A model for the propagation of a redox reaction through microcrystals

Chronoamperometry of reversible redox reactions with the insertion of cations into solid particles immobilised at an electrode surface is analysed theoretically using a semiinfinite planar diffusion model. A coupled diffusion of electrons and ions within the crystal lattice is separated in two differential equations. The redox reaction is initiated by the polarisation of the three-phase boundary, where the crystal is in contact with both the electrode and the solution. From this contact line the redox reaction advances on the surface and into the crystal body by the diffusion of ions and conductance of electrons. The effects of the geometry and conductivity of the particles on the current are discussed.