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Fluid Phase Equilibria 260 (2007) 354358

Short communication

Binary interaction parameter kij for calculating the second

cross-virial coefficients of mixtures
Long Meng a , Yuan-Yuan Duan a, , Xiao-Dong Wang b
a

Key Laboratory for Thermal Science and Power Engineering of MOE, Tsinghua University, Beijing 100084, PR China
Department of Thermal Engineering, School of Mechanical Engineering, University of Science and Technology Beijing, Beijing 100083, PR China
Received 1 June 2007; received in revised form 15 July 2007; accepted 16 July 2007
Available online 20 July 2007

Abstract
The binary interaction parameters, kij , of 119 mixtures were determined by fitting the second cross-virial coefficients of mixtures with correlations
for pure compounds [L. Meng, Y.Y. Duan, L. Li, Fluid Phase Equilib. 226 (2004) 109120; L. Meng, Y.Y. Duan, Fluid Phase Equilib., 258 (2007)
2933] and classical mixing rules. The mixtures included nonpolar/polar (associated), polar/polar, quantum/nonpolar (quantum) binaries. Very
simple correlations for kij of H2 O/n-alkane, CO/nonpolar and quantum/nonpolar (quantum) binaries were successfully developed. The results show
that the present correlations can accurately predict the second cross-virial coefficients.
2007 Elsevier B.V. All rights reserved.
Keywords: Second cross-virial coefficients; Mixtures; kij ; Correlation

1. Introduction
Meng et al. [1] presented an empirical correlation for the second virial coefficients of both nonpolar and polar fluids based on
the corresponding-states principle and then extended the correlation to associated and quantum fluids [2]. Meng and Duan [3]
also reported the values of kij for nonpolar/nonpolar mixtures.
The correlation for pure compounds has the form [1]:
BPc
= f (0) (Tr ) + f (1) (Tr ) + f (2) (Tr )
RTc

(1)

where B is the second virial coefficient, Tr (=T/Tc ) the reduced

temperature, Pc and Tc the critical pressure and temperature,
R = 8.314471 J mol1 K1 the universal gas constant, and is
the acentric factor. f (0) is the spherical term, f (1) is the nonpolar
term and f (2) is the polar, associated or quantum term [2]. For
binary mixtures, the classical mixing rule is
Bm =


i

xi xj Bij

Corresponding author. Tel.: +86 10 6279 6318; fax: +86 10 6277 0209.
E-mail address: yyduan@mail.tsinghua.edu.cn (Y.-Y. Duan).

0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.044

(2)

where xi is the mole fraction of component i, Bm is termed the

mixture virial coefficient and Bij is the second cross-virial coefficient. When Eq. (1) is used to calculate Bij , Pc , Tc and should
be replaced by Pcij , Tcij and ij defined by
Tcij = (Tci Tcj )1/2 (1 kij )
Pcij =

ij =

4Tcij (Pci vci /Tci + Pcj vcj /Tcj )

1/3

1/3 3

(vci + vcj )
i + j
2

(3)
(4)

(5)

where vci and vcj are the critical volumes of components i and
j. The characteristic parameter kij expresses the deviation from
the geometric mean for Tcij . The values of kij obtained using different methods can differ. Inappropriate use of these results may
then lead to misleading observations concerning the inherent law
for kij . Therefore, only second cross-virial coefficient data were
used to evaluate the binary interaction parameters kij in this work
to improve the representation of the second virial coefficients for
binary mixtures. Many new, high-quality experimental data for
the second cross virial coefficient has been published since the
1980s. Most of them were recently collected by Dymond et al.
[4]. This data with new correlations for the second virial coefficients of pure fluids [1,2] can be used to update the binary

L. Meng et al. / Fluid Phase Equilibria 260 (2007) 354358

355

Table 1
Optimum values of kij and deviations for binary mixtures
Compound i

Compound j

No. of points

kij

RMSD (cm3 mol1 )

Present worka

Nonpolar +polar
Argon
Argon
Argon
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Nitrous oxide
Nitrous oxide
Nitrogen
Nitrogen
Nitrogen
Nitrogen
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Carbon monoxide
Butane
Methane
Ethane
Propane
Hexane

Chloromethane
Fluoromethane
1,1-Difluoroethane
Propanone
Diethyl ether
Chloromethane
Trichloromethane
Dichloromethane
3-Pentanone
Propanone
Dichloromethane
Diethyl ether
Chloromethane
Trichloromethane
3-Pentanone
Naphthalene
Phenanthrene
Propanone
Trichloromethane
Dichloromethane
Nitric oxide
Argon
Carbon dioxide
Krypton
Nitrogen
Methane
Ethene
Propane
Butane
2-Methylpropane
Pentane
Benzene
Octane
Acetonitrile
Propanone
Chloromethane
1,1,1,2-Tetrafluoroethane
Diethyl ether

9
4
6
14
10
11
8
11
8
6
11
10
11
8
8
13
11
8
5
11
9
22
18
5
13
11
7
11
5
5
8
11
7
4
7
7
8
4

0.266
0.153
0.145
0.024
0.019
0.054
0.067
0.060
0.009
0.143
0.084
0.030
0.135
0.024
0.033
0.158
0.199
0.142
0.192
0.019
0.035
0.006
0.045
0.011
0.002
0.0002
0.014
0.020
0.032
0.002
0.074
0.049
0.100
0.313
0.120
0.030
0.125
0.005

18.2
1.8
3.6
77.5
7.2
10.5
4.4
5.2
2.2
10.6
11.9
13.0
1.2
6.5
10.6
14.7
17.2
16.8
28.3
4.6
8.0
2.1
3.8
1.2
1.3
1.1
0.4
0.9
2.2
4.5
4.0
3.6
10.0
12.3
32.9
1.9
2.0
10.3

Nonpolar + associated
Water
Water
Water
Water
Water
Water
Water
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol

Argon
Oxygen
Nitrogen
Carbon dioxide
Ethene
Benzene
Cyclohexane
Argon
Nitrogen
Carbon dioxide
Benzene
Cyclohexane
Hexane
Methane
Ethene
Ethane
Argon
Cyclohexane
Nitrogen
Benzene
Carbon dioxide

16
45
29
36
8
10
12
5
15
11
29
16
11
10
5
7
4
15
5
17
4

0.288
0.405
0.276
0.167
0.233
0.276
0.468
0.063
0.043
0.087
0.178
0.294
0.313
0.060
0.098
0.110
0.159
0.224
0.079
0.133
0.076

4.8
2.5
4.4
12.8
4.5
6.5
14.4
3.9
5.5
99.3T
6.5
9.8
14.9
27.8
9.3
9.3
3.8
14.1
22.3
10.8
23.0

Present workb

2.1
11.5
5.1
1.4
1.2
0.4
2.7
4.2
11.8
6.2
3.6
10.0

356

L. Meng et al. / Fluid Phase Equilibria 260 (2007) 354358

Table 1 (Continued )
Compound i

Compound j

No. of points

kij

RMSD (cm3 mol1 )

Present worka

Ammonia
Ammonia
Ammonia
1-Propanol
Nitrogen

Present workb

Argon
Nitrogen
Methane
Heptane
1-Butanol

10
6
6
7
4

0.153
0.113
0.154
0.198
0.059

Polar + polar
Chloromethane
Trichloromethane
Trichloromethane
Trichloromethane
Chlorodifluoromethane
Chlorodifluoromethane
Chlorodifluoromethane
Chlorodifluoromethane
Difluoromethane
Pentafluoroethane
Pentafluoroethane
Pentafluoroethane

Propanone
Propanone
Dimethyl ether
Diethyl ether
Dichlorodifluoromethane
1,2-Dichloro-1,1,2,2-tetrafluoroethane
1-Chloro-1,1-difluoroethane
1,1-Difluoroethane
1,1,1,2-Tetrafluoroethane
Difluoromethane
1,1,1,2-Tetrafluoroethane
1,1,1,2-Tetrafluoroethane

6
26
6
11
13
21
8
8
3
11
4
5

0.004
0.090
0.157
0.131
0.070
0.055
0.007
0.040
0.028
0.029
0.017
0.011

7.0
127.4
36.7
82.8
17.2
13.0
4.4
13.8
0.7
1.3
2.8
3.3

Quantum + nonpolar
Helium
Helium
Helium
Helium
Helium
Helium
Helium
Helium
Helium
Helium
Helium
Neon
Neon
Neon
Neon
Neon
Neon
Neon
Neon
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen

Argon
Krypton
Nitrogen
Oxygen
Xenon
Tetrachloromethane
Tetrafluoromethane
Methane
Butane
Sulfur hetrafluoride
Carbon dioxide
Argon
Oxygen
Xenon
Methane
Krypton
Nitrogen
Carbon dioxide
Sulfur hetrafluoride
Carbon dioxide
Propane
Argon
Octane
Benzene
Krypton
Nitrogen
Xenon
Tetrachloromethane
Tetrafluoromethane
Methane
Ethane

21
15
56
19
9
5
19
18
12
16
35
30
10
28
8
48
12
6
6
17
10
36
11
9
15
42
19
6
9
16
14

0.283
0.425
0.281
0.248
0.570
0.700
0.180
0.483
0.792
0.212
0.169
0.142
0.095
0.353
0.298
0.220
0.167
0.252
0.175
0.151
0.094
0.112
0.058
0.009
0.060
0.037
0.038
0.153
0.087
0.038
0.020

1.7
0.9
2.5
17.5
3.1
9.3
2.9
1.7
4.0
1.7
10.1
1.5
2.8
3.8
1.5
2.9
1.2
2.8
1.5
8.7
6.3
1.9
6.1
1.4
2.1
3.4
3.2
13.2
4.6
1.9
3.3

2.2
2.0
2.7
29.4
3.1
9.5
3.3
1.8
4.0
2.4
11.5
2.9
22.2
4.2
2.6
2.9
2.6
2.8
3.4
9.7
6.7
2.6
20.2
20.7
2.6
25.3
3.4
18.5
5.9
2.0
4.1

Quantum + quantum
Helium
Helium
Helium
Hydrogen

Neon
Hydrogen
Deuterium
Neon

18
28
5
8

0.100
0.328
0.210
0.173

2.9
4.2
0.3
0.2

4.6
4.2
3.1
0.7

a
b

Calculated with optimum values of kij .

Calculated using the corresponding correlations.

2.1
0.9
2.2
48.3T
2.1

L. Meng et al. / Fluid Phase Equilibria 260 (2007) 354358

357

interaction parameters, kij and extend their range. Before analyzing the data, the experimental data were carefully selected,
mostly following Dymonds recommendations [4].
2. Nonpolar/polar (associated) binaries
When fitting the second cross-virial coefficient for kij using
Eqs. (1)(5), the polar or associated f (2) term should be set
equal to zero as recommended by Tsonopoulos [5]. The optimum values of kij for 38 nonpolar/polar binaries and 34
nonpolar/associated binaries were determined by minimizing
the deviations between the calculated and experimental second
cross-virial coefficients, with the results listed in Table 1. All
the property parameters used for the correlation in this study,
namely, Pc , Tc , vc and were taken from the DIPPR database
[6].
For binaries containing CO, which has a small dipole
moment, the simple correlation can be used:
kij = 0.0086 + 0.27

(6)

where is the acentric factor of the nonpolar component. Fig. 1

presents the optimum kij s for CO/nonpolar binaries together
with the straight line calculated with Eq. (6), which shows that
Eq. (6) gives a good fit of the optimum values of kij for most binaries except CO/CO2 and CO/C4 H10 (2-methylpropane) binaries.
The predicted and experimental Bij values for the CO/Ar binary,
for which we have the most extensive information, are shown in
Fig. 2 with the RMSDs listed in Table 1.
For binaries containing H2 O, the kij are difficult to correlate,
however, there is an excellent linear relationship between kij
and the carbon number, nc , of H2 O/n-alkane binaries as shown
in Fig. 3.
kij = 0.31 + 0.0264nc

(7)

This correlation is compared in Table 2 with that of Tsonopoulos

and Dymond [7] whose correlation for H2 O/n-alkane binaries used the critical volume vc which shows that the two
correlations are roughly equivalent. Note that experimental

Fig. 1. Optimum values of kij for CO/nonpolar binaries: () optimum values;
() Eq. (6).

Fig. 2. Second cross-virial coefficients for CO/Ar binary: () experimental data
[4]; () calculated with Eq. (6).

data with large uncertainties may lead to large uncertainties

in kij .
3. Polar/polar binaries
For polar/polar binaries, the parameter a in f (2) term can be
used with the following mixing rule:
aij = 0.5(ai + aj )

(8)

with the values of a given by Meng et al. [1]. The optimum kij
for 12 polar/polar binaries are listed in Table 1.
4. Quantum/nonpolar (quantum) binaries
For binary mixtures containing a quantum component, the
quantum term, f (2) , in Eq. (1) must be included as suggested by
Meng and Duan [2]. The quantum contribution to Bij was then
calculated by assuming that
= 0.5(i + j )

(9)

Fig. 3. Optimum values of kij for H2 O/n-alkane binaries: () optimum values;
() Eq. (7).

358

L. Meng et al. / Fluid Phase Equilibria 260 (2007) 354358

Table 2
Optimum values of kij and deviations for binary mixtures containing H2 O
Mixture

H2 O/CH4
H2 O/C2 H6
H2 O/C3 H8
H2 O/C4 H10
H2 O/C5 H12
H2 O/C6 H14
H2 O/C7 H16
H2 O/C8 H18

kij

0.321
0.353
0.409
0.430
0.445
0.470
0.489
0.512

RMSD (cm3 mol1 )

No. of points

29
19
12
8
5
16
19
12

Present work

Tsonopoulos and Dymond [7]

6.5
6.7
15.4
10.5
8.3
18.6
47.3
24.5

6.2
10.1
14.4
7.9
4.5
17.0
38.0
33.4

by regression of only second cross-virial coefficient data. Simple correlations were developed for CO/nonpolar, H2 O/n-alkane
and quantum/nonpolar (quantum) binary mixtures. The predicted kij accurately represent the experimental data for kij .
List of symbols
B
second virial coefficient
f (0) , f (1) , f (2) dimensionless functions of Tr
kij
binary interaction parameter
P
pressure
1 1
R
universal gas constant, R = 8.314471
 J mol K
n
2
RMSD root mean square deviation,
i=1 (Bexp Bcal ) /n
T
temperature
v
specific volume

Fig. 4. Optimum values of kij for binaries containing quantum component: ()
optimum values; () Eq. (10).

where is the reduced de Broglie wavelength taken from

Hirschfelder et al. [8]. The optimum kij values are also listed
in Table 1.
Hiza and Duncan [9] developed a correlation using the ionization potential (IP) parameter I. However, since the HizaDuncan
correlation was developed using rather different, limited kij data
sets, their correlation cannot be compared with the kij values of
this work using values of I taken from the CRC handbook [10].
However, there is a strong relationship between kij and (Ii /Ij ) as
shown in Fig. 4, which can be correlated by
 
Ii
kij = 0.88 + 0.714
(Ii > Ij )
(10)
Ij
as shown in Fig. 4. The RMSDs in Table 1 for most of the binary
mixtures containing a quantum component are very small, which
indicates that Eq. (10) gives good predictions of kij for this group.
5. Conclusions
The optimum kij values for 119 binary mixtures are presented using the correlations for pure compounds given by
Meng and co-workers [1,2]. Optimum kij s were determined

Greek letters
*
reduced de Broglie wavelength

acentric factor
Subscripts
c
critical property
r
reduced property
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (No. 50636020).
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[2]
[3]
[4]

[5]
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