The New Simple Extended Corresponding-States Principle Vapor Pressure and Second Virial Coefficient
The New Simple Extended Corresponding-States Principle Vapor Pressure and Second Virial Coefficient
The New Simple Extended Corresponding-States Principle Vapor Pressure and Second Virial Coefficient
www.elsevier.com/locate/ces
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: [email protected] (H. W. Xiang).
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
(1)
= (Zc 0:29)2 ;
(2)
(3)
(4)
(5)
(6)
(7)
1441
1442
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
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
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
Methanol
Ethanol
Lydersen and Tsochev (1990), Ambrose, Sprake, and Townsend (1975) and Ambrose and Sprake (1970)
1-Propanol
Acetone
Acetic acid
Acetonitrile
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
Benzene
and Smith
and Smith
(1986)
and Smith
and Smith
(1986)
1444
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
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
-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. 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.
0.7
0.9
1.1
0
-2
B/Vc
-4
-6
-8
-10
-12
Tr
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.
1445
1446
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
!
Acknowledgements
The author would like to express heartfelt gratitude to
Professor William A. Wakeham, Dr. J.P. Martin Trusler,
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