A Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN) 6 ] 3–/4– Process by AC Voltammetry

Handle URI:
http://hdl.handle.net/10754/597236
Title:
A Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN) 6 ] 3–/4– Process by AC Voltammetry
Authors:
Morris, Graham P.; Simonov, Alexandr N.; Mashkina, Elena A.; Bordas, Rafel; Gillow, Kathryn; Baker, Ruth E.; Gavaghan, David J.; Bond, Alan M.
Abstract:
Fully automated and computer assisted heuristic data analysis approaches have been applied to a series of AC voltammetric experiments undertaken on the [Fe(CN)6]3-/4- process at a glassy carbon electrode in 3 M KCl aqueous electrolyte. The recovered parameters in all forms of data analysis encompass E0 (reversible potential), k0 (heterogeneous charge transfer rate constant at E0), α (charge transfer coefficient), Ru (uncompensated resistance), and Cdl (double layer capacitance). The automated method of analysis employed time domain optimization and Bayesian statistics. This and all other methods assumed the Butler-Volmer model applies for electron transfer kinetics, planar diffusion for mass transport, Ohm's Law for Ru, and a potential-independent Cdl model. Heuristic approaches utilize combinations of Fourier Transform filtering, sensitivity analysis, and simplex-based forms of optimization applied to resolved AC harmonics and rely on experimenter experience to assist in experiment-theory comparisons. Remarkable consistency of parameter evaluation was achieved, although the fully automated time domain method provided consistently higher α values than those based on frequency domain data analysis. The origin of this difference is that the implemented fully automated method requires a perfect model for the double layer capacitance. In contrast, the importance of imperfections in the double layer model is minimized when analysis is performed in the frequency domain. Substantial variation in k0 values was found by analysis of the 10 data sets for this highly surface-sensitive pathologically variable [Fe(CN) 6]3-/4- process, but remarkably, all fit the quasi-reversible model satisfactorily. © 2013 American Chemical Society.
Citation:
Morris GP, Simonov AN, Mashkina EA, Bordas R, Gillow K, et al. (2013) A Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN) 6 ] 3–/4– Process by AC Voltammetry . Anal Chem 85: 11780–11787. Available: http://dx.doi.org/10.1021/ac4022105.
Publisher:
American Chemical Society (ACS)
Journal:
Analytical Chemistry
KAUST Grant Number:
KUK-C1-013-04
Issue Date:
17-Dec-2013
DOI:
10.1021/ac4022105
PubMed ID:
24160752
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. Authors are grateful to Mr. Blair Bethwaite (Monash eResearch Centre, Monash University, Australia), Dr. Jeff Tan (IBM Research, Melbourne, Australia), and Prof. David Abramson (University of Queensland, Australia) for their generous assistance with processing experimental data using Nimrod tools.
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Full metadata record

DC FieldValue Language
dc.contributor.authorMorris, Graham P.en
dc.contributor.authorSimonov, Alexandr N.en
dc.contributor.authorMashkina, Elena A.en
dc.contributor.authorBordas, Rafelen
dc.contributor.authorGillow, Kathrynen
dc.contributor.authorBaker, Ruth E.en
dc.contributor.authorGavaghan, David J.en
dc.contributor.authorBond, Alan M.en
dc.date.accessioned2016-02-25T12:28:38Zen
dc.date.available2016-02-25T12:28:38Zen
dc.date.issued2013-12-17en
dc.identifier.citationMorris GP, Simonov AN, Mashkina EA, Bordas R, Gillow K, et al. (2013) A Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN) 6 ] 3–/4– Process by AC Voltammetry . Anal Chem 85: 11780–11787. Available: http://dx.doi.org/10.1021/ac4022105.en
dc.identifier.issn0003-2700en
dc.identifier.issn1520-6882en
dc.identifier.pmid24160752en
dc.identifier.doi10.1021/ac4022105en
dc.identifier.urihttp://hdl.handle.net/10754/597236en
dc.description.abstractFully automated and computer assisted heuristic data analysis approaches have been applied to a series of AC voltammetric experiments undertaken on the [Fe(CN)6]3-/4- process at a glassy carbon electrode in 3 M KCl aqueous electrolyte. The recovered parameters in all forms of data analysis encompass E0 (reversible potential), k0 (heterogeneous charge transfer rate constant at E0), α (charge transfer coefficient), Ru (uncompensated resistance), and Cdl (double layer capacitance). The automated method of analysis employed time domain optimization and Bayesian statistics. This and all other methods assumed the Butler-Volmer model applies for electron transfer kinetics, planar diffusion for mass transport, Ohm's Law for Ru, and a potential-independent Cdl model. Heuristic approaches utilize combinations of Fourier Transform filtering, sensitivity analysis, and simplex-based forms of optimization applied to resolved AC harmonics and rely on experimenter experience to assist in experiment-theory comparisons. Remarkable consistency of parameter evaluation was achieved, although the fully automated time domain method provided consistently higher α values than those based on frequency domain data analysis. The origin of this difference is that the implemented fully automated method requires a perfect model for the double layer capacitance. In contrast, the importance of imperfections in the double layer model is minimized when analysis is performed in the frequency domain. Substantial variation in k0 values was found by analysis of the 10 data sets for this highly surface-sensitive pathologically variable [Fe(CN) 6]3-/4- process, but remarkably, all fit the quasi-reversible model satisfactorily. © 2013 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. Authors are grateful to Mr. Blair Bethwaite (Monash eResearch Centre, Monash University, Australia), Dr. Jeff Tan (IBM Research, Melbourne, Australia), and Prof. David Abramson (University of Queensland, Australia) for their generous assistance with processing experimental data using Nimrod tools.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleA Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN) 6 ] 3–/4– Process by AC Voltammetryen
dc.typeArticleen
dc.identifier.journalAnalytical Chemistryen
dc.contributor.institutionUniversity of Oxford, Oxford, United Kingdomen
dc.contributor.institutionMonash University, Melbourne, Australiaen
kaust.grant.numberKUK-C1-013-04en

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