title: 1,4-hydroxycarbonyl products of the OH radical initiated reactions of C5-C8 n-alkanes in the presence of NO.
abstract: Alkanes account for approximately 50% of nonmethane organic compounds present in urban atmospheres. Previous studies have shown that hydroxycarbonyls are important products ofthe OH radical initiated reactions of > or = C5 n-alkanes, but isomer-specific identifications and quantifications of these products have not been carried out. In this work, we have used solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl-containing compounds with subsequent analyses by combined gas chromatography-mass spectrometry (GC-MS) and GC with flame ionization detection (GC-FID). GC-MS analyses showed the presence of the oximes of 5-hydroxy-2-pentanone and 4-hydroxypentanal from the n-pentane reaction; 5-hydroxy-2-hexanone, 6-hydroxy-3-hexanone, and 4-hydroxyhexanal from the n-hexane reaction; 5-hydroxy-2-heptanone, 6-hydroxy-3-heptanone, 1-hydroxy-4-heptanone, and 4-hydroxyheptanal from the n-heptane reaction; and 5-hydroxy-2-octanone, 6-hydroxy-3-octanone, 7-hydroxy-4-octanone, and 4-hydroxyoctanal from the n-octane reaction. The formation yields of these 1,4-hydroxycarbonyls were determined from GC-FID analyses. By use of the yields of 1,4-hydroxycarbonyls formed from n-hexane, n-heptane, and n-octane at 50% relative humidity (and those from n-pentane at both 5 and 50% relative humidity), then formation of 1,4-hydroxycarbonyls accounts for 54% of the reaction products from n-pentane, 57% from n-hexane, 51% from n-heptane, and 53% from n-octane. Combined with previously measured yields of carbonyls, alkyl nitrates, and hydroxyalkyl nitrates, we can now accountfor approximately 74-118% of the products formed from the n-pentane through n-octane reactions.
authors.affiliation: Air Pollution Research Center, University of California, Riverside, California 92521, USA.
authors.forename: Fabienne
authors.initials: F
authors.lastname: Reisen
authors.forename: Sara M
authors.initials: SM
authors.lastname: Aschmann
authors.forename: Roger
authors.initials: R
authors.lastname: Atkinson
authors.forename: Janet
authors.initials: J
authors.lastname: Arey
mesh_terms: D000447:Aldehydes / Q000032:analysis; D000473:Alkanes / Q000737:chemistry*; D005410:Flame Ionization; D008401:Gas Chromatography-Mass Spectrometry; D017665:Hydroxyl Radical / Q000737:chemistry*; D006898:Hydroxylamines; D009569:Nitric Oxide / Q000737:chemistry*; D010091:Oximes / Q000032:analysis*; D005466:Fluorocarbons
chemical_list: D000447:Aldehydes; D000473:Alkanes; D017665:Hydroxyl Radical; D006898:Hydroxylamines; D009569:Nitric Oxide; D010091:Oximes; C010277:Florox Reagent; D005466:Fluorocarbons