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Kinetic study of the reaction of BrO radicals with dimethylsulfide
Author(s) -
Bedjanian Yu.,
Poulet G.,
Le Bras G.
Publication year - 1996
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/(sici)1097-4601(1996)28:5<383::aid-kin7>3.0.co;2-r
Subject(s) - chemistry , radical , torr , reaction rate constant , kinetics , branching (polymer chemistry) , reaction mechanism , dimethyl sulfide , analytical chemistry (journal) , branching fraction , organic chemistry , sulfur , thermodynamics , catalysis , physics , atomic physics , quantum mechanics
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 = (1.5 ± 0.4) × 10 −14 exp [(845 ± 175)/T] cm 3 molecule −1 s −1 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 the branching ratio of (0.94 ± 0.11) 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 3 SCH 3 →[CH 3 S(OBr)CH 3 ]* → CH 3 S(O)CH 3 + Br. The atmospheric application of the data is briefly discussed. © 1996 John Wiley & Sons, Inc.