Catalysis homogeneity assumption

This survey has been concerned with the enumeration of all possible mechanisms for a complex chemical reaction system based on the assumption of given elementary reaction steps and species. The procedure presented for such identification has been directly applied to a number of examples in the field of heterogeneous catalysis. Application to other areas is clearly indicated. These would include complex homogeneous reaction systems, many of which are characterized by the presence of intermediates acting as catalysts or free radicals. Enzyme catalysis should also be amenable to this approach. 

This section surveys the use of various di-, tri-, and polynuclear ruthenium complexes as precursors for the homogeneous hydroformylation of alkenes. Several arbitrary assumptions have been made so as to include dinuclear starting complexes which are strictly not cluster compounds. Moreover, no distinction is made between neutral and anionic precursors. Also, in several cases, particularly in the patents, information is lacking concerning the intermediate species involved in the catalytic cycles. Interestingly, half of the described systems come from patents, and there are few fundamental studies which clearly establish the implication of cluster species during the catalysis. 

Today there is ample evidence in catalysis that the assumption of a homogeneous surface is not valid. Thus, surface irregularities exist such as crystallographic dislocations, defects, and planes with different activity adsorbing molecules may interact with the surface and with each other several adsorption states of a species may exist on a single plane. These... 

The transport equation for the component A must be solved separately for each kind of reaction kinetics. An analytical solution for eq. (9.31) is possible in some special cases, which one can encounter in homogeneous catalysis, e.g. zero or first order kinetics. The liquid film must, however, be considered as isothennal, which is a quite reasonable assumption. Below we present an analytical solution for the mass balance equation of the liquid film,... 

Much of the justification for the extensive study of transition metal cluster chemistry is embedded in the assumption that reactions of metal clusters are realistic structural models for reactions at metal surfaces in such processes as heterogeneous catalysis (9,10,11). For example, the metal carbonyl clusters, Ir4(CO)i2 and Os3(CO)i2, were demonstrated to be effective homogeneous catalysts for methanation (12). Additionally, Demitras and Muetterties (13) have found Ir4(CO)i2 to be a homogeneous catalyst in the Fischer-Tropsch synthesis of aliphatic hydrocarbons. Homogeneous catalysis of the water gas shift reaction by metal carbonyl clusters (e.g., Ru3(CO)i2) in alkaline solution has been reported by Laine, Rinker, and Ford (14), and more recently by Pettit s group (15). Nevertheless, mononuclear metal carbonyls (e.g., Fe(CO)s and the group VIb metal hexacarbonyls) have been demonstrated to have considerable activity above 120°C as soluble catalysts for Reaction 2 (16),... 

In heterogeneous catalysis, nth-order kinetics may be the result of adsorption on a nonideal catalyst surface. In homogeneous systems, nth-order kinetics may represent the overall rate of the underlying elementary reactions, e.g., the classical Rice-Herzfeld mechanism for thermal cracking of hydrocarbonsFor simplicity, n is assumed to be constant for all species. This is not a strong assumption for many petroleum processes. 

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