Investigation of open circuit reactions of polymer films using the quartz crystal microbalance. Reactions of polyvinylferrocene films

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Abstract

Bimolecular reactions between polyvinylferrocene (PV-Fc) films at open circuit and solution species that are accompanied by mass changes in the polymer have been investigated with a quartz crystal microbalance (QCM). PV-Fc oxidation by I2/I3- and PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ can be monitored with the QCM by following the formation of PV-FcI3 in the former reaction and the expulsion of counteranions from the polymer film in the latter two processes. Rate constants can be estimated and reaction mechanisms postulated based on the temporal response of the frequency shift that occurs upon switching the films to open circuit from a potential which electrochemically maintains the active redox state of the polymer. Oxidation of PV-Fc by I2/I3- in 1.0 M KNO3 proceeds by a rate-determining oxidation step followed by the formation of the triiodide salt. The oxidation can be reversed by electrochemical reduction of the PV-FcI3 film, resulting in quantitative expulsion of iodide. Rate constants for PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ have also been determined; however, the polymer films eventually become inert in the presence of high concentrations of FeII(CN)64- due to irreversible partitioning of ferro(ferri)cyanide into the polymer film. In contrast, the positively charged Ru(NH3)62+ does not exchange and the redox chemistry is reversible.

Original languageEnglish (US)
Pages (from-to)2049-2054
Number of pages6
JournalJournal of Physical Chemistry
Volume92
Issue number7
StatePublished - 1988

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Quartz crystal microbalances
quartz crystals
Polymer films
microbalances
Oxidation
Networks (circuits)
polymers
Rate constants
oxidation
expulsion
Polymers
Cyanides
Iodides
cyanides
Salts
iodides
frequency shift
polyvinylferrocenium
chemistry
salts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

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title = "Investigation of open circuit reactions of polymer films using the quartz crystal microbalance. Reactions of polyvinylferrocene films",
abstract = "Bimolecular reactions between polyvinylferrocene (PV-Fc) films at open circuit and solution species that are accompanied by mass changes in the polymer have been investigated with a quartz crystal microbalance (QCM). PV-Fc oxidation by I2/I3- and PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ can be monitored with the QCM by following the formation of PV-FcI3 in the former reaction and the expulsion of counteranions from the polymer film in the latter two processes. Rate constants can be estimated and reaction mechanisms postulated based on the temporal response of the frequency shift that occurs upon switching the films to open circuit from a potential which electrochemically maintains the active redox state of the polymer. Oxidation of PV-Fc by I2/I3- in 1.0 M KNO3 proceeds by a rate-determining oxidation step followed by the formation of the triiodide salt. The oxidation can be reversed by electrochemical reduction of the PV-FcI3 film, resulting in quantitative expulsion of iodide. Rate constants for PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ have also been determined; however, the polymer films eventually become inert in the presence of high concentrations of FeII(CN)64- due to irreversible partitioning of ferro(ferri)cyanide into the polymer film. In contrast, the positively charged Ru(NH3)62+ does not exchange and the redox chemistry is reversible.",
author = "Michael Ward",
year = "1988",
language = "English (US)",
volume = "92",
pages = "2049--2054",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "7",

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TY - JOUR

T1 - Investigation of open circuit reactions of polymer films using the quartz crystal microbalance. Reactions of polyvinylferrocene films

AU - Ward, Michael

PY - 1988

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N2 - Bimolecular reactions between polyvinylferrocene (PV-Fc) films at open circuit and solution species that are accompanied by mass changes in the polymer have been investigated with a quartz crystal microbalance (QCM). PV-Fc oxidation by I2/I3- and PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ can be monitored with the QCM by following the formation of PV-FcI3 in the former reaction and the expulsion of counteranions from the polymer film in the latter two processes. Rate constants can be estimated and reaction mechanisms postulated based on the temporal response of the frequency shift that occurs upon switching the films to open circuit from a potential which electrochemically maintains the active redox state of the polymer. Oxidation of PV-Fc by I2/I3- in 1.0 M KNO3 proceeds by a rate-determining oxidation step followed by the formation of the triiodide salt. The oxidation can be reversed by electrochemical reduction of the PV-FcI3 film, resulting in quantitative expulsion of iodide. Rate constants for PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ have also been determined; however, the polymer films eventually become inert in the presence of high concentrations of FeII(CN)64- due to irreversible partitioning of ferro(ferri)cyanide into the polymer film. In contrast, the positively charged Ru(NH3)62+ does not exchange and the redox chemistry is reversible.

AB - Bimolecular reactions between polyvinylferrocene (PV-Fc) films at open circuit and solution species that are accompanied by mass changes in the polymer have been investigated with a quartz crystal microbalance (QCM). PV-Fc oxidation by I2/I3- and PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ can be monitored with the QCM by following the formation of PV-FcI3 in the former reaction and the expulsion of counteranions from the polymer film in the latter two processes. Rate constants can be estimated and reaction mechanisms postulated based on the temporal response of the frequency shift that occurs upon switching the films to open circuit from a potential which electrochemically maintains the active redox state of the polymer. Oxidation of PV-Fc by I2/I3- in 1.0 M KNO3 proceeds by a rate-determining oxidation step followed by the formation of the triiodide salt. The oxidation can be reversed by electrochemical reduction of the PV-FcI3 film, resulting in quantitative expulsion of iodide. Rate constants for PV-Fc+ reduction by FeII(CN)64- and Ru(NH3)62+ have also been determined; however, the polymer films eventually become inert in the presence of high concentrations of FeII(CN)64- due to irreversible partitioning of ferro(ferri)cyanide into the polymer film. In contrast, the positively charged Ru(NH3)62+ does not exchange and the redox chemistry is reversible.

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