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Probing chemical dynamics near electrode surfaces with ultramicroelectrodes


Pylkki, Russell John (1993) Probing chemical dynamics near electrode surfaces with ultramicroelectrodes. Dissertation (Ph.D.), California Institute of Technology.


This thesis describes work carried out to observe the dynamics of diffusion layer growth near electrode surfaces. For the first time, these processes are observed within 1 µm of an electrode. This is accomplished by positioning an ultramicroelectrode near an electrode surface with a scanning tunneling microscope. A bipotentiostat is integrated with the scanning tunneling microscope to allow potential control of the sample cell, permitting independent control of both the electrode substrate and the ultramicroelectrode tip potentials.

The response of the diffusion layer to potentiostatic and galvanostatic stimulus of the substrate is described. The responses to the stimulus in the absence of coupled chemical reactions are shown to agree well with theory. The observed effects of a coupled chemical reaction are also reported and compared to the responses generated from a simulation program. Good agreement of the experimental data to the simulated data is shown, which demonstrates the ability of the instrument to study homogeneous kinetics.

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:Restricted to Caltech community only
Research Advisor(s):
  • Anson, Fred C. (advisor)
  • Lewis, Nathan Saul (advisor)
Thesis Committee:
  • unknown, unknown
Defense Date:14 October 1992
Record Number:CaltechTHESIS:01022013-155536079
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7364
Deposited By: Benjamin Perez
Deposited On:03 Jan 2013 00:07
Last Modified:03 Jan 2013 00:07

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