Selectivity Principles in Anion Separation by Crystallization of Hydrogen-Bonding Capsules
- ORNL
The fundamental factors controlling anion selectivity in the crystallization of hydrogen-bonding capsules [Mg(H2O)6][X L2] (X = SO42-, 1a; SeO42-, 1b; SO32-, 1c; CO32-, 1d; L = tris[2-(3-pyridylurea)ethyl]-amine) from water have been investigated by solution and solid-state thermodynamic measurements, anion competition experiments, and X-ray structural analysis. The crystal structures of 1a-d are isomorphous, thereby simplifying the interpretation of the observed selectivities based on differences in anion coordination geometries. The solubilities of 1a-d in water follow the order: 1a < 1b < 1c < 1d, which is consistent with the selectivity for the tetrahedral sulfate and selenate anions observed in competitive crystallization experiments. Crystallization of the capsules is highly exothermic, with the most favorable {Delta}H{sub cryst}{sup o} of -99.1 and -108.5 kJ/mol corresponding to SO42- and SeO42-, respectively, in agreement with the X-ray structural data showing shape complementarity between these tetrahedral anions and the urea-lined cavities of the capsules. Sulfite, on the other hand, has a significantly less negative {Delta}H{sub cryst}{sup o} of -64.6 kJ/mol, which may be attributed to its poor fit inside the capsules, involving repulsive interactions. The more favorable entropy of crystallization for this anion, however, partly offsets the enthalpic disadvantage, resulting in a solubility product very similar to that of the selenate complex. Because of their very similar shape and size, SO42- and SeO42- have a propensity to form solid solutions, which limits the selectivity between these two anions in competitive crystallizations. In the end, a comprehensive picture of contributing factors to anion selectivity in crystalline hydrogen-bonding capsules emerges.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC05-00OR22725
- OSTI ID:
- 1003738
- Journal Information:
- Journal of the American Chemical Society, Vol. 132, Issue 20; ISSN 0002--7863
- Country of Publication:
- United States
- Language:
- English
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