Hydrodynamic boundary layer, rotating electrodes

The convective diffusion theory was developed by V.G. Levich to solve specific problems in electrochemistry encountered with the rotating disc electrode. Later, he applied the classical concept of the boundary layer to a variety of practical tasks and challenges, such as particle-liquid hydrodynamics and liquid-gas interfacial problems. The conceptual transfer of the hydrodynamic boundary layer is applicable to the hydrodynamics of dissolving particles if the Peclet number (Pe) is greater than unity (Pe > 1) (9). The dimensionless Peclet number describes the relationship between convection and diffusion-driven mass transfer ... 

In many respects, similar to the diffusion layer concept, there is that of the hydrodynamic boundary layer, <5H. The concept was due originally to Prandtl [16] and is defined as the region within which all velocity gradients occur. In practice, there has to be a compromise since all flow functions tend to asymptotic limits at infinite distance this is, to some extent, subjective. Thus for the rotating disc electrode, Levich [3] defines 5H as the distance where the radial and tangential velocity components are within 5% of their bulk values, whereas Riddiford [7] takes a figure of 10% (see below). It has been shown that... 

Hydrodynamic boundary layer — is the region of fluid flow at or near a solid surface where the shear stresses are significantly different to those observed in bulk. The interaction between fluid and solid results in a retardation of the fluid flow which gives rise to a boundary layer of slower moving material. As the distance from the surface increases the fluid becomes less affected by these forces and the fluid velocity approaches the freestream velocity. The thickness of the boundary layer is commonly defined as the distance from the surface where the velocity is 99% of the freestream velocity. The hydrodynamic boundary layer is significant in electrochemical measurements whether the convection is forced or natural the effect of the size of the boundary layer has been studied using hydrodynamic measurements such as the rotating disk electrode [i] and - flow-cells [ii]. 

Both qualitative and quantitative insight can be garnered from transient X -i, i-t and r -t measurements in quiescent or stirred solutions, while measurements of steady-state behavior are best performed under well-defined hydrodynamic conditions. Typically, a rotating disc electrode (RDE), or a related method, is used to specify and/or modulate the hydrodynamic boundary layer thickness, 8. With an RDE the boundary layer is specified by... 

In a real electrochemical system, convection is usually introduced by such means as rotating electrode, stirring, or other forced circulation. In any case, the electrolyte moves relative to electrode surfaces. Due to the mechanical friction between electrolyte solution and electrode surface, a velocity v(x) variation exists. The velocity of solution flow is generally a constant (vqo) in bulk solution (far from the electrode surface and the wall of solution container) and decreases while approaching the solid surfaces [6]. The solution flow velocity v(x) = 0 at solid surface (x = 0). A hydrodynamic (or Prandtl) boundary layer is defined as [6]... 

Both Sq and S have the same value over the entire electrode surface, which has given rise to the description of the electrode as a uniformly accessible surface. The concepts of a hydrodynamic and a diffusion boundary layer have no theoretical significance as such but serve mainly to provide a suitable model for the hydrodynamic conditions related to the rotating electrode. 

A schematic of the RDE is presented in Fig. 2.2. The hydrodynamics of this electrode system are well-known, and they have been discussed in detail elsewhere. In simple terms the rotating electrode acts as a pump drawing fresh solution from bulk regions of the fluid toward the electrode surface, then spinning it around, and subsequently flinging it sideways. This flow pattern is illustrated in Fig. 2.5. The electrode action establishes a stationary boundary layer, called the diffusion layer, at the electrode... 

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