Hofmeister effects in surface tension of aqueous electrolyte solution
Hofmeister effects in surface tension of aqueous electrolyte solution
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DOI：
10.1021/la047437v
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发表时间：
2005-03-15
期刊：
影响因子：
3.9
通讯作者：
Ninham, BW
中科院分区：
文献类型：
--
作者：
Boström, M;Kunz, W;Ninham, BW
电解质溶液的表面张力表现出明显的特殊离子效应。我们在这里展示了离子溶剂化能和离子色散势在确定盐溶液的离子比表面张力中的重要作用。当离子从体溶液进入界面区时，离子的自自由能随其水密度分布的减小而变化。我们将证明不同离子的溶剂化能与盐溶液的表面张力有很好的相关性。包含这种与距离相关的自自由能贡献带来了与实验和正确的霍夫迈斯特级数的定性一致。这不仅适用于表面张力的变化，也适用于测量的表面电位。离子分散相互作用势的引入进一步提高了与实验的一致性。我们讨论了如何在盐的表面张力理论上取得进一步的进展。
The surface tension of electrolyte solutions shows marked specific ion effects. We here show an important role for both ionic solvation energies and ionic dispersion potentials in determining this ion specific surface tension of salt solutions. The ion self-free energy changes when an ion moves from bulk solution into the interfacial region, with its decreasing water density profile. We will show that the solvation energies of different ions correlate very well with the surface tension of salt solutions. Inclusion of this distance-dependent self-free energy contribution brings qualitative agreement with experiments and the right Hoffmeister series. This is so not only for surface tension changes but also for measured surface potentials. The inclusion of ionic dispersion interaction potentials further improves the agreement with experiments. We discuss how further progress in the theory of the surface tension of salts can be achieved.