Zielstellung dieser Arbeit ist die experimentelle Aufklärung und computergestützte Simulation von Phasengleichgewichten im binären System Kupfer-Sauerstoff und im quaternären System Eisen-Samarium-Zirkonium-Molybdän. Damit wird ein Beitrag zu Phasendiagrammen in den Stoffgruppen der keramischen Materialien und der Seltenerd-basierenden magnetischen Materialien geleistet. Zur Charakterisierung der einzelnen Systeme und ihrer Subsysteme nach der CALPHAD-Methode werden die Stöchiometrie der einzelnen Phasen, ihre Phasenanteile in den jeweiligen Legierungen sowie ihre druckabhängige und thermische Stabilität unter angenäherten Gleichgewichtsbedingungen betrachtet. Zusammen mit den kristallographischen und magnetischen Eigenschaften der Phasen ergeben sich daraus thermodynamische Modelle, die durch ihre parametrisierte Darstellungsweise eine Optimierung an die jeweiligen experimentellen Befunde gestatten. Durch Extra- und Interpolation der so gewonnenen Zustandsfunktionen der einzelnen Phasen ergibt sich ein möglichst weitgehendes Bild aller wesentlichen, das stoffliche Gesamtsystem charakterisierenden thermodynamischen Zustände, welches auch über die experimentellen Einschränkungen hinaus noch Aussagen über die Phasenkonstitution, etwa die Primärkristallisation von Phasen bei hohen Drücken und Temperaturen sowie die Phasenstabilität in höherkomponentigen Systemen, ermöglicht. Schließlich werden die thermodynamischen Funktionen in einer Datenbank zusammengefasst, womit auch die Möglichkeit ihrer Weiterverwendung in anderen Systemen besteht. Die Arbeit kann in den Bereich der Grundlagenuntersuchungen zu den behandelten Stoffsystemen mit werkstoffwissenschaftlichem Hintergrund eingeordnet werden.

The knowledge of phase equilibrium is essential for the planning and realisation of separation processes in chemical engineering. In this work an equipment for measurement of precise isothermal vapour–liquid equilibria (VLE) using the dynamic method was developed. The pool of experimental data for cyclohexylamine was extended significantly. Isothermal VLE were measured in 3 binary and 4 ternary systems, liquid-liquid equilibria (LLE) were measured in 4 ternary systems and in one quarternary system, in each case for two temperatures, whereas in 2 ternary systems and in the quarternary system even liquid-liquid-liquid equilibria (LLLE) occur. Furthermore, activity coefficients at infinite dilution in 4 binary systems and excess molar volumes in 7 binary systems have been estimated. Binary VLE and LLE data of the components water, octane, cyclohexylamine and aniline of this work and data from literature were fitted with the activity coefficient models NRTL and UNIQUAC, as well as with the equations of state Elliott-Suresh-Donohue (ESD) and Perturbed-Chain-Statistical Associating Fluid Theory (PC-SAFT) which contain both a term to consider explicit hydrogen bonds. In addition, the predictive capabilities of the equations of state (EoS) were investigated. With parameters obtained by simultaneous fitting of VLE and, if available, LLE data similar results with the models NRTL and UNIQUAC could be obtained. Each time the deviations for the vapour pressure were lower than 3 % and lower than 2 % in vapour phase composition. The deviations, in three out of the six systems for vapour pressure and vapour phase composition, were larger with the ESD-EoS than with the activity coefficient models. NRTL, UNIQUAC and ESD delivered similar results with the simultaneously fitted parameters for the LLE, whereas the deviations were lower than 5 %. Comparable results were delivered by the ESD-EoS and PC-SAFT for the fitting and the prediction in the investigated binary systems. Also a fitting for NRTL, UNIQUAC and ESD was carried out, but only to one data set. The intention was to show the effect of parameterization on prediction in ternary systems. Predictions were made for VLE and LLE in ternary systems of the above mentioned components, solely with interaction parameters fitted to binary data. For the models NRTL, UNIQUAC und ESD predictions of simultaneously and separately fitted parameters are presented. It is shown that with parameters simultaneously fitted to several data sets significantly better results could be obtained compared to the parameters separately fitted to a single data set. Additionally, for the equations of state ESD and PC-SAFT predictions for the LL(L)E in ternary systems are compared, but here only with separately fitted parameters. For three out of the four investigated ternary systems a too large miscibility gap is calculated with the models NRTL, UNIQUAC and ESD. In the system water+octane+aniline good results could be obtained for the prediction of the LLLE. In summary the equations of state deliver similar results. In the systems water+octane+CHA and octane+CHA+aniline also too large two phase regions were delivered. Better predictions could be obtained in the systems water+octane+aniline and water+CHA+aniline. The forecasts of the VLE in the ternary systems are good with the simultaneously fitted parameters. The deviations for the vapour phase compositions are as for the vapour pressures under 6 %. Larger deviations occur for the system water+octane+aniline only. As evaluation result for the thermodynamic models can be mentioned that the activity coefficient models NRTL and UNIQUAC deliver somewhat better results for the fitting of the binary data than the equations of state ESD and PC-SAFT however, with a larger number of adjustable parameters. The prediction of the VLE is satisfactorily in the ternary systems and with similar quality of all considered models. Larger deviations occur for the prediction of the LL(L)E in the ternary systems. The results of the ESD-EoS were, with one exception, each time better than those of the activity coefficient models. There is no significant difference between the prediction of the ternary systems for the ESD-EoS and the PC-SAFT.

Polyhalite is an abundant distributed mineral in rock salt formations, and considered to respond as a natural heavy metal sink because the Mg2+ ion can be substituted by other bivalent metal ions like Mn2+, Co2+, Ni2+, Cu2+ and Zn2+. One of the quantities needed to predict mineral solubilities in multi-electrolyte solutions is the solubility constant Ksol. Since polyhalite forms slowly over months or years at 298 K, the solid-liquid phase equilibria experiments were accomplished at 313 K. Enthalpies of dissolution were measured and used to extrapolate lnKsol from 313 K to 298 K. Pitzer’s equations have been applied to describe activities of solute and water, with Pitzer parameters estimated from experimental data. The solubility constants for the polyhalites were applied to calculate the solubility equilibria in the quaternary systems K+, M2+, Ca2+ / SO42- // H2O (M = Mg, Mn, Co, Cu, Zn) at 298 K and 313 K, and in case of Mg-polyhalite also in the hexary system Na+, K+, Mg2+, Ca2+ / Cl-, SO42- // H2O.