Kinetics and thermochemistry of the reaction of benzyl radical with O2: Investigations by discharge flow/laser induced fluorescence between 393 and 433 K
✍ Scribed by L. Elmaimouni; R. Minetti; J. P. Sawerysyn; P. Devolder
- Publisher
- John Wiley and Sons
- Year
- 1993
- Tongue
- English
- Weight
- 838 KB
- Volume
- 25
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Abstract
The kinetics of the reaction of the benzyl radical with molecular oxygen has been studied between 393 and 433 K. The Discharge Flow technique with detection of benzyl radicals by Laser Induced Fluorescence in their visible absorption band has been used. All experiments have been performed at ≈1 torr in helium as the buffer gas. The radical benzyl decay plots are characteristic of the approach to equilibrium between benzyl and benzylperoxy: benzyl + O~2~ \documentclass{article}\pagestyle{empty}\begin{document}$ \mathbin{\lower.3ex\hbox{$\buildrel\textstyle\longrightarrow\over {\smash{\longleftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}} $\end{document} benzylperoxy (k~3~, k~−3~). Thanks to a reasonable assumption concerning the standard entropy of the reaction (3) (Δ__S__~298~°=−29 cal mol^−1^ K^−1^), based on the additivity rules of Benson, the following reaction enthalpy is derived for reaction (3): Δ__H__~298~°=(−20 ± 1 kcal mol^−1^). This latter value is compared with a few enthalpies of other related reactions available in the literature. © 1993 John Wiley & Sons, Inc.