Thermal Decomposition of Fluoroform in a Single-Pulse Shock Tube. II. Pressure Dependence of the Rate
- 15 May 1965
- journal article
- conference paper
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 42 (10) , 3639-3642
- https://doi.org/10.1063/1.1695772
Abstract
The thermal decomposition of CF3H has been studied in a single‐pulse shock tube between 1200° and 1600°K using dilute CF3H–Ar mixtures at total pressures of about 18.7 and 0.90 atm. The results, together with earlier work at about 4 atm indicate that the observed rate constants for the rate of disappearance of CF3H are those of a second‐order energy‐transfer process, where collisional activation is rate determining. Kassel's model of unimolecular reaction‐rate theory is used to show that the observed pressure dependence of the rate constants is not unreasonable. From the classical Kassel theory for such processes it is calculated that the mean lifetime of a critically energized CF3H* at 1400°K is 1.2×10−11 sec with five effective oscillators.Keywords
This publication has 6 references indexed in Scilit:
- Thermal Decomposition of Fluoroform in a Single-Pulse Shock Tube. IThe Journal of Chemical Physics, 1965
- Pyrolysis of Chlorodifluoromethane and the Heat of Formation of Chlorodifluoromethane and DifluoromethyleneNature, 1964
- THE ACTIVATION ENERGY FOR THE PYROLYSIS OF METHANE1The Journal of Physical Chemistry, 1963
- Predissociation in the absorption spectra of CF and CF2Transactions of the Faraday Society, 1963
- Combustion calorimetry with fluorine: constant pressure flame calorimetryJournal of Research of the National Bureau of Standards Section A: Physics and Chemistry, 1960
- The Heats of Formation of CHF3and CH2F2The Journal of Physical Chemistry, 1958