Anodic Stripping Voltammetry at Hydrodynamic Mercury Electrodes. Square Wave Voltammetry: Numerical Theory for Electrochemically Reversible Systems
Anodic Stripping Voltammetry at Hydrodynamic Mercury Electrodes. Square Wave Voltammetry: Numerical Theory for Electrochemically Reversible Systems
复制标题
流体动力汞电极的阳极溶出伏安法。
DOI：
10.1021/jp980749k
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发表时间：
1998
影响因子：
3.3
通讯作者：
R. Compton
中科院分区：
文献类型：
--
作者：
J. C. Ball;R. Compton
利用随时间变化的向后隐式方法的数值模拟被用来开发方波伏安法的理论，适用于电化学可逆过程进行阳极剥离在平面汞电极具有任意的膜和扩散层厚度。计算使用的时间尺度扭曲，以反映在短时间内的瞬态响应的科特里性质被发现是非常有效的，当应用到这个问题。对于溶液相中半无限扩散的极限情况，注意到与现有分析理论的极好一致性（Kounaves等人，Anal. 1987，59，386）。脉冲频率的影响进行了研究，特别是扩散层厚度的影响，其特征在于。偏离半无限理论的预测和合理化的情况下，后者的幅度是可比的溶液相物种的扩散长度在一个单一的脉冲宽度可能会发生.
Numerical simulations exploiting the time-dependent backward implicit method are used to develop the theory of square wave voltammetry as applied to electrochemically reversible processes undergoing anodic stripping at planar mercury electrodes having arbitrary film and diffusion layer thicknesses. Computations made using a time scale distorted to reflect the Cottrellian character of the transient response at short times are found to be extremely efficient when applied to this problem. For the limiting case of semi-infinite diffusion in the solution phase, excellent agreement with existing analytical theory is noted (Kounaves et al. Anal. Chem. 1987, 59, 386). The effects of the pulse frequency are investigated and, in particular, the effect of diffusion layer thickness characterized. Deviations from semi-infinite theory are predicted and rationalized for the case when the magnitude of the latter is comparable to the diffusion length of the solution-phase species during a single pulse width as might occur...