Iron is the most common impurity in hydrometallurgy which is usually removed by precipitation of insoluble iron compounds, such as hematite and jarosite. The knowledge of iron solubility in multicomponent solutions is important for design and optimization of the iron removal steps. The OLI Software package is a chemical modeling tool that incorporates the powerful mixed-solvent electrolyte (MSE) model capable of performing simulations of multicomponent electrolyte solutions from the freezing point up to the limit of fused salt and near the critical temperature of the solution. Literature or experimental solubility data was fitted on the OLI MSE model to improve the performance in simulating multicomponent Fe(II)/Fe(III) solutions. The particular focus of this work aimed at developing simulation capability for the FeCl3-MgCl2-HCl-H2O system through experimental solubility measurement and modeling, relevant to atmospheric processing of saprolites by HCl using MgCl2 brines.

Iron is the most common impurity in hydrometallurgy which is usually removed by precipitation of insoluble iron compounds, such as hematite and jarosite. The knowledge of iron solubility in multicomponent solutions is important for design and optimization of the iron removal steps. The OLI Software package is a chemical modeling tool that incorporates the powerful mixed-solvent electrolyte (MSE) model capable of performing simulations of multicomponent electrolyte solutions from the freezing point up to the limit of fused salt and near the critical temperature of the solution. Literature or experimental solubility data was fitted on the OLI MSE model to improve the performance in simulating multicomponent Fe(II)/Fe(III) solutions. The particular focus of this work aimed at developing simulation capability for the FeCl3-MgCl2-HCl-H2O system through experimental solubility measurement and modeling, relevant to atmospheric processing of saprolites by HCl using MgCl2 brines.

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This thesis is missing pages 9, 39, 108-110. The pages are not in the other copies of the thesis. -Digitization Centre / This work describes efforts towards creating chemical models for a variety of zinc based metalloenzymes. A background on the current progress of modeling zinc enzymes is presented, as is a brief review of zinc biochemistry. The structure of triaquo(tris-2-pyridylphosphine)nickel(ll) dinitrate is presented and compared with its zinc analogue. Both structures have octahedral geometry with no unusual bond lengths. The synthesis and characterization of bis(2,4,5-tribromoimidazole)(diaquo)zinc(II). (II) is also presented in this work. A similar compound, Zn(Im)2 (III) was also prepared in this work. Both compounds were characterized by X-ray crystallography, IR spectroscopy, and elemental analysis. Neutron crystallography was used to characterize (II) as a peraquo species. Both (II) and (III) possess tetrahedral geometry about the zinc atom. (III) is multiply catenated and cannot be considered as a discrete molecular species. The pKa2 of 2,4,5-tribromoimidazole, the organic ligand in (II), was measured and found to be 10.7(2). Bond valence theory was used to analyze (II). Extended Huckel molecular orbital calculations were carried out on (II). (II) was compared with a variety of other zincimidazole compounds. It was discovered that (II) has unusually small carbon-nitrogen-carbon angles within its tribromoimidazole rings. It is uncertain whether this feature is because of the coordination of the tribromoimidazole rings to the zinc atom, or whether it is an inherent feature of the tribromoimidazole rings. A copper analogue of (II) has also been synthesized and has been tentatively assigned the formula Cu(lmBr3)2(OH2)2 . X-ray characterization of this compound has not yet been accomplished. / Thesis / Master of Science (MS)

In the present thesis, the reaction mechanisms of several di-zinc hydrolases have been explored using quantum chemical modeling of the enzyme active sites. The studied enzymes are phosphotriesterase (PTE), aminopeptidase from Aeromonas proteolytica (AAP), glyoxalase II (GlxII), and alkaline phosphatase (AP). All of them contain a binuclear divalent zinc core in the active site. The density functional theory (DFT) method B3LYP functional was employed in the investigations. The potential energy surfaces (PESs) for various reaction pathways have been mapped and the involved transition states and intermediates have been characterized. The hydrolyses of different types of substrates were examined, including phosphate esters (PTE and AP) and the substrates containing carbonyl group (AAP and GlxII). The roles of zinc ions and individual active-site residues were analyzed and general features of di-zinc enzymes have been characterized. The bridging hydroxide stabilized by two zinc ions has been confirmed to be capable of the nucleophile in the hydrolysis reactions. PTE, AAP, and GlxII all employ the bridging hydroxide as the direct nucleophile. Furthermore, it is shown that either one of or both zinc ions provide the main catalytic power by stabilizing the negative charge developing during the reaction and thereby lowering the barriers. In the cases of GlxII and AP, one of zinc ions also contributes to the catalysis by stabilizing the leaving group. These features perfectly satisfy the two requisites for the hydrolysis, i.e. sufficient nucleophilicity and stabilization of charge. A competing mechanism, in which the bridging hydroxide acts as a base, was shown to have significantly higher barrier in the case of PTE. For phosphate hydrolysis reactions, it is important to characterize the nature of the transition states involved in the reactions. Associative mechanisms were observed for both PTE and AP. The former uses a step-wise associative pathway via a penta-coordinated intermediate, while the latter proceeds through a concerted associative path via penta-coordinated transition states. Finally, with PTE as a test case, systematic evaluation of the computational performance of the quantum chemical modeling approach has been performed. This assessment, coupled with other results of this thesis, provide an effective demonstration of the usefulness and powerfulness of quantum chemical active-site modeling in the exploration of enzyme reaction mechanisms and in the characterization of the transition states involved. / QC 20100715 / Quantum Chemical Modeling of Binuclear Zinc Enzymes

Chemical modeling has become an important subject of research in applied thermodynamics for designing, developing, optimizing and controlling of different industrial processes. In this work, a new database for successful modeling of solid-aqueous phase equilibria in specific hydrometallurgical processes was developed using the Mixed Solvent Electrolyte (MSE(H3O+)) model of the OLI Systems software. The ionic interaction parameters between dominant species in the solution were determined by fitting available binary and ternary experimental data such as mean activity, heat capacity and solubility data; then they were validated in multi-component systems. Developed model predicted the phase behaviour in ammoniacal solutions containing cobalt, nickel, copper, and zinc in the Copper Boil process. New sets of double-salt solubility data were measured and used for accuracy validation of the model. Using HSC 6.1 software linked with MSE model, the copper boil processes was simulated successfully to provide some practical recommendations for the optimum process operation.

Chemical modeling has become an important subject of research in applied thermodynamics for designing, developing, optimizing and controlling of different industrial processes. In this work, a new database for successful modeling of solid-aqueous phase equilibria in specific hydrometallurgical processes was developed using the Mixed Solvent Electrolyte (MSE(H3O+)) model of the OLI Systems software. The ionic interaction parameters between dominant species in the solution were determined by fitting available binary and ternary experimental data such as mean activity, heat capacity and solubility data; then they were validated in multi-component systems. Developed model predicted the phase behaviour in ammoniacal solutions containing cobalt, nickel, copper, and zinc in the Copper Boil process. New sets of double-salt solubility data were measured and used for accuracy validation of the model. Using HSC 6.1 software linked with MSE model, the copper boil processes was simulated successfully to provide some practical recommendations for the optimum process operation.

A suite of lightning strike glasses and unmelted starting materials has been studied by electron microscope and Mossbauer spectroscopy to determine Fe oxidation states. Nine of eleven samples are reduced compared to the starting materials; four of the glasses contain Fe0. Only one sample contained evidence of reduction by carbon, and the results support the reduction of Fe as intrinsic to the rapid, high temperature processing during lightning strikes.A thermodynamic modeling code is used to model the formation of moldavite tektites and the reduction of Fe from sediments around the Ries crater. During isentropic cooling from a strong shock, Fe3+ is reduced to Fe2+ at all modeled conditions. The best matches to an average moldavite composition and the compositions of the Bohemian and Bohemian:Radomilice sub-strewn fields occur with a mixture of surface and subsurface sands along a 4500 J/kg-K isentropic cooling path, consistent with an asteroid impact. The Lusatian and Moravian sub-strewn fields are better represented by starting materials of entirely surface sands, consistent with the uppermost layers of surface material having traveled the farthest from the impact.The thermodynamic code is also used to investigate the formation of lunar regolith agglutinates and reduction of Fe to Fe0. Forming Fe0 requires assuming Fe0 is miscible in silicate liquid at elevated temperatures and pressures. When Fe0 is included in the liquid solution, it is stable at modeled conditions. Simple separation of liquid from vapor is not sufficient to reproduce agglutinate glass. When the vapor phase is allowed to partially redeposit and some Fe0 is directly condensed from vapor, the resulting liquid better reproduces mare agglutinate glasses. This model cannot reproduce highland agglutinate glass, because the Al concentration remains too high in the liquid. The best match to mare glass is produced using the <10 µm fraction of the mare soil along the 8000 J/kg-K cooling isentrope at 100 bars, 4370 K with 95% vapor redeposition and 50% of the Fe(g) directly condensed as Fe0. The reduced fulgurite samples and the results of the impact models suggest that Fe reduction is intrinsic to the rapid, high temperature processing of silicates.

Les rayons cosmiques (RC) ont un rôle fondamental sur la dynamique et l'évolution chimique des nuages moléculaires interstellaires, qui sont le lieu de formation stellaire et planétaire. Les RC sont probablement accélérés dans les enveloppes en expansion des rémanents de supernova (SNR), ainsi les nuages moléculaires situés à proximité peuvent être soumis à d'intenses flux de RC. Les protons relativistes ont principalement deux effets sur les nuages moléculaires : 1) en rencontrant le milieu dense, les protons de haute énergie (>280 MeV) induisent via la désintégration des pions l'émission de photons gamma. à cause de ce processus, les associations SNR-nuages moléculaires sont des sources intenses d'émission GeV et/ou TeV présentant des spectres similaires à celui des protons incidents. 2) à plus basse énergie, les RC pénètrent le nuage et ionisent le gaz, induisant la formation d'espèces moléculaires caractéristiques appelées traceurs de l'ionisation. L'étude de ces traceurs permet de déduire des informations sur les RC de basse énergie inaccessibles aux autres méthodes d'observation. J'ai étudié l'ionisation des nuages moléculaires par les RC près de trois SNR : W28, W51C et W44. Il existe des preuves observationnelles d'interaction avec le nuage voisin pour chaque SNR (présence de gaz choqué, masers OH, émission gamma). Mon travail repose sur la comparaison d'observations millimétriques des traceurs de l'ionisation à des modèles de chimie appliqués à ces nuages denses. Dans chaque région, nous avons déterminé un taux d'ionisation supérieur à la valeur standard, confortant l'hypothèse d'une origine des RC dans l'enveloppe du SNR voisin. L'existence d'un gradient d'ionisation en s'éloignant de l'onde de choc du SNR apporte des contraintes précieuses sur les propriétés de propagation des RC de basse énergie. La méthode utilisée repose sur l'observation des ions moléculaires HCO+ et DCO+, qui montre des limitations importantes à haute ionisation. C'est pourquoi j'ai également cherché à identifier des traceurs alternatifs de l'ionisation, par un effort croisé de modélisation et d'observation. En particulier, dans la région W44, les observations de N2H+ ont permis de mieux contraindre les conditions physiques, les abondances volatiles dans le nuage et l'état d'ionisation du gaz. Ce projet de recherche a amené une meilleure compréhension de la chimie induite par les RC dans les nuages moléculaires. Il a également ouvert de nouvelles perspectives de recherche interdisciplinaire vers la compréhension des RC, des observations millimétriques aux observations gamma. / Cosmic rays (CR) are of tremendous importance in the dynamical and chemical evolution of interstellar molecular clouds, where stars and planets form. CRs are likely accelerated in the shells of supernova remnants (SNR), thus molecular clouds nearby can be irradiated by intense fluxes of CRs. CR protons have two major effects on dense molecular clouds: 1) when they encounter the dense medium, high-energy protons (>280 MeV) create pions that decay into gamma-rays. This process makes SNR-molecular cloud associations intense GeV and/or TeV sources whose spectra mimic the CR spectrum. 2) at lower energies, CRs penetrate the cloud and ionise the gas, leading to the formation of molecular species characteristic of the presence of CRs, called tracers of the ionisation. Studying these tracers gives information on low-energy CRs that are unaccessible to any other observations. I studied the CR ionisation of molecular clouds next to three SNRs: W28, W51C and W44. These SNRs are known to be interacting with the nearby clouds, from the presence of shocked gas, OH masers and pion-decay induced gamma-ray emission. My work includes millimeter observations and chemical modeling of tracers of the ionisation in these dense molecular clouds. In these three regions, we determined an enhanced CR ionisation rate, supporting the hypothesis of an origin of the CRs in the SNR nearby. The evolution of the CR ionisation rate with the distance to the SNR brings valuable constraints on the propagation properties of low-energy CRs. The method used relies on observations of the molecular ions HCO+ and DCO+, which shows crucial limitations at high ionisation. Therefore, I investigated, both through modeling and observations, the chemical abundances of several other species to try and identity alternative tracers of the ionisation. In particular, in the W44 region, observations of N2H+ bring additional constraints on the physical conditions, volatile abundances in the cloud, and the ionisation state. This research brought valuable insight into the CR induced chemistry in the interstellar medium. It also brought new perspectives of interdisciplinary research towards the understanding of CRs, from millimeter to gamma-ray observations.

Irrigation of the municipal cemetery in Brigham City, Utah resulted in stained headstones in 2001 and 2002. The water used in the irrigation came from Mantua reservoir, a medium sized impoundment situated near the mouth of Box Elder Canyon. In order for Brigham City to establish a city wide secondary pressurized irrigation system using water from Mantua reservoir, the cause and the source of staining problem must be determined. Previous research (Wallace 2006) determined that the source of the staining was the reduction of iron found in Mantua Reservoir sediments that occurred when seasonal variations in the reservoir caused anaerobic conditions. The reduced iron then dissolved in the water and was used in the irrigation system, causing re-oxidation of the iron. The oxidized iron then precipitated out on the headstones causing the staining. The purpose of this investigation is to determine the iron oxidation kinetics after the re-aeration of the water which will help determine appropriate mitigation methods. A secondary purpose is to confirm the Mantua reservoir's capacity to become anaerobic, resulting in the conditions which cause staining. Using laboratory investigations and computer modeling, I determined that on re-aeration, fifty percent of the dissolved iron in the water precipitates in five hours. Using first-order kinetics to model this process, I found the rate constant of the kinetic reaction to be 0.0029 min-1. Fitting a geochemical computer model of the iron oxidation kinetics in Mantua reservoir, which uses a higher-order kinetics model to better model this process, to experimental kinetic data yielded a rate constant of 4x1013 /atm x min. I also recreated the staining process in the laboratory using concrete. This was successful and provided visual evidence that the iron precipitates out of the water and stained the concrete within a couple of hours of application. Field data collected from Mantua reservoir showed that the dissolved oxygen concentration in the reservoir drops regularly below levels consistent with equilibrium to the atmosphere. While my field measurements did not record anaerobic conditions, based on the patterns shown, this study shows that it would be possible for anaerobic conditions to occur during warmer weather.