Atmospheric Chemistry of CF3CFHCF3 (HFC-227ea): Spectrokinetic Investigation of the CF3CFO2'CF3 Radical, Its Reactions with NO and NO2, and Fate of the CF3CFO'CF3 Radical

Trine E. Møgelberg; Jens Sehested; Merete Bilde; Timothy J. Wallington; Ole J. Nielsen

Atmospheric Chemistry of CF₃CFHCF₃ (HFC-227ea): Spectrokinetic Investigation of the CF₃CFO₂'CF₃ Radical, Its Reactions with NO and NO₂, and Fate of the CF₃CFO'CF₃ Radical

Trine E. Møgelberg^*, Jens Sehested, Merete Bilde, Timothy J. Wallington, Ole J. Nielsen

^*Corresponding author for this work

30 Citations (Scopus)

Abstract

The ultraviolet absorption spectrum of the CF₃CFO₂CF₃ radical, the kinetics of its self-reaction and reactions. with NO and NO₂ have been studied in the gas phase at 296K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF₃CFO'CF₃ radical. Absorption cross sections for the CF₃CFO₂'CF₃ radical were quantified over the wavelength range 220-270 nm. At 230 nm, a(CF₃CFO₂'CF₃) = (351 ±73) × 10^-20 cm² molecule^-1. The observed rate constant for the CF₃CFO₂'CF₃ self-reaction was (1.8 ±0.4) × 10^-12 cm³ molecule^-1 s^-1. The rate constants for the reaction of CF₃CFO₂'CF₃ radicals with NO and NO₂ were k₃ = (2.1 ±0.9) × 10^-11 and fc, = (4.8 ±1.4) × 10^-12 cm³ molecule^-1 s^-1. The atmospheric fate of CF₃CFO'CF₃ radicals is decomposition via C-C bond scission to give CF₃ radicals and CF₃C(O)F. In 1000 mbar of SF6 at 296 K decomposition of CF₃CFO'CF₃ radicals proceeds at a rate greater than 1 × 105 s^-1. As part of this work relative rate techniques were used to measure k(C1+CF₃CFHCF₃) = (4.5 ±1.2) × 10^-17 and k(F+CF₃CFHCF₃) = (1.5 ±0.5) × 10^-13 cm³ molecule^-1 s^-1. This compares well with the value of k(F+CF₃CFHCF₃) = (1.9 ±0.4) × 10^-13 cm³ molecule^-1 s^-1 obtained by pulse radiolysis. The results are discussed in the context of the atmospheric chemistry of HFC-227ea.

Original language	English
Journal	Journal of Physical Chemistry
Volume	100
Issue number	21
Pages (from-to)	8882-8889
Number of pages	8
ISSN	0022-3654
Publication status	Published - 1 Dec 1996

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Atmospheric Chemistry of CF₃CFHCF₃ (HFC-227ea) : Spectrokinetic Investigation of the CF₃CFO₂'CF₃ Radical, Its Reactions with NO and NO₂, and Fate of the CF₃CFO'CF₃ Radical. / Møgelberg, Trine E.; Sehested, Jens; Bilde, Merete et al.

In: Journal of Physical Chemistry, Vol. 100, No. 21, 01.12.1996, p. 8882-8889.

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

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title = "Atmospheric Chemistry of CF3CFHCF3 (HFC-227ea): Spectrokinetic Investigation of the CF3CFO2'CF3 Radical, Its Reactions with NO and NO2, and Fate of the CF3CFO'CF3 Radical",

abstract = "The ultraviolet absorption spectrum of the CF3CFO2CF3 radical, the kinetics of its self-reaction and reactions. with NO and NO2 have been studied in the gas phase at 296K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF3CFO'CF3 radical. Absorption cross sections for the CF3CFO2'CF3 radical were quantified over the wavelength range 220-270 nm. At 230 nm, a(CF3CFO2'CF3) = (351 ±73) × 10-20 cm2 molecule-1. The observed rate constant for the CF3CFO2'CF3 self-reaction was (1.8 ±0.4) × 10-12 cm3 molecule-1 s-1. The rate constants for the reaction of CF3CFO2'CF3 radicals with NO and NO2 were k3 = (2.1 ±0.9) × 10-11 and fc, = (4.8 ±1.4) × 10-12 cm3 molecule-1 s-1. The atmospheric fate of CF3CFO'CF3 radicals is decomposition via C-C bond scission to give CF3 radicals and CF3C(O)F. In 1000 mbar of SF6 at 296 K decomposition of CF3CFO'CF3 radicals proceeds at a rate greater than 1 × 105 s-1. As part of this work relative rate techniques were used to measure k(C1+CF3CFHCF3) = (4.5 ±1.2) × 10-17 and k(F+CF3CFHCF3) = (1.5 ±0.5) × 10-13 cm3 molecule-1 s-1. This compares well with the value of k(F+CF3CFHCF3) = (1.9 ±0.4) × 10-13 cm3 molecule-1 s-1 obtained by pulse radiolysis. The results are discussed in the context of the atmospheric chemistry of HFC-227ea.",

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T2 - Spectrokinetic Investigation of the CF3CFO2'CF3 Radical, Its Reactions with NO and NO2, and Fate of the CF3CFO'CF3 Radical

AU - Møgelberg, Trine E.

AU - Sehested, Jens

AU - Bilde, Merete

AU - Wallington, Timothy J.

AU - Nielsen, Ole J.

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N2 - The ultraviolet absorption spectrum of the CF3CFO2CF3 radical, the kinetics of its self-reaction and reactions. with NO and NO2 have been studied in the gas phase at 296K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF3CFO'CF3 radical. Absorption cross sections for the CF3CFO2'CF3 radical were quantified over the wavelength range 220-270 nm. At 230 nm, a(CF3CFO2'CF3) = (351 ±73) × 10-20 cm2 molecule-1. The observed rate constant for the CF3CFO2'CF3 self-reaction was (1.8 ±0.4) × 10-12 cm3 molecule-1 s-1. The rate constants for the reaction of CF3CFO2'CF3 radicals with NO and NO2 were k3 = (2.1 ±0.9) × 10-11 and fc, = (4.8 ±1.4) × 10-12 cm3 molecule-1 s-1. The atmospheric fate of CF3CFO'CF3 radicals is decomposition via C-C bond scission to give CF3 radicals and CF3C(O)F. In 1000 mbar of SF6 at 296 K decomposition of CF3CFO'CF3 radicals proceeds at a rate greater than 1 × 105 s-1. As part of this work relative rate techniques were used to measure k(C1+CF3CFHCF3) = (4.5 ±1.2) × 10-17 and k(F+CF3CFHCF3) = (1.5 ±0.5) × 10-13 cm3 molecule-1 s-1. This compares well with the value of k(F+CF3CFHCF3) = (1.9 ±0.4) × 10-13 cm3 molecule-1 s-1 obtained by pulse radiolysis. The results are discussed in the context of the atmospheric chemistry of HFC-227ea.

AB - The ultraviolet absorption spectrum of the CF3CFO2CF3 radical, the kinetics of its self-reaction and reactions. with NO and NO2 have been studied in the gas phase at 296K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF3CFO'CF3 radical. Absorption cross sections for the CF3CFO2'CF3 radical were quantified over the wavelength range 220-270 nm. At 230 nm, a(CF3CFO2'CF3) = (351 ±73) × 10-20 cm2 molecule-1. The observed rate constant for the CF3CFO2'CF3 self-reaction was (1.8 ±0.4) × 10-12 cm3 molecule-1 s-1. The rate constants for the reaction of CF3CFO2'CF3 radicals with NO and NO2 were k3 = (2.1 ±0.9) × 10-11 and fc, = (4.8 ±1.4) × 10-12 cm3 molecule-1 s-1. The atmospheric fate of CF3CFO'CF3 radicals is decomposition via C-C bond scission to give CF3 radicals and CF3C(O)F. In 1000 mbar of SF6 at 296 K decomposition of CF3CFO'CF3 radicals proceeds at a rate greater than 1 × 105 s-1. As part of this work relative rate techniques were used to measure k(C1+CF3CFHCF3) = (4.5 ±1.2) × 10-17 and k(F+CF3CFHCF3) = (1.5 ±0.5) × 10-13 cm3 molecule-1 s-1. This compares well with the value of k(F+CF3CFHCF3) = (1.9 ±0.4) × 10-13 cm3 molecule-1 s-1 obtained by pulse radiolysis. The results are discussed in the context of the atmospheric chemistry of HFC-227ea.

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Atmospheric Chemistry of CF₃CFHCF₃ (HFC-227ea): Spectrokinetic Investigation of the CF₃CFO₂'CF₃ Radical, Its Reactions with NO and NO₂, and Fate of the CF₃CFO'CF₃ Radical

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