Molecular Thermodynamics of Methane Solvation intert-Butanol−Water Mixtures
- 2 December 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of Chemical Theory and Computation
- Vol. 3 (1), 194-200
- https://doi.org/10.1021/ct600226h
Abstract
We studied solvation structure and thermodynamics of methane in mixtures of tert-butanol and water using computer simulations. We show that for alcohol mole fractions below 20%, methane is preferentially solvated by hydrated alcohol clusters. Because methane expels water molecules from these clusters, a large endothermic solvent reorganization enthalpy occurs. This process is responsible for the experimentally observed maximum of the heat of methane solvation close to 5% alcohol in the mixture and contributes to a positive entropy change relative to solvation in pure water. Because the structural solvent reorganization enthalpy is enthalpy−entropy compensating, the methane solvation free energy is a smoothly varying function of the alcohol/water solution composition.Keywords
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