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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).
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 Figure 4. Experimental and calculated bubble point pressures for the
systems: {CO2 (1) + [0.750 ethyl acetate (2) + 0.250 oleic acid (3)]} ternary system {CO2 (1) + [0.900 ethyl acetate (2) + 0.100 oleic acid
at T = 308 K (■); 338 K (□); {CO2 (1) + [0.900 ethyl acetate (2) + (3)]} at T = 308 K (■); 318 K (●); 328 K (▲); 338 K (▼).
0.100 oleic acid (3)]} at T = 308 K (●); 338 K (○); and {CO2 (1) + Calculations with the Peng−Robinson equation of state and
[0.995 ethyl acetate (2) + 0.005 oleic acid (3)]} at T = 308 K (▲); parameters from Table 5.
338 K (△).
Figures 3−5 compare experimental and calculated VLE Impregnated with Progesterone by Supercritical Fluid Technology.
values for systems formed by CO2 + ethyl acetate + oleic acid, Can. J. Chem. Eng. 2016, 94, 1336−1341.
showing that the thermodynamic modeling can represent the (8) Giufrida, W. M.; Cabral, V. F.; Cardoso-Filho, L.; dos Santos
experimental results fairly well. Although the studied systems Conti, D.; de Campos, V. E. B.; da Rocha, S. R. P. Medroxyprogester-
one-Encapsulated poly(3-Hydroxybutirate-Co-3-Hydroxyvalerate)
have nonhydrocarbons (especially polar and associating fluids)
Nanoparticles Using Supercritical Fluid Extraction of Emulsions. J.
and long chain molecules, which characterize asymmetric Supercrit. Fluids 2016, 118, 79−88.
systems, the Peng−Robinson equation can represent the (9) Hintermair, U.; Leitner, W.; Jessop, P. Expanded Liquid Phases in
experimental data satisfactorily. Catalysis: Gas-Expanded Liquids and Liquid-Supercritical Fluid
Table 5 shows the pure-component35 properties used and Biphasic Systems. In Handbook of Green Chemistry; Wiley-VCH
the binary interaction parameters fitted in this work. Verlag GmbH & Co. KGaA: Weinheim, 2010.
(10) Magee, C.; Earla, A.; Petraitis, J.; Higa, C.; Braslau, R.;
5. CONCLUSIONS Zetterlund, P. B.; Aldabbagh, F. Synthesis of Fluorinated Alkoxyamines
and Alkoxyamine-Initiated Nitroxide-Mediated Precipitation Polymer-
We presented new experimental data of vapor−liquid transition
izations of Styrene in Supercritical Carbon Dioxide. Polym. Chem.
of ternary systems {CO2 (1) + ethyl acetate (2) + oleic acid 2014, 5, 5725−5733.
(3)} at the temperatures of 308, 318, 328, and 338 K. In the (11) Beckman, E. J. Supercritical and near-Critical CO2 in Green
studied systems, the phase transition pressures increase with the Chemical Synthesis and Processing. J. Supercrit. Fluids 2004, 28, 121−
increase in temperature and with the decrease of oleic acid 191.
concentration. The Peng−Robinson equation of state repre- (12) Oakes, R. S.; Clifford, A. A.; Rayner, C. M. The Use of
sents this highly asymmetric system well. The data measured in Supercritical Fluids in Synthetic Organic Chemistry. J. Chem. Soc.
this work are useful for the proper design of processes that use Perkin Trans. 1 2001, 9, 917−941.
the chemo-enzymatic or the chemical method for the (13) Méndez-Sánchez, D.; Ríos-Lombardía, N.; Gotor, V.; Gotor-
epoxidation of vegetable oils. Fernández, V. Chemoenzymatic Epoxidation of Alkenes Based on
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Peracid Formation by a Rhizomucor Miehei Lipase-Catalyzed
Perhydrolysis Reaction. Tetrahedron 2014, 70, 1144−1148.
AUTHOR INFORMATION
(14) Corrêa, F. A.; Sutili, F. K.; Miranda, L. S. M.; Leite, S. G. F.;
Corresponding Author Souza, R. O. M. A.; Leal, I. C. R. Epoxidation of Oleic Acid Catalyzed
*Tel.: +55 44 30114749. E-mail: lucio.cardozo@gmail.com. by PSCI-Amano Lipase Optimized by Experimental Design. J. Mol.
ORCID Catal. B: Enzym. 2012, 81, 7−11.
(15) Zanette, A. F.; Zampakidi, I.; Sotiroudis, G. T.; Zoumpanioti,
Lúcio Cardozo-Filho: 0000-0002-1764-9979 M.; Leal, I. C. R.; de Souza, R. O. M. A.; Cardozo-Filho, L.; Xenakis, A.
Funding Chemo-enzymatic epoxidation catalyzed by C. antarctica lipaseimmo-
We thank the following Brazilian agencies for financial support: bilized in microemulsion-based organogels. J. Mol. Catal. B: Enzym.
CAPES (Ministry of Education) and CNPq (National Council 2014, 107, 89−94.
for Scientific and Technological Development). (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−
Notes 1571.
The authors declare no competing financial interest.
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(17) Sun, S.; Ke, X.; Cui, L.; Yang, G.; Bi, Y.; Song, F.; Xu, X.
Enzymatic Epoxidation of Sapindus Mukorossi Seed Oil by Perstearic
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E DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article
F DOI: 10.1021/acs.jced.7b00163
J. Chem. Eng. Data XXXX, XXX, XXX−XXX