BMIM

All the halide exchange reactions mentioned above proceed more or less quantitatively, causing greater or lesser quantities of halide impurities in the final product. The choice of the best procedure to obtain complete exchange depends mainly on the nature of the ionic liquid that is being produced. Unfortunately, there is no general method to obtain a halide-free ionic liquid that can be used for all types of ionic liquid. This is explained in a little more detail for two defined examples the synthesis of [BMIM][(CF3S02)2N] and the synthesis of [EMIM][BF4]. 

Erotic impurities have to be taken into account for two groups of ionic liquids those that have been produced by an exchange reaction involving a strong acid (often the case, for example, for [BMIM][PEg]), and those that are sensitive to hydrolysis. In the latter case, the protons may originate from the hydrolysis of the anion, forming an acid that may be dissolved in the ionic liquid. 

Without special drying procedures and completely inert handling, water is omnipresent in ionic liquids. Even the apparently hydrophobic ionic liquid [BMIM][(CF3S02)2N] saturates with about 1.4 mass% of water [15], a significant molar amount. For more hydrophilic ionic liquids, water uptake from air can be much greater. Imidazolium halide salts in particular are laiown to be extremely hygroscopic, one of the reasons why it is so difficult to make completely proton-free chloroaluminate ionic liquids. 

Preparation of ionic liquids for catalysis [BMIM][HS04], [HNR3][HS04] BP Ghemicals, UK Akzo Nobel NV, Netherlands Elemen-tis Specialities, UK 2000 30... 

Table 3.1-5 Melting points and heats of fusion for isomeric [BMIM][PFg] and [PMIM][PFs] ionic liquids, showing melting point and crystal stability increasing with the degree of branching in the alkyl substituent.

The viscosities of non-haloaluminate ionic liquids are also affected by the identity of the organic cation. For ionic liquids with the same anion, the trend is that larger allcyl substituents on the imidazolium cation give rise to more viscous fluids. For instance, the non-haloaluminate ionic liquids composed of substituted imidazolium cations and the bis-trifyl imide anion exhibit increasing viscosity from [EMIM], [EEIM], [EMM(5)IM], [BEIM], [BMIM], [PMMIM], to [EMMIM] (Table 3.2-1). Were the size of the cations the sole criteria, the [BEIM] and [BMIM] cations from this series would appear to be transposed and the [EMMIM] would be expected much earlier in the series. Given the limited data set, potential problems with impurities, and experimental differences between laboratories, we are unable to propose an explanation for the observed disparities. 

The reported densities of ionic liquids vary between 1.12 g cm for [(n-QHi7)(C4H9)3N][(CF3S02)2N] and 2.4 g cm for a 34-66 mol% [(CH3)3S]Br/AlBr3 ionic liquid [21, 23]. The densities of ionic liquid appear to be the physical property least sensitive to variations in temperature. For example, a 5 degree change in temperature from 298 to 303 K results in only a 0.3 % decrease in the density for a 50.0 50.0 mol % [EMIM]C1/A1C13 [17]. In addition, the impact of impurities appears to be far less dramatic than in the case of viscosity. Recent work indicates that the densities of ionic liquids vary linearly with wt. % of impurities. For example, 20 wt. % water (75 mol %) in [BMIM][BF4] results in only a 4 % decrease in density [33]. 

BMIM][PFg] and urea-appended (dashed lines) or thiourea-appended (solid lines) TSILs as the extracting phase. 

We have recently shown that the hydrophobic hexafluorophosphate ILs can in fact be made totally miscible with water by addition of alcohols [47, 48] the ternary phase diagram for [BMIM][PF(3]/water/ethanol (left part of Figure 3.3-7) shows the... 

Figure 3.3-7 Ethanol/water/[BMIM][PFg] ternary phase diagram (a, left) and solute distribution...

The advantage of the stoichiometric technique is that it is extremely simple. Care has to be taken to remove all gases dissolved in the IL sample initially, but this is easily accomplished because one does not have to worry about volatilization of the IL sample when the sample chamber is evacuated. The disadvantage of this technique is that it requires relatively large amounts of ILs to obtain accurate measurements for gases that are only sparingly soluble. At ambient temperature and pressure, for instance, 10 cm of l-n-butyl-3-methylimida2olium hexafluorophosphate ([BMIM][PFg]) would take up only 0.2 cm of a gas with a Henry s law constant of... 

Table 3.4-1 Henry s Law Constants, for water in [OMIM][BF4], [BMIM][PFg], and [OMIM][PFg].

The solubilities of the various gases in [BMIM][PFg] suggests that this IL should be an excellent candidate for a wide variety of industrially important gas separations. There is also the possibility of performing higher-temperature gas separations, thanks to the high thermal stability of the ILs. For supported liquid membranes this would require the use of ceramic or metallic membranes rather than polymeric ones. Both water vapor and CO2 should be removed easily from natural gas since the ratios of Henry s law constants at 25 °C are -9950 and 32, respectively. It should be possible to scrub CO2 from stack gases composed of N2 and O2. Since we know of no measurements of H2S, SO, or NO solubility in [BMIM][PFg], we do not loiow if it would be possible to remove these contaminants as well. Nonetheless, there appears to be ample opportunity for use of ILs for gas separations on the basis of the widely varying gas solubilities measured thus far. 

Finally, none of the ionic liquids were found to be hydrogen bond acids [5], although this may well be a consequence of the salts selected, none of which had a cation that would be expected to act as a hydrogen bond donor. Earlier qualitative measurements on ionic liquid stationary phases of mono-, di-, and trialkylammo-nium salts suggest that hydrogen bond donation can be important where a potentially acidic proton is available [7-9]. More recent work, with [BMIM] salts, also indicates that these ionic liquids should be considered to be hydrogen bond donor solvents [10]. However, this has yet to be quantified. 

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