Aggregation Behavior of Several Ionic Liquids in Molecular Solvents of Low Polarity--Indication of a Bimodal...

The structure and dynamics of ion pairing and aggregation is studied by concentration- and temperature-dependent measurements of (1) H and (19) F self-diffusion coefficients, viscosity, and conductivity for the following five solutions: 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([Cn mim][NTf2], n=2, 4, 6) in dichloromethane (CH2Cl2), and [C6 mim][NTf2] in tetrahydrofuran (THF) and chlorobenzene (C6 H5 Cl). The temperature dependence of these properties at constant IL concentrations follows the Arrhenius law for all five solutions. The IL-concentration dependence of the respective activation energies obtained from the Arrhenius analysis is nonlinear in the case of conductivity, but indicates linear relationships for viscosity and self-diffusion. All five solutions studied display average solute radius maxima as plotted against IL concentration. The maximum average solute radii follow an order of solvents of CHCl3 >C6 H5 Cl>CH2 Cl2 ≈THF, which corresponds to the order of increasing solvent dielectric constant. The observed trends in the physical properties of these solutions indicate the development of a bimodal distribution of solute size with increasing IL concentration. Specifically, the presence of aggregates is supported by the analysis of the conductivity data and the observation of the same self-diffusion coefficients for the cation and anion. The concurrent presence of freely dissolved ions is supported by the obtained average solute radii that do not exceed the radii of the corresponding ion pairs.