Lewis, Edward S.2018-12-182018-12-181984Hu, Daniel David. "Identity and near identity rates and equilibria for methyl group transfers between arenesulfonate ions." (1984) Master’s Thesis, Rice University. <a href="https://hdl.handle.net/1911/104492">https://hdl.handle.net/1911/104492</a>.https://hdl.handle.net/1911/104492Text includes handwritten formulasRates 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.92 ppengCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.ThesisRICE2127reformatted digitalThesis Chem. 1984 Hu