Rate constants for CN reactions with hydrocarbons and the product HCN vibrational populations: Examples of heavy–light–heavy abstraction reactions

Abstract

The rate constants for the reactions of CN radicals with methane, ethane, propane, cyclo-propane, isobutane, and neopentane have been measured over a temperature range from 275 to 455 K. Laser photolysis was used to produce the radicals and time delayed laser induced fluorescence was used to follow the radical concentration as a function of time. The temperature dependence of the observed rate constants could be fitted with a three-parameter Arrhenius plot. The activation energies that were observed were all small and in some cases they were negative. Time resolved ir emission was used to follow the formation of the HCN(0n2) and HCN(0n′1) product emission. The time dependence of the relative emission intensities, as well as computer modeling of the decay curves, suggest that vibrational population inversion occurs for all of the hydrocarbons studied except methane and cyclopropane. These observations are discussed in terms of the current theories for these type of reactions.