The Effective Diffusion Coefficient

The question of when the catalyst particle can be treated as isothermal is discussed in more detail in Section 9.3.7. 

Estimation of the effective diffusion coefficient X A,eff begins with the equation 

p(r) is the diffusion coefficient of A in an assembly of straight, round pores that has the same distribution of pore sizes as the catalyst for which I A,eff is to be calculated. The 

The parameter Tp is referred to as the tortuosity of the catalyst particle. Originally, Tp was intended to correct for the fact that the pores in a catalyst are not straight and are not all parallel to the direction of diffusion. As a result, the diffusing molecules must follow a tortuous path and must travel a longer distance than a straight line in the direction of the net diffusive flux. In reality, Tp corrects for many other nonidealities, such as the variation in cross section along the length of a pore. 

For many commercial catalysts, the value of Tp lies in the region 

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Note that the effective diffusion coefficient relating N and dc /dz in... 

Hence, from equation (10.48), the effective diffusion coefficient determined by "chromatographic" testing is given by... 

The first thing to notice about these results is that the influence of the micropores reduces the effective diffusion coefficient below the value of the bulk diffusion coefficient for the macropore system. This is also clear in general from the forms of equations (10.44) and (10.48). As increases from zero, corresponding to the introduction of micropores, the variance of the response pulse Increases, and this corresponds to a reduction in the effective diffusion coefficient. The second important point is that the influence of the micropores on the results is quite small-Indeed it seems unlikely that measurements of this type will be able to realize their promise to provide information about diffusion in dead-end pores. 

As a reactant molecule from the fluid phase surrounding the particle enters the pore stmcture, it can either react on the surface or continue diffusing toward the center of the particle. A quantitative model of the process is developed by writing a differential equation for the conservation of mass of the reactant diffusing into the particle. At steady state, the rate of diffusion of the reactant into a shell of infinitesimal thickness minus the rate of diffusion out of the shell is equal to the rate of consumption of the reactant in the shell by chemical reaction. Solving the equation leads to a result that shows how the rate of the catalytic reaction is influenced by the interplay of the transport, which is characterized by the effective diffusion coefficient of the reactant in the pores, and the reaction, which is characterized by the first-order reaction rate constant. 

Figure 10 shows that Tj is a unique function of the Thiele modulus. When the modulus ( ) is small (- SdSl), the effectiveness factor is unity, which means that there is no effect of mass transport on the rate of the catalytic reaction. When ( ) is greater than about 1, the effectiveness factor is less than unity and the reaction rate is influenced by mass transport in the pores. When the modulus is large (- 10), the effectiveness factor is inversely proportional to the modulus, and the reaction rate (eq. 19) is proportional to k ( ), which, from the definition of ( ), implies that the rate and the observed reaction rate constant are proportional to (1 /R)(f9This result shows that both the rate constant, ie, a measure of the intrinsic activity of the catalyst, and the effective diffusion coefficient, ie, a measure of the resistance to transport of the reactant offered by the pore stmcture, influence the rate. It is not appropriate to say that the reaction is diffusion controlled it depends on both the diffusion and the chemical kinetics. In contrast, as shown by equation 3, a reaction in solution can be diffusion controlled, depending on D but not on k. 

The mass transport influence is easy to diagnose experimentally. One measures the rate at various values of the Thiele modulus the modulus is easily changed by variation of R, the particle size. Cmshing and sieving the particles provide catalyst samples for the experiments. If the rate is independent of the particle size, the effectiveness factor is unity for all of them. If the rate is inversely proportional to particle size, the effectiveness factor is less than unity and

experimental points allow triangulation on the curve of Figure 10 and estimation of Tj and ( ). It is also possible to estimate the effective diffusion coefficient and thereby to estimate Tj and ( ) from a single measurement of the rate (48). 

The diffusional transport model for systems in which sorbed molecules can be divided in two populations, one formed by completely immobilized molecules and the other by molecules free to diffuse, has been developed by Vieth and Sladek 33) in a modified form of the Fick s second law. However, if linear isotherms are experimentally found, as in the case of the DGEBA-TETA system in Fig. 4, the diffusion of the penetrant may be described by the classical diffusion law with constant value of the effective diffusion coefficient,... 

Sorption curves obtained at activity and temperature conditions which have been experienced to be not able to alter the polymer morphology during the test, i.e. a = 0.60 and T = 75 °C, for as cast (A) and for samples previously equilibrated in more severe conditions, a = 0.99 and T = 75 °C (B), are shown in Fig. 13. According to the previous discussion, the diffusion coefficient, calculated by using the time at the intersection points between the initial linear behaviour and the equilibrium asymptote (a and b), for the damaged sample is lower than that of the undamaged one, since b > a. The morphological modification which increases the apparent solubility lowers, in fact, the effective diffusion coefficient. 

In the case that the effective diffusion coefficient approach is used for the molar flux, it is given by N = —Da dci/dr), where Dei = (Sp/Tp)Dmi according to the random pore model. Standard boundary conditions are applied to solve the particle model Eq. (8.1). 

Previously (e.g.. Ref. 344), it has been noted that Eq. (26) will still be valid if the point concentration variable is replaced by the average concentration however, the diffusion coefficient was fonnd to differ from the molecular diffusion coefficient obtained in the pnre flnid. This diffusion coefficient was termed the effective diffusion coefficient. The... 

The objective of most of the theories of transport in porous media is to derive analytical or numerical functions for the effective diffusion coefficient to use in the preceed-ing averaged species continuity equations based on the structure of the media and, more recently, the structure of the solute. 

When a two- or higher-phase system is used with two or more phases permeable to the solute of interest and when interactions between the phases is possible, it would be necessary to apply the principle of local mass equilibrium [427] in order to derive a single effective diffusion coefficient that will be used in a one-equation model for the transport. Extensive justification of the principle of local thermdl equilibrium has been presented by Whitaker [425,432]. If the transport is in series rather than in parallel, assuming local equilibrium with equilibrium partition coefficients equal to unity, the effective diffusion coefficient is... 

This example will be of particular interest in our consideration of electrophoresis, and it is also of interest from the point of view of introducing anisotropy into the media structure. Figure 20 shows plots of the effective diffusion coefficient versus porosity for various... 

The standard Rodbard-Ogston-Morris-Killander [326,327] model of electrophoresis which assumes that u alua = D nlDa is obtained only for special circumstances. See also Locke and Trinh [219] for further discussion of this relationship. With low electric fields the effective mobility equals the volume fraction. However, the dispersion coefficient reduces to the effective diffusion coefficient, as determined by Ryan et al. [337], which reduces to the volume fraction at low gel concentration but is not, in general, equal to the porosity for high gel concentrations. If no electrophoresis occurs, i.e., and Mp equal zero, the results reduce to the analysis of Nozad [264]. If the electrophoretic mobility is assumed to be much larger than the diffusion coefficients, the results reduce to that given by Locke and Carbonell [218]. 

The effective diffusion coefficient of a solute in soil is thus... 

Strictly speaking, in this formulation the effective diffusion coefficient, is replaced by an empirical dispersion coefficient, D, to account for the effect of water flow on diffusion. However, in practice, the rate of transpirational water flow is sufficiently slow that dispersion effects are minimal and Eq. (8) can be used without error. This is because the Peclet number (see Sect. F.2) is small. For the same reason, in almost all cases diffusion is the most important process in moving nutrients to the root and the convection term can be omitted entirely. 

The aqueous diffusivities of charged permeants are equivalent to those of uncharged species in a medium of sufficiently high ionic strength. The product DF(r/R) is the effective diffusion coefficient for the pore. It is implicit in k that adsorption of the cations does not occur, so that the fixed surface charges on the wall of the pore are not neutralized. Adsorption is more likely to occur with multivalent cations than with univalent ones. 

Gas diffusion in the nano-porous hydrophobic material under partial pressure gradient and at constant total pressure is theoretically and experimentally investigated. The dusty-gas model is used in which the porous media is presented as a system of hard spherical particles, uniformly distributed in the space. These particles are accepted as gas molecules with infinitely big mass. In the case of gas transport of two-component gas mixture (i = 1,2) the effective diffusion coefficient (Dj)eff of each of the... 

It must be noted that the effective diffusion coefficient (Di)eff is obtained by electrochemical measurements of air gas-diffusion electrodes with sufficiently thick gas layer so that the limiting process is the gas... 

The transport of heat between latitude bands is assumed to be diffusive and is proportional to the temperature difference divided by the distance between the midpoints of each latitude band. This is the temperature gradient. In this simulation all these distances are equal, so the distance need not appear explicitly. The temperature gradient is multiplied by a transport coefficient here called diffc, the effective diffusion coefficient. The product of the diffusion coefficient and the temperature gradient gives the energy flux between latitude zones. To find the total energy transport, we must multiply by the length of the boundary between the latitude zones. In... 

All in all, the tritium data present something of a mystery, but at least they set a lower limit for the effective diffusion coefficient in the range 400-500°C, a limit rather higher than some estimates that have been given in the literature for similar temperatures but which we shall not discuss until Section 3 because thay are based on experiments in which hydrogen-acceptor complex formation was clearly important. 

Exposure of bulk GaAs Si wafers to a capacitively coupled rf deuterium plasma at different temperatures generates deuterium diffusion profiles as shown in Fig. 1. These profiles are close to a complementary error function (erfc) profile. At 240°C, the effective diffusion coefficient is 3 x 10 12 cm2/s. The temperature dependence of the hydrogen diffusion coefficient is given by (Jalil et al., 1990) ... 

The situation with respect to grain boundary diffusion is similar. The contribution of the grain boundaries to the effective diffusion coefficient can be written as follows ... 

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