Estimating the solubility of 1:1 electrolyte aqueous solutions: the chemical potential difference rule

被引：23
作者：
Benavides, A. L. [1 ]
Portillo, M. A. [2 ]
Abascal, J. L. F. [2 ]
Vega, C. [2 ]
机构：
[1] Univ Guanajuato, Div Ciencias Ingn, Guanajuato, Mexico
[2] Univ Complutense Madrid, Fac Ciencias Quim, Dept Quim Fis, E-28040 Madrid, Spain
来源：
MOLECULAR PHYSICS | 2017年 / 115卷 / 9-12期
关键词：
Solubility; 1:1 electrolyte aqueous solutions; simulation; MOLECULAR-DYNAMICS SIMULATIONS; ALKALI-HALIDES; FREE-ENERGY; SODIUM-CHLORIDE; FORCE-FIELD; BIOMOLECULAR SIMULATIONS; COMPUTER-SIMULATION; NACL SOLUTIONS; WATER; PHASE;
D O I：
10.1080/00268976.2017.1288939
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：
A simple empirical rule to estimate the solubility of force fields of 1:1 aqueous electrolyte solutions at ambient conditions is proposed. The empirical prescription states that the logarithm of the solubility can be described by a second-order polynomial of the chemical potential difference of the salt in the solid and the salt in the standard state in solution. The rule will be denoted as the chemical potential difference rule . It is shown that the recipe is able to provide reasonable values of the solubility of 1:1 aqueous electrolytes (having the NaCl structure in the solid phase) for a number of different force fields for which the solubility has been computed in a rigorous way. This clearly indicates that reproducing only the experimental values of the free energy of hydration of ions at infinite dilution (which yield the standard state chemical potential of the salt in water) is not enough to foresee the experimental values of the solubility. The difference between the chemical potential of the salt in the solid phase and in the standard state seems to be the variable that controls the value of the solubility. This finding should be taken into account in the future when developing force fields for 1:1 electrolytes in water aimed at reproducing the experimental solubilities. [GRAPHICS] .
引用
收藏
页码：1301 / 1308
页数：8
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