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Fluid Phase Equilibria 238 (2005) 229238

Prediction of the second cross virial coefficients of

nonpolar binary mixtures
Long Meng, Yuan-Yuan Duan
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Tsinghua University, Beijing 100084, PR China
Received 29 June 2005; received in revised form 6 October 2005; accepted 10 October 2005

Abstract
The binary interaction parameter, kij , of 268 nonpolar mixtures were determined from the database of second cross virial coefficients containing
1728 experimental data points by fitting the second cross virial coefficients with a new correlation for pure compounds [L. Meng, Y.Y. Duan, L.
Li, Fluid Phase Equilib. 226 (2004) 109120] and classical mixing rules. Regularity distributions were found for both n-alkane/n-alkane binaries
and fluorocarbon/fluorocarbon binaries. Correlations were developed following Tsonopoulos ideas [C. Tsonopoulos, Adv. Chem. Ser. 182 (1979)
143162] with the quantity of binary compounds enlarged using Dymonds latest complication [J.H. Dymond, K.N. Marsh, R.C. Wilhoit, Virial
Coefficients of Pure Gases and Mixtures, Subvolume B, Virial Coefficients of Mixtures, Series IV/21B, Landolt-Bornstein, 2002]. Correlations
were also developed for inorganic/n-alkane binaries using new kij values. The predictions do not need any thermodynamic property parameters
besides the carbon number. Comparisons with the existing correlations show that the present work is more accurate for nonpolar binary mixtures.
2005 Elsevier B.V. All rights reserved.
Keywords: Second cross virial coefficients; Mixtures; Binary interaction parameters; n-Alkane

1. Introduction
The thermodynamic properties of gas mixtures may be readily calculated from a knowledge of the mixing virial coefficients
and their dependence on temperature. The virial equation of
state, truncated after the second virial coefficient, is a useful
expression for calculating the gaseous properties for reduced
densities less than 0.5. For binary mixtures, the importance of
the second cross virial coefficient, Bij , can be easily understood
from Eqs. (1) and (2),
1

Bm =
xi xj Bij

Z = 1 + Bm

(1)
(2)

where Z is the compressibility factor, the volume, and Bii and

Bjj are the second virial coefficients of the pure components i and
j, which can be calculated from correlations for pure fluids. Bm is
termed the mixing virial coefficient. Bij is usually predicted with

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

the help of mixing rules and the binary interaction parameter,

kij . The parameter kij arises from the assumptions used to derive
the equation of state (EoS) mixing rules and also corrects for the
deviation between the EoS prediction and experimental data.
Much new, high-quality experimental data for the second
cross virial coefficient Bij has been published since the 1980s,
with most of it recently collected by Dymond et al. [3]. This
data with a new correlation for the second virial coefficients
of pure fluids [1] can be used to update the binary interaction
parameter, kij . In recent years, optimum values of kij have been
reported by Chueh and Prausnitz [4] and Hiza and Duncan [5],
with extensions to the collection of kij presented by Morrison
and McLinden [6], Tsonopoulos [2] and Kis and Orbey [7].
Recently, Abusleme and Vera [8] and Plyasunov et al. [9] published some kij s of strongly polar mixtures. Several empirical
correlations for kij have also been presented in the literature. Katz
and Firoozabadi [10], Nishiumi et al. [11], and Gao et al. [12]
proposed correlations for hydrocarbon binary mixtures and correlations for mixtures containing carbon dioxide were reported
by Coutinho et al. [13], Kato et al. [14], Nishiumi et al. [11],
Darridon [15], Bartle et al. [16] and Kordas et al. [17]. However, there are so many of them that it is impossible to detail
all the references here. Lately, the group contribution method

0378-3812/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2005.10.007

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

230

[18,19] has also been used to predict kij . Many researchers have
found that it is extremely difficult to correlate kij with respect
to substance types or other characteristics. In some references,
the authors assumed kij to be a temperature dependent parameter
to obtain better results [2023]. However, for many substances,
the assumption that kij is independent of temperature, density,
and composition still gives good approximations for predicting
Bij within the experimental uncertainties and is certainly more
convenient.
Meng et al. [1] presented a modified corresponding-state correlation that compares well with experimental data for the second
virial coefficient for most nonpolar pure compounds, since the
predictions have been corrected for most physical adsorption
effects. Detailed comparisons with the well-known Tsonopoulos
correlation [1] showed that the model is somewhat better than
Tsonopoulos correlation for nonpolar compounds. This paper
will extend the correlation to binary mixtures. The correlation
for nonpolar fluids is:
BPc
= f (0) (Tr ) + f (1) (Tr )
RTc

(3)

f (0) = 0.13356

0.30252 0.15668 0.00724 0.00022

Tr
Tr2
Tr 3
Tr 8
(4)

f (1) = 0.17404

0.15581 0.38183 0.44044 0.00541

+

Tr
Tr 2
Tr 3
Tr 8
(5)

where Tr (=T/Tc ) is the reduced temperature, Pc and Tc the critical

pressure and critical temperature, R = 8.314472 J mol1 K1 is
the universal gas constant, and is the acentric factor. When
Eqs. (3)(5) are used to calculate Bij , Pc , Tc , and should be
replaced by Pcij , Tcij , and ij , which are defined by the following
mixing rules,
Tcij = (Tci Tcj )1/2 (1 kij )
Pcij =

(6)

4Tcij (Pci ci /Tci + Pcj cj /Tcj )

3

(ci 1/3 + cj 1/3 )

(7)

i + j
(8)
2
where ci and cj are the critical volumes of components i and j.
As mentioned in many references, the values of kij obtained
using different methods can be different. The inappropriate use
of these results may mislead observations concerning the inherent law for kij . Therefore, only the second cross virial coefficient
data for 268 nonpolar binary mixtures containing 1728 experimental data points were used to evaluate the binary interaction
parameter kij in this work to improve the representation of the
second virial coefficients for binary mixtures.
ij =

2. n-Alkane/n-alkane binaries
The values of kij for n-alkane/n-alkane binaries have been
reported in many references [2,4,11]. As the classical binaries,

they are the preferred binary types for analysis to test new ideas.
Among these references, the relationship proposed by Chueh and
Prausnitz [24] using critical volumes as the correlating parameters is most commonly used
kij = 1

8(ci cj )1/2
3

(ci 1/3 + cj 1/3 )

(9)

This correlation was developed from Londons theory of dispersion forces, which makes it a theoretically based correlation.
This correlation gives satisfactory results for all paraffin/paraffin
mixtures. More generally, this equation has been applied by
Tarakad and Danner [25] to systems in which both species
were hydrocarbons. Fender and Halsey [26] also proposed a
geometricarithmetic mean correlation with critical temperatures as correlating parameters using the expression:
kij = 1

2(Tci Tcj )1/2

Tci + Tcj

(10)

This correlation was developed for Ar/Kr mixtures; however, it

can also be used for some inorganic binaries and hydrocarbon
binaries. Later, Tsonopoulos [2] proposed a quite different correlation with carbon numbers as correlating parameters, which
gives better results for methane/hydrocarbon binaries. Moreover, he suggested a general form for hydrocarbon binaries
using
kij = m[ln(ncj nci + 1)]2

(11)

where nci is the carbon number of component i. However,

Tsonopoulos did not give a method to calculate the parameter
m, which makes Eq. (11) of limited use.
In this work, the optimum values of kij for n-alkane/n-alkane
binaries were recalculated by minimizing the deviations between
calculated and experimental second cross virial coefficient data,
with the results listed in Table 1. All the property parameters
used for fitting in this study, namely, Pc , Tc , c and were taken
from the DIPPR 801 database [27].
To obtain reliable values of kij , the data quality was carefully
investigated and doubtful data points were rejected. Each data
point was weighted by the authors recommended experimental
uncertainty. Also, some kij s were slightly adjusted within the
experimental data uncertainties. Most kij s in Table 1 are less
positive than those of Tsonopoulos work, because the present
correlation for pure compounds at low temperatures predicts
higher values than Tsonopoulos correlation [28], which is sensitive to kij . Surprisingly, when the sum of the carbon numbers of
components i and j was used as the x-coordinate and the value of
kij as the y-coordinate, an interesting distribution was observed
as shown in Fig. 1.
Fig. 1 shows that each group in C1 C8 has the trend that the
values of kij increase with increasing carbon numbers. This relationship is abstractly illustrated in Fig. 2, where Cij denotes the
Ci /Cj binary (Cii = 0 and Cij = Cji ). The trends show that the values of kij (j i) increase with increasing carbon number for each
group having the same component i and decrease with increasing carbon number for each group having the same component
j. A similar distribution can also be found for kij when plotted as

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

231

Table 1
Optimum values of kij for n-alkane/n-alkane, fluorocarbon/fluorocarbon, N2 /n-alkane, CO2 /n-alkane binaries and their deviations
i

No. of points

kij

RMSD in Bij (cm3 mol1 )

Present worka

Present workb

Tsonopoulosc

Chueh and Prausnitzc

Fender and Halseyc

CH4

C2 H6
C3 H8
C4 H10
C5 H12
C6 H14
C7 H16
C8 H18
C9 H20
C10 H22
C12 H26
C16 H34
C20 H42
C30 H62

55
26
36
19
14
12
6
3
4
4
5
4
2

0.0054
0.0181
0.0205
0.0301
0.0419
0.0476
0.0658
0.0713T
0.1497T
0.1413
0.2058
0.1817
0.3371T

3.1
6.0
6.5
13.0
8.9
17.6
3.7
31.0
48.3
16.8
38.5
40.7
29.6

3.1
5.9
6.4
13.1
8.9
18.0
3.6
32.3
46.7
14.6
35.5
45.2
35.6

3.9
4.7
9.8
22.9
21.1
45.8
35.6
88.2
18.5
17.3
29.7
32.7
59.5

3.1
4.1
6.6
17.6
14.0
33.8
22.5
66.2
28.7
4.54
38.5
11.7
101.6

6.4
9.5
15.1
29.7
28.7
55.4
43.6
97.0
17.4
12.6
40.0
12.0
139.8

C2 H6

C3 H8
C4 H10
C5 H12
C6 H14
C8 H18
C16 H34
C20 H42
C30 H62

27
11
8
7
2
3
4
2

0.00002
0.0018
0.0110
0.0217
0.0452
0.1339T
0.1839
0.3141T

3.7
9.1
15.6
5.3
1.4
26.4
14.5
23.7

3.6
9.0
15.5
5.1
3.3
19.2
13.5
53.4

2.9
10.2
17.5
11.5
9.8
45.9
12.3
38.5

3.7
10.8
17.8
12.0
10.7
23.3
50.2
203.4

3.8
11.0
17.2
8.8
1.6
106.0
150.3
376.0

C3 H8

C4 H10
C5 H12
C6 H14
C7 H16
C8 H18

9
4
7
3
3

0.0001
0.0064
0.0114
0.0134
0.0254

8.1
3.3
5.8
11.8
3.0

8.2
3.2
5.8
12.0
3.1

6.1
1.9
5.8
17.7
10.4

6.1
2.8
5.2
11.5
4.5

C4 H10

C5 H12
C6 H14
C8 H18

4
8
3

0.0002
0.0070
0.0136

4.6
11.8
5.9

4.6
11.6
6.9

3.7
16.9
11.8

4.3
19.4
5.1

C5 H12

C6 H14
C7 H16
C8 H18

7
3
2

0.0007
0.0039
0.0067

10.8
2.1
2.4

10.8
2.0
3.0

9.4
2.4
5.4

10.1
3.5
3.9

C6 H14

C8 H18

0.0032

1.8

1.8

2.8

5.6

C7 H16

C8 H18

0.0006

1.6

1.6

3.9

5.2

CF4

C 2 F6
C3 F8
C4 F10
C5 F12
C6 F14

2
2
2
2
2

0.0232
0.0368
0.0471
0.0744
0.0969

7.3
10.0
9.6
0.7
8.5

7.5
9.2
8.3
3.0
10.7

9.5
5.6
6.0
5.6
12.2

9.9
5.0
6.9
18.5
33.4

C2 F6

C 3 F8
C4 F10
C5 F12
C6 F14

2
2
2
2

0.0255
0.0318
0.0443
0.0632

10.1
7.8
11.4
6.3

9.4
8.3
14.0
10.6

16.7
17.8
21.9
30.8

16.8
21.1
32.5
54.6

C4 F10

C5 F12
C6 F14

1
1

0.0160
0.0304

1.6
0.7

3.6
9.2

34.0
47.7

37.5
57.5

N2

CH4
C2 H6
C3 H8
C4 H10
C5 H12
C6 H14
C7 H16
C8 H18
C9 H20
C10 H22
C12 H26

28
10
18
17
17
26
15
6
4
7
4

0.0346
0.0502
0.0354
0.0642
0.1147
0.1167
0.1353
0.1418
0.1548
0.1593
0.1755

2.8
0.8
8.1
6.9
7.6
8.6
11.0
5.6
10.2
9.0
1.9

3.3
1.8
6.9
7.0
7.1
9.6
11.9
10.8
19.9
17.8
19.4

4.5
6.2
5.3
8.1
17.2
15.6
21.7
17.6
21.6
17.9
16.1

3.1
4.4
17.3
18.8
15.3
25.5
28.1
31.1
44.2
33.9
30.5

CO2

CH4

31

0.0399

2.2

8.2

3.9

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

232
Table 1 (Continued )
i

No. of points

kij

RMSD in Bij (cm3 mol1 )

Present worka

C2 H6
C3 H8
C4 H10
C5 H12
C6 H14
C7 H16
C8 H18
C9 H20
C10 H22

26
15
6
8
2
2
1
1
2

0.0847
0.1097
0.1433
0.1749T
0.2742
0.2620
0.2505
0.2629
0.2259T

3.1
11.2
19.4
44.8
51.2
33.4
5.7
1.6
63.1

Present workb

Tsonopoulosc

Chueh and Prausnitzc

Fender and Halseyc

26.4
42.7
67.7
116.3
157.6
163.4
128.8
143.9
123.2

29.1
50.9
85.4
144.5
198.2
220.9
189.7
223.1
238.2

Superscript T denotes strong temperature dependence.

a k was calculated with the values of m listed in Table 2.
ij
b By Eqs. (12) and (13) for n-alkane/n-alkane binaries and by Eq. (14) with m = 0.01747 for fluorocarbon/fluorocarbon binaries.
c With Tsonopoulos correlation for pure fluids [28].

a function of various thermodynamic properties of the two components such as Tci Tcj , i j , ci cj , and i + j on the abscissa,
where the subscripts i and j are transposable.
In addition, the slope of the curve for each group decreases
as the series number of the group increase. As a result, heavier n-alkane/n-alkane binaries probably have kij values closer
to zero. This behavior makes it possible to correlate all the nalkane/n-alkane binaries using only one equation if the kij values
of each group can be correlated with just one fitting coefficient.
Such a correlation can be compared with the Chueh and Prausnitz correlation for all n-alkane/n-alkane binaries. Therefore, the
correlation developed here follows the approach suggested by
Tsonopoulos,
kij = m[ln(ncj nci + 1)]7/2
Fig. 1. Distribution of kij s for n-alkane/n-alkane binaries: () C1 group; (
)
C2 group; () C3 group; () C4 group; () C5 group; () C6 group; () C7
group; () C8 group.

where m is a variable coefficient defined for each n-alkane group.

Although the relationship between (ncj + nci ) and kij s is clearly
shown in Fig. 2, using (ncj nci ) instead of (ncj + nci ) as the
correlating parameter does not affect the correlation results. Eq.
(12) implies that (ncj nci ) and when ncj = nci , kij is equal to zero.
Since these kij results were somewhat different from Tsonopoulos, the exponent of the bracketed quantity was changed to 7/2 to
get better results. The values of m were listed in Table 2. Finally,
the trends of m for n-alkane/n-alkane binaries can be correlated
by
m=

Fig. 2. Abstract distribution of kij values as a function of the carbon number

sum of components i and j.

(12)

0.00678
1 + 0.336nci

(13)

where nci is the carbon number of component i(j i). This correlation is shown in Fig. 3, which shows that m decreases as
nci increases, with a limiting value of zero for an infinitely long
chain. The optimized kij s for the CH4 group and the C2 H6 group
together with Eqs. (12) and (13) are plotted in Fig. 4 as two
examples to show the present correlation results.
The resulting deviations between experimental and calculated Bij for n-alkane/n-alkane binaries, along with the work of
Tsonopoulos, are given in Table 1. First, it should be noted that
the RMSD values in the column marked a in Table 1 are not
always be smaller than those in the column marked b, because
the values of m used in the column a is not to give the minimum

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

Table 2
Values of m for nonpolar binaries
Component i (nci )
n-Alkane/n-alkane binaries
C1
C2
C3
C4
C5
C6
C7

Component j (ncj )

n-Alkane

0.00496
0.00436
0.0334
0.00273
0.00244
0.00227
0.00209

Fluorocarbon/fluorocarbon binaries
CF4
C2 F6
Fluorocarbon
C4 F10

0.01855
0.01583
0.01536

Inorganic/n-alkane binaries
N2
CO2

0.04311
0.07475

n-Alkane
n-Alkane

233

RMSD for each kind of substances, but for overall substances in

this group. Although larger RMSD for some substances in the
column marked a, but the overall RMSD of this group is definitely smaller than that in the column marked b. Comparison
of the present result with the Tsonopoulos model with the two
well-known correlations for kij , Eqs. (9) and (10), shows that
the present model has a smaller overall RMSD of 13 cm3 mol1
compared to 24 cm3 mol1 for Eq. (9) and 43 cm3 mol1 for
Eq. (10). Note that the present work has a 35.6 cm3 mol1
RMSD for the methane/squalane binary, while Eqs. (9) and
(10) have much worse results, 101.6 cm3 mol1 for Eq. (9) and
139.8 cm3 mol1 for Eq. (10). Such case was also found for the
ethane/squalane binary with an RMSD of 53.4 cm3 mol1 for
this work and a much larger 203.4 cm3 mol1 RMSD for Eq. (9)
and 376.0 cm3 mol1 RMSD for Eq. (10). Therefore, the present
correlation is quite successful for long chain n-alkane binaries
with carbon numbers up to 30. The present prediction results for
the second virial cross coefficient for n-alkane/n-alkane binaries
all show that Eqs. (12) and (13) are superior to the well-known
correlations, Eqs. (9) and (10), even though both give good representations of the experimental data for short n-alkane binaries.
Furthermore, the present work only used carbon numbers as
the correlating parameters, which is obviously more convenient
than the Chueh and Prausnitz [24] and Fender and Halsey [26]
correlations. In addition, as shown in column c of Table 1, even
with comparisons between Eqs. (12) and (13) and the correlation
given only for methane/hydrocarbon and ethane/hydrocarbon
binaries proposed by Tsonopoulos [2], the present work still
gives better results for these two groups.
3. Fluorocarbon/ uorocarbon binaries

Fig. 3. Parameter m as a function of nci for n-alkane/n-alkane binaries: (
)

values of m as listed in Table 2 and () Eq. (13).

As mentioned in the previous section, Fig. 2 strongly implies

some regularity for the n-alkane/n-alkane binaries. The relationship can also be investigated for other species by examining the
data for fluorocarbon/fluorocarbon binaries. The resulting optimized kij s are listed in Table 1. The distribution of kij s for
fluorocarbon/fluorocarbon binaries is similar to that in Fig. 1.
The slight difference is that the optimized kij s for each group
of fluorocarbon/fluorocarbon binaries possibly increase linearly
with increasing carbon numbers, although there are not enough
values to provide assured evidence at present. This behavior
more or less supports the case of n-alkane/n-alkane binaries.
Although a similar method can be used to describe the kij values for fluorocarbon/fluorocarbon binaries, a substantially better
fit of the data is suggested,
kij = m(ncj nci ),

Fig. 4. Optimum kij values for CH4 and C2 H6 groups: () optimum values of
CH4 group; () optimum values of C2 H6 group; () Eqs. (12) and (13) with
nci = 1; (- - -) Eqs. (12) and (13) with nci = 2.

(ncj nci )

(14)

where the values of m for each fluorocarbon group are listed

in Table 2. The predictions show good agreement with the
experimental data, with an overall RMSD for the fluorocarbon/fluorocarbon binaries of 8.1 cm3 mol1 . However, since
very few data are available for these binaries, no attempt was
made to correlate m. As new experimental Bij data become
available, the correlation for m should be established. However, for now, a rough estimated value of m is 0.01747 for all


234

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

Fig. 5. Optimum values of kij for fluorocarbon/fluorocarbon binaries: (
) optimum values and () Eq. (14) with m = 0.01747.

the fluorocarbon/fluorocarbon binaries which gives an overall

RMSD of 9.2 cm3 mol1 , less than 20.2 cm3 mol1 by Eq. (9)
and 29.6 cm3 mol1 by Eq. (10). The RMSDs from experimental data are listed in Table 1 with the representation of kij shown
in Fig. 5.
4. Inorganic/n-alkane binaries

bon number increases, such behavior observed in the present

work, which was induced by only optimizing the second cross
virial coefficient, was not taken into account for correlating kij s,
until more kij s are reported to establish the true trend.
5. Other nonpolar binaries

For inorganic/n-alkane binaries, Table 1 also presents optimum kij values for N2 /n-alkane and CO2 /n-alkane binaries.
When Eq. (12) was used for the correlation, the exponent should
be changed to 3/2 to gain better results.
kij = m[ln(ncj + 1)]3/2

Fig. 6. Optimum kij values for N2 /n-alkane and CO2 /n-alkane binaries: ()
optimum values of N2 /n-alkane binaries, () optimum values of CO2 /n-alkane
binaries, () Eq. (15) with m = 0.04311, and (- - -) Eq. (15) with m = 0.07475.

(15)

As compared with Eq. (12), Eq. (15) implies that nci is equal
to zero for the inorganic component. The values of m are
listed in Table 2. The comparisons with the Tsonopoulos correlation for N2 /n-alkane binaries as listed in Table 1 show
that the present work gives a better representation of Bij than
Tsonopoulos correlation. The total RMSD for the present work
is 7.3 cm3 mol1 versus 9.4 cm3 mol1 for Tsonopoulos. However, the total RMSD using Eq. (9) is 13.6 cm3 mol1 and up to
21.5 cm3 mol1 using Eq. (10). As for the CO2 /n-alkane binaries, the total RMSD of present work is 19.6 cm3 mol1 versus
61.4 cm3 mol1 using Eq. (9) and up to 83.0 cm3 mol1 using
Eq. (10). Since the RMSDs of Eqs. (9) and (10) from experimental data are too large, these two equations can not be extended
to the binaries of n-alkane with CO2 or N2 .
Fig. 6 presents all the optimum kij s for N2 /n-alkane and
CO2 /n-alkane binaries along with the relationship in Eq. (15),
which shows that Eq. (15) gives a satisfactory fit of the data with
the corresponding values of m. However, the figure shows a step
in the values of kij when the carbon number increases from 5
to 6, and then kij deceases as the carbon number increases for
CO2 /n-alkane binaries. A similar unusual behavior was found
in the case of Ar/n-alkane binaries, which is not shown here.
Although many authors have mentioned, the kij s of CO2 /longchain hydrocarbon binaries (most of their kij s were obtained
from VLE data) may decrease as the heavy hydrocarbons car-

The kij s of 202 nonpolar binary systems are listed in Table 3

to update and enlarge the kij database. Substances with small
dipole moments (according to the DIPPR 801 database [27])
were not discussed in this work. Some nonpolar binaries show
strong temperature dependent characteristics. The optimum kij s
must be careful used because some were obtained from just two
or three experimental data points, which leads to less reliability
of the optimum values. Further work is needed to update the
results in Table 3. Those mixtures could not be easily correlated
into reasonable groupings. However, when all 268 optimum kij s
are plotted together in Fig. 7 with (Tci Tcj )1/2 as the x-coordinate,
some additional interesting information is obtained. Almost all

Fig. 7. Distribution of optimum kij values for nonpolar binaries: (
) optimum
values and () Eq. (16).

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

235

Table 3
Optimum values of kij for nonpolar binaries
Component j

kij

Component j

kij

Argon+
Carbon dioxide
Sulfur hetrafluoride
Krypton
Nitrogen
Oxygen
Xenon
Tetrachloromethane
Tetrafluoromethane
Methane
Hexafluoroethane
Ethane
Propane
Octafluorocyclobutane
Butane
Cyclopentane
Pentane
2,2-Dimethylpropane
Cyclohexane
Methylcyclopentane
Hexane
2,2-Dimethylbutane
2,3-Dimethylbutane
2-Methylpentane
3-Methylpentane

0.0675
0.0420
0.0015
0.0082
0.0265
0.0528
0.1443
0.0396
0.0000
0.0730
0.0556
0.0607
0.0535
0.0392
0.1411
0.1384
0.0817
0.1510
0.1446
0.1357
0.1352T
0.1924
0.1403
0.1962T

Benzene
1,1-Dimethylcyclopentane
cis-1,3-Dimethylcyclopentane
trans-1,2-Dimethylcyclopentane
trans-1,3-Dimethylcyclopentane
Heptane
2,2-Dimethylpentane
2,3-Dimethylpentane
2,4-Dimethylpentane
2-Methylhexane
3,3-Dimethylpentane
3-Methylhexane
2,2,3-Trimethylbutane
1,4-Dimethylbenzene
Octane
2,2,4-Trimethylpentane
1,3,5-Trimethylbenzene
Nonane
Naphthalene
1-Methyl-4-propylbenzene
1,4-Diethylbenzene
1,2,4,5-Tetramethylbenzene
Anthracene

0.1496
0.1614
0.1604
0.1629
0.1628
0.1338T
0.1892
0.1788
0.1844
0.1776
0.1876
0.1748
0.1937
0.0576
0.1219
0.1796T
0.0621
0.1177
0.2344T
0.0848
0.0917
0.0693
0.2330

Krypton+
Xenon
Sulfur hetrafluoride
Carbon dioxide
Tetrafluoromethane

0.0155
0.0792
0.0699
0.0588

Methane
Hexafluoroethane
Ethane
Octafluorocyclobutane

0.0115
0.0780
0.0269T
0.0543

Xenon+
Carbon dioxide
Sulfur hetrafluoride
Nitrogen
Tetrafluoromethane
Methane

0.0921
0.0826
0.0736
0.1018
0.0082

Hexafluoroethane
Ethene
Ethane
Octafluorocyclobutane

0.1043
0.0200
0.0070
0.0759

Tetrachloromethane+
Carbon dioxide
Nitrogen
Methane

0.2115T
0.1735
0.0944

Ethene
Benzene
Cyclohexane

0.0769T
0.0186
0.0082

Tetrafluoromethane+
Carbon dioxide
Sulfur hetrafluoride
Nitrogen
Oxygen
Methane

0.0737
0.0125
0.0060
0.0380
0.0829

Ethane
Butane
Pentane
Hexane

0.1061
0.1081
0.0691
0.1117

Hexafluoroethane+
Methane
Ethane

0.1042
0.1138T

Butane
Pentane

0.1073
0.1114

Octafluoropropane+
Propane

0.0919

Decafluorobutane+
Methane
Ethane

0.1009
0.1008

Butane
Hexane

0.0726
0.0959

Dodecafluoropentane+
Methane

0.1424

Pentane

0.1040

Tetradecafluorohexane+
Methane
Pentane

0.2949
0.1004

Hexane

0.0909


236

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

Table 3 (Continued )
Component j

kij

Component j

kij

Methane+
Oxygen
Sulfur hetrafluoride
Ethene
Octafluorocyclobutane
2,2-Dimethylpropane
Benzene
Cyclohexane

0.0470
0.0745
0.0397
0.0714
0.0619
0.0725
0.1150T

2-Methylpentane
2,2-Dimethylbutane
2,2,5-Trimethylhexane
Naphthalene
Bicyclohexyl
Phenanthrene
Anthracene

0.0201T
0.1014T
0.1914
0.1467T
0.2197T
0.1605
0.1839

Ethene+
Nitrogen
Carbon dioxide
Ethane
Benzene
Naphthalene

0.0408T
0.0192
0.0108
0.1110
0.0838

Bicyclohexyl
Phenanthrene
Anthracene
Hexadecane

0.1455
0.1406
0.1509
0.1573

Ethane+
Naphthalene
Bicyclohexyl

0.1150
0.1087

Anthracene

0.1587

Benzene+
Pentane
Cyclohexane
Hexane

0.0499
0.0147
0.0088

Heptane
Octane

0.0105
0.0302

Cyclohexane+
Hexane

0.0072

Carbon dioxide+
Sulfur hetrafluoride
Nitrogen
Oxygen
1,3-Butadiene
Cyclopentane
Benzene
Cyclohexane
Methylcyclopentane
2-Methylpentane
3-Methylpentane
2,2-Dimethylbutane
2,3-Dimethylbutane
2-Methylhexane
3-Methylhexane

0.0989
0.0199
0.0473
0.1955
0.2544
0.0469T
0.1797T
0.2554
0.2967
0.2930
0.3407
0.2977
0.2680
0.2628

2,2-Dimethylpentane
2,3-Dimethylpentane
2,4-Dimethylpentane
3,3-Dimethylpentane
3-Ethylpentane
2,2,3-Trimethylbutane
1,4-Dimethylbenzene
2,2,4-Trimethylpentane
1,3,5-Trimethylbenzene
Naphthalene
1-Methyl-4-propylbenzene
1,2,4,5-Tetramethylbenzene
Anthracene
Phenanthrene

0.2867
0.2715
0.2914
0.2877
0.2475
0.3142
0.1602
0.2371
0.1618
0.1905T
0.2075
0.1655
0.2325
0.2185

Sulfur hetrafluoride+
Nitrogen
Oxygen

0.0008
0.0434

Pentane

0.1146

Nitrogen+
Boron trifluoride
Oxygen
Cyclopentane
(E)-2-Pentene
2,2-Dimethylpropane
Benzene
Cyclohexane
Methylcyclopentane
(E)-2-Hexene
(E)-3-Hexene
2-Methylpentane
3-Methylpentane
2,2-Dimethylbutane
2,3-Dimethylbutane

0.0086
0.0075
0.1475
0.0912
0.1159
0.1070
0.1221
0.0876
0.1034T
0.0999T
0.1188T
0.1309T
0.1546T
0.1288

2-Methylhexane
3-Methylhexane
3-Ethylpentane
2,2-Dimethylpentane
2,3-Dimethylpentane
2,4-Dimethylpentane
3,3-Dimethylpentane
2,2,3-Trimethylbutane
2,2-Dimethylhexane
2,2,4-Trimethylpentane
2,2,3,3-Tetramethylbutane
2,2,5-Trimethylhexane
Naphthalene

0.1301
0.1411T
0.1087
0.0479T
0.1394T
0.1360
0.1327
0.1598T
0.0878
0.2392T
0.1457
0.2326
0.1891

Oxygen+
Pentane
Cyclopentane
Benzene
Cyclohexane

0.0232
0.0121
0.1486T
0.0667

2-Methylhexane
3-Methylhexane
3-Ethylpentane
2,3-Dimethylpentane

0.1024
0.0906
0.1025
0.1140

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L. Meng, Y.-Y. Duan / Fluid Phase Equilibria 238 (2005) 229238

237

Table 3 (Continued )
Component j
2-Methylpentane
3-Methylpentane
2,2-Dimethylbutane
2,3-Dimethylbutane
Hexane
Heptane

kij

Component j

kij

0.0827
0.0672
0.0937
0.0840
0.0766
0.0976

2,4-Dimethylpentane
3,3-Dimethylpentane
2,2,3-Trimethylbutane
Naphthalene
Anthracene

0.1098
0.1191
0.1228
0.2480
0.2369

Superscript T denotes strong temperature dependence.

universal gas constant R = 8.314472 J mol1 K1

temperature
pressure
molar volume

of the optimum kij s are located in the hatched area and the
hatched area shape is consistent with that of Fig. 2. The importance of the hatched area is that it gives a rough range for kij s for
unknown nonpolar binaries. The upper limit of kij s is roughly
given by

R
T
P

kij = 0.17553 + 0.00135(Tci Tcj )1/2

Greek letters

acentric factor

(16)

while the lower limit is zero for all the nonpolar binaries. The
predicting values of Eq. (10) are exactly located in this bound
area above about 150 K.
However, it is hard to say whether kij will tend to decrease
with increasing molecular size as with the second cross virial
coefficients, although such trends have already been found in
some cases using VLE data [13,17,29], because the experimental
second cross virial coefficient data for heavy molecules are still
too scarce to draw any conclusions. Another reason is that the
present regression method to find the optimum kij s is based on
fitting just the second cross virial coefficient data while most
other references also used VLE data.
6. Conclusions
The optimum kij s for 268 nonpolar binary systems are presented using the correlation for pure compounds proposed by
Meng et al. [1]. Optimum kij s were determined by regressing only the second cross virial coefficient data. The kij s for
n-alkane/n-alkane binaries have an interesting regular distribution and were successfully correlated using Eqs. (12) and (13)
with the carbon numbers as the correlating parameters. The
model was found to perform very well, even for binaries with
carbon numbers up to 30. The present correlation gives less
standard deviations than the Tsonopoulos, Chueh and Prausnitz
and Fender and Halsey correlations, and is more convenient to
use. The kij values for fluorocarbon/fluorocarbon binaries have
a similar distribution. For N2 /n-alkane and CO2 /n-alkane binaries, the carbon number was also successfully used to correlate
the data with better representations than previous works.
List of symbols
B
second virial coefficient
f(0) , f(1) dimensionless functions of Tr in Eq. (3)
kij
binary interaction parameter
n
(B
Bij,cal )2
i=1 ij,exp
RMSD root mean square deviation,
n
nc
carbon number
Z
compressibility factor

Subscripts
c
critical property (not including nci , ncj )
r
reduced property
i, j
property of component i, j
ij
characteristic property used in the calculation of the
second cross virial coefficient
m
mixture property
Acknowledgements
This work was supported by The National Natural Science Foundation of China (No. 50225622) and FANEDD (No.
200336).
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