Product distribution study of the Cl-atom initiated oxidation of ethyl methyl sulfide and diethyl sulfide

•First product study of Cl-initiated oxidation of two non-CH3SCH3 sulfides.•FTIR study in a large volume photoreactor at 298 K and 760 Torr.•HCl, SO2 and CH3CHO as major products of photodegradation of (CH3CH2)2S.•HCl, SO2, CH3CHO and HCHO were determined for the reaction Cl + CH3CH2SCH3.•Atmospheric degradation mechanisms are postulated.

The products formed in the gas-phase reactions of Cl atoms with (CH3CH2)2S and CH3CH2SCH3 have been investigated in a large volume reactor in NOx-free air at atmospheric pressure and (298 ± 2) K using long path “in situ” FTIR spectroscopy for the analysis. HCl, SO2 and CH3CHO were identified as the major products for both reactions. For the Cl + CH3CH2SCH3 reaction HCHO was also identified as a major product. The yields of the products obtained for the reaction of Cl with (CH3CH2)2S were (59 ± 2) %, (52 ± 5) % and (103 ± 4) % for HCl, SO2 and CH3CHO, respectively. For the reaction of Cl with CH3CH2SCH3 yields of (43 ± 5) %, (55 ± 3) %, (58 ± 3) % and (53 ± 5) % were obtained for HCl, SO2, CH3CHO and HCHO, respectively. This is the first products and mechanistic study for the gas-phase Cl-initiated oxidation of non-CH3SCH3 alkyl sulfides. Comparison with previous results for the reaction of Cl with dimethyl sulfide is made and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

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