Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, United Kingdom OX1 3QZ.
J Phys Chem B. 2010 Apr 8;114(13):4521-8. doi: 10.1021/jp911986k.
A Nernst-Planck-Poisson finite difference simulation is used to model the dynamic evolution of a series of liquid junctions of the type A(+)X(-)|B(+)Y(-), in which all ionic species are monovalent and present in equal concentration (a subset of Lingane's type 3), from a nonequilibrium initial condition to a condition of steady-state potential difference. Simulations are performed in a linear space without constrained diffusion. Analysis of the dynamics shows very good agreement with recently presented revisions for the type 1 and 2 cases [ J. Phys. Chem. B 2010 , 114 , 187 - 197 ] Considerable deviation of the value of the limiting liquid junction potential from that predicted by the classical Henderson equation [ Z. Phys. Chem. 1907 , 59 , 118 - 127 ] is shown in many cases and investigated as a function of the size of the various diffusion coefficients. Significantly, the formation of a "multilayer liquid junction", characterized by the existence of more than one instantaneous point of electroneutrality and thus more than one stationary point in the electric field (in a finite range of space), is inferred for the first time in a number of cases. The conditions for such a multilayer liquid junction are determined.
采用 Nernst-Planck-Poisson 有限差分模拟方法，对一系列类型为 A(+)X(-)|B(+)Y(-)的液体界面的动态演化进行建模，其中所有离子物种均为单价且浓度相等（Lingane 类型 3 的子集），从非平衡初始条件到稳定状态的电位差条件。模拟在没有约束扩散的线性空间中进行。动力学分析与最近提出的类型 1 和 2 情况的修订版非常吻合[J. Phys. Chem. B 2010, 114, 187-197]。在许多情况下，发现极限液体结电位的值与经典 Henderson 方程[Z. Phys. Chem. 1907, 59, 118-127]的预测值有很大偏差，并研究了其与各种扩散系数大小的关系。重要的是，首次在多种情况下推断出存在多个瞬时电中性点，从而在电场中存在多个稳定点（在有限的空间范围内）的“多层液体结”的形成。确定了形成多层液体结的条件。
