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

Abstract

The selective solvation behavior of sllver(I) sulfate and sllver(I) acetate has been studied In the binary solvent mixtures dioxane + acetonitrile (AN) and dioxane + dimethyl sulfoxide (Me2SO) at 30 °C by solubility and emf measurements. The solubility of both salts Increases continuously with the addition of AN or Me2SO and these data were used to calculate the Gibbs transfer energies of the salts from dioxane to Its mlxures with AN and Me2SO. The transfer energies of the salts were split Into their Ionic contributions by using the transfer energies of the silver Ion In these mixtures determined on the basis of negligible liquid Junction potential (nLJP) method. The solvent transport numbers A of AN and Me2SO have been determined by emf measurements using a galvanic cell with transference. The results have been Interpreted In terms of a heteroselectlve solvation of the salts with the silver ion being selectively solvated by AN or Me2SO and the anions by dioxane.

Ion Solvation of Some Copper(II) Salts in Water + N-Methyl-2-pyrrolidinone Solvent Mixtures at 30 °C

“…The solvent transport number of NMP (∆ NMP ) was evaluated from the emf data of cell B using the relation In eq 6, x′ N ′ MP and x′ NMP represent the mole fractions of NMP in the two half-cells of cell B, x NMP ) (x′ N ′ MP + x′ NMP )/2, and f NMP is the rational activity coefficient of NMP referred to pure water as the standard state. E refers to the emf of cell B, F is the Faraday constant, R is the gas constant, and T is the temperature in degrees Kelvin (Rajendran and Kalidas, 1986). In view of the nonavailability of vapor pressure data of water + NMP mixtures, a quantity ∆′ defined by was calculated.…”

Preferential solvation of some silver(I) salts in iso‐dielectric mixtures of methanol and N‐Methyl‐2‐pyrrolidinone at 30°

“…(1) and (2) XkMp and XgMP are the mole fractions of NMP in the two half cells and XNMP(ave) = X h p + XfjMp/2 and all other terms have their usual significance [16]. Because the vapour pressure data of methanol + NMP mixtures are not available, the term d In fNMP/d In XNMp was not evaluated and instead A' was calculated from the experimental EMF.…”