Chemical Engineering Science 57 (2002) 1439 1449

www.elsevier.com/locate/ces

The new simple extended corresponding-states principle:

vapor pressure and second virial coe'cient
H. W. Xiang
Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun, Haidian, Beijing 100080, China
Received 9 October 2000; received in revised form 6 June 2001; accepted 6 October 2001

Abstract
A new simple extended corresponding-states principle has been developed to represent and predict the thermophysical properties of
4uids. The extended corresponding-states principle only requires the substance-dependent critical parameters and acentric factor which
enhances the corresponding-states principle of Pitzer et al. to include the behavior of substances whose force 8elds deviate strongly from
spherical symmetry. The additional corresponding-states parameter de8ned in terms of the deviation of the critical compression factor of
a real molecule from that of spherical molecules is independent of experimental data for any speci8c property. The new simple extended
corresponding-states principle presented here remarkably improves the representation of the vapor pressure from the triple point to the
critical point and the second virial coe'cient from the triple point to the highest temperatures over which experimental data exist. Accurate
results for these two well-understood properties are given for simple, normal, polar, hydro-bonding and associating compounds. The
results also show that the new simple extended corresponding-states principle is more reliable and accurately predicts the vapor pressure
and second virial coe'cient of a strongly nonspherical 4uid than any other existing methods. ? 2002 Published by Elsevier Science Ltd.
Keywords: Complex 4uids; Corresponding-states principle; Critical parameters; Phase equilibria; Theory of liquids; Thermodynamics

1. Introduction
Physical and thermodynamic data on chemical compounds are required for e'cient design and operation
of chemical industrial applications. It is useful to predict these properties by use of suitable models since the
experimental determination of all the required data is a
formidable proposition. Of the many predictive approaches
that have been proposed, the corresponding-states principle
has proved to be the most powerful framework (Leland
& Chappelear, 1968). The corresponding-states principle
was the most useful and accurate derivative of the work
of van der Waals on his famous equation of state (van der
Waals, 1873). The general corresponding-states principle
has proved to be much better than has often been thought
in the past (Huber & Hanley, 1996). The methods based
on the principle are theoretical and predictive, rather than
empirical and correlative. It has a 8rm basis in statistical
mechanics and kinetic theory and has a great range and
accuracy. While the corresponding-states principle cannot

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E-mail address: hwxiang@hotmail.com (H. W. Xiang).

0009-2509/02/$ - see front matter ? 2002 Published by Elsevier Science Ltd.

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always reproduce a set of data within its claimed experimental accuracy, as can an empirical correlation. Nevertheless it can not only represent data to a reasonable degree of
accuracy but, more importantly can also predict properties
beyond the range of existing data which a correlation cannot
do (Huber & Hanley, 1996).
In its original form, the corresponding-states principle
involves two independent parameters which accurately
characterizes the behavior of simple monatomic force 8elds
(van der Waals, 1873). An additional third parameter,
the acentric factor proposed by Pitzer, Lippmann, Curl,
Huggins, and Petersen (1955), enhances the scope of the
corresponding-states principle to include 4uids whose force
8elds slightly deviate from spherical symmetry. However,
the corresponding-states principle of Pitzer et al. did not
include systems containing highly polar species and species
exhibiting speci8c interactions such as hydrogen bonding,
for which modeling involves an additional fourth parameter
to account for the polarity eCects. Many attempts have been
made to derive a four-parameter corresponding-states principle to include polar 4uids (Su, 1937; Meissner & Seferian,
1951; Riedel, 1954; Eubank & Smith, 1962; Halm & Stiel,
1967, 1971; Leach et al., 1968; Leland & Chappelear, 1968;

1440

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Kreglewski, 1969; Polak & Lu, 1972; Tsonopoulos, 1974,

1975; Hayden & OConnell, 1975; Tarakad & Danner, 1977;
Wu & Stiel, 1985; Wilding & Rowley, 1986; Weber, 1994;
Tsonopoulos & Dymond, 1997). Various candidate parameters have been proposed such as the critical compression factor, Riedel parameter, polarity factor, polarizability, radius
of gyration, dipole moments, and molecular shape factor.
None of these attempts to introduce a fourth parameter into
the corresponding-states principle have been fully successful. This fourth parameter suCers from one or more of the
following drawbacks: insu'cient capability, lack of physical
signi8cance, dependence on speci8c thermophysical property, and no generalization to all classes of 4uids and to other
properties. Therefore, these results led to complicated correlations, inconsistent results, and di'culties in extending the
method to mixtures and other properties. In this work, a new
fourth parameter is introduced to successfully extend the
corresponding-states principle of Pitzer et al. for normal 4uids to highly nonspherical substances for the representation
of the vapor pressure and the second virial coe'cient, which
have been extensively studied and are well-understood
properties.
2. Development
Spherical molecules obey the two-parameter corresponding-states principle in that a property of a substance
may be equated with that of another at a reduced state.
The two-parameter corresponding-states method applies
accurately only to the spherical molecules such as argon, krypton, and xenon. Consequently, the property is
an universal function of the reduced state. To apply the
corresponding-states principle to molecular 4uids, Pitzer
et al. (1955) proposed the acentric factor ! to take
into account the nonspherical nature of the molecules
as
! = 1 log pr |Tr =0:7 ;

(1)

which de8ned in terms of the slope of the vapor-pressure

curve to provide a single measurable macroscopic parameter
that is related to the degree of anisotropy. Here, pr =p=pc is
the reduced saturated vapor pressure with p being the vapor
pressure and pc the critical pressure. Tr =T=Tc is the reduced
temperature with T being the temperature and Tc the critical temperature. This three-parameter corresponding-states
method works well for normal substances but is generally not accurate for polar, hydro-bonding and associating
molecules, which strongly deviate from spherical symmetry. The fourth parameter for typical polar 4uids corresponds, in general to an intermolecular potential function
which accounts for dispersion and dipoledipole interaction
eCects. An eCective fourth parameter may better describe
polar 4uids than a three-parameter corresponding-states
model. For polar molecules, the critical parameters are in4uenced by the dipole and quadrupole moments (Eubank &

Smith, 1962). The critical compression factor, Zc , which is

substance-dependent characteristic parameter, was used as
an additional parameter by Meissner and Seferian (1951)
and by Leland and Chappelear (1968). Using a de8nition
similar to the acentric factor, a new corresponding-states parameter
is introduced to measure the deviation of a highly
nonspherical molecule from the spherical molecule argon, as

= (Zc 0:29)2 ;

(2)

Zc = pc =Rc Tc is the critical compression factor and R is

the gas constant. Zc = 0:29 is the value for monatomic 4uid
argon. Based on the concept of the corresponding-states
principle, the extended parameter
considers the deviation of the critical compression factor, Zc , of a real nonspherical molecule from that of spherical molecules to
extend the corresponding-states principle of Pitzer et al.
for normal substances to more complex substances (Xiang,
1998, 2001ac). Any relation between the de8ned parameter
and the acentric factor ! is only approximate
for a speci8c class of 4uids and cannot be universally
correct. The relation between the critical compression
factor and the acentric factor, Zc = 0:29 0:08!, is
only approximate for the normal substances given by
Pitzer et al. (1955) and by Reid, Prausnitz, and Poling
(1987), which is not applicable to highly nonspherical
substances. It may be deduced that for normal 4uids the
new extended corresponding-states principle corresponds
to adding a quadratic term 0:0064!2 to the expression of
Pitzer et al.
Consequently, the extended corresponding-states principle is expressed as
f = f(0) + f(1) ! + f(2)
;

(3)

where f represents a property. The corresponding-states

principle is applied here to represent the vapor pressure
and the second virial coe'cient of some representative substances in diCerent classes of 4uids. The calculated values
are then compared with the most recent accurate experimental data which are widely accepted.

3. Application to the vapor pressure and second virial

coecient
To test the extended corresponding-states principle, it
is important to select a reference equation that is valid
over the entire range so that any contribution due to the
corresponding-states principle can be clearly displayed. For
the vapor pressure, the empirical equation proposed by Xiang and Tan (1994) is valid and accurate over the entire
range from the triple point to the critical point. The equation
is
ln pr = (a0 + a1 1:89 + a2 5:67 ) ln Tr ;

(4)

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

where  = 1 Tr is a temperature-dependent parameter.

a0 ; a1 , and a2 are three substance-dependent parameters
with a0 being the Riedel parameter. The exponent 1.89 in
the second term of Eq. (4) was derived from the critical
exponent 0.11 of the renormalization-group theory of critical phenomena. The exponent 5.67 in the third term is
equal to 3 1:89. The equation was shown to accurately
represent and extrapolate the vapor-pressure behaviors
of simple, normal, polar, hydrobonding, and associating
compounds. According to Eq. (3), the vapor pressure
can be described by the corresponding-states principle
as
a0 = a00 + a01 ! + a02
;
a1 = a10 + a11 ! + a12
;
a2 = a20 + a21 ! + a22
:

(5)

The coe'cients aij of Eq. (5) are determined from

8tting the experimental data of argon, the weakly nonspherical molecules ethane, propane, di4uoromethane,
1; 1; 1; 2-tetra4uoroethane and 1; 1-di4uoroethane, and the
highly nonspherical molecule water.
For the second virial coe'cient, B, the PitzerCurl equation and the Tsonopoulos equation are accurate in representing the behavior of a normal substance, however, these
equations are not for polar substances. For example, Weber
(1994) found that by deleting the last term in the Tsonopoulos equation, a better representation of the behavior of
halocarbon substances was obtained. Therefore, a simple
empirical equation with the least number of adjustable
parameters is used here for the second virial coe'cient
(Xiang, 1993),
Br = Bc = b0 Tr3=4 exp(b1 Tr3 ) + b2 Tr1=2 ;

(6)

where b0 ; b1 , and b2 are substance-dependent parameters.

According to Eq. (3), the corresponding-states principle describes the second virial coe'cient as follows:
b0 = b00 + b01 ! + b02
;
b1 = b10 + b11 ! + b12
;
b2 = b20 + b21 ! + b22
:

(7)

The coe'cients bij are found in the same way as aij .

The critical parameters and the acentric factors of these
substances and other substances listed only for comparison are given in Table 1 with the data sources in Table
2. These experimental data are the most accurate to date
and have been widely used to test proposed models. Most
critical parameters are taken from the recommended data
(Ambrose & Tsonopoulos, 1995; Gude & Teja, 1995;
Tsonopoulos & Ambrose, 1995; Rosenthal, Gude, Teja, &
MendezSantiago, 1997). The parameters aij and bij given
in Table 3 for the empirical equations for vapor pressure
and the second virial coe'cient are independent of the
temperature and the speci8c substance and are expected

1441

to be universally applicable to all classes of molecules. For

the second virial coe'cient, although b02 and b22 in Eq.
(7) were found to be zero, they may have small values to
better represent experimental data when future measurement
accuracy is improved.
4. Comparison with experimental data
Figs. 1 6 show how the present model represents recent reliable and accurate vapor-pressure and second-virialcoe'cient data for various typical real 4uids over their entire
temperature ranges. In the 8gures, only one symbol is used
for all of the data sets for each 4uid for the sake of clarity. For
most cases the agreement between the model and the data is
generally comparable with the agreement between the diCerent data sets for each substance. Generally, the new extended
corresponding-states principle can describe the vapor pressure and second virial coe'cient to almost within the experimental uncertainties over their entire temperature ranges,
so the presented method is almost within the experimental
errors.
For highly accurate vapor-pressure data above the
normal-boiling point, the deviations of the method from
the experimental data are almost within 0.1% as shown in
Fig. 1 for nonpolar substances while for other substance
classes may refer to Xiang (2001a). For substances with
high boiling temperatures, high-temperature experimental
data are usually not known or may be experimentally inaccessible because of decomposition. In the low-temperature
region, both properties are subject to large uncertainties
especially at very low temperatures. The vapor-pressure
values are usually very small at low temperatures so the
relative error is large due to experimental di'culties. Usually, the experimental uncertainties for the vapor pressure
and the second virial coe'cient can be 5 10% at low
temperatures. In general, the experimental di'culties in
obtaining accurate low-temperature data mean that experimental results are scarce and uncertainties are large and
the measured vapor pressures are even less accurate at
very low-temperatures close to the triple-point temperature.
The new simple extended corresponding-states principle
accurately predicts the vapor pressure even at reduced
temperatures down to 0.3 0.2 for ethane and propane as
shown in Fig. 1 while for benzene the deviation is slightly
larger. The results in Fig. 2 show that the predictions for
the second virial coe'cient at the lowest temperatures
deviate by 5% even for argon for which highly accurate
experimental data are available. The relative deviation is
8% at the lowest temperature 290 K (Tr = 0:515) and 5%
at 310 K (Tr = 0:55) for benzene in Fig. 3, which has a
triple-point temperature of 278:7 K (Tr = 0:496). Considering that a very small low-temperature vapor-phase compressibility change has a large eCect on the second virial
coe'cient, the new method may predict the vapor-phase
compressibility for any class of 4uids over the whole

1442

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Table 1
Molar mass M , critical temperature Tc , critical pressure pc , critical density c , acentric factor !, critical compression factor Zc , and new extended
corresponding-states parameter
for pure 4uids

Substance

M
(kg kmol1 )

Tc
(K)

pc
(kPa)

c
(kg m3 )

Zc

103

Argon
Nitrogen
Methane
Carbon dioxide
Ethylene
Ethane
Propane
Benzene
Decane
R12
R22
R32
R123
R125
R134a
R152a
Diethyl ether
Ammonia
Water
Methanol
Ethanol
1-Propanol
Acetone
Acetic acid
Acetonitrile
Ethyne
1; 3-Dimethylbenzene
1; 4-Dimethylbenzene
Phenol
Fluoromethane
Methyl chloride
1, 2-Dichloroethane
Bromomethane
Dimethyl ether
2-Propanol
2-Methyl-1-propanol
2-Methyl-2-propanol
1-Butanol
2-Butanol
Methyl ethyl ketone
Methyl-n-propyl ketone
Methyl isopropyl ketone
Diethyl ketone
Methyl formate
Propyl formate
Methyl acetate
Ethyl formate
Methyl propionate
Methyl ethyl sul8de
Hydrogen cyanide
Dimethylamine
Nitromethane
Sulfur dioxide
Hydrogen sul8de

39.948
28.013
16.043
44.010
28.054
30.070
44.097
78.114
142.86
120.91
86.470
52.020
152.93
120.02
102.03
66.050
74.123
17.031
18.015
32.042
46.069
60.096
58.080
60.052
41.053
26.038
106.168
106.168
94.113
34.033
50.488
98.959
94.939
46.069
60.096
74.123
74.123
74.123
74.123
72.107
86.134
86.134
86.134
60.052
88.107
74.079
74.079
88.107
76.157
27.026
45.085
61.041
64.063
34.080

150.69
126.19
190.564
304.13
282.35
305.32
369.83
562.05
617.70
385.12
369.28
351.26
456.83
339.17
374.18
386.41
466.6
405.4
647.10
512.5
514.0
536.8
508.1
590.7
545.4
308.3
617.1
616.2
694.3
315.0
416.2
561.0
464.0
400.0
508.0
547.8
506.2
563.0
536.1
536.8
561.1
553.3
561.0
487.2
538.0
506.8
508.5
530.6
533.0
456.6
437.7
588.0
430.8
373.2

4863
3395
4598
7377
5041
4872
4248
4895
2110
4130
4988
5782
3662
3620
4055
4516
3640
11345
22050
8084
6137
5169
4696
5780
4830
6140
3540
3510
6100
5600
6680
5370
6610
5330
4780
4300
3970
4420
4180
4210
3690
3850
3730
6000
4060
4690
4740
4000
4260
5390
5310
6310
7880
8940

535.6
313.3
162.7
467.6
214.2
206.6
220
305
228
565
520
424
550
572
508
368
264
234
325
263
275
276
268
330
225
231
282
280
400
302
363
450
618
270
271
270
269
268
275
270
286
282
260
350
309
325
320
310
290
205
247
360
525
346

0
0.037
0.011
0.225
0.086
0.099
0.152
0.210
0.489
0.180
0.221
0.277
0.282
0.306
0.327
0.275
0.281
0.256
0.344
0.560
0.644
0.623
0.308
0.450
0.338
0.190
0.325
0.320
0.438
0.187
0.152
0.278
0.157
0.197
0.665
0.592
0.612
0.593
0.277
0.322
0.346
0.332
0.344
0.257
0.314
0.326
0.285
0.35
0.216
0.405
0.302
0.310
0.256
0.081

0.289
0.289
0.286
0.275
0.281
0.279
0.277
0.268
0.257
0.276
0.270
0.243
0.268
0.269
0.262
0.252
0.263
0.245
0.227
0.231
0.241
0.252
0.241
0.214
0.194
0.270
0.260
0.260
0.249
0.241
0.268
0.253
0.263
0.273
0.251
0.259
0.260
0.261
0.253
0.252
0.238
0.256
0.265
0.254
0.259
0.254
0.260
0.258
0.252
0.187
0.266
0.219
0.268
0.284

0.000
0.000
0.015
0.238
0.077
0.114
0.171
0.472
1.061
0.190
0.394
2.219
0.481
0.427
0.796
1.422
0.706
2.03
3.95
3.47
2.444
1.431
2.41
5.752
9.15
0.400
0.915
0.914
1.71
2.41
0.463
1.36
0.718
0.274
1.52
0.950
0.905
0.832
1.39
1.45
2.69
1.18
0.629
1.29
0.974
1.32
0.928
1.04
1.41
10.6
0.560
5.06
0.464
0.039

temperature range within experimental uncertainty for the

compressibility.
In contrast to existing models, the new extended
corresponding-states principle can describe the vapor

pressure and the second virial coe'cient of highly polar and hydrobonding and associating substances, such
as dichlorodi4uoromethane, chlorodi4uoromethane, di4uoromethane, 1; 1-dichloro-2; 2; 2-tri4uoroethane, penta4u-

Table 2
Data sources for vapor pressure p and second virial coe'cient B of pure 4uids listed in Table 1

Fluid

Refs. (p)

Refs. (B)

Argon
Nitrogen
Methane
Carbon dioxide
Ethylene
Ethane

Gilgen, Kleinrahm, and Wagner (1994)

Nowak, Kleinrahm, and Wagner (1997)
Kleinrahm and Wagner (1986)
Duschek, Kleinrahm, and Wagner (1990)
Nowak, Kleinrahm, and Wagner (1996)
Pal, Pope, Arai, Carnahan, and Kobayashi (1976), Straty and Tsumura (1976), Carruth and Kobayashi (1973)
and Douslin and Harrison (1973)
Kratzke and Mueller (1984), Thomas and Harrison (1982), Carruth and Kobayashi (1973) and Kemp and
Egan (1938)
Ambrose (1981), Ambrose, Broderick, and Townsend (1967), Connolly and Kandalic (1962) and Bender,
Furukawa, and Hyndman (1952)
Ruzicka and Majer (1994) and Chirico, Nguyen, Steele, Strube, and Tsonopoulos (1989)
Blanke and Weiss (1992a), Haendel, Kleinrahm, and Wagner (1992), Fernandez-Fassnacht and del Rio (1985)
and Michels, Wassenaar, Wolkers, Prins, and Klundert (1966)
Blanke and Weiss (1992a), Haendel, Kleinrahm, and Wagner (1992), Goodwin, De8baugh, and Weber (1992b),
and Kohlen, Kratzke, and Mueller (1985)

Dymond
Dymond
Dymond
Dymond
Dymond
Dymond

Propane

Decane
R12
R22

R32

R152a

Magee (1996), Fu, Han, and Zhu (1995), De8baugh, Morrison and Weber (1994), Weber and Silva (1994)
and Weber and Goodwin (1993)
Goodwin, De8baugh, Morrison, and Weber (1992a)
Magee (1996), Tsvetkov, Kletski, Laptev, Asambaev, and Zausaev (1995), Weber and Silva (1994) and Boyes
and Weber (1995)
Blanke, Klingenberg, and Weiss (1995), Goodwin, De8baugh, and Weber (1992b), Baehr and Tillner-Roth
(1991) and Weber (1989)
Silva and Weber (1993), Blanke and Weiss (1992a, b) and Baehr and Tillner-Roth (1991)

Diethyl ether
Ammonia
Water

Ambrose, Sprake, and Townsend (1972)

Zander and Thomas (1979), Baehr, Garnjost, and Pollak (1976) and Cragoe, Meyers, and Taylor (1920)
IAPWS (1994)

Methanol

Gibbard and Creek (1974) and Ambrose and Sprake (1970)

Ethanol

Lydersen and Tsochev (1990), Ambrose, Sprake, and Townsend (1975) and Ambrose and Sprake (1970)

1-Propanol

Lydersen and Tsochev (1990) and Ambrose and Sprake (1970)

Acetone
Acetic acid
Acetonitrile

Ambrose, Sprake, and Townsend (1974)

Ambrose, Ellender, Sprake, and Townsend (1977)
Kratzke and Mueller (1985) and Mousa (1981)

R123
R125
R134a

(1980)
(1980)
(1980)
(1980)

Dymond (1986)
Dymond and Smith (1980)
Natour, Schuhmacher, and Schramm (1989)
Demiriz, Kohlen, Koopmann, Moeller, Savermann,
IglesiasSilva, and Kohler (1993), Natour, Schuhmacher, and Schramm (1989) and Kohlen, Kratzke,
and Mueller (1985)
Bignell and Dunlop (1993a, b)

1443

Goodwin and Moldover (1991) and Weber (1990)

Boyes and Weber (1995) and Bignell and Dunlop
(1993a, b)
Tillner-Roth and Baehr (1992) and Goodwin and
Moldover (1990)
Bignell and Dunlop (1993a, b) and Tillner-Roth and
Baehr (1992)
Dymond and Smith (1980)
Dymond and Smith (1980)
Eubank, JoCrion, Patel, and Warowny (1988) and
Dymond and Smith (1980)
Boyes, Ewing, and Goodwin (1992), Kerl and
Varchmin (1991), Abusleme and Vera (1989), Olf,
Schnitzler, and Gaube (1989), Tsonopoulos, Dymond, and Szafranski (1989) and Dymond and
Smith (1980)
Abusleme and Vera (1989), Tsonopoulos, Dymond,
and Szafranski (1989) and Dymond and Smith
(1980)
Tsonopoulos et al. (1989) and Dymond and Smith
(1980)
Dymond and Smith (1980)
Dymond and Smith (1980)
Demiriz, Kohlen, Koopmann, Moeller, Sauermann,
IglesiasSilva, Kohler (1993), Olf, Schnitzler, and
Gaube (1989), and Dymond and Smith (1980)

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Benzene

and Smith
and Smith
(1986)
and Smith
and Smith
(1986)

1444

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Table 3
General coe'cients of Eqs. (5) and (7)

5.790206
4.888195
33.91196
4.553
4.172
0

a10
a11
a12
b10
b11
b12

6.251894
15.08591
315:0248
0.02644
0.075
16.5

-1

-2
B/Vc

100(1-p calc/p expt)

a00
a01
a02
b00
b01
b02

11.65859
46.78273
1672:179
3.530
4.297
0

-3
-4

-2

-5

-4

-6

-6
-8

a20
a21
a22
b20
b21
b22

0.2

0.4

0.6

0.8

-7
0.5

1.0

1.5

2.0

Tr
Fig. 1. Comparison of vapor-pressure data for normal substances with
values calculated from the new simple extended corresponding-states principle: () argon; (
) methane; ( ) ethane; () propane; () nitrogen;
() ethylene; (+) benzene.

2.5

3.0

3.5

Tr

Fig. 3. Comparison of second-virial-coe'cient data for normal substances

with values calculated from the new simple extended corresponding-states
principle: () methane; ( ) carbon dioxide; () propane; (4) ethylene;
(
) benzene.

-1

-2

B/Vc

B/Vc

-3

-1

-4

-2

-5
-6

-3

0.5

0.7

0.9

1.1

1.3

1.5

Tr

-4
Tr

Fig. 2. Comparison of second-virial-coe'cient data for argon with values

calculated from the new corresponding-states principle.

oroethane, 1; 1; 1; 2-tetra4uoroethane, 1; 1-di4uoroethane,

water, methanol, ammonia, acetone, and acetonitrile as
shown in Figs. 4 6, and of Xiang (2001a, c). There are
several sets of vapor-pressure and second-virial-coe'cient
data for acetonitrile, all of which agree reasonably well.
For the highly polar substances such as di4uoromethane,

Fig. 4. Comparison of second-virial-coe'cient data for chloro4uoroand hydro4uoro-carbons with values calculated from the new simple
extended corresponding-states principle: (4) dichlorodi4uoromethane;
() chlorodi4uoromethane; (
) 1; 1-dichloro-2; 2; 2-tri4uoroethane; ()
1; 1; 1; 2-tetra4uoroethane; () 1; 1-di4uoroethane.

1; 1; 1; 2-tetra4uoroethane and 1; 1-di4uoroethane, the

method is in agreement with recent high-accuracy data
over the entire region within the experimental uncertainties,
which are better than any existing model. As Weber (1994)
stated, the reduced dipole moment cannot follow the strongly
negative second virial coe'cient behavior of the data

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

0.5

0.7

0.9

1.1

0
-2

B/Vc

-4
-6
-8
-10
-12

Tr

Fig. 5. Comparison of second-virial-coe'cient data for diethyl ether

and acetone with values calculated from the new simple extended
corresponding-states principle: () diethyl ether; () acetone.

0
-5
-10
B/V c

-15
-20
-25
-30
-35
0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Tr
Fig. 6. Comparison of second-virial-coe'cient data for water, methanol,
and acetonitrile with values calculated from the new simple extended
corresponding-states principle: (
) water; (4) methanol; () acetonitrile.

with diCerences ranging from 20% at 450 K (Tr = 0:825)

to almost a factor of two at 300 K (Tr = 0:55) for acetonitrile. However, the new extended corresponding-states
principle accurately predicts the second virial coe'cient
of acetonitrile as shown in Fig. 6. The reduced dipole
moment cannot be used as a fourth parameter since the
dipole moment location and direction with respect to the
entire molecule has an important in4uence on the compressibility. Meanwhile the reduced dipole moment also
cannot describe the second virial coe'cients of less polar
4uids (OConnell & Prausnitz, 1967; Tsonopoulos, 1974,
1975; Weber, 1994; Tsonopoulos & Dymond, 1997), the
new method gives excellent results as shown in Figs.
4 and 5, for example, for dichlorodi4uoromethane and
1; 1-dichloro-2; 2; 2-tri4uoroethane, which have less polar
dipole moments. Comparisons with existing methods for
second virial coe'cient for polar substances are listed in
Table 4.

1445

The methods proposed by Lee and Kesler (1975),

Ambrose and Patel (1984), Gupte and Daubert (1985)
and Edalat, Bozr-Jomehri, and Mansoori (1993) do not
have the prediction accuracy of this new method which
agrees well with highly accurate vapor pressure data in
the high-temperature range and with less accurate data at
the low temperatures. Compared with previous models,
the new extended corresponding-states model for vapor
pressure, Eq. (5), has an average overall relative error of
0.62% (for example, Edalat et al., 2.1%), an average overall
root-mean-square deviation of 1.2% (for example, Edalat
et al., 5.1%), and an overall maximum deviation which
occurs at a triple point of 0.07% for water and of 14% for
ethylene (for example, Edalat et al., 37% for water and 14%
for ethylene). The calculated deviation of 14% for vapor
pressure of ethylene means only 17 Pa uncertainty considering that the vapor pressure value is 122 Pa at a triple-point
temperature of 104 K. The results show that the new extended corresponding-states method is substantially superior to conventional linear or quadratic corresponding-states
correlations. It also testi8es that a quadratic correlation for
the acentric factor is not good to represent the vapor pressure for all classes of 4uids. For polar substances, the other
four-parameter corresponding-states models by Wilding and
Rowley (1986) and Wu and Stiel (1985) require the critical
parameters, the radius of gyration or the acentric factor, and
a pressuredensitytemperature data point, which depends
on a speci8c property. The present results for vapor pressure are also better than that obtained from any currently
available method for a more wide range of polar molecules
(Xiang, 2001a).
5. Conclusions
The corresponding-states principle of Pitzer et al. for
normal 4uids has been extended to include highly nonspherical molecules into the corresponding-states principle
framework. Only the critical parameters and acentric factor are required for the new extended corresponding-states
method. An additional corresponding-states parameter has been de8ned in terms of the deviation of
the critical state of a molecule from that of spherical molecules. Comparisons with the vapor pressure
and the second virial coe'cient, which have been
extensively studied and are well-understood properties, show that the new extended corresponding-states
method provides a convenient means for accounting
for the main nonspherical eCects on the physical properties of 4uids. The natures of the third and fourth
parameters make it possible to separate the eCects
of molecular structure from the eCects of nonspherical molecules so that the new corresponding-states
parameter re4ect the physical behavior of a strongly
nonspherical real substance from that of spherical
molecules.

1446

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Table 4
Percentage deviation of second-virial-coe'cient predictions by various methods for substances

Compound
Ethyne
1; 3-Dimethylbenzene
1; 4-Dimethylbenzene
Phenol
Methyl chloride
Fluoromethane
1; 2-Dichloroethane
Bromomethane
Dimethyl ether
Methanol
Ethanol
1-Propanol
Water
2-Propanol
2-methyl-1-propanol
2-methyl-2-propanol
1-Butanol
2-Butanol
Acetone
Methyl ethyl ketone
Methyl-n-propyl-ketone
Methyl isopropyl ketone
Diethy ketone
Methyl formate
Propyl formate
Methyl acetate
Ethyl formate
Methyl proptonate
Methyl ethyl sul8de
Hydrogen cyanide
Acetonitrile
Dimethylamine
Nitromethane
Sulfur dioxide
Hydrogen sul8de
Ammonia
Overall

Tr; min

Tr; max

Br; min

Br; max

AAD
PC

RMS
PC

Max
PC

AAD
TD

RMS
TD

Max
TD

AAD
ECS

RMS
ECS

Max
ECS

3
5
5
3
57
22
16
26
25
94
15
7
97
12
4
4
7
4
76
5
5
3
3
11
18
22
13
14
5
5
50
10
7
28
12
31
756

0.89
0.61
0.61
0.62
0.57
0.87
0.65
0.53
0.68
0.55
0.61
0.65
0.45
0.66
0.72
0.75
0.62
0.71
0.56
0.59
0.6
0.59
0.6
0.66
0.61
0.64
0.64
0.62
0.56
0.66
0.57
0.71
0.54
0.62
0.74
0.67
0.45

1.02
0.71
0.71
0.65
1.5
1.34
1.03
0.83
0.82
1.17
0.78
0.79
1.93
0.83
0.8
0.84
0.78
0.79
0.94
0.69
0.7
0.66
0.67
0.81
0.74
0.77
0.78
0.75
0.64
0.84
0.95
0.93
0.64
1.1
1.32
1.41
1.93

1.69
5.76
5.58
6.35
5.49
2.23
3.84
6.77
3.6
23.1
12.8
6.74
22.6
7.26
3.78
3.39
6.04
4.2
12.6
7.37
8.75
6.61
6.85
4.9
5.37
5.44
4.71
5.66
5.55
12.2
29.3
3.27
18.3
4.73
2.52
4.7
22.6

1.18
3.19
3.11
4.97
0.34
0.77
1.27
1.94
2.16
0.85
3.13
2.68
0.14
2.35
2.3
1.96
2.28
2.57
1.75
4.23
4.25
4.68
4.56
2.56
2.96
3.25
2.55
3.18
4.74
3.85
3.06
1.69
8.84
1.03
0.53
0.6
0.14

2.4
6.4
7.8
10
10
11
6
7.1
14
24
23
10
8.4
9.9
4.9
8
8.9
15
26
19
20
16
20
16
5.7
18
6.5
13
7.6
38
54
8.5
49
7.5
8.8
12
17

2.6
8
8.6
10
12
11
9.8
9.1
15
29
28
13
9.8
12
7.3
10
11
16
28
19
21
16
20
17
6.2
18
6.9
13
8.8
40
55
8.6
49
8.1
11
13
23

4
14
12
12
41
14
21
19
31
59
49
23
22
26
14
19
24
23
43
22
32
16
22
21
10
23
10
16
15
53
71
10
52
13
21
22
71

2.1
7
4.9
6.2
7.9
7.2
7.2
14
6.4
15
15
10
24
10
23
25
7.1
17
6
3.3
6.6
2.8
1
2.6
1.7
4.8
1.3
2.4
37
14
7.6
4.9
3.7
3.4
8
6.7
10

2.5
8.1
6.6
6.3
11
7.4
9.4
17
9.5
17
18
13
34
12
23
25
9.7
17
10
3.4
7.4
3
1.2
3.2
2.2
5.8
1.7
3.4
40
15
9.9
5.5
4.5
4.1
10
7.3
16

4
12
12
8.1
45
10
21
36
27
41
29
19
107
19
31
35
20
22
54
4.4
9.9
4.4
1.7
5.8
4.4
11
3.2
8.4
60
22
20
8.4
7.2
9.8
22
11
107

2.1
4.8
5.2
4.9
11
9.4
7.7
6.9
15
22
18
14
19
16
19
22
19
9.7
14
11
4.4
9.6
18
11
2
11
2.6
6.8
8
18
13
6.2
14
7.2
9.7
8.4
13

2.3
5.7
5.8
5.5
13
9.5
9
9.1
16
25
20
16
20
18
20
25
23
11
17
11
6.3
9.6
18
11
2.4
11
3.3
7.1
9.6
20
14
6.3
14
7.8
11
8.9
16

3.1
10
8.4
8.5
38
11
16
19
32
60
32
24
44
29
32
38
42
17
53
14
13
10
21
15
5
16
6.6
10
14
29
26
8.6
15
12
22
15
60

M
M is the number of data points.
Bcalc |=Bexpt ]=M , where Bexpt and Bcalc are theexperimental data and the corresponding

AAD = 100[ 1 |Bexpt
2
1=2
|
B

B
|
calculated values. RMS = 100{[ M
expt
calc =Bexpt ] =M } , where Bexpt and Bcalc are the experimental data and the corresponding calculated
1
values. n.a. = not available. Max: = The maximum percentage deviation of experimental pressure from the calculated value. PC = Pitzer and
Curl (1957). TD = Tarakad and Danner (1977). ECS = the new simple extended corresponding-states principle, Eqs. (6) and (7).

Notation
ai
aij
bi
bij
B
p
pc
pr
T
Tc
Tr
Zc

Greek letters
substance-dependent parameters in Eq. (4)
general parameters in Eq. (5)
substance-dependent parameters in Eq. (6)
general parameters in Eq. (7)
second virial coe'cient
vapor pressure
critical pressure
reduced pressure
temperature
critical temperature
reduced temperature
critical compression factor

c

!

new extended corresponding states aspherical

factor
critical density
temperature-dependent parameter
(=1 Tr )
acentric factor

Acknowledgements
The author would like to express heartfelt gratitude to
Professor William A. Wakeham, Dr. J.P. Martin Trusler,

H. W. Xiang / Chemical Engineering Science 57 (2002) 14391449

Dr. Abdel Fenghour, and K. Marjorie de Reuck for their

kind, productive and constructive comments during the period of his visit at Imperial College London, which was
presented at the 15th IUPAC International Conference on
Chemical Thermodynamics in Porto, Portugal. The author
is grateful to Dr. John H. Dymond at University of Glasgow
and Dr. Lloyd A. Weber at NIST for their encouragement
and exchange of ideas, and Dr. Weber at NIST and Dr. W.
Blanke at Braunschweig for providing their papers on vapor
pressure. The author is indebted to Professor John Bridgwater, Professor Lynn F. Gladden, and Ms. Shirley L. Whitehouse at University of Cambridge for their editorial contributions during the process, of the manuscript, for review.

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