A. Walcarius et al., THE METHYL VIOLOGEN INCORPORATED ZEOLITE MODIFIED CARBON-PASTE ELECTRODE .2. ION-EXCHANGE AND ELECTRON-TRANSFER MECHANISM IN AQUEOUS-MEDIUM, Electrochimica acta, 38(15), 1993, pp. 2267-2276
An investigation of ion exchange between methyl viologen ions (MV++) a
nd sodium ions (Na+) in zeolite Y has been completed in order to descr
ibe the electron transfer mechanism operative in a zeolite modified ca
rbon paste electrode (ZMCPE). Preliminary work needed the characteriza
tion of the Linde Y-54 zeolite batch used and the search for equilibri
um conditions. The ion exchange isotherm for the MV++ exchange for Na demonstrates the great selectivity for the large organic cation and a
maximum capacity of 1.0 x 10(-3) mole MV++ per gram of zeolite, corre
sponding to an occupation of about 64% of the total exchanging sites.
The use of zeolite containing different amounts of methyl viologen has
emphasized that the selectivity is greatly influenced by the activity
coefficients of the exchanging species within the zeolite framework.
This property of the ion exchange equilibrium allowed to determine the
electron transfer mechanism that is operative for the cathodic reduct
ion of MV++ initially exchanged in a ZMCPE. In aqueous solution, MV+is reduced after being exchanged for the electrolyte cation. Finally,
a structural model of the electrode has been proposed. It is in good a
greement with experimental results and takes into account all the elec
trochemical behaviour of the ZMCPE and the advocated electron transfer
mechanism.