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

doi:10.1021/jp064029m

Atmospheric chemistry of n-C_xF_2x+1CHO (x = 1, 2, 3, 4): fate of n-C_xF_2x+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

Department of Chemistry

26 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 language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	110
Issue number	45
Pages (from-to)	12443–12447
Number of pages	5
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp064029m
Publication status	Published - 2006

Keywords

Air Pollutants
Aldehydes
Atmosphere
Carboxylic Acids
Fluorocarbons
Free Radicals
Peroxides

Access to Document

10.1021/jp064029m

Cite this

Hurley, M. D., Ball, J. C., Wallington, T. J., Andersen, M. P. S., Nielsen, O. J., Ellis, D. A., Martin, J. W., & Mabury, S. A. (2006). Atmospheric chemistry of n-C_xF_2x+1CHO (x = 1, 2, 3, 4): fate of n-C_xF_2x+1C(O) radicals. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 110(45), 12443–12447. https://doi.org/10.1021/jp064029m

Atmospheric chemistry of n-C_xF_2x+1CHO (x = 1, 2, 3, 4) : fate of n-C_xF_2x+1C(O) radicals. / Hurley, M. D.; Ball, J. C.; Wallington, T. J. et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 110, No. 45, 2006, p. 12443–12447.

Research output: Contribution to journal › Journal article › Research › peer-review

Hurley, MD, Ball, JC, Wallington, TJ, Andersen, MPS , Nielsen, OJ, Ellis, DA, Martin, JW & Mabury, SA 2006, 'Atmospheric chemistry of n-C_xF_2x+1CHO (x = 1, 2, 3, 4): fate of n-C_xF_2x+1C(O) radicals', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 110, no. 45, pp. 12443–12447. https://doi.org/10.1021/jp064029m

@article{340b1befdb7d463db3b4db725d64ed66,

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

keywords = "Air Pollutants, Aldehydes, Atmosphere, Carboxylic Acids, Fluorocarbons, Free Radicals, Peroxides",

author = "Hurley, {M. D.} and Ball, {J. C.} and Wallington, {T. J.} and Andersen, {Mads Peter Sulb{\ae}k} and Nielsen, {Ole John} and Ellis, {D. A.} and Martin, {J. W.} and Mabury, {S. A.}",

year = "2006",

doi = "10.1021/jp064029m",

language = "English",

volume = "110",

pages = "12443–12447",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "45",

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TY - JOUR

T1 - Atmospheric chemistry of n-CxF2x+1CHO (x = 1, 2, 3, 4)

T2 - fate of n-CxF2x+1C(O) radicals

AU - Hurley, M. D.

AU - Ball, J. C.

AU - Wallington, T. J.

AU - Andersen, Mads Peter Sulbæk

AU - Nielsen, Ole John

AU - Ellis, D. A.

AU - Martin, J. W.

AU - Mabury, S. A.

PY - 2006

Y1 - 2006

N2 - 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.

AB - 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.

KW - Air Pollutants

KW - Aldehydes

KW - Atmosphere

KW - Carboxylic Acids

KW - Fluorocarbons

KW - Free Radicals

KW - Peroxides

U2 - 10.1021/jp064029m

DO - 10.1021/jp064029m

M3 - Journal article

C2 - 17091948

SN - 1089-5639

VL - 110

SP - 12443

EP - 12447

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 45

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