Characterization of the Autoxidation of Terpenes at Elevated Temperature Using High-Resolution Mass Spectrometry: Formation of Ketohydroperoxides and Highly Oxidized Products from Limonene - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2022

Characterization of the Autoxidation of Terpenes at Elevated Temperature Using High-Resolution Mass Spectrometry: Formation of Ketohydroperoxides and Highly Oxidized Products from Limonene

Résumé

Low-temperature experiments on the oxidation of limonene-O2-N2 mixtures were conducted in a jet-stirred reactor (JSR) over a range of temperatures (520 to 800 K), fuel-lean conditions (equivalence ratio φ = 0.5), short residence time (1.5 s) and a pressure of 1 bar. Collected samples of the reacting mixtures were analyzed by (i) on-line Fourier transform infrared spectroscopy (FTIR) and (ii) Orbitrap Q-Exactive® high resolution mass spectrometry after direct injection or chromatographic separation using reversed-phase ultra-high-performance liquid chromatography (RP-UHPLC) and soft ionization (+/‒ heated electrospray ionization and +/‒ atmospheric pressure chemical ionization). H/D exchange using deuterated water (D2O) and reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH) were performed to probe the presence of OH, OOH and C=O groups in the oxidized products, respectively. A broad range of oxidation products ranging from water to highly oxygenated products, containing five and more O-atoms, was detected (C7H10O4,5, C8H12O2,4, C8H14O2,4, C9H12O, C9H14O1,3-5, C10H12O2, C10H14O1-9, C10H16O2-5, and C10H18O6). Mass spectrometry analyzes were only qualitative whereas quantification was performed with FTIR. The results are discussed in terms of reaction routes involving the initial formation of peroxy radicals, H-atom transfer and O2 addition sequences producing a large set of chemical products among which ketohydroperoxides and more oxygenated products. Carbonyl compounds deriving from the Waddington oxidation mechanism on exo- and endo-double bonds (C=C) were observed as well as their products of further oxidation. Products of the Korcek mechanism (carboxylic acids and carbonyls) were also detected.
Fichier principal
Vignette du fichier
JPCA_terpenes_rev2.pdf (936.58 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Licence : Copyright (Tous droits réservés)

Dates et versions

hal-03967581 , version 1 (01-02-2023)

Licence

Copyright (Tous droits réservés)

Identifiants

Citer

Zahraa Dbouk, Nesrine Belhadj, Maxence Lailliau, Roland Benoit, Philippe Dagaut. Characterization of the Autoxidation of Terpenes at Elevated Temperature Using High-Resolution Mass Spectrometry: Formation of Ketohydroperoxides and Highly Oxidized Products from Limonene. Journal of Physical Chemistry A, 2022, 126 (48), pp.9087-9096. ⟨10.1021/acs.jpca.2c06323⟩. ⟨hal-03967581⟩
18 Consultations
52 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More