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

Pulsed field gradient nuclear magnetic resonance (PFG-NMR) measurements were successfully applied to the Al ( I = 5/2) nucleus in concentrated electrolytes to investigate the diffusion of aluminate ions [Al(OH)] in simulant high-level nuclear waste (3 M NaOH) between 25 and 85 °C. The temperature-dependent diffusion coefficients obtained from H, Na, and Al PFG-NMR were well fit by a Vogel-Fulcher-Tammann model and a power law equation. Comparison of Al diffusion coefficients of 0.1 M Al(OH) in ∼3 M MOH (where M = Na, K, (CH)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) monomers. This 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.