Orientador: Martin Aznar / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-11T20:46:38Z (GMT). No. of bitstreams: 1 Cunha_EvelynVilmaCaravazi_M.pdf: 1619492 bytes, checksum: 1e4afeecf37b0da40904e4da5be5eb20 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho são determinados experimentalmente dados de equilíbrio líquido ¿ líquido dos sistemas de duas fases aquosas, água + PEG 8000 + sulfato de magnésio e água + PEG 8000 + sulfato de sódio, nas temperaturas de 25 e 50ºC. As composições de ambas as fases em equilíbrio foram obtidas por gravimetria, utilizando a técnica de liofilização (freeze-drying) para a determinação da quantidade de água e a calcinação em forno mufla para quantificação de PEG, sendo que a composição de sal foi obtida por diferença de massa. Os dados assim obtidos foram modelados através dos modelos NRTL e UNIFAC para o cálculo do coeficiente de atividade. O modelo NRTL, com a estimação de novos parâmetros de interação energética entre as espécies envolvidas, apresentou excelentes resultados de correlação, com baixos desvios entre as composições experimentais e as calculadas. O modelo UNIFAC, que é basicamente preditivo, foi capaz de representar satisfatoriamente os sistemas estudados com alguns grupos funcionais e parâmetros de interação existentes na literatura e outros estimados a partir dos dados experimentais obtidos nesse trabalho / Abstract: In this work, experimental data of the liquid-liquid equilibrium for the aqueous twophase systems water + PEG8000 + magnesium sulfate and water + PEG8000 + sodium sulfate were determined at 25 e 50°C. The compositions of both equilibrium phases were obtained by a gravimetric method, using the lyofilization (freeze-drying) technique for the water determination and the calcination in a muffle furnace for the PEG determination; in this way the salt was determined by mass difference. The experimental data were modeled by the NRTL and UNIFAC models for the activity coefficient. The NRTL model, with new energy interaction parameters, showed excellent correlation results, with low deviations between experimental and calculated compositions. The UNIFAC model, which is a predictive one, was able to represent the studied systems with some energy interaction parameters form the literature and others estimated from the experimental data determined in this work / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Maria Alvina Krahenbuhl / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-04T13:24:40Z (GMT). No. of bitstreams: 1 Mafra_MarcosRogerio_D.pdf: 5218448 bytes, checksum: 82785bbe534f8328a5b2d6c5c2a8c306 (MD5) Previous issue date: 2005 / Resumo: O estudo dos fenômenos físico-químicos presentes nos processos químicos industriais é de extrema relevância, desde o projeto ata a operação das unidades que compõem a planta. Dentre as etapas do processo, a separação e purificação costumam concentrar os maiores custos do projeto. Um importante segmento da indústria petroquímica é a produção de fenol, empregando na fabricação de resinas. Nesse processo duas colunas de destilação e um decantador são responsáveis pela purificação do fenol e recuperação da matéria-prima (cumeno). O equilíbrio de fases é um dos fenômenos mais importantes dessas unidades, havendo a possibilidade de ocorrer em alguns pratos o equilíbrio trifásico (LLV). Embora termodinamicamente possível, as tentativas de descrever essa forma de equilíbrio, utilizando dados exclusivamente bifásicos (LL /ou LV), não apresentam bons resultados. Este trabalho teve como objetivo o estudo termodinâmico do equilíbrio líquido-líquido e líquido-vapor na região próxima ao equilíbrio líquido-líquido-vapor de sistemas que compõem as etapas de separação do processo de produção fenol (água, acetona, 'alfa¿-metil estireno, cumeno e fenol), de forma a contribuir com o estudo do equilíbrio trifásico, presente nesse processo. Foram obtidos dados isotérmicos de equilíbrio líquido-líquido a 50 e ¿60 GRAUS¿C e dados isobáricos de equilíbrio líquido-vapor à 760 mmHg... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: Studies concerning physical and chemical phenomena are very important for the chemical industry, form the early stages of design up to full plant operation. Among the many units that make up a chemical plant, the last steps of separation and purification stands as the most expensive. Phenol, used to produce resins as well as other products, is an important feedstock to petrochemical industries. Two distillations columns and one decanter are used to purify phenol and separate cumene in the phenol production process, in which phase equilibrium plays an important role. In a tray distillation tower, one may find two liquid phases and one vapor phase in equilibrium (VLLE). Although possible, attempts to describe this equilibrium condition from two phase equilibrium conditions, either liqui-liquid (LLE) or vapor-liquid (VLE), haven¿t succeed. The objective of this work was to study the LLE and VLE of systems comprising components of the phenol production process, i.e., water, acetone, cumene, phenol and 'alfa¿-methyl styrene, at conditions close to the liquid-liquid-vapor equilibrium. Equilibrium data were successfully obtained at ¿50 DEGREES¿C and ¿60 DEGREES¿C and at 760 mmHg for a variety of compositions. Unfortunately data at high acetone contents could not be obtained due to the high pressure generated in the experimental apparatus... Note: The complete abstract is available with the full electronic digital thesis or dissertations / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Poly(1,4-diethynylbenzene) ( -conjugated polymer) was prepared as an insoluble polymer network via chain coordination polymerization of 1,4-diethynylbezene catalyzed with [Rh(NBD)acac] complex. Thermodynamic properties and acid-base characteristics of the prepared poly(1,4-diethynylbenzene) were studied by means of Inverse Gas Chromatography (IGC) in the temperature range 80-100 řC. Retention data of selected testing substances were used to determine the Gibbs energy of sorption, the sorption enthalpy and their acid-base and disperse parts as well as the disperse contribution to the surface energy and parameters of KA, KD, ANHPS and DNHPS quantifying the acid-base character of the studied polymer. The results showed that poly(1,4-diethynylbenzene) interacted more efficiently with Lewis bases than with Lewis acids. The values of experimental sorption enthalpy were used for the determination of the parameters KA and KD. Values of these parameters classify poly(1,4-diethynylbenzene) as the material with a slightly acid character. This conclusion is further supported by the results of H. P. Schreiber method based on the application of ANHPS and DNHPS parameters for the evaluation of the acid-base properties of the material. The infrared spectroscopy proved that poly(1,4-diethynylbenzene) contained...

Humic acids and humates are principal components of humic substances major organic constituents of soil, peat, coal and water around the world. I was involved in research into molecular dynamics simulations of interactions of quartz surfaces with aqueous solutions of ions and small organic molecules representing basic building blocks of larger biomolecules and functional groups of organic matter. We studied interactions of molecules with surfaces for a set of surface charge densities corresponding to the experimentally or environmentally relevant ranges of pH values employing molecular mechanics, molecular dynamics and ab initio techniques. Simulated quartz surfaces covered the range of surface charge densities 0.00, -0.03, -0.06 and -0.12 C-m-2, approximately corresponding to pH values 4.5, 7.5, 9.5 and 11. As model molecules, benzoic acid, phenol, o-salicylic acid and their conjugated bases were chosen. My task was to prepare topologies and parametric models of selected organic matter basic building blocks organic molecules. I focused on studying interactions of these molecules in an aqueous environment with mineral surface quartz. The aim was to process simulation results and analyse conformations of the adsorption complexes and their thermodynamic properties such as interaction energies, free energies and adsorption geometries.