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.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

doi:10.1002/chem.201504651

Title: Aqueous Sulfate Separation by Sequestration of [(SO ₄ ) ₂ (H ₂ O) ₄ ] ⁴⁻ Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals

Journal Article · Tue Dec 08 00:00:00 EST 2015 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201504651· OSTI ID:1454902

Custelcean, Radu ^[1]; Williams, Neil J. ^[2]; Seipp, Charles A. ^[3]; Ivanov, Alexander S. ^[1]; Bryantsev, Vyacheslav S. ^[1]

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

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1454902

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 22 Journal Issue: 6; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 34 works

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References (33)

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Title: Aqueous Sulfate Separation by Sequestration of [(SO ₄ ) ₂ (H ₂ O) ₄ ] ⁴⁻ Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals