Abstract
We describe electrochemical quartz crystal microbalance (EQCM) measurements of salt and solvent transfers that accompany redox switching of poly(vinylferrocene) (PVF) films exposed to aqueous solutions of NaClO4. At low salt concentration (csalt ⩽ 0.1 mol dm−3), oxidized and reduced PVF films are both permselective. At high salt concentration, salt partitions into the film upon film oxidation; this effect is significant for csalt 1 mol dm−3. In order to explain salt partition quantitatively, we develop a new thermodynamic model that directly incorporates the variation of electroactive polymer film volume with film redox state and salt concentration. Application of the model to the PVF–NaClO4 system shows that oxidized PVF films shrink appreciably (typically 35%) under non-permselective conditions. The salt and solvent partition coefficients into oxidized PVF are Ksalt,Ox≈ 1.0 and Ksolv,Ox ≈ 0.15, respectively.
Published Version
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