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

Low-temperature experiments on the oxidation of limonene-O2-N2 mixtures were conducted in a jet-stirred reactor (JSR) over a range of temperatures (520-800 K) under fuel-lean conditions (equivalence ratio φ = 0.5) with a short residence time (1.5 s) and a pressure of 1 bar. Collected samples of the reaction mixtures were analyzed by (i) online 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 (with positive or negative heated electrospray ionization and atmospheric-pressure chemical ionization). H/D exchange using deuterated water (D2O) and a 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. A broad range of oxidation products ranging from water to highly oxygenated products containing five and more O atoms were detected (C7H10O4,5, C8H12O2,4, C8H14O2,4, C9H12O, C9H14O1,3-5, C10H12O2, C10H14O1-9, C10H16O2-5, and C10H18O6). Mass spectrometry analyses were only qualitative, and 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, including ketohydroperoxides and more oxygenated products. Carbonyl compounds derived from the Waddington oxidation mechanism on exo- and endo-double bonds (C═C) were observed in addition to their products of further oxidation. Products of the Korcek mechanism (carboxylic acids and carbonyls) were also detected.