Influence of cellulose on ion diffusivity in 1-ethyl-3-methyl-imidazolium acetate cellulose solutions
Résumé
Solutions of microcrystalline cellulose in 1-ethyl-3-methyl-imidazolium acetate have been investigated using pulsedfield gradient 1H NMR. In all cases the geometrically larger cation was found to diffuse faster than the smaller anion. Arrhenius temperature analysis has been applied to the ion diffusivities giving activation energies. The diffusion and published viscosity data for these solutions were shown to follow the Stokes-Einstein relationship, giving hydrodynamic radii of 1.6 A˚ (cation) and 1.8 A˚ (anion). Theories for obstruction, free-volume and hydrodynamic effects on solvent diffusion have been applied. The Mackie-Meares and Maxwell-Fricke obstruction models provided a correct trend only when assuming a certain fraction of ions are bound to the polymer. From this fraction it was shown that the maximum dissolvable cellulose concentration is ˜27% w/w, which is consistent with the highest known prepared concentration of cellulose in this ionic liquid. The Phillies' hydrodynamic model is found to give the best description for the cellulose concentration dependence of the ion diffusivities