Effect of additive polyfunctional substituents on the thermal decomposition rate of R1,R2,R3-nitromethanes

Kinetics of thermal decomposition of polyfunctionally substituted nitromethanes has been studied by manometric method as well as IR and chromato-mass spectrometry. Activation parameters of the ratelimiting stage of C-NO₂ homolysis have been determined. The rate constant and the activation energy are correlated with additive steric constants of the substituents; this enables prediction of reactivity (thermal stability) of the unstudied mononitrocompounds which decompose with the break of C-NO₂ bond.