“Green” explosives are an important sub-family of explosives due to the banning of explosives based on heavy metals, such as lead azide and lead styphnate, according to the REACH list. A substitute to lead azide is potassium 4,6-dinitrobenzofuroxane (KDNBF) which is an alternative “green” explosive. Hence there is an upcoming need for analytical and quality control protocols for KDNBF. In this report is HPLC-UV/VIS, GC-FID and potentiometric titration evaluated for their suitability as methods for testing of KDNBF. The results implies that KDNBF can be analyzed by GC-FID, when dissolved in DMSO and caffeine is used as internal standard. To analyze KDNBF by HPLC-UV/VIS was isocratic mode used together with a porous graphitic carbon (PGC) (Hypercarb ®) column. However, degradation of the analyte was severe and quantitative results were not obtained. Potentiometric titration indicated that KDNBF equilibrate with four hydrogen ions during titration, instead of the one to one ratio with potassium and hydrogen ion, as in previously proposed theory. Despite this and with careful titration is potentiometric titration and GC-FID analysis combined suitable as a quality control protocol for KDNBF.

Light-addressable potentiometric sensors (LAPS) and scanning photo-induced impedance microscopy (SPIM) have been extensively applied as chemical sensors and biosensors. This thesis focuses on the investigation of LAPS and SPIM for electrochemical imaging based on two different semiconductor substrates, silicon on sapphire (SOS) and indium tin oxide (ITO) coated glass. Firstly, SOS substrates were modified with 1,8-nonadiyne self-assembled organic monolayers (SAMs), which served as the insulator. The resultant alkyne terminals provided a platform for the further functionalization of the sensor substrate with various chemicals and biomolecules by Cu(I)-catalyzed azide alkyne cycloaddition (CuAAC) 'click' reactions. The CuAAC reaction combined with microcontact printing (μCP) was successfully used to create chemical patterns on alkyne-terminated SOS substrates. The patterned monolayers were found to be contaminated with the copper catalyst used in the click reaction as visualized by LAPS and SPIM. Different strategies for avoiding copper contamination were tested. Only cleaning of the silicon surfaces with an ethylenediaminetetraacetic acid tetrasodium salt (EDTA) solution containing trifluoroacetic acid after the 'click' modification proved to be an effective method as confirmed by LAPS and SPIM results, which allowed, for the first time, the impedance of an organic monolayer to be imaged. Furthermore, the 1,8-nonadiyne modified SOS substrate was functionalized and patterned with an RGD containing peptide, which was used to improve the biocompatibility of the substrate and cell adhesion. By seeding cells on the peptide patterned sensor substrate, cell patterning was achieved. Single cell imaging using LAPS and SPIM was attempted on the RGD containing peptide modified SOS substrate Finally, an ITO coated glass substrate was used as a LAPS substrate for the first time. The photocurrent response, the pH response, LAPS and SPIM imaging and its lateral resolution using ITO coated glass without any modification were investigated. Importantly, single cell images were obtained with this ITO-based LAPS system.

Acid/base and metal ion adsorption properties have been investigated for a range of chemically modified bleached Kraft fibre materials (pulps). The studies were performed via potentiometric titrations, Flame Atomic Absorbtion (and Emission) Spectroscopy, Inductively Coupled Plasma Optical Emission Spectroscopy and Extended X-ray Absorbtion Fine Structure measurements. As a result of a chemical modification procedure, the total concentration of acidic carboxylate groups in the fibre materials ranged between 43 and 590 μmol/g. The preferable surface potential model for modelling the ionic strength dependent acid/base properties of fibre materials with low charge densities, i.e. unmodified fully bleached Kraft fibre materials, was found to be the Basic Stern Model. For fibre materials with high total charge, ≳100 μmol/g, this model resulted in poor fits to data, and for such materials a number of Constant Capacitance Models, one at each ionic strength, must be recommended. With respect to metal ion adsorption, the results have indicated that the unspecific Donnan theory could correctly model the simultaneous adsorption of several metal ions, i.e. K+, Na+, Mg2+, Ca2+ and Cu2+, provided that the salt concentration in the fibre suspension is low. In suspensions of high salt concentration it was, however, found that this very same model strongly underestimated the adsorption of Ca2+ and Cu2+. Here, the Donnan model had to be complemented by specific ion exchange equilibria. These results were corroborated by spectroscopic evidence of specific interactions between Cu2+-ions and fibres. The spectroscopic indication of a complex formed between two fibre surface carboxylate groups and one Cu2+-ion, agree with the specific ion exchange model. It was therefore concluded that specific metal ionfibre interactions cannot be neglected, especially at high salt concentrations. The interactions occurring between the polycation GaO4Al12(OH)24(H2O)127+ and fibre materials were studied by both adsorption and spectroscopic measurements. These indicate that GaO4Al12(OH)24(H2O)127+ is surprisingly stable in fibre suspensions and that intact GaO4Al12(OH)24(H2O)127+- ions are strongly adsorbed onto the fibres. Also for this ion, specific interactions has to be considered, since the strong adsorption registered was too strong to be explained by Donnan equilibria. In the thesis, the stochiometric composition and an equilibrium constant characterising these interactions is presented.

Research Doctorate - Doctor of Philosophy (PhD) / This work presents the development and application of modern data acquisition and analysis techniques for the investigations of equilibrium and kinetic reactions. The analytical technique is known as second order global analysis and a background of this relatively novel approach has been given. The theory behind and characteristics of the computer programs developed analysis as part of this research are described in Chapter Two along with descriptions of the instrumentation and programs developed for the acquisition of both potentiometric and spectrophotometric data. Applications of the developed programs include a potentiometric and spectrophotometric study of the protonation and stability equilibria of a series of polydentate N-donor ligands, as detailed in Chapter Three. The combination of potentiometric and spectrophotometric analysis has been shown to be a powerful analytical tool. Spectrophotometric titrations were also combined with fast stop-flow experiments in order to elucidate the complex reaction mechanisms associated with helicating ligands. The helication of the ligand ‘PepdaH₂’ with copper(II) and nickel(II) is examined in Chapter Four, along with discussions concerning the ability to induce chirality in the helicates from the addition of a chiral counter ion. Investigations into chirality were further continued in Chapter Five where the stereoselectivity of a benzimidazole-based ligand was investigated with circular dichroism titrations. The synthesis and characterisation of the benzimidazole-based ligands are provided, including a study of the ability of the ligands to form higher order complexes as investigated using electrospray mass spectroscopy. Chapter Six provides an in-depth discussion concerning the use of combined glass hydrogen selective electrodes for the determination of equilibrium constants, as this was a major focus of this research. Different calibration techniques are discussed and a description of the internal calibration technique developed is provided along with examples of the advantages of performing internal calibration of the electrode.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Nesse trabalho, foram caracterizadas 238 amostras de Ãgua produzida, oriundos de quatro campos de produÃÃo diferentes, todos provenientes de campos marÃtimos da bacia do CearÃ, denominados campo de produÃÃo A, campo de produÃÃo B, campo de produÃÃo C e campo de produÃÃo D. Foram determinados, os Ãnions (Acetato, Cloreto, Formiato, Sulfato) utilizando-se a cromatografia de Ãons; exceto, para o Ãnion Bicarbonato que foi determinado utilizando-se a titulaÃÃo potenciomÃtrica. E, os cÃtions (BÃrio, CÃlcio, EstrÃncio, Ferro Total, LÃtio, MagnÃsio, PotÃssio, SÃdio) utilizando-se a espectrometria de emissÃo Ãptica com plasma acoplado indutivamente. Para tratamento estatÃstico, utilizou-se como ferramenta, a PCA (anÃlise de componentes principais) e a HCA (anÃlise de agrupamento hierÃrquico). Na avaliaÃÃo da qualidade dos dados, utilizou-se o balanÃo iÃnico. Para visualizaÃÃo dos resultados, utilizou-se o grÃfico boxplot, onde se pode observar que o campo de produÃÃo A, seguido do campo de produÃÃo B, possuem tendÃncia à corrosÃo e à incrustaÃÃo, respectivamente. Como tambÃm, o campo de produÃÃo D que apresentou propensÃo à corrosÃo, mas em menor escala. Vale salientar a necessidade de uma caracterizaÃÃo individual das amostras, para conhecimento dos principais constituintes existentes. Pois, esses constituintes podem acarretar elevados custos na manutenÃÃo do processo produtivo da indÃstria petrolÃfera; devido, a corrosÃo do tipo pite, que promove a modificaÃÃo da aparÃncia e estrutura dos aÃos inoxidÃveis, muito utilizados na indÃstria petrolÃfera; e, as incrustaÃÃes, que tendem a se depositar nas paredes das tubulaÃÃes, que podem causar problemas como perda de pressÃo, diminuiÃÃo do escoamento da produÃÃo e aumento no consumo de energia. / In this study, we characterized 238 samples of water produced from four different production fields, all from offshore fields of the Cearà basin, called The field of production, production field B, C production and field production field D. were determined anions (acetate, chloride, formate, sulfate) using ion chromatography; except for the bicarbonate anion was determined using potentiometric titration. And, cations (Barium, Calcium, Strontium, total iron, lithium, magnesium, potassium, sodium) using the optical emission spectrometry with inductively coupled plasma. For statistical analysis, we used as a tool, the PCA (principal component analysis) and HCA (hierarchical cluster analysis). In evaluating the quality of the data, we used the ionic balance. To visualize the results, we used the box plot graph where one can observe that the production field, followed by the production field B, are prone to corrosion and fouling, respectively. As well, the D production field that showed propensity to corrosion, but on a smaller scale. It is worth stressing the need for individual characterization of the samples, to knowledge of the main existing constituents. For these constituents can incur high costs in maintaining the productive process of the oil industry; due to corrosion pitting type, which promotes change the look and structure of stainless steel, widely used in the oil industry; and incrustations which tend to deposit on the walls of pipes, which may cause problems such as pressure loss, decreased production flow and an increase in power consumption.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Submitted by MARCIA ROVADOSCHI (marciar@unifra.br) on 2018-08-16T19:29:02Z No. of bitstreams: 2 Dissertacao_ElvandiDaSilvaJunior.pdf: 2386435 bytes, checksum: 7211425c98b6f5ed13fc2da4477d22d7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-08-16T19:29:02Z (GMT). No. of bitstreams: 2 Dissertacao_ElvandiDaSilvaJunior.pdf: 2386435 bytes, checksum: 7211425c98b6f5ed13fc2da4477d22d7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-11-28 / The wine win more consumers in Brazil day-by-day, due to increased quality and association of daily use of small doses to health benefits. The perception and increase the quality of the product are given by their organoleptic properties and the advances in its manufacturing process. Some equipments are used by professionals involved in the production of wine, such as assistance with obtaining data and physicochemical properties during the process. The need to use multiple measurement equipment during the processing procedure leads to loss of time and convenience. In order to possible an alternative to minimize these matters an equipment has been developed and tested employing nanostructured sensors detectors involving metal/oxide interface to evaluate the pH of wine and phenolic compounds. These systems were obtained by chemical and electrochemical techniques, and the evaluation of their performance was done by using potentiometric or potentiodynamic measurements. An electronic system was developed to acquire and process data in real time. Tests have shown that among the electrodes developed and tested pH electrode with composition the was Ir0,3Ti0,7O2 system that showed the best linear response with a sensitivity of 57.6 mV/pH in the pH region of 2-8, with excellent agreement with Nerstiniana response expected for this system (59.16 mV/pH). The copper electrodes anodized at 2 V for 30 min, sensitive to the amount of caffeic acid in aqueous solutions of 0.1 M NaOH. The responses observed in voltammograms indicate inhibition of cathodic solutions with the addition of 1 mL of wine and the increase in oxidation current at 0.7 V, which is associated with the oxidation of phenolic compounds. Using the current associated with this process, it was possible to classify the sample by phenolic content of wine. At the end, the nanostructured proved feasible to determine the pH and phenolic compounds in wine samples. / O vinho, a cada dia, ganha maior número de consumidores no Brasil, devido ao aumento da sua qualidade e da associação do uso diário de pequenas doses a benefícios à saúde. A percepção e o aumento da qualidade do produto se dão por suas propriedades organolépticas e pelos avanços no seu processo de fabricação. Alguns equipamentos são utilizados pelos profissionais envolvidos na produção do vinho, como auxílio à obtenção de dados e propriedades físico-químicas durante o processo. A necessidade de utilização de vários equipamentos de medição durante o procedimento de produção acarreta em perda de praticidade e de tempo. Buscando uma alternativa possível de minimizar esses problemas, foram desenvolvidos e testados detectores constituídos por sensores nanoestruturados, envolvendo interfaces do tipo metal/óxido, para avaliar o pH e compostos fenólicos dos vinhos. Estes sistemas foram obtidos por meio de técnicas químicas e eletroquímicas, e a avaliação de seu desempenho foi feita através da utilização de medidas potenciométricas ou potenciodinâmicas. Foi desenvolvido um sistema eletrônico para aquisição e tratamento de dados em tempo real. Os testes demonstraram que, dentre os eletrodos de pH desenvolvidos e testados, o eletrodo com composição Ir0,3Ti0,7O2 foi o sistema que apresentou a melhor resposta linear, com uma sensibilidade de 57,6 mV/pH na região de pH de 2 a 8, com excelente concordância com a resposta Nerstiniana esperada para esse sistema (59,16 mV/pH). Os eletrodos de cobre anodizados em 2 V durante 30 min, são sensíveis ao teor de ácido cafeico em soluções aquosas de NaOH 0,1 M. As respostas observadas nos voltamogramas indicam a inibição de processos catódicos em soluções com a adição de 1 mL de vinho e o aumento da corrente de oxidação em 0,7 V, que é associada a oxidação de compostos fenólicos. Utilizando a corrente associada a esse processo, foi possível classificar a amostra de vinho pelo teor fenólico. Ao final, os sistemas nanoestruturados mostraram-se viáveis para determinar o pH e os compostos fenólicos nas amostras de vinho.

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