Diffusion potentials as source of error in electrochemical measurements in concrete

Condition assessment or controlling systems for cathodic protection of reinforced concrete structures are usually based on potential measurements. In case of permanent monitoring systems, reference electrodes are embedded in the concrete, whereas for occasional investigations external reference electrodes are normally used and placed on the concrete surface. However, ionic concentration gradients between the inner solution of the reference electrode and the concrete pore solution give rise to liquid junction potentials. In addition, internal gradients in pH or chloride content, as well as permselective properties of the cement paste lead to membrane potentials. Although these phenomena are usually not considered to be significant, they might be underestimated in many cases and lead to misinterpretation of measurement results. This is especially important with regard to applications of potentiometric sensors such as chloride or pH sensors, where accurate potential readings are fundamental. This article presents the theoretical background and summarises available literature with regard to diffusion potentials in concrete. Liquid junction potentials between various solutions have been measured experimentally. Practical consequences and possible attempts to minimise measurement errors are discussed.