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6 Using Individual Carbon Fiber Electrodes to Quantify Effects of Thermal Activation When the peak separation is small it becomes very difficult to accurately estimate the apparent rate constant, as small changes in peak separation lead to large changes in the calculated apparent rate constant. For instance, a peak separation of 0.128 V will return ð0 = ððð 0.04 ððð â1, whilst a peak separation of 0.116 V will return ð0 = 0.08 ððð â1. This ððð sensitivity increases further with smaller peak separation and thus for large apparent rate constants the peak separation is sensitive to the diameter of the fiber, (Figure 6.6). Figure 6.6: Peak separation dependence on fiber diameter and apparent rate constant, specific values from CVs modelled at a sweep rate of 200 mVs-1. As an example, a 0.124 V peak potential separation at a 12 Ξm electrode will return ð0 = ððð 0.04 cm s-1, but with a 8 Ξm electrode the same peak potential separation will give ð0 = ððð 0.08 cm s-1. As the apparent rate constants calculated from cyclic voltammetry are sensitive to small errors in the calculation of the peak separation and differences in fiber diameter, a more reliable method for calculating the apparent rate constant of these activated fibers is desired. 84PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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