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The decomposition of nitromethane behind shock waves was studied at T = 1190-1490 K and P ≈ 1.5 atm; the reaction was monitored based on the formation and consumption of radicals, which were detected by their absorption in the region of λ = 405 nm. It was found that the curves of the yield of have a convex shape, which is characteristic of the formation of primary decomposition products. Based on an analysis of the initial sections of the experimental curves of the yield of , the temperature dependence of the rate constants of formation of these radicals upon the decomposition of nitromethane was found for the first time: k 1 ( ) = (6.3 ± 2) × 10 12 exp(-48.9 ± 2/RT) s -1 (the dimensionality of E a is kcal/mol). It was found that the rate constants of nitromethane decomposition measured from the consumption of the parent substance and the yield of radicals almost coincide with each other. A kinetic simulation of the forma tion and consumption of upon the decomposition of nitromethane was performed. A good agreement between experimental and calculated data was achieved. A brief theoretical analysis of competition between the channels of direct disintegration and isomerization under conditions of the thermal decomposition of nitromethane was performed. The advantage of the direct disintegration channel with the rupture of the C-N bond was shown. Both experimental and published data on the isomerization of nitromethane into methyl nitrite upon its thermal decomposition and photolysis were analyzed.

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