La peroxydation de l’éther éthylique : étude théorique et expérimentale

Abstract : Numerous organic compounds spontaneously decompose, by reaction of a free-radical of the carbon chain with molecular oxygen, in a self-propagating process of auto-oxidation, which may generate a large variety of peroxide molecules. Many laboratory accidents can be ascribed to the presence of such peroxides in chemicals storage, often under poor conditions, for over-long periods. Ethers are typical solvents showing such a behavior. However, few works are focused on the mechanistic study of their reaction of oxidation. This work, carried out within the INERIS research project named RIPER (for “study of RIsk linked to the PERoxidation of chemical products”), presents the results of an in-depth theoretical study based on DFT calculations, aiming to identify all the reaction paths (and products) involved in the diethyl ether oxidation process (at ambient temperature and under conditions that reflect normal storage conditions). DFT calculations indicate that this mechanism follows a classical scheme of chain initiation, chain propagation, and chain branching and termination. Different competitions have been identified between several chain branching pathways (such as hydroperoxides decomposition and isomerization pathways). They also indicate that industrial hazards could be related to hydroperoxide accumulation due to the relatively high activation barrier to further decomposition. Coupled with experimental work aiming to measure the amount of experimental products (such as acetaldehyde, acetic acid and organic peroxides) during accelerated oxidation of DEE at various temperatures, all energetic parameters calculated in this theoretical work will be used to develop a detailed chemical kinetic model of the oxidation process of DEE.
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Wassila Benaissa, Stefania Di Tommaso, Peggy Gruez, Patricia Rotureau. La peroxydation de l’éther éthylique : étude théorique et expérimentale. Rapport Scientifique INERIS, 2011, 2010-2011, pp.34-38. ⟨ineris-01869385⟩

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