Abstract

The electrochemical oxygen demand (ECOD) is an additional sum parameter, which has not yet found the attention it deserves. It is defined as the oxygen equivalent of the charge consumed during an electrochemical oxidation of the solution. Only one company has yet developed an instrument to determine the ECOD. This instrument uses <TEX>$PbO_2$</TEX>-electrodes for the oxidation and has been successfully implemented in an automatic on-line monitor. A general problem of the ECOD determination is the high overpotential of electrochemical oxidations of most organic compounds at conventional electrodes. Here we present a new approach for the ECOD determination, which is based on the use of a solid composite electrodes with highly efficient electro-catalysts for the oxidation of a broad spectrum of different organic compounds. Lead dioxide as an anode material has found commercial application in processes such as the manufacture of sodium per chlorate and chromium regeneration where adsorbed hydroxyl radicals from the electro-oxidation of water are believed to serve as the oxidizing agent. The ECOD sensors based on the Au/<TEX>$PbO_2$</TEX> electrode were operated at an optimized applied potential, +1.6 V vs. Ag/AgCl/sat. KCl, in 0.01 M <TEX>$Na_2SO_4$</TEX> solution, and reduced the effect of interference (<TEX>$Cl^-$</TEX> and <TEX>$Fe^{2-}$</TEX>) and an expended lifetime (more than 6 months). The ECOD sensors were installed in on-line auto-analyzers, and used to analyze real samples.

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