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Organisationseinheit der BAM
The term „Alternative Solvents“ often refers to ionic liquids (ILs), mainly to distinguish these substances from traditional (i.e., molecular) solvents.
In applications, any „alternative“ is required to perform better than something that is proven and tested.
To bring ILs into practical use, availability and costs are the fundamental points to be addressed.
There are two ways to proceed:
▬ tailoring a molecule, implanting the expected characteristics
advantage: optimization of the targeted performance possible
risks: outcome not always foreseeable, costly and time-intensive (“trial and error“)
▬ to target on mixtures of well-characterized ILs with molecular solvents
advantage: substance characteristics are known, less costly, less time-consuming,
mixture composition another tunable parameter
risks: the same but with less impact
For the basic engineering of technical processes, knowledge of phase equilibria, particularly of
mixtures, over a broad (p,T) range is mandatory.
This contribution reports on recent experimental results from our laboratory:
▬ the solubility of CO2 in a mixture of water and [bmim][CH3SO4]
▬ the solubility of CO2 in a mixture of methanol and [bmim][PF6]
In the last two decades, the solubility of gases in ionic liquids has attracted a lot of attention. While at the beginning most publications dealt with the solubility of a single gas in a pure ionic liquid, recently the interest starts to shift to the – from an application-oriented point of view – more challenging area of the simultaneous solubility of several gases in an ionic liquid and/or the solubility of a single gas in solvent mixtures with ionic liquids. The current state of information on experimental data (and the phenomena encountered) in such systems is summarized and discussed.
Solubility data of carbon dioxide (CO2) in the two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium tetrachloroferrate [BMIM][FeCl4] at T = (273.15-413.15) K and pressures up to p = 4.5 MPa are presented. In Addition to the experiments, a literature review was done to compare the new results with published solubility data. The measurements were carried out using an isochoric method which operates in decrements of deltaT = 20 K within the investigated temperature range and at selected four different pressure steps ranging from a pressure p of around 4.5 MPa to around 0.5 MPa. The solubility of CO2 decreases in both ionic liquids with increasing temperatures. Within the p,T-range investigated, CO2 displayed a solubility in [BMIM][BF4] from a mole fraction x = 0.0117 and a corresponding molality m = 0.0526 mol/kg at T = 413.15 K and p = 0.417 MPa up to x = 0.4876 and m = 4.2094 mol/kg at T = 293.15 K and p = 4.349 MPa. The corresponding values for the solubility in [BMIM][FeCl4] start at a mole fraction x = 0.0268 and a corresponding molality m = 0.0818 mol/kg at T = 413.15 K and p = 0.443 MPa and end at x = 0.5126 and m = 3.1216 mol/kg at T = 293.15 K and p = 4.478 MPa. At a constant temperature, CO2 is better soluble in [BMIM][FeCl4] than in [BMIM][BF4] and the mean value of the solubility difference related to mole fraction x over the pressure range investigated amounts to about 4 % at T = 273.15 K and monotonously increases to about 92 % at T = 413.15 K. Henry's law constant as well as derived thermodynamic properties, such as the Gibbs energy of solvation, the enthalpy of solvation, the entropy of solvation, and the heat capacity of solvation, were calculated and discussed regarding the solute-solvent molecular interactions.