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The work presented in this thesis involves the application of room temperature ionic liquids (RTILs) as solvents for use in electrochemical experiments. Initially, the fundamentals of electrochemistry is presented, followed by a comprehensive overview of RTILs in terms of their properties, applications and their behaviour as electrochemical solvents compared to conventional aprotic solvents. The results of 8 original studies are then presented as follows: X-Ray photoelectron spectroscopy is used to quantify the concentration of bromide ions in an ionic liquid, and is independently confirmed by potential-step chronoamperometry. The reaction mechanisms and kinetics for the electrochemical reduction of some aromatic nitro compounds (namely nitrobenzene and 4-nitrophenol) are determined. The electrochemistry of phosphorus trichloride and phosphorus oxychloride is studied in detail for the first time, due to the unusual stability of these highly reactive compounds in RTILs. The reductions and oxidations of sodium and potassium nitrate are studied, giving rise to 'melt'-like behaviour. The electrodeposition of sodium oxide on platinum is also demonstrated. The electrochemical oxidation of nitrite and the oxidation and reduction of the toxic gas, nitrogen dioxide, is presented. The oxidation of hydrogen gas is studied in ten RTILs with a range of different cations and anions, and contrasting interactions with the RTIL anions are seen. The electrochemical oxidation of ammonia gas is studied in five RTILs with different anions and a general reaction mechanism is suggested. The reduction of benzoic acid is studied in six RTILs, and the kinetics of the dissociation step are found to be very fast. The first five studies are all carried out in one particular ionic liquid, and the reactions and mechanisms are compared to that observed in conventional aprotic solvents. The last three studies employ several RTILs with different cations and anions to look at the contrasting interaction of protons with the RTIL cation/anion and ultimately help to understand the pH properties of the solvent. The overall findings from the work in this thesis are that some reactions and mechanisms (e.g bromide, nitro derivatives and ammonia) are generally the same in RTILs as in conventional aprotic solvents, but other species (e.g. nitrates, phosphorus derivatives) show remarkably different behaviour. It has also been demonstrated that RTILs are suitable media for the detection of nitrogen dioxide, hydrogen and ammonia gases. This suggests that RTILs could potentially offer many advantages when employed as solvents in electrochemical reactions and in amperometric gas sensors.

Thesis (Sc. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1972. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Vita. / Bibliography: leaves 308-329. / by Bingham H. Van Dyke, Jr. / Sc.D.

Dai, Zhuojun. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Abstracts in English and Chinese. / 摘要 --- p.i / ABSTRACT --- p.iii / ACKNOWLEDGEMENT --- p.v / Chapter Chapter 1 --- Introduction and Background --- p.-1- / Chapter 1.1 --- General introduction to internal motions --- p.-1- / Chapter 1.1.1 --- Definition of translational diffusion and internal motions --- p.-1- / Chapter 1.1.2 --- Theoretical background of internal motions --- p.-1- / Chapter 1.2 --- Investigation of internal motions on LLS --- p.-4- / Chapter 1.2.1 --- General introduction on investigation of internal motion by LLS --- p.-4- / Chapter 1.2.2 --- Theory on internal motion detected by LLS --- p.-5- / Chapter 1.3 --- Laser light scattering --- p.-6- / Chapter 1.3.1 --- General introduction to laser light scattering --- p.-6- / Chapter 1.3.2 --- Data process about internal motions in LLS --- p.-9- / Chapter 1.4 --- Notes and References --- p.-12- / Chapter Chapter 2 --- Internal motions of PNIPAM chains in 6 and bad solvent --- p.-15- / Chapter 2.1 --- Introduction --- p.-15- / Chapter 2.2 --- Experimental section --- p.-15- / Chapter 2.2.1 --- Sample preparation --- p.-15- / Chapter 2.2.2 --- Dynamic laser light scattering --- p.-16- / Chapter 2.3 --- Result and discussion --- p.-16- / Chapter 2.4 --- Conclusion --- p.-23- / Chapter 2.5 --- Notes and References --- p.-25- / Chapter Chapter 3 --- Internal motions of PNIPAM microgels in 6 and bad solvent --- p.-26- / Chapter 3.1 --- Introduction --- p.-26- / Chapter 3.2 --- Experimental section --- p.-26- / Chapter 3.2.1 --- Sample preparation --- p.-26- / Chapter 3.2.2 --- Dynamic laser light scattering --- p.-21- / Chapter 3.3 --- Result and discussion --- p.-27- / Chapter 3.4 --- Conclusion --- p.-30- / Chapter 3.5 --- Notes and References --- p.-31- / Chapter Chapter 4 --- Examination on the internal motions variations with solvent quality of Polystyrene chains --- p.-32- / Chapter 4.1 --- Introduction --- p.-32- / Chapter 4.2 --- Experimental Section --- p.-32- / Chapter 4.2.1 --- Sample preparation --- p.-32- / Chapter 4.2.2 --- Dynamic laser light scattering --- p.-33- / Chapter 4.3 --- Result and discussion --- p.-33- / Chapter 4.4 --- Conclusion --- p.-36- / Chapter 4.5 --- Notes and References --- p.-38- / Chapter Chapter 5 --- Examination on the internal motions variations with solvent quality of Poly(methyl methacrylate) chains --- p.-40- / Chapter 5.1 --- Introduction --- p.-40- / Chapter 5.2 --- Experimental Section --- p.-40- / Chapter 5.2.1 --- Sample preparation --- p.-40- / Chapter 5.2.2 --- Dynamic laser light scattering --- p.-41- / Chapter 5.3 --- Result and discussion --- p.-41- / Chapter 5.4 --- Conclusion --- p.-45- / Chapter 5.5 --- Notes and References --- p.-46-

Thesis (Ph. D.)--University of Oregon, 2007. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 178-191). Also available for download via the World Wide Web; free to University of Oregon users.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 258-270). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 103-116). Available also in a digital version from Dissertation Abstracts.

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