Atmospheric chemistry of n-CxF2x+1CHO (x = 1, 2, 3, 4): fate of n-CxF2x+1C(O) radicals

M. D. Hurley, J. C. Ball, T. J. Wallington, Mads Peter Sulbæk Andersen, Ole John Nielsen, D. A. Ellis, J. W. Martin, S. A. Mabury

Research output: Contribution to journalJournal articleResearchpeer-review

35 Citations (Scopus)

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.
Original languageEnglish
JournalJournal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume110
Issue number45
Pages (from-to)12443–12447
Number of pages5
ISSN1089-5639
DOIs
Publication statusPublished - 2006

Keywords

  • Air Pollutants
  • Aldehydes
  • Atmosphere
  • Carboxylic Acids
  • Fluorocarbons
  • Free Radicals
  • Peroxides

Cite this