Oxidation of the Benzyl Radical: Mechanism, Thermochemistry, and Kinetics for the Reactions of Benzyl Hydroperoxide

Abstract

Oxidation of the benzyl radical plays a key role in the autoignition, combustion, and atmospheric degradation of toluene and other alkylated aromatic hydrocarbons. Under relevant autoignition conditions of moderate temperature and high pressure, and in the atmosphere, benzyl reacts with O2 to form the benzylperoxy radical, and the further oxidation reactions of this radical are not yet fully characterized. In this contribution, we further develop the reaction chemistry, thermodynamics, and kinetics of benzyl radical oxidation, highlighting the important role of benzyl hydroperoxide and the benzoxyl (benzyloxyl) radical. The benzylperoxy + H reaction mechanism is studied using computational c..