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 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.
- Authors:
-
- 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:
- Journal Article: 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. https://doi.org/10.1021/cg501656s
Custelcean, Radu, Sloop, Frederick V., Rajbanshi, Arbin, Wan, Shun, and Moyer, Bruce A. 2014.
"Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1185753},
journal = {Crystal Growth and Design},
issn = {1528-7483},
number = 1,
volume = 15,
place = {United States},
year = {Thu Dec 04 00:00:00 EST 2014},
month = {Thu Dec 04 00:00:00 EST 2014}
}
Web of Science
Works referenced in this record:
A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes
journal, June 2012
- Moyer, Bruce A.; Custelcean, Radu; Hay, Benjamin P.
- Inorganic Chemistry, Vol. 52, Issue 7
Sulfate Separation from Aqueous Alkaline Solutions by Selective Crystallization of Alkali Metal Coordination Capsules
journal, July 2011
- Rajbanshi, Arbin; Moyer, Bruce A.; Custelcean, Radu
- Crystal Growth & Design, Vol. 11, Issue 7
Urea-functionalized crystalline capsules for recognition and separation of tetrahedral oxoanions
journal, January 2013
- Custelcean, Radu
- Chemical Communications, Vol. 49, Issue 22
Comparing the salting-out effects of alkali-metal nitrates on the water-isopropanol system
journal, October 2011
- Il’in, K. K.; Cherkasov, D. G.; Kurskii, V. F.
- Russian Journal of Inorganic Chemistry, Vol. 56, Issue 10
The kinetics of crystal growth of calcium sulfate dihydrate
journal, March 1970
- Liu, Sung-Tsuen; Nancollas, George H.
- Journal of Crystal Growth, Vol. 6, Issue 3
The growth of crystals in solution
journal, January 1979
- Nancollas, George H.
- Advances in Colloid and Interface Science, Vol. 10, Issue 1
Influence of calcium/sulfate molar ratio on the growth rate of calcium sulfate dihydrate at constant supersaturation
journal, April 1992
- Zhang, Jingwu; Nancollas, G. H.
- Journal of Crystal Growth, Vol. 118, Issue 3-4
Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
journal, July 2011
- Stack, Andrew G.; Raiteri, Paolo; Gale, Julian D.
- Journal of the American Chemical Society, Vol. 134, Issue 1
Works referencing / citing this record:
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
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, Vol. 130, Issue 40
Aqueous Sulfate Separation by Crystallization of Sulfate-Water Clusters
journal, August 2015
- Custelcean, Radu; Williams, Neil J.; Seipp, Charles A.
- Angewandte Chemie, Vol. 127, Issue 36
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
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
Receptors for sulfate that function across a wide pH range in mixed aqueous–DMSO media
journal, January 2019
- Qin, Lei; Wright, James R.; Lane, Jakob D. E.
- Chemical Communications, Vol. 55, Issue 82
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
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
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