Kinetics of the self-reactions of benzyl and o-xylyl radicals studied by cavity ring-down spectroscopy

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The kinetics of the self-reactions of benzyl and o-xylyl radicals was studied experimentally over the temperature range 295–800K. The radicals were produced by the 248-nm photolysis of oxalyl chloride followed by the H-abstraction reactions from toluene or o-xylene by Cl atoms and detected by cavity ring-down spectroscopy. The visible absorption cross sections of the radicals were determined relative to that of the HCO radical. The rate constants determined were k(benzyl+benzyl)=1.29×10−3T−2.669exp(−674/T)cm3molecule−1s−1 (Δlog10k=±0.096) and k(o-xylyl+o-xylyl)=2.57T−3.784exp(−1025/T)cm3molecule−1s−1 (Δlog10k=±0.107).