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<p> The nature of the coloured solutions of selenium and tellurium in sulfuric acid has been investigated using mainly cryoscopic, conductimetric, and spectrophotometric techniques. Evidence has been obtained for the new species Se₈²⁺ and Se₄²⁺ in the green and yellow solutions of selenium respectively. Evidence on red solutions of tellurium seems consistent with the formulation Te₄²⁺. Solid compounds analysing as Se₄S₄O₁₃, Se₄(HS₂O₇)₂ and TeO(HS₂O₇)₂ have been prepared and characterised. </p> <P> Solutions of some selenium(IV) and selenium(VI) compounds have been examined. It is shown that a number of phosphates and arsenates ionise in sulfuric acid to give the P(OH)₄⁺ and As(OH)₄⁺ ions respectively. Ammonium metavanadate and vanadium pentoxide ionise to give the complex acid H[VO(HSO₄)₄]. Potassium chromate and dichromate ionise to give the compound CrO₂(HSO₄)₂ and potassium permanganate ionises to give the non-electrolyte MnO₃∙SO₄H. </p> / Thesis / Doctor of Philosophy (PhD)

<p> The preparation of compounds containing polyatomic cations of sulphur, selenium and tellurium has been investigated by using oxidising agents such as AsF5, SbF5, S2O6F2 and SO3. New compounds, containing polyatomic cations Se8 2+, Se4 2+, Te3n n+, Te4 2+ Ten n+, S16 2+, S8 2+ and S4 2+, and anions of very strong acids such as Sb2F11- and AsF6- were isolated and characterised by a combination of the stoichiometry of the preparation reactions, UV-visible spectrophotometry, Infrared and Raman spectroscopy and magnetic susceptibility measurements.</p> <p> Solutions of sulphur in various concentrations of oleum were investigated in detail by UV-visible spectrophotometry and e.s.r. spectroscopy. Evidence is presented for the formation of the sulphur cations S16 2+, S8 2+ and S4 2+ in these media, and for the presence of low concentrations of the radical cations S8+ and S4+.</p> / Thesis / Doctor of Philosophy (PhD)

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Le sélénium et le tellurium partagent des propriétés chimiques communes et appartiennent à la colonne des éléments chalcogènes de la classification périodique des éléments. Ces métalloïdes ont des propriétés physico-chimiques remarquables et ils ont été utilisés dans un grand nombre d'applications dans le domaine des hautes technologies (électronique, semi-conducteurs, alliages). Ces éléments, qui se retrouvent généralement sous formes d'oxyanions, sont extrêmement solubles dans l'eau et présentent une forte toxicité. Leur libération dans l'environnement est donc d'un enjeu capital. Différentes méthodes physico-chimiques ont été développées pour la récupération de ces metalloïdes, en particulier pour le sélénium. Néanmoins, ces méthodes requièrent un équipement lourd et couteux et ne sont pas très recommandables sur le plan écologique. Le traitement biologique est donc une bonne alternative pour la récupération de Se et de Te provenant des effluents pollués. Cette approche réside dans la bioréduction des différents oxyanions sous formes métalliques. Ceux-ci sont moins toxiques et d'intérêts commerciales notables surtout lorsqu'ils se présentent sous forme nanométrique. L'utilisation de micro-champignons comme microorganismes catalyseur de la réduction de Se et de Te a été démontrée dans cette étude. La réactivité du champignon responsable de la pourriture blanche, Phanerochaete chrysosporium en présence de sélénite et de tellurite a été évaluée, ainsi que son application potentielle pour le traitement des eaux contaminées et la production de nanoparticules. La présence de Se et de Te a une influence importante sur la croissance et la morphologie du champignon. Il s'avère que P. chrysosporium est très sensible à la présence de sélénites. La synthèse de Se° et de Te° sous forme de nanoparticules piégées dans la biomasse fongique a été observée, ainsi que la formation de nano-composites Se-Te lorsque le champignon était cultivé simultanément en présence des deux métalloïdes. L'usage potentiel de biofilm fongiques pour le traitement des effluents semi-acides (pH 4.5) contenant du Se et du Te a été suggéré. De plus, le traitement en mode continu de sélénite dans un réacteur à biofilm fongique granulaire a été évalué. Le réacteur a montré un rendement d'élimination du sélénium en régime permanent de 70% pour differentes conditions opératoires. Celui-ci s'est montré efficace pendant une période supérieure à 35 jours. La bonne sédimentation du biofilm granulaire facilite la séparation du sélénium de l'effluent traité. L'utilisation du biofilm granulaire contenant du sélénium élémentaire comme bio-sorbant a également été étudiée. Cet adsorbant hybride s'est montré prometteur pour l'immobilisation du zinc présent dans les effluents semi-acides. La plupart des recherches effectuées se sont focalisées sur l'utilisation des biofilms granulaires. Toutefois, la croissance du champignon suite à l'exposition à des concentrations différentes de sélénites a également été étudiée. Des micro-électrodes à oxygène et un microscope confocal à balayage laser ont été utilisées pour évaluer l'effet du sélénium sur la structure des biofilms fongiques. Quel que soit le mode de croissance de P. chrysosporium, le mécanisme de réduction du sélénite semble être toujours le même tout en menant à la formation de sélénium élémentaire. Cependant, l'architecture des biofilms et l'activité en oxygène sont influencées par la présence de sélénium / Selenium (Se) and tellurium (Te) are particular elements, they are part of the chalcogens (VI-A group of the periodic table) and share common properties. These metalloids are of commercial interest due to their physicochemical properties, and they have been used in a broad range of applications in advanced technologies. The water soluble oxyanions of these elements (i.e., selenite, selenate, tellurite and tellurate) exhibit high toxicities, thus their release in the environment is of great concern. Different physicochemical methods have been developed for the removal of these metalloids, mainly for selenium. However, these methods require specialized equipment, high costs and they are not ecofriendly. The biological treatment is a green alternative to remove Se and Te from polluted effluents. This remediation technology consists on the microbial reduction of Se and Te oxyanions in wastewater to their elemental forms (Se0 and Te0), which are less toxic, and when synthesized in the nano-size range, they can be of commercial value due to their enhanced properties. The use of fungi as potential Se- and Te-reducing organisms was demonstrated in this study. Response of the model white-rot fungus, Phanerochaete chrysosporium, to the presence of selenite and tellurite was evaluated, as well as their potential application in wastewater treatment and production of nanoparticles. The presence of Se and Te had a clear influence on the growth and morphology of the fungus. P. chrysosporium was found to be more sensitive to selenite. Synthesis of Se0 and Te0 nanoparticles entrapped in the fungal biomass was observed, as well as the formation of unique Se-Te nanocomposites when the fungus was cultivated concurrently in the presence of Se and Te. Potential use of fungal pellets for the removal of Se and Te from semi-acidic effluents (pH 4.5) was suggested. Moreover, the continuous removal of selenite in a fungal pelleted reactor was evaluated. The reactor showed to efficiently remove selenium at steady-state conditions (~70%), and it demonstrated to be flexible and adaptable to different operational conditions. The reactor operated efficiently over a period of 35 days. Good settleability of the fungal pellets facilitated the separation of the selenium from the treated effluent. The use of elemental selenium immobilized fungal pellets as novel biosorbent material was also explored. This hybrid sorbent was promising for the removal of zinc from semi-acidic effluents. The presence of selenium in the fungal biomass enhanced the sorption efficiency of zinc, compared to Se-free fungal pellets. Most of the research conducted in this study was focused on the use of fungal pellets. However, the response of the fungus to selenite in a different kind of growth was also evaluated. Microsensors and confocal imaging were used to evaluate the effects of selenium on fungal biofilms. Regardless of the kind of fungal growth, P. chrysosporium seems to follow a similar selenite reduction mechanism, leading to the formation of Se0. Architecture of the biofilm and oxygen activity were influenced by the presence of selenium

>Magister Scientiae - MSc / Tellurium is a member of the chalcogen group in the periodic table and is known to be a better semiconductor material when compared to sulfur and selenium. By introducing tellurium into the kesterite structure there would be an improvement in the semiconducting property of the kesterite material. This research focused on incorporating tellurium into kesterite structure in order to reduce its band-gap thereby improving its light absorption and ultimately lead to a more efficient photovoltaic effect. For a typical synthesis, kesterite nanoparticles were synthesized by anion hot injection process which involved the injection of the anion precursor comprising of sulfur, selenium and tellurium in diethylene glycol into a solution containing the cation precursor which are copper (II) chloride, Zinc chloride and tin (II) chloride which are dissolved in diethylene glycol. The synthesized nanoparticles were copper zinc tin sulfide (CZTS), copper zinc tin sulfide selenide telluride (CZTSSeTe) and copper zinc tin sulfide telluride (CZTSTe). Morphological characterization of the synthesized nanoparticles was carried out by high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM) to obtain the shape of the surface and internal structure of the nanoparticles respectively. The micrograph obtained from HRSEM shows that all synthesized nanoparticles had a flower-like surface appearance which is a common morphology obtained for non-vacuum synthesized kesterite nanoparticles. The micrograph obtained from TEM showed that all nanoparticles were agglomerated and had a black surface covering which attributable to the solvent used during synthesis, washing and centrifugation. The internal structure of the synthesized nanoparticles was obtained through small angle x-ray scattering (SAXS) plot of the shapes. The shape obtained for the nanoparticles were core shell hollow sphere for CZTS, core shell dumb-bell for CZTSSeTe and solid sphere for CZTSTe.

There are a number of impurity elements present in sulphide ores that can have a deleterious effect on the properties of the final copper metal product. In this thesis, an equilibrium distribution technique was used to determine the thermodynamic behaviour of selenium and tellurium in molten slags used in copper production. Calcium ferrite based slags and copper or silver alloy were equilibrated in magnesia crucibles at temperatures of 1200 to 1400 °C and oxygen partial pressures of 10-11 to 10-0.68 atm. Under conditions typical of those employed during copper converting, the minor elements were found to enter the slag as negatively charged species. The partitioning of selenium and tellurium to the slag was greatest at high temperature, low oxygen partial pressure and at highest concentration of basic oxide (CaO or BaO). The experimentally derived data were combined with published information to calculate the selenide and telluride capacities of the slag, and also to generate fundamental thermodynamic activity data for selenium and tellurium in the slag phase. It was found that the activity coefficients of selenium and tellurium were independent of their concentration in the slag over the range studied, but were strongly dependent on the temperature, slag chemistry and oxidation state of the slag. Experiments were also designed and carried out to determine what effect the presence of iron oxide and its oxidation state has on the behaviour of selenium in the slag. A series of experiments involving iron oxide additions to a calcium aluminate slag was conducted under increasingly oxidising conditions to assess the effect of total iron on the selenide capacity as the dominant oxidation state of iron in the slag changed. It was shown that at a constant ratio of CaO:Al2O3, the selenide capacity increased with total iron in the slag. However, the effect on the selenide capacity did not appear any more significant as the Fe3+:Fe2+ ratio changed in a particular direction. 4 Another series of experiments was carried out with iron calcium silicate slags to determine the stability of phases within the slag, and how this affected the equilibrium distribution and activity coefficient of selenium in the slag. A number of solid phases were identified and their composition determined by scanning electron microscopy, energy dispersive spectroscopy and electron microprobe analysis. The composition and minor element content of the remaining liquid was calculated using a thermodynamic model. From this it was found that the capacity of the liquid slag has a region of independence against slag chemistry, before increasing strongly with increasing lime content to the calcium ferrite composition. Some of the implications of this work are discussed with reference to the practicality of adjusting the process variables in a large-scale industrial process for the purpose of managing minor element content of the molten phases. Considerations include the effect on copper recovery and rate of wear of furnace refractory materials.

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