Surface and interfacial tensions of Hofmeister electrolytes

被引:50
作者
dos Santos, Alexandre P. [1 ]
Levin, Yan [1 ]
机构
[1] Univ Fed Rio Grande do Sul, Inst Fis, BR-91501970 Porto Alegre, RS, Brazil
关键词
MOLECULAR-DYNAMICS SIMULATIONS; WATER LIQUID/VAPOR INTERFACE; DENSITY-FUNCTIONAL THEORY; AIR/WATER INTERFACE; AQUEOUS-SOLUTION; SALT-SOLUTIONS; THERMODYNAMIC QUANTITIES; HYDRATED PROTON; VAPOR INTERFACE; IONS;
D O I
10.1039/c2fd20067h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present a theory that is able to account quantitatively for the surface and interfacial tensions of different electrolyte solutions. It is found that near the interface, ions can be separated into two classes: the kosmotropes and the chaotropes. While the kosmotropes remain hydrated near the interface and are repelled from it, the chaotropes loose their hydration sheath and become adsorbed to the surface. The anionic adsorption is strongly correlated with the Jones-Dole viscosity B-coefficient. Both hydration and polarizability must be taken into account to obtain a quantitative agreement with the experiments. To calculate the excess interfacial tension of the oil-electrolyte interface, the dispersion interactions must also be included. The theory can also be used to calculate the surface and the interfacial tensions of acid solutions, predicting a strong surface adsorption of hydronium ion.
引用
收藏
页码:75 / 87
页数:13
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