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Experimental Studies of Interfacial Electrochemistry


Parkinson, Bruce Alan (1978) Experimental Studies of Interfacial Electrochemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/5byg-v343.


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.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Anson, Fred C.
Thesis Committee:
  • Anson, Fred C.
Defense Date:12 December 1977
Record Number:CaltechTHESIS:08272018-142532405
Persistent URL:
Parkinson, Bruce Alan0000-0002-8950-1922
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11164
Deposited By: Benjamin Perez
Deposited On:04 Sep 2018 16:55
Last Modified:16 Apr 2021 22:21

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