Some Comments on Electrostatic Volumes and Entropies of Solvation

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Abstract
The volume of solvation of an ion with dipole and quadrupole moments in a cavity in a continuous dielectric has been examined. In highly polar solvents like water, the compression of the cavity due to the electrostatic interaction contributes much more to the electrostatic volume of solvation than does electrostriction of the solvent, if electric saturation is not important. The importance of quadrupole moments on transition states has been emphasized. The compression of the ion has an unimportant effect on the free energy, entropy, or enthalpy of solvation, but the thermal expansion of the cavity containing the ion contributes significantly to the electrostatic entropy of solvation.