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Distinctive Interactions of Cesium and Hexaniobate in Water

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https://ir.library.oregonstate.edu/concern/articles/7m01bn343

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Abstract
  • The Cs-effect states Cs⁺ has more covalent character in bonding interactions than the lighter alkalis. It is exploited in organic synthesis and influences behavior in water, most notably radioactive ¹³⁷Cs in nuclear wastes or the environment. Niobium polyoxometalates (Nb-POMs) provide a unique opportunity to probe aqueous phase ion-pairing responsible for cesium's solution behavior, because Nb-POMs are most soluble in conditions of maximum ion-association. Moreover, POMs broadly resemble metal-oxide surfaces representative of interfaces found in the environment and industrial processes. Aqueous dissolution calorimetry reveals that Cs−Nb-POM exhibits greater concentration dependence in its endothermic dissolution, compared to the lighter alkali analogues. This phenomenon is attributed to persistent ion-pairs upon dissolution, even in very dilute and otherwise ion-free solutions. While dissociation of these cation-anion interactions in the crystalline lattice is the dominant endothermic step of dissolution, deprotonation of the Nb-POM is the most exothermic. These studies highlight the importance of the competing effects of aqueous ion association and acid-base chemistry that control solubility of compounds from simple oxoanions to metal-oxo clusters to supramolecular assemblies to solid metal oxides.
  • Keywords: polyoxometalate, cesium, thermochemistry, calorimetry, ion pairs
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  • Sures, D. J., Sahu, S. K., Molina, P. I., Navrotsky, A., & Nyman, M. (2016). Distinctive Interactions of Cesium and Hexaniobate in Water. ChemistrySelect, 1(9), 1858-1862. doi:10.1002/slct.201600493
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  • 1
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  • 9
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  • DJS and MN acknowledge support by the U.S. Department of Energy, Office of Basic Energy Sciences, Divisions of Materials Sciences and Engineering, under award DE-SC0010802. SKS and AN acknowledge support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical and Geosciences, under award FG02-97ER14749.
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