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The PatelTeja and the PengRobinson EoSs performance when Soave alpha
function is replaced by an exponential function
Luis A. Forero G., Jorge A. Velsquez J.
Pulp and Paper Research Group, Faculty of Chemical Engineering, Universidad Ponticia Bolivariana, Circular 1a # 70-01 Medelln, Antioquia, Colombia
a r t i c l e
i n f o
Article history:
Received 10 January 2012
Received in revised form 27 April 2012
Accepted 4 May 2012
Available online 14 July 2012
Keywords:
Alpha function
Cubic equations of state
PatelTeja EoS
PengRobinson EoS
a b s t r a c t
A comparative study was made to establish how is altered the performance of PatelTeja EoS and
PengRobinson EoS, to represent thermodynamic properties of saturated pure uids when the alpha
function of Soave is substituted by an exponential function with one, two or three parameters. Results
show that the Soave function should be replaced by a two parameter exponential function to get adequate
representation of the vapor pressure and the saturated vapor volume of pure substances; especially in the
low pressure zone (1101.325 kPa). Additionally the performance of equations of state to represent saturated liquid volume and vaporization enthalpy was found practically independent of the alpha function.
Comparison between the two equations of state, show that PatelTeja EoS is superior than PengRobinson
EoS to represent the saturated liquid volume of pure substances with critical compressibility factor lower
than 0.25 or higher than 0.285. Also it has been demonstrated that using the two-parameter alpha function of Heyen with the WongSandler-NRTL mixing rules the capability of cubic EoS to represent the
vapor liquid equilibria below 1 atm for alcohol/alkane and alcohol/aromatic systems can be improved.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Engineers use the cubic equations of state (EoSs) to simulate,
evaluate, design and optimize chemical processes. EoSs are considered powerful tools to represent some thermodynamic properties
from pure substances and mixtures [1]. A cubic equation of state
is a simple expression that can be used to make fast and reliable
calculations in different practical applications [2,3]. The most popular EoSs are formulated using the repulsive term proposed by van
der Waals and an empiric attractive term [4]. A cubic equation of
state can be classied according to the number of parameters that
appear in its repulsive and attractive terms.
A rst group is formed by the two-parameter cubic equations
of state. Two-parameter EoSs like the PengRobinson equation [5]
and the SoaveRedlichKwong equation [6] are widely used to simulate chemical processes [7]. A two-parameter cubic equation of
state predicts a critical compressibility factor independent of the
uid. This fact can generate great errors in the density prediction
for saturated liquids [8].
A second group is formed by the three-parameter cubic equations of state. These equations appeared in the early 1980s and they
are considered a step in the development of the cubic equations of
state [7]. According to the literature [9], the more recognized models of this type are those of SchmidtWenzel [10], HarmensKnapp
[11], PatelTeja [12], YuLu [13] and Twu et al. [14]. In a recent
study, 23 generalized equations of state were compared and the
PatelTeja equation has been chosen as a member of the equations
of state group that provide the better results to correlate and predict
the thermodynamic properties of 102 pure substances [15,16]. In
general, the cubic equations of state with three parameters have a
substance-dependent empirical critical compressibility factor and
as consequence they are better than two-parameter EoSs to represent liquid densities [17].
Finally, there are equations like the TrebbleBishnoi equation
and the SalimTrebble equation that have four and ve parameters respectively [18,19]. Recently, Polishuk, Wisniak and Segura
presented an approximate method to develop four-parameter
equations of state [20]. However, when equations of state with four
or more parameters are used to represent thermodynamic properties of pure substances, there is not signicant improvement in the
performance of the cubic equations of state [9].
For the three groups described, two kinds of parameters can
be identied: the parameters related to the volume occupied by
the molecules or covolumes and the cohesion parameter that is
related to the interaction potential function of the molecules [7].
The temperature dependence of the parameters is very important
to guarantee the good performance of a cubic equation of state. In
the case of the covolumes, it has been shown that these have to
56
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
the Soave alpha function [6] and the exponential alpha functions
proposed by Haghtalab et al. [1], Gasem et al. [32], Melhem et al.
[36], Joshipura et al. [38] and Heyen [39]. The last ve functions
were selected to determine how the EoSs performance changes
when the number of the parameters in the exponential alpha function is altered. The evaluation is made including hydrocarbons,
halogens, inorganic and polar substances. To perform proper analysis, the parameters of the six alpha functions and the two equations
of state were determined using vapor pressure data between 1 kPa
and the critical pressure for each pure substance. Additionally,
results for the PengRobinson EoS and the PatelTeja EoS were
compared. Finally, vapor liquid equilibrium calculations for some
binary systems have been made to show the inuence of alpha
function in mixture calculations.
2. Equations of state
The pressure explicit form for the PatelTeja EoS is [12]:
P=
RT
vb
(1)
v2 + (b + c)v bc
(2)
R2 Tc 2
(3)
Pc
b = b
RTc
Pc
(4)
c = c
RTc
Pc
(5)
(6)
+ (2 3c )b2
+ 3c2 b
c3
=0
(7)
(8)
Eqs. (6)(8) can be obtained after restrict Eq. (1) to the critical point criteria [42]. c is substance-dependent and it is an
empiric critical compressibility factor. b value corresponds to
the smallest positive real root in Eq. (7) [10]. On the other hand,
the PengRobinson EoS can be obtained when the parameter b is
equal to parameter c in Eq. (1). The PengRobinson EoS has only
two parameters and the critical point criteria lead to the following
constants values [5]: a = 0.45724, b = 0.07780 and c = 0.307.
3. Alpha functions
To calculate the parameter a in the cubic equations of state, it
is necessary an expression to estimate the cohesion function that
appears in Eq. (2). A correct alpha function must comply with four
requirements [43]: (i) It must be a positive real number. (ii) It must
be a decreasing function that approaches to a positive value when
the temperature tends to innite. (iii) Its value must to be equal
to one at the critical temperature. (iv) It and its rst and second
derivatives must be continuous. In this work ve exponential alpha
functions, that in theory satisfy these conditions, are evaluated:
3.1. The Soave function [6]
= [1 + F(1
Tr )]
(9)
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
For the PengRobinson EoS the parameter F in Eq. (9) is calculated for each pure substance using the acentric factor and the
following generalized expression [5]:
F = 0.37464 + 1.54226 0.269922
(10)
(11)
The functionality of the Joshipura et al. alpha function was proposed by Trebble and Bishnoi [18]. A switching function depending
of the acentric factor magnitude can be found in the literature [45].
However Joshipura et al. correlated the parameter J that appears
in Eq. (11) as a linear function in terms of the acentric factor. The
expression to calculate J is:
J = 1.252 + 0.4754
(12)
(13)
Eq. (13) shows that the Joshipura et al. alpha function is monotonically decreasing for all substances
3.3. The Heyen function [39]
= exp(H1 (1 Tr H2 ))
(14)
(15)
From Eq. (15), it can be observed that the function of Heyen does
not present a minimum for any set for the parameters H1 and H2 .
3.4. The Melhem et al. function [36]
= exp(M1 (1 Tr ) + M2 (1
Tr ) )
(16)
(M2 M1 ) Tr M2
d
=
(17)
dTr
Tr
57
M2
M2 M1
(18)
(19)
The PR EoS can predict the vapor pressure of heavy hydrocarbons in good agreement with experimental data when the Soave
function is replaced by the Gasem et al. function. The parameters
G1 and G2 in Eq. (19) are constants and their values are 2 and
0.836 respectively. The third parameter G3 in Eq. (19) is substancedependent. For the PR EoS, the generalized expression to calculate
G3 is:
G3 = 0.134 + 0.508 0.04672
(20)
(21)
(22)
Hagtalab et al. developed a three-parameter EoS. Eq. (22) corresponds to the alpha function developed exclusively for that EoS.
The Haghtalab function is a modied Gasem et al. alpha function. In
similar way like the Gasem et al. function, in Eq. (22) the parameters
Ht1 and Ht2 are constants. The parameter Ht3 was also correlated
in a quadratic function in terms of the acentric factor.
The expression for the rst derivative respect to the reduced
temperature for the Haghtalab et al. function is:
d
=
[(Ht1 + Ht2 Tr )Ht3 ln Tr ln Ht3 + Ht2 Tr (1 Ht3 ln Tr )] (23)
Tr
dTr
In the same form as the Gasem et al. function, Eq. (23) can be
zero and a minimum alpha value can be predicted for the Haghtalab
et al. function.
4. Parameters estimation
To perform adequate comparison of the selected alpha functions, it is needed that all the parameters are determined under the
same conditions, i.e., using the same experimental data set and the
same objective function. For the six alpha functions evaluated, all
the parameters were considered as substance-dependent and they
were estimated for 66 pure substances.
The NIST reference [47] data for 60 pure uids were used. Inside
this group of substances there are alkanes with a carbon number
between 1 and 12. Additionally, there are refrigerants, inorganic
gases and polar substances like water, ammonia and methanol.
Experimental data reported in Perrys chemical engineer handbook were used for ethanol [48]. For acetone and diethyl ether
data reported by Ambrose et al. were consulted [49,50]. In the
case of dimethyl ether the vapor pressures measured by Wu were
used [51]. For aniline and alcohols from n-propanol to n-heptanol
experimental data can be extracted for the Design Institute for
Physical Property Data (DIPPR) database [5257]. In Table 1 the
58
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
Table 1
Classication, critical properties, reduced temperature range for the studied substances.
No.
Classication
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Hydrocarbons
Inorganics
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
Halogens
Substance
Tc (K)
Pc (kPa)
Methane
Ethane
Propane
2Methylpropane
Butane
2,2Dimethylpropane
2Methylbutane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Dodecane
Benzene
Methylbenzene
Ethene
Prop-1-ene
Argon
Kripton
Xenon
Oxygen
Nitrogen
Fluor
Carbon
disulde
Sulfur
hexauoride
Sulfur dioxide
Water
Ammonia
Carbon dioxide
Peruoroethane
Diuoromethane
Dichloromonouoromethane
Trichlorouoromethane
Dichlorodiuoromethane
Chlorotriuoromethane
Tetrauoromethane
Chlorodiuoromethane
Triuoromethane
Fluoromethane
1,1,2Trichloro1,2,2triuoroethane
1,2-Dichloro1,1,2,2tetrauroethane
1-Chloro1,1,2,2,2pentauoroethane
2,2-Dichloro1,1,1triuoroethane
2-Chloro1,1,1,2tetrauoroethane
1,1,1,2,2Pentauoroethane
1,1,1,2Tetrauoroethane
1,1-Dichloro-1uoroethane
Dodecauoropentane
Decauorobutane
1,1,1,3,3Pentauoropropane
1,1,2,2,3Pentauoropropane
1,1,1,2,3,3Hexauoropropane
190.56
305.33
369.825
407.81
4599.2
4871.8
4247.66
3629
Omega
0.0115
0.099
0.1524
0.184
Zc
0.286
0.279
0.276
0.278
Tr
0.476
0.409
0.431
0.445
0.985
0.971
0.99
0.991
2400
2578
2611
2631
425.125
433.8
3796
3200
0.201
0.197
0.274
0.272
0.447
0.592
0.993
0.998
2624
2705
460.35
3395.7
0.2296
0.27
0.457
0.992
2651
469.7
507.5
540.3
569.32
594.6
617.7
658.2
562.2
591.75
282.35
365.57
150.8
209.4
289.733
154.6
126.2
144.414
378.77
3370
3010
2740
2497
2290
2120
1820
4890
4126.3
5041.8
4664.6
4870
5500
5842
5040
3390
5172.4
6370
0.251
0.299
0.349
0.393
0.445
0.489
0.57639
0.212
0.266
0.0866
0.1408
0.00219
0.0009
0.00363
0.022
0.0372
0.054
0.098
0.27
0.266
0.261
0.259
0.253
0.247
0.238
0.268
0.264
0.281
0.281
0.291
0.288
0.286
0.288
0.289
0.287
0.275
0.4681
0.47
0.471
0.495
0.506
0.506
0.551
0.5215
0.452
0.406
0.419
0.556
0.553
0.557
0.388
0.5032
0.4051
0.4099
0.9874
0.989
0.999
0.989
0.979
0.989
0.98
0.9832
0.989
0.986
0.991
0.985
0.988
0.986
0.964
0.9784
0.9867
0.9873
2578
2528
2466
2427
2361
2324
2257
3376
3146
2500
2675
2057
2834
3818
1838
1388
1467
3210
318.7
3760
0.21
0.282
0.6997
0.9941
1923
430.8
647.3
405.4
304.1
293.03
351.255
451.48
471.11
385
302
227.6
369.3
299.3
317.28
487.3
7880
22120
11,333
7380
3048
5782
5181.2
4407.638
4140
3870
3740
4970
4860
5897
3410
0.256
0.344
0.253
0.224
0.257
0.2769
0.2061
0.189
0.179
0.172
0.1785
0.221
0.263
0.201
0.252
0.269
0.23
0.242
0.274
0.281
0.243
0.271
0.279
0.28
0.275
0.277
0.269
0.256
0.24
0.274
0.4596
0.423
0.482
0.7136
0.594
0.451
0.443
0.444
0.432
0.444
0.435
0.44
0.458
0.552
0.486
0.9896
0.981
0.986
0.9949
0.994
1
0.983
0.979
0.977
0.988
0.98
0.988
0.989
0.992
0.986
2339
2979
2215
1774
1588
1827
2751
2999
2518
2014
1491
2170
1601
1958
2669
418.9
3260
0.252
0.275
0.654
0.992
2294
353.2
3120
0.252
0.271
0.493
0.984
1934
456.83
3661.8
0.282
0.269
0.469
0.988
2352
395.425
3624.296
0.288
0.271
0.466
0.988
2012
339.173
3617.7
0.305
0.271
0.51
0.984
1671
374.21
4059.28
0.327
0.259
0.472
0.99
1772
477.5
4212
0.22
0.276
0.463
0.989
2812
420.55
386.326
427.2
2045
2323.4
3640
0.423
0.374
0.3724
0.276
0.287
0.266
0.5192
0.5063
0.4948
0.9904
0.9746
0.9827
1719
1695
1879
447.57
3925
0.354
0.27
0.4837
0.9716
2026
398.07
3200
0.379
0.269
0.4979
0.9825
1733
min
Tr
max
T* (K)
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
59
Table 1 (Continued)
No.
Classication
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Polarorganics
Substance
Tc (K)
Pc (kPa)
Omega
Zc
Tr
Chlorodiuoroethane
1,1,1Triuoroethane
1,1Diuoroethane
Heptauoropropane
Octauoropropane
Octauorocyclobutane
Methoxymethane
Ethoxyethane
Propan-2-one
Aniline
Methanol
Ethanol
Propan-2-ol
Propanol
Butanol
Pentanol
Hexanol
Heptanol
410.26
346.3
4055
3760
0.232
0.2615
0.267
0.255
0.457
0.4678
0.9885
0.9823
2349
1859
386.7
4500
0.275
0.252
0.4606
0.9882
2019
375.95
345.02
388.38
400
466.7
508.1
699
512.6
514
508.3
536.8
563
588.1
610.3
632.6
2999
2640
2777.5
5240
3640
4700
5310
8103.5
6137
4760
5169
4414
3897
3417
3058
0.354
0.317
0.355
0.2
0.281
0.30653
0.3777
0.565
0.649
0.667
0.62043
0.58946
0.57314
0.57636
0.56702
0.281
0.279
0.279
0.274
0.263
0.233
0.247
0.222
0.241
0.25
0.252
0.258
0.26
0.261
0.253
0.4921
0.4921
0.6025
0.5327
0.5358
0.5101
0.4816
0.488
0.603
0.5902
0.555
0.525
0.549
0.513
0.532
0.9874
0.9894
0.9929
0.9704
0.9921
0.9836
0.9773
0.988
0.953
0.984
0.975
0.978
0.975
0.972
0.953
1702
1663
1755
2475
2407
2496
3049
1778
1651
1609
1768
1907
2023
2093
2189
min
Tr
max
T* (K)
T* represents the temperature value in the alpha functions of Soave where minimum is presented.
F.O =
ND
i=1
exp
exp
EoS
EoS
Psat Psat
Vsat Vsat
w1
exp
+ w2 V exp
P
sat
(24)
sat
Fig. 1. Parameters for the Soave and the Joshipura et al. alpha functions for the PR
EoS in terms of the acentric factor. (a) : F values from Table 2, : calculated values
with Eq. (A1), - - -: calculated values with Eq. (10). (b) : J values from Table 2, :
calculated values with Eq. (A2), - - -: calculated values with Eq. (12).
60
Table 2
PengRobinson EoS parametersfor the evaluated alpha functions.
No.
1
2
3
4
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Methane
Ethane
Propane
2Methylpropane
Butane
2,2Dimethylpropane
2Methylbutane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Dodecane
Benzene
Methylbenzene
Ethene
Prop-1-ene
Argon
Kripton
Xenon
Oxygen
Nitrogen
Fluor
Carbon
disulde
Sulfur
hexauoride
Sulfur dioxide
Water
Ammonia
Carbon dioxide
Peruoroethane
Diuoromethane
Dichloromonouoromethane
Trichlorouoromethane
Dichlorodiuoromethane
Chlorotriuoromethane
Tetrauoromethane
Chlorodiuoromethane
Triuoromethane
Alpha function
Soave Eq. (9)
Joshipura et al.
Eq. (11)
M1
M2
0.393750
0.530259
0.610302
0.657361
0.42638
0.57992
0.65702
0.70164
0.3964
0.5137
0.5866
0.6272
0.2318
0.3700
0.4198
0.4612
0.677396
0.666546
0.72079
0.69305
0.6572
0.6506
0.718385
0.75952
0.747634
0.817099
0.887874
0.950915
1.015136
1.077475
1.185079
0.687970
0.771162
0.519661
0.597314
0.373180
0.376178
0.384366
0.415419
0.434750
0.457764
0.531789
Heyen Eq.(16)
Ht1
Ht2
0.1324
0.1842
0.1987
0.2243
1.460
1.467
1.795
2.017
0.744
0.531
0.683
0.763
1.2007
1.3002
1.2728
1.2581
0.908
0.776
0.2291
0.2308
1.934
1.957
0.840
0.702
1.2728
1.2795
1.991
0.890
0.2466
1.869
0.786
1.3065
0.6989
0.7062
0.7284
0.7498
0.8156
0.8627
0.9119
0.5548
0.6957
0.5258
0.5815
0.6125
0.6696
0.6750
0.5746
0.5651
0.4810
0.5894
1.999
2.034
2.029
2.064
1.994
1.997
1.976
2.192
2.016
2.066
2.039
1.962
1.910
1.907
1.943
2.036
2.101
2.042
0.837
0.836
0.822
0.821
0.861
0.934
0.887
0.595
0.864
0.746
0.782
0.895
0.978
0.975
0.926
0.783
0.660
0.750
0.2595
0.2787
0.3043
0.3216
0.3505
0.3645
0.4098
0.2361
0.2631
0.1775
0.2051
0.1309
0.1319
0.1350
0.1441
0.1518
0.1577
0.1845
2.100
1.940
1.837
1.790
1.762
1.726
1.743
2.327
1.635
1.587
1.826
1.771
1.724
1.724
1.516
2.502
2.565
2.501
0.923
0.755
0.646
0.566
0.597
0.625
0.607
0.680
0.528
0.442
0.631
0.773
0.847
0.847
0.618
1.063
0.907
1.054
1.2759
1.3454
1.4176
1.4812
1.5254
1.5737
1.6462
1.2450
1.4178
1.2776
1.2652
1.1583
1.1597
1.1634
1.2131
1.1277
1.1339
1.1564
0.7059
0.9973
1.709
1.202
0.2427
1.852
1.377
1.2447
1.1191
0.9042
0.9076
0.9268
0.9833
0.9307
1.1149
1.0368
0.9936
1.0457
0.9906
1.0786
0.9734
0.6440
0.9735
0.8223
0.7461
0.7516
0.8319
0.5864
0.6093
0.6276
0.5796
0.6214
0.6235
0.7728
2.070
1.713
1.838
2.019
2.000
1.848
2.099
2.051
2.022
2.078
2.021
2.052
1.903
0.751
1.270
1.036
0.811
0.836
1.087
0.709
0.768
0.844
0.731
0.808
0.769
0.976
0.2598
0.3018
0.2644
0.2453
0.2624
0.2695
0.2373
0.2286
0.2230
0.2201
0.2224
0.2433
0.2667
2.201
1.888
1.483
2.444
0.982
1.520
1.755
1.997
1.634
1.685
1.643
1.551
1.492
0.851
1.520
0.656
1.107
0.000
0.717
0.468
0.728
0.531
0.460
0.522
0.385
0.562
1.2717
1.3026
1.4256
1.2158
2.1219
1.4233
1.3484
1.2667
1.3418
1.3328
1.3359
1.4233
1.4517
H2
G1
G2
0.5791
0.8262
0.9395
1.0179
0.6816
0.6201
0.6227
0.6148
1.927
1.949
2.101
2.055
1.122
0.908
0.913
0.791
0.3971
0.4132
0.9694
0.9653
0.6761
0.6739
2.015
2.065
0.6980
0.3935
1.0179
0.6148
0.78139
0.85285
0.91954
0.97535
1.03315
1.08986
1.18348
0.71820
0.81149
0.56977
0.64598
0.40071
0.40403
0.41212
0.46371
0.46582
0.50071
0.57666
0.7250
0.7877
0.8547
0.9157
0.9880
1.0543
1.1614
0.6521
0.7445
0.4874
0.5666
0.3699
0.3767
0.3850
0.4019
0.4222
0.4272
0.5037
0.4118
0.4291
0.4272
0.4211
0.3296
0.2595
0.1846
0.5691
0.4193
0.4559
0.4572
0.2696
0.2371
0.2388
0.3295
0.3593
0.4480
0.4508
1.0359
1.1126
1.1704
1.2185
1.2092
1.2204
1.2727
1.1742
1.0670
0.9260
0.9723
0.6019
0.5618
0.5696
0.6978
0.7464
0.8889
0.8656
0.687450
0.70431
0.7046
0.0039
0.755645
0.851411
0.745741
0.698093
0.751052
0.772977
0.696210
0.665464
0.653094
0.642673
0.644994
0.709552
0.763137
0.79239
0.88674
0.78249
0.71207
0.77528
0.81267
0.74032
0.71001
0.69969
0.68771
0.69099
0.75387
0.80254
0.7208
0.8808
0.7478
0.6919
0.7399
0.7760
0.6549
0.6331
0.6253
0.6072
0.6170
0.6742
0.7541
0.4976
0.0387
0.2382
0.3371
0.3455
0.2310
0.5230
0.4730
0.4410
0.4937
0.4444
0.4824
0.3100
H1
G3
Ht3
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
5
6
Substance
Table 2 (Continued)
No.
40
41
42
43
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Fluoromethane
1,1,2Trichloro1,2,2triuoroethane
1,2-Dichloro1,1,2,2tetrauroethane
1-Chloro1,1,2,2,2pentauoroethane
2,2-Dichloro1,1,1triuoroethane
2-Chloro1,1,1,2tetrauoroethane
1,1,1,2,2Pentauoroethane
1,1,1,2Tetrauoroethane
1,1-Dichloro-1uoroethane
Dodecauoropentane
Decauorobutane
1,1,1,3,3Pentauoropropane
1,1,2,2,3Pentauoropropane
1,1,1,2,3,3Hexauoropropane
Chlorodiuoroethane
1,1,1Triuoroethane
1,1Diuoroethane
Heptauoropropane
Octauoropropane
Octauorocyclobutane
Methoxymethane
Ethoxyethane
Propan-2-one
Aniline
Methanol
Ethanol
Propan-2-ol
Propanol
Butanol
Pentanol
Hexanol
Heptanol
Alpha function
Soave Eq. (9)
Joshipura et al.
Eq. (11)
Heyen Eq.(16)
M1
M2
H1
0.668564
0.756610
0.69881
0.79274
0.6818
0.7251
0.1463
0.4704
0.741703
0.76127
0.7401
0.745186
0.78239
0.795700
H2
G1
G2
0.7723
1.1013
0.8821
0.6570
1.780
2.139
1.137
0.829
0.2574
0.9069
0.8155
2.000
0.7246
0.4109
1.0376
0.6968
0.82910
0.7581
0.5058
1.1399
0.803234
0.83555
0.7673
0.4947
0.823199
0.85014
0.7944
0.853407
0.88285
0.709952
G3
Ht1
Ht2
Ht3
0.2364
0.2478
1.422
1.525
0.749
0.353
1.3734
1.4769
0.836
0.2600
2.112
1.078
1.2627
1.987
0.812
0.2623
2.179
0.969
1.2629
0.6672
2.092
0.725
0.2727
2.137
0.758
1.3039
1.1443
0.6715
2.075
0.748
0.2759
2.111
0.780
1.3094
0.4566
1.1408
0.6951
2.061
0.764
0.2845
2.101
0.797
1.3196
0.8260
0.4172
1.1325
0.7279
2.012
0.813
0.2964
2.102
0.887
1.3232
0.74737
0.6698
0.5424
1.1533
0.5794
2.022
0.593
0.2595
2.290
0.775
1.2484
1.026914
0.919168
0.922528
1.04231
0.94265
0.94539
0.9594
0.8725
0.8744
0.6755
0.5613
0.5503
1.5219
1.3174
1.3096
0.6288
0.6611
0.6662
2.265
2.183
2.141
0.542
0.670
0.676
0.3444
0.3089
0.3141
2.375
2.306
2.277
0.619
0.762
0.782
1.3815
1.3330
1.3357
0.889276
0.91455
0.8599
0.4182
1.1623
0.7386
2.021
0.797
0.3090
2.162
0.923
1.3263
0.927339
0.95019
0.8856
0.4977
1.2397
0.7157
2.109
0.731
0.3155
2.258
0.856
1.3338
0.724023
0.751829
0.76156
0.78609
0.6927
0.7339
0.4750
0.3823
1.0852
1.0183
0.6365
0.7190
2.019
1.968
0.740
0.870
0.2551
0.2626
2.192
2.102
0.875
0.989
1.2584
1.2729
0.771358
0.80678
0.7549
0.3655
1.0239
0.7351
1.959
0.899
0.2685
2.056
0.991
1.2866
0.893112
0.841577
0.887422
0.661137
0.790374
0.816449
0.925843
1.127210
1.266252
1.300593
1.261490
1.229461
1.209652
1.255557
1.243820
0.91892
0.86992
0.90265
0.69201
0.81923
0.84891
0.94909
1.13443
1.25473
1.28418
1.25540
1.22102
1.20392
1.24625
1.23571
0.8593
0.8100
0.8600
0.6414
0.7580
0.8148
0.8918
1.2095
1.2378
1.1569
1.1273
1.0832
1.0616
1.0677
1.0255
0.4545
0.4578
0.4692
0.4365
0.4926
0.2410
0.4482
0.5318
0.1714
1.3586
1.0500
1.2647
1.2551
1.3327
1.6695
1.1178
1.1589
1.1703
0.9953
1.1399
0.9743
1.2194
0.9498
1.3469
2.6894
2.0273
2.5108
2.5071
2.5113
4.1724
0.7787
0.6973
0.7375
0.6434
0.6648
0.8346
0.7300
1.2826
0.9173
0.4309
0.5594
0.4323
0.4242
0.4303
0.2471
2.062
2.051
2.107
2.058
2.077
1.861
2.036
1.426
2.011
2.817
2.516
2.586
2.577
2.600
2.836
0.766
0.775
0.703
0.745
0.738
1.003
0.795
1.311
0.842
0.027
0.243
0.029
0.035
0.030
0.302
0.3075
0.2905
0.3081
0.2308
0.2731
0.2889
0.3203
0.4522
0.4377
0.4072
0.4106
0.4151
0.4084
0.4165
0.4040
2.152
2.140
2.282
2.499
2.502
2.075
2.388
0.982
2.451
3.000
3.182
3.294
3.292
3.303
3.504
0.839
0.851
0.834
1.043
1.047
1.239
1.119
0.116
1.230
0.098
0.580
0.336
0.330
0.257
0.150
1.3373
1.3160
1.3203
1.2006
1.2420
1.2841
1.2958
3.0462
1.4016
1.4537
1.3521
1.3505
1.3439
1.3529
1.3588
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
44
Substance
61
62
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
Table 3
Generalized expressions to estimate the parameters in the PR and the PT EoSs with six different alpha functions.
Alpha function
PR EoS
F = 0.3905 + 1.4119
(A1)
(A2)
H2 =
Heyen (Eq. (14))
PT EoS
1.3642 + 0.3788
H1 =
H2
F = 1.1383 + 0.4538
c = 0.07122 0.1033 + 0.3266
F = 1.0715 + 0.5102
c = 0.08662 0.1145 + 0.3292
c = 0.08212 0.1131 + 0.3282
H2 =
(A3)
(B2)
1.8437 0.2792
+ 1.0058 + 1.4647 (B3)
1.0058 + 0.4647
1.0058 + 0.4647
H2
c = 0.08132 0.1126 + 0.328
H1 =
M1 = 1.3637 + 0.3806
M1 = 0.9967 + 0.4675
(A4)
(B4)
G1 = 2.06
Gasem et al. (Eq. (19))
(B1)
G2 = 0.828
G2 = 0.953
(A5)
(B5)
Fig. 2. Parameters for the Gasem et al. alpha function for the PR EoS in terms of the acentric factor. (a) : G1 values from Table 2, (b) : G2 values from Table 2 and (c) : G3
values form hydrocarbons, inorganic and halogen compounds from Table 2, : calculated values with Eq. (28).
for all substances and 0.828 for non-polar substances, this value is
practically the same reported by Gasem et al. In Fig. 2, it can be
observed that the parameter G2 has high variability. For many substances the optimum G2 value is far from the average value even for
non-polar substances like methane and benzene (see Table 2). The
maximum differences between the optimum value and the average value corresponds to methanol and n-heptanol again. Finally,
parameter G3 can be generalized in terms of the acentric factor (see
Table 3).
Eq. (A5) from Table 3 does not include optimal G3 values for
alcohols. The R2 value for Eq. (A3) in Table 3 is 0.9958. In Fig. 2,
it is shown that the proposed generalized function can correlate
the parameter G3 very well. Values estimated for G3 parameter
using the expression proposed by Gasem et al. (Eq. (20)) produce
for practical purpose the same values predicted by Eq. (A3) as can
be observed in Fig. 2.
In the case of two-parameter exponential alpha functions, in
principle there are not simple relations between the parameters
of each model and the acentric factor. However, recently some
authors have been demonstrated that two parameter alpha function can be generalized using the derivatives of the alpha function
at the critical point [60,61]. For example, Figueira et al. [60] developed generalized expression to estimate the parameters for the
StryjekVera and the GibbonsLaughton alpha functions using the
rst derivative of the alpha function at the critical point. More
recently, Valderrama and Forero extend the idea of Figueira et al.
using both the rst and the second derivatives of the alpha function
at the critical point to obtain generalized expressions to estimate
the vapor pressure of ionic liquids using a simplied model based
on the PR EoS and the Heyen alpha function [61]. To obtain the generalized expressions for both the Melhem et al. and Heyen functions
it is necessary to estimate the following derivatives [61]:
=
d(/Tr )
d
= Tr
dTr
d(1/Tr )
(25)
=
d2
d
= Tr
dTr
dTr2
(26)
Applying Eqs. (25) and (26) at the critical point for the Melhem
et al. function the following expressions are obtained:
c = 1 + M1
c = M12 +
M2
2
(27)
(28)
(29)
c = [H2 (1 + H1 H2 )]H1 H2
(30)
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
63
Fig. 3. The rst derivative (c ) and the second derivative ( c ) at the critical point for the Melhem (Eqs. (27)(28)) and the Heyen (Eqs. (29)(30)) alpha functions for the PR
EoS and non-polar compounds.
observed in Fig. 3. Combining Eqs. (27) and (28) and the expressions reported in Fig. 3(a) and (b) generalized expressions can be
derived for the parameters in the Melhem et al. function. In a similar
way, combining Eqs. (29) and (30) with the correlations reported
in Fig. 3(c) and (d) the parameters in the Heyen function can be
generalized.
Generalized expressions for the Melhem et al. and the Heyen
alpha functions were derived using the optimum parameters of the
n-alkanes and they are reported in Table 3. For the rest of non-polar
substances Eqs. (A4) and (A5) are totally predictive. Finally for the
Haghtalab et al. alpha function case, generalized expressions were
not found to correlate the parameters of this alpha function.
4.2. The PatelTeja EoS
The weight factors in PT EoS are: w1 = 0.8 and w2 = 0.2, i.e.,
vapor pressure and liquid volume data are used simultaneously.
The parameters which have to be estimated for the PT EoS are
those that belong to the alpha function and the empiric critical compressibility factor. The weight factors employed are those chosen
by Dashtizadeh et al. [58].
In Table 4 the alpha function parameters and the empiric critical
compressibility factor are reported for the six cases evaluated. For
substances like aniline, dimethyl ether, diethyl ether, acetone, and
alcohols for ethanol to n-heptanol experimental data for liquid volume were generate with the Daubert expression recommended by
the literature [62,63]. Results for the empiric critical compressibility factor (see Table 4) show that the optimal c value for practical
purposes does not depend of the alpha function.
For the PT EoS and the six alpha functions evaluated, the alpha
function parameters can be correlate in terms of the acentric factor
only for hydrocarbons and gases. A quadratic form in terms of the
acentric factor is obtained for c . The same procedure described in
Section 4.1 that was used the PR EoS can be employed to deduce
generalized expressions for the Melhem et al. and the Heyen functions. For the Gasem et al. function average values for parameters
G1 and G2 were estimated. The parameter G3 can be correlated as a
64
Table 4
PatelTeja EoS parameters for the evaluated alpha functions.
No.
Substance
Alpha function
Joshipura et al.
Eq. (11)
1
2
3
4
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
M1
M2
H1
H2
G1
G2
Ha1
Ha2
0.455780
0.578805
0.632823
0.680712
0.325
0.321
0.313
0.313
0.5049
0.6206
0.6825
0.7392
0.328
0.318
0.314
0.317
0.4894
0.5794
0.6142
0.6522
0.0875
0.2811
0.3797
0.4115
0.327
0.321
0.313
0.311
0.5446
0.7904
0.9163
0.9812
0.8974
0.7327
0.6686
0.6627
0.327
0.322
0.313
0.311
1.819
1.804
2.043
2.069
1.539
1.045
0.983
0.926
0.1479
0.2089
0.2077
0.2223
0.327
0.321
0.313
0.312
1.278
1.403
1.772
2.008
0.937
0.650
0.757
0.877
1.2527
1.3353
1.2816
1.2595
0.327
0.321
0.313
0.312
0.688391
0.681116
0.310
0.310
0.7345
0.7124
0.311
0.311
0.6700
0.6862
0.3772
0.2141
0.310
0.310
0.9600
0.8222
0.6959
0.8343
0.310
0.310
2.107
1.922
1.037
1.071
0.2175
0.2312
0.310
0.311
1.943
1.957
0.893
0.702
1.2725
1.2795
0.310
0.308
0.733118
0.311
0.7880
0.314
0.7164
0.3472
0.310
0.9718
0.7350
0.310
2.056
1.055
0.2350
0.310
1.864
0.872
1.3058
0.310
0.770557
0.793682
0.854917
0.906619
0.973830
1.011738
1.100826
0.714375
0.760035
0.569751
0.635044
0.430095
0.424899
0.425377
0.472802
0.511294
0.530646
0.582167
0.312
0.301
0.299
0.297
0.298
0.293
0.291
0.313
0.304
0.321
0.317
0.322
0.320
0.318
0.324
0.328
0.328
0.321
0.8096
0.8327
0.8904
0.9359
1.0360
0.9965
1.1148
0.7450
0.7965
0.6230
0.6866
0.4640
0.4590
0.4589
0.5289
0.5472
0.5777
0.6306
0.314
0.302
0.300
0.298
0.295
0.298
0.292
0.313
0.303
0.322
0.318
0.324
0.322
0.319
0.326
0.329
0.329
0.322
0.7424
0.7556
0.8098
0.8563
0.9339
0.9686
1.0528
0.6751
0.7181
0.5529
0.6143
0.4555
0.4526
0.4510
0.4819
0.5218
0.5213
0.5523
0.3874
0.4847
0.5068
0.5351
0.4384
0.4362
0.4425
0.5219
0.4617
0.3690
0.3906
0.0644
0.0478
0.0607
0.2353
0.1964
0.3286
0.3914
0.310
0.301
0.299
0.297
0.298
0.293
0.290
0.311
0.302
0.321
0.317
0.323
0.321
0.319
0.325
0.328
0.328
0.318
1.0199
1.1426
1.2108
1.2770
1.2500
1.2790
1.3599
1.1645
1.0774
0.8564
0.9295
0.4923
0.4787
0.4850
0.6584
0.6546
0.7849
0.8753
0.7305
0.6595
0.6671
0.6693
0.7456
0.7559
0.7730
0.5702
0.6671
0.6432
0.6586
0.9256
0.9461
0.9304
0.7289
0.7986
0.6620
0.6283
0.311
0.301
0.299
0.297
0.298
0.293
0.290
0.310
0.302
0.321
0.317
0.323
0.321
0.319
0.325
0.328
0.328
0.317
1.960
2.091
2.148
2.209
2.138
2.253
2.201
2.173
2.043
1.958
2.011
1.644
1.610
1.624
1.712
1.772
1.898
1.988
0.860
0.779
0.784
0.760
0.845
0.943
0.802
0.685
0.833
0.950
0.945
1.369
1.397
1.363
1.096
1.100
1.029
0.917
0.2675
0.2673
0.2803
0.2922
0.3171
0.3072
0.3538
0.2385
0.2555
0.1953
0.2127
0.1531
0.1525
0.1530
0.1769
0.1844
0.1859
0.1964
0.310
0.301
0.299
0.297
0.298
0.293
0.290
0.311
0.302
0.321
0.317
0.323
0.321
0.319
0.325
0.328
0.330
0.319
2.065
1.958
1.954
1.918
4.529
2.009
2.011
2.316
1.725
1.497
1.791
1.494
1.460
1.479
1.341
2.222
2.349
2.430
0.964
0.675
0.631
0.532
2.967
0.720
0.626
0.766
0.571
0.563
0.761
1.199
1.218
1.195
0.726
1.517
1.380
1.278
1.2846
1.3380
1.3742
1.4242
1.1351
1.4324
1.4958
1.2472
1.3763
1.3156
1.2789
1.1869
1.1867
1.1863
1.2709
1.1521
1.1557
1.1670
0.311
0.301
0.299
0.297
0.298
0.293
0.290
0.311
0.302
0.321
0.317
0.323
0.321
0.319
0.325
0.328
0.329
0.319
0.713410
0.312
0.7352
0.314
0.7555
-0.1722
0.315
0.6838
1.1060
0.316
1.588
1.417
0.2531
0.316
1.852
1.377
1.2447
0.314
0.755645
0.308
0.7924
0.308
0.7229
0.4935
0.307
1.1266
0.6393
0.307
2.065
0.759
0.2606
0.308
2.200
0.851
1.2723
0.307
0.707490
0.643108
0.707496
0.272
0.282
0.309
0.7526
0.6938
0.7268
0.273
0.285
0.310
0.6887
0.6074
0.7029
0.3467
0.4711
0.2885
0.271
0.280
0.309
0.9472
1.0140
0.9067
0.7262
0.5980
0.7733
0.271
0.280
0.309
1.727
2.077
2.017
0.760
0.741
0.813
0.2826
0.2189
0.2477
0.272
0.280
0.308
1.967
1.619
2.384
0.949
0.431
1.181
1.2709
1.3498
1.2192
0.271
0.280
0.309
0.808463
0.658356
0.703165
0.699061
0.686290
0.677179
0.696149
0.700870
0.719082
0.320
0.279
0.309
0.316
0.316
0.316
0.320
0.305
0.296
0.8323
0.7161
0.7499
0.7580
0.7488
0.7364
0.7571
0.7707
0.7625
0.320
0.282
0.310
0.320
0.320
0.320
0.325
0.311
0.297
0.8135
0.6163
0.6607
0.6707
0.6642
0.6457
0.6822
0.6598
0.6890
0.1763
0.4820
0.5143
0.4071
0.3761
0.4249
0.3387
0.5041
0.4176
0.320
0.276
0.308
0.314
0.314
0.314
0.320
0.304
0.295
0.9218
1.0332
1.1076
0.9921
0.9557
0.9908
0.9344
1.0944
1.0170
0.8820
0.5981
0.5953
0.6739
0.6924
0.6498
0.7276
0.6018
0.6757
0.320
0.277
0.308
0.314
0.314
0.314
0.320
0.304
0.295
2.998
2.048
2.089
2.071
1.955
2.016
1.935
2.073
2.183
2.218
0.744
0.722
0.945
0.926
0.856
0.992
0.737
0.997
0.1575
0.2260
0.2393
0.2272
0.2357
0.2295
0.2384
0.2393
0.2208
0.320
0.277
0.308
0.314
0.315
0.314
0.320
0.304
0.295
1.411
1.619
1.748
2.082
1.593
1.644
1.555
1.607
1.673
0.552
0.439
0.478
0.954
0.608
0.554
0.630
0.396
0.576
1.5173
1.3572
1.3515
1.2531
1.3604
1.3482
1.3749
1.3968
1.3650
0.320
0.277
0.308
0.314
0.315
0.314
0.320
0.304
0.295
G3
Ha3
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
5
6
Methane
Ethane
Propane
2Methylpropane
Butane
2,2Dimethylpropane
2Methylbutane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Dodecane
Benzene
Methylbenzene
Ethene
Prop-1-ene
Argon
Kripton
Xenon
Oxygen
Nitrogen
Fluor
Carbon
disulde
Sulfur
hexauoride
Sulfur
dioxide
Water
Ammonia
Carbon
dioxide
Peruoroethane
Diuoromethane
Dichloromonouoromethane
Trichlorouoromethane
Dichlorodiuoromethane
Chlorotriuoromethane
Tetrauoromethane
Chlorodiuoromethane
Triuoromethane
Table 4 (Continued)
No.
Substance
Alpha function
Soave Eq. (9)
40
41
42
43
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
M1
M2
H1
H2
G1
G2
Ha1
Ha2
0.554752
0.778480
0.280
0.312
0.5920
0.8252
0.281
0.315
0.5372
0.7486
0.3995
0.4141
0.279
0.311
0.8735
1.0627
0.6139
0.7027
0.279
0.311
2.249
2.178
0.903
0.979
0.1724
0.2411
0.279
0.311
1.601
1.623
0.488
0.508
1.2965
1.4273
0.279
0.311
0.765394
0.312
0.7704
0.309
0.7652
0.0558
0.309
0.7931
0.9655
0.309
1.781
1.179
0.2602
0.309
2.418
1.904
1.1952
0.309
0.790564
0.318
0.8184
0.316
0.7575
0.3401
0.313
1.0005
0.7553
0.313
1.933
0.904
0.2712
0.313
2.140
1.096
1.2686
0.313
0.814279
0.312
0.8521
0.313
0.7742
0.4777
0.310
1.1471
0.6733
0.310
2.063
0.761
0.2782
0.310
2.106
0.787
1.3115
0.310
0.832860
0.314
0.8690
0.315
0.7937
0.4445
0.312
1.1378
0.6931
0.311
2.033
0.787
0.2854
0.312
2.077
0.826
1.3199
0.312
0.849826
0.313
0.8772
0.313
0.8174
0.4075
0.311
1.1209
0.7275
0.311
2.016
0.814
0.2934
0.312
2.095
0.800
1.3259
0.310
0.840546
0.304
0.8739
0.305
0.7957
0.4700
0.301
1.1357
0.7043
0.302
2.051
0.764
0.2874
0.302
2.141
0.837
1.3120
0.302
0.739915
0.314
0.7784
0.315
0.6973
0.4986
0.312
1.1255
0.6142
0.312
1.983
0.653
0.2683
0.312
2.244
0.841
1.2580
0.312
1.066206
0.992629
0.941775
0.315
0.323
0.311
1.0784
1.0137
0.9656
0.315
0.324
0.312
0.9900
0.9379
0.8862
0.6148
0.4297
0.5293
0.312
0.318
0.309
1.4852
1.3164
1.2916
0.6629
0.6899
0.6855
0.312
0.315
0.309
2.234
2.092
2.126
0.612
0.809
0.699
0.3511
0.3274
0.3176
0.312
0.318
0.309
2.325
2.226
2.264
0.680
0.919
0.811
1.3947
1.3524
1.3393
0.312
0.318
0.309
0.921906
0.314
0.9501
0.315
0.8938
0.3533
0.313
1.1378
0.7838
0.313
1.968
0.848
0.3214
0.313
2.101
0.977
1.3422
0.313
0.948534
0.312
0.9737
0.313
0.8968
0.4766
0.309
1.2447
0.7212
0.309
2.109
0.731
0.3155
0.310
2.242
0.882
1.3383
0.309
0.739149
0.714696
0.311
0.298
0.7794
0.7521
0.312
0.299
0.7007
0.6739
0.4619
0.4845
0.309
0.296
1.0788
1.0299
0.6459
0.6643
0.308
0.297
2.010
2.028
0.745
0.718
0.2575
0.2503
0.308
0.296
2.173
2.211
0.895
0.846
1.2624
1.2523
0.309
0.296
0.718323
0.294
0.7577
0.295
0.6742
0.5021
0.292
1.0873
0.6243
0.293
2.055
0.705
0.2491
0.293
2.203
0.812
1.2564
0.293
0.946434
0.900169
0.940942
0.682197
0.801626
0.717211
0.319
0.320
0.318
0.312
0.310
0.283
0.9715
0.9301
0.9617
0.7111
0.8302
0.7570
0.320
0.321
0.319
0.312
0.310
0.284
0.9181
0.8765
0.9178
0.6568
0.7667
0.6772
0.3398
0.3285
0.3220
0.4087
0.4775
0.4824
0.317
0.319
0.316
0.310
0.309
0.281
1.1479
1.1228
1.1216
0.9783
1.1396
1.0780
0.7987
0.7697
0.8183
0.6691
0.6724
0.6272
0.317
0.317
0.316
0.310
0.309
0.282
2.040
2.027
2.067
2.043
2.075
2.101
0.928
0.954
0.898
0.830
0.743
0.758
0.3135
0.2984
0.3120
0.2325
0.2753
0.2403
0.317
0.319
0.316
0.311
0.309
0.281
2.083
2.064
2.237
2.499
2.467
2.207
0.969
0.987
1.052
1.043
1.064
0.863
1.3564
1.3382
1.3248
1.2028
1.2471
1.2526
0.317
0.319
0.316
0.308
0.309
0.282
0.931193
0.951873
1.260777
1.162288
1.24589
1.22861
1.21489
1.25054
1.23761
0.308
0.270
0.300
0.288
0.304
0.307
0.308
0.306
0.306
0.9548
0.9859
1.2486
1.1597
1.2414
1.2156
1.2086
1.2417
1.2298
0.308
0.273
0.300
0.288
0.304
0.306
0.308
0.306
0.306
0.8900
1.0093
1.0842
1.0824
1.1000
1.0792
1.0631
1.0516
1.0008
0.4472
-0.1188
1.5850
0.6934
1.0561
1.2729
1.2474
1.3613
1.7251
0.307
0.274
0.297
0.286
0.304
0.306
0.307
0.304
0.303
1.2211
0.9447
2.8440
1.5513
2.1122
2.5448
2.4907
2.7551
4.5157
0.7271
1.0694
0.3918
0.7026
0.5267
0.4241
0.4273
0.3832
0.2240
0.307
0.274
0.299
0.287
0.304
0.306
0.307
0.304
0.303
2.034
1.557
2.734
1.967
2.486
2.568
2.577
2.603
2.483
0.794
1.106
-0.174
0.240
0.179
0.000
0.035
-0.124
-0.438
0.3205
0.3883
0.4292
0.4926
0.4176
0.4198
0.4084
0.4203
0.4860
0.307
0.275
0.299
0.286
0.304
0.306
0.307
0.304
0.303
2.387
0.925
3.081
2.806
3.183
3.320
3.292
3.516
3.563
1.118
-0.043
0.001
0.818
0.574
0.329
0.330
0.192
-0.225
1.2960
3.1579
1.4319
1.3505
1.3472
1.3463
1.3439
1.3274
1.3504
0.307
0.275
0.299
0.286
0.304
0.306
0.307
0.304
0.303
G3
Ha3
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
44
Fluoromethane
1,1,2Trichloro1,2,2triuoroethane
1,2-Dichloro1,1,2,2tetrauroethane
1-Chloro1,1,2,2,2pentauoroethane
2,2-Dichloro1,1,1triuoroethane
2-Chloro1,1,1,2tetrauoroethane
1,1,1,2,2Pentauoroethane
1,1,1,2Tetrauoroethane
1,1-Dichloro1uoroethane
Dodecauoropentane
Decauorobutane
1,1,1,3,3Pentauoropropane
1,1,2,2,3Pentauoropropane
1,1,1,2,3,3Hexauoropropane
Chlorodiuoroethane
1,1,1Triuoroethane
1,1Diuoroethane
Heptauoropropane
Octauoropropane
Octauorocyclobutane
Methoxymethane
Ethoxyethane
Propan-2one
Aniline
Methanol
Ethanol
Propan-2-ol
Propanol
Butanol
Pentanol
Hexanol
Heptanol
Joshipura et al.
Eq. (11)
65
66
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
Table 5
Average absolute deviation in the saturation pressure for the PR EoS and PT EoS with the 6 evaluated alpha functions.
Classication
Alpha function
Hydrocarbons
Inorganics
Halogens
Polarorganics
Global average
Haghtalab et al.
(Eq. (22))
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
1.01
0.89
1.16
3.86
1.52
1.06
0.69
1.01
3.84
1.44
2.78
2.02
2.80
4.39
2.91
2.68
1.91
2.53
4.39
2.75
0.54
0.31
0.45
0.61
0.47
0.55
0.35
0.48
0.67
0.50
0.56
0.34
0.48
0.61
0.50
0.58
0.36
0.51
0.66
0.52
0.36
0.22
0.29
0.62
0.35
0.37
0.31
0.42
0.68
0.43
0.37
0.21
0.30
0.62
0.35
0.39
0.52
0.35
0.67
0.44
Table 6
Average absolute deviation in the saturated liquid volume for the PR EoS and PT EoS with the 6 evaluated alpha functions.
Classication
Alpha function
Hydrocarbons
Inorganics
Halogens
Polarorganics
Global average
Haghtalab et al.
(Eq. (22))
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
5.62
8.91
5.79
7.00
6.48
3.72
3.93
3.40
3.07
3.52
5.60
8.91
5.73
6.95
6.44
3.54
3.73
3.25
3.00
3.36
5.68
8.88
5.82
7.31
6.56
3.84
3.90
3.54
3.18
3.62
5.68
8.88
5.82
7.30
6.55
3.84
3.91
3.55
3.21
3.63
5.65
8.86
5.79
7.28
6.53
3.78
3.85
3.47
3.18
3.57
5.65
8.86
5.79
7.29
6.53
3.81
3.86
3.48
3.18
3.58
2
1.6
1.2
0.8
0.4
0
0
10
12
14
Tr
Fig. 4. Alpha function against reduced temperature for n-heptanol employing the
PT EoS (: Soave function Eq. (9), : Joshipura et al. function Eq. (11), x: Heyen
function Eq. (14), : Melhem et al. Eq. (16), - - -: Gasem et al. function Eq. (19), :
Haghtalab et al. function Eq. (22)).
Table 7
Average absolute deviation in the saturated vapor volume for the PR EoS and PT EoS with the 6 evaluated alpha functions.
Classication
Hydrocarbons
Inorganics
Halogens
Global average
Alpha function
Soave (Eq. (9))
Haghtalab et al.
(Eq. (22))
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
1.70
1.65
2.03
1.85
1.59
1.30
1.78
1.63
3.57
2.71
3.77
3.50
3.45
2.50
3.45
3.25
1.02
1.38
1.31
1.23
0.84
0.90
1.09
0.98
1.03
1.40
1.33
1.25
0.86
0.91
1.12
1.00
0.93
1.33
1.23
1.16
0.74
0.85
1.05
0.92
0.93
1.33
1.23
1.16
0.75
1.09
1.00
0.95
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
67
Table 8
Average absolute deviation in the vaporization enthalpy for the PR EoS and PT EoS with the 6 evaluated alpha functions.
Classication
Alpha function
Soave (Eq. (9))
Hydrocarbons
Inorganics
Halogens
Global average
Joshipura et al.
(Eq. (11))
Heyen et al.
(Eq. (14))
Melhem et al.
(Eq. (16))
Gasem et al.
(Eq. (19))
Haghtalab et al.
(Eq. (22))
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
PR
PT
1.82
1.91
2.06
1.96
1.89
1.97
2.01
1.96
2.76
2.36
2.92
2.76
2.76
2.36
2.83
2.71
1.68
1.85
1.89
1.82
1.65
1.77
1.87
1.78
1.71
1.86
1.89
1.83
1.69
1.78
1.86
1.79
1.50
1.75
1.73
1.66
1.46
1.65
1.68
1.60
1.51
1.75
1.73
1.67
1.47
1.84
1.69
1.66
Fig. 5. Vapor pressure average absolute deviation in terms of the reduced temperature for some pure substances with the PR EoS. (a) Ethylene, (b) dichlorouorotethane, (c)
methanol and (d) n-butanol (: Soave function Eq. (9), : Heyen function Eq. (14), ; Gasem et al. function Eq. (19)).
3.20% when the Soave function is changed for any of the exponential functions containing more than one parameter. From Table 5,
it can be noticed that the obtained average absolute deviations for
polar substances are the same for the Melhem et al., Heyen, Gasem
et al. and Haghtalab et al. alpha functions.
Comparing results for the two equations, it can be noticed that
deviations are almost the same when the same alpha function is
employed. In Fig. 5, the relative absolute deviation in terms of
the reduced temperature is presented for ethylene, dichlorouoromethane, methanol and butanol. In all the cases, it can be
appreciate that exponential alpha functions with two and three
parameters are highly superior in the vapor pressure range from
1 kPa and the corresponding pressure to a reduced temperature of
0.80. In the nearly critical region, the Soave function is better than
the other functions. However, the Soave function superiority is not
considerable respecting to the two exponential functions that have
been illustrated.
The maximum deviation with the Soave function can be
observed in Fig. 5, at the lowest temperature worked. The value of
this deviation is above 5% for substances like ethylene and dichlorouoromethane. In methanol case the deviation is close to 10%.
For butanol maximum absolute relative deviation is 34%. Substituting the Soave function by a two or three-parameter exponential
function like the Heyen and the Gasem et al. models, the calculated deviation for an experimental vapor pressure of 1 kPa is lower
than 2.00%. The deviation at the normal boiling point is near to
the rst local maximum that appears in the Soave function case in
Fig. 5 for all the substances illustrated. The local maximum has a
value between 2.5% and 4% for uids like ethylene, dichlorouoromethane and methanol. For butanol case local maximum is close
to 10.0%. For ethylene, dichlorouoromethane and methanol at the
reduced temperature where the Soave function local maximum is
obtained, the estimated deviations with the Heyen and the Gasem
et al. functions are lower than 0.8%. For butanol, the deviation is
lower to 2.00%. In methanol and n-butanol cases, the average relative deviation behavior predicted by the Heyen and the Gasem
et al. functions are practically the same. In order to explain differences in vapor pressure correlation the alpha functions of Soave,
Joshipura and Heyen are presented for n-butanol and n-heptane in
Fig. 6. For n-butanol (Fig. 6a) values for the alpha functions are calculated using the parameters from Table 2. It can be noticed that for
the low reduced temperature range (0.40.6) there are signicant
differences between the three alpha functions while similar alpha
function values are estimated for reduced temperatures between
0.6 and 1.0. For n-heptane (Fig. 6b) alpha function values are calculated employing generalized expressions from Table 3. In this
case it can be observed some little differences in the very low
reduced temperature range (0.40.55). Both cases allow explaining
the differences between deviations for vapor pressure presented
in Fig. 5, especially for the low temperature range. In the other
hand, in Fig. 6, it is shown that the Soave function is closer than
the Joshipura to the Heyen alpha function. According to this fact,
the worst behavior of the alpha function is that predicted by the
Joshipura function. Additionally parameters from Tables 2 and 4
show that the exponent in the Heyen function is lower than 1, the
value that is assumed in the Joshipura function. According to Fig. 6
68
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
Fig. 6. Alpha function in terms of the reduced temperature for n-butanol (a) and n-heptane (b). - - -: Joshipura function, : Heyen function, Soave function.
0.25
0.20
AAD V sat
0.15
0.10
0.05
0.00
0.220 0.230 0.240 0.250 0.260 0.270 0.280 0.290 0.300
Zc
Fig. 7. Average absolute deviation in terms of the experimental critical compressibility factor (: PR EoS, : PT EoS).
(i) A rst zone is formed by substances with critical compressibility factor lower than 0.255. For this kind of substances the PT
EoS has a great superiority over the PR EoS to represent liquid
volume. Some substances in this group are methanol, ethanol,
acetone, water, ammonia and even a non-polar substance like
dodecane. Average deviations with the PR EoS are above 10.0%
and even above 20.0% for water and methanol. From Table 3, it
Fig. 8. Saturated liquid volume relative deviation in terms of the reduced temperature with the PR and PT EoS employing the Heyen alpha function. (a) Dodecane Zc = 0.238,
(b) n-butanol Zc = 0.258 and (c) argon Zc = 0.291 (: PR EoS, : PT EoS).
Table 9
Average absolute deviations in binary vapor liquid equilibrium predictions using the van der Waals one uid mixing rules.
System
Substance 1
Substance 2
T (K)
P (kPa)
ND
PR-Heyen
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
1,3-Butadiene
1-Butene
Butane
2,2-Dimethylbutane
1-Hexene
Pentane
p-Xylene
Methylbenzene
Benzene
Ethylbenzene
p-Xylene
Benzene
Ethylbenzene
Methylbenzene
p-Xylene
Dodecane
Ethylbenzene
Octane
Methylbenzene
Benzene
Benzene
Cyclohexane
Benzene
Benzene
Cyclohexane
Butane
1,3-Butadiene
Hexane
Hexane
Hexane
Hexane
Heptane
Heptane
Heptane
Heptane
Octane
Octane
Octane
Octane
Decane
Decane
Decane
Decane
Decane
Decane
1-Octene
1-Octene
Cyclohexene
1-Hexene
2,2,4-Trimethylpentane
310.9
311325
253273
298.2
333.2
298.2
313.2
298313
298313
313.2
313.2
313.2
313.2
313.2
313.2
393430
313.2
349393
3133934
313.2
283.323
313.2
273298
283323
318348
366415
416610
595
2240
7889
2563
412
412
724
312
34
623
34.1
4.57.5
0.62.6
20.0
0.72.7
20.0
1127
223
233
924
313
740
1781
9.0
18.0
30.0
9.0
10.0
8.0
12.0
27.0
32.0
13.0
13.0
13.0
11.0
10.0
22.0
27.0
17.0
27.0
39.0
19.0
24.0
12.0
30.0
24.0
19.0
3.3
1.2
0.4
0.2
1.1
0.9
3.8
2.7
2.4
4.7
2.1
0.5
1.6
1.0
1.5
0.8
0.8
1.4
5.1
5.3
2.7
1.5
1.7
1.2
3.0
2.15
PR-Soave
PT-Heyen
PT-Soave
AAD y1
AAD y2
AAD P
AAD y1
AAD y2
AAD P
AAD y1
AAD y2
3.1
0.6
0.2
0.6
0.7
1.4
5.0
3.0
1.9
5.9
3.2
0.3
1.5
1.4
1.0
3.8
1.1
1.1
1.4
0.1
3.1
0.7
5.3
0.7
0.8
2.1
0.9
2.3
4.2
4.3
1.2
1.7
2.5
1.0
5.9
1.5
2.7
3.7
4.4
6.1
3.0
0.6
0.5
0.3
0.7
1.0
4.6
2.9
2.0
6.3
2.8
0.6
1.5
1.7
1.5
5.2
1.6
1.7
1.3
0.1
3.1
0.7
9.0
0.6
0.8
2.1
1.3
2.7
4.0
5.1
1.1
1.6
2.9
1.4
7.5
1.9
4.4
4.8
5.6
8.2
3.1
0.7
5.5
0.8
0.8
2.2
0.9
2.4
4.1
4.4
1.1
2.1
2.6
0.4
4.7
1.5
1.0
3.6
5.1
10.6
3.3
6.2
0.4
5.4
2.6
6.2
0.9
5.4
4.4
6.2
4.1
1.90
5.0
3.13
4.0
2.03
5.1
3.82
3.2
1.1
1.2
0.5
1.1
1.1
4.2
2.7
1.9
5.0
2.7
1.3
2.0
0.9
1.3
0.7
0.8
1.3
5.8
8.4
3.9
2.4
1.8
1.0
3.5
2.50
3.1
0.6
0.2
0.8
0.7
1.5
5.0
2.8
1.5
5.9
3.0
0.4
1.4
0.6
0.4
4.2
0.3
1.0
2.0
0.4
0.7
5.4
3.7
1.1
1.2
1.5
0.8
1.8
1.5
1.1
1.1
2.1
2.7
2.7
3.3
3.0
6.3
2.2
6.7
3.2
6.9
7.8
6.0
3.7
3.3
1.2
4.2
3.34
4.4
1.89
5.3
3.31
AAD P
3.3
1.1
1.5
0.9
1.4
1.3
2.3
0.8
1.2
3.0
0.9
2.5
1.3
1.6
4.7
1.0
5.4
1.4
6.8
9.7
5.5
3.3
2.5
0.9
3.8
2.90
AAD y1
Ref
AAD y2
3.0
0.6
0.3
0.6
0.7
1.2
4.6
2.8
1.6
6.3
2.5
0.1
1.4
1.0
0.8
4.6
0.9
1.2
1.9
0.2
3.1
0.7
7.8
0.7
0.8
2.3
1.2
2.6
3.8
5.1
1.0
0.5
2.9
0.9
6.6
1.6
3.2
4.2
5.4
10.9
0.7
5.4
3.7
6.2
4.3
1.92
5.2
3.67
[66]
[66]
[66]
[66]
[66]
[66]
[67]
[68]
[67,69]
[67]
[67]
[67]
[67]
[67]
[67]
[70]
[67]
[70]
[67,71]
[67]
[72]
[73]
[66]
[72]
[66]
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
AAD P
69
70
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
6. Statistical analysis
In Fig. 8, the absolute relative deviation in terms of the reduced
temperature is presented for three substances, one for zone in order
to compare the behavior of both EoS in each zone. For the rst zone
dodecane is represented. From Fig. 8(a), it can be noticed that for all
the reduced temperature ranged covered the PT EoS is highly superior than the PR EoS. To illustrate the behavior of pure substances
that belong to the second zone, an alcohol (n-butanol) was elected.
Behavior of the relative deviation in saturated volume represented
in Fig. 8 is practically the same for Both EoSs. Finally for the third
zone (Fig. 8c) argon was selected. In this zone, the PT EoS is better than the PR EoS. However in the nearly critical region PR EoS
predict volume deviations lower than those estimated with the PT
EoS. For all the compounds the volume representation in the critical region is bad and similar to those substances presented in Fig. 8.
These results were expected and there are theoretical reasons in
literature that explains this behavior [65].
Another property evaluated was the saturated vapor volume.
Summary of the results are reported in Table 7 for three of the four
groups presented in Table 1. Polar compounds are not included in
Table 7 due to there are not experimental vapor volume data for
all the substances in this group. The highest deviation with both
EoS are calculated when the Joshipura et al. function is employed.
The average deviation for the two equations of state is 3.51%. For
the other 5 alpha functions, the average AAD is lower than 2.00%.
Results for the Melhem et al. and the Heyen functions are for practical purposes the same obtained for the Gasem et al. and Haghtalab
et al. functions. The differences between the average AAD for two
and three-parameter exponential functions are lower than 0.1%.
The average AADs for the Melhem et al., Heyen, Gasem et al. and
Hahghtalab et al. functions are lower than 1.00% with the PT EoS.
For the same alpha function, the average deviations in the saturated
vapor volume with both EoS are similar. For the six alpha functions
the PT EoS is slightly better than the PR EoS to predict vapor volume.
When the Soave function is replaced by a two or threeparameter exponential functions, the EoSs performance to estimate
vapor volumes can be improved. For example, for the PT EoS the
Soave alpha function AAD is 1.62 and 1.72 times the Heyen and the
Haghtalab et al. AADs respectively.
In Fig. 9, the AAD against reduced temperature is presented for
propene and octane for the Soave and the Heyen functions. Fig. 9
illustrates how the vapor volume prediction, is improved when the
Soave function is replaced by an exponential function with two or
three parameters. Results reported in Fig. 9, are similar to those
reported in Fig. 5 for vapor pressure, i.e., using exponential alpha
functions, the saturated vapor volume can be represented very well
in the low vapor pressure region. For the two substances represented in Fig. 9, the AAD in vapor volume is greater than 1% only in
the nearly critical region.
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
71
Fig. 9. Saturated liquid volume relative deviation in terms of the reduced temperature with the PR and PT EoS employing the Soave and the Melhem alpha functions. (a)
Octane and (b) propene (: Soave-PR, : Soave-PT EoS, : Melhem-PR EoS, x: Melhem-PT EoS).
Fig. 10. Means and 95.0 percent LSD intervals for AAD of the studied substances properties for each level of alpha function (a) PR PSAT , (b) PT VlSAT , (c) PT VvSAT and (d) PR
Hlv.
(c)
0.4
Soave
Soave
Melhem
Heyen
Gasem
Soave
Melhem
Joshipura
Heyen
Gasem
Joshipura
Alpha function
Melhem
Alpha function
1.2
0.8
1.6
Joshipura
Heyen
AAD PSAT
2.4
Gasem
(b)
AAD PSAT
AAD PSAT
(a)
Alpha function
Fig. 11. Means and 95.0 percent LSD intervals for AAD in vapor pressure of hydrocarbons, gases and halogens for each level of alpha function (a) entire Tr range, (b) Psat
below 1 atm and (c) Psat from 1 atm to Pc.
72
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
above 1 atm show that the Soave and the two or three-parameter
exponential functions means intervals overlap 95.0% of the time.
7. Binary vapor liquid equilibria calculations
Taking in account that two and three-parameter exponential
alpha functions are better than the Soave function to represent
the vapor liquid equilibria of pure substances in the low pressure
region, vapor liquid equilibrium calculations at low pressures for
some binary systems formed only by hydrocarbons and some alkanol/alkane and alkanol/aromatic systems were made with both
EoS in order to analyze the inuence of the alpha function over
mixtures calculations. For exponential alpha functions calculations were made with the Heyen function. The rest of two and
three-parameters alpha functions were not considered according
to Section 6 they are not statistically different from the Heyen
function.
7.1. Hydrocarbon/hydrocarbon mixtures calculations
VLE calculations for 25 binary alkane/alkane, alkane/aromatic,
alkene/aromatic and alkane/alkene systems were performed. Due
to the nature of the systems analyzed the van der Waals one uid
mixing rules were employed for the PR and the PT EoSs. According
to literature the vdW-1F mixing rules to estimate mixture parameters with the PT EoS are [12]:
am =
i
bm =
xi xj
ai aj (1 kij )
(31)
xi bi
(32)
cm =
xi ci
(33)
Fig. 12. Vapor liquid equilibrium calculations with the PR and PT EoS with the
WongSandler-NRTL mixing rule. (a) Pentanolbenzene system at 313.15 K (: exp.
Data, - - -: PRHeyen EoS, : PRSoave EoS). (b) Butanolheptane system at 333.15 K
(: exp. data, - - -: PTHeyen EoS, : PT Soave EoS).
cm
=
xi
bm
c
= i
bi
(34)
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
73
Table 10
PT and PR + WongSandler-NRTL model parameters for alkanol/alkane or aromatic systems with the Heyen and Soave alpha functions.
System
Alkanol
Alkane/aromatic
P (kPa)
T (K)
ND
Ethanol
Hexane
298.15
19.0925.68
11
Methanol
Benzene
298.15
12.7124.43
15
Propanol
Benzene
313.15
7.04726.09
25
Propanol
Hexane
298.15
2.8421.13
11
Propanol
Nonane
333.15
3.9720.84
25
Propanol
Toluene
313.15
7.8911.35
21
Butanol
Benzene
298.15
0.8512.59
Butanol
Pentane
303.15
1.2882.07
14
Butanol
Hexane
288.15
0.4112.927
15
10
Butanol
Heptane
333.15
8.0130.73
24
11
Butanol
Decane
358.15
5.0927.63
14
12
Pentanol
Benzene
313.15
0.8924.509
24
13
Pentanol
Heptane
348.15
7.3248.79
21
14
Pentanol
Decane
363.27
6.3816.58
13
15
Hexanol
Hexane
298.23
0.11520.24
11
m =
i =
bm =
1
1+6
1
1+6
ln
3+
ij
m
m
3+
3+
x x (b (a/RT )ij
i j
1 + 1/m AE
a
b
RT
ln
3+
1+6
1+6
+
+
1+6
am =
1+6
bm
m
xi i
2790.033
2489.709
3050.886
2071.006
2739.564
3044.468
2982.543
3108.328
1993.051
2038.691
2202.964
2235.297
2145.809
2190.927
2142.081
2011.315
2753.081
2777.740
2681.731
2769.344
2323.509
2885.589
2195.973
2927.979
1813.328
856.471
1815.415
814.410
1739.948
1636.355
1719.857
1638.240
2500.398
1657.347
2540.743
1798.720
2187.279
2732.395
2174.332
3265.738
1778.559
1560.101
1833.526
1756.731
506.839
289.648
360.332
290.092
3178.367
3339.076
3143.864
3444.679
1444.518
1557.414
1524.406
1543.757
2042.718
1605.366
1651.439
1704.848
ai
AE
bi
A21 (kJ/kmol)
8573.133
8002.047
8737.786
8631.895
7271.800
7433.422
7208.661
7211.820
5749.994
5960.419
5605.391
6179.803
8082.222
6984.015
8079.413
7059.772
8039.063
7390.948
8051.248
7365.151
5869.943
5750.834
5702.404
5963.913
4859.931
2820.686
4639.618
3021.784
7493.160
18,478.239
7441.220
18,688.002
8701.360
5682.551
9079.151
6566.984
7150.857
7074.337
7229.925
8376.238
6171.573
6295.022
6148.487
6148.525
4907.840
3266.376
4457.351
3470.593
9313.936
9487.200
9284.369
9641.619
5703.591
5049.197
5848.823
5621.915
8472.420
7337.054
7889.669
7750.037
k12
0.385
0.374
0.376
0.401
0.274
0.237
0.231
0.205
0.064
0.028
0.048
0.001
0.254
0.210
0.255
0.236
0.428
0.405
0.436
0.416
0.129
0.001
0.140
0.001
0.006
0.164
0.005
0.165
0.089
0.356
0.090
0.361
0.080
0.123
0.084
0.117
0.169
0.103
0.173
0.064
0.384
0.380
0.382
0.382
0.121
0.267
0.151
0.263
0.665
0.668
0.662
0.694
0.238
0.217
0.234
0.206
0.007
0.017
0.016
0.019
(37)
(36)
(1 kij )
A12 (kJ/kmol)
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
PR-Heyen
PR-Soave
PT-Heyen
PT-Soave
(35)
xi i (ai /bi )
2
EoS
74
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
Table 11
Average absolute deviations in vaporliquid-equilibrium calculations for alkanol/alkane or aromatic systems.
System
Alkanol (1)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Alkane/aromatic (2)
Ethanol
Methanol
Propanol
Propanol
Propanol
Propanol
Butanol
Butanol
Butanol
Butanol
Butanol
Pentanol
Pentanol
Pentanol
Hexanol
Average
PR-Heyen
Hexane
Benzene
Benzene
Hexane
Nonane
Toluene
Benzene
Pentane
Hexane
Heptane
Decane
Benzene
Heptane
Decane
Hexane
PR-Soave
= RT
NC
i=1
AAD y2
AAD P
AAD y1
AAD y2
AAD P
AAD y1
AAD y2
AAD P
AAD y1
AAD y2
2.10
0.68
0.36
0.96
1.46
0.25
0.98
0.79
1.29
0.37
0.51
0.77
2.46
1.56
1.93
1.04
3.01
0.98
1.50
5.63
0.55
2.20
3.62
1.78
3.55
1.37
0.54
9.00
5.99
0.93
6.85
3.11
1.37
1.05
0.60
0.86
2.68
1.51
0.23
0.20
0.17
0.43
10.12
0.68
3.51
2.89
0.05
1.76
1.20
1.81
1.47
1.01
1.56
0.72
6.63
3.29
3.54
2.17
1.63
2.69
2.51
3.06
3.18
2.21
2.48
2.10
1.96
6.97
0.93
3.30
34.84
20.96
38.19
7.28
0.84
34.16
9.59
1.34
28.11
11.64
1.03
2.21
0.89
0.88
3.48
3.60
2.35
1.23
2.19
2.98
11.02
2.54
5.01
3.52
0.17
2.97
2.39
1.11
0.49
0.98
1.57
0.26
1.13
0.74
1.36
0.38
0.51
0.80
2.48
1.67
1.94
1.12
3.54
1.25
1.76
5.72
0.64
1.85
3.36
1.85
3.69
1.46
0.55
8.96
6.07
1.15
8.39
3.25
1.65
1.35
0.82
0.88
3.11
1.39
0.22
0.21
0.19
0.44
10.30
0.68
3.44
3.08
0.06
1.86
0.65
1.62
1.12
0.93
1.48
0.76
6.45
3.20
3.54
2.08
1.43
2.60
2.94
2.10
3.15
2.08
1.37
1.66
2.39
8.15
0.46
2.56
35.55
21.26
37.60
7.52
0.63
34.38
10.17
1.05
28.86
11.65
0.50
1.79
1.12
1.00
2.47
3.47
2.37
1.23
2.17
3.19
10.47
2.53
4.96
3.99
0.17
2.85
NC
xi
(38)
For a binary system it can be noticed that four binary interaction parameters for the mixture are needed to perform calculations.
Parameters corresponds to k12 in Eq. (36), A12 , A21 and 12 in Eq.
(38). For 12 a value of 0.47 can be xed according to the literature
taking in account that systems are formed by an alcohol (associative
polar) and an alkane or an aromatic (non-polar) [75]. In this paper,
values for k12 , A12 and A21 are those that minimize the following
objective function proposed for Paunovic et al. [76]:
ND
L y V
L y V
x1i 1i
x2i 2i
1i 1i
2i 2i
O.F =
+
y1i V
y2i V
i
1i
PT-Soave
AAD y1
PT-Heyen
AAD P
(39)
2i
of 2.91% calculated for the Soave function. In Fig. 12, the VLE calculations for the butanolheptane and pentanolbenzene have been
represented in PXY diagrams in order to illustrate the superiority of
the Heyen function over the Soave function. In both cases, it can be
seen from Fig. 12 that bubble pressure line for the two alpha functions are in good agreement with experimental data. However, for
the dew line, it can be observed than differences between the values
estimated with Soave function and experimental data are greater
than those calculated between the Heyen function an experimental
data.
In spite of differences in average deviations for both alpha functions, the Heyen alpha function is not signicant superior to the
Soave function for all the analyzed systems. From Table 10, it can
be observed for the propanolhexane and propanolnonane systems that AADs in pressure and vapor molar fractions are similar
in both alpha function cases. This behavior is expected because the
accurate to represent the pure substance vapor pressure of both
alpha functions is very similar at the temperatures which the studies were made. For the propanolhexane case at 298.15 K the AAD
in the propanol vapor pressure is 5.87% for Soave case and 5.88%
for Heyen case using both EoS. For the propanolnonane case at
333.15 K the AAD in the propanol vapor pressure is 1.60% for Soave
case and 1.31% for Heyen case using both EoS. These two examples
illustrate that similar vapor predictions using different alpha functions or different EoS produce similar results when VLE is correlated
using the same mixing rules.
8. Conclusions
Despite a one-parameter exponential alpha function, as the
Joshipura et al. expression is theoretically correct. It is not an alternative to replace the Soave alpha function in EoSs. Results obtained
for the Soave function are better than those estimated using the
Joshipura et al. function for vapor pressure, saturated vapor volume
and vaporization enthalpy.
In a cubic equation of state, when the Soave function is replaced
by an exponential function with two or three parameters, the vapor
pressure correlation capability is improved and as consequence, the
performance to predict saturated vapor volume is also improved.
For these thermodynamic properties, two or three exponential
alpha functions enhance the quantitative adjust for the low pressure interval between 1 kPa and 101.325 kPa for all the substances
studied. For non-polar compounds and vapor pressures above
1 atm two or three parameter exponential alpha functions does
not produce better results than those estimated using the Soave
function. Additionally in this paper it has been demonstrated that
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
75
76
L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576
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S. Jovanovic,
A. Mihajlov, Fluid Phase Equilib. 6 (1981) 141148.
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