THE ELECTRODE POTENTIAL OF IRON IN RELATION TO HYDROGEN ION CONCENTRATION

The electrode potential of iron immersed in phosphate, borate and citrate buffers of varying hydrogen ion concentration was measured, using a normal calomel electrode as the second half of the cell. Breaks in the potential of the iron electrode amounting to as much as 0.7 volts were found to occur at definite pH values for each series of buffers. The electrode exhibited an "initial" and "final" potential depending on the pH of the electrolyte and the time of immersion, the "final" value requiring several days to become established. The "final" break in the electrode potential of 0.74 volts in the pure phosphate buffer occurred between a pH of 3.1 and 4.0, that in the pure borate buffer, of 0.75 volts, occurred between a pH of 4.3 and 4.6, and in the pure citrate buffer, of 0.77 volts, between a pH of 10.1 and 10.9. The effect of chloride ion and de-aeration on the electrode potential was observed. It is suggested that the potential of the iron electrode is determined by the presence or absence of a non electrically conducting film or deposit on the iron, the formation of which is a function of the nature of the electrolyte and its hydrogen ion concentration. De-aeration apparently had no effect on the electrode potential, but the presence of chloride ion affected the establishing of the "final" potential and caused the break in voltage to appear irregularly at a much lower hydrogen ion concentration.At pH values below that at which the break in potential occurred, corrosion of the iron electrode was marked, and the electrode potential remained high, while, at pH values above the break, corrosion was virtually inhibited or confined to local spots on the electrode, and the electrode potential remained low. The presence of the chloride ion stimulated local corrosion and permitted general corrosion to proceed at a lower hydrogen ion concentration.