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Direct identification of reactive routes and measurement of rate constants in the reactions of oxygen atoms with methanethiol, ethanethiol, and methylsulfide
Author(s) -
Slagle Irene R.,
Graham Ronald E.,
Gutman David
Publication year - 1976
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550080310
Subject(s) - chemistry , ethanethiol , methanethiol , reaction rate constant , adduct , electrophile , photochemistry , pericyclic reaction , medicinal chemistry , oxygen , thiol , sulfur , computational chemistry , kinetics , organic chemistry , catalysis , physics , quantum mechanics
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 ).