Thermal dissociation and recombination of alkyl and haloalkyl peroxynitrates: An SACM modelling study

Recent experimental results on the thermal decomposition and the reverse recombination of alkyl and haloalkyl peroxynitrates are modelled with an SACM formalism. The molecules RO2NO2 with R = CH3, CF3, CF2Cl, CFCl2, CCl3, and C2H5 are considered. Detailed and simplified reduced falloff expressions are compared. Limiting low (ko) and high pressure (kx) rate constants, such as derived from a fit of these falloff expressions to the experiments, are compared with absolute predictions, based on general knowledge about energy transfer (〈ΔE〉 in ko) and on a recently proposed simple SACM estimate for kx. The analysis also allows for a derivation of the bond energies of the mentioned molecules.