Comparison of activation parameters for ionization reactions within zeolites and in aqueous solution

Absolute rate constants for the ionization of chloride from the 2-chloro-1-(4-methoxyphenyl)ethyl radical are measured in aqueous methanol and in alkali-metal cation zeolites as a function of temperature. The absolute rate constants are very fast in the two distinct media. However, the activation parameters are considerably different. In solution, the reaction proceeds with low enthalpies of activation and large, negative entropies of activation, while in zeolites, the reaction is characterized by significantly higher activation enthalpies and large, positive entropies of activation. These differences reveal that the fundamental factors allowing for such rapid reactions are not the same in the two media.