Universiẗat, Diss., 2001--München.

Zugl.: Dortmund, Techn. Univ., Diss., 2008

Konstanz, Univ., Diplomarb., 1998.

Zugl.: Dortmund, Techn. Universiẗat, Diss., 2008.

Techn. University, Diss., 2003--Darmstadt.

Universiẗat, Diss., 2000--München.

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.

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.

The quasiparticle model, based on quark and gluon degrees of freedom, has been developed for the description of the thermodynamics of a hot plasma of strongly interacting matter which is of enormous relevance in astrophysics, cosmology and for relativistic heavy-ion collisions as well. In the present work, this phenomenological model is extended into the realm of imaginary chemical potential and towards including, in general, different and independent quark flavour chemical potentials. In this way, nonzero net baryon-density effects in the equation of state are self-consistently attainable. Furthermore, a chain of approximations based on formal mathematical manipulations is presented which outlines the connection of the quasiparticle model with the underlying gauge field theory of strong interactions, QCD, putting the model on firmer ground. A comparison of quasiparticle model results with available lattice QCD data for, e. g., basic bulk thermodynamic quantities and various susceptibilities such as diagonal and off-diagonal susceptibilities, which provide a rich and sensitive testing ground, is found to be successful. Furthermore, different thermodynamic quantities and the phase diagram for imaginary chemical potential are faithfully described. Thus, the applicability of the model to extrapolate the equation of state known from lattice QCD at zero baryon density to nonzero baryon densities is shown. In addition, the ability of the model to extrapolate results to the chiral limit and to asymptotically large temperatures is illustrated by confrontation with available first-principle lattice QCD results. These extrapolations demonstrate the predictive power of the model. Basing on these successful comparisons supporting the idea that the hot deconfined phase can be described in a consistent picture by dressed quark and gluon degrees of freedom, a reliable QCD equation of state is constructed and baryon-density effects are examined, also along isentropic evolutionary paths. Scaling properties of the equation of state with fundamental QCD parameters such as the number of active quark flavour degrees of freedom, the entering quark mass parameters or the numerical value of the deconfinement transition temperature are discussed, and the robustness of the equation of state in the regions of small and large energy densities is shown. Uncertainties arising in the transition region are taken into account by constructing a family of equations of state whose members differ from each other in the specific interpolation prescription between large energy density region and a realistic hadron resonance gas equation of state at low energy densities. The obtained family of equations of state is applied in hydrodynamic simulations, and the implications of variations in the transition region are discussed by considering transverse momentum spectra and differential elliptic flow of directly emitted hadrons, in particular of strange baryons, for both, RHIC top energy and LHC conditions. Finally, with regard to FAIR physics, implications of the possible presence of a QCD critical point on the equation of state are outlined both, in an exemplary toy model and for an extended quasiparticle model.

Thesis (Doctoral)--Universiteit van Amsterdam, 1982.