Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates

Graham, Trent R.; Gorniak, Rafal; Dembowski, Mateusz; Zhang, Xin; Clark, Sue B.; Pearce, Carolyn I.; Clark, Aurora E.; Rosso, Kevin M.

doi:10.1021/acs.inorgchem.0c00258

Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates

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

DOI:https://doi.org/10.1021/acs.inorgchem.0c00258· OSTI ID:1631324

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

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Washington State Univ., Pullman, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Crystallization of Al-bearing solid phases from highly alkaline Na₂O:Al₂O₃:H₂O solutions commonly necessitates an Al³⁺ coordination change from tetrahedral to octahedral, but intermediate coordination states are often difficult to isolate. Here, a similar Al³⁺ coordination change process is examined during the solid-state recrystallization of sodium oxohydroxoaluminate hydrate (MSA) to nonasodium bis(hexahydroxy aluminate) trihydroxide hexahydrate (NSA) at ambient temperature. While the MSA structure contains solely polymerized tetrahedral Al³⁺, the NSA structure is a molecular aluminate salt solely based upon monomeric octahedral Al³⁺. Spontaneous recrystallization of MSA and excess sodium hydroxide hydrate into NSA over 3 days of reaction time was clearly evident in X-ray diffractograms and in Raman spectra. In situ ²⁷Al multiple quantum MAS NMR spectroscopy showed no evidence of intermediate aluminates, suggesting that intermediates, such as pentacoordinate Al³⁺, are short-lived and require more highly time resolved spectroscopies to detect. Such research is advancing upon detailed mechanistic understanding of Al³⁺ coordination change mechanisms in these highly alkaline systems, with relevance to aluminum refining, corrosion sciences, and nuclear waste processing.

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)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1631324

Report Number(s):: PNNL-SA--150728

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (41)

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
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
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
The Crystal Structure of Hydrated Sodium Aluminate, NaAlO2 · 5/4H2O, and Its Dehydration Product Kaduk, James A.; Pei, Shiyou Journal of Solid State Chemistry, Vol. 115, Issue 1 https://doi.org/10.1006/jssc.1995.1111	journal	February 1995
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
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
Lithium isotope fractionation during uptake by gibbsite Wimpenny, Josh; Colla, Christopher A.; Yu, Ping Geochimica et Cosmochimica Acta, Vol. 168 https://doi.org/10.1016/j.gca.2015.07.011	journal	November 2015
Crystallization of monosodium aluminate hydrate from a concentrated aluminate solution containing silica You, Shaowei; Zhang, Yifei; Cao, Shaotao Hydrometallurgy, Vol. 115-116 https://doi.org/10.1016/j.hydromet.2012.01.001	journal	March 2012
Precipitation of monosodium aluminate hydrate from concentrated sodium aluminate solution You, Shaowei; Guo, Tao; Liu, Pengfei Hydrometallurgy, Vol. 183 https://doi.org/10.1016/j.hydromet.2018.12.005	journal	January 2019
Two-dimensional one pulse MAS of half-integer quadrupolar nuclei Massiot, Dominique; Hiet, Julian; Pellerin, Nadia Journal of Magnetic Resonance, Vol. 181, Issue 2 https://doi.org/10.1016/j.jmr.2006.05.007	journal	August 2006
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
Spectra study hydrogen bonds dynamics of water molecules at NaOH solutions Li, Fabing; Wang, Ying; Sun, Chenglin Journal of Molecular Liquids, Vol. 277 https://doi.org/10.1016/j.molliq.2018.12.031	journal	March 2019
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
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
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
Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide Graham, Trent R.; Hu, Jian Zhi; Zhang, Xin Inorganic Chemistry, Vol. 58, Issue 18 https://doi.org/10.1021/acs.inorgchem.9b02000	journal	September 2019
Transitions in Al Coordination during Gibbsite Crystallization Using High-Field ²⁷ Al and ²³ Na MAS NMR Spectroscopy Hu, Jian Zhi; Zhang, Xin; Jaegers, Nicholas R. The Journal of Physical Chemistry C, Vol. 121, Issue 49 https://doi.org/10.1021/acs.jpcc.7b10424	journal	November 2017
Nucleation and Morphology of Monosodium Aluminate Hydrate from Concentrated Sodium Aluminate Solutions Cao, Shaotao; Zhang, Yifei; Zhang, Yi Crystal Growth & Design, Vol. 10, Issue 4 https://doi.org/10.1021/cg901164r	journal	April 2010
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
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
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
Multiple-Quantum and Cross-Polarized ²⁷ Al MAS NMR of Mechanically Treated Mixtures of Kaolinite and Gibbsite Ashbrook, Sharon E.; McManus, Jamie; MacKenzie, Kenneth J. D. The Journal of Physical Chemistry B, Vol. 104, Issue 27 https://doi.org/10.1021/jp000316t	journal	July 2000
Structure of Aqueous Sodium Aluminate Solutions: A Solution X-ray Diffraction Study Radnai, Tamás; May, Peter M.; Hefter, Glenn T. The Journal of Physical Chemistry A, Vol. 102, Issue 40 https://doi.org/10.1021/jp981244x	journal	October 1998
Aqueous sodium hydroxide (NaOH) solutions at high pressure and temperature: insights from in situ Raman spectroscopy and ab initio molecular dynamics simulations Stefanski, Johannes; Schmidt, Christian; Jahn, Sandro Physical Chemistry Chemical Physics, Vol. 20, Issue 33 https://doi.org/10.1039/C8CP00376A	journal	January 2018
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
Chemical speciation in concentrated alkaline aluminate solutions in sodium, potassium and caesium media. Interpretation of the unusual variations of the observed hydroxide activity Sipos, P?l; Schibeci, Mark; Peintler, G?bor Dalton Transactions, Issue 15 https://doi.org/10.1039/b513357b	journal	January 2006
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
Synthesis and thermochemical characteristics of Na2O · Al2O3 · 2.5H2O Grishchenko, R. O.; Emelina, A. L. Russian Journal of Physical Chemistry A, Vol. 87, Issue 1 https://doi.org/10.1134/S0036024413010081	journal	December 2012
A Raman Study of Aqueous KOH Solution in Glassy State Kanno, Hitoshi; Hiraishi, Jiro Bulletin of the Chemical Society of Japan, Vol. 58, Issue 9 https://doi.org/10.1246/bcsj.58.2701	journal	September 1985
Raman, IR, and ²⁷ Al-MAS-NMR Spectroscopic Studies of Sodium (Hydroxy)Aluminates Watling, H. R.; Sipos, P. M.; Byrne, L. Applied Spectroscopy, Vol. 53, Issue 4 https://doi.org/10.1366/0003702991946875	journal	April 1999

Similar Records

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 · OSTI ID:1633402

Disordered interfaces of alkaline aluminate salt hydrates provide glimpses of Al³⁺ coordination changes

Journal Article · Wed Jan 04 23:00:00 EST 2023 · Journal of Colloid and Interface Science · OSTI ID:1968855

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
NMR
Sodium Aluminate

Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates

Citation Formats

References (41)

Similar Records

Related Subjects