Temperature dependence of disproportionation–combination ratios for alkyl radicals in liquid methane

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DOIResolve DOI: http://doi.org/10.1139/v71-475
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TypeArticle
Journal titleThe Canadian Journal of Chemistry
ISSN0008-4042
Volume49
IssueSeptember 17
Pages28612867; # of pages: 7
AbstractThe ratios of rate constants for disproportionation to combination have been measured for ethyl radicals and for i-propyl radicals in liquid methane between −181 and −94 °C. The radicals were generated by γ-radiolysis of dilute methane solutions of ethylene-d4 or propylene-d6. The activation energy for combination was found to exceed that for disproportionation by 290 ± 30 cal mol−1 for ethyl radicals and by 255 ± 25 cal mol−1 for i-propyl radicals. In both cases the disproportionation—combination ratio in the liquid, extrapolated to room temperature, is greater than that in the gas phase by a factor of about 2.5. These results are interpreted as indicating that disproportionation and combination reactions proceed by way of different transition states.
Publication date
LanguageEnglish
AffiliationNRC Institute for National Measurement Standards; National Research Council Canada
Peer reviewedNo
Identifier10000872
NRC number3700
NPARC number8896874
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Record identifiercfd4adee-4809-4067-b001-00c11dafadfe
Record created2009-04-22
Record modified2016-05-09
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