Thesis (Ph. D.)--Ohio state University, 1918.

Thesis (Ph. D.)--University of Pittsburgh, 1915. / Vita.

The aim of this work is to quantify the concentration of chromic acid (CA) in a saturated solution of chromium trioxide and sodium dichromate using Artificial Neural Networks (ANNs). A set of titration curves was obtained by automated acid-base titration according to a factorial experimental design that was developed for this purpose. These titration curves were divided into three subsets, a learning, training and test set for use by ANNs. Once trained, ANNs have the ability to recognize, generalize and relate the input to a particular output. Concentration of chromic acid (CA), total chromium(VI) and/or dichromate was used as the outputs and titration curves as the inputs to ANNs. Our aim here was to establish whether ANNs would be able to predict the concentration of chromic acid with an absolute error below 1%. For real world problem, the neural networks are only given the inputs and are expected to produce reasonable outputs corresponding to that inputs without any prior ‘knowledge’ about theory involved – here, no interpretation of titration curves was performed by ANNs. The test set of data that was not used for learning process, was used to validate the performance of the neural networks, to verify whether the ANNs learned the input-output patterns properly and how well trained ANNs were able to predict the concentrations of chromic acid, dichromate and total chromium. A number of ANNs models have been considered by varying the number of neurons in the hidden layer and parameters related to the learning process. It has been shown that ANNs can predict the concentration of chromic acid with required accuracy. A number of factors that affect the performance of the neural networks, such as the number of points in a titration curve, number of test points and their distribution within the training set, has been investigated. This work demonstrates that ANNs can be used for online monitoring of an electrolytic industrial process to manufacture chromic acid. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

During the last ten years, several patients have presented to the Renal Unit of Groote Schuur Hospital with acute renal failure following the use of traditional (N'anga or Gqirha) medication. The history together with abnormal liver-function tests and renal failure was thought to be suggestive of a toxic aetiology. The specific toxin however remained unknown, until during the admission of one patient, a relative brought in the medication, analysis of which revealed a high concentration of potassium dichromate. Subsequently elevated levels of chromium were demonstrated by atomic absorption spectrometry in the blood and urine of this patient. Following this case there have been six further cases of acute renal failure resulting from use of dichromate containing traditional remedies. These remedies were obtained from a variety of sources including street-hawkers, herbal chemists, and traditional healers. Clinical and laboratory data relating to these seven patients will be presented.

During the last ten years, several patients have presented to the Renal Unit of Groote Schuur Hospital with acute renal failure following the use of traditional (N'anga or Gqirha) medication. The history together with abnormal liver-function tests and renal failure was thought to be suggestive of a toxic aetiology. The specific toxin however remained unknown, until during the admission of one patient, a relative brought in the medication, analysis of which revealed a high concentration of potassium dichromate. Subsequently elevated levels of chromium were demonstrated by atomic absorption spectrometry in the blood and urine of this patient. Following this case there have been six further cases of acute renal failure resulting from use of dichromate containing traditional remedies. These remedies were obtained from a variety of sources including street-hawkers, herbal chemists, and traditional healers. Clinical and laboratory data relating to these seven patients will be presented.

Made available in DSpace on 2014-06-11T19:28:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-07-23Bitstream added on 2014-06-13T19:37:07Z : No. of bitstreams: 1 basile_ag_me_jabo.pdf: 453267 bytes, checksum: 5548cfe22a8e4806904cc2253ea1c709 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / No Brasil os testes ecotoxicológicos são realizados com diversos organismos, porém para a avaliação da poluição dos solos apenas as minhocas são utilizadas como organismo-teste ou bioindicador e não há normas de testes para os outros organismos. Assim, o objetivo deste trabalho foi determinar a sensibilidade e a variação da resposta do fungo A. cassiae ao dicromato de potássio como substância de referência. Para a determinação da concentração efetiva (CE (I)50;7d), foram realizados sete testes com as concentrações 0,0; 50,0; 90,0; 130,0; 170,0; 210,0; e 250,0 mg.L-1 de dicromato de potássio no meio de cultivo BDA, mantido em placas de Petri. O dicromato de potássio foi adicionado ao meio após a autoclavagem, quando este ainda apresentava consistência líquida. Após o resfriamento e solidificação do meio, nas placas, foi colocado um disco com 6,5 mm de A. cassiae. As placas inoculadas foram incubadas a 25ºC com fotoperíodo de 12 horas, durante sete dias. O crescimento do fungo foi avaliado por meio de medidas transversais do diâmetro da colônia. A CE (I)50;7d estimada foi de 65,97 ± 9,48 mg.L-1. No controle não ocorreu inibição do crescimento. Em 50 mg.L-1 a inibição foi de 29%; em 90 mg.L-1, de 72%; em 130 mg.L-1, de 86%; em 170 mg.L-1, de 92%; em 210 mg.L-1, de 95%; e em 250 mg.L-1. de 94%. Assim, há viabilidade na utilização do fungo A. cassiae como representante dos microorganismos do solo em testes ecotoxicológicos e o dicromato de potássio pode ser utilizado como substância de referência. / In Brazil the ecotoxicological tests are conducted with various organisms, but among the soil organisms only earthworms have standardized tests. For other soil organisms there are not standard methods for these studies. The objective of this study was to evaluate the adequacy of potassium dichromate as substance reference to the fungus Alternaria cassiae. To determine the effective concentration (EC (I)50;7d), seven tests were conducted using the concentrations (0.0, 50.0, 90.0, 130.0, 170.0, 210.0, and 250 , 0 mg.L-1) in the BDA media. The respective potassium dichromate concentrations were introduced in the BDA medium while it had liquid consistency. After cooling and solidification of the medium was placed on each plate, a disc with 6.5 mm of A. cassiae, which were incubated at 25 °C with photoperiod of 12 hours for seven days. The EC (I)50;7d estimated was 65.97 ± 9.48 mg.L-1. In concentration of 0.0 mg.L-1 there was no growth inhibition. In 50 mg.L-1 inhibition was 29%, in 90 mg.L-1, 72%; in 130 mg.L-1, 86%; in 170 mg.L-1, 92%; in 210 mg.L-1, of 95% and in 250 m.L-1 was 94%. Thus, it is feasible using the fungus A. cassiae as the representative of microorganisms in the soil ecotoxicological tests and the potassium dichromate as reference substance.

Made available in DSpace on 2014-06-11T19:23:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-28Bitstream added on 2014-06-13T20:10:45Z : No. of bitstreams: 1 godoi_lm_me_jabo.pdf: 221877 bytes, checksum: d6a13644f869b633dd790316dd00f0f4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Para conhecer o potencial de plantas de cobertura no fornecimento de nitrogênio para o milho, em sistema de plantio direto, foi avaliado o N potencialmente mineralizável (N0) do solo por meio de ensaio de incubação aeróbia de longa duração e o N disponível por meio dos extratores químicos KCl a quente, Dakota do Sul modificado e tampão fosfato borato a pH 11,2. Foram utilizadas amostras de solo de experimento a campo, instalado em área de Latossolo Vermelho argiloso e conduzido em delineamento em blocos casualizados, com cinco tratamentos: testemunha com vegetação espontânea, sorgo, milheto, mucuna-preta e feijão-de-porco, e cinco repetições. A coleta de solo nas parcelas foi feita após a dessecação das plantas de cobertura e antes do cultivo de milho, nos anos agrícolas de 2007/2008 e 2008/2009. O solo coletado, representativo da profundidade de 0 a 10 cm, foi utilizado no ensaio de incubação aeróbia, em experimento em vasos, com milho, e para as análises químicas. A eficiência dos extratores foi avaliada por meio de testes de correlação, empregando como variáveis de referência o N0 e o N mineralizado acumulado por 30 semanas, obtidos no ensaio de incubação aeróbia, e a produção de matéria seca e o N acumulado na parte aérea do milho, obtidos no experimento em vasos. As plantas de cobertura não diferem entre si quanto ao potencial de fornecimento de N para o milho. O método do KCl a quente é capaz de predizer a mineralização de N, porém os métodos químicos avaliados para predizer o N disponível não são eficientes / Aiming to determine the potential of cover crops to supply nitrogen for corn in no-tillage system, it was evaluated the soil potentially mineralizable N (N0) by long-term aerobic incubation and available N by chemical extractants (hot KCl, modified South Dakota and pH 11.2 phosphate-borate buffer). Soil samples were collected from a field experiment, installed in an Udox and carried out in a randomized block design with five treatments (control with spontaneous vegetation, Sorghum bicolor, Pennicetum glaucum, Mucuna aterrima and Canavalia ensiformis) and five replications. Plots soil sampling was made after the cover crops desiccation and before growing the corn in the agricultural seasons of 2007/2008 and 2008/2009. Soil samples collected from 0 to10 cm depth were used for long-term aerobic incubation, pots experiment with corn, and for soil chemical analysis. Extractants efficiency was evaluated by correlation tests, using as reference the N0 and the mineralized accumulated N over 30 weeks obtained from long-term aerobic incubation, dry matter production and N accumulated in maize shoots, obtained from pots experiment. Cover crops do not differ in their potential to supply nitrogen for corn. Hot KCl is able to predict the N mineralization but the chemical methods evaluated to predict the available nitrogen are not efficients

Resumo: No Brasil os testes ecotoxicológicos são realizados com diversos organismos, porém para a avaliação da poluição dos solos apenas as minhocas são utilizadas como organismo-teste ou bioindicador e não há normas de testes para os outros organismos. Assim, o objetivo deste trabalho foi determinar a sensibilidade e a variação da resposta do fungo A. cassiae ao dicromato de potássio como substância de referência. Para a determinação da concentração efetiva (CE (I)50;7d), foram realizados sete testes com as concentrações 0,0; 50,0; 90,0; 130,0; 170,0; 210,0; e 250,0 mg.L-1 de dicromato de potássio no meio de cultivo BDA, mantido em placas de Petri. O dicromato de potássio foi adicionado ao meio após a autoclavagem, quando este ainda apresentava consistência líquida. Após o resfriamento e solidificação do meio, nas placas, foi colocado um disco com 6,5 mm de A. cassiae. As placas inoculadas foram incubadas a 25ºC com fotoperíodo de 12 horas, durante sete dias. O crescimento do fungo foi avaliado por meio de medidas transversais do diâmetro da colônia. A CE (I)50;7d estimada foi de 65,97 ± 9,48 mg.L-1. No controle não ocorreu inibição do crescimento. Em 50 mg.L-1 a inibição foi de 29%; em 90 mg.L-1, de 72%; em 130 mg.L-1, de 86%; em 170 mg.L-1, de 92%; em 210 mg.L-1, de 95%; e em 250 mg.L-1. de 94%. Assim, há viabilidade na utilização do fungo A. cassiae como representante dos microorganismos do solo em testes ecotoxicológicos e o dicromato de potássio pode ser utilizado como substância de referência. / Abstract: In Brazil the ecotoxicological tests are conducted with various organisms, but among the soil organisms only earthworms have standardized tests. For other soil organisms there are not standard methods for these studies. The objective of this study was to evaluate the adequacy of potassium dichromate as substance reference to the fungus Alternaria cassiae. To determine the effective concentration (EC (I)50;7d), seven tests were conducted using the concentrations (0.0, 50.0, 90.0, 130.0, 170.0, 210.0, and 250 , 0 mg.L-1) in the BDA media. The respective potassium dichromate concentrations were introduced in the BDA medium while it had liquid consistency. After cooling and solidification of the medium was placed on each plate, a disc with 6.5 mm of A. cassiae, which were incubated at 25 °C with photoperiod of 12 hours for seven days. The EC (I)50;7d estimated was 65.97 ± 9.48 mg.L-1. In concentration of 0.0 mg.L-1 there was no growth inhibition. In 50 mg.L-1 inhibition was 29%, in 90 mg.L-1, 72%; in 130 mg.L-1, 86%; in 170 mg.L-1, 92%; in 210 mg.L-1, of 95% and in 250 m.L-1 was 94%. Thus, it is feasible using the fungus A. cassiae as the representative of microorganisms in the soil ecotoxicological tests and the potassium dichromate as reference substance. / Orientador: Robinson Antonio Pitelli / Coorientador: Claudinei da Cruz / Banca: Joaquim Gonçalves machado Neto / Banca: Pedro Antonio Zagatto / Mestre

X-ray diffraction experiments have been used to determine the structure of cesium methylsulfonate (CsCH₃SO₃), lithium hydrazinium sulfate (LiN₂H₅SO₄), above 160ºC and triclinic potassium dichromate (K₂Cr₂O₇). The solved CsCH₃SO₃ structure is compared with BaSO₄ and the CsCH₃SO₃⁻¹ ion stereochemistry is dicussed in terms of a current theory of bonding for such groups. The previously known structure of room temperature ferroelectric LiN₂H₅SO₄ has recieved additional refinement and a comparison is made with the structure determined above 160ºC. The symmetry and structure found for K₂Cr₂O₇ are compared with similar compounds and predictions are given for the yet unsolved structures of other K₂Cr₂O₇ phases. The first accurate data for the Cr₂O₇⁻² ion stereochemistry is presented. This ion is compared to similar ones, and the possibility of extending a bonding theory to such ions involving chromium is discussed. / Thesis / Doctor of Philosophy (PhD)

A produção de biodiesel em larga escala deve impulsionar a pesquisa e desenvolvimento de tecnologias mais limpas e de menor custo relacionadas à obtenção e controle de qualidade desse combustível. A extração de óleo de soja com o solvente etanol resulta na produção de uma miscela rica em óleo, semi-refinada, que pode ser diretamente esterificável para produzir ésteres etílicos, sem a necessidade de evaporação do solvente. A transesterificação de miscelas por catálise heterogênea pode adicionar os benefícios do reaproveitamento do catalisador. O objetivo deste trabalho foi promover a otimização da transesterificação de miscelas etanólicas ricas em óleo de soja sob catálise heterogênea do fosfato de potássio tribásico (K3PO4), analisar o rendimento obtido com reutilizações do catalisador recuperado e promover sua regeneração. Foi realizada a adequação de uma técnica para quantificação do teor de ésteres, envolvendo separação por cromatografia em camada delgada associada à análise de coloração por espectrofotometria. Amostras de biodiesel de teor de ésteres conhecido foram oxidadas pela ação do dicromato de potássio em ácido sulfúrico, quantificando-se a mudança de cor do reagente de laranja para verde. O dicromato ácido foi capaz de oxidar completamente a fração isolada de ésteres, determinando os teores corretamente, à variação máxima de 2,05%, estabelecendo uma relação fixa de 0,08?g de dicromato consumido para cada ?g de biodiesel. A transesterificação com K3PO4 foi otimizada, alcançando rendimentos de 96,4% nas condições de RM 1:12, catalisador 5% e agitação 400rpm em 100 minutos de reação. O K3PO4 é um catalisador prático, pois sua utilização não requer etapas de preparação, no entanto apresentou indícios de solubilização no meio reacional. Os rendimentos obtidos com catalisador reutilizado foram baixos para todos os tratamentos de lavagem, sendo a lavagem moderada o escolhido devido a menor variabilidade de massa recuperada após as reutilizações. O catalisador regenerado resultou em rendimentos de 58,72%, equivalente a 84% do obtido com catalisador novo. O K3PO4 teve sua atividade prejudicada pelos fenômenos de saponificação e emulsificação, exigindo que mudanças sejam realizadas para que sua reutilização seja viável. A utilização de catalisadores heterogêneos e miscelas etanólicas lipídicas tem o potencial para redução dos custos de produção devido a obtenção de óleo vegetal sem a necessidade de refino e ao reaproveitamento de catalisador. / Large scale biodiesel production motivates research and development of cleaner low cost technologies related to the manufacture and quality control of this fuel. The extraction of soybean oil with the solvent ethanol results in the production of a rich in oil semi-refined miscella that can be directly esterified to produce ethyl esters, without the need of solvent evaporation. The transesterification of micellae by heterogeneous catalysis can add the benefits of reusing the catalyst. The aim of this work was to promote optimization of the transesterification of ethanolic soybean oil miscellae under heterogeneous catalysis of tripotassium phosphate (K3PO4), analyze the yield of reaction with reused catalyst and promote its regeneration. A technique for quantification of the ester content involving separation with thin layer chromatography and color analysis by spectrophotometry was also performed. Biodiesel samples of known ester content were oxidized by the potassium dichromate in sulfuric acid, and the change in color of the reagent from orange to green was quantified. The acid dichromate was able to completely oxidize the isolated fraction esters, correctly determining their content with a maximum variation of 2.05%, and revealing a fixed relation of 0,08?g of dichromate consumed per ?g of biodiesel. The transesterification with K3PO4 was optimized, reaching yields of 96.4% under the conditions of 1:12 molar ratio, 5% catalyst and 400rpm stirring in 100 minutes of reaction. The use of K3PO4 does not require preparation steps, but showed evidence of solubility in the reaction medium. Yields obtained with reused catalyst were low for all treatments, being the moderate washing (LM) chosen due to lower variability of mass recovered after reuses. The regenerated catalyst resulted in yields of 58.72%, equivalent to 84% of that obtained with fresh catalyst. The K3PO4 had its activity impaired by saponification and emulsification phenomena, requiring changes to make its reuse feasible. The use of heterogeneous catalysts with ethanolic rich in oil miscellae has the potential to reduce production costs due to the production of vegetable oil without the need of refining and the reuse of solid catalyst.