Differential pulse voltammetry is one of the most widely used analytical polarographic techniques especially for trace inorganic analysis. Up to now mercury electrode and different types of carbon electrodes were used for such analysis. The emphasis of the present dissertation is on the design of a new class of electrodes, namely mono crystalline diamond paste based electrodes, to be used in differential pulse voltammetry for trace analysis of inorganic compounds. Monocrystalline diamond and boron doped polycrystalline diamond based electrodes exhibit several superior electrochemical properties that are significantly different from those of other carbon allotropes based electrodes, e.g., glassy carbon electrodes, highly oriented pyrolytic graphite based electrodes, which have been widely used for many years. The advantages are: (a) lower background currents and noise signals, which lead to improve SIB and SIN ratios, and lower detection limits; (b) good electrochemical activity ( pre-treatment is not necessary); (c) wide electrochemical potential window in aqueous media; (d) very low capacitance; ( e) extreme electrochemical stability; and (f) high reproducibility of analytical information. Furthermore, later studies shown the superiority of the mono crystalline diamond as electrode material due to high mobilities measured for electrons and holes. The design selected for the electrodes is simple, fast and reproducible. The diamond powder was mixed with paraffine oil to give the diamond paste used as electroactive material in the electrodes. The results obtained by employing the diamond paste based electrodes proved a high sensitivity, selectivity, accuracy and high reliability. These characteristics made them suitable to be used for the analysis of different cations (e.g., Fe(ll), Fe(Ill), Cr(Ill), Cr(VI), Pb(ll), Ag(I)) as well as of anions (e.g., iodide) in pharmaceutical, food and environmental matricies. / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

This thesis uses solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to study local structure and disorder in inorganic materials. Initial work concerns microporous aluminophosphate frameworks, where the importance of semi-empirical dispersion correction (SEDC) schemes in structural optimisation using DFT is evaluated. These schemes provide structures in better agreement with experimental diffraction measurements, but very similar NMR parameters are obtained for any structures where the atomic coordinates are optimised, owing to the similarity of the local geometry. The ³¹P anisotropic shielding parameters (Ω and κ) are then measured using amplified PASS experiments, but there appears to be no strong correlation of these with any single geometrical parameter. In subsequent work, a range of zeolitic imidazolate frameworks (ZIFs) are investigated. Assignment of ¹³C and ¹⁵N NMR spectra, and measurement of the anisotropic NMR parameters, enabled the number and type of linkers present to be determined. For ¹⁵N, differences in Ω may provide information on the framework topology. While ⁶⁷Zn measurements are experimentally challenging and periodic DFT calculations are currently unreliable, calculations on small model clusters provide good agreement with experiment and indicate that ⁶⁷Zn NMR spectra are sensitive to the local structure. Finally, a series of pyrochlore-based ceramics (Y₂Hf₂₋ₓSnₓO₇) is investigated. A phase transformation from pyrochlore to a disordered defect fluorite phase is predicted, but ⁸⁹Y and ¹¹⁹Sn NMR reveal that rather than a solid solution, a significant two-phase region is present, with a maximum of ~12% Hf incorporated into the pyrochlore phase. The use of ¹⁷O NMR to provide insight into the local structure and disorder in these materials is also investigated. Once the different T₁ relaxation and nutation behaviour is considered it is shown that quantitative ¹⁷O enrichment of Y₂Sn₂O₇ is possible, and that ¹⁷O does offer a promising future tool for study.