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Oxygen Analyzer Sensor Types By Polycarp Keraka Western Technical College

Present oxygen analyzers use one of a several types of oxygen sensors. As applications call for improved
measurement accuracy and repeatability, the demand for oxygen analyzers that require a minimum of
maintenance and calibration has grown. The various gas phase oxygen sensors provided below should be used
in conjunction with information gathered from manufacturers of oxygen analyzers. This combination will help to
ensure the selection of the right sensor type for the application under consideration.

Electrochemical-Oxygen Analyzer

The ambient temperature electrochemical sensor, often referred to as a galvanic sensor, is typically a small,
partially sealed, cylindrical device (1-1/4 diameter by 0.75 height) that contains two dissimilar electrodes
immersed in an aqueous electrolyte, commonly potassium hydroxide. As oxygen molecules diffuse through a
semi-permeable membrane installed on one side of the sensor, the oxygen molecules are reduced at the
cathode to form a positively charge hydroxyl ion. The hydroxyl ion migrates to the sensor anode where an
oxidation reaction takes place. The resultant reduction/oxidation reaction generates an electrical current
proportional to the oxygen concentration in the sample gas. The current generated is both measured and
conditioned with external electronics and displayed on a digital panel meter either in percent or parts per million
concentrations. With the advance in mechanical designs, refinements in electrode materials, and enhanced
electrolyte formulations, the galvanic oxygen sensor provides extended life over earlier versions, and are
recognized for their accuracy in both the percent and traces oxygen ranges. Response times have also been
improved. A major limitation of ambient temperature electrochemical sensors is their susceptibility to damage
when used with samples containing acid gas species such as hydrogen sulfide, hydrogen chloride, sulfur
dioxide, etc. Unless the offending gas constituent is scrubbed prior to analysis, their presence will greatly
shorten the life of the sensor. The galvanic sensor is also susceptible to over pressurization. For oxygen
analyzer applications where the sample pressure is > 5 psig, a pressure regulator or control valve is normally
recommended.

Paramagnetic Oxygen Analyzer

The magnetodynamic type of design is the predominate sensor type. Oxygen has a relatively high magnetic
susceptibility as compared to other gases such as nitrogen, helium, argon, etc. and displays a paramagnetic
behavior. The paramagnetic oxygen sensor consists of a cylindrical shaped container inside of which is placed a
small glass dumbbell. The dumbbell is filled with an inert gas such as nitrogen and suspended on a taut
platinum wire within a non-uniform magnetic field. The dumbbell is designed to move freely as it is suspended
from the wire. When a sample gas containing oxygen is processed through the sensor, the oxygen molecules
are attracted to the stronger of the two magnetic fields. This causes a displacement of the dumbbell which
results in the dumbbell rotating. A precision optical system consisting of a light source, photodiode, and amplifier
circuit is used to measure the degree of rotation of the dumbbell. In some paramagnetic oxygen sensor designs,
an opposing current is applied to restore the dumbbell to its normal position. The current required to maintain
the dumbbell in it normal state is directly proportional to the partial pressure of oxygen and is represented
electronically in percent oxygen. There are design variations associated with the various manufacturers of
magnetodynamic paramagnetic oxygen analyzer types. Also, other types of sensors have been developed that
use the susceptibility of oxygen to a magnetic field which include the thermomagnetic or `magnetic wind' type
and the magnetopneumatic sensor. In general, paramagnetic oxygen sensors offer very good response time
characteristics and use no consumable parts, making sensor life, under normal conditions, quite good. It also
offers excellent precision over a range of 1% to 100% oxygen. The magnetodynamic sensor is quite delicate
and is sensitive to vibration and/or position. Due to the loss in measurement sensitivity, in general, the
paramagnetic oxygen sensor is not recommended for trace oxygen measurements. Other gases that exhibit a
magnetic susceptibility can produce sizeable measurement errors. Manufacturers of the paramagnetic oxygen
analyzer should provide details on these interfering gases

Polarographic Oxygen Sensors The polarographic oxygen sensor is often referred to as a Clark Cell [J. L.

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Oxygen Analyzer - BMET Wiki

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 Faradays 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%.

Zirconium Oxide Oxygen Sensors

This type of sensor is occasionally referred to as the high temperature electrochemical sensor and is based on
the Nernst principle [W. H. Nernst (1864-1941)]. Zirconium oxide sensors use a solid state electrolyte typically
fabricated from zirconium oxide stabilized with yttrium oxide. The zirconium oxide probe is plated on opposing
sides with platinum which serves as the sensor electrodes. For a zirconium oxide sensor to operate properly, it
must be heated to approximately 650 degrees Centigrade. At this temperature, on a molecular basis, the
zirconium lattice becomes porous, allowing the movement of oxygen ions from a higher concentration of oxygen
to a lower one, based on the partial pressure of oxygen. To create this partial pressure differential, one
electrode is usually exposed to air (20.9% oxygen) while the other electrode is exposed to the sample gas. The
movement of oxygen ions across the zirconium oxide produces a voltage between the two electrodes, the
magnitude of which is based on the oxygen partial pressure differential created by the reference gas and sample
gas. The zirconium oxide oxygen sensor exhibits excellent response time characteristics. Another virtue is that
the same sensor can be used to measure 100% oxygen, as well as parts per billion concentrations. Due to the
high temperatures of operation, the life of the sensor can be shortened by on/off operation. The coefficients of
expansions associated with the materials of construction are such that the constant heating and cooling often
causes sensor fatigue. A major limitation of zirconium oxide oxygen sensors is their unsuitability for trace
oxygen measurements when reducing gases (hydrocarbons of any species, hydrogen, and carbon monoxide)
are present in the sample gas. At operating temperatures of 650 degrees Centigrade, the reducing gases will
react with the oxygen, consuming it prior to measurement thus producing a lower than actual oxygen reading.
The magnitude of the error is proportional to the concentration of reducing gas. Zirconium oxide oxygen sensors
are the defacto standard for in-situ combustion control applications.

Other types of oxygen measuring techniques are under development and in some cases being used for specific
applications. They include, but are not limited to, luminescence polarization, opto-chemical sensors, laser gas
sensors, et al. As these techniques are further developed and improved, they may represent viable alternatives
to the major oxygen sensor types currently in use.

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