How does a reversible electrode respond in a.c. voltammetry? Part 2: solutions for the periodic current amplitudes

In a.c. voltammetry, a programmed electrical potential—a linear ramp modulated by a sine wave of frequency ω and modest amplitude—is applied to the working electrode of a voltammetric cell. If the electrolyte solution contains a solute that undergoes a reversible electron exchange at the electrode,...

Full description

Saved in:
Bibliographic Details
Published in:Journal of solid state electrochemistry 2019-07, Vol.23 (7), p.2061-2071
Main Authors: Myland, Jan C., Oldham, Keith B.
Format: Article
Language:English
Subjects:
Amplitudes
Analytical Chemistry
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Computer simulation
Condensed Matter Physics
Electrochemistry
Electrodes
Energy Storage
Fourier transforms
Mathematical models
Original Paper
Physical Chemistry
Sine waves
Time dependence
Voltammetry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:In a.c. voltammetry, a programmed electrical potential—a linear ramp modulated by a sine wave of frequency ω and modest amplitude—is applied to the working electrode of a voltammetric cell. If the electrolyte solution contains a solute that undergoes a reversible electron exchange at the electrode, then the ensuing faradaic current incorporates two aperiodic components, together with a pseudosinusoidal component of every frequency that is an integer multiple of ω . An exact mathematical model is presented that predicts how the time-dependent amplitudes of each of these latter harmonic currents evolve during the experiment. This analytical model, which does not invoke simulation or Fourier transformation, is useful only at early voltammetric times, but a numerical scheme extends the solution to encompass the entire scan. Amazingly, the time-dependent amplitudes of the periodic currents match their semiintegrals in shape.
ISSN:1432-8488
1433-0768
DOI:10.1007/s10008-019-04238-0