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.
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.
Hurley
M D
MD
Ford Motor Company, P.O. Box 2053, Dearborn, Michigan 48121-2053, USA. mhurley3@ford.com
Ball
J C
JC
Wallington
T J
TJ
Sulbaek Andersen
M P
MP
Nielsen
O J
OJ
Ellis
D A
DA
Martin
J W
JW
Mabury
S A
SA
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
D000393:Air Pollutants; D000447:Aldehydes; D002264:Carboxylic Acids; D005466:Fluorocarbons; D005609:Free Radicals; D010545:Peroxides