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Title: Parameter recovery in AC solution-phase voltammetry and a consideration of some issues arising when applied to surface-confined reactions
Author: Morris, Graham Peter
ISNI:       0000 0004 5365 8551
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2014
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A major problem in the quantitative analysis of AC voltammetric data has been the variance in results between laboratories, often resulting from a reliance on "heuristic" methods of parameter estimation that are strongly dependent on the choices of the operator. In this thesis, an automatic method for parameter estimation will be tested in the context of experiments involving electron-transfer processes in solution-phase. It will be shown that this automatic method produces parameter estimates consistent with those from other methods and the literature in the case of the ferri-/ferrocyanide couple, and is able to explain inconsistency in published values of the rate parameter for the ferrocene/ferrocenium couple. When a coupled homogeneous reaction is considered in a theoretical study, parameter recovery is achieved with a higher degree of accuracy when simulated data resulting from a high frequency AC voltammetry waveform are used. When surface-confined reactions are considered, heterogeneity in the rate constant and formal potential make parameter estimation more challenging. In the final study, a method for incorporating these "dispersion" effects into voltammetric simulations is presented, and for the first time, a quantitive theoretical study of the impact of dispersion on measured current is undertaken.
Supervisor: Gavaghan, David J.; Gillow, Kathryn; Baker, Ruth E. Sponsor: King Abdullah University of Science and Technology
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Mathematics ; Biology and other natural sciences (mathematics) ; Partial differential equations ; Computational chemistry ; Electrochemistry and electrolysis ; voltammetry ; AC voltammetry ; electrochemistry ; mathematical modelling ; numerical solutions ; inverse problems ; parameter estimation