Atmospheric chemistry of CF{sub 3}CFHCF{sub 3} (HFC-227ea): Spectrokinetic investigation of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, its reactions with NO and NO{sub 2}, and fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical
Abstract
The ultraviolet absorption spectrum of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, the kinetics of its self-reaction and reactions with NO and NO{sub 2} have been studied in the gas phase at 296 K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical. Absorption cross sections for the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical were quantified over the wavelength range 220-270 nm. The rate constant for the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} self-reaction was determined, as well as those of the reaction of CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radicals with NO and NO{sub 2}. The atmospheric fate of CF{sub 3}CFO{sup .}CF{sub 3} radicals is decomposition via C-C bond scission to give CF{sub 3} radicals and CF{sub 3}C(O)F. In 1000 mbar of SF{sub 6} at 296 K decomposition of CF{sub 3}CFO{sup .}CF{sub 3} radicals proceeds at a rate greater than 1 x 10{sup 5} s{sup -1}. The results are discussed in the context of the atmospheric chemistry of HFC-227ea. 31 refs., 10 figs., 2 tabs.
- Authors:
-
- Riso National Lab., Roskilde (Denmark)
- Ford Motor Co., Dearborn, MI (United States)
- Ford Forschungscenter Aachen (Germany)
- Publication Date:
- OSTI Identifier:
- 263208
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Physical Chemistry
- Additional Journal Information:
- Journal Volume: 100; Journal Issue: 21; Other Information: PBD: 23 May 1996
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 40 CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; ORGANIC FLUORINE COMPOUNDS; ATMOSPHERIC CHEMISTRY; ABSORPTION SPECTRA; CHEMICAL REACTIONS; CHEMICAL REACTION KINETICS; NITRIC OXIDE; NITROGEN DIOXIDE; RADICALS
Citation Formats
Mogelberg, T E, Sehested, J, Bilde, M, Wallington, T J, and Nielsen, O J. Atmospheric chemistry of CF{sub 3}CFHCF{sub 3} (HFC-227ea): Spectrokinetic investigation of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, its reactions with NO and NO{sub 2}, and fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical. United States: N. p., 1996.
Web. doi:10.1021/jp953614c.
Mogelberg, T E, Sehested, J, Bilde, M, Wallington, T J, & Nielsen, O J. Atmospheric chemistry of CF{sub 3}CFHCF{sub 3} (HFC-227ea): Spectrokinetic investigation of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, its reactions with NO and NO{sub 2}, and fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical. United States. https://doi.org/10.1021/jp953614c
Mogelberg, T E, Sehested, J, Bilde, M, Wallington, T J, and Nielsen, O J. 1996.
"Atmospheric chemistry of CF{sub 3}CFHCF{sub 3} (HFC-227ea): Spectrokinetic investigation of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, its reactions with NO and NO{sub 2}, and fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical". United States. https://doi.org/10.1021/jp953614c.
@article{osti_263208,
title = {Atmospheric chemistry of CF{sub 3}CFHCF{sub 3} (HFC-227ea): Spectrokinetic investigation of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, its reactions with NO and NO{sub 2}, and fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical},
author = {Mogelberg, T E and Sehested, J and Bilde, M and Wallington, T J and Nielsen, O J},
abstractNote = {The ultraviolet absorption spectrum of the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical, the kinetics of its self-reaction and reactions with NO and NO{sub 2} have been studied in the gas phase at 296 K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF{sub 3}CFO{sup .}CF{sub 3} radical. Absorption cross sections for the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radical were quantified over the wavelength range 220-270 nm. The rate constant for the CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} self-reaction was determined, as well as those of the reaction of CF{sub 3}CFO{sub 2}{sup .}CF{sub 3} radicals with NO and NO{sub 2}. The atmospheric fate of CF{sub 3}CFO{sup .}CF{sub 3} radicals is decomposition via C-C bond scission to give CF{sub 3} radicals and CF{sub 3}C(O)F. In 1000 mbar of SF{sub 6} at 296 K decomposition of CF{sub 3}CFO{sup .}CF{sub 3} radicals proceeds at a rate greater than 1 x 10{sup 5} s{sup -1}. The results are discussed in the context of the atmospheric chemistry of HFC-227ea. 31 refs., 10 figs., 2 tabs.},
doi = {10.1021/jp953614c},
url = {https://www.osti.gov/biblio/263208},
journal = {Journal of Physical Chemistry},
number = 21,
volume = 100,
place = {United States},
year = {Thu May 23 00:00:00 EDT 1996},
month = {Thu May 23 00:00:00 EDT 1996}
}