Absolute rate constant for the reaction of O(/sup 3/P) with ethanol
The rate constant for the reaction of atomic oxygen with ethanol was measured directly by two experimental techniques: flash photolysis-resonance fluorescence (FP-RF, 297-886 K) and discharge flow-resonance fluorescence (DF-RF, 298-706 K). Kinetic complications in the DF-RF experiments from a fast secondary reaction and heterogeneous effects were overcome by operating at very low initial O-atom concentrations combined with the addition of excess O/sub 2/. Under these conditions results obtained in the DF-RF experiments were in very close agreement with those from the FP-RF work, which was not perturbed by any apparent complication. The combined results show slight non-Arrhenius behavior and the data were accordingly fit to a three-parameter expression, 298-886 K, k/sub 1/(T) = 9.88 x 10/sup -19/T/sup 2/ /sup 46/ exp(-932/T), in units of cm/sup 3/ molecule/sup -1/ s/sup -1/, with an error limit of about +- 15% over the given temperature range. In addition, initial (O) variation experiments were carried out at 298 K in the DF-RF apparatus to investigate the mechanism of this reaction, and model calculations for an assumed mechanism were performed. Finally, the branching ratios for the three possible H-abstraction channels are discussed in light of the non-Arrhenius behavior displayed in the present rate data.
- Research Organization:
- Brookhaven National Lab., Upton, NY
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 5628956
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:11; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
ALCOHOLS
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMBUSTION
DATA
DECOMPOSITION
ELEMENTS
EQUATIONS
ETHANOL
EXPERIMENTAL DATA
FLUORESCENCE
HIGH TEMPERATURE
HYDROXY COMPOUNDS
INFORMATION
KINETICS
LUMINESCENCE
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXYGEN
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
RESONANCE FLUORESCENCE
THERMOCHEMICAL PROCESSES