|Title:||Enthalpies of Formation and Bond Dissociation Energies of Lower Alkyl Hydroperoxides and Related Hydroperoxy and Alkoxy Radicals|
|Authors:||John M. Simmie, Grainne Black, Henry J. Curran, John P. Hinde, 2008|
The enthalpies of formation and bond dissociation energies, D(ROO−H), D(RO−OH), D(RO−O), D(R−O2) 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) ≈ 357, D(RO−OH) ≈ 190 and D(RO−O) ≈ 263 kJ mol^−1 for all R, whereas both D(R−OO) and D(R−OOH) strengthen with increasing methyl substitution at the α-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.
|ICHEC Project:||BurnQuest: Towards a World Class Combustion Chemistry Centre|
|Publication:||Journal of Physical Chemistry A (2008) 112(22) 5010–5016|