KINETICS AND MECHANISMS OF THE THERMAL DECOMPOSITION OF ACETALDEHYDE: II. THE REACTION IN THE PRESENCE OF NITRIC OXIDE

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Abstract
The decomposition of acetaldehyde has been reinvestigated in the presence of various amounts of nitric oxide, over a range of temperatures (495 to 525 °C) and acetaldehyde pressures (36 to 340 mm Hg). At higher acetaldehyde pressures there is no inhibition, the rate steadily increasing with increasing nitric oxide concentration; at low acetaldehyde concentrations increasing amounts of nitric oxide first give inhibition and then give catalysis. The degree of inhibition increases with decrease in temperature. As the nitric oxide concentration is increased, the order rises above 3/2 and then falls to 3/2 again. At higher nitric oxide concentrations the rate varies with [CH3CHO]3/2 [NO]1/2. All of the facts are explained by a mechanism according to which initiation occurs by[Formula: see text]together with the processes occurring in the absence of nitric oxide (cf. Part I). Termination is considered to involve the reaction occurring in the case of no inhibition (CH3 + CH3 + X → C2H6 + X) together with[Formula: see text][Formula: see text]Application of the mechanism to the results is discussed in detail.

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