MIT Libraries logoDSpace@MIT

MIT
View Item 
  • DSpace@MIT Home
  • MIT Open Access Articles
  • MIT Open Access Articles
  • View Item
  • DSpace@MIT Home
  • MIT Open Access Articles
  • MIT Open Access Articles
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes

Author(s)
Caldwell, Andrew Harvey; Allanore, Antoine
Thumbnail
DownloadAccepted version (2.337Mb)
Publisher with Creative Commons License

Publisher with Creative Commons License

Creative Commons Attribution

Terms of use
Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/
Metadata
Show full item record
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.
Date issued
2020-03
URI
https://hdl.handle.net/1721.1/131072
Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering; MIT Materials Research Laboratory
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
ISSN
1572-6657

Collections
  • MIT Open Access Articles

Browse

All of DSpaceCommunities & CollectionsBy Issue DateAuthorsTitlesSubjectsThis CollectionBy Issue DateAuthorsTitlesSubjects

My Account

Login

Statistics

OA StatisticsStatistics by CountryStatistics by Department
MIT Libraries
PrivacyPermissionsAccessibilityContact us
MIT
Content created by the MIT Libraries, CC BY-NC unless otherwise noted. Notify us about copyright concerns.