The tropospheric oxidation of unsaturated hydrocarbons is a central issue in atmospheric chemistry. These hydrocarbons are emitted into the atmosphere from both natural and anthropogenic sources, and their atmospheric oxidation leads to different atmospheric pollutants, including ground level ozone, photochemical smog and secondary organic aerosols. Isoprene and 1,3-butadiene represent a biogenic and an anthropogenic hydrocarbon, respectively, which primarily undergo electrophilic addition of OH radical, followed by chain propagating radical reactions. Their oxidation is the major source for ground level ozone formation in both rural and urban area and understanding their chemistry is essential for regional air quality modeling. Until recently, most of the studies of isoprene chemistry have been non-isomer specific, reflecting the reactivity of combined pathways and therefore were insensitive to specific details of the isomeric pathways. An isomeric selective approach to studying unsaturated hydrocarbon oxidation is described in this dissertation. A synthesized precursor, whose photolysis can provide a route to the formation of energy selected single isomer in the isoprene oxidation pathway, enables the study of important channels that are difficult to unravel in non isomer specific experiments. The major addition channel in OH isoprene oxidation has been studied following the isomeric selective approach and using Laser Photolysis-Laser Induced Fluorescence (LP-LIF) as the primary experimental technique. The study reveals important information about the oxidative chemistry of the δ-peroxy radicals, accounting for about 20 percent of missing carbon balance in isoprene oxidation, and isomeric specific rate constants. A similar approach was applied to study the oxidation of 1,3-butadiene, and the photolytic precursor for the dominant hydroxy alkyl isomer in the OH initiated oxidation of 1,3-butadiene was synthesized. The subsequent experiments and analysis revealed detailed information about the oxidative chemistry accounting for approximately 26 percent of the missing chemistry. Finally, non isomeric selective OH cycling experiments were carried out on the1,3-butadiene system. By analyzing the OH cycling data with the combined information obtained from the isomeric specific studies of the two isomeric channels of 1,3-butadiene oxidation, the relative branching between the two isomeric channels of OH-1,3-butadiene oxidation was determined.

Polybutadiene, the homopolymer of 1,3-butadiene, is a synthetic rubber especially important in the production of tires. Industrially, it is polymerized using multi-site catalysts that do not offer significant control over molecular weight distribution resulting in polymers with poor mechanical properties. Single-site polymerization of 1,3-butadiene results in narrow molecular weight distribution and thus increased impact resistance and durability. Complexes of chromium and neodymium bearing bis-phosphinimine pincer ligands have been synthesized and studied for their behavior in 1,3-butadiene polymerization in combination with methylaluminoxane. The complexes that were active produced highly cis-1,4-polybutadiene with high molecular weight and narrow polydispersities. The co-polymerization of acrylonitrile and 1,3-butadiene with the bis-phosphinimine chromium (III) complexes and methylaluminoxane to produce nitrile-butadiene rubber was also explored. The insertion of 1,3-butadiene into nickel-methyl and nickel-hydride complexes bearing the bis-phosphinimine pincer ligands was examined using nuclear magnetic resonance spectroscopy and will also be discussed.

Polybutadiene, the homopolymer of 1,3-butadiene, is a synthetic rubber especially important in the production of tires. Industrially, it is polymerized using multi-site catalysts that do not offer significant control over molecular weight distribution resulting in polymers with poor mechanical properties. Single-site polymerization of 1,3-butadiene results in narrow molecular weight distribution and thus increased impact resistance and durability. Complexes of chromium and neodymium bearing bis-phosphinimine pincer ligands have been synthesized and studied for their behavior in 1,3-butadiene polymerization in combination with methylaluminoxane. The complexes that were active produced highly cis-1,4-polybutadiene with high molecular weight and narrow polydispersities. The co-polymerization of acrylonitrile and 1,3-butadiene with the bis-phosphinimine chromium (III) complexes and methylaluminoxane to produce nitrile-butadiene rubber was also explored. The insertion of 1,3-butadiene into nickel-methyl and nickel-hydride complexes bearing the bis-phosphinimine pincer ligands was examined using nuclear magnetic resonance spectroscopy and will also be discussed.

The infrared, Raman and ultraviolet spectra of pyridine-d0 and pyridine-d5 were recorded and assigned with a focus on the low-frequency vibrational modes in the S1(n,pi*) electronic excited state. An energy map for the low-frequency modes was constructed and the data for the v18 mode allowed a highly anharmonic one-dimensional potential energy function to be determined for the S1 excited state. In this S1(n,pi*) state, pyridine is quasi-planar and very floppy with a barrier to planarity of 3 cm^-1. The infrared, Raman and ultraviolet spectra of 2-fluoropyridine (2FPy) and 3-fluoropyridine (3FPy) have been collected and assigned. For 2FPy about 150 bands were observed for the transitions to the vibronic levels of the S(pi, pi*) state at 38,030.4 cm^-1. For 3FPy more than a hundred absorption bands associated with the S(n,pi*) state at 35,051.7 cm^-1 and about forty broad bands associated with the S(pi, pi*) state at 37,339 cm^-1 were observed. The experimental work was complemented by ab initio calculations and these also provided calculated structures for 2FPy, 3FPy, and pyridine. They showed that the fluorine atom on the ring participates in the pi bonding. The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d2, 1,1,4,4-d4, and d6 isotopomers have been recorded with high sensitivity in the region below 350 cm-1, in order to investigate the internal rotation (torsional) vibration. The data for all the isotopomers were then fit using a one-dimensional potential energy function of the form V = (1/2)Sigma(Vn(1-cos (phi))). The energy difference between trans and gauche forms was determined to be about 1030 cm^-1 (2.94 kcal/mol), and the barrier between the two equivalent gauche forms to be about 180 cm^-1 (0.51 kcal/mol), which agrees well with high-level ab initio calculations. The results from an alternative set of assignments also fits the data quite well are also presented. Combination and hot band series involving the v13 torsional vibration of the trans rotamer were observed for each of the butadiene isotopomers. In addition, the high signal to noise of the Raman spectra made it possible to detect several dozen bands of the gauche rotor which makes up only about 2% of the molecules at ambient temperature.

En aquesta tesi, proposem la fabricació y la caracterització d’un microconcentrador de gasos, per ser acoblat amb un microsistema de detecció, per millorar el seu límit de detecció davant els gasos tòxics. Aquest estudi s’aplica especialment al benzè, que es un compost d’alta cancerigenitat. El preconcentrador proposat esta basat en estructura plana, que, es una opció de fabricació més simple y permet una millor aïllament tèrmic amb el resta d’unitats del microsistema, qu’els estructures 3D proposats a la literatura. No obstant, els factors de concentració obtinguts amb l’estructura plana queden generalment més baixos, per causa de la menor quantitat de material absorbent que pot acollir. En aquesta tesis, es va superar aquest problema mitjançant l’utilització del carboní actiu, un adsorbent d’alta capacitat d’adsorció, així com l’optimització de les condicions de funcionament del dispositiu. Finalment, acoblant el microconcentrador amb un micro-cromatògraf, vam aconseguir una detecció sensible y selectiva del benzè en barreja amb altres volàtils a l’aire. / The present thesis focuses on the fabrication and characterization of a gas microconcentrator for to be coupled with a detection microsystem, in order to lower its detection limit towards toxic gases and vapours in contaminated areas. This study was more especially applied to the preconcentration of benzene, a cancerigenic compound at low ppb level. A preconcentrator based on a planar structure was proposed regarding its simpler fabrication, better thermal insulation and lower power consumption, compared to the 3D structures proposed conventionally in literature. In order to obtain higher concentration factors with such structure, its small size was compensated by using a high adsorption capacity adsorbent such as activated carbon as well as the optimization of the preconcentration conditions of the device. Finally, the microconcentrator was validated as injection unit when coupled with a microchromatographic system, where a sensitive and selective analysis of benzene in mixture with other VOCs was achieved.

A construção de um analisador virtual é sustentada basicamente por três pilares: o modelo, as variáveis que integram o modelo e a estratégia de correção/atualização do modelo. Os modelos matemáticos são classificados quanto ao nível de conhecimento do processo contido nele, indo de modelos complexos baseados em relações fundamentais e leis físico-químicas, denominados white-box, até modelos obtidos através de técnicas de análise multivariável, como técnicas de regressão multiváriavel e redes neurais, referenciados como black box. O presente trabalho objetiva uma análise de dois dos pilares: os modelos, focando em modelos obtidos através das técnicas de redução de dimensionalidade do tipo PLS, e metodologias de seleção de variáveis para a construção dessa classe de modelos. Primeiramente é realizada uma revisão das principais variantes lineares e não lineares da metodologia PLS, compreendendo desde o seu desenvolvimento até a sua combinação com redes neurais. Posteriormente são apresentadas algumas das técnicas popularmente utilizadas para a seleção de variáveis em modelos do tipo black-box, técnicas de validação cruzada e técnicas de seleção de dados para calibração e validação de modelos. São propostas novas abordagens para os procedimentos de seleção de variáveis, originadas da combinação das técnicas de seleção de dados com duas metodologias de seleção de variáveis. Os resultados produzidos por essas novas abordagens são comparados com o método clássico através de casos lineares e não lineares. A viabilidade das técnicas analisadas e desenvolvidas é verificada através da aplicação das mesmas no desenvolvimento de um analisador virtual para uma coluna de destilação simulada através do simulador dinâmico Aspen Dynamics®. Por fim são apresentadas as etapas e desafios da implementação de um analisador virtual baseados em técnicas PLS em uma Torre Depropanizadora de uma central de matérias primas de um pólo petroquímico. / The construction of a virtual analyzer is sustained basically by three pillars: the model, the variables that integrate the model and the updating strategy of the model. The mathematical models are classified with relationship at the level of the process knowledge within it, going from complex models, based on fundamental relationships and physical-chemistries laws, called white-box, until models obtained through multivariable analysis techniques, as multiple linear regression and neural networks, also called as black box. The focus of the present work is the analysis of two of the pillars: the models, specially the ones obtained by dimension reduction techniques, like PLS, and methodologies used in the development of this class of models. Initially, a revision of the main linear and non linear variants of the PLS methodology is done, embracing since its development to its combination with neural networks. Later on, some popularly variables selection techniques for black-box models are explained, as well as some cross validation techniques and strategies for data selection for calibration and validation of models. New approaches for variables selection procedures are proposed, originated by the combination of data selection strategies and two variables selection techniques. The results produced by those new approaches are compared with the classic method through linear and non linear case studies. The viability of the analyzed and developed techniques is verified through the application of the same ones in the development of a virtual analyzer for a distillation column, simulated by the dynamic simulator Aspen Dynamics®. The steps and challenges faced in the implementation of a virtual analyzer based on PLS technical for a Depropanizer Unit are finally presented.

A construção de um analisador virtual é sustentada basicamente por três pilares: o modelo, as variáveis que integram o modelo e a estratégia de correção/atualização do modelo. Os modelos matemáticos são classificados quanto ao nível de conhecimento do processo contido nele, indo de modelos complexos baseados em relações fundamentais e leis físico-químicas, denominados white-box, até modelos obtidos através de técnicas de análise multivariável, como técnicas de regressão multiváriavel e redes neurais, referenciados como black box. O presente trabalho objetiva uma análise de dois dos pilares: os modelos, focando em modelos obtidos através das técnicas de redução de dimensionalidade do tipo PLS, e metodologias de seleção de variáveis para a construção dessa classe de modelos. Primeiramente é realizada uma revisão das principais variantes lineares e não lineares da metodologia PLS, compreendendo desde o seu desenvolvimento até a sua combinação com redes neurais. Posteriormente são apresentadas algumas das técnicas popularmente utilizadas para a seleção de variáveis em modelos do tipo black-box, técnicas de validação cruzada e técnicas de seleção de dados para calibração e validação de modelos. São propostas novas abordagens para os procedimentos de seleção de variáveis, originadas da combinação das técnicas de seleção de dados com duas metodologias de seleção de variáveis. Os resultados produzidos por essas novas abordagens são comparados com o método clássico através de casos lineares e não lineares. A viabilidade das técnicas analisadas e desenvolvidas é verificada através da aplicação das mesmas no desenvolvimento de um analisador virtual para uma coluna de destilação simulada através do simulador dinâmico Aspen Dynamics®. Por fim são apresentadas as etapas e desafios da implementação de um analisador virtual baseados em técnicas PLS em uma Torre Depropanizadora de uma central de matérias primas de um pólo petroquímico. / The construction of a virtual analyzer is sustained basically by three pillars: the model, the variables that integrate the model and the updating strategy of the model. The mathematical models are classified with relationship at the level of the process knowledge within it, going from complex models, based on fundamental relationships and physical-chemistries laws, called white-box, until models obtained through multivariable analysis techniques, as multiple linear regression and neural networks, also called as black box. The focus of the present work is the analysis of two of the pillars: the models, specially the ones obtained by dimension reduction techniques, like PLS, and methodologies used in the development of this class of models. Initially, a revision of the main linear and non linear variants of the PLS methodology is done, embracing since its development to its combination with neural networks. Later on, some popularly variables selection techniques for black-box models are explained, as well as some cross validation techniques and strategies for data selection for calibration and validation of models. New approaches for variables selection procedures are proposed, originated by the combination of data selection strategies and two variables selection techniques. The results produced by those new approaches are compared with the classic method through linear and non linear case studies. The viability of the analyzed and developed techniques is verified through the application of the same ones in the development of a virtual analyzer for a distillation column, simulated by the dynamic simulator Aspen Dynamics®. The steps and challenges faced in the implementation of a virtual analyzer based on PLS technical for a Depropanizer Unit are finally presented.

A construção de um analisador virtual é sustentada basicamente por três pilares: o modelo, as variáveis que integram o modelo e a estratégia de correção/atualização do modelo. Os modelos matemáticos são classificados quanto ao nível de conhecimento do processo contido nele, indo de modelos complexos baseados em relações fundamentais e leis físico-químicas, denominados white-box, até modelos obtidos através de técnicas de análise multivariável, como técnicas de regressão multiváriavel e redes neurais, referenciados como black box. O presente trabalho objetiva uma análise de dois dos pilares: os modelos, focando em modelos obtidos através das técnicas de redução de dimensionalidade do tipo PLS, e metodologias de seleção de variáveis para a construção dessa classe de modelos. Primeiramente é realizada uma revisão das principais variantes lineares e não lineares da metodologia PLS, compreendendo desde o seu desenvolvimento até a sua combinação com redes neurais. Posteriormente são apresentadas algumas das técnicas popularmente utilizadas para a seleção de variáveis em modelos do tipo black-box, técnicas de validação cruzada e técnicas de seleção de dados para calibração e validação de modelos. São propostas novas abordagens para os procedimentos de seleção de variáveis, originadas da combinação das técnicas de seleção de dados com duas metodologias de seleção de variáveis. Os resultados produzidos por essas novas abordagens são comparados com o método clássico através de casos lineares e não lineares. A viabilidade das técnicas analisadas e desenvolvidas é verificada através da aplicação das mesmas no desenvolvimento de um analisador virtual para uma coluna de destilação simulada através do simulador dinâmico Aspen Dynamics®. Por fim são apresentadas as etapas e desafios da implementação de um analisador virtual baseados em técnicas PLS em uma Torre Depropanizadora de uma central de matérias primas de um pólo petroquímico. / The construction of a virtual analyzer is sustained basically by three pillars: the model, the variables that integrate the model and the updating strategy of the model. The mathematical models are classified with relationship at the level of the process knowledge within it, going from complex models, based on fundamental relationships and physical-chemistries laws, called white-box, until models obtained through multivariable analysis techniques, as multiple linear regression and neural networks, also called as black box. The focus of the present work is the analysis of two of the pillars: the models, specially the ones obtained by dimension reduction techniques, like PLS, and methodologies used in the development of this class of models. Initially, a revision of the main linear and non linear variants of the PLS methodology is done, embracing since its development to its combination with neural networks. Later on, some popularly variables selection techniques for black-box models are explained, as well as some cross validation techniques and strategies for data selection for calibration and validation of models. New approaches for variables selection procedures are proposed, originated by the combination of data selection strategies and two variables selection techniques. The results produced by those new approaches are compared with the classic method through linear and non linear case studies. The viability of the analyzed and developed techniques is verified through the application of the same ones in the development of a virtual analyzer for a distillation column, simulated by the dynamic simulator Aspen Dynamics®. The steps and challenges faced in the implementation of a virtual analyzer based on PLS technical for a Depropanizer Unit are finally presented.

Les suies et les hydrocarbures polyaromatiques, qui sont émis à l’échappement des moteurs Diesel, constituent une part importante de la pollution urbaine. Depuis plusieurs années, de nombreuses recherches ont permis de progresser dans le domaine de la cinétique de la combustion des hydrocarbures qui est maintenant relativement bien connue. Il reste néanmoins des zones d’ombre concernant la formation des composés aromatiques (benzène, toluène,…) et des hydrocarbures aromatiques polycycliques (HAP) dont la formation provient d’espèces composées de deux à six atomes de carbone et qui mènent directement ou indirectement à la formation des suies.L’allène, le propyne, le butadiène et le cyclopentène sont des produits intermédiaires importants de la combustion dans les moteurs. Dans ce contexte, ce travail de thèse a permis de mieux comprendre les voies réactionnelles importantes dans la formation du benzène et du toluène. Le chapitre I de ce mémoire présente une revue bibliographique des travaux antérieurs sur l’oxydation du méthane, de l’allène, de propyne, de 1,3-butadiène et du cyclopentène. Le chapitre II présente une description détaillée du montage expérimental utilisé durant cette étude afin d’étudier la structure de la flamme laminaire de prémélange. Les chapitres III, IV et V présentent les résultats expérimentaux obtenus en flamme laminaire de prémélange, ainsi qu’une comparaison avec des simulations effectuées à l’aide de mécanismes réactionnels élaborés durant ce travail de thèse / Soots and polyaromatic hydrocarbons (PAH), which are present in the exhaust gas of diesel engines, represent a large part of the urban pollution. Many efforts have then been focused on reducing the emissions of these compounds. The formation of soot precursors and PAH in combustion involves small unsaturadted hydrocarbons the chemistry of which is still very uncertain. Allene, propyne, 1,3-butadiene and cyclopentene are intermediate products in the combustion in cars engines. This work has led to a better understanding of several important paths in the formation of benzene and toluene. The chapter I of this report presents a bibliographic review of former work on the oxidation of methane, allene, propyne, 1,3-butadiene and cyclopentene. Chapter II gives a detailed description of the experimental set up used during this work to study the structure of the premixed flat laminar flames. Chapters III, IV and V present our experimental results obtained in laminar premixed flat flames and also the comparison with simulations

Nesta Dissertação, foram realizadas reações de copolimerização de 1,3-butadieno com diferentes alfa-olefinas (1-hexeno, 1-octeno e 1-dodeceno) utilizando-se um sistema catalítico do tipo Ziegler-Natta ternário constituído por versatato de neodímio, hidreto de diisobutilalumínio e cloreto de t-butila. O sistema catalítico também foi avaliado em reações de homopolimerização com cada alfa-olefina. As condições reacionais, tanto da síntese do catalisador como das reações de polimerização, foram mantidas constantes. Foi estudada a influência de diferentes teores de cada alfa-olefina (1, 3, 5, 10, 20 e 30 % em relação ao 1,3-butadieno) sobre a conversão da polimerização, a microestrutura, a massa molar, as propriedades viscosimétricas e a estabilidade térmica dos polímeros obtidos. Foi avaliada, ainda, a influência do tamanho da cadeia da alfa-olefina sobre as características da polimerização. Os polímeros foram caracterizados por espectroscopia na região do infravermelho (FTIR), cromatografia por exclusão de tamanho (SEC), viscosimetria capilar e termogravimetria (TG). A microestrutura dos polímeros, praticamente, não variou com a adição das alfa-olefinas. A massa molar numérica média (Mn) não sofreu alterações significativas, enquanto que a massa molar ponderal média (Mw) apresentou tendência ao aumento, quanto maior foi a incorporação de comonômero. A viscosidade intrínseca não apresentou uma tendência com a adição da alfa-olefina na reação, permanecendo na faixa de 2,015 a 3,557 dL/g. A estabilidade térmica do copolímero mostrou uma tendência a aumentar com a incorporação das alfa-olefinas / In this work, were performed copolymerization reactions of 1,3-butadiene with different alpha-olefins (1-hexene, 1-octene and 1-dodecene), using a ternary catalytic system of Ziegler-Natta, constituted by neodymium versatate, diisobutylaluminum hydride and t-butyl chloride. The catalytic system was also evaluated in homopolymerization reactions with the alpha-olefins. The reaction conditions, both the catalyst synthesis as the polymerization reactions, were kept constant. The influence of different content of each alpha-olefin (1, 3, 5, 10, 20 and 30% compared to 1,3-butadiene) on the polymerization conversion, the microstructure, molar mass, viscometric properties and thermal stability of polymers was studied. The influence of alpha-olefin chain size on polymerization characteristics was also evaluated. The polymers were characterized by infrared spectroscopy (FTIR), size exclusion chromatography (SEC), capillary viscometry and thermogravimetry (TG). The polymer microstructure, practically, did not change with the addition of alpha-olefins. The number average molecular mass (Mn) has not changed; while the weight average molecular mass (Mw) trended to increase. The intrinsic viscosity did not show a trend with the alpha-olefin addition, remaining in the range from 2.015 to 3.557 dL/g. The copolymer thermal stability showed a tendency to increase with the incorporation of alpha-olefins