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Orientador: Massao Ionashiro / Banca: João Oimpio Tognolli / Banca: Eder Tadeu Gomes Cavalheiro / Banca: Lázaro Moscardini D'Assunção / Banca: Maria Inês Gonçalves Leles / Resumo: Foram sintetizados no estado sólido os compostos Ln-2-MeO-Bz, sendo que Ln representa os lantanídeos trivalentes e Y (III) e 2-MeO-Bz representa o 2-methoxibenzoato. Os compostos foram sintetizados por adição estequiométrica, sob agitação, do ligante nas respectivas soluções de cloretos ou nitratos de lantanídeos. A precipitação dos compostos só ocorreram quando as soluções foram parcialmente evaporadas em banho maria. A caracterização dos compostos foi realizada utilizando-se de métodos convencionais: difratometria de raios X pelo método do pó, espectroscopia de absorção na região do infravermelho, análise elementar e as técnicas termoanalíticas TG/DTG (termogravimetria / termogravimetria derivada simultânea) e TG - DTA (termogravimetria - análise térmica diferencial simultânea) e DSC (Calorimetria exploratória diferencial). Estas técnicas puderam dar informações sobre desidratação, modos de coordenação, comportamento térmico, estequiometria e estrutura dos compostos sintetizados. Com os resultados das curvas TG e da complexometria, pôde-se estabelecer a fórmula geral de cada composto sintetizado. Pela análise dos difratogramas de raios X foi observado que todos os compostos sintetizados são cristalinos e que os compostos de lutécio e itérbio são isomorfos. A observação dos espectros de infravermelho teórico e experimental sugerem uma coordenação bidentada sem equalização de cargas entre o 2-metoxibenzoato e os seus respectivos centros metálicos. As curvas TG-DTA e DSC forneceram informações inéditas e importantes sobre o comportamento e a decomposição térmica dos compostos sintetizados. / Abstract: Solid state Ln 2-MeO-Bz compounds, where Ln stands for trivalent La to Lu and Y (III) and 2-MeO-Bz is 2-methoxybenzoate, have been synthesized. The solid state compounds were prepared by stoichiometric relation adding slowly, with continuous stirring the ligand solution to the respective metal chloride or nitrate solutions. No precipitate was observed during the addition of sodium 2-methoxybenzoate; however the precipitate was obtained when the solution was evaporated in a water bath. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffraction, infrared spectroscopy, elemental analysis and complexometry, were used to characterize and to study the thermal behaviour of these compounds. The results led to information about composition, dehydration, coordination mode, structure, thermal behaviour and thermal decomposition of the isolated compounds. From TG curves and complexometry results, a general formula could be established for these compounds in the solid state. The X-ray powder patterns pointed out that the synthesized compounds have a crystalline structure without evidence concerning to the formation of isomorphous series, except the ytterbium and lutetium compounds. The experimental and theoretical infrared spectroscopy data suggest that 2-metoxibenzoate acts as a bidentate bond with an incomplete equalization of bond lenghts in the carboxylate anion. The TG-DTA and DSC curves provided previously unrerported information concerning the thermal behaviour and thermal decomposition of these compounds. / Doutor

Hydroxylamine nitrate (HAN), an important agent for the nuclear industry and the U.S. Army, has been involved in several costly incidents. To prevent similar incidents, the study of HAN safe storage and handling boundary has become extremely important for industries. However, HAN decomposition involves complicated reaction pathways due to its autocatalytic behavior and therefore presents a challenge for definition of safe boundaries of HAN storage and handling. This research focused on HAN decomposition behavior under various conditions and proposed isothermal aging testing and kinetic-based simulation to determine safety boundaries for HAN storage and handling. Specifically, HAN decomposition in the presence of glass, titanium, stainless steel with titanium, or stainless steel was examined in an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC). n-th order kinetics was used for initial reaction rate estimation. Because stainless steel is a commonly used material for HAN containers, isothermal aging tests were conducted in a stainless steel cell to determine the maximum safe storage time of HAN. Moreover, by changing thermal inertia, data for HAN decomposition in the stainless steel cell were examined and the experimental results were simulated by the Thermal Safety Software package. This work offers useful guidance for industries that manufacture, handle, and store HAN. The experimental data acquired not only can help with aspects of process safety design, including emergency relief systems, process control, and process equipment selection, but also is a useful reference for the associated theoretical study of autocatalytic decomposition behavior.

The pyrolysis of sec-butyllithium in solution was studied in an attempt to understand the loss of stereo-specificity and the atypical kinetics that have been reported. Additionally, the effect of added lithium alkoxides was studied to determine their effects on the highly reactive sec-butyllithium substrate.

The MixAlco process uses an anaerobic, mixed-culture fermentation to convert lignocellulosic biomass to carboxylate salts. The fermentation broth must be clarified so that only carboxylate salts, water, and minimal impurities remain. Carboxylate salts are concentrated by evaporation and thermally decomposed into ketones. The ketones can then be chemically converted to a wide variety of chemicals and fuels. The presence of excess lime in the thermal decomposition step reduced product yield. Mixtures of calcium carboxylate salts were thermally decomposed at 450 degrees C. Low lime-to-salt ratios (g Ca(OH)2/g salt) of 0.00134 and less had a negligible effect on ketone yield. In contrast, salts with higher lime-to-salt ratios of 0.00461, 0.0190, and 0.272 showed 3.5, 4.6, and 9.4% loss in ketone yield, respectively. These losses were caused primarily by increases in tars and heavy oils; however, a three-fold increase in hydrocarbon production occurred as well. To predict ketone product distribution, a random-pairing and a Gibbs free energy minimization model were applied to thermal decompositions of mixed calcium and sodium carboxylate salts. Random pairing appears to better predict ketone product composition. For sodium and calcium acetate, two types of mixed sodium carboxylate salts, and two types of mixed calcium carboxylate salts, activation energy (EA) was determined using three isoconversional methods. For each salt type, EA varied significantly with conversion. The average EA for sodium and calcium acetate was 226.65 and 556.75 kJ/mol, respectively. The average EA for the two mixed sodium carboxylate salts were 195.61, and 218.18 kJ/mol. The average EA for the two mixed calcium carboxylate salts were 232.78, and 176.55 kJ/mol. In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak-Berggren model was the best overall. Possible reactor designs and configurations that address the challenges associated with the continuous thermal decomposition of carboxylate salts are also presented and discussed. Methods of fermentation broth clarification were tested. Flocculation showed little improvement in broth purity. Coagulation yielded broth of 93.23% purity. Filtration using pore sizes from 1 micrometer to 240 Daltons increased broth purity (90.79 to 98.33%) with decreasing pore size.

Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-07-18Bitstream added on 2014-06-13T20:06:29Z : No. of bitstreams: 1 siqueira_ab_dr_araiq.pdf: 1539576 bytes, checksum: 6e539e939ace621bbe4c448e761c8893 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Foram sintetizados no estado sólido os compostos Ln-2-MeO-Bz, sendo que Ln representa os lantanídeos trivalentes e Y (III) e 2-MeO-Bz representa o 2-methoxibenzoato. Os compostos foram sintetizados por adição estequiométrica, sob agitação, do ligante nas respectivas soluções de cloretos ou nitratos de lantanídeos. A precipitação dos compostos só ocorreram quando as soluções foram parcialmente evaporadas em banho maria. A caracterização dos compostos foi realizada utilizando-se de métodos convencionais: difratometria de raios X pelo método do pó, espectroscopia de absorção na região do infravermelho, análise elementar e as técnicas termoanalíticas TG/DTG (termogravimetria / termogravimetria derivada simultânea) e TG – DTA (termogravimetria - análise térmica diferencial simultânea) e DSC (Calorimetria exploratória diferencial). Estas técnicas puderam dar informações sobre desidratação, modos de coordenação, comportamento térmico, estequiometria e estrutura dos compostos sintetizados. Com os resultados das curvas TG e da complexometria, pôde-se estabelecer a fórmula geral de cada composto sintetizado. Pela análise dos difratogramas de raios X foi observado que todos os compostos sintetizados são cristalinos e que os compostos de lutécio e itérbio são isomorfos. A observação dos espectros de infravermelho teórico e experimental sugerem uma coordenação bidentada sem equalização de cargas entre o 2-metoxibenzoato e os seus respectivos centros metálicos. As curvas TG-DTA e DSC forneceram informações inéditas e importantes sobre o comportamento e a decomposição térmica dos compostos sintetizados. / Solid state Ln 2-MeO-Bz compounds, where Ln stands for trivalent La to Lu and Y (III) and 2-MeO-Bz is 2-methoxybenzoate, have been synthesized. The solid state compounds were prepared by stoichiometric relation adding slowly, with continuous stirring the ligand solution to the respective metal chloride or nitrate solutions. No precipitate was observed during the addition of sodium 2-methoxybenzoate; however the precipitate was obtained when the solution was evaporated in a water bath. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffraction, infrared spectroscopy, elemental analysis and complexometry, were used to characterize and to study the thermal behaviour of these compounds. The results led to information about composition, dehydration, coordination mode, structure, thermal behaviour and thermal decomposition of the isolated compounds. From TG curves and complexometry results, a general formula could be established for these compounds in the solid state. The X-ray powder patterns pointed out that the synthesized compounds have a crystalline structure without evidence concerning to the formation of isomorphous series, except the ytterbium and lutetium compounds. The experimental and theoretical infrared spectroscopy data suggest that 2-metoxibenzoate acts as a bidentate bond with an incomplete equalization of bond lenghts in the carboxylate anion. The TG-DTA and DSC curves provided previously unrerported information concerning the thermal behaviour and thermal decomposition of these compounds.

Les incendies de tunnels sont des phénomènes violents, à l’évolution rapide qui engendrent la plupart du temps des dommages importants aux personnes et aux biens. La sécurité incendie dans les tunnels routiers est basée sur l’utilisation de modèles empiriques très simplifiés de description de l’évolution de la cinétique de développement de l’incendie. Ces modèles ne prennent cependant pas en compte le type de combustible impliqués dans le phénomène, tels que les polymères constitutifs des enveloppes des véhicules routiers, ni leurs réactivité en phase solide (décomposition thermique). Dans l’optique de faire évoluer la description de l’incendie en fonction des conditions ambiantes caractéristiques d’un tunnel, un modèle prédictif de la décomposition thermique des matériaux a été développé. Ce modèle mathématique a été construit sur la base d’une approche expérimentale à petite échelle faisant intervenir le dispositif du cône calorimètre à atmosphère contrôlée couplé à un spectromètre infrarouge à transformée de Fourrier. Trois matériaux ont fait l’objet d’une étude approfondie de leur décomposition thermique, en fonction de deux paramètres clés influençant la décomposition des solides lors d’un incendie de tunnel : la concentration d’oxygène ambiante et l’éclairement énergétique imposé aux matériaux. Les résultats obtenus pour les trois matériaux choisis (une mousse Polyisocyanurate, un Ethylène Propylène Diène Monomère et un Acrylonitrile Butadiène Styrène) ont été utilisés pour la construction de régressions polynomiales multifactorielles, méthode également connue sous le nom de méthodologie des surfaces de réponses.Le modèle permet de définir la réponse de la cinétique de décomposition (variable expliquée) et son évolution, en fonction de la concentration d’oxygène locale et de l’éclairement énergétique imposé à la surface d’un matériau (variables explicatives). La comparaison des résultats numériques et expérimentaux a alors montré la pertinence de ce type d’approche / Tunnel fires are severe phenomenon whose evolution, usually very fast, can lead to important damages to persons and properties. Tunnel fire safety is based on the use of empirical models, very simplified that describes the evolution of the fire kinetic. Nevertheless, these models does not take into account neither the type of material that are involved in the phenomenon, such as constitutive polymers of road vehicles nor their reactivity in solid phase (thermal decomposition). In order to provide an evolution of the fire description, function of the conditions usually encountered in a tunnel, a predictive model aiming to describe materials’ thermal decomposition has been developed. This mathematical model has been established on the basis of an experimental approach, at small scale, using the Controlled Atmosphere Cone Calorimeter coupled to a Fourier Transform Infrared Spectrometer. The thermal degradation of three different materials (Polyisocyanurate foam, Acrylonitrile Butadiene Styrene and Ethylene Propylene Diene Monomer) has been thoroughly assessed function of key parameters that drives the decomposition process during fire: oxygen concentration and heat flux imposed to the materials. Obtained results for the three materials have then been used to construct multifactorial polynomial regressions, using the methodology known as surface response methodology. The model allows defining the response of the decomposition kinetics (explained variable), function of both the oxygen concentration and the heat flux received at the surface of the material (explanatory variable). Comparisons between numerical and experimental obtained results show the relevance of this approach.

<p> This work was initiated with a view to elucidating the hitherto little-studied thermolysis of esters of oxalic acid. A number of symmetrical diesters were synthesized and several were investigated thoroughly by use of product studies, kinetic methods and kinetic isotope-effect measurements. Both preparative and pyrolytic procedures and results are recorded. The literature regarding previous studies of the effect of heat on oxalate esters is surveyed, and a review of the principles and uses of the investigative methods employed is presented. The results are discussed in the light of more recent work and both general and specific mechanisms for oxalate thermolysis are suggested.</p> / Thesis / Doctor of Philosophy (PhD)

Dimethylsilene, generated from the thermal gas phase reaction of 1,1-dimethyl-1-silacyclobutane, reacts with alkynes to produce silacyclobutenes or acyclic silanes. The temperature dependence of the product ratios have been determined and the relative reactivities of three different alkynes toward the 1,1-dimethylsilene has been determined. 1-Hydrido-1-methylsilene has been generated by gas phase thermal decomposition from three different precursors. Trapping studies with butadiene and trimethylsilane lead to products expected from dimethylsilylene. The most plausible explanation for these observations is that hydridomethylsilenes undergo a facile isomerization to divalent dimethylsilylene. Cycloaddition of 1,1-dimethylsilene to allene at 600°C in a flow vacuum pyrolysis system affords the first synthesis of 2-methylene-1,1-dimethylsilacyclobutane and smaller amounts of six other products. For static pyrolysis at 421°C, the 2-methylene-1,1-dimethyIsilacyclobutane isomerizes to 1,1-dimethylsilacyclopentenes. The kinetics of gas phase thermal decomposition of cyclopropyltrimethylsilane has been studied over the temperature range, 689.6-751.1 K at pressures near 14 torr. The Arrhenius parameters for formation of allyltrimethylsilane are k_1(sec^-1)=10^14.3 ± 0.1 exp(-56.5 ± 0.2 kcal mol^-1/RT) and those for the formation of E- and Z-1-propenyltrimethyIsilane are k_2(sec^-1)=10^14.9 ± 0.3 exp(-61.9 ± 0.8 kcal mol^-1/RT). The difference between activation energies has been interpreted in terms of anchimeric assistance or the β effect of the silicon atom. The syntheses of 3-trimethylsilyl-1-pyrazoline and 1-trimethyl-2-pyrazoline are described. The thermal decomposition of either pyrazoline affords four different products along with elimination of a nitrogen molecule. It was suggested that the relative rates of methylene-hydrogen migration to radical centers α and γ to silicon are approximately equal. The thermal isomerization of 3-trimethylsilyl-1-pyrazoline to 1-trimethylsilyl-2-pyrazoline has been investigated kinetically at 65°C by proton NMR spectroscopy and the reverse reaction has been detected by gas phase pyrolysis.

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