Intermediate Species in the Crystallization of Sodium Aluminate Hydroxy Hydrates

Graham, Trent R.; Dembowski, Mateusz; Hu, Jian Zhi; Jaegers, Nicholas R.; Zhang, Xin; Clark, Sue B.; Pearce, Carolyn I.; Rosso, Kevin M.

doi:10.1021/acs.jpcc.0c00205

Intermediate Species in the Crystallization of Sodium Aluminate Hydroxy Hydrates

Journal Article · Wed Apr 15 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c00205· OSTI ID:1633402

^[1]; ^[1]; ^[1]; ^[2]; ^[1]; Clark, Sue B. ^[2]; ^[3]; ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States

In highly alkaline “water-in-salt” Na₂O/Al₂O₃/H₂O solutions where the monomeric Al(OH)₄^- anion dominates, isolation of transitional species that seed crystallization of sodium aluminate salt hydrates has been challenging. For example, discrimination of dimeric [e.g., Al₂O(OH)₆^2-] from species via ²⁷Al nuclear magnetic resonance (NMR) spectroscopy is limited via fast interconversion through hydrolysis and condensation reactions. Despite this, using magic-angle spinning NMR (²⁷Al MAS NMR) at high magnetic field strengths (14.1 and 20.0 T) on crystals of nonasodium bis(hexahydroxyaluminate) trihydroxide hexahydrate [NSA, Na₉[Al(OH)₆]₂·3(OH)·6(H₂O)], we observed a ²⁷Al resonance consistent with Na₂Al₂O(OH)₆. This tetrahedral dimeric species was also identified in the mother liquor by Raman spectroscopy while remaining expectedly unresolved by high-field liquid-state ²⁷Al NMR. Its substantial abundance in the mother liquor and as either an interstitial or an adsorbate on precipitated solids suggest that it plays a crucial role in NSA crystallization. Here, our detailed characterization, which includes single-pulse ²⁷Al MAS NMR, nutation ²⁷Al MAS NMR, and multiple quantum ²⁷Al MAS NMR, provides new molecular insights into how aluminate transitions from tetrahedral in solution to octahedral in solid. This understanding could ultimately lead to better predictions of aluminum phase change behavior in caustic sodium hydroxide with wide-ranging technological and environmental implications.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1633402

Report Number(s):: PNNL-SA--150266

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 23 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Graphical representation of particle shape using triangular diagrams: an Excel spreadsheet method Graham, David J.; Midgley, Nicholas G. Earth Surface Processes and Landforms, Vol. 25, Issue 13 https://doi.org/10.1002/1096-9837(200012)25:13<1473::AID-ESP158>3.0.CO;2-C	journal	October 2000
Raman spectroscopy and multivariate curve resolution of concentrated Al2O3-Na2O-H2O solutions Schoonover, Jon R.; Zhang, Shuliang L.; Johnston, Cliff T. Journal of Raman Spectroscopy, Vol. 34, Issue 6 https://doi.org/10.1002/jrs.1011	journal	January 2003
Zur Kenntnis der kristallinen Phasen in den Systemen M2IO?Al2O3?H2O (MI = K, Na) Gessner, Wolfgang; Weinberger, Martin; M�ller, Dirk Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 547, Issue 4 https://doi.org/10.1002/zaac.19875470404	journal	April 1987
Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl Weinberger, M.; Schneider, M.; M�ller, D. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 620, Issue 4 https://doi.org/10.1002/zaac.19946200432	journal	April 1994
Die Kristallstruktur des Natriumoxohydroxoaluminathydrates Na2[Al2O3(OH)2] � 1,5 H2O Weinberger, M.; Schneider, M.; Ge�ner, W. Habil Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 621, Issue 4 https://doi.org/10.1002/zaac.19956210430	journal	April 1995
Nonanatrium-bis(hexahydroxoaluminat)-trihydroxid-hexahydrat (Na9[Al(OH)6]2(OH)3 � 6H2O) - Kristallstruktur, NMR-Spektroskopie und thermisches Verhalten Weinberger, M.; Schneider, M.; Zabel, V. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 10 https://doi.org/10.1002/zaac.19966221027	journal	October 1996
Aluminum speciation and equilibria in aqueous solution: I. The solubility of gibbsite in the system Na-K-Cl-OH-Al(OH)4 from 0 to 100°C Wesolowski, David J. Geochimica et Cosmochimica Acta, Vol. 56, Issue 3 https://doi.org/10.1016/0016-7037(92)90047-m	journal	March 1992
Aluminum hydrolysis constants to 250°C from boehmite solubility measurements Bourcier, William L.; Knauss, Kevin G.; Jackson, Kenneth J. Geochimica et Cosmochimica Acta, Vol. 57, Issue 4 https://doi.org/10.1016/0016-7037(93)90166-t	journal	February 1993
Multinuclear studies of aluminium compounds Akitt, J. W. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 21, Issue 1-2 https://doi.org/10.1016/0079-6565(89)80001-9	journal	January 1989
The aluminum chemistry and corrosion in alkaline solutions Zhang, Jinsuo; Klasky, Marc; Letellier, Bruce C. Journal of Nuclear Materials, Vol. 384, Issue 2 https://doi.org/10.1016/j.jnucmat.2008.11.009	journal	February 2009
The structure of Al(III) in strongly alkaline aluminate solutions — A review Sipos, Pál Journal of Molecular Liquids, Vol. 146, Issue 1-2 https://doi.org/10.1016/j.molliq.2009.01.015	journal	May 2009
Challenges with vitrification of Hanford High-Level Waste (HLW) to borosilicate glass – An overview Goel, Ashutosh; McCloy, John S.; Pokorny, Richard Journal of Non-Crystalline Solids: X, Vol. 4 https://doi.org/10.1016/j.nocx.2019.100033	journal	December 2019
Recent advances in application of 27 Al NMR spectroscopy to materials science Haouas, Mohamed; Taulelle, Francis; Martineau, Charlotte Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 94-95 https://doi.org/10.1016/j.pnmrs.2016.01.003	journal	May 2016
27Al NMR and Raman spectroscopic studies of alkaline aluminate solutions with extremely high caustic content – Does the octahedral species Al(OH)63− exist in solution? Sipos, Pál; Hefter, Glenn; May, Peter M. Talanta, Vol. 70, Issue 4 https://doi.org/10.1016/j.talanta.2006.02.008	journal	November 2006
Phase study of the system NaO-AlO-HO Qiu, G.; Chen, N. Canadian Metallurgical Quarterly, Vol. 36, Issue 2 https://doi.org/10.1016/s0008-4433(96)00044-4	journal	April 1997
Thermodynamic model for equilibrium solubility of gibbsite in concentrated NaOH solutions Li, Xiao-bin; Yan, Li; Zhou, Qiu-sheng Transactions of Nonferrous Metals Society of China, Vol. 22, Issue 2 https://doi.org/10.1016/s1003-6326(11)61197-7	journal	February 2012
Calibration of methanol and ethylene glycol nuclear magnetic resonance thermometers Raiford, David S.; Fisk, Cherie L.; Becker, Edwin D. Analytical Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ac50048a040	journal	October 1979
Fast Synthesis of Gibbsite Nanoplates and Process Optimization using Box-Behnken Experimental Design Zhang, Xin; Zhang, Xianwen; Graham, Trent R. Crystal Growth & Design, Vol. 17, Issue 12 https://doi.org/10.1021/acs.cgd.7b01400	journal	October 2017
Size and Morphology Controlled Synthesis of Boehmite Nanoplates and Crystal Growth Mechanisms Zhang, Xin; Cui, Wenwen; Page, Katharine L. Crystal Growth & Design, Vol. 18, Issue 6 https://doi.org/10.1021/acs.cgd.8b00394	journal	April 2018
Review of the Scientific Understanding of Radioactive Waste at the U.S. DOE Hanford Site Peterson, Reid A.; Buck, Edgar C.; Chun, Jaehun Environmental Science & Technology, Vol. 52, Issue 2 https://doi.org/10.1021/acs.est.7b04077	journal	January 2018
Gibbsite Solubility in Hanford Nuclear Waste Approached from above and below Saturation Reynolds, Jacob G.; McCoskey, Jacob K.; Herting, Daniel L. Industrial & Engineering Chemistry Research, Vol. 55, Issue 19 https://doi.org/10.1021/acs.iecr.6b00743	journal	May 2016
Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates Graham, Trent R.; Gorniak, Rafal; Dembowski, Mateusz Inorganic Chemistry, Vol. 59, Issue 10 https://doi.org/10.1021/acs.inorgchem.0c00258	journal	April 2020
Solid-State ²⁷ Al NMR Spectroscopy of the γ-Al ₁₃ Keggin Containing Al Coordinated by a Terminal Hydroxyl Ligand Phillips, Brian L.; Ohlin, C. André; Vaughn, John Inorganic Chemistry, Vol. 55, Issue 23 https://doi.org/10.1021/acs.inorgchem.6b01968	journal	November 2016
Impact of Amino Acids on the Isomerization of the Aluminum Tridecamer Al ₁₃ Deschaume, Olivier; Breynaert, Eric; Radhakrishnan, Sambhu Inorganic Chemistry, Vol. 56, Issue 20 https://doi.org/10.1021/acs.inorgchem.7b01699	journal	September 2017
In Situ ²⁷ Al NMR Spectroscopy of Aluminate in Sodium Hydroxide Solutions above and below Saturation with Respect to Gibbsite Graham, Trent R.; Dembowski, Mateusz; Martinez-Baez, Ernesto Inorganic Chemistry, Vol. 57, Issue 19 https://doi.org/10.1021/acs.inorgchem.8b00617	journal	July 2018
Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation Pouvreau, Maxime; Dembowski, Mateusz; Clark, Sue B. The Journal of Physical Chemistry B, Vol. 122, Issue 29 https://doi.org/10.1021/acs.jpcb.8b04377	journal	June 2018
Coupled Multimodal Dynamics of Hydrogen-Containing Ion Networks in Water-Deficient, Sodium Hydroxide-Aluminate Solutions Graham, Trent R.; Semrouni, David; Mamontov, Eugene The Journal of Physical Chemistry B, Vol. 122, Issue 50 https://doi.org/10.1021/acs.jpcb.8b09375	journal	November 2018
²⁷ Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions Graham, Trent R.; Han, Kee Sung; Dembowski, Mateusz The Journal of Physical Chemistry B, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpcb.8b10145	journal	October 2018
Free-Energy Landscape of the Dissolution of Gibbsite at High pH Shen, Zhizhang; Kerisit, Sebastien N.; Stack, Andrew G. The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00484	journal	March 2018
Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes Wildman, Andrew; Martinez-Baez, Ernesto; Fulton, John The Journal of Physical Chemistry Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acs.jpclett.8b00642	journal	April 2018
Countercations Control Local Specific Bonding Interactions and Nucleation Mechanisms in Concentrated Water-in-Salt Solutions Wang, Hsiu-Wen; Graham, Trent R.; Mamontov, Eugene The Journal of Physical Chemistry Letters, Vol. 10, Issue 12 https://doi.org/10.1021/acs.jpclett.9b01416	journal	May 2019
Boehmite and Gibbsite Nanoplates for the Synthesis of Advanced Alumina Products Zhang, Xin; Huestis, Patricia L.; Pearce, Carolyn I. ACS Applied Nano Materials, Vol. 1, Issue 12 https://doi.org/10.1021/acsanm.8b01969	journal	November 2018
Raman Study of Aluminum Speciation in Simulated Alkaline Nuclear Waste Johnston, Cliff T.; Agnew, Stephen F.; Schoonover, Jon R. Environmental Science & Technology, Vol. 36, Issue 11 https://doi.org/10.1021/es011226k	journal	June 2002
A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes Moyer, Bruce A.; Custelcean, Radu; Hay, Benjamin P. Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3016832	journal	June 2012
Conversion of Coarse Gibbsite Remaining in Hanford Nuclear Waste Tank Heels to Solid Sodium Aluminate [NaAl(OH) ₄ ·1.5H ₂ O] Herting, Daniel L.; Reynolds, Jacob G.; Barton, W. Blaine Industrial & Engineering Chemistry Research, Vol. 53, Issue 36 https://doi.org/10.1021/ie5014212	journal	August 2014
Structure of the aluminate ion in solutions at high pH Moolenaar, Robert J.; Evans, John Cyril; McKeever, L. D. The Journal of Physical Chemistry, Vol. 74, Issue 20 https://doi.org/10.1021/j100714a014	journal	October 1970
Equilibria in the Systems Na ₂ O–SiO ₂ –H ₂ O and Na ₂ O–Al ₂ O ₃ –H ₂ O at 25°C. Sprauer, J. W.; Pearce, D. W. The Journal of Physical Chemistry, Vol. 44, Issue 7 https://doi.org/10.1021/j150403a009	journal	July 1940
Multiple-Quantum Magic-Angle Spinning NMR: A New Method for the Study of Quadrupolar Nuclei in Solids Medek, Ales; Harwood, John S.; Frydman, Lucio Journal of the American Chemical Society, Vol. 117, Issue 51 https://doi.org/10.1021/ja00156a015	journal	December 1995
Solid-state sodium-23 and aluminum-27 MAS NMR study of the dehydration of sodium aluminate hydrate (Na2O.cntdot.Al2O3.cntdot.3H2O) Dec, Steven F.; Maciel, Gary E.; Fitzgerald, John J. Journal of the American Chemical Society, Vol. 112, Issue 25 https://doi.org/10.1021/ja00181a006	journal	December 1990
Designing Solid Materials from Their Solute State: A Shift in Paradigms toward a Holistic Approach in Functional Materials Chemistry Gebauer, Denis; Wolf, Stephan E. Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.8b13231	journal	February 2019
Phase Diagram for the System Na ₂ O−Al ₂ O ₃ −H ₂ O at High Alkali Concentration Zhang, Yifei; Li, Yinghui; Zhang, Yi Journal of Chemical & Engineering Data, Vol. 48, Issue 3 https://doi.org/10.1021/je025611g	journal	March 2003
Phase Diagram for the Na ₂ O−Al ₂ O ₃ −H ₂ O System at 130 °C Ma, Shuhua; Zheng, Shili; Zhang, Yifei Journal of Chemical & Engineering Data, Vol. 52, Issue 1 https://doi.org/10.1021/je060244k	journal	January 2007
Solubility of Al ₂ O ₃ in the Na ₂ O−Al ₂ O ₃ −H ₂ O−CH ₃ OH System at (30 and 60) °C Zhang, Ying; Zheng, Shili; Du, Hao Journal of Chemical & Engineering Data, Vol. 55, Issue 3 https://doi.org/10.1021/je900611g	journal	March 2010
Dielectric Relaxation of Concentrated Alkaline Aluminate Solutions Buchner, Richard; Sipos, Pál; Hefter, Glenn The Journal of Physical Chemistry A, Vol. 106, Issue 28 https://doi.org/10.1021/jp0143589	journal	July 2002
Raman Studies of the Solution Structure of Univalent Electrolytes in Water Dillon, Stephanie R.; Dougherty, Ralph C. The Journal of Physical Chemistry A, Vol. 106, Issue 34 https://doi.org/10.1021/jp020655h	journal	August 2002
Hydrogen bonded associates in the Bayer process (in concentrated aluminate lyes): the mechanism of gibbsite nucleation Buvári-barcza, Ágnes; Rózsahegyi, Márta; Barcza, Lajos Journal of Materials Chemistry, Vol. 8, Issue 2 https://doi.org/10.1039/a705468h	journal	January 1998
Alumina: discriminative analysis using 3D correlation of solid-state NMR parameters Chandran, C. Vinod; Kirschhock, Christine E. A.; Radhakrishnan, Sambhu Chemical Society Reviews, Vol. 48, Issue 1 https://doi.org/10.1039/c8cs00321a	journal	January 2019
Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH) ₃ ) with sodium nitrite/nitrate Dembowski, Mateusz; Snyder, Michelle M.; Delegard, Calvin H. Physical Chemistry Chemical Physics, Vol. 22, Issue 8 https://doi.org/10.1039/c9cp05856g	journal	January 2020
Solid-state aluminium-27 nuclear magnetic resonance chemical shift and quadrupole coupling data for condensed AlO ₄ tetrahedra Müller, Dirk; Gessner, Wolfgang; Samoson, Ago J. Chem. Soc., Dalton Trans., Issue 6 https://doi.org/10.1039/dt9860001277	journal	January 1986
Separation of NaOH by Solvent Extraction Using Weak Hydroxy Acids Haverlock, Tamara J.; Bonnesen, Peter V.; Moyer, Bruce A. Solvent Extraction and Ion Exchange, Vol. 21, Issue 4 https://doi.org/10.1081/sei-120022517	journal	January 2003
Nonasodium Bis(hexahydroxoaluminate) Trihydroxide Hexahydrate Zabel, V.; Schneider, M.; Weinberger, M. Acta Crystallographica Section C Crystal Structure Communications, Vol. 52, Issue 4 https://doi.org/10.1107/s0108270195015277	journal	April 1996
The Origin of Aluminum Flocs in Polluted Streams Furrer, G. Science, Vol. 297, Issue 5590 https://doi.org/10.1126/science.1076505	journal	September 2002
Adatom Fe(III) on the hematite surface: Observation of a key reactive surface species Eggleston, Carrick M.; Stack, Andrew G.; Rosso, Kevin M. Geochemical Transactions, Vol. 5, Issue 2 https://doi.org/10.1186/1467-4866-5-33	journal	June 2004
Theoretical studies on aluminate and sodium aluminate species in models for aqueous solution; Al(OH) ₃ , Al(OH) (super -) ₄ , and NaAl(OH) ₄ Tossell, J. A. American Mineralogist, Vol. 84, Issue 10 https://doi.org/10.2138/am-1999-1019	journal	October 1999
The Crystal Structure of the Potassium Aluminate K2[Al2O(OH)6]. Johansson, Georg; Hope, Håkon; Nevald, R. Acta Chemica Scandinavica, Vol. 20 https://doi.org/10.3891/acta.chem.scand.20-0505	journal	January 1966

Similar Records

Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates

Journal Article · Tue Apr 07 00:00:00 EDT 2020 · Inorganic Chemistry · OSTI ID:1631324

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystallization
Ions
NMR
Nuclear magnetic resonance spectroscopy
Resonance structures
Sodium
Sodium Aluminate

Intermediate Species in the Crystallization of Sodium Aluminate Hydroxy Hydrates

Citation Formats

References (55)

Similar Records

Related Subjects