Unifying the solution thermochemistry of molecules, radicals, and ions

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DOIResolve DOI: http://doi.org/10.1021/ja00202a031
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume111
Issue20
Pages78727876; # of pages: 5
AbstractA general cycle was developed that defines the thermodynamics for all of the homolytic and heterolytic cleavage reactions of a hydrocarbon, R-R’, in solution. Only seven experimental parameters were needed in order to define the energetics for all 11 of the possible cleavage reactions of R-R’. These parameters were the oxidation and reduction potentials of R-R’, R’, and R” and the homolytic, R-R’, bond energy. The utility of this approach was demonstrated for the case where R was an arylmethyl group and R’ was hydrogen. The oxidation and reduction potentials of the arylmethyl radicals were measured by modulation voltammetry in acetonitrile, and the homolytic C-H bond energies of the corresponding hydrocarbons were measured by photoacoustic calorimetry. The cycle was also extended to a case where R-R’ was a radical rather than a closed-shell molecule.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Institute for Chemical Process and Environmental Technology
Peer reviewedNo
Identifier10072378
NPARC number12339048
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Record identifier83a8b86a-746d-4c45-9eaa-92aa475e8aae
Record created2009-09-11
Record modified2016-05-09
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