Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH)3) Crystallization from Alkaline Aqueous Solution

Krzysko, Anthony J.; Graham, Trent R.; Dembowski, Mateusz; Beck, Chelsie; Zhang, Xin; Rosso, Kevin M.; Clark, Sue B.; Pearce, Carolyn I.

doi:10.1021/acsearthspacechem.1c00385

Title: Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH)₃) Crystallization from Alkaline Aqueous Solution

Journal Article · Mon Mar 28 00:00:00 UTC 2022 · ACS Earth and Space Chemistry

DOI: https://doi.org/10.1021/acsearthspacechem.1c00385 · OSTI ID:1959833

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Argonne National Lab. (ANL), Lemont, IL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Understanding molecular-scale factors governing the precipitation of aluminum hydroxides, such as gibbsite, under alkaline conditions is important for the formation of laterite deposits, as well as aluminum processing. However, mechanisms enabling tetrahedral aluminate ions to assemble into octahedral sites of the gibbsite lattice remain unclear. Formation of oligomeric complexes has been hypothesized as a critical intermediate step. Here, we report a study of gibbsite solubility in highly alkaline solutions using deuterium substitution to probe equilibrium and kinetic factors that could affect oligomeric intermediate formation, including the reactivity and the diffusivity of aluminate ions. When substituting sodium hydroxide with sodium deuteroxide, solution analysis shows a nearly 40% and 50% increase in gibbsite solubility in 2.4 and 3.3 mol·kg^–1 total sodium solutions, respectively. Raman spectroscopy indicated that monomeric aluminate ions are the predominant species in solution irrespective of deuteration. However, both ²⁷Al and ²³Na nuclear magnetic resonance (NMR) spectroscopy revealed significant differences in chemical shifts in deuterated solutions, and analysis of ¹H, ²³Na, and ²⁷Al diffusion coefficients with pulsed-field gradient, stimulated echo NMR spectroscopy shows a decrease in ion diffusivity with increasing total deuterium in solution, consistent with the notion of increasing strength in the hydrogen/deuterium bonding network. In conclusion, because the relative change in ¹H diffusion coefficients are commensurate with the difference in apparent solubility constants, there is evidence for an oligomeric intermediate whose steady-state concentration is maintained by the collision frequency of aluminate ions.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Environmental Molecular Sciences Laboratory (EMSL), Richland, WA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: 89233218CNA000001; AC02-06CH11357; AC05-76RL01830

OSTI ID:: 1959833

Report Number(s):: LA-UR--22-20255; 173101

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 4 Vol. 6; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Gibbsite
aluminate
deuterium
isotopic substitution
solubility

Title: Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH)3) Crystallization from Alkaline Aqueous Solution

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Title: Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH)₃) Crystallization from Alkaline Aqueous Solution