SPECTROELECTROCHEMICAL DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE CONSTANTS

The theory underlying the single potential step spectroelectrochemical determination of heterogeneous electron transfer rate constants is presented. The resulting expressions are experimentally verified using the quasi-reversible oxidation of ferrocyanide at tin oxide optically transparent electrodes at pH 7.00. For this model system, good agreement is obtained between values of k,f h and α determined spectroelectro-chemically [FORMULA OMMITED] and those determined by the previously reported technique of chronocoulometry [FORMULA OMITED] The present methodology was devised to quantitatively characterize and thereby compare the rates of heterogeneous electron transfer at chemically modified electrodes. © 1979, American Chemical Society. All rights reserved.