Diffusion equation, forced rotational

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). 

All the electrode kinetic methodology described until now has assumed a steady state (or quasi-steady state in the case of the DME). Many techniques at stationary electrodes involve perturbation of the potential or current in combination with forced convection, this offers new possibilities in the evaluation of a wider range of kinetic parameters. Additionally, we have the possibility of modulating the material flux, the technique of hydrodynamic modulation which has been applied at rotating electrodes. Unfortunately, the mathematical solution of the convective-diffusion equation is considerably more complex and usually has to be performed numerically. 

Debye obtained his result by solving a forced diffusion equation Ci.e., with torque of the applied field included) for the distribution of dipole coordinate p - pcosS, with 6 the polar angle between the dipole axis and tSe field, and the same result for the model follows very simply from equation (3) using the time dependent distribution function in the absence of the field (5). The relaxation time is given by td = 1/2D, which for a molecular sphere of volume v rotating in fluid of viscosity n becomes... 

The rale of collection of Brownian particles under the influence of interaction forces between the collector surface and the particles is calculated by (a) incorporating the interaction forces in the rate constant of a virtual, first order, chemical reaction taking place on the surface of the collector, and by (b) solving the convective diffusion equation subject to that chemical reaction as a boundary condition. Several geometries (sphere, cylinder, rotating disc) are considered for the collector. 

When van der Waals and double-layer forces are effective over a distance which is short compared to the diffusion boundary-layer thickness, the rate of deposition may be calculated by lumping the effect of the particle-collector interactions into a boundary condition on the usual convective-diffusion equation. This condition takes the form of a first-order irreversible reaction (10, 11). Using this boundary condition to eliminate the solute concentration next to the disk from Levich s (12) boundaiy-kyersolution of the convective-diffusion equation for a rotating disk, one obtains... 

In Section 5.9, we show how to solve the convective-diffusion equation for the rotating disc electrode in order to calculate the diffusion-limited current. When the forced convection is constant, then dc/dt = 0, which simplifies the mathematical solution. 

The RDE consists of a disk electrode embedded in an insulating rod material as shown in Fig. 14 (44). The composite electrode can be rotated about its axis, which causes electrolyte to be drawn up against, and forced outwards across, the face of the metal disk electrode, as shown in Fig. 15 (45). The convection and diffusion equations that describe solution flow in this situation have been rigorously established making this experimental approach a powerful one for the study of the effects of forced convection of electrochemical reactions. 

We now consider forced convection. We have seen that the diffusion layer thickness (5) is a crucial parameter in the diffusion equations. It is a fitting parameter in fact, a thickness from the electrode surface within which no hydrodynamic motion of the solution is assumed, i.e., the mass transport occurs by molecular mechanism, mostly by diffusion. The exact solution of the respective convective-diffusion equations is very complicated therefore, only the essential features are surveyed for two cases stirring of the solution and rotating disc electrode (RDE). 

The diffusivities thus obtained are necessarily effective diffusivities since (1) they reflect a migration contribution that is not always negligible and (2) they contain the effect of variable properties in the diffusion layer that are neglected in the well-known solutions to constant-property equations. It has been shown, however, that the limiting current at a rotating disk in the laminar range is still proportional to the square root of the rotation rate if the variation of physical properties in the diffusion layer is accounted for (D3e, H8). Similar invariant relationships hold for the laminar diffusion layer at a flat plate in forced convection (D4), in which case the mass-transfer rate is proportional to the square root of velocity, and in free convection at a vertical plate (Dl), where it is proportional to the three-fourths power of plate height. 

In this form one sees an analogy in the vorticity equation to the other transport equations— a substantial-derivative description of advective transport, a Laplacian describing the diffusive transport, and possibly a source term. It is interesting to observe that the vorticity equation does not involve the pressure. Since pressure always exerts a normal force that acts through the center of mass of a fluid packet (control volume), it cannot alter the rotation rate of the fluid. That is, pressure variations cannot cause a change in the vorticity of a flow field. 

By definition chirality involves a preferred sense of rotation in a three-dimensional space. Therefore, it can only be affected by a modification of the nonscalar fields appearing in the rate equations. For a reaction-diffusion system [equations (1)] these fields are descriptive of a vector irreversible process, namely, the diffusion flux J of constituent k in the medium. According to irreversible thermodynamics, the driving force conjugate to diffusion is... 

For many purposes, it is more convenient to characterize the rotary Brownian movement by another quantity, the relaxation time t. We may imagine the molecules oriented by an external force so that the a axes are all parallel to the x axis (which is fixed in space). If this force is suddenly removed, the Brownian movement leads to their disorientation. The position of any molecule after an interval of time may be characterized by the cosine of the angle between its a axis and the x axis. (The molecule is now considered to be free to turn in any direction in space —its motion is not confined to a single plane, but instead may have components about both the b and c axes.) When the mean value of cosine for the entire system of molecules has fallen to ile(e — 2.718... is the base of natural logarithmus), the elapsed time is defined as the relaxation time r, for motion of the a axis. The relaxation time is greater, the greater the resistance of the medium to rotation of the molecule about this axis, and it is found that a simple reciprocal relation exists between the three relaxation times, Tj, for rotation of each of the axes, and the corresponding rotary diffusion constants defined in equation (i[Pg.138]

If the particles are non-spherical then, first, the simple form of Stokes equation does not apply and, secondly, the unsymmetrical. forces exerted on the particle by solvent molecules cause the particles to rotate and undergo Brownian rotation or rotational diffusion [Figure 6.2(b)]. 

Impedance may also be studied in the case of forced diffusion. The most important example of such a technique is a rotating disk electrode (RDE). In a RDE conditions a steady state is obtained and the observed current is time independent, leading to the Levich equation [17]. The general diffusion-convection equation written in cylindrical coordinates y, r, and q> is [17]... 

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