Thermodynamics of aqueous systems containing hydrophilic polymers or gels

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Abstract
A quasichemical partition function is applied to represent the thermodynamic properties of aqueous solutions of nonelectrolytes, including linear polymers and crosslinked polymers (gels). The partition function extends conventional lattice theory; to take into account strong specific interactions (hydrogen bonds) as encountered in aqueous solutions, each molecule (polymer segment) may possess three energetically different types of contact sites. We distinguish between sites that interact through dispersion forces and sites that can participate in a hydrogen bond; hydrogen‐bonding sites are divided into electron‐pair donating sites and electron‐pair accepting sites. The Helmholtz energy of the mixture is obtained using an oriented quasichemical approximation. The final equation contains three independent adjustable binary parameters; these are the exchange energies for different types of contact paris. To represent quantitatively upper or lower critical solution phenomena, we include the semitheoretical fluctuation correction recently proposed by de Pablo. Comparison with experimental data indicates that the proposed molecular‐thermodynamic model may be useful for representing phase equilibria for a variety of aqueous systems including swelling equilibria for hydrophilic gels.

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