Paramagnetic Oxygen Sensor

Principle of Operation
The paramagnetic oxygen analyzer is based on the scientific principle that oxygen is a paramagnetic
material, which means that it can be attracted into a magnetic field, or is magnetically susceptible.
Magnetic susceptibility is a measure of the intensity of the magnetization of a substance when it is
placed in a magnetic field. Oxygen has an exceptionally high magnetic susceptibility compared to
other gases actually several hundred times greater than that of most other gases. Three types of
paramagnetic oxygen analyzers are most generally used in industry: the magnetodynamic, or
dumbbell type; the thermomagnetic, or magnetic wind type; and the magnetopneumatic.

The magnetodynamic oxygen analyzer is the most popular of the three techniques, and consists of a
small dumbbell-shaped body made of glass and charged with nitrogen or some other gas of low
magnetic susceptibility, a light source, a photocell, a mirror, and a calibrated indicating unit. The
dumbbell body is suspended in an enclosed test cell by a quartz or platinum fiber within the magnetic
field of a permanent magnet and is free to rotate in the space between the poles of the magnet. Since
the dumbbell body is somewhat diamagnetic i.e., has negative magnetic susceptibility because of
its nitrogen content, the balls of the dumbbell naturally deflect slightly away from the point of
maximum magnetic field strength.
When a test sample containing oxygen is introduced into the test cell, the oxygen in the sample is
attracted to the point of maximum field strength. the magnitude of dumbbell displacement is
proportional to the amount of oxygen in the sample. The movement of the dumbbell is detected by a
light beam from a light source exterior to the test cell. The light beam is reflected from a mirror on the
dumbbell body to an exterior photocell. The output of the photocell is amplified and transmitted to an
indicating unit that is calibrated to read out the oxygen content in the test sample in percent. Since
the difference in magnetic susceptibility between the dumbbell and the gas sample is very subtle for
low oxygen concentrations, this method is used only when measuring percent levels of oxygen and
not for trace levels. The operation of the magnetodynamic oxygen analyzer is illustrated in the figure
below.

The thermomagnetic oxygen analyzer is based on the principle that the magnetic susceptibility of
oxygen decreases inversely with the square of its temperature. It consists of a test chamber
containing two tubes for the entry of a test sample. The tubes are connected by a cross tube
containing electrical heating filaments at each end of the crossover passage. The two filaments are
the arms of a Wheatstone bridge. One end of the cross tube with its heating filament lies in a strong
magnetic field created by the poles of a permanent magnet. The test sample is introduced in two
equal streams through the two side tubes. Any oxygen in the sample is attracted to the magnetic field
because the heating filaments, and the magnetic susceptibility of any oxygen in the sample decreased
rapidly as the temperature is increased. The heated sample is displaced by cool oxygen attracted to
the magnetic field, and this flow of gas, or magnetic wind, cools the filament in the magnetic field,
causing its resistance to be different from the heating filament at the other (unmagnetized) end of the
cross tube. The difference in resistance is measured on a bridge-type instrument, and a signal
proportional to the oxygen concentration in the test sample is transmitted to a recording or display
instrument.
The magnetpneumatic oxygen analyzer operates on the principle that a test sample containing
oxygen molecules, when drawn into a nonhomogeneous magnetic field and mixed with a reference
gas having a different oxygen content, will generate a differential pressure. The sample gas is
introduced into a test chamber containing a nonhomogeneous magnetic field created by an
electromagnet. Oxygen molecules in the sample, because of their paramagnetic properties, flow
toward the greatest magnetic field strength. A reference gas with known properties is introduced into
the test chamber through two inlets. The reference gas from one inlet mixes with the test sample in
the magnetic field and the difference in paramagnetism between the two gases creates a differential
pressure, resulting in a balancing flow of reference gas from the other inlet. This balancing flow is
measured by a miniature flow sensor and converted into an electrical signal proportional to the
pressure differential.

Advantages
The magnetodynamic oxygen analyzer provides a direct measurement of magnetic susceptibility and,
consequently, is not influenced by the thermal properties of the background gas. It has excellent
speed of response. The most significant limitation of the dumbbell-type analyzer is that it is a delicate
instrument with moving parts and, thus, is sensitive to vibration and precise positioning requirements.

Therefore, this type of analyzer is not ideally suited for many industrial applications, on ships, or as a
portable analyzer.
The magnetic susceptibility of the sample is a function of temperature, and significant errors will result
if sample temperature deviates from the calibrated temperature unless temperature controls and
compensation are implemented. In addition, the dumbbell-type analyzer can be affected by the
magnetic susceptibility of the background gas, as shown in the table below.
Coexisting Gas Interference (100%) with
Interference Ratio of Oxygen as 100.
Acetylene (C2H2)
Ammonia (NH3)
Argon (Ar)
Carbon dioxide (CO2)
Carbon monoxide (CO)
Ethylene (C2H4)
Hexane (normal) (C6H14)
Methane (Ch4)
Nitric oxide (NO)
Nitrogen (N2)
Nitrogen dioxide (NO2)
Oxygen (O2)

-0.24
-0.26
-0.22
-0.27
+0.01
-0.26
-1.7
-0.2
+43.0
0.0
+28.0
100.0

The thermomagnetic and magnetopneumatic analyzers, on the other hand, can be made quite
rugged. For this reason, they are used in many applications in place of the magnetodynamic
analyzer. Both of these analyzers have excellent response speed.

Disadvantages
The most significant disadvantage of the thermomagnetic analyzer is that the accuracy of the
readings can be adversely affected by the thermal properties of the background gas, unless
compensation is made for variations in temperature or thermal conductivity. High temperatures can
also cause stability and reliability problems.
The magnetopneumatic analyzer is sensitive to vibration. Some manufacturers have installed
vibration detection systems in their equipment to offset the effects of vibration.
Because of the limitation of the measuring technique, the magnetodynamic, thermomagnetic, and
magnetopneumatic oxygen analyzers are limited to percent oxygen measurements and are not
recommended for trace oxygen measurements. Also, in applications where interference effects
cannot be accurately predicted or compensated for (i.e., varying background gas compositions
containing other paramagnetic/diamagnetic gases), even percent measurements may not be reliable.

Typical Usage
The paramagnetic types of oxygen analyzers are most commonly used in the analysis of combustion
efficiency, testing the purity of breathing air and protective atmospheres, for laboratory measurements
and in medical applications, and for selected industrial process monitoring and control applications.

Galvanic Fuel Cell (GFC) Oxygen Cell

Principle of Operation
The primary element of the galvanic sensor oxygen analyzer is an electrochemical cell consisting of
two electrodes in contact with a liquid or semisolid basic electrolyte (usually potassium hydroxide).
This type of sensor is commonly called the Hersch cell, after its discoverer. The cell electrodes are
made of dissimilar metals, such as silver and lead. When a gas sample is introduced into the cell, it
diffuses through a membrane usually made out of teflon. The oxygen in the sample contacts the silver

cathode and is chemically reduced to hydroxyl ions. The hydroxyl ions then flow toward the lead
anode, where an oxidation reaction occurs with the lead. This oxidation/reduction reaction results in a
flow of electrons proportional to the oxygen concentration of the sample. The electron flow (current) is
measured by an external metering circuit connected to the cell electrodes. This current is proportional
to the rate of consumption of the oxygen and is indicated on a meter as a percentage or parts per
million of oxygen in the sample.

The cathode reaction involved in the reduction of oxygen is:

The anode reaction is:

The overall reaction is:

Advantages
The galvanic sensor oxygen analyzer is essentially a battery that produces energy when exposed to
oxygen and, hence, is consumed by exposure to oxygen. It is rugged and insensitive to shock and
vibration. The cell can be mounted in virtually any position without changing its sensitivity. The
sensor can be packaged as a relatively small, self-contained, disposable cell. It can then be used as
a fairly inexpensive means of oxygen measurement in small portable devices. The sensor measures
percentage or trace levels of oxygen directly. When properly calibrated, it can provide reliable and
accurate measurements. Some sensors can be refurbished rather than replaced by replacing the
sensor anode.
Galvanic sensors have several major disadvantages. Because they operate on a battery principle,
their life expectancy is a function of usage. Furthermore, as these sensors age, they have a tendency
to read low due to a loss in sensitivity. For most process control applications, false low oxygen
readings can produce dire consequences. As a result, analyzers that use battery-type sensors must

be recalibrated on a frequent basis, sometimes as often as once per day, depending on the criticality
of the application.
Another major drawback of battery-type sensors, particularly when used for trace oxygen
measurements, is their susceptibility to oxygen shock. If exposed to a large concentration of
oxygen, these sensors can take several hours to recover. The combination of false low readings,
frequent recalibrations, susceptibility to oxygen shock, and relatively short life span greatly lessens
the value of galvanic sensor oxygen analyzers in many critical applications.

Typical Usage
The galvanic sensor oxygen analyzer is typically used to validate the quality of semiconductor grade
gases; monitor the quality of breathing air; measure oxygen content in annealing furnaces or other
heat-treatment operations; measure oxygen levels in potentially explosive or hazardous atmospheres
or environments; and monitor oxygen levels in food processing and food storage, and similar
applications where product purity can be affected by the presence or absence of oxygen.