Chemical phenomena in solid-state voltammetry in polymer solvents

Journal Article · Wed Mar 01 04:00:00 EST 1989 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00187a013· OSTI ID:5844858

Geng, L; Reed, R A; Kim, M H; Wooster, T T; Oliver, B N; Egekeze, J; Kennedy, R T; Jorgenson, J W; Parcher, J F; Murray, R W

This paper, aimed at delineating significant chemical effects in solid-state voltammetry, describes electrochemical oxidations and reductions of electroactive monomer solutes dissolved in and diffusing through rigid and semirigid polymer electrolyte solvents. Sorption of organic monomer vapors into poly(ethylene oxide) films yields polymer solvents whose chemistry is dominated by that of the sorbed monomer as shown by coordination and precipitation effects. The dynamics of plasticization-induced changes in transport rates are quite rapid. Physical diffusion in the polymer solvent in slow enough that electron hopping reactions measurably enhance charge transport rates; the effect was used to estimate a lower limit for the (Co(bpy)/sub 3/)/sup 2+/+/ self-exchange rate constant of 2 /times/ 10/sup 9/ M/sup /minus/1/ s/sup /minus/1/. It is possible to erect polymeric film transport barriers at the electrode/polymer solvent interface and to measure the rate of permeation of monomer complexes from the polymer solvent into the polymer transport barrier film. Polymeric films of Os and Ru polypyridine complexes can be electropolymerized from polymer solutions of the corresponding monomers. Solid-state voltammetry can be extended to other polymer solvents including sulfonated polystyrene, poly(vinyl chloride), Nafion, and poly(acrylamide) gel.

• Research Organization: Univ. of North Carolina, Chapel Hill (USA)
• DOE Contract Number: FG05-87ER13675
• OSTI ID: 5844858
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 111:5; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
AZINES
BIPYRIDINES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COBALT COMPLEXES
COMPLEXES
DATA
DIFFUSION
ELECTROCHEMISTRY
ELECTRON TRANSFER
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
MASS TRANSFER
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
OSMIUM COMPLEXES
POLYMERS
PYRIDINES
REACTION KINETICS
REDOX REACTIONS
RUTHENIUM COMPLEXES
SOLIDS
SOLUTES
SOLVENT PROPERTIES
SOLVENTS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY