Applications of cubic equations of state for determination of the solubilities

of industrial solid compounds in supercritical carbon dioxide:

A comparative study
Mohammad Yazdizadeh
a
, Ali Eslamimanesh
b
, Feridun Esmaeilzadeh
a,n
a
School of Chemical and Petroleum Engineering, Shiraz University, P.O. Box 71348-51154, Namazi Square, Shiraz, Iran
b
MINES ParisTech, CEP/TEPCentre E

nergetique et Procede s, 35 Rue Saint Honore , 77305 Fontainebleau, France

a r t i c l e i n f o
Article history:
Received 29 June 2010
Received in revised form
19 October 2011
Accepted 25 October 2011
Available online 19 November 2011
Keywords:
Supercritical carbon dioxide
m-ER EoS
Comparative study
Thermodynamic model
Solid compounds
Solubility
a b s t r a c t
Representation/predictions of the solubilities of industrial solid compounds in supercritical carbon
dioxide have been a challenge since the last two decades. In this communication, the SoaveRedlich
Kwong (SRK), the PengRobinson (PR), the PatelTejaValderrama (PTV), the EsmaeilzadehRoshanfekr
(ER) and the modied EsmaeilzadehRoshanfekr (m-ER) equations of state (EoS) accompanied with
several mixing rules including the WongSandler (WS), the covolume-dependent (CVD) and the van der
Waals one (vdW1) and two (vdW2) uid mixing rules are applied to calculate/estimate the solubilities
of 23 mostly used solid compounds in supercritical carbon dioxide. In addition, the Van-Laar excess
Gibbs energy (G
ex
) activity model is also used in phase equilibrium calculations. The probable global
optimal values of the proposed thermodynamic model parameters are evaluated by the differential
evolution (DE) optimization strategy. The results indicate that the combination of the m-ER EoS with
the WS mixing rule leads to more accurate predictions (AARD7%) in comparison with other ones.
Finally, application of Chrastil semi-empirical correlation for estimation of the solubilities of several
compounds in supercritical carbon dioxide is investigated at wide ranges of temperatures.
& 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Truth be told, applications of supercritical uids (SCF) in
chemical industry have been of much interest in the past decades.
It has been widely used in extractions, purications, separations,
crystal growth, reactions and fractionations of different com-
pounds (Esmaeilzadeh et al., 2009; Gharagheizi et al., 2011;
Yazdizadeh et al., 2011; Huang et al., 2001). Carbon dioxide is
considered to be a suitable uid in supercritical processes as it is a
non-toxic compound that is inexpensive, non-explosive, available
and easy to remove from the extracted products. Possible applica-
tions of CO
2
are the extraction of fatty acid esters, vegetable oils
and antioxidants in food engineering industries and solvation of
solid phenazopyridine, propranolol and methyl salicylate in phar-
maceutical processes (Esmaeilzadeh et al., 2009; Gharagheizi et al.,
2011; Yazdizadeh et al., 2011; Huang et al., 2001; Housaindokht
et al., 2007; Yamini et al., 2003; Ismadji 2008).
In order to design optimized supercritical processes, reliable
experimental solubility data of the proposed compounds are
required. The difculties for accurate measurements of the
corresponding data especially at elevated pressures (Cheng
et al., 2003) have brought about the recent attempts to present
different thermodynamic approaches for solving the problem. A
detailed literature survey shows that the presented models fall
into three main categories: equations of state, empirical and
cluster solvation models.
In the rst group, different EoSs along with various mixing
rules are applied to investigate the phenomenon. Kurnik and Reid
(1982), Kosal and Holder (1987), Goldman et al. (1996), Cortesi
et al. (1999) and Goodarznia and Esmaeilzadeh (2002) were
among the researchers, who developed thermodynamic models
based on the cubic equations of state such as the RedlichKwong
(RK) (Redlich and Kwong, 1949), the SoaveRedlichKwong (SRK)
(Soave, 1972) and the PengRobinson (PR) (Peng and Robinson,
1976) EoSs with conventional mixing rules. However, the mixing
rules may be accompanied with excess Gibbs energy (G
ex
) models
mainly due to the facts that the performance of the traditional
two-parameter equations of state is doubtful in supercritical uid
region and to deal with highly non-ideal mixtures involving polar
and quadrupolar compounds. The PatelTeja (PT) EoS (Patel and
Teja, 1982) was rstly used by Sheng et al. (1992) with modied
HuronVidal (Huron and Vidal, 1979) mixing rule to estimate the
solubilities of aromatic compounds in supercritical carbon dioxide.
Later, Huang et al. (2001) applied mixing rules with the UNIFAC
activity coefcient model to calculate the solid solubilities of
Contents lists available at SciVerse ScienceDirect
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Chemical Engineering Science
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doi:10.1016/j.ces.2011.10.055
n
Corresponding author. Tel.: 98 711 2303071; fax: 98 711 6287294.
E-mail addresses: yazdizadeh.m@gmail.com (M. Yazdizadeh),
ali.eslamimanesh@mines-paristech.fr (A. Eslamimanesh),
esmaeil@shirazu.ac.ir (F. Esmaeilzadeh).
Chemical Engineering Science 71 (2012) 283299
aromatic, fatty acid, and heavy alcohol compounds in supercritical
CO
2
. Their proposed model contributed to reliable results for both
polar and non-polar compounds. In 1997, Zhong and Masuoka
(1997) developed a new UNIFAC G
ex
/EoS thermodynamic model
using perturbed hard-sphere (PHS) theory. This technique was
also applied by Esmaeilzadeh et al. (2009) to derive a new mixing
rule, based on the NRTL model for the SRK (Soave, 1972) and the
PR (Peng and Robinson, 1976) equations of state. Their model was
successful in representation/prediction of solubilities of hydro-
carbons, aliphatic carboxylic acids, aromatic acids and aromatic
alcohols in supercritical carbon dioxide. In addition, a novel lattice
EoS developed by Kumar (1986) has been applied successfully
for triglyceride solubility calculations (Bamberger et al., 2008).
Another recent attempt has been done by Martinez-Correa et al.
(2010), in which the solubility of squalene in supercritical carbon
dioxide is calculated using the group contribution equation of
state (GC-EoS). Tsivintzelis et al. (2009) also predicted the phase
behavior of mixtures of pharmaceuticals with liquid or super-
critical solvents applying the nonrandom hydrogen-bonding
(NRHB) theory and obtained reliable results. Descriptions of other
EoS-based models can be found elsewhere (Johnston et al., 1989;
Brennecke and Eckert, 1989; Mukhopadhyay and Rao, 1993; Song
and Sadus, 2000; Madras, 2004; Khimeche et al., 2007).
Several studies have been done on possibility of using empiri-
cal equations for phase equilibrium calculation/estimation of the
supercritical carbon dioxidesolid compound systems. Chrastil
(1982) related the solubility of a solute to the density of the
supercritical solvent (gas) with this assumption that the molecule
of a solute associates with the certain number of molecules of gas
with the formation of a solvate complex, which is in equilibrium
with the gas (Knez et al., 1998). This semi-empirical model, which
contains three adjustable parameters to minimize the deviation of
the predictions from experimental solubility data, was used
to accurately calculate the solubilities of Ametryn, Prometryn,
Atrazine and Simazine in supercritical CO
2
by Knez et al. (1998).
An alternative method was proposed by Mendez-Santiago and
Teja (1999), who applied a semi-empirical equation including
three parameters for each binary system (Huang et al., 2001).
The above methods have been extended by other authors to model
the phase behavior of the systems containing mixtures of various
solid compoundssupercritical CO
2
(Mendez-Santiago and Teja,
2000; Liong et al., 1992).
The third class of thermodynamic models includes those ones,
which investigate the equilibrium constant of the association
reactions between the molecules of solutes and solvent (gas)
through application of standard heat of solvation and the stan-
dard entropy change of solvation. Zhong et al. (1998) and Jiang
et al. (1998) developed such models correlating the solubility of
solid materials in supercritical uid. Using temperature-depen-
dent parameters, they reported satisfactory results of their
theoretical approaches for binary systems but no attempt was
done to extend the model to multi-component mixtures until
2003, when Cheng et al. (2003) presented a simplied cluster
solvation method for this purpose. They also compared the
obtained results with the previous models from all the three
categories described earlier.
In spite of the fact that the proposed models are successful in
calculation/estimation of many kinds of solid compounds in
supercritical carbon dioxide, they have several weaknesses.
Firstly, some of them may not be general to use for other
compounds except those investigated. In addition, the large
deviations of the results of several ones from the related experi-
mental solubility data may cause the users not to have condence
on their reliability. Furthermore, the engineers may prefer to
apply more famous models that can be easily joined with
simulation softwares. Therefore, there is a need to search for
reliable general methods, which represent/predict solubilities of
solid compounds in supercritical carbon dioxide to be used in
ever-growing SCF industrial processes.
In this work, the focus has been on the presentation of
thermodynamic models based on cubic equations of state includ-
ing the SRK (Soave, 1972), the PR (Peng and Robinson, 1976),
the PatelTejaValderrama (PTV) (Valderrama, 1990), the
EsmaeilzadehRoshanfekr (ER) (Esmaeilzadeh and Roshanfekr,
2006) and the modied EsmaeilzadehRoshanfekr (m-ER)
(Bonyadi and Esmaeilzadeh, 2008) equations of state with differ-
ent mixing rules along with Van-Laar Gibbs energy activity
model. The model is later applied to calculate the solubilities of
various solid compounds in supercritical CO
2
. The optimal values
of the model adjustable parameters are obtained using a robust
population-based optimization strategy for 863 experimental
data points. In the nal analysis, Chrastil (1982) semi-empirical
correlation is used to correlate the solubility of specic solid
compounds in supercritical CO
2
for wide ranges of pressures and
temperatures.
2. Theory
For phase equilibrium calculations, the equality of the fugacity
of pure solute to its fugacity in supercritical uid has been
assumed as follows:
f
pure solid
i
f
supercritical
i
1
where f refers to the fugacity and i stands for ith solute in the
mixture. In this study, the derivation of the required equations is
based on the following assumptions:
1. The supercritical uid is assumed to be insoluble in the
solute phase.
2. The fugacity of pure solid i stands for the fugacity of the solute
i in the mixture.
3. The molar volume of the solute is pressure-independent.
4. Solid phase is incompressible.
5. The fugacity coefcient of the solute at sublimation point
is unity.
Therefore, Eq. (1) is rewritten as the following equation:
P
sat
i
exp
v
s
i
PP
sat
i

RT
_ _
y
i
j
i
P 2
where P is the pressure, n is the solid molar volume, R is the
universal gas constant, T refers to temperature, superscripts s and
sat stand for solid and saturation conditions, respectively, y and j
are the mole fraction and fugacity coefcient of the solute in
supercritical phase, respectively. The saturation or the sublima-
tion pressure (P
sat
i
) is either taken from the literature shown in
Table 1 or calculated by
logp
sat
A
B
TKC
3
where A, B and C are the Antoine equation constants reported in
Table 2.
3. Methodology
3.1. Investigated compounds
The supercritical operations include many compounds nowa-
days. 23 well-known chemical compounds have been investigated
in this study to present a general comparative study. Table 3
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 284
reports the physical properties of these compounds. A group
contribution method (Valderrama et al., 2008; Valderrama and
Robles, 2007) has been applied to evaluate the properties when
the experimental data were not available.
3.2. Equations of state
As already stated, the SRK (Soave, 1972), the PR (Peng and
Robinson, 1976), the PTV (Valderrama, 1990), the ER (Esmaeilzadeh
and Roshanfekr, 2006) and the m-ER (Bonyadi and Esmaeilzadeh,
2008) EoSs have been used to calculate the fugacity coefcients. The
ER (Esmaeilzadeh and Roshanfekr, 2006) and the m-ER (Bonyadi and
Esmaeilzadeh, 2008) equations of state accompanied with the applied
mixing rules are described in Appendix A. It was shown in previous
works (Yazdizadeh et al., 2011; Eslamimanesh and Esmaeilzadeh,
2010) that the ER (Esmaeilzadeh and Roshanfekr, 2006) and m-ER
(Bonyadi and Esmaeilzadeh, 2008) equations of state are able to
reliably represent/predict the corresponding uid phase behavior in
both subcritical and supercritical uid regions.
3.3. Chrastil correlation
As Chrastil (1982) assumed in 1982, the solute molecules,
associated with the supercritical gas molecules, are in chemical
equilibrium with the resulted complex (solvate complex) as
follows (Chrastil, 1982; Ismadji and Bhatia, 2003):
A
0
k
0
B
0
2A
0
B
0
k
0 4
where k
0
represents the association term, A
0
denotes the solute
molecule and B
0
is the supercritical gas (solvent) molecule.
Therefore, the solubility of the solute can be calculated using
(Chrastil, 1982; Ismadji and Bhatia, 2003):
c r
k
exp
f
T
g
_ _
5
In the above equation, c is the solubility, r denotes the density
of the solvent (gas), f and g are the adjustable parameters of
the equation, respectively. It has been demonstrated that (Ismadji
and Bhatia, 2003) the association term is a characteristic of the
Table 1
Experimental sublimation vapor pressures.
Compound Temperature (K) Pressure
unit
Refs.
308.15, Pressure
unit (10
6
)
313.15 318, Pressure
unit (10
6
)
328.18, Pressure
unit (10
6
)
333.2, Pressure
unit (10
6
)
Triphenylene 11.1 46.9 183 Pa Esmaeilzadeh and Roshanfekr (2006)
Phenazopyridine 0.0055 0.014 0.034 bar Bonyadi and Esmaeilzadeh (2008)
Propranolol 0.0039 0.0013 0.0037 bar Bonyadi and Esmaeilzadeh (2008)
Methimazole 79 180 390 bar Bonyadi and Esmaeilzadeh (2008)
Fluoranthene 2570 9050 29,500 Pa Esmaeilzadeh and Roshanfekr (2006)
O-hydroxy benzoic acid 2.25 6.65 bar Esmaeilzadeh et al. (2009)
P-Chlorophenol 10,290 0.0244 MPa Barna et al. (1996)
2,4-dichlorophenol 8178 0.0208 MPa Barna et al. (1996)
2,6-dichlorophenol 3110 0.0118 MPa Barna et al. (1996)
2,4,6-trichlorophenol 918 0.00376 MPa Barna et al. (1996)
Table 2
Constants used in Eq. (3) for calculation of solid sublimation vapor pressures.
Compound A B C Pressure unit Refs.
Methyl salicylate 12.51 6163.1 0 bar Housaindokht and Bozorgmehr (2008)
a
Naphthalene 11.7 2620 52.5 Pa Gharagheizi et al. (2011)
Cholesterol 8.95 4681.8 0 bar Housaindokht and Bozorgmehr (2008)
Benzocaine 10.28 4572.3 0 bar Housaindokht and Bozorgmehr (2008)
Benzoin 36.38 13200 0 KPa Esmaeilzadeh et al. (2009)
Aspirin 7.59 3131.2 0 bar Housaindokht and Bozorgmehr (2008)
Benzoic acid 12.53 6511.2 0 bar Housaindokht and Bozorgmehr (2008)
Acenaphthene 10.95 6038.5 0 bar Housaindokht and Bozorgmehr (2008)
Perylene 19.94 15347 0 bar Housaindokht and Bozorgmehr (2008)
Mandelic acid 49.8 17200 0 Pa Esmaeilzadeh et al. (2009
Propyl 4-hydroxybenzoate 41.1 14200 0 Pa Esmaeilzadeh et al. (2009)
Hexamethylbenzene 13.1 385 21 bar Esmaeilzadeh et al. (2009)
Lactic acid 11.03 4354 0 bar Housaindokht and Bozorgmehr (2008)
Phenanthrene 9.6 4870 0 bar Esmaeilzadeh et al. (2009)
Anthracene 9.7 5310 0 bar Gharagheizi et al. (2011)
Carbazole 20.4 17000 1600 KPa Esmaeilzadeh et al. (2009)
Fluorene 9.43 4420 0 bar Esmaeilzadeh et al. (2009)
Pyrene 8.35 4900 0 bar Gharagheizi et al. (2011)
1-Hexadecanol 22.8 8740 0 KPa Esmaeilzadeh et al. (2009)
1-Octadecanol 25 9780 0 KPa Esmaeilzadeh et al. (2009)
Palmitic acid 19.3 8070 0 KPa Esmaeilzadeh et al. (2009)
Stearic acid 6.17 2160 1540 KPa Esmaeilzadeh et al. (2009)
1-Eicosanol 28.9 1140 0 KPa Gharagheizi et al. (2011)
Phenol 13.7 3580 0 Pa Gharagheizi et al. (2011)
a
Evaluated by the Antoine Equation proposed in Ref. Smith et al. (2004).
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 285
proposed system and can be treated as an adjustable parameter
due to the fact that the solvate complex is not stoichiometric in
most cases. Several authors have applied this semi-empirical
equation to correlate the experimental data (Ismadji and Bhatia,
2003; Fathi et al., 1998; Medina and Bueno, 2000, 2001; Lin et al.,
2001). They also reported the tted values of the equation
parameters for each selected temperature range.
4. Problem formulation
The probable global optimum values of the model parameters
including the binary interaction parameters (k
ij
) in case of applying
vdW1 mixing rule (Mukhopadhyay, 2000), k
ij
and l
ij
in using vdW2
(Mukhopadhyay, 2000) mixing rule, A
ij
and k
ij
in calculations by WS
mixing rule (Wong and Sandler, 1992) method, and M
ij
in case of
using CVD mixing rule (Mukhopadhyay, 2000), have been evaluated
by the DE optimization strategy (Chiou and Wang, 1999; Storn and
Price, 1997). This simple and robust strategy (Chiou and Wang, 1999;
Storn and Price, 1997), which has several advantages over the
conventional evolutionary optimization methods (Babu and Angira,
2006), has been investigated to have high capabilities in phase
behavior calculation (Yazdizadeh et al., 2011; Eslamimanesh and
Esmaeilzadeh, 2010; Eslamimanesh and Shariati, 2009). The details
of this optimization technique can be found elsewhere Storn and
Price, 1997.
The model parameters have been treated to be the decision
variables of the optimization algorithm. The following objective
function is to be minimized:
f unction
100
ndp

ndp
i
9y
Cal:
i,solid
y
Exp:
i,solid
9
y
Exp:
i,solid
6
where ndp is the number of data points used in the optimization
procedure, and the superscripts Cal. and Exp. are the calculated
and experimental mole fractions of the solid compounds in
supercritical phase, respectively. The above objective function
has been subjected to the following constraints:
Zb40 7
Z1

2
p
b
Z1

2
p
b
_ _
40 8
where b is a parameter dened in Appendix A. Both of the above
constraints have been selected to avoid trivial results from the
exponential terms of the fugacity expressions because the DE
(Storn and Price, 1997) is based on the random search method and
may result in negative values of these parameters. The concept of the
penalty functions is generally considered to deal with the optimiza-
tion problems subjected to several constraints, which penalize
infeasible solutions (eliminate the unexpected results). Based on this
method, the penalty function takes a nite value when a constraint is
violated and a value of zero when constraint is satised. The
penalized function is generally written as (Deb, 2002):
OFy f unctionyRN

L
l 1
g
i
y
_

M
m 1
9h
m
y9
_ _
9
Table 3
The physical properties of the compounds used in this work.
Compound T
c
(K) P
c
(bar) o u
s
(cm
3
/mol) Refs.
Carbon dioxide 304.2 73.83 0.224 Housaindokht and Bozorgmehr (2008)
Triphenylene 1013.6 29.28 0.492 175 Yamini et al. (2003)
Phenazopyridine 1148.4 27.56 0.735 160.3 Bonyadi and Esmaeilzadeh (2008)
Propranolol 958.5 22 1.061 214.3 Bonyadi and Esmaeilzadeh (2008)
Methimazole 731.7 60.75 0.442 162.1 Bonyadi and Esmaeilzadeh (2008)
Methyl salicylate 700 40.7 0.631 130 GCM
a
Fluoranthene 905 26.1 0.587 161.55 GCM
Naphthalene 748.35 40.51 0.302 112.43 Esmaeilzadeh et al. (2009))
Cholesterol 959 12.5 0.95 367.54 GCM
Benzocaine 699.4 42.2 0.36 141.87 GCM
Benzoin 853.52 26.6 0.599 162 Esmaeilzadeh et al. (2009))
Aspirin 762.9 32.8 0.817 128.68 GCM
Benzoic acid 752 45.6 0.62 92.51 Yamini et al. (2003))
Acenaphthene 803.15 31 0.38 126.19 GCM
Perylene 863 8.68 0.915 201.85 GCM
Mandelic acid 903.79 34.73 0.645 117 Esmaeilzadeh et al. (2009)
Propyl 4-hydroxybenzoate 815.92 31.3 0.722 131.6 Esmaeilzadeh et al. (2009)
Hexamethylbenzene 758 24.4 0.515 152.7 Esmaeilzadeh et al. (2009))
Lactic acid 627 59.6 1.029 75 GCM
Phenanthrene 882.65 31.72 0.437 182 Esmaeilzadeh et al. (2009))
Anthracene 869.15 30.8 0.353 142.6 Esmaeilzadeh et al. (2009)
Carbazole 899.1 32.65 0.496 151.5 Esmaeilzadeh et al. (2009)
Fluorene 826.4 29.5 0.406 139.3 Esmaeilzadeh et al. (2009)
Pyrene 936 25.7 0.509 158.5 Esmaeilzadeh et al. (2009)
O-hydroxy benzoic acid 739 51.8 0.832 95.7 Esmaeilzadeh et al. (2009)
1-Hexadecanol 761 14.9 0.748 296.5 Esmaeilzadeh et al. (2009)
1-Octadecanol 777 13.4 0.863 333 Esmaeilzadeh et al. (2009)
Palmitic acid 776 14.9 1.083 285.7 Esmaeilzadeh et al. (2009)
Stearic acid 779 13.4 1.084 302.4 Esmaeilzadeh et al. (2009)
1-Eicosanol 792 12.2 0.937 355.2 Yamini et al. (2003))
Phenol 692.2 60.5 0.45 89 Yamini et al. (2003))
P-chlorophenol 724.75 53.61 0.456 101.4 GCM
2,4-dichlorophenol 718.38 53.04 0.608 117.9 GCM
2,6-dichlorophenol 718.38 53.04 0.608 117.9 GCM
2,4,6-trichlorophenol 745.96 51.52 0.522 132.6 GCM
a
Properties were evaluated by the group contribution method used in Refs. Valderrama et al. (2008), Valderrama and Robles (2007).
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 286
where g
l
(y) is the inequality constraint, h(y) is the equality constraint,
L and M refer to the number of inequality and equality constraints,
respectively. In Eq. (9), RN denotes the penalty parameter which is
dened by the user. The value of this parameter depends on the
order of magnitude of the functions values of the problem and
normally lies between 1 and 10
6
(Deb, 2002). The higher selected
values for R, the more effects of constraints on the computations are
expected. In this study, the penalty parameter has been set to 10. The
bracket-operator / S denotes the absolute value of the operand, if
operand is negative. Therefore, the nal formulation of the objective
function is given by
OF f unction10

2
l 1
/g
l
S 10
where
g
1
maxf0,Zbg 11
g
2
max 0,
Z1

2
p
b
Z1

2
p
b
_ _ _ _
12
5. Results and discussion
Different combinations of the SRK (Soave, 1972), the PR (Peng and
Robinson, 1976), the PTV (Valderrama, 1990), the ER (Esmaeilzadeh
and Roshanfekr, 2006) and the m-ER (Bonyadi and Esmaeilzadeh,
2008) equations of state with four mixing rules are used in this work
Table 4
Typical probable optimum values of the model parameters for the m-ER EoS (Bonyadi and Esmaeilzadeh, 2008).
Compound T (K) P range (bar) ndp
a
Ref.
b
Mixing rule Model parameters
K
ij
L
ij
M
ij
A
ij
A
ji
Triphenylene 308.15 85247 10 Barna et al. (1996) vdW1 0.28
vdW2 0.33 0.08
CVD 1.9
WS 0.14 1.4 0.8
318.15 96252 10 Barna et al. (1996) vdW1 0.25
vdW2 0.36 0.15
CVD 0.28
WS 0.17 0.45 1.5
328.15 107251 8 Barna et al. (1996) vdW1 0.22
vdW2 0.14 0.12
CVD 0.3
WS 0.18 1.1 1.36
Phenazopyridine 308 122355 9 Huang et al. (2001) vdW1 0.17
vdW2 0.24 0.26
CVD 0.15
WS 0.13 - 0.43 1.1
318 122355 9 Huang et al. (2001) vdW1 0.22
vdW2 0.27 0.11
CVD 0.58
WS 0.08 0.66 1
328 122355 9 Huang et al. (2001) vdW1 0.19
vdW2 0.21 0.13
CVD 0.32
WS 0.18 1.4 0.97
338 122355 9 Huang et al. (2001) vdW1 0.16
vdW2 0.22 0.14
CVD 0.17
WS 0.14 0.14 1.27
348 122355 9 Huang et al. (2001) vdW1 0.1
vdW2 0.22 0.21
CVD 0.11
WS 0.12 1.9 1.53
Propranolol 308 122355 9 Huang et al. (2001) vdW1 0.26
vdW2 0.16 0.09
CVD 0.59
WS 0.13 2.7 1.21
318 122355 9 Huang et al. (2001) vdW1 0.36
vdW2 0.16 0.11
CVD 1.1
WS 0.19 - 1.58 2.87
328 122355 9 Huang et al. (2001) vdW1 0.28
vdW2 0.23 0.15
CVD 0.15
WS 0.11 3.52 2.1
338 122355 9 Huang et al. (2001) vdW1 0.38
vdW2 0.25 0.2
CVD 1.47
WS 0.23 1.1 1.37
348 122355 9 Huang et al. (2001) vdW1 0.17
vdW2 0.08 0.14
CVD 0.93
WS 0.12 1.84 1.01
a
Number of experimental data points.
b
References of experimental solubility data.
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 287
Table 5
Absolute average relative deviations of the presented model results from the experimental data.
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
Triphenylene 308.15 85247 10 Barna et al. (1996) SRK 22 20 48 7.3
PR 21 20 46 6.5
PTV 21 20 35 7.7
ER 20 17 31 7.3
m-ER 17 16 25 5.5
318.15 96252 10 Barna et al. (1996) SRK 44 38 43 27
PR 46 37 30 20
PTV 40 34 41 17
ER 40 34 26 14
m-ER 30 27 26 10
328.15 107251 8 Barna et al. (1996) SRK 17 16 25 17
PR 15 13 14 13
PTV 12 11 12 12
ER 12 9.6 17 8.7
m-ER 8.5 7.5 11 4.3
Phenazopyridine 308 122355 9 Huang et al. (2001) SRK 18 17 28 16
PR 17 15 25 13
PTV 17 13 21 11
ER 19 12 34 9.9
m-ER 17 11 19 7.5
318 122355 9 Huang et al. (2001) SRK 37 26 34 17
PR 38 18 54 9.3
PTV 36 17 23 8.1
ER 36 17 47 5.5
m-ER 27 13 19 5.3
328 122355 9 Huang et al. (2001) SRK 17 17 30 17
PR 16 14 25 16
PTV 16 12 20 12
ER 15 12 23 10
m-ER 11 11 17 9.7
338 122355 9 Huang et al. (2001) SRK 35 21 37 14
PR 29 18 28 9.7
PTV 27 14 32 9.0
ER 27 13 31 6.6
m-ER 18 11 24 6.3
348 122355 9 Huang et al. (2001) SRK 33 24 39 14
PR 26 13 42 6.4
PTV 25 14 36 8.0
ER 20 11 47 4.5
m-ER 13 9.6 26 4.1
Propranolol 308 122355 9 Huang et al. (2001) SRK 20 19 34 9.6
PR 14 17 28 5.7
PTV 11 11 28 7.2
ER 8.7 9 24 5.6
m-ER 7.7 7.4 17 4.4
318 122355 9 Huang et al. (2001) SRK 22 25 33 15
PR 11 9.8 33 8.6
PTV 12 11 32 8.0
ER 13 8.4 28 4.1
m-ER 9.6 8.2 18 4.0
328 122355 9 Huang et al. (2001) SRK 35 19 29 15
PR 29 14 22 12
PTV 22 13 29 13
ER 18 12 27 11
m-ER 18 16 22 8.8
338 122355 9 Huang et al. (2001) SRK 34 28 39 21
PR 32 25 24 18
PTV 30 23 31 16
ER 31 20 27 12
m-ER 24 22 27 10
348 122355 9 Huang et al. 92001) SRK 37 30 42 20
PR 28 24 30 20
PTV 29 21 28 19
ER 29 19 29 18
m-ER 25 17 27 12
Methimazole 308 122355 9 Huang et al. (2001) SRK 17 16 24 21.1
PR 15 16 20 25.6
PTV 12 11 19 17.2
ER 10 8.6 19 16.5
m-ER 8.8 8.1 7.9 5.2
318 122355 9 Huang et al. (2001) SRK 32 19 29 17
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 288
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
PR 27 11 24 13
PTV 24 11 19 11
ER 24 11 24 9.6
m-ER 19 9.7 19 8.3
328 122355 9 Huang et al. (2001) SRK 16 14 20 12
PR 8.0 17 24 7.9
PTV 8.0 10 13 6.5
ER 7.2 12 20 3.6
m-ER 7.1 7.1 12 3.2
338 122355 9 Huang et al. (2001) SRK 27 28 32 23
PR 28 22 27 17
PTV 24 19 24 16
ER 22 18 27 14
m-ER 17 12 20 9.7
348 122355 9 Huang et al. (2001) SRK 27 27 32 22
PR 27 26 46 19
PTV 24 20 26 18
ER 22 19 37 14
m-ER 14 12 22 8.5
Methyl salicylate 343.15 90170 5 Housaindokht et al. (2007) SRK 18 14 27 16
PR 23 18 34 15
PTV 22 17 26 14
ER 21 12 29 11
m-ER 14 10 17 9.1
363.15 90210 7 Housaindokht et al. (2007) SRK 23 22 30 20
PR 21 19 26 16
PTV 19 16 25 15
ER 16 14 26 13
m-ER 13 11 17 9.4
383.15 90250 9 Housaindokht et al. (2007) SRK 24 29 35 18
PR 18 11 29 6.7
PTV 19 10 23 7.3
ER 20 9.8 24 4.4
m-ER 18 9.0 19 3.2
403.15 90290 11 Housaindokht et al. (2007) SRK 43 32 40 26
PR 34 26 37 19
PTV 33 24 43 17
ER 33 21 44 14
m-ER 21 16 25 11
423.15 90310 12 Housaindokht et al. (2007) SRK 17 17 23 15
PR 14 14 24 9.8
PTV 12 11 21 7.6
ER 11 8.4 19 5.6
m-ER 9.4 8.0 13 4.2
Fluoranthene 308.15 89247 12 Barna et al. (1996) SRK 29 39 43 33
PR 25 12 29 30
PTV 15 10 27 27
ER 23 11 29 23
m-ER 19 9.6 17 14
318.15 86249 10 Barna et al. (1996) SRK 19 17 24 12
PR 19 16 19 8.9
PTV 17 15 20 8.5
ER 14 15 22 7.8
m-ER 11 11 16 9.4
328.15 100209 6 Barna et al. (1996) SRK 25 21 28 19
PR 18 13 23 17
PTV 16 13 21 12
ER 12 6.5 21 7.6
m-ER 12 6.2 16 8.3
Naphthalene 308.15 86.8225.3 9 McHugh and Paulaitis (1980) SRK 25 21 31 19
PR 19 17 21 12
PTV 19 15 19 12
ER 15 10 20 9.4
m-ER 12 9 17 8.8
308.2 98.2199.5 5 McHugh and Paulaitis (1980) SRK 25 20 29 19
PR 26 21 33 15
PTV 22 18 26 13
ER 18 17 25 8.4
m-ER 15 11 17 10
328.15 82.2287.8 16 McHugh and Paulaitis (1980) SRK 25 22 32 18
PR 23 20 29 14
PTV 21 19 24 12
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 289
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
ER 21 17 21 12
m-ER 19 11 20 9.6
328.2 92.3189.6 10 McHugh and Paulaitis (1980) SRK 26 22 28 21
PR 25 19 43 19
PTV 25 17 34 18
ER 25 16 32 17
m-ER 17 13 20 11
333.55 108.4291.4 19 McHugh and Paulaitis (1980) SRK 17 16 29 11
PR 14 10 26 8.5
PTV 13 11 19 7.5
ER 10 8.9 17 4.6
m-ER 8.5 8.4 14 6.4
338.05 151.8232.2 7 McHugh and Paulaitis (1980) SRK 25 29 33 19
PR 29 17 28 15
PTV 24 13 29 12
ER 18 13 30 12
m-ER 13 10 19 8.4
Cholesterol 313.1 100250 6 Yun et al. (1991) SRK 27 28 38 21
PR 31 22 39 21
PTV 29 17 32 11
ER 24 13 31 10
m-ER 16 11 22 10
323.1 100250 6 Yun et al. (1991) SRK 28 26 34 18
PR 28 12 29 9.5
PTV 25 11 29 6.4
ER 23 9.7 27 3.1
m-ER 15 8.5 17 3.5
333.1 100250 5 Yun et al. (1991) SRK 16 15 39 18
PR 14 14 44 12
PTV 14 12 33 10
ER 12 8.1 29 7.6
m-ER 11 7.7 15 5.7
Benzocaine 308 122355 8 McHugh and
Paulaitis (1980)
SRK 19 14 23 11
PR 18 13 27 7.3
PTV 15 11 24 7.2
ER 14 10 21 6.5
m-ER 12 9.4 17 5.4
318 122355 8 McHugh and
Paulaitis (1980)
SRK 31 25 36 23
PR 33 23 38 18
PTV 30 20 38 17
ER 28 17 37 15
m-ER 23 12 23 10
328 122355 8 McHugh and
Paulaitis (1980)
SRK 17 14 22 11
PR 11 8.2 18 6.2
PTV 10 7.4 16 5.7
ER 8.4 4.1 15 3.9
m-ER 8.0 3.5 11 3.2
338 122355 8 McHugh and
Paulaitis (1980)
SRK 23 20 28 18
PR 20 18 29 15
PTV 18 15 23 13
ER 16 13 20 12
m-ER 12 11 14 8.8
348 122355 8 McHugh and
Paulaitis (1980)
SRK 19 17 26 16
PR 17 15 20 10
PTV 14 13 18 10
ER 12 8.8 16 6.3
m-ER 11 7.5 13 6.1
298 84248 9 Yun et al. (1991) SRK 29 15 27 12
PR 25 9.8 27 7.5
PTV 21 9.3 25 6.3
ER 20 7.1 26 4.8
m-ER 15 7.3 17 2.7
308 88251 10 Yun et al. (1991) SRK 13 12 34 13
PR 8.7 13 28 6.2
PTV 8.3 12 23 7.1
ER 8.0 11 19 4.4
m-ER 7.1 9.5 14 3.9
318 99250 10 Yun et al. (1991) SRK 30 21 35 20
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 290
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
PR 21 20 27 14
PTV 20 18 24 13
ER 19 19 21 12
m-ER 14 10 18 8.6
Benzoin 308.15 121.6236.1 6 Garmroodi et al. (2004) SRK 27 19 39 17
PR 27 18 43 14
PTV 25 14 39 13
ER 25 11 33 8.2
m-ER 15 9.4 19 8.6
318.15 111.3244.3 7 Garmroodi et al. (2004) SRK 28 20 39 23
PR 27 21 30 19
PTV 23 16 29 15
ER 20 16 28 13
m-ER 19 12 23 10
328.15 114.8244.3 6 Garmroodi et al. (2004) SRK 22 19 27 11
PR 19 13 25 9.9
PTV 17 11 19 7.8
ER 17 11 19 6.6
m-ER 14 9.8 16 6.4
Aspirin 308.15 120250 8 Weinstein et al. (2004) SRK 45 25 44 29
PR 30 20 44 17
PTV 23 16 37 15
ER 25 15 35 10
m-ER 18 11 23 9.1
318.15 120250 8 Weinstein et al. (2004) SRK 27 22 32 14
PR 29 19 32 12
PTV 24 16 28 12
ER 21 16 28 9.1
m-ER 19 12 18 8.4
328.15 120250 8 Weinstein et al. (2004) SRK 22 18 27 11
PR 22 13 44 7.5
PTV 18 12 39 5.9
ER 17 12 35 5.5
m-ER 13 8.4 18 4.2
Acenaphthene 308.15 121.6354.6 9 Cheng et al. (2002) SRK 17 14 24 11
PR 16 12 20 8.7
PTV 15 12 22 8.1
ER 14 9.9 22 6.3
m-ER 12 8.7 18 3.3
318.15 121.6354.6 9 Cheng et al. (2002) SRK 19 14 23 13
PR 14 12 20 8.8
PTV 14 10 18 8.3
ER 13 8.4 17 5.1
m-ER 10 8.9 13 4.5
328.15 121.6354.6 9 Cheng et al. (2002) SRK 29 22 35 15
PR 27 15 26 8.7
PTV 26 14 21 9.1
ER 29 13 21 8.3
m-ER 19 11 23 7.3
338.15 121.6354.6 9 Cheng et al. (2002) SRK 26 17 43 9.6
PR 24 12 38 6.8
PTV 19 11 30 5.4
ER 18 9.7 27 4.1
m-ER 15 7.4 17 3.0
348.15 121.6354.6 9 Cheng et al. (2002) SRK 21 19 34 11
PR 19 18 27 5.2
PTV 18 16 23 7.5
ER 18 14 19 9.6
m-ER 13 11 20 5.0
Perylene 313 100450 8 Huang et al. (2004) SRK 20 13 37 12
PR 12 11 28 9.8
PTV 15 9.8 20 8.3
ER 9.1 8.4 17 6.3
m-ER 8.9 6.2 11 3.4
373 100450 8 Huang et al. (2004) SRK 30 21 34 16
PR 25 18 26 14
PTV 20 16 23 12
ER 17 14 19 12
m-ER 14 12 17 9.6
423 100450 8 Huang et al. (2004) SRK 36 24 31 19.9
PR 28 22 33 17
PTV 23 19 31 14
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 291
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
ER 21 17 28 13
m-ER 17 12 19 10
473 100450 8 Huang et al. (2004) SRK 28 25 29 18
PR 27 21 32 18
PTV 23 20 28 16
ER 20 19 27 16
m-ER 14 13 19 11
523 100450 8 Huang et al. (2004) SRK 19 17 30 13
PR 19 13 25 10
PTV 15 11 24 9.7
ER 15 9.6 23 9.3
m-ER 13 7.8 15 5.6
Mandelic acid 308.15 101228.5 7 Garmroodi et al. (2004) SRK 28 17 37 14
PR 27 12 29 9.7
PTV 27 11 27 8.6
ER 28 8.7 26 4.1
m-ER 20 6.3 27 3.6
318.15 102.3255.7 7 Garmroodi et al. (2004) SRK 19 17 28 12
PR 18 16 28 8.8
PTV 18 14 22 7.8
ER 17 12 19 7.4
m-ER 11 11 18 6.7
328.15 104.4230.6 6 Garmroodi et al. (2004) SRK 30 22 35 17
PR 26 23 31 15
PTV 26 23 31 15
ER 25 21 31 14
m-ER 17 13 22 11
Propyl 4-hydroxybenzoate 308.15 94.1220.9 7 Garmroodi et al. (2004) SRK 28 21 37 21
PR 29 27 32 18
PTV 25 20 31 16
ER 21 17 29 14
m-ER 17 12 20 10
318.15 96.8214.7 7 Garmroodi et al. (2004) SRK 26 24 38 16
PR 24 21 29 15
PTV 19 15 31 13
ER 19 15 33 11
m-ER 17 12 18 9.8
328.15 105.1220.2 7 Garmroodi et al. (2004) SRK 29 22 44 18
PR 30 25 36 20
PTV 30 20 32 17
ER 29 19 27 14
m-ER 23 14 28 11
Lactic acid 313 58.2196.1 10 Yamini and
Bahramifar (2000)
SRK 29 22 31 18
PR 29 27 33 17
PTV 27 19 29 13
ER 24 18 27 11
m-ER 20 17 19 10
318 70.1181.5 9 Yamini and
Bahramifar (2000)
SRK 17 13 24 14
PR 13 10 18 8.2
PTV 12 9.4 17 7.7
ER 9.4 6.0 17 5.3
m-ER 9.1 5.7 14 3.8
328 70.7197.1 10 Yamini and
Bahramifar (2000)
SRK 25 17 25 16
PR 19 12 23 11
PTV 19 11 20 10
ER 19 11 17 8.6
m-ER 15 9.1 19 6.1
Stearic acid 318 145.4361.5 6 Miller et al. (1996) SRK 17 10 33 12
PR 12 12 27 8.5
PTV 12 10 21 8.1
ER 10 10 18 7.8
m-ER 8.5 7.2 11 5.7
328 154.8467.5 6 Miller et al. (1996) SRK 23 15 31 15
PR 24 11 31 13
PTV 23 9.1 29 10
ER 22 8.3 25 7.2
m-ER 16 6.2 17 4.4
338 161.5463.8 5 Miller et al. (1996) SRK 19 18 27 12
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 292
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
PR 17 14 22 8.7
PTV 17 14 20 9.1
ER 15 15 20 8.5
m-ER 12 10 18 8.3
1-Eicosanol 308.2 37.5209 8 Yan and Tsai, 1994 SRK 27 20 29 16
PR 23 17 32 13
PTV 22 17 28 13
ER 21 16 24 12
m-ER 16 12 17 11
318.2 36.2212.6 8 Yan and Tsai, 1994 SRK 19 16 33 10
PR 14 10 28 6.8
PTV 13 9.2 27 4.6
ER 13 7.5 21 3.5
m-ER 10 6.4 17 2.5
328.2 37.5210.4 8 Yan and Tsai, 1994 SRK 29 20 30 14
PR 24 13 30 11
PTV 19 11 28 11
ER 19 11 29 11
m-ER 13 11 16 8.8
Phenol 309.2 80198.4 21 Garca-Gonza lez et al., 2001 SRK 31 26 38 13
PR 24 14 32 11
PTV 25 12 30 10
ER 26 12 27 9.2
m-ER 15 9.4 19 5.4
318.2 90198.4 15 Garca-Gonza lez et al., 2001 SRK 24 20 30 11
PR 23 11 27 8.9
PTV 19 9.8 26 8.0
ER 15 8.7 25 6.8
m-ER 13 7.3 18 4.3
333.2 80198.4 12 Garca-Gonza lez et al., 2001 SRK 13 14 26 10
PR 12 11 24 8.1
PTV 12 10 21 5.9
ER 11 9.5 19 3.3
m-ER 9.7 6.8 13 3.1
333.15 100350 11 Garca-Gonza lez et al., 2001 SRK 19 17 28 13
PR 17 12 26 8.5
PTV 16 12 21 9.1
ER 13 11 19 7.4
m-ER 9 8.9 11 4.6
348.15 100350 11 Garca-Gonza lez et al., 2001 SRK 24 19 29 19
PR 23 20 33 12
PTV 22 19 29 13
ER 20 17 28 11
m-ER 19 13 21 9.9
363.15 100350 11 Garca-Gonza lez et al., 2001 SRK 13 10 26 12
PR 10 8.2 21 5.2
PTV 9.8 8.0 20 7.2
ER 8.4 7.6 18 5.0
m-ER 8.0 6.6 10 3.6
P-Chlorophenol 309.2 80198.4 13 Housaindokht and
Bozorgmehr (2008)
SRK 25 17 30 14
PR 20 12 28 12
PTV 20 12 26 10
ER 17 12 25 9.6
m-ER 14 9.9 19 7.4
318.2 90198.4 12 Housaindokht and
Bozorgmehr (2008)
SRK 17 13 34 14
PR 16 10 30 9.2
PTV 14 10 28 8.4
ER 13 9.2 26 6.4
m-ER 10 8.6 18 5.7
333.2 80198.4 11 Housaindokht and
Bozorgmehr (2008)
SRK 29 20 33 12
PR 23 7.7 25 5.7
PTV 22 7.9 22 4.7
ER 18 8.9 18 3.4
m-ER 13 5.3 14 2.7
2,4-dichlorophenol 309.2 80198.4 17 Housaindokht and
Bozorgmehr (2008)
SRK 16 11 33 9.8
PR 12 9.2 26 4.2
PTV 11 8.9 25 4.1
ER 9.4 7.5 22 2.6
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 293
to calculate the solubilities of solid compounds in supercritical
carbon dioxide. Table 4 shows the typical optimal values of the
model parameters using the m-ER EoS (Bonyadi and Esmaeilzadeh,
2008) for selected data sets. The represented solubilities for 23
investigated chemical compounds are reported in Table 5. Wide
pressure and temperature ranges of the calculations and numerous
experimental data applied (863 data points) insure the generality of
the presented study. As can be seen, the combination of the m-ER
EoS (Esmaeilzadeh and Roshanfekr, 2006) with the WS mixing rule
(Wong and Sandler, 1992) results in less average absolute relative
errors (7%), which would be satisfactory for industrial applications.
The deviations of the EoS-based models may be mainly due to this
fact that cubic equations of state generally lead to weak solubility
predictions in supercritical uid regions. However, the m-ER EoS
(Bonyadi and Esmaeilzadeh, 2008) has shown reliable results
for this region (it has been already proven that this EoS is successful
in predictions of the pure CO
2
liquid and vapor densities
(Esmaeilzadeh and Roshanfekr, 2006; Bonyadi and Esmaeilzadeh,
2008; Eslamimanesh and Esmaeilzadeh, 2010).
Fig. 1 compares the calculated results by the set of m-ER EoS
(Bonyadi and Esmaeilzadeh, 2008) and WS mixing rule (Wong
and Sandler, 1992) for the corresponding solubility data of 5 solid
Table 5 (continued )
Compound T (K) P range (bar) ndp Ref.
a
EoS AARD
b
(%)
vdW1 vdW2 CVD WS
m-ER 8.7 5.6 14 2.1
318.2 90198.4 13 Housaindokht and
Bozorgmehr (2008)
SRK 23 17 38 15
PR 19 14 28 10
PTV 19 13 22 10
ER 17 11 22 8.6
m-ER 11 9.9 18 6.7
333.2 80198.4 13 Housaindokht and
Bozorgmehr (2008)
SRK 29 22 34 21
PR 24 20 35 16
PTV 22 18 37 15
ER 22 14 36 12
m-ER 16 11 27 9.6
2,6-dichlorophenol 309.2 80198.4 12 Housaindokht and
Bozorgmehr (2008)
SRK 29 19 32 15
PR 24 17 27 14
PTV 22 13 26 13
ER 22 11 25 11
m-ER 19 9.9 21 8.8
318.2 90198.4 13 Housaindokht and
Bozorgmehr (2008)
SRK 18 12 32 11
PR 17 11 30 8.8
PTV 14 10 29 8.1
ER 12 8.4 26 6.3
m-ER 12 8.5 17 4.6
333.2 80198.4 14 Housaindokht and
Bozorgmehr (2008)
SRK 24 28 32 15
PR 25 14 55 13
PTV 21 12 46 12
ER 18 12 42 7.5
m-ER 14 11 21 6.5
2,4,6-trichlorophenol 309.2 80198.4 11 Housaindokht and
Bozorgmehr (2008)
SRK 20 17 30 14
PR 19 15 29 11
PTV 15 13 26 11
ER 15 11 26 8.5
m-ER 11 9.4 16 5.4
318.2 90198.4 13 Housaindokht and
Bozorgmehr (2008)
SRK 23 14 36 19
PR 21 11 33 9.7
PTV 18 11 29 8.8
ER 15 11 25 5.6
m-ER 12 9.4 13 3.4
333.2 80198.4 14 Housaindokht and
Bozorgmehr (2008)
SRK 21 21 27 14
PR 15 10 27 8.7
PTV 13 9.7 24 8.0
ER 13 8.4 22 6.6
m-ER 11 7.0 15 5.6
Total AARD (%) 308523 36.2467.5 863 SRK 25 20 32 16
PR 22 16 30 12
PTV 20 14 26 11
ER 18 13 26 8.9
m-ER 14 10 18 7.0
a
References of the experimental data.
b
%AARD
100
ndp

ndp
i
9CalculatediExperimentali9
Experimentali
.
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 294
compounds in supercritical CO
2
. It is observed that the proposed
model results have coincided well with the existing experimental
data. Simultaneous effects of pressure and temperature on the
solubility of the solid phenazopyridine in the supercritical CO
2
are
also indicated in Fig. 2. This gure interprets that increasing
pressure at constant temperature brings about increasing the
solubility of this compound. Furthermore, increase of tempera-
ture at constant pressure contributes to the same effect. Also in
this case, the selected set of equations successfully represents the
solubility of phenazopyridine.
The results of application of the Chrastil (1982) equation are
reported in Table 6. It is shown that the adjustable parameters of
this correlation can be calculated for wide ranges and tempera-
tures. This table also proves that the assumptions of the Chrastil
(1982)) equation lead to obtaining reliable results for the inves-
tigated compounds as a compromise has been achieved for the
values of the objective function at different temperatures. In other
words, the three parameters of the correlations have been so
evaluated that the temperature dependency of the parameters is
taken into account through the tting procedure.
6. Conclusions
A comparative study was undertaken to investigate the appli-
cations of several cubic equations of state (SRK, Soave, 1972; PR,
Peng and Robinson, 1976; PTV, Valderrama, 1990; ER,
Esmaeilzadeh and Roshanfekr, 2006 and m-ER, Bonyadi and
Esmaeilzadeh, 2008) with different mixing rules (vdW1,
Mukhopadhyay, 2000; vdW2 Mukhopadhyay, 2000; CVD,
Mukhopadhyay, 2000) and WS, Wong and Sandler, 1992) for
representation of the solubilities of solid compounds in super-
critical carbon dioxide. The probable global optimal values of the
parameters of the model were calculated applying the DE opti-
mization strategy (Mukhopadhyay, 2000) for 23 mostly used
chemical species. For the equilibrium calculations, 863 experi-
mental data points were used including large pressure and
temperature ranges. It was observed that the combination of
the m-ER EoS (Bonyadi and Esmaeilzadeh, 2008) and WS mixing
rule (Wong and Sandler, 1992) leads to less absolute average
relative deviation (7%) of the results from the corresponding
experimental values compared with other combinations.
Using this set of equations, which can represent the investigated
uids phase behavior especially in supercritical regions, and the
robust DE optimization technique (Storn and Price, 1997) may be
the reasons of the more accuracy of this combination in calcula-
tion of the solubilities. In addition, the optimal values of the
Chrastil (1982) semi-empirical correlation parameters were
reported for wide temperature ranges for several industrial
compounds.
50 100 150 200 250
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Pressure (bar)
M
o
l
e

f
r
a
c
t
i
o
n
Exp.Triphenylene
Cal.Triphenylene
Exp.Benzoin
Cal.Benzoin
Exp.Mandalic acid
Cal.Mandalic acid
Exp.Aspirin
Cal.Aspirin
x 10
-3
Fig. 1. Comparison between the model representations (using m-ER EoS, Bonyadi
and Esmaeilzadeh, 2008) with WS mixing rule (Wong and Sandler, 1992) with
experimental data at 308.15 K.
100 150 200 250 300 350 400
0
0.5
1
1.5
2
2.5
x 10
-4
Pressure (bar)
M
o
l
e

f
r
a
c
t
i
o
n
Exp.T=308K
Cal.T=308K
Exp.T=318K
Cal.T=318K
Cal.T=328K
Exp.T=328K
Exp.T=338K
Cal.T=338K
Exp.T=348K
Cal.T=348K
Fig. 2. The effects of pressure and temperature on the solubility of solid
phenazopyridine in supercritical carbon dioxide. The m-ER EoS (Bonyadi and
Esmaeilzadeh, 2008) with WS mixing rule (Wong and Sandler, 1992) has been
used in calculations.
Table 6
Typical probable optimum values of the Chrastil equation (Eq. (5)) parameters for selected industrial solid compounds.
Compound T range (K) r range (Kg/m
3
) ndp Ref.
a
Parameters AARD (%)
k d f
Phenazopyridine 308348 327955 45 Huang et al. (2001) 6.096 6327.12 31.120 11
Methimazole 308348 327955 40 Huang et al. (2001) 5.597 5547.24 30.147 13
Benzoin 308.15328.15 433.42897.99 19 Garmroodi et al. (2004) 3.500 4558.04 17.260 7.0
Aspirin 308 .15328.15 792.381757.9 24 Weinstein et al. (2004) 1.480 3541.94 8.1219 13
Acenaphthene 308.15348.15 327955 45 Cheng et al. (2002) 2.699 5759.89 5.795 6.6
Mandelic acid 308.15328.15 356.78892.63 21 Garmroodi et al. (2004) 8.315 10228.8 30.016 12
Propyl 4-hydroxybenzoate 308.15328.15 361885 21 Garmroodi et al. (2004) 5.693 7767.97 21.564 12
a
References of the experimental data.
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 295
Acknowledgment
The authors are grateful to Shiraz University for supporting
this research.
Appendix A
Equations of state and fugacity coefcient expressions used in
this study:
The m-ER EoS (Bonyadi and Esmaeilzadeh, 2008)
Recently, a new three-parameter equation of state has been
presented by Esmaeilzadeh and Roshanfekr (2006) with the
following pressure-explicit form:
P
RT
vb

aT
vvccvc
A1
where a is the temperature-dependent parameter, b and c are the
second and third parameters of the equation of state and R is the
universal gas constant. The preceding parameters are evaluated
by the following relations:
aT O
a
R
2
T
c
2
P
c
_ _
aT
r
A2
b O
b
RT
c
P
c
_ _
A3
c O
c
RT
c
P
c
_ _
A4
where,
O
b
2O
c
13x
c
A5
O
a
3x
c
2
O
2
c
2O
b
O
c
2O
c
A6
a m
1
m
2
1T
r
0:5

2
A7
and O
c
is the smallest positive root of the cubic:
O
3
c
3x
c

5
8
_ _
O
2
c
3x
2
c

3
4
x
c
_ _
O
c
x
3
c

3
8
x
2
c
_ _
0 A8
The values of the parameters x
c
, m
1
and m
2
have been
correlated with the acentric factor to make a general EoS form.
The resulting correlations are given by
x
c
0:32844380:0690264o0:0078711o
2
A9
m
1
0:9990350:01061842o0:0081174o
2
A10
m
2
0:44001081:5297151o0:4710752o
2
A11
In Eqs. (A5)(A9), x
c
is the empirical compressibility factor and
the subscripts c and r denote the critical and reduced properties,
respectively. They also found that the value of x
c
is constant to a
specic point (T
0
r
) and then reduces by a denite function to the
critical point by the following equations:
For T
r
oT
0
r
x
c
is evaluated by Eq. (A9) and for T
0
r
oT
r
x
0
c
x
c
x
c
Z
c

T
0
r
T
r
T
0
r
1
_ _
2
A12
where
T
0
r
0:7892160:1585581o0:133193o
2
A13
In Eq. (A12), x
0
c
is the corrected compressibility factor and Z
c
is
the critical compressibility factor that could be obtained by the
Nath (Ahmed, 1989) equation for the substances for which the
experimental data are not available and also the heavy hydro-
carbons:
Z
c
0:29180:0928o A14
Later, some modications to the original ER EoS (Esmaeilzadeh
and Roshanfekr, 2006) have been made by Bonyadi and
Esmaeilzadeh (2008). These authors used Eq. (A15) to evaluate
T
0
r
and stated that in the region where T
r
oT
0
r
, the value of x
c
has
been correlated as follows:
T
0
r
0:474o
2
0:689o0:49 A15
x
c
0:018o
2
0:064o0:33 A16
After the point T
0
r
, the region is divided into two distinct parts
and the next correlations have been presented:
For (T
0
r
oT
r
o0.9)
x
0
c
x
c
AT
r
T
0
r

2
A17
where,
A 0:3o0:06 A18
For (0.9oT
r
r1)
x
0
c
10x
c
Z
c
1T
r
Z
c
A19
Further calculations (Eslamimanesh and Esmaeilzadeh, 2010)
showed that for the supercritical uid region, the x
c
and x
0
c
functions have symmetric behaviors. Thus, for this region, below
correlations are presented:
For (1oT
r
r1.1)
x
0
c
10x
c
Z
c
1T
r
Z
c
A20
For (1.1oT
r
r2T
0
r
)
x
0
c
x
c
AT
r
T
0
r

2
A21
and for (2T
0
r
oT
r
)
x
c
0:018o
2
0:064o0:33 A22
where the values of Z
c
and T
0
r
are again obtained by Eqs. (A13)
and (A15), respectively.
To evaluate the afunction, the next equations have been
recommended:
aT X1X2

T
r
_

2
A23
In Eq. (A23), X1 and X2 are given by
X1 0:856o
2
1:609o1:44 A24
X2 0:889o
2
1:634o0:441 A25
Regarding the above equations, the following relation was
derived to calculate the fugacity of a component in a mixture:
Ln ^ j
i

^
b
i
b
m
b
Zb
_ _
LnZb
^ c
i
c
m
Z
Z
Zb
_ _

a
m
=c
m
RT
C
1
C
2
1
^ a
i
a
m

^ c
i
c
m
_ _
Ln
Zsb
Zeb
_ _
A26
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 296
where
^ a
i

@na
m

@n
i

_ _
T,P,n
j ai
A27
^
b
i

@nb
m

@n
i

_ _
T,P,n
j ai
A28
^ c
i

@nc
m

@n
i

_ _
T,P,n
j ai
A29
c
m

j
y
j
c
j
A30
b
b
m
P
RT
A31
Z
c
m
P
RT
A32
s 1

2
p
A33
e 1

2
p
A34
Appendix B
vdW1 mixing rule (Mukhopadhyay, 2000)
a
m

j
y
i
y
j
a
ij
A35
b
m

j
y
j
b
j
A36
a
ij

a
ii
a
jj
_
1k
ij
A37
where k is the binary interaction parameter. Therefore, the deriva-
tives related to the attractive and repulsive parameters of the
equations of state (Eqs. (A27) and (A28)) are written as follows:
^ a
i

@na
m

@n
i

_ _
T,P,n
j ai
2

N
j 1
y
j
a
ij
a
m
A38
^
b
i

@nb
m

@n
i

_ _
T,P,n
j ai
b
i
A39
vdW2 mixing rule (Mukhopadhyay, 2000)
a
m

j
y
i
y
j
a
ij
A40
b
m

j
y
i
y
j
b
ij
A41
a
ij

a
ii
a
jj
_
1k
ij
A42
b
ij

b
i
b
j
2
1l
ij
A43
and
^ a
i

@na
m

@n
i

_ _
T,P,n
j ai
2

N
j 1
y
j
a
ij
a
m
A44
^
b
i

@nb
m

@n
i

_ _
T,P,n
j ai
2

N
j 1
y
j
b
ij
b
m
A45
CVD mixing rule (Mukhopadhyay, 2000)
a
m

j
y
i
y
j
a
ij
b
m
b
ij
_ _
M
ij
A46
b
m

j
y
j
b
j
A47
a
ij

a
ii
a
jj
_
A48
b
ij

b
i
b
j
_
A49
and
^ a
i

@na
m

@n
i

_ _
T,P,n
j ai
2

N
j 1
y
j
a
ji
b
m
b
ji
_ _
M
ji
_ _

b
i
b
m
1
_ _

i

j
y
i
y
j
a
ij
M
ij
b
m
b
ij
_ _
M
ij
_
_
_
_
a
m
A50
^
b
i

@nb
m

@n
i

_ _
T,P,n
j ai
2

N
j 1
y
j
b
ij
A51
where M is the binary interaction parameter which subjected to
the following relations:
M
ii
M
jj
1 A52
M
ij
M
ji
A53
WS mixing rule (Wong and Sandler, 1992)
b
m

Q
1D
A54
a
m
RTDb
m
A55
where
Q

N
i

N
j
y
i
y
j
b
a
RT
_ _
ij
A56
D

N
i
y
i
a
i
b
i
RT

G
E
ORT
A57
where
b
a
RT
_ _
ij
b
i

a
i
RT
b
j

a
j
RT
_ _
1k
ij
2
_ _
A58
O 0:6232 A59
^
b
i

@nb
m

@n
i

_ _
T,P,n
j ai

1
1D
@n
2
Q
n@n
i
_ _

Q
1D
2
1
@nD
@n
i
_ _
A60
^ a
i

@na
m

@n
i

_ _
T,P,n
j ai
RT D
@nb
@n
i
b
@nD
@n
i
_ _
a
m
A61
@nD
@n
i

a
i
b
i
RT

Lng
i
O
A62
@n
2
Q
n@n
i
2

j 1
y
j
b
a
RT
_ _
ij
A63
According to Van-Laar activity model, the excess Gibbs energy
is calculated by
G
E
RT

A
12
A
21
y
1
y
2
A
12
y
1
A
21
y
2
A64
M. Yazdizadeh et al. / Chemical Engineering Science 71 (2012) 283299 297
Lng
1
A
12
1
A
12
y
1
A
21
y
2
_ _
2
A65
Lng
2
A
21
1
A
21
y
2
A
12
y
1
_ _
2
A66
where A is the adjustable parameter of the Van-Laar activity
model and subscripts 1 and 2 refer to the rst and second
components in the mixture, respectively.
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