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The thermal decomposition of gaseous methyl azide has been investigated at conversions of less than 1 % at 155, 170, and 200 "C. The reaction has been shown to be homogeneous and unimolecular, the first-order rate constant being k,,' = 2.85 x 1014 exp -(40 5001RT). The decomposition results in the formation of CH3N(X3Z-) and N2(X1Z,+). The CH3N(X3C-) d o not react with CH3N3 to produce N2, but d o form a polymer of composition similar to hexamethylene tetramine and also react wlth olefins. The major products are N 2 and polymer; small amounts of H 2 and CH4, but no C2H6, are formed.

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