School of Chemistry - Theses
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ItemThe adsorption of polydisperse nonionic surfactants at the solid/aqueous interface( 1987)A high resolution capillary gas chromatography technique has been adapted to the analysis of polydisperse non-ionic surfactants. This technique has enabled the complete characterization of the oligomer distributions of very small samples of surfactants (typically 0.1 µg to 0.5 µg). It has made possible the determination of changes in the oligomer distribution on adsorption of surfactant at the solid/aqueous interface. Isotherms have been measured for the adsorption of a series of polyoxyethylene nonylphenol surfactants from aqueous solution on to various solids. These isotherms indicate that the surfactant – surface interaction increases with an increase in the hydrophobicity of the adsorbent. They also show a dependence upon the average length of the ethylene oxide chain and the ratio of the surface area/solution volume. These latter factors affect both the total partition of surfactant between the surface and the solution, and also the selectivity of the solid surface. A detailed study of the adsorption of N8 (a commercial non-ionic surfactant) by a precipitated silica at various surface area/solution ratios, has been undertaken, where the equilibrium surfactant oligomer distributions in the adsorbed and solution phases have been determined. At surfactant concentrations above the critical micelle concentration, the phase separation approach has been used to estimate the surfactant oligomer distributions in free monomer solution and in micelles. This information has been combined with a surface phase model to interpret the results of the adsorption distribution studies.
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ItemInterfacial effects on aqueous sonochemistry and sonoluminescence( 1999-06)The dissolution of quantum sized CdS and MnO2 particles in water was conducted using 20 kHz ultrasound. CdS particles were found to dissolve chemically via an oxidation process while MnO2 particles dissolved via a reductive process. It was found that the dissolution of the colloids could be controlled via the addition of surface active chemicals to solution and by varying the saturation gas type. In the presence of Na2S or propan-2-ol and argon gas, the dissolution of CdS was inhibited, whereas the addition of alcohols (methanol, ethanol, propan-2-ol, butan-1-ol and pentan-1-ol) to the MnO2 system led to an increase in the amount of dissolution for a given time of sonication. This increase in dissolution was found to be dependent on the ability of the surface active radical scavenger to accumulate around the bubble interface during the cavitation process. Eventually, at higher alcohol concentration there was a plateau or a limiting value reached for the efficiency of colloid dissolution which was common for each alcohol. (For complete abstract open document)
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ItemIodine speciation in the Yarra River estuary( 1992)An oxygen-deficient (12.8 microM dissolved oxygen and oxygen saturation 5.0-7.4% in the water of the deep hole) isolated water system in the deep hole of the Yarra River estuary was investigated to discover the relationship between iodate and iodide. The iodate concentration in the water of the deep hole was very low (0.039 to 0.062 microM at bottom water, salinity from 26.8-30.0 Practical Salinity Scale, 1978), because iodate reduced to iodide in the water by reducing agents (S2-, Fe2+ and Mn2+) diffused from the sediment of the deep hole. The concentrations of iodine species in the sediment pore water and suspended material in the water of the deep hole were determined to investigate iodine cycling in the deep hole. The iodine flux from sediment into overlying water in the deep hole was 15.6 micromol/m^2.day. The concentration of total inorganic iodine (iodate+iodide) in the dry suspended material from the water of the deep hole was 0.117 micro mol/g. The water residence time in the deep hole was studied. In winter especially, the seawater of high density may intrude into the deep hole with the highest tides. The seawater remains trapped in the deep hole below the halocline, which allows the development of oxygen-deficient conditions. It was found that in the deep hole the iodide concentration increase resulted from sediment diffusion (36%), iodate reduction (27%) and release from suspended material (37%) during the water residence time in the water of the deep hole. The iodine cycling in the deep hole was: iodate in the water reduced to iodide by reducing agents diffused from sediment; suspended material containing soluble or particular iodine may release iodide and also trap iodate and iodide from water during precipitation; iodate in the sediment reduced to iodide and iodide diffused from sediment into overlying water. Iodine is accumulated in the isolated water in the deep hole and might be moved out at the next water exchange.
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ItemOptical properties of silica-coated metal particles( 1999)The significance of silica coating technology for stabilising metal semiconductor nanoparticles was demonstrated. The physicochemical properties of silica coated colloidal silver (Ag@Si02) and the optical properties of films containing uncoated and silica coated colloidal gold (Au@Si02) were investigated. The factors governing the deposition of silica onto silane-primed silver particles were examined and the deposition conditions (pH and reagent concentrations) optimised. Thin silica shells deposited from aqueous/ethanolic sodium silicate solutions were porous and non-rigid. The shells remained insensitive to boiling in an aqueous-ethanolic solution but were substantially dissolved when boiled in pure water. The silver cores participated in a variety of chemical reactions with charged and neutral molecules to form new structures such as hollow silica nonobubbles, semiconductor cores and silica coated alloys of silver and gold. The rate of the reactions of the core with solution phase substrates decreased with increasing silica shell thickness. The silver cores of Ag@Si02 still remained catalytically active and colloidally stable during the reduction of water. Homogeneous films containing uncoated and silica coated gold particles were prepared using a self-assembly technique. The optical properties of the films were investigated as a function of film thickness and the separation between core particles. For interparticle separations below a silica shell thickness of ≈ 6.3 nm, the absorption band red-shifted and narrowed with increasing film thickness. Moreover, with increasing interparticle separation, the band blue-shifted, and both the transmittance and reflectance spectra increasingly began to resemble those of the same isolated particles in solution, in agreement with the Maxwell-Garnett model. In contrast, above a shell thickness of ≈ 6.3 nm, the absorption peak position remained insensitive to film thickness and interparticle separation, suggesting that the gold cores were no longer electromagnetically coupled. For silica shell thicknesses above 12.2 nm, the dependence of the reflectance spectra o interparticle separation and film thickness still needs to be quantified. Possible scientific and industrial applications associated with the Ag@Si02 particles and Au@Si02 particle films are suggested.
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ItemRadionuclide determination and behaviour in marine and freshwater systems( 1997)A range of radio analytical techniques have been developed and optimised for the determination of naturally occurring and artificial radionuclides present in the Australian environment. The behaviour of these radionuclides has been investigated to provide a basis for dose assessments from the human consumption of potable waters, estimates of fish ages and estimates of sedimentation rates in marine sediments.
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ItemAdsorption of polyphosphate dispersants onto oxide surfaces( 1993)The production of high-performance advanced material products based on controlled colloidal dispersions has received increased attention in recent times. In many cases, the mechanical strength of the final product relies on a homogenous microstructure resulting from a well-dispersed slurry. This may be achieved by the addition of dispersing agents to the colloidal dispersion. Inorganic dispersions offer greater durability than many of the organic compounds currently available. Polyphosphate dispersants are thought to act through electrostatic stablization, however the exact method of their action is unclear. The adsorption of polyphosphates onto colloidal zirconia (ZrO2) and titania (TiO2) particles has been studied as a function of chain length and pH. Adsorption isotherms and electroacoustic measurements have been used to study the adsorption process. Isotherms showed "high-affinity" type behavior. The extent of adsorption increased in each case as the pH decreased. Adsorption onto both oxide surfaces increased in the order P1 < P2 < P-5, where the subscript refers to the number of phosphate units in the chain. The shape of the adsorption isotherms indicated that the polyphosphates were adsorbed in a flat configuration in the plane of the surface. Electroacoustic results showed on a molar basis that the longer chain polyphosphates are more efficient at shifting the isoelectric point of the oxides. This was attributed to the greater specific adsorption of these molecules. The results of this study were consistent with an adsorption mechanism that is electrostatic in nature.