Reactions of CH3S and CH3SOO with O3, NO2, and NO

Article abstract of DOI:10.1021/j100124a025

The atmospherically important reactions of both CH3S and CH3SOO were examined using the technique of pulsed laser photolysis/laser-induced fluorescence.Rate coefficients for the reactions CH3S + O3 -> products (1) and CH3S + NO2 -> CH3SO + NO (2) were measured to be k₁(T) = (1.98 +/- 0.38) x 10^-12 exp<(290 +/- 40)/T> cm³ molecule^-1 s^-1 and k₂(T) = (2.06 +/- 0.44) x 10^-11 exp<(320 +/- 40)/T> cm³ molecule^-1 s^-1.The reactions of the weakly bound CH3SOO adduct with O3, NO2, and NO were studied at low temperatures.The rate coefficients for the adduct reactions are as follows: CH3SOO + O3 -> products (4), k₄ < 8 x 10^-13 cm³ molecule^-1 s^-1 at T = 227 K; CH3SOO + NO2 -> products (5), k₅ = (2.2 +/- 0.6) x 10^-11 cm³ molecule^-1 s^-1 at T = 227-246 K; and CH3SOO + NO -> products (6), k₆ = (1.1 +/- 0.4) x 10^-11 cm³ molecule^-1 s^-1 from T = 227-256 K.The measured values of k₅ and k₆ were independent of temperature and pressure over the limited ranges employed.The atmospheric implications of these findings are discussed.