The Hydrolysis of t-Butyl Chloride in Aquo-Organic Mixtures: Heat Capacity of Activation and Solvent Structure

Abstract

The temperature dependence of the rate of solvolysis of t-butyl chloride in mixtures of tetrahydrofuran and of acetonitrile in water have been determined. In the high-water range both minor co-solvents lead to a reduction in the value of ΔH≠ similar to that found previously where alcohol was the co-solvent. However, a remarkable difference in the values of [Formula: see text] across the same concentration range reflected a difference in the effect of these two co-solvents on the structural properties of the several solvent media. Where tetrahydrofuran or alcohols are the minor co-solvent, [Formula: see text] becomes much more negative until that concentration is reached where the quasi-aqueous structure collapses. Where acetonitrile is the minor co-solvent [Formula: see text] becomes more positive relative to the value found for hydrolysis in water until a value of about −40 cal deg−1 mol−1 is reached. The implication of these findings concerning the nature of solvation of weakly polar solutes in such mixtures is discussed.