Electrical conductivity of aqueous polyelectrolyte solutions in the presence of counterion condensation: the scaling approach revisited.

Abstract

The conductometric properties of aqueous polyelectrolyte solutions in the absence of added salt are reviewed in the light of the dynamic scaling description of the polymer conformation in different concentration regimes, recently proposed by Dobrynin and Rubinstein [Macromolecules 28, 1859 (1995); 32, 915 (1999)]. The scaling approach to the transport properties of polyelectrolyte solutions allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to the dilute and semidilute regimes. Moreover, the quality of the solvent, influencing the polyion-counterion interactions, can be properly taken into account. The electrical conductivity predicted by this scaling approach compares reasonably well with the observed values for a model polyelectrolyte (polyacrylate sodium salt in aqueous solutions, good solvent condition) over an extended concentration range from the dilute to the semidilute regime.