Abstract
Gas phase bimoleuclar rate constants at 294 ± 3 K (ambient temperature) for the reaction of CN radicals in the ν″ = 0 and 1 levels with a number of aliphatic organic compounds were measured using laser-induced fluorescence (LIF). Most of the rate constants are very large. The rate constants for CN(ν″ = 0) reactions with the saturated hydrocarbons increases from 5.6 × 10 −13 cm 3 s −1 molecule −1 for CH 4 to 2.6 × 10 −10 cm 3 s −1 molecule −1 for C 7H 16. Except for CH 4 the vibrational energy of the CN radical has little or no effect on the observed rate constants, indicating that any barriers occur early in the reaction coordinate. Theoretical model calculations using a long-range attractive potential suggest that many of these reactions are driven by long-range forces. These long-range forces may enhance the probability for the reaction by increasing the interaction time between the two molecules.
Published Version
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