Oxidation reaction mechanism and kinetics between OH radicals and alkyl-substituted aliphatic thiols: H-abstraction pathways

Abstract

Kinetic rate constants for the oxidation reaction of the hydroxyl radical with CH3SH, C2H5SH, n-C3H7SH, and iso-C3H7SH under inert (Ar) conditions over the temperature range 252–430 K have been studied theoretically using density functional theory along with various exchange–correlation functionals as well as the benchmark CBS-QB3 quantum chemical approach. Bimolecular rate constants were estimated using transition state theory and the statistical Rice–Ramsperger–Kassel–Marcus theory. Comparison with experiment confirms that in the OH addition reaction pathways leading to the related products, the first bimolecular reaction steps have effective negative activation energy barriers. Effective rate constants have been calculated according to a steady-state analysis of a two-step model reaction mechanism. As a consequence of the negative activation energies, pressures higher than 104 bar are required to reach the high-pressure limit. Both from thermodynamic and kinetic viewpoints, the most favorable process here is the oxidation reaction of hydroxyl radicals with n-C3H7SH.