Thermodynamic properties of the species resulting from the phenyl radical with O2 reaction system

Phenyl radicals are formed in combustion and oxidation systems by abstraction of the phenyl—hydrogen from benzene or aromatics by active radical species and by oxidation and thermal reactions of the benzylic carbon on alkyl‐substituted aromatics. The reaction of phenyl with O₂ leads to chain‐branching reactions and a number of unsaturated oxygenated hydrocarbon intermediates that may need to be included in detailed combustion models. Thermochemical parameters and structures on important species resulting from the phenyl radical + O₂ association and reaction are reported in this study. Enthalpies, Δ_f H, of a series of stable molecules, radicals, and transition state structures are calculated using ab initio (G3MP2B3 and G3) and density functional (DFT, B3LYP/6–311g(d,p) calculations, group additivity (GA), and literature data. The ab initio and density functional calculations are combined with isodesmic reaction analysis, whenever possible, to improve the accuracy of the enthalpy values. Entropies, S, and heat capacities, Cp_f298 (T), are calculated using density functional calculations, group additivity, and literature data. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 583–604, 2008