Abstract
Use has been made of the affinity of silver ions for a large variety of organic solvents to study the nature of solvation and its effects on the dissociation of electrolytes and their ionic radii. The conductivities of silver perchlorate, nitrate and nitrite have been studied in a variety of solvents and binary solvent mixtures. The large majority of the binary solvent mixtures have been of the type where one component was present in large excess of the other and the minor component exhibited a strong affinity for silver ions. The results have been interpreted in the light of modern electrolyte theory and values of the dissociation constant, Stokes radius and Bjerrum parameter have been calculated for all the solutions investigated. The effect of benzene as an additive to solutions of silver perchlorate in acetone, has been observed to be very small compared with the effects of organic bases, cyclopentadiene, dicyclopentadiene and polystyrene. These very small conductivity changes induced by benzene have been measured at high frequencies using an oscilloscope as a detector unit, and have been explained on the basis of the formation of loose aggregates of benzene molecules round silver ions as opposed to the. formation of stoichiometric complex ions for the other additives. The conductivity of silver perchlorate in pure and binary mixtures of solvents having closely similar dielectric constants has also been studied in order to eliminate the effect of variation of the dielectric constant in the immediate vicinity of a solvated ion. The Walden products for these solutions were found to conform more closely to constancy when divided by the dielectric constant but no theoretical explanation has been found for this.