Na presente tese investigou-se a adsorção induzida de um cátion metálico (cádmio(II)) na presença simultânea de dois ligantes (um pseudo-haleto e uma amina ou haleto) na interface eletrodo de mercúrio/solução aquosa, com vistas a uma melhor compreensão desse processo. Os estudos de adsorção foram precedidos por estudos de equilíbrio dos compostos de coordenação formados em solução aquosa. Medidas experimentais foram feitas por potenciometria com eletrodo de amálgama, em força iônica 1,00 M, ajustada com NaCl04. Análise dos dados por programas computacionais adequados levou à quantificação das constantes de estabilidade de 7 espécies binárias e 9 espécies mistas para o sistema Cd(II)/ SCN-/C6H12N4 e de 8 espécies binárias e 6 mistas para o sistema Cd(II)/I-/SCN-, sendo todas estas espécies mononucleares. Para possibilitar um maior grau de automação das medidas cronocoulométricas de adsorção, o eletrodo de gota pendente de mercúrio, anteriormente desenvolvido no IQ-USP, teve seu sistema mecânico aperfeiçoado e passou a ser controlado por computador. O \"software\" se incumbe de calcular e comandar o tempo de abertura da micro-válvula do eletrodo para gerar gotas com a área solicitada. Aproveitando a possibilidade de realizar aquisição (de dados de carga durante e após a formação das gotas de mercúrio, introduziu-se um novo método para corrigir a componente faradaica que interfere nos experimentos de determinação da carga absoluta do eletrodo por extrusão. Após provar o bom funcionamento do método, conseguiu-se a combinação inédita do método de extrusão de gotas com acronocoulometria num único experimento automatizado feito com a mesma gota de mercúrio. Com as informações assim geradas, torna-se possível conhecer e optar entre o potencial e a carga absoluta como parâmetro que define o estado elétrico da interface eletrodo/solução. Com esta combinação de técnicas, foi investigada a adsorção de cádmio induzida por tiocianato e hexametilenotetramina. Este sistema apresentou um interessante comportamento: a hexametilenotetramina, ao contrário do tiocianato, não induz a adsorção de ions cádmio, mas na presença desse pseudo-haleto provoca um intenso reforço na adsorção induzida que pode alcançar um fator de 50 vezes. Também foi possível realizar estimativas sobre as espécies que adsorvem preferencialmente, e da área média ocupada pelos complexos na condição de máxima adsorção. A energia livre de adsorção pode ser estimada pela isoterma de Henry, para baixas concentrações de ligantes. A adsorção de cádmio induzida por iodeto e tiocianato foi investigada de maneira preliminar. Nos estudos deste sistema ficou bem evidenciada a importância da utilização da carga como variável independente, ao invés do potencial. / The induced adsorption of a metallic cation (cadmium (II)) in the presence of two ligands, simultaneously (a pseudo-halide and an amine or halide), has been investigated at the mercury electrode/aqueous solution interface with the purpose of gaining a better understanding about such kind of process. The adsorption studies have been preceded by studies of the equilibria of the coordination compounds formed in aqueous solutions. Experimental measurements have been made by potentiometry with an amalgam electrode with 1,00 M ionic strength adjusted with NaClO4. Analysis of the data with adequated software allowed the quantification of the stability constants of 7 binary and 8 mixed species for the system Cd(II)/ SCN-/C6H12N4</sub and 8 binary and 6 mixed species for the system Cd(II)/I-/SCN-, all species being mononuclear. To provide a greater degree of automation of the chronocoulometric measurements of adsorption, the hanging drop mercury electrode, formely developed at the Chemistry Institute-USP, has had its mechanical parts perfectioned and wasput under computer control. A software was written to calculate and control the opening and closure of the micro-solenoid valve of the electrode to generate drops with the required area. A new method for the correction of the faradaic component that interferes with the absolute electrode charge during extrusion experiments was introduced and applied to charge measurements obtained making data aquisition during and shortly after the drop formation. Once proved that the method works, efforts were directed to combine the extrusion with the chronocoulometric measurements in one automated experiment dane with the same mercury drop. As a result, it is now a simple matter to make a choice between potential or charge on the electrode to define the electric state of the electrode/solution interface. With this combination of techniques, the adsorption of cadmium(II) induced by thiocyanate and hexamethylenetetramine has been investigated. An interesting behavior whas observed: the hexamethylenetetramine alone, doesn\'t induce adsorption of cadmium (II) as does the thiocyanate but provides a strong reinforcement (up to a factor of 50) of the induced adsorption when it is present simultaneously with the pseudo-halide. Some estimatives about the species that can adsorb preferentially has been made, as well as an evaluation of the mean area ocupied by the complexes at the maximum adsorption condition. The free energy of adsorption has been calculated, considering an Henry isotherm for the lowest concentration range. Preliminary studies of the induced adsorption of the Cd(II)/I-/SCN- system revealed a slight reinforcement of the adsorption, when both ligands are presente. The iodide always controls the process. The advantage of using the charge in place of potential as the independent variable is evident for this system.

This diploma thesis deals with the constructional and calculation design of boiler for blast furnace and coke gas mixture combustion, including sizing of the heating surfaces. The opening section is dedicated to a brief characterization of burned fuels. The following chapter shows the parameters and composition of the resulting fuel mixture. The main part of this thesis involves; determining the stoichiometric amount air required for combustion and the resulting flue gas, determining the boiler efficiency and steam production rate, calculations regarding the combustion chamber and the detailed design of the individual heat exchangers. At the end of the thesis the heat balance of the entire boiler is verified. Drawing documentation of boiler is also part of this diploma thesis.

In this Diploma Thesis, an interaction of genotoxic environmental pollutant 2-nitrofluorene with a double-stranded calf thymus DNA has been studied using a hanging mercury drop electrode (HMDE) as an electrochemical sensor. Two types of DNA damage were investigated and electrochemically detected (using cyclic voltammetry and differential pulse voltammetry): (i) The DNA damage caused by the direct interaction with 2-nitrofluorene and (ii) the DNA damage caused by short-lived radicals generated by the electrochemical reduction of the nitro group in 2-nitrofluorene. For the study of direct interaction, HMDE was modified by DNA and the interaction of DNA with 2-nitrofluorene was studied, after their incubation, right at the HMDE surface (adsorptive transfer stripping technique) or the DNA was preincubated with 2-nitrofluorene and, subsequently, the interaction was studied voltammetrically (DNA titration technique). Using both detection techniques, the formation of DNA - 2-nitrofluorene complex was observed and the mutual interaction was interpreted as an intercalation between the DNA base pairs, although such interaction was not clearly confirmed by UV-visible absorption spectroscopy. An electrostatic binding of 2-nitrofluorene on DNA sugar-phosphate backbone was partially formed at low concentrations of...

The main objective of this Diploma Thesis is studying the possibility of detection of nitro derivatives of aromatic hydrocarbons by using chemically modified working electrodes in electrochemical analysis. Compounds analyzed in this work were 1-nitronaphthalene and 6- nitrochrysene - these compounds were chosen on previous experience with surface modified working electrodes (the chemical/physical properties of these substances). All the analyses were performed by using differential pulse voltammetry (DPV) on hanging mercury drop electrode (HMDE) in classic three-electrode system. The original premise of chemical modification of electrode surface is the change of its selectivity towards different compounds - meaning the change of the electrochemical response. The modification agent used in this thesis is 1-octanethiol. Its thiol group offers great potential of strong interaction with the metal surface of the mercury electrode. Voltammetric responses of both compounds were recorded in acidic, neutral and basic solutions (pH=2, pH=7, pH=12) including the responses when the electrode surface was modified. Next objective was the optimization of the modification procedure itself (transferring of the mercury drop from one media to another without damaging or tearing it off from the capillary orifice)....

"The Great Hanging" is a documentary film that tells the story of the largest extra-legal mass hanging in U.S. History. This story is told through stage play recital of "October Mourning" written by historian and professor Dr. Pat Ledbetter. Using the stage play as a vehicle, the film showcases cinematic re-enactments based in the events in Gainesville, Texas during October 1862. These events show how a small community became overwhelmed by the fog of war and delved into madness as the Civil War crept closer and closer to their doorstep.

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La modélisation des massifs rocheux fracturés est un problèmes important dans de nombreux secteurs industriels, y compris, mais sans s'y limiter à l'exploitation pétrolière et gazière. Dans la littérature, les roches fracturées sont reconnues comme des milieux à double porosité et double perméabilité dans lesquels le réseau de fractures fournit la perméabilité primaire et la matrice rocheuse la perméabilité secondaire. L'idée de la dissociation de l'écoulement à l'intérieur du réseau de fractures et de la matrice,la double perméabilité, est toujours contestée pour les réservoirs fracturés. De nombreuses contributions sur cette question ont été présentées dans la littérature et les méthodes utilisées pourraient être classées dans deux approches principales : approches continues et discontinues. Chaque approche a ses avantages et ses limites. Pour surmonter les limites en gardant les avantages de ces deux approches, une approche nommée Embedded Fracture Continumm Approach (EFCA) qui emprunte le concept du modèle continu et intègre également l'effet des fractures explicites est considérée dans cette thèse. L'idée principale de cette approche repose sur le concept de la « cellule fracturée » représentant un milieu poreux qui a ses propres propriétés calculées à partir des propriétés de la matrice poreuse et des fractures qui la traversent. Le code de calcul développé dans le cadre de ce travail est basé sur la bibliothèque source DEAL.II. L'exactitude de l'EFCA a été étudiée à travers de différents tests. Plusieurs applications traitées dans ce travail comme la détermination des propriétés hydro-mécaniques effectives d'un site réel, estimation de la production de puits dans laquelle les fractures sont modélisées explicitement, démontrent la performance de l'EFCA dans la modélisation des roches fracturées ainsi que l'effet de la double porosité et de la double perméabilité aux comportements des réservoirs fracturés. / Fractured rock masses modeling is a challenge issue in many field of industry including but not limited to oiland gas exploitation. In the literature, fractured rock masse are in many cases recognized as double permeability medium in which fracture network provides the primary permeability and rock matrix plays asthe second one. The idea of dissociation of flow inside the fracture network and the matrix, the double permeability, is still challenged for fractured reservoirs. Numerous contributions on this issue have been presented in the past could be cast in two main approaches: continuum media approach and discontinuous approach. Each approach has its advantages and limitations. To overcome the limitation and to take advantage of these two approaches, the Embedded Fractured Continuum Approach (EFCA) which borrows the concept of continuum models and also incorporates the effect of explicit fractures is considered in this thesis. The principal idea of this approach lies on the concept of fracture cell representing a porous medium that has their own properties calculated from the properties of porous matrix and fractures intersecting it.The development in this work was conducted by using the library source code DEAL.II. The accuracy of EFCA was investigated through different verifications. Through some applications: determination of effective hydro-mechanical properties of an actual site, estimation of well production in which necessary fractures are modeled explicitly, we demonstrate the performance of the EFCA in the modeling fracture drock masses as well as the effect of double porosity and double permeability on behaviours of fractured reservoirs.

Presented Diploma Thesis is focused on electroanalytical determination of genotoxic 4-nitroindane, one of the nitrated polycyclic aromatic hydrocarbons (NPAHs). A hydrocarbon indane (a component of petrol) is a precursor of 4-nitroindane. NPAHs are produced all above by combustion processes in gasoline and diesel engines. It has been shown that NPAHs can be many times more mutagenic or carcinogenic than their parent PAHs, so the analysis of these dangerous pollutants becomes important for modern environmental analytical chemistry. Optimal conditions for determination of 4-nitroindane have been investigated in buffered water-methanolic solutions and electrochemical transformations of 4-nitroindane have been studied by DC voltammetry (DCV), differential pulse voltammetry (DPV) and cyclic voltammetry at a hanging mercury drop electrode (HMDE) and at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). For voltammetric determination of 4-nitroindane, the following techniques were used: DCV (limit of quantification (LQ) ~ 7. 10-8 mol. l-1 ), DPV (LQ ~ 1. 10-7 mol. l-1 ) and adsorptive stripping voltammetry (AdSV; LQ ~ 7. 10-9 mol. l-1 ) at HMDE, and DCV (LQ ~ 1. 10-7 mol. l-1 ) and DPV (LQ ~ 1. 10-7 mol l-1 ) at m-AgSAE. The applicability of the newly developed...

Presented Diploma Thesis is focused on electroanalytical determination of the herbicide Aclonifen, which belongs to a group of herbicides derived from diphenylether. These herbicides are used due to their effects - inhibition of protoporfyrinogen oxidase synthesis and also inhibition of biosynthesis of carotenoids. Due to its widespread use in agricultural, toxical effects on humans and because of its negative impacts particularly on aquatic ecosystems there is a need for methods capable of determining the presence of Aclonifen in the environment to monitor its ecological impacts. Optimal conditions for the determination of Aclonifen have been investigated in BR buffer - methanolic solution and in BR buffer. Electrochemical behavior of the substance has been studied using direct current voltammetry (DCV), differential pulse voltammetry (DPP) and adsorptive stripping voltammetry (AdSV) on the hanging mercury drop electrode (HMDE) and by using TAST polarography and differential pulse polarography (DPP) on the dropping mercury electrode (DME). UV/VIS spectrophotometric detection was used for comparison to electrochemical detection. Used wavelengths were 308 nm and 388 nm. For electrochemical determination of Aclonifen the above mentioned techniques were used and following results were obtained: DCV...

This thesis is concerned with several issues of a posteriori error estimates for linear problems. In its first part error estimates for the heat conduction equation discretized by the backward Euler method in time and discontinuous Galerkin method in space are derived. In the second part guaranteed and locally efficient error estimates involving algebraic error for Poisson equation discretized by the discontinuous Galerkin method are derived. The technique is based on the flux reconstruction where meshes with hanging nodes and variable polynomial degree are allowed. An adaptive strategy combining both adaptive mesh refinement and stopping criteria for iterative algebraic solvers is proposed. In the last part a numerical method for computing guaranteed lower and upper bounds of principal eigenvalues of symmetric linear elliptic differential operators is presented. 1