Electrochemical oxidation of white liquor in a membrane cell is a process of great potential for the pulp and paper industry. The process produces polysulfide-containing white liquor in the anode chamber, and pure sodium hydroxide solution in the cathode chamber. The anode reaction has been investigated using cyclic voltammetry at temperatures between 25 and 90 degrees C on rotating disc and ring-disc electrodes. It was further investigated using chronoamperometry on rotating disc electrodes at 90 degrees C. The experiments, which were mainly run in dilute alkaline sulfide solutions, using platinum electrodes, show that the electrochemical production of polysulfide ions, at lower anode potentials (-0.1 to +0.1 V vs SCE), proceeds via formation of elemental sulfur on the electrode surface. The sulfur is dissolved by hydrosulfide and polysulfide ions producing (longer-chain) polysulfide ions. The rate of dissolution, and thus the overall reaction rate, increases strongly with temperature. Polysulfide ions have an autocatalytic effect on the anode reaction due to their ability to dissolve adsorbed sulfur. At higher anode potentials (greater than or equal to 0.2 V vs SCE), a change of reaction mechanism is observed. In this region the reaction rate depends on electrode potential and is not catalysed by polysulfide ions.