The Photochemical Decomposition of Methyl Azide

The photolysis of methyl azide has been investigated in the vapor phase at low conversions and over suitable ranges of pressure, temperature, intensity, and wavelength. Under all conditions the principal gaseous product was N2 with small amounts of H2 (5–11%), and traces of CH4, C2H4, and C2H6. A condensate identified as (CH3N)x was also found.The quantum yield for the production of N2 is approximately 2, independent of intensity (over a 45-fold range), temperature (17–100 °C), and pressure (14–300 mm Hg). The quantum yield decreases slightly with increasing wavelength. Experiments with added CO2, CH3N2CH3, and C2H4 indicate the presence of a short chain carried mainly by the CH3N radical. Excited species probably play some role in the reaction.