Transference numbers, polyion mobilities, and charge fractions in aqueous solutions of lithium, sodium, and potassium...

Results of Hittorf type transference number measurements are reported for aqueous solutions of lithium, sodium, and potassium dextransulfate (DS) in the concentration range 0.008-0.09 moles of sulfate groups per liter. The results for the polyion transference number are combined with equivalent conductance measurements reported earlier to calculate the polyion equivalent conductance, and the polyion charge fraction based on Wall's method. Our results show that the transference number of this high charge density polyion is larger than unity over the entire concentration range studied, and decreases monotonously with increasing concentration. The calculated charge fraction f of the polyion increases with increasing concentration, and at any concentration/decreases in the order LiDS > NaDS > KDS. A comparison between the conclusions derived from these transport experiments and from both mean and single ion activity measurements in dextransulfate solutions shows the considerable uncertainties involved in either of these methods, and emphasizes the need for the application of a variety of techniques, including spectroscopic techniques, to determine differential ion binding by polyions.