Linear sweep voltammetry at the RDE

In LSV experiments at stationary electrodes, there can be unwanted effects due to natural convection forced convection and a uniformly accessible electrode obviate this problem. The minimum voltage scan rate at which LSV effects appear (i.e. steady-state assumptions fail) will depend on the electrode kinetics and flow parameters. We can immediately identify two extreme situations. 

The mathematical solution was first studied by Girina et al. [274] based on the same approximation as that for potential step studies, by dropping the highest-order convective term [237], and by Fried and Elving by using the Nernst diffusion-layer concept [275]. 

Cheh and co-workers [276—278] also investigated LSV at the RDE for first-order reversible, quasi-reversible, and irreversible systems. Whilst for the quasi-reversible case numerical solution cannot be approximated by any analytical expression, for the other cases this is possible. 

We can see from Table 6 and eqns. (219) and (220) that, besides the suppression of natural convection, other advantages of LSV at the RDE are weak dependence on the physical properties of the electrolyte and the simultaneous determination of peak and limiting current in a single experiment. 

Recently, a numerical solution has been obtained for the LSV response to a homogeneous catalytic reaction at an electroactive-monolayer-film-covered rotating disc electrode [279]. 

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