Abstract:

In accordance with the physical picture of boundary layer in the stationary electrode processes with hysteretic diffusion-convection transport we suggest a simple stochastic model to describe this kind of electrode reaction system including the effect of non-equilibrium fluctuations. As a result, a stochastic thermodynamics is established for the concentration polarization arising from hysteresis of the diffusion-convection. Based on it, we further show that the non-Nernst concentration polarization originates in the non-equilibrium fluctuation which departs from the Poisson distributions and even from the central limit theorem, but decreases by the convection companying with diffusion. An example is also given to illustrate the stochastic calculation of the non-Nernst concentration polarization affected by convection.

Key words: Electrode process with hysteretic diffusion-convection, Stochastic modeling, Non-Poisson fluctuation, Non-Nernst concentration polarization, Stochastic thermodynamics