The Photo-Oxidation of Azomethane

The photo-oxidation of azomethane has been studied at low oxygen pressures (0.02 to 1 mm.) in the temperature range ca. 25 °C. to 161 °C. The primary process in the normal photolysis of azomethane is essentially unaffected by the presence of oxygen. Carbon monoxide is probably a secondary product of the oxidation of methyl radicals. Carbon dioxide formation is quite small, and therefore neither methyl radicals nor CH 3 N=N—CH 2 radicals are oxidized appreciably to carbon dioxide. Nitrous oxide, which is a major product of the oxidation, is most likely formed from the oxidation of CH 3 N=NCH 2 radicals. The suggested mechanism of N 2 O formation is:[Formula: see text] The reaction of methyl radicals with oxygen was found to proceed with a negligible activation energy and a steric factor of the order of 10 −2 . Evidence for the occurrence of the reactions[Formula: see text]at room temperature was obtained.