New Insights into the Radical Chemistry and Product Distribution in the OH-Initiated Oxidation of Benzene

Emissions of aromatic compounds cause air pollution and detrimental health effects. Here, we explore the reaction kinetics and products of key radicals in benzene photo-oxidation. After initial OH addition and reaction with O₂, the effective production rates of phenol and bicyclic peroxy radical (BCP-peroxy) are experimentally constrained at 295 K to be 420 ± 80 and 370 ± 70 s⁻¹, respectively. These rates lead to approximately 53% yield for phenol and 47% yield for BCP-peroxy under atmospheric conditions. The reaction of BCP-peroxy with NO produces bicyclic hydroxy nitrate with a branching ratio