Abstract
Abstract A consequence of an improved model of dissolution process passing through the cavity creation stage is discussed. The improvement consists in accounting for the scales of initial density fluctuations (appropriate vacancies) necessary for creation of the cavities. The radii (R 1u v ) of the cavities in solvents with flexible molecules containing benzene as a solute, evaluated from solvent-induced spectral shifts, and radii of the vacancies, calculated from volume balance involving the R 1u v 's, have been used for determining the changes in conformational equilibrium in the solvents caused by the solute. In free energy balance calculations performed with this aim, the free energy of a cavity is estimated according to Sinanoglu, when the cavity size is equal to or exceeds the size of the room occupied by a solvent molecule, but in the submolecular region it is expressed in terms of the probability of accidental collision of little cavity defects. The reasonable values obtained confirm the picture of dissolution deduced from spectroscopy data.
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