Potentiometric determination of the chloride ion activity in cement based materials

The chloride content at the reinforcement is one of the decisive factors for the initiation and propagation of localised corrosion in concrete structures. A monitoring technique for the chloride concentration which is accurate, non-destructive and continuous would thus be highly desirable. For this reason, the performance of ion selective electrodes (ISEs) was investigated both in alkaline solutions and embedded in mortar. The Ag/AgCl electrodes used in this work showed Nernstian behaviour with a slope of –59 ± 1 mV per decade and a detection limit for chloride ions below 10^?2 mol dm^?3 even at pH close to 14; the selectivity coefficient for hydroxide interference was estimated at \( k_{{{\text{Cl}}^{ - } ,{\text{OH}}^{ - } }}^{\text{pot}} \approx 4 \cdot 10^{ - 3} \). The Ag/AgCl membranes show good long-term stability over more than 6 months even in highly alkaline solutions as long as chloride ions are present; in the complete absence of chloride the measured potentials were affected by the pH of the solution. The sensors are, however, able to recover fast as soon as they come into contact with chloride. When using ISEs embedded in concrete, diffusion potentials between the reference electrode and the ISE, as arising e.g. from gradients in pH, significantly affect the potential measurement and present a most important error source for the application of direct potentiometry to concrete. To minimise such errors, the reference electrode has to be positioned as close to the ISE as possible.