USAF - SCEEE (Southeastern Center for Electrical Engineering Education) Summer Faculty Research Program (1980). A Model for the Thermal Decomposition of TNT (Trinitrotoluene); Theoretical Reaction Profiles

摘要

The molecule l-nitropropylene has been investigated as a model system for the simulation of the thermal decomposition of TNT. Two distinct types of reaction mechanisms were considered: Intramolecular Mechanisms and Bimolecular Mechanisms. Intramolecular mechanisms investigated include an oxidative hydrogen atom transfer to form the diradical aci nitropropylene and an oxidative oxygen atom insertion reaction to form l-nitro-3-hydroxy propylene. Semi empirical molecular orbital calculations (MNDO and MINDO/3) were carried out to obtain a reaction profile for these mechanisms, and indicated that the oxygen atom insertion reaction should lead to the reaction products, methyl nitrite and acetylene. This is not in accord with experiment. The profile for the oxidative hydrogen atom transfer was found to reproduce many of the features known for the thermal decomposition of TNT. Bimolecular mechanisms considered included an oxidative hydrogen atom transfer from one nitropropylene molecule to another to form the 1-nitropropylene radical and the aci form of nitropropylene and an intermolecular oxidative insertion reaction to form l-nitro-3-hydroxy propylene and l-nitroso propylene. Preliminary reports are given for these bimolecular mechanisms. (Author)