Effect of Pressure on the Solvolysis of Dimethyl-t-butyl Sulfonium Iodide in Ethanol–Water Mixtures

Abstract

The pressure dependence of the rate of solvolysis of dimethyl-t-butyl sulfonium iodide has been studied in ethanol-water mixtures at 60.00 "C. Determination of the partial molal volume of the substrate ions has enabled the volumes of activation to be dissected into initial and transition state components. The solvent composition dependence of the partial molal volumes of the two states provides further details of the nature of the reaction mechanism. L'influence de la pression sur la vitesse de solvolyse de I'iodure de dimethyl-I-butylsulfonium a etC etudiee dans des melanges eau-alcool i 60.00 O C . La determination du volume molaire partiel des ions substrats a rendu possible la division des volumes d'activation en composantes Ctat initial et &at de transition. L'influence de la composition du solvant sur les volumes molaires partiels des deuxttats fournit des details supplementaires sur la nature du mecanisme de la rtaction.