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Thermodynamics of mixing methanol with supercritical CO 2 as seen from computer simulations and thermodynamic integration

The changes in extensive thermodynamic quantities, such as volume, energy, Helmholtz free energy and entropy, occurring upon mixing liquid methanol with supercritical CO , are calculated using Monte Carlo simulations and thermodynamic integration for all eight combinations of four methanol and two C...

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Published in:Physical chemistry chemical physics : PCCP 2020-05, Vol.22 (20), p.11652-11662
Main Authors: Horváth, Réka A, Horvai, George, Idrissi, Abdenacer, Jedlovszky, Pál
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cited_by cdi_FETCH-LOGICAL-c1336-c016e39acc003a33aaece5443f071fe558fe3c24e1972eddc122d50159a16d9b3
cites cdi_FETCH-LOGICAL-c1336-c016e39acc003a33aaece5443f071fe558fe3c24e1972eddc122d50159a16d9b3
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container_title Physical chemistry chemical physics : PCCP
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creator Horváth, Réka A
Horvai, George
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Jedlovszky, Pál
description The changes in extensive thermodynamic quantities, such as volume, energy, Helmholtz free energy and entropy, occurring upon mixing liquid methanol with supercritical CO , are calculated using Monte Carlo simulations and thermodynamic integration for all eight combinations of four methanol and two CO potential models in the entire composition range at 313 K. The obtained results are also compared with experimental data whenever possible. The transition of the system from liquid to a supercritical state is found to occur at this temperature around a CO mole fraction value of 0.95 with all model combinations considered. This liquid to supercritical transition is always accompanied by positive Helmholtz free energy of mixing values and, consequently, by the non-miscibility of the two components. Furthermore, both this non-miscibility around the liquid to supercritical transition and also the miscibility of the two components below this transition, in the liquid regime, are found to be primarily of the energetic rather than entropic origin; the entropy of mixing turns out to be very close to zero, and around the liquid to supercritical transition even its qualitative behaviour is strongly model dependent. Finally, it is found that the methanol expansion coefficient is not sensitive to the details of the potential models, and it is always in excellent agreement with the experimental data. On the other hand, both the volume and the energy of mixing depend strongly on the molar volume of neat CO in the model being used, and in this respect the TraPPE model of CO [J. J. Potoff and J. I. Siepmann, AIChE J., 2001, 47, 1676] performs considerably better than that of Zhang and Duan [Z. Zhang and Z. Duan, J. Chem. Phys., 2005, 122, 214507].
doi_str_mv 10.1039/D0CP01241F
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The obtained results are also compared with experimental data whenever possible. The transition of the system from liquid to a supercritical state is found to occur at this temperature around a CO mole fraction value of 0.95 with all model combinations considered. This liquid to supercritical transition is always accompanied by positive Helmholtz free energy of mixing values and, consequently, by the non-miscibility of the two components. Furthermore, both this non-miscibility around the liquid to supercritical transition and also the miscibility of the two components below this transition, in the liquid regime, are found to be primarily of the energetic rather than entropic origin; the entropy of mixing turns out to be very close to zero, and around the liquid to supercritical transition even its qualitative behaviour is strongly model dependent. 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The obtained results are also compared with experimental data whenever possible. The transition of the system from liquid to a supercritical state is found to occur at this temperature around a CO mole fraction value of 0.95 with all model combinations considered. This liquid to supercritical transition is always accompanied by positive Helmholtz free energy of mixing values and, consequently, by the non-miscibility of the two components. Furthermore, both this non-miscibility around the liquid to supercritical transition and also the miscibility of the two components below this transition, in the liquid regime, are found to be primarily of the energetic rather than entropic origin; the entropy of mixing turns out to be very close to zero, and around the liquid to supercritical transition even its qualitative behaviour is strongly model dependent. 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Theoretical and
title Thermodynamics of mixing methanol with supercritical CO 2 as seen from computer simulations and thermodynamic integration
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