Shapes of polyelectrolyte titration curves. 1. Well-behaved strong polyelectrolytes

The charge content of aqueous polymers is measured routinely by polyelectrolyte titrations in which an unknown polymer is titrated with an oppositely charged standard polymer solution, usually poly(diallyldimethyl ammonium chloride) or potassium poly(vinyl sulfate). Polyelectrolyte titration end points are frequently determined with a streaming current detector (SCD). The shapes of polyelectrolyte titration curves from polyelectrolytes with fixed electrical charges were simulated by a diffuse electrical double layer model. Well-behaved titration curves obtained with fixed charged polyelectrolytes were fit by the modeling, giving support for the basic hypothesis that the net charge of material adsorbed on the SCD wall is a linear function of the volume of added titrant. The shapes of titration curves from deviant systems such as poly(vinyl alcohol)-borate cannot be predicted by the model.