Experimental Studies of Interfacial Electrochemistry

Citation

Parkinson, Bruce Alan (1978) Experimental Studies of Interfacial Electrochemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/5byg-v343. https://resolver.caltech.edu/CaltechTHESIS:08272018-142532405

Abstract

Part I. Eu⁺², V⁺² and Co(NH₃)₆³⁺ as Electrode Kinetic Probes of the Structure of the Diffuse Layer in Dilute Electrolytes

The structure of the diffuse double layer at positive electrode charges in dilute perchlorate, fluoride, chloride and bromide electrolytes is inferred from the kinetics of oxidation of the Eu⁺², V⁺² and Co(NH₃)₆³⁺ cations, Diffuse layer potentials calculated from the measured kinetics of the V⁺² and Eu⁺² probes disagree, both in magnitude and (in some cases) in sign with potentials calculated from electrocapillary data and Gouy-Chapman-Stern theory. A different kinetic response is observed for Co(NH₃)₆³⁺ and is attributed to the formation of an ion pair with an adsorbed anion. The possible origin of these effects and their consequences in attempts to apply Frumkin double layer corrections or to detect discreteness-of-charge effects is discussed

Part II. The Formation of Polymeric Surface Phases on Mercury Electrodes from Solutions Containing Thioethercarboxylates and White Metal Cations

The adsorption of thioethercarboxylate ligands and complexes formed by these ligands with white metals (Pb⁺² in particular) on a mercury surface is investigated, Two distinct phases are apparent in many systems one at positive potentials and the other on more negative electrodes. The large adsorption of metal cations measured in both potential regions is attributed to the formation of a monolayer of polymeric surface phase which has a structure not unlike those observed in the molecular crystals of analogous compounds.

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