Kinetics for the reaction of phenyl radical with phenylacetylene and styrene

Abstract

The kinetics for the reactions of C 6H 5 with phenylacetylene and styrene have been measured by CRDS in the temperature range 297–409 K under an Ar pressure of 3.6 Torr. The total rate constants can be given by the following Arrhenius expressions (in units of cm 3 mol −1 s −1): k 1(C 6H 5 + C 6H 5C 2H) = 10 13.0±0.1exp [−(2430 ± 150)/ RT] and k 2(C 6H 5 + C 6H 5C 2H 3) = 10 13.3±0.1 exp [−(2570 ± 180)/ T]. Additional DFT and MP2 calculations have been carried out to assist our interpretation of the measured kinetic data. The addition of C 6H 5 to the terminal CH x ( x = 1 or 2) sites is predicted to be the dominant channel for both reactions. The calculated bimolecular rate constants are in reasonable agreement with experimental values for the temperature range studied.