Role of Active Modes in Unimolecular Reactions. Volume 2. Thermal Decomposition of Fluoroform and Methane

摘要

A recently developed model has been applied to the Rice-Ramsperger-Kassel-Marcus (RRKM) theory of unimolecular reactions to calculate rate constants for the thermal decomposition of fluoroform and methane. Unlike previous failures to determine the pressure dependence for the thermal decomposition of fluoroform and methane by means of the quantum statistical RRKM theory of unimolecular reactions, the new model correlates available experimental data for both fluoroform and methane. In addition, the new model predicts a pressure dependence for the thermal decomposition of methane in the second-order region at high pressures. The latter result suggests that further experiments are required to measure the pressure dependence of the unimolecular rate constants for the thermal decomposition of methane. (Author)