Diffusivity Knudsen

Note the use of a script for the binary pair mutual diffusion coefficient, as distinct from the Roman D already used to represent Knudsen diffusion coefficients. This convention will be adhered to throughout. 

Let us now turn attention to situations in which the flux equations can be replaced by simpler limiting forms. Consider first the limiting case of dilute solutions where one species, present in considerable excess, is regarded as a solvent and the remaining species as solutes. This is the simplest Limiting case, since it does not involve any examination of the relative behavior of the permeability and the bulk and Knudsen diffusion coefficients. 

The solute species therefore diffuse independently, rather as in Knudsen diffusion, but with effective diffusion coefficients D, where... 

The limiting cases of greatest interest correspond to conditions in which the mean free path lengths are large and small, respectively, compared with the pore diameters. Recall from the discussion in Chapter 3 that the effective Knudsen diffusion coefficients are proportional to pore diameter and independent of pressure, while the effective bulk diffusion coefficients are independent of pore diameter and inversely proportional to pressure. 

The Knudsen diffusion coefficients are given by equations (2.11) in which K. is independent of pressure and proportional to pore diameter a, so that we can write... 

It may seem curious that Knudsen diffusion coefficients still appear in equations (5.18) and (5.19), which supposedly give the flux relations at the limit of bulk diffusion control. However, inspection reveals that only ratios of these coefficients are effectively present, and from equation (2,11) it follows that... 

The first case corresponds to a situation in which all Knudsen diffusion coefficients are equal, and all binary pair bulk diffusion coefficients are equal ... 

It ls not surprising chat such a relation should hold at the Limit of Knudsen diffusion, since Che Knudsen diffusion coefficients are themselves inversely proportional to the square roots of molecular weights, but the pore diameters in Graham s stucco plugs were certainly many times larger chan the gaseous mean free path lengths at the experimental conditions. 

Knudsen diffusion, but the dependence on physical and geometric conditions... 

Che Knudsen diffusion coefficient is independent of composition and pressure,... 

In general, tests have tended to concentrate attention on the ability of a flux model to interpolate through the intermediate pressure range between Knudsen diffusion control and bulk diffusion control. What is also important, but seldom known at present, is whether a model predicts a composition dependence consistent with experiment for the matrix elements in equation (10.2). In multicomponent mixtures an enormous amount of experimental work would be needed to investigate this thoroughly, but it should be possible to supplement a systematic investigation of a flux model applied to binary systems with some limited experiments on particular multicomponent mixtures, as in the work of Hesse and Koder, and Remick and Geankoplia. Interpretation of such tests would be simplest and most direct if they were to be carried out with only small differences in composition between the two sides of the porous medium. Diffusion would then occur in a system of essentially uniform composition, so that flux measurements would provide values for the matrix elements in (10.2) at well-defined compositions. 

Knudsen diffusion coefficient for the test gas in a micropore. represents the total void fraction and c that part of of the void fraction... 

For an Isothermal pellet with pores sufficiently small that Knudsen diffusion controls, the flux relations are required to take the form (8.1), which can be written... 

It remains to check Chat our supposedly general equations (11.20) -(11.23) reduce to the previously obtained limiting forms at the extremes of bulk diffusion and Knudsen diffusion. The bulk diffusion limit is easily obtained by letting — and assuming that for all r, s,... 

In practice it would not be reasonable to solve the balances at the limit of Knudsen diffusion control by considering the n simultaneous boundary value problems (11.7). All the partial pressures can be expressed in terms of by integrating equations (11,25), with the result... 

In simple cases it is not difficult to estimate the magnitude of the pressure variation within the pellet. Let us restrict attention to a reaction of the form A nB in a pellet of one of the three simple geometries, with uniform external conditions so that the flux relations (11.3) hold. Consider first the case in which all the pores are small and Knudsen diffusion controls, so that the fluxes are given by... 

The above estimates of pressure variations suggest that their magni-tude as a percentage of the absolute pressure may not be very large except near the limit of Knudsen diffusion. But in porous catalysts, as we have seen, the diffusion processes to be modeled often lie in the Intermediate range between Knudsen streaming and bulk diffusion control. It is therefore tempting to try to simplify the flux equations in such a way as to... 

At the limit of Knudsen diffusion control it is not reasonable to expect that any of the proposed approximation methods will perform well since, as we know, percentage variations in pressure are quite large. Nevertheless it is interesting to examine their results, which are shown in Figure 11 4 At this limit it is easy to check algebraically that equations (11.54) and (11.55) become the same, while (11.60) differs from the other two. Correspondingly the values of the effectiveness factor calculated using the approximation of Kehoe and Aris coincide with the results of Apecetche et al., and with the exact solution, ile Hite and Jackson s effectiveness factors differ substantially. 

In chapter 5 we showed that the dusty gas model flux relations could be solved (fjite easily at the limit of Knudsen diffusion control, when they reduce to the form given in equation (5.25), namely... 

In our earlier discussion of the dynamical equations at the opposite limit of Knudsen diffusion control, we obtained a final simplified form, represented by equations (12.15) and (12.16) (or (12.20) and (12.21) for an Irreversible reaction with a single reactant), after introducing certain... 

For the same reaction in a pellet of finely porous structure, where Knudsen diffusion controls, the appropriate dynamical equations sre (12.20) and (12.21) if we once more adopt approximations which are a consequence of Che large size of K. These again have a dimensionless form, which may be written... 

In Chase equaclons Che symbols Z u, A, b and id are noc defined quite as In equations (12.39), since Che bulk diffusion coefficient muse now be replaced by a Knudsen diffusion coefficient. Thus... 

At the limit of Knudsen diffusion control, while the remaining... 

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