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Center of Gravity (COG) Method as a Tool in Processing of Voltammetric Signals

机译：重心（COG）方法作为伏安信号处理工具

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The center of gravity method (COG) was applied (for the first time) in voltammetry (polarography) as a tool for very precise determination of peak potentials, and signal shifts. Basically, the adjustment of the method consists of finding the optimal fraction of the peak that contains information about peak position, either of original signal or of its 1(st) or 2(nd) derivatives, along with optimal selection of parameters for SavitzkyGolay smoothing of original curves and elimination of baseline influence. The principle of the method and its validation were demonstrated and checked on simulated differential pulse polarograms (DPP) representing a series of curves for the determination of stability constants of labile metal complexes (DeFord-Hume method). It was shown that COG outperforms the classical one-point method (OPM) in precision and accuracy, providing excellent results even if a very large step potential (e.g. 10mV) was used. The problems of reduced accuracy and precision in case of curved (non-ideal) baseline and asymmetric peaks were successfully overcome by applying COG on curves transformed by 1(st) and/or 2(nd) derivatives. The method was additionally examined in details on a simple experimental dataset of cadmium chloride complexes in 4moldm(-3) ionic strength solution and on a more complex dataset of uranyl selenate complexes in 3moldm(-3) ionic strength solution. Stability constants obtained by COG agree well with those in the literature with much better precision than the classical one-point method (checked by standard error of the fit).
机译：重心法（COG）在伏安法（极谱法）中首次（首次使用）是一种非常精确地确定峰值电势和信号偏移的工具。基本上，该方法的调整包括找到包含原始信号或其1（st）或2（nd）导数的峰位置信息的峰的最佳部分，以及用于SavitzkyGolay平滑的参数的最佳选择原始曲线和消除基线影响。演示了该方法的原理及其验证，并在模拟微分脉冲极谱图（DPP）上进行了检验，该曲线代表了确定不稳定金属络合物稳定常数的一系列曲线（DeFord-Hume方法）。结果表明，即使在使用非常大的步进电位（例如10mV）时，COG的精度和准确性也优于传统的单点方法（OPM），可提供出色的结果。通过将COG应用于由1（st）和/或2（nd）导数转换的曲线，可以成功克服在弯曲（非理想）基线和不对称峰的情况下降低精度和精度的问题。该方法还另外在4moldm（-3）离子强度溶液中的氯化镉配合物的简单实验数据集和3moldm（-3）离子强度溶液中的更复杂的铀酰硒酸酯配合物的详细实验数据中进行了详细检查。通过COG获得的稳定常数与文献中的稳定常数相比较，其精度要比经典的单点方法好得多（通过拟合的标准误差检查）。

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