- Title
- A mechanistic and kinetic study on the decomposition of morpholine
- Creator
- Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.
- Relation
- Journal of Physical Chemistry A Vol. 116, Issue 29, p. 7703-7711
- Publisher Link
- http://dx.doi.org/10.1021/jp303463j
- Publisher
- American Chemical Society
- Resource Type
- journal article
- Date
- 2012
- Description
- 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.
- Subject
- morpholine; C₄H₈ONH; decomposition reactions
- Identifier
- http://hdl.handle.net/1959.13/1311849
- Identifier
- uon:22300
- Identifier
- ISSN:1089-5639
- Language
- eng
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