Abbott, Andrew Peter (1989) Transition metal electrochemistry in aromatic solvents. University of Southampton, Doctoral Thesis.
Abstract
This thesis describes a new type of solvent for electrochemistry. The use of polyaromatic hydrocarbons as solvents is demonstrated in the field of metal deposition, where the electroplating of several transition metals are shown as examples. Ideas for dissolving such metallic species in aprotic solvent of low dielectric constant are also discussed. The first part of this work is concerned with the characterisation of this type of solvent, in terms of the conductivity and solubility of various tetra-alkylammonium salts. A simple method for predicting the solubilities by measuring the u.v. absorbtion spectra of a dye in these solvents is demonstrated. The theory of conductivity in low dielectic constant solvents is also discussed in terms of ion pair and triple ion formation. Data is analysed using a modified Fuoss-Kraus theory which takes the activity coefficient of the undissociated electrolyte into account. The second part of this thesis discusses the suitability of this type of solvent to metal deposition, and the difficulties associated with the deposition of certain of the more reactive transition metals. The plating of some simple alloys is also shown. The role of the ligand and the oxidation state at which the transition metal is first introduced into the solvent is discussed.
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