ANALYSIS OF KINETIC DATA FOR REACTIONS IN BINARY AQUEOUS MIXTURES USING KIRKWOOD-BUFF INTEGRAL-FUNCTIONS CHARACTERIZING PREFERENTIAL SOLVATION

The basis is described Of a method for analyzing the dependence of rate constants on solvent composition using Kirkwood-Buff integral functions. The background to the treatment is examined with reference to the analysis of thermodynamic properties of binary aqueous mixtures. Procedures are outlined for combining this information and kinetic data to yield parameters characterizing interactions between solutes (i.e. initial and transition states) and the components of a binary aqueous solvent mixture. These calculations yield information concerning the affinities of solutes for components of the solvent mixture and hence describing the phenomenon of preferential solvation. Examples are quoted using kinetic data describing reactions involving organic and inorganic substances.