Recombination of methyl radicals and atomic cracking of ethyl radicals

Abstract

The characteristics of this atomic cracking reaction and of the pressure and steric effects associated with the recombination of methyl radicals are all intimately related. The available data on these reactions are correlated by means of a previously developed theory. Some experimental results on the steric factor and the data on the remaining subjects appear to be consistent with the assumption that the methyl radicals must be highly oriented with respect to each other in order that recombination occur. However, experimental steric factors of unity have also been reported in the literature. The corresponding assumption of no orientation leads to disagreement with the remaining data unless some of the rotational degrees of freedom of the "active" molecule, in addition to the vibrations, are assumed to be "active." Even then, the difficulties are not completely removed. Further experimental work on these reactions is needed.

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