Tracking nitrite's deviation from Stokes–Einstein predictions with pulsed field gradient 15N NMR spectroscopy

Abstract

Predicting the behavior of oxyanions in radioactive waste stored at the Department of Energy legacy nuclear sites requires the development of novel analytical methods. This work demonstrates ¹⁵N pulsed field gradient nuclear magnetic resonance spectroscopy to quantify the diffusivity of nitrite. Experimental results, supported by molecular dynamics simulations, indicate that the diffusivity of free hydrated nitrite exceeds that of free hydrated sodium despite the greater hydrodynamic radius of nitrite. Investigations are underway to understand how the compositional and dynamical heterogeneities of the ion networks at high concentrations affect rheological and transport properties.