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 for this work

34 Citations (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.

Original language	English
Journal	Chemical Physics Letters
Volume	192
Issue number	1
Pages (from-to)	82-88
Number of pages	7
ISSN	0009-2614
DOIs	https://doi.org/10.1016/0009-2614(92)85432-A
Publication status	Published - 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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DO - 10.1016/0009-2614(92)85432-A

M3 - Journal article

AN - SCOPUS:0038138534

SN - 0009-2614

VL - 192

SP - 82

EP - 88

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1

ER -

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

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