Thermal decomposition of CF[sub 3]Cl
- Univ. of Illinois, Chicago, IL (United States)
- Argonne National Lab., IL (United States)
The unimolecular decomposition CF[sub 3]Cl + Kr [yields] CF[sub 3] + Cl + Kr has been studied using two different techniques, atomic resonance absorption spectrometry (ARAS) and laser schlieren (LS) density gradients, in two laboratories. As in our previous joint investigation of CCl[sub 4] dissociation, the ARAS and LS techniques give completely consistent results over the overlapping temperature range, 1800-2200 K. The title reaction is found to be fairly close to the low-pressure limit. The ARAS measurements between 1521 and 2173 K give k[sub 2nd] = 1.73 x 10[sup [minus]7] exp([minus]33837 K/T) cm[sup 3] molecule [sup [minus]1] s[sup [minus]1] ([+-]27% at 1[sigma]). This is in good agreement with the earlier ARAS measurements of Kruger and Wagner. k[sub 2nd] = 1.15 x 10[sup [minus]8] exp([minus]28339 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] ([+-]20% at 1[sigma]) is obtained from the LS results between 1800 and 3000 K. The good agreement between methods verifies both the C-Cl fission path for the Cf[sub 3]Cl dissociation and the curve-of-growth used in the Cl atom ARAS analysis. RRKM analysis of these rate data indicated a larger than usual magnitude for [Delta]E[sub down], in agreement with our previous findings on CCl[sub 4], but here it was necessary that it increase with T. 30 refs., 6 figs., 4 tabs.
- DOE Contract Number:
- FG02-85ER13384; W-31109-ENG-38
- OSTI ID:
- 6717860
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:47; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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ABSORPTION SPECTROSCOPY
CHEMICAL REACTIONS
COMPILED DATA
DATA
DECOMPOSITION
ELEMENTS
FLUIDS
GASES
HELIUM
INFORMATION
KRYPTON
LASERS
NONMETALS
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
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