The selective solvation of Ag(I) bromate and iodate was studied in dimethyl sulfoxide–water mixtures at 30 °C by solubility and EMF measurements. The solubility of silver bromate decreases down to XDmso=0.2 and thereafter increases with addition of dimethyl sulfoxide, the solubility of silver iodate continuously decreasing under the same conditions. The transfer free energy of silver cation decreases while that of halate ions increases with the addition of dimethyl sulfoxide. The solvent transport number, Δ, passes through a maximum around XDmso=0.5 in both cases. These results were interpreted in terms of a heteroselective solvation of both the salts, the silver ion being preferentially solvated by dimethyl sulfoxide and the halate ions selectively hydrated by water in the mixtures.

The solubiltiy of silver bromate, the Gibbs transfer energy of Ag

No abstract

The conductances of silver (I) perchlorate, nitrate and bromate have been determined in water‐dimethylsulfoxide (DMSO) mixtures at 30°C over the complete range of solvent compositions. The data were analyzed by the 1980 Fuoss equation and the limiting molar conductances (<Λ0) and association constants (KA) of the salts were evaluated at all compositions. The Λ0 values have been split into their ionic values and the ionic Walden products of all the ions were calculated using the transference number data derived from a concentration cell with transference. The initial increase of the Walden product of silver ion up to 20 wt% DMSO and its subsequent decrease beyond this composition with addition of DMSO, indicates that it is preferentially solvated by water at high compositions of water and subsequently by DMSO. For anions, the Walden products vary in a complex manner and seem to be strongly influenced by solvent‐solvent interactions.

Mittels EMK‐ und Löslichkeitsmessungen wird die Lösungsmitteltransportzahl von DMSO und die Gibbs′sche Solvatationsenergie von Silberacetat in den binären Lösungsmittel systemen HzO/DMSO und MeOH/DMSO er‐ 21 mittelt.