Nucleophilic substitutions in mixed solvents. Part I. General considerations

Abstract

The change in the free energy of activation of reactions in solution with change in solvent is considered to be more closely related than the corresponding heat of activation changes to the solvation of the transition state. Although the free energy of solvation of the ground state may change considerably with solvent composition, these deviations from ideality will in general be also present in the transition state. The specific solvation of polar transition states in hydroxylic solvents is discussed.