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

Abstract

Oxidation of methyl ethyl sulfide (CH 3 SCH 2 CH 3 , 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 O 2 to form chemically activated and stabilized peroxyl radical adducts. The kinetics of the chemically activated reaction between the CH 3 SCH 2 CH 2 • 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), B97XD/6-311+G(2d,p) density functional theory, and CBS-QB3, G3MP2B3, and G4 composite methods. The reaction of CH 3 SCH 2 CH 2 • with O 2 forms an energized peroxy adduct CH 3 SCH 2 CH 2 OO• 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 CH 3 SCH 2 CH 2 OO• 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• + CH 3 (branching) is a potentially important new pathway for other alkyl-sulfide peroxy radical systems under thermal or combustion conditions. K E Y W O R D Skinetics, methyl ethyl sulfide, oxidation, thermochemistry 618