Nonreversible Electrochemistry Charge Transport

When the characteristic time for charge diffusion is lower than the experiment timescale, not all the redox sites in the film can be oxidized/reduced. From experiments performed under these conditions, an apparent diffusion coefficient for charge propagation, 13app can be obtained. In early work choroamperometry and chronocoulometry were used to measure D pp for both electrostatically [131,225] and covalently bound ]132,133] redox couples. Laviron showed that similar information can be obtained from cyclic voltammetry experiments by recording the peak potential and current as a function of the potential scan rate [134, 135]. Electrochemical impedance spectroscopy (EIS) has also been employed to probe charge transport in polymer and polyelectrolyte-modified electrodes [71, 73,131,136-138]. The methods 

From a theoretical point of view, charge propagation in films containing space-distributed redox centers can be achieved either by the physical displacement of the sites or by the transference (hopping) of electrons from neighboring reduced to oxidized sites or by the combination of both processes. In the case of free diffusing couples immobilized in oppositely charged polyelectrolytes, both processes occur and an apparent diffusion coefficient can be defined and measured [136, 142, 143]  

In the case of redox sites covalently bound to a polymer backbone, when only Dg contributes to charge transport. Equation 2.12 has systematically failed to explain the dependence of D pp with the concentration of redox sites. Blauch and Saveant have shown that for completely immobile centers, charge transport is basically a percolation process random distribution of isolated clusters of electrochemically coimected sites [33,40]. Only by dynamic rearrangements can these clusters become in contact and charge transport occur, giving rise to the concept of bound diffusion where each 

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