Atmospheric DMSO degradation in the gas phase: Cl-DMSO reaction. Temperature dependence and products

The reactions of Cl atoms and ClO radicals with CH3-SOCH3 (DMSO) have been studied using the discharge flow method with direct detection of DMSO, CO, and products by mass spectrometry. The absolute rate constant at room temperature measured for reaction 1, (CH3)2SO + Cl --> products, was k(1) = (1.7 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1). For reaction 2, (CH3)2SO + ClO --> products, only an upper limit could be established, k(2) < or = 6 x 10(-14) cm3 molecule(-1) s(-1) Reaction 1 has been found to proceed through adduct formation and further decomposition involving the cleavage of the C-S bound. The pressure effect on the Cl-DMSO reaction from 0.5 to 3 Torr was negligible, and the temperature dependence in the range 273-335 K was also very slight. The results obtained are related to previous studies of sulfur compounds, and the atmospheric implications are also discussed in relation to the homogeneous sinks of DMSO. Tropospheric lifetimes of DMSO based on average Cl and ClO concentrations and the measured rate constants have been calculated showing that the contribution of reaction 1 must be of minor relevance in the marine boundary layer. Reaction 2 is so slow that it does not play any role within the atmospheric sulfur chemistry.