Nonaqueous solutions association behavior

In aqueous electrolyte solutions the molar conductivities of the electrolyte. A, and of individual ions, Xj, always increase with decreasing solute concentration [cf. Eq. (7.11) for solutions of weak electrolytes, and Eq. (7.14) for solutions of strong electrolytes]. In nonaqueous solutions even this rule fails, and in some cases maxima and minima appear in the plots of A vs. c (Eig. 8.1). This tendency becomes stronger in solvents with low permittivity. This anomalons behavior of the nonaqueous solutions can be explained in terms of the various equilibria for ionic association (ion pairs or triplets) and complex formation. It is for the same reason that concentration changes often cause a drastic change in transport numbers of individual ions, which in some cases even assume values less than zero or more than unity. 

The properties of ionic polymers in nonaqueous media have only recently become the subject of systematic studies. In solvents of low dielectric constant, salt groups resist dissociation and are poorly solvated. Thus, ionic moieties promote intra- and inter-polymer association in organic solvents. The tendency of ionic groups to aggregate or cluster resembles the coalescence of such groups in reversed micelles. Similar considerations underly the formation of ionic "cross-links" that modify the behavior of ionomers in the solid state. Solutions of polyions in nonaqueous media thus provide systems in which a powerful array of experimental techniques can be used to probe phenomena that are important to the bulk properties of a commercially important group of materials. The article by Teyssie and Varoqui in Part IV describe significant explorations in this novel field. 

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