Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

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

doi:10.1021/jp0493576

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

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

Department of Chemistry

50 Citations (Scopus)

Abstract

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27 respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration. For the experimental conditions used herein and employing > 98% consumption of 4:2 fluorotelomer alcohol, the molar yields of CF3(CF2)(3)COOH were <0.011, 0.031, 0.042, and 0.056 in experiments conducted with 10, 140, 400, and 700 Torr O-2, respectively. These results suggest that the atmospheric oxidation of fluorotelomer alcohols may be a significant source of the perfluorinated carboxylic acids that are observed in remote areas.

Original language	Undefined/Unknown
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	108
Issue number	26
Pages (from-to)	5635-5642
Number of pages	8
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp0493576
Publication status	Published - 1 Jul 2004

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Hurley, MD., Ball, JC., Wallington, TJ., Andersen, M. P. S., Ellis, DA., Martin, JW., & Mabury, SA. (2004). Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 108(26), 5635-5642. https://doi.org/10.1021/jp0493576

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation. / Hurley, MD; Ball, JC; Wallington, TJ et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 108, No. 26, 01.07.2004, p. 5635-5642.

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

Hurley, MD, Ball, JC, Wallington, TJ, Andersen, MPS, Ellis, DA, Martin, JW & Mabury, SA 2004, 'Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 108, no. 26, pp. 5635-5642. https://doi.org/10.1021/jp0493576

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title = "Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation",

abstract = "Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27 respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration. For the experimental conditions used herein and employing > 98% consumption of 4:2 fluorotelomer alcohol, the molar yields of CF3(CF2)(3)COOH were <0.011, 0.031, 0.042, and 0.056 in experiments conducted with 10, 140, 400, and 700 Torr O-2, respectively. These results suggest that the atmospheric oxidation of fluorotelomer alcohols may be a significant source of the perfluorinated carboxylic acids that are observed in remote areas.",

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T1 - Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

AU - Hurley, MD

AU - Ball, JC

AU - Wallington, TJ

AU - Andersen, Mads Peter Sulbæk

AU - Ellis, DA

AU - Martin, JW

AU - Mabury, SA

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N2 - Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27 respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration. For the experimental conditions used herein and employing > 98% consumption of 4:2 fluorotelomer alcohol, the molar yields of CF3(CF2)(3)COOH were <0.011, 0.031, 0.042, and 0.056 in experiments conducted with 10, 140, 400, and 700 Torr O-2, respectively. These results suggest that the atmospheric oxidation of fluorotelomer alcohols may be a significant source of the perfluorinated carboxylic acids that are observed in remote areas.

AB - Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27 respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration. For the experimental conditions used herein and employing > 98% consumption of 4:2 fluorotelomer alcohol, the molar yields of CF3(CF2)(3)COOH were <0.011, 0.031, 0.042, and 0.056 in experiments conducted with 10, 140, 400, and 700 Torr O-2, respectively. These results suggest that the atmospheric oxidation of fluorotelomer alcohols may be a significant source of the perfluorinated carboxylic acids that are observed in remote areas.

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DO - 10.1021/jp0493576

M3 - Tidsskriftartikel

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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

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