Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 110-113).

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 129-147).

Thesis (Ph. D.)--Lund University, 1997. / Published dissertation.

Thesis (doctoral)--Lund University, 1994.

Thesis (Ph. D.)--Lund University, 1997. / Published dissertation.

Thesis (doctoral)--Lund University, 1994.

No description available.

Inspired by the need to study injectant flow patterns near the test surface, a supersonic free-jet facility was designed and constructed. This facility provides a Mach 1.95 flow over a test section area of 6.35 cm by 5.08 cm. The facility was thoroughly tested and proved that it is durable, versatile, and capable of providing repeatable test conditions. When compared to the main supersonic tunnel at VPI & SU, the free-jet facility has many advantages, including greater optical and spatial access, longer available test durations, and less time needed between tests for the storage tanks to be refilled. As a part of the project, several diagnostic techniques were evaluated in the facility. Normal, sonic injection of helium through a circular injector was studied as a way to evaluate nanoshadowgraph photography, oil flow photography, and infrared imaging as qualitative flow visualization methods. Quantitative measurements of the local helium concentration within the boundary layer were taken to evaluate the effectiveness of an existing hot-film concentration probe. The tests showed that oil flow visualization is a very effective technique in the free-jet facility, producing clear photographs that could be directly scaled. Nanoshadowgraph photography also produced clear photographs of the flow field, although this method was more difficult to implement in the free-jet facility than in the main supersonic tunnel. Finally, infrared imaging, which was not possible in the main supersonic tunnel without major hardware reconfigurations, showed great promise as a method for studying normal injection. Although the tests revealed no conclusive information about injectant flow patterns in the boundary layer, a heat transfer analysis showed that it may be possible in future studies to use this technique as a way to quantitatively measure local helium concentration at the surface. Helium concentration was measured for test cases with both air and helium injection. The measurements were taken at two axial locations with the probe positioned at a distance of 0.1 injector diameters above the test surface. The air injection tests showed helium concentration levels up to 30 percent mole fraction, which is erroneous since no helium was present in the flow. Based on these results it was concluded that the existing probe was ineffective in the free-jet facility, with an uncertainty level of no less than 25 percent mole fraction helium. The cause of the high uncertainty and overall ineffectiveness was most likely the probe calibration and data reduction methods. / Master of Science

Flow injection analysis offers distinct advantages in reproducibility, flexibility, sample throughput and cost performance. Since it was introduced in 1975, there are more than 10 000 publications to date. The present study focuses on the development of process analysers for the determination of nitrogen compounds (namely, nitrate, nitrite and protein), nickel, and phosphate in various combination in samples originating from various fields, such as foodstuffs, water, and fertilisers. Nitrite is potentially unstable; it decomposes with time under acidic medium with an increase in decomposition rate as the concentration of acid increases. Raman spectroscopy was employed as a means of determining the rate of decomposition of nitrite in solutions at various pH values. A simple method for the determination of nitrite in foodstuffs by flow injection analysis (FIA) is described. The foodstuffs containing nitrite are digested in a microwave oven and then treated with 1 moℓ/Q NH4CI solution at pH 9. The simultaneous determination of nitrate and nitrite in foodstuffs and water was also studied. Cadmium (coarse powder) was used to reduce nitrate to nitrite. The effect of pH, length of reductor column, and various types of cadmium reductor on the yield of nitrite are investigated. The flow injection method was developed for the spectrophotometric determination of nickel in cured meat. Dimethylglyoxime (DMG) in acetate buffer at pH 6.4 nickel forms a red complex which is measured at 475 nm. The effects of chemical and physical parameters in flow injection analysis were studied. A new bienzymatic amperometric sensor is proposed for the assay of proteins in milk. The sensor is based on two enzymes, namely, carboxypeptidases A and L-amino acid oxidase. The use of flow injection analysis and Raman spectroscopy for the determination of phosphate in foodstuffs and fertilisers, is also compared in this study. / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Sistemas de análises em fluxo com minibombas solenoide foram desenvolvidos para a determinação de glicerol livre e total em biodiesel e manganês em águas. Em um primeiro trabalho, glicerol livre foi determinado por espectrofotometria após oxidação com periodato, levando à formação de formaldeído, que reagiu com acetilacetona, formando o composto 3,5-diacetil-1,4-dihidrolutidina (DDL). O analito foi extraído com água, em substituição à extração utilizando solventes orgânicos. Resposta linear foi observada de 5 a 50 mg L-1, com limite de detecção estimado em 1 mg L-1 (99,7% de confiança), equivalente a 0,0004% em massa de biodiesel, valor 50 vezes menor que o limite estabelecido pelas legislações Brasileira, Norte americana e Europeia. O coeficiente de variação foi inferior a 1,5% (n = 10) e a frequência de amostragem foi estimada em 34 amostras h-1, com consumo de 340 µg de KIO4 e 15 mg de acetilacetona por determinação. A mesma reação foi explorada para detecção fluorimétrica de glicerol livre e total em biodiesel, sendo essa espécie quantificada após reação de saponificação dos mono-, di- e triglicerídeos remanescentes no biodiesel. Para a determinação de glicerol livre, resposta linear foi observada no intervalo de 5 - 70 mg L-1, com limite de detecção estimado em 0,5 mg L-1, equivalente a 0,0002% (m/m) de biodiesel, com coeficiente de variação menor que 1,0 % (n = 20). Na determinação de glicerol total, faixa linear foi observada no intervalo de 25 - 300 mg L-1, com limite de detecção de 1,5 mg L-1 e coeficiente de variação de 1,4% (n = 10). As frequências de amostragem foram de 35 e 30 amostras h-1, para glicerol livre e total, respectivamente, consumindo 190 µg de KIO4 e 13 mg de acetilacetona por determinação. Os resultados obtidos para as análises de biodiesel foram concordantes com os procedimentos de referência. A formação do complexo Mn(III)/EDTA foi explorada para a determinação de manganês em amostras de águas. Mn(II) foi oxidado em linha em um reator contendo dióxido de chumbo imobilizado em um poliéster. Espectrofotometria com longo caminho óptico foi empregada para aumento de sensibilidade, visando atender o limite máximo tolerado deste metal, estabelecido pelas legislações ambientais vigentes. Resposta linear foi observada no intervalo de 25 a 1500 µg L-1, com limite de detecção estimado em 6 µg L-1 (99,7% de confiança). Frequência de amostragem e coeficiente de variação foram estimados em 36 amostras h-1 e 2,6 % (n = 10), respectivamente, consumindo 500¨µg de EDTA por determinação. A quantidade de chumbo no resíduo corresponde a 250 µg por determinação e, com o reator empregado, é possível realizar até 1600 determinações. Interferências causadas por matéria orgânica nas amostras foram observadas e carvão ativo foi usado para remoção destes interferentes. Os resultados obtidos pelo procedimento proposto e por GF AAS foram concordantes (99,7 % de confiança). / Flow injection procedures based on solenoid micro pump were developed for free and total glycerol determination in biodiesel samples and manganese in fresh water. In a first work, free glycerol was determined by spectrophotometry, after glycerol oxidation by periodate, yielding formaldehyde, followed by formation of the colored product 3,5-diacetil-1,4-dihidrolutidine (DDL) upon reaction with acetylacetone. The analyte was extracted with water in replacement of organic solvents. A linear response was observed from 5 to 50 mg L-1, and detection limit was estimated as 1 mg L-1 (99.7% confidence level) equivalent to 0.0004% (w/w), 50 times lower than the threshold value established by Brazilian, European and American regulations. The coefficient of variation was lower than 1.5% (n=10) and sampling rate was estimated at 34 samples h-1, consuming 340 µg of KIO4 and 15 mg of acetylacetone per determination. The same reaction was exploited for fluorimetric detection of free and total glycerol in biodiesel, and glycerol total was quantified after saponification of mono-, di- and triglycerides remaining in biodiesel. To free glycerol determination a linear response was observed from 5 to 70 mg L-1, with a detection limit of 0.5 mg L-1, which corresponds to 0.0002% (w/w) in biodiesel, and coefficient of variation was lower than 1.0% (n=10). To total glycerol determination, a linear response was observed from 25 to 300 mg L-1, with a detection limit of 1.5 mg L-1, and coefficient of variation of 1.4% (n=10). The sampling rate was estimated at 35 and 30 samples h-1, to free and total glycerol, respectively. The results obtained to biodiesel samples agreed at the 95% confidence level with reference procedures. The formation of the Mn(III)/EDTA complex was exploited for manganese determination in water. Mn(II) was oxidized in a reactor containing lead dioxide immobilized on polyester. Long pathlength spectrometry was exploited to increase sensitivity, aiming to reach the threshold limit established by environmental legislation. A linear response was observed from 25 to 1500 µg L-1, with a detection limit of 6 µg L-1(99.7% confidence level). Sample throughput and coefficient of variation were 36 samples h-1 and 2.6% (n=10), respectively, consuming 500 µg of EDTA. The amount of lead in the residue corresponds to 250 µg per determination, and it is possible to perform up to 1600 measurements. Interferences by organic matter were observed and active charcoal was employed to remove the interfering species. Results were in agreement with those attained by GF AAS at the 95% confidence level.