Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.