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

Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A.

doi:10.1021/cg501656s

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

Journal Article · Thu Dec 04 00:00:00 EST 2014 · Crystal Growth and Design

DOI:https://doi.org/10.1021/cg501656s· OSTI ID:1185753

Custelcean, Radu ^[1]; Sloop, Frederick V. ^[1]; Rajbanshi, Arbin ^[1]; Wan, Shun ^[1]; Moyer, Bruce A. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na₂³⁵SO₄ provided a practical way to monitor the sulfate concentration in solution by 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. Moreover, 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 h and 24 h, respectively.

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Environmental Management (EM)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1185753

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 1 Vol. 15; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Self‐Assembly of an Anion‐Binding Cryptand for the Selective Encapsulation, Sequestration, and Precipitation of Phosphate from Aqueous Systems Rice, Craig R.; Slater, Christopher; Faulkner, Robert A. Angewandte Chemie, Vol. 130, Issue 40 https://doi.org/10.1002/ange.201805633	journal	September 2018
Aqueous Sulfate Separation by Crystallization of Sulfate-Water Clusters Custelcean, Radu; Williams, Neil J.; Seipp, Charles A. Angewandte Chemie International Edition, Vol. 54, Issue 36 https://doi.org/10.1002/anie.201506314	journal	August 2015
Self-Assembly of an Anion-Binding Cryptand for the Selective Encapsulation, Sequestration, and Precipitation of Phosphate from Aqueous Systems Rice, Craig R.; Slater, Christopher; Faulkner, Robert A. Angewandte Chemie International Edition, Vol. 57, Issue 40 https://doi.org/10.1002/anie.201805633	journal	September 2018
Aqueous Sulfate Separation by Sequestration of [(SO ₄ ) ₂ (H ₂ O) ₄ ] ⁴⁻ Clusters within Highly Insoluble Imine-Linked Bis-Guanidinium Crystals Custelcean, Radu; Williams, Neil J.; Seipp, Charles A. Chemistry - A European Journal, Vol. 22, Issue 6 https://doi.org/10.1002/chem.201504651	journal	December 2015
Efficient and selective separation of aqueous sulfate through recognition and precipitation Ke, Ya-Ting; Chou, Wei-Tzu; Chiang, Yi-Fen New Journal of Chemistry, Vol. 41, Issue 6 https://doi.org/10.1039/c6nj03710k	journal	January 2017
Selective separation of aqueous sulphate anions via crystallization of sulphate–water clusters Luo, Yang-Hui; Wang, Jing-Wen; Li, Yao-Jia CrystEngComm, Vol. 19, Issue 24 https://doi.org/10.1039/c7ce00693d	journal	January 2017
Selective binding of (thio)sulfate and phosphate in water by quaternary ammonium functionalized oligo-ureas Huang, Zhe; Jia, Chuandong; Wu, Biao Chemical Communications, Vol. 55, Issue 12 https://doi.org/10.1039/c8cc09550g	journal	January 2019
Receptors for sulfate that function across a wide pH range in mixed aqueous–DMSO media Qin, Lei; Wright, James R.; Lane, Jakob D. E. Chemical Communications, Vol. 55, Issue 82 https://doi.org/10.1039/c9cc06812k	journal	January 2019

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