UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298 K

Ole J. Nielsen; Thomas Ellermann; Elzbieta Bartkiewicz; Timothy J. Wallington; Michael D. Hurley

doi:10.1016/0009-2614(92)85432-A

UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF₂O₂ radicals in the gas phase at 298 K

Ole J. Nielsen^*, Thomas Ellermann, Elzbieta Bartkiewicz, Timothy J. Wallington, Michael D. Hurley

^*Corresponding author af dette arbejde

34 Citationer (Scopus)

Abstract

The ultraviolet-absorption spectrum and the self-reaction of CHF₂O₂ radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm. The measured cross section near the absorption maximum was σ_CHF₂O₂ (240 nm) = (2.66 ± 0.46) × 10^-18 cm² molecule^-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF₂O₂ + CHF₂O₂ → products, defined as d[R]/dt = 2k_1obs[CHF₂O₂]², k_1obs = (5.0 ± 0.7) × 10^-12 cm³ molecule^-1 s^-1 (± 2σ). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals.

Originalsprog	Engelsk
Tidsskrift	Chemical Physics Letters
Vol/bind	192
Udgave nummer	1
Sider (fra-til)	82-88
Antal sider	7
ISSN	0009-2614
DOI	https://doi.org/10.1016/0009-2614(92)85432-A
Status	Udgivet - 24 apr. 1992

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@article{48ca978fe99b4ccc91d86f4edabd1963,

title = "UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298 K",

abstract = "The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm. The measured cross section near the absorption maximum was σCHF2O2 (240 nm) = (2.66 ± 0.46) × 10-18 cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 → products, defined as d[R]/dt = 2k1obs[CHF2O2]2, k1obs = (5.0 ± 0.7) × 10-12 cm3 molecule-1 s-1 (± 2σ). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals.",

author = "Nielsen, {Ole J.} and Thomas Ellermann and Elzbieta Bartkiewicz and Wallington, {Timothy J.} and Hurley, {Michael D.}",

year = "1992",

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doi = "10.1016/0009-2614(92)85432-A",

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journal = "Chemical Physics Letters",

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TY - JOUR

T1 - UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298 K

AU - Nielsen, Ole J.

AU - Ellermann, Thomas

AU - Bartkiewicz, Elzbieta

AU - Wallington, Timothy J.

AU - Hurley, Michael D.

PY - 1992/4/24

Y1 - 1992/4/24

N2 - The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm. The measured cross section near the absorption maximum was σCHF2O2 (240 nm) = (2.66 ± 0.46) × 10-18 cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 → products, defined as d[R]/dt = 2k1obs[CHF2O2]2, k1obs = (5.0 ± 0.7) × 10-12 cm3 molecule-1 s-1 (± 2σ). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals.

AB - The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm. The measured cross section near the absorption maximum was σCHF2O2 (240 nm) = (2.66 ± 0.46) × 10-18 cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 → products, defined as d[R]/dt = 2k1obs[CHF2O2]2, k1obs = (5.0 ± 0.7) × 10-12 cm3 molecule-1 s-1 (± 2σ). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals.

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U2 - 10.1016/0009-2614(92)85432-A

DO - 10.1016/0009-2614(92)85432-A

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JO - Chemical Physics Letters

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