Contrasting the hydration thermodynamics of methane and methanol

Literature Information

Publication Date 2019-09-11
DOI 10.1039/C9CP03213D
Impact Factor 3.676
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Abstract

Experimental hydration thermodynamic functions of methane and methanol over a large temperature range and at 1 atm (coming from previous studies of others) are analysed by means of a theoretical approach grounded in statistical mechanics. It is shown that the hydration Gibbs energy change can be reproduced quite well for both solutes by adding the large positive reversible work of cavity creation to the solute–water van der Waals and H-bond energetic attractions. The large negative hydration entropy change of both methane and methanol comes from the decrease in translational entropy of water molecules due to the solvent-excluded volume effect caused by cavity creation in water. The reorganization of water–water H-bonds upon solute insertion is characterized by almost complete enthalpy–entropy compensation and so cannot affect the hydration Gibbs energy change. In addition, such reorganization is endothermic above 4 °C, suggesting that no significant increase in water structure occurs upon methane or methanol insertion.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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