The measurement of the free chloride concentration in the pore solution of cement paste or concrete is of interest for assessing the probability of corrosion of the steel reinforcements embedded in concrete. This determination is performed through leaching or pore-pressing methods or through embedded potentiometric sensors into the hardened cementitious material. The potentiometric determination of chloride in cement paste pore solutions is limited by hydroxide ion interference, due to the high alkalinity of such media. The potentiometric selectivity coefficients, kCl-,OH-, are determined for a chloride ionic selective electrode in alkaline solutions simulating the electrolyte present within the pore network of cement paste and concrete. This is done using a fixed interference methodology, with least-squares non-linear curve fitting for obtaining the selectivity coefficients together with other relevant electrode parameters. The limit of detection of the Cl− ISE, due to OH− interference, varies with pH. For the pore solution corresponding to an ordinary Portland cement paste or concrete, this limit can be set between 3 × 10–3 m, and 7 × 10–3 m, i.e., approximately below a chloride concentration value of 1 × 10–2 molal. Taking into account these limits of detection the free Cl− concentrations able to depassivate the steel, can be adequately determined by potentiometric measurements with calibrated ISEs in the expressed pore solutions of Portland cement concretes, without significant influence of OH− interference. Nevertheless, this effect can prevent the adequate measurement of low free Cl− concentrations, below the corresponding limit of detection valu

In the application of the electrochemical chloride extraction (ECE) technique, traditionally, the Ti-RuO2 wire netting has been used as the external anode. This article provides the results of the research based on the use of conductive cement paste with addition of carbon nanofibers (CNF) as anodes and its application in ECE. The tests were developed in concrete specimens previously contaminated with chloride. The efficiencies achieved were compared with those obtained using a traditional anode (Ti-RuO2) and cement pastes with the addition of other carbonaceous materials. The results show the feasibility of using conductive cement paste with CNF as the anode in the electrochemical extraction of chlorides in concrete, finding similar efficiencies to those obtained with traditional Ti-RuO2 wire netting but with the added advantage that it can be adapted to complex structural geometries as it can be applied as a paste.

This article shows the research carried out by the authors focused on how the shape of structural reinforced concrete elements treated with electrochemical chloride extraction can affect the efficiency of this process. Assuming the current use of different anode systems, the present study considers the comparison of results between conventional anodes based on Ti-RuO₂ wire mesh and a cement-based anodic system such as a paste of graphite-cement. Reinforced concrete elements of a meter length were molded to serve as laboratory specimens, to closely represent authentic structural supports, with circular and rectangular sections. Results confirm almost equal performances for both types of anode systems when electrochemical chloride extraction is applied to isotropic structural elements. In the case of anisotropic ones, such as rectangular sections with no uniformly distributed rebar, differences in electrical flow density were detected during the treatment. Those differences were more extreme for Ti-RuO₂ mesh anode system. This particular shape effect is evidenced by obtaining the efficiencies of electrochemical chloride extraction in different points of specimens.