A series of chitosan/chitin samples with DA's varying between 5.2 and 89% was prepared from the reacetylation under soft conditions of a unique chitosan sample allowing the preservation of the chain distribution. The study of the variation of pH for the same concentration of amine groups, at different ionic strengths, on the scale of DA's allows us to extrapolate the variation of pK(a) at dissociation degrees (alpha) 0 and 1. A modeling of all the curves was obtained by means of only one equation. Then, for given concentration of chitosan and ionic strength, it is possible to predict the pH of the solution whatever the DA and alpha. The role of DA through the participation of hydrophobic interactions and hydrogen bondings on the electrostatic parameters is discussed. The results allow a better understanding of some physicochemical and biological propel-ties of chitosan and chitin.