Correlations between the transfer thermodynamics of simple electrolytes and structural parameters with particular reference to steric hindrance

Abstract

Structural studies on Li⁺, Na⁺, Ca²⁺, and Ag⁺ in aqueous solution by neutron diffraction and computer simulation explain certain trends in the free energies of transfer of these ions from water to mixed aqueous solvents; in particular, the thermodynamic evidence of decreasing steric hindrance to solvation by bulky ligands in the order Li⁺ > Na⁺ > Ag⁺ is consistent with the structures of the ion-complexes in aqueous solution.