Solute Diffusion in Ionic Liquids, NMR Measurements and Comparisons to Conventional Solvents

Diffusion coefficients of a variety of dilute solutes in the series of 1-alkyl-1-methylpyrrolidinium bis­(trifluoromethanesulfonyl)­imides ([Pr_n1]­[Tf₂N], n = 3, 4, 6, 8, and 10), trihexyltetracedecylphosphonium bis­(trifluoromethanesulfonyl)­imide [P_14,666]­[Tf₂N], and assorted imidazolium ionic liquids are measured using pulsed field gradient ¹H NMR. These data, combined with available literature data, are used to try to uncover the solute and solvent characteristics most important in determining tracer diffusion rates. Discussion is framed in terms of departures from simple hydrodynamic predictions for translational friction using the ratio ζ_obs/ζ_SE, where ζ_obs is the observed friction, determined from the measured diffusion coefficient D via ζ_obs = k_BT/D, and ζ_SE = 6πηR is the Stokes friction on a sphere of radius R (determined from the solute van der Waals volume) in a solvent with viscosity η. In the case of neutral solutes, the primary determinant of whether hydrodynamic predictions are accurate is the relative size of solute versus solvent molecules. A single correlation, albeit with considerable scatter, is found between ζ_obs/ζ_SE and the ratio of solute-to-solvent van der Waals volumes, ζ_obs/ζ_SE = {1 + a(V_U/V_V)^−p}, with constants a = 1.93 and p = 1.88. In the case of small solutes, the observed friction is over 100-fold smaller than predictions of hydrodynamic models. The dipole moment of the solute has little effect on the friction, whereas solute charge has a marked effect. For monovalent solutes of size comparable to or smaller than the solvent ions, the observed friction is comparable to or even greater than what is predicted by hydrodynamics. These general trends are shown to be quite similar to what is observed for tracer diffusion in conventional solvents.