Measurement of Diffusion in Porous Solids

One should take into account the specific features of gas diffusion in porous solids when measuring effective diffusion coefficients in the pores of catalysts. The measurements are usually carried out with a flat membrane of the porous material. The membrane is washed on one side by one gas and on the other side by another gas, the pressure on both sides being kept... 

The most widely used unsteady state method for determining diffusivities in porous solids involves measuring the rate of adsorption or desorption when the sample is subjected to a well defined change in the concentration or pressure of sorbate. The experimental methods differ mainly in the choice of the initial and boundary conditions and the means by which progress towards the new position of equilibrium is followed. The diffusivities are found by matching the experimental transient sorption curve to the solution of Fick s second law. Detailed presentations of the relevant formulae may be found in the literature [1, 2, 12, 15-17]. For spherical particles of radius R, for example, the fractional uptake after a pressure step obeys the relation... 

External mass transfer, such as diffusion to particles or to the outside of pipes or cylinders, requires different correlations from those for internal mass transfer, because there is boundary-layer flow over part of the surface, and boundary-layer separation is common. The mass-transfer coefficients can be determined by studying evaporation of liquid from porous wet solids. However, it is not easy to ensure that there is no effect of internal mass-transfer resistance. Complications from diffusion in the solid are eliminated if the solid is made from a slightly soluble substance that dissolves in the liquid or sublimes into a gas. This method also permits measurement of local mass-transfer coefficients for different points on the solid particle or cylinder. 

The effective diifusivity measurement of gases by tracer-pulse chromatography in porous solids has been extended to include zeolites [faujasites, mordenites, 3A and 5A molecular sieves (35)]. The measured diffusions in this case were a strong function of molecular size. 

The rest of the book is dedicated to adsorption kinetics. We start with the detailed description of diffusion and adsorption in porous solids, and this is done in Chapter 7. Various simple devices used to measure diffusivity are presented, and the various modes of transport of molecules in porous media are described. The simplest transport is the Knudsen flow, where the transport is dictated by the collision between molecules and surfaces of the pore wall. Other transports are viscous flow, continuum diffusion and surface diffusion. The combination of these transports is possible for a given system, and this chapter will address this in some detail. 

Nuclear magnetic resonance is sensitive to molecular mobility and local magnetic fields. Motion is modified in liquids contained in confined geometry. Local magnetic field variation results from susceptibility effects at interfaces. Both phenomena are observed for liquids contained in porous solids. This paper critically examines these effects and their use in characterisation of porous materials. The principles are illustrated with porous silicas and preliminary results are given of diffusion measurements on n-butane in silica as a function of temperature and pore geometry. 

The ratio of the overall rate of reaction to that which would be achieved in the absence of a mass transfer resistance is referred to as the effectiveness factor rj. SCOTT and Dullion(29) describe an apparatus incorporating a diffusion cell in which the effective diffusivity De of a gas in a porous medium may be measured. This approach allows for the combined effects of molecular and Knudsen diffusion, and takes into account the effect of the complex structure of the porous solid, and the influence of tortuosity which affects the path length to be traversed by the molecules. 

The porous structure of either a catalyst or a solid reactant may have a considerable influence on the measured reaction rate, especially if a large proportion of the available surface area is only accessible through narrow pores. The problem of chemical reaction within porous solids was first considered quantitatively by Thiele [1] who developed mathematical models describing chemical reaction and intraparticle diffusion. Wheeler [2] later extended Thiele s work and identified model parameters which could be measured experimentally and used to predict reaction rates in... 

---