Mechanism of heterogeneous reactions

The chemical properties of oxide surfaces have been studied by several methods, including oxygen exchange. This method has been used to investigate the mechanisms of heterogeneous reactions for which oxides are active catalysts [36]. The dimerization step does not necessarily precede desorption and Malinin and Tolmachev [634], in one of the few reviews of decomposition kinetics of solid metal oxides, use this criterion to distinguish two alternative reaction mechanisms, examples being... 

At the beginning of this century, attempts were made to understand the mechanisms of chemical oscillations. However, the mechanisms of heterogeneous reactions are too complicated since they involve phase transitions and transport processes. Homogeneous reactions are much simpler, and it was natural to begin theoretical study with them. 

The mechanism of heterogeneous reactions of propylene on Y-type decationized molecular sieve catalysts at about or below 200 °C yielding saturated hydrocarbons such as propane, 2-methylpropane (isobutane), 2-methylbutane and 2-methylpentane has been studied using propene-[l- C]. The specific activity of propane has been found to be the same as the initial radioactivity of propene. The specific activity of 2-methylpentane... 

The concept of a structure element and that of non-stoichiometry are most important in understanding phenomena involving solids, such as electrical conductivity, the mechanisms of heterogeneous reactions and certain optical and magnetic properties. 

Mechanism of Heterogeneous Reaction Dissolution in the Active State... 

The commonly accepted mechanism of heterogeneously catalyzed hydrogenation involves activation of both the hydrogen and the C—C multiple bond adsorbed on the metal surface. First one hydrogen atom is transferred to the least hindered position of the multiple bond to give a half-hydrogenated adsorbed species. This reaction is fully reversible and ac-... 

The study of catalytic polymerization of olefins performed up to the present time is certain to hold a particular influence over the progress of the concepts of the coordination mechanism of heterogeneous catalysis. With such an approach the elementary acts of catalytic reaction are considered to proceed in the coordination sphere of one ion of the transition element and, to a first approximation, the collective features of solids are not taken into account. It is not surprising that polymerization by Ziegler-Natta catalysts is often considered together with the processes of homogeneous catalysis. 

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 examples of the model studies presented show how the meshing of modern surface techniques with reaction kinetics can provide valuable Insights Into the mechanisms of surface reactions and serve as a useful complement to the more traditional techniques. Close correlations between these two areas holds great promise for a better understanding of the many subtleties of heterogeneous catalysis. 

Solid-state reactions between two phases of constant composition are called heterogeneous solid-state reactions. The mechanism of heterogeneous solid-state reactions... 

The complexity and inhomogenicity of catalytic sites of metals and metal oxides make it difficult to interpret the mechanism of catalytic reactions on solid surfaces. Investigations that may lead to a better characterization of adsorbed species on catalytic sites could add much to our understanding of heterogeneous catalysis. 

Although microwave activation of catalytic reactions has been the subject of many studies (Sects. 10.3.1 and 10.3.2), the mechanism of these reactions is not yet fully understood. In heterogeneous catalytic liquid/solid and gas/solid systems many results have revealed significant differences between the rates of conventionally and microwave heated reactions. As a rule, at the same temperature microwave heated reactions were faster than conventional and their rate enhancement was over one or-... 

Metallacyclobutanes have been proposed as intermediates in a number of catalytic reactions, and model studies with isolated transition metallacyclobutanes have played a large part in demonstrating the plausibility of the proposed mechanisms. Since the mechanisms of heterogeneously catalysed reactions are especially difficult to determine by direct study, model studies are particularly valuable. This article describes results which may be relevant to the mechanisms of isomerization of alkanes over metallic platinum by the bond shift process and of the oligomerization or polymerization of alkenes. 

Study of the kinetics of the oxidation of asymmetric secondary hydroxylamines to nitrones with H2O2, catalyzed by methylrhenium trioxide, has led to the elucidation of the mechanism of the reaction (104). Full transformation of N,N -disubstituted hydroxylamines into nitrones upon treatment with H2O2 occurs on using polymeric heterogeneous catalysts such as polymer-supported methylrhenium trioxide systems (105). 

A. A. Davydov, N. A. Rubene and T. M. Yurieva, All-Union Conference on the Mechanism of Heterogeneous Catalytic Reactions, Moscow, USSR, September 3-9, 1974, Preprint 39. 

Out of the above four steps, steps (i) and (iii) are rapid and normally do not play any part in the overall rate determination of reaction. Mechanism of heterogeneous catalysis is discussed in Section 6.9. 

Selectivity in homogeneous reactions is treated in Refs. [2-6], while the selectivi-ties that are influenced in heterogeneous reactions by diffusion and adsorption are dealt with in Refs. [7, 8]. Kinetics and mechanisms of electrochemical reactions are covered in Chap. 1 of this volume and in Refs. [9-11]. 

---