期刊
FLUID PHASE EQUILIBRIA
卷 186, 期 1-2, 页码 103-122出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/S0378-3812(01)00507-6
关键词
dielectric constant; mixed solvents; electrolyte solutions; ion pairing; ion solvation
A general model has been developed for calculating the static dielectric constant of mixed-solvent electrolyte solutions. For mixtures of solvents without electrolyte components, the model is based on an empirical modification of the Kirkwood theory for multicomponent systems. For systems containing electrolytes, the model takes into account the effects of ions and ion pairs and, therefore. it is capable of reproducing the dependence of the dielectric constant on electrolyte concentration. For most solvent mixtures, dielectric constants can be reasonably predicted using only pure solvent properties. In the case of strongly nonideal solvent mixtures, the results can be significantly improved by adjusting a single binary parameter. The model has also been verified for a number of electrolyte solutions in various solvents over wide composition and temperature ranges. In particular, the increase in the dielectric constant due to ion pairing and its decrease due to the presence of ions and their solvation can be accurately represented. (C) 2001 Elsevier Science B.V. All rights reserved.
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