Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals
Abstract
Abstract Selective crystallization of sulfate with a simple bis‐guanidinium ligand, self‐assembled in situ from terephthalaldehyde and aminoguanidinium chloride, was employed as an effective way to separate the highly hydrophilic sulfate anion from aqueous solutions. The resulting bis‐iminoguanidinium sulfate salt has exceptionally low aqueous solubility ( K sp =2.4×10 −10 ), comparable to that of BaSO 4 . Single‐crystal X‐ray diffraction analysis showed the sulfate anions are sequestered as [(SO 4 ) 2 (H 2 O) 4 ] 4− clusters within the crystals. Variable‐temperature solubility measurements indicated the sulfate crystallization is slightly endothermic ( ΔH cryst =3.7 kJ mol −1 ), thus entropy driven. The real‐world utility of this crystallization‐based approach for sulfate separation was demonstrated by removing up to 99 % of sulfate from seawater in a single step.
- Authors:
-
- Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831-6119 USA
- Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831-6119 USA, Department of Chemistry The University of Tennessee Buehler Hall 1420 Circle Dr. Knoxville TN 37996-1600 USA
- Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831-6119 USA, Department of Chemistry The University of Texas at Austin 1 University Station-A5300 Austin TX 78712-0165 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1454902
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 22 Journal Issue: 6; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Custelcean, Radu, Williams, Neil J., Seipp, Charles A., Ivanov, Alexander S., and Bryantsev, Vyacheslav S. Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals. Germany: N. p., 2015.
Web. doi:10.1002/chem.201504651.
Custelcean, Radu, Williams, Neil J., Seipp, Charles A., Ivanov, Alexander S., & Bryantsev, Vyacheslav S. Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals. Germany. https://doi.org/10.1002/chem.201504651
Custelcean, Radu, Williams, Neil J., Seipp, Charles A., Ivanov, Alexander S., and Bryantsev, Vyacheslav S. Tue .
"Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals". Germany. https://doi.org/10.1002/chem.201504651.
@article{osti_1454902,
title = {Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals},
author = {Custelcean, Radu and Williams, Neil J. and Seipp, Charles A. and Ivanov, Alexander S. and Bryantsev, Vyacheslav S.},
abstractNote = {Abstract Selective crystallization of sulfate with a simple bis‐guanidinium ligand, self‐assembled in situ from terephthalaldehyde and aminoguanidinium chloride, was employed as an effective way to separate the highly hydrophilic sulfate anion from aqueous solutions. The resulting bis‐iminoguanidinium sulfate salt has exceptionally low aqueous solubility ( K sp =2.4×10 −10 ), comparable to that of BaSO 4 . Single‐crystal X‐ray diffraction analysis showed the sulfate anions are sequestered as [(SO 4 ) 2 (H 2 O) 4 ] 4− clusters within the crystals. Variable‐temperature solubility measurements indicated the sulfate crystallization is slightly endothermic ( ΔH cryst =3.7 kJ mol −1 ), thus entropy driven. The real‐world utility of this crystallization‐based approach for sulfate separation was demonstrated by removing up to 99 % of sulfate from seawater in a single step.},
doi = {10.1002/chem.201504651},
journal = {Chemistry - A European Journal},
number = 6,
volume = 22,
place = {Germany},
year = {Tue Dec 08 00:00:00 EST 2015},
month = {Tue Dec 08 00:00:00 EST 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/chem.201504651
https://doi.org/10.1002/chem.201504651
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 34 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Selectivity Principles in Anion Separation by Crystallization of Hydrogen-Bonding Capsules
journal, May 2010
- Custelcean, Radu; Bock, Aurelien; Moyer, Bruce A.
- Journal of the American Chemical Society, Vol. 132, Issue 20
Lipophilic ditopic guanidinium receptors: selective extractants for tetrahedral oxoanions
journal, September 1995
- Stephan, Holger; Gloe, Karsten; Schiessl, Petra
- Supramolecular Chemistry, Vol. 5, Issue 4
A bis-salicylaldoximato-copper( ii ) receptor for selective sulfate uptake
journal, January 2011
- Wenzel, Marco; Knapp, Quintin W.; Plieger, Paul G.
- Chem. Commun., Vol. 47, Issue 1
The Structure of Aqueous Guanidinium Chloride Solutions
journal, September 2004
- Mason, Philip E.; Neilson, George W.; Enderby, John E.
- Journal of the American Chemical Society, Vol. 126, Issue 37
Highly Efficient Extraction of Sulfate Ions with a Tripodal Hexaurea Receptor
journal, December 2010
- Jia, Chuandong; Wu, Biao; Li, Shaoguang
- Angewandte Chemie International Edition, Vol. 50, Issue 2
Selektive Wirt-Gast-Bindung von Anionen ohne Hilfe von Wasserstoffbrücken: die Entropie als Designwerkzeug
journal, November 2011
- Ursu, Andrei; Schmidtchen, Franz P.
- Angewandte Chemie, Vol. 124, Issue 1
Encapsulation of [(SO 4 ) 4 (H 2 O) 12 ] 8− clusters in a metal organic framework of pyridyl functionalized cyanuric acid based tris-urea
journal, January 2015
- Dutta, Ranjan; Akhuli, Bidyut; Ghosh, Pradyut
- Dalton Transactions, Vol. 44, Issue 34
Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization
journal, December 2014
- Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin
- Crystal Growth & Design, Vol. 15, Issue 1
Supramolecular organization of calix[4]pyrrole with a methyl-trialkylammonium anion exchanger leads to remarkable reversal of selectivity for sulfate extraction vs. nitrate
journal, January 2011
- Borman, Christopher J.; Custelcean, Radu; Hay, Ben P.
- Chemical Communications, Vol. 47, Issue 27
Ion separation by selective crystallization of organic frameworks
journal, June 2009
- Custelcean, Radu
- Current Opinion in Solid State and Materials Science, Vol. 13, Issue 3-4
Novel endotoxin-sequestering compounds with terephthalaldehyde-bis-guanylhydrazone scaffolds
journal, March 2006
- Khownium, Kriangsak; Wood, Stewart J.; Miller, Kelly A.
- Bioorganic & Medicinal Chemistry Letters, Vol. 16, Issue 5
Urea-functionalized crystalline capsules for recognition and separation of tetrahedral oxoanions
journal, January 2013
- Custelcean, Radu
- Chemical Communications, Vol. 49, Issue 22
A polar/ π model of interactions explains face-to-face stacked quinoid rings: a case study of the crystal of potassium hydrogen chloranilate dihydrate
journal, January 2015
- Molčanov, Krešimir; Stare, Jernej; Kojić-Prodić, Biserka
- CrystEngComm, Vol. 17, Issue 45
Cationic Tripodal Receptor Assisted Formation of Anion and Anion–Water Clusters: Structural Interpretation of Dihydrogen Phosphate Cluster and Sulfate–Water Tetramer [(SO 4 ) 2 –(H 2 O) 2 ] 4–
journal, April 2014
- Hoque, Md. Najbul; Das, Gopal
- Crystal Growth & Design, Vol. 14, Issue 6
Supramolekulare Chemie von Anionen: von der Erkennung zur chemischen Anwendung
journal, September 2014
- Evans, Nicholas H.; Beer, Paul D.
- Angewandte Chemie, Vol. 126, Issue 44
Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion
journal, October 2014
- Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J.
- Journal of the American Chemical Society, Vol. 136, Issue 42
Octamethyl-octaundecylcyclo[8]pyrrole: A Promising Sulfate Anion Extractant
journal, September 2007
- Eller, Leah R.; Stȩpień, Marcin; Fowler, Christopher J.
- Journal of the American Chemical Society, Vol. 129, Issue 36
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
Applications of Supramolecular Anion Recognition
journal, May 2015
- Busschaert, Nathalie; Caltagirone, Claudia; Van Rossom, Wim
- Chemical Reviews, Vol. 115, Issue 15
Highly Efficient Extraction of Sulfate Ions with a Tripodal Hexaurea Receptor
journal, December 2010
- Jia, Chuandong; Wu, Biao; Li, Shaoguang
- Angewandte Chemie, Vol. 123, Issue 2
Selective total encapsulation of the sulfate anion by neutral nano-jars
journal, January 2012
- Fernando, Isurika R.; Surmann, Stuart A.; Urech, Alexander A.
- Chemical Communications, Vol. 48, Issue 54
Zwitterionic Guanidinium Compounds Serve as Electroneutral Anion Hosts
journal, November 1999
- Berger, Michael; Schmidtchen, Franz P.
- Journal of the American Chemical Society, Vol. 121, Issue 43
Limitations and Extensions of the Lock-and-Key Principle: Differences between Gas State, Solution and Solid State Structures
journal, March 2015
- Schneider, Hans-Jörg
- International Journal of Molecular Sciences, Vol. 16, Issue 12
Sulfate scale problems in oil fields water injection operations
journal, November 2006
- Bader, M. S. H.
- Desalination, Vol. 201, Issue 1-3
Pyridine–Urea-Based Anion Receptor: Formation of Cyclic Sulfate–Water Hexamer and Dihydrogen Phosphate–Water Trimer in Hydrophobic Environment
journal, December 2013
- Hoque, Md. Najbul; Basu, Arghya; Das, Gopal
- Crystal Growth & Design, Vol. 14, Issue 1
Preferential Interactions of Guanidinum Ions with Aromatic Groups over Aliphatic Groups
journal, November 2009
- Mason, Philip E.; Dempsey, Christopher E.; Neilson, George W.
- Journal of the American Chemical Society, Vol. 131, Issue 46
The Binding of Sulfate Anions by Guanidinium Receptors is Entropy-Driven
journal, October 1998
- Berger, Michael; Schmidtchen, Franz P.
- Angewandte Chemie International Edition, Vol. 37, Issue 19
Selective Host-Guest Binding of Anions without Auxiliary Hydrogen Bonds: Entropy as an Aid to Design
journal, November 2011
- Ursu, Andrei; Schmidtchen, Franz P.
- Angewandte Chemie International Edition, Vol. 51, Issue 1
Die Erkennung von Sulfationen durch Guanidinium-Rezeptoren ist entropiebestimmt
journal, October 1998
- Berger, Michael; Schmidtchen, Franz P.
- Angewandte Chemie, Vol. 110, Issue 19
A new reagent for the detection and determination of small amounts of the sulphate Ion
journal, June 1970
- Stephen, William I.
- Analytica Chimica Acta, Vol. 50, Issue 3
Sulfate removal technologies for oil fields seawater injection operations
journal, January 2007
- Bader, M. S. H.
- Journal of Petroleum Science and Engineering, Vol. 55, Issue 1-2
Advances in Anion Supramolecular Chemistry: From Recognition to Chemical Applications
journal, September 2014
- Evans, Nicholas H.; Beer, Paul D.
- Angewandte Chemie International Edition, Vol. 53, Issue 44
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