SCHEDULED MAINTENANCE
Reactions of oxygenated radicals in the gas phase. Part 9.—Self-reactions of isopropylperoxy radicals
Abstract
The principal products of the photo-oxidation of trans-2,2′-azopropane between 333 and 373 K are acetone, isopropyl alcohol, isopropyl hydroperoxide, acetaldehyde, formaldehyde, methyl alcohol and cis-2,2′-azopropane. The reaction mechanism has been simulated in detail, and, in conjunction with results obtained earlier for the overall self-reaction of isopropylperoxy radicals, the following rate data have been obtained for the reactions 2(CH3)2CHO2·→(CH3)2CHOH +(CH3)2CO + O2(3a), 2(CH3)2CHO2·→ 2(CH3)2CHO·+ O2(3b)k3b/k3a increases with temperature, from 1.39 ± 0.04 at 302 K to 1.83 ± 0.04 at 333 K and 2.80 ± 0.08 at 373 K. Values of A3a and A3b of 2.44 ± 0.31 × 107 and 1.38 ± 0.26 × 109 dm3 mol–1 s–1 and E3a and E3b of 12.0 ± 1.0 and 21.3 ± 1.5 kJ mol–1 were determined.
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