Thermochemistry and Kinetics of the Atmospheric Oxidation Reactions of Propanesulfinyl Chloride Initiated by OH Radicals: A Computational Approach.

Abstract

The thermochemistry and kinetics of the atmospheric oxidation mechanism for propanesulfinyl chloride (CH3-CH2-CH2-S(═O)Cl; PSICl) initiated by the hydroxyl (OH) radical were investigated with high level quantum chemistry calculations and the Master equation solver for multi-energy well reaction (Mesmer) kinetic code. The mechanism for the oxidation of PSICl in the presence of OH radical can proceed via H-abstraction and substitution pathways. The CCSD(T)/aug-cc-pV(T+d)Z//MP2/aug-cc-pV(T+d)Z level calculated energies revealed addition of the OH radical to the S-atom of the sulfinyl (-S(═O)) moiety, followed by cleavage of the Cl-S(═O) single bond, leading to formation of propanesulfinic acid (PSIA) and the Cl radical to be the major pathway when compared to all other possible channels. The transition state barrier height for this reaction was found to be -3.0 kcal mol-1 relative to the energy of the starting PSICl + OH radical reactants. The rate coefficients were calculated for all possible paths in the atmospherically relevant temperature range of 200-320 K and at 1 atm. The rate coefficient for the formation of the PSIA + Cl radical from the PSICl + OH radical reaction was found to be 8.2 × 10-12 cm3 molecule-1 s-1 at 298 K and a pressure of 1 atm. From branching ratio calculations, it was revealed that the reaction resulting in the formation of the PSIA + Cl radical contributed ∼52% to the total reaction. The overall rate coefficient for the PSICl + OH reaction was also calculated and found to be 1.6 × 10-11 cm3 molecule-1 s-1 at 298 K and a pressure of 1 atm. In the aggregate, the results indicate the atmospheric lifetime of PSICl to be ∼12-20 h in the temperature range between 200 and 320 K, which suggests that its contribution to global warming is negligible. However, the degradation products revealed to be formed in its interactions with the OH radical, which include that SO2, Cl radical, HO2 radical, and propylene have significant effects on the formation of acid rain, secondary organic aerosols, the ozone layer, and global warming.