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Title: 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]

Journal Article · · J. Org. Chem.; (United States)
DOI:https://doi.org/10.1021/jo00881a024· OSTI ID:7248989

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