ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 k1 = (1.5 ± 0.4) × 10-14 exp [(845 ± 175)/T] cm3 molecule-1s-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 + CH3SCH3 →[CH3S(OBr)CH3]* → CH3S(O)CH3 + Br. The atmospheric application of the data is briefly discussed. © 1996 John Wiley & Sons, Inc.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.7
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