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Thus, (9.55) (9.56) 9.3.1.2 General Current-Potential Curves at the RDE For no limiting-current conditions, only a change in integration limits is required. In general, at y=0, CO=CO(y=0) and (∂CO/∂y)y=0 is given by an analogue to (9.53), which yields For a Nerstian reaction, combination of the Nernst equation for the O,R couple with the equations for the various currents yields the familiar voltammetric wave equation: where (9.57) (9.58) Note that the shape of the wave for a reversible reaction is independent of ω. Thus, since il varies as ω1/2, I at any potential should also vary as ω1/2. A deviation of a plot of i vs. ω1/2 from a straight line intersecting the origin suggests that a kinetic limitation is involved in the electron-transfer reaction. For example, for a totally irreversible one-step, one-electron reaction, the disk current is where kf(E) = k0 exp[-αf(E-E0’)]. Or, with rearrangement and defining (9.59) (9.60) (9.61) 233PDF Image | Redox Flow Batteries Vanadium to Earth Quinones
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