Energetics of Single Ion Solvation in Nonaqueous Solvents and the Effects on Electrode Kinetics

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Abstract
Individual ionic energies of solvation are estimated for solvation in methanol and in a 20% dioxane‐water mixture. As found in a previous paper (1), these solvation energies are about 10 to 15 kcal/mole larger (more positive) than most previous estimates. A detailed discussion is presented on these differences. The medium effect is discussed in relation to the kinetics at electrode surfaces and it is proposed, and demonstrated, that the standard chemical free energy of transfer of the activated complex from water to an organic solvent is, effectively, zero. Based on this assumption, a new method is presented for the calculation of differences in surface potentials between water and an organic solvent.

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