Ruthenium based DSA® in chlorate electrolysis—critical anode potential and reaction kinetics

Ruthenium based DSA®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/m² 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.