimental VLE data were also correlated with the
Wilson-HOC, the NRTL-HOC, and the UNIQUAC-HOC models,
respectively. The binary parameters of the solution models were
determined on the basis of the maximum likelihood principle by
minimization of the following objective function, :
 =

np 
expt 2

(P calc P
)

k=1

u(T) = 0.1 K; u(x1 ) = 0.001; u(y1 ) = 0.001.


Table 9. Vi L is the liquid molar volume of pure component i at equilibrium temperature which was obtained from modied Racket
equation (Yamada and Gunn [29]).
To check the quality of experimental data, we used Herington
area test method [11] to check the thermodynamic consistency of
all the experimental data. The isobaric VLE data was considered as
thermodynamically consistent if DJ < 10. The results of the consistency test are listed in Table 10, indicating that all the systems are
passed the consistency test.

p
expt

calc x
(x1,k
)
1,k

x1


+


+

expt

(Tkcalc Tk

2

T

expt

calc y
(y1,k
)
1,k

y1

(3)

expt

where Tk
and Tkcalc are the experimental and the calculated boiling point temperatures, respectively. Summation was performed
overall experimental points. The standard deviations () of the
measured variables are 0.2 kPa for pressure, 0.1 K for temperature,
0.001 for liquid composition, and 0.001 for vapor composition. In
the VLE data reduction, the value of ij in the NRTL model was xed

Table 8
Parameters of the extended Antoinea , b equation.
Compound

A1

B2

C3

D4

E5

F6

G7

TL /K

TU /K

Nonane
Cyclohexane
Benzene
Toluene
m-Xylene
p-Xylene

102.44
44.17
76.19
70.03
78.19
81.81

9030.40
5226.40
6486.20
6729.80
7615.90
7741.20

0
0
0
0
0
0

0
0
0
0
0
0

12.88
4.22
9.21
8.17
9.30
9.86

7.85 106
9.75 1018
6.98 106
5.30 106
5.56 106
6.07 106

2.0
6.0
2.0
2.0
2.0
2.0

219.66
279.69
278.68
178.18
255.30
286.41

594.60
553.80
562.05
591.75
617.00
616.20

a
b

Taken from Aspen property databank.

Extended Antoine equation: ln(PS ) = A1 + B2 /(T + C3 ) + D4 T + E5 lnT + F6 TG7 for TL < T < TU , where PS is in kPa and T in K.

Table 9
Physical properties and parameters of pure components.a
Compound

TC /K

PC /kPa

VC /(cm3 mol1 )

/Debye

ZC

Nonane
Cyclohexane
Toluene
m-Xylene
p-Xylene

594.60
553.80
591.75
617.00
616.20

2290
4080
4108
3541
3511

551
308
316
375
378

0
0
0.3597
0.2997
0

0.255
0.273
0.264
0.259
0.259

0.4435
0.2080
0.2640
0.3265
0.3218

5.476
3.240
2.968
3.536
3.536

6.523
4.047
3.923
4.658
4.658

All the properties were taken from Aspen properties databank.

194

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 313 (2012) 190195

Table 11
Calculated results of VLE data correlation.
Model

Parameters

RMSD Ta /K

RMSD Pa /kpa

RMSD x1 a

RMSD y1 a

Nonane (1) + cyclohexane (2)

M12 = 14.94
Wilsonb
M21 = 2.46
NRTLc , d
A12 = 4.21
A21 = 5.42
P12 = 2.13
UNIQUACe
P21 = 5.06

N12 /K = 7026.76
N21 /K = 1369.88
B12 /K = 544.64
B21 /K = 1578.66
Q12 /K = 1107.99
Q21 /K = 2441.28

0.36

0.009

0.005

0.018

0.62

0.017

0.006

0.007

0.37

0.009

0.005

0.018

Nonane (1) + toluene (2)

M12 = 1.08
Wilsonb
M21 = 0.71
NRTLc,d
A12 = 0.30
A21 = 2.58
P12 = 1.39
UNIQUACe
P21 = 2.08

N12 /K = 1075.08
N21 /K = 544.44
B12 /K = 375.70
B21 /K = 1514.28
Q12 /K = 761.10
Q21 /K = 1161.51

0.40

0.012

0.004

0.016

0.53

0.015

0.005

0.014

0.39

0.011

0.003

0.017

Nonane (1) + m-xylene (2)

Wilsonb
M12 = 0.94
M21 = 1.37
NRTLc , d
A12 = 0.14
A21 = 0.08
e
UNIQUAC
P12 = 8.45
P21 = 6.20

N12 /K = 584.04
N21 /K = 616.71
B12 /K = 141.57
B21 /K = 188.94
Q12 /K = 3334.69
Q21 /K = 2449.27

0.19

0.005

0.001

0.009

0.20

0.006

0.001

0.009

0.21

0.006

0.001

0.009

Nonane (1) + p-xylene (2)

M12 = 6.24
Wilsonb
M21 = 3.90
c,d
NRTL
A12 = 2.51
A21 = 4.40
UNIQUACe
P12 = 0.04
P21 = 0.20

N12 /K = 2465.03
N21 /K = 1522.17
B12 /K = 871.47
B21 /K = 1618.26
Q12 /K = 71.89
Q21 /K = 27.75

0.14

0.004

0.0008

0.005

0.15

0.004

0.0008

0.005

0.15

0.004

0.0008

0.005

a
b
c
d
e

RMSD M = 1/np

np

exp t 2

k=1

(Mkcalc Mk

0.5

, where np is the number of data points and M represents T, P, x1 or y1 .

Wilson model: ln Aij = [Mij + Nij /T].

NRTL model:
ij = [Aij + Bij /T].
The value of was xed to be 0.3 for each binary system.
UNIQUAC model:
ij = [exp(Pij +Qij /T)].

to be 0.3. The extended Antoine equation was used to calculate the

saturated vapor pressure and Table 8 lists the Antoine constants for
each constituent compound.
The correlated results are listed in Table 11 and also illustrated graphically in Figs. 2 and 3. A close observation of these
graphs reveals that the curves of these three models are almost

35

GE = RT (x1 ln 1 + x2 ln 2 )

30

where the activity coefcients,  i , were calculated from the Wilson

model with the binary parameters as given in Table 11. Fig. 5 illustrates the excess Gibbs free energy varying with composition for
these four systems. Positive deviations from the Raoults law were
found from all these four binary systems. The values of the excess
Gibbs free energy for these nonane-containing systems follow the
order of m-xylene > toluene > cyclohexane  p-xylene.

25

GE/R/K

overlapping with the experimental data points. All these three

models with the tabulated parameters represent satisfactorily for
the VLE properties of the nonane-containing systems at 101.3 kPa.
In general, the Wilson model yields slightly better results than two
other models.
To evaluate the non-ideality of these investigated systems, we
estimated the excess Gibbs free energies GE from the following
equation:

20

(4)

15

5. Conclusion
10
5
0
0.0

0.1

0.2

0.3

0.4

0.5

x1

0.6

0.7

0.8

0.9

1.0

Fig. 5. Plot of calculated excess Gibbs free energy from the Wilson model
against mole fraction of nonane: - -, nonane (1) + cyclohexane (2); - - - -, nonane
(1) + toluene (2); , nonane (1) + m-xylene (2); . . .., nonane (1) + p-xylene (2).

Isobaric VLE data were measured for the binary systems

composed of nonane with cyclohexane, toluene, m-xylene, or
p-xylene at 101.3 kPa over the entire composition range. All
the experimental data were passed the Herington thermodynamic consistency test and exhibited positive deviations from
the Raoults law. No azeotrope was formed in these four binary
systems. It was also found that the non-ideality in the liquid
phase for these nonane-containing systems followed the order of
m-xylene > toluene > cyclohexane  p-xylene. These new VLE data
were used to examine the predictive capability of two solution

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 313 (2012) 190195

models, the UNIFAC and the COSMO-RS models. It was found that
both two models failed to quantitatively predict the VLE properties
for nonane + p-xylene, while the COSMO-RS model was also invalid
to nonane + m-xylene. The new VLE data were also correlated with
three activity coefcient models incorporating with the HOC model.
In general, the correlations are satisfactorily well, and the Wilson
model yielded slightly better results.
List of symbols

Aij , Bij
A1 G7
B
D, J
G
Mij , Nij
np
P
Pij , Qij
q
r
R
T
u
V
x
y
Z

parameters of the NRTL model

coefcients of the extended Antoine equation
second virial coefcient (cm3 mol1 )
variables used in Herington consistency test
Gibbs free energy (J mol1 )
parameters of the Wilson activity coefcient models
number of data points
pressure (kPa)
parameters of the UNIQUAC model
surface area parameter of the UNIQUAC model
volume parameter of the UNIQUAC model
gas constant (J mol1 K1 )
temperature (K)
uncertainty
molar volume (cm3 mol1 )
mole fraction in liquid phase
mole fraction in vapor phase
compressibility factor

Greek letters

non-randomness parameter of the NRTL model


activity coefcient
dipole moment (debye)


objective function
density (g cm3 )


standard deviation
acentric factor

Subscripts
b
normal boiling
c
critical property
i, j
components i and j
ij
i-j pair interaction
lower bound
L
U
upper bound

195

Superscripts
calculated value
calc
expt
experimental value
excess property
E
S
saturation
Acknowledgements
The authors are grateful for nancing provided by the National
Science Council, Taiwan, through grant no. NSC99-2221-E-011079-MY3, and also thank for Dr. Ho-mu Lin for valuable discussions.
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