An experimental and theoretical high temperature kinetic study of the thermal unimolecular dissociation of fluoroethane.
The thermal dissociation of fluoroethane has been studied using shock tube (ST)/time-of-flight mass spectrometry (TOF-MS) at 500 and 1200 Torr over the temperature range 1200-1550 K. The ST/TOF-MS experiments confirm that elimination of HF is the only reaction channel and rate coefficients for this reaction were extracted from concentration/time profiles derived from the mass spectra. Results from a novel diaphragmless shock tube coupled to the TOF-MS are also presented and demonstrate the unique ability of this apparatus to generate sufficiently reproducible shock waves that signal averaging can be performed over multiple experiments; something that is not possible with a conventional shock tube. The dissociation is also studied with ab initio transition state theory based master equation simulations. A modest increase in the calculated barrier height i.e., by 1 kcal mol{sup -1} yields predicted high pressure rate coefficients that are in good agreement with the existing literature data. The present pressure dependent observations are accurately reproduced for a downwards energy transfer for neon at 1200 to 1500 K of {approx} 270 cm{sup -1}, which is somewhat smaller than that found in previous studies on fluorinated ethanes with the same bath gases.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 981318
- Report Number(s):
- ANL/CSE/JA-61797; TRN: US201012%%1302
- Journal Information:
- Phys. Chem. Chem. Phys., Vol. 10, Issue 41 ; 2008; ISSN 1463-9076
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Dissociation of 1,1,1-trifluoroethane behind reflected shock waves :shock tube/time-of-flight mass spectrometry experiments.
Initiation reactions in the high temperature decomposition of styrene