²⁷Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions

Journal Article · Wed Oct 24 00:00:00 EDT 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.8b10145· OSTI ID:1489787

Graham, Trent R.  ^[1]; Han, Kee Sung  ^[2]; Dembowski, Mateusz  ^[2]; Krzysko, Anthony J.  ^[3]; Zhang, Xin  ^[2]; Hu, Jianzhi  ^[2]; Clark, Sue B. ^[4]; Clark, Aurora E.  ^[3]; Schenter, Gregory K. ^[2]; Pearce, Carolyn I.  ^[2]; Rosso, Kevin M.  ^[2]

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1. Pacific Northwest National Laboratory, Richland, Washington 99354, United States; The Voiland School of Chemical and Biological Engineering, Washington State University, Pullman, Washington 99164, United States
2. Pacific Northwest National Laboratory, Richland, Washington 99354, United States
3. Department of Chemistry, Washington State University, Pullman, Washington 99164, United States
4. Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Department of Chemistry, Washington State University, Pullman, Washington 99164, United States

Pulsed field gradient diffusion ordered nuclear magnetic resonance spectroscopy (DOSY-NMR) was successfully applied to the ²⁷Al nucleus in concentrated electrolytes to investigate the diffusion of aluminate [Al(OH)₄^-] in simulant high-level nuclear waste (3M NaOH) between 25 and 85°C. The temperature dependent diffusion coefficients obtained from ¹H, ²³Na and ²⁷Al PFG-NMR were well fit by a Vogel-Fulcher-Tammann model and a power law equation. Comparison of ²⁷Al diffusion coefficients of 0.1 M Al(OH)₄^- in 3M sodium hydroxide, 3M potassium hydroxide (KOH) and 25 wt % tetramethylammonium hydroxide (TMAOH) at room temperature varied in agreement with expected changes in viscosity. ²⁷Al DOSY-NMR studies extend an established methodology to a previously unexplored nucleus, and demonstrate the advantages of this technique for exploring ion transport, speciation and solution structure in concentrated electrolytes.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1489787
• Report Number(s): PNNL-SA-138291
• Journal Information: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 122, Issue 48; ISSN 1520-6106
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

quadrupolar Diffusion NMR
Electrolytes
Sodium Aluminate
Aluminum Hydroxide