Reactions of alkoxy radicals. III. The kinetics of the t-butyl hypochlorite chlorination of toluene

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DOIResolve DOI: http://doi.org/10.1021/ja00995a011
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume89
Issue19
Pages48854891; # of pages: 7
AbstractThe kinetics have been determined for the photochemically initiated (24°) and thermally initiated (30°) radical chain chlorination of toluene in CCl4 by t-butyl hypochlorite. In the initial stages of the reaction the rate is approximately proportional to the first power of the toluene concentration and to the square root of the rate of initiation. These kinetics apply over a wide range of relative and absolute toluene and hypochlorite concentrations. They imply that hydrogen atom abstraction from the toluene by t-butoxy radicals is the rate-controlling step of chain propagation and that chain termination involves the mutual destruction of two t-butoxy radicals. At high conversions the reaction is strongly autoaccelerating, and the kinetics become more complex. It is suggested that the autoacceleration is due to the formation of an unstable intermediate which can break down and initiate new reaction chains.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276443
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Record identifier0ec6e1ca-a168-4fca-9e4f-e937dd1afa98
Record created2015-10-13
Record modified2016-05-09
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