UV absorption spectra and self-reaction rate constants for primary peroxy radicals arising from the chlorine-initiated oxidation of carbonyl compounds
✍ Scribed by J. P. Le Crane; E. Villenave
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- English
- Weight
- 168 KB
- Volume
- 38
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Abstract
A flash photolysis setup coupled to UV absorption spectrometry detection was used to measure the UV absorption spectra of the (CH~3~)~2~(CH~2~O~2~.)CC(O)C(CH~3~)~3~ and (CH~3~)~2~(CH~2~O~2~.)CC(O)CH~3~ radicals between 207 and 290 nm. The self‐reaction rate constants of these radicals were measured at 298 K: k((CH~3~)~2~(CH~2~O~2~.)CC(O)C(CH~3~)~3~ + (CH~3~)~2~(CH~2~O~2~.)CC(O)C(CH~3~)~3~) = (4.57 ± 0.38) × 10^−12^ cm^3^ molecule^−1^ s^−1^; k((CH~3~)~2~(CH~2~O~2~.) CC(O)CH~3~ + (CH~3~)~2~(CH~2~O~2~.)CC(O)CH~3~) = (4.77 ± 0.35) × 10^−12^ cm^3^ molecule^−1^ s^−1^, where quoted uncertainties only represent 2σ errors. Because of the similarities in both UV spectra and self‐reaction kinetics between (CH~3~)~2~(CH~2~O~2~.)CC(O)C(CH~3~)~3~ and (CH~3~)~2~(CH~2~O~2~.)CC(O)CH~3~ radicals, it was suggested to extend this results to all (CH~3~)~2~(CH~2~O~2~.)CC(O)R peroxy radicals (with R = H, alkyl), arising from the chlorine‐initiated oxidation of carbonyl compounds. This trend has been tested successfully in the case of the Cl‐initiated oxidation of pivalaldehyde (Le Crâne et al., J Phys Chem A 2004, 108, 795). © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 276–283, 2006