N. Kobayashi et Fc. Anson, EFFECTS OF ADSORPTION AND ASSOCIATION WITH MULTIPLY-CHARGED COUNTERIONS ON THE ELECTROCHEMICAL RESPONSES OF AN ELECTROACTIVE POLYELECTROLYTE, Journal of electroanalytical chemistry [1992], 421(1-2), 1997, pp. 99-104
The preparation of two copolymers of vinylferrocene and 4-(vinylpyridi
ne) containing a few per cent of ferrocene groups and having molar mas
ses of 2.3 X 10(5) and 2.4 X 10(4) gmol(-1) is described. The copolyme
rs were dissolved in aqueous hydrochloric acid, where their electro-ox
idation was examined by voltammetry at rotating disk electrodes, Sever
e adsorption on the electrode surface of the higher molar mass copolym
er interfered with the evaluation of its diffusion coefficient, but va
lues were obtained for the lower molar mass copolymer. The effects of
pH, ionic strength and electrostatic binding of multiply charged count
erions on the diffusion of both copolymers were examined. The uncertai
nties inherent in the use of electrochemical methods to evaluate appar
ent diffusion coefficients of polymers in mixtures with varying molar
masses are pointed out.