Journal of Physical Chemistry A, Vol.116, No.29, 7703-7711, 2012
A Mechanistic and Kinetic Study on the Decomposition of Morpholine
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.