8282

Ind. Eng. Chem. Res. 2007, 46, 8282-8287

CORRELATIONS
Prediction of Molar Volumes of CO2-Expanded Liquids Using a New Generalized
Method
Sameer V. Dalvi and Mamata Mukhopadhyay*

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

Chemical Engineering Department, IIT Bombay, Mumbai 400076, India

A new, easy-to-use generalized method is presented in this work for accurate computation of VL, the molar
volume of the carbon dioxide (CO2)-expanded liquids. This method calculates the liquid-phase compressibility
factor, ZL, of the binary mixture of CO2 and solvent. The uniqueness of this method is that it does not involve
computation to solve a cubic equation, nor does it require any binary interaction constants and critical
temperatures of the pure components, as in the case of the equation of state (EOS) method. ZL is obtained
directly from a generalized correlation in terms of the pseudo-reduced pressure (Pr) with two systemspecific constants. These two constants are simply dependent on the acentric factor of the solvent, 2. The
computation of VL by this method has been validated for 17 CO2-solvent systems at temperatures in the
range of 290.8-328.2 K and at pressures in the range of 4-96 bar with the experimental data available in
the literature.
1. Introduction

Table 1. Comparison of % AARD of Liquid Molar Volumes of

CO2-Solvent Systems Estimated by Different EOSsa

It is well-known that dense carbon dioxide (CO2), either in

supercritical or subcritical state, can be tailor-made for a variety
of applications, including recently explored gas-expanded liquids
(GELs), by fine-tuning its thermodynamic and transport properties. The CO2-expanded organic solvents are employed for
micronization of varied chemical substances and also as reaction
media for many catalytic and synthesis reactions. In recent years,
supercritical or subcritical CO2 has been utilized in several
processes, such as gas-antisolvent (GAS),1 supercritical antisolvent (SAS),2 depressurization of expanded liquid organic
solvent (DELOS),3 and precipitation by pressure reduction of
gas (CO2)-expanded liquids (PPRGEL)4 for formation of
ultrafine/submicron particles. In these processes, CO2 is dissolved in the organic solution of a solid to be micronized.
However, the extent of dissolution of CO2 in the solution is
constrained by the availability of the required total volume of
the vessel, as it causes a volume expansion of the CO2-solvent
system, despite the fact that the liquid molar volume decreases
with dissolution of CO2.5 In other words, a vessel does not allow
more dissolution of CO2 in the solution, after it is completely
filled with the liquid with dissolved CO2. Conversely, in case
the vessel is not completely filled with the expanded liquid,
then CO2 may continue to dissolve in the solvent till the phase
equilibrium is attained at the prevailing condition. Thus, the
knowledge of molar volume of the CO2-expanded solvent with
dissolution of CO2 is needed in order to ascertain the extent of
CO2 that can be dissolved at a particular temperature or pressure
in the liquid phase in a vessel of given volume. This information
is needed in the design of the process equipment where CO2expanded liquids can be effectively utilized. The molar volumes
can also be used to predict the nonideality of the liquid phase
* To whom correspondence should be addressed. E-mail: sameervd@
iitb.ac.in/mm@che.iitb.ac.in. Phone: +91-22-25767248. Fax: +9122-25726895.

%AARD
EOS
PR
PRSV
V-TPR
PT
SRK

298 K
Nd ) 15

303 K
Nd ) 15

CO2-Acetone
5.85
6.23
5.81
6.21
11.49
6.75
6.78
7.24
3.31
4.95

EOS

290.8 K
Nd ) 11

PR
PRSV
V-TPR
PT
SRK

2.09
2.21
1.72
0.79
6.67

EOS

308.2 K
Nd ) 7

PR
PRSV
V-TPR
PT
SRK

6.99
6.90
6.96
6.11
12.91

300.9 K
Nd ) 15

CO2-Toluene
1.51
1.61
1.44
0.73
6.52
318.2 K
Nd ) 10

313 K
Nd ) 15
7.92
7.88
8.46
8.70
9.06
310.11 K
Nd ) 17
1.68
1.79
1.53
0.57
11.84
328.2K
Nd ) 10

CO2-DCM

6.92
6.88
6.33
6.61
30.22

5.26
5.22
5.22
4.92
11.49

Nd ) number of data points.

in terms of the liquid-phase fugacity coefficient required for

computations of various phase equilibria involving CO2expanded liquids. Therefore, a liquid-phase molar volume is
one of the important thermodynamic properties of the CO2expanded liquids.
Several cubic equations of state (EOSs), like Peng-Robinson
(PR), Soave-Redlich-Kwong (SRK), Patel-Teja (PT), PengRobinson-Stryjek-Vera (PRSV), etc., are now available for
the calculation of liquid molar volumes, VL. However, the EOS

10.1021/ie070814p CCC: $37.00 2007 American Chemical Society

Published on Web 10/30/2007

Ind. Eng. Chem. Res., Vol. 46, No. 24, 2007 8283

Figure 1. Calculated molar volumes of CO2-expanded acetone solutions

at 303 K using different CEOSs.

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

Table 2. CEOS Parameters for Calculation of Liquid Molar

Volumes of CO2-Solvent Systems
PRSV
system

k1

VTPR
k2

k31

k32

N1

N2

CO2-acetone 0.042 85 -0.003 0 0.289 96 0.056 48 0.113 33 0.144 57

CO2-toluene 0.042 85 0.031 9 0.289 96 0.287 40 0.113 33 0.168 98
CO2-DCM 0.042 85 -0.055 6 0.289 96 0.108 12 0.113 33 0.252 64

method involves complicated and time-consuming computations

in order to obtain the roots for a cubic equation, and the values
of VL calculated by most of these EOSs are found to deviate
from the corresponding experimental data. Moreover, these
EOSs generally require two or more interaction parameters,
which are regressed from the experimental data, in addition to
the critical constants. Therefore, the objective of the present
work involves development of a simple, easy-to-use, reliable
generalized method using limited information for accurate
prediction of the liquid molar volumes of CO2-expanded solvents
over a wide range of pressures and temperatures.

cubic EOSs, like PR,6 SRK,7 PT,8 PRSV,9 and volume-translated

Peng-Robinson equation of state (VTPR EOS).10,11 Table 1
presents the %AARD in the calculated VL for these three binary
systems, and Table 2 lists some characteristic parameters of
PRSV and VTPR EOS taken from the literature and used in
the present work. Figure compares the variations of VL for the
CO2-acetone system with CO2 mole fraction at 303 K predicted
using different EOSs and their deviations from the corresponding
experimental data.12 It can be noted that all EOSs consistently
predict higher molar volumes at all CO2 mole fractions, except
the SRK EOS, for which the deviation is large at either high or
low CO2 mole fractions. These high deviations in the computed
values of VL by the EOS method may be due to the inability of
an EOS to take into account the CO2-solvent interactions.
Accordingly, the new generalized method aims to correct for
this discrepancy of VL to achieve better agreement with
experimental data at all CO2 mole fractions.
2.2. Present Generalized Method. A new generalized
correlation has been developed in this work for the liquid molar
volumes of CO2-expanded solvents, by correlating the compressibility factor ZL in terms of pseudo-reduced pressure Pr as

ZL ) APrB

where ZL ) PVL/RT and Pr ) P/(Pc,1x1 + Pc,2x2).

The two system-specific constants A and B in the generalized
correlation are regressed from the experimental data of liquid
molar volumes, VL, of binary CO2-solvent mixtures of different
CO2 mole fractions at all temperatures. These constants are
independent of temperature but dependent on acentric factor
2.
In order to make the above method predictive, the two
constants A and B are correlated in terms of acentric factor 2
as

A ) A12A2 and B ) B12B2

2. Computation of Liquid Molar Volumes

2.1. EOS Method. In order to ascertain the accuracy of the
EOS method, VL for three CO2-expanded solvent systems,
namely, (i) CO2-acetone, (ii) CO2-toluene, and (iii) CO2dichloromethane (DCM), have been calculated using different

(1)

(2)

Thus, the liquid molar volumes for CO2-expanded liquids can

be predicted just by using the acentric factor and the critical
pressures of the solvent and CO2 as compared to other EOSs
that require two or more parameters (as detailed in Table 3).

Figure 2. ZL vs Pr for (a) CO2-DCM, (b) CO2-ethanol, and (c) CO2-acetone systems.

8284

Ind. Eng. Chem. Res., Vol. 46, No. 24, 2007

Table 3. Details of Different CEOSs

EOS

requirements
1. pure-component properties such as Pc, Tc,
2. mixing rules
3. interaction parameters (for mixing rules) such as
kij and lij that are regressed from experimental data

Peng-Robinson EOS
P ) RT/(V - b) - a(T)/V(V + b) + b(V - b)
ac ) 0.45724R2Tc2/Pc
b ) 0.0778RTc/Pc
a(T) ) acR(T, )
xR(Tr,) ) 1 + [ki(1 - Tr,i0.5)]
) 0.37464 + 1.54226 - 0.269922

4. solving a cubic equation for molar volume

1. pure-component properties such as Pc, Tc,
2. mixing rules
3. interaction parameters (for mixing rules) such as
kij and lij that are regressed from experimental data

Peng-Robinson-Stryjek-Vera EOS
P ) RT/(V - b) - a(T)/V(V + b) + b(V - b)
ac ) 0.45724R2Tc2/Pc
b ) 0.0778RTc/Pc
a(T) ) acR(T, )
xR(Tr,) ) 1 + [ki(1 - Tr,i0.5)]

4. 1 is a constant specific for each pure component and

is regressed from low-temperature saturation pressures

) 0 + 1(1 + Tr
- Tr)
0 ) 0.378893 + 1.4897153 - 0.171318482 + 0.0196553

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

0.5)(0.7

5. solving a cubic equation for molar volume

1. pure-component properties such as Pc, Tc,
2. mixing rules
3. interaction parameters (for mixing rules) such as
kij and lij that are regressed from experimental data

Patel-Teja EOS
P ) RT/(V - b) - a(T)/V(V + b) + c(V - b)
a ) a(R2Tc2/Pc)R(T)
b ) b(RTc/Pc)
c ) c(RTc/Pc)
xR(Tr,) ) 1 + [ki(1 - Tr,i0.5)]

4. solving two cubic equations, one for molar volume and

one for b

) 0.452413 + 1.30982 - 0.2959372

c ) 1 - c
c ) 0.329032 - 0.076799 + 0.02119472
a ) 3c2 + 3(1 - 2c)b + b2 + 1 - 3c
b3 + (2 - 3c)b2 + 3c2b - c3 ) 0

1. pure-component properties such as Pc, Tc,

2. mixing rules
3. interaction parameters (for mixing rules) such as
kij and lij that are regressed from experimental data

Soave-Redlich-Kwong EOS
P ) RT/(V - b) - a(T)/V(V + b)
ac ) 0.42747R2Tc2/Pc
b ) 0.08664RTc/Pc
a(T) ) acR(T, )
xR(Tr,) ) 1 + [ki(1 - Tr,i0.52)]
) 0.48 + 1.574 - 0.176

4. solving a cubic equation for molar volume

1. pure-component properties such as Pc, Tc,
2. mixing rules
3. interaction parameters (for mixing rules) such as
kij and lij that are regressed from experimental data

volume-translated Peng-Robinson EOS

P ) RT/(V + t - b) - a(T)/(V + t)(V + t + b) + b(V + t - b)
ac ) 0.45724R2Tc2/Pc
b ) 0.0778RTc/Pc
a(T) ) acR(T, )
R(T) ) [1 + M(1 - Tr) + N(1 - Tr)(0.7 - Tr)]2
M ) 0.20473 + 0.83548 - 0.184702 + 0.166753 - 0.098814
t ) RTc/Pc[k1 + k2(1 - Tr2/3) + k3(1 - Tr2/3)2]
k1 ) 0.00185 + 0.00438 + 0.363222 - 0.908313 + 0.558854
k2 ) -0.00542 - 0.51112k3 + 0.04533k32 + 0.07447k33 - 0.03831k34

4. k3 and N, the pure-component parameters, which are

fitted to saturated liquid density and vapor pressure
data up to a reduced temperature of Tr ) 0.8
5. Solving a cubic equation for molar volume

Table 4. Constants A and B and the %AARD in Estimated Liquid Molar Volumes of CO2-Solvent Systems
system

type

Pc2, bar

P, bar

T, K

Nd

%AARD

CO2-acetone
CO2-cyclohexanone
CO2-THF
CO2-DMSO
CO2-ethyl acetate
CO2-DMF
CO2-NMP
CO2-toluene
CO2-DCM
CO2-MNB
CO2-ENB
CO2-DFP
CO2-1,4-dioxane
CO2-methanol
CO2-ethanol
CO2-2-propanol
CO2-TFE

NP-PA
NP-PA
NP-PA
NP-PA
NP-PA
NP-PA
NP-PA
NP-NP
NP-NP
NP-NP
NP-NP
NP-NP
NP-NP
NP-PP
NP-PP
NP-PP
NP-PP

47.0
39.0
51.9
57.05
38.3
50.9
47.8
41.1
63.0
22.28
20.07
22.88
52.1
80.9
61.4
47.0
48.7

0.309
0.443
0.225
0.350
0.363
0.312
0.358
0.265
0.190
0.380
0.443
0.547
0.281
0.566
0.643
0.670
0.634

8-71
14-78
6-96
4-66
5-67
7-79
7-78
10-75
19-70
18-72
7-64
15-64
5-72
8-80
10-80
7-76
11-78

298-318
290-310
298-333
298-303
298-313
290-313
313
290-310
308-328
298-308
298
298
298-313
298-313
298-313
313
298-313

60
40
26
37
40
80
11
42
25
46
25
13
12
66
50
18
21

0.1501
0.1548
0.1556
0.1484
0.1600
0.1471
0.1606
0.1709
0.1576
0.1871
0.1868
0.1826
0.1500
0.1648
0.1454
0.1519
0.1389

1.0253
0.8931
1.001
0.9585
0.9974
0.9481
0.9488
0.932
1.0070
1.1613
0.9719
0.8948
0.9119
1.0406
1.0098
1.0343
1.0412

1.16
1.78
2.61
1.84
1.13
1.00
3.57
2.49
1.45
1.59
2.27
3.59
2.07
2.06
1.85
1.60
5.92

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

Ind. Eng. Chem. Res., Vol. 46, No. 24, 2007 8285

Figure 3. Comparison of experimental ([) molar volumes of CO2-expanded solvents, using (i) A and B (s), (ii) predicted A and B (), and (iii) PR EOS
(---) for (a) CO2-DCM at 328.2 K, (b) CO2-cyclohexanone at 310.1 K, and (c) CO2-ethanol at 303.1 K.

3. Results and Discussions

The generalized correlation has been validated for 17 CO2expanded solvent systems at temperatures in the range of 290.8333.2 K and at pressures in the range of 4-90 bar at different
CO2 mole fractions by taking experimental data of VL for CO2expanded organic solvents from the literature.12-20 The critical
pressures and acentric factors are listed in Table 4. Figure 2
present the behavior of ZL vs Pr for three representative systems
of CO2-DCM (nonpolar-nonpolar), CO2-cyclohexanone (nonpolar-polar aprotic), and CO2-ethanol (nonpolar-polar protic).
It can be observed that the plot of ZL vs Pr appears to be a
nearly straight line for all systems and that the ZL values
calculated at different temperatures for a particular system lie
on the same line. Thus, it is inferred that ZL is independent of
temperature. That is, ZL is only a function of pressure for a
particular CO2-solvent system. All other systems studied in
this work show the same behavior. The constants A and B in
eq 1, which have been regressed separately for each system for
all temperatures, are presented in Table 4. The generalized
correlation has been validated by computing the values of VL
for all 17 CO2-solvent systems at all compositions, using these
values of A and B, and their %AARD are presented in Table 4.
It can be seen from Figure 3 that VL calculated by this
generalized correlation are in very good agreement with the
experimental data and are even better than that predicted by
the original PR EOS.
It can also be seen that the present generalized method does
not require any binary interaction constants and critical temperatures of the pure components, nor does it require any
complicated computations. This method only requires pressure
and CO2 mole fraction as the input information in addition to
the critical pressures, and it subsequently calculates VL from ZL
at the required temperature (which should be less than or equal
to the saturation temperature at the given pressure). It is
interesting to note that, though A and B are independent of
temperature for all systems, the generalized correlation is able
to correctly estimate the temperature dependency of liquid molar
volumes.
For the predictive method, the CO2-expanded solvent systems
have been classified into three different groups depending on

Table 5. Constants for Predicting A and B in Terms of 2 for

CO2-Solvent Systems
system

A1

A2

B1

B2

NP-NP
NP-PA
NP-PP

0.2126
0.1522
0.1229

0.193
-0.0089
-0.4328

0.953
0.8168
1.0101

-0.0216
-0.1563
-0.0453

Table 6. %AARD in the Liquid Molar Volumes of CO2-Solvent

Systems at 290.8-333.2 K and 4-90 bar by Using (i) A and B, (ii) A
and B Predicted by 2, and (iii) PR EOS
%AARD
system

Nd

A&B

predicted
A&B

PR-EOS

CO2-acetone
CO2-cyclohexanone
CO2-DMF
CO2-DMSO
CO2-THF
CO2-ethyl acetate
CO2-NMP
CO2-ethanol
CO2-methanol
CO2-2-propanol
CO2-TFE
CO2-DCM
CO2-toluene
CO2-1,4-dioxane
CO2-MNB
CO2-ENB
CO2-DFP
total data points
avg. %AARD

60
40
80
37
26
40
10
50
65
8
21
25
42
46
21
13
12
596

1.16
1.78
1.00
1.84
2.61
1.13
3.57
1.85
2.06
1.60
5.92
1.45
2.49
2.07
1.59
2.27
3.59

5.70
2.81
4.46
3.24
3.90
2.32
5.31
2.28
3.67
5.59
6.98
1.77
4.26
5.88
4.92
4.18
2.85

6.95
4.96
5.08
0.71
3.19
3.97
7.82
4.51
11.89
4.17
6.23
5.21
2.78
2.45
17.11
12.68
5.47

2.61

4.12

6.19

the nature of the organic solvent. Accordingly, the constants A

and B have been correlated in terms of 2, separately for each
class of the commonly occurring solvents, such as polar protic
(PP), polar aprotic (PA), and nonpolar (NP) involved in all 17
systems. The dependencies of constants A1, A2, B1, and B2 on
2 (as per eq 2) are presented in Table 5 for these three groups
of CO2-expanded solvents. The %AARD of the predicted values
of VL using 2 for all 17 CO2-solvent systems are reported in
Table 6. The agreements of the experimental data with the
corresponding predicted values are exemplary as the lowest is
1.77% (for CO2DCM, Figure 3a) and the highest % AARD is
6.98% (for CO2TFE, Figure 4). It is gratifying to note that the

8286

Ind. Eng. Chem. Res., Vol. 46, No. 24, 2007

P ) pressure (bar)
T ) temperature (K)
x ) liquid-phase mole fraction
Z ) compressibility factor
Subscripts
r ) related to reduced parameter
cal ) calculated data
exp ) experimental data
1 ) related to CO2
2 ) related to solvent

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

Figure 4. Comparison of experimental ([) molar volumes of CO2expanded solvents, using (i) using A and B (s), (ii) predicted A and B (),
and (iii) PR EOS (---) for CO2-TFE at 313 K.

average %AARD in the values of VL calculated for all 17

systems by using (i) A and B and (ii) predicted A and B is 2.61%
and 4.21%, respectively, whereas by using (iii) PR EOS,
%AARD is 6.19%. It can be seen from Figure 3 that VL
calculated by a predictive method for solvents (ethanol as polar
protic, cyclohexanone as polar aprotic, and DCM as nonpolar)
from each of the three classes are in a very good agreement
with the experimental data and are even better than that by the
original PR EOS. It is thus established that the predicted values
of VL are in very good agreement with the corresponding
experimental data of all three groups of CO2-expanded solvent
systems. However, it can be noted that %AARD for CO2-TFE
is 6.98. The predictions of the ZL(Pr)-correlation of molar
volumes above x1 > 0.8 deviate significantly from the experimental data (as shown in Figure 4) because of the high
compressibility of CO2. This requires additional pressure
corrections to improve the correlation further for mixtures with
x1 > 0.8 for a few systems and will be considered separately.
4. Conclusions
The liquid molar volumes VL of the CO2-expanded solvents
calculated by most cubic EOSs are found to be consistently
higher than the corresponding experimental data, despite the
fact that the EOS method involves time-consuming complicated computations. It is gratifying to note that the new
generalized method proposed in this work predicts more
accurate values of VL of CO2-solvent binary systems, though
the method is very easy-to-use, temperature-invariant, and does
not require the knowledge of the interaction constants and
critical temperatures. The dependency of the constants in the
generalized correlation on 2 has been established separately
for different classes of solvents, such as polar protic (PP), polar
aprotic (PA), and nonpolar (NP). The method has been validated
by predicting VL of CO2-expanded solvents from the knowledge
of critical pressure and 2, in very good agreement with the
corresponding experimental data of all three groups of CO2expanded solvent systems, with the %AARD varying in the
range of 1.8-7.0% for 17 systems. In the absence of binary
interaction constants and the critical temperature of the
solvent, as required by the EOS method, the present generalized
method provides a reliable alternative and accurate method for
prediction of liquid molar volumes of the CO2-expanded solvent
systems.
Nomenclature
A, B ) constants in ZL (Pr) correlation
Nd ) number of data points

AbbreViations
AARD ) absolute average relative deviation defined as |(VLcal
- VLexp)/VLexp|/Nd
CEOS ) cubic equation of state
DCM ) dichloromethane
DELOS ) depressurization of expanded-liquid organic solutions
DFP ) 1,1,1,2,3,4,4,5,5,5-decafluoropentane
DMF ) N,N-dimethylformamide
DMSO ) dimethylsulfoxide
ENB ) ethoxynonafluorobutane
MNB ) methoxynonafluorobutane
NMP ) N-methylpyrrolidone
NP ) nonpolar
PA ) polar aprotic
PP ) polar protic
PPRGEL ) precipitation by pressure reduction of gas-expanded
liquids
PR EOS ) Peng-Robinsn equation of state
PRSV EOS ) Peng-Robinson-Stryjek-Vera equation of state
PT EOS ) Patel-Teja equation of state
SRK EOS ) Soave-Redlich-Kwong equation of state
THF ) tetrahydrofuran
TFE ) triflouroethanol
VTPR EOS ) volume-translated Peng-Robinson equation of
state
Literature Cited
(1) Mukhopadhyay, M.; Dalvi, S. Mass and heat transfer analysis of
SAS: Effects of thermodynamic states and flow rates on droplet size. J.
Supercrit. Fluids 2004, 30 (3), 333.
(2) Badilla, J.; Peters, C.; Swaan Arons, J. Volume expansion in relation
to the gas-antisolvent process. J. Supercrit. Fluids 2000, 17, 13.
(3) Ventosa, N.; Sala, S.; Veciana, J. DELOS Process: a crystallization
technique using compressed fluids: 1. Comparison to GAS crystallization
method. J. Supercrit. Fluids 2003, 26, 33.
(4) Mukhopadhyay, M.; Dalvi, S. A. Novel Method for Production of
Nanoparticles using Subcritical Carbon Dioxide. Indian Patent No. 544/
MUM/2004.
(5) Mukhopadhyay, M. Reduction of Partial Molar Volume of Solvent
For Solute Crystallization Using Carbon Dioxide as Antisolvent. J.
Supercritic. Fluids 2003, 25 (3), 213.
(6) Peng, D.; Robinson, D. A. New Two-constant Equation of State.
Ind. Eng. Chem. Fundam. 1976, 15, 59.
(7) Soave, G. Equilibrium Constants from a Modified Redlich-Kwong
Equation of State. Chem. Eng. Sci. 1972, 27, 1197.
(8) Patel N.; Teja, A. A. New Cubic Equation of State for Fluids and
Fluid Mixtures. Chem. Eng. Sci. 1982, 37 (3), 463.
(9) Ghosh, P.; Tarapdhar, T. Prediction of vapor-liquid equilibria using
PRSV equation of state and Wong-Sandler mixing rules. Chem. Eng. J.
1998, 70, 15.
(10) Ahlers, J.; Gmehling, J. Development of an universal group
contribution euation of state. I. Prediction of liquid densities for pure
compounds with a volume translated Peng-Robinson equation of state.
Fluid Phase Equilib. 2001, 191, 177.

Ind. Eng. Chem. Res., Vol. 46, No. 24, 2007 8287

Downloaded by CAPES ADMIN ACCOUNT on September 3, 2015 | http://pubs.acs.org

Publication Date (Web): October 30, 2007 | doi: 10.1021/ie070814p

(11) Tsai, J.; Chen, Y. Application of volume-translated Peng-Robinson

equation of state on vapor-liquid equilibrium calculations. Fluid Phase
Equilib. 1998, 145, 193.
(12) Chang, C.; Day, C.; Ko, C; Chiu, K. Densities and P-x-y diagrams
for carbon dioxide dissolution in methanol, ethanol and acetone mixtures.
Fluid Phase Equilib. 1997,131, 243.
(13) de la Fuente Badilla, J.; Peters, C.; de Swaan Arons, J. Volume
expansion in relation to the gas-antisolvent process. J. Supercrit. Fluids
2000, 17 (1), 13.
(14) Kordikowsk, A.; Schenk, A.; Nielen, R.; Peters, C. Volume
Expansions and V-L E of Binary Mixtures of a Variety of Polar
Solvents and Certain Near Critical Solvents. J. Supercrit. Fluids 1995, 8
(3), 205.
(15) Rajasingam, R.; Lioe, L.; Tuan Pham, Q.; Lucien, F. Solubility of
carbon dioxide in dimethyl sulfoxide and N-methyl-2-pyrrolidone at elevated
pressure. J. Supercrit. Fluids 2004, 31 (3), 227.
(16) Chang, C.; Chen, C. Solubilities of Carbon Dioxide and Nitrous
Oxide in Cyclohexanone, Toluene, and N,N-Dimethylformamide at Elevated
Pressures. J. Chem. Eng. Data 1995, 40, 850.

(17) Yaginuma, R.; Nakajima, T.; Tanaka, H.; Kato, M. Densities of

Carbon Dioxide + 2-Propanol at 313.15 K and Pressures to 9.8 MPa. J.
Chem. Eng. Data 1997, 42 (4), 814.
(18) Kho, Y.; Conard, D.; Knutson, B. Phase equilibria and thermophysical properties of carbon dioxide-expanded flourinated solvents. Fluid
Phase Equilib. 2003, 206, 179.
(19) Lazzaroni, M.; Bush, D.; Brown, J.; Eckert, C. High-Pressure
Vapor-Liquid Equilbria of Some Carbon Dioxide + Organic Binary
Systems. J. Chem. Eng. Data 2005, 50 (1), 60.
(20) Tsivintzelis, I.; Missopolinou, D.; Kalogiannis, K.; Panayiotou, C.
Phase compositions and saturated densities for binary systems of carbon
dioxide with ethanol and dichloromethane. Fluid Phase Equilib. 2004, 224,
89.

ReceiVed for reView June 13, 2007

ReVised manuscript receiVed August 14, 2007
Accepted September 7, 2007
IE070814P