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

Abstract

Pulsed field gradient nuclear magnetic resonance (PFG-NMR) measurements were successfully applied to the 27 Al (I = 5/2) nucleus in concentrated electrolytes to investigate the diffusion of aluminate ions [Al(OH) 4- ] in simulant high-level nuclear waste (3 M NaOH) between 25 and 85 °C. The temperature-dependent diffusion coefficients obtained from 1 H, 23 Na, and 27 Al PFG-NMR were well fit by a Vogel-Fulcher-Tammann model and a power law equation. Comparison of 27 Al diffusion coefficients of 0.1 M Al(OH) 4- in ∼3 M MOH (where M = Na + , K + , (CH 3 ) 4 N + ) at room temperature varied in agreement with the expected changes in solution viscosity via Stokes-Einstein relationship, confirming that the dominant Al species at these conditions are Al(OH) 4- monomers. This 27 Al PFG-NMR study extends an established methodology to a previously unexplored nucleus enabling this experimental technique to be leverage for exploring ion transport, speciation, and solution structure in concentrated electrolytes.