Thesis (Ph. D.)--Lehigh University, 2006. / Includes vita. Includes bibliographical references (leaves 141-148).

Th.--Sci.--Aix-Marseille 2, 1981.

[No abstract available] / Science, Faculty of / Chemistry, Department of / Graduate

[No abstract available] / Science, Faculty of / Chemistry, Department of / Graduate

No description available.

No description available.

No description available.

M.Sc. / Inorganic pollutants like heavy metals are some of the major water pollutants worldwide. They are toxic and in some cases carcinogenic even at low concentrations. Their removal from industrial aqueous solutions, wastewater and hydrometallurgical process solutions prior to their release to the environment is necessary for a healthy biosphere which includes human beings, aquatic life and plants. There are several technologies used to remove metals such as Cu, Co, Zn, Hg from water. These include among others, ion exchange, membrane filtration, activated carbon, electrochemical treatment, chemical precipitation, reverse osmosis, coagulation and flocculation. Although they have been used in the removal of metal pollutants from water, these technologies produce high quantities of sludge. They are also expensive to operate and need well trained personnel to operate large chemical plants. Since current metal removal techniques have limitations, a need exists for the development of environmentally friendly and cost effective techniques for the removal of metal ions from aqueous media. The focus of this research project is on the use of micro-organisms as biosorbents for copper and cobalt pollutants in aqueous solutions. The experimental work was carried out on a laboratory scale and a summary of our findings is presented as follows: Synthetic sulphate solutions of copper and cobalt were prepared using CuSO4. 7H2O and CoSO4. 5H2O powders. Concentrations of 0.002 M, 0.07 M and 0.2 M copper and cobalt ions in solution were used as test synthetic solutions for our experiments. Mixed strains of bioleaching bacteria were sourced from Mintek (Randburg, South Africa) to test the viability of this research project. This consortium contained Acidithiobacillus caldus, Leptospirillum spp, Ferroplasma spp and Sulphobacillus spp. These bacteria were able to remove up to 55% copper and 25% cobalt from low concentrated copper and cobalt sulphate solutions with 69% and 58% removal demonstrated in the case of mine effluents emanating from metallurgical operations. Different strains of micro-organisms (bacteria) were isolated from mine dumps and mine operation effluents and soil from the Palabora Mining Company in Limpopo, a northern province in South Africa and Nigel Town in the Gauteng Province. The isolated bacterial strains were then identified using PCR analysis and strains from the Bacillus genre were found to be predominant. Shewanella spp was also present. Pseudomonas spp was isolated using Pseudomonas agar base. These bacteria were then cultured at different species-specific culture conditions and their capabilities to remove copper and cobalt ions first from synthetic solutions and subsequently from mine effluents emanating from metallurgical operations were tested. In the first stage of biosorption experiments, factors that affect biosorption mechanisms which include, solution concentration, biomass concentration, pH, contact time and the presence of other metal co-ions were investigated. A decrease in the amount of metal sorbed as solution concentrations increased was observed with all the bacterial strains. An increase in metal sorption was also observed when biomass concentration was increased. The pH was found to be a species dependant parameter.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. Johannesburg, October 2016. / The adsorption of molecules on a metal surface is core in heterogeneous catalysis. Surface sensitive techniques such as low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) are key tools to study adsorption geometries and structures of molecules and atoms on a metal surface. As our first model system we investigated the dissociation of NO on Ir{100}. The LEED experimental results showed a p(2 X 2) diffraction pattern at 300 K using. In this study two options were explored: phase mixing where dissociated nitrogen and oxygen are on the same unit cell, as well as phase separation where both nitrogen and oxygen form their own separate unit cell which results in a p(2 x 2) unit cell. Calculations were done on atop, bridge and hollow sites, with only perpendicular parameters and vibrational amplitude being varied initially. Results for phase mixing calculations gave the lowest R-factor of 0.70 ± 0.11 for atop site. We further considered phase separation for hollow and bridge sites for nitrogen and oxygen respectively because these two sites were found to be the most stable sites using DFT from previous studies. The lowest R-factors were 0.37 ± 0.06 for nitrogen c(2x2) and 0.24 ± 0.13 for oxygen p(2 X 1) For oxygen significant row pairing of iridium atoms stabilized the structure as mentioned in previous studies. Therefore from our results it is evident that phase separation models the experimental data better than phase mixing. Nitrogen and oxygen form c(2 X 2) and p(2 X 1) overlayer structures respectively which in combination result in a p(2 X 2) pattern that is in agreement with experimental results. The second system involves enantio-selectivity and chiral resolution at the organic-inorganic interfaces. The d-serine molecule was adsorbed on the Cu{110} surface. Density functional theory (DFT) calculations were used as a benchmark for our CLEED calculations. LEED experiments showed a (- 1 + 2: 40) overlayer pattern for d-serine adsorbed on Cu{110} surface. Three structures from DFT calculations with the lowest energy were used for CLEED calculations. These structures differed by the way they bond to the surface and molecular interactions. Calculations were carried out on these three structures and the structure with intra-dimer bonding was the best structure. The searches for this structure were further optimized by introducing pairing of the atoms in the row reconstruction on the copper surface and angle search. The lowest value obtained was 0.37 ± 0.09, which suggests that further understanding of this system is needed. The ultra-high vacuum (UHV) chamber was fully commissioned and is now ready for TPD and XPS studies. / LG2017

La compréhension des phénomènes d’adsorption de gaz en présence d’eau dans des milieux confinés est une problématique importante tant d’un point de vue fondamental que du point de vue des applications industrielles Les travaux menés dans cette thèse ont principalement porté sur le développement d’un nouveau couplage NLDFT/SAFT-VR (Non-Local Density Functional Theory/ Statistical Associating Fluid Theory for potentials of Variable Range) pour modéliser les propriétés interfaciales et l’adsorption de méthane, d’eau et de leur mélange en milieu confiné. Les résultats théoriques obtenus sur ces fluides ont été comparés avec succès à des calculs de simulation moléculaire. Par ailleurs, des isothermes d’adsorption expérimentales de méthane et d’eau sur des charbons actifs ont été mesurées par la technique gravimétrique sur une balance à suspension magnétique. Afin de pouvoir comparer les isothermes expérimentales et théoriques, il est nécessaire de connaître la distribution en taille de pore des solides poreux. C’est pourquoi un nouveau modèle thermodynamique de caractérisation des milieux microporeux a été développé. Les comparaisons des isothermes d’adsorption de méthane ont montré un excellent accord entre résultats théoriques et expérimentaux. / Understanding the gas/water adsorption phenomena in confined media is an important issue from a fundamental point of view and for industrial applications. The main aim of this thesis was to develop a new NLDFT/SAFT-VR coupling (Non-Local Density Functional Theory/ Statistical Associating Fluid Theory for potentials of Variable Range) to model the interfacial properties and the adsorption of methane, water and their binary mixture in porous media. A successful comparison was found between theoretical results from this model and molecular simulation calculations. Moreover, experimental adsorption isotherms of methane and water were measured on activated carbons by gravimetric method on a magnetic suspension balance. In order to compare experimental and modeled adsorption isotherms, it is necessary to get the pore size distribution of the porous solids. To do this, a new thermodynamic model for the characterization of microporous media was developed. The comparison between adsorption isotherms of methane has shown an excellent agreement between theoretical results and experimental measurements.