Preferential solvation of ions in mixed solvents. 5. The alkali metal, silver, and Thallium(I) cations in aqueous organic solvents according to the inverse kirkwood-buff integral (IKBI) approach

被引:14
|
作者
Marcus, Yizhak [1 ]
机构
[1] Hebrew Univ Jerusalem, Dept Inorgan & Analyt Chem, IL-91904 Jerusalem, Israel
关键词
aqueous-organic solvent mixtures; Kirkwood-Buff integrals; preferential solvation; univalent cations;
D O I
10.1007/s10953-007-9196-4
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
The inverse Kirkwood-Buff integral (IKBI) approach is applied, as far as the relevant data exist in the literature, to the preferential solvation of Li-+,Li- Na+ K+ Rb+ Cs+ Ag+ and Tl+ in aqueous mixtures of methanol, ethanol, 1,2-ethanediol (EG), acetonitrile, formamide, N,N,-dimethylformamide (DMF), N,N,N',N',N",N"-hexamethyl phosphoric triamide (HMPT), and dimethyl sulfoxide (DMSO). In aqueous EG and formamide the preferential solvation is very small. Water is the preferred solvent in the solvation shells in aqueous methanol, ethanol and acetonitrile (except for Ag+ in the latter solvent) but the co-solvent is preferred in aqueous mixtures of DMF, HMPT, and DMSO over most or all of the composition range. For the latter three mixtures the larger donicity of the co-solvents causes their preference, whereas where water is preferred over other protic solvents, it is the small size of the water molecules that appears to be the cause.
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页码:1385 / 1399
页数:15
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