Polymer solvent dynamic effects on an electron-transfer cross-reaction rate at a redox polymer/polymer solution interface

Journal Article · Tue Mar 23 23:00:00 EST 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00059a030· OSTI ID:6250684

Zhang, Honghua; Murray, R W ^[1]

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1. Univ. of North Carolina, Chapel Hill (United States)

Electron-transfer cross-reaction rate constants (k[sub 12]) for the oxidation of polyether solutions of [Fe(4,7-dimethyl-phenanthroline)[sub 3]][sup 2+] at a poly[Os(bpy)[sub 2]/(vpy)[sub 2]][sup 3+] redox polymer surface have been measured as a function of the polyether solvent employed. Previous measurements in monomer solvents produced values of k[sub 12] adherent to a theoretical model incorporating the monomer solvent longitudinal relaxation time ([tau][sub L]), dielectric constant, and the cross-reaction free energy. Values of k[sub 12] are smaller in polyether solvents, consistent with reaction rate control by solvent dipole relaxation times ([tau][sub L][prime]) that are longer in polymeric relative to monomeric solvents. Further, k[sub 12] decreases under conditions where polyether chain segment fluctuations are expected to be slowed, e.g., longer polyether chain length and increased LiClO[sub 4] and Zn(CF[sub 3]SO[sub 3])[sub 2] electrolyte concentrations. The diffusion coefficient of the iron complex in the polymer solution, for analogous reasons of slowed chain segmental mobility, also decreases in longer polyether chain solvents and at higher electrolyte concentrations. 30 refs., 6 figs., 3 tabs.

• OSTI ID: 6250684
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:6; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
ALCOHOLS
ALKALI METAL COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DIFFUSION
DISPERSIONS
ELECTROLYTES
ELECTRON TRANSFER
EXPERIMENTAL DATA
GLYCOLS
HYDROXY COMPOUNDS
INFORMATION
IRON COMPLEXES
KINETICS
LITHIUM COMPOUNDS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC POLYMERS
OSMIUM COMPLEXES
OXIDATION
POLYETHYLENE GLYCOLS
POLYMERIZATION
POLYMERS
REACTION KINETICS
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
VISCOSITY
VOLTAMETRY
ZINC COMPOUNDS