Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation
Résumé
The reactions of chain-branching agents, such as H2O2 and hydroperoxides, have a decisive role in the occurrence of autoignition. The formation of these agents has been investigated in an atmospheric-pressure jet-stirred reactor during the low-temperature oxidation of n-pentane (initial fuel mole fraction of 0.01, residence time of 2 s) using three different diagnostics: time-of-flight mass spectrometry combined with tunable synchrotron photoionization, time-of-flight mass spectrometry combined with laser photoionization, and cw-cavity ring-down spectroscopy. These three diagnostics enable a combined analysis of H2O2, C1–C2, and C5 alkylhydroperoxides, C3–C5 alkenylhydroperoxides, and C5 alkylhydroperoxides including a carbonyl function (ketohydroperoxides). Results using both types of mass spectrometry are compared for the stoichiometric mixture. Formation data are presented at equivalence ratios from 0.5 to 2 for these peroxides and of two oxygenated products, ketene and pentanediones, which are not usually analyzed during jet-stirred reactor oxidation. The formation of alkenylhydroperoxides during alkane oxidation is followed for the first time. A recently developed model of n-pentane oxidation aids discussion of the kinetics of these products and of proposed pathways for C3–C5 alkenylhydroperoxides and the pentanediones.
Domaines
Chimie théorique et/ou physique
Fichier principal
2017 PROCI hydroperoxides.pdf (1.38 Mo)
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JSR exp data.xlsx (47.91 Ko)
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Supplementary Description.pdf (782.95 Ko)
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Origine | Fichiers produits par l'(les) auteur(s) |
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Origine | Fichiers produits par l'(les) auteur(s) |
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Origine | Fichiers produits par l'(les) auteur(s) |
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