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Molecules 2019, 24(5), 961; https://doi.org/10.3390/molecules24050961

Cohesive Energy Densities Versus Internal Pressures of Near and Supercritical Fluids

Institute of Analytical Chemistry of the Czech Academy of Sciences, Veveří 97, 60200 Brno, Czech Republic
Received: 11 February 2019 / Revised: 6 March 2019 / Accepted: 7 March 2019 / Published: 8 March 2019
(This article belongs to the Special Issue Supercritical Fluids and Green Chemistry)
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Abstract

Over half a century ago, Wiehe and Bagley suggested that a product of the internal pressure and molar volume of a liquid measures the energy of nonspecific intermolecular interactions whereas the cohesive energy reflects the total energy of intermolecular interactions in the liquid. This conjecture, however, has never been considered in connection with near and supercritical fluids. In this contribution, the cohesive energy density, internal pressure and their ratios are calculated from high precision equations of state for eight important fluids including water. To secure conformity to the principle of corresponding states when comparing different fluids, the calculations are carried out along the line defined by equality between the reduced temperature and the reduced pressure of the fluid (Tr = Pr). The results provide additional illustration of the tunability of the solvent properties of water that stands apart from those of other near and supercritical fluids in common use. In addition, an overview is also presented of the derivatives of cohesive energy density, solubility parameter and internal pressure with respect to temperature, pressure and molar volume. View Full-Text
Keywords: cohesive energy density; internal pressure; supercritical fluid; tunable solvent; equation of state; water cohesive energy density; internal pressure; supercritical fluid; tunable solvent; equation of state; water
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Roth, M. Cohesive Energy Densities Versus Internal Pressures of Near and Supercritical Fluids. Molecules 2019, 24, 961.

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