Termolysiys of Nitromethane in Pressurized Supercritical Media

Article abstract of DOI:10.1021/jo00251a021

The decomposition of supercritical nitromethane at liquid-like densities gives HCN and CO2 as the principal carbon-containing product whereas at low pressure CH4 and CO predominate.The decomposition is powerfully accelerated by increased density, and a contact ion-pair transition state is inferred.The activation volume is -85 mL/mol.A new method of measurement is described.Various lines of evidence indicate a shift from homolysis at low pressure to rearrangement in dielectric media.