FREE RADICAL CHEMISTRY OF THE MONO- AND DIHALONITROMETHANES

摘要

The bimolecular reaction rates for nine halonitromethanes have been published1 as has a detailed discussion of destruction mechanism for trichloronitromethane, chloropicrin however, no reports of the destruction mechanism for the five, mono or dihalonitromethanes has appeared. The halogens in our study were CI and Br The defining consideration in the destruction mechanisms is the formation of peroxyl radicals, their dimerization to form tetroxides and the subsequent intra-molecular decomposition to products. We proposed that the tetroxide of trichloronitromethane went to the corresponding alkoxy-radicals and then decomposed. However for these five compounds several potential paths of decomposition are possible through the Russell and Bennett mechanisms. Using product studies with increasing dose (energy) a mechanism is proposed that accounts for the product distribution when irradiated using cobalt-60 irradiation. This then allows us to build a kinetic model that describes their destruction.