Abstract
AbstractThe role of ethenoxy radicals in the pyrolysis of CH3CDO 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 CH3CHO and CH3CDO were pyrolyzed in order to minimize H‐D scrambling in the methyl group of the aldehyde. A kinetic treatment of the methyl radical reactions equation image and equation image furnished the rate constant ratios (k2a + k2b)/k1a = 2.7 and k1b/k1a = 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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