Atmospheric chemistry of HFC-236cb: Spectrokinetic investigation of the CF3CF2CFHO2 radical, its reaction with NO and NO2, and the fate of the CF3CF2CFHO radical

Trine E. Møgelberg; Anders Feilberg; Anders M.B. Giessing; Jens Sehested; Merete Bilde; Timothy J. Wallington; Ole J. Nielsen

doi:10.1021/j100048a013

Atmospheric chemistry of HFC-236cb: Spectrokinetic investigation of the CF₃CF₂CFHO₂ radical, its reaction with NO and NO₂, and the fate of the CF₃CF₂CFHO radical

Trine E. Møgelberg, Anders Feilberg, Anders M.B. Giessing, Jens Sehested, Merete Bilde, Timothy J. Wallington^*, Ole J. Nielsen

^*Corresponding author af dette arbejde

8 Citationer (Scopus)

Abstract

A pulse radiolysis technique was used to study the UV absorption spectrum of CF₃CF₂CFHO₂ radicals (at 250 nm σ = (175 ± 36) × 10^-20 cm² molecule^-1). The observed bimolecular rate constant for the self reaction of CF₃CF₂CFHO₂ radicals was k_13obs = (5.2 ± 1.4) × 10^-12 cm³ molecule^-1 s^-1. Rate constants for reactions of CF₃CF₂CFHO₂ radicals with NO and NO₂ were k₃ > × 10^-12 and k₄ = (6.3 ± 0.7) × 10^-12 cm³ molecule^-1 s^-1, respectively. Using a FTIR spectrometer/smog chamber technique it was shown that, under atmospheric conditions, reaction with O₂ and decomposition via C-C bond scission are competing loss mechanisms for CF₃CF₂CFHO radicals. A lower limit of 10⁵ s^-1 was deduced for the rate of decomposition of CF₃CF₂CFHO radicals via C-C bond scission at 296 K in 1 bar of SF₆ diluent. It is estimated that in the atmosphere approximately 98% of CF₃CF₂CFHO radicals will undergo decomposition into C₂F₅ radicals and HC(O)F and 2% will react with O₂ to give C₂F₅C(O)F. As part of this work relative rate methods were used to measure rate constants of (1.3 ± 0.3) × 10^-12 and (1.5 ± 0.3) × 10^-15 cm³ molecule^-1 s^-1 for the reactions of CF₃CF₂CFH₂ with F and Cl atoms, respectively.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry
Vol/bind	99
Udgave nummer	48
Sider (fra-til)	17386-17393
Antal sider	8
ISSN	0022-3654
DOI	https://doi.org/10.1021/j100048a013
Status	Udgivet - 1 jan. 1995

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10.1021/j100048a013

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Citationsformater

Møgelberg, T. E., Feilberg, A., Giessing, A. M. B., Sehested, J., Bilde, M., Wallington, T. J., & Nielsen, O. J. (1995). Atmospheric chemistry of HFC-236cb: Spectrokinetic investigation of the CF₃CF₂CFHO₂ radical, its reaction with NO and NO₂, and the fate of the CF₃CF₂CFHO radical. Journal of Physical Chemistry, 99(48), 17386-17393. https://doi.org/10.1021/j100048a013

Atmospheric chemistry of HFC-236cb : Spectrokinetic investigation of the CF₃CF₂CFHO₂ radical, its reaction with NO and NO₂, and the fate of the CF₃CF₂CFHO radical. / Møgelberg, Trine E.; Feilberg, Anders; Giessing, Anders M.B. et al.

I: Journal of Physical Chemistry, Bind 99, Nr. 48, 01.01.1995, s. 17386-17393.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

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title = "Atmospheric chemistry of HFC-236cb: Spectrokinetic investigation of the CF3CF2CFHO2 radical, its reaction with NO and NO2, and the fate of the CF3CF2CFHO radical",

abstract = "A pulse radiolysis technique was used to study the UV absorption spectrum of CF3CF2CFHO2 radicals (at 250 nm σ = (175 ± 36) × 10-20 cm2 molecule-1). The observed bimolecular rate constant for the self reaction of CF3CF2CFHO2 radicals was k13obs = (5.2 ± 1.4) × 10-12 cm3 molecule-1 s-1. Rate constants for reactions of CF3CF2CFHO2 radicals with NO and NO2 were k3 > × 10-12 and k4 = (6.3 ± 0.7) × 10-12 cm3 molecule-1 s-1, respectively. Using a FTIR spectrometer/smog chamber technique it was shown that, under atmospheric conditions, reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CF2CFHO radicals. A lower limit of 105 s-1 was deduced for the rate of decomposition of CF3CF2CFHO radicals via C-C bond scission at 296 K in 1 bar of SF6 diluent. It is estimated that in the atmosphere approximately 98% of CF3CF2CFHO radicals will undergo decomposition into C2F5 radicals and HC(O)F and 2% will react with O2 to give C2F5C(O)F. As part of this work relative rate methods were used to measure rate constants of (1.3 ± 0.3) × 10-12 and (1.5 ± 0.3) × 10-15 cm3 molecule-1 s-1 for the reactions of CF3CF2CFH2 with F and Cl atoms, respectively.",

author = "M{\o}gelberg, {Trine E.} and Anders Feilberg and Giessing, {Anders M.B.} and Jens Sehested and Merete Bilde and Wallington, {Timothy J.} and Nielsen, {Ole J.}",

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T2 - Spectrokinetic investigation of the CF3CF2CFHO2 radical, its reaction with NO and NO2, and the fate of the CF3CF2CFHO radical

AU - Møgelberg, Trine E.

AU - Feilberg, Anders

AU - Giessing, Anders M.B.

AU - Sehested, Jens

AU - Bilde, Merete

AU - Wallington, Timothy J.

AU - Nielsen, Ole J.

PY - 1995/1/1

Y1 - 1995/1/1

N2 - A pulse radiolysis technique was used to study the UV absorption spectrum of CF3CF2CFHO2 radicals (at 250 nm σ = (175 ± 36) × 10-20 cm2 molecule-1). The observed bimolecular rate constant for the self reaction of CF3CF2CFHO2 radicals was k13obs = (5.2 ± 1.4) × 10-12 cm3 molecule-1 s-1. Rate constants for reactions of CF3CF2CFHO2 radicals with NO and NO2 were k3 > × 10-12 and k4 = (6.3 ± 0.7) × 10-12 cm3 molecule-1 s-1, respectively. Using a FTIR spectrometer/smog chamber technique it was shown that, under atmospheric conditions, reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CF2CFHO radicals. A lower limit of 105 s-1 was deduced for the rate of decomposition of CF3CF2CFHO radicals via C-C bond scission at 296 K in 1 bar of SF6 diluent. It is estimated that in the atmosphere approximately 98% of CF3CF2CFHO radicals will undergo decomposition into C2F5 radicals and HC(O)F and 2% will react with O2 to give C2F5C(O)F. As part of this work relative rate methods were used to measure rate constants of (1.3 ± 0.3) × 10-12 and (1.5 ± 0.3) × 10-15 cm3 molecule-1 s-1 for the reactions of CF3CF2CFH2 with F and Cl atoms, respectively.

AB - A pulse radiolysis technique was used to study the UV absorption spectrum of CF3CF2CFHO2 radicals (at 250 nm σ = (175 ± 36) × 10-20 cm2 molecule-1). The observed bimolecular rate constant for the self reaction of CF3CF2CFHO2 radicals was k13obs = (5.2 ± 1.4) × 10-12 cm3 molecule-1 s-1. Rate constants for reactions of CF3CF2CFHO2 radicals with NO and NO2 were k3 > × 10-12 and k4 = (6.3 ± 0.7) × 10-12 cm3 molecule-1 s-1, respectively. Using a FTIR spectrometer/smog chamber technique it was shown that, under atmospheric conditions, reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CF2CFHO radicals. A lower limit of 105 s-1 was deduced for the rate of decomposition of CF3CF2CFHO radicals via C-C bond scission at 296 K in 1 bar of SF6 diluent. It is estimated that in the atmosphere approximately 98% of CF3CF2CFHO radicals will undergo decomposition into C2F5 radicals and HC(O)F and 2% will react with O2 to give C2F5C(O)F. As part of this work relative rate methods were used to measure rate constants of (1.3 ± 0.3) × 10-12 and (1.5 ± 0.3) × 10-15 cm3 molecule-1 s-1 for the reactions of CF3CF2CFH2 with F and Cl atoms, respectively.

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