What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.
What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.
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DOI：
10.1039/c7sc02691a
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发表时间：
2017-10-01
期刊：
影响因子：
8.4
通讯作者：
Craig VSJ
中科院分区：
文献类型：
--
作者：
Mazzini V;Craig VSJ
许多溶剂中离子特异性的一致趋势。电解质溶液的重要性怎么强调都不过分。除了电解质溶液的离子强度之外，存在的离子的特定性质在控制许多性质方面是至关重要的。因此，离子特异性在物理化学、工程和生物学中具有根本重要性。观察到的离子的影响的强度往往遵循既定的系列表明，一个单一的预测和定量描述的特定离子的影响，涵盖了广泛的系统是可能的。这样的理论将彻底改变物理化学的应用，从聚合物沉淀到药物设计。目前理解特定离子效应的方法包括考虑离子本身、溶剂和相关界面以及它们之间的相互作用。本文研究了电解质在水和十一种非水溶剂中的标准偏摩尔体积和电致伸缩体积的比离子效应趋势。我们选择这些措施，因为它们与无限稀释时的本体性质有关，因此它们是最简单的电解质系统。这样做是为了测试的假设，即单独的离子表现出一个特定的离子效应系列，是独立的溶剂和无关的表面性能。在这项工作中检查的标准偏摩尔体积和归一化的电致伸缩体积的特定离子效应的趋势显示了一个基本的离子特定的系列，是跨溶剂，这是Hofmeister系列的阴离子和阳离子的反向溶致系列，支持的假设。这一结果是重要的，在证明离子特异性，观察到在无限稀释，并表明，在一个非常广泛的系统中的特定离子效应的表现形式中观察到的复杂性是由于扰动的溶剂，表面和浓度上的基本系列。这方面的知识将指导一般的理解特定的离子效应，并协助发展的定量预测理论的离子特异性。
Consistent trends in ion-specificity across many solvents. The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.
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影响因子：
4.4
作者：
DESNOYER, JE;VERRALL, RE;CONWAY, BE
通讯作者：
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影响因子：
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通讯作者：
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