The formation of sodium sulfate by-product in sulfuric acid-based chlorine dioxide generating processes is decreased and preferably eliminated entirely, by effecting electrochemical treatment of sodium ion-containing feed materials for the generator to remove sodium ions and to add hydrogen ions. Sodium hydroxide may be produced as a by-product. The process is generally applicable to the electrochemical treatment of alkali metal chlorates, alkali metal sulfates and mixtures thereof to produce acidified solutions useful in providing chlorate ion-containing feeds to such chlorine dioxide generating processes or for other purposes.