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Kinetic study of the reaction of BrO radicals with dimethylsulfide

✍ Scribed by Yu. Bedjanian; G. Poulet; G. Le Bras

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 482 KB
Volume: 28
Category: Article
ISSN: 0538-8066
DOI: 10.1002/(sici)1097-4601(1996)28:5<383::aid-kin7>3.0.co;2-r

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✦ Synopsis

The kinetics and mechanism of the reaction of BrO with dimethylsulfide [ DMS) have been studied by the mass spectrometric discharge-flow method in the temperature range (233-320) K and at a total pressure around 1 torr. The temperature dependence of the reaction rate constant k , = [ 1.5 ? 0 4 ) X 10-'4exp ((845 2 175I/TI cm' molecule-' s -' has been determined under pseudo-first-order conditions in excess of DMS over BrO radicals. Mass spectrometric calibration of the reaction product dimethylsulfoxide [ DMSO) allowed for a determination of t h e branching ratio of 10.94 t 0. I I ) for the DMSO forming channel. These data indicate that the reaction is likely to proceed through a channel involving a long-lived intermediate BrO + CH,SCH, -ICH,S(OBr)CH,I* -+ CH,S[O)CH, + Br. The atmospheric application of the data is briefly discussed. o 1996 lohn ~i l e y G Sons Inc. ~

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