Lorna Crowhurst

Understanding the polarity of ionic liquids

The polarities of a wide range of ionic liquids have been determined using the Kamlet-Taft empirical polarity scales α, β and π*, with the dye set Reichardts Dye, N,N-diethyl-4-nitroaniline and 4-nitroaniline. These have been compared to measurements of these parameters with different dye sets and to different polarity scales. The results emphasise the importance of recognising the role that the nature of the solute plays in determining these scales. It is particularly noted that polarity scales based upon charged solutes can give very different values for the polarity of ionic liquids compared to those based upon neutral probes. Finally, the effects of commonplace impurities in ionic liquids are reported.

Self-assembly in the electrical double layer of ionic liquids.

We have studied the structure of two ionic liquids confined between negatively charged mica sheets. Both liquids exhibit interfacial layering, however the repeat distance is dramatically different for the two liquids. Our results suggest a transition from alternating cation-anion monolayers to tail-to-tail cation bilayers when the length of the cation hydrocarbon chain is increased.

Salts dissolved in salts: ionic liquid mixtures

Solvents and solutions are ubiquitous in chemistry. For instance, in synthesis the solvent allows reagents to mix intimately so that reactions between these may occur. Consequently, understanding how solutes behave in solutions has been one of the major themes of chemistry throughout its history. Ionic liquids (liquid salts) are an exciting recent addition to the range of available solvents. Here we show that these solvents interact with dissolved salts to give solutions that are completely different from those of salts in either traditional organic solvents or water. Observations of these ideal salt solutions will require new models of solvation and polarity and have the potential to lead to new chemical processes.

Solvent?solute interactions in ionic liquidsElectronic supplementary information (ESI) available: synthesis of ionic liquids. See http://www.rsc.org/suppdata/cp/b3/b303095d/

A range of ionic liquids has been investigated using the Kamlet–Taft parameters α, β, and π*. It was found that π* is high for all of the ionic liquids studied and varies with both anion and cation, α is generally moderate and depends mainly on the cation, β is also moderate and depends mainly on the anion. Comparison is made with other polarity measurements in ionic liquids.

Unexpected preferential dehydration of artemisinin in ionic liquids.

Thermodynamic measurements (at 298 K) reveal that a crucial step in the extraction process of the key antimalarial drug artemisinin by ionic liquids (ILs), namely, precipitation through the addition of water, is driven by artemisinin dehydration due to the differences in the waters interaction with the bulk ILs, rather than with the artemisinin itself.