New preparative routes to chromyl fluoride were sought. It was found that chlorine monofluoride reacts with chromium trioxide and chromyl chloride to produce chromyl fluoride. Attempts were made to define a mechanism for the reaction of ClF and Cr03 in light of by-products observed and previous investigations. Carbonyl fluoride and chromium trioxide react to form chromyl fluoride and carbon dioxide. A mechanism was also proposed for this reaction. Chromium trioxide with MoF6 or WF6 to produce chromyl fluoride and the respective oxide tetrafluoride.

No description available.

No description available.

M.Tech. / A study was undertaken to develop and test the process for the recovery of high purity chromium oxide green from chromium waste. The process developed has a combination of leaching, ion exchange, coagulation, chelation and calcination. Based on the research findings, strong acid cation resin (Purolite 106) and weak acid cation exchange (Lewatit NCP 80) resins were selected for extraction of aluminium Ill ions and chromium Ill ions respectively. The optimal conditions for extraction of chromium (Ill) with ion exchange resins from chromium leachate solution were established taking into account the composition and the parameters of the chromium solution, the resin manufacturer's defined operating conditions and the empirical dependencies established in previous studies on model solutions of chromium (Ill). The effects of pH, compositions and the temperature on the extraction of chromium (Ill) were also examined. The yield of chromium (Ill) from tannery chromium hydroxide solid was about 96-98% after 35 min of phase contact with the sulphuric acid solution. Chromium hydroxide with Cr20 3 content of 88% was achieved by extracting chromium (Ill) with weak acid cation resin. The ferric and calcium ions present in the treated chromium hydroxide product were then removed by soaking the hydroxide cake in 0.1 to 0.2M ethyldiaminetretraacetic (EDTA) acid solution. The final product, chromium oxide green, with a Cr20 3 content of at least 95.14% achieved with the described process.

A detailed study has been carried out to investigate the dissolution characteristics of unstabilized and stabilized CrO₂ particles. It has been found that on contact of CrO₂ with aqueous solutions, it dissolves by disproportionation reaction to HCrO₄ and Cr2O₃. XPS study has shown that stabilization of CrO₂ particles with bisulfite solution leads to the formation of Cr2O₃. However, because of agglomeration of the CrO₂ particles due to their magnetic properties, not all of the surface is completely stabilized. The electrokinetic characteristics of Cr(IV) and Cr(III) oxides in aqueous solutions have been investigated. Experiments suggest that sulfite ions chemisorb strongly on Cr₂O₃ particles. Experiments have also been carried out to study the adsorption of sodium dodecyl sulfate (SDS) on Cr₂O₃ particles. With increasing SDS concentration, Cr₂O₃ becomes less positively charged and ultimately negatively charged when the surfactant concentration exceeds 10⁻³ M. This suggests that SDS specifically adsorbs onto the oxide.

­^¤åºK­n¬°none

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Ultimamente as nanopartÃculas tÃm sido o foco principal dos pesquisadores. Esse empenho reside no fato de que novas e incomuns propriedades fÃsicas e quÃmicas, ausentes no mesmo material em tamanho macro e microscÃpico, sÃo observadas nessa nova escala. O direcionamento desse estudo à voltado à obtenÃÃo de nanopartÃculas de Ãxidos de cromo (Cr2O3) utilizando o mÃtodo sol-gel protÃico, tendo a gelatina como precursor orgÃnico e com o uso reduzir o custo de produÃÃo. Esse processo surge como uma nova alternativa para obtenÃÃo de Ãxidos com alta eficiÃncia e baixo custo. O interesse nesse material à devido Ãs diversas aplicaÃÃes como pigmentos verdes, revestimentos de materiais para proteÃÃo tÃrmica e principalmente como catalisador de inÃmeros produtos oriundos da indÃstria do petrÃleo, entre outras. AtravÃs dessa nova rota e utilizando um sal como fonte de cromo, foram obtidas partÃculas de tamanho mÃdio variando entre 20 e 60nm. Esses valores foram retirados de diferentes direÃÃes cristalogrÃficas atravÃs da tÃcnica de DifraÃÃo de Raios-X (DRX) e apÃs o refinamento da estrutura pelo mÃtodo Rietveld em diversas amostras preparadas em diferentes temperaturas. Outras tÃcnicas foram utilizadas para complementar os resultados obtidos pela DRX. / In the last years, nanoparticles have becoming important to several researchers. This research reside in the fact that new and uncommon physical and chemical properties, absent in the same material in macro and microscopic size, are observed in this new scale. The subject of this study is obtaining chromium oxide nanoparticles (Cr2O3) by solâgel proteic process using gelatin as an organic precursor. This process appears as a new alternative for the synthesis of oxides for great applications with high efficiency and low cost. The interest in that material is due to the several applications such as green pigments, coverings of materials for thermal protection and mainly as catalyst of countless products originating from of the industry of the petroleum, among others. This new route, using chromium salt as chromium source, produces nanoparticles with average particle size between 20 and 60nm. These values were obtained for different crystallographic direction by means of X-Ray Diffraction (XRD) technique and the structure refinement by Rietveld method were applied in several samples prepared at different temperatures. Other techniques have been used in order to complement the XRD results.

Structural and electronic effects in hydrocarbon reactions over metal oxides have been examined by comparing the reactions of methyl (-CH₃) and methylene (=CH₂) fragments on three different oxide single crystal surfaces: α-Cr₂O₃(101̅2), α-Cr₂O₃(0001), and α-Fe₂O₃(101̅2). The intermediates have been generated through the decomposition of halogenated hydrocarbons. The primary reactions of methyl and methylene over α-Cr₂O₃ are methyl dehydrogenation to methylene, and methylene coupling (C-C bond formation) to ethylene (CH₂=CH₂). The different surface geometric structures of α-Cr₂O₃(101̅2) and (0001) lead to an increase in the activation barrier for methylene surface migration, a critical step in the coupling reaction, of 5.9 kcal/mol over the (0001) surface. For methyl dehydrogenation, differences in the local site pair (cation/anion) geometry and the proximity of surface lattice oxygen to the methyl group do not result in a significant difference in the barrier for dehydrogenation, suggesting that the surface anions play a minor role in the dehydrogenation of methyl on these surfaces. Electronic differences in the Fe³⁺ (𝑑⁵) and Cr³⁺ (𝑑³) cations on structurally-similar α-Cr₂O₃(101̅2) and α-Fe₂O₃(101̅2) surfaces lead to major differences in reaction selectivity. α-Cr₂O₃(101̅2) is nonreducible under the reaction conditions of this study, but α-Fe₂O₃(101̅2) is highly reducible due to the difference in the d electron configuration. Hydrocarbons are formed over α-Cr₂O₃(101̅2), but nonselective oxidation products (CO₂, CO, H₂O) are formed over the stoichiometric α-Fe₂O₃(101̅2) surface along with surface reduction. Reduction of the α-Fe₂O₃(101̅2) leads to a shift in the product selectivity towards formaldehyde (CH₂O) and ethylene. For the limited number of systems examined in this study, examples of geometric structure sensitive (methylene coupling) and structure insensitive (methyl dehydrogenation) reactions have been found on α-Cr₂O₃, and electronic effects are observed for the reactions on α-Cr₂O₃(101̅2) and α-Fe₂O₃. For the structure sensitive reaction, the differences in surface geometry impact the reactions kinetics over Cr₂O₃ but not the types of products formed, while the electronic differences give rise to dramatic changes in the selectivity associated with the very different products formed over α-Cr₂O₃(101̅2) and α-Fe₂O₃(101̅2). / Ph. D.

As pesquisas com utilização de adubação nitrogenada em papuã têm avaliado principalmente as características do pasto e a produção animal. Este trabalho foi realizado com o objetivo de estudar a eficiência de uso do nitrogênio em papuã por meio de informações sobre características da pastagem e consumo de forragem de novilhas de corte. O experimento foi desenvolvido na Universidade Federal de Santa Maria (UFSM), de janeiro a maio de 2014. Os tratamentos foram constituídos por doses de zero, 150 ou 300 kg/ha de nitrogênio (N), na forma de ureia. O método de pastejo foi o de pastoreio rotacionado, sendo utilizadas 16 novilhas-teste Angus, com idade e peso corporal (PC) médio inicial de 15 meses e 276,0 ±17,4 kg, respectivamente. Foi utilizado como critério de manejo do pasto a altura do dossel na ocasião da saída dos animais dos potreiros, mantendo-os em 30 cm de altura. A avaliação do consumo de forragem foi realizada dosificando duas novilhas-teste por piquete, com óxido de cromo (Cr2O3) como indicador externo da produção fecal, fornecendo-o por 11 dias (sete dias para adaptação e quatro dias para coleta fecal). O delineamento experimental foi o inteiramente casualizado, com medidas repetidas no tempo, com três tratamentos e duas repetições de área. Para as avaliações de consumo foram utilizadas quatro repetições por tratamento, onde cada animal foi considerado uma unidade experimental. A massa de forragem, lâminas foliares e colmos nos piquetes com 300 kg/ha de N foram 23,7%, 18,6% e 28,8% superiores, respectivamente, quando comparado a dose zero. O teor de PB foi 3,4% superior quando utilizado adubação nitrogenada de 300kg/ha em relação a dose de 150kg/ha de N (18,7%). Independente das doses de N utilizadas, as novilhas consumiram 2,2±0,09 kg MS/100kg PC de forragem. A adubação nitrogenada em papuã modifica a estrutura do pasto, aumentando a produção total e a qualidade da forragem. O uso de 150 e 300kg/ha de N aumenta a massa de lâminas foliares. Novilhas em pastejo em papuã adubado com 300kg/ha de N colhem forragem com maior teor de proteína bruta. A mudança na estrutura do dossel faz com que as novilhas reduzam o consumo de forragem ao final do ciclo de utilização do papuã. / Several researches on nitrogen fertilization in Alexandergrass have mainly assessed pasture characteristics and animal production. The efficiency of nitrogen in Alexandergrass through information on the features of pasture and forage intake by beef heifers was analyzed. This study was carried out at the Universidade Federal de Santa Maria (UFSM), Santa Maria RS Brazil, from January to May 2014. Treatments comprised doses of 0, 150 and 300 kg/ha of nitrogen (N), in form of urea. Experimental animals were sixteen Angus heifers with initial age and body weight (BW) of 15 months and 276.0 ± 17.4 kg, respectively. The grazing method was rotational with variable number of animals. Pasture management criterion comprised canopy height of 30 cm at the output of the animals from the paddocks. Forage intake was estimated in two heifers per paddock using chromium oxide (Cr2O3) as an indicator of fecal output. The dosing period was 11 days, with seven days for adaptation and four days for feces collection. The experimental design was completely randomized with repeated measurements over time, with three treatments (0, 150, 300 kg/ha N) and two area replications. Forage intake assessment comprised four replications per treatment in which each animal was the experimental unit. Forage, leaf blades and stems mass in paddock with 300 kg/ha of N were 23.7%, 18.6% and 28.8%, respectively, higher when compared to dose zero. Crude protein content (CP) was 3.4% higher at 300 kg/ha nitrogen fertilization when compared to dose 150kg/ha of N (18.7%). Regardless of N doses, heifers consumed 2.2±0.09 kg DM/100kg BW of forage. Nitrogen fertilization of Alexandergrass modified the pasture structure, increased total production and forage quality. Doses 150 and 300 kg/ha of N increased the leaf blades mass. Heifers grazing on Alexandergrass fertilized with 300 kg of N/ha harvest forage with the highest CP content. Changes in canopy structure makes reduce the forage intake at the end of the Alexandergrass cycle.

[pt] Ligas ferrosas são importantes insumos nos processos de obtenção de aços especiais. A obtenção de ligas Fe-Cr se dá principalmente por meio de dois processos, empregando-se como agentes redutores C ou Si, sendo o primeiro associado à síntese de ligas FeCrAC, e o segundo às ligas FeCrBC. Neste contexto, ligas do sistema Fe-Cr, com teor de Cr típico variando entre 45 a 95 por cento em massa, apresentam destaque, principalmente na fabricação de aços inoxidáveis. Durante processo de obtenção das referidas ligas, há considerável produção de finos, os quais podem ser reaproveitados mediante tratamento químico (piro e hidrometalúrgico) apropriado. No presente trabalho investigouse a extração de cromo de finos gerados durante a produção de uma liga Fe-Cr com alto teor de C. Para tanto foram realizadas ustulações nas temperaturas de 700, 800, 900 e 1000 graus Celsius com excessos de 100, 200, 300 e 400 graus Celsius NaOH e estequiométrico, 125, 150 e 200 graus Celsius de excesso de Mg(OH)2 em atmosfera oxidante, seguida de solubilização em meio aquoso e redução com H2O2 em diferente valores de pH, seguido-se da precipitação com NaOH em pH alcalino. Matéria prima, intermediários e produtos foram caracterizados por MEV/EDS, FTIR, DRX e ICP-OES. As recuperações de Cr em solução máximas alcançadas foram da ordem de 98 por cento, e a etapa de redução e precipitação em aproximadamente 95 por cento sugerindo que a rota de processamento químico proposta foi satisfatória no que tange à extração do cromo inicialmente presente. / [en] Ferrous alloys are important inputs in the process of obtaining special steels. The obtained Fe-Cr alloy is mainly by two processes, employing reducing agents such as C or Si, the first being associated with the synthesis of FeCrAC alloy and the second alloy to FeCrBC. In this respect, alloys of Fe-Cr system with varying Cr content typically between 45 to 95 percent by weight show prominence, particularly in the manufacture of stainless steel. During the process of obtaining these alloys, there is considerable production of fines which can be reused by appropriate chemical treatment (hydro-and pyro). In the present work we investigated the extraction of chrome fines generated during the production of a Fe-Cr alloy with high content of C. For both ustulações were performed at temperatures of 700, 800, 900 and 1000 Celsius degrees in excess of 100, 200, 300 and 400 percent stoichiometric NaOH and 125, 150 and 200 percent excess of Mg (OH) 2 in an oxidizing atmosphere, followed by solubilization in an aqueous medium and in H2O2 reduction with different pH values was followed by precipitation with-NaOH alkaline pH. Raw materials, intermediates and products were characterized by MEV/ EDS, FTIR, XRD and ICP-OES. The recoveries of Cr on maximal solution achieved were of the order of 98 percent, and the stage of reduction and precipitation by about 95 percent suggesting that the route of chemical processing proposal was satisfactory with regard to the extraction of chromium initially present.