The crystal structure of Ba [Cu(C₂0₄)₂(H₂O)].5H₂O has been determined using single crystal X-ray diffractometry. It crystallises in the triclinic system, space group Pī , with a = 6.539(2) Å, b = 9.211(3) Å, c = 10.928(3) Å, a = 85.42(3)°, β = 79.22(3)° , γ = 80.30(3)°, V = 636.08(8)ų and Z = 2. The structure consists of [Cu(C₂0₄)₂(H₂O)]²⁻ ions weakly bridged by barium ions and water molecules. The copper(II) ions are in a tetragonally elongated square-pyramidal environment with some trigonal distortion. The two oxalate groups occupy the equatorial positions and a water molecule occupies the axial position. The barium ion is surrounded by nine oxygens: five oxygens from water molecules and four oxygens from oxalate groups. The thermal behaviour of Ba [Cu(C₂0₄)₂(H₂O)].5H₂0 in N₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (~80°C), but continues until the onset of the decomposition (~280°C). The decomposition takes place in two major stages. The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311 ±30 kJ mol⁻¹. The overall enthalpy change for the decomposition of Ba[Cu(C₂0₄)₂]in N₂ was estimated from the combined area of the peaks of the DSC curve as -347 kJ mol⁻¹. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three-dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125 ±4 kJ mol⁻¹ and (1.38 ±0.08)x10¹⁵ min⁻¹, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model with n = 5. The other process was slow and could also be described by the contracting-geometry model , but with n = 2. The values of Eₐ and A were 206 ±23 kJ mol⁻¹ and (2.2 ±O.5)xl0¹⁹min⁻¹, respectively, for the fast process, and 259 ±37 kJ mol⁻¹ and (6.3 ±1.8)x10²³min⁻¹, respectively, for the slow process.The crystal structure of zinc oxalate dihydrate ([Zn(C₂0₄)(H₂O)₂]n) has also been determined by X-ray diffraction methods. It crystallises in the monoclinic system, space group C2/c with a = 11.786(2) Å, b = 5.397(1)Å, c = 9.712(1) Å, B = 126.19(5)°, V = 498.58(8)ų, Z = 4 and R = 0.037 for 435 absorption-corrected independent reflections and 50 parameters. The asymmetric unit consists of half the monomeric unit [Zn(C₂0₄)(H₂O)₂). The structure consists of infinite, linear chains of zinc ions bridged by oxalate groups. The geometry of the coordination polyhedron surrounding the zinc ion is octahedral, with the oxalate oxygens occupying the equatorial positions and water molecules occupying the axial positions.

M.Sc. (Geology) / Despite Chrissie Lake being South Africa's largest freshwater lake, the chemistry of this lake and the surrounding lakes and pans in the Mpumalanga Lake District has never been studied in detail. These closed systems show varying chemistry while being in very close proximity to one another, adding to the uniqueness of this area where pans, usually typical of arid regions, are found in a humid area. The factors affecting the water chemistry of these lakes needed to be identified and explained. In order to evaluate the water chemistry in this unique environment, water samples were taken at the end ofthe wet and dry seasons, in April and September 2007 respectively. The major pans were sampled, as were adjacent fountains or springs, indicative of the perched groundwater aquifers found in this area, as well as borehole water from the surrounding farms. Alkalinity was determined by manual titration upon returning from the field while pH and conductivity measurements were performed on site. Major cations and anions were analysed for using ICP-OES and Ion Chromatography respectively. Sediment samples were collected from the floor of each pan in the summer sampling and the mineralogy determined by X-ray diffraction (XRD). During September 2007 sampling, precipitates found on the floors and banks of the pans were also collected and analysed using XRD, to identify mineral species precipitating from solution. Initial results show pH values ranging from 7.0-10.5 for the lakes and pans and from 6.0-8.0 for the borehole water and springs. Values as low as 100 mglL Total Dissolved Solids (TDS) were measured for the pans, with maximum values set at 10 giL for the most saline of these bodies of water in the wet season and as much as 90glL for a pan almost completely dried out in the dry season. The water in the closed pan systems are dominated by Na-CI- HCO~ and have varying concentrations of major cations. The dilute spring waters have TDS values ranging from 20-200 mg/L, indicating the excellent quality of the groundwater, while some boreholes reach values of I 000 mg/L TDS showing possible linkage to pans or leaking of the pan water into the surrounding strata. To understand the main processes affecting the inorganic chemistry of the surface and shallow groundwater of this area, major ions were plotted against chloride. The latter behaves conservatively and can thus be used to monitor the behaviour of solutes in the pan waters. These plots illustrate that the dominant process in the evolution of the waters in the MLD is evaporative concentration. Removal of species through mineral precipitation is clearly seen; carbonate species...