Peak Position and Donnan Potential

Due to the presence of interactions, the apparent redox potential of a redox couple inside a polyelectrolyte film can differ from that of the isolated redox couple in solution (i.e. the standard formal redox potential) [121]. In other words, the free energy required to oxidize a mole of redox sites in the film differs from that needed in solution. One particular case is when these interations have an origin in the presence of immobile electrostatically charged groups in the polymer phase. Under such conditions, there is a potential difference between this phase and the solution (reference electrode in the electrolyte), knovm as the Donnan or membrane potential that contributes to the apparent potential of the redox couple. The presence of the Donnan potential in redox polyelectrolyte systems was demonstrated for the first time by Anson [24, 122]. Considering only this contribution to peak position, we can vwite  

Equation 2.5 provides a way to determine the concentration and sign of immobile charges inside the film and also to probe whether the peak shift is caused by the presence of an interfacial potential or an alternative explanation is required. As an 

Manipulation of the Donnan potential in random polymer-modified electrodes can also be achieved. In the case of cast redox polyelectrolyte-modified electrodes one can control ion permselectivity by mixing the redox polymer with an oppositely charged polyelectrolyte in an appropriate ratio before film casting [123]. The same strategy can be followed in electropolymerized films by mixing the electroactive monomer with one of opposite charge [124]. 

One of the main assumptions of the Donnan partition model is that two well-defined phases (polymer and solution) exist and the electrostatic potential presents a sharp transition between them. This approximation is fulfilled when the typical decay length of the electrostatic potential (Debye length) is much shorter than the film thickness. The other limiting situation is that where all the redox sites are located in a plane and thus the Debye length is larger than the film thickness. This situation can be described by the surface potential model  

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