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Products of the OH Radical-Initiated Reactions of Furan, 2- and 3‑Methylfuran, and 2,3- and 2,5-Dimethylfuran in the Presence of NO

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journal contribution
posted on 16.01.2014, 00:00 by Sara M. Aschmann, Noriko Nishino, Janet Arey, Roger Atkinson
Products of the gas-phase reactions of OH radicals with furan, furan-d4, 2- and 3-methylfuran, and 2,3- and 2,5-dimethylfuran have been investigated in the presence of NO using direct air sampling atmospheric pressure ionization tandem mass spectrometry (API-MS and API-MS/MS), and gas chromatography with flame ionization and mass spectrometric detectors (GC–FID and GC–MS) to analyze samples collected onto annular denuders coated with XAD solid adsorbent and further coated with O-(2,3,4,5,6-pentafluorobenzyl)­hydroxylamine for derivatization of carbonyl-containing compounds to their oximes. The products observed were unsaturated 1,4-dicarbonyls, unsaturated carbonyl-acids and/or hydroxy-furanones, and from 2,5-dimethylfuran, an unsaturated carbonyl-ester. Quantification of the unsaturated 1,4-dicarbonyls was carried out by GC–FID using 2,5-hexanedione as an internal standard, and the measured molar formation yields were: HC­(O)­CHCHCHO (dominantly the E-isomer) from OH + furan, 75 ± 5%; CH3C­(O)­CHCHCHO (dominantly the E-isomer) from OH + 2-methylfuran, 31 ± 5%; HC­(O)­C­(CH3)CHCHO (a E-/Z-mixture) from OH + 3-methylfuran, 38 ± 2%; and CH3C­(O)­C­(CH3)CHCHO from OH + 2,3-dimethylfuran, 8 ± 2%. In addition, a formation yield of 3-hexene-2,5-dione from OH + 2,5-dimethylfuran of 27% was obtained from a single experiment, in good agreement with a previous value of 24 ± 3% from GC–FID analyses of samples collected onto Tenax solid adsorbent without derivatization.