Selective solvation of silver(I) bromate in methanol—acetonitrile and ethanol—acetonitrile mixtures at 30°C

Abstract

The selective solvation of silver(I) bromate in the binary solvent mixtures of methanol + acetonitrile and ethanol + acetonitrile has been studied at 30°C by solubility and emf measurements. The solubility of the salt increases with the addition of acetonitrile up to a mole fraction ( X AN) of 0.6 and 0.7 in the case of methanol + acetonitrile and ethanol + acetonitrile respectively and then decreases with further addition of the same. The transfer free energy of the silver ion (molal scale) decreases continuously with the addition of acetonitrile in both the mixtures. The transfer free energies of bromate ion (molal scale) are found to be quite small up to X AN ≈ 0.7 in both methanol + acetonitrile and ethanol + acetonitrile mixtures and then increase. The solvent transport number Δ, of acetonitrile is positive with a maximum at X AN = 0.55 (Δ = 2.7) and at X AN = 0.45 (Δ = 2.2) for methanol + acetonitrile and ethanol + acetonitrile systems respectively. These results have been interpreted as arising due to a heteroselective solvation of the salt with the silver ion being preferentially solvated by acetonitrile and the bromate ion by the amphiprotic component which is marked especially at higher compositions.