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1	Acetate-Catalyzed Bromination and Deuterium Exchange of 2-Butanone (I). The Mechanism for the Bimolecular Displacement Reactions of α-Haloketones (II) Thorpe, James William 10 1900 (has links) <p> The regioselectivities of bromination and deuterium exchange of 2-butanone are shown to be the same, under identical conditions. This work firmly establishes that enolization is the rate-determining step for the former reaction, contrary to some recent reports in the literature.</p> <p> The steric effects and activation parameters in the bimolecular nucleophilic displacement reactions of a series of α-haloketones and alkyl halides are shown to be inconsistent with either a bridging or conjugation mechanism for the observed rate enhancements of haloketone over alkyl halide.</p> <p> The stereoelectronic requirements of this mechanism are tested in a system where the stereochemistry is known (cis- and trans-chlorocyclohexanones). The activation parameters suggest that only in the case where the geometry is correct for maximum conjugation (trans-chlorocyclohexanone) is there an appreciable difference in mechanism (stereoelectronically) from displacement at ordinary saturated carbon.</p> / Thesis / Doctor of Philosophy (PhD)
2	Processing of Aluminum Alloys Containing Displacement Reaction Products Stawovy, Michael Thomas 27 April 2000 (has links) Aluminum and metal-oxide powders were mixed using mechanical alloying. Exothermic displacement reactions could be initiated in the powders either by mechanical alloying alone or by heat treating the mechanically alloyed powders. Exponential relationships developed between the initiation time of the reaction and the mechanical alloying charge ratio. The exponential relationships were the result of changes in the intensity and quantity of collisions occurring during mechanical alloying. Differential thermal analysis of the mechanically alloyed powders indicated that increased milling time inhibited the initiation of the displacement reactions. It is believed that the reactions were inhibited because of heat dissipation from reacting oxide particles in the surrounding metal. Determining the effects of mechanical alloying on displacement reactions will lead to a more thorough understanding of the kinetics of mechanical alloying. Reacted powders were densified by uniaxial compaction and extrusion. Metallographic analysis of the reacted specimens confirmed the findings of the thermal analysis. Increased mechanical alloying inhibited the chemical reactions. Densified specimens from longer-milled mechanically alloyed specimens showed finer, more uniformly dispersed reaction products. These samples also showed increased mechanical properties as a result of their finer microstructure. Current particle strengthening models were used to accurately predict room temperature properties. Because of the fine microstructures produced, it may be possible to use similar techniques to yield new high-temperature aluminum alloys. / Ph. D. displacement reactions high temperature aluminum alloys mechanical alloying
3	Indolizidine alkaloids and asymmetric synthesis of carbocycles Wingert, David Alexander Unknown Date No description available. indolizidine (+)-ipalbidine assymmetric synthesis Diels-Alder reactions Myers asymmetric alkylation asymmetric carbocycle synthesis conjugate additions
4	Reactive replacement and addition of cations in bioclastic silica and calcite Allan, Shawn Michael 05 May 2005 (has links) Numerous organisms produce ornately detailed inorganic structures (often known as shells) with features on length scales from 50 nm to several centimeters. One class of such organisms are the diatoms; microscopic algae that form silica frustules. Another group of algae, the coccolithophorids, produce similar calcium carbonate structures. Over 100,000 species comprise these two classes of algae, every one of which is endowed with a unique cytoskeleton structure. Using various types of displacement reactions, the chemistry of the original structure can be modified to produce a new material. Magnesium vapor has been found to displace the silicon in diatom frustules to yield an MgO structure. The conversion has been reported at temperatures from 650°C to 900°C. In the current work, the conversion and processing of silica frustules to MgO was examined in depth. The effect of reaction temperature on grain size and extent of conversion was evaluated. With the goal of obtaining high purity MgO structures, various methods for removing the silicon products of reaction were investigated. Wet chemistry and high temperature vapor etches were evaluated. The MgO reaction served as an intermediate step in the production of magnesium tungstate diatoms, which were imbued with photoluminescent properties. Reactions were identified to allow the conversion of calcium carbonate (calcite) structures to alternative chemistries. Calcite sand-dollars were converted to calcium tungstate or calcium molybdate by aqueous solution chemistry. In this process, sand dollar tests (shells) and coccolithophore frustules were reacted with ammonium para-molybdate or ammonium para-tungstate. The reactions were evaluated for shape preservation, phase purity, and photoluminescence of the structures. Self-replication Phosphor Diatom Coccolithophore Shape-preserving reaction Magnesium tungstate Silicon etching Displacement reactions Calcium molybdate Calcium tungstate Magnesium Mangesium oxide Chlorine etching X-ray diffraction Bioclastic Fluorescence Bio mineral Scanning electron microscopy Calcite Cations Substitution reactions Silicates Calcium carbonate Nanostructured materials Synthesis Biotechnological microorganisms Diatoms Microstructure Ammonium Photoluminescence

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