published_or_final_version / Chemistry / Master / Master of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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No description available.

No description available.

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Laccase (E.C 1.10.3.2) catalyzes the oxidation of aromatic substrates with the simultaneous reduction of molecular oxygen to water. It has significant potential for use in many applications due to its high reaction rates, broad substrate-specificity, and use of oxygen as an inexpensive co-factor. The objective of this research was to investigate the ability of laccase from Trametes versicolor to catalyze oxidation reactions under a variety of reaction conditions and to model the kinetics of these transformations. Phenol was selected as a model substrate. / Laccase was very stable when incubated at temperatures less than 30°C and pHs between 6 and 7. The optimum pH for phenol transformation was 6, but when present in sufficient quantities, laccase was able to significantly transform phenol at pHs from 4 to 7 and temperatures from 10 to 60°C. Laccase stability was negatively impacted by the presence of four common redox mediators. Of these, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and 2,2',6,6'-tetramethylpiperidine-N-oxyl (TEMPO) significantly enhanced phenol transformation but large quantities were required, which may limit the feasibility of the use of these mediators in many applications. / A series of kinetic models was developed in order to achieve a better understanding of the mechanisms and kinetics of laccase-catalyzed reactions and to eventually assist in the choice and design of suitable reactor systems. These models were designed to predict the transient oxygen and phenol concentrations during laccasecatalyzed reactions at pH 6 and 25°C. Over the course of developing and validating these models, it was observed that: (1) the rate-limiting step in the catalytic reactions is the reaction between the oxidized form of laccase and phenol; (2) the stoichiometric ratio, which is defined as the molar ratio of phenol transformed to oxygen consumed in the catalytic reaction, was found to increase with phenol concentration in the reaction mixture from a theoretical lower limit of 1 and to approach a theoretical upper limit of 4; and (3) laccase inactivation occurs over the course of the reaction and was found to be dependent on the rate of substrate transformation. / Ultimately, these findings were incorporated into a comprehensive kinetic model to predict transient species concentrations in an open-system environment where the degree of substrate transformation was not limited by oxygen availability. The model accounts for enzyme kinetics, oxygen mass-transfer, variable reaction stoichiometry, and inactivation related to reaction products. Excellent agreement was observed between measured and modeled phenol and oxygen concentrations for a wide range of initial phenol concentrations and enzyme activities. Simplified models were also developed by incorporating an assumption, referred to as the pseudo-steady-state assumption, that at any instant during the reaction, the enzyme achieves an approximate steady-state distribution of its various forms around the catalytic cycle. The pseudo-steady-state assumption had the advantage of reducing the complexity of model equations without sacrificing their predictive abilities and allowing enzyme quantities to be expressed in activity units instead of molar concentrations.

Alkaline pressure oxidation, particularly in the presence of trona as additive, can be used to oxidize high carbonate refractory gold ores as it prevents the formation of CO2 in the autoclave. However, the presence of silica in the ore can lead to the encapsulation of pyrite due to the formation of a passive layer. This phenomenon occurs due to the high solubility of silica in alkaline solutions and its subsequent re-precipitation on the reacting pyrite surface. The present study investigated the chemical composition and thickness of the passive layer on a rotating pyrite surface in an aqueous slurry containing silica sand, sodium carbonate and calcium carbonate at 230°C and under 7 bar of oxygen overpressure. Results obtained from XPS and SEM show that a concentration of 2.5 g/L sodium carbonate gave the maximum thickness of passivation on pyrite and that the passive layer consisted primarily of silicates and aluminosilicates.

Nickel-based Superalloys are widely used in the steam turbine power generation and aerospace industries. They possess the desirable qualities of high-temperature strength, oxidation and corrosion resistance and can operate in some of the highest temperature ranges of the structural metals. The oxidation resistance of a Superalloy is achieved primarily through the formation of a dense alumina and/or chromia oxide layer(s) including spinels. This resistance has been further improved in wrought and cast alloys through the addition of reactive elements such as silicon, yttrium and lanthanum, although the exact effects of these elements have not been well defined. This project concentrated on a powder metallurgy ternary master alloy consisting of Ni-12Cr-9Fe (w/o) with additions of 6w/o aluminum, 0.5w/o Si, and 0.1w/o Y, in various combinations. Specifically, the primary goal was to produce and characterize a PM manufactured nickel-based Superalloy with minor additions of reactive elements and to assess the effectiveness of the Si and/or Y in improving the oxidation resistance. JMatPro modeling software was first used to help determine temperatures at which various events would occur in the alloys such as solutionizing and liquation temperatures. Subsequently green compacts were produced by a press (uni-axially) and sinter route to create transverse rupture strength bars (TRS bars). These bars were then thermomechanically deformed using a Gleeble tester to reduce porosity followed by a heat treatment to restore a microstructure better suited for high temperature oxidation. Sectioned TRS bars were then oxidized (static) 900?C in air for times up to 1000h and the influence of the Si/Y additions on oxidation resistance was determined via a combination of weight gain data and microstructural examination. Whereas JMatPro predicted solutionizing temperature of the compositions studied (1010°C quaternary; 1020°C quaternary + Si, respectively) these values were slightly lower than the results observed through DSC experiments (1045°C quaternary; 1065°C quaternary + Si, respectively). A w/o ?’ of approximately 25% was predicted by the modeling tool, but values of 58.3% to 61.7% were determined using a point count method. Finally, the addition of 0.5w/o Si to the quaternary Ni-Cr-Fe-Al PM system provided a measureable improvement in the oxidation resistance both in terms of thickness of oxide layer and in overall weight gain. Conversely, 0.1w/o Y provided little benefit, and was shown to be detrimental to alloys not containing Si.