Journal article
A mechanistic and kinetic study on the decomposition of morpholine
The Journal of Physical Chemistry A, Vol.116(29), pp.7703-7711
2012
Abstract
The combustion chemistry of morpholine (C4H8ONH) has been experimentally investigated recently as a representative model compound for O- and N-containing structural entities in biomass. Detailed profiles of species indicate the self-breakdown reactions prevailing over oxidative decomposition reactions. In this study, we derive thermodynamic and kinetic properties pertinent to all plausible reactions involved in the self-decomposition of morpholine and its derived morphyl radicals as a crucial task in the development of comprehensive combustion mechanism. Potential energy surfaces have been mapped out for the decomposition of morpholine and the three morphyl radicals. RRKM-based calculations predict the self-decomposition of morpholine to be dominated by 1,3-intramolecular hydrogen shift into the NH group at all temperatures and pressures. Self-decomposition of morpholine is shown to provide pathways for the formation of the experimentally detected products such as ethenol and ethenamine. Energetic requirements of all self-decomposition of morphyl radicals are predicted to be of modest values (i.e., 20-40 kcal/mol) which in turn support the occurrence of breaking-down reactions into two-heavy-atom species and the generation of doubly unsaturated four-heavy-atom segments. Calculated thermochemical parameters (in terms of standard enthalpies of formation, standard entropies, and heat capacities) and kinetic parameters (in terms of reaction rate constants at a high pressure limit) should be instrumental in building a robust kinetic model for the oxidation of morpholine.
Details
- Title
- A mechanistic and kinetic study on the decomposition of morpholine
- Authors/Creators
- M. Altarawneh (Author/Creator)B.Z. Dlugogorski (Author/Creator)
- Publication Details
- The Journal of Physical Chemistry A, Vol.116(29), pp.7703-7711
- Publisher
- American Chemical Society
- Identifiers
- 991005545195707891
- Copyright
- © 2012 American Chemical Society.
- Murdoch Affiliation
- Murdoch University
- Language
- English
- Resource Type
- Journal article
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InCites Highlights
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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, Physical
- Physics, Atomic, Molecular & Chemical
- ESI research areas
- Chemistry