### Filtern

#### Erscheinungsjahr

- 2005 (2) (entfernen)

#### Dokumenttyp

- Dissertation (1)
- Preprint (1)

#### Schlagworte

- Modellierung (2) (entfernen)

#### Fachbereich / Organisatorische Einheit

This thesis aims at an overall improvement of the diffusion coefficient predictions. For this reason the theoretical determination of diffusion, viscosity, and thermodynamics in liquid systems is discussed. Furthermore, the experimental determination of diffusion coefficients is also part of this work. All investigations presented are carried out for organic binary liquid mixtures. Diffusion coefficient data of 9 highly nonideal binary mixtures are reported over the whole concentration range at various temperatures, (25, 30, and 35) °C. All mixtures investigated in a Taylor dispersion apparatus consist of an alcohol (ethanol, 1-propanol, or 1-butanol) dissolved in hexane, cyclohexane, carbon tetrachloride, or toluene. The uncertainty of the reported data is estimated to be within 310-11 m2s-1. To compute the thermodynamic correction factor an excess Gibbs energy model is required. Therefore, the applicability of COSMOSPACE to binary VLE predictions is thoroughly investigated. For this purpose a new method is developed to determine the required molecular parameters such as segment types, areas, volumes, and interaction parameters. So-called sigma profiles form the basis of this approach which describe the screening charge densities appearing on a molecule’s surface. To improve the prediction results a constrained two-parameter fitting strategy is also developed. These approaches are crucial to guarantee the physical significance of the segment parameters. Finally, the prediction quality of this approach is compared to the findings of the Wilson model, UNIQUAC, and the a priori predictive method COSMO-RS for a broad range of thermodynamic situations. The results show that COSMOSPACE yields results of similar quality compared to the Wilson model, while both perform much better than UNIQUAC and COSMO-RS. Since viscosity influences also the diffusion process, a new mixture viscosity model has been developed on the basis of Eyring’s absolute reaction rate theory. The nonidealities of the mixture are accounted for with the thermodynamically consistent COSMOSPACE approach. The required model and component parameters are derived from sigma-profiles, which form the basis of the a priori predictive method COSMO-RS. To improve the model performance two segment parameters are determined from a least-squares analysis to experimental viscosity data, whereas a constraint optimisation procedure is applied. In this way the parameters retain their physical meaning. Finally, the viscosity calculations of this approach are compared to the findings of the Eyring-UNIQUAC model for a broad range of chemical mixtures. These results show that the new Eyring-COSMOSPACE approach is superior to the frequently employed Eyring-UNIQUAC method. Finally, on the basis of Eyring’s absolute reaction rate theory a new model for the Maxwell-Stefan diffusivity has been developed. This model, an extension of the Vignes equation, describes the concentration dependence of the diffusion coefficient in terms of the diffusivities at infinite dilution and an additional excess Gibbs energy contribution. This energy part allows the explicit consideration of thermodynamic nonidealities within the modelling of this transport property. If the same set of interaction parameters, which has been derived from VLE data, is applied for this part and for the thermodynamic correction, a theoretically sound modelling of VLE and diffusion can be achieved. The influence of viscosity and thermodynamics on the model accuracy is thoroughly investigated. For this purpose diffusivities of 85 binary mixtures consisting of alkanes, cycloalkanes, halogenated alkanes, aromatics, ketones, and alcohols are computed. The average relative deviation between experimental data and computed values is approximately 8 % depending on the choice of the gE-model. These results indicate that this model is superior to some widely used methods. In summary, it can be said that the new approach facilitates the prediction of diffusion coefficients. The final equation is mathematically simple, universally applicable, and the prediction quality is as good as other models recently developed without having to worry about additional parameters, like pure component physical property data, self diffusion coefficients, or mixture viscosities. In contrast to many other models, the influence of the mixture viscosity can be omitted. Though a viscosity model is not required in the prediction of diffusion coefficients with the new equation, the models presented in this work allow a consistent modelling approach of diffusion, viscosity, and thermodynamics in liquid systems.

The following three papers present recent developments in nonlinear Galerkin schemes for solving the spherical Navier-Stokes equation, in wavelet theory based on the 3-dimensional ball, and in multiscale solutions of the Poisson equation inside the ball, that have been presented at the 76th GAMM Annual Meeting in Luxemburg. Part A: A Nonlinear Galerkin Scheme Involving Vectorial and Tensorial Spherical Wavelets for Solving the Incompressible Navier-Stokes Equation on the Sphere The spherical Navier-Stokes equation plays a fundamental role in meteorology by modelling meso-scale (stratified) atmospherical flows. This article introduces a wavelet based nonlinear Galerkin method applied to the Navier-Stokes equation on the rotating sphere. In detail, this scheme is implemented by using divergence free vectorial spherical wavelets, and its convergence is proven. To improve numerical efficiency an extension of the spherical panel clustering algorithm to vectorial and tensorial kernels is constructed. This method enables the rapid computation of the wavelet coefficients of the nonlinear advection term. Thereby, we also indicate error estimates. Finally, extensive numerical simulations for the nonlinear interaction of three vortices are presented. Part B: Methods of Resolution for the Poisson Equation on the 3D Ball Within the article at hand, we investigate the Poisson equation solved by an integral operator, originating from an ansatz by Greens functions. This connection between mass distributions and the gravitational force is essential to investigate, especially inside the Earth, where structures and phenomena are not sufficiently known and plumbable. Since the operator stated above does not solve the equation for all square-integrable functions, the solution space will be decomposed by a multiscale analysis in terms of scaling functions. Classical Euclidean wavelet theory appears not to be the appropriate choice. Ansatz functions are chosen to be reflecting the rotational invariance of the ball. In these terms, the operator itself is finally decomposed and replaced by versions more manageable, revealing structural information about itself. Part C: Wavelets on the 3–dimensional Ball In this article wavelets on a ball in R^3 are introduced. Corresponding properties like an approximate identity and decomposition/reconstruction (scale step property) are proved. The advantage of this approach compared to a classical Fourier analysis in orthogonal polynomials is a better localization of the used ansatz functions.