On the accuracy of oxygen pressure measurements

Zirconia-based oxygen sensors are used in many applications and in research. However, the measurement of oxygen partial pressures with these devices is not necessarily correct. Reasons for deviation between sensor reading and nominal composition of the gas mixture are reviewed in this work. The sensor electrochemical permeability is introduced as a starting point. The impact of this oxygen leak on the composition of the surrounding atmosphere is evaluated from mass balances to all species in the system. This procedure shows that even the use of mixtures like CO+CO₂ to establish a given oxygen partial pressure has a limited range of applicability. This is due to the small buffer behavior of some of these mixtures. The gas phase transport of oxygen away from the sensor electrode is also studied. High concentration overpotentials are expected to develop under the circumstances where the buffer behavior of the gas mixture is small. In fact, high concentrations of the CO/CO₂ couple are required both to optimize the gas-mixture buffer effect and the oxygen transport in the gas phase. The latter instead of consisting exclusively of simple diffusion of free oxygen molecules might also involve combined diffusion and counter diffusion of both carbon oxides as oxygen carriers.