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Eingeladener Vortrag
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The solubility of carbon dioxide in three ionic liquids (ILs) under supercritical fluid condition was measured at pressures up to 32 MPa and at temperatures of 313.15, 323.15, and 333.15 K in a high-pressure view cell. The imidazolium-derivative ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF4]) were employed in this research. The effects of pressure, temperature, nature of anion and cation as well as the water content on the solubility of CO2 in the ILs were investigated experimentally. The solubility of CO2 in the IL was higher for the ILs with longer cationic alkyl group and for the ILs with lower anion polarity. The lower the water content or the lower the temperature as well as the higher the pressure, the higher was the solubility of CO2.
Some homogeneous liquid mixtures of an ionic liquid and a lower alkanol (e.g., methanol) can be forced to undergo a liquidliquid phase split (resulting in a three-phase liquid–liquid–vapor (L1L2V) equilibrium) by pressurization with a gas. Such systems exhibit the phenomenon of "salting out by a nearcritical gas". That phenomenon is often observed at temperatures around the critical temperature of the gas in liquid mixtures where at least one of the liquid components is a good solvent for that gas. New experimental results for both the L1L2V equilibrium and the corresponding critical endpoint lines of the two ternary systems (carbon dioxide + methanol + 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6]) and (carbon dioxide + 1-butanol + 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide [hmim][Tf2N]) at temperatures between 293 and 333 K are reported. The experiments were performed with an "analytical method". The liquid–liquid phase split exists only at pressures between a lower critical endpoint line (where both liquid phases become critical and coexist with a vapor phase) and an upper critical endpoint line (where one of the phases becomes critical with the vapor phase while the critical phases coexist with another liquid phase). The compositions of the coexisting three phases L1, L2, and V differ considerably; a high-density, ionic liquid-rich liquid phase (L1) coexists with an alkanol-rich liquid phase (L2) of lower density and a vapor phase (V) that is virtually ionic liquid-free. For both systems, it was observed that, at constant temperature, increasing pressure shifts the L1 phase towards higher contents of ionic liquid and gas and less alkanol, whereas in the L2 phase the mole fractions of ionic liquid and alkanol decrease. Higher temperatures result in a smaller difference between the pressures of both critical endpoint lines. Experimental results for both critical endpoint lines and for the compositions of the coexisting liquid phases are reported.
Two different ordered mesoporous solids, a hexagonal SBA-15 silica sample and its inverse CMK-3 carbon structure were applied in liquid-phase adsorption. By means of the analysis of experimental data of a binary liquid model mixture with one polar and one non-polar component, the general way is outlined how to obtain essential and trustworthy solid information from liquid-phase adsorption.
The solubility of a single gas as well as the simultaneous solubility of several gases in an ionic liquid is of great interest in many areas of chemical engineering, particularly in heterogeneous catalysis. One of the most interesting features involved in the study of the simultaneous solubility of several gases in a pure ionic liquid is the difference between experimental data and predictions for the simultaneous solubility (based on experimental data for the solubility of the single gases). The well soluble gas might act as a cosolvent or as an antisolvent for a sparsely soluble second gas. New experimental results and a correlation are presented for the simultaneous solubility of hydrogen (i.e., a sparsely soluble gas) and carbon dioxide (a well soluble gas) in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) at temperatures between 293 K and 373 K and pressures up to about 9.2 MPa. The experimental results reveal that carbon dioxide acts as a cosolvent for hydrogen in that particular ionic liquid. A correlation shows that the cosolvency effect can be modeled by considering interaction parameters between hydrogen and carbon dioxide in liquid [hmim][Tf2N]. The correlation can also be used to quantify that cosolvency effect: one mole of carbon dioxide in 1000 g of [hmim][Tf2N] increases the solubility of (small amounts of) hydrogen by about 20%.
Poly(p-phenylenediamine) (PpPD)/carboxylic acid-functionalized multiwalled carbon nanotubes (c-MWCNTs) nanocomposites were prepared by chemical oxidative polymerization using potassium persulfate (K2S2O8) as an oxidant. Field-emission scanning electron microscopy (FE–SEM) and field-emission Transmission electron microscopy (FE–TEM) showed that a tubular layer of PpPD was coated on the surface of carbon nanotubes with a thickness of 10–20 nm. FT–IR analysis provided an evidence for the formation of nanocomposites. The thermal stability of nanocomposites was improved by addition of c-MWCNTs as confirmed by thermogravimetric analysis (TGA). XRD spectra showed that the crystalline nature of PpPD was not affected much by the addition of c-MWCNTs. As the content of c-MWCNTs was increased, the electrical conductivity of the nanocomposites increased due to the interaction between polymer and nanotubes that enhances electron delocalization.
Experimental results are reported for the solubility of carbon dioxide in liquid mixtures of water and the ionic liquid 1-n-butyl-3-methylimidazolium methylsulfate ([bmim][CH3SO4]). Three (gas-free) solvent compositions were considered with mass fractions of [bmim][CH3SO4] of w' ≈ 0.15, 0.50, and 0.87 (mole fractions x' ≈ 0.013, 0.066, and 0.33). In the isothermal experimental series, the temperature was about (293, 333, and 373) K. The total pressure ranged up to about 10 MPa. The molality of carbon dioxide in the solvent mixture of (water + [bmim][CH3SO4]) (the mole fraction of carbon dioxide in the liquid) ranged up to approximately 1.64 mol·kg1 (about 0.0332). The experimental results are used to determine Henry's constant of carbon dioxide in the liquid mixtures of (water + [bmim][CH3SO4]) as well as the partial molar volume of that gas at infinite dilution in those solvent mixtures. The phase equilibrium is described by applying an extension (to solvent mixtures) of Pitzer's molality scale-based equation for the Gibbs excess energy.