Mass diffusion Subject

Mass transfer can result from several different phenomena. There is a mass transfer associated with convection in that mass is transported from one place to another in the flow system. This type of mass transfer occurs on a macroscopic level and is usually treated in the subject of fluid mechanics. When a mixture of gases or liquids is contained such that there exists a concentration gradient of one or more of the constituents across the system, there will be a mass transfer on a microscopic level as the result of diffusion from regions of high concentration to regions of low concentration. In this chapter we are primarily concerned with some of the simple relations which may be used to calculate mass diffusion and their relation to heat transfer. Nevertheless, one must remember that the general subject of mass transfer encompasses both mass diffusion on a molecular scale and the bulk mass transport, which may result from a convection process. 

Consider a solid plane wall (medium B) of area A, thickness L, and density p. The wall is subjected on both sides to different concentrations of a species A to which it is permeable. The boundary surfaces at.t = 0 and x - L are located within the solid adjacent to the interfaces, and the mass fractions of A at those surfaces are maintained at and 2. respectively, at all times (Fig. 14-19). The mass fraction of species A in the wall varies in the. v-direction only and can be expressed as >v (.t). Therefore, mass transfer through the wall in this case can be modeled as steady and one-dimensional. Here we determine the rate of mass diffusion of species A through the wall using a similar approach to that used in Chapter 3 for heat conduction. 

The discussion up to this point has focused on the role of free surfaces and internal interfaces, such as grain boundaries, in mass diffusion. Surfaces produced internally in the material as a consequence of permanent deformation and damage induced by stress can also serve, in some cases, as paths along which enhanced atomic diffusion may occur. In amorphous solids undergoing active plastic flow, such increased atomic mobility along shear bands can result in the formation of nanocrystalline particles locally at the bands. An example of such crystallization process is illustrated in this section for the case of a bulk amorphous metallic alloy subjected to quasi-static nanoindentation at room temperature. 

The Langmuir-Hinshelwood picture is essentially that of Fig. XVIII-14. If the process is unimolecular, the species meanders around on the surface until it receives the activation energy to go over to product(s), which then desorb. If the process is bimolecular, two species diffuse around until a reactive encounter occurs. The reaction will be diffusion controlled if it occurs on every encounter (see Ref. 211) the theory of surface diffusional encounters has been treated (see Ref. 212) the subject may also be approached by means of Monte Carlo/molecular dynamics techniques [213]. In the case of activated bimolecular reactions, however, there will in general be many encounters before the reactive one, and the rate law for the surface reaction is generally written by analogy to the mass action law for solutions. That is, for a bimolecular process, the rate is taken to be proportional to the product of the two surface concentrations. It is interesting, however, that essentially the same rate law is obtained if the adsorption is strictly localized and species react only if they happen to adsorb on adjacent sites (note Ref. 214). (The apparent rate law, that is, the rate law in terms of gas pressures, depends on the form of the adsorption isotherm, as discussed in the next section.)... 

Work in the area of simultaneous heat and mass transfer has centered on the solution of equations such as 1—18 for cases where the stmcture and properties of a soHd phase must also be considered, as in drying (qv) or adsorption (qv), or where a chemical reaction takes place. Drying simulation (45—47) and drying of foods (48,49) have been particularly active subjects. In the adsorption area the separation of multicomponent fluid mixtures is influenced by comparative rates of diffusion and by interface temperatures (50,51). In the area of reactor studies there has been much interest in monolithic and honeycomb catalytic reactions (52,53) (see Exhaust control, industrial). Eor these kinds of appHcations psychrometric charts for systems other than air—water would be useful. The constmction of such has been considered (54). 

Oxidation of Adsorbed CO The electro-oxidation of CO has been extensively studied given its importance as a model electrochemical reaction and its relevance to the development of CO-tolerant anodes for PEMFCs and efficient anodes for DMFCs. In this section, we focus on the oxidation of a COads monolayer and do not cover continuous oxidation of CO dissolved in electrolyte. An invaluable advantage of COads electro-oxidation as a model reaction is that it does not involve diffusion in the electrolyte bulk, and thus is not subject to the problems associated with mass transport corrections and desorption/readsorption processes. 

An overview of this kind is, of necessity, limited in detail. Readers interested in a more thorough development of mass transfer principles are encouraged to consult the references listed at the end of the chapter. In particular, Cussler s excellent textbook on diffusion is an accessible introduction to the subject geared toward the physical scientist [11], Those with a more biological orientation may prefer Friedman s text on biological mass transfer [12], which is also exceptional. A classic reference in the field is Crank s Mathematics of Diffusion [13], which contains solutions to many important diffusion problems. 

The steady-state continuity equations which describe mass balance over a fluid volume element for the species in the stagnant film which are subject to uniaxial diffusion and reaction in the z direction are... 

One must understand the physical mechanisms by which mass transfer takes place in catalyst pores to comprehend the development of mathematical models that can be used in engineering design calculations to estimate what fraction of the catalyst surface is effective in promoting reaction. There are several factors that complicate efforts to analyze mass transfer within such systems. They include the facts that (1) the pore geometry is extremely complex, and not subject to realistic modeling in terms of a small number of parameters, and that (2) different molecular phenomena are responsible for the mass transfer. Consequently, it is often useful to characterize the mass transfer process in terms of an effective diffusivity, i.e., a transport coefficient that pertains to a porous material in which the calculations are based on total area (void plus solid) normal to the direction of transport. For example, in a spherical catalyst pellet, the appropriate area to use in characterizing diffusion in the radial direction is 47ir2. 

While microscopic techniques like PFG NMR and QENS measure diffusion paths that are no longer than dimensions of individual crystallites, macroscopic measurements like zero length column (ZLC) and Fourrier Transform infrared (FTIR) cover beds of zeolite crystals [18, 23]. In the case of the popular ZLC technique, desorption rate is measured from a small sample (thin layer, placed between two porous sinter discs) of previously equilibrated adsorbent subjected to a step change in the partial pressure of the sorbate. The slope of the semi-log plot of sorbate concentration versus time under an inert carrier stream then gives D/R. Provided micropore resistance dominates all other mass transfer resistances, D becomes equal to intracrystalline diffusivity while R is the crystal radius. It has been reported that the presence of other mass transfer resistances have been the most common cause of the discrepancies among intracrystaUine diffusivities measured by various techniques [18]. 

Consider then a mixture of A and B which are being subjected to a uniform gravitational acceleration or centrifugal acceleration g in the — z direction. It should be noted that there is no mass flux due to forced diffusion according to Eq. (35) inasmuch as jt(F) vanishes when we replace t by —g. The effect of the gravitational field is to produce a pressure gradient, the latter being determined by Eq. (25), which for the case under consideration becomes ... 

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