Multinuclear PFGSTE NMR description of 39K, 23Na, 7Li, and 1H specific activation energies governing diffusion in alkali nitrite solutions

Graham, Trent R.; Kennedy, Ashley R.; Felsted, Robert G.; Colina-Ruiz, Roberto A.; Nienhuis, Emily T.; Reynolds, Jacob G.; Pearce, Carolyn I.

doi:10.1016/j.jmr.2024.107707

Multinuclear PFGSTE NMR description of ³⁹K, ²³Na, ⁷Li, and ¹H specific activation energies governing diffusion in alkali nitrite solutions

Journal Article · Mon Jun 03 00:00:00 EDT 2024 · Journal of Magnetic Resonance

DOI:https://doi.org/10.1016/j.jmr.2024.107707· OSTI ID:2476327

^[1]; Kennedy, Ashley R. ^[2]; Felsted, Robert G. ^[1]; Colina-Ruiz, Roberto A. ^[1]; Nienhuis, Emily T. ^[1]; Reynolds, Jacob G. ^[3]; Pearce, Carolyn I. ^[4]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Savannah River National Laboratory (SRNL), Aiken, SC (United States)
Washington River Protection Solutions, Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 (³⁹K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that ³⁹K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Further, analysis of the results indicates that ³⁹K NMR diffusometry is feasible when the nuclei exhibit spin–lattice and spin–spin relaxation coefficients on the order of 60–100 ms and 50–100 ms, respectively. The diffusivity of ³⁹K followed Arrhenius behavior, and comparative ²³Na, ⁷Li, and ¹H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of ³⁹K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

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:: 2476327

Report Number(s):: PNNL-SA--197007

Journal Information:: Journal of Magnetic Resonance, Journal Name: Journal of Magnetic Resonance Vol. 364; ISSN 1090-7807

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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