Analysis of the kinetics of solvolysis of p-nitrophenylsulfonylmethyl perchlorate in binary alcoholic mixtures in terms of the thermodynamic properties of the solvent mixtures

Abstract

Rate constants are reported for the solvolysis of p-nitrophenylsulfonylmethyl perchlorate in binary ethanolic and methanolic mixtures at 298.2 K. Co-solvents include hydrocarbons, chlorinated hydrocarbons and 1,4-dioxane. The kinetic data are examined in terms of the effect of decreasing mole fraction of reactant alcohol and in terms of deviations from the ideal of the thermodynamic properties of the solvent, a binary liquid mixture, as measured by the rational activity coefficients of the alcohols. Mixtures are identified where one of these two effects dominates and where they cancel such that the transfer chemical potentials of substrate and transition state are equal.