Abstract
The thermal decomposition mechanisms of gaseous nitromethane, methyl nitrite, dimethylnitramine and 1,3,3,-trinitroazetidine (TNAZ) have been reanalyzed using sensitivity and principal component analyses. For each system an adequate, much simplified mechanism was developed, and the fragmentation/reaction sequence leading to the final products was made transparent. The critical roles of free radicals (CH3, H, OH, HCO, HNO, CH3O, etc.) at different stages of these pyrolyses were then identified. The predicted product distributions for these compounds were calculated to facilitate the assessment of their explosive performance parameters. Comparison of the products generated by nitromethane with those produced by methyl nitrite showed that the contribution of a nitro-nitrite isomerization reaction is negligible in the nitromethane pyrolysis. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 655–673, 1999
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