Abstract

The dependence on temperature (298–328°K) of the acid dissociation constants pK0 in aqueous-methanolic mixtures and in methanol of a fibrous complexite based on cellulose containing hydroxamic acid and amidoxime groups was studied. The changes in the free energy, enthalpy, and entropy of the dissociation process for the two groups were determined. The influence of the electrostatic, conformational, and solvational effects on the pK0 of dissociation of the groups in the polymer was established. The entropy term provides the main contribution to the change in the free energy of dissociation. The thermodynamic characteristics obtained indicate that the acid properties of the complexite groups, which depend on the composition of the solvent and temperature, are determined mainly by the nature of its functional groups.

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