Identity and near identity rates and equilibria for methyl group transfers between arenesulfonate ions
Hu, Daniel David
Lewis, Edward S.
Master of Arts
Rates and equilibria were measured for the reaction of methyl arenesulfonates with arenesulfonates in sulfolane. The identity rates for a series of arenesulfonates were measured at a variety of temperatures; a Hammett P was obtained. A Hammett P of ~22.9 was obtained for nonidentity equilibria. Arrhenius plots are inconclusive due to large error limits. The transition state for the identity reaction lies near the area predicted by Albery and Kreevoy. Using the identity rates and measured mixed case equilibrium constants, a test of the Marcus equation with and without the quadratic term was conducted. The test suggests that the Marcus equation is a decent predictive tool for the rate of methyl transfers in solution. The Marcus equation was used to estimate an identity rate for methyltriflate.