Simplified Mass-Transfer Theories

Simplified Mass-Transfer Theories In certain simple situations, the mass-transfer coefficients can be calculated from first principles. The film, penetration, and surface-renewal theories are attempts to extend these theoretical calculations to more complex situations. Although these theories are often not accurate, they are useful to provide a physical picture for variations in the mass-transfer coefficient. 

For the special case of steady-state unidirectional diffusion of a component through an inert-gas film in an ideal-gas system, the rate of mass transfer is derived as 

The film thickness SG depends primarily on the hydrodynamics of the system and hence on the Reynolds number and the Schmidt number. Thus, various correlations have been developed for different geometries in terms of the following dimensionless variables  

According to this analysis one can see that for gas-absorption problems, which often exhibit unidirectional diffusion, the most appropriate driving-force expression is of the form (y — y )/uBM, and the most appropriate mass-transfer coefficient is therefore kG. This concept is to be found in all the key equations for the design of mass-transfer equipment. 

The Sherwood-number relation for gas-phase mass-transfer coefficients as represented by the film diffusion model in Eq. (5-299) can be rearranged as follows  

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Equation 39 can often be simplified by adopting the concept of a mass transfer unit. As explained in the film theory discussion eadier, the purpose of selecting equation 27 as a rate equation is that is independent of concentration. This is also tme for the Gj /k aP term in equation 39. In many practical instances, this expression is fairly independent of both pressure and Gj as increases through the tower, increases also, nearly compensating for the variations in Gj. Thus this term is often effectively constant and can be removed from the integral ... 

Various mathematical concepts and techniques have been used to derive the functions that describe the different types of dispersion and to simplify further development of the rate theory two of these procedures will be discussed in some detail. The two processes are, firstly, the Random Walk Concept [1] which was introduced to the rate theory by Giddings [2] and, secondly, the mathematics of diffusion which is both critical in the study of dispersion due to longitudinal diffusion and that due to solute mass transfer between the two phases. The random walk model allows the relatively simple derivation of the variance contributions from two of the dispersion processes that occur in the column and, so, this model will be the first to be discussed. 

On the basis of the simplified view of the flow patterns just described, a model for predicting mass transfer rates can be developed using penetration theory and the fact that mass is transferred simultaneously from both the nip and the wiped film. We can therefore write that the total molar mass transfer rate from an element of fluid over a length dk in the extruder is... 

This simple mass transfer model based on simplified film theory has been proposed to describe the process of facilitated transport of penicillin-G across a SLM system [53]. In the authors laboratory, CPC transport using Aliquat-336 as the carrier was studied [56] using microporous hydrophobic polypropylene membrane (Celgard 2400) support and the permeation rate was found to be controlled by diffusion across the membrane. 

The film theory was originally proposed by Whitman,195 who obtained his idea from the Nernst117 concept of the diffusion layer. It was first applied to the analysis of gas absorption accompanied by a chemical reaction by Hatta.85,86 It is a steady-state theory and assumes that mass-transfer resistances across the interface are restricted to thin films in each phase near the interface. If more than one species is involved in a multiphase reaction process, this theory assumes that the thickness of the film near any interface (gas-liquid or liquid-solid) is the same for all reactants and products. Although the theory gives a rather simplified description of the multiphase reaction process, it gives a good answer for the global reaction rates, in many instances, particularly when the diffusivities of all reactants and products are identical. It is simple to use, particularly when the... 

Mathematically, the combustion process has been modelled for the most general three-dimensional case. It is described by a sum of differential equations accounting for the heat and mass transfer in the reacting system under the assumption of energy and mass conservation laws At present, it is impossible to obtain an analytical solution for the three-dimensional form. Therefore, all the available condensed system combustion theories are based on simplified models with one-dimensional or, at best, two-dimensional heat and mass transfer schemes. In these models, the kinetics of the chemical processes taking place in the phases or at the interface is described by an Arrhenius equation (exponential relationship between the reaction rate constant and temperature), and a corresponding reaction order with respect to reactant concentrations. 

While the film and surface-renewal theories are based on a simplified physical model of the flow situation at the interface, the boundary layer methods couple the heat and mass transfer equation directly with the momentum balance. These theories thus result in anal3dical solutions that may be considered more accurate in comparison to the film or surface-renewal models. However, to be able to solve the governing equations analytically, only very idealized flow situations can be considered. Alternatively, more realistic functional forms of the local velocity, species concentration and temperature profiles can be postulated while the functions themselves are specified under certain constraints on integral conservation. Prom these integral relationships models for the shear stress (momentum transfer), the conductive heat flux (heat transfer) and the species diffusive flux (mass transfer) can be obtained. 

Equations 15.9 and 15.10 are empirical with respect to the dehnition of the mass transfer coefficients, but the form of the equations is based on molecular diffusion theory. Applying the theory to a multi-component mixture where each component has a distinct diffusivity is impractically complex and must rely on diffusivity data for all the components in the mixture. To derive usable equations from the diffusion theory, certain simplifying assumptions must be made. The basis for the derivation of Equations 15.9 and 15.10 is to assume that mass transfer takes place either as equimolar counterdiffusion or as unimolar diffusion under dilute conditions. 

For the design and optimization of melt crystallization processes it is vital to have a complete understanding of the process. To this, a detailed knowledge about the crystallization kinetics is essential. Nevertheless, there is only little theory available to describe melt crystallization processes mathematically or to predict their separation efficiency. This is mainly a consequence of the complex heat and mass transfer processes prevailing in the crystallizers which lead to a non-linerar system of differential equations for the transfer processes. These equations can only be solved numerically and even then require a considerable number of simplifying assumptions and boundary conditions. 

For a number of nonlinear and competitive isotherm models analytical solutions of the mass balance equations can be provided for only one strongly simplified column model. This is the ideal model of chromatography, which considers just convection and neglects all mass transfer processes (Section 6.2.3). Using the method of characteristics within the elegant equilibrium theory, analytical expressions were derived capable to calculate single elution profiles for single components and mixtures (Helfferich and Klein, 1970 Helfferich and Carr 1993 Helfferich and Whitley 1996 Helfferich 1997 Rhee, Aris, and Amundson, 1970 ... 

Several elementary aspects of mass diffusion, heat transfer and fluid flow are considered in the context of the separation and control of mixtures of liquid metals and semiconductors by crystallization and float-zone refining. First, the effect of convection on mass transfer in several configurations is considered from the viewpoint of film theory. Then a nonlinear, simplified, model of a low Prandtl number floating zone in microgravity is discussed. It is shown that the nonlinear inertia terms of the momentum equations play an important role in determining surface deflection in thermocapillary flow, and that the deflection is small in the case considered, but it is intimately related to the pressure distribution which may exist in the zone. However, thermocapillary flows may be vigorous and can affect temperature and solute distributions profoundly in zone refining, and thus they affect the quality of the crystals produced. 

The preceding discussion assumes that no convection exists in the melt, and this is rarely, if ever, the case. Next we shall consider two approaches which account for convection in the melt, a transport mechanism which is especially important in mass transfer because Dl is small and even weak convection markedly alters solute concentration profiles and may cause macrosegregation. First we shall discuss film theory which is a very simple approach that gives qualitative information and often provides considerable physical insight into the mechanisms involved. Second, we shall discuss a simplified model of zone refining. 

Lekhal et al. [6] proposed a pseudo-homogeneous gas-liquid-liquid model based on the Higbie penetration theory to account for simultaneous absorption of two gases into the liquid phases. Because of the assumption of rapid liquid-liquid mass transfer of reactants leading to the equilibrium between two liquid phases, the model was simplified greatly and the detail of phase dispersion and distribution and multiphase flow was avoided. Reasonable success was achieved and the results of analysis suggested that the only limitation to the conversion of hydroformylation of 1-octene was the gas-liquid mass transfer of CO and H2. 

An analysis of chemical desorption has recently been published (Chem.Eng.Sci., 21 0980)), which is based on a number of simplifying assumptions the film theory model is assumed, the diffusivities of all species are taken to be equal to each other, and in the solution of the differential equations an approximation which is second order with respect to distance from the gas-liquid interface is used this approximation was introduced as early as 1948 by Van Krevelen and Hoftizer. However, the assumptions listed above are not at all drastic, and two crucial elements are kept in the analysis reversibility of the chemical reactions and arbitrary chemical mechanisms and stoichiometry.The result is a methodology for developing, for any given chemical mechanism, a highly nonlinear, implicit, but algebraic equation for the calculation of the rate enhancement factor as a function of temperature, bulk-liquid composition, interface gas partial pressure and physical mass transfer coefficient The method of solution is easily gene ralized to the case of unequal diffusivities and corrections for differences between the film theory and the penetration theory models can be calculated. 

In theory it is not necessary to have experimental mass-transfer coefficients for laminar flow, since the equations for momentum transfer and for diffusion can be solved. However, in many actual cases it is difficult to describe mathematically the laminar flow for geometries, such as flow past a cylinder or in a packed bed. Hence, experimental mass-transfer coefficients are often obtained and correlated. A simplified theoretical derivation will be given for two cases in laminar flow. 

The experimental results of this work were analysed using the theory of mass transfer with chemical reaction. The data presented in this work have been obtained at conditions where the mathematical treatment of the problem was simplified assuming a pseudo-first-order assumption for kinetics. In this case, the concentration of the amine across the cross section of the liqitid boundary layer was assumed to be uniform. Thus, transforming the second-order reaction expression of carbon dioxide with amine into an approximated first-order expression. Hence, For piperazine ... 

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