Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx

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

doi:10.1021/jp045672g

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH): products and mechanism of Cl atom initiated oxidation in the presence of NO_x

Mads Peter Sulbæk Andersen, Ole John Nielsen, M. D. Hurley, J. C. Ball, T. J. Wallington, 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 Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C4F9CH2CH2OH to give C4F9CH2C.HOH radicals which add O-2 to give chemically activated alpha-hydroxyperoxy radicals, [C4F9CH2C(OO.)HOH]*. In 700 Torr of N-2/ O-2 at 296 K, approximately 50% of the [C4F9CH2C(OO.)HOH]* radicals decompose ``promptly'' to give HO2 radicals and C4F9CH2CHO, the remaining [C4F9CH2C(OO.)HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C4F9CH2C(OO.)HOH. Decomposition to HO2 and C4F9CH2CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C4F9CH2C(O-.)HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C4F9CH2.. The primary products of 4:2 FTOH oxidation in the presence of excess NOx are C4F9CH2CHO, C4F9CHO, and HCOOH. Secondary products include C4F9CH2C(O)O2NO2, C4F9C(O)O2NO2, and COF2. In contrast to experiments conducted in the absence of NOx, there was no evidence (

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	109
Issue number	9
Pages (from-to)	1849-1856
Number of pages	8
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp045672g
Publication status	Published - 2005

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Andersen, M. P. S., Nielsen, O. J., Hurley, M. D., Ball, J. C., Wallington, T. J., Ellis, D. A., Martin, J. W., & Mabury, S. A. (2005). Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH): products and mechanism of Cl atom initiated oxidation in the presence of NO_x. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 109(9), 1849-1856. https://doi.org/10.1021/jp045672g

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH) : products and mechanism of Cl atom initiated oxidation in the presence of NO_x. / Andersen, Mads Peter Sulbæk ; Nielsen, Ole John; Hurley, M. D. et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 109, No. 9, 2005, p. 1849-1856.

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

Andersen, MPS , Nielsen, OJ, Hurley, MD, Ball, JC, Wallington, TJ, Ellis, DA, Martin, JW & Mabury, SA 2005, 'Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH): products and mechanism of Cl atom initiated oxidation in the presence of NO_x', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 109, no. 9, pp. 1849-1856. https://doi.org/10.1021/jp045672g

Andersen MPS , Nielsen OJ, Hurley MD, Ball JC, Wallington TJ, Ellis DA et al. Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH): products and mechanism of Cl atom initiated oxidation in the presence of NO_x. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2005;109(9):1849-1856. doi: 10.1021/jp045672g

Andersen, Mads Peter Sulbæk ; Nielsen, Ole John ; Hurley, M. D. et al. / Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH) : products and mechanism of Cl atom initiated oxidation in the presence of NO_x. In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2005 ; Vol. 109, No. 9. pp. 1849-1856.

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title = "Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx",

abstract = "Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C4F9CH2CH2OH to give C4F9CH2C.HOH radicals which add O-2 to give chemically activated alpha-hydroxyperoxy radicals, [C4F9CH2C(OO.)HOH]*. In 700 Torr of N-2/ O-2 at 296 K, approximately 50% of the [C4F9CH2C(OO.)HOH]* radicals decompose ``promptly'' to give HO2 radicals and C4F9CH2CHO, the remaining [C4F9CH2C(OO.)HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C4F9CH2C(OO.)HOH. Decomposition to HO2 and C4F9CH2CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C4F9CH2C(O-.)HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C4F9CH2.. The primary products of 4:2 FTOH oxidation in the presence of excess NOx are C4F9CH2CHO, C4F9CHO, and HCOOH. Secondary products include C4F9CH2C(O)O2NO2, C4F9C(O)O2NO2, and COF2. In contrast to experiments conducted in the absence of NOx, there was no evidence (",

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

year = "2005",

doi = "10.1021/jp045672g",

language = "English",

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pages = "1849--1856",

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

issn = "1089-5639",

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T1 - Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH)

T2 - products and mechanism of Cl atom initiated oxidation in the presence of NOx

AU - Andersen, Mads Peter Sulbæk

AU - Nielsen, Ole John

AU - Hurley, M. D.

AU - Ball, J. C.

AU - Wallington, T. J.

AU - Ellis, D. A.

AU - Martin, J. W.

AU - Mabury, S. A.

PY - 2005

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N2 - Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C4F9CH2CH2OH to give C4F9CH2C.HOH radicals which add O-2 to give chemically activated alpha-hydroxyperoxy radicals, [C4F9CH2C(OO.)HOH]*. In 700 Torr of N-2/ O-2 at 296 K, approximately 50% of the [C4F9CH2C(OO.)HOH]* radicals decompose ``promptly'' to give HO2 radicals and C4F9CH2CHO, the remaining [C4F9CH2C(OO.)HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C4F9CH2C(OO.)HOH. Decomposition to HO2 and C4F9CH2CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C4F9CH2C(O-.)HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C4F9CH2.. The primary products of 4:2 FTOH oxidation in the presence of excess NOx are C4F9CH2CHO, C4F9CHO, and HCOOH. Secondary products include C4F9CH2C(O)O2NO2, C4F9C(O)O2NO2, and COF2. In contrast to experiments conducted in the absence of NOx, there was no evidence (

AB - Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C4F9CH2CH2OH to give C4F9CH2C.HOH radicals which add O-2 to give chemically activated alpha-hydroxyperoxy radicals, [C4F9CH2C(OO.)HOH]*. In 700 Torr of N-2/ O-2 at 296 K, approximately 50% of the [C4F9CH2C(OO.)HOH]* radicals decompose ``promptly'' to give HO2 radicals and C4F9CH2CHO, the remaining [C4F9CH2C(OO.)HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C4F9CH2C(OO.)HOH. Decomposition to HO2 and C4F9CH2CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C4F9CH2C(O-.)HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C4F9CH2.. The primary products of 4:2 FTOH oxidation in the presence of excess NOx are C4F9CH2CHO, C4F9CHO, and HCOOH. Secondary products include C4F9CH2C(O)O2NO2, C4F9C(O)O2NO2, and COF2. In contrast to experiments conducted in the absence of NOx, there was no evidence (

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DO - 10.1021/jp045672g

M3 - Journal article

C2 - 16833516

SN - 1089-5639

VL - 109

SP - 1849

EP - 1856

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 - 9

ER -

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx

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Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH): products and mechanism of Cl atom initiated oxidation in the presence of NO_x