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Case study of enthalpy-entropy noncompensation.
Journal of Chemical Physics 2004 March 2
Enthalpy-entropy noncompensation characterizes the relative changes in the hydration thermodynamic functions upon "transforming" ethane into fluoromethane, chloromethane, bromomethane, and iodomethane. An analysis grounded on a simple statistical mechanical theory of hydration allows a plausible rationalization of such enthalpy-entropy noncompensation. It is shown that increasing the strength of solute-water attractive interactions modifying the chemical nature of a part of the solute molecule, but not its size, is a largely noncompensating process for the hydration of noncharged and nonhydrogen bonding species, and dominates the compensating contribution coming from the reorganization of water H bonds.
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