Quantitative model of electrochemical Ostwald ripening and its application to the time-dependent electrode potential of nanocrystalline metals

The contact of a metastable nanocrystalline metal ensemble with a metal ion electrolyte leads to an electrochemical Ostwald ripening. The kinetics is modeled on the level of irreversible thermodynamics for the case that the rate is controlled by the electrode/electrolyte transfer resistance. In particular, the kinetic behavior of medium-sized particles and the time dependence of the electromotive force is investigated. Even though it is expressed in electrochemical terms (mixed potential), the modeling is also applicable to chemical Ostwald ripening as long as it is interfacially controlled. Under these conditions, the kinetics exhibits, even though not self-accelerating, strong similarities to selection dynamics, with the competition stemming from the cannibalistic nature of the process.