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Reactions of methyl radicals with acetaldehyde and acetaldehyde-d1. I. relative rates of atom abstraction reactions at 785°K

✍ Scribed by I. Bárdi; T. Bérces; I. Szilágyi

Publisher
John Wiley and Sons
Year
1976
Tongue
English
Weight
523 KB
Volume
8
Category
Article
ISSN
0538-8066

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✦ Synopsis

The role of ethenoxy radicals in the pyrolysis of CHaCDO was studied by mass spectrometric analysis of the isotopic composition of the methane, ethane, and recovered aldehyde. Experimental evidence was obtained for the formation of ethenoxy radicals and for their reaction with acetaldehyde.

Mixtures of CH&HO and CHICDO were pyrolyzed in order to minimize H-D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions

CH3 + CHSCHO CHI + CHZCHO furnished the rate constant ratios (kb + kib)/kla = 2.7 and klb/kla = 0.62 at 785°K. It is concluded that at the usual temperatures of CH3CHO pyrolysis the rate of alkyl hydrogen capture is comparable to that of formyl hydrogen abstraction.

The results and conclusions are discussed and compared with previous work.

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