Convective Diffusion Layer

Diffusion—Convection Layer Near the Electrode Surface 173... 

The central part of the RDE theory and technique is the convection of electrolyte solution. Due to the solution convection, the reactant in the solution will move together with the convection at the same transport rate. Let s first consider the situation where the flow of electrolyte solution from the bottom of the electrode edge upward with a direction parallel to the electrode surface to see how the diffusion— convection layer can be formed and what is its mathematic expression. 

Note that this do (cm) is different from that of diffusion layer thickness because within the diffusion layer, there is no solution convection, hut within this diffusion—convection layer, both diffusion and convection coexist. Based on convection kinetic theory, this diffusion—convection layer thickness can be approximately expressed as Eqn (5.1) ... 

We assume that the concentration distribution within the diffusion—convection layer can be treated in the similar way to that described in Chapter 2, and then the concentration distribution of the oxidant near the electrode surface can be schematically expressed in Figure 5.2. Thus, the diffusion—convection current density (ioc.o) can be expressed in a similar form to those Eqns (2.57) and (2.58) ... 

In order to get the current—potential relationship on the RDE, particularly the expression of limiting current density as the function of the electrode rotating rate and the reactant concentration, Pick s second law has to be used to give the equations of reactant concentration change with time at the steady-state situation of diffusion—convection. When the surface concentration of oxidant reaches zero during the reaction at the steady-state situation, the concentration distribution within the diffusion—convection layer is not changing with time anymore, meaning that the diffusion rate is... 

Comparing Eqn (5.14a) with (5.3), it can define the thickness of diffusion—convection layer for a rotating electrode ... 

It can be seen that this thickness of the diffusion—convection layer is not a function of the location on the electrode surface, which is different from that of Eqn (5.1), and therefore, the current density over the entire RDE surface is uniformly distributed. 

As we discussed above, the RDE theory is based on the convection kinetics of the electrolyte solution. If the electrode rotating rate is too small, meaning that the solution flow rate is too slow, it will be difficult to establish the meaningful diffusion-convection layer near the electrode surface. In order to make meaningful measurement, there is a rough formula that can be used to obtain the limit of electrode rotating rate (wiow) ... 

A simplified model usiag a stagnant boundary layer assumption and the one-dimension diffusion—convection equation has been used to calculate wall concentration ia an RO module. The iategrated form of this equation, the widely appHed film theory (41), is given ia equation 8. 

Fluid flow and reaction engineering problems represent a rich spectrum of examples of multiple and disparate scales. In chemical kinetics such problems involve high values of Thiele modulus (diffusion-reaction problems), Damkohler and Peclet numbers (diffusion-convection-reaction problems). For fluid flow problems a large value of the Mach number, which represents the ratio of flow velocity to the speed of sound, indicates the possibility of shock waves a large value of the Reynolds number causes boundary layers to be formed near solid walls and a large value of the Prandtl number gives rise to thermal boundary layers. Evidently, the inherently disparate scales for fluid flow, heat transfer and chemical reaction are responsible for the presence of thin regions or "fronts in the solution. 

Diffusion in a convective flow is called convective diffusion. The layer within which diffnsional transport is effective (the diffnsion iayer) does not coincide with the hydrodynamic bonndary layer. It is an important theoretical problem to calcnlate the diffnsion-layer thickness 5. Since the transition from convection to diffnsion is gradnal, the concept of diffusion-layer thickness is somewhat vagne. In practice, this thickness is defined so that Acjl8 = (dCj/ff) Q. This calcniated distance 5 (or the valne of k ) can then be used to And the relation between cnrrent density and concentration difference. 

In free-convection mass transfer at electrodes, as well as in forced convection, the concentration (diffusion) boundary layer (5d extends only over a very small part of the hydrodynamic boundary layer <5h. In laminar free convection, the ratio of the thicknesses is... 

The introduction of Equation (9.71) for Equation (9.26e) makes this a new problem identical to what was done for the pure diffusion/convective modeling of the burning rate. Hence L is simply replaced by L,n to obtain the solution with radiative effects. Some rearranging of the stagnant layer case can be very illustrative. From Equations (9.61) and (9.42) we can write... 

Lionbashevski et al. (2007) proposed a quantitative model that accounts for the magnetic held effect on electrochemical reactions at planar electrode surfaces, with the uniform or nonuniform held being perpendicular to the surface. The model couples the thickness of the diffusion boundary layer, resulting from the electrochemical process, with the convective hydrodynamic flow of the solution at the electrode interface induced by the magnetic held as a result of the magnetic force action. The model can serve as a background for future development of the problem. 

For convective crystal dissolution, the dissolution rate is u = (p/p )bD/8. For diffusive crystal dissolution, the dissolution rate is u = diffusive boundary layer thickness as 5 = (Df), the diffusive crystal dissolution rate can be written as u = aD/5, where a is positively related to b through Equation 4-100. Therefore, mass-transfer-controlled crystal dissolution rates (and crystal growth rates, discussed below) are controlled by three parameters the diffusion coefficient D, the boundary layer thickness 5, and the compositional parameter b. The variation and magnitude of these parameters are summarized below. 

Figure 3.3. Various features of diffusion and convection associated with crystal growth in solution (a) in a beaker and (b) around a crystal. The crystal is denoted by the shaded area. Shown are the diffusion boundary layer (db) the bulk diffusion (D) the convection due to thermal or gravity difference (T) Marangoni convection (M) buoyancy-driven convection (B) laminar flow, turbulent flow (F) Berg effect (be) smooth interface (S) rough interface (R) growth unit (g). The attachment and detachment of the solute (solid line) and the solvent (open line) are illustrated in (b).

Figure 3.6. Schlieren photographs showing the changes in thickness of the diffusion boundary layer and the behavior of buoyancy-driven convection shown in relation to bulk supersaturation [1], [2]. The figure shows the (111) faceofaBa(N03)2 crystal from an aqueous solution. In region I, only the thickness of the diffusion boundary layer increases in region II, we see unstable lateral convection (HA) and intermittently rising plumes (IIB) and in region III we see steady buoyancy-driven convection.

In a hydrodynamically free system the flow of solution may be induced by the boundary conditions, as for example when a solution is fed forcibly into an electrodialysis (ED) cell. This type of flow is known as forced convection. The flow may also result from the action of the volume force entering the right-hand side of (1.6a). This is the so-called natural convection, either gravitational, if it results from the component defined by (1.6c), or electroconvection, if it results from the action of the electric force defined by (1.6d). In most practical situations the dimensionless Peclet number Pe, defined by (1.11b), is large. Accordingly, we distinguish between the bulk of the fluid where the solute transport is entirely dominated by convection, and the boundary diffusion layer, where the transport is electro-diffusion-dominated. Sometimes, as a crude qualitative model, the diffusion layer is replaced by a motionless unstirred layer (the Nemst film) with electrodiffusion assumed to be the only transport mechanism in it. The thickness of the unstirred layer is evaluated as the Peclet number-dependent thickness of the diffusion boundary layer. 

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