Isotopic equilibration of carbon monoxide catalyzed by supported ruthenium
- Istituto Guido Donegani SpA, Novara, Italy
The rate of isotopic equilibration of CO has been studied at 373/sup 0/K on a ruthenium/Al/sub 2/O/sub 3/ catalyst. CO partial pressures from 5 x 10/sup 2/ to 15 x 10/sup 3/ Pa were used, and the effect of H/sub 2/ (0 to 10% vol) was studied. The analysis of kinetic data and the absence of CO/sub 2/ or CH/sub 4/ in the reaction products show that CO is present on the catalyst surface in an undissociated and reactive form. Hydrogen has a strong inhibiting effect on the exchange reaction, and does not react with CO under these conditions. It is argued that carbon monoxide can be adsorbed as a single carbonyl or in geminal dicarbonyl form, on metallic or partially oxidized ruthenium sites. This latter form displays a lower back-donation effect and with a contiguous similar group can form a square planar transition complex, by means of which the exchange reaction occurs. The inhibiting effect of H/sub 2/ is two-fold, namely, competitive adsorption against CO and stabilization of the carbonyl bond. Ab initio molecular calculations on a simplified model (H instead of Ru) seem to support this mechanism.
- OSTI ID:
- 6721552
- Journal Information:
- J. Catal.; (United States), Vol. 65:1
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
CARBON 13
ISOTOPE EFFECTS
CARBON MONOXIDE
HYDROGENATION
METHANE
PRODUCTION
OXYGEN 16
RUTHENIUM
CATALYTIC EFFECTS
ALUMINIUM OXIDES
CATALYST SUPPORTS
ALKANES
ALUMINIUM COMPOUNDS
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
ELEMENTS
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
HYDROCARBONS
ISOTOPES
LIGHT NUCLEI
METALS
NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
PLATINUM METALS
REFRACTORY METALS
STABLE ISOTOPES
TRANSITION ELEMENTS
400302* - Organic Chemistry- Isotope Effects- (-1987)
090121 - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989)