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首页> 外文期刊>Environmental Science & Technology >Kinetic limitations in measuring stabilities of metal complexes by Competitive Ligand Exchange-Adsorptive Stripping Voltammetry (CLE-AdSV)
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Kinetic limitations in measuring stabilities of metal complexes by Competitive Ligand Exchange-Adsorptive Stripping Voltammetry (CLE-AdSV)

机译：竞争性配体交换-吸附溶出伏安法（CLE-AdSV）测定金属配合物稳定性的动力学限制

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摘要

The kinetic limitations of Competitive Ligand Exchange-Adsorptive Stripping Voltammetry, CLE-AdSV, for the determination of very stable metal complexes are explained in detail. For a given type of metal, from a certain lower limit of the complex stability constant, K, the usual simple equilibrium interpretation of CLE-AdSV measurements is not generally valid. By critical assessment of data for natural waters we show that in many cases the reported stability constants appear to derive from nonequilibrium conditions in the bulk sample and hence overestimate the real values. Fe(Ill) is a special case due to the particular kinetic features of hydroxide as a ligand. Our results call for validation of such data by analysis on the basis of the kinetics involved and/or by independent kinetic-free experimental approaches. Earlier speculations from CLE-AdSV results on very strong ligands and derived features such as the potential bioavailability of trace metals in natural waters require reconsideration.
机译：详细解释了竞争性配体交换-吸附溶出伏安法CLE-AdSV的动力学局限性。对于给定类型的金属，从复杂稳定常数K的某个下限开始，通常对CLE-AdSV测量的简单平衡解释是无效的。通过对天然水的数据进行严格评估，我们表明，在许多情况下，所报告的稳定性常数似乎源于大量样品中的非平衡条件，因此高估了实际价值。由于氢氧化物作为配体的特殊动力学特征，Fe（III）是一种特殊情况。我们的结果要求通过对所涉及的动力学进行分析和/或通过独立的无动力学实验方法来验证此类数据。 CLE-AdSV的早期推测是关于非常强的配体和衍生特征（例如天然水中痕量金属的潜在生物利用度）需要重新考虑的。

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