Homogeneous catalysis of the water gas shift reaction with the use of groupd 6 transition metal carbonyls: Cr(CO)/sub 6/, Mo(CO)/sub 6/, and W(CO)/sub 6/

Journal Article · Wed May 20 04:00:00 EDT 1981 · J. Am. Chem. Soc.; (United States)

OSTI ID:6052361

Kind, Jr, A D; King, R B; Yang, D B

Measurements have been carried out to determine the rate of hydrogen production by the water gas shift reaction (CO + H/sub 2/O ..-->.. CO/sub 2/ + H/sub 2/) operating at temperatures of 200/sup 0/C and lower with hexacarbonyls of chromium, molybdenum, and tungsten serving as catalyst precursors in basic methanol-water solutions. The catalytic behavior of each of these systems is similar and turnover numbers as great as 12,000 mol of H/sub 2//mol of metal hexacarbonyl per day can be achieved at 200/sup 0/C. The rate of hydrogen production is found to be (a) proportional to the amount of metal hexacarbonyl present in the system, (b) inversely proportional to carbon monoxide pressure; and (c) increasing with base concentration. Under conditions of constant base concentration and pressure, the temperature dependence of this reaction is found to be quite similar for each system corresponding to activation energies of 35, 35, and 32 kcal/mol for Cr(CO)/sub 6/, Mo(CO)/sub 6/, and W(CO)/sub 6/, respectively. The overall kinetics of this reaction can be explained by a mechanism involving formate decomposition rather than activation of carbon monoxide.

• Research Organization: Univ. of Georgia, Athens
• OSTI ID: 6052361
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:10; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
080104* -- Hydrogen-- Production-- Water Gas Processes
CARBONYLS
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
DATA
EXPERIMENTAL DATA
HYDROGEN PRODUCTION
INFORMATION
KINETICS
MOLYBDENUM COMPOUNDS
NUMERICAL DATA
REACTION KINETICS
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
WATER GAS PROCESSES