Surface reaction rate

Reaction A2 -t B R -I- S, with A2 dissociated upon adsorption and with surface reaction rate controlling ... 

Chemical reactions of surfeces. Diffraction can be used qualitatively to identify different surface phases resulting from adsorption and chemical reaction at surfaces. Reaction rates can be investigated by following the evolution of diffracted beam intensities. 

For the first assumption, the value of Kw for the shift appears to be too high. It must be this high because it is necessary to make C02 appear while both C02 and CO are being consumed rapidly by methanation. The data may be tested to see if the indicated rate appears unreasonable from the standpoint of mass transfer to the gross catalyst surface. Regardless of the rate of diffusion in catalyst pores or the surface reaction rate, it is unlikely that the reaction can proceed more rapidly than material can reach the gross pill surface unless the reaction is a homogeneous one that is catalyzed by free radicals strewn from the catalyst into the gas stream. 

A reaction with a high activation energy tends to have a weaker interaction with the surface and hence will have enhanced mobihty that is reflected in a larger activation entropy. For this reason, the pre-exponents of surface desorption rate constants are lO — lO larger than the pre-exponents of surface reaction rates. 

A central problem In relating catalytic processes on well-defined surfaces In the laboratory with those encountered under technological conditions Is the large pressure difference a factor of 10 . It Is therefore highly questionable to extrapolate surface coverages or surface reaction rates measured between 10 and 10" Torr In order to predict behavior expected In process environments (one Torr to several atmospheres)(1). 

Figure 1. Schematic diagrams of systems used to obtain surfac reaction rates at high pressures on surfaces cleaned before reaction and analyzed after reaction by AES and TED.

Kinetic Term The designation kinetic term is something of a misnomer in that it contains both rate constants and adsorption equilibrium constants. For thfe cases where surface reaction controls the overall conversion rate it is the product of the surface reaction rate constant for the forward reaction and the adsorption equilibrium constants for the reactant surface species participating in the reaction. When adsorption or desorption of a reactant or product species is the rate limiting step, it will involve other factors. 

The complete chemical modelling of a cloud in the ISM looks tractable, if complicated, although there will always be assumptions, some of which will be rather gross, such as surface reaction rates, but they can all be refined in time. Molecular cloud modelling is at the frontier of astrochemistry and it would be hard to consider all of the results. The basic process of generating a kinetic model for a molecular cloud must follow the pathway ... 

Now the surface reaction rates alter the gas-phase reactant concentrations. Cutlip (38) has studied CO oxidation over Pt/Al203 in a gradientless reactor under conditions often leading to complete conversion. The feed gas alternated between 2% CO and 3% 02 in argon. Figure 9 shows some typical results. Clearly there is no hope of simulating such data by anthing but a complicated computer model. 

By combining surface-reaction rate laws with the Langmuir expressions for surface coverages, we can obtain Langmuir-Hinshelwood (LH) rate laws for surface-catalyzed reactions. Although we focus on the intrinsic kinetics of the surface-catalyzed reaction, the LH model should be set in the context of a broader kinetics scheme to appreciate the significance of this. 

As noted by Froment and Bischoff (1990, p. 209), the case of surface-reaction-rate control is not consistent with the existence of a sharp core boundary in the SCM, since this case implies that diffusional transport could be slow with respect to the reaction rate. 

Corresponding equations for the two special cases of gas-film mass-transfer control and surface-reaction-rate control may be obtained from these results (they may also be derived individually). The results for the latter case are of the same form as those for reaction-rate control in the SCM (see Table 9.1, for a sphere) with R0 replacing (constant) R (and (variable) R replacing rc in the development). The footnote in Example 9-2 does not apply here (explain why). 

The starting points for the continuity and energy equations are again 21.5-1 and 21.5-6 (adiabatic operation), respectively, but the rate quantity7 (—rA) must be properly interpreted. In 21.5-1 and 21.5-6, the implication is that the rate is the intrinsic surface reaction rate, ( rA)int. For a heterogeneous model, we interpret it as an overall observed rate, (—rA)obs, incorporating the transport effects responsible for the gradients in concentration and temperature. As developed in Section 8.5, these effects are lumped into a particle effectiveness factor, 77, or an overall effectiveness factor, r]0. Thus, equations 21.5-1 and 21.5-6 are rewritten as... 

As shown in Example 22-3, for solid particles of the same size in BMF, the form of the reactor model resulting from equation 22.2-13 depends on the kinetics model used for a single particle. For the SCM, this, in turn, depends on particle shape and the relative magnitudes of gas-film mass transfer resistance, ash-layer diffusion resistance and surface reaction rate. In some cases, as illustrated for cylindrical particles in Example 22-3(a) and (b), the reactor model can be expressed in explicit analytical form additional results are given for spherical particles by Levenspiel(1972, pp. 384-5). In other f l cases, it is convenient or even necessary, as in Example 22-3(c), to use a numerical pro-... 

In such cases, the overall rate equals the rate of the surface reaction and the surface reaction rate is said to be controlling. The stoichiometric equation is... 

A triatomic molecule undergoes the reaction, A3 B + C, in contact with a catalytic surface. It dissociates completely on adsorption. Write rate equations for the two cases (a) Surface reaction rate controlling, adsorptive equilibrium of all participants maintained (b) Rate of desorption of substance B controlling, surface reaction equilibrium maintained. 

The effect of system pressure on the initial rate of the reaction, A2 => B, was observed with the results tabulated. All experiments started with pure A. It is expected that the controlling step is a surface reaction rate, but it is not known if dissociation occurs on adsorption. Check this point. 

Net desorption rate of B controlling. (1) Surface reaction rate controlling,. 

Initial rate data of the catalytic dehydration of butanol-1 are believed controlled by the surface reaction rate with this rate equation in terms of the fugacity, f,... 

At steady state the diffusional and surface reaction rates are equal,... 

Here the pseudo-homogeneous rate r is related to the surface reaction rate r" through the area of active catalyst per unit volume of reactor. Assuming further a plug-flow regime, the integration of the mass balance equation for this simple rate expression gives an expression for CO conversion ... 

Blum, A. E., and A. C. Lasaga (1987), "Monte Carlo Simulations of Surface Reaction Rate Laws", in W. Stumm, Ed., Aquatic Surface Chemistry, pp. 255-292. 

Surface reaction rate laws for dislocation-free surfaces. No surface diffusion allowed. Crystal growth for InS > 0, dissolution for InS < 0. Solid line, /kT = 3.5 dashed line, d>/kT = 3.0. 

Figure 9.16 shows a plot of [(mlk)s = Tos] versus Y0. for different values of ks. The points on this figure were extracted from experimental data obtained by Benning et al. [22] for the burning of aluminum alloy rods in oxygen with an argon impurity. These data correspond to a ks close to 36. Large values of ks specify very fast surface reaction rates. For a ks value of 50, an impurity... 

The extent to which a given reactant, such as oxygen, is able to utilize this additional surface area depends on the difficulty in diffusing through the particle to reach the pore surfaces and on the overall balance between diffusion control of the burning rate and kinetic control. To broadly characterize these competing effects, three zones of combustion of porous particles have been identified, as shown in Fig. 9.21. In Zone I the combustion rate is fully controlled by the surface reaction rate (kinetically controlled), because the diffusion... 

Here kgr is the surface reaction rate constant, Rr is the adsorption equilibrium constant for product R, Pr is the partial pressure of R and Kp is the reaction equilibrium constant. At low loading the reaction rate simply becomes proportional to the product of the intrinsic rate constant and the Henry coefficient. 

In catalytic reactors we assume that there is no reaction in the fluid phase, and all reaction occurs on the surface of the catalyst. The surface reaction rate has the units of moles per unit area of catalyst per unit time, which we will call r". We need a homogeneous rate r to insert in the mass balances, and we can write this as... 

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