Reaction of nitrogen dioxide with hydrocarbons and its influence on spontaneous ignition. A computational study

Abstract

Estimates are made, by using BHandHLYP/6-311G** density functional molecular orbital theory, of the activation energies and frequency factors for the reaction of NO₂ with methane, ethane, propane, isobutane, and benzene. For the aliphatic hydrocarbons, over the temperature range 600–1100 K, the rate of formation of a new isomer of nitrous acid, HNO₂, is very similar to that for the formation of the common isomer, HONO. This complicates our description of the acceleration of spontaneous ignition of diesel fuels by organic nitrates. These rate data are used in a reduced kinetic model to examine the effect of NO₂ upon the spontaneous ignition of some linear- and branched-chain aliphatic hydrocarbons. It is concluded that, under typical diesel engine operating conditions, the spontaneous ignition of linear-chain paraffins is accelerated by the presence of NO₂, but may be retarded for heavily branched-chain isomers. An Appendix discusses the relative importance of tunnelling in hydrogen-transfer reactions.