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      New dimensions in salt–solvent mixtures: a 4th evolution of ionic liquids

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          Abstract

          The important properties and applications of molecular liquid mixtures with ionic liquids and low melting organic salts are discussed.

          Abstract

          In the field of ionic liquids (ILs) it has long been of fundamental interest to examine the transition from salt-in-solvent behaviour to pure liquid–salt behaviour, in terms of structures and properties. At the same time, a variety of applications have beneficially employed IL–solvent mixtures as media that offer an optimal set of properties. Their properties in many cases can be other than as expected on the basis of simple mixing concepts. Instead, they can reflect the distinct structural and interaction changes that occur as the mixture passes through the various stages from pure coulombic medium, to “plasticised” coulombic medium, into a meso-region where distinct molecular and ionic domains can co-exist. Such domains can persist to quite a high dilution into the salt-in-solvent regime and their presence manifests itself in a number of important synergistic interaction effects in diverse areas such as membrane transport and corrosion protection. Similarly, the use of ionic liquids in synthetic processes where there is a significant volume fraction of molecular species present can produce a variety of distinct and unexpected effects. The range of these salt–solvent mixtures is considerably broader than just those based on ionic liquids, since there is only minor value in the pure salt being a liquid at the outset. In other words, the extensive families of organic and metal salts become candidates for study and use. Our perspective then is of an evolution of ionic liquids into a broader field of fundamental phenomena and applications. This can draw on an even larger family of tuneable salts that exhibit an exciting combination of properties when mixed with molecular liquids.

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          Structure and nanostructure in ionic liquids.

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            Ionic liquids and their solid-state analogues as materials for energy generation and storage

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              On the concept of ionicity in ionic liquids.

              Ionic liquids are liquids comprised totally of ions. However, not all of the ions present appear to be available to participate in conduction processes, to a degree that is dependent on the nature of the ionic liquid and its structure. There is much interest in quantifying and understanding this 'degree of ionicity' phenomenon. In this paper we present transport data for a range of ionic liquids and evaluate the data firstly in terms of the Walden plot as an approximate and readily accessible approach to estimating ionicity. An adjusted Walden plot that makes explicit allowance for differences in ion sizes is shown to be an improvement to this approach for the series of ionic liquids described. In some cases, where diffusion measurements are possible, it is feasible to directly quantify ionicity via the Nernst-Einstein equation, confirming the validity of the adjusted Walden plot approach. Some of the ionic liquids studied exhibit ionicity values very close to ideal; this is discussed in terms of a model of a highly associated liquid in which the ion correlations have similar impact on both the diffusive and conductive motions. Ionicity, as defined, is thus a useful measure of adherence to the Nernst-Einstein equation, but is not necessarily a measure of ion availability in the chemical sense.
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                Author and article information

                Journal
                FDISE6
                Faraday Discussions
                Faraday Discuss.
                Royal Society of Chemistry (RSC)
                1359-6640
                1364-5498
                2018
                2018
                : 206
                : 9-28
                Affiliations
                [1 ]School of Chemistry
                [2 ]The Australian Centre of Excellence for Electromaterials Science
                [3 ]Monash University
                [4 ]Clayton
                [5 ]Australia
                [6 ]Institute for Frontier Materials
                [7 ]The Australian Centre of Excellence for Electromaterials Science Deakin University
                [8 ]Melbourne
                Article
                10.1039/C7FD00189D
                29034392
                4a495bd5-1533-4d31-b69c-93b2f1512e8b
                © 2018

                http://rsc.li/journals-terms-of-use

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