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The results of conductance and transference measurements on dilute, salt-free aqueous solutions of poly(4-vinyl-N-n-butyl pyridinium bromide) and poly(vinylbenzy1 trimethyl ammonium chloride) are recorded. From conductance and transference data the charge fraction of the polyions is found to remain essentially constant with dilution down to concentrations of less than 10-4 equiv/l. The principles of the methods used and the experimental details are critically discussed and the results compared with recent theories of ion binding in polyelectrolyte solutions. The effects of the dielectric constant of the solvent and of the temperature have been briefly studied and factors influencing the electrochemical properties of polyelectrolyte solutions are discussed.

Equivalent conductances and transference numbers were determined in dilute aqueous solutions of isotactic and atactic poly(styrene sulphonic acid) and of the corresponding sodium salts. The polyion mobilities in the polyacid and polysalt solutions differed significantly although the mobilities were independent of the stereoregularity of the polyion. The results obtained are interpreted in terms of the counterion association and of the counter ion retardation models.

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