Differential scanning coulometric titrometry: Application to the system CoNiO at 1000°C

A novel technique involving solid state coulometric titration using stabilized zirconia electrolytes is presented. The method is termed differential scanning coulometric titrometry (DSCT). It is useful for the phase equilibrium studies of multicomponent oxide systems. In the DSCT, two independent and isostructural galvanic cells are used. One is a sample cell in which a sample is charged, while the other is a reference cell without a sample. Under the condition that oxygen activities in both cells are equal to each other, coulometric titration is carried out continuously in both cells. The difference between the titration currents provided to both cells corresponds to the amount of oxygen which is allowed to react with a sample per unit time. If the difference is recorded with respect to the oxygen activity, it starts to deviate from a base line when the sample starts to be oxidized or reduced. This method was successfully applied to the system CoNiO at 1000°C. The phase diagram of the system and related thermodynamic data were obtained.