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Fluid Phase Equilibria 332 (2012) 5576

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Fluid Phase Equilibria


journal homepage: www.elsevier.com/locate/fluid

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

Corresponding author. Tel.: +57 4488388x14118.


E-mail address: jorge.velasquezj@upb.edu.co (J.A. Velsquez J.).
0378-3812/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2012.05.026

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

be constants for each pure substance. A temperature-dependent


covolume can lead to results without physical sense in some properties like the heat capacity at constant volume and the speed of
the sound [21,22].
On the other hand, the attraction parameter of the cubic equations of state is calculated by means of the product of a constant and
a value calculated from a function that is known as the alpha function. The temperature dependence of the alpha function is essential
to ensure proper representation of the vapor pressure of pure uids. The vapor pressure of pure components is fundamental to make
accurate vaporliquid equilibria calculations in mixtures [23]. The
alpha function proposed by Soave [6] was the rst expression that
became popular to make process simulation. Using the Soave function, the cubic equations of state can correlate the vapor pressure
of non-polar compounds in a reduced temperature range between
0.6 and 0.9 [9]. The Soave function has been incorporated in some
recent EoSs that can be found in the literature [2,8]. However, some
researchers have been proposed some modications to the original Soave alpha function to improve the correlation of the vapor
pressures for polar compounds. Some researchers have added one
or more terms to the Soave alpha function [2428]. Other authors
have developed polynomial functions as alternatives to replace the
Soave function [2931].
A correct alpha function has to be non-monotonic descending with the temperature [32]. The Soave alpha function does not
satisfy this condition. As a consequence of this fact, the cubic equations of state that use the Soave alpha function always predict a
Boyle temperature without physical sense [33]. Also, as has been
demonstrated by Segura et al. [33], non-monotonic descendent
alpha functions can predict multiple critical points that affect the
global topology of phase diagrams. For pure substances multiple
critical points can cause intersection between high and low temperature isotherms in a PV diagram. The same mathematical behavior
described above is obtained with some modied Soave alpha functions [34]. To solve this problem, some exponentials alpha functions
has been proposed [9]. In the literature, there are different exponential functions available [1,14,18,32,3539].
Normally, exponential alpha functions have been developed to
modify the temperature dependence of the SoaveRedlichKwong
and the PengRobinson equations of state. The most recent exponential alpha expressions are generalized in terms of the acentric
factor and mainly, they have been proposed to represent the vapor
pressure for heavy hydrocarbons correctly [1,32,37]. However, the
capability to predict the vapor pressure for polar substances has
not been evaluated for functions like those proposed by Haghtalab
et al. [1] and Gasem et al. [32].
In a general way, when an alpha function is developed, the
authors compare the proposed function with other functions that
are available in the literature. In many cases, results are not
denitive, because the uids and the temperature and pressure
conditions used to develop each model are different. For these reason is hard to choose the adequate or the best alpha function for
a cubic equation of state [40]. Some studies to compare the Soave
alpha function and some of its modications have been made with
the PengRobinson equation of state [40,41]. However and taking in account that the mathematical behavior of the Soave type
alpha functions is incorrect, it is necessary to perform a systematic
analysis of different exponential alpha functions in order to choose
the best function. A better analysis should be to include a three
parameter equation of state.
In this paper, the performance to represent the thermodynamic
properties of saturated pure uids is evaluated for six alpha functions coupled to the PengRobinson and the PatelTeja equations
of state. Vapor pressure, saturated liquid volume, saturated vapor
volume and vaporization enthalpy experimental data have been
employed to make the evaluation. The chosen alpha functions are:

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

The parameters a, b and c in Eq. (1) are calculated according to:


a = ac
ac = a

(2)
R2 Tc 2

(3)

Pc

b = b

RTc
Pc

(4)

c = c

RTc
Pc

(5)

Tc and Pc are the critical temperature and the critical pressure


respectively. R is the universal constant for ideal gases. The a ,
b and c values are substance-dependent and they are dened
by the following expressions [12]:
c = 1 3c
b3

(6)

+ (2 3c )b2

+ 3c2 b

c3

=0

a = 3c2 + 3(1 2c )b + b2 + 1 3c

(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)

For the PatelTeja EoS a generalized expression is available for


non-polar substances. Additionally, for 498 non-polar and polar
substances the F value has been reported [44]. The Soave function
exhibits a minimum value in the alpha vs. reduced temperature
diagram [34]. Despite this fact, it has been used to compare the
PengRobinson and the PatelTeja original EoSs with the modied versions obtained employing the different exponential alpha
functions.
3.2. The Joshipura et al. function [38]
= exp(J(1 Tr ))

(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)

To obtain better results, pure substances have been divided in


some families and a quadratic generalized polynomial have been
presented for each family [46]. The rst derivative of the Joshipura
et al. function is:
d
= J
dTr

(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)

Heyen develop an exponential alpha function specically for a


three-parameter EoS [39]. The expression developed by Heyen has
been incorporated to the PatelTeja EoS. In Eq. (14), H1 and H2 are
non-generalized parameters. Values for these parameters are available for 38 substances in the PatelTeja original work [12]. The rst
derivative for the function of Heyen is:
d
= H1 H2 TrH2 1
dTr

(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)

Melhem et al. developed a function to modify the temperature


dependence of the PengRobinson EoS. The Melhem et al. function
was proposed to represent adequately the vapor pressure of pure
substances including polar and non-polar substances. The parameters M1 and M2 in Eq. (16) are substance-dependent and their
values are available for 100 substances approximately [36]. The rst
derivative for the Melhem et al. function is:



(M2 M1 ) Tr M2
d
=
(17)

dTr
Tr

57

Eq. (17) can be zero when:


Tr 1/2 =

M2
M2 M1

(18)

In Eq. (18), if the parameter M2 is greater than the parameter M1 ,


a minimum above the critical temperature can be predicted with
the Melhem et al. function.
3.5. The Gasem et al. function [32]
= exp((G1 + G2 Tr )(1 Tr G3 ))

(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)

For the Gasem et al. function the rst derivative is [32]:


d
= [(1 TrG3 )G2 (G1 + G2 Tr )G3 TrG3 1 ]
dTr

(21)

Depending of the values for the parameters G1 , G2 and G3 , Eq.


(21) can be equal to zero and the Gasem et al. function can present
a minimum at certain Tr value.
3.6. The Haghtalab et al. function [1]
= exp((Ht1 + Ht2 Tr )(1 Ht3ln(Tr ) )

(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.

critical constants, the acentric factor, the critical compressibility


factor and the reduced temperature range worked for each substance are reported. Also in Table 1, the last column represents the
temperature which the minimum in the alpha function is predicted
by the PengRobinson EoS using the Soave generalized model Eq.
(10). Results from Table 1 show that this minimum value appears
at very high temperatures (above 2000 K for many of the components). Taking in account this fact, the Soave function can also
be considered as a monotonic descendent alpha function for the
typical industrial application range.
To estimate the parameters, experimental data for vapor presexp
exp
sure (Psat ) and saturated liquid volumes (Vsat ) were used. The
employed objective function was:

F.O =

ND

i=1

 exp

 exp

EoS 
EoS 
 Psat Psat
 Vsat Vsat




w1 
exp
 + w2  V exp 
P
sat

(24)

sat

Equivalent expressions to Eq. (24) have been proposed and used


for some authors to determine parameters in their respective equations of state [1,58,59]. The weight factors w1 and w2 are xed
according to the equation of state.
4.1. The PengRobinson EoS
The weight factors for the PR EoS are w1 = 1 and w2 = 0, i.e., the
alpha function parameters are estimated from vapor pressure data
only. Estimated values for Eqs. (9), (11), (14), (16), (19) and (22) are
presented in Table 2.
The parameters for the Soave (Eq. (9)) and the Joshipura et al.
(Eq. (11)) functions can be correlated in terms of the acentric factor
for non-polar substances. For the Soave function the parameters
can be correlated as a linear function of the acentric factor that is
presented in Table 3. However the original expression proposed by
Peng and Robinson (Eq. (10)) can also be used as is illustrated in
Fig. 1. It can be noticed from Fig. 1 that values estimated from Eq.
(10) are in good agreement with those values reported in Table 2.
In the case of the Joshipura function, in Fig. 1 it can be noticed
considerable deviations between optimum J values reported in
Table 2 and those estimated using Eq. (12) especially for substances
with very low acentric factors (00.15). A quadratic function in
terms of the acentric factor can be used to cover the entire acentric
factor range used in this work. Generalized expression to estimate
the parameter J is presented in Table 3.

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).

Generalized expressions for both alpha functions are illustrated


in Fig. 1. The determination coefcients are 0.9948 to the parameter
J in the Joshipura et al. function and 0.9953 to the parameter F in
the Soave function.
On the other hand, in Fig. 2 is illustrated the behavior of the
parameters G1 , G2 and G3 against the acentric factor. G1 average
value for the 71 substances is 2.06. This value is practically equal to
the value proposed for Gasem et al. from 27 compounds [32]. However, for polar substances like water and all alcohols, the optimum
G1 value is not close to the average value (see Table 2). The minimum G1 value is 1.57 for methanol and the maximum value is 2.84
for n-heptanol. For the parameter G2 , the average value is 0.7707

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)

Melhem et al. Eq. (14)

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

Gasem et al. Eq. (19)

Heyen Eq.(16)

Haghtalab et al. Eq. (22)

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)

Melhem et al. Eq. (14)

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

Gasem et al. Eq. (19)

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

Haghtalab et al. Eq. (22)

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

Soave (Eq. (9))

F = 0.3905 + 1.4119

(A1)

Joshipura et al. (Eq. (11))

J = 0.4165 + 1.5652 0.4192

(A2)

H2 =
Heyen (Eq. (14))

Melhem et al. (Eq. (16))

PT EoS

0.33272 1.8678 0.2626


+ 1.3642 + 1.3788
1.3642 + 0.3788

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)

M2 = 2(0.39172 + 1.8272 + 0.2567 M12 )

(B4)

M2 = 2(1.8312 + 0.2715 M12 )


G1 = 2.109

G1 = 2.06
Gasem et al. (Eq. (19))

(B1)

G2 = 0.828

G2 = 0.953

(A5)

G3 = 0.11162 + 0.4314 + 0.1424

G3 = 0.1315 + 0.5265 0.08482

(B5)

c = 0.082 0.112 + 0.328

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)

For the Heyen function the following expressions can be derived


from Eqs. (25) and (26) at the critical point:
c = 1 + H1 H2

(29)

c = [H2 (1 + H1 H2 )]H1 H2

(30)

For both alpha functions parameters c and  c were found as


functions of the acentric factor for non-polar substances as can be

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

quadratic function of the acentric factor. Generalized expressions


are reported in Table 3.
On the other hand, regarding to the alpha functions behavior,
the following facts can be noticed for the two equations of state:
(i) For the Melhem function (Eq. (16)), the function is nonmonotonic descendent for alcohols from n-butanol to
n-heptanol. For those substances, parameter M2 is greater than
M1 . However, the minimum value in the alpha function is presented for a Tr above 19, for n-butanol until n-hexanol. For the
n-heptanol case, the Tr value is close to 6. Minimum values are
calculated employing Eq. (18).
(ii) For the Gasem et al. function (Eq. (19)), optimal G2 values
become negative for n-hexanol and heptanol. For these two
alcohols the alpha function reaches a minimum value. The minimum value for each substance is estimated nding the Tr value
that produces zero value in Eq. (21). The minimum values are
predicted for a Tr value close to 8 for n-hexanol and a Tr value
close to 4 in the n-heptanol case for both EoSs.
(iii) In the same form as the Gasem et al. function the parameter
Ht2 for the Haghtalab et al. function (Eq. (22)) is negative for
n-heptanol and a minimum is predicted for this alcohol. The
minimum value is calculated using Eq. (23) and it is predicted
for a Tr value of 9.01 for the PR EoS and 6.05 for the PT EoS.
The six evaluated alpha functions are illustrated for n-heptanol
with the PT EoS in Fig. 4. For the Soave, Melhem et al., Gasem
et al. and Haghtalab alpha functions it can be noticed the reduced
temperature which the minimum alpha value is reached for each
function. From Fig. 4, it can be observed that the worst behavior is
obtained by the Gasem et al. function. The Soave and the Joshipura
et al. functions are very similar until the Soave function reaches the
minimum value in alpha. The functions of Heyen, Melhem et al. and
Haghtalab et al. are practically the same until the reduced temperature zone when the minimum in alpha is presented for the last
two functions.

64

Table 4
PatelTeja EoS parameters for the evaluated alpha functions.
No.

Substance

Alpha function
Joshipura et al.
Eq. (11)

Soave Eq. (9)

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

Haghtalab et al. Eq. (16)

Gasem et al. Eq. (15)

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

Heyen Eq. (14)

Melhem et al. Eq. (13)

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

Melhem et al. Eq. (13)

Heyen Eq. (14)

Gasem et al. Eq. (15)

Haghtalab et al. Eq. (16)

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

Soave (Eq. (9))

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

1.01
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

Soave (Eq. (9))

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

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)).

5. Thermodynamic properties evaluation


To validate a thermodynamic model is necessary evaluating its
capability to correlate and to predict thermodynamic properties
[64]. The properties employed to evaluate the 12 models considered in this paper (6 for each equation of state) were: the vapor
pressure, saturated liquid volume, the saturated vapor volume and
the enthalpy of vaporization. For the PR EoS the vapor pressure is

the property used to estimate the EoS correlation performance. The


equation is fully predictive for the remaining properties.
In the case of the PT EoS, the vapor pressure and the saturated
liquid volume are used to evaluate the correlation capability of this
model. The vapor volume and the enthalpy of vaporization are used
to make a measure of the PT EoS prediction potential. Results are
summarized in Tables 58. The calculated average absolute relative
deviations (AAD) for each group presented in Table 1 and the global
absolute relative deviation are reported.
Results for the vapor pressure are presented in Table 5. The
Joshipura et al. function presents the highest global AAD. The average value between the two equations of state is 2.8%. The global
representation for the Soave function appears to be good. The average AAD is around 1.50%. However for alcohols the average relative
deviation is 5.64% and 5.53 for the PR EoS and the PT EoS respectively. For water case, using the PengRobinson-Soave EoS the AAD
is 2.65%. On the other hand, the two-parameter exponential models (Eqs. (14) and (16)) have a great correlation capability for all the
vapor pressure range covered. The average absolute deviations are
0.49% and 0.51% for the Melhem et al. function and the Heyen model
respectively. The lowest deviation in vapor pressure is obtained
with the three-parameter functions (Eqs. (19) and (22)). The average deviation is 0.39%. This value is the same for the Gasem et al.
and the Haghatalab et al. functions. Results by families show that
replacing the Soave alpha function for a two or three-parameter
exponential alpha function the PR and the PT EoSs can reproduce
with high accuracy the vapor pressure of the 4 groups studied. In the
case of polar substances the AAD in vapor pressure is decreased by

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))

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

1.70
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

and Tables 2 and 4, the Joshipura function is not enough to represent


the entire liquidvapor coexistence curve and a second parameter
is needed to get the adequate representation of the vapor pressure
curve when exponential alpha functions are used. From the alpha
functions curves form it is expected that deviations predicted for
other thermodynamic properties like vapor volume or vaporization enthalpy employing cubic EoS with Joshipura function will be
higher than those predicted using the remaining alpha functions.
Results for liquid volume are reported in Table 6. Employing
the same EoS, the calculated AADs are practically the same for the
six alpha functions evaluated. The average AAD for the PR EoS is
6.5% while the AAD estimated for the PT EoS is 3.5%. For the four
groups analyzed, when the PT EoS is used instead of the PR EoS
the saturated liquid volume estimation is improved. For example
for inorganic substances and organic polar substances, the average
deviation in saturated liquid volume for the PR EoS is around 2.25
times the PT average deviation. However it does not mean that for
all the inorganic and polar substances analyzed the PT EoS is superior than the PR EoS. The superiority of the PT EoS over the PR EoS
to represent the saturated liquid volume depends of the empirical critical compressibility factor ( c ) value which is characterized
by being larger than the experimental critical compressibility factor
(Zc ). In Fig. 7, the average deviations for all the evaluated substances
are presented in terms of Zc for both EoSs. From Fig. 7 it can be
identied three zones:

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

can be observed that for substances in this zone c values are


well below from the c constant value used in the PR EoS.
(ii) A second zone can be identied for substances with Zc between
0.255 and 0.285. In this zone the differences between the
average deviations with both EoSs are lower than 2.00%. To
this zone belong the most of hydrocarbons and halogenated
compounds and even some polar compounds like aniline,
diethylether and alcohols between n-propanol and n-heptanol.
c values for substances in this zone are close to the constant
value used in the PR EoS.
(iii) A nal zone can be identied for substances with Zc values
greater than 0.285. Simple substances like argon, krypton, oxygen and methane belong to this group. The average deviation
estimated for the PR EoS is around two times the deviation
obtained with PT EoS. c values for substances in this zone are
greater than 0.321.

The last evaluated property is the enthalpy of vaporization. In


Table 8, results for this property are reported. Organic polar compounds were not included for the same reason exposed for vapor
volume. In the same way as the other analyzed properties, the highest AAD is obtained for the Joshipura et al. alpha function. The AAD
for the Joshipura et al. function is close to 2.7%. Results for the Soave
and the resting exponential functions show that there is not difference between these functions, when the pure uids vaporization
enthalpy is predicted. When an alpha functions is xed, results from
Table 8 show that the vaporization enthalpy predictions employing
both EoS are practically the same. In all cases, i.e., for the six alpha
functions the difference between the average AAD for the PR EoS
and the PT EoS are less than 0.06%. The lower AAD is 1.604% and it
is obtained for the PT EoS using the Gasem et al. function.

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.

In order to verify if the improvement of the AADs by the change


of alpha function is signicant a one-way analysis of variance was
performed. The behavior of PR and PT EoSs is very similar. The
results shows that for saturated liquid volume the change of alpha
function is not statistically signicant at the 95.0% condence level,
while that for vaporization enthalpy, saturated pressure and saturated vapor volume the change is statistically signicant. Fig. 10
shows the mean AAD of the studied substances properties for each
level of alpha function. It also shows an interval around each mean.
The intervals displayed are based on Fishers least signicant difference (LSD) procedure. They are constructed in such a way that
if two means are the same, their intervals will overlap 95.0% of the
time. Any pair of intervals that do not overlap vertically correspond
to a pair of means which have a statistically signicant difference.
According to the results from Fig. 10, for vapor pressure and saturated vapor volume (Fig. 10a and c) the six alpha functions can be
classied in three groups: the rst group is formed by the Joshipura
et al. function, the second one corresponds to the function of Soave
and the last group is formed by the Heyen, Melhem et al., Gasem
et al. and Haghtalab et al. functions. Results from Fig. 10a and c
show that replacing the Soave function by an exponential function
with two parameters statistically improve the performance of cubic
EoS to represent the vapor pressure and vapor volumes of pure
substances. For liquid volume (Fig. 10b) the six means intervals
overlap each other and conrm that liquid volume is not improved
by changing the alpha function in a cubic EoS. However, the interval
for the Joshipura et al. function does not overlap with the Melhem
et al. and Heyen intervals showing a statistically difference between
these three functions. Finally, for the enthalpy of vaporization functions can be divided in two groups (Fig. 10d). The rst group, which
produces the lowest deviation, is formed by the Soave and all the
exponential functions with two or three parameters. The last group
corresponds to the Joshipura et al. alpha function.
Additionally, three one-way analysis were performed to evaluate the generalized expressions presented in Table 3 for the PR EoS
(Eqs. (A1)(A5)). In the rst case, the AAD in the vapor pressure
for hydrocarbons, gases and halogens was estimated for each substance in the whole reduced temperature range reported in Table 1.
In the second case, the AAD in vapor pressures below 1 atm was analyzed. Finally, an analysis for the deviations in vapor pressures from
1 atm to the critical pressure of each substance was made. Results
for all cases are reported in Fig. 11. For the entire range covered (see
Fig. 11(a)) results conrms that even replacing the Soave function
by a generalized exponential function like the Heyen, Melhem et al.
or Gasem et al. the vapor pressure of non-polar pure substances can
be statistically improved. However from Fig. 11(b) and (c) it can
be observed that the improvement is statistically signicant only
for the low pressure range (Fig. 11b). Results for vapor pressures

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)

Calculations with PR EoS can be performed when b = c. In this


work, the binary interaction parameters (kij in Eq. (31)) were
xed to zero, i.e., binary systems calculations are totally predictive
because pure substances parameters were estimated employing generalized expressions from Table 3. The evaluated systems
and deviations in bubble pressure and vapor molar fractions are
reported in Table 9. The critical constants and acentric factors for
those substances used in mixtures calculations but not reported in
Table 1 corresponds to those reported Poling et al. [62].
Results from Table 9 show that using both alpha functions good
results can be obtained for the systems evaluated. However, results
also show that average deviations with both EoSs and the Heyen
function are lower than those predicted employing the Soave function. However, differences are more signicant for the PR case. The
AADs for the PR-Heyen generalized EoS are 2.15% and 3.13% for
bubble pressure and the second component vapor molar fraction
while the AADs are 3.34% and 3.83% for the same properties with
the PR-Soave generalized EoS. In the PT EoS case the PT-Heyen EoS
AAD for bubble pressure is 2.5% while a value of 2.9% is predicted
for the PT-Soave EoS. Comparison between both EoS and the same
alpha function show that predictions are very similar for the two
models evaluated. In the other hand, a more detailed analysis for
the results reported in Table 9 can be identied the following facts:
(i) For the two systems with bubble pressure above 1 atm
(n-hexane/1,3-butadiene and 1-butene/1,3-butadiene) bubble
pressure prediction are practically the same for both alpha
function and both EoSs.
(ii) For the systems with bubble pressure below 1 atm, the Heyen
function predicts better results than the Soave function for systems involving octane, decane and 1-octene. Bubble pressure

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).

average deviations predicted for systems with octane was 1.3%


and 2.9% for the PR-Heyen and the PR-Soave EoSs respectively.
For systems containing decane the PT-Heyen AAD corresponds
to 3.2% while for the PT-Soave model the AAD value is 4.7%.
However, it has to be signed that not for all systems below
1 atm the Heyen functions is superior than the Soave function.
In the case of systems with n-heptane, the AAD estimated for
the PT-Soave EoS is 1.8% while a value of 3.5% is predicted for
the PT-Heyen model.

7.2. Alkanol/hydrocarbon mixtures calculations


Vapor liquid equilibrium calculations at low pressures for binary
mixtures for alkanol/alkane and alkanol/aromatic systems were
made with both EoS and the WongSandler mixing rules [23] to
show the inuence of the alpha function over this type of mixtures.
For the PT EoS parameters for any mixture using the
WongSandler mixing rules can be calculated according to the following expressions [74]:


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

(bi (ai /RT )) + (bj (aj /RT ))

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

Parameters for pure substances ai , bi and ci are calculated using


Eqs. (2)(8). Calculations for the PR EoS can be estimated doing b = c
for pure substances and mixtures. The excess Helmholtz energy at
innite pressure can be calculated from a model to estimate the
excess Gibbs energy at low pressure. In this case the NRTL model

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

x (A )/(RT ) exp(ji (Aji )/(RT ))


j=1 j ji
NC
x exp(ki (Aki )/(RT ))
k=1 k

(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

was chosen and the expression to estimate AE according to the


literature is [75]:
AE

PT-Heyen

AAD P

(39)

2i

In Eq. (39) ND is the number of experimental data, x1 , x2 ,


y1 and y2 are the experimental liquid and vapor molar fractions
respectively. Experimental bubble pressures and temperatures are
needed to estimate fugacity coefcients of liquid and vapor phases
that appear in Eq. (39). Parameters for 15 binary systems and both
the PR and PT EoS were determined using isothermal vapor liquid equilibrium data (PTXY) recommended by Goral et al. [77,78].
Estimations were made for the Soave and the Heyen alpha functions. Parameters of the pure substances were determined using
generalized expressions from Table 3 for the alkanes and the aromatic compounds. For alcohols optimum parameters reported in
Tables 2 and 4 for the PR and PT EoS respectively were used following recommendations according to the literature [7].
In Table 10 parameters for the EoS + WongSandler-NRTL models are reported for the two EoS and the two alpha functions
considered in this work. The average absolute deviations for the
bubble pressure ant the vapor phase compositions are reported in
Table 11. Results show that a good correlation of the bubble pressure can be obtained with both alpha functions. However, for the
Heyen function an average absolute deviation of 1.00% is calculated
with both EoS while a deviation of 2.10% is estimated employing the
Soave function. For vapor phase compositions results for the Heyen
function are superior to those obtained with the Soave function.
For the molar fraction of the alcohol the average deviation corresponds to 11.65% for the Soave function while a value around 3.1%
is obtained for the Heyen function case. For the alkane or aromatic
vapor phase compositions Heyen function is also superior with an
estimated average deviation of 1.80% for both EoS against the value

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

exponential two-parameter alpha functions can be generalized in


terms of the acentric factor for non-polar compounds using the
rst and second derivative of the alpha function at the critical
temperature. In the case of polar substances, especially alcohols,
exponential functions with two or three parameter are needed to
obtain a good correlation of the vapor pressure.
Estimations of the saturated liquid volume are almost independent of the alpha function. Deviations in saturated liquid densities
estimated with the Joshipura et al. function are statistically different and slighty better than those estimated with the Melhem et al.
and Heyen functions. For this property, the PT EoS is better than
the PR EoS for all the substances analyzed. However for some substances the optimum c value is closed to the predicted value by
the PR EoS. To obtain a better representation of the saturated liquid volume, the PT EoS has to be used instead of the PR EoS for
pure substances with critical compressibility factors below 0.245
and above 0.290.
Two or three parameter exponential functions, does not produce signicant improve of the capability to predict vaporization
enthalpy of pure substances. Results for the two EoSs evaluated
are equivalent and none of them present advantages to predict this
property.
Differences in average absolute deviations between two or three
exponential functions are not considerable for the four thermodynamic properties analyzed. In the other hand, the Melhem et al.,
Gasem et al. and Haghtalab et al. alpha functions are no monotonic
descendent for some alcohols. For these two reasons the Heyen
et al. function is recommended to replace the Soave function in
any EoS to improve its capability to represent saturated pure uids
properties.
Finally, it has been demonstrated that using the Heyen function
instead of the Soave function in cubic EoS with the WongSandlerNRTL mixing rules the capability to correlate the bubble pressure
and especially the vapor phase compositions can be improved for
alcohol/alkane or alcohol/aromatic systems.
Acknowledgment
Authors thanks to the Colciencias program Doctorados
Nacionales-Generacin Bicentenario for nancial support during
the present research.
References
[1] A. Haghtalab, M.J. Kamali, S.H. Mazloumi, P. Mahmoodi, Fluid Phase Equilib.
293 (2010) 209218.
[2] A.H. Farrokh-Niae, H. Moddarress, M. Mohsen-Nia, J. Chem. Thermodyn. 40
(2008) 8495.
[3] G.M. Kontogeorgis, G.K. Folas, Thermodynamic Models for Industrial Applications: From Classical and Advanced Mixing Rules to Association Theories, rst
ed., Wiley, Chippenham, 2010.
[4] J.D. van der Waals, J.S. Rowlinson, On the Continuity of the Gaseous and Liquid
States, rst ed., Dover Publications, New York, 2004.
[5] D.-Y. Peng, D.B. Robinson, Ind. Eng. Chem. Fundam. 15 (1976) 5964.
[6] G. Soave, Chem. Eng. Sci. 27 (1972) 11971203.
[7] J.O. Valderrama, Ind. Eng. Chem. Res. 42 (2003) 16031618.
[8] F. Esmaeilzadeh, M. Roshanfekr, Fluid Phase Equilib. 239 (2006) 8390.
[9] J.V. Sengers, R.F. Kayser, C.J. Peters, H.J. White Jr. (Eds.), Equations of State for
Fluids and Fluid Mixtures, rst ed., Elsevier, Amsterdam, 2000.
[10] G. Schmidt, H. Wenzel, Chem. Eng. Sci. 35 (1980) 15031512.
[11] A. Harmens, H. Knapp, Ind. Eng. Chem. Fundam. 19 (1980) 291294.
[12] N.C. Patel, A.S. Teja, Chem. Eng. Sci. 37 (1982) 463473.
[13] J.-M. Yu, B.C.Y. Lu, Fluid Phase Equilib. 34 (1987) 119.
[14] C.H. Twu, D. Bluck, J.R. Cunningham, J.E. Coon, Fluid Phase Equilib. 69 (1991)
3350.
[15] F. Abdollahi-Demneh, M.A. Moosavian, M.M. Montazer-Rahmati, M.R. Omidkhah, H. Bahmaniar, Fluid Phase Equilib. 288 (2010) 6782.
[16] F. Abdollahi-Demneh, M.A. Moosavian, M.M. Montazer-Rahmati, M.R. Omidkhah, H. Bahmaniar, Fluid Phase Equilib. 291 (2010) 4858.
[17] J.O. Valderrama, M. Alfaro, Oil. Gas Sci. Technol. 55 (2000) 523531.
[18] M.A. Trebble, P.R. Bishnoi, Fluid Phase Equilib. 35 (1987) 118.
[19] M.A. Trebble, P.R. Bishnoi, Fluid Phase Equilib. 40 (1988) 121.

75

[20] I. Polishuk, J. Wisniak, H. Segura, Chem. Eng. Sci. 55 (2000) 57055720.


[21] I. Polishuk, Ind. Eng. Chem. Res. 48 (2009) 1070810717.
[22] V. Kalikhman, D. Kost, I. Polishuk, Fluid Phase Equilib. 293 (2010)
164167.
[23] D.S.H. Wong, H. Orbey, S.I. Sandler, Ind. Eng. Chem. Res. 31 (1992)
20332039.
[24] L. Raimondi, Chem. Eng. Sci. 35 (1980) 12691275.
[25] P.M. Mathias, Ind. Eng. Chem. Proc. Des. Dev. 22 (1983) 385391.
[26] P.M. Mathias, T.W. Copeman, Fluid Phase Equilib. 13 (1983) 91108.
[27] R.M. Gibbons, A.P. Laughton, J. Chem Soc. Faraday Trans. 2. Mol. Chem. Phys. 80
(1984) 10191038.
[28] R. Stryjek, J.H. Vera, Can. J. Chem. Eng. 64 (1986) 323333.
[29] I.P. Androulakis, N.S. Kalospiros, D.P. Tassios, Fluid Phase Equilib. 45 (1989)
135163.
[30] G. Soave, Fluid Phase Equilib. 84 (1993) 339342.
[31] N.C. Patel, Int. J. Thermophy 17 (1996) 673682.
[32] K.A.M. Gasem, W. Gao, Z. Pan, R.L. Robinson, Fluid Phase Equilib. 181 (2001)
113125.
[33] H. Segura, T. Kraska, A. Meja, J. Wisniak, I. Polishuk, Ind. Eng. Chem. Res. 42
(2003) 56625673.
[34] E. Neau, O. Hernndez-Garduza, J. Escandell, C. Nicolas, I. Raspo, Fluid Phase
Equilib. 276 (2009) 8793.
[35] M.S. Graboski, T.E. Daubert, Ind. Eng. Chem. Proc. Des. Dev. 17 (1978)
443448.
[36] G.A. Melhem, R. Saini, B.M. Goodwin, Fluid Phase Equilib. 47 (1989)
189237.
[37] H. Li, D. Yang, Energy & Fuels 25 (2010) 215223.
[38] M.H. Joshipura, S.P. Dabke, N. Subrahmanyam, Int. J. Chem. Eng. Res. 1 (2009)
123134.
[39] G. Heyen, A cubic equation of state with extended range of application, in:
Proceedings of the 2nd World Congress of Chemical Engineering, Frankfurt,
1980, pp. 913.
[40] N. Kleiman, F. Barragan, E. Baza, Rev. Mex. Ing. Qum. 1 (2002)
119135.
[41] O. Hernndez-Garduza, F. GarcIa-Snchez, D. pam-MartInez, R. VzquezRomn, Fluid Phase Equilib. 198 (2002) 195228.
[42] J.R. Elliott, C.T. Lira, Introductory Chemical Engineering Thermodynamics, rst
ed., Prentice Hall PTR, Upper Saddle River, 1999.
[43] C. Coquelet, A. Chapoy, D. Richon, Int. J. Thermophys. 25 (2004) 133158.
[44] L.A. Forero, J.A. Velsquez, J. Chem. Eng. Data 55 (2010) 50945100.
[45] J.L. Daridon, B. Lagourette, H. Saint-Guiros, P. Xans, Fluid Phase Equilib. 91
(1993) 3154.
[46] M.H. Joshipura, S.P. Dabke, N. Subrahmanyam, J. Taiwan Inst. Chem. Eng. 41
(2010) 570578.
[47] W.G. Mallard, P.J. Linstrom (Eds.), NIST Chemistry WebBook, NIST Standard Reference Database Number 69, National Institute of Standards and Technology,
Gaithersburg, MD, 1998.
[48] R.H. Perry, D.W. Green, Perrys Chemical Engineers Handbook, seventh ed.,
McGraw-Hill, 1997.
[49] D. Ambrose, C.H.S. Sprake, R. Townsend, J. Chem. Thermodyn. 6 (1974)
693700.
[50] D. Ambrose, C.H.S. Sprake, R. Townsend, J. Chem. Thermodyn. 4 (1972)
247254.
[51] J. Wu, J. Yin, J. Chem. Eng. Data 53 (2008) 22472249.
[52] T.E. Daubert, R.P. Danner, Physical and Thermodynamic Properties of Pure
Chemicals Data Compilation, Hemisphere Publishing Corporation, London, UK,
1992.
[53] A.J. Kubicek, P.T. Eubank, J. Chem. Eng. Data 17 (1972) 232235.
[54] H.R. Kemme, S.I. Kreps, J. Chem. Eng. Data 14 (1969) 98102.
[55] D. Ambrose, R. Townsend, J. Chem. Soc. (1963) 36143625.
[56] R.C. Wilhoit, B.J. Zwolinski, J. Phys. Chem. Ref. Data 2 (Suppl. 1) (1973).
[57] T. Boublk, V. Fried, E. Hala, The Vapour Pressure of Pure Substances, rst ed.,
Elsevier, Amsterdam, 1973.
[58] A. Dashtizadeh, G.R. Pazuki, V. Taghikhani, C. Ghotbi, Fluid Phase Equilib. 242
(2006) 1928.
[59] M. Mohsen-Nia, H. Modarress, G.A. Mansoori, Fluid Phase Equilib. 206 (2003)
2739.
[60] F.L. Figueira, L. Lugo, C. Olivera, Fluid Phase Equilib. 259 (2007)
105115.
[61] J.O. Valderrama, L.A. Forero, Fluid Phase Equilib. 317 (2012) 7783.
[62] B.E. Poling, J.M. Prausnitz, J.P. OConnell, The Properties of Gases and Liquids,
McGraw-Hill, 2001.
[63] T.E. Daubert, Ind. Eng. Chem. Res. 37 (1998) 32603267.
[64] U.K. Deiters, K.M. De Reuck, Fluid Phase Equilib. 161 (1999) 205219.
[65] S.B. Kiselev, Fluid Phase Equilib. 147 (1998) 723.
[66] J. Gmehling, U. Onken, W. Arlt, VaporLiquid Equilibrium Data Collection
Chemistry Data Series, vol. 1, DECHEMA, Frankfurt, 1982.
[67] M. Gral, Fluid Phase Equilib. 102 (1994) 275286.
[68] S.J. Ashcroft, A.D. Clayton, R.B. Shearn, J. Chem. Eng. Data 24 (1979)
195199.

Fluid Phase Equilib.


[69] L.M. Lozano, E.A. Montero, M.C. Martn, M.A. Villamanan,
133 (1997) 155162.
[70] A. Dejoz, V. Gonzales-Alfaro, P.J. Miguel, M.I. Vsquez, J. Chem. Eng. Data 41
(1993) 9396.
[71] B. Willman, A.S. Teja, J. Chem. Eng. Data 30 (1985) 116119.
[72] J.H. Vera, J.M. Prausnitz, J. Chem. Eng. Data 16 (1971) 149154.

76

L.A. Forero G., J.A. Velsquez J. / Fluid Phase Equilibria 332 (2012) 5576

[73] K.L. Young, R.A. Mentzer, R.A. Greenkorn, K.C. Chao, J. Chem. Thermodyn. 9
(1977) 979985.
[74] T. Yang, G.J. Chen, W. Yan, T.M. Guo, Chem. Eng. J. 67 (1997) 2736.
[75] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135144.

S. Jovanovic,
A. Mihajlov, Fluid Phase Equilib. 6 (1981) 141148.
[76] R. Paunovic,
[77] M. Gral, P. Oracz, J. Phys. Chem. Ref. Data 31 (2002) 701748.
[78] M. Gral, A. Skrzecz, A. Bok, A. Maczynski, J. Phys. Chem. Ref. Data 33 (2004)
959997.

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