Potential step methods heterogeneous kinetics

An SECM feedback response to an electroactive polymer film can be controlled either by ET kinetics at the film-solution interface or by film conductivity. The contribution of lateral film conductivity to the effective ET rate measured by SECM was addressed in the recent study of polyaryl multilayers attached with ferrocenes [65] or ferrocene-terminated dendrimers [69] on unbiased carbon electrodes. In the latter study, the dependence of apparent ET rate constant, feei. on the generation of dendrimers (Table 6.2) was ascribed to the different efficiencies of electron transport inside and between dendrimers (Figure 6.22). Interestingly, the theory of the aforementioned triple potential step method predicts its potential to separately determine heterogeneous ET rate and lateral conductivity for a thin polymer film coated on an insulating surface [70]. 

The current-potential curves discussed so far can be used to measure concentrations, mass-transfer coefficients, and standard potentials. Under conditions where the electron-transfer rate at the interface is rate-determining, they can be employed to measure heterogeneous kinetic parameters as well (see Chapters 3 and 9). Often, however, one is interested in using electrochemical methods to find equilibrium constants and rate constants of homogeneous reactions that are coupled to the electron-transfer step. This section provides a brief introduction to these applications. 

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