Front Dynamics during Diffusion-Limited Corrosion of Ramified Electrodeposits

Experiments on the diffusion-limited corrosion of porous copper clusters in thin gap cells containing cupric chloride are reported. By carefully comparing corrosion front velocities and concentration profiles obtained by phase-shift interferometry with theoretical predictions, it is demonstrated that this process is well-described by a one-dimensional mean-field model for the generic reaction A + B (static) → C (inert) with only one diffusing reactant (cupric chloride) and one static reactant (copper) reacting to produce an inert product (cuprous chloride). The interpretation of the experiments is aided by a mathematical analysis of the model equations, which allows the reaction order and the transference number of the diffusing species to be inferred. Physical arguments are given to explain the surprising relevance of the one-dimensional mean-field model in spite of the complex (fractal) structure of the copper clusters.