Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

Mads Peter Sulbæk Andersen; A. Toft; O.J. Nielsen; M.D. Hurley; T.J. Wallington; H. Chishima; K. Tonokura; S.A. Mabury; J.W. Martin; D.A. Ellis

doi:10.1021/jp060404z

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

Mads Peter Sulbæk Andersen, A. Toft, O.J. Nielsen, M.D. Hurley, T.J. Wallington, H. Chishima, K. Tonokura, S.A. Mabury, J.W. Martin, D.A. Ellis

Department of Chemistry

19 Citations (Scopus)

Abstract

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) <2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic 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	32
Pages (from-to)	9854-60
Number of pages	7
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp060404z
Publication status	Published - 2006

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Andersen, M. P. S., Toft, A., Nielsen, O. J., Hurley, M. D., Wallington, T. J., Chishima, H., Tonokura, K., Mabury, S. A., Martin, J. W., & Ellis, D. A. (2006). Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 110(32), 9854-60. https://doi.org/10.1021/jp060404z

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4) : hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation. / Andersen, Mads Peter Sulbæk; Toft, A.; Nielsen, O.J. et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 110, No. 32, 2006, p. 9854-60.

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

Andersen, MPS, Toft, A, Nielsen, OJ, Hurley, MD, Wallington, TJ, Chishima, H, Tonokura, K, Mabury, SA, Martin, JW & Ellis, DA 2006, 'Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 110, no. 32, pp. 9854-60. https://doi.org/10.1021/jp060404z

Andersen MPS, Toft A, Nielsen OJ, Hurley MD, Wallington TJ, Chishima H et al. Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2006;110(32):9854-60. doi: 10.1021/jp060404z

Andersen, Mads Peter Sulbæk ; Toft, A. ; Nielsen, O.J. et al. / Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4) : hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation. In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2006 ; Vol. 110, No. 32. pp. 9854-60.

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title = "Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation",

abstract = "Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) <2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.",

author = "Andersen, {Mads Peter Sulb{\ae}k} and A. Toft and O.J. Nielsen and M.D. Hurley and T.J. Wallington and H. Chishima and K. Tonokura and S.A. Mabury and J.W. Martin and D.A. Ellis",

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T1 - Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4)

T2 - hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

AU - Andersen, Mads Peter Sulbæk

AU - Toft, A.

AU - Nielsen, O.J.

AU - Hurley, M.D.

AU - Wallington, T.J.

AU - Chishima, H.

AU - Tonokura, K.

AU - Mabury, S.A.

AU - Martin, J.W.

AU - Ellis, D.A.

PY - 2006

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N2 - Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) <2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.

AB - Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) <2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.

U2 - 10.1021/jp060404z

DO - 10.1021/jp060404z

M3 - Journal article

C2 - 16898686

SN - 1089-5639

VL - 110

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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 - 32

ER -

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

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