Sonoelectroanalysis : theory and experiment
This thesis reports the development of sonoelectrochemistry as a technique for sample analysis. Complementary modelling gives an insight into the mass transport and electrode reaction mechanisms. Separate studies were conducted as follows: - Initially an copper(II) acetate buffer system was used as its speciation can be determined. In order to establish under which conditions analysis could be conducted the effect of speciation was examined. These were applied to the Anodic Stripping Voltammetry (ASV) determination of copper in the acetate solution and to facilitate the use of a traditionally inhospitable electrochemical medium: real ale with minimal pre-treatment. Both gave detection limits of the range (1-100) μg L-1 and in quantitative agreement with Atomic Absorption Spectroscopy. - The effect of acoustic streaming under mild insonation was studied by modelling Square Wave Voltammetry (SWV) of ASV and was found, when compared to experiment, to be the dominating factor. When the latter is strongly present two distinct mass.transport regimes were identified. Studies of chemical and electrochemical processes suggested that the acoustic streaming model fails under more extreme conditions. - SWV voltammetry was modelled for reversible electrochemical reactions leading to a refinement of existing analytical theory and the ASV modelling extended to account for surface morphology and finite electrode kinetics. Droplets on an electrode surface subjected to a potential sweep give rise to voltammetric traces attributed to charge insertion. Three mechanisms for this are proposed: (i) charge injection at the droplets surface, (ii) charge injection at the three phase boundary and (iii) the droplet is saturated with counter ions and electron transfer occurs at the electrode surface. These are solved numerically and incorporate Regular Solution Theory to account for non-ideal interactions. Comparing with experimental data an approximate model identified the processes occurring for small droplets. A Marangoni-type convection is suggested for larger droplets.