Hydration of ion exchangers: Thermodynamics and quantum chemistry calculations

Comparative studies of the state of water molecules in carboxylic acid resins were carried out using classic thermodynamics and ab initio quantum chemical calculation of the structure of representative fragments of their polymeric matrix in the presence of different amounts of water molecules. Water sorption isotherms were obtained for H+, Li+, Na+, K+ Mg2+, Ca2+ and Ba2+ forms of the carboxylic acid ion exchanger Lewatit S8227 using the isopiestic method. Quantum chemistry calculations were performed by the Firefly QC package, which is partially based on the GAMESS (US) source code, on the theory level RHF/MINI. Atomic structures of fragments of the resin interior containing 1-6 monomeric residues and 0-10 water molecules per functional group were computed. It has been shown that the water sorption isotherms are well described by the previously derived equation on the assumption of the presence in the swollen ion exchanger of one or two formal hydrates. Quantum chemistry calculations allow independent evaluation of the number of water molecules in the hydrates and in so doing reduce the number of fitting parameters needed for quantitative description of the water sorption isotherms. They also allow classifying the water molecules in the resin according to the type of interaction with fixed ion-counter-ion ion pair.