Journal of Chemical Thermodynamics, Vol.101, 227-235, 2016
Thermodynamic, transport and frictional properties in semidilute aqueous sodium carboxymethylcellulose solution
Electrical conductivities of aqueous solutions of an anionic polyelectrolyte sodium carboxymethylcellulose with different degrees of substitution have been reported as a function of concentration and temperature. The conductance-concentration data have been analyzed with the modified Manning counterion-condensation model appropriate for semidilute polyelectrolyte solutions, considering the de Gennes scaling description of the polyion configuration. 36-55% of the counterions were found to remain condensed and the condensation process was shown to be spontaneous. Although the level of counterion-condensation depends appreciably on the degree of substitution, it was found to remain invariant with the polyelectrolyte concentration and the temperature. The free energies of counterion-condensation, the ratios of the mobility of the polyion to that of the counterion, the polyion transference numbers, and the coefficients of monomer-solvent friction have been evaluated. The effects of the polyion charge, its size, and the bulk viscosity of the media on the polyion-counterion interactions have also been discussed. (C) 2016 Elsevier Ltd.
Keywords:Polyelectrolyte conductivity;Sodium carboxymethylcellulose;Degree of substitution;Fraction of free counterions;Free energy of counterion-condensation;Monomer friction coefficient