Abstract
Measurements of NMR spin-lattice relaxation times T 1 were performed for sorbed H2O and D2O in a sulfonated ion-exchange resin at varying degrees of hydration with alkaline cations as counter ions. From the sorption isotherms at three different temperatures the partial molar enthalpiesΔ\(\bar H\) and entropiesΔ\(\bar S\) of sorption show a minimum for all alkaline cations at water concentrations of n ≈0.8, i.e., there are 0.8 water molecules per −SO −3 group. The first water molecules sorbed in the ion-exchange resin matrix are characterized by anisotrtopic rotational diffusion processes with correlation times of the order of τ1 ≈ 50 ns and τ2 ≈ 30 ps, respectively. This indicates that they are located in the electrostatic field between the corresponding ion pair. Although these two correlation times are very similar at a given temperature for all alkaline cations studied in the present investigation, the existence of a second spin-lattice relaxation time for sorbed H2O at n=0.8 indicates that for Cs about 50% of the sorbed water diffuses between locations in the resin. This fraction decreases with ionic radii and with falling temperatures. For Li the amount is less than 20%.
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Busch, M., v. Goldammer, E. Thermodynamic and magnetic resonance studies on the hydration of polymers: I. Interactions of water in a synthetic cation-exchange resin. J Solution Chem 11, 777–791 (1982). https://doi.org/10.1007/BF00650518
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DOI: https://doi.org/10.1007/BF00650518