SOLVOLYSIS IN HYDROGEN AND DEUTERIUM OXIDE: III. ALKYL HALIDES

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Abstract
Rate data for the hydrolysis of a series of α- and β-methylated allyl, benzyl, and cycloalkyl halides in light and heavy water are compared. The major factor determining the rate ratio [Formula: see text] appears to be the relative stability of the initial solvation shell. When the relative viscosity of H2O and D2O is used as a measure of the relative stability of structure in bulk solvent, the observed kinetic isotope effect and the temperature dependence of the isotope effect can be rationalized in terms of accepted properties of aqueous solutions.Attention is drawn to the anomalous rate ratio kRBr/kRI > 1 which appears to be characteristic of solvolysis of these alkyl halides in pure water in contrast to other media.