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Chapter 3. Characterisation Methods As a direct extension of the Levich equation, the Koutecký-Levich equation describes how the current in the kinetic region is affected by both IL and the kinetically limited current IK, written here for an oxidation: 1=1+1=1+ 1 (3.11) Ia IKa ILa IKa 0.62nF AD2/3 u−1/6cRedω1/2 Red IKa =nFAka(E)c∗Red (3.12) −αnF E−E0′ αnF ka(E) = k0e RT = k0e− RT η (3.13) where ka is the rate constant for oxidation. Combining Equations 3.12 and 3.13 and applying the natural logarithm on both sides results in the Tafel approximation of the Butler-Volmer equation: ln(IKa) = −αnF η + lnnFAk0c∗Red (3.14) RT According to Equation 3.11, a plot of I−1 against ω−1/2 results in a straight line with y-axis intercept I−1. If ln (IK) is further plotted against η, a straight line is obtained from K which the standard rate constant k0 and the transfer coefficient α can be determined from the y-axis intercept and slope, respectively. RDE voltammetry is carried out in a three-electrode configuration similar to the one shown in Figure 3.3, with the main differences being the WE centred in the electrolyte container and rotating around its cylindrical axis. The RDE tip is attached to the shaft of an electric motor that spins the electrode at a well-defined rotation rate. A schematic of the electrolyte streamlines generated at an RDE is shown in Figure 3.5. Electrode shroud Disk electrode Figure 3.5: (Upper) Schematic cross-section of an RDE tip and the streamlines of elec- trolyte transported to it. (Lower) Top-down view of the electrolyte streamlines. Adapted from [62]. 24PDF Image | Organic Redox Flow Batteries 2023
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