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Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine

Kobayashi, Junya and Anson, Fred C. (1991) Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine. Journal of Physical Chemistry, 95 (6). pp. 2595-2601. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20180316-141224548

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Abstract

A soluble polysiloxane containing 4,4'-bipyridine as a singly quaternized pendant group was synthesized and allowed to interact with Fe(CN)_6^(4-), Fe(CN)_5(OH_2)^(3-), and Ru(edta)OH_2^- as counterions. The electrochemical responses (formal potentials and mass-transfer-limited oxidation or reduction currents) of the electroactive counterions were utilized to evaluate diffusion coefficients and equilibrium binding constants. The latter were also measured by equilibrium dialysis. The moderate agreement between the equilibrium constants obtained by the two independent methods lent support to the general procedures employed in analyzing the electrochemical data, although some of the assumptions required for the data analysis may not be fully justified. The results obtained indicate that the polyelectrolyte-counterion binding equilibrium is static rather than dynamic on the electrochemical time scale of a few hundred milliseconds.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/j100159a089DOIArticle
https://pubs.acs.org/doi/abs/10.1021/j100159a089PublisherArticle
Additional Information:© 1991 American Chemical Society. This work was supported in part by the National Science Foundation and the U.S. Army Research Office. J.K. received support from the Shimadzu Corp. (Kyoto). Discussions with Dr. Manshi Ohyanagi were helpful during the initial stages of this work.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Shimadzu CorporationUNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics8170
Issue or Number:6
Record Number:CaltechAUTHORS:20180316-141224548
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180316-141224548
Official Citation:Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine. Junya Kobayashi and Fred C. Anson. The Journal of Physical Chemistry 1991 95 (6), 2595-2601 DOI: 10.1021/j100159a089
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85347
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Mar 2018 22:53
Last Modified:03 Oct 2019 19:30

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