title: Products and mechanism of the reaction of OH radicals with 2,2,4-trimethylpentane in the presence of NO.
abstract: Alkanes are important constituents of gasoline fuel and vehicle exhaust, with branched alkanes comprising a significant fraction of the total alkanes observed in urban areas. Products of the gas-phase reactions of OH radicals with 2,2,4-trimethylpentane and 2,2,4-trimethylpentane-d18 in the presence of NO at 298+/-2 K and atmospheric pressure of air have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography-mass spectrometry (GC-MS), and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS). Acetone, 2-methylpropanal, and 4-hydroxy-4-methyl-2-pentanone were identified and quantified by GC-FID from 2,2,4-trimethylpentane with molar formation yields of 54+/-7%, 26+/-3%, and 5.1+/-0.6%, respectively; upper limits to the formation yields of acetaldehyde, 2,2-dimethylpropanal, and 4,4-dimethyl-2-pentanone were obtained. Additional products observed from 2,2,4-trimethylpentane by API-MS and API-MS/MS analyses using positive and negative ion modes were hydroxy products of molecular weight 130 and 144, a product of molecular weight 128 (attributed to a C8-carbonyl), and hydroxynitrates of molecular weight 135, 177, and 191 (attributed to HOC4H8ONO2, HOC7H14ONO2, and HOC8H16-ONO2, respectively). Formation of HOC8H16ONO2 and HOC7H14-ONO2 is consistent with the observation of products of molecular weight 207 (HOC8D16ONO2) and 191 (HOC7D14-ONO2), respectively, in the API-MS analyses of the 2,2,4-trimethylpentane-d18 reaction (-OD groups rapidly exchange to -OH groups under our experimental conditions). These product data allow the reaction pathways to be delineated to a reasonable extent, and the reaction mechanism is discussed.
authors.affiliation: Air Pollution Research Center, University of California, Riverside 92521, USA.
authors.forename: Sara M
authors.initials: SM
authors.lastname: Aschmann
authors.forename: Janet
authors.initials: J
authors.lastname: Arey
authors.forename: Roger
authors.initials: R
authors.lastname: Atkinson
mesh_terms: D016166:Free Radical Scavengers / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry*; D008970:Molecular Weight; D009569:Nitric Oxide / Q000737:chemistry; D009795:Octanes / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*
chemical_list: D016166:Free Radical Scavengers; D009795:Octanes; D016877:Oxidants; D009569:Nitric Oxide; D017665:Hydroxyl Radical; C045798:2,2,4-trimethylpentane