Diffusional Mass Transfer

When the mass transfer (diffusional) effects are significant, the design equations for immobilized biocatalyst reactors can be modified, by introducing the concept of the... 

Reactions mediated by enzymes immobilized by coacervation, interfacial polymerization, retention by semipermeable membranes, or gelation are particularly susceptible to mass transfer/diffusional limitations on the rate. 

On the other hand, use of whole cells as the vehicle for immobilization of enzymes is not without problems. These disadvantages include the susceptibility to mass transfer/diffusional limitations on reaction rates and possible losses in the yield of the desired product as a consequence of unwanted side reactions. In addition, there are potential problems associated with maintaining the integrity of the immobilized cells—supplying the nutrients, energy sources, or cofactors necessary to maintain the cells in a sufficiently viable condition to mediate the reaction(s) of interest. 

Given the availability of hollow fiber membranes adequately permeable to substrates and products, and the control of fluid flow all around the fibers in the bundle in order to assure uniform flow distribution and to avoid stagnation (in order to reduce mass transfer diffusional resistances), the technique offers several advantages. Enzyme proteins can be easily retained within the core of the fibers with no deactivation due to coupling agents or to shear stresses, and the enzyme solution can be easily recovered and/or recycled. 

As illustrated ia Figure 6, a porous adsorbent ia contact with a fluid phase offers at least two and often three distinct resistances to mass transfer external film resistance and iatraparticle diffusional resistance. When the pore size distribution has a well-defined bimodal form, the latter may be divided iato macropore and micropore diffusional resistances. Depending on the particular system and the conditions, any one of these resistances maybe dominant or the overall rate of mass transfer may be determined by the combiaed effects of more than one resistance. 

Fig. 6. Concentration profiles through an idealized biporous adsorbent particle showing some of the possible regimes. (1) + (a) rapid mass transfer, equihbrium throughout particle (1) + (b) micropore diffusion control with no significant macropore or external resistance (1) + (c) controlling resistance at the surface of the microparticles (2) + (a) macropore diffusion control with some external resistance and no resistance within the microparticle (2) + (b) all three resistances (micropore, macropore, and film) significant (2) + (c) diffusional resistance within the macroparticle and resistance at the surface of the...

Diffusion and Mass Transfer During Leaching. Rates of extraction from individual particles are difficult to assess because it is impossible to define the shapes of the pores or channels through which mass transfer (qv) has to take place. However, the nature of the diffusional process in a porous soHd could be illustrated by considering the diffusion of solute through a pore. This is described mathematically by the diffusion equation, the solutions of which indicate that the concentration in the pore would be expected to decrease according to an exponential decay function. 

Below about 0.5 K, the interactions between He and He in the superfluid Hquid phase becomes very small, and in many ways the He component behaves as a mechanical vacuum to the diffusional motion of He atoms. If He is added to the normal phase or removed from the superfluid phase, equiHbrium is restored by the transfer of He from a concentrated phase to a dilute phase. The effective He density is thereby decreased producing a heat-absorbing expansion analogous to the evaporation of He. The He density in the superfluid phase, and hence its mass-transfer rate, is much greater than that in He vapor at these low temperatures. Thus, the pseudoevaporative cooling effect can be sustained at practical rates down to very low temperatures in heHum-dilution refrigerators (72). 

Ordinary diffusion involves molecular mixing caused by the random motion of molecules. It is much more pronounced in gases and Hquids than in soHds. The effects of diffusion in fluids are also greatly affected by convection or turbulence. These phenomena are involved in mass-transfer processes, and therefore in separation processes (see Mass transfer Separation systems synthesis). In chemical engineering, the term diffusional unit operations normally refers to the separation processes in which mass is transferred from one phase to another, often across a fluid interface, and in which diffusion is considered to be the rate-controlling mechanism. Thus, the standard unit operations such as distillation (qv), drying (qv), and the sorption processes, as well as the less conventional separation processes, are usually classified under this heading (see Absorption Adsorption Adsorption, gas separation Adsorption, liquid separation). 

Siegel, Sparrow, and Hallman, Appl. Sd. Res. Sec. A., 7, 386 (1958). SissomandPitts, Elements of Transpoit Phenomena, McGraw-HiU, 1972. Skelland, Diffusional Mass Transfer, Wiley (1974). 

The phenomenological aspects of diffusional mass transfer in adsorption systems can be described in terms of Fick s law ... 

To evaluate the average diffusional flux, the total mass-transfer rate from the entire surface of the bubble must be divided by that entire surface ... 

Since the total mass transfer rate of B is zero, there must be a bulk flow of the system towards the liquid surface exactly to counterbalance the diffusional flux away from the surface, as shown in Figure 10.1, where ... 

Whatever the physical constraints placed on the system, the diffusional process causes the two components to be transferred at equal and opposite rates and the values of the diffusional velocities uDA and uDB given in Section 10.2.5 are always applicable. It is the bulk How velocity uF which changes with imposed conditions and which gives rise to differences in overall mass transfer rates. In equimolecular counterdiffusion. uF is zero. In the absorption of a soluble gas A from a mixture the bulk velocity must be equal and opposite to the diffusional velocity of B as this latter component undergoes no net transfer. 

The effectiveness factor accounts for the diffusional resistances in the liquid-filled catalyst pores. It does not account for the mass transfer resistance between the liquid and gas phases. This is the job of the ki and kg terms. 

Confined flows typically exhibit laminar-flow regimes, i.e. rely on a diffusion mixing mechanism, and consequently are only slowly mixed when the diffusion distance is set too large. For this reason, in view of the potential of microfabrication, many authors pointed to the enhancement of mass transfer that can be achieved on further decreasing the diffusional length scales. By simple correlations based on Fick s law, it is evident that short liquid mixing times in the order of milliseconds should result on decreasing the diffusion distance to a few micrometers. 

There is a need for rigorous analysis of such systems. The thickness of the water film may be less than or comparable to the diffusional film thickness and this has particular relevance to reactions that have mass-transfer limitations. The effect of local pH has to be assessed properly. The mechanism of uptake of the substrate also needs elucidation. 

In diffusional mass transfer, the transfer is always in the direction of decreasing concentration and is proportional to the magnitude of the concentration gradient the constant of proportionality being the diffusion coefficient for the system. 

The treatment of the two-phase SECM problem applicable to immiscible liquid-liquid systems, requires a consideration of mass transfer in both liquid phases, unless conditions are selected so that the phase that does not contain the tip (denoted as phase 2 throughout this chapter) can be assumed to be maintained at a constant composition. Many SECM experiments on liquid-liquid interfaces have therefore employed much higher concentrations of the reactant of interest in phase 2 compared to the phase containing the tip (phase 1), so that depletion and diffusional effects in phase 2 can be eliminated [18,47,48]. This has the advantage that simpler theoretical treatments can be used, but places obvious limitations on the range of conditions under which reactions can be studied. In this section we review SECM theory appropriate to liquid-liquid interfaces at the full level where there are no restrictions on either the concentrations or diffusion coefficients of the reactants in the two phases. Specific attention is given to SECM feedback [49] and SECMIT [9], which represent the most widely used modes of operation. The extension of the models described to other techniques, such as DPSC, is relatively straightforward. 

To extend the applicability of the SECM feedback mode for studying ET processes at ITIES, we have formulated a numerical model that fully treats diffusional mass transfer in the two phases [49]. The model relates to the specific case of an irreversible ET process at the ITIES, i.e., the situation where the potentials of the redox couples in the two phases are widely separated. A further model for the case of quasireversible ET kinetics at the ITIES is currently under development. For the case where the oxidized form of a redox species, Oxi, is electrolytically generated at the tip in phase 1 from the reduced species, Red], the reactions at the tip and the ITIES are ... 

The problems relating to mass transfer may be elucidated out by two clear-cut yet different methods one using the concept of equilibrium stages, and the other built on diffusional rate processes. The selection of a method depends on the type of device in which the operation is performed. Distillation (and sometimes also liquid extraction) are carried out in equipment such as mixer settler trains, diffusion batteries, or plate towers which contain a series of discrete processing units, and problems in these spheres are usually solved by equilibrium-stage calculation. Gas absorption and other operations which are performed in packed towers and similar devices are usually dealt with utilizing the concept of a diffusional process. All mass transfer calculations, however, involve a knowledge of the equilibrium relationships between phases. 

Various models of SFE have been published, which aim at understanding the kinetics of the processes. For many dynamic extractions of compounds from solid matrices, e.g. for additives in polymers, the analytes are present in small amounts in the matrix and during extraction their concentration in the SCF is well below the solubility limit. The rate of extraction is then not determined principally by solubility, but by the rate of mass transfer out of the matrix. Supercritical gas extraction usually falls very clearly into the class of purely diffusional operations. Gere et al. [285] have reported the physico-chemical principles that are the foundation of theory and practice of SCF analytical techniques. The authors stress in particular the use of intrinsic solubility parameters (such as the Hildebrand solubility parameter 5), in relation to the solubility of analytes in SCFs and optimisation of SFE conditions. 

Let us systematically delineate the transport pathways of the nondissociated and protonated species of the P-blockers by applying Eq. (82). The insignificance of the mass transfer resistance of the ABL on the overall transport process, as evidenced by the lack of influence of stirring on Pe, indicates that the passive diffusional kinetics are essentially controlled by the cell monolayer and filter. Therefore, Eq. (82) simplifies to... 

Marchiano and Arvia (M3) also measured mass transfer by thermal and diffusional free convection at a vertical plate. They derived on theoretical grounds a combined Grashof number as follows ... 

The Grashof number given by Eq. (40) appears to have a weaker theoretical basis than that given by Eq. (37), since it is based on an analysis that approximates the profile of the vertical velocity component in free convection, for example, by a quadratic function of the distance to the electrode. The choice of an appropriate Grashof number, as well as the experimental conditions in the work of de Leeuw den Bouter et al. (DIO) and Marchiano and Arvia (M3), has been reviewed critically by Wragg and Nasiruddin (W10). They measured mass transfer by combined thermal and diffusional, turbulent, free convection at a horizontal plate [see Eq. (31) in Table VII], and correlated their results satisfactorily with the Grashof number of Eq. (37). 

Weder s experiments were carried out with opposing body forces, and large current oscillations were found as long as the negative thermal densification was smaller than the diffusional densification. [Note that the Grashof numbers in Eq. (41) are based on absolute magnitudes of the density differences.] Local mass-transfer rates oscillated by 50%, and total currents by 4%. When the thermal densification dominated, the stagnation point moved to the other side of the cylinder, while the boundary layer, which separates in purely diffusional free convection, remained attached. 

Steps 1 and 7 are highly dependent on the fluid flow characteristics of the system. The mass velocity of the fluid stream, the particle size, and the diffusional characteristics of the various molecular species are the pertinent parameters on which the rates of these steps depend. These steps limit the observed rate only when the catalytic reaction is very rapid and the mass transfer is slow. Anything that tends to increase mass transfer coefficients will enhance the rates of these processes. Since the rates of these steps are only slightly influenced by temperature, the influence of these processes... 

The numerator of the right side of this equation is equal to the chemical reaction rate that would prevail if there were no diffusional limitations on the reaction rate. In this situation, the reactant concentration is uniform throughout the pore and equal to its value at the pore mouth. The denominator may be regarded as the product of a hypothetical diffusive flux and a cross-sectional area for flow. The hypothetical flux corresponds to the case where there is a linear concentration gradient over the pore length equal to C0/L. The Thiele modulus is thus characteristic of the ratio of an intrinsic reaction rate in the absence of mass transfer limitations to the rate of diffusion into the pore under specified conditions. 

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