Abstract
Phase diagram mixtures of the salt choline chloride (ChCl) with ethylene glycol (EG) surprisingly seem to behave as ideal binary nonelectrolyte mixtures [Agieienko, V.; Buchner, R.Phys. Chem. Chem. Phys.2022, 24, 5265]. To shed some light on this conundrum, results of broad-band dielectric relaxation spectroscopy (DRS) and quantum-chemical calculations are reported for solutions of ChCl, choline ...
Abstract
Phase diagram mixtures of the salt choline chloride (ChCl) with ethylene glycol (EG) surprisingly seem to behave as ideal binary nonelectrolyte mixtures [Agieienko, V.; Buchner, R.Phys. Chem. Chem. Phys.2022, 24, 5265]. To shed some light on this conundrum, results of broad-band dielectric relaxation spectroscopy (DRS) and quantum-chemical calculations are reported for solutions of ChCl, choline iodide (ChI), and chlorocholine chloride (ClChCl), in EG up to saturation at 298.15 K. The data revealed that all three solutes are only weakly solvated in the sense that on average per equivalent of solute only one EG OH-group is dynamically affected. While contact ion pairs are significant for solute concentrations of less than or similar to 1 M, free cation concentrations are rather low. Instead, over the entire concentration range a large fraction of the dipolar cations could not be detected by DRS. We argue that the latter are embedded in large solute aggregates, explaining thus the phase diagram of ChCl + EG and the very low ionicity of all systems.
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