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One obtains the Koutecký-Levick equation: Here, ik represents the current in the absence of any mass-transfer effects, that is, the current that would flow under the kinetic limitation if the mass transfer were efficient enough to keep the concentration at the electrode surface equal to the bulk value, regardless of the electrode reaction. Clearly, i/ω1/2C is a constant only when ik [or kf (E)] is very large. Otherwise, a plot of i vs. ω1/2 will be curved and tend toward the limit i = ik as ω1/2 tend to infinite (Figure 9.7). Figure 9.7 – Variation of i with ω1/2 at an RDE (at constant ED) for an electrode reaction with slow kinetics. A plot of 1/i vs. 1/ω1/2 should be linear and can be extrapolated to ω-1/2 = 0 to yield 1/iK. Determination of iK at different values of E then allows determination of the kinetic parameter k0 and α (Figure 9.8). (9.62) 234PDF Image | Redox Flow Batteries Vanadium to Earth Quinones
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