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

Abstract

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 Na 2 35SO 4 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 Na 2SO 4(L1) 2(H 2O) 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.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Environmental Management (EM)
OSTI Identifier:
1185753
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 15; Journal Issue: 1; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Custelcean, Radu, Sloop, Frederick V., Rajbanshi, Arbin, Wan, Shun, and Moyer, Bruce A. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization. United States: N. p., 2014. Web. doi:10.1021/cg501656s.
Custelcean, Radu, Sloop, Frederick V., Rajbanshi, Arbin, Wan, Shun, & Moyer, Bruce A. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization. United States. doi:10.1021/cg501656s.
Custelcean, Radu, Sloop, Frederick V., Rajbanshi, Arbin, Wan, Shun, and Moyer, Bruce A. Thu . "Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization". United States. doi:10.1021/cg501656s. https://www.osti.gov/servlets/purl/1185753.
@article{osti_1185753,
title = {Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization},
author = {Custelcean, Radu and Sloop, Frederick V. and Rajbanshi, Arbin and Wan, Shun and Moyer, Bruce A.},
abstractNote = {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.},
doi = {10.1021/cg501656s},
journal = {Crystal Growth and Design},
number = 1,
volume = 15,
place = {United States},
year = {2014},
month = {12}
}

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Works referencing / citing this record:

Aqueous Sulfate Separation by Crystallization of Sulfate-Water Clusters
journal, August 2015

  • Custelcean, Radu; Williams, Neil J.; Seipp, Charles A.
  • Angewandte Chemie International Edition, Vol. 54, Issue 36
  • DOI: 10.1002/anie.201506314

Self-Assembly of an Anion-Binding Cryptand for the Selective Encapsulation, Sequestration, and Precipitation of Phosphate from Aqueous Systems
journal, September 2018

  • Rice, Craig R.; Slater, Christopher; Faulkner, Robert A.
  • Angewandte Chemie International Edition, Vol. 57, Issue 40
  • DOI: 10.1002/anie.201805633

Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine-Linked Bis-Guanidinium Crystals
journal, December 2015

  • Custelcean, Radu; Williams, Neil J.; Seipp, Charles A.
  • Chemistry - A European Journal, Vol. 22, Issue 6
  • DOI: 10.1002/chem.201504651

Efficient and selective separation of aqueous sulfate through recognition and precipitation
journal, January 2017

  • Ke, Ya-Ting; Chou, Wei-Tzu; Chiang, Yi-Fen
  • New Journal of Chemistry, Vol. 41, Issue 6
  • DOI: 10.1039/c6nj03710k

Selective separation of aqueous sulphate anions via crystallization of sulphate–water clusters
journal, January 2017

  • Luo, Yang-Hui; Wang, Jing-Wen; Li, Yao-Jia
  • CrystEngComm, Vol. 19, Issue 24
  • DOI: 10.1039/c7ce00693d

Selective binding of (thio)sulfate and phosphate in water by quaternary ammonium functionalized oligo-ureas
journal, January 2019

  • Huang, Zhe; Jia, Chuandong; Wu, Biao
  • Chemical Communications, Vol. 55, Issue 12
  • DOI: 10.1039/c8cc09550g