Metals in industrial settings such as power plants are often subjected to high temperature and pressure aqueous environments, where failure to control corrosion compromises worker and environment safety. For instance, zircaloy (1.2-1.7 wt.% Sn) fuel rods are exposed to aqueous 250-310 oC coolant in CANDU reactors. The Pourbaix (EH-pH) diagram is a plot of electrochemical potential versus pH, which shows the domains of various metal species and by inference, corrosion susceptibility. Elevated temperature data for tin +II and tin +IV species were obtained using solid-aqueous phase equilibria with the respective oxides, in a batch vessel with in-situ pH measurement. Solubilities, determined via spectroscopic techniques, were used to calculate equilibrium constants and the Gibbs energies of Sn complexes for E-pH diagram construction. The SnOH3+ and Sn(OH) species were incorporated, for the first time, into the 298.15 K and 358.15 K diagrams, with novel G ͦ values determined at 358.15 K. / UOIT

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Total lead release in drinking water in the presence of free chlorine and chloramine residuals was investigated in field, laboratory and fundamental investigations for finished waters produced from ground (GW), surface (SW), saline (RO) and blended (B) sources. Field investigations found more total lead was released in the presence of chloramines than in the presence of free chlorine for RO and blended finished waters; however, there were no statistical differences in total lead release to finished GW and SW. Laboratory measurements of finished waters oxidation-reduction potential (ORP) were equivalent by source and were not affected by the addition of more than 100 mg/L of sulfates or chlorides, but were significantly higher in the presence of free chlorine relative to chloramines. Development of Pourbaix diagrams revealed the PbO2 was the controlling solid phase at the higher ORP in the presence of free chlorine and Pb3(CO3)2(OH)2(s) (hydrocerussite) was the controlling solid phase in the presence of chloramines at the lower ORP, which mechanistically accounted for the observed release of total lead as PbO2 is much less soluble than hydrocerussite. The lack of differences in total lead release to finished GW and SW was attributed to differences in water quality and intermittent behavior of particulate release from controlling solid films.

Motor car exhaust catalysts are some of the most important users of platinum, and much attention is given to the recycling of scrap platinum from spent exhaust systems. The dissolution of platinum from waste exhausts was previously only possible by pyrometallurgical processes or by the use of aggressive chemicals, such as aqua regia and cyanide, all of which, however, cause pollution problems. Recently the potential for the development of hydrometallurgical processes was identified. These processes are more efficient and more environmentally friendly than traditional processes. It was the aim of this study to investigate the oxidation of platinum with ozone as oxidizing agent in the presence of chloride as complexing agent. The influence of various factors, such as chloride ion concentration, pH and temperature were studied thermodynamically and electrochemically in order to achieve efficient leaching. The thermodynamic investigation, leading to the construction of Pourbaix diagrams of platinum in the presence of chloride, confirmed the possibility of the formation of stable aqueous complexes, as well as platinum oxides. From the electrochemical results obtained it can be concluded that ozone may be useful as an oxidizing agent, but according to the leaching results obtained, ozone holds few benefits compared to aqua regia and cyanide, although they still present some environmental challenges. The relatively low percentages of recovery obtained with leaching may be attributed to the rapid decomposition of ozone, which is affected by several factors, such as temperature, pH, initial concentration of ozone, ionic strength and stirring rate. Further optimisation of these factors can possibly prove ozone to be a useful oxidizing agent for the recovery of platinum. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

Motor car exhaust catalysts are some of the most important users of platinum, and much attention is given to the recycling of scrap platinum from spent exhaust systems. The dissolution of platinum from waste exhausts was previously only possible by pyrometallurgical processes or by the use of aggressive chemicals, such as aqua regia and cyanide, all of which, however, cause pollution problems. Recently the potential for the development of hydrometallurgical processes was identified. These processes are more efficient and more environmentally friendly than traditional processes. It was the aim of this study to investigate the oxidation of platinum with ozone as oxidizing agent in the presence of chloride as complexing agent. The influence of various factors, such as chloride ion concentration, pH and temperature were studied thermodynamically and electrochemically in order to achieve efficient leaching. The thermodynamic investigation, leading to the construction of Pourbaix diagrams of platinum in the presence of chloride, confirmed the possibility of the formation of stable aqueous complexes, as well as platinum oxides. From the electrochemical results obtained it can be concluded that ozone may be useful as an oxidizing agent, but according to the leaching results obtained, ozone holds few benefits compared to aqua regia and cyanide, although they still present some environmental challenges. The relatively low percentages of recovery obtained with leaching may be attributed to the rapid decomposition of ozone, which is affected by several factors, such as temperature, pH, initial concentration of ozone, ionic strength and stirring rate. Further optimisation of these factors can possibly prove ozone to be a useful oxidizing agent for the recovery of platinum. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

This Master’s thesis is related to corrosion degradation processes on metal surfaces exposed in different environments. The theoretical part is concern with basic principles in electrochemical and atmospheric corrosion. Practical part describes experimentation of corrosion process of aluminium (99,5) and low carbon steel (11321) in two different atmospheric environments. The conclusion of thesis includes evaluations of the results from practical part and comparison with the theoretical part.