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Theoretical studies on the initiation oxidation reactions of selected hydrocarbons by singlet oxygen

Zeinali, Nassim (2019) Theoretical studies on the initiation oxidation reactions of selected hydrocarbons by singlet oxygen. PhD thesis, Murdoch University.

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Singlet oxygen, the lowest excited state of molecular oxygen, continues to play crucial roles in natural and anthropogenic processes. Singlet oxygen signifies a prominent chemical species in a wide array of prominent chemical and biochemical phenomena. This thesis explores the thermodynamic and kinetic aspects of singlet oxygen-assisted oxidation of biogenic, industrially-valuable, and environmentally-accumulating hydrocarbons. The work embodied in this thesis has elucidated the governing mechanisms of the initiation oxidation reactions of selected organic compounds by the highly reactive singlet oxygen species, as well as characterised the physicochemical implications of the systems.

The selected organic substrates include biogenic hydrocarbons such as isoprene (C5) and monoterpenes (C10) that influence the atmospheric chemistry owing to their emission from vegetation; oxazole, an active industrial ingredient whose photo-oxidation holds important implications in syntheses of various pharmaceutical materials; coal surrogate, i.e., pyrrole to shed light and insight into the occurrence of spontaneous fires in coal mines; and notorious toxic environmental pollutants, including dioxins and furans compounds.

The method deployed a comprehensive atomistic molecular simulation, employing an unrestricted density functional theory DFT-B3LYP functional in conjunction with the 6-311+G(d,p) basis set, as well as energy refinements based on the approximated spin-projection scheme. Due to the trivial enthalpic requirements of the entrance reaction channels, relatively small at around 100 kJ/mol, the molecular interactions of the selected hydrocarbon with singlet oxygen should be termed as “spontaneous reactions”, contrasting those initiated at higher temperatures by the ground-state molecular oxygen that typically ensures via very sizable entrance barriers in the window of 200 -350 kJ/mol.

Item Type: Thesis (PhD)
Murdoch Affiliation(s): Chemistry and Physics
Supervisor(s): Altarawneh, Mohammednoor, Dlugogorski, Bogdan and Oluwoye, Ibukun
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