Kinetic analysis of alkane polychlorination with molecular chlorine. Chlorine atom/monochloride geminate pairs and the effect of reactive "cage walls" on the competition between monochloride rotation and chlorine atom escape

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DOIResolve DOI: http://doi.org/10.1021/ja00219a028
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume110
Issue11
Pages35193524; # of pages: 6
AbstractThe free-radical chlorination of alkanes produces polychlorides even at low conversions. These are formed by reaction of chlorine atom/monochloride (or dichloride) geminate pairs. This process has been studied in detail in various solvent systems, and a kinetic scheme has been proposed. Deviations from this scheme have been rationalized as being due to competition between monochloride rotation and reaction of the chlorine atom with reactive molecules in the "cage walls" surrounding the chlorine atom/chloride geminate pair. Analysis of the dichloride products supports the suggestion that monochloride rotation is not completely "free" within the lifetime of the geminate pair.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276663
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Record identifierf37de4f6-8258-49eb-8343-538ad535882a
Record created2015-10-13
Record modified2016-05-09
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