In the first phase of the study, the effect of five Safol surfactants on the aqueous solubility of phenanthrene and acenaphthene was determined. The fixed variables were temperature and ionic strength, while surfactant concentration and pH were varied. Quantification of the polyaromatic hydrocarbons (PAHs) was conducted by UV-Visible spectrophotometry. The surfactants had little or no effect on analyte solubilisation below the critical micelle concentration (CMC) while a linear relationship between surfactant concentration and amount of solubilised phenanthrene was observed above CMC concentrations. Safol 45E5 had the highest phenanthrene molar solubilisation ratio (0.83) of the five surfactants tested. The solubilisation of phenanthrene increased marginally (4.1 % for Safol 45E12 and 15.2 % for Safol 45E7) by decreasing the pH from 8 to 5. The concentration of solubilised acenaphthene was 8.4 % higher than phenanthrene in a 1 mM solution of Safol 45E7. The aqueous solubility of phenanthrene was enhanced 11.0, 21.2, 19.6, 15.9 and 14.7 times in 1 mM solutions of Safol 45E3, 45E5, 45E7, 45E9 and 45E12 respectively. Seasand, Longlands sand, Longlands soil and a standard soil sample were spiked with the two PAHs and aged for two weeks. API sludge provided by Sasol and unspiked samples of the above mentioned sorbents were subjected to determinations of organic matter content, particle size distribution and moisture content. The spiked soils and sands and the sludge samples were then washed in various concentrations of Safol 45E7 (0.5, 1.0 and 2.0 mM) at the same temperature used in the solubility studies. A soil mass to solution volume of lg to 10 mL was used. Analyses of the soil and sand samples were conducted by High Pressure Liquid Chromatography (HPLC). Using a 2 mM Safol 45E7 surfactant solution, 100 % and 90 % of phenanthrene and acenaphthene were respectively extracted from Longlands sand and 88 % and 100 % of phenanthrene and acenaphthene were removed from seasand. 8.4 % phenanthrene and 8.17 % of acenaphthene was removed from Longlands soil, while 7.03 % phenanthrene and 6.64 % acenaphthene was removed from the standard soil sample. In the sand desorption studies, the amount of desorbed contaminants initially increased rapidly with increasing surfactant concentration, before levelling off at equilibrium. The amount of desorbed acenaphthene and phenanthrene increased exponentially with increasing surfactant concentration while contaminant concentrations decreased with increasing time in the Longlands soil and standard soil desorption experiments. Dry API sludge samples were also subjected to soil washing studies. The washed samples were Soxhlet extracted and analysed by gas chromatography. The 0.5 mM and 1 mM Safol 45E7 washed sludge samples showed respective phenanthrene peak area percent reductions representing a 44 % and 47 % extraction of phenanthrene from the API sludge. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2005.

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The manufacture of nonionic surfactants generally involves ethoxylation via ethylene oxide condensation onto a hydrophobe substrate, mostly in the presence of an alkaline catalyst. Nonionic surfactants are used widely in industrial applications, such as detergents, health and personal care, coatings, and polymers. In Australia, approximately one-third of the annual consumption of nonionic surfactants is imported from offshore manufacturers; the market is highly competitive with the local manufacturer facing increasing competition from imports. Optimisation is a pressing need for the current manufacturing plant of the industrial partner for this research project, Huntsman Corporation Australia Pty Limited, the sole domestic manufacturer of nonionic surfactants in Australia. Therefore, the objectives of this research project were to gain a better understanding of the various chemical and physical processes occurring simultaneously in an ethoxylation process; to identify the process limitation in an existing production plant operated by Huntsman Corporation Australia, and to explore measures for enhancing the asset productivity of the production plant. An ethoxylation process working model, describing the chemical kinetics and the physical transport processes involved, was developed to aid the exploration of optimisation opportunities, which would otherwise be empirical. Accordingly, this research project was structured into a two-stage program. The first stage determined the ethoxylation kinetics experimentally. The second stage investigated the interactions of physical transport processes numerically using a computational fluid dynamics (CFD) technique. The manufacturing scheme discussed in this thesis gave particular emphasis to the ethoxylation process operated in semi-batch stirred reactors. In the first stage, a series of kinetic experiments was performed in a well-stirred laboratory autoclave under base-catalysed conditions. The experimental outcomes were developed into a comprehensive kinetic model which took into account the non-ideal features in the reactor operation. Time-dependent physical changes of the reaction system, such as liquid volume, ethylene oxide solubility and density were also included. The ethoxylation behaviour predicted by the model was shown to be in good agreement with the experimental measurements. This indicated that the kinetic model was sufficiently robust to reproduce the reaction behaviour of a commercially operated ethoxylation operation. In the second stage, numerical simulations of an existing ethoxylation reactor system were presented. In addition, two components were addressed: identification of the process limitation and increasing productivity of the industrial-scale ethoxylation plant. An important assumption was made for the ethylene oxide injection system used in this research project which subsequently simplified the ethoxylation system into a single liquid with miscible chemical species. In the identification of the process limitation, three possible rate-limiting factors were examined: mixing, heat removal and reactor pressure rating. Examination and analysis of the physical data available from plant batch reports found that the reactor pressure rating and the presence of nitrogen padding were the rate-limiting factors to the ethoxylation operations in the industrial reactors. It was recommended that the reactor pressure rating be increased to raise the asset productivity of the reactor. In the numerical simulations of the ethoxylation reactor, time-dependent CFD models were developed for two systems: the ethylene oxide injection pipe and the stirred ethoxylation reactors. The heat transfer of ethylene oxide liquid injection was calculated in a two-dimensional model of the dip-leg pipe used in an industrial-scale ethoxylation reactor. The computation gave the temperature of the injection outflow which was validated against the calculated value by empirical correlation. The effects of various surrounding reaction temperatures, injection rates and pipe sizes on the heat transfer rate were investigated. From these, a range of operating conditions yielding a liquid ethylene oxide outflow was selected. Furthermore, it was found that boiling of ethylene oxide was significantly reduced with increasing pipe diameters. It was recommended that the asset productivity of the reactor be improved by keeping more ethylene oxide injected as a liquid in the reaction mixture to raise the reaction rate and shorten the reaction time. Three-dimensional simulations of a baffled reactor agitated by a single- or a dual-Rushton impeller were presented for both non-reactive and reactive flows. Multiple frames of reference and sliding grid methods were used in sequence to describe the relative motion between the rotating impeller and the stationary baffles. The turbulence parameters were modelled with the standard k- � turbulence model. The simulations of non-reactive flow were compared with the literature velocity data obtained from both the experiments and simulations. Good agreement was achieved. The model was then extended to incorporate ethoxylation flow with integration of the kinetics established in the first stage. Both the laboratory autoclave and the industrial-scale reactors were simulated. The former took into account the ethoxylation exotherm and the latter was carried out isothermally. Both simulations were validated against reaction data obtained from physical experiments, either the kinetic experiments or the plant batch productions. The validated model allowed us to determine the optimum operating condition and explore a new reactor system with enhanced asset productivity. A 50% increase in productivity could be accomplished if the ethoxylation was operated closer to the current design pressure limit. Furthermore, the operating pressure of a new reactor system needed to be doubled if the asset productivity were to be increased to approximately three times the current performance.

Nonionic surfactants are commonly used to stabilize proteins during upstream and downstream processing and drug formulation. Surfactants stabilize the proteins through two major mechanisms: (i) their preferential location at nearby interfaces, in this way precluding protein adsorption; and/or (ii) their association with protein into "complexes" that prevent proteins from interacting with surfaces as well as each other. In general, both mechanisms must be at play for effective protein stabilization against aggregation and activity loss, but selection of surfactants for protein stabilization currently is not made with benefit of any quantitative, predictive information to ensure that this requirement is met. In certain circumstances the kinetics of surface tension depression (by surfactant) in protein-surfactant mixtures has been observed to be greater than that recorded for surfactant alone at the same concentration. We compared surface tension depression by poloxamer 188 (Pluronic�� F68), polysorbate 80 (PS 80), and polysorbate 20 (PS 20) in the presence and absence of lysozyme and recombinant protein, at different surfactant concentrations and temperatures. The kinetic results were interpreted with reference to a mechanism for surfactant adsorption governed by the formation of a rate-limiting structural intermediate (i.e., an "activated complex") comprised of surfactant aggregates and protein. The presence of lysozyme was seen to increase the rate of surfactant adsorption in relation to surfactant acting alone at the same concentrations for the polysorbates while less of an effect was seen for Pluronic�� F68. However, the addition of salt was observed to accelerate the surface tension depression of Pluronic�� F68 in the presence of lysozyme. The addition of a more hydrophobic, surface active protein (Amgen recombinant protein) in place of lysozyme resulted in greater enhancement of surfactant adsorption than that recorded in the presence of lysozyme. A simple thermodynamic analysis indicated the presence of protein caused a reduction in ���G for the surfactant adsorption process, with this reduction deriving entirely from a reduction in ���H. We suggest that protein accelerates the adsorption of these surfactants by disrupting their self associations, increasing the concentration of surfactant monomers near the interface. Based on these air-water tensiometry results, it is fair to expect that accelerated surfactant adsorption in the presence of protein (observed with PS 20 and PS 80) will occur with surfactants that stabilize protein mainly by their own adsorption at interfaces, and that the absence of accelerated surfactant adsorption (observed with F68) will be observed with surfactants that form stable surfactant-protein associations. Optical waveguide lightmode spectroscopy was used to test this expectation. Adsorption kinetics were recorded for surfactants (PS 20, PS 80, or F68) and protein (lysozyme or Amgen recombinant protein) at a hydrophilic solid (SiO���-TiO���) surface. Experiments were performed in sequential and competitive adsorption modes, enabling the adsorption kinetic patterns to be interpreted in a fashion revealing the dominant mode of surfactant-mediated stabilization of protein in each case. Kinetic results confirmed predictions based on our earlier quantitative analysis of protein effects on surface tension depression by surfactants. In particular, PS 20 and PS 80 are able to inhibit protein adsorption only by their preferential location at the interface, and not by formation of less surface active, protein-surfactant complexes. On the other hand, F68 is able to inhibit protein adsorption by formation of protein-surfactant complexes, and not by its preferential location at the interface. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Sept. 24, 2012 - Feb. 24, 2013.

In particle induced desorption-ionization mass spectrometry the strength of an analyte's signal under a given set of bombardment conditions is usually considered to be representative of the analytes relative surface activity. This rationale is generally used to explain differences in the technique's sensitivity between and within various classes of compound. In liquid matrix assisted secondary ion mass spectrometry (SIMS) sensitivity enhancement of ionic analytes by pairing with surface active counterions has been demonstrated by several groups. This technique has been utilized in this work to achieve a 10,000 fold enhancement in the signal for ATP on a double focusing magnetic sector instrument and to detect femtomole quantities of nucleoside monophosphates on a time-of-flight instrument. The analyte's signal, however, is dependent on both the analyte bulk concentration and that of the surfactant. Additionally, the surfactant concentration that produces the maximum analyte signal changes with the analyte concentration. In this study, this phenomenon has been modeled in terms of conventional solution equilibria and surface chemical principles. It is assumed that the initial surface composition and the bulk concentration are the boundary conditions of a steady state established by the competing processes of surface sputtering and surface replenishment from the bulk during analysis. Calculated surface excesses correlate well with observed relative ion intensities, suggesting that equilibrium conditions are approached in the sample matrices despite the outwardly dynamic nature of the sputtering processes. / Graduation date: 1994

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

A major factor complicating the cleanup at many sites is co-contamination by both organic compounds and heavy metals. Whereas much research has focused on the removal of either organic compounds or metals, relatively few studies have investigated simultaneous removal of organic and inorganic pollutants from soil. / The studies reported in this thesis have evaluated a novel technique for the simultaneous mobilization of polychlorinated biphenyl (PCB) compounds and heavy metals (HMs) from a field contaminated soil. Soil extraction with washing aids {surfactants/cyclodextrin in combination with chelating reagent(s)} was optimized for mobilization efficiency, recovery/recycle of washing additives, and in parallel detoxification of mobilized contaminants. PCB extraction efficiencies were determined with a method that converted all the PCB congeners to dicyclohexyl by hydrogenation over palladium. Studies demonstrated that 10 minutes of ultrasonic mixing of field contaminated soil with a combination of surfactant (30 mL L-1) or cyclodextrin (100 g L-1) and a sparing quantity (2 mmoles) of EDTA, simultaneously mobilized appreciable quantities of PCBs and most analyte metals (Cd, Cu, Mn, Pb, Zn, Ni, Cr). / Relative to individual reagents, combinations of surfactant (Brij 98, Triton X-301, or Triton XQS-20) or cyclodextrin (RAMEB or HPCD) with EDTA did not influence PCB extraction efficiencies perceptibly. The presence of surfactant or cyclodextrin in admixture with EDTA did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb with nonionic surfactant and cyclodextrin. When coupled with PCB removal by hexane back-extraction and precipitation of the HMs (mediated by hydrolysis of zero-valent magnesium (Mg0)}, aqueous washing suspension was regenerated and recycled twice to mobilize more contaminants from the soil. Three sonication-washes with the same charge of reagent mobilized appreciable quantities of PCBs (68 - 83%) and virtually all of the available Cd, Cu, Mn, and Pb and lesser amounts of the Zn (56%), Ni (59%), and Cr (50%) but only small quantities of Al (28%) and Fe (30%). / The release of EDTA from heavy metals complexes was efficient for most metals (99%) but was influenced by the nature of surfactant. EDTA recovery (62-65%) post three cycles of soil washing, hexane back-extraction, and Mg 0 treatment was similar for all reagent combinations. Among surfactants and cyclodextrin, only anionic surfactants suffered losses to Mg0 treatment.