High-speed electrochemistry using ultramicroelectrodes
Walsh, Michael Ralph
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/20596
Description
Title
High-speed electrochemistry using ultramicroelectrodes
Author(s)
Walsh, Michael Ralph
Issue Date
1989
Doctoral Committee Chair(s)
Faulkner, Larry R.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Analytical
Language
eng
Abstract
This research investigates the use of ultramicroelectrodes in performing electrochemistry on microsecond and nanosecond time scales. Other researchers have used ultramicroelectrodes for this purpose, but their studies have centered on dissolved species and generally use cyclic voltammetry experiments. One purpose of this research was to look at new ways to apply ultramicroelectrodes to high speed experiments. Some of the aspects that are discussed in this thesis are: (a) A novel technique was developed for measuring currents on short time scales that involves conversion of the current to light using a light emitting diode and measuring the light intensity as a function of time using time correlated single photon counting (TCSPC). Computer processing of the light intensity data can convert this data back to current. The technique is capable of measurements on nanosecond time scales, but TCSPC requires tens or hundreds of millions of experiments to obtain a complete set of data and this frequently results in severe electrode fouling problems. (b) Potential step experiments were used instead of potential sweep experiments. Potential step experiments enable the separation in time of the faradaic and charging currents for chemical systems in which the faradaic impedance is greater than the uncompensated solution resistance. (c) For systems in which the faradaic impedance and uncompensated resistance are of the same order of magnitude, a computer simulation was developed which accounts for the interaction of the faradaic and double layer charging processes. (d) Application of short time scale experiments to the study of surface processes. Some processes studied in this work are the oxidation of clean platinum surfaces, electrode reactions of anthraquinone-2,6-disulfonic acid adsorbed on mercury, reductive hydrogen adsorption on platinum and double layer charging. (e) A study of the smallest available time constants was performed, taking into account non-idealities in the electrode such as stray capacitance and resistance of the electrode itself. This study indicates that time constants in the tens of nanoseconds are probably the shortest attainable using the conventional setups for ultramicroelectrode experiments. (f) A discussion of techniques for cleaning electrodes which are often necessary for repetitive experiments due to electrode fouling problems. One technique useful in cleaning platinum electrodes for hydrogen adsorption studies is to use a double pulse waveform in which the first pulse oxidizes and reduces the platinum to clean the electrode. The second pulse, which occurs microseconds or milliseconds after the first pulse, causes the hydrogen adsorption process.
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
