Article

pubs.acs.org/jced

Vapor−Liquid Equilibrium of Carbon Dioxide + Ethyl Acetate + Oleic

Acid Mixtures at High Pressures
Leandro Ferreira-Pinto,† Andreia Zanette,‡ Fernando Augusto Pedersen Voll,§ Vladimir Ferreira Cabral,∥
Marcelo Castier,⊥ and Lúcio Cardozo-Filho*,∥,#
†
Chemical Engineering Department, Federal University of Alagoas, Maceio, Alagoas 57072-970, Brazil
‡
Energy of Engineering, São Paulo State University, Campus of Rosana, Rosana, São Paulo 19274-000, Brazil
§
Chemical Engineering Department, Federal University of Parana, Curitiba, Paraná 81531-970, Brazil
∥
Chemical Engineering Program, State University of Maringa, Maringa, Paraná 87020-900, Brazil
⊥
Chemical Engineering Program, Texas A&M University at Qatar, Doha, 23874, Qatar
#
Agronomy Department, Centro Universitário da Fundaçaõ de Ensino Octávio Bastos, São João da Boa Vista, São Paulo 13874-149,
Brazil

ABSTRACT: In this work, experimental data for the phase transition of

ternary systems {CO2 (1) + ethyl acetate (2) + oleic acid (3)} at global
CO2 mole fraction values from 0.5 to 1, at the temperatures of 308, 318,
328, and 338 K are reported. A variable volume cell was used, following
the static synthetic method for pressures of up to 21 MPa. The ethyl
acetate/oleic acid molar ratio was set to 3:1 [0.750 ethyl acetate +
0.250 oleic acid], 9:1 [0.900 ethyl acetate + 0.100 oleic acid], and 199:1
[0.995 ethyl acetate + 0.005 oleic acid]. In all of these ternary systems,
bubble point and dew points were observed.

1. INTRODUCTION from a carboxylic acid and an oxidant. The generated peroxy

Extensive studies1−6 support the idea of using supercritical
carbon dioxide (scCO2) as a solvent for organic reactions and
polymerizations.7,8 In particular, scCO2 has gained prominence
in chemical and enzymatic chemistries because its thermody-
namic and transport properties can be readily tuned to emulate
liquid-like or gas-like behavior.9,10
The advantages of using carbon dioxide include the facts
that it is environmentally acceptable, nontoxic, inexpensive,
nonflammable, inert to oxidation, and easy to handle.11 As a
supercritical reaction medium, it presents excellent potential for
increasing reaction rates, improving selectivity, and facilitating
the separation of reagents, products, and catalysts.12 Accord-
ing to Beckman,11 the use of scCO2 as a reaction medium for
chemical syntheses and enzymatic reactions is desirable because
of the synergistic effects of the transport properties, density,
and polarity.
In this context, scCO2 can be used as a reaction medium
for the epoxidation reaction of vegetable oils to produce
plasticizers and lubricants from renewable sources. In the past
few years, the chemo-enzymatic method for the epoxidation of
vegetable oils has been applied by several authors.13−18 Such a
method is more environmentally friendly than the traditional
processes, which use a chemical route. The chemo-enzymatic
method is also more selective than the usual epoxidation
process. It uses lipases to catalyze the formation of peroxy acids
acids donate oxygen to the double bond in the olefinic
substrate, producing an epoxide and regenerating the carboxylic
acid.19,20 Organic solvents, such as ethyl acetate, can be used as
solvent in the epoxidation reactions.15 Most of the papers that
study the epoxidation of olefins using the chemo-enzymatic
method do not use scCO2 as a reaction medium. By partially
replacing the organic solvents by scCO2, it is possible to fit the
reaction medium properties in order to guarantee the solubility
of reactants and products in the supercritical medium and,
consequently, improve the selectivity and the reaction yield, as
McHugh and Krukonis21 state in their book. The replacement
of organic solvents by scCO2 also enhances the environmental
friendliness of the process.12,22−25 Therefore, the use of scCO2
as a reaction medium, besides the environmental benefits, can
encourage the research of alternative chemical pathways.22−24
However, the use of scCO2 as a reaction medium requires
knowledge of the phase diagram of reagents and products for
proper equipment design and pricing.3,26,27 The production of
epoxy stearic acid using the chemo-enzymatic method can be
Special Issue: Memorial Issue in Honor of Ken Marsh
Received: February 13, 2017
Accepted: July 12, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.7b00163

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

performed using oleic acid, ethyl acetate, lipase, and H2O2 nc nc ⎛ bi + bj ⎞

(oxidant). In this way, the objective of this work is to measure bm = ∑ ∑ xixj⎜ ⎟(1 − lij)
the vapor−liquid equilibrium data for ternary system CO2 (1) + i=1 j=1 ⎝ 2 ⎠ (5)
ethyl acetate (2) + oleic acid (3) in temperature range 308−
338 K, using the static synthetic method in a high-pressure 0.0778RTci
bi =
variable-volume cell. The global compositions used in the Pci (6)
experiments were similar to those employed in the chemo-
where ai and bi are the Peng−Robinson parameters for the pure
enzymatic method. In this paper, we only focus on the phase
component i, Tci is the critical temperature of component i, Pci
behavior of the reactants in scCO2. This kind of data presented
is critical pressure of component i, and ωi is the acentric factor of
here can help in choosing operation conditions for the enzy-
component i. The binary interaction parameters are symmetrical,
matic epoxidation reactions in scCO2 media.
that is, kij = kji and lij = lji. The fitted values of the kij and lij
2. EXPERIMENTAL SECTION parameters were obtained by minimizing the objective function:
no
2.1. Materials. Oleic acid (99 wt %) for synthesis was
purchased from Vetec (Brazil). Ethyl acetate (99.5 wt %) was
OF = ∑ (Poexp − Pocalc)2
o=1 (7)
purchased from Sigma-Aldrich. Carbon dioxide (99.9 wt % in
the liquid phase) was obtained from White Martins S.A. where no is the number of experimental observations, and Pexp
o
(Brazil). All substances were used without any pretreatment. Pcalc
o are the experimental and calculated pressures in experi-
Table 1 shows the suppliers and purities of the materials used mental observation o, respectively. These may be bubble point
in this work. pressures or dew point pressures, depending on the experimental
observation.
Table 1. Materials Used with Suppliers and Purities The procedure to minimize the objective function is the
same as that applied in a previous work of our group.32 Such a
materials suppliers purity/wt % CASRN procedure uses the “Solver” tool available in the Microsoft Excel
oleic acid Vetec 99 112-80-1 (2016 version) spreadsheet for Windows and the XSEOS33 Excel
ethyl acetate Sigma-Aldrich 99.5 141-78-6 add-in to fit the Peng−Robinson interaction parameters.
CO2 White Martins 99.9 (in the liquid phase) 124-38-9
4. RESULTS AND DISCUSSION
2.2. Apparatus and Experimental Procedure. The Tables 2−4 present the phase transition data measured in this
apparatus used in this work was a high-pressure variable- work for the systems CO2 + ethyl acetate + oleic acid at global
volume cell, following the static synthetic method. The meth-
odology and apparatus have been described in a previous Table 2. Phase Equilibrium VLE Data for the Temperature
work.3,27−29 Uncertainties in mole fractions were evaluated as (T), Pressure (p) with Standard Uncertainty u(p), and the
in the work of Rodriguez-Reartes et al.,30 and the value was Global Mole Fractions of CO2 and Ethyl Acetate (x1 and x2)
found to be close to 0.001 for carbon dioxide. The standard for the Ternary System {CO2 (1) + [0.750 Ethyl Acetate (2)
deviations in pressure were determined to be in the range + 0.250 Oleic Acid (3)]}
0.01−0.05 MPa based on three repetitions of each experimental x1b x2b p/MPa u(p)/MPa transitionc
point. The temperature controller was connected to a thermo- a
T/K = 308
couple (T type, accuracy of ±1.0 K), which was in direct
0.500 0.375 3.44 0.02 VLE (BP)
contact with the fluid mixture inside the equilibrium cell. The
0.600 0.300 4.00 0.03 VLE (BP)
desired temperature was controlled within 0.5 K. The phase
0.700 0.225 5.06 0.03 VLE (BP)
transitions (bubble point and dew point) were determined
0.800 0.150 5.20 0.02 VLE (BP)
visually, as described by McHugh and Krukonis.21
0.900 0.075 12.6 0.01 VLE (DP)
3. THERMODYNAMICS MODELING T/Ka = 318
0.500 0.375 3.24 0.01 VLE (BP)
The experimental VLE data were correlated using the Peng− 0.600 0.300 4.06 0.01 VLE (BP)
Robinson equations of state with quadratic mixing rules for 0.700 0.225 4.98 0.02 VLE (BP)
a and b parameters (see eqs 1−6).31 0.800 0.150 6.24 0.03 VLE (BP)
RT am 0.900 0.075 13.55 0.02 VLE (DP)
P= − 2
v − bm v − bm(bm − 2v) (1) T/Ka = 328
0.500 0.375 3.81 0.03 VLE (BP)
where 0.600 0.300 5.09 0.03 VLE (BP)
nc nc 0.700 0.225 6.17 0.02 VLE (BP)
am = ∑ ∑ aijxixj 0.800 0.150 7.49 0.01 VLE (BP)
i=1 j=1 (2) 0.900 0.075 15.25 0.02 VLE (DP)
T/Ka = 338
aij = (aiaj)0.5 (1 − kij) (3) 0.500 0.375 4.50 0.02 VLE (BP)
0.600 0.300 5.85 0.03 VLE (BP)
⎛ ⎛ ⎞⎞ 2
2
0.700 0.225 7.45 0.02 VLE (BP)
0.45724R2⎜1 + (0.37464 + 1.54226ωi − 0.26992ωi2)⎜1 − T
⎟⎟ Tci
⎝ ⎝ Tci ⎠⎠ 0.800 0.150 9.34 0.01 VLE (BP)
ai = 0.900 0.075 16.92 0.01 VLE (DP)
Pci
a
(4) u(T) = 0.5 K. bu(x) = 0.001. c(BP, bubble points/DP, dew points).

B DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 3. Phase Equilibrium VLE Data for the Temperature Table 4. Phase Equilibrium VLE Data for the Temperature
(T), Pressure (p) with Standard Uncertainty u(p), and the (T), Pressure (p) with Standard Uncertainty u(p), and the
Global Mole Fractions of CO2 and Ethyl Acetate (x1 and x2) Global Mole Fractions of CO2 and Ethyl Acetate (x1 and x2)
for the Ternary System {CO2 (1) + [0.900 Ethyl Acetate (2) + for the Ternary System {CO2 (1) + [0.995 Ethyl Acetate (2) +
0.100 Oleic Acid (3)]} 0.005 Oleic Acid (3)]}
x1b x2b p/MPa u(p)/MPa transitionc x1b x2b p/MPa u(p)/MPa transitionc
a a
T/K = 308 T/K = 308
0.500 0.450 3.34 0.01 VLE (BP) 0.500 0.498 3.45 0.02 VLE (BP)
0.600 0.360 4.45 0.03 VLE (BP) 0.600 0.398 4.03 0.03 VLE (BP)
0.700 0.270 4.62 0.01 VLE (BP) 0.700 0.299 4.70 0.01 VLE (BP)
0.800 0.180 5.55 0.03 VLE (BP) 0.800 0.199 5.88 0.02 VLE (BP)
0.850 0.135 6.14 0.01 VLE (BP) 0.850 0.149 5.83 0.01 VLE (DP)
0.900 0.090 6.48 0.02 VLE (BP) 0.900 0.100 6.56 0.01 VLE (DP)
0.950 0.045 13.37 0.01 VLE (BP) 0.950 0.050 7.00 0.01 VLE (DP)
T/Ka = 318 T/Ka = 318
0.500 0.450 4.02 0.02 VLE (BP) 0.500 0.498 3.81 0.01 VLE (BP)
0.600 0.360 4.52 0.03 VLE (BP) 0.600 0.398 4.87 0.03 VLE (BP)
0.700 0.270 5.59 0.02 VLE (BP) 0.700 0.299 5.59 0.02 VLE (BP)
0.800 0.180 6.81 0.01 VLE (BP) 0.800 0.199 6.58 0.02 VLE (BP)
0.850 0.135 7.27 0.01 VLE (BP) 0.850 0.149 7.01 0.01 VLE (DP)
0.900 0.090 8.83 0.02 VLE (BP) 0.900 0.100 7.62 0.01 VLE (DP)
0.950 0.045 15.66 0.03 VLE (BP) 0.950 0.050 8.20 0.02 VLE (DP)
T/Ka = 328 T/Ka = 328
0.500 0.450 4.25 0.03 VLE (BP) 0.500 0.498 4.43 0.01 VLE (BP)
0.600 0.360 5.31 0.03 VLE (BP) 0.600 0.398 5.34 0.01 VLE (BP)
0.700 0.270 6.58 0.01 VLE (BP) 0.700 0.299 6.47 0.01 VLE (BP)
0.800 0.180 7.87 0.02 VLE (BP) 0.800 0.199 7.53 0.02 VLE (BP)
0.850 0.135 8.61 0.01 VLE (BP) 0.850 0.149 8.13 0.01 VLE (DP)
0.900 0.090 11.33 0.01 VLE (DP) 0.900 0.100 9.03 0.03 VLE (DP)
0.950 0.045 18.28 0.01 VLE (DP) 0.950 0.050 9.47 0.01 VLE (DP)
T/Ka = 338 T/Ka = 338
0.500 0.450 4.93 0.01 VLE (BP) 0.500 0.498 4.96 0.01 VLE (BP)
0.600 0.360 6.28 0.04 VLE (BP) 0.600 0.398 6.12 0.02 VLE (BP)
0.700 0.270 7.62 0.03 VLE (BP) 0.700 0.299 7.41 0.01 VLE (BP)
0.800 0.180 9.19 0.02 VLE (BP) 0.800 0.199 8.67 0.02 VLE (BP)
0.850 0.135 10.14 0.01 VLE (DP) 0.850 0.149 9.42 0.02 VLE (DP)
0.900 0.090 13.75 0.01 VLE (DP) 0.900 0.100 10.15 0.01 VLE (DP)
0.950 0.045 21.35 0.01 VLE (DP) 0.950 0.050 10.68 0.01 VLE (DP)
a
u(T) = 0.5 K. bu(x) = 0.001. c(BP, bubble points/DP, dew points). a
u(T) = 0.5 K. bu(x) = 0.001. c(BP, bubble points/DP, dew points).

CO2 mole fraction values from 0.5 to 1, at the temperatures of

308, 318, 328, and 338 K. The ethyl acetate/oleic acid molar
ratio was set to 3:1 [0.750 ethyl acetate + 0.250 oleic acid], 9:1
[0.900 ethyl acetate + 0.100 oleic acid], or 199:1 [0.995 ethyl
acetate + 0.005 oleic acid]. The ethyl acetate/oleic acid mole
ratios and temperatures used here were the same used in a
previous work of the group.15 In that work, we performed the
chemo-enzymatic oleic acid epoxidation at atmospheric
pressure. For all of these ternary systems, we have found
bubble points and dew points. Tables 2−4 present the experi-
mental data in terms of global mole fraction of CO2, ethyl
acetate, phase transition pressure (p) value, with standard
uncertainty u(p) of replicated pressure measurements, and
transition type (BP, bubble point; DP, dew point).
For the 3:1 {CO2 (1) + [0.750 ethyl acetate (2) + 0.250 oleic
acid (3)]} mole ratio, most of the observed transitions were
bubble points (BP), but for CO2 fractions of 0.9, the experi- Figure 1. Pressure−composition diagram with data from this work and
ments have shown the occurrence of dew points (DP). For the from the literature. This work: ternary system {CO2 (1) + [0.995 ethyl
9:1 {CO2 (1) + [0.900 ethyl acetate (2) + 0.100 oleic acid (3)]} acetate (2) + 0.005 oleic acid (3)]} at T = 308 K (■), 318 K (●),
mole ratio, most of phase transitions were BP type. Only at 328 K (▲), and, 338 K (▼). Literature:25 binary system {CO2 (1) +
328 and 338 K did we observed DP transitions for CO2 mole ethyl acetate (2)})]} at T = 323 K (□), 333 K (☆), 343 K (dotted ◁),
fractions of 0.9 or higher in temperature of 328 K and for CO2 353 K (dotted ▷).

C DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Figure 2. Comparison of the pressure−composition diagrams of the
systems: {CO2 (1) + [0.750 ethyl acetate (2) + 0.250 oleic acid (3)]}
at T = 308 K (■); 338 K (□); {CO2 (1) + [0.900 ethyl acetate (2) +
0.100 oleic acid (3)]} at T = 308 K (●); 338 K (○); and {CO2 (1) +
[0.995 ethyl acetate (2) + 0.005 oleic acid (3)]} at T = 308 K (▲);
338 K (△).
Figure 4. Experimental and calculated bubble point pressures for the
ternary system {CO2 (1) + [0.900 ethyl acetate (2) + 0.100 oleic acid
(3)]} at T = 308 K (■); 318 K (●); 328 K (▲); 338 K (▼).
Calculations with the Peng−Robinson equation of state and
parameters from Table 5.

Figure 5. Experimental and calculated bubble point pressures for the

Figure 3. Experimental and calculated bubble point pressures for the ternary system {CO2 (1) + [0.995 ethyl acetate (2) + 0.005 oleic acid
ternary system {CO2 (1) + [0.750 ethyl acetate (2) + 0.250 oleic acid (3)]} at T = 308 K (■); 318 K (●); 328 K (▲); 338 K (▼).
(3)]} at T = 308 K (■); 318 K (●); 328 K (▲); 338 K (▼). Calculations with the Peng−Robinson equation of state and
Calculations with the Peng−Robinson equation of state and parameters from Table 5.
parameters from Table 5.
Table 5. Critical Temperature, Critical Pressure, Acentric
mole fractions of 0.85 or higher in temperature of 338 K. For Factor,30 and Binary Interaction Parameters Used in the
the 199:1 {CO2 (1) + [0.995 ethyl acetate (2) + 0.005 oleic Computations
acid (3)]} mole ratio, most of the observed phase transitions factors CO2 (1) ethyl acetate (2) oleic acid (3)
were bubble points but dew points were observed for CO2
critical temperature (K) 304.21 523.3 781
mole fractions of 0.85 or higher.
critical pressure (bar) 73.83 38.8 13.9
Figure 1 shows a comparison between the experimental data
acentric fator 0.22362 0.36641 1.182
of the ternary system {CO2 (1) + [0.995 ethyl acetate (2) +
binary interaction kij 0 0.02289 0.02194
0.005 oleic acid (3)]} obtained in this work with the binary
0.02289 0 −0.01269
system {CO2 (1) + ethyl acetate (2)} reported in the work of
0.02194 −0.01269 0
Sima et al.34 There is a good agreement between the experi-
Binary interaction lij 0 0.02601 0.02190
mental data obtained here and the literature data. The chosen
0.02601 0 −0.06201
system is very diluted on oleic acid. In this way, its behavior
0.02190 −0.06201 0
must converge to the behavior of the binary system {CO2 (1) +
ethyl acetate (2)}. Such a fact is verified in Figure 2, validating
the experimental data obtained in this work. ratio, the relative amount of oleic acid is very small and the
The phase diagrams (Figures 2−5) show that the phase phase transition pressures are similar to those of the binary
transition pressures increase as the system temperatures system carbon dioxide + ethyl acetate. However, as the con-
increase, for every ethyl acetate/oleic acid molar ratio studied centrations of oleic acid increase, the phase transition pressures
in this work. For the 199:1 ethyl acetate/oleic acid molar decrease.
D DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figures 3−5 compare experimental and calculated VLE
values for systems formed by CO2 + ethyl acetate + oleic acid,
showing that the thermodynamic modeling can represent the
experimental results fairly well. Although the studied systems
have nonhydrocarbons (especially polar and associating fluids)
and long chain molecules, which characterize asymmetric
systems, the Peng−Robinson equation can represent the
experimental data satisfactorily.
Table 5 shows the pure-component35 properties used and
the binary interaction parameters fitted in this work.
5. CONCLUSIONS
We presented new experimental data of vapor−liquid transition
of ternary systems {CO2 (1) + ethyl acetate (2) + oleic acid
(3)} at the temperatures of 308, 318, 328, and 338 K. In the
studied systems, the phase transition pressures increase with the
increase in temperature and with the decrease of oleic acid
concentration. The Peng−Robinson equation of state repre-
sents this highly asymmetric system well. The data measured in
this work are useful for the proper design of processes that use
the chemo-enzymatic or the chemical method for the
epoxidation of vegetable oils.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +55 44 30114749. E-mail: lucio.cardozo@gmail.com.
ORCID
Lúcio Cardozo-Filho: 0000-0002-1764-9979
Funding
We thank the following Brazilian agencies for financial support:
CAPES (Ministry of Education) and CNPq (National Council
for Scientific and Technological Development).
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Carrara, V. D. S.; Serra, L. Z.; Cardozo-Filho, L.; Cunha, E. F.;
Torres-Santos, E. C.; Cortez, D. A. G. HPLC Analysis of Supercritical
Carbon Dioxide and Compressed Propane Extracts from Piper
Amalago L. with Antileishmanial Activity. Molecules 2012, 17, 15−33.
(2) Favareto, R.; Pereira, J. R. D.; Santana, C. C.; Madureira, E. H.;
Cabral, V. F.; Tavares, F. W.; Cardozo-Filho, L. High-Pressure Phase
Diagram of the Drug Mitotane in Compressed And/or Supercritical
CO2. J. Chem. Thermodyn. 2010, 42, 286−290.
(3) Pinto, L. F.; Rodriguez-Reartes, S. B.; Corazza, M. L.; Cabral, V.
F.; de Araújo, P. H. H.; Madureira, E. H.; Zabaloy, M. S.; Cardozo-
Filho, L. Phase Behavior of Carbon Dioxide+medroxyprogesterone
Acetate System at High Pressures. Fluid Phase Equilib. 2013, 349, 1−
11.
(4) Santos, J. C.; Mazzer, H. R.; Machado, G. D.; Andreaus, J.;
Cabral, V. F.; Zabaloy, M. S.; Cardozo-filho, L. High-Pressure Phase
Behaviour of the System (CO 2 + C. I. Disperse Orange 30 Dye). J.
Chem. Thermodyn. 2012, 48, 284−290.
(5) Lemos, C. O. T.; Garcia, V. A. D. S.; Gonçalves, R. M.; Leal, I. C.
R.; Siqueira, V. L. D.; Filho, L. C.; Cabral, V. F. Supercritical Extraction
of Neolignans from Piper Regnelli Var. Pallescens. J. Supercrit. Fluids
2012, 71, 64−70.
(6) Garcia, V. A. D. S.; Cabral, V. F.; Zanoelo, É. F.; da Silva, C.;
Filho, L. C. Extraction of Mucuna Seed Oil Using Supercritical Carbon
Dioxide to Increase the Concentration of L-Dopa in the Defatted
Meal. J. Supercrit. Fluids 2012, 69, 75−81.
(7) Giufrida, W. M.; Voll, F. A.; Feihrmann, A. C.; Kunita, M. H.;
Madureira, E. H.; Guilherme, M. R.; Vedoy, D. R. L.; Cabral, V. F.;
Cardozo-Filho, L. Production of Microparticles of PHBV Polymer
E DOI: 10.1021/acs.jced.7b00163
Article
Impregnated with Progesterone by Supercritical Fluid Technology.
Can. J. Chem. Eng. 2016, 94, 1336−1341.
(8) Giufrida, W. M.; Cabral, V. F.; Cardoso-Filho, L.; dos Santos
Conti, D.; de Campos, V. E. B.; da Rocha, S. R. P. Medroxyprogester-
one-Encapsulated poly(3-Hydroxybutirate-Co-3-Hydroxyvalerate)
Nanoparticles Using Supercritical Fluid Extraction of Emulsions. J.
Supercrit. Fluids 2016, 118, 79−88.
(9) Hintermair, U.; Leitner, W.; Jessop, P. Expanded Liquid Phases in
Catalysis: Gas-Expanded Liquids and Liquid-Supercritical Fluid
Biphasic Systems. In Handbook of Green Chemistry; Wiley-VCH
Verlag GmbH & Co. KGaA: Weinheim, 2010.
(10) Magee, C.; Earla, A.; Petraitis, J.; Higa, C.; Braslau, R.;
Zetterlund, P. B.; Aldabbagh, F. Synthesis of Fluorinated Alkoxyamines
and Alkoxyamine-Initiated Nitroxide-Mediated Precipitation Polymer-
izations of Styrene in Supercritical Carbon Dioxide. Polym. Chem.
2014, 5, 5725−5733.
(11) Beckman, E. J. Supercritical and near-Critical CO2 in Green
Chemical Synthesis and Processing. J. Supercrit. Fluids 2004, 28, 121−
191.
(12) Oakes, R. S.; Clifford, A. A.; Rayner, C. M. The Use of
Supercritical Fluids in Synthetic Organic Chemistry. J. Chem. Soc.
Perkin Trans. 1 2001, 9, 917−941.
(13) Méndez-Sánchez, D.; Ríos-Lombardía, N.; Gotor, V.; Gotor-
Fernández, V. Chemoenzymatic Epoxidation of Alkenes Based on
Peracid Formation by a Rhizomucor Miehei Lipase-Catalyzed
Perhydrolysis Reaction. Tetrahedron 2014, 70, 1144−1148.
(14) Corrêa, F. A.; Sutili, F. K.; Miranda, L. S. M.; Leite, S. G. F.;
Souza, R. O. M. A.; Leal, I. C. R. Epoxidation of Oleic Acid Catalyzed
by PSCI-Amano Lipase Optimized by Experimental Design. J. Mol.
Catal. B: Enzym. 2012, 81, 7−11.
(15) Zanette, A. F.; Zampakidi, I.; Sotiroudis, G. T.; Zoumpanioti,
M.; Leal, I. C. R.; de Souza, R. O. M. A.; Cardozo-Filho, L.; Xenakis, A.
Chemo-enzymatic epoxidation catalyzed by C. antarctica lipaseimmo-
bilized in microemulsion-based organogels. J. Mol. Catal. B: Enzym.
2014, 107, 89−94.
(16) Sun, S.; Yang, G.; Bi, Y.; Liang, H. Enzymatic Epoxidation of
Corn Oil by Perstearic Acid. J. Am. Oil Chem. Soc. 2011, 88, 1567−
1571.
(17) Sun, S.; Ke, X.; Cui, L.; Yang, G.; Bi, Y.; Song, F.; Xu, X.
Enzymatic Epoxidation of Sapindus Mukorossi Seed Oil by Perstearic
Acid Optimized Using Response Surface Methodology. Ind. Crops
Prod. 2011, 33, 676−682.
(18) Mushtaq, M.; Tan, I. M.; Nadeem, M.; Devi, C.; Lee, S. Y. C.;
Sagir, M.; Rashid, U. Epoxidation of Methyl Esters Derived from
Jatropha Oil: An Optimization Study. Grasas Aceites 2013, 64, 103−
114.
(19) Orellana-Coca, C.; Billakanti, J.; Mattiasson, B.; Hatti-Kaul, R.
Lipase Mediated Simultaneous Esterification and Epoxidation of Oleic
Acid for the Production of Alkylepoxystearates. J. Mol. Catal. B:
Enzym. 2007, 44, 133−137.
(20) Piazza, G. J.; Nunez, A.; Foglia, T. A. Epoxidation of Fatty Acids,
Fatty Methyl Esters, and Alkenes by Immobilized Oat Seed
Peroxygenase. J. Mol. Catal. B: Enzym. 2003, 21, 143−151.
(21) McHugh, M.; Krukonis, V. Supercritical Fluid Extraction;
Butterworth-Heinemann: Stoneham, 1994.
(22) Hyatt, J. A. Liquid and Supercritical Carbon Dioxide as Organic
Solvents. J. Org. Chem. 1984, 49, 5097−5101.
(23) Pollet, P.; Davey, E. A.; Ureña-Benavides, E. E.; Eckert, C. A.;
Liotta, C. L. Solvents for Sustainable Chemical Processes. Green Chem.
2014, 16, 1034−1055.
(24) Wimmer, Z.; Zarevúcka, M. A Review on the Effects of
Supercritical Carbon Dioxide on Enzyme Activity. Int. J. Mol. Sci. 2010,
11, 233−253.
(25) Alper, E.; Yuksel Orhan, O. CO2 Utilization: Developments in
Conversion Processes. Petroleum 2017, 3, 109−126.
(26) Giufrida, W. M.; Rodriguez-Reartes, S. B.; Alonso, C. G.;
Zabaloy, M. S.; Cabral, V. F.; Tavares, F. W.; Cardozo-Filho, L. High-
Pressure Experimental Data of CO 2 + Mitotane and CO 2 + Ethanol
+ Mitotane Mixtures. J. Chem. Eng. Data 2011, 56, 4333−4341.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

(27) Ferreira, M. O.; Ferreira-Pinto, L.; Souza, E. M. B. D.; Castier,

M.; Voll, F. A. P.; Cabral, V. F.; Cardozo-Filho, L. Experimental
Vapor−Liquid Equilibria for the Systems {2-Ethyl-1-Hexanol +
Glycerol + CO 2 } and {2-Methyl-2-Propanol + Glycerol + CO 2 }.
J. Chem. Eng. Data 2013, 58, 2506−2512.
(28) Giufrida, W. M.; Pinto, L. F.; Zanette, A. F.; Voll, F. A. P.;
Kunita, M. H.; Cabral, V. F.; Cardozo-Filho, L. Liquid−vapor
Equilibrium Data of CO2+dichloromethane+medroxyprogesterone
System. Fluid Phase Equilib. 2014, 362, 307−312.
(29) Zanette, A. F.; Ferreira-Pinto, L.; Giufrida, W. M.; Zuber, A.;
Feirhmann, A. C.; Castier, M.; Cardozo-Filho, L.; Cabral, V. F. Vapor−
Liquid Equilibrium Data for Carbon Dioxide + (R, S)-1,2-
Isopropylidene Glycerol (Solketal) + Oleic Acid Systems at High
Pressure. J. Chem. Eng. Data 2014, 59, 1494−1498.
(30) Rodriguez-Reartes, S. B.; Cismondi, M.; Franceschi, E.; Corazza,
M. L.; Oliveira, J. V.; Zabaloy, M. S. High-Pressure Phase Equilibria of
Systems Carbon Dioxide + N-Eicosane and Propane + N-Eicosane. J.
Supercrit. Fluids 2009, 50, 193−202.
(31) Peng, D.-Y.; Robinson, D. B. A New Two-Constant Equation of
State. Ind. Eng. Chem. Fundam. 1976, 15, 59−64.
(32) Ferreira, M. O.; Ferreira-Pinto, L.; Souza, E. M. B. D.; Castier,
M.; Voll, F. A. P.; Cabral, V. F.; Cardozo-Filho, L. Experimental
Vapor−Liquid Equilibria for the Systems {2-Ethyl-1-hexanol +
Glycerol + CO2} and {2-Methyl-2-propanol + Glycerol + CO2}. J.
Chem. Eng. Data 2013, 58, 2506−2512.
(33) Castier, M. An Open Software for Chemical Engineering
Thermodynamics. Chem. Eng. Educ. 2008, 42, 74−81.
(34) Sima, S.; Feroiu, V.; Geană, D. New High Pressure Vapor−
liquid Equilibrium Data and Density Predictions for Carbon Dioxide
+ethyl Acetate System. Fluid Phase Equilib. 2012, 325, 45−52.
(35) DIPPR 801, Evaluated Process Design Data; American Institute of
Chemical Engineers: Provo, UT, 2003.

F DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX