We report here the first systematic study of the effect of impurities and additives (e.g., water, chloride, and cosolvents) on the physical properties of room-temperature ionic liquids. Remarkably, it was discovered that the viscosity of mixtures was dependent mainly on the mole fraction of added molecular solvents and only to a lesser extent upon their identity, allowing viscosity changes during the course of a reaction to be entirely predictable. While the addition of such molecular solvents decreases the viscosity and density, chloride impurities, arising from the preparation of the ionic liquids, increase viscosity dramatically. The commonly used methods of preparation were validated with respect to chloride impurity.
Motivated by the prevailing need for a sustainable development and taking the principles of Green Chemistry as a starting point, the present paper describes new and updated findings regarding a sustainable product design for ionic liquids. The focus is on environmental risk. Nevertheless, cytotoxicity testing and first indicative results from a genotoxicity study extend present knowledge also with regard to possible effects on humans. The structural variability of commercially available ionic liquids as well as the abundance of theoretically accessible ionic liquids is illustrated and the consequences for an integrated risk assessment accompanying the development process are discussed. The side chain effect on toxicity for imidazolium type ionic liquids was confounded by more complex biological testing. Also, an influence of an anion on cytotoxicity is shown for the first time. Testing of presumed metabolites of the imidazolium type cations showed a significantly lower biological activity in cytotoxicity studies than their parent compounds. The importance of a purity assessment for ionic liquids is pointed out and a collection of methods that is believed to be adequate is presented. In addition to risk analysis, the use of life cycle analysis for the multi-objective problem of designing ionic liquids is sketched and an eco-design scheme for ionic liquids is proposed. In conclusion, the paper illustrates the complex nature of the development processes ionic liquids are currently undergoing and provides guidance on which aspects have to be kept in mind.
Industrially performed catalytic oxidation reactions often suffer from drawbacks such as poor conversion and selectivity due to over-oxidation, corrosive reaction media, lack of solvent and catalyst recycling, and negative environmental impact due to evaporation of the solvents. In order to provide a methodology that addresses these problems, ionic liquids have been investigated as reaction media. For the example of the oxidation of benzyl alcohol to benzaldehyde (dehydrogenation), it was shown that the palladium metal catalysed oxidation can be brought about, leading to better TOFs than those observed in dimethyl sulfoxide, with the added advantage of facile catalyst and solvent recycling. It was found that the selectivity to benzaldehyde is strongly dependent on the level of chloride ion, which leads to the formation of dibenzyl ether. Secondly, the amount of water present in the ionic liquid determines the extent of benzoic acid formation. Interestingly, ionic liquids are able to deactivate the water formed in the oxidation of benzyl alcohol and thus prevent it from further reaction to benzoic acid. The oxidation of toluene and ethylbenzene showed that the introduction of oxygen into the molecule is feasible using the same methodology.
1 June 2005 in The Journal of Chemical Thermodynamics