DOUBLE-LAYER DYNAMICS IN THE ADSORPTION OF TETRABUTYLAMMONIUM IONS ATTHE MERCURY WATER INTERFACE .4. THE REDUCTION OF HEXAMMINE-COBALT(III) THROUGH TETRABUTYLAMMONIUM FILMS
T. Wandlowski et R. Delevie, DOUBLE-LAYER DYNAMICS IN THE ADSORPTION OF TETRABUTYLAMMONIUM IONS ATTHE MERCURY WATER INTERFACE .4. THE REDUCTION OF HEXAMMINE-COBALT(III) THROUGH TETRABUTYLAMMONIUM FILMS, Journal of electroanalytical chemistry [1992], 380(1-2), 1995, pp. 201-207
The reduction of hexamminecobalt(III) at the mercury-water interface i
s strongly affected by the presence of a condensed tetrabutylammonium
film. When the anions present are fluoride and/or tetrafluoroborate, e
lectron transfer through the film proceeds via an inner-sphere mechani
sm, i.e. the film must be opened so that hexamminecobalt(III) can make
direct contact with the metal. In the presence of bromide anions, an
outer-sphere pathway is indicated, probably involving bridging by brom
ide ions. Unusual current-time transients of the reduction of hexammin
ecobalt(III) in the presence of tetrabutylammonium ions are correlated
with the kinetics of film formation.