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Experimental Study of the Reaction between Vinyl and Methyl Radicals in the Gas Phase. Temperature and Pressure Dependence of Overall Rate Constants and Product Yields

Published

Author(s)

S I. Stoliarov, Vadim D. Knyazev, I R. Slagle

Abstract

The vinyl-methyl cross-radical reaction was studied by laser photolysis / photoionization mass spectroscopy. Overall rate constants and quantitative product yields were obtained in direct real-time experiments in the temperature region 300 K to 900 K and bath gas (He) density (3 to 12) x 1016 molecules cm-3. The observed overall C2H3 + CH3 rate constant is independent of pressure and demonstrates a slight negative temperature dependence, which can be represented by the expression k4 = 5.1 x 10-7T-1.26exp(-362/T) molecule-1cm3s-1. Propene, acetylene and allyl radicals were identified as primary products of the C2H3 + CH3 reaction. At room temperature, propene and acetylene are the major products of the reaction, whereas at 900 K, production of allyl radicals becomes the dominating channel. On the basis of these experimental results, a mechanism consisting of two major routes is proposed. One route proceeds via direct abstraction of a hydrogen atom from vinyl radical by the methyl radical resulting in the formation of acetylene and methane. The other route proceeds via the formation of chemically activated propene that can undergo either collisional stabilization or further decomposition into allyl radical and hydrogen atom.
Citation
Journal of Physical Chemistry A
Volume
104
Issue
No. 43

Keywords

chemical kinetics, methyl radical, reaction kinetics, vinyl radical

Citation

Stoliarov, S. , Knyazev, V. and Slagle, I. (2000), Experimental Study of the Reaction between Vinyl and Methyl Radicals in the Gas Phase. Temperature and Pressure Dependence of Overall Rate Constants and Product Yields, Journal of Physical Chemistry A (Accessed May 25, 2024)

Issues

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Created October 31, 2000, Updated October 12, 2021