Étude théorique des mécanismes de combustion des alcènes à basse température

Abstract : This work focused on the study of the unimolecular decomposition of the low-temperature reactions of alkenes. The oxidation of these molecules is essential in the understanding of the mechanisms of combustion, because they are initially present in conventional fuels or formed as intermediates in the oxidation process. The theoretical study can be divided in two parts: - The study of the decomposition of hydroxyalkylperoxyl radicals (HOROO•) obtained from the addition of an •OH radical on the alkene, followed by a subsequent addition of the formed radical •ROH on molecular oxygen. This study was conducted in a systematic way on a set of representative radicals of alkenes in order to highlight the influence of the intramolecular environment on the rate constants. The results clearly showed the major influence of parameters such as the presence of a hydroxyl group in [beta] position with respect to the reactive carbon atom, the nature of the carbon atoms bearing the transferred hydrogen, the size of the transition state ring and the presence of intramolecular hydrogen bonds. - The study of the unimolecular decomposition of the allylperoxy radicals obtained from the addition of a resonance-stabilized radical on molecular oxygen. The complexity of these systems, specifically induced by the mesomeric structures of heavy allyl radicals and the role of cis and trans conformations alkenes parents, have been highlighted in this work. It has been shown that the formation of a compound 1-alkenyloxirane is favored at low-temperatures, which shows the importance of these reactions, usually neglected in the kinetic models for the combustion of alkenes
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Juan Carlos Lizardo Huerta. Étude théorique des mécanismes de combustion des alcènes à basse température. Alimentation et Nutrition. Université de Lorraine, 2015. Français. ⟨NNT : 2015LORR0015⟩. ⟨tel-01751428⟩

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