Experimental and theoretical study of the sec-C[sub 4]H[sub 9] [r reversible] CH[sub 3] + C[sub 3]H[sub 6] reaction
- Catholic Univ. of America, Washington, DC (United States)
The kinetics of the unimolecular decomposition of the sec-C[sub 4]H[sub 9] radical has been studied experimentally in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were determined in time-resolved experiments as a function of temperature (598-680 K) and bath gas density (3-18) [times] 10[sup 16] molecules cm[sup [minus]3] in three bath gases: He, Ar, and N[sub 2]. The rate constants are in the falloff region under the conditions of the experiments. The results of earlier studies of the reverse reaction were reanalyzed and used to create a transition state model of the reaction. This transition state model was used to obtain values of the microcanonical rate constants, k (E). Falloff behavior was reproduced using master equation modeling with the energy barrier height for decomposition (necessary to calculate k(E)) obtained from optimization of the agreement between experimental and calculated rate constants. The resulting model of the reaction provides the high-pressure limit rate constants for the decomposition reaction and the reverse reaction. 52 refs., 7 figs., 3 tabs.
- DOE Contract Number:
- FG05-89ER14015
- OSTI ID:
- 6718584
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 98:43; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BUTYL RADICALS
DECOMPOSITION
CHEMICAL REACTION KINETICS
COMBUSTION
MASS SPECTROMETERS
MASS SPECTROSCOPY
MATHEMATICAL MODELS
METHYL RADICALS
PHOTOIONIZATION
PROPYLENE
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0400-1000 K
ALKENES
ALKYL RADICALS
CHEMICAL REACTIONS
HYDROCARBONS
IONIZATION
KINETICS
MEASURING INSTRUMENTS
ORGANIC COMPOUNDS
OXIDATION
RADICALS
REACTION KINETICS
SPECTROMETERS
SPECTROSCOPY
TEMPERATURE RANGE
THERMOCHEMICAL PROCESSES
400200* - Inorganic
Organic
& Physical Chemistry
400800 - Combustion
Pyrolysis
& High-Temperature Chemistry