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Disproportionation-combination ratios of large branched alkyl radicals

✍ Scribed by J. H. Georgakakos; B. S. Rabinovitch; C. W. Larson

Publisher
John Wiley and Sons
Year
1971
Tongue
English
Weight
790 KB
Volume
3
Category
Article
ISSN
0538-8066

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✦ Synopsis

The disproportionation-combination reactions of radicals 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, produced by collisional stabilization of the respective chemically activated species, have been studied at 298"K, with and without getter radicals. Use of getters t-C4H9 and CzHs with 4,4-dimethylpentyl-2, and of iso-C3HT with 2,4-dimethylpentyl-2 yielded disproportionation-combination ratios A for parent-getter and t-C4H9-C 2H6 cross reactions, and for the mutual reaction of t-CqH9 radicals. The unstabilized hot radicals decompose, and these experiments also yielded values for the high-pressure rate constant k,, of 1.7OX 108sec-1 and 2.11 X 105ec-' for 4,4-dimethylpentyl-2 and 2,4dimethylpentyl-2, respectively. The results, compared to those for other large alkyl radical systems obtained earlier, suggest that steric effects influence the accessibility of H atoms for transfer .

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