Diffusion mass-transport processes

Table 1 Summary of Experimental Methods for Evaluating Diffusion Coefficients and Investigating Mass Transport Processes of Pharmaceutical Interest... 

Whether Knudsen or bulk diffusion dominates the mass transport process depends on the relative magnitudes of the two terms in the denominator of equation 12.2.6. The ratio of the two diffusivity parameters is obviously important in establishing these magnitudes. In this regard, it is worth noting that DK is proportional to the pore diameter and independent of pressure whereas DAB is independent of pore size and inversely proportional to the pressure. Consequently, the higher the pressure and the larger the pore, the more likely it is that ordinary bulk diffusion will dominate. 

Bulk or forced flow of the Hagan-Poiseuille type does not in general contribute significantly to the mass transport process in porous catalysts. For fast reactions where there is a change in the number of moles on reaction, significant pressure differentials can arise between the interior and the exterior of the catalyst pellets. This phenomenon occurs because there is insufficient driving force for effective mass transfer by forced flow. Molecular diffusion occurs much more rapidly than forced flow in most porous catalysts. 

There are three types of mass transport processes within a microfluidic system convection, diffusion, and immigration. Much more common are mixtures of three types of mass transport. It is essential to design a well-controlled transport scheme for the microsystem. Convection can be generated by different forces, such as capillary effect, thermal difference, gravity, a pressurized air bladder, the centripetal forces in a spinning disk, mechanical and electroosmotic pumps, in the microsystem. The mechanical and electroosmotic pumps are often used for transport in a microfluidic system due to their convenience, and will be further discussed in section 11.5.2. The migration is a direct transport of molecules in response to an electric field. In most cases, the moving... 

In analysis of a mass transport process, the Peclet number, Pe, the ratio of the direct flow to the diffusion, is used and given as... 

As suggested before, the role of the interphasial double layer is insignificant in many transport processes that are involved with the supply of components from the bulk of the medium towards the biosurface. The thickness of the electric double layer is so small compared with that of the diffusion layer 8 that the very local deformation of the concentration profiles does not really alter the flux. Hence, in most analyses of diffusive mass transport one does not find any electric double layer terms. For the kinetics of the interphasial processes, this is completely different. Rate constants for chemical reactions or permeation steps are usually heavily dependent on the local conditions. Like in electrochemical processes, two elements are of great importance the local electric field which affects rates of transfer of charged species (the actual potential comes into play in the case of redox reactions), and the local activities... 

If only linear diffusion is the operating mass transport process, it has been shown that the current (i) in a planar electrode is related to the concentration (c) gradient at the surface of the electrode (x = 0) by [332]... 

Mass transfer (continued) in monolith, 27 89 in porous catalyst, 27 60-63, 68 in tubular reactor, 27 79, 82, 87 Mass transport processes, 30 312-318 convective, 30 312-313 diffusive, 30 313-315 selectivity, 30 316... 

The two major causes of uneven current distribution are diffusion and ohmic resistance. Nonuniformity due to diffusion originates from variations in the effective thickness of the diffusion layer 8 over the electrode surface as shown in Figure 10.13. It is seen that 8 is larger at recesses than at peaks. Thus, if the mass-transport process controls the rate of deposition, the current density at peaks ip is larger than that at recesses since the rate of mass transport by convective diffusion is given by... 

In this study the ratio of the particle sizes was set to two based on the average value for the two samples. As a result, if the diffusion is entirely controlled by secondary pore structure (interparticle diffusion) the ratio of the effective diffusion time constants (Defl/R2) will be four. In contrast, if the mass transport process is entirely controlled by intraparticle (platelet) diffusion, the ratio will become equal to unity (diffusion independent of the composite particle size). For transient situations (in which both resistances are important) the values of the ratio will be in the one to four range. Diffusional time constants for different sorbates in the Si-MCM-41 sample were obtained from experimental ZLC response curves according to the analysis discussed in the experimental section. Experiments using different purge flow rates, as well as different purge gases... 

There are three kinds of mass transport process relevant to electrode reactions migration, convection and diffusion. The Nernst—Planck equation... 

Mass transport processes are involved in the overall reaction. In these processes the substances consumed or formed during the electrode reaction are transported from the bulk solution to the interphase (electrode surface) and from the interphase to the bulk solution. This mass transport takes place by diffusion. Pure diffusion overpotential t]A occurs if the mass transport is the slowest process among the partial processes involved in the overall electrode reaction. In this case diffusion is the rate-determining step. 

In these electrode processes, the use of macroelectrodes is recommended when the homogeneous kinetics is slow in order to achieve a commitment between the diffusive and chemical rates. When the chemical kinetics is very fast with respect to the mass transport and macroelectrodes are employed, the electrochemical response is insensitive to the homogeneous kinetics of the chemical reactions—except for first-order catalytic reactions and irreversible chemical reactions follow up the electron transfer—because the reaction layer becomes negligible compared with the diffusion layer. Under the above conditions, the equilibria behave as fully labile and it can be supposed that they are maintained at any point in the solution at any time and at any applied potential pulse. This means an independent of time (stationary) response cannot be obtained at planar electrodes except in the case of a first-order catalytic mechanism. Under these conditions, the use of microelectrodes is recommended to determine large rate constants. However, there is a range of microelectrode radii with which a kinetic-dependent stationary response is obtained beyond the upper limit, a transient response is recorded, whereas beyond the lower limit, the steady-state response is insensitive to the chemical kinetics because the kinetic contribution is masked by the diffusion mass transport. In the case of spherical microelectrodes, the lower limit corresponds to the situation where the reaction layer thickness does not exceed 80 % of the diffusion layer thickness. 

We note first that immediately following the injection of a sample at the head of the channel, the flow of carrier is stopped briefly to allow time for the sample particles to accumulate near the appropriate wall. As the particles concentrate near the wall, the growing concentration gradient leads to a diffusive flux which counteracts the influx of particles. Because channel thickness is small (approximately 0.25 mm), these two mass transport processes quickly balance one another, leading to an equilibrium distribution near the accumulation wall. This distribution assumes the exponential form... 

See also - diffusion overpotential, -> diffusion time, -> fractals in electrochemistry, -> mass transport overpotential, -> mass transport processes. 

Mass transport processes - diffusion, migration, and - convection are the three possible mass transport processes accompanying an - electrode reaction. Diffusion should always be considered because, as the reagent is consumed or the product is formed at the electrode, concentration gradients between the vicinity of the electrode and the bulk solution arise, which will induce diffusion processes. Reactant species move in the direction of the electrode surface and product molecules leave the interfacial region (- interface, -> interphase) [i-v]. The - Nernst-Planck equation provides a general description of the mass transport processes. Mass transport is frequently called mass transfer however, it is better to reserve that term for the case that mass is transferred from one phase to another phase. 

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