Abstract
We emphasize that the thermodynamics of cavity creation in a liquid is well established on statistical mechanical grounds. Theoretical relations demonstrate that the Gibbs energy cost to create a cavity is due to the excluded volume effect arising from the selection of the constrained molecular configurations possessing the cavity in the full statistical ensemble of the pure solvent. The enthalpic cost of cavity creation is exactly compensated by a corresponding entropic gain: rupture of intermolecular interactions raises the energy of the solvent molecules and their degrees of freedom in a compensating manner. These fundamental points are used to interpret the results of scaled particle theory calculations in different solvents and to provide a molecular explanation for hydrophobicity.
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