Laser photolysis/resonance fluorescence study of the rate constants for the reaction of OH radicals with C/sub 2/H/sub 4/ and C/sub 3/H/sub 6/
Absolute rate constants for the reactions of OH radicals with (1) C/sub 2/H/sub 4/ and (2) C/sub 3/H/sub 6/ have been measured by using excimer laser photolysis to generate OH and time-resolved resonance fluorescence as its monitor. Reaction 1 was studied at total pressures between 4 and 130 mbar and over the temperature region 296-524 K. k/sub 1/ was found to show a falloff behavior with the extrapolated high-pressure limit given by k/sub 1/ /sup infinity/ (T) = (2.0 +/- 0.8) x 10/sup 12/ exp((320 +/- 150)K/T) cm/sup 3//(mol.s). The observed pressure dependence is consistent with the accepted mechanism OH + C/sub 2/H/sub 4/ in equilibrium C/sub 2/H/sub 4/OH* /sup +M/..-->.. C/sub 2/H/sub 4/OH. Possible modifications of k(p) due to bimolecular product channels are discussed. Reaction 2 was studied at 298 K and total pressures of Ar between 1.3 and 130 mbar. k/sub 2/ is also found to show a falloff behavior. In the limit of high pressure k/sub 2//sup infinity/ = (1.8 +/- 0.3) x 10/sup 13/ cm/sup 3//(mol.s).
- Research Organization:
- Universitaet Gottingen, Federal Republic of Germany
- OSTI ID:
- 7050969
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 88:5
- Country of Publication:
- United States
- Language:
- English
Similar Records
Atmospheric chemistry of cyclohexane: UV spectra of c-C{sub 6}H{sub 11}{sup {sm_bullet}} and (c-C{sub 6}H{sub 11})O{sub 2}{sup {sm_bullet}} radicals, kinetics of the reactions of (c-C{sub 6}H{sub 11})O{sub 2}{sup {sm_bullet}} radicals with NO and NO{sub 2}, and the fate of the alkoxy radical (c-C{sub 6}H{sub 11})O{sup {sm_bullet}}
Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
ACETYLENE
CHEMICAL REACTION KINETICS
PHOTOCHEMICAL REACTIONS
RESONANCE FLUORESCENCE
HYDROXYL RADICALS
PROPYLENE
EXPERIMENTAL DATA
LASER RADIATION
PHOTOLYSIS
PRESSURE DEPENDENCE
ALKENES
ALKYNES
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
FLUORESCENCE
HYDROCARBONS
INFORMATION
KINETICS
LUMINESCENCE
NUMERICAL DATA
ORGANIC COMPOUNDS
RADIATIONS
RADICALS
REACTION KINETICS
400500* - Photochemistry
090110 - Hydrocarbon Fuels- Properties- (1979-1989)