Surface rate-determining step pressure

A first limit rate expression is obtained when surface rate contributions are rate determining.The concentration profile is plotted in Fig. 18.22. Although the use of Henry s law (Equation [18.1]) as boundary conditions is usually limited to the case of molecular diffusion (polymer membranes), it can also be used to describe permeation across metallic membranes with surface rate-determining step (rds). In such cases, the dissociative physisorption step of H2 into H is assumed to be fast and at equilibrium. Steps (3) and (5) of the sorption mechanism are rds and the relationship between surface hydrogen ad-atoms and pressure is given by Equation [18.8] ... 

Some early observations on the catalytic oxidation of SO2 to SO3 on platinized asbestos catalysts led to the following observations (1) the rate was proportional to the SO2 pressure and was inversely proportional to the SO3 pressure (2) the apparent activation energy was 30 kcal/mol (3) the heats of adsorption for SO2, SO3, and O2 were 20, 25, and 30 kcal/mol, respectively. By using appropriate Langmuir equations, show that a possible explanation of the rate data is that there are two kinds of surfaces present, 5 and S2, and that the rate-determining step is... 

Calderbank et al. (C6) studied the Fischer-Tropsch reaction in slurry reactors of 2- and 10-in. diameters, at pressures of 11 and 22 atm, and at a temperature of 265°C. It was assumed that the liquid-film diffusion of hydrogen from the gas-liquid interface is a rate-determining step, whereas the mass transfer of hydrogen from the bulk liquid to the catalyst was believed to be rapid because of the high ratio between catalyst exterior surface area and bubble surface area. The experimental data were not in complete agreement with a theoretical model based on these assumptions. 

It is important to realize that the assumption of a rate-determining step limits the scope of our description. As with the steady state approximation, it is not possible to describe transients in the quasi-equilibrium model. In addition, the rate-determining step in the mechanism might shift to a different step if the reaction conditions change, e.g. if the partial pressure of a gas changes markedly. For a surface science study of the reaction A -i- B in an ultrahigh vacuum chamber with a single crystal as the catalyst, the partial pressures of A and B may be so small that the rates of adsorption become smaller than the rate of the surface reaction. 

The evolution of methylchlorosilanes between 450 and 600 K is consistent with the 550 - 600 K typical for the catalytic Rochow Process [3]. It is also reasonably consistent with the evolution of methylchlorosilanes at 500 - 750 K reported by Frank and Falconer for a temperature programmed reaction study of the monolayer remaining on a CuaSi surface after catalytic formation of methylchlorosilanes from CHaCl at higher pressures [5]. Both of these observations suggest that the monolayer formed by methyl and chlorine adsorption on pure CuaSi is similar to that present on active catalysts. For reference, methylchlorosilanes bond quite weakly to tiie surface and desorb at 180 - 220 K. It can thus be concluded that the rate-determining step in the evolution of methylchlorosilanes at 450 - 600 K is a surface reaction rather an product desorption. 

In heterogeneous systems, the rate expressions have to be developed on the basis of (a) a relation between the rate and concentrations of the adsorbed species involved in the rate-determining step and (b) a relation between the latter and the directly observable concentrations or partial pressures in the gas phase. In consequence, to obtain adequate kinetic rate expressions it is necessary to have a knowledge of the reaction mechanism, and an accurate means of relating gas phase and surface concentrations through appropriate adsorption isotherms. The nature and types of adsorption isotherm appropriate to chemisorption processes have been discussed in detail elsewhere [16,17] and will not be discussed further except to note that, in spite of its severe theoretical limitations, the Langmuir isotherm is almost invariably used for kinetic interpretations of surface hydrogenation reactions. The appropriate equations are... 

Kinetic and equilibrium studies of the sorption of methanol on various coals and on partially acety-lated samples of these coals have been used to elucidate a mechanism for this process. The data are interpreted in terms of partial acetylation blocking surface sites and perhaps interfering with intermolecular hydrogen bonding. It is proposed that the rate-determining step is a set of parallel, competing, second-order reactions involving transfer of methanol from the surface to the interior of the coal. All types of surface sites appear to participate, and the pressure-independent rate constant is considered to be the sum of the rate constants for each type of surface site. The dependence of the experimental rate constant on methanol pressure is a characteristic of the coal rank. 

Theories relating the combustion of NC based proplnts to pressure are fairly well developed, the most successful being those proposed by Daniels(Ref 1), Rice (Ref 2), Crawford(Ref 3), Boys 8cCorner-(Ref 5), and others(Ref 4). The classification of these theories is contingent on the proposed position of the rate-determining step in the surface-flame structure... 

If the adsorption of A is the rate determining step in the sequence of adsorption, surface reaction and desorption processes, then equation 3.71 will be the appropriate equation to use for expressing the overall chemical rate. To be of use, however, it is first necessary to express CA, Cv and Cs in terms of the partial pressures of reactants and products. To do this an approximation is made it is assumed that all processes except the adsorption of A are at equilibrium. Thus the processes involving B and P are in a state of pseudo-equilibrium. The surface concentration of B can therefore be expressed in terms of an equilibrium constant KB for the adsorption-desorption equilibrium of B ... 

Jenkins and Rideal (61) have suggested for Ni that the rate-determining step is the adsorption of H2 on a small part of the surface that is not covered with ethylene. The kinetic equation for Ni suggests that this assumption is valid. If, however, it is considered that the same assumption also should cover the reactions over Rh and Ru, difficulties arise, since the negative exponents of the ethylene partial pressures cannot be explained. One should hence make the additional assumption that coverage by ethylene may occur at low temperatures for some metals. Even so, it is possible that other assumptions will just as well explain the experimental facts. 

From the linear temperature dependence of In k on 1/T an Arrhenius activation energy of 253 kJ was obtained. Since, at any temperature in the above range, the decomposition pressure of FeS04 is greater than that of Fe2(S04)3 the rate-determining step for decomposition of the former is decomposition of the ferric salt. Decomposition appears to occur exclusively on the surface of the original material, rather than in the interior of the grains. 

---