A model of chronoamperometry of a two electrons electro-deposition reaction with the adsorption of intermediate
Original scientific paper
DOI:
https://doi.org/10.5599/jese.2026Keywords:
Two steps electrode mechanisms, adsorption of intermediate, logarithmic analysis, simultaneous electrons transfer, theory of electro-deposition reactions
Abstract
A single step chronoamperometry of reversible reactions complicated by the intermediate adsorption and the product deposition on inert electrodes is compared theoretically with an initial state of a simple two electrons electro-deposition. If the intermediate is highly unstable, these two mechanisms are similar, but the mechanism with successive electron transfers is needed to explain the responses appearing generally. The stability of intermediate depends on standard potentials of two steps and on the strength of adsorption. Two limiting cases are analysed and the difference between them is described.
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References
D. S. Rappleye, R. G. Fuller, Bringing the analysis of electrodeposition signal in voltammetry out of the shadows, Journal of The Electrochemical Society 170 (2023) 063505. https://doi.org/10.1149/1945-7111/acd879
T. Berzins, P. Delahay, Oscillographic polarographic waves for the reversible deposition of metals on solid electrodes, Journal of the American Chemical Society 75 (1953) 555-559. https://dx.doi.org/10.1021/ja01099a013
M. Paunović, M. Schlesinger, Fundamentals of Electrochemical Deposition, John Wiley & Sons, Hoboken, N. J. (2006) p. 113-138. https://doi.org/10.1002/0470009403.ch7
T. M. Braun, D. T. Schwartz, The emerging role of electrodeposition in additive manufacturing, Electrochemical Society Interface 25 (2016) 69-73. https://doi.org/10.1149/2.F07161if
N. Krishnamurthy, C. K. Gupta, Rare earth metals and alloys by electrolytic methods, Mineral Processing and Extractive Metallurgy Review 22 (2002) 477-507. https://doi.org/10.1080/08827500208547426
A. M. Abdelkader, K. T. Kilby, A. Cox, D. J. Pray, DC voltammetry of electro-deoxidation of solid oxides, Chemistry Reviews 113 (2013) 2863-2886. https://doi.org/10.1021/cr200305x
D. Krulic, N. Fatouros, D. Liu, A complementary survey of staircase voltammetry with metal ion deposition on macroelectrodes, Journal of Electroanalytical Chemistry 754 (2015) 30-39. https://doi.org/10.1016/j.jelechem.2015.06.012
I. Atek, S. Maye, H. H. Girault, A. M. Affoune, P. Peljo, Semi-analytical modelling of linear scan voltammetric responses for soluble - insoluble systems: the case of metal deposition. Journal of Electroanalytical Chemistry 818 (2018) 35-43. https://doi.org/10.1016/j.jelechem.2018.04.021
M. Yang, R. G. Compton, Voltammetry of adsorbed species: nonideal interactions leading to phase transtions, The Journal of Physical Chemistry C 124 (2020) 18031-18044. https://dx.doi.org/10.1021/acs.jpcc.0c03791
N. Arulmozhi, S. Hanselman, V. Tudor, X. Chen, D. van Velden, G. F. Schneider, F. Calle-Vallejo, M. T. M. Koper, Energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode, Journal of the American Chemical Society Au 3 (2023) 526-535. https://doi.org/10.1021/jacsau.2c00648
M. C. Arevalo, E. Pastor, S. Gonzalez, A. J. Arvia, Coadsorption phenomena and adsorbate competition in surface electrochemical reactions involving carbon monoxide and other organic residues, Electrochimica Acta 36 (14) (1991) 2183-2187. https://doi.org/10.1016/0013-4686(91)85227-X
A. M Chaparro, Current at a rotating disk electrode under electrosorption and surface diffusion limitations, Journal of The Electrochemical Society 164 (11) (2017) E3522-E3530. http://dx.doi.org/10.1149/2.0491711jes
J. Gonzalez, M. Lopez-Tenes, A. Molina, Non-Nernstian two-electron transfer reactions for immobilized molecules: a theoretical study in cyclic voltammetry, The Journal of Physical Chemistry C 117 (2013) 5208-5220. https://dx.doi.org/10.1021/jp312621u
M. Lopez-Tenes, J. Gonzalez, E. Laborda, A. Molina, Insights into the cyclic voltammetry of surface-confined molecules undergoing two-electron transfers of any reversibility and any ordering of the formal potentials: unravelling the apparent governing factors, Electrochimica Acta 462 (2023) 142694. https://doi.org/10.1016/j.electacta.2023.142694
D. H. Evans, One-electron and two-electron transfers in electrochemistry and homogeneous solution reactions, Chemistry Reviews 108 (2008) 2113. https://doi.org/10.1021/cr068066l
C. Batchelor-McAuley, R. G. Compton, Voltammetry of multi-electron electrode processes of organic species, Journal of Electroanalytical Chemistry 669 (2012) 73-81. https://doi.org/10.1016/j.jelechem.2012.01.016
A. J. Bard, L. R. Faulkner, Electrochemical Methods. Fundamentals and Applications, John Wiley & Sons, New York, 2001. ISBN 0-471-04372-9
P. Pirabaharan, M. Chitra Devi, L. Rajendran, Analytical expression of transient catalytic current for EC' mechanism using Danckwerts expression or Laplace transform, Results in Chemistry 5 (2023) 100940. https://doi.org/10.1016/j.rechem.2023.100940
M. Fayette, U. Bertocci, G. F. Stafford, In situ stress measurements during cobalt electrodeposition on (111)-textured Au. Journal of The Electrochemical Society 163 (2016) D146-D153. https://doi.org/10.1149/2.0511605jes
D. Anastasiadou, J. T. D. Janssen, E. J. M. Hensen, M. Costa Figueiredo, A study of Cu-Rh electrodeposition, ChemElectroChem 10 (2023) e202200842. https://doi.org/10.26434/chemrxiv-2022-dr5cd
M. Lovrić, Linear scan voltammetry of two-step irreversible electro-oxidation enhanced by the immobilization of an intermediate on the electrode surface, Portugaliae Electrochimica Acta 42 (2024) 223-232. https://doi.org/10.4152/pea.2024420305
Š. Komorsky-Lovrić, M. Lovrić, A simplified model of reactant adsorption in normal pulse voltammetry, Croatica Chemica Acta 91 (4) (2018) 525-531. https://doi.org/10.5562/cca3453
Š. Komorsky-Lovrić, M. Branica, Comparison of potentiometric stripping analysis and square-wave voltammetry with respect to the influence of Triton X-100, Analytica Chimica Acta 276 (1993) 361-366. https://doi.org/10.1016/0003-2670(93)80405-A
Š. Komorsky-Lovrić, M. Branica, Effects of surface-active substances in square-wave voltammetry and potentiometric stripping analysis of amalgam-forming metal ions, Fresenius Journal of Analytical Chemistry 349 (1994) 633-638. https://doi.org/10.1007/BF00323469
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