Modélisation de la chimie de la combustion des alcanes et des alcènes à basse température par des approches de chimie quantique

Abstract : Detailed chemical kinetic models for the low-temperature combustion of fuels involve a large number of species and reactions. Automatic generation of kinetic mechanisms is a powerful tool to deal with this complexity. These softwares are based on correlations that predict thermodynamic (enthalpies of formation, entropies and heat capacities) and kinetic (rate constants) properties associated with species and reactions. However, these correlations are generally based on a limited number of reference data. In this work, we used a method involving quantum chemistry to develop new correlations for EXGAS, a software for the automatic generation of kinetic mechanisms. For thermodynamic data, new Benson groups associated with hydroxyl and hydroperoxyl functions were evaluated. Bond dissociation energies of C-H bonds and O-H bonds of these groups were also evaluated. For the kinetic data, we focused our study on the isomerization reactions of alkylperoxyl and hydroxyalkylperoxyl radicals, and on the reactions of formation of cyclic ethers. We also studied the impact of some rules of globalization and introduced new reactions to account for the formation of minor combustion products usualy neglected or imperfectly predicted by the current models. The results obtained have been introduced into detailed chemical mechanisms generated by EXGAS. These mechanisms were used to simulate the combustion of propane and n-butane at low temperatures. The results of these simulations were compared with recent experimental results to validate the calculations. The simulations showed that taking into account the new correlations and the modifications of the rules of globalization in the mechanisms improved the prediction of some minor pollutants that can have major health and environmental impacts
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Maximilien Cord. Modélisation de la chimie de la combustion des alcanes et des alcènes à basse température par des approches de chimie quantique. Autre. Université de Lorraine, 2012. Français. ⟨NNT : 2012LORR0199⟩. ⟨tel-01749390⟩

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