Chan Sze-Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 65-73). / Abstracts in English and Chinese. / Acknowledgment --- p.i / Table of Contents --- p.ii / Abstract --- p.v / Abstract (Chinese Version) --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Molybdenum in the Environment --- p.1 / Chapter 1.1.1 --- General Chemistry of Molybdenum --- p.1 / Chapter 1.1.2 --- Molybdenum in Animals and Plants --- p.1 / Chapter 1.1.3 --- Uses of Molybdenum Compounds --- p.3 / Chapter 1.2 --- Inductively Coupled Plasma Atomic Emission Spectrometry --- p.4 / Chapter 1.2.1 --- Principle of ICP-AES --- p.4 / Chapter 1.2.2 --- Inductively Coupled Plasma Emission Source --- p.5 / Chapter 1.2.3 --- Optical System --- p.6 / Chapter 1.2.4 --- Advantages of ICP-AES --- p.7 / Chapter 1.2.5 --- Disadvantages of ICP-AES --- p.8 / Chapter 1.3 --- Preconcentration Method --- p.9 / Chapter 1.4 --- Polysiloxane --- p.11 / Chapter 1.4.1 --- Introduction of Silica-gel --- p.11 / Chapter 1.4.2 --- Introduction of Sol-gel Processes --- p.13 / Chapter 1.4.3 --- Hybrid Inorganic-organic Sol-gel Materials --- p.14 / Chapter 1.4.4 --- Advantages Using Sol-gel Preparation of Organomodified Silica --- p.16 / Chapter 1.5 --- Chelating Resin --- p.19 / Chapter 1.6 --- Scope of Work --- p.21 / Chapter Chapter 2 --- Experimental --- p.22 / Chapter 2.1 --- Apparatus and Instrument --- p.22 / Chapter 2.2 --- Chemicals --- p.24 / Chapter 2.3 --- Samples --- p.25 / Chapter 2.4 --- Procedures --- p.26 / Chapter 2.4.1 --- Preparation of Diethylenetriaminetetraacetic-acid Functionalized Polysiloxane --- p.26 / Chapter 2.4.1.1 --- Preparation of Silica Precursor --- p.26 / Chapter 2.4.1.2 --- Functionalization with Diethylenetriamine --- p.27 / Chapter 2.4.1.3 --- Carboxymethylation of the amine groups of the Polysiloxane --- p.28 / Chapter 2.4.2 --- Preconcentration and Determination of Molybdenum --- p.29 / Chapter 2.4.2.1 --- Optimum pH for Adsorption --- p.29 / Chapter 2.4.2.2 --- Amount of Polysiloxane Required for Sorption of Trace Amount of Molybdenum --- p.29 / Chapter 2.4.2.3 --- Equilibrium Time --- p.30 / Chapter 2.4.2.4 --- Total Adsorption Capacity --- p.30 / Chapter 2.4.2.5 --- Adsorption Isotherm of Molybdenum --- p.30 / Chapter 2.4.2.6 --- Desorption Studies --- p.31 / Chapter 2.4.2.7 --- Effect of Foreign Ions on Preconcentration --- p.31 / Chapter 2.4.2.8 --- Preparation of the Mini-column --- p.32 / Chapter 2.4.2.9 --- Effect of Flow Rate --- p.33 / Chapter 2.4.2.10 --- Reusability of the Mini-column --- p.33 / Chapter 2.4.2.11 --- Preconcentration Factor and Detection Limit --- p.33 / Chapter 2.4.2.12 --- Determination of Mo(VI) in Seawater by ICP-AES --- p.33 / Chapter Chapter 3 --- Results and Discussion --- p.35 / Chapter 3.1 --- Characterization of Diethylenetriaminetetraacetic-acid Functionalized Polysiloxane --- p.35 / Chapter 3.2 --- pH Dependence of Mo(VI) Ion Uptake --- p.44 / Chapter 3.3 --- Amount of Polysiloxane Required for Adsorption of Trace Amount of Mo(VI) --- p.45 / Chapter 3.4 --- Equilibrium Time --- p.46 / Chapter 3.5 --- Total Adsorption Capacity --- p.47 / Chapter 3.6 --- Adsorption Isotherm of Molybdenum --- p.48 / Chapter 3.7 --- Desorption Studies --- p.54 / Chapter 3.8 --- Effect of Foreign Ions on Preconcentration --- p.55 / Chapter 3.9 --- Effect of Flow Rate on the Recovery of Mo(VI) --- p.57 / Chapter 3.10 --- Reusability of the Column --- p.58 / Chapter 3.11 --- Preconcentration Factor --- p.59 / Chapter 3.12 --- Detection Limit --- p.59 / Chapter 3.13 --- Accuracy --- p.60 / Chapter 3.14 --- Determination of Mo(VI) in Seawater Samples --- p.61 / Chapter 3.15 --- Precision --- p.62 / Chapter Chapter 4 --- Conclusion --- p.63 / Chapter Chapter 5 --- References --- p.65

Thesis (M.S.)--Brigham Young University. Dept. of Chemistry and Biochemistry, 2004. / Includes bibliographical references.

The application of inductively coupled plasma time-of-flight mass spectrometers (ICP-TOFMS) coupled to electrothermal vaporization (ETV) presents several unique analytical opportunities for isotopic analysis. This dissertation explores several subjects that utilize these characteristics in specific analytical applications. The viability of using the thermal programming abilities of the ETV in order to separate Rb and Sr is explored. These elements are isobaric at m/z 87, and must normally be separated prior to analysis for isotopic studies. Their disparate thermal properties allow them to be separated in time by the ETV allowing for simpler, faster isotope ratio analysis with less opportunity for contamination. A test case using standard potassium feldspar is found to produce moderately accurate and precise results. TOF instruments are of interest for isotope ratio analysis due to inherent isotope ratio precision. However, it has been observed that when operated in the analog data collection mode the isotope ratios observed possess a previously uncharacterized inaccuracy. This bias is rooted in variable detection efficiency of arriving ions, which can be corrected for with an algorithm described within. A method of determining the effective detector efficiency as a function of signal is presented, as well as an evaluation of the effectiveness of ratio correction. The use of ETV with TOF for isotope dilution analysis is explored. Correction of transient signals for efficiency effects is discussed, as well as the viability of using the autosampler for mixing of the solution and spike. A final study presents explores the combination of the ETV and TOF for analysis of a large number of elements from a brief transient signal. A library of peptide covered beads is analyzed for binding capacity to a variety of metals. Solutions containing metals stripped from the beads are analyzed to determine the binding capacity and specificity of the peptide sequence. The beads themselves are also analyzed for metal content using the ETV as an indicator of the efficiency of metal stripping off of the beads. / text

published_or_final_version / abstract / toc / Chemistry / Master / Master of Philosophy

Thesis (M.Sc.) - Carleton University, 2006. / Includes bibliographical references (p. 85-86). Also available in electronic format on the Internet.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

>Magister Scientiae - MSc / The main aim of this study is to investigate theelectrochemical determination of two beneficial (selenium and zinc) and two toxic (chromium and vanadium) metals in the potable water within the City of Cape Town's distribution area. The Water Laboratory of the City's Scientific Services Branch analyses for these metals in their elemental state, using the Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). This is a standard method used for the detection of trace metals. The most sensitive voltammetric method for determining these metals is by adsorptive stripping voltammetry, using a thin mercury film electrode with a glassy carbon support. This voltammetric method is used for quantitative determination of specific ionic species. Because of mercury's toxicity it is not really favoured for trace metals anymore. Many other possibilities are under investigation, e.g. bismuth-film, modified glassy carbon and antimony electrodes. The boron-doped diamond (BDD) electrode has distinct advantages when used to determine metal concentrations. Advantages of BDD electrodes include lower detection limit, speciation and wider potential window. In this study cyclic voltammetry (CV) was used to determine the copper, cadmium and lead concentrations in potable water by means of square wave voltammetry (SWV) and a bare glassy carbon electrode (GCE). Furthermore, a boron-doped diamond electrode (BDDE) was used to investigate the possibilities of determining selenium, chromium and vanadium by SWV. Real samples (potable water samples) were analysed electrochemically to qualify and quantify these metals and determine whether they comply with the SANS 241:2006 drinking water guidelines.The copper, cadmium, lead and selenium peaks appear very close to the theoretical values, which indicate that these metals can be detected by SWV method, but further analysis with more samples is advised. Even though responses were observed for vanadium and chromium, it was not reliable and requires further investigation. Further studies into the analyses of zinc are also advised.

Le calcul des caractéristiques de détonation d’un explosif solide requiert l’utilisation d’équations d’état pour modéliser le comportement des produits de détonation. Cependant, les pressions et les températures auxquelles sont soumis ces produits rendent difficile la mise au point d’une équation d’état valide de la centaine de kilobars à la centaine de bar si l’on souhaite couvrir l’ensemble des effets d’une détonation. Les nombreuses recherches effectuées dans ce domaine ont abouti à l’élaboration d’un grand nombre d’équations d’état à caractère plus ou moins théorique ou empirique. Malheureusement aucune d’elle ne s’est révélée être entièrement satisfaisante. Dans ces travaux nous nous intéressons au domaine de validité à basse pression de l’équation d’état JWL implémentée dans les codes d’hydrodynamique et de l’équation BKW utilisée dans les codes de thermochimie pour les produits des matériaux énergétiques sous oxygénés. La première équation d’état considère le mélange des produits à une échelle macroscopique tandis que la seconde assure une description plus fine du mélange en considérant les différentes phases présentes. En effet, les produits de détonation comprennent en plus des molécules simples des particules solides de carbone. A cette fin, une étude numérique et expérimentale a été menée pour deux compositions explosives : la Composition B (RDX/TNT) et l’octoviton (HMX/Viton). Des expérimentations d’adaptation d’impédance entre des matériaux énergétiques et des matériaux inertes ont été réalisées afin de détendre les produits de détonation de la centaine de kilobars à quelques bars. Ce dispositif est instrumenté avec des métrologies innovantes dans le domaine de la détonique. La spectrométrie d’émission ultra rapide est utilisée pour effectuer l’analyse spectrale des produits de détonation au cours de leur détente dans le domaine spectral du visible. Deux signatures thermiques sont identifiées sur les spectres obtenus : l’une liée au rayonnement des gaz ionisés, l’autre liée au rayonnement des particules solides de carbone. L’interférométrie haute fréquence permet un enregistrement continu de la propagation du choc dans les différents milieux (explosif, matériau inerte). Ces expériences font l’objet de simulations numériques avec le code d’hydrodynamique Ouranos et le code de thermochimie SIAME du CEA. Les résultats expérimentaux et numériques concordent jusqu’à des pressions de l’ordre du kilobar. Ces deux mesures permettent d’avancer dans la validation de l’équation d’état des produits de détonation implémentée dans les codes numériques. / The calculation of detonation characteristics of condensed explosives requires the use of equations of state to model the behavior of the detonation products. However, the extreme pressures and temperatures of these products complicate the development of an equation of state, which is valid from hundreds of kilobars to hundreds of bars range. Numerous investigations in this field have resulted in the development of a large number of theoretical or empirical equations of state. Unfortunately, none of them have been entirely satisfactory. This work addressed the low-pressure range validity of the JWL equation of state and the BKW equation, respectively, used in hydrodynamic codes and the thermochemical codes for the products of energetic materials. The first equation of state considers the mixture of products on a macroscopic scale whereas the second one provides a more detailed description by considering the various phases of the products. The detonation products are composed of simple molecules and solid carbon particles. To this end, a numerical and experimental investigation was undertaken involving two explosive compositions: Composition B (RDX/TNT) and octoviton (HMX/Viton). Impedance matching of energetic materials with inert materials tests were performed to expand the detonation products from a hundred kilobars to a few bars. The setup was instrumented with innovative diagnostics not commonly used in detonation research: ultra-fast emission spectroscopy and high frequency interferometry. The former was used for carrying out the spectral analysis in the visible spectrum range of detonation products during their expansion. Two thermal signatures were identified in the experimental spectra: one associated with radiation from ionised gases, the other with radiation from solid particles of carbon. The latter was used to continuously record shock-wave propagation in the different media (explosive and inert materials). These experiments were simulated using the Ouranos hydrodynamic code and the SIAME thermochemical code from CEA. The experimental and numerical results were in agreement up to pressures of the order of 1 kbar. These measurements offer a set of validation points for the equations of state of detonation products implemented in numerical codes.

A água de coco é um isotônico natural, uma bebida pouco calórica e muito nutritiva, representando 1,4 % do mercado de refrigerantes e de isotônicos artificiais. Aliado ao crescente mercado interno e externo, surge os processos de conservação com o intuito de preservação da água de coco fora do fruto, facilitando a comercialização e aumentando o tempo de vida de prateleira. Considerando o pressuposto, esse trabalho teve como objetivo principal avaliar a influência dos processos de conservação, ultrafiltração, congelamento e pasteurização, na concentração de Al, Ca, Cu, Fe, K, Mg, Mn, Na, Se e Zn em água de coco. As determinações foram feitas por espectrometria de emissão óptica com plasma indutivamente acoplado e espectrometria de absorção atômica com atomização eletrotérmica. Investigação no sentido de determinar espécies livres de Se4+ e Se6+, em água de coco, por geração de hidretos e pré-concentração na superfície de um tubo de grafite modificada com Ir também foi objetivo desse trabalho. Os estudos foram realizados por meio das determinações das concentrações totais dos elementos e em diferentes frações (filtrado e resíduo), obtidas após ultrafiltração com membrana de celulose (0,100 e 0,025 µm). Em todos os processos de conservação estudados, exceto na ultrafiltração, as concentrações totais dos elementos de interesse foram preservadas. A ultrafiltração com filtro de 0,025 μm promoveu a retenção de uma quantidade significativa de Fe (30%) e Zn (50 %). A influência dos processos de conservação, com base na distribuição dos elementos de interesse, mostrou uma tendência de variação na distribuição de Cu, Fe e Zn na água de coco pasteurizada e em todos os elementos na congelada, sobretudo para aquelas com tempo de congelamento superior a 30 dias. A especiação de Se6+ e Se4+ foi feita após redução do Se6+ com 2,0 mol L-1 HCl + 1 mol L-1 KBr e aquecimento por microondas focalizadas em microfrascos, apresentando cerca de 95 % de eficiência na redução na ausência da amostra de água de coco. / The coconut water is a natural isotonic, nutritive and low caloric drink, corresponding to 1.4 % of the soft drink and artificial isotonic market store. The conservation processes of the coconut water appear in association to the expansion of the internal and external market, increasing the shelf-life of the product and its comercialization. The objective of this work was evaluate the influence of the conservation processes, such as, ultrafiltration, freezing and pasteurization based on the concentrations of Al, Ca, Cu, Fe, K, Mg, Mn, Na, Se and Zn in the coconut water. The determinations were done by inductively coupled plasma-optical emission spectrometry and electrothermal atomic absorption spectrometry. The investigation of free-species of Se4+ and Se6+, in coconut water, by hydride generation and pre-concentration on the modified graphite tube surface with Ir was also the aim of this project. The studies were carried out through the determinations of the total concentration of the interest elements and in different fractions (filtrate and residue), obtained after ultrafiltration with cellulose membrane filters (0.100 and 0.025 µm). In all processes of conservation studied, except the ultrafiltration, the total concentrations were preserved. The ultrafiltration with filters of 0.025 µm promoted the retention of significant concentration of Fe (30%) e Zn (50%). Considering the distribuituion of the interest elements, the influence of the conservation processes showed a tendency of the variation in the Cu, Fe and Zn distribuition for the pasteurized coconut water, and for all elements in the frozen, mainly for frozen samples storaged for more than 30 days. The speciation of Se4+ and Se6+ was carried out after reduction of Se6+ with 2 mol L-1 HCl + 1 mol L-1 KBr and using microvials heated in a focused microwave. The reduction efficiency of the Se6+ to Se4+ was 95 %, in absence of coconut water.

In the present work, the abnormal glow discharge at atmospheric pressure was generated in the nitrogen-methane (1 to 5 %) gaseous mixtures related to the atmosphere of Titan. The discharge itself was monitored by optical emission spectrometry that confirmed presence of active nitrogen species and various radicals formed from methane. Besides them, the CN spectral bands were observed. Intensities of all light emitting species were studied in the dependence on applied power and composition of nitrogen-methane mixture. The rotational temperature of about 2000 K was calculated from the second positive nitrogen system. The vibrational temperature also obtained from neutral nitrogen molecule increased nearly directly with methane from 3000 K (1 % CH4) to 3600 K (5 % CH4). In the contrary, vibrational temperature obtained from nitrogen molecular ion decreased with methane in the gaseous mixture and increased with applied discharge power from 3700 K to 4200 K. The same trend showed the vibrational temperature calculated from violet system of CN with value from 4600 K to 5800 K. The stable discharge products were analysed by proton transfer time of flight mass spectrometry of the exhausting gas. Presence of many aliphatic and some aromatic hydrocarbons was confirmed as well as quite a lot of amino and cyano compounds. Increasing concentrations of methane have produced more substances with higher molecular weight and less simple substances that were likely to be consumed on more complex substances. Their relative intensities were determined under the same conditions as optical emission spectra were collected.