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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.

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Digitized by Kansas State University Libraries

Call number: LD2668 .T4 1936 S31

Call number: LD2668 .T4 1960 H47

New phosphonium and ammonium ionic liquids were prepared for use in two green applications. Ionic liquids are generating considerable current interest as media for electrochemical processes such as electrodeposition, which can be used to create thin films of a variety of compounds. For the first time, silicon deposition has been achieved in the phosphonium ionic liquid triethyl(2-methoxyethyl)phosphonium bis(trifluoromethylsulfonyl)amide (P201-TFSI). Subsequently, silicon has been deposited from a wide variety of precursors in order to optimize the thickness and morphology of the deposited films. The silicon films electrodeposited in the phosphonium ionic liquid show marked differences from those deposited in organic solvents, imidizolium and pyrrolidinium based ionic liquids. Phosphonium and ammonium ionic liquids were also investigated for use in carbon dioxide capture. Task-specific ionic liquids have shown great promise as agents for the physisorption and chemisorption of CO2 from combustion gas streams. Efforts to synthesize new task specific ionic liquids with multiple amine functionalities for CO2 capture are reported. Four different reaction pathways were explored for the synthesis of these materials. While this goal was not achieved in this work, task-specific phosphonium and ammonium ionic liquids offer the promise of opening up new areas in ionic liquid research. / text

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