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Role of linear charge density and counterion quality in thermodynamic properties of strong acid type polyelectrolytes: divalent transition metal cations.Horvath J, Nagy M Institute of Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112, Hungary. holmes@ludens.elte.hu Thermodynamic properties of aqueous solutions of poly[(vinyl alcohol)-co-(vinyl sulfate)] (PVAS) copolymer polyelectrolytes with divalent transition metal (Co(II), Ni(II), and Cu(II)) counterions have been determined by the gel deswelling method in the concentration range of 0.0005-0.12 mol of counterion/kg of water (0.09-9 w/w% of the polymer). The influence of the chemical nature of the counterion as well as the effect of the composition of the copolymer from small to medium linear charge density have been systematically studied. Solvent activity, reduced osmotic pressure, the Flory-Huggins pair interaction parameter, rational osmotic coefficients, and degrees of dissociation were calculated from the measured data. No difference could have been observed between the three counterions. Reduced osmotic pressure curves are found to be convex from above, as for Na+ counterions studied previously, which is contrary to the usual behavior of neutral polymers. Intercepts are increasing, and the calculated apparent molar masses and degrees of dissociation at infinite dilution are decreasing with increasing linear charge density of the polyelectrolytes. The pair interaction parameters show a considerable negative deviation from linearity, except for the high volume fraction region. From the differences, concentration dependence of degrees of dissociation could have been calculated. The values at infinite dilution are in good agreement with those obtained from the intercepts of the reduced osmotic pressure curves. Degrees of dissociation seem to decrease approximately linearly with increasing concentration and reach zero at finite concentrations. Rational osmotic coefficients have been calculated in three different ways, both regarding and neglecting the change in the degrees of dissociation. Published 12 December 2006 in Langmuir, 22(26): 10963-71.
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