Dynamic ionic radius of alkali metal ions in aqueous solution: a pulsed-field gradient NMR study

Abstract

The dynamic behavior of alkali metal ions, Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ in aqueous solutions is one of the most important topics in solution chemistry. Since these alkali metals contain nuclear magnetic resonance (NMR) active nuclei, it is possible to directly measure the diffusion constants of the alkali metal ions using the pulsed field gradient (PFG) NMR method. In this paper, the ⁷Li, ²³Na, ⁸⁷Rb, ¹³³Cs and ¹H resonances are observed for diffusion constants in aqueous solution and the solvent H₂O. Until now, the values of the diffusion constant have been lacking when discussing hydration effects around alkali metal ions. It is known that the static ionic radius (R_ion) increases with increasing the atomic number, and the experimental diffusion constants also increase with increasing the atomic number, which is opposite to the Stokes–Einstein (SE) relation. It suggests that alkali metal ions diffuse through a space of 10⁻⁶ m accompanying the hydrated spheres with a time interval of 10⁻³ s. For each alkali metal ion, the dynamic ionic radius is evaluated.