Heterogeneous catalysis reaction directions

All these steps can influence the overall reaction rate. The reactor models of Chapter 9 are used to predict the bulk, gas-phase concentrations of reactants and products at point (r, z) in the reactor. They directly model only Steps 1 and 9, and the effects of Steps 2 through 8 are lumped into the pseudohomoge-neous rate expression, a, b,. ..), where a,b,. .. are the bulk, gas-phase concentrations. The overall reaction mechanism is complex, and the rate expression is necessarily empirical. Heterogeneous catalysis remains an experimental science. The techniques of this chapter are useful to interpret experimental results. Their predictive value is limited. 

Steps 1 through 9 constitute a model for heterogeneous catalysis in a fixed-bed reactor. There are many variations, particularly for Steps 4 through 6. For example, the Eley-Rideal mechanism described in Problem 10.4 envisions an adsorbed molecule reacting directly with a molecule in the gas phase. Other models contemplate a mixture of surface sites that can have different catalytic activity. For example, the platinum and the alumina used for hydrocarbon reforming may catalyze different reactions. Alternative models lead to rate expressions that differ in the details, but the functional forms for the rate expressions are usually similar. 

The idea that /3 continuously shifts with the temperature employed and thus remains experimentally inaccessible would be plausible and could remove many theoretical problems. However, there are few reaction series where the reversal of reactivity has been observed directly. Unambiguous examples are known, particularly in heterogeneous catalysis (4, 5, 189), as in Figure 5, and also from solution kinetics, even when in restricted reaction series (187, 190). There is the principal difficulty that reactions in solution cannot be followed in a sufficiently broad range of temperature, of course. It also seems that near the isokinetic temperature, even the Arrhenius law is fulfilled less accurately, making the determination of difficult. Nevertheless, we probably have to accept that reversal of reactivity is a possible, even though rare, phenomenon. The mechanism of such reaction series may be more complex than anticipated and a straightforward discussion in terms of, say, substituent effects may not be admissible. 

The hydrogenation of p-unsaturated alcohols is a classical example of competing reaction processes in heterogeneous catalysis. In principle, either isomerization to an enol followed by tautomerization to the ketone can occur, or direct hydrogenation to the saturated alcohol is possible (1). It is fair to state that interest in this type of chemistry is derived from both basic scientific... 

In principle, sites a, IT, and c need not be association sites as depicted by Ogston but could be steric sites that form obstructions such that the adsorbed molecule is chirally directed. Only one active site is actually required providing the remaining two sites (protuberances or cavities) are different from each other and from the active site that catalyzes the reaction. They could be identical providing they are not symmetrically oriented with respect to the active site (not an isosceles triangle). These are the basic concepts for a chiral environment on a surface and they lead to the three basic methods for creating chiral surfaces in heterogeneous catalysis. 

Moreover, the use of heat-flow calorimetry in heterogeneous catalysis research is not limited to the measurement of differential heats of adsorption. Surface interactions between adsorbed species or between gases and adsorbed species, similar to the interactions which either constitute some of the steps of the reaction mechanisms or produce, during the catalytic reaction, the inhibition of the catalyst, may also be studied by this experimental technique. The calorimetric results, compared to thermodynamic data in thermochemical cycles, yield, in the favorable cases, useful information concerning the most probable reaction mechanisms or the fraction of the energy spectrum of surface sites which is really active during the catalytic reaction. Some of the conclusions of these investigations may be controlled directly by the calorimetric studies of the catalytic reaction itself. 

Contact with a mineral surface can in many cases allow a redox reaction to proceed at a rate considerably greater than attainable within an aqueous solution itself. The catalyzing mineral sorbs the electron donating and accepting species, then, within its structure or along its surface, conducts electrons from one to the other. Where electron transfer by this pathway proceeds more rapidly than via a direct transfer in solution between colliding molecules, the redox reaction proceeds preferentially by heterogeneous catalysis. 

Electrochemistry is in many aspects directly comparable to the concepts known in heterogeneous catalysis. In electrochemistry, the main driving force for the electrochemical reaction is the difference between the electrode potential and the standard potential (E — E°), also called the overpotential. Large overpotentials, however, reduce the efficiency of the electrochemical process. Electrode optimization, therefore, aims to maximize the rate constant k, which is determined by the catalytic properties of the electrode surface, to maximize the surface area A, and, by minimization of transport losses, to result in maximum concentration of the reactants. 

Our own group is also involved in the development of domino multicomponent reactions for the synthesis of heterocycles of both pharmacologic and synthetic interest [156]. In particular, we recently reported a totally regioselective and metal-free Michael addition-initiated three-component substrate directed route to polysubstituted pyridines from 1,3-dicarbonyls. Thus, the direct condensation of 1,3-diketones, (3-ketoesters, or p-ketoamides with a,p-unsaturated aldehydes or ketones with a synthetic equivalent of ammonia, under heterogeneous catalysis by 4 A molecular sieves, provided the desired heterocycles after in situ oxidation (Scheme 56) [157]. A mechanistic study demonstrated that the first step of the sequence was a molecular sieves-promoted Michael addition between the 1,3-dicarbonyl and the cx,p-unsaturated carbonyl compound. The corresponding 1,5-dicarbonyl adduct then reacts with the ammonia source leading to a DHP derivative, which is spontaneously converted to the aromatized product. 

Heterogeneous catalysis is a dynamic process and gas-catalyst reactions occur at the atomic level. In gas-catalyst reactions, the dynamic atomic structure of catalysts under operating conditions therefore plays a pivotal role in catalytic properties. Direct observations of the microstructural evolution and active sites of... 

---