Thermal Decomposition of Aliphatic Nitro-compounds

Two mechanisms of decomposition of nitro-compounds are discussed: molecular, when a molecule of HNO₂ is detached and the corresponding alkene is formed, and free-radical, in which the reaction starts with the breaking of the C–N bond. Study of the reactions of the first type is of considerable interest in the light of the general theory of elimination reactions in the gas phase. The radical decomposition of nitroalkanes is characterised by high values of the pre-exponential factors. The activation energy in this instance equals the energy for breaking the bond. Secondary reactions have little influence on the rate of radical decomposition of gem-polynitroalkanes, therefore the study of the kinetics of the decomposition can be an effective method of determining the energy for the breaking of the C–N bond in these compounds. Bibliography of 48 references.