Boundary conditions effective diffusivity model

In the case that the effective diffusion coefficient approach is used for the molar flux, it is given by N = —Da dci/dr), where Dei = (Sp/Tp)Dmi according to the random pore model. Standard boundary conditions are applied to solve the particle model Eq. (8.1). 

Experimental methods which yield precise and accurate data are essential in studying diffusion-based systems of pharmaceutical interest. Typically the investigator identifies a mechanism and associated mass transport model to be studied and then constructs an experiment which is consistent with the hypothesis being tested. When mass transport models are explicitly involved, experimental conditions must be physically consistent with the initial and boundary conditions specified for the model. Model testing also involves recognition of the assumptions and constraints and their effect on experimental conditions. Experimental conditions in turn affect the maintenance of sink conditions, constant surface area for mass transport, and constant and known hydrodynamic conditions. 

Farmer (6) reviewed the various diffusion models for soil and developed solutions for several of these models. An appropriate model for field studies is a nonsteady state model that assumes that material is mixed into the soil to a depth L and then allowed to diffuse both to the surface and more deeply into the soil. Material diffusing to the surface is immediately removed by diffusion and convection in the air above the soil. The effect of this assumption is to make the concentration of a diffusing compound zero at the soil surface. With these boundary conditions the solution to Equation 8 can be converted to the useful form ... 

An important theoretical development for the outer-sphere relaxation was proposed in the 1970s by Hwang and Freed (138). The authors corrected some earlier mistakes in the treatment of the boundary conditions in the diffusion equation and allowed for the role of intermolecular forces, as reflected in the IS radial distribution function, g(r). Ayant et al. (139) proposed, independently, a very similar model incorporating the effects of molecular interactions. The same group has also dealt with the effects of spin eccentricity or translation-rotation coupling (140). 

In practice, of course, it is rare that the catalytic reactor employed for a particular process operates isothermally. More often than not, heat is generated by exothermic reactions (or absorbed by endothermic reactions) within the reactor. Consequently, it is necessary to consider what effect non-isothermal conditions have on catalytic selectivity. The influence which the simultaneous transfer of heat and mass has on the selectivity of catalytic reactions can be assessed from a mathematical model in which diffusion and chemical reactions of each component within the porous catalyst are represented by differential equations and in which heat released or absorbed by reaction is described by a heat balance equation. The boundary conditions ascribed to the problem depend on whether interparticle heat and mass transfer are considered important. To illustrate how the model is constructed, the case of two concurrent first-order reactions is considered. As pointed out in the last section, if conditions were isothermal, selectivity would not be affected by any change in diffusivity within the catalyst pellet. However, non-isothermal conditions do affect selectivity even when both competing reactions are of the same kinetic order. The conservation equations for each component are described by... 

We adopt the following simple picture. Initially, we assume that steps are far enough apart that the effects of step repulsions can be ignored. The relevant physics for evaporation involves the detachment of adatoms from step edges, their surface diffusion on the adjacent terraces, and their eventual evaporation. This is quite well described by a generalization of the classical BCF model "- which considers solutions to the adatom diffusion equation with boundary conditions at the step edges. 

We shall look at the boundary conditions for this equation in the next section. I want to mention here a very important model introduced by Wes-terterp and his collaborators4 and to do so will revert to the classical form of the Taylor problem, in which there is no reaction, the tube is circular (radius R), and the flow is laminar (average velocity U). Also, we ignore the effect of molecular diffusion in the longitudinal direction and are concerned only with the effects of the lateral diffusion across the flow profile. Thus, we have... 

Mechanisms 1 and 2 are included in the model that is used here for comparison with experimental data. Interface recombination and dark current effects are not included however, the experimental data have been adjusted to exclude the effects of dark current. To include the additional bulk and depletion layer recombination losses, the diffusion equation for minority carriers is solved using boundary conditions relevant to the S-E junction (i.e., the photocurrent is linearly related to the concentration of minority carriers at the interface). Using this boundary condition and assuming quasi-equilibrium conditions (flat quasi-Fermi levels) ( 4 ) in the depletion region, the following current-voltage relationship is obtained. 

Figure 2.16 Illustration of isotopic fractionation effects in diffusion. The model is that 132Xe and 134Xe are initially uniformly distributed throughout spheres in the ratio 134Xe/132Xe = 0.382 and then allowed to escape by diffusion with the boundary condition that the concentration vanishes on the surface. The figure shows the instantaneous composition of the released gas at various stages, assuming that the diffusion coefficients varies as m 112. The single-component locus is for all spheres having the same radius the mixed-component locus is for distribution of sizes. Reproduced from Funk, Podosek, and Rowe (1967).

Imposed Field Effects. In this section we have set forth a set of equations to describe pattern formation in a multicellular electrophysiological system. A central goal of the theory is to study the effects of applied electric fields. This is done by imposing appropriate boundary conditions on the equations developed here. For example, assume we subject a one dimensional tissue to fixed ionic currents 1. Then if the tissue is in the interval 0 x along the x axis, the boundary conditions for the electro-diffusion model of the small gradient theory, i.e. (6k), are replaced by J = I at x = 0, L. One expects the richness of effects to include hyperpolarizability, induction of new phenomena and imperfect bifurcations to be found in these systems... 

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. 

Wei [107] in 1982 was the first to come up with a continuous pseudohomogeneous model which allowed to simulate shape-selective effects observed during the alkylation of toluene using methanol to yield xylene isomers on a HZSM-5 catalyst. He treated diffusion and reaction of the xylene isomers inside the pores in a one-dimensional model. The isomer concentration at the pore mouth was set to zero, as a boundary condition. This allowed the model equations to be solved analytically, but it also limited the application of the results to small conversions. 

As our first application, we consider the classical Taylor-Aris problem (Aris, 1956 Taylor, 1953) that illustrates dispersion due to transverse velocity gradients and molecular diffusion in laminar flow tubular reactors. In the traditional reaction engineering literature, dispersion effects are described by the axial dispersion model with Danckwerts boundary conditions (Froment and Bischoff, 1990 Levenspiel, 1999 Wen and Fan, 1975). Here, we show that the inconsistencies associated with the traditional parabolic form of the dispersion model can be removed by expressing the averaged model in a hyperbolic form. We also analyze the hyperbolic model and show that it has a much larger range of validity than the standard parabolic model. 

Here x is the conversion of SiH4. combines the effect of the molar expansion in the deposition process as well as the change in the volumetric flow and the dispersion coefficient, D, with temperature. At low pressures and small Re in LPCVD reactors the dispersion occurs mainly by molecular diffusion, therefore, we have used (D/D0) = (T/T0)l 65. e is the expansion coefficient and the stoichiometry implies that e = (xi)q, the entrance mole fraction of SiH4. The expansion coefficient, e is introduced as originally described by Levenspiel (33) The two reaction terms refer to the deposition on the reactor wall and wafer carrier and that on the wafers, respectively. The remaining quantities in these equations and the following ones are defined at the end of the paper. The boundary conditions are equivalent to the well known Danckwerts1 boundary conditions for fixed bed reactor models. 

The second approach was to employ periodic boundary conditions and molecular mechanics (COMPASS) to model the solvated SFA.55 73 These simulations were performed with Cerius2 4.2 (Accelrys, Inc.). Periodic boundary conditions create a bulk system with no surface effects and hence, this situation is more realistic compared to the experimental system of SFA dissolved in water. H20 molecules, however, must diffuse to allow motion of the SFA model, so that the SFA model conformations may be restricted due to this limited motion of the surrounding H20 molecules. Note also that periodic simulations must be charge neutral within the... 

The radiation flux af fhe wall of radiation entrance (Figure 22) was determined by actinometric measurements (Zalazar et al., 2005). Additionally, the boundary condition for fhis irradiafed wall (x = 0) was obtained using a lamp model with superficial, diffuse emission (Cassano et al., 1995) considering (i) direct radiation from fhe two lamps and (ii) specularly reflected radiation from fhe reflectors (Brandi et al., 1996). Note that the boundary conditions at the irradiated and opposite walls consider the effect of reflection and refraction at the air-glass and glass-liquid interfaces, as well as the radiation absorption by the glass window at low wavelengths (the details were shown for fhe laboratory reactor). The radiation model also assumes that no radiation arrives from fhe top and bottom reactor walls (x-y plane at z = 0 and z = Zr). 

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