Studies on the decomposition of tetra-alkylammonium salts in solution. Part II. Dependence of the activation parameters on the structure of the substrate

Abstract

The enthalpy and entropy of activation for the decomposition reaction of seven tetra-alkylammonium iodides in chloroform solution have been measured. All the salts contained the benzyl group attached to the nitrogen atom and decomposed to yield benzyl iodide and a tertiary amine as the only products.A Hammett free energy correlation is made and used to deduce the nature of the transition state, and a rationalization of the variation of the enthalpy and entropy of activation with the structure of the substrate is given.