Previous work on the acetaldehyde pyrolysis is shown to be vitiated by the presence, in the acetaldehyde, of impurities, mainly ethanol and crotonaldehyde. The reaction has been reinvestigated with the use of acetaldehyde, prepared from paraldehyde, which is free from these and other impurities. On the basis of a study of the kinetics of formation of the major products (methane and carbon monoxide) and of a number of minor products (hydrogen, acetone, propionaldehyde, ethane and ethylene) a reaction mechanism is proposed. This includes all of the reactions in the original Rice-Herzfeld scheme, together with a number of other elementary processes, in particular CH3 + CH3CHO → CH4 + CH2CHO. The decomposition of the radical CH2CHO into CH2CO and H provides an additional source of hydrogen, the rate of production of which is therefore not a measure of the rate of the initiation process. Acetone is believed to arise mainly by the reaction CH3 + CH3CHO → CH3COCH3 + H, and only to a negligible extent by the combination of CH3 and CH3CO. The main chain-ending step is concluded to be CH3 + CH3 → C2H6, with a small contribution from CH3 + CH2CHO → CH3CH2CHO. The work provides further evidence for the falling off, at low pressures, of the second order coefficient for the combination of methyl radicals. Rate constants for various elementary processes are deduced from the rates of formation of the various products, and are shown to be consistent with values obtained directly.
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