Catalytic heterogeneous reactions surfaces

Catalytic exchange of hydrocarbons, 11 223 Catalytic heterogeneous reactions, 37 134-151 Arrhenius expression, 37 134, 136 C H, transformation on transition-metal surfaces, 37 141-147... 

The deposition of tungsten by CVD is essentially a catalytic heterogeneous reaction. The tungsten surface acts as the catalyst to activate either the H2 or the SiH4 molecules depending on what chemistry is in use. It is well known from heterogeneous catalysis that extremely low concentrations of surface active contaminants can deactivate the surface and block or slow down the reaction rate. However, it is also possible that certain active molecules can accelerate the deposition once they become adsorbed to the tungsten surface. 

While it is often possible to demonstrate that a surface process is rate limiting, identification of the step concerned is not always so readily achieved (as in heterogeneous catalysis which involve comparable mechanistic steps). Reaction rates are determined by reactant areas and are slow compared with the rate of diffusive transport of material to the appropriate boundaries. Surface limited reactions are also sensitive to the ease of removal of volatile products, which may be hampered by the presence of an inert gas. Readsorption may influence the effective concentrations of participating surface intermediates. As in catalytic heterogeneous reactions, the sequence of changes which precede product evolution may involve several interlinked steps, and the parameters which determine the overall progress of reaction are not always readily identified. 

Heterogeneous reactions. Components of water or air pollution are usually in the fluid phase. Hence we may write equations such as equations 6.2, 6.6, 6.8, and 6.12 for the fluid. The fluid may have non-permeable boundaries (the reactor walls) and permeable boundaries (entrances and exits of the system as well as catalytic surfaces where mass fluxes must be equal to the superficial reaction rates). Usually, these reaction rates are modeled as pseudo-homogeneous and, moreover, concentration measurements are almost always made in the fluid phase. Heterogeneous reactions are the result of a process that occurs at phase interfaces. This means that for the differential equation written for the fluid phase, heterogeneous reactions (surface reactions, for example) are just boundary conditions. The problem is very simple to formulate at steady state and at the boundary of an active surface, the normal mass or molar fluxes must be made equal to the heterogeneous, superficial reaction rate. Then,... 

As described in Chapter 2, prior to catalytic heterogeneous reaction, which takes place on the surface of a solid catalyst, the reactant molecules have to first reach... 

His researches and those of his pupils led to his formulation in the twenties of the concept of active catalytic centers and the heterogeneity of catalytic and adsorptive surfaces. His catalytic studies were supplemented by researches carried out simultaneously on kinetics of homogeneous gas reactions and photochemistry. The thirties saw Hugh Taylor utilizing more and more of the techniques developed by physicists. Thermal conductivity for ortho-para hydrogen analysis resulted in his use of these species for surface characterization. The discovery of deuterium prompted him to set up production of this isotope by electrolysis on a large scale of several cubic centimeters. This gave him and others a supply of this valuable tracer for catalytic studies. For analysis he invoked not only thermal conductivity, but infrared spectroscopy and mass spectrometry. To ex-... 

There is a wide variety of solid electrolytes and, depending on their composition, these anionic, cationic or mixed conducting materials exhibit substantial ionic conductivity at temperatures between 25 and 1000°C. Within this very broad temperature range, which covers practically all heterogeneous catalytic reactions, solid electrolytes can be used to induce the NEMCA effect and thus activate heterogeneous catalytic reactions. As will become apparent throughout this book they behave, under the influence of the applied potential, as active catalyst supports by becoming reversible in situ promoter donors or poison acceptors for the catalytically active metal surface. 

In Chapter 1 we emphasized that the properties of a heterogeneous catalyst surface are determined by its composition and structure on the atomic scale. Hence, from a fundamental point of view, the ultimate goal of catalyst characterization should be to examine the surface atom by atom under the reaction conditions under which the catalyst operates, i.e. in situ. However, a catalyst often consists of small particles of metal, oxide, or sulfide on a support material. Chemical promoters may have been added to the catalyst to optimize its activity and/or selectivity, and structural promoters may have been incorporated to improve the mechanical properties and stabilize the particles against sintering. As a result, a heterogeneous catalyst can be quite complex. Moreover, the state of the catalytic surface generally depends on the conditions under which it is used. 

In conclusion, we note that the appearance of hydrogen atoms in the gas volume in catalytic reaction of dehydration of alcohol at low pressures observed in [25] by the sensor technique confirms that dehydration of alcohol on the surface of the zinc oxide catalyzer yields hydrogen atoms. In other words, this heterogeneous reaction does not result in production of hydrogen molecules through the process... 

Many heterogeneous catalytic organic reactions are run in the liquid-phase, and liquid phase reactions present special mass transfer problems. Diffusion barriers exist between the gas and the liquid and between the liquid and the solid, so there are gas-liquid-solid diffusion barriers. When these barriers are too large, the true chemical rate at the surface is not observed. 

Dioxygen and oxidized substances react on the surface of the catalyst only. The pure heterogeneous reaction occurs only after diffusion of reactants to the catalytic surface and back diffusion of products from the surface into the solution. A combination of a few mechanisms of such types are possible. 

The mechanisms, and hence theoretically derived rate laws, for noncatalytic heterogeneous reactions involving solids are even less well understood than those for surface-catalyzed reactions. This arises because the solid surface changes as the reaction proceeds, unlike catalytic surfaces which usually reach a steady-state behavior. The examples discussed here are illustrative. 

However, the use of the heterogeneous catalysts in applicative enantioselective syntheses has a limited success. Several factors contribute to this situation (1) a long time is required to achieve an effective heterogeneous enantioselective catalyst compared with the homogeneous ones, (2) a more complex structure of the heterogeneous catalyst surface on which centers coexist with different catalytic activity and selectivity, which can lead to undesired secondary reactions, and (3) an increased difficulty to create an effective asymmetric environment and to accommodate it with the multitude of reactions that are interesting to be carried out under enantioselective restrictions. 

In furnaces using residual oils, heterogeneous catalysis is a possible route for the conversion of S02 to S03. Sulfur dioxide and molecular oxygen will react catalytically on steel surfaces and vanadium pentoxide (deposited from vanadium compounds in the fuel). Catalytic reactions may also occur at lower temperatures where the equilibrium represented by reaction (8.94) favors the formation of S03. 

The particle surface may function as a catalytic site for heterogeneous reactions involving the generation or removal of gaseous pollutants (11, 15-17). 

Surface Chemical Analysis. Electron spectroscopy of chemical analysis (ESCA) has been the most useful technique for the identification of chemical compounds present on the surface of a composite sample of atmospheric particles. The most prominent examples Include the determination of the surface chemical states of S and N in aerosols, and the investigation of the catalytic role of soot in heterogeneous reactions involving gaseous SO2, NO, or NH3 (15, 39-41). It is apparent from these and other studies that most aerosol sulfur is in the form of sulfate, while most nitrogen is present as the ammonium ion. A substantial quantity of amine nitrogen also has been observed using ESCA (15, 39, 41). 

The surface layer composition may effect catalytic activity. Surface enrichments of trace metals, for example, may enhance the catalytic role of particles in heterogeneous reactions in the atmosphere involving gaseous pollutants such as SO2 (54, 55). 

Figure 10.1 Strategies for the advanced chemical design of catalytically active reaction space at heterogeneous surfaces with supported metal complexes.

There can be, however, no doubt that in catalytic processes, purely physical factors play an important role, in addition to the chemical valence forces. This is particularly true for the solid catalysts of heterogeneous reactions for which the properties of surfaces, as the seats of catalytic action are of prime importance. The total surface areas, the fine structure of the surfaces, the transport of reactants to and from surfaces, and the adsorption of the reactants on the surfaces, can all be considered as processes of a predominantly physical nature which contribute to the catalytic overall effect. Any attempt, however, to draw too sharp a line between chemical and physical processes would be futile. This is illustrated clearly by the fact that the adsorption of gases on surfaces can be described either as a mere physical condensation of the gas molecules on top of the solid surface, as well as the result of chemical affinities between adsorbate and adsorbent. Every single case of adsorption may lie closer to either one of the hypothetical extremes of a purely physcial or of a purely chemical adsorption, and it would be misleading to maintain an artificial differentiation between physical and chemical factors. 

From a consideration of the velocity of a number of heterogeneous gas reactions (Eideal and Taylor, Gatalysis in Theory and Practice) a certain number of conclusions may be drawn in respect to the valency of the adsorbate and the number of elementary spaces on the crystal lattice which the adsorbate occupies or adheres to. If we consider a unimolecular reaction to occur catalytically at a surface, e.g. Xg 2X, and that the reactant is but feebly adsorbed by the catalyst, then adopting the previous notation the rate of condensation of the gas on the surface of the catalyst (since the catalyst is almost bare) will be ay,. If the reactant occupies a fraction 6 and each molecule n elementary spaces on the lattice the rate of evaporation of the unchanged product will be vd -. Provided the chemical reaction occur but slowly we obtain (1) ay = vO. ... 

Moreover, as neither the concept of surface initiated homogeneous-heterogeneous reaction (11) can be invoked to explain our results, it can be stated that the methane partial oxidation reaction proceeds via a surface catalysed process which likely involves specific catalyst requirements. However, by comparing the HCHO productivity of the different catalytic systems previously proposed (9) with that of our 5% V205/Si02 catalyst, it emerges that our findings constitute a relevant advancement in this area (23),... 

Liquid phase hydrogenation catalyzed by Pd/C is a heterogeneous reaction occurring at the interface between the solid catalyst and the liquid. In our one-pot process, the hydrogenation was initiated after aldehyde A and the Schiff s base reached equilibrium conditions (A B). There are three catalytic reactions A => D, B => C, and C => E, that occur simultaneously on the catalyst surface. Selectivity and catalytic activity are influenced by the ability to transfer reactants to the active sites and the optimum hydrogen-to-reactant surface coverage. The Langmuir-Hinshelwood kinetic approach is coupled with the quasi-equilibrium and the two-step cycle concepts to model the reaction scheme (1,2,3). Both A and B are adsorbed initially on the surface of the catalyst. Expressions for the elementary surface reactions may be written as follows ... 

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