TY - JOUR A1 - Tuma, Dirk A1 - Ulanova, T. A1 - Chobanov, K. A1 - Maurer, G. T1 - Neue Untersuchungen zum Phänomen Aussalzen mit einem nahekritischen Gas N2 - Untersuchungen zur gasinduzierten Phasentrennung bzw. zum Aussalzen mit nahekritischen Gasen wurden an verschiedenen wässrigen Lösungen (auch mit ionischem Fluid) durchgeführt. Ziel war der Nachweis und die Charakterisierung von Hochdruckmehrphasengleichgewichten, die sich für eine technische Anwendung eignen. Kriterien hierfür sind Auftreten des Flüssig/flüssig-Phasenzerfalls bei relativ niedrigem Druck, seine Existenz über einen weiten Druck- und Zusammensetzungsbereich und damit verbunden eine druckinduzierte Änderung der Zusammensetzung der koexistierenden Flüssigphasen. Die eingesetzten ionischen Fluide zeigen zwar das gewünschte Phasenverhalten, erfüllen die Kriterien aber nur teilweise. Im Vorgriff auf eine mögliche Anwendung wurde die Verteilung eines hochmolekularen, amphiprotischen Naturstoffs auf die koexistierenden Flüssigphasen untersucht und durch Einstellung des pH-Werts gezielt verändert. ------------------------------------------------------------------------------------------------------------------------------------- Investigations on gas-induced phase split, i.e., salting out by a nearcritical gas, were carried out for several aqueous solutions (including an ionic liquid). The research aimed to verify and characterize high-pressure multiphase equilibria that might be suitable for technical applications. The respective criteria are occurrence at relatively low pressures and the existence of the phase equilibrium phenomenon over a significant region of both composition and pressure, which is related to a pressure-induced significant alteration of the compositions of the coexisting liquid phases. The employed ionic liquids revealed the expected phase behavior but without full compliance of all criteria. In anticipation of an application, the partitioning of an amphiprotic, high-molecular biomolecule to the coexisting liquid phases was successfully administered via a pH variation. KW - Dampf/flüssig/flüssig-Gleichgewicht KW - Dissoziationsgleichgewicht KW - Ionische Fluide KW - Nahekritisches Gas KW - Dissociation equilibrium KW - Ionic liquids KW - Nearcritical gas KW - Ternary systems KW - Vapor-liquid-liquid equilibrium PY - 2012 DO - https://doi.org/10.1002/cite.201100180 SN - 0009-286X SN - 1522-2640 VL - 84 IS - 4 SP - 456 EP - 464 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25930 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chobanov, K. A1 - Tuma, Dirk A1 - Maurer, G. ED - Renon, H. T1 - High-pressure phase behavior of ternary systems (carbon dioxide + alkanol + hydrophobic ionic liquid) N2 - Some homogeneous liquid mixtures of an ionic liquid and a lower alkanol (e.g., methanol) can be forced to undergo a liquid–liquid 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. KW - Room-temperature ionic lilquids KW - [bmim][PF6] and [hmim][Tf2N] KW - Alkanol KW - Carbon dioxide KW - High-pressure phase equilibria KW - Salting-out behavior KW - Critical endpoints PY - 2010 DO - https://doi.org/10.1016/j.fluid.2010.02.015 SN - 0378-3812 VL - 294 IS - 1-2 SP - 54 EP - 66 PB - Elsevier CY - Amsterdam AN - OPUS4-22060 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -