Analysis of potentiometric titrations of heterogeneous natural polyelectrolytes in terms of counterion condensation theory: application to humic acid Original Research Article

A model, developed within the framework of the counterion condensation theory of linear polyelectrolytes, is presented in this paper to describe the acid–base properties of linear polyelectrolytes, consisting of several types of functional ionizable groups. This formalism has been successfully applied to Fluka humic acid under salt-free conditions, as well as in the presence of supporting simple 1:1 salt (KNO3) at three different concentrations. As part of this approach, the charge density of the humic acid is obtained from the activity coefficient measurements of potassium counterions at different humic acid concentrations at a constant degree of dissociation of the polyelectrolyte. The humic acid average charge density was found to be 0.80±0.05. Using the present model, we are able to satisfactorily describe the experimental data obtained from acid–base potentiometric titrations. Four main functional groups making up the polymer are determined through their fractional abundances (Xi) and intrinsic pK pKi0 values. The fractional abundances remained constant and independent of the ionic strength, indicating that the humic acid constitution does not depend on the concentration of excess salts. The pKi0 values show a small change with ionic strength, which can be explained by the polyelectrolytic behavior of the solution.