A mechanistic and kinetic study on the decomposition of morpholine. 2012

Mohammednoor Altarawneh, and Bogdan Z Dlugogorski
Priority Research Centre for Energy, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan NSW 2308, Australia. Mohammednoor.Altarawneh@newcastle.edu.au

The combustion chemistry of morpholine (C(4)H(8)ONH) 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.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D009025 Morpholines Tetrahydro-1,4-Oxazines,Tetrahydro 1,4 Oxazines
D009584 Nitrogen An element with the atomic symbol N, atomic number 7, and atomic weight [14.00643; 14.00728]. Nitrogen exists as a diatomic gas and makes up about 78% of the earth's atmosphere by volume. It is a constituent of proteins and nucleic acids and found in all living cells.
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D011312 Pressure A type of stress exerted uniformly in all directions. Its measure is the force exerted per unit area. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Pressures
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D005609 Free Radicals Highly reactive molecules with an unsatisfied electron valence pair. Free radicals are produced in both normal and pathological processes. Free radicals include reactive oxygen and nitrogen species (RONS). They are proven or suspected agents of tissue damage in a wide variety of circumstances including radiation, damage from environment chemicals, and aging. Natural and pharmacological prevention of free radical damage is being actively investigated. Free Radical
D006859 Hydrogen The first chemical element in the periodic table with atomic symbol H, and atomic number 1. Protium (atomic weight 1) is by far the most common hydrogen isotope. Hydrogen also exists as the stable isotope DEUTERIUM (atomic weight 2) and the radioactive isotope TRITIUM (atomic weight 3). Hydrogen forms into a diatomic molecule at room temperature and appears as a highly flammable colorless and odorless gas. Protium,Hydrogen-1
D013696 Temperature The property of objects that determines the direction of heat flow when they are placed in direct thermal contact. The temperature is the energy of microscopic motions (vibrational and translational) of the particles of atoms. Temperatures

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