Mass diffusion process theory

If ordinary molecular diffusion is the dominant mass transfer process, the kinetic theory of gases indicates that the diffusivity is proportional to T3/2 and it is easily shown that... 

The theory of premixed flames essentially consists of an analysis of factors such as mass diffusion, heat diffusion, and the reaction mechanisms as they affect the rate of homogeneous reactions taking place. Inasmuch as the primary mixing processes of fuel and oxidizer appear to dominate the burning processes in diffusion flames, the theories emphasize the rates of mixing (diffusion) in deriving the characteristics of such flames. 

Since interaction phenomena due to simultaneous diffusion of several components play an important role, the Maxwell-Stefan theory has been selected to describe the mass transfer processes. The general form of the flux expressions can be represented by (Taylor and Krishna, 1993)... 

Rapid evaporation introduces complications, for the heat and mass transfer processes are then coupled. The heat of vaporization must be supplied by conduction heat transfer from the gas and liquid phases, chiefly from the gas phase. Furthermore, convective flow associated with vapor transport from the surface, Stefan flow, occurs, and thermal diffusion and the thermal energy of the diffusing species must be taken into account. Wagner 1982) reviewed the theory and principles involved, and a higher-order quasisteady-state analysis leads to the following energy balance between the net heat transferred from the gas phase and the latent heat transferred by the diffusing species ... 

The simplest problems are those in which the diffusion process is independent of the time. The solutions to these problems are important in the film theories of mass transfer and in steady state experiments for measuring diffusion and self-diffusion. 

In this text we are concerned exclusively with laminar flows that is, we do not discuss turbulent flow. However, we are concerned with the complexities of multicomponent molecular transport of mass, momentum, and energy by diffusive processes, especially in gas mixtures. Accordingly we introduce the kinetic-theory formalism required to determine mixture viscosity and thermal conductivity, as well as multicomponent ordinary and thermal diffusion coefficients. Perhaps it should be noted in passing that certain laminar, strained, flames are developed and studied specifically because of the insight they offer for understanding turbulent flame environments. 

A wide range of condensed matter properties including viscosity, ionic conductivity and mass transport belong to the class of thermally activated processes and are treated in terms of diffusion. Its theory seems to be quite well developed now [1-5] and was applied successfully to the study of radiation defects [6-8], dilute alloys and processes in highly defective solids [9-11]. Mobile particles or defects in solids inavoidably interact and thus participate in a series of diffusion-controlled reactions [12-18]. Three basic bimolecular reactions in solids and liquids are dissimilar particle (defect) recombination (annihilation), A + B —> 0 energy transfer from donors A to unsaturable sinks B, A + B —> B and exciton annihilation, A + A —> 0. 

MD simulation is advantageous for obtaining dynamic properties directly, since the MD technique provides not only particle positions but also particle velocities that enable us to utilize the response theory (e.g., the Kubo formula [175,176]) to calculate the transport coefficients from time-dependent correlation functions. For example, we will examine the self-diffusion process of a tagged PFPE molecular center of mass (Fig. 1.49) from the simulation to gain insight into the excitation of translational motion, specifically, spreading and replenishment. The squared displacement of the center mass of a molecule or a bead is used as a measure of translational movement. The self-diffusion coefficient D can be represented as a velocity autocorrelation function... 

Transport phenomena modeling. This type of modeling is applicable when the process is well understood and quantification is possible using physical laws such as the heat, momentum, or diffusion transport equations or others. These cases can be analyzed with principles of transport phenomena and the laws governing the physicochemical changes of matter. Transport phenomena models apply to many cases of heat conduction or mass diffusion or to the flow of fluids under laminar flow conditions. Equivalent principles can be used for other problems, such as the mathematical theory of elasticity for the analysis of mechanical, thermal, or pressure stress and strain in beams, plates, or solids. 

The phenomenological coefficients are important in defining the coupled phenomena. For example, the coupled processes of heat and mass transport give rise to the Soret effect (which is the mass diffusion due to heat transfer), and the Dufour effect (which is the heat transport due to mass diffusion). We can identify the cross coefficients of the coupling between the mass diffusion (vectorial process) and chemical reaction (scalar process) in an anisotropic membrane wall. Therefore, the linear nonequilibrium thermodynamics theory provides a unifying approach to examining various processes usually studied under separate disciplines. 

The thermal diffusion factor a is proportional to the mass difference, (mi — mo)/(mi + m2). The thermal diffusion process depends on the transport of momentum in collisions between unlike molecules. The momentum transport vanishes for Maxwellian molecules, particles which repel one another with a force which falls off as the inverse fifth power of the distance between them. If the repulsive force between the molecules falls off more rapidly than the fifth power of the distance, then the light molecule will concentrate in the high temperature region of the space, while the heavy molecule concentrates in the cold temperature region. When the force law falls off less rapidly than the fifth power of the distance, then the thermal diffusion separation occurs in the opposite sense. The theory of the thermal diffusion factor a is as yet incomplete even for classical molecules. A summary of the theory has been given by Jones and Furry 15) and by Hirschfelder, Curtiss, and Bird 14), Since the thermal diffusion factor a for isotope mixtures is small, of the order of 10", it remained for Clusius and Dickel (8) to develop an elegant countercurrent system which could multiply the elementary effect. 

Mass transfer in real absorption equipment resembles a molecular diffusion process only in the basic idea of a concentration difference driving force. However, the two-film theory of Whitman can be used to construct a model similar in many respects to molecular diffusion equations. Fig. 1 is a schematic representing the Whitman two-film theory ... 

The result obtained from the film theory is that the mass transfer coefficient is directly proportional to the diffusion coefficient. However, the experimental mass transfer data available in the literature [6], for gas-liquid interfaces, indicate that the mass transfer coefficient should rather be proportional with the square root of the diffusion coefficient. Therefore, in many situations the film theory doesn t give a sufficient picture of the mass transfer processes at the interfaces. Furthermore, the mass transfer coefficient dependencies upon variables like fluid viscosity and velocity are not well understood. These dependencies are thus often lumped into the correlations for the film thickness, 1. The film theory is inaccurate for most physical systems, but it is still a simple and useful method that is widely used calculating the interfacial mass transfer fluxes. It is also very useful for analysis of mass transfer with chemical reaction, as the physical mechanisms involved are very complex and the more sophisticated theories do not provide significantly better estimates of the fluxes. Even for the description of many multicomponent systems, the simplicity of the model can be an important advantage. 

The determination of the real surface area of the electrocatalysts is an important factor for the calculation of the important parameters in the electrochemical reactors. It has been noticed that the real surface area determined by the electrochemical methods depends on the method used and on the experimental conditions. The STM and similar techniques are quite expensive for this single purpose. It is possible to determine the real surface area by means of different electrochemical methods in the aqueous and non-aqueous solutions in the presence of a non-adsorbing electrolyte. The values of the roughness factor using the methods based on the Gouy-Chapman theory are dependent on the diffuse layer thickness via the electrolyte concentration or the solvent dielectric constant. In general, the methods for the determination of the real area are based on either the mass transfer processes under diffusion control, or the adsorption processes at the surface or the measurements of the differential capacitance in the double layer region [56],... 

Tha transport mechanisms of molecular diffusion and mass carried by eddy motion are again assumed edditive although the contribution of the molecular diffusivity term is quite small except in the region nenr a wall where eddy motion is limited. The eddy diffusivity is directly applicable to problems snch as the dispersion of particles or species (pollutants) from a souree into a homogeneously turbulent air stream in which there is little shear stress. The theories developed by Taylor.36 which have been confirmed by a number of experimental investigations, can describe these phenomena. Of more interest in chemical engineering applications is mass transfer from a turbolent fluid to a surface or an interface. In this instance, turbulent motion may he damped oni as the interface is approached aed the contributions of both molecolar and eddy diffusion processes must he considered. To accomplish this. 9ome description of the velocity profile as the interface is approached must be available. 

Consider the idealized picture of a mass-transfer process based on the two-film theory as shown in Figure 7.27. The partial pressure profile in the gas film is linear, as called for by steady-state diffusion, but the concentration profile in the liquid film falls below a linear measure as a result of a first-order chemical reaction removing the absorbed gas. A normal mass balance over the differential segment dz (we may assume unit area normal to the direction of diffusion) produces a familiar result ... 

In theory, how many steps are required to enrich a uranium sample from 0.700% to 3.00% using the UFg multistage diffusion process. The molar masses of UFg and UFg are 349.03 g/mol and 352.05 g/mol, respectively. 

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