High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Design Optimization of Submerged Jet Nozzles for Enhanced Mixing

The purpose of this thesis was to identify the optimal design parameters for a jet nozzle which obtains a local maximum shear stress while maximizing the average shear stress on the floor of a fluid filled system. This research examined how geometric parameters of a jet nozzle, such as the nozzle's angle, height, and orifice, influence the shear stress created on the bottom surface of a tank. Simulations were run using a Computational Fluid Dynamics (CFD) software package to determine shear stress values for a parameterized geometric domain including the jet nozzle. A response surface was created based on the shear stress values obtained from 112 simulated designs. A multi-objective optimization software utilized the response surface to generate designs with the best combination of parameters to achieve maximum shear stress and maximum average shear stress. The optimal configuration of parameters achieved larger shear stress values over a commercially available design.

Derivation of lake mixing and stratification indices from high-resolution lake buoy data

Lake Analyzer is a numerical code coupled with supporting visualization tools for determining indices of mixing and stratification that are critical to the biogeochemical cycles of lakes and reservoirs. Stability indices, including Lake Number, Wedderburn Number, Schmidt Stability, and thermocline depth are calculated according to established literature definitions and returned to the user in a time series format. The program was created for the analysis of high-frequency data collected from instrumented lake buoys, in support of the emerging field of aquatic sensor network science. Available outputs for the Lake Analyzer program are: water temperature (error-checked and/or down-sampled), wind speed (error-checked and/or down-sampled), metalimnion extent (top and bottom), thermocline depth, friction velocity, Lake Number, Wedderburn Number, Schmidt Stability, mode-1 vertical seiche period, and Brunt-Väisälä buoyancy frequency. Secondary outputs for several of these indices delineate the parent thermocline depth (seasonal thermocline) from the shallower secondary or diurnal thermocline. Lake Analyzer provides a program suite and best practices for the comparison of mixing and stratification indices in lakes across gradients of climate, hydro-physiography, and time, and enables a more detailed understanding of the resulting biogeochemical transformations at different spatial and temporal scales.

Mercury interactions with suspended solids at the Upper East Fork Poplar Creek, Oak Ridge, Tennessee

A water quality model was developed to analyze the impact of hydrological events on mercury contamination of the Upper East Fork Poplar Creek, Tennessee. The model simulates surface and subsurface hydrology and transport (MIKE SHE and MIKE 11) and it is coupled with the reactive transport of sediments and mercury (ECOLAB). The model was used to simulate the distribution of mercury contamination in the water and sediments as a function of daily hydrological events. Results from the model show a high correlation between suspended solids and mercury in the water due to the affinity of mercury with suspended organics. The governing parameters for the distribution of total suspended solids and mercury contamination were the critical velocity of the stream for particle resuspension, the rates of resuspension and production of particles, settling velocity, soil-water partition coefficient, and desorption rate of mercury in the water. Flow and load duration curves at the watershed exit were used to calibrate the model and to determine the impact of hydrological events on the total maximum daily load at Station 17. The results confirmed the strong link between hydrology and mercury transport.