Polarographic Oxygen Sensors

The polarographic oxygen sensor is often referred to as a Clark Cell [J. L. Clark (1822- 1898)]. In this type of sensor, both the anode (typically silver) and cathode (typically gold) are immersed in an aqueous electrolyte of potassium chloride. The electrodes are separated from the sample by a semi-permeable membrane that provides the mechanism to diffuse oxygen into the sensor. The silver anode is typically held at a potential of 0.8V (polarizing voltage) with respect to the gold cathode. Molecular oxygen is consumed electrochemically with an accompanying flow of electrical current directly proportional to the oxygen concentration based on Faraday’s law. The current output generated from the sensor is measured and amplified electronically to provide a percent oxygen measurement. One of the advantages of the polarographic oxygen sensor is that while inoperative, there is no consumption of the electrode (anode). Storage times are almost indefinite. Similar to the galvanic oxygen sensor, they are not position sensitive. Because of the unique design of the polarographic oxygen sensor, it is the sensor of choice for dissolved oxygen measurements in liquids. For gas phase oxygen measurements, the polarographic oxygen sensor is suitable for percent level oxygen measurements only. The relatively high sensor replacement frequency is another potential drawback, as is the issue of maintaining the sensor membrane and electrolyte.

A variant to the polarographic Oxygen Sensor is what some manufacturers refer to as a non-depleting coulometric sensor where two similar electrodes are immersed in an electrolyte consisting of potassium hydroxide. Typically, an external EMF of 1.3 VDC is applied across both electrodes which acts as the driving mechanism for reduction/oxidation reaction. The electrical current resulting from this reaction is directly proportional to the oxygen concentration in the sample gas. As is the case with other sensor types, the signal derived from the sensor is amplified and conditioned prior to displaying. Unlike the conventional polarographic oxygen sensor, this type of sensor can be used for both percent and trace oxygen measurements. However, unlike the zirconium oxide, one sensor cannot be used to measure both high percentage levels as well as trace concentrations of oxygen. One major advantage of this sensor type is its ability to measure parts per billion levels of oxygen. The sensors are position sensitive and replacement costs are quite expensive, in some cases, paralleling that of an entire analyzer of another sensor type. They are not recommended for applications where oxygen concentrations exceed 25%.