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Abstract
A modified form of the well-known Tsonopoulos correlation for second virial coefficients was developed based on the corresponding-states
principle. Comparisons with the new, high-quality experimental data and existing models show that the present correlation is more accurate,
reliable and satisfactory for nonpolar compounds. The results also show that the present work is roughly equivalent to the Tsonopoulos and
Weber correlations for second virial coefficients of polar fluids.
The Weber correlation for the third virial coefficients was also improved since it did not well represent the experimental data of nonpolar
gases. The new correlation gives a satisfactory fit for nonpolar compounds as the Orbey and Vera correlation did and can also accurately
represent the literature data for the third virial coefficients of polar fluids, which was well represented by the Weber correlation. The two
correlations for the second and third virial coefficients need the same additional parameters, such as the critical temperature, critical pressure,
acentric factor and reduced dipole moment.
2004 Elsevier B.V. All rights reserved.
Keywords: Virial coefficients; PVT; Nonpolar fluids; Haloalkanes; Polar fluids
1. Introduction
The thermodynamic properties of gases may be easily calculated from a knowledge of the virial coefficients and their
dependence on temperature. The density explicit virial equation of state, truncated after the third virial coefficient, is a
useful expression for calculating the thermodynamic properties of gases for reduced densities less than 0.5. The virial
coefficients are basic thermodynamic properties that represent the nonideal behavior of real gases. The importance of
the virial coefficients lies in the fact that they are related
directly to the interactions between molecules. The second
virial coefficient represents the departure from ideality due to
interactions between pairs of molecules, the third virial coefficient gives the effects of interactions of molecular triplets,
and so on. All of the equilibrium gas-phase thermodynamic
properties can be calculated from the virial coefficients combined with the ideal gas heat capacity. The fourth and higher
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 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.09.023
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
BPc
= f (0) (Tr ) + f (1) (Tr ) + f (2) (Tr )
RTc
(1)
where
f (0) = 0.1445
Tr
Tr2
Tr3
Tr8
(2a)
f (1) = 0.0637 +
Tr2
Tr3
Tr8
f (2) =
a
Tr6
(2b)
(3)
2 Pc
1.01325Tc2
(4)
(5)
aWeber = 9 107 2r
(6)
(7)
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
111
Eq. (1) is also used in this work. For nonpolar fluids, Eqs.
(2a) and (2b) are redefined here as
f (0) = 0.13356
0.00724 0.00022
Tr3
Tr8
f (1) = 0.17404
0.30252 0.15668
Tr
Tr2
(8)
0.15581 0.38183
+
Tr
Tr2
0.44044 0.00541
Tr3
Tr8
(9)
Fig. 2. Deviations of measured second virial coefficient data for argon ( = 0.0022) from the present correlation: () Gilgen et al. [21];
( ) Estrada-Alexanders and Trusler [22]; (- - -) Tsonopoulos [3]; ( )
PitzerCurl [1]; (---) Weber [7].
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
Fig. 4. Deviations of measured second virial coefficients for ethane from the
present correlation: () Estrada-Alexanders and Trusler [33]; ( ) Douslin
and Harrison [34]; () Pompe and Spurling [35]; () Jaeschke [36]; (- - -)
Tsonopoulos [3]; ( ) PitzerCurl [1]; (---) Weber [7].
(11)
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
113
Table 1
Optimum values and RMSD for some polar fluids
Substance
R11
R12
R13
R22
R23
R32
R40
R41
R114
R115
R141b
R142b
R123
R124
R125
R134a
R143a
R152a
R227ea
R236ea
Propanone
2-Butanone
2-Pentanone
3-Pentanone
Dimethyl ether
Diethyl ether
Diisopropyl ether
Ethanol
Acetonitrile
3.97
7.16
10.92
76.76
144.77
180.95
136.80
198.08
7.93
6.68
77.50
109.29
31.84
49.36
75.82
121.17
169.91
152.76
43.58
25.90
149.03
111.29
84.42
92.84
55.98
21.80
14.26
191.44
249.48
Optimum a
0.00614
0.00171
0.00856
0.00469
0.01469
0.02586
0.01053
0.05129
0.00264
0.01404
0.00132
0.00452
0.00091
0.00069
0.00069
0.00740
0.01703
0.01661
0.00245
0.00078
0.03410
0.02313
0.01803
0.01308
0.01752
0.00449
0.00277
0.04482
0.12116
(12)
Here we roughly ignored the associating effects of nonhydrogen bonding compounds. Both equations are plotted in
Fig. 7. The values of a for haloalkanes are mostly positive
for r < 100 as already mentioned above. Although we have
Tsonopoulos
Weber
33.4
10.2
4.7
8.3
4.9
7.8
10.7
5.7
23.3
11.0
54.8
22.6
6.5
10.8
7.7
3.0
6.4
22.0
12.5
21.6
38.1
65.5
163.6
65.9
64.2
63.8
68.7
38.0
175.5
35.3
16.9
6.0
11.9
3.7
5.4
10.2
6.3
35.4
13.5
37.0
15.3
22.8
5.7
4.5
6.2
14.9
9.9
7.3
25.7
35.3
74.1
142.8
76.9
54.2
44.7
71.0
36.7
178.5
28.2
8.9
4.2
14.2
3.6
7.9
13.0
8.9
18.3
12.2
7.7
21.4
76.2
21.3
4.5
3.7
11.4
7.3
7.1
28.1
Fig. 8. Deviations of measured second virial coefficients for R22 from the
present correlation: () Zander [42]; ( ) Lisal et al. [43]; () Schramm and
Weber [44]; () Natour et al. [45]; () Schramm et al. [46]; () Demiriz et
al. [47]; () Haendel et al. [48]; () Haworth and Sutton [49]; () Esper et
al. [50]; (- - -) Tsonopoulos [3]; (---) Weber [7].
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
Fig. 10. Deviations of measured second virial coefficients for R134a from
the present correlation: () Schramm et al. [46]; () Tillner-Roth and Baehr
[56]; ( ) Qian et al. [57]; () Bignell and Dunlop [58]; () Goodwin and
Moldover [59]; () Beckermann and Kohler [60]; () Weber [61]; (- - -)
Tsonopoulos [3]; (---) Weber [7].
Since the experimental values of the third virial coefficients are often very much in error and scarce because of
inherent difficulties in avoiding systematic measurement and
evaluation errors, general correlations which directly fit the
data are not appropriate. The Van Nhu et al. [18] model is
often considered to be better than most for correlating the
experimental data for the third virial coefficients with the advantage that the uncertainty in the individual coefficients, B
and C, is offset to a large extent by their close association
when the truncated virial equation is used to represent the
PVT data. Weber [7] successfully simplified the model using
the critical volume as a parameter:
C = Ch + (B Bh )2 c (Tr )
(13)
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
115
(15)
Tr0.1
Tr0.2
Tr0.3
(16)
f1 (Tr ) = 2.0243
0.85902
Tr
1010
(17)
The first term, f0 (Tr ), was determined by fitting the C data for
argon, carbon dioxide, methane, nitrogen and benzene, which
have zero reduced dipole moments. f1 (Tr ) was determined by
fitting the data for some haloalkanes, such as R134a, R143a,
R152a, R32 and R23. Noted that f0 (Tr ) is equal to 0.174 when
the reduced temperature is equal to unity, which is in agreement with the calculated value at the critical temperature in
the Weber correlation. Weber suggested that the polar term
should be correlated using the cube of the reduced dipole
moment, however, we got better results with the quartic of
the reduced dipole moment which is similar to the case of
Van Nhu et al. [18]. Although f1 (Tr ) was somewhat arbitrary,
the results show that it accurately represents the experimental data of haloalkanes. Furthermore, as Weber also found,
the location of the maximum in C shifts to lower temperatures with increasing reduced dipole moment. In fact the
present correlation describes this phenomenon so well that
f1 (Tr ) need not be a function of r as was necessary in the
Weber correlation. The calculated results for the third virial
coefficients for argon, carbon dioxide, nitrogen and methane,
as classical nonpolar gases, are shown in Figs. 1215.
Figs. 1215 show that Eq. (15) agrees well with the Orbey
and Vera correlation in giving a satisfactory representation of
C for nonpolar fluids within the experimental uncertainties.
Since the equation of Weber was established to represent
small polar substances, it does not describe these nonpolar
substances well. For example, visible positive deviations can
be seen for Tr = 1.01.5 with obvious negative deviations for
Tr > 1.5.
The results obtained with the present correlation for R23,
R32, R134a, R143a, R152a, R125 are shown together with
the Weber correlation and the Orbey and Vera correlation
in Figs. 1621. Figs. 1621 show that Eq. (15) is in excellent agreement with the Weber correlation which accurately
represents the data for polar haloalkanes within the experimental uncertainties. Since the Orbey and Vera correlation
is not for polar fluids, their results are not as good as those
of the present work. Thus, Eq. (15) incorporates the advantages of the other two correlations to represent the third virial
Fig. 12. Third virial coefficients of argon: () Holborn and Otto [64]; ()
Michels et al. [65]; () Whalley et al. [66]; () Kalfoglou and Miller [67];
() Gilgen et al. [21]; ( ) Tanner and Masson [68]; () Onnes and Crommelin [9]; () Crain and Sonntag [69]; () Michels et al. [70]; () EstradaAlexanders and Trusler [71]; () Eq. (15); (- - -) Orbey and Vera [17]; (---)
Weber [7].
Fig. 13. Third virial coefficients of nitrogen: () Roe [25]; () Zhang et al.
[72]; () Michels et al. [73]; () Holborn and Otto [64]; () Michels et al.
[74]; ( ) Canfield et al. [75]; () Onnes and Van Urk [9]; () Hoover et al.
[76]; () Duschek et al. [77]; () Otto et al. [78]; () Eq. (15); (- - -) Orbey
and Vera [17]; (---) Weber [7].
Fig. 14. Third virial coefficients of carbon dioxide: () Patel et al. [79]; ()
Vukalovich and Masalov [80]; () Glowka [81]; () Pfefferle et al. [82];
() Holste et al. [83]; ( ) Butcher and Dadson [84]; () Duschek et al.
[85]; () Katayama et al. [86]; () Michels and Michels [87]; () Holste et
al. [88]; () Eq. (15); (- - -) Orbey and Vera [17]; (---) Weber [7].
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
Fig. 15. Third virial coefficients of methane: () Kleinrahm et al. [89]; ()
Michels and Nederbragt [90]; () Trusler et al. [91]; () Dymond et al. [9];
() Haendel et al. [26]; ( ) Hoover et al. [92]; () Schamp et al. [93]; ()
Douslin et al. [31]; () Roe [25]; () Pope et al. [16]; ( ) Trappeniers et
al. [29]; ( ) Holleran [32]; () Eq. (15); (- - -) Orbey and Vera [17]; (---)
Weber [7].
Fig. 16. Third virial coefficients of R23: ( ) Timoshenko et al. [94]; ()
Rasskazov et al. [95]; () Lange and Stein [96]; () Yokozeki et al. [97];
() Eq. (15); (- - -) Orbey and Vera [17]; (---) Weber [7].
Fig. 18. Third virial coefficients of R134a: ( ) Qian et al. [57]; ()
Yokozeki et al. [97]; () Goodwin and Moldover [59]; () Eq. (15); (- -) Orbey and Vera [17]; (---) Weber [7].
Fig. 17. Third virial coefficients of R32: () Sato et al. [52]; () Kuznetsov
and Los [98]; ( ) Zhang et al. [99]; () Yokozeki et al. [97]; () Fu et al.
[100]; () Defibaugh et al. [53]; () Eq. (15); (- - -) Orbey and Vera [17];
(---) Weber [7].
Fig. 20. Third virial coefficients of R152a: () Yokozeki et al. [97]; ( )
Tamatsu et al. [104]; () Gillis [103]; () Eq. (15); (- - -) Orbey and Vera
[17]; (---) Weber [7].
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
interesting to note that the predicted value is in good agreement with the only data point of Boyes and Weber [108], with
only one other set of data available.
Eq. (15) has a positive minimum at Tr equal to about 5
for nonpolar molecules, which is certainly wrong for high
reduced temperatures. However, this error does not contribute
to a large numerical error in C here. The Weber correlation has
a similar problem, which we attribute to the assumption that
Bh (T) and Ch (T) are constants, and neglecting an important
term of the Van Nhu model for high temperatures. As Van
Nhu emphasized, his model is probably wrong for the limit
of Tr .
The correlation was also compared to data for strongly
polar and associating substances. The results for ammonia
(Br obtained using Eq. (10)) are shown in Fig. 23. Surprisingly, although no experimental data for low temperatures are
available, Eq. (15) is in good agreement with the experimental data above 300 K. However, all three correlations cannot
give satisfactory predictions for water, which indicates that a
association term should be added to Eq. (15) to improve the
prediction.
Fig. 22. Third virial coefficients of R124: () Gillis [103]; () Boyes and
Weber [108]; () Eq. (15); (- - -) Orbey and Vera [17]; (---) Weber [7].
117
4. Discussion
The importance of the virial coefficients lies in the fact
that they are very useful for representing the PVT behavior
of real gases at low densities. Although good-quality PVT
measurements in the gas phase have an experimental accuracy of about 0.1% in density, corresponding-states type correlations, including the present one and Webers work, do not
normally achieve this accuracy. The virial equation of state,
truncated after the third virial coefficient, can provide a very
good fit to precise PVT data for densities up to about 0.5c
for nonpolar gases. For polar gases, this maximum density
decreases to about 0.25c or even lower.
The accuracies of the present correlation and the Weber
correlation for the nonpolar gases argon and nitrogen and
polar gas R134a are shown in Figs. 2426. For these three
gases, the present correlation is better than Webers in representing the gas-phase densities over the whole range. Estimates for the density error for the nonpolar gases methane,
ethane, propane, butane, carbon dioxide and oxygen and the
polar gases R143a, R125a, R32 and R22 are shown in Table 2.
For most nonpolar fluids and polar haloalkanes, the present
Fig. 24. Density deviations of argon from EOS of Tegeler et al. [110]; present
work: () 105.15 K, () 181.15 K, () 303.15 K, ( ) 453.15 K; Weber [7]:
() 105.15 K, ( ) 181.15 K, () 303.15 K, ( ) 453.15 K.
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118
Table 2
Estimated density uncertainties of nonpolar and polar fluids
Temperature range
Tr = 0.60.9
Tr = 0.91.2
Tr >1.2
Pr < 0.6
Pr > 0.7
Pr < 0.3
0.2
0.2
0.1
0.3
0.2
2.0
1.0
0.2
0.5
0.5
2
2
Greek letters
acentric factor
5. Conclusions
Subscripts
c
critical property
cal
calculated result
exp
experimental result
r
reduced property (not including r )
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L. Meng et al. / Fluid Phase Equilibria 226 (2004) 109120
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 50225622) and the Fok Ying Tung
Education Foundation (No. 81051).
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