title: Kinetics and products of the reactions of OH radicals with cyclohexene, 1-methyl-1-cyclohexene, cis-cyclooctene, and cis-cyclodecene.
abstract: Rate constants for the reactions of OH radicals with four C(6)-C(10) cycloalkenes have been measured at 297 ± 2 K using a relative rate technique. The rate constants (in units of 10(-11) cm(3) molecule(-1) s(-1)) were cyclohexene, 6.35 ± 0.12; cis-cyclooctene, 5.16 ± 0.15; cis-cyclodecene, 4.18 ± 0.06; and 1-methyl-1-cyclohexene, 9.81 ± 0.18, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate constant for the reference compound 1,3,5-trimethylbenzene. In addition, a rate constant of (4.8 ± 1.3) × 10(-11) cm(3) molecule(-1) s(-1) was derived for the reaction of OH radicals with 1,6-hexanedial, relative to our measured rate constant for OH + cyclohexene. Analyses of products of the OH + cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene reactions by direct air sampling atmospheric pressure ionization mass spectrometry and/or by combined gas chromatography-mass spectrometry showed the presence of products attributed to cyclic 1,2-hydroxynitrates and the dicarbonyls 1,6-hexanedial, 6-oxo-heptanal, and 1,8-octanedial, respectively. These dicarbonyl products, which are those formed after decomposition of the intermediate cyclic 1,2-hydroxyalkoxy radicals, were quantified as their dioximes, with molar formation yields of 76 ± 10%, 82 ± 12%, and 84 ± 18% from the cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene reactions, respectively. Combined with literature data concerning 1,2-hydroxynitrate formation from OH + alkenes and the estimated fractions of the overall reactions proceeding by H-atom abstraction, 90 ± 12%, 95 ± 13% and 108 ± 20% of the products or reaction pathways from the OH radical-initiated reactions of cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene in the presence of NO are accounted for.
authors.affiliation: Air Pollution Research Center, University of California, Riverside, California 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: D043822:Cyclodecanes / Q000737:chemistry*; D053138:Cyclohexenes / Q000737:chemistry*; D034242:Cyclooctanes / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D043822:Cyclodecanes; D053138:Cyclohexenes; D034242:Cyclooctanes; D017665:Hydroxyl Radical