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The UV absorption spectra of CH2Br and CH2BrO2 and the reaction kinetics of CH2BrO2 with itself and with HO2 at 298 K

✍ Scribed by Eric Villenave; Robert Lesclaux

Publisher: Elsevier Science
Year: 1995
Tongue: English
Weight: 904 KB
Volume: 236
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(95)00253-z

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✦ Synopsis

The UV absorption spectra of the bromomethyl (CH2Br) and bromomethylperoxy (CH2BrO 2) radicals have been determined using the flash photolysis technique. CH 2 Br exhibits the typical absorption band of halomethyl radicals, peaking near 230 nm, and CH2BrO 2 exhibits the typical broad absorption of peroxy radicals, with a maximum at 240 nm. Rate coefficients were determined at 298 K for the self-reaction (CH 2 BrO2BrO 2 + CH 2 BrO 2 --~ 2 CH 2BrO + 0 2 (3), k 3 -(1.05 4-0.4) × 10 -12 cm 3 molecule-! s-t) and for the reaction with HO 2 (CH2BrO 2 + HO 2 --, products (5), k 5 = (6.7 4-3.8) × 10-n2 cm 3 molecule-n s-~). As for fluorine and chlorine substitution, bromine substitution enhances the rate constant of the self-reaction, compared to that of the methylperoxy radical, whereas it does not significantly change the rate constant for the reaction with HO 2.

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