Understanding Oxygen Sensor Performance -- Occupational Health & Safety

8/26/2019 Understanding Oxygen Sensor Performance -- Occupational Health & Safety
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Understanding Oxygen Sensor

Performance
May 01, 2005
OXYGEN deficiency is one of the most common of all categories of atmospheric hazards.
It stands to reason that the sensors used to measure oxygen concentration are one of
the most widely used types of sensors included in portable atmospheric monitors,
especially those used in confined space monitoring procedures. In spite of the millions of
oxygen sensor-equipped atmospheric monitors in service in the United States, however,
there is still a lot of misunderstanding when it comes to the performance characteristics
and limitations of this very important type of sensor.
Death in Confined Spaces

Fatal industrial accidents that stem from oxygen deficiency are unfortunately very
common. Tragically, the same conditions and factors appear over and over again in
confined space accidents. In one recent accident, four men died and three others
suffered serious injuries due to oxygen deficiency in a confined space on board a barge.
The lack of oxygen was due to rusting (oxidation) of the exposed metal in the confined
space. Workers had been engaged in maintenance work on the barge earlier in the day.
During a mid-morning break, they realized one of the workers had failed to return and
was still inside the barge. The worker and three who tried to save him died during the
attempted rescue. Several more rescuers were seriously injured.
In another accident, a welder who had entered the hull of a barge became unconscious
in the oxygen-deficient atmosphere. Again, the oxygen deficiency was due to rusting of
the exposed metal in the shipboard compartment. Four other workers entered the hull to
attempt a rescue of the unconscious welder and also were overcome. The welder died,
and the other four workers suffered lung damage. In yet another recent incident, the
owner of a small winery collapsed while taking a sample from a wine fermentation tank.
A second person entered the tank to attempt a rescue and was overcome. Both people
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died. The cause of the accident was attributed to a lack of oxygen due to displacement by
carbon dioxide created by the fermentation process.
In another accident, a worker at a pulp mill entered a tank without testing the air. The
tank had been filled with colorless, odorless nitrogen as part of an inerting process, and
the worker collapsed from oxygen deficiency. A second worker at the entrance to the
tank also collapsed. Neither worker could be revived.
In all of these accidents, the cause of the fatalities was asphyxiation due to lack of
oxygen. Oxygen deficiencies are extremely dangerous. At concentrations of 10 percent
oxygen or lower, a single breath is normally all it takes to result in immediate
unconsciousness, followed by irreversible brain damage or death if the unconscious
individual is not quickly revived. Oxygen deficiencies are invisible to human senses.
Without the use of an instrument capable of directly measuring the absence of oxygen,
the only indication of the existence of an oxygen deficiency very well may be when
workers begin to pass out.
What Is an Oxygen Deficiency?

The concentration of oxygen in normal air is approximately 20.9 percent. The balance
(more than 78 percent) consists primarily of nitrogen. The remaining fraction includes
small amounts of water vapor, carbon dioxide, and argon, as well as traces of other
gases.
OSHA's 29 CFR 1910.146, "Permit Required Confined Spaces," contains the requirements
for practices and procedures to protect employees in general industry from the hazards
of entry into permit-required confined spaces. The standard defines an oxygen-deficient
atmosphere as any atmosphere containing less than 19.5 percent oxygen by volume. Any
atmosphere that contains less than 19.5 percent oxygen is hazardous and may not be
entered by unprotected workers.
Confined spaces are particularly prone to the development or containment of oxygen-

deficient atmospheres. The reason that oxygen deficiency is common in confined spaces
is that they develop by mechanisms that affect the contents of the space and boundary
surfaces. Causes of oxygen deficiency include microbial action, displacement,
combustion, oxidation, and absorption and adsorption. Work activity is also an important
cause. Use of solvents, paints, and degreasers or hot work can affect oxygen levels.
Any oxygen concentration other than 20.9 percent indicates an abnormal condition. A
less-than-normal concentration of oxygen by definition indicates a greater-than-normal
concentration of some other component or the presence of a contaminant in the
atmosphere being sampled. Even when the oxygen concentration does not constitute a
statutory hazardous condition, workers should determine the cause of the abnormal
reading prior to entering a confined space. The safest approach is to initiate entry only
when monitoring has determined that a "fresh air" oxygen concentration of 20.9 percent
exists in the space.
Oxygen Enrichment
The concentration of oxygen in confined spaces is a concern from two standpoints. Too
little oxygen can cause asphyxiation. Excessively high (or "enriched") levels of oxygen
above normal oxygen concentrations dramatically promote or accelerate combustion
and other chemical processes.
The definition of oxygen enrichment varies between different standards and regulatory
documents. OSHA's 1910.146 references 23.5 percent as the concentration for oxygen
enrichment. However, OSHA's 1915-Subpart B, "Standard for shipyard employment,"
specifies 22 percent. The latter value is consistent with non-mandatory recommendations
from groups such as the National Fire Protection Association (NFPA). The most
conservative standards specify 22 percent as the concentration above which the
atmosphere is deemed to be hazardous due to oxygen enrichment. For this reason, an
increasing number of instrument manufacturers use 22 percent as the default high-
alarm setpoint.
Oxygen Detection
Most portable or survey instruments utilize fuel-cell type oxygen sensors, which are
mechanically complex. Oxygen sensors generally contain a diffusion barrier used to limit
or control the amount of oxygen that enters the sensor; a sensing electrode (cathode)
made from a noble metal such as gold or platinum; a working electrode (anode) made
from a base metal such as lead or zinc; and other components, such as external moisture
barriers or filters. The internal sensor components are bathed in a basic electrolyte, such
as a solution of potassium hydroxide or potassium acetate.
The principle of detection is very straightforward. Oxygen diffusing into the sensor is
reduced to hydroxyl ions at the cathode:
O2 + 2 H2O + 4 e- ? 4 OH-
Hydroxyl ions in turn oxidize the lead (or zinc) anode:
2 Pb + 4 OH- ? 2 PbO + H2O + 4 e-
This yields an overall reaction of:
2 Pb + O2 ? 2 PbO
Fuel cell oxygen sensors generate electrical current. The amount of current generated is
proportional to the amount of oxygen consumed. Oxygen-detecting instruments simply
monitor current output from the sensor. Of course, this is a simplification of the way
oxygen sensing instruments are designed.
The electrolyte may be buffered or consist of a solution (such as potassium acetate) that
is less prone to poisoning or being ruined by gases such as carbon dioxide. The
electrolyte also may be a semi-solid gel rather than a liquid. Use of a gel electrolyte
improves low temperature performance as well as reducing the potential for leakage or
drying out.
The working electrode seldom is a simple chunk of lead because this surface must be
available and accessible for contact with oxygen molecules before the electrochemical
reaction can occur. The working electrode usually consists of lead wool or some other
finely divided form of the metal that provides a good surface area-to-volume ratio. Other
design features can include temperature compensating thermistor-resistors, internal
membranes, spacers, wicks, and current collectors. Numerous variations on these
general design features are used to optimize the performance of an oxygen sensor for
use in a specific product.
One of the most important design constraints is the build-up of lead oxide that develops
in the sensor capsule over the life of the sensor. As lead is converted into lead oxide, an
increasing fraction of the volume of the sensor capsule is occupied by solid material. If
the sensor design does not include a provision for this increase, it will eventually rupture,
possibly leading to leakage of electrolyte into delicate and expensive instrument
electronics.
The lead wool in the working electrode in a fuel-cell oxygen sensor is consumed over
time. When all available surface area of the lead (Pb) anode is converted to lead oxide
(PbO), electrochemical activity ceases and current output falls to zero. At this point, the
sensor must be rebuilt or replaced. Most fuel-cell sensors are designed to last no more
than one to two years.
In most instruments, even when the instrument is not being used, the oxygen sensor
continues to generate current and use itself up. Some instrument designs prevent the
flow of electricity by breaking the circuit. This blocks the electrochemical reaction as long
as the instrument is turned off and increases the effective life span of the sensor. The
drawback to this approach is the need for a restabilization period (sometimes lengthy)
when the instrument is turned back on.
The temperature of the atmosphere influences the output from fuel-cell oxygen sensors.
The warmer the atmosphere, the faster the electrochemical reaction proceeds. For this
reason, oxygen sensors usually include a temperature-compensating load resistor to
hold current output steady. Microprocessor-based designs usually provide additional
signal correction in software to improve accuracy further.
Cold temperatures can be a major factor that limits performance. The freezing
temperature of electrolyte mixtures used in some oxygen sensors can be as high as
minus 20°C (minus 5°F). Once the electrolyte freezes, electrical output falls to zero. The
gel and liquid electrolyte mixtures used in more recent sensor designs, however, show
much better cold temperature performance.
There are two fundamental variations in designs of fuel-cell oxygen sensors: "partial
atmospheric pressure" and "capillary-pore" type designs. These variations reflect the
mechanism by which oxygen diffuses into the sensor.
The partial pressure of oxygen (or pO2) is that fraction of the total pressure due to
oxygen. Partial pressure oxygen sensors rely on the partial pressure of oxygen to drive
molecules through the diffusion barrier into the sensor. Table 1 lists the partial pressure
of oxygen versus the percent volume concentration at varying altitudes above sea level.
As long as pO2 remains constant, current output is a reliable indicator of oxygen
concentration. Shifts in barometric pressure, altitude, or other conditions that affect
atmospheric pressure will cause a systemic change in sensor output. To illustrate this
problem, consider a sensor calibrated at sea level where atmospheric pressure is 760 mm
Hg. Now consider the same sensor at an elevation of 3,000 m (10,000 ft).
TABLE 1
PARTIAL PRESSURE O2 VS. % VOL AT VARYING ALTITUDES
Height above sea Atmospheric Partial Atmospheric Concentration

level pressure Pressure O2 (pO2)
Feet Meters mmHg mmHg kPa* % Volume
16,000 4,810 421.8 88.4 11.8

20.9%
10,000 3,050 529.7 111.0 14.8

20.9%
5,000 1,525 636.1 133.3 17.8

20.9%
3,000 915 683.3 143.3 19.1

20.9%
1,000 305 733.6 153.7 20.5

20.9%
0 0 760.0 159.2 21.2

20.9%
*19.5% O2 at sea level = 18 kPa
Although at both elevations the air contains 20.9 percent oxygen, at 10,000 feet the total
atmospheric pressure is only 514 mm Hg, and the partial pressure for O2 is only about
107 mm Hg. Because there is almost one-third less force driving oxygen molecules
through the diffusion barrier into the sensor, current output is significantly lower.
It should be noted that most instrument designs that use pO2 sensors include software
to correct sensor readings for barometric pressure fluctuation. In the case of these
designs, oxygen readings will not be affected by changes in ambient pressure within
design parameters.
Figure 1 provides a simplified diagram of a capillary-pore oxygen sensor. These sensors

utilize a narrow-diameter tube through which oxygen diffuses into the sensor. Oxygen is
drawn into the sensor by capillary action in much the same way water or fluid is drawn
up into the fibers of a paper towel.
Capillary-pore sensors are much less influenced by changes in pressure than partial
pressure oxygen sensor designs. Although rapidly changing pressure leads to a change
in sensor output, as soon as the diffusion barrier capillary has stabilized at the new
pressure, the output will return to the previous level. Because the volume of atmosphere
contained in the diffusion barrier capillary is very small, stabilization at the new pressure
is usually achieved within 10 to 30 seconds.
This effect can be seen clearly when a properly calibrated capillary-pore oxygen sensor is
taken on board a commercial jet. Initially the sensor reads 20.9%. As the jet takes off and
begins to gain altitude, the pO2 drops, causing a drop in oxygen sensor readings. When
the jet reaches cruising altitude (actually, when cabin pressure is stabilized at normal
operational levels), the readings return to 20.9%. As the jet begins its descent prior to
landing, pO2 increases, causing a rise in readings. As soon as the sensor is back at
ground level (and the cabin is once again depressurized), readings will return to 20.9%.
Capillary-pore designs are potentially vulnerable to blockage of the capillary. For this
reason, capillary-pore sensors include an external moisture barrier to prevent the pore
from being blocked or plugged by solid materials, water, or other fluids.
Oxygen reading instruments used in confined spaces generally display readings in units
of percent by volume concentration, regardless of the type of sensor that is employed.
Readings are usually in increments of plus or minus 0.1 percent O2, with a full instrument
range on the order of 0 to 25 percent oxygen.
Mechanisms of Oxygen Sensor Failure

Oxygen sensors may be affected by prolonged exposure to acid gases, such as carbon
dioxide. Most oxygen sensors should not be used continuously in atmospheres
containing more than 25 percent CO2. In some cases, prolonged exposure to the acid gas
damages the basic (alkaline) sensor electrolyte. In other situations, high concentrations
of acid gas produce a current flux that alters the normal expected output of the sensor at
a given concentration of oxygen.
Use in extreme conditions can affect data provided by the instrument. Extreme
conditions are any that exceed published operating specifications for the instrument.
Users should always consult the owner's manual or contact the manufacturer directly
before using an instrument in any unusual or extreme environment, including operation
in cold or excessively hot temperatures. While the instrument may not pose an ignition or
intrinsic safety hazard, the accuracy of readings may be adversely affected during use
outside of design parameters.
As indicated previously, the working electrode in a fuel-cell sensor is consumed over

time. When all available surface area of the lead (Pb) anode is converted to lead oxide
(PbO2), electrochemical activity ceases and current output falls to zero. This is the type of
sensor failure most frequently experienced by users. This failure is fail-safe because the
oxygen deficiency alarm activates whenever current output falls below a minimum level.
At this point the instrument will alarm continuously until the sensor is replaced, making it
unlikely anyone would attempt to use it.
The standard method used to calibrate most oxygen sensors is to let the instrument
automatically adjust its readings to match 20.9 percent while the sensor is located in
fresh air. It is very important to "bump test" the oxygen sensor before each day's use.
During the bump test, the proper performance of the sensor and alarms are verified by
exposing the sensor to a concentration of oxygen below the oxygen deficiency alarm
setpoint. Bump testing the O2 sensor can be done by exposing it to calibration gas
packaged in small 34- or 58-liter cylinders or simply by exhaling onto the sensor.
Readings should decrease to a level low enough to activate the low-oxygen alarm, then
recover. Readings that fail to decrease or that require an abnormally long time to recover
fully may indicate a problem with the sensor.
Oxygen sensors are among the most dependable, stable, and reliable type of gas-
detecting sensors available. But no sensor can detect gas unless it is used.
Understanding your instrument is important; using your instrument is critical.
This article appeared in the May 2005 issue of Occupational Health & Safety.
About the Author

Bob Henderson (bhenderson@gfg-inc.com) is President of GfG Instrumentation in Ann Arbor,
Mich.
Copyright 1996-2018 1105 Media Inc. All rights reserved.

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8/26/2019 Understanding Oxygen Sensor Performance -- Occupational Health & Safety