Deep eutectic

Many of these problems may be overcome by using ionic liquids based on sugars [35] or deep eutectic mixtures. Deep eutectic mixtures such as that derived from choline chloride and urea (m. pt. 12°C [36]) or carboxylic acids [37] can be liquids and have very low vapour pressure. They have been successfully used as electrochemical solvents, but their use in catalysis remains little explored. Urea is a fertiliser and choline chloride (Vitamin B4) is a component of chicken feed so the mixture is environmentally acceptable. 

Related to ionic liquids are substances known as deep eutectic solvents or mixtures. A series of these materials based on choline chloride (HOCH2CH2NMe3Cl) and either zinc chloride or urea have been reported (Abbott et al., 2002 2003). The urea/choline chloride material has many of the advantages of more well-known ionic liquids (e.g. low volatility), but can be sourced from renewable feedstocks, is non-toxic and is readily biodegradable. However, it is not an inert solvent and this has been exploited in the functionalisation of the surface of cellulose fibres in cotton wool (Abbott et al, 2006). Undoubtedly, this could be extended to other cellulose-based materials, biopolymers, synthetic polymers and possibly even small molecules. 

It has recently been shown that the same principle can be applied to deep eutectic solvents by using small quaternary ammonium cations such as ethylammonium and fluorinated hydrogen bond donors such as trifluoroacetamide. However, there is only a limited benefit that can be achieved using this approach as the physical parameters cannot be varied totally independently of one another. For example there will be an optimum ion size too small and the lattice energy will increase the surface tension, too large and the ionic mobility will be impeded. 

Section 4.3 is devoted to electrodeposition in a special class of deep eutectic solvents/ionic liquids which are based on well-priced educts such as e.g. choline chloride. The impressive aspect of these liquids is their easy operation, even under air, as well as their large-scale commercial availability. One disadvantage has to be mentioned the choline chloride-based liquids especially are currently not yet... 

The electrodeposition of chromium in a mixture of choline chloride and chromium(III) chloride hexahydrate has been reported recently [39]. A dark green, viscous liquid is obtained by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties of this deep eutectic solvent are characteristic of an ionic liquid. The eutectic composition is found to be 1 2 choline chloride/chromium chloride. From this ionic liquid chromium can be electrode-posited efficiently to yield a crack-free deposit [39]. Addition of LiCl to the choline chloride-CrCl3-6H20 liquid was found to allow the deposition of nanocrystalline black chromium films [40], The use of this ionic liquid might offer an environmentally friendly process for electrodeposition of chromium instead of the current chromic acid-based baths. However, some efforts are still necessary to get shining... 

Abbott et al. [98-103] reported the synthesis and characterization of new moisture-stable, Lewis acidic ionic liquids made from metal chlorides and commercially available quaternary ammonium salts (see Chapter 2.3). They showed that mixtures of choline chloride (2-hydroxyethyltrimethylammonium chloride, [Me3NC2H40H]Cl and MCU (M=Zn, Sn) give conducting and viscous liquids at or around room temperature. These deep eutectic solvents/ionic liquids are easy to prepare, are water-and air-stable, and their low cost enables their use in large-scale applications. Furthermore, they reported [104] that a dark green, viscous liquid can be formed by mixing choline chloride with chromium(III) chloride hexahydrate and that the... 

Ethylene Clycol-based Deep Eutectic Solvent... 

Recently a novel class of deep eutectic solvents based on choline chloride have been developed. These can be handled easily under environmental conditions and circumvent many problems that occur in aqueous solutions. They also offer the first economically viable liquids that can be used on an industrial scale. As the interest of electrochemists and classical electroplaters in ionic liquids has risen strongly in the last few years we decided, in 2006, to collect the key aspects of the electrodeposition from ionic liquids in the present book. The book has been written by a panel of expert authors during late 2006 and the first half of 2007 and thus describes the state of the art as of that point in time. 

Most inorganic salts, when they melt, are found to flow and conduct electricity according to a simple Arrhenius law at all temperatures down to their melting points. For instance, unless measurements of high precision are used, the alkali halides appear to remain obedient to the Arrhenius equation even down to the deep eutectic temperatures of their mixtures with other salts. LiCl and KCl form a eutectic mixture with a freezing point of 351°C, some 300 K below either pure salt freezing point, yet the viscosity of the melt barely departs from Arrhenius behavior before freezing. 

Although many ionic liquids and deep eutectic mixtures based on choline have the advantages to be cheap and no-toxic, they are all hydrophilic and miscible with aqueous solvents. This may be a problem for applications such as the extraction of metal ions from an aqueous phase or the electrodeposition of reactive metals (aluminium, magnesium, tantalum..). 

Cost and biodegradabiUty have also been major concerns, and new families of ILs derived from renewable feedstock or from low-cost starting materials have beat described. These Bio-ILs are entirely composed of biomaterials [183]. An example to be cited is the development of the deep eutectic mixtures liquid systems based on choline chloride [ 184] for which the qualification of ILs is stiU the subject of controversies. Choline can be used as alternative cation in combination with suitable anion to generate ILs. The biodegradable properties of these ILs have been reported [185]. 

Abbott AP, Boothby D, Capper G et al (2004) Deep eutectic solvents formed between choline chloride and carboxylic acids versatile alternatives to ionic liquids. J Am Chem Soc 126 9142-9147... 

Abbott AP, Capper G, Davies DL et al (2006) Solubility of metal oxides in deep eutectic solvents based on choline chloride. J Chem Eng 51 1280-1282... 

The binary phase diagram of Ca0-Al203 shows two refractory end-members CaO and A1203 with melting points of 2,570°C and 2,050°C, respectively [25, 26], There is a deep eutectic with a minimum at 1,390°C and five intermediate crystalline phases, of which three hydrates are important as cements [27],... 

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