Rotating disk electrode estimates with

Figure 9 Comparison of previously reported values of kSA for reduction by Fe° with external mass transport coefficients estimated for batch, column, and rotating disk electrode reactors. References for the overall rate coefficients are given in Fig. 1 of Ref. 101. Mass transport coefficients were estimated for the batch and column reactors based on empirical correlations discussed in Refs. 125 and 101. Mass transport coefficients for the RDE were calculated using the Levich equation [178].

As mentioned in the introduction of the amperometry techniques, the voltammetry with periodical renewal of the diffusion layer is particularly effective in monitoring a process differently involving an electroactive species, e.g., in the already mentioned amperometric titrations, in the determination of the stability of a species, etc. In particular cases, also simple chronoamperometry, i.e., at a fixed, suitably chosen potential, may be effective to this purpose. Noteworthy, it will be clear in the following that the much more widely diffused linear potential scan and cyclic voltammetric techniques are not always suitable to substitute for voltammetry with periodical renewal of the diffusion layer to the purpose of monitoring electroactive species during their transformation. Voltammetry with periodical renewal of the diffusion layer, as well as the voltammetry at rotating disk electrode, only allows the estimation of the concentrations of both partners of a redox couple, on the basis of the ratio between the anodic and cathodic limiting currents. 

The RHSE has the same limitation as the rotating disk that it cannot be used to study very fast electrochemical reactions. Since the evaluation of kinetic data with a RHSE requires a potential sweep to gradually change the reaction rate from the state of charge-transfer control to the state of mass transport control, the reaction rate constant thus determined can never exceed the rate of mass transfer to the electrode surface. An upper limit can be estimated by using Eq. (44). If one uses a typical Schmidt number of Sc 1000, a diffusivity D 10 5 cm/s, a nominal hemisphere radius a 0.3 cm, and a practically achievable rotational speed of 10000 rpm (Re 104), the mass transfer coefficient in laminar flow may be estimated to be ... 

This approximate relationship is similar to those for centrifugal atomization of normal liquids in both Direct Droplet and Ligament regimes. However, it is uncertain how accurately the model for K developed for normal liquid atomization could be applied to the estimation of droplet sizes of liquid metals Tombergl486 derived a semi-empirical correlation for rotating disk atomization or REP of liquid metals with the proportionality between the mean droplet size, rotational speed, and electrode or disk diameter similar to the above equation. Tornberg also presented the values of the constants in the correlation for some given operation conditions and material properties. 

A number of questions remain concerning the dynamics of the protein-electrode interaction. Do experimental data give any idea about the rates, relative or otherwise, of the electron-transfer step The clearest result so far has been the determination of ke, for horse heart cytochrome c at 4,4 -bipyridyl-modified Au with the rotating ring-disk technique as mentioned above [65], There have been a number of determinations of compound heterogeneous rate constants for protein electrochemistry, mostly using Nicholson s method [124] for their estimation from CV peak separations. All calculations have assumed that the mass transport can be treated in terms of linear diffusion to a uniform planar electrode surface. Bond and co-workers have pointed out [125,126] that in many instances this is unlikely to be... 

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