对流扩散传质滞后的电极过程中之非Poisson涨落与非Nernst浓度极化

根据对流扩散传质滞后的恒稳电极过程中边界层的物理图像, 提出了该类电极过程的简化随机模型, 建立了相应的浓度极化的随机热力学理论, 揭示了非Nernst浓度极化来自于随电流密度增大电极化学反应体系涨落分布的非Poisson化与对中心极限律的偏离, 进一步阐明了与滞后的扩散步骤共存的对流传质对非Nernst浓度极化的效应及其规律. 同时, 给出了对流引起的非Nernst浓度极化的随机热力学算例.

Non-Poisson Fluctuation and Non-Nernst Concentration Polarization in Irreversible Electrode Processes with Hysteretic Diffusion-convection Transport

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 ...