In this thesis, first we propose a new approach to solve Semi Infinite Linear Optimization Problems (SILP). The new algorithm uses the idea of adding violated cut or cuts at each iteration. Our proposed algorithm distinguishes itself from Luo, Roos, and Terlaky's logarithmic barrier decomposition method, in three aspects: First, the violated cuts are added at their original locations. Second, we extend the analysis to the case where multiple violated cuts are added simultaneously, instead of adding only one constraint at a time. Finally, at each iteration we update the barrier parameter and the feasible set in the same step. In terms of complexity, we also show that a good approximation of an optimal solution will be guaranteed after finite number of iterations. Our focus in this thesis is mainly on the implementation of our algorithm to approximate an optimal solution of the SILP. Our numerical experiences show that unlike other SILP solvers which are suffering from the lack of accuracy, our algorithm can reach high accuracy in a competitive time. We discuss the linear algebra involved in efficient implementation and describe the software that was developed. Our test problem set includes large scale second order conic optimization problems. / Thesis / Master of Applied Science (MASc)

The main objective of this Doctoral thesis is the preparation of hybrid active catalysts using the SILP (Supported Ionic Liquid Catalysis) methodology and employing carbon materials as support. For that, in first place, SILP samples have been prepared and characterized. In second place, hybrid the SILP catalysts have been prepared, characterized and tested in some hydrogenation reactions, including an asymmetric hydrogenation. The investigated variables are mainly the amount and kind of ionic liquid and the physical, chemical and morphological properties of the support.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-02T12:29:28Z No. of bitstreams: 1 mateusjosefernandesmartins.pdf: 4703203 bytes, checksum: 8dd717329ae701bf544278cc49bc48ff (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-13T13:08:33Z (GMT) No. of bitstreams: 1 mateusjosefernandesmartins.pdf: 4703203 bytes, checksum: 8dd717329ae701bf544278cc49bc48ff (MD5) / Made available in DSpace on 2017-05-13T13:08:33Z (GMT). No. of bitstreams: 1 mateusjosefernandesmartins.pdf: 4703203 bytes, checksum: 8dd717329ae701bf544278cc49bc48ff (MD5) Previous issue date: 2014-02-24 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico / Existem diversos tipos de sais, inclusive alguns que são líquidos à temperatura ambiente, os Líquidos Iônicos. Esses compostos vêm sendo utilizados em diversas aplicações, dentre elas, uma nova técnica de catálise heterogênea denominada de método SILP (do inglês, supported ionic liquid phase). Essa inovadora técnica consiste em suportar um líquido iônico na superfície de um sólido poroso para que a fase líquida, o líquido iônico, atue como solvente, membrana ou catalisador. Nesse trabalho foi realizado um estudo teórico-experimental para compreender como se dá a interação entre o filme ultrafino de líquido iônico e um suporte sólido e propor um mecanismo para a degradação do sal suportado, predizendo as temperaturas em que esse processo ocorre. A parte experimental do estudo consistiu em experimentos de análises termogravimétricas e de obtenção de espectros vibracionais na região do infravermelho. Os experimentos de termogravimetria ajudaram a definir o grau de hidratação da superfície, utilizado nas simulações de adsorção e, aliados aos espectros vibracionais obtidos experimentalmente, serviram como base na concepção das propostas para os mecanismos de degradação do [C4C1Im]+[BF4]- suportado. A combinação das duas análises experimentais levou a mecanismos de degradação onde a superfície é fluoretada pelo ânion, perdendo uma hidroxila. Esse resultado levou a uma investigação teórica da fluoretação da superfície de gama-alumina, com simulação de espectros de RMN de 19F, obtenção de espectros vibracionais e estudo termodinâmico. A simulação de espectros de ressonância magnética nuclear foi realizada para que fossem feitas atribuições com o intuito de auxiliar na discrepância existente entre trabalhos previamente publicados. A simulação da adsorção do líquido iônico no suporte foi realizada através de cálculos de teoria do funcional da densidade. Nessa parte do trabalho foram obtidos resultados geométricos e energéticos de várias conformações do líquido iônico sobre as superfícies mais importantes do óxido para depois serem realizados cálculos de pós-processamento, tais como, análise de Bader, análise da densidade de cargas, análise da contribuição das forças de dispersão e obtenção das frequências vibracionais para estudo termodinâmico da simulação da degradação do líquido iônico suportado. / There are various types of salts, including some that are liquid at room temperature. The Ionic Liquids. These compounds have been used in several applications, among them , a new technique for heterogeneous catalysis called SILP method (supported ionic liquid phase). This innovative technique is to adsorp an ionic liquid in a porous surface so that the ionic liquid acts as a liquid phase solvent, membrane or solid catalyst. In this work, a theoretical and experimental study was conducted to understand how the interaction between the ultrathin film of ionic liquid and the solid support is and to propose a mechanism for the degradation of the supported salt, predicting the temperatures at which this process occurs. The experimental section of this study consisted of thermogravimetric analysis and obtaining vibrational spectra in the infrared region. The thermogravimetric experiments helped to define the degree of hydration on the surface used in the simulations of adsorption and, combined with the acquired vibrational spectra, served as the basis of design proposals for mechanisms of the degradation of the supported [C4C1Im]+[BF4]-. The combination of the experimental analyses led to the degradation mechanisms where the surface is fluoridated by the anion, therefore losing a hydroxyl. This result led to an investigation of the gamma-alumina fluoridation surface with the simulated 19F NMR spectra, vibrational spectra and thermodynamic study. The simulated spectra of nuclear magnetic resonance was conducted in order to make the assignments with the intention of assisting in the divergence between previously published works. The simulation of the ionic liquid adsorption was performed by ab initio electronic structure. In this part of the job, geometrical and energy results of multiple conformations of the ionic liquid on the most important oxide surfaces were obtained for later post-processing calculations such as Bader charge, analysis of the dispersion forces contribution and vibrational frequencies to obtain the thermodynamic simulation study of the supported ionic liquid degradation.