title: Atmospheric chemistry of 3-pentanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX.
abstract: Smog chamber/FTIR techniques were used to study the atmospheric chemistry of 3-pentanol and determine rate constants of k(Cl+3-pentanol) = (2.03 +/- 0.23) x 10 (-10) and k(OH+3-pentanol) = (1.32 +/- 0.15) x 10 (-11) cm (3) molecule (-1) s (-1) in 700 Torr of N 2/O 2 diluent at 296 +/- 2 K. The primary products of the Cl atom initiated oxidation of 3-pentanol in the absence of NO were (with molar yields) 3-pentanone (26 +/- 2%), propionaldehyde (12 +/- 2%), acetaldehyde (13 +/- 2%) and formaldehyde (2 +/- 1%). The primary products of the Cl atom initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (51 +/- 4%), propionaldehyde (39 +/- 2%), acetaldehyde (44 +/- 4%) and formaldehyde (4 +/- 1%). The primary products of the OH radical initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (58 +/- 3%), propionaldehyde (28 +/- 2%), and acetaldehyde (37 +/- 2%). In all cases the product yields were independent of oxygen concentration over the partial pressure range 10-700 Torr. The reactions of Cl atoms and OH radicals with 3-pentanol proceed 26 +/- 2 and 58 +/- 3%, respectively, via attack on the 3-position to give an alpha-hydroxyalkyl radical, which reacts with O 2 to give 3-pentanone. The results are discussed with respect to the literature data and atmospheric chemistry of 3-pentanol.
authors.affiliation: Systems Analytics and Environmental Sciences Department, Ford Motor Company, Mail Drop RIC-2122, Dearborn, Michigan 48121-2053, USA. mhurley3@ford.com
authors.forename: M D
authors.initials: MD
authors.lastname: Hurley
authors.forename: T J
authors.initials: TJ
authors.lastname: Wallington
authors.forename: M
authors.initials: M
authors.lastname: Bjarrum
authors.forename: M S
authors.initials: MS
authors.lastname: Javadi
authors.forename: O J
authors.initials: OJ
authors.lastname: Nielsen
mesh_terms: D000393:Air Pollutants / Q000737:chemistry; D001272:Atmosphere / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D009569:Nitric Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D000439:Pentanols / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D000393:Air Pollutants; D000439:Pentanols; D009569:Nitric Oxide; D017665:Hydroxyl Radical; D002713:Chlorine