Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): Kinetics and Mechanisms of the Chlorine Atom Initiated Oxidation

Mads P Sulbaek Andersen; Vibeke Friis Andersen; Ole John Nielsen; Stanley P Sander; Timothy J Wallington

doi:10.1002/cphc.201000438

Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): Kinetics and Mechanisms of the Chlorine Atom Initiated Oxidation

Mads P Sulbaek Andersen, Vibeke Friis Andersen, Ole John Nielsen, Stanley P Sander, Timothy J Wallington

Kemisk Institut

9 Citationer (Scopus)

Abstract

Smog chamber/FTIR techniques were used to measure k(Cl+HCF ₂O(CF₂CF₂O)_xCF₂H)=(5. 3±1.5)× 10^-17 cm³ molecule^-1 s^-1 in 700 Torr of N₂/O₂ diluent at 296±1 K. The Cl-initiated atmospheric oxidation of HCF ₂O(CF₂CF₂O)_xCF₂H, x=2,3 and 4, gave COF₂ in molar yields of (593±41) %, (758±71) % and (939±73) %, respectively, with no other observable carbon-containing products (i.e., essentially complete conversion of the hydrofluoropolyethers into COF₂). Quantitative infrared spectra for HCF₂O(CF₂CF₂O)_xCF₂H (x=2-4) were recorded and used to estimate the radiative efficiencies of the title compounds (1.07, 1.33, and 1.36 W m^-2 ppb^-1). Global warming potentials (100 year time horizon) of 3870, 4730 and 5060 were estimated for HCF₂O(CF₂CF₂O)_xCF ₂H, x=2, 3 and 4, respectively. The results are discussed with respect to the atmospheric chemistry and environmental impact of hydrofluoropolyethers.

Originalsprog	Engelsk
Tidsskrift	ChemPhysChem
Vol/bind	11
Sider (fra-til)	4035-4041
Antal sider	7
ISSN	1439-4235
DOI	https://doi.org/10.1002/cphc.201000438
Status	Udgivet - 17 dec. 2010

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10.1002/cphc.201000438

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@article{bed4c168c95d4c9cb0f31798b37e1858,

title = "Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): Kinetics and Mechanisms of the Chlorine Atom Initiated Oxidation",

abstract = "Smog chamber/FTIR techniques were used to measure k(Cl+HCF 2O(CF2CF2O)xCF2H)=(5. 3±1.5)× 10-17 cm3 molecule-1 s-1 in 700 Torr of N2/O2 diluent at 296±1 K. The Cl-initiated atmospheric oxidation of HCF 2O(CF2CF2O)xCF2H, x=2,3 and 4, gave COF2 in molar yields of (593±41) %, (758±71) % and (939±73) %, respectively, with no other observable carbon-containing products (i.e., essentially complete conversion of the hydrofluoropolyethers into COF2). Quantitative infrared spectra for HCF2O(CF2CF2O)xCF2H (x=2-4) were recorded and used to estimate the radiative efficiencies of the title compounds (1.07, 1.33, and 1.36 W m-2 ppb-1). Global warming potentials (100 year time horizon) of 3870, 4730 and 5060 were estimated for HCF2O(CF2CF2O)xCF 2H, x=2, 3 and 4, respectively. The results are discussed with respect to the atmospheric chemistry and environmental impact of hydrofluoropolyethers.",

author = "Andersen, {Mads P Sulbaek} and Andersen, {Vibeke Friis} and Nielsen, {Ole John} and Sander, {Stanley P} and Wallington, {Timothy J}",

year = "2010",

month = dec,

day = "17",

doi = "10.1002/cphc.201000438",

language = "English",

volume = "11",

pages = "4035--4041",

journal = "ChemPhysChem",

issn = "1439-4235",

publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

}

TY - JOUR

T1 - Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): Kinetics and Mechanisms of the Chlorine Atom Initiated Oxidation

AU - Andersen, Mads P Sulbaek

AU - Andersen, Vibeke Friis

AU - Nielsen, Ole John

AU - Sander, Stanley P

AU - Wallington, Timothy J

PY - 2010/12/17

Y1 - 2010/12/17

N2 - Smog chamber/FTIR techniques were used to measure k(Cl+HCF 2O(CF2CF2O)xCF2H)=(5. 3±1.5)× 10-17 cm3 molecule-1 s-1 in 700 Torr of N2/O2 diluent at 296±1 K. The Cl-initiated atmospheric oxidation of HCF 2O(CF2CF2O)xCF2H, x=2,3 and 4, gave COF2 in molar yields of (593±41) %, (758±71) % and (939±73) %, respectively, with no other observable carbon-containing products (i.e., essentially complete conversion of the hydrofluoropolyethers into COF2). Quantitative infrared spectra for HCF2O(CF2CF2O)xCF2H (x=2-4) were recorded and used to estimate the radiative efficiencies of the title compounds (1.07, 1.33, and 1.36 W m-2 ppb-1). Global warming potentials (100 year time horizon) of 3870, 4730 and 5060 were estimated for HCF2O(CF2CF2O)xCF 2H, x=2, 3 and 4, respectively. The results are discussed with respect to the atmospheric chemistry and environmental impact of hydrofluoropolyethers.

AB - Smog chamber/FTIR techniques were used to measure k(Cl+HCF 2O(CF2CF2O)xCF2H)=(5. 3±1.5)× 10-17 cm3 molecule-1 s-1 in 700 Torr of N2/O2 diluent at 296±1 K. The Cl-initiated atmospheric oxidation of HCF 2O(CF2CF2O)xCF2H, x=2,3 and 4, gave COF2 in molar yields of (593±41) %, (758±71) % and (939±73) %, respectively, with no other observable carbon-containing products (i.e., essentially complete conversion of the hydrofluoropolyethers into COF2). Quantitative infrared spectra for HCF2O(CF2CF2O)xCF2H (x=2-4) were recorded and used to estimate the radiative efficiencies of the title compounds (1.07, 1.33, and 1.36 W m-2 ppb-1). Global warming potentials (100 year time horizon) of 3870, 4730 and 5060 were estimated for HCF2O(CF2CF2O)xCF 2H, x=2, 3 and 4, respectively. The results are discussed with respect to the atmospheric chemistry and environmental impact of hydrofluoropolyethers.

U2 - 10.1002/cphc.201000438

DO - 10.1002/cphc.201000438

M3 - Journal article

C2 - 20981750

SN - 1439-4235

VL - 11

SP - 4035

EP - 4041

JO - ChemPhysChem

JF - ChemPhysChem

ER -

Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): Kinetics and Mechanisms of the Chlorine Atom Initiated Oxidation

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