Use of the kinetic isotope effect as a test for homogeneous unimolecular gas phase reactions in thermolytic processes. [To discriminate between homogeneous and heterogeneous surface catalyzed reactions]
Experiments are described employing the kinetic isotope effect to discriminate between homogeneous and heterogeneous surface catalyzed reactions. Advantage is taken of the differences in isotope effect expected between the nonequilibrium statistical weight isotope effect (NESWIE) observed at low pressures and the conventional isotope effect observed at higher pressures for molecules containing up to approximately 15 atoms. No change in isotope effect as a function of pressure is expected for surface-catalyzed processes. The k/sub H//k/sub D/ ratio for the thermal decomposition of diketene to ketene in a flow system is reported. At low pressures a value of k/sub H//k/sub D/ of 0.91 was obtained while at pressures of 140 mm, k/sub H//k/sub D/ was found to be 1.04 at 420/sup 0/C.
- Research Organization:
- Univ. of Missouri, St. Louis
- OSTI ID:
- 7248989
- Journal Information:
- J. Org. Chem.; (United States), Vol. 41:19
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
KETENES
CHEMICAL REACTION KINETICS
PYROLYSIS
CATALYSIS
GAS ANALYSIS
HIGH TEMPERATURE
PRESSURE DEPENDENCE
SURFACE PROPERTIES
CHEMICAL REACTIONS
DECOMPOSITION
HYDROGEN ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)
400800 - Combustion
Pyrolysis
& High-Temperature Chemistry