OH-initiated oxidation of toluene. 2. Master equation simulation of toluene oxide isomerisation

Abstract

In this work we continue our investigation of the toluene-OH-O2 system. We describe master equation modeling of the isomerization of toluene oxide, focusing on the formation of the cresols. A 15 isomer model is used. Simulations of both thermally activated processes and photolysis processes are described. In accord with experiment, it is found that photolysis with a high-energy light source should be expected to give a high yield of the thermal distribution of cresol products (dominated by the para isomer). Photolysis with a low-energy light source, on the other hand, favors formation of the thermally disfavored ortho isomer. Though the 15 isomer system is potentially an excellent test bed for the development of scalable master equation solution methods, existing scalable solution methods were found to fail on this system.