Direct identification of reactive routes and measurement of rate constants in the reactions of oxygen atoms with methanethiol, ethanethiol, and methylsulfide

Abstract The room temperature reactions between oxygen atoms and methanethiol, ethanethiol, and methylsulfide have been studied in crossed jets to directly detect and identify the free‐radical and stable products they produce. Knowledge of the products was used to assign reactive routes. The overall rate constants for all three O‐atom reactions were also measured at 300 ± 2°K using a fast‐flow reactor. They are 1.9 (CH 3 SH), 2.8 (C 2 H 5 SH), and 63 (CH 3 SCH 3 ) × 10 −12 cm 3 /mol · sec. The identity of the detected products and the trend in rate constants in these reactions support an electrophilic addition mechanism followed by decomposition of the excited adduct by S‐R bond cleavage (R = H, CH 3 , or C 2 H 5 ).