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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

✍ Scribed by Irene R. Slagle; Ronald E. Graham; David Gutman

Publisher: John Wiley and Sons
Year: 1976
Tongue: English
Weight: 394 KB
Volume: 8
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550080310

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✦ Synopsis

The room temperature reactions between oxygen atoms and methanethiol, ethanethiol, and methylsulfide have been studied in crossed jets to directly detect and identify the freeradical and stable products they produce. Knowledge of the products was used to assign reactive routes. The overall rate constants for all three 0-atom reactions were also measured at 300 f 2°K using a fast-flow reactor. They are 1.9 (CHaSH), 2.8 (CzHaSH), and 63 (CHISCH,) X 10-i2cm3/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, CHI, or C2H5).

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