Quantitative comparison between detailed (state selected) relative rate data and averaged (thermal) absolute rate data for complex forming reactions
The application of statistical theories to complex forming reactions involving polyatomic species is discussed briefly. The fundamental assumptions and the corresponding criteria of validity of statistical theories are pointed out. Model dependent assumptions with particular reference to phase space theory are introduced. It is shown that removing one of the assumptions of phase space theory by allowing for an angular dependence of the interaction potential leads to an improved overall agreement with experiment. A parametrization for the angular potential is proposed. General and simplified expressions from this statistical model are summarized for thermal cross sections for complex formation, vibrational relaxation cross sections, and product translational energy distributions in molecular beam collisions involving quasi-bound intermediates. Experimental data for thermal recombination reactions of nine different reaction systems, for vibrational relaxation, and for a molecular beam investigation of the reaction F + C/sub 6/H/sub 5/Cl ..-->.. C/sub 6/H/sub 5/F + Cl are analyzed on these lines. Common trends for the parameter ..cap alpha.. of the angular potential are observed and it is demonstrated how quantitative relationships between detailed relative rate data and thermally averaged absolute rate data can be established in terms of this parameter. 6 figures, 49 references, 2 tables.
- Research Organization:
- Universitaet Goettingen, Germany
- OSTI ID:
- 6487448
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 83:1
- Country of Publication:
- United States
- Language:
- English
Similar Records
Dynamics of endoergic substitution reactions. I. Br+chlorinated aromatic compounds
Electron capture and drift in polyatomic gases. [Cross sections, rates, lifetime, slow electron energy losses]
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHEMICAL REACTION KINETICS
CHLORINATED AROMATIC HYDROCARBONS
CHEMICAL REACTIONS
CHLORINE
FLUORINE
HYDROXYL RADICALS
METHYLENE RADICALS
NITRIC OXIDE
NITROUS OXIDE
OXYGEN
COLLISIONS
COMPLEXES
CORRELATIONS
CROSS SECTIONS
DATA
ENERGY SPECTRA
HIGH TEMPERATURE
HYPOTHESIS
MEDIUM TEMPERATURE
MOLECULAR BEAMS
PHASE SPACE
QUANTITATIVE CHEMICAL ANALYSIS
QUANTUM MECHANICS
REACTION INTERMEDIATES
RELAXATION
SPECIFICATIONS
STATISTICAL MODELS
TEMPERATURE DEPENDENCE
VERY HIGH TEMPERATURE
AROMATICS
BEAMS
CHALCOGENIDES
CHEMICAL ANALYSIS
CRYOGENIC FLUIDS
ELEMENTS
FLUIDS
HALOGENATED AROMATIC HYDROCARBONS
HALOGENS
INFORMATION
KINETICS
MATHEMATICAL MODELS
MATHEMATICAL SPACE
MECHANICS
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS
SPACE
SPECTRA
400201* - Chemical & Physicochemical Properties