DETERMINATION OF THE STANDARD HETEROGENEOUS RATE-CONSTANT IN POLYELECTROLYTE USING STEADY-STATE MICRODISK VOLTAMMOGRAMS

The steady state voltammogram at a microdisk electrode is used to meas ure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtaine d is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by th e relaxation rates of the ether dipole sites on the polymer chains, wh ich are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.