Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals
dc.contributor.author | Simmie, John M. | |
dc.contributor.author | Black, Gráinne | |
dc.contributor.author | Curran, Henry J. | |
dc.contributor.author | Hinde, John P. | |
dc.date.accessioned | 2018-09-20T16:24:45Z | |
dc.date.available | 2018-09-20T16:24:45Z | |
dc.date.issued | 2008-06-01 | |
dc.identifier.citation | 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 | |
dc.identifier.issn | 1089-5639,1520-5215 | |
dc.identifier.uri | http://hdl.handle.net/10379/13915 | |
dc.description.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. | |
dc.publisher | American Chemical Society (ACS) | |
dc.relation.ispartof | The Journal of Physical Chemistry A | |
dc.subject | sulfate-reducing aquifer | |
dc.subject | set model chemistry | |
dc.subject | gas-phase acidity | |
dc.subject | thermochemical properties | |
dc.subject | peroxy-radicals | |
dc.subject | group additivity | |
dc.subject | thermodynamic properties | |
dc.subject | natural attenuation | |
dc.subject | united-states | |
dc.subject | kinetics | |
dc.title | Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals | |
dc.type | Article | |
dc.identifier.doi | 10.1021/jp711360z | |
dc.local.publishedsource | http://www.nuigalway.ie/ccaps/documents/simmie_2008_alkyl_hydroperoxides.pdf | |
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