High-temperature photochemistry kinetics study of the reaction of O(/sup 3/P) atoms with ethylene from 290 to 1510 K

Journal Article · Thu Mar 12 04:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100290a056· OSTI ID:7043920

Mahmud, K; Marshall, P; Fontijn, A

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), Journal Name: J. Phys. Chem.; (United States) Vol. 91:6; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400500 -- Photochemistry
ABSORPTION
ALKENES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELEMENTS
EMISSION SPECTROSCOPY
ETHYLENE
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HIGH TEMPERATURE
HYDROCARBONS
INFORMATION
KINETICS
LOW PRESSURE
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
PULSE TECHNIQUES
REACTION KINETICS
RESONANCE ABSORPTION
SPECTROSCOPY
VERY HIGH TEMPERATURE