Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations - Université de Lille Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2022

Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations

Résumé

Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure JSR at 570 K and ϕ = 0.8. Numerous intermediates including hydroperoxides and highly oxygenated molecules were detected using synchrotron vacuum ultraviolet photoelectron photoion coincidence spectroscopy. Supported by high-level quantum calculations the analysis of photoelectron spectra allowed the firm identification of molecular species formed during the oxidation of cyclohexane. Besides, this work validates recently published gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry data. Unambiguous detection of characteristic hydroperoxides (e.g. γ-ketohydroperoxides) and their respective decomposition products provide support for the conventional O2-addition channels up to the third addition and their relative contribution to the cyclohexane oxidation. The results were also compared to the predictions of a recently proposed new detailed kinetic model of cyclohexane oxidation. Most of the predictions are in line with the current experimental findings highlighting the robustness of the kinetic model. However, the analysis of the recorded slow photoelectron spectra indicating the possible presence of C5 species in the kinetic model provides hints that substituted cyclopentyl radicals from cyclohexyl ring opening might play a minor role in cyclohexane oxidation. Potentially important missing reaction are discussed.
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hal-03827417 , version 1 (24-10-2022)

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Jérémy Bourgalais, Hans-Heinrich Carstensen, Olivier Herbinet, Gustavo A. Garcia, Philippe Arnoux, et al.. Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations. Journal of Physical Chemistry A, 2022, 126 (34), pp.5784-5799. ⟨10.1021/acs.jpca.2c04490⟩. ⟨hal-03827417⟩
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