On choosing a reference redox system for electrochemical measurements: A cautionary tale

Torriero, Angel A.J., Feldberg, Stephen W., Zhang, Jie, Simonov, Alexandr N. and Bond, Alan M. 2013, On choosing a reference redox system for electrochemical measurements: A cautionary tale, Journal of solid state electrochemistry, vol. 17, no. 12, pp. 3021-3026, doi: 10.1007/s10008-013-2183-3.

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Title On choosing a reference redox system for electrochemical measurements: A cautionary tale
Author(s) Torriero, Angel A.J.ORCID iD for Torriero, Angel A.J. orcid.org/0000-0001-8616-365X
Feldberg, Stephen W.
Zhang, Jie
Simonov, Alexandr N.
Bond, Alan M.
Journal name Journal of solid state electrochemistry
Volume number 17
Issue number 12
Start page 3021
End page 3026
Total pages 6
Publisher Springer
Place of publication Berlin, Germany
Publication date 2013-12
ISSN 1432-8488
Keyword(s) Analyte system
Cyclic voltammetry
Formal potential
Internal reference redox system
Midpoint potential
Potential zone
Quasi-reference electrode
Summary The potential of a quasi-reference electrode can be determined by introducing an internal reference redox system (IRRS) which comprises either the oxidizable or reducible form of a reversible (and, ideally, outer-sphere) redox couple and then observing the cyclic voltammetric responses. The objective is to choose the IRRS so that the cyclic voltammetric response for the simultaneously present electroactive analyte system (ANS) can be observed independently of the IRRS response. We identify three fundamental paradigms describing the relative positioning of the IRRS and ANS on the potential scale, the operative redox components for the IRRS and ANS, and the starting potential (E start), reversing potential (E rev), and ending potential (E end) for the cyclic voltammetric scan as follows: paradigm A, an optimal paradigm which can produce completely independent cyclic voltammetric responses for the IRRS or for ANS; paradigm B, a less-than-optimal paradigm which can produce an independent cyclic voltammetry (CV) response for the ANS or a mixed response for the IRRS with that response on top of the ANS response; paradigm C, a problematic paradigm that can produce an independent CV response for the IRRS or a mixed response for the ANS with that response on top of the IRRS response; and any mixed response produces a thermodynamically favored redox cross-reaction which couples the IRRS and ANS systems and which can complicate the analysis of the ANS and IRRS responses. The conclusion is that paradigm C is to be avoided.
Language eng
DOI 10.1007/s10008-013-2183-3
Field of Research 030604 Electrochemistry
030102 Electroanalytical Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2013, Springer
Persistent URL http://hdl.handle.net/10536/DRO/DU:30061717

Document type: Journal Article
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