Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes
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 ef...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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Elsevier BV
2021
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| Online Access: | https://hdl.handle.net/1721.1/131072 |
| _version_ | 1826199059933691904 |
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| author | Caldwell, Andrew Harvey Allanore, Antoine |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Caldwell, Andrew Harvey Allanore, Antoine |
| author_sort | Caldwell, Andrew Harvey |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T11:14:06Z |
| format | Article |
| id | mit-1721.1/131072 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:14:06Z |
| publishDate | 2021 |
| publisher | Elsevier BV |
| record_format | dspace |
| spelling | mit-1721.1/1310722022-10-01T02:15:52Z Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes Caldwell, Andrew Harvey Allanore, Antoine Massachusetts Institute of Technology. Department of Materials Science and Engineering MIT Materials Research Laboratory 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. 2021-07-13T16:14:49Z 2021-07-13T16:14:49Z 2020-03 2019-12 2021-07-12T16:24:32Z Article http://purl.org/eprint/type/JournalArticle 1572-6657 https://hdl.handle.net/1721.1/131072 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. en http://dx.doi.org/10.1016/j.jelechem.2019.113709 Journal of Electroanalytical Chemistry Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Elsevier BV Prof. Allanore via Ye Li |
| spellingShingle | Caldwell, Andrew Harvey Allanore, Antoine Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title | Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title_full | Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title_fullStr | Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title_full_unstemmed | Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title_short | Alternating current voltammetry of electrode reactions with constant surface activity: Application to electrolysis of molten electrolytes |
| title_sort | alternating current voltammetry of electrode reactions with constant surface activity application to electrolysis of molten electrolytes |
| url | https://hdl.handle.net/1721.1/131072 |
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