Rotating diffusion layer

The diffusion layer widtli is very much dependent on tire degree of agitation of tire electrolyte. Thus, via tire parameter 5, tire hydrodynamics of tire solution can be considered. Experimentally, defined hydrodynamic conditions are achieved by a rotating cylinder, disc or ring-disc electrodes, for which analytical solutions for tire diffusion equation are available [37, 4T, 42 and 43]. 

Volt mmetiy. Diffusional effects, as embodied in equation 1, can be avoided by simply stirring the solution or rotating the electrode, eg, using the rotating disk electrode (RDE) at high rpm (3,7). The resultant concentration profiles then appear as shown in Figure 5. A time-independent Nernst diffusion layer having a thickness dictated by the laws of hydrodynamics is estabUshed. For the RDE,... 

Examples of such irreversible species (12) include hydroxjiamine, hydroxide, and perchlorate. The electrochemistries of dichromate and thiosulfate are also irreversible. The presence of any of these agents may compromise an analysis by generating currents in excess of the analytically usehil values. This problem can be avoided if the chemical reaction is slow enough, or if the electrode can be rotated fast enough so that the reaction does not occur within the Nemst diffusion layer and therefore does not influence the current. 

Fig. 3. Steady state concentration profiles of catalyst and substrate species in the film and diffusion layer for for various cases of redox catalysis at polymer-modified electrodes. Explanation of layers see bottom case (S + E) f film d diffusion layer b bulk solution i, limiting current at the rotating disk electrode other symbols have the same meaning as in Fig. 2 (from ref.

Let CO be the angular velocity of rotation this is equal to Inf where/is the disk frequency or number of revolutions per second. The distance r of any point from the center of the disk is identical with the distance from the flow stagnation point. The hnear velocity of any point on the electrode is cor. We see when substituting these quantities into Eq. (4.34) that the effects of the changes in distance and hnear vefocity mutuaUy cancel, so that the resulting diffusion-layer thickness is independent of distance. 

The constancy of the diffusion layer over the entire surface and thus the uniform current-density distribution are important features of rotating-disk electrodes. Electrodes of this kind are called electrodes with uniformly accessible surface. It is seen from the quantitative solution of the hydrodynamic problem (Levich, 1944) that for RDE to a first approximation... 

It follows from Eqs. (4.37) and (4.38) that the diffusion-layer thickness will increase without limits and the diffusion flux will decrease to zero when the electrolyte is not stirred (v = 0) or the electrode not rotated (co = 0). This implies that a steady electric cnrrent cannot flow in such cells. But this conclusion is at variance with the experimental data. 

Most successful is a rotating Pt wire microelectrode as illustrated in Fig. 3.75 as a consequence of the rotation, which should be of a constant speed, the steady state is quickly attained and the diffusion layer thickness appreciably reduced, thus raising the limiting current (proportional to the rotation speed to the 1/3 power above 200 rpm140 and 15-20-fold in comparison with a dme) and as a result considerably improving the sensitivity of the amperometric- titration. 

The dependence of the limiting current density on the rate of stirring was first established in 1904 by Nernst (N2) and Brunner (Blla). They interpreted this dependence using the stagnant layer concept first proposed by Noyes and Whitney. The thickness of this layer ( Nernst diffusion layer thickness ) was correlated simply with the speed of the stirring impeller or rotated electrode tip. 

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. 

The dissolution rate of a solid from a rotating disc is governed by the controlled hydrodynamics of the system, and it has been treated theoretically by Levich [104]. This theory considers only forced convection due to rotation and ignores natural convection, which may occur at low speeds of rotation. Figure 16 shows the solvent flow held near the surface of the rotating disc. The apparent thickness, h, of the diffusion layer next to the surface of the disc is given by... 

At a rotating disc the thickness of the diffusion layer decreases with increasing rotation rate according to ... 

In contrast to the rotating disc electrode, mass transport to the ring is nonuniform. Nevertheless, the thickness of the diffusion layer Spj, which depends on the coordinate x in the direction of flow, and the rate of mass transport can be calculated. We consider a simple redox reaction, and rewrite Eq. (14.5) in the form ... 

There are a few electrochemical techniques in which the working electrode is moved with respect to the solution (i.e. either the solution is agitated or the electrode is vibrated or rotated). Under these conditions, the thickness of the diffusion layer decreases so that the concentration gradient increases. Since the rate of the mass transport to an electrode is proportional to the concentration gradient (Chapter 1, Section 4.2.2), the thinning of the diffusion layer leads to an increase of the mass transport, and hence to an increase of the faradaic currents. 

There is a complication, though a thin (c. cm) layer of solution exists between the electrode and the bulk solution that is relatively immobile. This forms because of the inherent viscous drag of the solution as it moves over the solid electrode. We call this thin film of immobile liquid the diffusion layer, where the latter has a thickness S. The thickness of the layer depends on the rotation speed according to the following ... 

For an RDE the diffusion layer thickness depends on the angular speed of rotation 0) according to... 

The designs of some early electrochemical cells for industrial use were based on the beaker-type laboratory cell. One improvement to mass transport conditions was to rotate the working electrode, which decreases the thickness of the diffusion layer [20]. As small a gap as is practical between the working electrode and the counter... 

Diffusion layer (cont.) polarography. 12-46 thickness, 1335 turbulent flow and, 1234 Diffusion coefficient, and rotating disk electrode. 1141... 

Rotating disk electrode (cont.) diffusion coefficient, 1141 diffusion layer in, 1234 disk current in, 1141 ECE reactions determination by. 1144 electrooxidation of methanol, 1139 kinematic viscosity, 1141,1234 intermediate radicals, determination of. 1139. 

Influence of Rotating Disk Electrode Condition (Stationary or Rotating) on the Diffusion-Layer Thickness and the Limiting Current Density for the Reaction... 

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