Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1977.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1994. / Vita. Abstract. Includes bibliographical references (leaves 84-86). Also available via the Internet.

Thesis (MScAgric)--University of Stellenbosch, 2007. / Bibliography. Also available via the Internet.

Thesis (Ph.D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Janata, Jiri; Committee Member: Bunz, Uwe; Committee Member: Collard, David; Committee Member: Josowicz, Mira; Committee Member: Kohl, Paul.

Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2009. / Full text also available online. Scroll down for electronic link.

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Ionic liquids (ILs), consisting of ions that are liquid at ambient temperatures, can act as solvents for a broad spectrum of chemical processes. These ionic liquids are attracting increasing attention from industry because they promise significant environmental as well as product and process benefits. ILs were used as solvents for two industrially important homogeneous reactions namely metathesis of 1-octene and the hydroformylation of vinyl acetate. In the metathesis of 1-octene, several reaction parameters were investigated, including temperature, catalyst (type and concentration) and influence of ionic solvent and conventional solvents. Temperature and catalyst concentration were found to be rate-determining factors, but played smaller roles in determining the outcomes of the reactions compared to the influence of individual ILs. It was discovered that more polar ILs were favourable in producing high rates and selectivities. Imidazolium-based cations and tetrafluoroborate anions were superior in activity when compared to other combinations of cations and anions. The addition of catalyst promoters such as phenol and tin(II) chloride were also investigated and found to enhance metathesis rates in “neat” reactions. These catalyst promoters inhibited metathesis rates when used in combination with ILs. In the hydroformylation of vinyl acetate, several reaction parameters were investigated, including temperature, catalyst concentration, vinyl acetate concentration, ligand concentration, syngas pressure and influence of ionic solvent and conventional solvents. It was shown that high n : i ratios of aldehyde products were formed with specific IL systems. Also, low ligand concentrations and low vinyl acetate concentrations increased selectivities, although rates of reactions were somewhat compromised. Lower syngas pressure and lower temperatures afforded enhanced selectivities, again at the expense of reaction rates. Depending on whether fast reaction rates or high regioselectivity is required, the IL and general reaction conditions can be tailored to fit the needs of the reaction. It was discovered that aromatic-containing ammonium-based ILs v afforded high rates at low selectivity. Bulkier ammonium cations tended to give lower rates but the selectivity was significantly enhanced. Impurities present in ILs have also been shown to have a marked effect on hydroformylation rates and selectivity. The reader will be accompanied along a path designed to discover an optimised set of reaction conditions, the path of which will take the reader from reactions providing low selectivities, low turnover numbers and low yields to a much brighter picture, namely extremely high selectivities, turnover numbers and yields. / Prof. D.B.G. Williams

Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models were created to standard deviations of 0.198 and 0.122 logunits for gas-to-PDMS wet and dry, respectively, as well as 0.164 and 0.134 log units for water-to-PDMS wet and dry, respectively. These models are particularly useful in solid phase microextraction separations. Micelles were studied to create predictive models of the measured micelle-water partition coefficient as well as models of measured MEKC chromatographic retention factors for CTAB and SDS. The resultant predictive models were created with standard deviations of 0.190 log units for the logarithm of the mole fraction concentration of water-to-CTAB, 0.171 log units for the combined logarithms of both the mole fraction concentration of water-to-CTAB and measured MEKC chromatographic retention factors for CTAB, and 0.153 log units for the combined logarithms of both the mole fraction concentration of water-to-SDS and measured MEKC chromatographic retention factors for SDS.

Ionic polymers are a recently discovered class of active materials that exhibit bidirectional electromechanical coupling. They are `soft' transducers that perform best when the mechanical deformation involves bending of the transducer. Ionic polymers are low voltage actuators -- they only require inputs on the order of 1V and cannot tolerate voltages above approximately 10V. The mechanisms responsible for the electromechanical coupling are not yet fully understood, and reports of the capabilities and limitations of ionic polymer transducers vary widely. In addition, suitable engineering models have not been developed. This document presents a dynamic model for ionic polymer transducers that is based on a pair of symmetric, linearly coupled equations with frequency dependent coefficients. The model is presented in the form of an equivalent circuit, employing an ideal transformer with a frequency dependent turns ratio to represent the electromechanical coupling. The circuit elements have clear physical interpretations, and expressions relating them to transducer dimensions and material properties are derived herein. The material parameters required for the model: modulus, density, electrical properties, and electromechanical coupling term are determined experimentally. The model is then validated by comparing simulated and experimental responses, and the agreement is good. Further validation is presented in the form of extensive experiments that confirm the predicted changes in transducer performance as transducer dimensions are varied. In addition, reciprocity between mechanical and electrical domains is demonstrated. This reciprocity is predicted by the model, and is a direct result of the symmetry in the equations on which the model is based. The capabilities of ionic polymer sensors and actuators, when used in the cantilevered bender configuration, are discussed and compared to piezoceramic and piezo polymer cantilevered benders. The energy density of all three actuators are within an order of magnitude of one another, with peak values of approximately 10J/m^3 and 4mJ/kg for ionic polymer actuators actuated with a 1.2V signal. Ionic polymer sensors compare favorably to piezoelectric sensors. Their charge sensitivity is approximately 320E-6C/m for a 0.2 x 5 x 17mm cantilevered bender, two orders of magnitude greater than a piezo polymer sensor with identical dimensions. This work is concluded with a demonstration of feedback control of a device powered by ionic polymer actuators. An ionic polymer sensor was used to provide the displacement feedback signal. This experiment is the first demonstration of feedback control using an ionic polymer sensor. Compensator design was performed using the model developed in the first chapter of this document, and experiments confirmed that implementation of the control scheme improved, in a narrow frequency range, the system's ability to track sinusoidal inputs. / Ph. D.

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