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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2];  [4]; ORCiD logo [3];  [2]; ORCiD logo [2]; ORCiD logo [2]
  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
Publication Date:
Research Org.:
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 Org.:
USDOE
OSTI Identifier:
1489787
Report Number(s):
PNNL-SA-138291
Journal ID: ISSN 1520-6106
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 48; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
quadrupolar Diffusion NMR, Electrolytes, Sodium Aluminate, Aluminum Hydroxide

Citation Formats

Graham, Trent R., Han, Kee Sung, Dembowski, Mateusz, Krzysko, Anthony J., Zhang, Xin, Hu, Jianzhi, Clark, Sue B., Clark, Aurora E., Schenter, Gregory K., Pearce, Carolyn I., and Rosso, Kevin M. 27Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions. United States: N. p., 2018. Web. doi:10.1021/acs.jpcb.8b10145.
Graham, Trent R., Han, Kee Sung, Dembowski, Mateusz, Krzysko, Anthony J., Zhang, Xin, Hu, Jianzhi, Clark, Sue B., Clark, Aurora E., Schenter, Gregory K., Pearce, Carolyn I., & Rosso, Kevin M. 27Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions. United States. doi:10.1021/acs.jpcb.8b10145.
Graham, Trent R., Han, Kee Sung, Dembowski, Mateusz, Krzysko, Anthony J., Zhang, Xin, Hu, Jianzhi, Clark, Sue B., Clark, Aurora E., Schenter, Gregory K., Pearce, Carolyn I., and Rosso, Kevin M. Wed . "27Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions". United States. doi:10.1021/acs.jpcb.8b10145.
@article{osti_1489787,
title = {27Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions},
author = {Graham, Trent R. and Han, Kee Sung and Dembowski, Mateusz and Krzysko, Anthony J. and Zhang, Xin and Hu, Jianzhi and Clark, Sue B. and Clark, Aurora E. and Schenter, Gregory K. and Pearce, Carolyn I. and Rosso, Kevin M.},
abstractNote = {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.},
doi = {10.1021/acs.jpcb.8b10145},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 48,
volume = 122,
place = {United States},
year = {2018},
month = {10}
}