Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes

MD Hurley; Mads Peter Sulbæk Andersen; TJ Wallington; DA Ellis; JW Martin; SA Mabury

doi:10.1021/jp036343b

Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes

MD Hurley, Mads Peter Sulbæk Andersen, TJ Wallington, DA Ellis, JW Martin, SA Mabury

Kemisk Institut

72 Citationer (Scopus)

Abstract

Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.

Originalsprog	Udefineret/Ukendt
Tidsskrift	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Vol/bind	108
Udgave nummer	4
Sider (fra-til)	615-620
Antal sider	6
ISSN	1089-5639
DOI	https://doi.org/10.1021/jp036343b
Status	Udgivet - 29 jan. 2004

Adgang til dokumentet

10.1021/jp036343b

Citationsformater

Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes. / Hurley, MD; Andersen, Mads Peter Sulbæk; Wallington, TJ et al.

I: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Bind 108, Nr. 4, 29.01.2004, s. 615-620.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

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title = "Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes",

abstract = "Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.",

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AU - Hurley, MD

AU - Andersen, Mads Peter Sulbæk

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AU - Ellis, DA

AU - Martin, JW

AU - Mabury, SA

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N2 - Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.

AB - Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.

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DO - 10.1021/jp036343b

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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 - 4

ER -