Gas-phase reactions of O(3P) atoms with methanethiol, ethanethiol, methyl sulfide, and dimethyl disulfide. 2. Reaction products and mechanisms

Article abstract of DOI:10.1021/ja00402a046

In conjunction with the determinations of the rate constants of reactions of the ground-state oxygen atoms, O(³P), with methanethiol, ethanethiol, methyl sulfide, and dimethyl disulfide described in the preceding paper,³ a parallel study was carried out of the products and mechanisms of the same reactions at 300 K. Oxygen atoms were generated by the mercury-photosensitized decomposition of N₂O, used in large excess, and the recovered products were analyzed by gas chromatography. The total pressure was varied from 300 to 1200 torr. Nitrogen formed in the photosensitized decomposition of N₂O provided a direct measure of the number of O atoms generated and allowed determination of the yields of some of the products per oxygen atom reacting with the sulfur organic compounds. From a detailed analysis of the experimental results obtained with single sulfur organics and their mixtures, it is possible to derive substantial quantitative information on the reaction mechanisms. The postulated overall reaction mechanisms include some novel features common to the thiols, sulfide, and disulfide studied, which provide a simple explanation for some unexpected experimental trends observed.