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Recombination of Tertiary Butyl Peroxy Radicals. Part 1.-Products Yields between 298 and 373 K

DOI: 10.1039/f19817700293

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 293 - 308 (1981)

Update date:2022-08-11

Topics:

Authors:

Kirsch, Leslie J.Kirsch, Leslie J.

Parkes, David A.Parkes, David A.

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Article abstract of DOI:10.1039/f19817700293

Overall product distributions resulting from the recombination of t-butyl peroxy radicals have been studied over the temperature range 298-373 K.The results indicate that over this range there is a switch from the terminating channels (forming alcohol and aldehyde/ketone) towards non-terminating channels (forming two alkoxy radicals) for the two further recombination processes that follow the initial combination of t-butyl peroxy radicals:.There is also direct evidence for the presence of a terminating channel to form di-t-butyl peroxide.This reaction proceeds at a rate of ca. 0.14 of the non-terminating recombination rate at 298 K, but this fraction falls to 0.025 at 333 K and the reaction is not evident at 373 K.Our results demonstrate the importance of abstraction reactions involving alkoxy radicals (t-butoxy and methoxy) and one of the principal recombination products, t-butyl hydroperoxide.Rate constant ratios involving these processes have been derived from the product distributions and from additional studies in which t-butyl hydroperoxide was added.Rate constants of ca. 10-13 cm3 molecule-1 s-1 for these abstraction processes are consistent with our results.

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Product name:Di-tert-butyl peroxide

Cas No:110-05-4

110-05-4

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