Abstract
The equilibrium Na(Hg) + 1/nM/sup n+/(S) = Na/sup +/(S) + 1/nM(Hg) was measured for M = K, Rb, Cs, and Sr, and S = 0.30, 0.80, and 1.00 mole fraction methanol (and for Sr also at 0.90 and 0.95 mole fraction methanol) in water- methanol mixtures. The results were combined with those from similar measurements using water as solvent to yield the standard free energy values for the reaction Na/sup +/(H/sub 2/O) + 1/nM/sup n+/(S) = Na/sup +/(S) + 1/nM/sup n+/ (H/sub 2/O). The results, when compared with the predictions of the simple Born equation, lead to the conclusion that specific cation solvation effects are of primary importance in determining the relative free energies of the alkali metal ions in those systems. It is also shown that calculations based on a simple ion- dipole model lead to values in reasonable agreement with experiment. (auth)
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