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A mechanistic and kinetic study on the decomposition of morpholine

Altarawneh, M.ORCID: 0000-0002-2832-3886 and Dlugogorski, B.Z. (2012) A mechanistic and kinetic study on the decomposition of morpholine. The Journal of Physical Chemistry A, 116 (29). pp. 7703-7711.

Link to Published Version: http://dx.doi.org/10.1021/jp303463j
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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.

Item Type: Journal Article
Publisher: American Chemical Society
Copyright: © 2012 American Chemical Society.
URI: http://researchrepository.murdoch.edu.au/id/eprint/22654
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