Ionic liquid thermal

Wu B, Reddy R G, Rogers R D. Novel ionic liquid thermal storge for solar thermal electric power system.Proceedings of solar forum, solar energy the power to choose. Washington, DC. 2001. 

Murugesan S, Wiencek J M, Ren R X, et al. Benzoate-based room temperature ionic liquids Thermal properties and glycosaminoglycan dissolution. Carbohydr. Polym. 2006. 63, 268-271. 

Reported values for ionic liquids using this technique indicate that ionic liquid thermal conductivities are similar to those of commonly used organic solvents. For example, Tomida et al. [121] determined the thermal conductivity for a series of [C niim][PF6] salts and reported values for [C4mim][PF6] which compared well with those of benzene, 0.145 and 0.16 W nr K-1, respectively. In their study they also concluded that the thermal conductivity was not a strong function of temperature, pressure or chain length. 

Only a few experimental measurements of ionic liquid thermal conductivity exist. For example, [C2mim][BF4] has a value of 0.193 0.006 W/(m K) at 350K, ° while [C4mim][PF6] has a thermal conductivity of 0.147 0.007W/ (m K) at 335 The computed values for [Cimim] [EtS04] thus appear to be reasonable. Note that the thermal conductivity of the pure ionic liquid is much lower than that of water, and, it remains low even at a water mole fraction of 0.75. 

Eerreira AGM, Simoes PN, Ferreira AF (2012) Quaternary phosphonium-based ionic liquids thermal stability and heat capacity of the liquid phase. J Chem Thermodyn 45 16-27... 

The following discussion concerns the thermal liquidus ranges available in different ionic liquids, as functions of cation and anion structure and composition. In particular, those structural features of cation and anion that promote these properties (while providing other desirable, and sometimes conflicting characteristics of the liquid, such as low viscosity, chemical stability, etc.) and variations in liquidus ranges and stabilities are the focus of this chapter. 

The thermal behavior of many ionic liquids is relatively complex. For a typical IL, cooling from the liquid state causes glass formation at low temperatures solidifica-... 

Ngo et al. [24] have shown that the thermal decomposition of ionic liquids, measured by TGA, varies depending on the sample pans used. Increased stabilization of up to 50 °C was obtained in some cases on changing from aluminium to alumina sample pans. 

A wide variety of physical properties are important in the evaluation of ionic liquids (ILs) for potential use in industrial processes. These include pure component properties such as density, isothermal compressibility, volume expansivity, viscosity, heat capacity, and thermal conductivity. However, a wide variety of mixture properties are also important, the most vital of these being the phase behavior of ionic liquids with other compounds. Knowledge of the phase behavior of ionic liquids with gases, liquids, and solids is necessary to assess the feasibility of their use for reactions, separations, and materials processing. Even from the limited data currently available, it is clear that the cation, the substituents on the cation, and the anion can be chosen to enhance or suppress the solubility of ionic liquids in other compounds and the solubility of other compounds in the ionic liquids. For instance, an increase in allcyl chain length decreases the mutual solubility with water, but some anions ([BFJ , for example) can increase mutual solubility with water (compared to [PFg] , for instance) [1-3]. While many mixture properties and many types of phase behavior are important, we focus here on the solubility of gases in room temperature IFs. 

Obviously, the use of a nonvolatile ionic liquid simplifies the distillative workup of volatile products, especially in comparison with the use of low-boiling solvents, where it may save the distillation of the solvent during product isolation. Moreover, common problems related to the formation of azeotropic mixtures of the volatile solvents and the product/by-products formed are avoided by use of a nonvolatile ionic liquid. In the Rh-catalyzed hydroformylation of 3-pentenoic acid methyl ester it was even found that the addition of ionic liquid was able to stabilize the homogeneous catalyst during the thermal stress of product distillation (Figure 5.2-1) [21]. This option may be especially attractive technically, due to the fact that the stabilizing effects could already be observed even with quite small amounts of added ionic liquid. 

Notwithstanding their very low vapor pressure, their good thermal stability (for thermal decomposition temperatures of several ionic liquids, see [11, 12]) and their wide operating range, the key property of ionic liquids is the potential to tune their physical and chemical properties by variation of the nature of the anions and cations. An illustration of their versatility is given by their exceptional solubility characteristics, which make them good candidates for multiphasic reactions (see Section 5.3.4). Their miscibility with water, for example, depends not only on the hydrophobicity of the cation, but also on the nature of the anion and on the temperature. 

In comparison with classical processes involving thermal separation, biphasic techniques offer simplified process schemes and no thermal stress for the organometal-lic catalyst. The concept requires that the catalyst and the product phases separate rapidly, to achieve a practical approach to the recovery and recycling of the catalyst. Thanks to their tunable solubility characteristics, ionic liquids have proven to be good candidates for multiphasic techniques. They extend the applications of aqueous biphasic systems to a broader range of organic hydrophobic substrates and water-sensitive catalysts [48-50]. 

ZnTe The electrodeposition of ZnTe was published quite recently [58]. The authors prepared a liquid that contained ZnGl2 and [EMIM]G1 in a molar ratio of 40 60. Propylene carbonate was used as a co-solvent, to provide melting points near room temperature, and 8-quinolinol was added to shift the reduction potential for Te to more negative values. Under certain potentiostatic conditions, stoichiometric deposition could be obtained. After thermal annealing, the band gap was determined by absorption spectroscopy to be 2.3 eV, in excellent agreement with ZnTe made by other methods. This study convincingly demonstrated that wide band gap semiconductors can be made from ionic liquids. 

Room temperature ionic liquids are air stable, non-flammable, nonexplosive, immiscible with many Diels-Alder components and adducts, do not evaporate easily and act as support for the catalyst. They are useful solvents, especially for moisture and oxygen-sensitive reactants and products. In addition they are easy to handle, can be used in a large thermal range (typically —40 °C to 200 °C) and can be recovered and reused. This last point is particularly important when ionic liquids are used for catalytic reactions. The reactions are carried out under biphasic conditions and the products can be isolated by decanting the organic layer. 

Recently, room temperature ionic liquids (RT-ILs) have attracted much attention for their excellent properties, e.g., wide temperature range of liquid phase, ultra-low vapor pressure, chemical stability, potential as green solvents, and high heat capacities [64,65]. These properties make them good candidates for the use in many fields, such as thermal storage [66], electrochemical applications, homogeneous catalysis [67], dye sensitized solar cells [68], and lubricants [69,70]. 

In a number of general properties, such as viscosity and thermal conductivity, melts differ little from solutions. Their surface tensions are two to three times higher than those of aqueous solutions. This leads to poorer wetting of many solids, including important electrode materials such as carbon and graphite, by the ionic liquids. 

The mobility of ions in melts (ionic liquids) has not been clearly elucidated. A very strong, constant electric field results in the ionic motion being affected primarily by short-range forces between ions. It would seem that the ionic motion is affected most strongly either by fluctuations in the liquid density (on a molecular level) as a result of the thermal motion of ions or directly by the formation of cavities in the liquid. Both of these possibilities would allow ion transport in a melt. 

Significant progress has been made in the application of ionic liquids (ILs) as alternative solvents to C02 capture because of their unique properties such as very low vapour pressure, a broad range of liquid temperatures, excellent thermal and chemical stabilities and selective dissolution of certain organic and inorganic materials. ILs are liquid organic salts at ambient conditions with a cationic part and an anionic part. 

Inter- and intramolecular hetero-Diels-Alder cycloaddition reactions in a series of functionalized 2-(lH)-pyrazinones have been studied in detail by the groups of Van der Eycken and Kappe (Scheme 6.95) [195-197]. In the intramolecular series, cycloaddition of alkenyl-tethered 2-(lH)-pyrazinones required 1-2 days under conventional thermal conditions involving chlorobenzene as solvent under reflux conditions (132 °C). Switching to 1,2-dichloroethane doped with the ionic liquid l-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) and sealed-vessel microwave technology, the same transformations were completed within 8-18 min at a reaction temperature of 190 °C (Scheme 6.95 a) [195]. Without isolating the primary imidoyl chloride cycloadducts, rapid hydrolysis was achieved by the addition of small amounts of water and subjecting the reaction mixture to further microwave irradia-... 

Ionic liquids are characterised by the following three definition criteria. They consist entirely out of ions, they have melting points below 100 °C and they exhibit no detectable vapour pressure below the temperature of their thermal decomposition. As a consequence of these properties most ions forming ionic liquids display low charge densities resulting in low intermolecular interaction. Figure 7.1 displays some of the most common ions used so far for the formation of ionic liquids. 

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