Ligas de níquel têm atualmente uma vasta gama de aplicações, sendo a agressividade do meio e as elevadas temperaturas que estas ligas suportam, um diferencial excepcional. A liga UNS N07090, objeto deste trabalho, encontra aplicações muito diversas, entre elas turbocompressores, sistemas de exaustão e de pós-tratamento de motores a diesel. Nestas aplicações a liga está exposta a gases, que ao condensarem formam ácido sulfúrico (H2SO4). Torna-se, assim, importante, o conhecimento da resistência à corrosão da liga nesse meio. O presente trabalho tem como objetivo caracterizar o comportamento eletroquímico da liga através de curvas de polarização potenciodinâmica em diferentes concentrações de ácido sulfúrico. Observou-se que quanto maior a concentração de ácido, maior é a corrosão da liga. Este fato pode ser discutido pela adsorção do íon sulfato (SO42-), que prejudica tanto a formação quanto a cinética de crescimento da película passiva do níquel. Em contrapartida, a presença de Cr na liga UNS N07090 apresentou um benefício sobre a resistência à corrosão desta muito acima do esperado, influenciando de forma direta as curvas de polarização da liga e mantendo-a em condição de elevada resistência à corrosão em detrimento do pior desempenho observado em outros elementos pertecentes à liga, como Co, Al e Ti. Tempos de imersão de 24h em ácido sulfúrico elevam discretamente os parâmetros de corrosão da liga, mantendo-os, no entanto em patamares bastante baixos, permitindo finalmente concluir que a liga UNS N07090, quando exposta a concentrações que variam de 1M a 4M H2SO4, a 25°C, apresenta boa resistência à corrosão e que esta não se altera com o tempo de exposição. A análise dos resultados mostrou que o processo corrosivo é controlado por reações catódicas de sulfato e hidrogênio, as quais podem ter diferentes contribuições dependendo da concentração do ácido e do tempo de imersão da liga UNS N07090 no meio corrosivo. / Nickel alloys have a wide range of application nowadays due to their excellent resistance to aggressive media and high temperatures. UNS N07090, the nickel alloy studied herein, is used for turbochargers, exhaust and after treatment systems of diesel engines. These applications expose the alloy to hot gases, which condensate forming sulfuric acid (H2SO4). It is thus important to know the corrosion resistance of the alloy in this media. The goal of this work is the characterization of the electrochemical behaviour of UNS N07090 alloy through potentiodynamic polarization curves in different sulfuric acid concentrations. On the one hand, higher acid concentrations were noticed to lead to higher corrosion of the alloy. This phenomenon can be discussed by sulfate (SO42-) adsorption, which negatively influences not only the formation but also the growth of the passive film on nickel. On the other hand, the presence of Cr in UNS N07090 composition, improves the corrosion resistance of the alloy far more than expected, directly affecting the shape of the polarization curves of the alloy, placing it in a condition of high corrosion resistance despite the worst performance shown by the other elements present in the chemical composition of the alloy, such as Co, Al and Ti. 24h immersion periods in sulfuric acid slightly raise corrosion parameters of UNS N07090 alloy, but still ranking the alloy in very good corrosion resistance. Finally, it can be concluded that UNS N07090 alloy exposed to 1M to 4M H2SO4 at 25°C presents good corrosion resistance and that this is not affected by longer immersion periods. The results showed that the corrosion process of alloy UNS N07090 is controlled by sulfate and hidrogen cathodic reactions, which have stronger or weaker contribution depending on acid concentration and immersion time on the corrosive media.

O presente trabalho tem como objetivo caracterizar o aco inoxidavel ferritico UNS S44400 quanto a sua resistencia a corrosao em comparacao a dois acos inoxidaveis austeniticos UNS S30403 e S31603, utilizando ensaios de perda de massa e eletroquimicos, tanto em meio acido quanto em meio contendo cloreto. A utilizacao dos inoxidaveis ferriticos vem crescendo em detrimento da utilizacao dos austeniticos tanto no Brasil, quanto no mundo, principalmente devido ao cenario instavel do preco do Ni. Sendo assim, cada vez mais se torna necessaria a obtencao de argumentos tecnicos e cientificos que permitam comparar diferencas entre as duas familias, mostrando suas vantagens e desvantagens. Os metodos utilizados para a avaliacao da resistencia a corrosao generalizada foram perda de massa (apos imersao) e polarizacao potenciodinamica em 0,5M H2SO4. A resistencia a corrosao por pite foi estudada atraves de polarizacao potenciodinamica ciclica em 3,5%NaCl. No caso especifico dos meios contendo cloreto, alem de se estudar os materiais com acabamento de lixa #600, obtido em laboratorio, optou-se por um estudo mais detalhado em funcao do acabamento superficial obtido em usina. Os acabamentos examinados foram: (i) material recozido, decapado em Usina e lixado em laboratório (até lixa #600) - (LL); (ii) material recozido e decapado em Usina - (RD); e (iii) material recozido, decapado em Usina, tratado termicamente em laboratório e lixado (até lixa #600) - (SL). Em meio acido, os acos austeniticos nao apresentaram corrosao, enquanto o ferritico apresentou uma taxa de corrosao constante de 0,0146 mg.cm-2.min-1 (8,4x10-4 A.cm-2) para imersoes ate 24h. Pela aplicacao do metodo de extrapolacao do trecho linear de Tafel foi obtido valor similar de densidade de corrente, de 4,57x10-4 A.cm-2, ou seja possuem a mesma ordem de grandeza. Diferentemente dos resultados obtidos em meio acido, nos ensaios de resistencia a corrosao em meio contendo cloreto, o aco UNS S44400 apresentou potencial de pite superior (em 3,5%NaCl) ao UNS S30403 e valores muito proximos ao do aco UNS S31603, para todas as condicoes de acabamento superficial examinadas. Alem disso, foi observado um relevante efeito das condicoes de tratamento termico de solubilizacao dos materiais: o tratamento de solubilizacao realizado em laboratorio aumentou o potencial de pite. Os resultados de potencial de pite medio - Ep - obtidos antes do tratamento termico foram: 77mVAg/AgCl para o UNS S44400, 43mVAg/AgCl para o UNS S30403 e 345mVAg/AgCl para o UNS S31603, sendo que apos solubilizacao o Ep medio foi de: 336mVAg/AgCl; 294mVAg/AgCl e 374mVAg/AgCl, respectivamente. Por sua vez, ha diferenca de desempenho quando aplicados os diferentes acabamentos superficiais. Com relacao ao acabamento proveniente de Usina, ou seja, recozido e decapado (RD), foi o que resultou em melhor desempenho. Apesar da media resultante alta para o acabamento RD, a dispersao dos resultados tambem foi alta. Comparando-se os acos UNS S44400 e UNS S31603, recozidos e decapados o 444 teve um potencial de pite de (500 + 173)mVAg/AgCl, e o aco 316 apresentou (568 + 167)mVAg/AgCl. Nota-se, portanto, que quando a aplicacao exige resistencia a corrosao em meio contendo ion cloreto, o aco 444 pode substituir o 316L. / The main reason of this work is the characterization of the ferritic stainless steel UNS44400 regarding its corrosion resistance when compared to two austenitic steels, UNS 30403 and UNS31603, using loss of weight and electrochemical tests, in acid and chloride environments. The application of ferritic stainless steel is increasing, both in the Brazilian an international market, especially because of the nickel cost instability. So, more information is necessary regarding each kind of material, allowing the comparison of these two families showing their advantages and disadvantages in different applications. For that reason, the main purpose of this work is the characterization of the corrosion resistance of a ferritic stainless steel, UNS S44400, comparing it with two austenitic stainless steels, UNS S30403 and S31603. Weight loss and electrochemical tests were conducted in acid or chloride environments. The general corrosion resistance was analyzed through weight loss measurements and electrochemical polarization in 0,5M H2SO4. The pitting corrosion resistance was studied through polarization in 3,5%NaCl. For the tests in chloride environment, it was done a study comparing laboratory and mill finishing proceducts: annealed and pickled and wet sand in laboratory - (LL); annealed and pickled - (RD); annealed and pickled, heat treated in laboratory and wet sand in laboratory - (SL). In acid environment, the austenitic stainless steel did not show weight loss, while the ferritic had a constant corrosion rate of 0,0146 mg.cm-2.min-1 (8,4x10-4. A.cm-2) until 24 hours of immersion. This result was confirmed by the extrapolation of linear portion of the polarization curves (Tafel method), whose current density was 4,57x10-4 A.cm-2. In chloride environment, the UNS S44400 steel showed higher pitting potential in 3,5%NaCl compared to UNS S30403 and similar results for all finishes when compared with UNS S31603. Besides, it was observed that the heat treatment that was done in laboratory raised pitting potential. The pitting potential results were: before heat treatment, 77mVAg/AgCl for UNS S44400, 43mVECS, for UNS S30403 and 345mVAg/AgCl for UNS S31603; and after heat treatment they were: 336mVAg/AgCl; 294mVAg/AgC; and 374mVAg/AgCl, respectively. The annealed and pickled material that was tested directly from the Mill (RD) presented the highest pitting potential showing the importance of pickling process. Comparing the annealed and pickled UNS S44400 steel with UNS S31603, the mean pitting potential was (500 + 173)mVAg/AgCl and (568 + 167)mVAg/AgCl respectively, and considering the deviation of the tests, it was proved that it is possible to apply both UNS S44400 or UNS S31603 when a high pit corrosion resistance is required.

O presente estudo investigou a participação do H2S04, como agente corrosivo no carste do Grupo Una, na bacia de Irecê e na bacia do rio Salitre, tendo como base o monitoramento hidroquímico e a determinação de fácies hidroquímicas. A fácies escoamento superficial alogênico é caracterizada por baixos valores de pH (\'X BARRA\'=4,79 ; CV=3,15%) e dos principais cátions e ânions, com destaque para S\'O IND. 4 POT. 2-\' (x=0,57 mg/L ; CV10,32%); A fácies fluxo freático profundo carbonático representa a maior concentração de HC\'O IND. 3 POT. -\' de todo conjunto amostrado, com média igual a 359,08 mg/L. Na média as águas desta fácies encontram-se saturadas para calcita (S\'l IND. c\' = 0,02) e insaturadas para gipsita (S\'l IND. g\' = -1,51). A concentração de S\'O IND. 4 POT. 2-\' também é alta (\'X BARRA\'=204,50 mg/L ; CV 135,00%), destacando-se um ponto de amostragem que exibe elevado valor médio para \'SO IND. 4 POT. 2-\' (\'X BARRA\'= 746,07 ; CV = 13,79%); Na fácies percolação vadosa a concentração de S\'O IND. 4 POT. 2-\' é expressiva, com média igual a 305,09mg/L; Nos reservatórios subterrâneos destaca-se a alta concentração de HC\'O IND. 3\'(média - 305,10 mg/L), Índice de Saturação para calcita muito próximo do equilíbrio (S\'l IND. c\'=-0,02) e concentração média para S\'O IND. 4 POT. 2-\' (\'X BARRA\'=17,79 mg/L; CV = 52,03%); Nas nascentes cársticas observou-se alto teor de HC\'O IND. 3 POT. -\' (\'X BARRA\'=246,96 mg/L ; CV = 11,0%), S\'l IND. c\'=0,00 (0,28 a -0,37), em equilíbrio de saturação para o mineral calcita e concentração de S\'O IND. 4 POT. 2-\' (\'X BARRA\'= 19,30mg/L ; CV = 31,47%). As águas meteóricas são caracterizadas por baixas concentrações dos principais cátions e ânions, com médias inferiores a 0,5mg/L. Cálculos estequiométricos foram aplicados aos dados hidroquímicos e conclui-se que no balanço molar as águas não seguem as razões clássicas para dissolução exclusiva por ácido carbônico, mas sim, adequam-se ao sistema \'H IND. 2\'S\'O IND. 4\' - CaMgC\'O IND. 3\'. Minerais secundários de cavernas foram analisados e detectou-se ocorrências expressivas de gipsita, sob a forma de crostas, estalactites e filamentos, que, vinculadas ao ambiente de formação, indicam a participação de soluções ricas em sulfato em seus processos. O evento principal de deposição de gipsita foi associado ao rebaixamento do NA após fase de ampliação paragenética dos condutos. Análises isotópicas de \'\'delta\' POT. 13\'CHC\'O IND. 3 POT. -\' em amostras de águas subterrâneas indicam valores enriquecidos (-10,4%o PDB-V) em relação ao esperado para a reação de dissolução da rocha carbonática por ácido carbônico (-17,1%o), condição relacionada à influência de \'ANTPOT. 13 C\' oriundo da rocha por ação do ácido sulfúrico. O \'delta\' POT. 34\'S de sulfato em água subterrânea (\'X BARRA\'=17,7%o CDT) é levemente empobrecido em relação à pirita (\'X BARRA\'=21,3%o), com valores na faixa de amplitude prevista para o processo de oxidação, condição que atesta a participação de ácido sulfúrico na dissolução da rocha carbonática. Análises microbiológicas na água subterrânea do aqüífero cárstico indicaram a presença de bactérias do gênero Acidithiobacillus e bactérias redutoras de sulfato (BRS), ambas presentes no ciclo do enxofre e responsáveis pela produção de ácido sulfúrico. Neste sentido, as variáveis estudadas possibilitam a confirmação da participação do ácido sulfúrico na dinâmica do sistema cárstico do Grupo Una no Estado da Bahia. / The main goal of this study is to determine the effectiveness of sulfuric acid as a corrosive agent in the karst system of the Una Group (lrecê geological basin and Salitre river basin), based on hydrochemical monitoring and the respective hydrochemical facies. The allogenic surface runoff is characterized by low ion concentrations and pH (ph=4,79 ; CV=3,15%). Sulfate is also low for this facies (\'X BARRA\'=0,57 mg/L ; CV 10,32%). With respect to the HC\'O IND. 3 POT. -\' content, the deep phreatic flux in the carbonate aquifer has the highest concentration compared to the other facies, with a mean of 359,08 mg/L. This deep phreatic flux is saturated with respect to calcite and undersaturated with respect to gypsum, showing average concentrations of 204,5 mg/L (CV 135,00%) for S\'O IND. 4 POT. 2-\', including one sampling site with average concentration of 746,07 mg/L (CV = 13,79%). Expressive sulfate concentration was also detected in the vadose seepage, with a mean of 305,09 mg/L. Underground reservoirs have high HC\'O IND. 3 POT. -\' content (\'X BARRA\'=305,10 mg/L) together with calcite saturation index close to equilibrium (S\'l IND. c\'=-0,02) and lower sulfate concentration (mean of 17,79 mg/L; CV = 52.03%). The karst springs revealed similar chemistry to the underground reservoirs, with high HC\'O IND. 3 POT. -\' content (\'X BARRA\'=246,96 mg/L ; CV = 11,0%), saturated with respect to calcite (mean of S\'l IND. c\' = 0,00; varying between 0,28 and -0,37) and mean sulfate concentration of 19,30mg/L (CV = 31.47%). The meteoric recharge has a very low solute load, with means of all ions lower than 0.5 mg/L. Stoichiometric balance calculations applied to the hydrochemical results showed that the molar balances of the various water facies do not follow the classical ratios of carbonate dissolution only due to carbonic acid, but on the contrary, they follow better the chemical system of \'H IND. 2\'S\'O IND. 4\' - CaMgC\'O IND. 3\'. The study of the expressive secondary gypsum deposits in caves, represented by crusts, stalactites and filaments, showed that their origin is related to the deep phreatic water and that the major deposition event of these deposits occurred during the water table lowering after the high water table period related to the paragenetic conduit enlargement. Isotopic composition of dissolved inorganic carbon in groundwater samples showed values of \'\'delta\' POT. 13\'CHC\'O IND. 3 POT. -\' around -10,4%o PDB-V, which are relatively enriched with respect to the predicted \'\'delta\' POT. 13\'CHC\'O IND. 3 POT. -\' of -17,1%o, if the system would be affected only by carbonic acid. This enrichment is attributed to the \'ANTPOT. 13 C\' originated by the reaction between carbonate rock and sulfuric acid. The \'delta\' POT. 34\'S of sulfate in water (\'X BARRA\'=17,7%o CDT) is slightly depleted than that of pyrite disseminated in carbonate rock (\'X BARRA\'=21,3%o), but still in the range predicted for the fractionation due to pyrite oxidation, indicating that carbonate rock is dissolved by sulfuric acid. Microbiological analysis of groundwater in the karstic aquifer revealed the presence of bacteria of the genera Acidithiobacillus and sulfate reducing bacteria (SRB). Both are typical of the sulfur cycle and produce sulfuric acid. Finally, it can be stated, based on the above described results, that sulfuric acid is an important agent in the dynamics of the studied karst.

Os depósitos de carvão no Brasil possuem conteúdos relativamente baixos de matéria orgânica. Aproximadamente 65% do carvão ROM (Run-of-min) extraído de minas subterrâneas na região carbonífera de Santa Catarina são descartados como resíduo em depósitos de rejeitos. Esse rejeito contem minerais sulfetados, principalmente a pirita, que oxida e pode gerar drenagem ácida de minas, com diversos impactos ambientais e custos econômicos. Entretanto, com o processamento do rejeito de carvão para concentração da pirita, esta pode-se tornar matéria prima para diversos produtos, entre eles o ácido sulfúrico (insumo deficitário no país, utilizado em grandes quantidades na indústria de fertilizantes). O objetivo deste trabalho foi caracterizar o rejeito de carvão para concentração da pirita proveniente da camada Bonito, no estado de Santa Catarina, avaliando-se o seu potencial uso na produção de ácido sulfúrico e os ganhos ambientais com a dessulfurização do material remanescente. Para isso, foram construídas as curvas de separabilidade densimétrica de uma amostra de rejeito grosso e de uma amostra de rejeito fino. Definiram-se densidades de cortes, de forma a recuperar um material carbonoso remanescente (d<2,2), um material dessulfurizado (2,2<d<2,7) e um concentrado de pirita (d>2,7). Efetuou-se a caracterização das frações densimétricas através de imagens fotográficas e análises de cinzas, enxofre, umidade, poder calorífico, difração de raio-x (DRX), fluorescência de raio-x (FRX) e análise termogravimétrica. As análises ambientais realizadas foram: classificação de resíduos conforme NBR 10.004 e teste estático de predição de acidez pelo método de contabilização de ácidos e bases. Estimou-se a produção de ácido sulfúrico a partir do concentrado piritoso obtido com o processamento do rejeito de carvão das camadas Barro Branco e Bonito e avaliaram-se os ganhos ambientais. Os resultados demonstraram que o rejeito proveniente do circuito de grossos (87,2% do material descartado) possui teor de enxofre de 7,8% e 79,9% de cinzas, já os finos (12,8% do material) tem um teor de enxofre de 4,9% e 70,8% de cinzas. Com a separação densimétrica do rejeito em 2,2 e 2,7, obteve-se uma fração d<2,2 g/cm³ com recuperação mássica de 20,7% para os grossos e 45,2% para os finos que só possui aproveitamento energético em termoelétricas se misturado com carvão de baixo enxofre. O material dessulfurizado (2,2<d<2,7 g/cm³) corresponde a 66% em massa do rejeito para os grossos, possui 3,8% de enxofre e potencial de geração de acidez 60% inferior ao rejeito original. Já a fração pirítica (d>2,7 g/cm³) possui recuperação mássica de 13% para os grossos e teor de enxofre de 33,1%. Quando comparada com a camada Barro Branco, a camada Bonito apresenta níveis superiores de S na fração intermediária, com maior potencial de geração de acidez. De qualquer forma, os rejeitos de carvão grossos, tanto da Camada Barro Branco como Bonito, são passíveis de beneficiamento por processos gravimétricos para obtenção de concentrados com no mínimo 30% de enxofre. Caso houvesse um planejamento global de aproveitamento da pirita na região carbonífera de Santa Catarina para produção de ácido sulfúrico, um acréscimo de 14% da demanda brasileira deste insumo poderia ser realizado com os atuais níveis de produção de carvão, reduzindo em até 75% o enxofre disposto no ambiente e trazendo benefícios econômicos e ambientais à região carbonífera de Santa Catarina. / The grade of coal deposits in Brazil is relatively low, and approximately 65% of the run-of-mine (ROM) coal extracted from underground mines in the carboniferous region of Santa Catarina is discarded as waste in dump deposits. These waste discards contain sulfide minerals, particularly pyrite, which oxidize and give rise to acid rock drainage (ARD) with recognized environmental impacts and economic costs. However, the coal waste could be gravimetrically processed to produce a pyrite concentrate to be used as a raw material for sulfuric acid production (an income with deficient production in the country, largely used in fertilizer industry). The aim of this work was to study the coal waste from the Bonito seam in the state of Santa Catarina, Brazil, evaluating its use for the production of sulfuric acid and the environmental implications of remaining material after the desulfurizing step. Washability curves of coarse and fine waste material from a coal preparation plant working with the Bonito seam was performed. Three different density fractions were separated: a carbonaceous material (d<2.2 g/cm3), a desulfurized material (2.2 and 2.7 g/cm³), and a pyrite concentrate (d>2.7 g/cm³). Characterization studies were carried out by photographic images and ash, sulfur, moisture, calorific value, X-ray diffraction (XRD), X-ray fluorescence (XRF), and thermogravimetric analysis (TGA). Environmental classification of the waste was conducted in terms of NBR 10.004 and static acid prediction test by the acid-base accounting method. It was also estimated the production of sulfuric acid from Barro Branco and Bonito seams as well the environmental benefits of such desulfurization procedures. The results showed that the coarse fraction of coal tailing from Bonito seam (87.2% of the discarded mass) presents 7.8% sulfur and 79.9% ash. The fine waste fraction from the spirals circuit (12.8% of the discarded mass) showed 4.9% sulfur and 70.8% ash. Both materials were subjected to density separation. The fraction d<2.2 g/cm³, with a mass recovery of 20.7% for the coarse fraction and 45.2% for the fine fraction, could be only used for energy production if a moisture with low sulfur coal was provided. The intermediate density material (2.2<d<2.7 g/cm³), which corresponds to a 66% of the mass coarse mass fraction and presents 3.8% sulfur, have a 60% lower acid generation material than the raw waste. The pyrite concentrate (d>2,7) reached a 13% mass recovery with 33.1% sulfur. Comparing the Barro Branco and Bonito seams, the Bonito seam showed superior levels of sulfur in the 2.2<d<2.7 g/cm³ fraction, with a higher an acid generation potential. Nevertheless, the coarse fraction of both seams can be processed for pyrite concentration, reaching the minimum of 30% sulfur necessary for sulfuric acid production by roasting. Considering the levels of coal production in the carboniferous region of Santa Catarina, an input of 14% in the national demand of sulfuric acid would by supplied. This procedure will also reduce in 75% the pyrite disposed in landfills, bringing economic and environmental benefits to the local coal chain production.

Baile Herculane, located in southwestern Romania, is a unique city that exploits its thermal waters. The geology consists of a granitic basement covered by 200 meters of limestone, marl, and flysch deposits. Extreme faulting carries heat ascending from the mantle, which intercepts percolating meteoric waters. Local springs have high concentrations of dissolved sulfide gas (H2S) and dissolved sulfate (SO4²-).These dissolved species indicate the progression of sulfate reduction in the aquifer. Water samples were collected in polyethylene syringes to prevent oxidation of sulfide. Then, sulfide and sulfate were quantitatively reacted for stable isotope analysis. Total sulfur isotopic composition was calculated to determine the source of the dissolved sulfur. The source of the sulfur is a sulfate of marine origin (𝛅34S≅20%0), which I found to come from impurities in the limestone since the Cerna Valley does not possess marine evaporites. The limestones of the Cerna Valley are host to a number of caves, which possess relatively large deposits of sulfates and exotic morphologic features that suggest speleogenesis by sulfuric acid. 𝛅34S of the sulfates relates to sulfide isotopic values from the springs, showing that the dissolved sulfide (upon oxidation) forms sulfuric acid s that reacts with limestone to produce sulfate minerals. A wide range of cave sulfate 𝛅34S values exist indicating that isotopic values of these deposits depend on several factors such as sulfur source, extent of sulfate reduction, and completeness of sulfide oxidation. This also implies that a single, narrow range of sulfur isotopic values does not represent sulfuric acid speleogenesis.

Thesis (Ph. D.)--Brigham Young University. Dept. of Chemical Engineering, 2006. / Includes bibliographical references (p. 141-147).

Thesis (Ph. D.)--University of Oregon, 2007. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 146-156). Also available for download via the World Wide Web; free to University of Oregon users.

In this thesis work, a high grade chromite concentrate obtained from PinarbaSi, Kayseri region of Turkey was reacted with sulfuric acid solution to determine the optimum conditions of leaching of chromite ores. Conventional methods for producing chromium are still valid in industry. The main process in production includes soda melting and taking it into solution in the form of chemical compounds such as sodium dichromate. Three and six valence states of chromium have importance in production. Trivalent chromium, chrome ore or chromite have no harmful effects. However, compounds of hexavalent chromium show toxic, irritating and corrosive action to people and environment. In the mentioned conventional method, main products consist of hexavalent chromium compounds. In this study, only trivalent chromium remained in the leach solution and did not change to hexavalent state. Obtained product after leaching was chromium(III) sulfate. The maximum extraction of chromium in the absence of perchloric acid was 94.1 % under the conditions of 175 &deg / C, 6 hours and 84.6 wt % sulfuric acid. The maximum extraction of chromium in the presence of perchloric acid was 98.7 % under the conditions of 175 &deg / C, 2 hours, 84.6 wt % sulfuric acid and &frac12 / perchloric acid / chromite ratio. The latter one was also the highest recovery value obtained during the experiments. Moreover, in none of the analyzed samples, appreciable amounts of hexavalent chromium was found during analyses.

Hydrogen production is dependent on natural gas, 90% in the U.S. and 48% of the world's production. Natural gas supply is dwindling and it's price is increasing. Greenhouse gases and air pollutants are emitted when natural gas is used. In a single product production facility, coal is not competitive with natural gas for hydrogen production at current prices. Hydrogen production by direct electrochemical dissociation of water requires a relatively high voltage.Techniques have been developed for manufacturing hydrogen as a lucrative byproduct of IGCC electric power generation, refinery sulfur production and sulfuric acid production for fertilizer production. Laboratory experiments have been conducted on small systems to advance the technology and full size commercial plants have been conceptualized and analyzed to establish economic viability.In this thesis, a low voltage electrochemical hydrogen production technique has been developed that entails scavenging of the anode with sulfur dioxide. In an electrochemical cell hydrogen is produced at the negative electrode while the positive electrode is bathed in sulfur dioxide which is oxidized with water to sulfuric acid. The presence of SO2 substantially reduces the equilibrium voltage relative to that required for the direct dissociation of water into hydrogen and oxygen. Also sulfuric acid is a more valuable byproduct than oxygen. More sulfuric acid is produced than any other chemical commodity in the U.S. and is a major economic indicator. Hydrogen produced by the electrochemical route being discussed in this thesis illustrates industrial possibilities for large scale-up, economical hydrogen production.In an electrochemical cell, an equilibrium voltage of 1.23 volts is required to decompose water into hydrogen and oxygen. The presence of sulfur dioxide to scavenge the anode can reduce the equilibrium voltage from 1.23 volts to 0.17 volts. The equations shown below are reactions showing the energy requirements.2H2Oâ?? 2H2 + O2 - 4 Faradays @ 1.2Vâ?? 2SO2 + 4H2O 2H2SO4 + 2H2 - 4 Faradays @ 0.17V The thermochemical free energy is reduced from 113kcal/mole to 15kcal/mole if sulfur dioxide is used as a scavenger.In this work, extensive studies to determine the most effective electrodes and catalysts have been carried out. The possibilities for photo electrochemical implementation have been investigated and cell design optimization has been performed Experimental methods and results will be presented and discussed.

M. Tech. Metallurgical Engineering. / Aims to provide a mineralogical basis for understanding the galvanic dissolution and interaction of sulphide ores in presence of hydrogen peroxide using electrochemical technique. The research aim to achieve the following objectives: study the mineralogical characteristics of different sulphide ores ; study the sulphuric acid dissolution behaviour of the sulphide ores in the presence of hydrogen peroxide and to investigate the interaction of the mineralogy on the ores and hydrogen peroxide during dissolution.