Mechanism and equivalent circuits in electrochemical impedance spectroscopy

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dc.contributor.authorHarrington, David A.
dc.contributor.authorDriessche, P. van den
dc.date.accessioned2019-06-27T15:28:38Z
dc.date.available2019-06-27T15:28:38Z
dc.date.copyright2011en_US
dc.date.issued2011-09
dc.description.abstractThe utility and limitations of using equivalent circuits to analyse electrochemical impedance spectroscopy (EIS) data for electrochemical reaction mechanisms are reviewed. The difficulty of assigning physical meaning to elements is discussed. The utility of equivalent circuits as measurement models is emphasized, and ways to use them to find mechanistic information are discussed. The rules about which mechanisms can show inductive behavior are of interest, since this is a visually obvious feature. We review our previous rules for mechanisms that can show inductive behavior, and show that inductive behavior is more common for mechanisms with two adsorbed species. We discuss two variations of a simple cycle mechanism (A → B → C → A) in more detail. The interpretation of the charge-transfer resistance and the polarization resistance has some subtleties. Transfer coefficients extracted from Tafel plots of steady-state current–potential measurments are often used to determine where in the mechanism the rate-determining step is. We show that transfer coefficients from Tafel plots of the charge-transfer resistance do not have the same mechanistic significance. The polarization resistance is simply related to the slope of the polarization curve. We discuss the validity of this relationship and its utility in interpreting spectra.en_US
dc.description.reviewstatusRevieweden_US
dc.description.scholarlevelFacultyen_US
dc.description.sponsorshipWe thank the Natural Sciences and Engineering Research Council of Canada and the University of Victoria for financial support of this research. We thank Frode Seland and Dan Bizzotto for useful discussions relating to this work.en_US
dc.identifier.citationHarrington, D.A. & Driessche, P. (2011). Mechanism and equivalent circuits in electrochemical impedance spectroscopy. Electrochimica Acta, 56(23), 8005-8013. https://doi.org/10.1016/j.electacta.2011.01.067en_US
dc.identifier.urihttps://doi.org/10.1016/j.electacta.2011.01.067
dc.identifier.urihttp://hdl.handle.net/1828/10941
dc.language.isoenen_US
dc.publisherElectrochimica Actaen_US
dc.subjectEquivalent circuit
dc.subjectMechanism
dc.subjectCharge-transfer resistance
dc.subjectPolarization resistance
dc.subjectInductive
dc.subjectImpedance
dc.subjectEIS
dc.subject.departmentDepartment of Chemistry
dc.subject.departmentDepartment of Mathematics and Statistics
dc.titleMechanism and equivalent circuits in electrochemical impedance spectroscopyen_US
dc.typePostprinten_US

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