By using the model of a randomly coiled chain, a relation is derived describing the equilibrium stress–strain behavior of variously ionized polyelectrolyte gels swollen in solutions of a uni–univalent salt. The effect of the concentration of bound counterions calculated on the basis of the cylindrical model and the effect of the change of length of the statistical chain segment with the change in ionization of the gel on stress–strain, swelling, and potentiometric equilibria is discussed.
The deformational, swelling, and potentiometric behavior of poly(methacrylic acid) gels was measured as a function of the degree of crosslinking, ionic strength, and degree of ionization. The comparison of the stress–strain behavior with theoretical relations derived in the preceding part has shown that the relations are valid only if an increase is assumed in the number of monomeric units in the statistical chain segment with increasing degree of neutralization of the gel. This dependence is affected by the salt content in the swelling solution and is also dependent on the activity coefficient of counterions. The pK0 values for an undissociated gel approach pK0 = 5.0 and increase somewhat with degree of neutralization. The swelling equilibria are in qualitative agreement with theoretical assumptions; their quantitative agreement depends on the activity coefficient of counterions.
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