Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals
Simmie, John M. Black, Gráinne Curran, Henry J. Hinde, John P.
Simmie, John M.
Black, Gráinne
Curran, Henry J.
Hinde, John P.
Identifiers
http://hdl.handle.net/10379/13915
https://doi.org/10.13025/28188
https://doi.org/10.13025/28188
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Publication Date
2008-06-01
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Article
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Simmie, John M. Black, Gráinne; Curran, Henry J.; Hinde, John P. (2008). Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals. The Journal of Physical Chemistry A 112 (22), 5010-5016
Abstract
The enthalpies of formation and bond dissociation energies, D(ROO-H), D(RO-OH), D(RO-O), D(R-O-2) and D(R-OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RO, have been computed at CBS-QB3 and APNO levels of theory via isodesmic and atomization procedures for R = methyl, ethyl, n-propyl and isopropyl and n-butyl, tert-butyl, isobutyl and sec-butyl. We show that D(ROO-H) approximate to 357, D(RO-OH) approximate to 190 and D(RO-O) approximate to 263 kJ mol(-1) for all R, whereas both D(R-OO) and D(R-OOH) strengthen with increasing methyl substitution at the cc-carbon but remain constant with increasing carbon chain length. We recommend a new set of group additivity contributions for the estimation of enthalpies of formation and bond energies.
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Publisher
American Chemical Society (ACS)
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Attribution-NonCommercial-NoDerivs 3.0 Ireland