Long-term equilibrium potential and electrochemical impedance study of Ag/AgCl electrodes used in Harned Cell measurements of pH

A long term study of the voltage and electrochemical impedance characteristics of Ag/AgCl electrodes used in Harned Cell measurement of pH is presented. By all the measures investigated the electrodes are shown to degrade only slowly until approximately 200 days after manufacture, after which time the rate of degradation and critical failure of the electrodes increases. The absolute voltage drift of the electrodes may not be easily measured, so parameters determined directed or indirectly by electrochemical impedance spectroscopy have been assessed as a method to produce an alternative indication of electrode integrity. In this respect, resistance to charge transfer has been shown to be a very sensitive measure of changes in the characteristics of the electrodes, and the most closely related to the observed changes in voltage. Evidence is presented to support the hypothesis that the majority of electrode degradation (excluding critical failure) comes from the increased blocking of the microporous structure of the electrodes.