The kinetics of the dissolution of gold and silver colloids in ammoniacal thiosulfate solutions has been studied using oxygen, copper(II) or oxygenated copper(II) as oxidants at pH 9 - 11 and temperature 22oC to 48oC. The effects of the concentration of the main reagents such as copper(II), ammonia and thiosulfate as well as various background reagents have been investigated. Gold and silver colloids have characteristic absorption peaks at 530 nm and 620 nm respectively. Thus, the extent of gold or silver dissolution in different lixiviant systems was monitored using an ultraviolet-visible spectrophotometer. A comparison of the behaviour of gold colloids and powders has also been made. The beneficial or detrimental effects of silver colloid, and background reagents such as silver nitrate, and sodium salts of nitrate, carbonate, sulfite, sulfate, trithionate, tetrathionate anions have also been investigated. Experimental results show that the relative rates and the extent of gold colloid dissolution at 25ºC in different lixiviant systems in a given time interval are in the order: oxygen-cyanide > copper(II)-ammonia-thiosulfate ≈ oxygen-copper(II)- ammonia-thiosulfate > oxygen ammonia-thiosulfate ≥ oxygen-ammonia > copper(II) ammonia. The analysis of electrode potentials shows that Au(S2O3)23- is the predominant gold(I) species in the lixiviant solutions containing oxygen or copper(II) as oxidant and thiosulfate or mixed ammonia-thiosulfate as ligands. During the reaction of copper(II) with thiosulfate in ammoniacal solution without oxygen, the measured potential using a platinum electrode represent the redox couple Cu(NH3)n2+/Cu(S2O3)m1-2m (n = 4 or 3, m = 3 or 2) depending on the concentrations of thiosulfate and ammonia. The initial dissolution rates of gold colloid by oxygen in copper-free solutions show a reaction order of 0.28 with respect to the concentration of dissolved oxygen, but independent of the concentration of ammonia and thiosulfate. The reaction activation energy of 25 kJ/mol in the temperature range 25°C to 48°C indicated a diffusion controlled reaction. The initial dissolution rates of gold colloid by oxidation with copper(II) in oxygenfree solutions show reaction orders of 0.41, 0.49, 0.60, 0.15 and 0.20 with respect to the concentrations of copper(II), thiosulfate, ammonia, chloride and silver respectively. The presence of silve (I) or chloride ions enhances the rate of gold dissolution, indicating their involvement in the surface reaction, possibly by interfering with or preventing a passivating sulfur rich film on gold surface. An activation energy of 40-50 kJ/mol for the dissolution of gold by oxidation with copper(II) in the temperature range 22°C to 48°C suggests a mixed chemically/diffusion controlled reaction. The dissolution of gold by oxidation with copper(II) in oxygen-free solutions appears to be a result of the reaction between gold, thiosulfate ions and the mixed complex Cu(NH3)p(S2O3)0. The half order reactions support electrochemical mechanisms in some cases. The initial dissolution rates of gold colloid, massive gold and gold-silver alloys by oxygenated copper(II) solutions also suggest a reaction that is first order with respect to copper(II) concentration. High oxygen concentration in solutions has a negative effect on the initial rate of gold dissolution and overall percentage of gold dissolution, indicating that oxygen affects the copper(II), copper(I) or sulfur species which in turn affects the gold dissolution. The surface reaction produces Au(NH3)(S2O3)- and Cu(NH3)p+. The mixed complexes Au(NH3)(S2O3)- and Cu(NH3)p+ re-equilibrate to the more stable complexes Au(S2O3)23- and Cu(S2O3)35- in solution. The dissolution of gold powder by oxidation with copper(II) in oxygen-free solutions shows the same trends as that of gold colloid. The presence of silver(I) or chloride ions enhances the initial rate and percentage dissolution of gold colloid and powder. The dissolution kinetics of gold powder and colloid follow a shrinking sphere kinetic model in solutions of relatively low concentrations of thiosulfate and ammonia, with apparent rate constants being inversely proportional to particle radius. The best system for dissolving gold based on the results of this work is the copper(II)-ammonia-thiosulfate solution in the absence of oxygen or in the presence of oxygen. In the absence of oxygen, copper(II) 1.5-4.5 mM, thiosulfate 20-50 mM, ammonia 120-300 mM and pH 9.3-10 are the best conditions. The presences of carbonate and sulfite have a significant negative effect on the dissolution of gold. The presence of sodium trithionate shows a beneficial effect in the first two hours, while sodium tetrathionate or lead nitrate have a small negative effect and sodium nitrate showed no effect on the dissolution of gold. Silver nitrate and sodium chloride also show beneficial effects. In the presence of oxygen, copper(II) 2.0-3.0 mM, thiosulfate 50 mM, ammonia 240 mM and pH 9.3-9.5 are the best conditions.

Made available in DSpace on 2014-12-17T14:06:54Z (GMT). No. of bitstreams: 1 FlaviaMA_DISSERT.pdf: 2525916 bytes, checksum: e66ea09a8c50d8b220412e1d5685d5d1 (MD5) Previous issue date: 2010-03-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work have been studied the preparation, characterization and kinetic study of decomposition of the polymerizing agent used in the synthesis under non-isothermal condition ceramics PrMO3 of general formula (M = Co and Ni). These materials were obtained starting from the respective metal nitrates, as a cations source, and making use of gelatin as polymerizing agent. The powders were calcined at temperatures of 500?C, 700?C and 900?C and characterized by X-ray Diffraction (XRD), Thermogravimetric Analysis (TG / DTG/ DTA), Infrared Spectroscopy (FTIR), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was detected in all the X-rays patterns. In the infrared spectroscopy observed the oxide formation as the calcination temperature increases with the appearance of the band metal - oxygen. The images of SEM revealed uniform distribution for the PrCoO3 and particles agglomerated as consequence of particle size for PrNiO3. From the data of thermal analysis, the kinetics of decomposition of organic matter was employed using the kinetics methods called Model Free Kinetics and Flynn and Wall, in the heating ratios 10, 20 and 30? C.min-1 between room temperature and 700?C. Finally, been obtained the values of activation energy for the region of greatest decomposition of organic matter in samples that were determined by the degree of conversion (α) / Neste trabalho foi realizado a prepara??o, caracteriza??o e um estudo cin?tico da decomposi??o t?rmica do agente polimerizante utilizado na s?ntese sob condi??o n?o isot?rmica de materiais cer?micos de f?rmula geral PrMO3 (M = Co ou Ni). Esses materiais foram obtidos partindo dos respectivos nitratos met?licos, como fonte de c?tions, e fazendo uso da gelatina como agente polimerizante. Os p?s-obtidos foram calcinados a temperaturas de 500?C, 700?C e 900?C e caracterizados pelas t?cnicas de Difra??o de Raios X (DRX), An?lise Termogravim?trica (TG/DTG/DTA), Espectroscopia na regi?o do infravermelho (FTIR), Redu??o ? Temperatura Programada (RTP) e Microscopia Eletr?nica de Varredura (MEV). A fase perovsquita foi evidenciada em todos os difratogramas de raios X para os materiais de PrCoO3 e PrNiO3. Nos espectros de FTIR foi observado a forma??o do ?xido na medida em que a temperatura de calcina??o aumenta com o aparecimento da banda referente ? liga??o Metal Oxig?nio. As imagens do MEV evidenciaram distribui??o uniforme para o PrCoO3 e part?culas aglomeradas em consequ?ncia do tamanho da part?cula para o PrNiO3. Com os dados da an?lise t?rmica, o estudo ci-n?tico da decomposi??o da mat?ria org?nica foi empregado utilizando-se os m?todos cin?ticos denominados Model Free Kinetics e Flynn e Wall, nas raz?es de aquecimento 10, 20 e 30?C.min-1 entre a temperatura ambiente e 700?C. Foram obtidos os valores das energias de ativa??o para a regi?o de maior decomposi??o da mat?ria org?nica nas amostras que foram determinadas como uma fun??o do grau de convers?o (α)

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Dans le travail de thèse, nous avons étudié le processus de croissance et l’évolution des propriétés structurales de l’alumine ultra-poreuse (UPA) monolithique pendant le traitement thermique dans le domaine des températures entre 20 et 1600 °C. Un modèle théorique a été proposé permettant de décrire et prédire sa structure. La formation de mullite à partir d’alumine imprégnée par la silice a été également étudiée. Les premières mesures conduites sur les propriétés diélectriques des UPA dans le domaine de fréquences GHz-THz montrent des possibilités d’application dans le domaine de l’optique réfractrice. L’installation expérimentale pour l'élaboration des monolithes ultra poreux est décrite. L’étude de la cinétique de croissance à partir d’aluminium technique, ultra pur et monocristallin a permis d’analyser l’influence des différentes impuretés présentes. Les matériaux ont été caractérisés par les méthodes DRX, MET/MEB, ICP/OES, TGA et PL. Les UPA modifiées chimiquement par imprégnation de TMES et TEOS en phase vapeur ont également été analysées. L’étude en fonction de la température des différents matériaux a été menée sur la taille des fibreuse, la surface spécifique, la densité massique, ainsi que la quantité de l’eau structurelle et adsorbée, d’une part, et la structure cristalline d’autre part. L’utilisation des méthodes DRX et PL corrélées a permis d’expliquer une transformation de la phase α de l’UPA en mullite 2:1.Le modèle proposé distingue deux principaux régimes de modification thermique de la structure des UPA : transport de masse sur la surface d’une fibre ou de la masse globalement (frittage). Des énergies d’activation du transport massique et des constantes pre-exponentielles ont été obtenues pour les deux régimes. Les résultats obtenus permettent de conclure que les transformations morphologiques, de la composition chimique et de la phase cristalline sont d’origine commune. / In this PhD work we investigated growth process and evolution of structural properties of ultraporous alumina (UPA) monoliths during thermal treatment in the range between 20 and 1600 °C. A simple theoretical model was proposed permitting description and prediction of the material structure. A particular extension of this study concerns the mullite formation with an increase of the silica loading. Furthermore, first measurements of dielectric properties (refraction index and losses) in GHz-THz range of frequencies were performed, indicating this material to be potentially interesting for fabrication of the refraction optics.The experimental installation for UPA elaboration is described, and the analysis is presented of principal impurities and their influence on the growth kinetics using technical, high-purity and monocrystalline aluminum. The obtained materials were characterized by XRD, TEM, SEM, ICP/OES, TGA and PL methods. UPA modified with TMES and TEOS vapor impregnations were also obtained and analyzed. The fibril size, specific surface area, mass density and content of structural, adsorbed water and crystalline phase were measured for different UPA materials as a function of the annealing temperature. The correlated XRD and PL analyses was performed explaining the conversion of α phase UPA to 2:1 mullite, which fundamental band gap was set to 7.55 eV.The proposed model distinguished two principal regimes of thermal modifications: surface diffusional mass transport over a single fibril and bulk mass transport involving total material mass (sintering). The activation energies of the mass transport and pre-exponential constants (diffusion coefficient and free volume) in both regimes were obtained, providing a better understanding of the underlying physical processes in different UPA materials. Based on these results, we conclude about a common origin of morphological, chemical composition and phase transformations.

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Neste trabalho, determinou-se a energia de ativação (Ea) no processo de combustão de três óleos combustíveis cedidos pela Petrobrás–Cenpes e denominados por A, B e C. Empregou-se análise termogravimétrica (TG) utilizando um sistema Shimadzu 51H e, para todas as amostras observaram-se três regiões oxidativas distintas identificadas como, oxidação à baixa temperatura (LTO), depósito de combustível (FD) e oxidação à alta temperatura (HTO). As energias de ativação foram determinadas como uma função do grau de conversão ('alfa') e temperatura na região LTO e utilizando-se dois métodos cinéticos, denominados ASTM E 1641 (Flynn eWall) e Model Free Kinetics de Vyazovkin. Empregaram-se as seguintes razões de aquecimento: 2,5; 5,0; 10,0; 15,0 e 20,0°C por min entre a temperatura ambiente e 600°C. As demais condições experimentais foram: massa da amostra de aproximadamente 20 mg, suporte de amostra de alumínio e gás de arraste ar sintético com vazão de 100 mL/min. Os valores de Ea encontrados foram os mesmos para ambos os métodos cinéticos: 44 ± 7% kJ/mol ('alfa'=0,1 a 0,9) para amostra A. Para a amostra B os valores de Ea foram em média de 48 ± 4% kJ/mol ('alfa'=0,1 a 0,5) e 66 ± 16% kJ/mol ('alfa'=0,5 a 0,9) e, para a amostra C os valores de Ea foram em média de 58 ± 4% kJ/mol ('alfa'=0,1 a 0,5) e 65 ± 5% kJ/mol ('alfa'=0,5 a 0,9). Conclui-se que a Ea pode ser usada como um parâmetro adequado para apontar uma tendência de comportamento e para caracterizar diferentes óleos sob processo de combustão / In this work activation energies (Ea) in the combustion of three fuels oils were determined through thermogravimetry. The oil samples, here named A, B and C were supplied by Petrobras-Cenpes. The thermogravimetric experiments were performed in a Shimadzu TGA-51H analyzer. In all the combustion experiments three distinct oxidation regions were observed, identified as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Activation energies were determined as a function of conversion degree ('alfa') and temperature for LTO region, following two different procedures, namely Model Free Kinetics and ASTM E 1641. Transient experiments were performed from room temperature up to 600°C, at heating rates of 2.5, 5.0, 10.0, 15.0 and 20.0°C for min. Samples of 20.0 ± 0.5 mg and aluminum crucibles were used. The reacting atmosphere was synthetic air, which was continuously blown over the samples, throughout the analyzer furnace, at a volumetric rate of 100 mL/min. The activation energies resulted equal for both considered methods. For oil A, the activation energy resulted 44 ± 7% kJ/mol ('alfa'=0.1 to 0.9). For oil B it resulted in average 48 ± 4% kJ/mol ('alfa'=0.1 to 0.5) and 66 ± 16% kJ/mol ('alfa'=0.5 to 0.9). For oil C the activation energy resulted 58 ± 3% kJ/mol ('alfa'=0.1 to 0.5) e 65 ± 5% kJ/mol ('alfa'=0.5 to 0.9). It is concluded that the oxidation activation energy is a suitable parameter concerning to point out a tendency of behavior and characterizing different oils under combustion process

As reações químicas genericamente referidas como reações de Belousov-Zhabotinsky (BZ) têm sido bastante utilizadas como paradigmas de complexidade em sistemas químicos homogêneos. Apesar dos avanços consideráveis realizados no estudo de tais sistemas, aspectos como o papel do fluxo de reagentes e da temperatura na dinâmica oscilatória ainda são pouco entendidos. O presente trabalho consiste na investigação experimental do efeito destes dois parâmetros em duas variantes da reação de BZ. Após alguns testes iniciais com o sistema bromato/hipofosfito-acetona/manganês-ferroína, a maioria dos experimentos foi feita com o sistema bromato/ácido oxálico-acetona/cério. A evolução temporal do sistema foi estudada a diferentes temperaturas e em condições de batelada e de fluxo por meio do monitoramento simultâneo do potencial de um eletrodo de platina e espectrofotometricamente na região do UV-vis. A discussão foi baseada na energia de ativação em regime oscilatório, Eω. Para o sistema com dois catalisadores não foram observadas oscilações nas condições de fluxo. Para o sistema com cério, em batelada, com Ce4+ é observado que Eω aumenta conforme o sistema evolui para o estado de equilíbrio termodinâmico. Com Ce3+, em batelada, Eω manteve-se praticamente constante e em fluxo, o valor de Eω foi menor do que o valor observado para o sistema em batelada. / The chemical reactions usually referred to as the Belousov-Zhabotinsky (BZ) reactions have been extensively employed as paradigms of complexity in homogeneous chemical systems. In spite of the considerable advance in the study of such systems, aspects such as the role played by the flux of reactants and temperature on the oscillatory dynamics are still poorly understood. The present work consists of the experimental investigation of the effect of these two parameters on two variants of the BZ reaction. After some initial tests with the bromate/hipophosphite-acetone/manganese-ferroin, most of the experiments were carried with the bromate/oxalic acid-acetone/cerium system. The time-evolution of the system was followed at different temperatures and under batch and flow conditions by means of potentiometric and spectrophotometric (UV-vis region) approaches. The discussion was based on the activation energy under oscillatory regime, Eω. For the two-catalyst system, no oscillations were observed under flow conditions. For the cerium-catalyzed system operated in batch, when Ce4+ is used, it is observed that Eω increases as the system evolves to the thermodynamic equilibrium. With Ce3+, the Eω under batch conditions remained virtually constant and in flow, the value of Eω was lower than the value observed for the batch system.

The master thesis deals with DSC measurments a calculation of kinetic parameters. In the theoretical part, iron alotropy is briefly described, followed by a description of the DSC analysis itself. The thesis also includes division and derivation of isoconversional methods for calculating the activation energy. In the experimental part, a series of measurments is perfomed on pure iron prepared by Cold Spray method. In the paper the influence of deformation on the Curie temperature of the magnetic transformation in -Fe and transformation > is investigated. The activation energy is calculated for transformation > for different degrees of deformation. The degree of deformation is monitored by channeling contrast.

The thesis is aimed to the study of spiropyrane behavior in polymeric matrix of poly(N-vinylkarbazole) (PVK) and poly[2-methoxy-5-(3´,7´-dimethyloctyloxy)-1,4-fenylenvinylene)] (MDMO-PPV). The photochromic transformation of spiropyrane to its isomeric merocyanine form (SPMC) was studied by absorption and emission spectroscopy. It was found, that photochromic reaction is markedly dependent on the environment. In the PVK polymer, which don’t absorb in the visible region, a high yield of photochromic reaction was achieved. Both, absorption and emission spectrums were observed for this system. From the measurement of time dependencies of the fotochromic reaction, the activation energy of the reverse reaction was determined. A different behavior, particularly in emissive spectrums, was found for the MDMO-PPV polymer doped with spiropyrane. Instead of formation of new band of merocyanine, decrease of the polymer fluorescence was observed. Subsequently, we studied the interaction between the polymeric matrix and the photochromic spiropyrane using fluorescence quenching method. On the basis of energy transfer theory, a critical radius of the fluorescence quenching sphere in solution and in solid was determined.

The purpose of this work was to recover uranium from residue originating from the production of molybdenum -99. Carbonate solutions containing hydrogen peroxide or oxygen gas as oxidants were used as leachants. Experimental parameters included: different peroxide and carbonate concentrations, dissolution time and temperature. Results indicate complete dissolution of the residue at 60 oC, after thirty minutes, in ammonium carbonate solution enriched with hydrogen peroxide. Almost two hours were needed to achieve the same extent in the presence of oxygen. The yield and rate of uranium extraction were found to increase as a function of both temperature, in the range of 25-60 oC, and hydrogen peroxide concentration. The leaching kinetics were determined for various leaching conditions and the activation energy was found to be 45.5kJ/mol. The order of reaction with respect to uranium concentration was found to be unity. / Dissertation (MSc)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted