Kinetic studies on the water-gas shift reaction catalyzed by magnetite/chromium oxide and copper/zinc oxide were carried out by using an in situ photoacoustic spectroscopic technique. The reactions were performed in a closed-circulation reactor system using a differential photoacoustic cell at total pressure of 40 Torr in the temperature range of 100 to 350 °C. The CO2 photoacoustic signal varying with the concentration of CO2 during the catalytic reaction was recorded as a function of time. The time-resolved photoacoustic spectra obtained for the initial reaction stage provided precise data of CO2 formation rate. The apparent activation energies determined from the initial rates were 74.7 kJ/mol for the magnetite/chromium oxide catalyst and 50.9 kJ/mol for the copper/zinc oxide catalyst. To determine the reaction orders, partial pressures of CO(g) and H2O(g) in the reaction mixture were varied at a constant total pressure of 40 Torr with N2 buffer gas. For the magnetite/chromium oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.93 and 0.18, respectively. For the copper/zinc oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.79 and 0, respectively.
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