A study of the importance of the cell geometry in non-Faradaic systems. A new definition of the cell constant for conductivity measurement

A new definition for the electrochemical cell constant in conductivity measurements is presented in this paper. Electrochemical Impedance Spectroscopy and DC pulses measurements have been carried out in non-Faradaic conditions in order to evaluate the effects of the cell geometry. The results obtained demonstrate that conductivity measurements are affected not only by the electrodes surface and separation but also by the cross section of the electrochemical cell. In order to obtain a linear behavior of the resistance versus the distance between electrodes, the cross section of the cell should be equal to the electrodes surface. Differences between the cell cross section and the electrodes surface produce a heterogeneous distribution of the electric field that causes the non-linear behavior for low values of the electrodes separation. This study shows that the reproducibility in electronic tongue and humid electronic nose measurements can be improved by designing an electrochemical cell structure that warrants a homogeneous distribution of the electrical field, which results in a reduction of the detection threshold in these types of system.