Abstract

Extensive results on the reactions of fluorine, chlorine, and bromine atoms with alkanes and with some other molecules have been obtained from the study of competitive halogenations. The comparison of the A factors of the reactions provides an excellent test of the transition state theory. The activation energies of the bromine atom reactions can be combined with measurements of the activation energies for the reactions of alkyl radicals with hydrogen bromide to yield unusually reliable values of bond strengths. Information on the influence of polar effects on the activation energies of atomic reactions can be obtained from results on the reactions of fluorine and chlorine atoms with methyl halides.

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