The redox conductivity of mixed valent poly(vinylferrocene) films is measured by a steady state method using interdigitated array electrodes. Spectroelectrochemistry shows that the Fc/Fc+ site concentration ratio has a simple Nernstian dependence on applied potential. Measurements of the bimolecular Fc/Fc+ electron self-exchange rate constant using concentration gradient- and electrical gradient-driven electron transfers are in agreement and give an average value of 2 × 105 M-1 s-1 for dry N2 bathed films. The solid state dispersive transport model of Scher, Montroll, and Pfister is used in interpretation of the electrical potential gradient-driven electron transport. The rate constant kEX remains roughly constant as the concentration ratio of Fc+ and Fc sites is varied from 0.04 to 3.0.
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Sullivan et al. (1994) studied this question.