Computer simulation of thermal decomposition reactions of alkyl nitrates

An approach to the construction of models for thermal decomposition of organic compounds based onrecombination reaction networks was developed. Each species (molecule, ion, or radical) is considered as a potential reagent. It was suggested that the newly formed species can react with all other species which are already present in the reaction mixture. The results of reactions are represented as a bipartite graph whose vertices are formed either by species generated or by the descriptions of interactions, while the oriented edges determine the relations between the reagents and the reaction products. Based on analysis of the experimental data on the mechanisms of thermal decomposition, empirical rules were developed for simulating possible thermal decomposition reactions of the major classes of energetic compounds. The proposed approach allows one to describe the complete spectrum of reactions occurring in the course of thermal decomposition. The approach was realized in the CASB computer program and was exemplified by simulation of thermal decomposition of methyl, ethyl, and isopropyl nitrates. All stages of the mechanisms (some of which have been reported in the literature) were reproduced. A number of new decomposition reactions, which have not been studied experimentally, are suggested.