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Title: Studying the altered reactivity of electrochemical systems in room temperature ionic liquids
Author: Ernst, Sven
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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The work presented in this thesis examines the electrochemical behaviour of a number of species, both surface-bound and in the solution phase, in various room-temperature ionic liquids (RTILs), in order to identify systems which show altered reactivities in room-temperature ionic liquids, compared to that in conventional, molecular, aprotic solvents. The fundamentals of electrochemistry are outlined and an introduction to room-temperature ionic liquids is given, after which the results of six original investigations are presented, as follows; The electrochemical response of surface-bound anthraquinonyl films was investigated as a function of RTIL cation size. The reduction of oxygen to superoxide in the [C2mim][NTf2] RTIL was studied at different carbon electrodes. The mechanisms of electrodeposition and stripping of Zn(II) onto bulk zinc deposits, on glassy carbon electrodes, in the [C4mPyrr][NTf2] RTIL were investigated. A novel and successful method for the fabrication of zinc microdisk electrodes was developed and the electrochemical behaviour of these electrodes was investigated. The mechanisms for the electrochemical reductions of some bromo- and nitrobenzenes at platinum microelectrodes were determined in the [C4mPyrr][NTf2] ionic liquid, in order to identify systems which displayed changed reactivities in RTILs compared to those in molecular aprotic solvents. The altered reactivity of 1-bromo-4-nitrobenzene in the [C4mPyrr][NTf2] ionic liquid was utilised via electrochemical reduction at zinc microelectrodes in order to form arylzinc compounds. The work presented in this thesis shows that the oft-taken view that the reactivity of a given species in an ionic liquid will mimic that in conventional aprotic solvents is not always the case. Reactivities can be markedly different between RTILs and aprotic solvents and can also be highly dependent on the specific ionic liquid employed.
Supervisor: Compton, Richard G. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Physical Sciences ; Chemistry & allied sciences ; Chemical kinetics ; Electrochemistry and electrolysis ; Physical & theoretical chemistry ; electrochemistry ; reactivity ; kinetics ; thermodynamics ; mechanistics ; room temperature ionic liquids ; microelectrodes ; cyclic voltammetry ; chronoamperometry ; simulation ; electrosynthesis