Fluid Phase Equilibria 385 (2015) 1024

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Correlating and estimating the solubilities of solid organic compounds

in supercritical CO2 based on the modied expanded liquid model and
the group contribution method
Hongru Li a, *, Dongdong Jia b , Ruihua Liu a , Bingqian Shen a
a
College of Pharmacy, State Key Laboratory of Medicinal Chemical Biology and Tianjin Key Laboratory of Molecular Drug Research, Nankai University,
Tianjin 300071, PR China
b
School of Chemistry and Chemical Engineering & Technology, Tianjin University of Technology, Tianjin 300384, PR China

A R T I C L E I N F O A B S T R A C T

Article history: The expanded liquid model was investigated and a modied solution model was proposed in this paper.
Received 16 August 2014 The results showed that in the expanded liquid model the accuracy of the solubility parameters of
Received in revised form 23 October 2014 supercritical CO2 (sc-CO2) can affect the change of the variables. If the solubility parameters of sc-CO2 are
Accepted 26 October 2014
accurate, the variables in the expanded liquid model are nearly temperature-independent. If the
Available online 31 October 2014
inaccurate solubility parameters of sc-CO2 were used, the variables in the model would be slightly
temperature-dependent. When using the solubility parameter of the solute as variable and calculating
Keywords:
the solubility parameters of sc-CO2 with accurate method in the expanded liquid model, it is found that
Supercritical CO2
Solubility
the solubility parameter of the solute is the linear function of the ratio of the solubility parameter and
Expanded liquid model molar volume of sc-CO2 (d1/v1). Based on this linear function, the expanded liquid model was modied. In
Correlation the modied model, the slope and the intercept of the linear function were used as the tting parameters.
Estimation The modied model was compared with the other two-parameter expanded liquid models and the
results showed the modied model can provide better correlation results with the average absolute
relative deviation (AARD) being 13.31%. A group contribution method was developed to estimate the
parameters in the modied model. Based on the modied model and the group contribution method, the
solubilitis of most of the solutes in sc-CO2 can be estimated in the order of magnitude.
2014 Elsevier B.V. All rights reserved.

1. Introduction accurate when the pressure is zero or approaches innity [35]. In

Carbon dioxide is often recognized as the green solvent and it is
often used as efcient solvent in reaction, separation, crystalliza-
tion and dyeing processes these days. In the use of sc-CO2, the
solubilities of related compounds are the fundamental data.
Determining the solubilities by experiments is laborious. So the
simple and quick solubility estimation methods are necessary
especially in the early process development when a lot of solubility
data are needed.
The compressed gas model is often used in solubility prediction
[12] and it is regarded as the most promising model for solubility
prediction. However, when using the compressed gas model,
empirical parameters are often included in the mixing rules to
improve the correlation results. The empirical parameters often
change with temperature and are difcult to correlate with the
properties and structures of the related compounds. The mixing
rules based on Gex have better theoretical basis, but they are only
* Corresponding author. Tel.: +86 22 23507760; fax: +86 22 23507760.
E-mail address: lihongru@nankai.edu.cn (H. Li).
addition to the mixing rules, the compressed gas model has some
other limitations. For example, the critical properties, ancentric
factors and sublimation pressures of related compounds are
necessary. For many compounds, these properties have to be
estimated and the estimation errors are unavoidable.
The expanded liquid model is often used in solubility
correlation. The advantage of using the expanded liquid model
is that only the melting point and melting enthalpy of related
compound are needed. These properties can be easily determined
by experiments. As the supercritical solution is not the ideal
solution, empirical parameters are often included in activity
coefcient. By estimating the empirical parameters with appro-
priate method, the expanded liquid model can also be used in
solubility prediction [6,7].
In this paper, the expanded liquid model is investigated. The
calculation methods of the solubility parameters of sc-CO2 and
their effect on the variables in the expanded models were studied.
A modied expanded liquid model was proposed and its
correlation capability was compared with the other two-
parameter expanded liquid models. A group contribution method
was developed to estimate the parameters in this new model.

http://dx.doi.org/10.1016/j.uid.2014.10.036
0378-3812/ 2014 Elsevier B.V. All rights reserved.
 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024 11

Nomenclature

List of symbols
y2 mole fraction of the solute in supercritical solution
[mol mol1] Eq.id=6#(1)
s
f2 fugacity of the pure solid solute [MPa], Eq. (1)
l
f2 fugacity of the pure liquid solute [MPa], Eq. (1)
DHm melting enthalpy of the solute [kJ mol1] Eq.id=6#(2)
Tm melting point of the solute [K] Eq. (2)
T temperature [K] Eq. (2)
R gas constant R = 8.3145 J mol1 K1 Eq.id=6#(2)
DCp difference of the heat capacity between the liquid
solute and the solid solute [kJ mol1 K1] Eq.id=6#(2)
vl2 liquid molar volume of the solute [cm3 mol1] Eq.
id=6#(4)
v1 molar volume of sc-CO2 [cm3 mol1] Eq.id=6#(5)
Fig. 1. Calculated solubility parameters of sc-CO2 using different methods at 313 K.
DE2 cohesive energy of the solute [J mol1]
pc critical pressure [atm] Eq. (14)
p pressure [MPa] Eq. (15)
yexp
2 experimental solubility of the solute in sc-CO2 [mol and the solid solute. The heat capacity terms are relatively small
mol1] Eq.id=6#(18) and can be neglected. So the solubility of solid solute in
ycal
2 calculated solubility of the solute in sc-CO2 [mol supercritical uid can be expressed as follows:
mol1] Eq.id=6#(18)
  
N number of solubility data Eq. (18) 1 DHm T m
y2 exp 1 (3)
g2 RT m T
Greek letters
g2 activity coefcient of the solute in sc-CO2 Eq. (1)
As the solubility of solid solute in supercritical CO2 is very low,
g12 innite dilution activity coefcient of the solute in
the activity coefcient can be regard as its innite dilution value.
sc-CO2 Eq. (4)
The innite dilution activity coefcient can be calculated using
f volume fraction of the solvent Eq. (4)
different method. According to the ScatchardHildebrand regular
d2 solubility parameter of the solute [MPa0.5] Eq. (4)
solution theory, the innite dilution activity coefcient can be
d1 solubility parameter of sc-CO2 [MPa0.5] Eq. (4)
expressed as follows:
r density of sc-CO2 [kg m3] Eq.id=6#(7)
b12 binary interaction parameter Eq. (12)   1 l 2
ln g 1
2
2 v f d2  d1 (4)
rr reduced density of the solvent Eq. (14) RT 2 1
rr (liq) reduced density of liquid Eq. (14) where F1 is the volume fraction of the solvent.
y1 v1
f1 (5)
y1 v1 y2 vl2
v2 is the liquid molar volume of the solute, v1 is the molar volume
Based on the group contribution method, the modied model can of sc-CO2,d2 is the solubility parameter of the solute and d1 is the
be used to predict the solubilities of most of the compounds in the
order of magnitude.

2. Theory

2.1. Mathematical model

If the supercritical uid is regarded as the expanded liquid, the

solubility of solid solute in the supercritical uid can be expressed as:
s
1 f2
y2 (1)
g 2 f l2
where y2 is the solubility of the solute, g 2 is the activity coefcient
of the solute. The fugacity ratio of pure solid solute and liquid
solute can be calculated according to Ref. [8].
!      
f
s
 DH m T m Dcp T m Dc p T m
ln 2l 1 1  ln (2)
f RT m T R T R T
2

Fig. 2. Calculated solubility parameters of phenanthrene using Eq. (6) versus the
where R is the gas constant, T is the temperature, 4Hm is the density of sc-CO2.
melting enthalpy of the solute, Tm is the melting point of the solute, (solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation
4cp is the difference of the heat capacity between the liquid solute and the solubilities were from Ref. [18].)
12 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

Fig. 3. Calculated solubility parameters of phenanthrene using Eq. (6) versus the Fig. 6. Calculated binary interaction parameters of phenanthrene and CO2 using
density of sc-CO2. Eq. (12) versus the density of sc-CO2.
(solubility parameters of sc-CO2 were derived from PR-EoS and the solubilities were (solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation
from Ref. [18].) and the solubilities were from reference [18].)

solubility parameter of sc-CO2. The solubility of solute can be

expressed as:
   
DHm 1 1 1 2 2
y2 exp   vl2 f1 d2  d1 (6)
R Tm T RT

In this model, the solubility parameter d2 is used as variable and

it changes with the density of supercritical uid. Guigard and Stiver
proposed two density dependent correlations (a linear t and a
power t) for the solute solubility parameter as follows [9]:

d2 ar b (7)

d2 arn b (8)
Usually, the power t provided better correlation results.
Fig. 4. Calculated liquid molar volumes of phenanthrene using Eq. (10) versus the The innite dilution activity coefcient can also be calculated
density of sc-CO2. by regular solution model coupled with the FloryHuggins
(solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation
and the solubilities were from Ref. [18].)
equation.

Fig. 5. Calculated liquid molar volumes of phenanthrene using Eq. (10) versus the Fig. 7. Calculated binary interaction parameters of phenanthrene and CO2 using
density of sc-CO2. Eq. (12) versus the density of sc-CO2.
(solubility parameters of sc-CO2 were derived from PR-EoS and the solubilities were (solubility parameters of sc-CO2 were derived from PR-EoS and the solubilities were
from Ref. [18].) from Ref. [18].)
 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024 13

Fig. 8. Calculated solubility parameters of phenanthrene versus d1/v1.

(solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation Fig. 10. Calculated solubility parameters of CI disperse orange 3 versus d1/v1.
and the solubilities were from Ref. [18].) (solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation
and the solubilities were from Ref. [20].)

! !
  vl2 vl2 vl
ln g 1
2
2 d1  d2 1  ln 2 (9)
RT v1 v1 Sometimes, the binary interaction parameter b12 is
introduced when calculating the innite dilution activity
where vl2 is the liquid molar volume of the solute, v1 is the molar coefcient using regular solution model coupled with the
volume of sc-CO2. The solubility of solute can be expressed as FloryHuggins equation.
follows: "   !#
" !# DH m 1 1 vl h 2
i vl vl
  y2 exp   2 d1  d2  b12  1 2  ln 2
DHm 1 1 vl 2 vl vl R Tm T RT v1 v1
y2 exp   2 d1  d2  1 2  ln 2 (10)
R Tm T RT v1 v1 (12)

 0:5
where d2 DE2 =vl2 and 4E2 is the cohesive energy of the
The parameter b12 is independent of temperature and dependent
solute, the liquid molar volume of solute is regarded as variable
on the density of supercritical CO2. In the literature [11], parameter
and it is the function of supercritical uid density [6]. The function
is expressed as:
b12 was correlated with the density of CO2 using a second order
  polynomial.
ln vl2 alnr b (11)
b12 a0 a1 r a2 r2 (13)

where the solubility parameter of the solute are calculated

according to Fedors [10]. 2.2. Methods of calculating solubility parameter of supercritical CO2

In the use of expanded liquid models, the solubility parameters

of sc-CO2 are necessary. More than three methods were used in the
related literatures to calculate the solubility parameters of sc-CO2.
Considering the accuracy of the solubility parameters of sc-CO2
may affect the change of the variables in the expanded liquid
models, the following calculation methods were compared and the
most accurate one was adopted.
Gidding proposed a semi-empirical expression to calculate the
solubility parameters for different solvent as follows [12]:

rr
d 1:25pc 1=2 (14)
rr liq

where pc is in atmosphere and rr(liq) is the reduced density of

Fig. 9. Calculated solubility parameters of 2,20 ,4,5,50 -pentachlorobiphenyl versus
d1/v1.
(solubility parameters of sc-CO2 were derived from Huangs 27-parameter equation
and the solubilities were from Ref. [19].)
liquid. For CO2, rr(liq) is equal to 2.66.
Williams et al. calculated the Hansen solubility parameters of
CO2 based on the assumption that the total cohesive energy is
made up of the additive contributions from nonpolar interactions,
polar interactions and hydrogen-bonding or other specic
association interactions [13].
The solubility parameters of solvents can also be calculated
according to the denition of the solubility parameter [14]:
14 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024
   0:5
@p 3. Results
d T p (15)
@T v
3.1. Effect of the solubility parameters of sc-CO2 from different
methods on the variables

where the partial derivative can be calculated according to
appropriate equation of state (EOS). In this paper, the Peng
Robinson EoS [15], Huangs 27-parameter equation [16] and
Wagners equation [17] were used to calculate the solubility
parameters of sc-CO2 respectively.
The solubility parameters of sc-CO2 were calculated according to
Giddings method (Eq. (14)), Williams method and the denition of
the solubility parameter. In Giddings method and Williams method,
the density or molar volume of sc-CO2 was calculated using Huangs
27-parameter EoS. The calculation results are showed in Fig. 1. It can

Table 1
Properties of the solid solutes.

Compounds Melting Melting enthalpy, 4Hm/ Liquid molar volume , Solubility Cohesive energy, 4Ev/J mol1
point, kJ mol1 vl2 /cm3 mol1 parameter,
Tm/K d2/(MPa)0.5
1-Chloro-2,4-dinitrobenzene 325.2a 20.2a 119.2 24.561 71905
m-Dinitrobenzene 363a 17.36a 116.4 23.202 62662
2,4-Dinitrophenol 388a 24.17a 107.4 29.342 92465
2,5-Dinitrophenol 381a 23.73a 107.4 29.342 92465
m-Nitrophenol 368a 19.19a 84.4 23.673 47300
p-Nitrophenol 385a 18.25a 94.4 28.579 77103
2-Triuoromethylbenzoic acid 375a 24b 127.7 23.065 67936
3-Triuoromethylbenzoic acid 375a 18b 127.7 23.065 67936
3-Aminobenzoic acid 452.9a 21.84a 100.1 26.842 72122
3-Nitrobenzoic acid 414.15a 19.33a 112.9 25.762 74927
Benzamide 401a 23.76a 88.9 28.812 73797
4-Methyl-N-phenylacetamide 421.3c 29.4c 128.9 24.096 74843
Hydroquinone 445a 26.5a 72.4 35.559 91545
o-Hydroxybenzoic acid 432a 24.6a 90.9 31.355 89368
p-Nitroaniline 420a 21.09a 103.6 24.037 59858
Hexamethylbenzene 438a 20.63a 177.4 18.420 60193
Salicylamide 413.58d 23.42d 79.9 36.009 103600
Aspirin 407.36e 23.01e 132.4 24.928 82273
Benzocaine 363.05e 20.51e 139.2 22.766 72143
Syringic acid 478.9e 27.05e 127.5 28.763 105483
Vanillic acid 482.61e 27.26e 109.2 29.869 97426
Benzoic Acid 395.52f 18.07f 99.9 24.418 59565
Methylparaben 402.27e 24.31e 130.2 26.023 84450
Caffeic acid 505.65g 27.68g 114.9 31.206 111888
p-Coumaric acid 492.35g 27.42g 117.9 28.829 97991
Ferulic Acid 445.15e 25.14e 136.2 27.904 106049
Methyl gallate 475.32e 26.85e 104.9 33.850 120197
Protocatechualdehyde 426.48e 24.09e 81.8 34.433 96986
Protocatechuic acid 472.98e 26.72e 87.9 34.275 103265
2,3,5-Trimethyl phenol 367.65h 1838h 124.9 24.646 75869
2,4,6-Trimethyl phenol 346.15h 17.31h 124.9 24.646 75869
2,3-Dimethyl phenol 347a 21.02a 110.4 25.388 71159
2,5-Dimethyl phenol 347.9a 23.38a 110.4 25.388 71159
4-Phenyl phenol 439.15h 19.43h 133.8 26.460 93679
4-tert-Butyl phenol 371.15h 17.79h 143.7 23.198 77334
Flutamide 384i 24.88i 187.7 23.312 102009
n-(4-Ethoxyphenyl) 409.07c 29.53c 155 26.590 109586
ethanamide
Pyrocatechol 377.75h 16.71h 78.4 31.061 75638
Salicylic acid 432.15h 21.61h 90.9 31.355 89368
N-Phenylacetamide 388a 21.657a 114.4 24.760 70134
Vanillin 354.65h 20.36h 103 29.748 91147
Biphenyl 343a 18.66a 142.8 21.150 63876
4-Chlorobiphenyl 348.55a 13.318a 151.8 21.947 73118
2,20 ,4,5,50 -Chlorobiphenyl 350.1a 18.8a 187.8 24.212 110088
Azobenzene 341a 22.52a 152.8 23.905 87317
p-Hydroxyazobenzene 425a 32.99a 162.8 26.822 117120
CI disperse orange 3 481j 14.2j 166 26.348 115236
CI disperse blue 79 420.2k 38.1k 393.4 25.023 246337
Naphthalene 353.2a 19.1a 118 21.309 53579
Perylene 543a 32.58a 176 24.152 86563
Anthracene 490a 29.37a 145.6 22.729 75220
Phenanthrene 372a 18.62a 145.6 22.729 75220
Pyrene 424a 17.36a 148.4 24.152 86563
Fluoranthene 385.2a 18.728a 148.4 24.152 86563
Acenaphthene 367a 21.46a 128.2 22.431 64504
Triphenylene 473.6a 24.19a 173.2 23.648 96861
2,3-Dimethylnaphthalene 378a 15.9a 147 20.701 62997
 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024 15

Table 1 (Continued)
Compounds Melting Melting enthalpy, 4Hm/ Liquid molar volume , Solubility Cohesive energy, 4Ev/J mol1
point, kJ mol1 vl2 /cm3 mol1 parameter,
Tm/K d2/(MPa)0.5
2,6-Dimethylnaphthalene 383.27a 25.06a 147 20.701 62997
2-Naphthol 394a 18.79a 97.4 28.477 78987
Acridine 383a 18.58a 139.3 24.107 80954
1,4-Naphthoquinone 399.15e 15.41e 117 25.545 76350
9,10-Anthraquinone 559.15a 31.59a 142.4 24.131 82922
p-Quinone 386a 18.45a 91.6 24.062 53035
Xanthene 373.7a 19.2a 140.7 22.811 73211
Xanthone 449.63a 26.12a 135.4 25.150 85642
CI disperse blue 3 453.6k 7.8785k 189.1 29.161 160799
CI disperse red 60 459.2j 22.56j 267 25.940 179657
AQ01 494.15l 27.34l 180.4 26.410 125827
AQ02 489.15l 34.31l 212.6 25.265 135705
AQ04 394.15l 39.31l 344 21.893 164881
AQ05 386.15l 44.22l 376.2 21.553 174759
AQ08 349l 55.46l 472.8 20.792 204395
Tetracosane 323.8m 54.93m 421.2 16.744 118083
Pentacosane 326.7m 57.78m 437.3 16.773 123022
Octacosane 334.4m 64.69m 485.6 16.848 137840
Nonacosane 336.6m 66.15m 501.7 16.870 142779
Dotriacontane 342.5m 76.62m 550 16.928 157597
Tritriacontane 344.3m 79.5* 566.1 16.945 162537
Hexatriacontane 349.1m 88.89m 614.4 16.990 177354
Stearic acid 342.75n 61.209n 319.6 18.667 111365
Stearyl alcohol) 331.05n 66.9n 311 17.202 92026
Arachidyl alcohol 339.65n 75.7n 343.2 17.231 101905
Budesonide 499.65e 28.22e 314.8 25.069 197216
Cholesterol 421.16e 28.19e 381.2 19.667 147447
Cholesteryl acetate 387.94e 25.97e 422.7 18.222 140352
Cholesteryl butyrate 372.15e 24.91e 454.9 18.173 150230
Cholesteryl benzoate 421.75e 28.23e 460.6 19.074 167581
Dutasteride 515i 31.47i 290.2 24.780 178192
Finasteride 525i 34.02i 311.5 22.272 154521
Medroxyprogesterone acetate 480.6e 27.15e 330.2 19.859 130222
Progesterone 402.15h 20.11h 280.5 20.498 117853
4,40 - 366a 9.23a 159.3 24.283 93930
Diaminodiphenylmethane
Acetamide 352a 15.5a 51 30.217 46568
Butanamide 388.8a 19.2o 83.2 26.047 56446
Propanamide 352.8a 12.9o 67.1 27.706 51507
Bisphenol A 429.6p 30.7p 172.6 27.901 134366
Triphenylmethane 365a 21.97a 213.2 21.576 99247
Phenylbutazone 378.58d 21.38d 243.2 22.981 128443
Nabumetone 353.15f 19.95f 198.2 21.339 90247
Flurbiprofen 383.9e 21.68e 187.8 23.418 102993
Ketoprofen 367.15e 20.74e 195.6 24.459 117015
Naproxen 427.24e 31.5e 182.7 22.689 94056
Metronidazole benzoate 375.15e 21.19e 197.2 23.951 113123
(S)-Boc-Piperazine 376.33e 21.26e 248.9 21.451 114525
Rac-Boc-Piperazine 381.05e 21.52e 248.9 21.451 114525
3,30 ,40 ,5,7- 587.15e 40.9e 123.4 42.925 227375
Pentahydroxyavone
7,8-Dihydroxyavone 558.1e 34.5e 150.4 30.287 137966
Amical-48 453.15e 25.6e 171 24.145 99686
Chlorothalonil 523.4e 29.56e 120.4 32.760 129217
Tebuconazole 377.85e 21.34e 240.8 24.324 142465
Artemisinin 429.65e 24.27e 307.7 16.839 87254
Methimazole 418.82e 23.66e 79 24.647 47991
Bisacodyl 408.27e 23.06e 269.7 23.746 152072
Carbamazepine 464.22e 26.22e 156.3 27.661 119590
Codeine 429.4e 24.25e 241.1 22.119 117957
Diazepam 401.9e 22.7e 186.2 26.357 129355
Eucimibe 403.15e 60.72e 398.4 21.729 188112
Nimodipine 398.15e 26.65e 320.4 21.895 153600
Zopiclone 451.15e 25.48e 215.5 29.332 185404
Nifedipine 446e 25.2e 251.9 22.911 132231
Nimesulide 421.65e 23.82e 198.1 24.795 121787
Piroxicam 469.15e 26.51e 181.6 31.565 180933
Sulfadimethoxine 475.9e 26.88e 219.6 25.416 141858
Sulfamerazine 515.2e 31.6e 231 23.764 130452
Antipyrine 385.65i 19.28i 145.7 24.114 84722
4-Aminoantipyrine 382.15i 19.11i 145.9 25.822 97279
4-Dimethylaminoantipyrine 381.15i 21.88i 184.7 23.073 98326
Climbazole 371.15i 28.17i 227.8 22.055 110812
Clobric acid 394.15q 25.54q 160.5 22.746 83039
Fenobrate 358.65i 31.2i 279.2 22.036 135571
16 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

Table 1 (Continued)
Compounds Melting Melting enthalpy, 4Hm/ Liquid molar volume , Solubility Cohesive energy, 4Ev/J mol1
point, kJ mol1 vl2 /cm3 mol1 parameter,
Tm/K d2/(MPa)0.5
Gembrozil 335.15i 29.16i 228.8 20.699 98033
Clotrimazole 418i 27.09i 256.5 23.061 136408
Clozapine 456i 22.8i 223.1 24.824 137476
Propyphenazone 375.8i 21.57i 192.7 22.502 97572
Triclocarban 528.65i 36.21i 183.8 27.779 141833
*
The value is interpolated with the data of other n-alkanes.
a
From Ref. [21].
b
From Ref. [22].
c
From Ref. [23].
d
From Ref. [24].
e
From Ref. [7].
f
From Ref. [25].
g
From Ref. [26].
h
From Ref. [27].
i
From Ref. [28].
j
From Ref. [20].
k
From Ref. [11].
l
From Ref. [29].
m
From Ref. [30].
n
From Ref. [6].
o
From Ref. [31].
p
From Ref. [32].
q
From Ref. [33].

be seen that the solubility parameters calculated using Eq. (15)
combined with Huangs 27-parameter equation or Wagners
equation is nearly the same. They are similar with the values
derived from Williams method. For the Giddings method and
Eq. (15) combined with PR-EoS, they can be applied to many solvents,
but they cannot provide quite accurate results for a specic solvent.
The accuracy of solubility parameters of sc-CO2 can affect the
change trend of the variables in the expanded liquid models. In
(Eqs. (6), (10) and (12), the solubility parameter of the solute, the
liquid molar volume of the solute and the binary interaction
parameter b12 were used as variables respectively. The changes of
these variables were calculated using the solubility data in the
references with different origin of the solubility parameters of
cs-CO2. To avoid the multiple solutions, the variables of liquid
molar volume and solubility parameter are conned to a
reasonable range. For the liquid molar volume, the value is
101000. For the solubility parameter, the value is 1040. Figs. 27
show that the change trends of the variables were slightly different
when the solvents solubility parameters were calculated with
different methods. When the accurate solvents solubility
parameters were used, the variables were independent of
temperature. When the solvents solubility parameters were
calculated using PR-EoS, slight temperature-dependence was
observed. So the accuracy of the solvents solubility parameters
is very important in the use of expanded liquid models.When the
solubility parameter was used as variable, it can be seen from Fig. 2
that the linear t of d2 and the density of CO2 would not give
satisfactory correlation results. Using the power t would
introduce additional tting parameter. The model with three
tting parameters is not feasible to be a predictive one. This is the
same case when the liquid molar volume of the solute was used as
variable (Fig. 4). When the binary interaction parameter b12 was
used as variable, the linear t of b12 and the density of sc-CO2 can
provide satisfactory correlation results (Fig. 6).
3.2. Modication of the expanded liquid model
variables, the correlation results were not satisfactory with
two tting parameters (which can also be seen in Table 2).
When the binary interaction parameter b12 was used as variable,
the correlation results were satisfactory with two tting param-
eters based on the linear t of b12 and the density of sc-CO2.
However, its tting parameters were not easy to correlate with the
properties of the solutes and this model cannot be used in
solubility prediction.
In our investigation, it is found that the solubility parameter of
the solute is the linear t of the ratio of the solvents solubility
parameter d1 and its molar volume v1 when the solubility
parameter of the solute is used as variable,
ad1
d2 b (16)
v1
Figs. 810 show that this linear function was independent of the
temperature even in a large temperature scope.
Based on this linear t, a modied expanded liquid model was
proposed. In this modied model, only two tting parameters are
needed. The correlation results of the modied model were
compared with the other two-parameter solution models, in which
the liquid molar volume of the solute and the binary interaction
parameter were used as variables respectively. The following linear
ts are adopted in the correlation.
lnvl2 alnr b (11)
b12 a  r b (17)
In all the correlation, the AARD was used as the objective function.
100X
N exp
jy2  ycal
2 j
AARD% % (18)
N 1 yexp
2

In the above investigation, it is found that when the solubility The related properties of the solid solutes are listed in Table 1,
parameter and the liquid molar volume of the solute were used as wherein the liquid molar volume, solubility parameter and the
Table 2
Correlation results of the modied model and the other two-parameter models.

Compounds Temperature/K Pressure range/ Liquid molar volume of the Solubility parameter of the solute was used as variable Binary interaction parameter Solubility
MPa solute was used as variable d2 = ad1/v1 + b b12 was used as variable reference
lnvl2 alnr b b12 = a*r+b*
Correlation Predicition
a b AARD a b AARD a b exp
2 =y2
ycal a* b* AARD
% % %
The derivatives of benzene and biphenyl
1-Chloro-2,4-dinitrobenzene 308,313 9.514.5 1.5663 15.3400 5.38 22.6112 17.1905 4.86 19.3040 18.9577 0.29 0.3874 362.7285 5.32 [34]
m-Dinitrobenzene 308,318,328 9.514.5 1.1373 12.5492 16.30 18.3707 17.6751 8.58 18.4476 18.7688 0.32 0.2588 283.5422 13.35 [34]
2,4-Dinitrophenol 308348 12.1644.58 1.4708 15.2099 25.96 17.5709 18.7234 25.21 17.5860 18.8469 0.83 0.4730 562.7140 27.07 [35]
2,5-Dinitrophenol 308348 12.1648.64 1.3660 14.4816 22.39 14.0499 19.7814 20.72 17.5860 18.8469 1.08 0.4398 529.4180 20.65 [35]
m-Nitrophenol 308348 12.1648.64 1.2986 12.6940 17.54 20.6316 21.3910 12.66 237044 20.6541 0.9 0.2618 207.9343 13.53 [35]
p-Nitrophenol 308348 12.1648.64 1.5218 15.0730 17.20 21.1182 20.9186 8.57 22.4138 19.5295 2.68 0.4507 446.9904 8.41 [35]
2-Triuoromethylbenzoic 308.2,313.2,323.2 9.3422.6 1.3059 13.7842 30.77 22.4932 16.6043 10.33 16.9290 16.4663 2.07 0.3279 295.8860 18.90 [22]
acid
3-Triuoromethylbenzoic 308.2,313.2,323.2 9.4122.54 1.1600 12.9824 35.50 19.2849 15.1642 20.16 16.9290 16.4663 0.49 0.2842 291.3789 29.79 [22]

H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

acid
3-Aminobenzoic acid 308,318,328 1021 1.5822 14.9601 25.23 29.3353 21.7051 11.41 24.5985 22.7418 0.79 0.4791 341.0102 11.86 [36]
3-Nitrobenzoic acid 308,318,328 1021 1.2448 12.9837 42.55 22.4756 21.2708 26.18 19.8527 20.7451 2.64 0.3516 265.6929 35.27 [36]
Benzamide 308,318,328 1121 1.5426 15.0326 24.05 25.1784 21.4521 19.07 22.3095 21.2692 2.16 0.4785 437.5930 18.70 [37]
Benzamide 308,318,328 1121 1.4982 14.7178 25.58 22.1500 22.2610 30.26 22.3095 21.2692 2.74 0.4523 412.7232 25.28 [38]
4-Methyl-N- 308.2,318.2,328.2 12.1622.5 1.5352 15.2167 16.71 21.3045 18.3746 14.74 27.0626 19.3845 0.11 0.3680 264.4578 18.73 [39]
phenylacetamide
Hydroquinone 333,348,363 1035 1.5137 15.1099 30.53 26.7395 24.1355 34.20 28.0558 20.6940 13.36 0.6308 741.1396 27.06 [40]
o-Hydroxybenzoic acid 308 9.819.5 1.6453 16.4568 6.99 13.8971 18.9943 6.95 20.7244 20.6683 0.07 0.5660 726.9227 7.15 [41]
o-Hydroxybenzoic acid 308,313,318,328 8.1120.26 1.3067 14.0261 40.66 20.5922 19.9328 10.48 20.7244 20.6683 0.48 0.4647 593.5980 32.73 [42]
p-Nitroaniline 308,318,328 1121 1.5084 14.2523 16.85 24.8358 21.1964 4.37 23.2505 20.6522 2.59 0.3543 209.4967 10.89 [43]
Hexamethylbenzene 323,343 7.6848.35 1.3249 13.7559 32.41 26.2005 13.7671 8.38 25.7223 13.7488 1.12 0.2367 160.6156 10.72 [44]
Salicylamide 308.2,318.2,328.2 1022 1.3816 14.5846 39.09 21.7246 22.2615 6.65 21.7106 21.6241 1.83 0.6251 852.9913 29.91 [24]
Aspirin 308.2,318.2,328.2 1225 1.6959 16.3581 13.24 25.0317 18.0113 4.94 25.7597 17.2896 1.95 0.4178 361.1167 5.80 [45]
Benzocaine 308348 12.235.5 1.4314 14.5058 35.17 24.0790 16.8363 11.96 25.5732 17.7844 0.22 0.3364 273.9092 18.05 [46]
Syringic acid 313,323,333 1050 1.0332 11.9665 42.53 14.3313 23.3934 34.16 21.6792 17.9891 266.92 0.2970 289.9861 40.44 [47]
Vanillic acid 313,323,333 1050 1.4479 14.8291 28.06 21.4446 20.9202 15.04 21.2234 19.1498 6.12 0.4978 524.1272 13.75 [47]
Benzoic Acid 308.15,318.15,328.15,343.15 10.136.41 1.2148 12.8993 26.75 18.9395 18.8627 14.47 21.3700 20.4272 0.14 0.2886 260.9698 19.68 [48]
Benzoic acid 308328 10.128 1.6809 16.0260 5.85 22.1357 18.0401 5.58 21.3700 20.4272 0.12 0.3742 333.2483 4.00 [49]
Methylparaben 308348 12.235.5 1.5461 15.3994 20.42 24.0216 18.4028 9.97 23.5532 16.1237 10.43 0.4405 404.7853 7.68 [50]
Caffeic acid 313,323,333 1550 1.3758 13.9610 24.88 16.6227 27.2560 25.96 24.9902 19.6010 2087.95 0.4247 345.1221 24.05 [51]
p-Coumaric acid 313,323,333 8.550 1.3076 13.5571 33.24 20.0832 23.5452 25.08 25.8578 19.9659 28.41 0.4025 338.5415 29.03 [51]
Ferulic Acid 301.15,313.15,323.15,333.15 1228 1.6781 16.3849 12.08 23.7635 20.3296 10.11 23.6821 17.8623 24.17 0.4902 452.3080 11.87 [52]
Methyl gallate 313,323,333 1050 1.4088 14.6562 29.13 20.5451 23.9101 10.52 28.7264 18.9460 62.86 0.5447 630.1413 19.55 [53]
p-Coumaric acid 313,323 8.525 1.3607 13.9220 25.88 21.9702 23.3065 19.88 25.8578 19.9659 41.69 0.4396 367.1124 21.79 [53]
Protocatechualdehyde 313,323,333 1050 1.3405 13.8794 33.21 18.9430 25.7358 19.45 21.1482 16.7026 1774.92 0.5260 592.6376 28.53 [53]
Protocatechuic acid 313,323,333 1050 1.2444 13.1819 41.82 17.4707 27.0472 24.37 22.6870 21.5268 156.94 0.4615 497.1329 38.91 [53]
2,3,5-Trimethyl phenol 308 10.128 1.9924 18.4898 1.49 25.3408 16.0227 1.03 26.2126 16.0736 0.77 0.4601 432.5974 3.24 [54]
2,4,6-Trimethyl phenol 308 10.124 1.9399 18.2767 0.67 26.6805 14.4986 0.91 26.2126 16.0736 0.22 0.4614 460.9225 2.70 [54]
2,3-Dimethyl phenol 308 10.128 1.8439 17.4729 2.92 22.9537 16.4944 3.25 25.7947 16.8146 0.43 0.4512 447.8936 6.05 [54]
2,5-Dimethyl phenol 308 10.128 2.0025 18.5291 1.79 26.2401 15.9145 1.16 25.7947 16.8146 0.46 0.4851 474.4030 2.20 [54]
4-Phenyl phenol 308 10.128 1.9808 18.4553 4.27 23.6457 18.4552 6.68 24.8993 17.2025 3.12 0.5064 472.4881 8.32 [54]
4-tert-Butyl phenol 308 10.128 1.8960 17.9057 1.24 24.4789 15.2429 0.98 24.8433 15.4685 0.72 0.3995 364.9383 4.05 [54]
Flutamide 308348 12.235.5 1.3996 14.5717 33.30 21.7930 17.7905 18.22 18.9691 14.8161 97.49 0.3312 265.6003 17.82 [55]
n-(4-Ethoxyphenyl) 308328 919 1.5208 15.5558 28.55 24.6813 17.9787 15.16 22.8903 16.2065 13.12 0.4575 440.8451 18.27 [56]
ethanamide

17
 18
Table 2 (Continued)
Compounds Temperature/K Pressure range/ Liquid molar volume of the Solubility parameter of the solute was used as variable Binary interaction parameter Solubility
MPa solute was used as variable d2 = ad1/v1 + b b12 was used as variable reference
lnvl2 alnr b b12 = a*r+b*
Correlation Predicition
a b AARD a b AARD a b exp
2 =y2
ycal a* b* AARD
% % %
Pyrocatechol 333.15,348.15,363.15 1035 1.3495 14.0268 17.62 20.4064 21.4057 12.69 23.4121 18.2971 7.84 0.4463 532.1610 13.59 [57]
Salicylic acid 308328 10.128 1.8244 17.4518 6.17 22.5622 19.7557 4.33 20.7244 20.6683 0.62 0.6165 705.9843 3.66 [49]
N-Phenylacetamide 308.2,313.2,323.2 940 1.3521 13.7347 21.56 16.9049 21.0834 26.30 22.6768 18.1053 6.35 0.3197 250.9581 22.64 [31]
N-Phenylacetamide 308.2,318.2,328.2 10.4422.5 1.4590 14.4683 23.93 23.9343 19.3796 16.60 22.6768 18.1053 5.02 0.3684 291.6893 15.63 [39]
Vanillin 313.2,333.2 8.4327.65 1.3049 14.4639 31.36 18.0434 13.3957 11.57 20.0148 14.6587 0.45 0.4945 700.1290 24.09 [58]
Biphenyl 309,318.5,322.5,328.35 10.4648.4 1.5793 15.5874 32.03 26.4178 14.5337 3.39 23.0489 16.2466 0.33 0.3052 256.3255 19.99 [59]
4-Chlorobiphenyl 313,323,333 1030 1.3083 13.8266 26.81 22.8938 16.0129 4.83 23.1409 16.1368 0.47 0.2991 248.7555 11.52 [19]
2,2,4,5,5- 313,323,333 1030 1.3603 14.5280 33.70 22.1553 16.9331 6.97 22.9186 16.3804 3.64 0.3714 335.3413 14.80 [19]
Penatchlorobiphenyl
Azoic compounds
Azobenzene 208.2,318.2 9.125.3 1.5429 15.6386 37.26 29.6792 14.1318 8.83 30.1111 12.6670 5.50 0.4270 400.1977 17.72 [60]

H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

p-Hydroxyazobenzene 308.2,318.2 9.125.3 1.5056 15.8867 41.44 29.1802 11.3921 3.74 29.9323 12.7391 0.11 0.5148 585.4574 25.94 [60]
CI disperse orange 3 323.7,353.7, 413.7 10.1331.06 1.2753 13.8239 47.44 23.0490 19.4746 27.50 28.9231 15.8123 78.70 0.3691 336.0418 41.67 [20]
CI disperse blue 79 323.7,353.7,383.7 9.9230.51 1.2652 14.7866 67.05 18.8704 15.9512 49.36 18.8704 15.9512 0.62 0.3847 383.7854 56.30 [11]

Polycyclic aromatic hydrocarbons and its analogues

Naphthalene 313,318,323,328 8.74718.955 1.1946 12.9413 22.07 22.5487 15.3195 13.91 22.3895 16.8700 0.21 0.2517 225.0770 19.41 [61]
Perylene 323,333 17.2335 1.7869 17.1694 9.53 22.7351 18.7111 9.17 22.7061 16.6211 17.81 0.4208 347.6000 12.00 [18]
Anthracene 313,323,333 11.8135.59 1.6577 16.0644 9.08 22.8302 17.1338 5.62 22.7289 16.5677 1.87 0.3404 274.2955 6.87 [18]
Phenanthrene 313,323,333 10.7135 1.4944 14.9994 15.08 22.1209 17.0914 4.76 22.7289 16.5677 0.57 0.3240 265.6210 7.18 [18]
Pyrene 313,323,333 10.735 1.5372 15.3548 17.74 22.4318 18.0466 2.65 22.3381 17.1356 2.98 0.3693 311.9841 7.16 [18]
Fluoranthene 308348 12.1635.46 1.5370 15.3685 23.98 23.9805 17.5147 8.25 21.1842 18.1500 0.93 0.3868 329.9650 8.45 [62]
Acenaphthene 308348 12.1635.46 1.5438 15.1798 26.93 25.8485 16.1020 7.32 22.2690 16.6961 1.23 0.3845 284.8440 11.09 [62]
Triphenylene 308348 12.1635.46 1.4242 14.6727 28.63 23.2549 17.7142 9.41 22.9671 16.3585 5.29 0.3531 286.1223 15.60 [62]
Naphthalene 308,318 8.0529.92 1.2493 13.1378 33.19 26.3598 14.8933 8.13 22.3895 16.8700 0.34 0.2858 238.3695 19.67 [63]
2,3-Dimethylnaphthalene 308,318,328 9.928 1.2485 12.2284 28.71 23.4411 15.6074 9.22 23.6979 15.5825 0.97 0.2631 200.7630 15.27 [64]
2,6-Dimethylnaphthalene 308,318,328 9.628 1.2505 13.3123 28.18 23.3282 15.1183 5.08 23.6979 15.5825 0.56 0.2741 218.2155 10.99 [64]
2-Naphthol 308.15,318.15,328.15,343.15 10.2836.36 1.4023 14.3822 33.2 22.4415 19.8150 13.62 26.0511 19.0872 1.25 0.4401 453.6712 21.19 [48]
Acridine 308.15,318.15,328.15,343.15 10.1636.41 1.3389 14.0342 32.41 21.8015 17.6363 9.60 21.9280 17.4538 1.24 0.3482 306.7887 15.37 [48]
1,4-Naphthoquinone 318.15,328.15,343.15 10.0936.4 1.2952 13.5506 32.89 22.3940 19.3000 6.52 19.7667 17.8427 6.97 0.3491 306.0581 22.28 [48]
9,10-Anthraquinone 308,318 8.4130.63 1.2966 13.8832 18.89 15.8212 18.0013 10.63 18.8367 17.6439 0.95 0.3204 304.6625 4.30 [65]
p-Quinone 308,318 8.6129.21 1.1785 12.8399 21.50 18.3972 16.9274 12.89 21.1639 18.1475 0.25 0.3003 308.0386 17.58 [65]
p-Quinone 333,348,363 1035 1.2493 13.2011 13.76 21.4502 17.0635 11.16 21.1639 18.1475 0.43 0.3019 297.6803 10.60 [40]
Xanthene 308.15,328.15 824 1.1540 12.8803 29.02 17.4963 16.6748 9.96 22.2685 16.4362 0.56 0.2756 257.4434 18.31 [66]
Xanthone 308.15,328.15 1230 1.4752 15.0611 15.97 19.3982 18.0169 10.35 20.0956 17.2418 1.89 0.3642 349.4451 12.66 [66]

1,4-Bis(alkylamino)-9,10-anthraquinone compounds
CI disperse blue 3 323.7,353.7, 413.7 10.5132.98 1.3906 15.0544 64.82 27.5543 18.0736 32.72 24.9037 18.2175 1.26 0.5266 554.6961 41.97 [11]
CI disperse red60 323.7,353.7, 413.7 10.1530.56 1.3330 14.8828 56.27 23.0757 16.3381 38.74 17.8453 15.6790 9.02 0.4389 433.7429 38.76 [20]
AQ01 299345 6.7918.81 1.4458 15.1436 34.21 21.9370 18.7567 10.61 23.5612 17.9182 2.35 0.4228 399.3138 21.82 [67]
AQ02 299.3346 7.718.69 1.3869 14.9189 42.59 21.6132 17.3319 12.41 23.9335 17.0648 0.82 0.3949 374.6994 25.78 [67]
AQ04 310.1340.1 8.4218.26 1.2993 14.5735 50.46 22.6041 14.6404 11.96 22.0056 14.2541 2.56 0.3312 282.2973 27.68 [67]
AQ05 299340 6.5618.75 1.3702 15.1049 55.26 22.7103 14.2095 17.62 22.3881 14.0398 1.54 0.3240 274.3177 32.55 [67]
AQ08 310.1340.1 9.0419.58 1.3188 14.8968 58.82 22.9695 14.1314 19.25 23.4473 13.4758 4.31 0.3090 245.0593 31.30 [67]

Alkanes, fatty acids and fatty alcohols

Tetracosane 308 1024 1.9802 18.7906 3.91 27.8100 12.4041 5.52 26.6998 12.2031 2.68 0.2102 121.9383 11.48 [68]
Pentacosane 308 1024 1.9704 18.7571 3.72 27.9974 12.3910 5.27 26.7438 12.1654 3.14 0.2138 124.3669 12.28 [68]
Octacosane 308,318 1024 1.5612 16.1609 37.23 27.3967 12.1658 14.92 26.8596 12.0667 1.49 0.2272 139.0069 14.49 [68]
Nonacosane 308,318 1024 1.5481 16.1159 38.53 27.1722 12.1604 14.73 26.8936 12.0379 1.36 0.2323 143.4434 13.52 [68]
Dotriacontane 308,318,328 1024 1.3219 14.7067 64.51 26.8908 11.9265 22.50 26.9844 11.9612 0.81 0.2265 141.6009 15.71 [68]
Tritriacontane 308,318,328,333 1024 1.3009 14.6185 68.70 26.3439 11.9030 25.53 27.0115 11.9385 0.66 0.2312 145.9520 16.46 [68]
Hexatriacontane 308,318,328,333 1024 1.2733 14.5353 71.91 25.5565 11.7896 26.29 27.0846 11.8772 0.38 0.2295 147.3410 18.26 [68]
Stearic acid 308 923.7 1.8951 18.1480 6.53 25.7634 13.7448 2.03 25.1458 14.1708 0.57 0.2766 189.0309 8.12 [6]
Stearyl alcohol 308 923.7 1.9538 18.6330 9.49 26.5485 12.8739 2.90 27.2715 13.1271 0.48 0.2210 137.5015 6.19 [6]
Arachidyl alcohol 308 8.923.7 1.9298 18.5592 7.10 26.8543 12.6265 2.10 27.3189 12.9531 0.45 0.2337 148.4311 10.74 [6]

Steroidal compounds
Budesonide 338,348,358 21.338.5 1.5624 16.5262 15.28 23.0316 15.5845 13.04 23.0365 15.5845 5.42 0.4257 410.5334 17.27 [69]
Cholesterol 313.15,318.15,323.15,333.15 1025 1.4426 15.4612 40.14 25.5282 13.3054 11.49 25.2584 13.1353 1.50 0.3001 224.9250 22.08 [70]
Cholesteryl acetate 308.15,318.15,328.15 924 1.3606 14.9140 50.99 24.8506 12.5380 9.15 24.8061 12.7407 0.65 0.2556 180.2894 16.96 [70]
Cholesteryl butyrate 308.15,318.15,328.15 1024 1.4995 15.9105 28.55 24.5060 12.5788 7.86 25.0141 12.6337 0.71 0.2523 176.2338 27.50 [70]
Cholesteryl benzoate 308.15,318.15,328.15 1227 1.6816 17.1657 15.63 24.6573 13.3860 6.77 24.6829 13.0176 2.38 0.2704 191.6313 20.06 [70]
Dutasteride 308348 12.235.5 1.3180 14.8675 43.44 17.8589 15.6094 14.48 21.8227 14.3759 2.59 0.3849 391.9774 14.52 [55]
Finasteride 308348 12.235.5 1.5517 16.3470 32.87 24.9560 12.7964 16.09 22.7117 14.8708 0.07 0.3618 331.7608 28.39 [55]
Medroxyprogesterone 308348 12.235.5 1.4877 15.7579 20.23 21.2575 14.2031 19.52 20.5559 13.1376 6.05 0.2777 225.3036 31.70 [71]
acetate
Medroxyprogesterone 313,333 1122 1.4740 15.7000 17.93 20.7547 14.1227 12.52 20.5559 13.1376 4.88 0.2867 237.2618 23.84 [72]

H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

acetate
Progesterone 313333 924 1.2545 13.9730 34.79 20.6919 14.9599 12.03 22.3348 12.0839 66.91 0.2696 210.5076 19.95 [72]

Other compounds
4,40 - 313.15,323.15,333.15 1120 1.4402 14.7192 32.21 25.5988 18.1941 8.63 28.2533 18.9851 0.16 0.2828 308.2300 18.18 [73]
Diaminodiphenylmethane
Acetamide 308.2,313.2,323.2 940 1.4156 13.5468 20.45 20.8263 24.6016 10.34 22.0304 24.5665 0.81 0.3995 355.1106 16.27 [31]
Butanamide 308.2,313.2,323.2 940 1.4627 13.9909 25.06 23.6210 20.3931 11.12 22.8173 20.4430 1.10 0.3744 310.6664 14.64 [31]
Propanamide 308.2,313.2,323.2 940 1.4540 14.0043 21.48 22.1535 22.2062 8.75 22.4254 22.1009 1.01 0.3919 332.2661 13.12 [31]
Bisphenol A 313,333,353 1319.1 1.4940 15.6894 32.65 27.5757 16.4071 27.17 26.0810 16.2761 1.43 0.5268 556.7617 18.84 [32]
Triphenylmethane 308.15,318.15.328.15 8.2528.37 1.3818 14.6627 39.83 25.2051 14.4354 8.03 23.6706 15.4650 0.33 0.3355 281.0198 15.13 [74]
Phenylbutazone 308.2,318.2,328.2 1022 1.2860 14.3548 44.62 22.6957 14.4028 6.84 22.3819 15.6793 0.15 0.3575 334.1959 24.41 [24]
Nabumetone 308.2,318.2,328.2 1022 1.2653 13.7203 38.35 23.8075 15.4489 7.94 22.3760 14.9134 3.04 0.3105 245.9150 17.45 [24]
Flurbiprofen 303,313,323 8.924.5 1.7272 16.8211 13.60 23.9274 17.1390 15.01 23.9274 17.139 1.01 0.3872 319.1632 9.87 [75]
Ketoprofen 313,328 925 1.4006 14.7965 42.58 21.8183 17.6729 11.73 21.7146 17.5546 1.28 0.3817 334.8837 23.67 [76]
Naproxen 308348 12.235.5 1.5099 15.2261 19.53 23.1355 17.3573 20.24 22.4550 17.0553 1.68 0.3320 255.3982 22.02 [46]
Metronidazole benzoate 308348 12.235.5 1.4668 15.3229 27.31 21.0717 16.2204 16.03 22.3659 15.9661 1.08 0.3754 347.2070 17.16 [46]
(S)-Boc-Piperazine 308.2,318.2,328.2 9.0120.5 1.3768 14.8862 54.79 24.8821 13.3828 22.41 25.8657 15.0311 0.05 0.3333 291.5865 34.93 [77]
Rac-boc-Piperazine 308.2,318.2,328.2 10.320.4 1.4433 15.1691 43.41 28.0862 14.2024 11.51 24.7037 14.3812 1.95 0.3514 282.1511 17.03 [77]
3,3,4,5,7- 308.2,318.2 10.125.3 1.7140 17.8952 34.46 25.0321 15.5368 6.51 26.8981 18.8101 0.02 1.0304 1691.3739 25.06 [78]
Pentahydroxyavone
7,8-Dihydroxyavone 308.2,318.2 9.125.3 1.7528 17.5713 29.18 27.5369 15.1032 12.12 23.4026 16.8517 0.36 0.6654 774.3907 14.71 [78]
Amical-48 318.15,328.15,338.15 1030 1.4099 14.6902 31.66 26.5734 16.6790 15.49 26.5734 16.6790 0.91 0.4056 349.7607 15.60 [79]
Chlorothalonil 318.15,328.15,338.15 1030 1.3885 15.0467 33.85 18.5275 18.3101 21.17 18.5275 18.3101 0.97 0.5689 770.8667 24.28 [79]
Tebuconazole 323.15,338.15 1030 1.3158 14.5878 46.69 22.2333 15.7506 20.72 23.8698 15.0057 2.48 0.3849 366.5304 20.35 [79]
Artemisinin 310.1,318.1,328.1,338.1 1027 1.3208 14.1875 29.17 25.6145 12.2617 17.03 25.6145 12.2617 0.99 0.2214 141.2416 29.93 [80]
Methimazole 308348 12.235.5 0.8581 9.3370 10.49 17.3293 24.5759 8.98 17.3293 24.5759 0.96 0.2195 65.4863 9.25 [50]
Bisacodyl 308348 12.235.5 1.5213 15.9936 30.23 22.8371 15.4943 13.75 24.0357 15.2781 0.91 0.3887 355.3903 13.97 [50]
Carbamazepine 308348 12.235.5 1.6084 16.3584 18.14 20.9954 17.3362 16.28 22.9309 18.1624 0.20 0.4864 524.1624 15.18 [81]
Codeine 308348 12.235.5 1.4854 15.5017 28.30 23.6463 14.9344 13.56 22.2213 13.7367 7.26 0.3476 295.3421 16.73 [81]
Diazepam 308348 12.235.5 1.5694 16.1575 22.35 22.2218 16.6550 16.45 23.3178 17.3511 0.24 0.4727 479.1033 20.79 [81]
Eucimibe 308.15,318.15 9.3330.19 1.4859 15.9351 45.58 23.9031 14.5804 15.56 23.9031 14.5804 0.93 0.3572 293.8281 21.44 [82]
Nimodipine 313,323,333 1025 1.4140 15.2006 54.95 27.7438 14.4985 10.80 27.3240 14.9912 0.38 0.3743 300.4599 18.62 [83]
Zopiclone 313,323,333 1025 1.4673 15.8380 53.94 28.0115 16.0755 15.60 22.3299 17.4188 0.60 0.5803 643.3859 29.67 [83]
Nifedipine 333.15,353.15,373.15 13.529.6 1.3815 14.8059 28.53 25.6249 16.0674 19.14 27.5580 15.9388 0.73 0.3689 299.8587 18.69 [84]
Nimesulide 312.5,331.5 1322 1.4683 15.3430 15.61 21.7459 17.2667 14.35 18.4496 18.1090 0.69 0.3894 359.6530 10.43 [85]
Piroxicam 312.5331.5 1022 1.5232 16.2471 22.92 19.9581 17.8596 11.77 19.9581 17.8596 0.97 0.5813 731.3406 17.14 [85]

19
 20
Table 2 (Continued)
Compounds Temperature/K Pressure range/ Liquid molar volume of the Solubility parameter of the solute was used as variable Binary interaction parameter Solubility
MPa solute was used as variable d2 = ad1/v1 + b b12 was used as variable reference
lnvl2 alnr b b12 = a*r+b*
Correlation Predicition
a b AARD a b AARD a b exp
2 =y2
ycal a* b* AARD
% % %
Sulfadimethoxine 313.15,333.15 13.148.8 1.3411 14.4638 42.57 16.0248 20.2621 40.70 20.6641 18.9741 0.81 0.3146 275.4206 43.77 [86]
Sulfamerazine 313.15,333.15 15.147.4 1.4515 15.1798 30.12 18.1559 18.5824 25.98 18.9813 18.3386 1.10 0.2929 240.6470 26.59 [86]
Antipyrine 308.2328.2 10.0222.04 1.3120 13.8839 33.30 22.6562 17.6329 6.55 23.5039 16.3387 3.94 0.3573 310.9372 19.22 [87]
4-Aminoantipyrine 308.2328.2 10.0322.04 1.3526 14.2868 37.05 23.1805 18.2006 7.51 25.5682 18.3224 0.47 0.4122 383.4653 22.05 [87]
4-Dimethylaminoantipyrine 308.2328.2 10.0222.04 1.3341 14.3391 38.36 23.8107 15.3003 4.41 24.8750 14.6393 1.84 0.3654 329.2298 1.98 [87]
Climbazole 313.2333.2 10.5539.89 1.5100 15.6896 25.65 20.1783 14.9322 18.02 21.6493 14.6585 0.96 0.3256 289.8653 24.42 [88]
Clobric acid 308.2328.2 10.0122.02 1.3211 13.9956 31.15 22.7858 16.4605 7.83 21.5952 17.2766 0.46 0.3289 277.6748 16.59 [33]
Fenobrate 308.2328.2 10.0122.02 1.3101 14.6421 41.64 22.2067 13.3111 12.14 23.0156 14.2579 0.16 0.3348 311.4601 23.63 [33]
Gembrozil 308.2328.2 10.0122.02 1.2170 13.5446 32.45 20.8950 15.2884 7.51 22.3239 15.1007 0.88 0.2678 211.3158 14.56 [33]
Clotrimazole 308348 12.235.5 1.3542 14.5811 39.16 21.4897 16.7836 7.78 22.7969 15.2388 9.42 0.3372 281.2244 9.75 [89]
Clozapine 318,338,348 12.1635.46 1.4923 15.5560 36.40 24.3752 17.1176 17.75 25.5725 17.1698 0.59 0.4154 367.4526 16.45 [90]
Propyphenazone 308328 919 1.3333 14.3241 39.22 25.0807 15.0717 8.35 24.4286 15.0784 1.14 0.3399 295.5870 18.16 [91]
1.5278 0.4898

H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024

Triclocarban 313.2333.2 10.9338.96 16.2227 25.83 14.0006 14.7173 8.43 18.0434 13.3957 1.68 593.4021 19.13 [88]
28.99 13.31 18.41

Underlined indicates that the estimated results are beyond the order of magnitude.
(solubility data were from Ref. [19].)
d1/v1.
Fig. 13. Solubility correlation results of pyrene in sc-CO2 with the linear t of d2 and

(solubility data were from Ref. [19].)

and r.
Fig. 12. Solubility correlation results of pyrene in sc-CO2 with the linear t of b12

(solubility data were from Ref. [19].)

and lnr.
Fig. 11. Solubility correlation results of pyrene in sc-CO2 with the linear t of lnv2l
 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024 21

Table 3
Atom and group contributions to the cohesive energy at different ratios of d1 and v1.

Atom or group 4ei J/mol Number of compounds containing the atom or

group
d1/v1 = 0 d1/v1 = 0.35
CH3 9408.86 20175.96 83
CH2 1995.711 7055.4 46
CH 5547.87 6369.75 28
C 14591.7 24289.5 24
CH 1705.646 8003.337 120
C 6647.44 6283.84 120
Ring closure 5 or more atoms 14869.55 19327.12 125
Ring closure 3 or 4 atoms 18199.52 61730.47 1
Conjugation in ring for each double bond 698.5763 3617.19 81
Halogen attached to carbon atom with double bond 2184.513 8738.962 15
COOH 22839.29 35592.14 21
CO2 3690.858 9466.92 18
CO 4237.245 4239.367 22
CHO 4926.487 6794.901 2
CONH2 21370.32 32956.56 6
CONH 9245.765 15201.32 12
CON 1080.101 2363.86 6
NHCONH 10217.6 27252.5 1
NH2 18438.36 34875.01 9
NH 10496.68 26426.28 11
N 9776.67 13321.7 16
N 4175.809 8404.593 13
Cl 8004.367 10296.71 13
NO2(aromatic) 15255.48 23073.44 15
O 158.9173 380.5885 23
OH 10255.85 19744.28 39
F 5294.62 8267.344 5
NN 13175.1 2132.3 4
Br 38379.32 11526.31 1
SO2 18634.8 13967.27 1
I(disubstituted) 25925.56 29860.37 1
SO2NH 23912.5 32471.44 3
SO2N 311.118 4308.84 1
S 6873.287 4383.25 1
SH 30875.47 37097.15 1
CN 11264.57 13552.03 1
Intramolecular hydrogen bonding 4757.71 12389.5 27

cohesive energy were calculated according to Fedors group 5) The solubility parameters of the solutes at different ratios of
contribution method [10]. The correlation results are listed in d1 and v1 (d1/v1 = 0 and d1/v1 = 0.35) were calculated using
Table 2 and Figs. 1113. It can be seen from the correlation results the regressed group contributions and the liquid molar
that the modied solution model provides satisfactory correlation volumes.
results with only two tting parameters. When the binary 0X 10:5
interaction parameter was used as variable, the linear t of b12 Dei
B i C
and r can also give acceptable correlation results. d2 B
@ vl A
C
By estimating the solubility parameters of the solutes, the 2
modied model can be used in solubility prediction. The feasibility
of estimating the solubility parameter of the solute with the group
contribution method was investigated. The estimation was based
6) The linear t of d2 and d1/v1 can be determined with the
on the assumption that the liquid molar volume of the solute is
calculated solubility parameters of the solutes at different ratios
constant while the cohesive energy changes with d1/v1 in the
of d1 and v1 (d1/v1 = 0 and d1/v1 = 0.35).
supercritical uid. The liquid molar volumes of the solutes can be
7) The solubilities can be predicted with the linear t of d2 and
estimated according to Fedors [10]. The estimation process is as
follows:
d1/v1 known.

1) The solubilities of the solid solutes were correlated with the

modied solution model;
2) The solubility parameters of the solutes at
d1/v1 = 0 and d1/
v1 = 0.35 were calculated according to the correlated linear t;
3) The cohesive energy of the solutes at d1/v1 = 0 and d1/
v1 = 0.35 was calculated using the calculated solubility param-
eters and the liquid molar volumes of the solutes.
DE2 d22  vl2
4) The solutes were divided into specic groups and their
contributions to the cohesive energy at different ratios of d1
an v1 (d1/v1 = 0 and d1/v1 = 0.35) was regressed;
The regressed group contributions are listed in Table 3. The
comparison of the cohesive energy derived from group contribu-
tion and derived from solubilities is shown in Figs. 14 and 15. It can
be seen that when the ratio of d1 and v1 is equal to zero, the
calculated cohesive energy of the solutes is not very satisfying. The
reason is that the extrapolation of d1/v1 to zero using the linear t is
not very accurate. Fig. 8 shows that when the value of d1/v1
approaches zero, the linear function cannot descript the relation-
ship of d2 and d1/v1. Actually, the actual liquid molar volumes of the
solutes may deviate from its estimated value when the value of
d1/v1 is relatively small. However, when the ratio of d1 and v1 is
high, the cohesive energy of the solutes can be estimated
satisfactorily using the group contribution method (Fig. 15). The
 22 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024
Fig. 14. Estimation results of the cohesive energy of solutes when d1/v1 is equal to
zero.
Fig. 15. Estimation results of the cohesive energy of solutes when d1/v1 is equal to
0.35.
reason is that when the ratio of d1 and v1 is high, the molar volumes
of the solutes in the sc-CO2 are close to their liquid molar volume.
So it can be concluded that the solubilities at higher d1/v1 can be
estimated more accurately using this group contribution method.
Fig. 16. Solubility prediction results of the modied solution model combined with
the group contribution method for polycyclic aromatic hydrocarbons and its
analogues, 1,4-bis(alkylamino)-9,10-anthraquinone compounds, alkanes, fatty acids
and fatty alcohols, steroidal compounds and other compounds.
Fig. 17. Solubility prediction results of the modied solution model combined with
the group contribution method for the derivatives of benzene, biphenyl and azoic
compounds.
The estimated slopes and intercepts of the linear ts of d2 and d1/v1
are listed in Table 2. The prediction results of the solubilities were
expressed as the ratio of calculated value and the experimental
value, which can be seen in Table 2. As the solubility data were
from different papers, the experimental errors are unavoidable. For
example, the regressed parameters in the modied model for the
solubilities of N-phenylacetamide and o-hydroxybenzoic acid from
different papers are quite different. The errors of melting enthalpy
may also introduce errors to the prediction results. For many
compounds, their melting enthalpies are different in different
references. Besides, the melting enthalpy and melting point are
also inuenced by crystal form of the solute while in most papers,
the crystal forms of the materials used in solubility determination
were not mentioned. Considering the above errors, the ratios of the
predicted and experimental solubilities between 0.1 and 10 were
regarded as acceptable (between the dot line in Figs. 16 and 17) in
this paper. It can be seen that for most of the compounds, the
solubilities can be predicted in the order of magnitude (Fig. 16).
However, for some derivatives of benzene, biphenyl and azoic
compounds, the prediction results were not quit satisfactory
(Fig. 17). The reason is that for these compounds, their properties
are determined not only by the types of the group, but also by the
positions of the substituents. However, in this group contribution
method, the positions of the substituents were not considered. For
the chiral compounds, such as (S)-Boc-piperazine, the effect of the
conguration of the group was not considered either and the
prediction results were not satisfying. In general, the electronic
environment of the group was not considered in the group
contribution method and this is one of the prediction error sources.
For example, the contribution of COOH in fatty acid is different
from the same group in benzoic acid because the carbonyl can
form conjugated structure with the benzene ring. It was the
same case for many other groups. With the accumulation of the
accurate solubility data, the groups can be divided more detailed
and more groups can be added into this group contribution
method.
4. Conclusions
The expanded liquid model and compressed gas model are
widely used in solubility prediction for compounds in supercritical
uids. For the compounds with accurate critical properties,
ancentric factor and sublimation pressures, the compressed gas
model can be used. However, for the compounds without these
accurate data, the expanded liquid model is the better choice. In
the expanded liquid model, only the melting point and the melting
 H. Li et al. / Fluid Phase Equilibria 385 (2015) 1024
enthalpy of the solute are needed and they can be obtained easily
by experiment. The estimation errors are excluded in the empirical
parameters and this makes the estimation of these parameters
possible.
The expanded liquid model was investigated in this paper. It is
found that the accuracy of the solubility parameter of the
supercritical solvent is very important. When the binary interac-
tion parameter b12, liquid molar volume and the solubility
parameter of the solute were used as variables respectively,
calculating the solubility parameter of supercritical solvent using
the inaccurate methods can cause temperature-dependence of the
variables in the models. When using accurate solubility
parameters of the solvent, the variables in the models were
temperature-independent. In order to correlate and further predict
the solubilities of solid solutes, a modied expanded liquid model
was proposed in this paper. In this modied model, the solubility
parameter of the solute was used as variable and it is the linear
function of d1/v1. This newly proposed model can be used to
correlate the solubilities in a large temperature range with only
two parameters and the average AARD is 13.31% for 135 solid
solutes. By estimating the parameters in this modied model with
the group contribution method, the solubilities of most of the
solutes can be predicted in the order of magnitude with only their
melting points and melting enthalpies.
Acknowledgement
This work was supported by the National Natural Science
Foundations of China (Grant No. 21206077, 21106107).
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