Carbon monoxide-nickel adsorption system

It is true, however, that many catalytic reactions cannot be studied conveniently, under given conditions, with usual adsorption calorimeters of the isoperibol type, either because the catalyst is a poor heat-conducting material or because the reaction rate is too low. The use of heat-flow calorimeters, as has been shown in the previous sections of this article, does not present such limitations, and for this reason, these calorimeters are particularly suitable not only for the study of adsorption processes but also for more complete investigations of reaction mechanisms at the surface of oxides or oxide-supported metals. The aim of this section is therefore to present a comprehensive picture of the possibilities and limitations of heat-flow calorimetry in heterogeneous catalysis. The use of Calvet microcalorimeters in the study of a particular system (the oxidation of carbon monoxide at the surface of divided nickel oxides) has moreover been reviewed in a recent article of this series (19). 

Carbon monoxide oxidation is a relatively simple reaction, and generally its structurally insensitive nature makes it an ideal model of heterogeneous catalytic reactions. Each of the important mechanistic steps of this reaction, such as reactant adsorption and desorption, surface reaction, and desorption of products, has been studied extensively using modem surface-science techniques.17 The structure insensitivity of this reaction is illustrated in Figure 10.4. Here, carbon dioxide turnover frequencies over Rh(l 11) and Rh(100) surfaces are compared with supported Rh catalysts.3 As with CO hydrogenation on nickel, it is readily apparent that, not only does the choice of surface plane matters, but also the size of the active species.18-21 Studies of this system also indicated that, under the reaction conditions of Figure 10.4, the rhodium surface was covered with CO. This means that the reaction is limited by the desorption of carbon monoxide and the adsorption of oxygen. 

Other workers have not investigated the effect of decomposition products on the rate. Many of the reactions carried out in flow systems must have been concerned with a poisoned reaction with a steady-state concentration of reaction products present. The effectiveness of water and hydrogen as poisons would tend to confirm the view of Schwab (1) that the reaction involves a transfer of electrons to the nickel from the formic acid and that this process is hindered by the accumulation of electrons from adsorbed water and hydrogen. If this were the only effect, carbon monoxide adsorption, which removes electrons (16) would be expected to accelerate the de-... 

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