Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit

Handle URI:
http://hdl.handle.net/10754/598604
Title:
Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit
Authors:
Simonov, Alexandr N.; Morris, Graham P.; Mashkina, Elena A.; Bethwaite, Blair; Gillow, Kathryn; Baker, Ruth E.; Gavaghan, David J.; Bond, Alan M.
Abstract:
Many electrode processes that approach the "reversible" (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the "quasi-reversible" model. Simulations based on "reversible" and "quasi-reversible" models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc0/+) in CH3CN (0.10 M (n-Bu)4NPF6) and reduction of [Ru(NH 3)6]3+ and [Fe(CN)6]3- in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (E0), heterogeneous electron transfer rate constant at E0 (k0), charge transfer coefficient (α), uncompensated resistance (Ru), and double layer capacitance (CDL) can be reported using the "quasi- reversible" model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling CDL with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc0/+ and [Ru(NH3)6]3+/2+ processes. In summary, for fast electrode kinetics approaching the "reversible" limit, it is recommended that the "reversible" model be used for theory-experiment comparisons with only E0, R u, and CDL being quantified and a lower limit of k 0 being reported; e.g., k0 ≥ 9 cm s-1 for the Fc0/+ process. © 2014 American Chemical Society.
Citation:
Simonov AN, Morris GP, Mashkina EA, Bethwaite B, Gillow K, et al. (2014) Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit. Anal Chem 86: 8408–8417. Available: http://dx.doi.org/10.1021/ac5019952.
Publisher:
American Chemical Society (ACS)
Journal:
Analytical Chemistry
KAUST Grant Number:
KUK-C1-013-04
Issue Date:
19-Aug-2014
DOI:
10.1021/ac5019952
PubMed ID:
25047798
Type:
Article
ISSN:
0003-2700; 1520-6882
Sponsors:
This publication is based on work supported by Award No. KUK-C1-013-04, made by King Abdullah University of Science and Technology (KAUST). Financial support from the Australian Research Council is also gratefully acknowledged.
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Full metadata record

DC FieldValue Language
dc.contributor.authorSimonov, Alexandr N.en
dc.contributor.authorMorris, Graham P.en
dc.contributor.authorMashkina, Elena A.en
dc.contributor.authorBethwaite, Blairen
dc.contributor.authorGillow, Kathrynen
dc.contributor.authorBaker, Ruth E.en
dc.contributor.authorGavaghan, David J.en
dc.contributor.authorBond, Alan M.en
dc.date.accessioned2016-02-25T13:32:58Zen
dc.date.available2016-02-25T13:32:58Zen
dc.date.issued2014-08-19en
dc.identifier.citationSimonov AN, Morris GP, Mashkina EA, Bethwaite B, Gillow K, et al. (2014) Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit. Anal Chem 86: 8408–8417. Available: http://dx.doi.org/10.1021/ac5019952.en
dc.identifier.issn0003-2700en
dc.identifier.issn1520-6882en
dc.identifier.pmid25047798en
dc.identifier.doi10.1021/ac5019952en
dc.identifier.urihttp://hdl.handle.net/10754/598604en
dc.description.abstractMany electrode processes that approach the "reversible" (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the "quasi-reversible" model. Simulations based on "reversible" and "quasi-reversible" models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc0/+) in CH3CN (0.10 M (n-Bu)4NPF6) and reduction of [Ru(NH 3)6]3+ and [Fe(CN)6]3- in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (E0), heterogeneous electron transfer rate constant at E0 (k0), charge transfer coefficient (α), uncompensated resistance (Ru), and double layer capacitance (CDL) can be reported using the "quasi- reversible" model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling CDL with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc0/+ and [Ru(NH3)6]3+/2+ processes. In summary, for fast electrode kinetics approaching the "reversible" limit, it is recommended that the "reversible" model be used for theory-experiment comparisons with only E0, R u, and CDL being quantified and a lower limit of k 0 being reported; e.g., k0 ≥ 9 cm s-1 for the Fc0/+ process. © 2014 American Chemical Society.en
dc.description.sponsorshipThis publication is based on work supported by Award No. KUK-C1-013-04, made by King Abdullah University of Science and Technology (KAUST). Financial support from the Australian Research Council is also gratefully acknowledged.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleInappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limiten
dc.typeArticleen
dc.identifier.journalAnalytical Chemistryen
dc.contributor.institutionMonash University, Melbourne, Australiaen
dc.contributor.institutionUniversity of Oxford, Oxford, United Kingdomen
kaust.grant.numberKUK-C1-013-04en
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