Sodium sesquisulfate produced in crystalline form in a high acidity highly efficient chlorine dioxide generating process is converted by metathesis to crystalline anhydrous neutral sodium sulfate and the acid recovered as a result is recycled to the chlorine dioxide generating step. The metathesis is effected by contacting the crystalline sodium sesquisulfate with aqueous sodium chlorate solution, aqueous sodium chloride solution, aqueous methanol or water alone. The metathesis is effected in such manner as to minimize the additional evaporative load imposed on the chlorine dioxide generating process by the metathesis medium.