Electrochimica Acta, Vol.48, No.5, 473-481, 2003
Ruthenium based DSA((R)) in chlorate electrolysis - critical anode potential and reaction kinetics
Ruthenium based DSA((R))s have been investigated in chlorate electrolyte using rotating discs made from commercial electrodes. Measurements of the voltammetric charge, q*, and of iR-corrected polarisation curves up to current densities of 40 kA/m(2) Were recorded on new anodes and on aged anodes from 3 years of production in a chlorate plant. Anodic polarisation curves in chloride containing electrolytes bend towards a higher slope at approximately 1.2 V versus Ag/AgCl, likely due to oxidation of ruthenium. The potential and current density at which the curves bend have been defined as the critical potential, E-cr, and the critical current density, i(cr). New anodes that operate at a relatively high potential, > E-cr, obtain an increase in real surface area and thereby a decrease in anode potential and in the selectivity for oxygen formation during the first months of operation. Experiments at constant ionic strength under chlorate process conditions showed that E-cr decreased with increasing chloride concentration with a factor of -0.09 V/log Cl-, whereas i(cr) increased with increasing chloride concentration. The chlorine evolution reaction was of the first order with respect to chloride concentration. A possible reaction mechanism for chlorine formation is suggested.