Journal of the Chemical Society - Faraday Transactions p. 1369 - 1376 (1992)
Update date:2022-08-04
Topics:
Rowley, David M.
Lightfoot, Phillip D.
Lesclaux, Robert
Wallington, Timothy J.
The kinetics and mechanism of the self-reaction of cyclopentylperoxy radicals: 2 c-C5H9O2 -> 2 c-C5H9O + O2 (1a) -> c-C5H9OH + c-C5H8O + O2 (1b) have been studied using both time-rsolved and end-product-analysis techniques.Determination of the product yields from the photolysis of Cl2 - c-C5H10 - O2 - N2 mixtures using FTIR spectroscopy demonstrates that ring-opening of the cyclopentoxy radical formed in channel (1a): c-C5H9O + M -> CH2(CH2)3CHO + M (3) dominates over reaction with oxygen: c-C5H9O + O2 -> c-C5H8O + HO2 (2) under atmospheric conditions.Flash photolysis-UV absorption experiments were used to obtain the UV spectrum of the cyclopentylperoxy radical and the kinetics of reaction (1).The spectrum of c-C5H9O2 is similar to those of other alkylperoxy radicals, with a maximum cross-section of (5.22 +/- 0.20) * 10-18 cm2 molecule-1 at 250 nm, measured relative to a value of 4.55*10-18 cm2 molecule-1 for CH3O2 at 240 nm.The observed second-order rate constant, kobs (-d
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