Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes
Name
acv_manuscript_4.pdf
Description
Accepted version
Size
2.34 MB
Format
Adobe PDF
Checksum (MD5)
0bde935359db7e09fd7eae9ca4151d31
Author(s)
Caldwell, Andrew Harvey
Allanore, Antoine
Date Issued
March 2020
Journal
Journal of Electroanalytical Chemistry
Publisher
Elsevier BV
Citation
Caldwell, Andrew H. and Antoine Allanore. "Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes." Journal of Electroanalytical Chemistry 861 (March 2020): 113709.
Version
Author's final manuscript
Abstract
Analytic solutions are derived for the alternating current voltammetry (ACV) harmonic waveforms of electrodeposition and gas evolution reactions where the surface activity of the reduced species R is constant. Reversible and quasi-reversible charge transfer kinetics are considered, as well as the effects of ohmic drop and double layer charging. It is shown that ohmic drop produces a characteristic distortion of the waveform envelopes, resulting in the emergence of waveform extrema in the higher harmonics that are distinct from those of the conventional ACV theory of soluble redox couples. A quantitative connection is made between the peak potential of the second harmonic and the electrode reaction parameters. The analytic solutions agree well with measurements of the fundamental, second, and third harmonic waveforms of Pb electrodeposition on liquid Pb and of Cl2 evolution on graphite in molten PbCl2-NaCl-KCl at 700 °C.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
MIT Materials Research Laboratory
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivs License
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1016/j.jelechem.2019.113709
