Journal of the American Chemical Society p. 4356 - 4361 (1984)
Update date:2022-08-12
Topics:
Slagle
Park
Heaven
Gutman
The kinetics and mechanism of the gaseous reaction of vinyl radicals with molecular oxygen have been studied between 297 and 602 K. The radicals were produced in a heated tubular reactor by the pulsed laser photolysis of C//2H//3Br at 193 nm. Reactant and product concentrations were monitored in real-time experiments using photoionization mass spectrometry. The products formed in this temperature range are HCO and H//2CO. The overall rate constant is pressure independent and is nearly constant with temperature: k equals 6. 6 ( plus or minus 1. 3) multiplied by 10** minus **1**2 exp(250 plus or minus 100 cal/RT) cm**3 molecule** minus **1 s** minus **1. The magnitude of the rate constant, its temperature and pressure dependence, and the identity of the products of this reaction indicate that it proceeds by an addition mechanism in which the adduct rapidly rearranges to form an energy-rich dioxetanyl intermediate which decomposes into the observed products. Two other reactions (C//2H//3 plus i-C//4H//1//0 and C//3H//5 (allyl radical) plus O//2) were investigated at elevated temperatures, but no reaction was detected.
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