New potential waveforms for cyclic and linear-sweep voltammetry
<p>This thesis is concerned with the simulation of electrochemical systems in general and of voltammetry using various potential waveforms in particular. Chapter 1 introduces the fundamental principles of electrochemistry essential to the understanding of this thesis, and Chapter 2 outlines th...
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| Format: | Thesis |
| Language: | English |
| Published: |
2019
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| Summary: | <p>This thesis is concerned with the simulation of electrochemical systems in general
and of voltammetry using various potential waveforms in particular. Chapter
1 introduces the fundamental principles of electrochemistry essential to the understanding
of this thesis, and Chapter 2 outlines the methodology used in the
numerical simulation of the systems of interest.</p>
<p>Chapters 3 and 4 discuss the application and benefit of a non-triangular/nonlinear
potential waveform to run cyclic voltammetry/potential-sweep voltammetry.
In both chapters, a one-dimensional macroelectrode system is modelled for a
one-electron electrochemically reversible reaction. Chapter 3 investigates the
effect of cosine-based potential waves on the capacitive and Faradaic currents
and proposes new opportunities to determine the formal potential of a redox couple
based on the peak-to-peak separation in measured voltammograms. Chapter 4
extends the concept of a non-linear potential wave and studies the effect of a
semi-circular potential wave on the current response for increased sensitivity of
detection in electroanalysis. In both chapters, an experimental verification of
the method are provided.</p>
<p>Chapters 5 and 6 extend the semi-circular potential wave method to a twodimensional
microelectrode system. Chapter 5 illustrates that the semi-circular
potential wave method produces similar trends at a microelectrode as it does at
a macroelectrode and shows the increased applicability of the method. Chapter 6
proposes a new method for determining the standard electrochemical rate constant
through the application of a semi-circular potential wave at a microelectrode based
on the voltammetric features.</p>
<p>Chapter 7 applies the semi-circular potential waveform to stripping voltammetry
for a one-electron electrochemically reversible reaction and shows how the unique
voltammetric curves resulting from the semi-circular potential wave markedly
increase the sensitivity.</p> |
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