Thermal Decomposition of CF3Cl
| Autor: | K. P. Lim, R. Sathyanarayana, J. V. Michael, John H. Kiefer |
|---|---|
| Rok vydání: | 1994 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry. 98:12278-12283 |
| ISSN: | 1541-5740 0022-3654 |
| Popis: | 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 necessarymore » that it increase with T. 30 refs., 6 figs., 4 tabs.« less |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|