Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide, CH3SCH2CH2•, with O2 to CH3SCH2CH2OO•

Abstract

AbstractOxidation of methyl ethyl sulfide (CH3SCH2CH3, methylthioethane, MES) under atmospheric and combustion conditions is initiated by hydroxyl radicals, MES radicals, generated after loss of a H atom via OH abstraction, will further react with O2 to form chemically activated and stabilized peroxyl radical adducts. The kinetics of the chemically activated reaction between the CH3SCH2CH2• radical and molecular oxygen are analyzed using quantum Rice‐Ramsperger‐Kassel theory for k(E) with master equation analysis and a modified strong‐collision approach to account for further reactions and collisional deactivation. Thermodynamic properties of reactants, products, and transition states are determined by the B3LYP/6‐31+G(2d,p), M062X/6‐311+G(2d,p), ωB97XD/6‐311+G(2d,p) density functional theory, and CBS‐QB3, G3MP2B3, and G4 composite methods. The reaction of CH3SCH2CH2• with O2 forms an energized peroxy adduct CH3SCH2CH2OO• with a calculated well depth of 34.1 kcal mol−1 at the CBS‐QB3 level of theory. Thermochemical properties of reactants, transition states, and products obtained under CBS‐QB3 level are used for calculation of kinetic parameters. Reaction enthalpies are compared between the methods. The temperature and pressure‐dependent rate coefficients for both the chemically activated reactions of the energized adduct and the thermally activated reactions of the stabilized adducts are presented. Stabilization and isomerization of the CH3SCH2CH2OO• adduct are important under high pressure and low temperature. At higher temperatures and atmospheric pressure, the chemically activated peroxy adduct reacts to new products before stabilization. Addition of the peroxyl oxygen radical to the sulfur atom followed by sulfur‐oxygen double bond formation and elimination of the methyl radical to form S(= O)CCO• + CH3 (branching) is a potentially important new pathway for other alkyl‐sulfide peroxy radical systems under thermal or combustion conditions.