Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

Mads Peter Sulbæk Andersen; MD Hurley; TJ Wallington; F Blandini; NR Jensen; V Librando; J Hjorth

doi:10.1021/jp036615a

Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

Mads Peter Sulbæk Andersen, MD Hurley, TJ Wallington, F Blandini, NR Jensen, V Librando, J Hjorth

Department of Chemistry

34 Citations (Scopus)

Abstract

Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH3OCF2CF2OCH3, CH3O(CF2CF2O)(2)CH3, and CH3O(CF2CF2O)(3)CH3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).

Original language	Undefined/Unknown
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	108
Issue number	11
Pages (from-to)	1964-1972
Number of pages	9
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp036615a
Publication status	Published - 18 Mar 2004

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10.1021/jp036615a

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Andersen, M. P. S., Hurley, MD., Wallington, TJ., Blandini, F., Jensen, NR., Librando, V., & Hjorth, J. (2004). Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 108(11), 1964-1972. https://doi.org/10.1021/jp036615a

Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials. / Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 108, No. 11, 18.03.2004, p. 1964-1972.

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

Andersen, MPS, Hurley, MD, Wallington, TJ, Blandini, F, Jensen, NR, Librando, V & Hjorth, J 2004, 'Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 108, no. 11, pp. 1964-1972. https://doi.org/10.1021/jp036615a

Andersen MPS, Hurley MD, Wallington TJ, Blandini F, Jensen NR, Librando V et al. Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2004 Mar 18;108(11):1964-1972. doi: 10.1021/jp036615a

Andersen, Mads Peter Sulbæk ; Hurley, MD ; Wallington, TJ et al. / Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials. In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2004 ; Vol. 108, No. 11. pp. 1964-1972.

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title = "Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials",

abstract = "Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH3OCF2CF2OCH3, CH3O(CF2CF2O)(2)CH3, and CH3O(CF2CF2O)(3)CH3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).",

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T1 - Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

AU - Andersen, Mads Peter Sulbæk

AU - Hurley, MD

AU - Wallington, TJ

AU - Blandini, F

AU - Jensen, NR

AU - Librando, V

AU - Hjorth, J

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N2 - Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH3OCF2CF2OCH3, CH3O(CF2CF2O)(2)CH3, and CH3O(CF2CF2O)(3)CH3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).

AB - Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH3OCF2CF2OCH3, CH3O(CF2CF2O)(2)CH3, and CH3O(CF2CF2O)(3)CH3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).

U2 - 10.1021/jp036615a

DO - 10.1021/jp036615a

M3 - Tidsskriftartikel

SN - 1089-5639

VL - 108

SP - 1964

EP - 1972

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 - 11

ER -