Unimolecular decomposition of SiH sub 4 , SiH sub 3 F, and SiH sub 2 F sub 2 at high temperatures
- Univ. of Tokyo (Japan)
The thermal decomposition of SiH{sub 4}, SiH{sub 3}F, and SiH{sub 2}F{sub 2} diluted in Ar was studied behind incident shock waves by monitoring IR emission from these reactant molecules. The rate constants of the unimolecular decomposition for all of three molecules were found to be in the pressure falloff region over the present experimental conditions (T = 1,190-2,150 K and P = 0.2-1.6 atm). The activation energies of measured rate constants were compared with heats of reactions for the various possible pathways for the thermal decomposition of these molecules and its was concluded that three-center H{sub 2} elimination reactions were the dominant pathways for unimolecular reactions of SiH{sub 4-n}F{sub n} (n = 0, 1, and 2). These rate constants decrease with increasing number of fluorine atoms, n, in SiH{sub 4-n}F{sub n}. RRKM falloff calculations have been performed to examine the effect of fluorine substitution on the unimolecular decomposition rates of these molecules.
- OSTI ID:
- 5169686
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:3; ISSN 0022-3654; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
DATA
ENERGY
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
REACTION KINETICS
SILANES
SILICON COMPOUNDS
SPECTRA
THERMAL DEGRADATION
VERY HIGH TEMPERATURE