title: Atmospheric chemistry of n-C(x)F(2)(x)(+1)CHO (x = 1, 2, 3, 4): fate of n-C(x)F(2)(x)(+1)C(O) radicals.
abstract: Smog chamber/FTIR techniques were used to study the atmospheric fate of n-C(x)F(2)(x)(+1)C(O) (x = 1, 2, 3, 4) radicals in 700 Torr O(2)/N(2) diluent at 298 +/- 3 K. A competition is observed between reaction with O(2) to form n-C(x)()F(2)(x)()(+1)C(O)O(2) radicals and decomposition to form n-C(x)F(2)(x)(+1) radicals and CO. In 700 Torr O(2)/N(2) diluent at 298 +/- 3 K, the rate constant ratio, k(n-C(x)F(2)(x)(+1)C(O) + O(2) --> n-C(x)F(2)(x)(+1)C(O)O(2))/k(n-C(x)F(2)(x)(+1)C(O) --> n-C(x)F(2)(x)(+1) + CO) = (1.30 +/- 0.05) x 10(-17), (1.90 +/- 0.17) x 10(-19), (5.04 +/- 0.40) x 10(-20), and (2.67 +/- 0.42) x 10(-20) cm(3) molecule(-1) for x = 1, 2, 3, 4, respectively. In one atmosphere of air at 298 K, reaction with O(2) accounts for 99%, 50%, 21%, and 12% of the loss of n-C(x)F(2)(x)(+1)C(O) radicals for x = 1, 2, 3, 4, respectively. Results are discussed with respect to the atmospheric chemistry of n-C(x)F(2)(x)(+1)C(O) radicals and their possible role in contributing to the formation of perfluorocarboxylic acids in the environment.
authors.affiliation: Ford Motor Company, P.O. Box 2053, Dearborn, Michigan 48121-2053, USA. mhurley3@ford.com
authors.forename: M D
authors.initials: MD
authors.lastname: Hurley
authors.forename: J C
authors.initials: JC
authors.lastname: Ball
authors.forename: T J
authors.initials: TJ
authors.lastname: Wallington
authors.forename: M P
authors.initials: MP
authors.lastname: Sulbaek Andersen
authors.forename: O J
authors.initials: OJ
authors.lastname: Nielsen
authors.forename: D A
authors.initials: DA
authors.lastname: Ellis
authors.forename: J W
authors.initials: JW
authors.lastname: Martin
authors.forename: S A
authors.initials: SA
authors.lastname: Mabury
mesh_terms: D000393:Air Pollutants / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry
chemical_list: D000393:Air Pollutants; D000447:Aldehydes; D002264:Carboxylic Acids; D005466:Fluorocarbons; D005609:Free Radicals; D010545:Peroxides