Ionic liquids (ILs) were studied as solvents for electrochemical reactions with the intent to devise metallurgical processes for Al, Mg and Ti that are less energy intensive and operate at lower temperatures than current industrial practice. Tetra-alkyl phosphonium ILs are on the low end of the IL cost spectrum and are regarded as understudied compared with imidazolium and pyridinium ILs. They are also known to be more thermally stable. The density, viscosity and conductivity of the phosphonium ILs and metal salt-IL mixtures were measured. The conductivity of the phosphonium ILs tested were found to be roughly an order of magnitude lower than imidazolium ILs; this is attributed to the relatively large cation size and localized charge. Linear density-temperature functions are presented. The viscosity and conductivity temperature relationship was modeled using the Vogel-Tamman-Fulcher (VTF) equation. The electrochemical window of A10341'14,6,6,610 was studied on a Pt substrate over a wide range of A1C13 concentrations using cyclic voltammetry (CV). It was found that the tetra-alkyl phosphonium cation is on the order of 800 mV more electrochemically stable than the 1-ethyl-3-methyl imidazolium (EMI+). Cathodic and anodic polarization of Al in A1C13-[P14,6,6,6]C1 (Xmc13 = 0.67) was studied at temperatures ranging from 347 to 423 K. The Butler-Volmer equation was fitted to the plots by varying the kinetic parameters. The cathodic reaction was found to be diffusion limited and the anodic reaction is limited by passivation at lower temperatures. The overpotential required for electrodissolution of Al was found to be higher than for electrodeposition. Aluminium was electrodeposited using both an electrowinning setup (chlorine evolution anode reaction) and electrorefining setup (Al dissolution anode reaction). The deposits were characterized in terms of morphology, current efficiency and power consumption. A variety of deposit morphologies were observed ranging from smooth, to spherical to dendritic, and in some cases, the IL was occluded in the deposit. The current efficiency and power consumption were negatively impacted by the presence of H2O and HCl present in the as-received ILs and by C12(g) generated by the anode reaction in the case of the electrowinning setup. HC1 was removed by cyclic polarization or corrosion of pure Al, resulting in current efficiencies above 90%. Aluminium was electrodeposited using the electrorefining setup with anode-cathode spacing of 2 mm at power consumption as low as 0.6 kWhr/kg-Al. This is very low compared with industrial Al electrorefining and Al electroplating using the National Bureau of Standards bath, which require 15-18 kWhr/kg-Al and 18 kWhr/kg-Al, respectively. However, due to low solution conductivity the power consumption increases significantly with increased anode-cathode spacing. Titanium tetrachloride was found to be soluble in [P14,6,6,6]Cl and increases the conductivity of the solution. Attempts to reduce the Ti(IV) included corrosion of titanium metal, corrosion of magnesium metal powder and cathodic polarization. Despite a few attempts, the electro-deposition of Ti was not observed. At this point, titanium electrodeposition from phosphonium based ILs does not appear feasible. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Optical techniques were used to study the critical behaviour of the pure fluids CHF₃, CCIF₃ and Xe, and binary mixtures He-Xe and nicotine + water. We find that for all these substances, the order parameter is described by a power law in the reduced temperature t = (Tc - T)/Tc with a leading exponent β = 0.327 ± 0.002. Also, we determine the first correction to scaling exponent to be Δ = 0.43 ± 0.02 for the pure fluids and Δ = 0.50 ± 0.02 for the He-Xe system. The coexistence curve diameter in CHF₃ and CCIF₃ exhibits a deviation from rectilinear diameter, in agreement with a modern theory which interprets this behaviour as resulting from three-body effects. In contrast, no such deviation is observed in Xe where, according to that theory, it should be more pronounced than in other substances. In the polar fluid CHF₃, the order parameter, isothermal compressibility and the chemical potential along the critical isotherm were simultaneously measured in the same experiment in an effort to ensure self-consistency of the results. From the data, two amplitude ratios which are predicted to be universal are determined: Γ+⃘ /Γ-⃘= 4.8 ± 0.6 and D⃘Γ+⃘B⃘δ-₁ = 1.66 ± 0.14. In the binary liquid system nicotine + water, the diffusivity was measured both by light scattering and by interferometry. The results agree qualitatively, but differ by a factor of ≈ 2. From the light scattering data, the critical exponent of the viscosity is found to be zη = 0.044 ± 0.008. The interferometric experiments on Xe and He-Xe furnish a direct way to maesure the effects of wetting: From the data, the exponent of the surface tension is found to be n = 1.24 ± 0.06. The similarity of the order parameter and compressibility in Xe and a He-Xe mixture containing 5% He indicate that the phase transition in this He-Xe mixture is of the liquid-gas type rather than the binary liquid type. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

This research explored the amination reaction of 1,3-bis-chloromethyl-tetramethyl-disiloxane in two different pathways. First, will discuss the synthesis of a new bipodal amino siloxane ligand which was achieved by the reaction of bis-chloromethyl-tetramethyl-disiloxane with t-BuNH3 in the presence of n-BuLi. The new ligand, of t-Butyl-[3-(t-butylamino-methyl)-1,1,3,3-tetramethyl disiloxanylmethyl]-amine (L1), is a model ligand designed to simulate the SOMC model of silica support and bipodal amido ligand that has been presented by the Basset group. Hence, developing this type of siloxane ligand and their complexes will be valuable in the synthesis of new homogenous catalyst, studying the reactivity and attempt to connect them with the SOMC examples. For this, the reaction of L1 with several Lewis acids and afforded several uncommon dimer and cluster complexes in the solid state. The second part of this research found that heating of bis-chloromethyl-tetramethyl-disiloxane with a 4-6 equivalent of amine, affording 4-N-Alkyl-tetramethyl- oxazadisilinane as six heterocycle ring by using a new simple and neat method. Using six different amine functional groups afforded six new oxazadisilinane compounds with different alkyls substituted. Each oxazadisilinane compound was utilized and reacted with four different acids, affording a series of twenty-one examples of new siloxane protic ionic liquids (Si-PILs). Also, the reaction of the cation with methyl iodide provided two examples of siloxane aprotic ionic liquids (Si-AILs). The new family of Si-ILs were well characterized by using NMR, mass, melting point, elemental analysis and thermal gravimetric analyses. Additionally, twelve crystals were suitable for X-ray diffraction as Si-PILs and one for Si-AILs. By studying their chemical and physical properties, a good library of the new Si-ILs has been built. Finally, one group of the new Si-PILs was used for butyl acetate esterification. The 5-X group of new Si-PILs salt was tested for esterification of butanol with acetic acid by thermal heat and under microwave irradiation. The salt 5-BF4- showed a good result in both systems with easy separation from the reaction mixture and recyclability discriminates the 5-BF4- as a good catalyst for the esterification reaction.

In two dimensions, non-trivial topology and enhanced correlation lead to amazing physical phenomena. Graphene offers a high-quality, ultra-tunable and integratable two dimensional electron system in the study of interacting and topological quantum fluids. In this thesis we studied in detail various emergent quantum phenomena of electron fluids due to both strong in-plane and out-of-plane interaction between electrons in single and multi-layer graphene systems. Using magnetoresistance measurement in the corbino disk geometry, we manged to quantitatively measure the viscosity of electrons in monolayer and bilayer graphene as a function of carrier density and temperature. We demonstrated a crossover between degenerate Fermi liquid and non-degenerate electron-hole liquid. In the quantum Hall regime, we applied the corbino geometry as a probe of the incompressible sample bulk, improving significantly the resolution of fragile quantum Hall states compared to Hall bar devices. The improved resolution enables quantitative studies over a much broader parameter space in both singlelayer and multi-layer graphene system. In double-layer graphene where two vertically stacked graphene layers are in close proximity but electrically separated by a thin hBN tunnel barrier, we observed sequence of FQHS which can be perfectly described by two-component composite fermion theory. Using a combination of different measurement configuration, we found evidence for a novel type of two-component non-abelian FQHS. At \nu = 1 in double-layer graphene where ground states of indirect excitons occur, we mappped out the entire phase diagram. We realized BEC-BCS crossover in the exciton condensation phase tunable with both magnetic field and electrostatic gating. At small exciton filling fraction, we discovered Wigner crystal of excitons. Lastly, we realized a strongly correlated triple-layer quantum Hall system with independent control of carrier density in each layer and demonstrated three-layer coherent quantum Hall effect at total integer filling fraction and possibly fractional filling fraction.

Solid-liquid phase equilibria studies were used to investigate possible compound formation in solutions of (i) N,N-dimethylformamide (DMF) and (ii) N,N-dimethylacetamide (DMA) with a series of halogenated hydrocarbons that were selected to give a wide range of acceptor properties. Solid 1:1 intermolecular compounds were identified from solutions of (i) DMF and (ii) DMA with CCl_4, CBrCl_3, and C_6H_5CCl_3. The intermolecular compounds (DMF)_2•CCl_4 and (DMF)_2•CBrCl_3 were also found. The results suggest charge transfer from DMF or DMA to the chlorine atoms of the acceptor molecule as the process for compound formation. Thermal methods were used to determine with high precision the solid-liquid phase equilibria diagram for the sodium-cesium system. Results differ greatly from those of earlier workers, especially near the eutectic composition where differences in melting points as large as 35°K occur. Although not conclusive, results support the proposal that the peritectic halt results from the formation of an Na_2Cs intermetallic compound by a very sluggish reaction. Thermal methods were also used to determine the mesophase transition temperatures for cholesteryl formate.

In the ocean, natural and artificial processes generate clouds of bubbles which scatter and attenuate sound. Measurements have shown that at the individual bubble resonance frequency, sound propagation in this medium is highly attenuated and dispersive. Theory to explain this behavior exists in the literature, and is adequate away from resonance. However, due to excessive attenuation near resonance, little experimental data exists for comparison. An impedance tube was developed specifically for exploring this regime. Using the instrument, unique phase speed and attenuation measurements were made for void fractions ranging from 6.2 × 10^−5 to 2.7 × 10^−3 and bubble sizes centered around 0.62 mm in radius. Improved measurement speed, accuracy and precision is possible with the new instrument, and both instantaneous and time-averaged measurements were obtained. Behavior at resonance was observed to be sensitive to the bubble population statistics and agreed with existing theory, within the uncertainty of the bubble population parameters. Scattering from acoustically compact bubble clouds can be predicted from classical scattering theory by using an effective medium description of the bubbly fluid interior. Experimental verification was previously obtained up to the lowest resonance frequency. A novel bubble production technique has been employed to obtain unique scattering measurements with a bubbly-liquid-filled latex tube in a large indoor tank. The effective scattering model described these measurements up to three times the lowest resonance frequency of the structure. / United States Navy Office of Naval Research Ocean Acoustics Program

Cavity ring-down (CRD) spectroscopy has emerged as a sensitive analytical technique. In this method, a laser pulse is injected through one of two highly-reflective mirrors which form a stable optical cavity and the rate that the light leaves the cavity is monitored by a detector placed behind the second mirror. In this research a CRD spectrometer has been designed and constructed. The light exiting the cavity is collected via a fiber optic cable which is then directed toward a photo multiplier tube (PMT) detector. The signal is digitized and averaged by an oscilloscope and the data are transferred by an I 488 interface to a personal computer where the data are analyzed. Instrument command and data acquisition are controlled by a Visual Basic computer program. A short review of several attempts to measure liquid samples using CRD spectroscopy is presented; most discuss the necessity for the incorporation of Brewster’s angle at the liquid interface. This study integrates a 1 cm standard quartz cuvette at normal incidence. It was determined that there are significant losses from scattering and reflection; however, these losses were not so large as to negate the efficacy of the technique. The hypothesis tested here is that the light “lost” as reflections are collected by the cavity mirrors and redirected back into the cavity. Rhodamine 6G was used as the primary model absorber in these studies. Absorbance measurements were extracted from the measured ring-down times and a detection limit was obtained. Four cavity lengths were constructed to determine the effect on the scattering losses with varying cavity lengths. The calculated detection limit for the CRD spectrometer used in this study was found to be in the range of 4-5 nM. It was found that the detection limit of the CRD spectrometer was 36 times lower than that of the commercial instrument. Aligning the cavity mirrors at longer cavity lengths proved to be more difficult; however, there were no significant additional losses observed by incorporating longer cavities.

No description available.

No description available.

Various innovative separation methods in chromatography have been proposed. The interaction of the 4-t-butylphenyl group with b-cyclodextrin is well-known; compounds tagged with the 4-t-butylphenyl group are separated from untagged compounds using b-cyclodextrin column. In this study, increasing the chain length of tagged molecules does not increase the retention time but depends on other functional groups present, while increasing the number of tags in a molecule increases retention time. The t-butyl group was also compared to adamantyl and lithocholic acid tags. In-house b-cyclodextrin columns were synthesized to observe the effect of the linkage of the cyclodextrin molecule to the support. Furthermore, tagged products could be separated from the starting materials using in-house columns employing flash b-cyclodextrin. Supported room temperature ionic liquids (SILs/MSILs) were explored for the extraction of polyunsaturated triacylglycerols (PUTAGs).Various room temperature ionic liquids (RTILs) with silver salts were tested for extraction effectiveness.The most hydrophobic RTIL [Hmim][PF6] in this study, with dissolved AgBF4 proved to be the best combination for effective extraction. RTILs supported on silica gel and mesoporous SBA-15 reacted with silver salts (psorbents) were synthesized and characterized. The later support revealed a conserved mesopore structure by SEM, TEM, SAXS and N2 isotherms. Trilinolenin (tri-18:3) quantification was explored by conversion to polyunsaturated fatty acid alcohols and methyl esters, Proton NMR spectroscopy and by non-aqueous reverse phase (NARP)-HPLC with evaporative light scattering detector (ELSD). Tri-18:3 and its free fatty acid (FFA-18:3) were extracted selectively and quantified using a two-step methodology. The extraction of a-tocopherol with RTILS modified with organic anions was also successfully demonstrated. Finally, studies of chiral stationary phases with on-resin cyclic oligoprolines were demonstrated. Cross linking of linear oligoprolines was shown to disrupt the poly-proline helix (II) thus leading to lower number of analytes resolved. On-resin cyclic oligoproline synthesis was successful for penta- and tetraproline but failed for the triproline. PyBOP/HOBt/DIPEA was employed for effective cyclization. The on-resin cyclic oligoproline CSP showed a lower number of resolved analytes, implying the importance of the poly-proline helix for chiral selectivity. The innovative separations in this study serve as starting points for developing mature separation methods.