High-temperature photochemistry kinetics study of the reaction of O(/sup 3/P) atoms with ethylene from 290 to 1510 K
The O + C/sub 2/H/sub 4/ reaction has been investigated in a high-temperature photochemistry (HTP) reactor at temperatures from 290 to 1510 K and pressures from 60 to 500 Torr. Ground-state O atoms were generated by flash photolysis of CO/sub 2/ and monitored by time-resolved atomic resonance fluorescence with pulse counting. Measurements were made under pseudo-first-order conditions (O) << (C/sub 2/H/sub 4/). Rate coefficients from 290 to 850 K are in good agreement with the numerous earlier measurements in that range. Above those temperatures a sharp rise in k(T) with increasing T is evident. On the basis of present and other measurements by isolated elementary reaction techniques they recommend k(T) = 1.3 x 10/sup -11/ exp(-830 K/T) + 1.9 x 10/sup -9/ x exp(-6940 K/T) cm/sup 3/ molecule/sup -1/ s/sup -1/ as a fit expression for the 290-1510 K range. Confidence limits are discussed in the text. It is shown that the accepted transition-state treatment for channels significant at T < 850 K cannot account for the sharp upward curvature. Other channels will have to be considered at higher temperatures.
- Research Organization:
- Rensselaer Polytechnic Institute, Troy, NY
- DOE Contract Number:
- FG02-84ER13224
- OSTI ID:
- 7043920
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 91:6
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON DIOXIDE
PHOTOLYSIS
ETHYLENE
CHEMICAL REACTIONS
OXYGEN
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HIGH TEMPERATURE
LOW PRESSURE
MEDIUM TEMPERATURE
PHOTOCHEMISTRY
PULSE TECHNIQUES
RESONANCE ABSORPTION
VERY HIGH TEMPERATURE
ABSORPTION
ALKENES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMISTRY
DATA
DECOMPOSITION
ELEMENTS
EMISSION SPECTROSCOPY
HYDROCARBONS
INFORMATION
KINETICS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
REACTION KINETICS
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry