Diffusion material balance

The differential material balances contain a large number of physical parameters describing the structure of the porous medium, the physical properties of the gaseous mixture diffusing through it, the kinetics of the chemical reaction and the composition and pressure of the reactant mixture outside the pellet. In such circumstances it Is always valuable to assemble the physical parameters into a smaller number of Independent dimensionless groups, and this Is best done by writing the balance equations themselves in dimensionless form. The relevant equations are (11.20), (11.21), (11.22), (11.23), (11.16) and the expression (11.27) for the effectiveness factor. 

A third approach is suggested by Hugo s formulation of material balances at the limit of bulk diffusion control, described in Section 11.3. Hugo found expressions for the fluxes by combining the stoichiometric conditions and the Stefan-Maxvell relations, and this led to no inconsistencies since there are only n - 1 independent Stefan-Maxwell relations for the n fluxes. An analogous procedure can be followed when the diffusion is of intermediate type, using the dusty gas model equations in the form (5.10) and (5.11). Equations (5.11), which have the following scalar form ... 

The material balance conditions (11.1) may be rewritten in terms of the total flux N and the diffusion fluxes J, when they take the form... 

In section 11.4 Che steady state material balance equations were cast in dimensionless form, therary itancifying a set of independent dimensionless groups which determine ice steady state behavior of the pellet. The same procedure can be applied to the dynamical equations and we will illustrate it by considering the case t f the reaction A - nB at the limit of bulk diffusion control and high permeability, as described by equations (12.29)-(12.31). 

Material Balances Whenever mass-transfer applications involve equipment of specific dimensions, flux equations alone are inadequate to assess results. A material balance or continuity equation must also be used. When the geometiy is simple, macroscopic balances suffice. The following equation is an overall mass balance for such a unit having bulk-flow ports and ports or interfaces through which diffusive flux can occur ... 

The material balance with bulk flow in the axial direction z and diffusion in the radial direction rwith diffusivity D gives rise to the equation... 

Dispersion model is based on Fick s diffusion law with an empirical dispersion coefficient substituted for the diffusion coefficient. The material balance is... 

A reartant A diffuses into a stagnant liquid film where the concentration of excess reactant B remains essentially constant at C q. At the inlet face the concentration is Making the material balance over a differential dz of the distance leads to the second-order diffusional equation,... 

A pure gas A diffuses into a liquid film where it reacts with B from the liquid phase. Material balances on the two participants are ... 

For the simplest one-dimensional or flat-plate geometry, a simple statement of the material balance for diffusion and catalytic reactions in the pore at steady-state can be made that which diffuses in and does not come out has been converted. The depth of the pore for a flat plate is the half width L, for long, cylindrical pellets is L = dp/2 and for spherical particles L = dp/3. The varying coordinate along the pore length is x ... 

In many applications of mass transfer the solute reacts with the medium as in the case, for example, of the absorption of carbon dioxide in an alkaline solution. The mass transfer rate then decreases in the direction of diffusion as a result of the reaction. Considering the unidirectional molecular diffusion of a component A through a distance Sy over area A. then, neglecting the effects of bulk flow, a material balance for an irreversible reaction of order n gives ... 

We will first consider the simple case of diffusion of a non-electrolyte. The course of the diffusion (i.e. the dependence of the concentration of the diffusing substance on time and spatial coordinates) cannot be derived directly from Eq. (2.3.18) or Eq. (2.3.19) it is necessary to obtain a differential equation where the dependent variable is the concentration c while the time and the spatial coordinates are independent variables. The derivation is thus based on Eq. (2.2.10) or Eq. (2.2.5), where we set xj> = c and substitute from Eq. (2.3.18) or Eq. (2.3.19) for the fluxes. This yields Fick s second law (in fact, this is only a consequence of Fick s first law respecting the material balance—Eq. 2.2.10), which has the form of a partial differential equation... 

The analysis of simultaneous diffusion and chemical reaction in porous catalysts in terms of effective diffusivities is readily extended to geometries other than a sphere. Consider a flat plate of porous catalyst in contact with a reactant on one side, but sealed with an impermeable material along the edges and on the side opposite the reactant. If we assume simple power law kinetics, a reaction in which there is no change in the number of moles on reaction, and an isothermal flat plate, a simple material balance on a differential thickness of the plate leads to the following differential equation... 

Mooney et al. [70] investigated the effect of pH on the solubility and dissolution of ionizable drugs based on a film model with total component material balances for reactive species, proposed by Olander. McNamara and Amidon [71] developed a convective diffusion model that included the effects of ionization at the solid-liquid surface and irreversible reaction of the dissolved species in the hydrodynamic boundary layer. Jinno et al. [72], and Kasim et al. [73] investigated the combined effects of pH and surfactants on the dissolution of the ionizable, poorly water-soluble BCS Class II weak acid NSAIDs piroxicam and ketoprofen, respectively. 

The theory on the level of the electrode and on the electrochemical cell is sufficiently advanced [4-7]. In this connection, it is necessary to mention the works of J.Newman and R.White s group [8-12], In the majority of publications, the macroscopical approach is used. The authors take into account the transport process and material balance within the system in a proper way. The analysis of the flows in the porous matrix or in the cell takes generally into consideration the diffusion, migration and convection processes. While computing transport processes in the concentrated electrolytes the Stefan-Maxwell equations are used. To calculate electron transfer in a solid phase the Ohm s law in its differential form is used. The electrochemical transformations within the electrodes are described by the Batler-Volmer equation. The internal surface of the electrode, where electrochemical process runs, is frequently presented as a certain function of the porosity or as a certain state of the reagents transformation. To describe this function, various modeling or empirical equations are offered, and they... 

Discovery of the hydrated electron and pulse-radiolytic measurement of specific rates (giving generally different values for different reactions) necessitated consideration of multiradical diffusion models, for which the pioneering efforts were made by Kuppermann (1967) and by Schwarz (1969). In Kuppermann s model, there are seven reactive species. The four primary radicals are eh, H, H30+, and OH. Two secondary species, OH- and H202, are products of primary reactions while these themselves undergo various secondary reactions. The seventh species, the O atom was included for material balance as suggested by Allen (1964). However, since its initial yield is taken to be only 4% of the ionization yield, its involvement is not evident in the calculation. 

The gradient of chemical potential along the surface may also drive surface diffusion. The gradient of V2h is therefore a driving force for a flux Ns of material parallel to the surface. A differential material balance gives,... 

Solutions are provided for external mass-transfer control, intraparticle diffusion control, and mixed resistances for the case of constant Vf and F0 in = FVi out = 0. The results are in terms of the fractional approach to equilibrium F = (ht — hf)/(nT — nf), where hf and are the initial and ultimate solute concentrations in the adsorbent. The solution concentration is related to the amount adsorbed by the material balance - (hi - nf )M,Ay. 

To obtain an expression for tj, we first derive the continuity equation governing steady-state diffusion of A through the pores of the particle. This is based on a material balance for A across the control volume consisting of the thin strip of width dx shown in Figure 8.10(a). We then solve the resulting differential equation to obtain the concentration profile for A through the particle (shown in Figure 8.10(b)), and, finally, use this result to obtain an expression for tj in terms of particle, reaction, and diffusion characteristics. 

Figure 9.7 shows concentration profiles schematically for A and B according to the two-film model. Initially, we ignore the presence of the gas film and consider material balances for A and B across a thin strip of width dx in the liquid film at a distance x from the gas-liquid interface. (Since the gas-film mass transfer is in series with combined diffusion and reaction in the liquid film, its effect can be added as a resistance in series.)... 

This diffusive flow must be taken into account in the derivation of the material-balance or continuity equation in terms of A. The result is the axial dispersion or dispersed plug flow (DPF) model for nonideal flow. It is a single-parameter model, the parameter being DL or its equivalent as a dimensionless parameter. It was originally developed to describe relatively small departures from PF in pipes and packed beds, that is, for relatively small amounts of backmixing, but, in principle, can be used for any degree of backmixing. 

A basis is Fick s diffusion law adapted to dispersion which states that the rate of mass transfer by dispersion is proportional to the concentration gradient. A material balance is made on a hollow cylindrical element of radii r and r+dr and length dx. This element is sketched. 

In reacting systems, transfer of matter and heat occurs by bulk flow and diffusion or conduction. Usually transfer in an axial direction is appreciable by bulk flow only. In a rectangular region the various elements of a material balance in one dimensional flow are,... 

For diffusion with reaction in uniform pores in a sphere, the steady material balance is... 

A reaction is conducted in an annular vessel with catalyst whose bulk density is pc. Porosity of the bed is e. The reaction is first order with specific rates kc per unit mass on the catalyst and kh per unit volume in the space not occupied by the granules. The two walls are maintained at temperatures Tx and T2 The reaction also proceeds on the walls with corresponding specific rates kwl and kw2 per unit area. Only radial diffusion occurs. Write equations of the material balances and the boundary conditions. 

Make the material balance over an elemental hollow cylinder with length dz and wall dr. In the axial direction change will accompany bulk flow, u, and in the radial direction change will accompany diffusion. 

Take the unsteady condition of diffusion in a radial direction with reaction in the fluid at rate kvC per unit volume and reaction at the wall at rate kvC per unit surface. The material balance is made over a ring shaped zone between z and z+dz in the axial direction and between r and r+dr in the radial direction. The material balance is... 

Note that since there are two independent variables of both length and time, the defining equation is written in terms of the partial differentials, dC/dt and dC/dZ, whereas at steady state only one independent variable, length, is involved and the ordinary derivative function is used. In reality the above diffusion equation results from a combination of an unsteady-state material balance, based on a small differential element of solid length dZ, combined with Fichs Law of diffusion. 

It is important to note that Eqs. 5, 8, and 9 were derived entirely from a silicon material balance and the assumption that physical sputtering is the only silicon loss mechanism thus these equations are independent of the kinetic assumptions incorporated into Eqs. 1, 2, and 7. This is an important point because several of these kinetic assumptions are questionable for example, Eq. 2 assumes a radical dominated mechanism for X= 0, but bombardment-induced processes may dominate for small oxide thickness. Moreover, ballistic transport is not included in Eq. 1, but this may be the dominant transport mechanism through the first 40 A of oxide. Finally, the first 40 A of oxide may be annealed by the bombarding ions, so the diffusion coefficient may not be a constant throughout the oxide layer. In spite of these objections, Eq. 2 is a three parameter kinetic model (k, Cs, and D), and it should not be rejected until clear experimental evidence shows that a more complex kinetic scheme is required. 

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