Describes adding an anolyte soluble amphoteric material, e.g., an aluminum compound, to the anolyte of a chlor-alkali diaphragm cell having a synthetic diaphragm during the start-up period of the cell to reduce the permeability of the diaphragm. Complementary inorganic porosity modifying materials, e.g., magnesium materials such as magnesium chloride, and clays are also added to the anolyte during the start-up period of the cell.