Experimental and Modelling Study of the Unimolecular Thermal Decompostion of CHF3
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Carlos J. Cobos
Abstract
The unimolecular thermal decomposition reaction CHF3 (+M)→CF2 + HF (+M) was studied in shock waves by monitoring the UV absorption of the forming CF2 radicals. The results of the present and previous experiments on the temperature and pressure dependence of the rate constants are analyzed in terms of unimolecular rate theory. Falloff curves (for 1500–1900 K) are represented in terms of fitted limiting low pressure rate constants k0 = [Ar] 1.1 × 1016exp(−53.0 kcal mol−1/RT) cm3mol−1s−1, limiting high pressure rate constants k∞ = 1.25 × 1015 exp(−75.8 kcal mol−1/RT) s−1 from quantum-chemical calculations, and center broadening factors Fcent = 0.170(± 0.04) including strong and weak collision contributions from unimolecular rate theory. With these results, approximate analytical expressions of the falloff curves well represent the measured and calculated rate constants over wide ranges of pressure and temperature.
© by Oldenbourg Wissenschaftsverlag, Göttingen, Germany
Artikel in diesem Heft
- Preface
- OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine
- Transient anisotropy in degenerate systems: A semi-classical approach
- First Cavity Ring-Down Spectroscopy HO2 Measurements in a Large Photoreactor
- Relaxation Dynamics of Electronically Excited C60− in o-Dichlorobenzene and Tetrahydrofuran Solution
- 3CH2 + O2: Kinetics and Product Channel Branching Ratios
- What Do We Know About the Iconic System CH3 + CH3 + M ↔ C2H6 + M?
- Thermochemistry and Kinetics for 2-Butanone-3yl Radical (CH3C(=O)CH•CH3) Reactions with O2
- Experimental and Modelling Study of the Unimolecular Thermal Decompostion of CHF3
- Combustion Chemistry of the Butane Isomers in Premixed Low-Pressure Flames
- Characterization of Rhodamine 6G Release in Electrospray Ionization by Means of Spatially Resolved Fluorescence Spectroscopy
- Femtosecond interferometry of molecular dynamics – the role of relative and absolute phase of two individual laser pulses
- Photodecarbonylation of Diphenylcyclopropenone – a Direct Pathway to Electronically Excited Diphenylacetylene?
- Yield of HO2 Radicals in the OH-Initiated Oxidation of SO2
- Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K
- Reaction of OH and NO at Low Temperatures in the Presence of Water: the Role of Clusters
Artikel in diesem Heft
- Preface
- OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine
- Transient anisotropy in degenerate systems: A semi-classical approach
- First Cavity Ring-Down Spectroscopy HO2 Measurements in a Large Photoreactor
- Relaxation Dynamics of Electronically Excited C60− in o-Dichlorobenzene and Tetrahydrofuran Solution
- 3CH2 + O2: Kinetics and Product Channel Branching Ratios
- What Do We Know About the Iconic System CH3 + CH3 + M ↔ C2H6 + M?
- Thermochemistry and Kinetics for 2-Butanone-3yl Radical (CH3C(=O)CH•CH3) Reactions with O2
- Experimental and Modelling Study of the Unimolecular Thermal Decompostion of CHF3
- Combustion Chemistry of the Butane Isomers in Premixed Low-Pressure Flames
- Characterization of Rhodamine 6G Release in Electrospray Ionization by Means of Spatially Resolved Fluorescence Spectroscopy
- Femtosecond interferometry of molecular dynamics – the role of relative and absolute phase of two individual laser pulses
- Photodecarbonylation of Diphenylcyclopropenone – a Direct Pathway to Electronically Excited Diphenylacetylene?
- Yield of HO2 Radicals in the OH-Initiated Oxidation of SO2
- Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K
- Reaction of OH and NO at Low Temperatures in the Presence of Water: the Role of Clusters
