X-ray photoelectron spectroscopic studies on the kinetics of photoreduction of FeIII in single-crystal K3(Fe,Co)(CN)6 surfaces cleaved in situ

Abstract

A study of the reduction of Fe^III in solid solutions of K₃Fe(CN)₆ and K₃Co(CN)₆ during X-ray photoelectron measurements is presented. Although the rate of the reduction process for K₃Fe(CN)₆ is first order, there are two stages in the reduction of K₃(Fe,Co)(CN)₆. The rates in the early stage, which are ruled by the first-order law, are faster than those in the second stage. Moreover, the early first-order rate constant increases with decrease of the Fe : Co atomic ratio.