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Activation parameters of solvent exchange and ligand substitution reactions of metal ions are discussed in relation to structural properties. Solvent exchange is treated as a particular case of ligand substitution. A general relation between enthalpy and entropy of activation is shown to hold for both types of reaction at divalent metal ions for a wide variety of solvents and ligands, after corrections have been made for ligand-field stabilisation. Water occupies a middle position in the range of solvents. The results are interpreted in terms of a structural model for a solvated ion in solution, based on that of Frank and Wen.
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Bennetto et al. (1971) studied this question.
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