Convective-diffusion theory

Originally, the concept of the Prandtl boundary layer was developed for hydraulically even bodies. It is assumed that any characteristic length L on the particle surface is much greater than the thickness (<5hl) of the boundary layer itself (L > Ojil) Provided this assumption is fulfilled, the concept can be adapted to curved bodies and spheres, including real drug particles. Furthermore, the classical ( macroscopic ) concept of the hydrodynamic boundary layer is valid solely for high Reynolds numbers of Re>104 (14,15). This constraint was overcome for the microscopic hydrodynamics of dissolving particles by the convective diffusion theory (9). 

The convective diffusion theory was developed by V.G. Levich to solve specific problems in electrochemistry encountered with the rotating disc electrode. Later, he applied the classical concept of the boundary layer to a variety of practical tasks and challenges, such as particle-liquid hydrodynamics and liquid-gas interfacial problems. The conceptual transfer of the hydrodynamic boundary layer is applicable to the hydrodynamics of dissolving particles if the Peclet number (Pe) is greater than unity (Pe > 1) (9). The dimensionless Peclet number describes the relationship between convection and diffusion-driven mass transfer ... 

A reciprocal proportionality exists between the square root of the characteristic flow rate, t/A, and the thickness of the effective hydrodynamic boundary layer, <5Hl- Moreover, f)HL depends on the diffusion coefficient D, characteristic length L, and kinematic viscosity v of the fluid. Based on Levich s convective diffusion theory the combination model ( Kombi-nations-Modell ) was derived to describe the dissolution of particles and solid formulations exposed to agitated systems [(10), Chapter 5.2]. In contrast to the rotating disc method, the combination model is intended to serve as an approximation describing the dissolution in hydrodynamic systems where the solid solvendum is not necessarily fixed but is likely to move within the dissolution medium. Introducing the term... 

The development of convective-diffusion theories is due principally to Prandtl9 and Schlichting10, and their application in electrochemistry to Levich11. Levich was the first to solve the equations for the rotating disc electrode. 

Although the diffusion layer model is the most commonly used, various alterations have been proposed. The current views of the diffusion layer model are based on the so-called effective diffusion boundary layer, the structure of which is heavily dependent on the hydrodynamic conditions, fn this context, Levich [102] developed the convection-diffusion theory and showed that the transfer of the solid to the solution is controlled by a combination of liquid flow and diffusion. In other words, both diffusion and convection contribute to the transfer of drug from the solid surface into the bulk solution, ft should be emphasized that this observation applies even under moderate conditions of stirring. 

Rigorous convective diffusion theory [19] doubtlessly brings a valuable contribution to the exact mathematical analytical description of FFF. On the other hand, it must be realized that under real experimental conditions a number of non-ideal conditions exist, such as imperfect smoothness of the surface of the FFF channel walls, and others which can cause fundamental deviations from the theory, of the data observed. The above, and a number of other possible conditions have not been considered by any of these theories. It is the simpleness and the easy distinction of the physical conception of the derived relationships that are, in spite of some simplifying asymptotic assumptions, an advantage of the non-equilibrium theory. 

MHD theory [9-14] has been applied extensively [e.g. 15-21] in conjunction with convective diffusion theory [22-26] to the analysis of external magnetic field effects in the hydrodynamic and concentration boundary layer existing at the electrode/electrolyte interface [2,5,27]. 

With considering concentration polarization effects, the performance of osmosis process can be predicted. There are generally two dominant theoretical models for osmosis phenomena, the thin-film theory and the convection-diffusion theory, which are separately elaborated as follow. 

According to the chemical theory of olfaction, the mechanism by which olfaction occurs is the emittance of particles by the odorous substances. These particles are conveyed to the olfactory epithelium by convection, diffusion, or both, and dkecdy or indkectly induce chemical changes in the olfactory receptors. 

Combining hindered diffusion theory with the diffusion/convection problem in the model pore, Trinh et al. [399] showed how the effective transport coefficients depend upon the ratio of the solute to pore size. Figure 28 shows that as the ratio of solute to pore size approaches unity, the effective mobility function becomes very steep, thus indicating that the resolution in the separation will be enhanced for molecules with size close to the size of the pore. Similar results were found for the effective dispersion, and the implications for the separation of various sizes of molecules were discussed by Trinh et al. [399]. 

For a number of flow situations, the mass-transfer rate can be derived directly from the equation of convective diffusion (see Table VII, Part A). The velocity profile near the electrode is known, and the equation is reduced to a simpler form by appropriate similarity transformations (N6). These well-defined flows, therefore, are being exploited increasingly by electrochemists as tools for the kinetic characterization of electrode reactions. Current distributions at, or below, the limiting current, transient mass transfer, and other aspects of these flows are amenable to analysis. Especially noteworthy are the systematic investigations conducted by Newman (review until 1973 in N7 also N9b, N9c, H6b and references in Table VII), by Daguenet and other French workers (references in Table VII), and by Matsuda (M4a-d). Here we only want to comment on the nature of the velocity profile near the electrode, and on the agreement between theory and mass-transfer experiment. 

In filtration, the particle-collector interaction is taken as the sum of the London-van der Waals and double layer interactions, i.e. the Deijagin-Landau-Verwey-Overbeek (DLVO) theory. In most cases, the London-van der Waals force is attractive. The double layer interaction, on the other hand, may be repulsive or attractive depending on whether the surface of the particle and the collector bear like or opposite charges. The range and distance dependence is also different. The DLVO theory was later extended with contributions from the Born repulsion, hydration (structural) forces, hydrophobic interactions and steric hindrance originating from adsorbed macromolecules or polymers. Because no analytical solutions exist for the full convective diffusion equation, a number of approximations were devised (e.g., Smoluchowski-Levich approximation, and the surface force boundary layer approximation) to solve the equations in an approximate way, using analytical methods. 

In the operator L, the first term represents convection and the second diffusion. Equation (44) therefore describes a balance of convective, diffusive, and reactive effects. Such balances are very common in combustion and often are employed as points of departure in theories that do not begin with derivations of conservation equations. If the steady-flow approximation is relaxed, then an additional term, d(p(x)/dt, appears in L this term represents accumulation of thermal energy or chemical species. For species conservation, equations (48) and (49) may be derived with this generalized definition of L, in the absence of the assumptions of low-speed flow and of a Lewis... 

The concentration polarization model, which is based on the stagnant fihn theory, was developed to describe the back-diffusion phenomenon during filtration of macromolecules. In this model, the rejection of particles gives rise to a thin fouling layer on the membrane surface, overlaid by a concentration polarization layer in which particles diffuse away from the membrane surface, where solute concentration is high, to the bulk phase, where the solute concentration is low [158]. At steady state, convection of particles toward the membrane surface is balanced by diffusion away from the membrane. Thus, integrating the onedimensional convective-diffusion equation across the concentration polarization layer gives... 

The starting point of a molecular constitutive theory is a simple mechanical model for the molecule that captures its most salient traits. Thus, flexible polymer molecules have been represented by elastic dumbbells and bead-spring chains, and rigid polymers by rigid dumbbells and rigid rods. For its simplicity, the evolution of the model molecule is easily described by a convection-diffusion equation. Then a Fokker-Planck equation is written for the probability distribution function of an ensemble of these molecules. Finally, the macroscopic stress tensor is derived in terms of the distribution function. This kinetic theory framework was pioneered by Kirkwood (see, for example, Ref. ). 

---