Pore size distribution model

Christman, P.G. and Edgar, T.F. (1983) "Distributed pore-size model for sulfation of limestone", 29, 388-95. 

In summary, a fairly narrow unimodal pore-size distribution can be adequately described by the simple mean pore-size model. A broad pore-size distribution, /(r), requires a more extensive treatment, such as the parallel path model. A bimodal pore-size distribution can also be described by the micro-macro random pore model. 

One approach in developing a pore-size model is to apply the Poisson polyhedron theory. Each deposited layer in the build-up to make the web is simulated by a two dimensional network of straight lines, a Poisson line network, forming a random distribution of polygons, as depicted in Fig. 8.18 showing two pore sizes defined as the diameter of largest circle inscribed within a given void. 

Sotirchos, S.V., and Zarkanitis, S., A distributed pore size and length model for porous media reacting with diminishing porosity, Chem. Eng. Sci., 48(8), 1487-1502 (1993). 

In principle, the separation properties of a multilayer porous ceramic membrane, such as permselectivity, should be dependent only on the pore size distribution of the top separation layer. However, they can be compromised if resistances in the intermediate layers and the macroporous support become significant. For transport through macro- and meso-pores, molecular diffusion, Knudsen diffusion and viscous flow all contribute to the total transport, while the activated surface flow of the adsorbed phase will affect microporous transport. Therefore, any theoretical models used in analysing the transport data of gases through a porous ceramic membrane with a distributed pore size must take the following contributions into consideration (1) viscous flow, (2) Knudsen flow, (3) surface flow and (4) molecular sieving... 

The relation between the dusty gas model and the physical structure of a real porous medium is rather obscure. Since the dusty gas model does not even contain any explicit representation of the void fraction, it certainly cannot be adjusted to reflect features of the pore size distributions of different porous media. For example, porous catalysts often show a strongly bimodal pore size distribution, and their flux relations might be expected to reflect this, but the dusty gas model can respond only to changes in the... 

The simplest way of introducing Che pore size distribution into the model is to permit just two possible sizes--Tnlcropores and macropotes--and this simple pore size distribution is not wholly unrealistic, since pelleted materials are prepared by compressing powder particles which are themselves porous on a much smaller scale. The small pores within the powder grains are then the micropores, while the interstices between adjacent grains form the macropores. An early and well known model due to Wakao and Smith [32] represents such a material by the Idealized structure shown in Figure 8,2,... 

Of course, these shortcomings of the Wakao-Smith flux relations induced by the use of equations (8.7) and (8.8) can be removed by replacing these with the corresponding dusty gas model equations, whose validity is not restricted to isobaric systems. However, since the influence of a strongly bidisperse pore size distribution can now be accounted for more simply within the class of smooth field models proposed by Feng and Stewart [49], it is hardly worthwhile pursuing this."... 

The pore size distribution function (a) appears parametrically in the flux relations of Feng and Stewart, so their models certainly cannot be completely predictive in nature unless this distribution is known. It is... 

In the pioneer work of Foster the correction due to film thinning had to be neglected, but with the coming of the BET and related methods for the evaluation of specific surface, it became possible to estimate the thickness of the adsorbed film on the walls. A number of procedures have been devised for the calculation of pore size distribution, in which the adsorption contribution is allowed for. All of them are necessarily somewhat tedious and require close attention to detail, and at some stage or another involve the assumption of a pore model. The model-less method of Brunauer and his colleagues represents an attempt to postpone the introduction of a model to a late stage in the calculations. 

These procedures proposed by Dubinin and by Stoeckli arc, as yet, in the pioneer stage. Before they can be regarded as established as a means of evaluating pore size distribution, a wide-ranging study is needed, involving model micropore systems contained in a variety of chemical substances. The relationship between the structural constant B and the actual dimensions of the micropores, together with their distribution, would have to be demonstrated. The micropore volume would need to be evaluated independently from the known structure of the solid, or by the nonane pre-adsorption method, or with the aid of a range of molecular probes. 

The models of Matranga, Myers and Glandt [22] and Tan and Gubbins [23] for supercritical methane adsorption on carbon using a slit shaped pore have shown the importance of pore width on adsorbate density. An estimate of the pore width distribution has been recognized as a valuable tool in evaluating adsorbents. Several methods have been reported for obtaining pore size distributions, (PSDs), some of which are discussed below. 

As described above, the code "SIFTING" requires several microstructural inputs in order to ealculate a failure probability distribution. We are thus able to assess the physieal soundness of the Burchell model by determining the change in the predicted distribution when microstructural input parameters, such as particle or pore size, are varied in the "SIFTING" code. Each microstructural input parameter... 

Modeling the pore size in terms of a probability distribution function enables a mathematical description of the pore characteristics. The narrower the pore size distribution, the more likely the absoluteness of retention. The particle-size distribution represented by the rectangular block is the more securely retained, by sieve capture, the narrower the pore-size distribution. 

A microscopic description characterizes the structure of the pores. The objective of a pore-structure analysis is to provide a description that relates to the macroscopic or bulk flow properties. The major bulk properties that need to be correlated with pore description or characterization are the four basic parameters porosity, permeability, tortuosity and connectivity. In studying different samples of the same medium, it becomes apparent that the number of pore sizes, shapes, orientations and interconnections are enormous. Due to this complexity, pore-structure description is most often a statistical distribution of apparent pore sizes. This distribution is apparent because to convert measurements to pore sizes one must resort to models that provide average or model pore sizes. A common approach to defining a characteristic pore size distribution is to model the porous medium as a bundle of straight cylindrical or rectangular capillaries (refer to Figure 2). The diameters of the model capillaries are defined on the basis of a convenient distribution function. 

However, in most cases the AW(D) dependencies are distinctly nonlinear (Fig. 9), which gives impulse to further speculations. Clearly, dependencies of this type can result only from mutual suppression of the hydrogel particles because of their nonuniform distribution over the pores as well as from the presence of a distribution with respect to pore size which does not coincide with the size distribution of the SAH swollen particles. A considerable loss in swelling followed from the W(D) dependencies, as shown in Fig. 9, need a serious analysis which most probably would lead to the necessity of correlating the hydrogel particle sizes with those of the soil pores as well as choice of the technique of the SAH mixing with the soil. Attempts to create the appropriate mathematical model have failed, for they do not give adequate results. 

In a further study, Rill et al. [325] developed a model of gel permeation chromatography that included a bimodal pore stracture. The smallest mode in the pore-size distribution represents the basic background polyacrylamide pore structure of about 1-mn mean radius, and the second mode was around 5 nm, i.e., in the range of size of the molecular templates. The introduction of this second pore structure was found to substantially improve the peak resolution for molecules with molecular sizes in the range of the pore size. 

Gel filtration chromatography has been extensively used to determine pore-size distributions of polymeric gels (in particle form). These models generally do not consider details of the shape of the pores, but rather they may consider a distribution of effective average pore sizes. Rodbard [326,327] reviews the various models for pore-size distributions. These include the uniform-pore models of Porath, Squire, and Ostrowski discussed earlier, the Gaussian pore distribution and its approximation developed by Ackers and Henn [3,155,156], the log-normal distribution, and the logistic distribution. 

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