Dihydrogen Phosphate Clusters: Trapping H₂PO₄^– Tetramers and Hexamers in Urea-Functionalized Molecular Crystals

Co-crystallization of two urea-functionalized ligands with tetrabutylammonium (TBA) dihydrogen phosphate resulted in the isolation of discrete (H₂PO₄^–)₄ and (H₂PO₄^–)₆ clusters stabilized in the crystalline state by multiple urea hydrogen bonds. Structural analysis by single-crystal X-ray diffraction, combined with a Cambridge Structural Database survey of (H₂PO₄^–)_<i>n</i> aggregates, established that these clusters display unique topologies and hydrogen-bonding connectivities

Dihydrogen Phosphate Clusters: Trapping H₂PO₄^– Tetramers and Hexamers in Urea-Functionalized Molecular Crystals

Co-crystallization of two urea-functionalized ligands with tetrabutylammonium (TBA) dihydrogen phosphate resulted in the isolation of discrete (H₂PO₄^–)₄ and (H₂PO₄^–)₆ clusters stabilized in the crystalline state by multiple urea hydrogen bonds. Structural analysis by single-crystal X-ray diffraction, combined with a Cambridge Structural Database survey of (H₂PO₄^–)_<i>n</i> aggregates, established that these clusters display unique topologies and hydrogen-bonding connectivities

Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15–55 °C temperature range for a fundamental understanding of the elementary steps involved in this sulfate separation method. The use of radiolabeled Na₂³⁵SO₄ provided a practical way to monitor the sulfate concentration in solution by β liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na₂SO₄(L1)₂­(H₂O)₄ capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77–91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 °C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 °C, 63% and 75% of sulfate was removed from solution within 8 and 24 h, respectively. These results indicate the capsule crystallization method is a viable approach to sulfate separation from nuclear wastes