Alexe-Ionescu A L, Barbero G, Lelidis I
Faculty of Applied Sciences, University Politehnica of Bucharest, Splaiul Independentei 313, 060042 Bucharest, Romania.
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy.
J Chem Phys. 2014 Aug 28;141(8):084505. doi: 10.1063/1.4893712.
We consider the influence of the spatial dependence of the ions distribution on the effective dielectric constant of an electrolytic solution. We show that in the linear version of the Poisson-Nernst-Planck model, the effective dielectric constant of the solution has to be considered independent of any ionic distribution induced by the external field. This result follows from the fact that, in the linear approximation of the Poisson-Nernst-Planck model, the redistribution of the ions in the solvent due to the external field gives rise to a variation of the dielectric constant that is of the first order in the effective potential, and therefore it has to be neglected in the Poisson's equation that relates the actual electric potential across the electrolytic cell to the bulk density of ions. The analysis is performed in the case where the electrodes are perfectly blocking and the adsorption at the electrodes is negligible, and in the absence of any ion dissociation-recombination effect.
我们考虑离子分布的空间依赖性对电解液有效介电常数的影响。我们表明,在泊松 - 能斯特 - 普朗克模型的线性版本中,必须认为溶液的有效介电常数与外部场引起的任何离子分布无关。这一结果源于以下事实:在泊松 - 能斯特 - 普朗克模型的线性近似中,由于外部场导致溶剂中离子的重新分布会引起介电常数的变化,该变化在有效势中为一阶,因此在将电解池两端的实际电势与离子体密度联系起来的泊松方程中必须忽略不计。该分析是在电极完全阻挡且电极上的吸附可忽略不计,以及不存在任何离子解离 - 重组效应的情况下进行的。