Polarization induced by external noise in irreversible electrode processes: A stochastic measure of thermodynamic effects driven by external noise in electro-chemical reaction systems
Polarization induced by external noise in irreversible electrode processes: A stochastic measure of thermodynamic effects driven by external noise in electro-chemical reaction systems
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DOI：
10.1063/1.1447910
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发表时间：
2002-03
影响因子：
4.4
通讯作者：
N. Zhao;Jiuli Luo
中科院分区：
文献类型：
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作者：
N. Zhao;Jiuli Luo
本文建立了受外界噪声影响的有限电化学反应体系的随机热力学。基于参数噪声驱动的不可逆电极过程的一般随机模型，讨论了这类重要的物理化学系统的波动和耗散。结果表明，在不可逆电极过程中，由外部噪声引起的额外极化是不可避免的。此外，还提出了一种定量估计稳态不可逆电极过程中由高斯白噪声引起的浓度极化和激活极化的完备形式。结果表明，即使在热力学极限下，噪声驱动极化的阶数也可以达到噪声强度的水平。并给出了在不同情况下加性噪声和乘性噪声驱动下的极化计算实例。本文提出的作为高斯白噪声诱导极化的随机度量的形式化方法，有助于在物理化学中进一步研究和普遍利用这种噪声驱动的电化学效应。
A stochastic thermodynamics of finite electrochemical reaction systems affected by external noise has been established in this article. Based on a general stochastic model of the irreversible electrode processes driven by parameter noise, both the fluctuation and the dissipation in this kind of important physico-chemical system are discussed. It shows that an additional polarization induced by external noise in irreversible electrode processes is inevitable. Furthermore, a perfect formalism to estimate quantitatively both the concentration polarization and the activation polarization induced by a Gaussian white noise in the steady irreversible electrode process has been proposed. It turns out that the order of this noise-driven polarization could arrive at the level as noise intensity even in thermodynamic limit. Some illustrations to calculate the polarizations driven by the additive noise and the multiplicative noise in different cases are also given categorically. The formalism as a stochastic measure of the polarization induced by Gaussian white noise proposed in this article is helpful to further study and utilize generally this electrochemical effect driven by noise in physical chemistry.