pH-potentiometirc study of polyion complexes between chitosan and poly(vinyl sulfate) or dodecylbenzene sulfonate.

Polyion complexes of three chitosans with poly(vinyl sulfate) (PVS) and dodecylbenzene sulfonate (DBS) were examined by a potentiometric study that was to separately measure the pH of sample solutions individually prepared. Apparent formation constants (Ki) of ion association between the protonated amines of chitosan and the sulfates of PVS or the sulfonates of DBS were determined. The effects of pH, coexistent salt concentration, and molecular weight on the values of Ki were investigated in order to reveal the properties of the complexation. The values of Ki for chitosan-PVS were quite larger than that for chitosan-DBS. The deducing effect of the coexistent salt was strong against chitosan-PVS, but was weak against chitosan-DBS. Thus, chitosan-PVS complexes possessed a strong electrostatic binding, and chitosan-DBS complexes included a hydrophobic interaction. For chitosan-PVS complexes the effect of the coexistent salt was weaker for a high molecular weight of chitosan than for a low molecular weight.