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Monitoring the Ejection and Incorporation of Ferricyanide Fe(CN)_6^(3-) and Ferrocyanide Fe(CN)_6^(4-) Counterions at Protonated Poly(4-vinylpyridine) Coatings on Electrodes with the Scanning Electrochemical Microscope

Kwak, Juhyoun and Anson, Fred C. (1992) Monitoring the Ejection and Incorporation of Ferricyanide Fe(CN)_6^(3-) and Ferrocyanide Fe(CN)_6^(4-) Counterions at Protonated Poly(4-vinylpyridine) Coatings on Electrodes with the Scanning Electrochemical Microscope. Analytical Chemistry, 64 (3). pp. 250-256. ISSN 0003-2700. doi:10.1021/ac00027a003. https://resolver.caltech.edu/CaltechAUTHORS:20180130-083252099

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Abstract

The precise positioning of microtlp electrodes close to the surface of substrate electrodes, as practiced in scanning electrochemlcal microscopy, was exploited to monitor the concentrations of Fe(CN)_6^(-3) and Fe(CN)_6^(-4) anions at the surfaces of protonated poly(4-vinylpyridine) coatings on glassy-carbon electrodes. Positive feedback, which enhanced the magnitude of currents at the monitoring tip electrode, gave way to negative feedback when reactant concentrations were increased to the point that electron propagation through the polyectrolyte coatings became the curent-limiting step. The election of counterions when cathodic currents were passed through coatings which were saturated with Fe(CN)_6^(3-) was readily detected, especially when current steps were applied to the coated substrate electrode. Delayed arrival of counterions at the monitoring tip could be associated with the time required for the ions to traverse the coatings before they were ejected. Reincorporation of multiply-charged counterions inmediately following their ejection appeared to be favored over the incorporation of singly charged anions present at much higher concentrations.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1021/ac00027a003DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ac00027a003PublisherArticle
Additional Information:© 1992 American Chemical Society. Published in print 1 February 1992. Publication Date: February 1992. This work was supported by the National Science Foundation. This is Contribution No. 8492 from the Division of Chemistry and Chemical Engineering, California Institute of Technology.
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Caltech Division of Chemistry and Chemical Engineering8492
Issue or Number:3
DOI:10.1021/ac00027a003
Record Number:CaltechAUTHORS:20180130-083252099
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180130-083252099
Official Citation:Monitoring the ejection and incorporation of ferricyanide [Fe(CN)63-] and ferrocyanide [Fe(CN)64-] counterions at protonated poly(4-vinylpyridine) coatings on electrodes with the scanning electrochemical microscope Juhyoun. Kwak and Fred C. Anson Analytical Chemistry 1992 64 (3), 250-256 DOI: 10.1021/ac00027a003
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84570
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:31 Jan 2018 18:36
Last Modified:15 Nov 2021 20:21

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