J.

of Supercritical Fluids 51 (2009) 148158

Contents lists available at ScienceDirect
The Journal of Supercritical Fluids
j our nal homepage: www. el sevi er . com/ l ocat e/ supf l u
Calculation of the solid solubilities in supercritical carbon dioxide using a new
G
ex
mixing rule
F. Esmaeilzadeh

, H. Asadi, M. Lashkarbolooki
Chemical and Petroleum Engineering Department, School of Engineering, Shiraz University, Shiraz, Iran
a r t i c l e i n f o
Article history:
Received 25 November 2008
Received in revised form 2 August 2009
Accepted 11 August 2009
Keywords:
Cubic equation of state
Mixing rules
Solid solubilities
Supercritical carbon dioxide
a b s t r a c t
The aim of this study is to develop a new EOS/G
ex
-type mixing rule with special attention to calculating
the solid solubilities of aromatic hydrocarbons, aliphatic carboxylic acids, aromatic acids, and heavy
aliphatic and aromatic alcohols in supercritical carbon dioxide. A volume correction term is applied with
a combination of second and third virial coefcients which the equation for the third virial coefcient is
quadratic, according to the suggestion by Hall and Iglesias-Silva. In this study, the cubic PengRobinson
(PR) and SoaveRedlichKwong (SRK) equations of state have been used to calculate the solid solubilities
of 23 solutes in supercritical CO
2
, by using six mixing rules, namely, the WongSandler (WS) rule, the
OrbeySandler (OS) rule, the van der Waals one uid rule with one (VDW1) and two (VDW2) adjustable
parameters, the covolume dependent (CVD) rule and the new mixing rule. In all cases, the NRTL model
was chosen as the excess Gibbs free energy model. The coefcients of the NRTL model and the binary
interaction parameters of six mixing rules with two EOSs (PR and SRK EOSs) have been determined for
100 data sets of 23 binary systems over a wide range of temperatures and pressures covering more than
970 experimental data points which are reported in the literature. The results showthat the PR EOS with
the new mixing rule model is more accurate than the PR and SRK EOSs with the other mixing rules for
solid solubility calculations in supercritical carbon dioxide.
The regressed interaction parameters of the binary system, without any further modication, were
then extended to four ternary mixtures, giving satisfactory results of the solid solubilities in supercritical
CO
2
.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Supercritical uids (SCF) have beenappliedtomany extractions,
reaction, separation and crystal growth processes [14]. In the pre-
vious decade, supercritical uid technology has become popular
due to its advantages when compared to conventional processes.
Some of these advantages are higher mass-transfer rates, favorable
selectivities, low operating temperatures and higher efciency.
Carbon dioxide is widely used in supercritical uid applications
because it has mild critical conditions (T
c
=304.25K, P
c
=7.38MPa),
is inexpensive, nonammable, nontoxic, and readily available. The
accurate measurement of the solid solubility insupercritical uid is
also difcult and time consuming. For the purpose of a wider range
of application, a suitable thermodynamic model should be used to
correlateandpredict theequilibriumsolubilitydatainthoserelated
elds.

Corresponding author at: Department of Chemical and PetroleumEngineering,

Faculty of Engineering, P.O. Box 7134851154, Namazi Square, Shiraz, Iran. Tel.: +98
7112343833; fax: +98 7116287294.
E-mail address: esmaeil@shirazu.ac.ir (F. Esmaeilzadeh).
EOS is an important and effective tool for calculations of ther-
modynamic properties and the phase equilibriumof pure and uid
mixtures. Accurate and simple EOSs are widely used for theoreti-
cal and practical studies in chemical process design, the petroleum
industry, reservoir uids, etc. There have been several papers
published on the development of EOSs and mixing rules for the
calculation of solubilities of solids in supercritical uids [59]. A
number of empirical mixing rules have been proposed for the rep-
resentationof solid-supercritical uidequilibrium; thesehavebeen
discussed in reviews by Johnston et al. [10] and Brennecke and Eck-
ert [2]. Since the parameters inthe empirical models are usually not
generalized, it is difcult to apply themfor predictive or multi com-
ponent computations. The traditional VDW1 and VDW2 mixing
rules are usually employed with optimally tted binary interaction
parameters. For example, Goldman et al. [11] have employed the
simpleRedlichKwongEOS[12] todescribethesolubilities of heavy
compounds insupercritical CO
2
using the mixing rules of the VdW1
conformal solution theory [13]. Unfortunately, those parameters
cannot be well correlated as a function of temperature or pressure,
especiallyfor systems involving heavyor complexcompounds [14].
0896-8446/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2009.08.005
F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158 149
Several mixing rules have been developed that make use of
excess Gibbs energy (G
ex
) models. At rst, this method was used
by HuronVidal [15], who assumed that no excess volume exists
at an innite pressure limit and determined the energy param-
eter by equating the excess Gibbs free energy calculated by the
EOS to that of a liquid model. This mixing model was capable of
correlating high temperature and pressure phase equilibrium, but
could not directly utilize parameter tables for existing G
ex
models
correlated for lowtemperature and pressure data. Mollerup devel-
oped the same approach than HuronVidal, but for a zero pressure
limit, allowing the use of existent tabulated parameters [16]. Dahl
and Michelsen [17] and Michelsen [18] developed the MHV1 and
MHV2 mixing rules within this framework, using UNIFAC and its
known parameters. After that, Wong and Sandler resolved this
problem using this A
ex
instead of G
ex
in their WS mixing rule [19].
Sheng et al. [20] calculated the solubilities of ve aromatic com-
pounds in supercritical carbon dioxide by a modied HuronVidal
type mixing model with a volume correction term using the Patel-
Teja EOS [21]. Since then, numerous publications have appeared
with more or less similar approaches for solving this problem and
some mixing rules have been suggested [2225]. For example,
Zhong and Masuoka [22] derived a new EOS/G
ex
mixing rule for
the Carnahan-Starling-Redlich-Kwong (CS-RK) EOS which is a per-
turbed hard-sphere EOS, by using the UNIFAC model as the G
ex
model for the calculation of solubility of solids and solid mixtures
in supercritical carbon dioxide. This kind of mixing rule, which is
commonly called the EOS/G
ex
-type mixing rule, is very successful,
allowing cubic EOSs to give good descriptions for complex systems
having a wide range of temperatures and pressures.
Several researchers havesuggestedthat theselectionof themix-
ing rules is more important than the EOS itself [26,27]. Therefore,
the focus of this work is to propose a newEOS/G
ex
-type mixing rule
for the determination of the solid solubilities of aromatic hydrocar-
bons, aliphatic carboxylic acids, aromatic acids, and heavy aliphatic
and aromatic alcohols in supercritical carbon dioxide. The cubic
PengRobinson (PR) and SoaveRedlichKwong (SRK) equations
of state have been used to calculate the solid solubilities of 23
solutes in supercritical CO
2
, by using six mixing rules, namely, the
WongSandler (WS) rule, the OrbeySandler (OS) rule, the van der
Waals one uid rule with one (VDW1) and two (VDW2) adjustable
parameters, the covolume dependent (CVD) rule and the newmix-
ing rule. In all cases, the NRTL model was chosen as the excess
Gibbs free energy model. The calculation results of the solid solu-
bilities of six mixing rules based on two EOSs (PR and SRK EOSs)
for 100 data sets of 23 CO
2
binary systems with the best-tted
binary interaction and the unknown parameters of the NRTL model
are demonstrated. Satisfactory calculation results are obtained by
the new G
ex
mixing rule and the PR EOS. The regressed parame-
ters of this model without using any further modication are then
extended to four ternary mixtures which give satisfactory results
of the solid solubilities in supercritical carbon dioxide for ternary
systems.
2. Solubility of solid solute in supercritical uid
At equilibrium, the fugacity of the solute in the solid phase must
be equal to that in the supercritical phase:

f
solid
i
=

f
supercritical
i
(1)
by assuming that the solutes in the solid phase are immiscible, and
given the fact that the solubility of the uid in the solid phase is
negligible, the fugacity of the solute i in the mixture is given by
the fugacity of pure solid i. The following correlation is obtained
assuming that the solid phase is incompressible and that the molar
volume of the solid is constant.

f
solid
i
= P
sat
i

sat.s
i
exp
_
v
s
i
(P P
sat
i
)
RT
_
(2)
wherePis pressure, Ris theuniversal gas constant, Tis temperature,
P
sat
i
is the sublimation pressure,

sat.s
i
is the fugacity coefcient of
solute i at saturation, v
s
i
is the solid molar volume, and the last term
of Eq. (2) is the pointing factor, accounting for the effect of pressure
on the condensed phase fugacity.
For the supercritical uid phase:

f
supercritical
i
= y
i

i
P (3)
where

i
is the fugacity coefcient of solute i in the supercritical
uidsolvent andis computedusingthe EOS (here PRandSRKEOSs).
Substituting Eqs. (2) and (3) in Eq. (1) provides an expression for
the solubility of a solid as a function of pressure and temperature:
y
2
=
P
sat
2
P

sat.s
2

2
exp
_
v
s
2
(P P
sat
2
)
RT
_
(4)
where subscript 2 indicates the heavy solute component. The sub-
limation pressure is obtained from the Antoine equation:
log P
sat
= A
B
T(K) C
(5)
The EOS/G
ex
model was used to correlate the CO
2
binary solid-
supercritical equilibrium of the system.
3. Equation of state and mixing rules
As discussed in this study, the solubility of heavy hydrocarbons
in supercritical carbon dioxide has been calculated with two equa-
tions of state (PR [28] and SRK [13]) and six mixing rules (VdW1,
Table 1
Summary of the mixing rules used in this work.
Mixing rules Functional form Refs.
WongSandler a = RT
QD
1D
[1929]
b =
Q
1D
a =

j
x
i
x
j
_
b
a
RT
_
ij
D =

i
x
i
a
i
b
i
RT
+
G
ex
CRT
b
a
RT
=

x
i
x
j
_
b
a
RT
_
ij
,
_
b
a
RT
_
ij
=
_
b
i

a
i
RT
+b
j

a
j
RT
_
1k
ij
2
OrbeySandler am = bRT
_
G
ex
C

RT
+
n

i=1
x
i
a
i
b
i
RT
_
[30]
bm =
RT

n
i1

n
j=1
x
i
x
j
(b(a/RT))
ij
RT
_
n
i=1
x
i
(a
i
/b
i
)+(G
ex
/C

_
b
a
RT
_
ij
=
_
b
i
+b
j
2
_

a
i
a
j
RT
_
(1 k
ij
)
CVD a =

x
i
x
j
a
ij
_
b
b
i
_
m
ij
, b =

x
i
b
i
[31]
a =
_
(a
i
a
j
), b =
_
(b
i
b
j
)
VdW1 a =

x
i
x
j
(a
i
a
j
)
0.5
(1 k
ij
), b =

x
i
b
i
[13]
VdW2 a =

x
i
x
j
(a
i
a
j
)
0.5
(1 k
ij
), [13]
b =

x
i
x
j
_
b
i
+b
j
2
_
(1 l
ij
)
150 F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158
Table 2
Summary of the new mixing rules.
EOS and combination rule PR SRK
P =
RT
b

a
(+c
1
b)(+c
2
b)
c
1
= 1

2, c
2
= 1 +

2 c
1
=0, c
2
=1
S
1
=

x
i
x
j
_
b
a
RT
_
ij
, b =
S
2
S
1
_
1.5
1+2m
0.5

b =
S
2
S
1
_
2
1+m
1

S
2
=

x
i
x
j
_
b
2
+(c
1
+c
2
)
a
RT
_
ij
m =
a
bRT
m =
a
bRT
_
b
a
RT
_
ij
=
_
(b
i
a
i
/RT)+(b
j
a
j
/RT)
2

(1 k
ij
) a
ij
=
_
(a
i
a
j
) a
ij
=
_
(a
i
a
j
)
_
b
2
+(c
1
+c
2
)
a
RT
_
ij
=
_
b
ij
+(c
1
+c
2
)
a
ij
RT
_
b
ij
=
b
i
+b
j
2
b
3/4
ij
=
b
3/4
i
+b
3/4
j
2
am =
a
bRT
=
N

i=1
x
i
a
i

G
ex
CRT
,
C =
1
c
1
c
2
ln
1+c
1
1+c
2
The k
ij
is the binary interaction parameter.
VdW2, CVD, WS, OS, newmodel). For the development of the ther-
modynamic models, it is necessary to know the forms of these
mixing rules. Table 1 shows a summary of the mixing rules.
In this study, a new type of mixing rule was developed to cal-
culate the solubility of heavy hydrocarbons in supercritical carbon
dioxide. In this model, by considering the correlation of volume
coefcient of mixture b and using the excess Gibbs free energy
thermodynamic model with an innite pressure basis, the terma
for a mixture can be obtained. The termb, which can be obtained
by combination of the second and third virial coefcients which
are bothbasedonthe statistical thermodynamic, is a functionof the
compositionand temperature. Inthe denitionof virial coefcients
composition dependence is obvious, but temperature dependence
is not evident. For n-body mixture, the second virial coefcient
includes the binary effect (two molecules) and the third coefcient
includes theternaryeffect (threemolecules) andsoon. In1993, Hall
and Iglesias-Silva proved an equation of second order with binary
effect (two molecules) assumption for all of the virial coefcients
[32]. This is logical because the second virial termusually accounts
for most of the deviations from ideality. Also from historical per-
spective, the van der Waals EOS contains both of its parameters
only in the second virial term. These assumptions appear to be
reasonable and the implication is that quadratic mixing rule are
either valid or at least good approximations for all virial terms. Hall
and Iglesias-Silva Work extend earlier work of McGregor et al. [33].
Therefore, in this investigation, this assumption has been used for
binary mixtures. Table 2 shows a summary of the newmixing rule.
The details of the investigation are given in Appendix A.
The free energy model used in this work is of Renon and Praus-
nitz NRTL model [34]:
G
ex
RT
=
N

i=1
x
i

N
j=1
x
i

ji
G
ji

N
k=1
x
k
G
ki
(6)
where

ij
=
g
ji
g
ii
RT
(7)
G
ji
= exp(
ji

ji
) (8)
whereg
ji
is anenergyparameter characteristic of theij interaction,
and the parameter
ij
=
ji
is related to the nonrandomness in the
mixture.
The adjustable parameters in the models were tted to the
experimental data using the MarquardtLevenberg method [35] by
Table 3
Physical properties of the studied components.
Component Tc (K) Pc (bar) Refs. v
s
2
(l/mol) Refs.
Carbon dioxide (solvent) 304.2 73.7 0.225 [36]
Naphthalene 748.4 40.51 0.302 [37,38] 0.111 [20]
Phenanthrene 882.65 31.715 0.437 [39] 0.182 [20]
Anthracene 869.15 30.8 0.353 [31] 0.1426 [31,4043]
Carbazole 899.1 32.65 0.496 [44] 0.1515 [31]
Fluorene 826.4 29.5 0.406 [31] 0.1393 [40,45]
Pyrene 936 25.7 0.509 [46] 0.1585 [40]
2,6-Dimethyl naphthalene 777 31.8 0.420 [15] 0.1392 [40]
2,7-Dimethyl naphthalene 777 32.2 0.420 [20,47] 0.136 [22,47]
Hexa methyl benzene 758 24.4 0.515 [43] 0.1527 [40,45]
O-hydroxy benzoic acid 739 51.8 0.832 [48] 0.0957 [49]
P-hydroxy benzoic acid 739 51.8 0.832 [48] 0.0924 [49]
O-methoxy phenyl acetic acid 819.5 32.5 0.8 [50] 0.1238 [50]
M-methoxy phenyl acetic acid 788.9 32.5 0.73 [50] 0.1238 [50]
P-methoxy phenyl acetic acid 788.1 32.5 0.8 [50] 0.1238 [50]
1-Hexadecanol 761 14.9 0.748 [10] 0.2965 [51]
1-Octadecanol 777 13.4 0.863 [10] 0.3330 [51]
Palmitic acid 776 14.9 1.083 [10] 0.2857 [52]
Stearic acid 779 13.4 1.084 [10] 0.3024 [32,51]
2,5-Xylenol 706.9 48 0.569 [36,53] 0.1257 [53,54]
3-4-Xylenol 729.8 49 0.576 [36,53] 0.1243 [53]
Mandelic acid 903.79 34.73 0.645 [40,55,56] 0.1170 [57]
Benzoin 853.52 26.6 0.599 [40,55,56] 0.1620 [58]
Propyl-4-hydroxy benzoate 815.92 31.30 0.722 [40,55,56] 0.1316 [59]
F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158 151
Table 4
Constant of Antoine equation.
Component A B C Pressure unit Refs.
Naphthalene 8.583 3733.9 0 bar [41]
Phenanthrene 9.631 4873.4 0 bar [56]
Anthracene 9.775 5313.7 0 bar [37]
Fluorene 9.429 4419.5 0 bar [40]
Pyrene 8.3496 4904 0 bar [37]
2,6-Dimethyl naphthalene 9.429 4419.5 0 bar [37]
2,7-Dimethyl naphthalene 12.431 4388.11 0 mmHg [47]
Hexa methyl benzene 13.134 3855 21 bar [60]
1-Hexadecanol 22.773 8736 0 kPa [61]
1-Octadecanol 24.99 9787 0 kPa [61]
Palmitic acid 19.342 8069 0 kPa [61]
Stearic acid 6.171 2157.5 153.78 kPa [61]
2,5-Xylenol 15.495 4438.6 0 Pa [62]
3-4-Xylenol 15.298 4478.2 0 Pa [62]
Mandelic acid 49.83
a
17256.62
a
0
a
Pa [63]
Benzoin 36.38
a
13160.97
a
0
a
Pa [63]
Propyl-4-hydroxy benzoate 41.15
a
14209.69
a
0
a
Pa [63]
Carbazoleb 20.37862 17015.82 160.529 kPa [64]
O-hydroxy benzoic acid 2.25E6@45

C
c
bar [48]
6.65E6@55

C
c
P-hydroxy benzoic acid 1.37E8@45

C
c
bar [48]
3.76E8@55

C
c
O-methoxy phenyl acetic acid 2.32E2@35

C
c
Pa [50]
M-methoxy phenyl acetic acid 4.77E2@35

C
c
Pa [50]
P-methoxy phenyl acetic acid 5.27E2@35

C
c
Pa [50]
a
lnP
sat
= A
B
T (K)C
,
b
lnp
sat
= A ln(T(K)) +B/T +C +D T
2
, D = 6.290932E 06
c
Sublimation pressure.
the following objective function:
OF =
N

i
_
y
exp.
solid,i
y
calc.
solid,i
y
exp.
solid,i
_
2
(9)
The accuracy of the calculations is evaluated by the Absolute
Average Relative Deviation dened as follows:
AARD(%) =
N

i
_

y
exp.
solid,i
y
calc.
solid,i
y
exp.
solid,i

1
n
_
100 (10)
where N is the number of solubility data points; y
exp.
solid,i
is the ith
experimental value of the solubility; and y
calc.
solid,i
is the solubility
calculated with the EOS model.
4. Results and discussion
4.1. Prediction of the solubility of binary systems in SCF-CO
2
Extensive experimental data of the solubilities of solid com-
ponents have been published, and the solubilities of some solids
in supercritical carbon dioxide are considered here. The critical
constants, acentric factors and solid molar volumes of these com-
pounds are taken from the literature and are listed in Table 3.
Table 4 shows the constant of Antoine equation.
The solubility of 100 data sets of binary systems for 23 heavy
hydrocarbons basedontheexcess Gibbs freeenergywithsixmixing
rules for the PR and SRK EOSs, have been calculated in a pres-
sure range between 76.8 and 1156.5bar, and a temperature range
between 308.15 and 368.15K. In total, 970 experimental data of
Table 5
Binary interaction and the unknown parameters of the NRTL model for the PR and SRK EOSs for the new mixing rule.
Solid P (bar) N
a
Refs. EOS K
ij

ij

ij

ji
AARD (%)
b
Benzoin 121.6236.1 6 [63] PR 0.08 0.58 7.75 1.20 2.26
SRK 0.06 0.58 8.04 1.29 2.21
3-4-Xylenol 82262 7 [53] PR 0.31 0.11 2.87 2.15 5.62
SRK 0.31 0.17 2.93 2.19 6.62
2,5-Xylenol 87267 7 [54] PR 0.31 0.13 3.19 1.55 2.74
SRK 0.31 0.14 2.30 1.63 3.89
Hexa methyl benzene 150350 4 [65] PR 0.04 0.13 3.64 1.34 3.69
SRK 0.07 0.37 3.41 3.31 4.21
Phenanthrene 100350 7 [65] PR 0.11 0.18 4.76 1.70 4.52
SRK 0.09 0.11 3.77 2.56 5.80
Anthracene 100350 6 [44] PR 0.07 0.18 2.77 1.37 10.81
SRK 0.04 0.34 2.53 1.39 11.19
Carbazole 103201 5 [66] PR 0.17 0.53 15.34 1.56 1.34
SRK 0.16 0.53 15.22 1.55 1.48
Mandelic acid 101228.15 7 [41] PR 0.15 0.58 1.20 3.16 5.58
SRK 0.16 0.40 1.44 3.75 5.75
Propyl-4-hydroxy benzoate 94.1220.9 7 [41] PR 0.12 0.29 2.86 1.45 2.03
SRK 0.12 0.47 4.79 0.48 2.36
a
N is the number of data points.
b
AARD(%) =
N

i
_

y
exp.
solid,i
y
calc.
solid,i
y
exp.
solid,i

1
n
_
100.
152 F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158
Table 6
Average Absolute Relative Deviation Percent for the solubility of pure component in supercritical CO
2
with six different mixing rules using the PR and SRK EOSs.
Component T (K) P range (bar) N
a
Refs. EOS AARD (%)
b
VdW1 VdW2 CVD WS OS This
Work
Naphthalene 308.15 86.8255.3 9 [67] PR 9.20 3.4.3 2.38 2.98 2.98 2.67
SRK 6.72 4.34 3.94 4.06 4.06 3.92
308.2 98.2199.5 5 [67] PR 7.95 1.16 1.51 1.14 1.13 1.21
SRK 6.03 1.44 1.46 1.24 1.24 1.19
328.15 82.2287.8 16 [67] PR 23.98 14.23 13.70 6.59 6.44 6.51
SRK 21.6 17.24 17.96 10.54 11.39 11.74
328.2 92.3189.6 10 [67] PR 18.98 6.78 7.65 3.26 3.26 3.23
SRK 20.24 9.20 10.17 5.49 5.48 5.40
333.55 108.4291.4 19 [67] PR 37.27 20.50 41.53 3.85 3.78 4.29
SRK 27.01 24.07 46.18 8.30 8.28 10.51
338.05 151.8232.2 7 [67] PR 32.99 14.18 26.24 1.05 1.02 1.10
SRK 30.60 16.78 28.73 1.08 1.41 1.04
Phenanthrene 308.15 100350 7 [44] PR 8.08 4.86 6.71 4.84 4.84 4.52
SRK 6.02 6.04 10.62 5.97 5.97 5.80
308.15 101181 5 [62] PR 3.71 3.30 3.30 2.97 2.98 3.13
SRK 3.46 3.64 3.51 2.94 2.92 3.56
308.2 78.3203.5 47 [62] PR 20.51 13.13 19.17 13.20 13.08 12.93
SRK 19.23 14.31 17.93 13.94 13.94 13.56
313.1 100200 5 [69] PR 22.27 6.39 21.08 6.41 6.42 5.56
SRK 20.79 7.12 19.67 6.70 6.68 5.83
318.15 101201 5 [70] PR 15.61 15.06 15.35 13.78 13.96 13.75
SRK 15.47 15.34 15.31 14.19 6.11 14.18
318.2 95254 20 [68] PR 18.19 9.46 16.10 8.90 8.76 8.73
SRK 16.52 10.57 14.41 10.01 10.1 9.79
323.15 104.3414.5 6 [56] PR 14.96 8.46 12.00 6.89 6.87 6.82
SRK 11.36 10.22 8.48 10.02 10.32 9.31
323.2 89.4228.5 38 [68] PR 21.38 7.23 18.95 6.15 6.11 5.81
SRK 20.95 9.50 23.61 7.84 9.37 7.48
328.2 90245 23 [68] PR 22.29 8.07 19.54 7.46 5.73 5.35
SRK 22.14 9.04 19.30 8.35 8.64 9.70
Anthracene 308 101.55269.53 5 [71] PR 24.79 21.58 24.89 21.63 20.50 20.43
SRK 27.22 20.48 27.36 19.98 19.44 18.22
308.15 100350 6 [62] PR 36.83 36.83 13.69 13.69 13.69 13.65
SRK 38.77 38.77 13.44 13.48 13.48 13.40
308.15 102181 5 [69] PR 16.73 11.87 16.71 10.94 10.98 11.05
SRK 15.53 12.40 15.51 11.44 11.43 11.69
313.1 100200 7 [72] PR 16.88 11.85 16.86 10.95 10.88 6.90
SRK 15.68 12.39 15.66 11.39 11.41 7.71
313.15 100200 7 [72] PR 20.65 23.21 20.64 23.19 23.15 23.15
SRK 23.55 24.90 23.52 24.96 24.85 24.86
313.15 80.4726.8 13 [71] PR 10.20 11.07 10.21 11.03 11.02 10.84
SRK 8.86 9.71 8.87 9.73 9.73 9.50
318 101.55269.53 6 [72] PR 31.89 24.40 31.88 24.30 24.30 24.29
SRK 38.98 24.29 38.96 24.24 24.23 24.21
318.15 84.4564.4 4 [69] PR 11.56 10.44 11.63 10.45 10.45 10.44
SRK 12.54 10.14 12.62 10.18 10.18 10.13
318.15 117201 5 [56] PR 22.89 19.99 23.05 19.99 20.00 18.85
SRK 29.31 19.06 29.51 18.91 18.92 18.49
323.2 90.6414.5 10 [72] PR 40.31 20.10 40.30 20.15 20.10 20.12
SRK 51.25 21.83 51.23 21.91 21.84 21.89
323.25 89836.3 6 [72] PR 36.88 19.62 36.82 19.63 19.62 19.64
SRK 40.49 20.56 40.47 20.57 20.56 20.60
328.15 94.789.09 5 [72] PR 34.67 18.49 34.64 18.45 18.46 18.51
SRK 42.81 19.58 42.78 19.49 19.57 19.62
333.15 99.8948.8 7 [72] PR 33.88 17.24 33.86 17.23 17.24 17.28
SRK 41.75 17.28 41.73 18.50 18.51 18.51
338.15 106.5999.1 7 [72] PR 33.15 16.24 33.09 16.27 16.24 16.31
SRK 40.86 17.87 40.88 17.86 17.91 18.00
343.15 113.71053.2 7 [56] PR 10.29 11.54 10.15 8.67 8.70 8.68
SRK 11.37 14.35 11.29 12.75 12.62 11.19
343.2 118.1414.5 9 [72] PR 34.42 14.79 34.41 14.74 14.82 14.89
SRK 42.59 16.43 42.56 16.54 16.46 16.19
Anthracene 348.15 118.41105.4 7 [72] PR 34.73 14.21 34.67 14.02 14.11 14.09
SRK 43.51 15.40 43.45 15.57 15.39 15.49
353.15 1241156.5 7 [72] PR 29.34 13.42 29.33 13.42 13.38 13.27
SRK 37.29 14.08 37.21 14.11 14.11 14.18
358.15 129930.3 6 [62] PR 36.83 36.83 13.69 13.69 13.69 13.65
SRK 38.77 38.77 13.44 13.48 13.48 13.40
363.15 132.6975.7 6 [72] PR 28.46 12.36 28.42 12.37 12.37 12.41
SRK 36.36 12.94 36.30 12.91 12.91 13.04
368.15 1371020.5 5 [72] PR 29.50 13.76 29.38 13.67 13.67 13.88
SRK 37.11 15.74 37.06 15.65 15.66 15.95
F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158 153
Table 6 (Continued).
Component T (K) P range (bar) N
a
Refs. EOS AARD (%)
b
VdW1 VdW2 CVD WS OS This
Work
Carbazole 308.15 103201 5 [62] PR 16.64 9.39 16.66 1.40 1.35 1.34
SRK 18.27 9.68 18.65 2.25 3.89 1.48
313.1 100200 7 [69] PR 6.18 6.25 6.18 3.94 3.95 5.07
SRK 6.65 6.63 6.66 4.36 4.36 5.64
318.15 111201 5 [69] PR 18.27 17.43 18.28 5.15 5.53 6.05
SRK 19.13 18.00 19.14 14.22 12.19 6.62
Fluorene 308.2 83.7414.5 6 [56] PR 29.94 4.51 31.22 5.66 5.44 6.10
SRK 38.63 6.35 39.59 5.77 5.68 6.11
308.2 78.3203.5 47 [44] PR 13.10 10.01 13.67 10.13 10.09 9.96
SRK 14.65 10.71 15.18 10.04 9.58 10.87
313.1 100200 5 [69] PR 5.70 4.97 4.97 4.93 4.93 4.35
SRK 5.32 5.54 4.49 5.50 5.52 4.80
318.2 85254 21 [44] PR 17.72 6.67 20.06 6.68 6.67 6.83
SRK 19.36 6.94 21.60 6.72 6.70 7.27
323.15 83.7414.5 8 [56] PR 40.23 13.75 43.76 13.61 13.61 13.08
SRK 42.97 11.10 46.14 10.79 10.82 10.76
323.2 89.4228.5 38 [44] PR 14.59 7.85 17.06 7.54 7.57 7.46
SRK 14.33 6.20 16.91 6.06 6.05 6.02
328.2 85245 24 [44] PR 21.84 10.45 25.25 9.96 9.98 9.92
SRK 20.18 7.91 23.60 7.71 7.71 7.72
343.15 83.7483.4 8 [56] PR 59.02 18.19 68.87 16.52 16.35 13.73
SRK 61.11 12.51 70.17 10.93 10.92 10.43
Pyrene 308.2 83.6483.4 7 [56] PR 39.70 16.87 39.65 13.06 13.00 13.15
SRK 45.51 19.45 45.77 19.35 19.17 19.81
308.2 80.4203.5 45 [44] PR 12.38 12.71 12.46 12.12 11.86 12.81
SRK 13.71 13.59 13.81 13.79 13.76 13.47
318.2 95254 20 [44] PR 9.46 10.09 9.53 10.33 10.52 10.47
SRK 11.50 11.30 11.63 11.57 11.45 11.31
323.15 104.3483.4 7 [56] PR 39.23 9.37 40.24 8.97 8.52 9.31
SRK 47.86 12.39 48.94 13.07 12.80 12.88
323.2 101.1228.5 35 [44] PR 4.90 6.22 4.84 6.13 6.01 5.97
SRK 5.82 7.71 5.75 7.58 7.63 7.21
343.15 104.3483.4 8 [56] PR 56.80 25.02 59.27 24.95 24.93 25.04
SRK 59.39 22.88 61.74 22.73 22.86 23.33
328.2 105.245 20 [44] PR 6.02 7.53 5.95 7.00 6.71 6.54
SRK 7.23 9.43 7.15 9.27 9.29 8.66
2,6-Dimethyl naphthalene 308.2 79146 4 [47] PR 32.08 21.50 30.80 20.49 20.55 19.75
SRK 32.09 21.60 30.98 21.39 21.40 20.70
328.2 100127 4 [47] PR 10.51 3.26 9.34 2.79 2.97 2.66
SRK 13.12 2.59 11.72 4.08 4.30 2.26
2,7-Dimethyl naphthalene 308.2 88242 5 [47] PR 15.97 7.95 12.40 7.72 7.59 6.13
SRK 13.33 9.15 10.52 8.78 8.36 7.13
328.2 100249 5 [47] PR 24.43 11.46 15.61 7.39 6.20 5.92
SRK 23.72 15.21 15.16 11.89 12.79 10.33
Hexa methyl benzene 308.15 150350 4 [65] PR 14.57 3.93 14.02 3.84 3.84 3.69
SRK 21.20 4.48 20.16 4.27 4.22 4.20
323.2 76.8345.6 9 [56] PR 14.86 15.66 15.04 15.37 15.36 13.91
SRK 19.07 19.61 20.01 19.28 19.31 17.87
343.2 83.7483.5 10 [56] PR 12.20 7.68 17.11 6.80 6.78 5.90
SRK 16.52 13.47 19.80 12.53 12.43 12.31
O-hydroxy benzoic acid 318.15 81.1202.6 12 [73] PR 24.33 5.94 24.05 5.93 5.93 5.92
SRK 24.15 6.96 23.88 6.81 6.81 6.80
328.15 101.3202.6 11 [73] PR 19.86 3.79 19.46 3.71 3.70 3.70
SRK 19.76 5.02 19.32 4.95 4.95 4.93
O-hydroxy benzoic acid 328.15 101.3202.6 6 [48] PR 24.93 1.68 24.52 1.64 1.64 1.66
SRK 24.89 3.38 24.45 3.26 3.27 3.17
P-hydroxy benzoic acid 318.15 101.3202.6 6 [48] PR 20.49 5.53 20.49 5.53 5.53 5.52
SRK 19.64 5.94 19.64 5.93 5.93 5.93
328.15 101.3202.6 6 [48] PR 16.36 4.62 16.36 4.11 4.10 4.62
SRK 16.44 3.32 16.44 3.32 3.32 3.31
O-methoxy phenyl acetic acid 308.2 122337 5 [50] PR 40.11 4.92 40.41 5.53 4.82 4.50
SRK 46.11 4.82 46.39 5.93 4.79 4.50
M-methoxy phenyl acetic acid 308.2 117339 5 [50] PR 20.32 3.60 25.26 4.11 3.89 2.26
SRK 25.93 4.07 30.74 3.32 4.33 4.84
P-methoxy phenyl acetic acid 308.2 121339 5 [50] PR 64.18 4.21 57.65 4.83 4.70 3.88
SRK 63.13 4.43 64.46 4.63 4.62 4.21
154 F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158
Table 6 (Continued).
Component T (K) P range (bar) N
a
Refs. EOS AARD (%)
b
VdW1 VdW2 CVD WS OS This
Work
1-Hexadecanol 308 92.203.7 7 [74] PR 13.04 9.13 16.20 9.09 9.09 5.87
SRK 15.73 10.16 19.25 10.13 10.05 5.84
318 152.1415.1 7 [75] PR 42.22 3.40 44.29 4.19 4.12 1.77
SRK 51.71 7.20 50.82 7.14 6.91 1.42
318 85.5201.3 6 [74] PR 24.54 24.51 27.02 24.24 24.36 17.78
SRK 25.78 25.62 29.53 25.39 25.45 16.72
323 85.52002.6 6 [74] PR 25.26 26.94 31.24 24.79 23.54 17.02
SRK 27.27 28.17 34.02 27.17 25.65 17.76
328 86.4203 6 [74] PR 29.65 32.44 31.52 29.67 27.56 19.31
SRK 32.30 33.56 33.84 31.30 30.98 16.01
328 141.8415.9 5 [75] PR 80.36 12.04 98.32 10.02 10.07 11.68
SRK 87.67 33.54 106.79 13.69 13.08 10.65
338 147.1373 6 [75] PR 80.32 2.34 108.27 2.34 2.21 1.69
SRK 84.32 7.56 114.38 7.47 6.33 2.28
1-Octadecanol 308 86.2199.6 6 [74] PR 33.02 25.69 32.77 26.80 27.10 12.73
SRK 35.01 26.56 34.37 26.61 27.63 13.69
318 86.2200.3 6 [74] PR 26.22 25.27 25.95 24.74 24.34 20.93
SRK 27.70 26.22 26.83 26.10 25.50 20.51
318 152437.9 4 [76] PR 9.44 3.71 9.04 3.56 3.56 0.57
SRK 25.37 4.36 20.95 4.07 4.01 0.59
1-Octadecanol 328 139.9447.7 7 [74] PR 94.02 12.09 111.85 8.51 9.04 5.90
SRK 95.11 19.86 120.81 17.24 16.89 6.42
328 87.6199.3 6 [74] PR 28.66 29.18 27.23 27.63 26.38 16.31
SRK 30.12 31.03 29.38 29.70 28.67 16.64
338 84.5204.4 6 [74] PR 32.09 32.60 32.68 31.35 29.60 25.25
SRK 34.26 34.60 35.08 33.13 32.25 26.06
338 145.8452.8 6 [76] PR 107.93 8.16 162.34 2.73 2.18 3.68
SRK 109.41 26.16 170.96 18.46 15.05 2.11
Palmitic acid 318 142.1360.6 5 [75] PR 46.57 6.56 52.42 2.50 2.41 0.79
SRK 55.13 11.61 64.14 9.47 6.52 0.66
328 144.1573.5 7 [75] PR 147.37 9.67 192.22 20.23 18.81 12.38
SRK 104.81 34.57 216.60 31.92 32.68 21.82
338 142.5574.8 7 [75] PR 249.07 41.57 440.83 50.56 48.87 26.64
SRK 96.46 105.60 463.95 64.72 52.00 31.89
Stearic acid 318 145.4361.5 6 [76] PR 12.56 7.29 11.34 6.89 6.85 3.26
SRK 9.37 9.02 7.67 8.42 8.49 4.08
328 154.8467.5 6 [76] PR 79.08 16.46 106.58 16.55 16.46 16.83
SRK 99.79 13.09 127.41 10.64 10.51 10.35
338 161.5463.8 5 [76] PR 81.91 13.65 115.82 9.29 9.54 5.54
SRK 93.41 19.60 130.73 9.40 9.83 5.28
2,5-Xylenol 308.15 87267 7 [54] PR 30.06 3.17 24.43 3.57 3.53 2.74
SRK 28.72 4.39 22.95 4.66 4.65 3.89
3-4-Xylenol 308.15 82262 7 [53] PR 26.00 6.15 21.86 6.04 6.04 5.62
SRK 25.04 7.04 20.43 7.09 7.04 6.62
Mandelic acid 308.15 101228.5 7 [63] PR 42.56 11.49 45.73 7.00 7.03 5.58
SRK 45.48 12.14 48.85 8.19 8.07 5.75
318.15 102.3225.7 7 [63] PR 36.34 5.49 40.86 4.70 4.72 4.41
SRK 26.22 5.48 44.32 4.66 4.65 4.10
328.15 104.4230.6 7 [63] PR 29.43 10.71 36.46 8.57 8.34 8.36
SRK 31.64 11.51 38.09 9.37 9.46 8.18
Benzoin 308.15 121.6236.1 6 [63] PR 2.83 2.62 3.01 2.58 2.59 2.26
SRK 4.47 2.67 4.63 2.60 3.00 2.21
Benzoin 318.15 111.3244.3 7 [63] PR 3.11 3.25 3.23 3.15 3.18 3.06
SRK 4.34 3.38 4.66 3.31 3.31 3.24
328.15 114.8244.3 6 [63] PR 11.06 5.75 10.59 5.70 5.71 5.53
SRK 9.42 6.81 8.90 6.73 6.74 6.56
Propyl-4-hydroxy benzoate 308.15 94.1220.9 7 [63] PR 16.13 2.07 16.51 2.08 2.08 2.03
SRK 18.46 2.31 18.86 2.38 2.39 2.36
318.15 96.8214.7 7 [63] PR 14.72 8.49 15.00 8.81 8.73 4.85
SRK 16.35 8.88 16.65 9.07 9.00 5.02
328.15 105.1220.2 7 [63] PR 19.83 18.91 20.06 19.98 20.12 8.43
SRK 21.51 19.72 21.76 20.76 20.86 10.58
Total AARD (%)
b
308.15368.15 76.81156.5 970 PR 30.61 11.90 34.70 10.90 10.75 9.41
SRK 31.12 14.21 38.18 12.45 12.22 10.23
a
N is the number of data points.
b
AARD(%) =
N

i
_

y
exp.
solid,i
y
calc.
solid,i
y
exp.
solid,i

1
n
_
100.
F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158 155
Fig. 1. Solubility of solid components in supercritical CO
2
using the PR EOS at T =308.15K in the new mixing rule (this work).
hydrocarbons solubilities in supercritical carbon dioxide have been
applied. The Average Absolute Relative Deviation Percent has been
calculated for all of the components. For 100 data sets of CO
2
binary systems, the best-tted binary interaction and the unknown
parameters of the NRTL model are demonstrated (Table 5 shows
some of these results). Fig. 1 shows the comparison of our calcu-
latedresults withthe experimental data for some solidcomponents
in supercritical carbon dioxide. In each binary systemit is seen that
our predicted results are in close agreement to the experimental
data. Fig. 2 typically shows the comparison of our calculated results
withtheexperimental datafor 2,7-dimethyl naphthaleneat 328.2K
with the VdW1, VdW2, CVD, WS, OS and the new mixing rules for
the PR EOS in supercritical carbon dioxide. It is observed that the
new mixing rule is better than the VdW1, VdW2, CVD, OS and WS
mixing rules.
Table 6 shows the comparison of our calculated results with
two EOSs and six mixing rules based on Average Absolute Relative
Deviation Percent (AARD (%)). Typically, Fig. 3 shows the solubil-
ity of naphthalene in supercritical carbon dioxide computed using
temperature-independent parameters in the new mixing rule for
the PREOS. It is observedthat the agreement withthe experimental
data is satisfactory.
The total AARDs (%) using the new mixing rule are 9.41% and
10.23% for the PR and SRK EOS (Table 6), respectively. As can be
seen, the solubilities of solids in supercritical CO
2
are calculated
quite accurately using the PRand SRKEOS and the newmixing rule.
Fig. 2. Absolute relative error of solubility for 2,7-dimethylnaphtalene in supercritical CO
2
using the PR EOS at T =328.2K with the VdW1, VdW2, CVD, OS, WS and the new
mixing rules.
156 F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158
Table 7
Average Absolute Relative Deviation Percent for the ternary systems using the PR and new mixing rule.
Components T (K) P range (bar) Refs. AARD (%)
a
Comp. (2) Refs. Comp. (3) Refs. Comp. (2) Comp. (3)
Phenanthrene (2) +anthracene (3) 308 101235 [64] 12.93 [42] 20.44 [64] 13.09 7.00
Phenanthrene (2) +anthracene (3) 318 101235 [64] 8.73 [42] 10.84 [64] 7.32 10.36
Fluorene(2) +anthracene (3) 313 100200 [42] 4.35 [42] 11.05 [42] 8.12 16.86
2,6-Dimethyl naphthalene (2) +2,7-dimethyl naphthalene (3) 308 90246 [46] 19.76 [46] 6.42 [46] 22.04 16.60
a
AARD(%) =
N

i
_

y
exp.
solid,i
y
calc.
solid,i
y
exp.
solid,i

1
n
_
100.
Fig. 3. Solubility of naphthalene in supercritical CO
2
using the PR EOS and
temperature-independent parameters in the new mixing rule (this work).
Inother words, for predicting the solubility of solids insupercritical
CO
2
, using the six mixing rules, the newmixing rule is superior. The
PR EOS with the new mixing rule has a lower total AARD (%). The
following conclusion can be obtained for the PR and SRK EOSs:
CVD > VdW1 > VdW2 > WS > OS > new model (this study)
In addition, it was found that for any mixing rule, the prediction
of solubility of solids in supercritical CO
2
with the PR EOS is better
than that with the SRK EOS.
4.2. Prediction the solubility of ternary systems in Scf CO
2
The obtained interaction parameters of the binary systems have
been used for the ternary mixtures without any further modica-
tion. Table 7 shows the results for supercritical solvent (1) +solid
(2) +solid (3) systems. Graphical presentations of our calculation
results for two ternary systems are shown in Figs. 4 and 5. In each
ternary system it can be seen that the new mixing rule gives an
excellent reproduction of the experimental data points.
Fig. 4. Prediction of the solubility of phenanthrene (2) +anthracene (3) in supercrit-
ical carbon dioxide at 308K using the PR and new mixing rule.
Fig. 5. Prediction of the solubility of phenanthrene (2) +anthracene (3) in supercrit-
ical carbon dioxide at 318K using the PR and new mixing rule.
5. Conclusions
The objective of this work was to evaluate the newEOS/G
ex
mix-
ing rule for predicting the solubility of solids in supercritical CO
2
.
The accuracy of the newmixing rule is compared to the ve mixing
rules including: WS, OS, CVD, VDW1 and VDW2 and two EOSs (PR
andSRK). For this purpose, 100 data sets of CO
2
binary systems over
awiderangeof temperatures andpressures coveringmorethan970
experimental data points from the literature were selected. It was
found that the new mixing rule has the minimum prediction error
and is the best model for the prediction of the solubility of solids in
supercritical CO
2
. The total average absolute deviations for calcu-
lating the solubility of solids in supercritical CO
2
in the newmixing
rule with the PR and SRK EOS were 9.41% and 10.23%, respectively.
However, it was found that the PR EOS with the newmixing rule is
more accurate for solid solubility calculations in supercritical car-
bon dioxide than the SRK EOS. Overall, the results of the PR EOS are
closer totheexperimental datapoints thantheSRKEOS. Inaddition,
the regressed interaction parameters of the binary system, without
any further modication, were extended to ternary mixtures. It is
observedthat the agreement withthe experimental data is satisfac-
tory. Our calculationresults are satisfactory for polar andnon-polar
solid mixtures, aromatic hydrocarbons, aliphatic carboxylic acids,
aromatic acids, heavy aliphatic and aromatic alcohols.
Acknowledgment
The authors are grateful to the Shiraz University for supporting
this research.
Appendix A.
Derivation of the new mixing rule:
Overall form of the virial equation is:
Z 1 = B
(2)
+B
(3)

2
+. . . =

K=1
B
(k+1)

k
(A1)
F. Esmaeilzadeh et al. / J. of Supercritical Fluids 51 (2009) 148158 157
The overall form of the PR and SRK EOSs are:
P =
RT
b

a
( +c
1
b)( +c
2
b)
(A2)
Hint:
for SRK, c
1
=0, c
2
=1 and for PR, c
1
=1

2, c
2
=1+

2
If substituting Z =P/RT and =1/ in Eq. (A2):
Z =
1
1 b

a
RT
_

c
1
c
2
b
2

2
+(c
1
+c
2
)b +1
_
(A3)
with derivating Z with respect to P, the following correlation is
obtained:
Z

=
b
(1 b)
2

a
RT
_
1 c
1
c
2
b
2

2
(c
1
c
2
b
2

2
+(c
1
+c
2
)b +1)
2
_
(A4)
from the second virial coefcient denition we have:
lim
0
Z

= B
(2)
B
(2)
= b
a
RT
(A5)
Second partial derivative of Eq. (A3) gives:

2
Z

=
2b
2
(1 b)
3

2a
RT
_
3c
1
c
2
b
2
c
2
1
c
2
2
b
4

3
+(c
1
+c
2
)b
(c
1
c
2
b
2

2
+(c
1
+c
2
)b +1)
3
_
(A6)
and according to the third virial coefcient denition we have:
1
2
lim
0

2
Z

= B
(3)
B
(3)
= b
2
+(c
1
+c
2
)
ab
RT
(A7)
According tothe thirdcoefcient assumptionfor twomolecules,
from the statistical thermodynamic, the equation for the second
and third virial coefcients can be written as shown below:
B
(2)
=

x
i
x
j
B
(2)
(A8)
B
(3)
=

x
i
x
j
B
(3)
(A9)
Using Eqs. (A5) and (A7) for the second virial coefcient and Eqs.
(A6) and (A8) for the third coefcient, the following conclusion can
be obtained:
b
a
RT
=

x
i
x
j
_
b
a
RT
_
ij
= S
1
(A10)
b
2
+(c
1
+c
2
)
ab
RT
=

x
i
x
j
_
b
2
+(c
1
+c
2
)
ab
RT
_
ij
= S
2
(A11)
from Eqs. (A10) and (A11), we can extract b:
b =
S
2
S
1
_
1
m
1 +(c
1
+c
2
)
m
_
(A12)
And
m

m
=
a
bRT
(A13)
For PR
b =
S
2
S
1
_
1.5
1 +2
m
0.5
_
(A14)
For SRK
b =
S
2
S
1
_
2
1 +
m
1
_
(A15)
S
1
=

x
i
x
j
_
b
a
RT
_
ij
(A16)
where
_
b
a
RT
_
ij
=
_
(b
i
(a
i
/RT)) +b
j
(a
j
/RT)
2
_
(1 k
ij
) (A17)
and
S
2
=

x
i
x
j
_
b
2
+(c
1
+c
2
)
a
RT
_
ij
(A18)
where
_
b
2
+(c
1
+c
2
)
a
RT
_
ij
=
_
b
ij
+(c
1
+c
2
)
a
ij
RT
_
(A19)
b
ij
=
b
i
+b
j
2
(A20)
a
ij
=
_
(a
i
a
j
) (A21)
For SRK:
b
3/4
ij
=
b
i
3/4
+b
j
3/4
2
(A22)
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