Hydration of ion exchangers: thermodynamics and quantum chemistry calculations. II an improved variant of the predominant hydrates model

Abstract

Valuable information on the state of water molecules in the ion exchanger can be obtained by joint application of thermodynamic and quantum chemistry methods to treatment of water sorption isotherms. An improved variant of the Predominant Hydrates model accounts for competitive process of formation in the resin of several hydrates forming an ideal mixture with the free water. The parameters of the model are number of hydrates, number of water molecules in each hydrate and Gibbs energies of the hydrates formation. The first two parameters can be obtained from quantum chemical calculation of structure of the molecular model of swollen ion exchanger and the energy state of the water molecules. The new approach was illustrated by its application to experimental data of Gregor H.P., Sundheim B.R., Held K.M., Waxman M.H. Studies on ion-exchange resins. V. Water vapor sorption, J. of Coll. Sci., 7: 5 (1952) 511–534 on isopiestic data of water sorption by Li+ and Na+ forms of sulfostyrene resin with 10% DVB. The experimental water sorption isotherms can be accurately described by the model accounting for the presence in the resin of two hydrates with the same number of water molecules for Li+ and Na+ forms. The difference in the intensity of hydration reveals in the different Gibbs energy of the hydrates formation. The mole fraction of water in different hydrates and the free water was calculated. It appeared that more than a half of water molecules in both cases are free and enter the resin phase due to the entropy increase upon distribution of the free water between the solution and the resin.