Preferential Solvation of Ag(I) Bromate and Iodate in Dimethyl Sulfoxide–Water Mixtures

Abstract

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.

Selective Solvation of Some Silver(I) Salts in Water‐Pyridine Mixtures at 30°C

“…Silver sulfate (S. Merck, Baroda) was dried over P205 under vacuum before use. Silver bromate and iodate were prepared as described earlier [4]. Silver perchlorate was prepared as described previously [lo].…”

“…These values of AR and a, are remarkably high, what may be the reason for the tendency of Hg-atoms to form dimers in the vapour phase on account of dispersion interactions. However, the values of AR and V, do not coincide with the correlation line: Vc/cm3 mol-' = 31.68(3.09) + 10.53(21)AR (&)/cm' mol-' given in [4]. Perhaps relativistic chemical effects of heavy atoms, which are discussed only recently (e.g.…”

“…Some technological applications relating to the electrorefining of silver(1) and copper(1) salts have been suggested on the basis of this principle [I -31. In earlier communications from this laboratory, the selective solvation of some silver salts in the binary protic-dipolar aprotic solvent mixtures of water-DMSO [4], water-AN [S] and water-DMF [6] mixtures has been reported. However, practically no such investigations have yet been reported in nitrogen containing solvents, where the nitrogen forms part of a heterocyclic moiety, and their aqueous mixtures, such as waterpyridine (Py) mixtures.…”

Solvation energies and solvent transport numbers of silver(I) sulfate and silver(I) acetate in acetonitrile, dimethyl sulfoxide, and their mixtures with dioxane

“…In earlier communications from this laboratory, the preferential solvation of some silver balates in the binary protlc-dlpolar aprotic solvent mixtures of water + Me2SO (6), methanol + Me2SO (7), and water + AN (8) has been reported. The present work deals with the selective solvation behavior of silver(I) sulfate and silver(I) acetate in the mixed solvent systems, viz., dioxane + AN and dioxane + Me2SO in order to elucidate the nature of ion-solvent interactions in these mixtures and further to understand the effect of replacement of the protic component by an aprotic component, viz., dioxane on ion solvation.…”

Limiting partial molar volumes of Potassium aluminium sulphate in dimethyl sulphoxide + water at different temperatures

“…Ion-solvation [2][3][4] and electrochemical studies [5][6] in aqueous-DMSO are popular. So the thermodynamics of ion-solvent interaction in this system is of considerable importance.…”