Physical Electrochemistry of Solutions of Strong Electrolytes (Partial dissociation and hydration from "zero to saturation")

Abstract

The near-success of the Debye-Hückel (DH) theory of interionic interaction for the non-ideality of very dilute solutions led scientists to assume that strong electrolytes are completely dissociated in water at all concentrations. Consequently, the DH equations were gradually extended to fit the data for higher concentrations until they became too complex to have any physical significance. A systematic research into the earlier ideas was therefore undertaken by the author and the results, summarized here, show unambiguously that non-ideality is indeed due to partial dissociation and hydration. With the degrees of dissociation and hydration numbers calculated from the osmotic coefficient data, simple mathematical relations are shown to account quantitatively for many solution properties even up to saturation.