Product Identification in the Low-Temperature ...
Document type :
Article dans une revue scientifique: Article original
DOI :
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Title :
Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations
Author(s) :
Bourgalais, Jérémy [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Carstensen, Hans-Heinrich [Auteur]
95355|||University of Zaragoza - Universidad de Zaragoza [Zaragoza]
Fundación Agencia Aragonesa para la Investigación y el Desarrollo [ARAID]
Herbinet, Olivier [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Garcia, Gustavo A. [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Arnoux, Philippe [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Tran, Luc-Sy [Auteur]
Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Vanhove, Guillaume [Auteur]
Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Nahon, Laurent [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Hochlaf, Majdi [Auteur]
Laboratoire Instrumentation, Simulation et Informatique Scientifique [COSYS-LISIS]
Battin-Leclerc, Frédérique [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Laboratoire Réactions et Génie des Procédés [LRGP]
Carstensen, Hans-Heinrich [Auteur]
95355|||University of Zaragoza - Universidad de Zaragoza [Zaragoza]
Fundación Agencia Aragonesa para la Investigación y el Desarrollo [ARAID]
Herbinet, Olivier [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Garcia, Gustavo A. [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Arnoux, Philippe [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Tran, Luc-Sy [Auteur]

Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Vanhove, Guillaume [Auteur]

Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Nahon, Laurent [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Hochlaf, Majdi [Auteur]
Laboratoire Instrumentation, Simulation et Informatique Scientifique [COSYS-LISIS]
Battin-Leclerc, Frédérique [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Journal title :
Journal of Physical Chemistry A
Abbreviated title :
J. Phys. Chem. A
Volume number :
126
Pages :
5784-5799
Publisher :
American Chemical Society (ACS)
Publication date :
2022-08-23
ISSN :
1089-5639
English keyword(s) :
Energy
Kinetic modeling
Mathematical methods
Oxidation
Oxides
Kinetic modeling
Mathematical methods
Oxidation
Oxides
HAL domain(s) :
Sciences de l'ingénieur [physics]
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
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 ...
Show more >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. ��-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.Show less >
Show more >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. ��-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.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
Université de Lille
CNRS
CNRS
Research team(s) :
PhysicoChimie de la Combustion (PC2)
Submission date :
2022-10-22T10:05:07Z
2022-10-24T14:11:12Z
2022-10-24T14:11:12Z
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