Journal article
Alkoxy radicals in the gaseous phase: β-scission reactions and formation by radical addition to carbonyl compounds
Canadian Journal of Chemistry, Vol.81(6), pp.431-442
2003
Abstract
The structures and reactivities of the alkoxy radicals methoxy (CH 3O•), ethoxy (CH3CH2O•), 1-propoxy (CH3CH2CH2O•), 2-propoxy ((CH3)2CHO•), 2-butoxy (CH3CH 2CH(CH3)O•), tert-butoxy ((CH3) 3CO•), prop-2-enoxy (CH2=CHCH2O• ), and but-3-en-2-oxy (CH2=CHCH(CH3)O•) have been investigated at the B3-LYP/6-31G(d) and CBS-RAD levels of theory. Enthalpies of formation (ΔfH298o) were calculated with CBS-RAD for all the alkoxy radicals, the carbonyl and radical products of β-scission reactions, and the transition structures leading to them. The mean absolute deviation between the predicted and available experimental ΔfH298o values is 5.4 kJ mol -1. Eyring (ΔH0‡, ΔH 298‡, ΔG298‡) and Arrhenius (log A, Ea) activation parameters for both the forward (β-scission) and reverse (radical addition to carbonyl) pathways were calculated. Agreement with available experimental data is very good, generally within 1-5 kJ mol -1 for Ea, and 0.5 for log A. The transition structures are found to be substantially polarized, with the departing radical slightly positive, the O atom negative, and the rest of the molecule positive. The barriers for the β-scission reactions decrease with decreasing endothermicity and with decreasing ionization energy of the departing radical.
Details
- Title
- Alkoxy radicals in the gaseous phase: β-scission reactions and formation by radical addition to carbonyl compounds
- Authors/Creators
- A. Rauk (Author/Creator)R.J Boyd (Author/Creator)S.L Boyd (Author/Creator)D.J. Henry (Author/Creator)L. Radom (Author/Creator)
- Publication Details
- Canadian Journal of Chemistry, Vol.81(6), pp.431-442
- Publisher
- NRC Research Press
- Identifiers
- 991005543333207891
- Copyright
- © 2003 NRC Canada
- Murdoch Affiliation
- Murdoch University
- Language
- English
- Resource Type
- Journal article
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- Collaboration types
- Domestic collaboration
- International collaboration
- Citation topics
- 7 Engineering & Materials Science
- 7.177 Combustion
- 7.177.238 Combustion Dynamics
- Web Of Science research areas
- Chemistry, Multidisciplinary
- ESI research areas
- Chemistry