Safetygram 33

The hazards of oxygen

and oxygen-enriched mixtures
Most people who use pure oxygen are aware of the hazards of and special precautions for handling this material.
Unfortunately, fewer are aware that these hazards extend to oxygen mixtures. This Safetygram reviews how to distin-
guish between the various mixtures of oxygen, the hazards of pure oxygen and oxygen mixtures, and how to safely
handle these products. The Safetygram concentrates on mixtures above 23.5% oxygen and pure oxygen because opera-
tionally they should be treated with the same precautions and requirements.

Oxygen-enriched classification
In the United States regulations define oxygen-enriched mixtures or atmo-
spheres as those containing more than 23.5% oxygen by volume. In oxygen-
enriched atmospheres, the reactivity of oxygen significantly increases the risk of
ignition and fire. Materials that may not burn in normal air may burn vigorously
in an oxygen-rich environment. Sparks normally regarded as harmless may
cause fires. And materials that burn in normal air may burn with a much hotter
flame and propagate at a much greater speed.

Oxygen mixtures are classified, labeled and valved differently. As with all gases,
the primary method of product identification is the label.

Hazards of oxygen and mixtures

One of the challenges in educating individuals about the dangers associated
with oxygen is their perception of the product. When one thinks about oxygen,
medical applications usually come to mind. Doctors, dentists, nurses, paramed-
ics and first aid teams administer oxygen to people when they are sick or in-
jured. These professionals would not allow us to intentionally inhale a hazard-
ous material. This perception can downplay or at least minimize respect for the
hazards of oxygen. But let’s look at oxygen from a different perspective.
Oxygen and its mixtures are packaged In an oxygen-enriched environ- Let’s look at the basic fire triangle.
as compressed gases. They are sup- ment, fire chemistry starts to change. All three legs of the triangle must be
plied at pressures up to 4500 psig (300 Materials become easier to ignite present to produce a fire—a fuel, an
bar). In addition to pressure, oxidizers because their flammable ranges start oxidizer, and an ignition source. If
carry other hazards. To fully under- to expand and their autoignition tem- asked to name some fuels, materials
stand these hazards, we must first peratures begin to drop. This includes like wood, coal, oil, and gas would be
understand some of the terms used: the materials of construction used mentioned. But would anyone list
in oxidizer systems, such as metals. materials like aluminum, steel, stain-
• Adiabatic Heat: A process in which This reactivity continues to increase less steel? What is the primary reason
there is no gain of heat to or from not only with the concentration of we can light a piece of wood with a
the system. With respect to this oxygen, but also with pressure and/or match but not a steel rod? The igni-
document, it is the heat picked up temperature. In other words, oxygen tion temperature of the wood is much
by the gaseous oxygen from the contacting a material at 2000 psig is lower than that of the steel rod, and
rapid pressurization of a system. more likely to react with the material the heat from the match is sufficient
• Autoignition Temperature: The low- than at atmospheric pressure. In the for ignition. Remember what we said
est temperature required to ignite case of a contaminant in a system, the about fire chemistry and oxygen—as
or cause self-sustained combustion contaminant may react and generate the oxygen concentration increases,
in the presence of air and in the enough heat to start another material the autoignition temperature decreas-
absence of a flame or spark. reacting. This is called the kindling es. So materials that cannot be ignited
chain. When temperature increases, in normal air may burn readily in
• Flammable Range: The range of it can lower the amount of energy oxygen-enriched atmospheres. With
concentration in volume percent of required to initiate a reaction. this in mind, it is easy to see that in
flammable gas or vapor between an oxidizer system we have two legs
the upper and lower flammability of the fire triangle present. All that is
limits. required for an ignition is an energy
source.
• Kindling Chain: The promotion of
ignition from materials of low igni-
tion temperatures to materials of
higher ignition temperatures.

• Limiting Oxygen Concentration: The

minimum oxygen concentration in
volume percent (at a given tempera-
ture) in a gaseous mixture contain-
ing a fuel below, which a flame will
not propagate.

• Lower Flammability Limit: The

minimum fuel mixture in volume
percent with air through which a
flame will just propagate.

• Upper Flammability Limit: The

maximum fuel mixture in volume
percent with air at which a flame
will just propagate.

2
Now let’s consider ignition sources. Adiabatic heat is sometimes con- All of these energy sources can be
Typical sources of ignition would be fused with the heat of compression. enhanced by the presence of a con-
fire, open flames, sparks, or cigarettes. The heat of compression causes the taminant. Contaminants are typically
But that is in the world of normal air, temperature of a system to rise. An easier to ignite than the components
not oxygen-enriched atmospheres. example would be a tire pump. The of the system. If they react with the
Remember the definition of autoigni- barrel or compression chamber builds oxygen, they may generate sufficient
tion temperature—the lowest temper- heat as the pump compresses air. heat to propagate a reaction to the
ature required to ignite a material in This process occurs relatively slowly, system. Or as in the case of the pipe in
the absence of a flame or spark. Could and the system takes on the heat. Figure 1, they may react so strongly as
gas velocity, friction, adiabatic heat, Adiabatic heat is caused by the rapid to compromise the system.
or contamination provide ignition pressurization of a system where
sources? Yes. the gas absorbs the energy and the
gas temperature rises. This heating
In the case of gas velocity, it is not the occurs at the point of compression
flow of gas that can cause ignition, or the point where the flow of gas is
but a particle that has been propelled stopped, such as at a valve or regula-
by the gas and impacts the system tor seat. Depending on the material in
with sufficient force to ignite. The use where the hot gas impinges, the
heat generated may be sufficient to heat may be sufficient to ignite the
start a fire, depending on the material material.
impacted. Friction from a component
malfunctioning or operating poorly
can generate heat. Friction between
two materials generates fine par-
ticles, which may ignite from the heat
generated.

3
Figure 1 depicts a section of an oxygen Figure 1
pipeline that ruptured. Here’s how
this happened. The oxygen supply
line at an installation needed to be
extended an additional 150 feet (45.7
meters). The line was solvent washed,
but shop air was used to dry the line
rather than clean, dry nitrogen. Most
shop air is compressed with a hydro-
carbon compressor, and in this case,
the compressor did not have a clean-
up system to remove any trapped
oil. When the line was purged, a thin
film of hydrocarbon oil coated the
interior of the pipe. The pipe was put
into service, and the operation went
smoothly until at the end of the shift
when a valve at the downstream end
was closed. This stopped the flow, and
the oxygen heated as it compressed
against the valve seat. The compres-
sion provided enough energy to Let’s take a look at a carbon steel The above examples show how con-
react with the hydrocarbon oil, and pipeline used to provide oxygen to a tamination in a system can enhance
a deflagration occurred. The speed of customer. Because most of these pipe- the potential for a reaction. It must
the pressure wave was such that it du- lines have large diameters, economy be stressed that systems must not
plicated the line rupture, as depicted and availability make carbon steel the only be cleaned to oxidizer service
in Figure 1, every 15 feet (4.57 meters). material of choice. Carbon steel is an requirements on initial construction
This is a very good example of how excellent fuel when used in oxygen but must be maintained in that condi-
materials that burn in normal air can service. In fact, due to the operat- tion of cleanliness. Contamination of
react in oxygen. ing pressure, the pipelines contain a materials like hydrocarbons or con-
flammable mixture. To prevent fires taminants that may be in the form of
It is critical to keep nontypical igni- in these pipelines, ignition sources particles can initiate a system fire.
tion sources in mind when designing must be considered. Since these lines
systems for oxygen use. Some applica- are underground, external sources
tions are very vulnerable to ignition. are usually not a problem. However,
For example, the elastomers used in carbon steel is prone to rust, which
valves and regulator seats have lower can generate particles. If a particle is
ignition energies than metals. Since picked up in the flow of oxygen, the
particle impingement or adiabatic particle may impinge on part of the
heat can be directed at these valves system. If the impingement gener-
and regulators, they are particularly ates sufficient heat, it may provide a
susceptible to ignition. source of ignition energy. Carbon steel
pipelines in oxygen service must be
designed and operated to minimize
the potential hazard. This is accom-
plished by following the gas velocity
limitations set forth in CGA Pamphlet
G-4.4. By limiting the velocity, the par-
ticle impact energy is reduced, which
minimizes the chance of an ignition.

4
These are potential problems in Figure 2
oxidizer systems, but what happens
when oxygen enters the atmosphere?
If oxygen leaks or escapes into the air
as part of a normal process, oxygen
enrichment may occur if the ventila-
tion is insufficient. If the surrounding
air becomes oxygen-enriched, the
same changes in fire chemistry take
place. In other words, materials
become easier to ignite because their
autoignition temperatures begin
to decrease and their flammability
ranges increase. Remember that ma-
terials which do not ordinarily burn
in air may ignite, and materials that
do burn in air will burn hotter and Figure 3
faster. Most areas where enrichment
is known to be a possibility are posted
with signs warning about smoking
or open flames. The real danger is if
oxygen enrichment occurs and people
carry the hazard with them when
leaving the area.

Clothes can trap and hold the oxygen-

enriched atmosphere in the countless
air spaces within the weave of the
fabric. Hair poses the same problem.
If someone comes in contact with an
enriched atmosphere, it is extremely
important to isolate the person from
any source of ignition for at least 30 Figure 2 shows a normal cotton work ment is possible, such as at a vent, a
minutes. Get him/her to fresh air, pat shirt, stuffed with paper and saturat- leak, or failure of a ventilation system.
the person’s clothing, and run fingers ed with oxygen. Inside the shirt is Sometimes a worker may intention-
through his/her hair. Think about a simple ignition device. The results ally saturate themselves with oxygen
how easily cloth and hair burn in air, of the ignition are shown in Figure 3. without recognizing the danger. Think
and then try to imagine how they Individuals must be aware of the about the person who may use the
would burn in an oxygen-enriched hazards of oxygen enrichment, since flow of oxygen from an oxyacetylene
environment. oxygen is not detectable by human torch to blow off dirt or to cool down.
senses. It is colorless, odorless, taste-
less and nonirritating. Likewise, they
must be aware where oxygen enrich-

5
Safe handling of oxygen The valve connections provided may Plant systems must be designed with
prevent the possible connection of an the special considerations required
and mixtures incompatible material, but they must for the safe handling of oxygen.
It is important that all personnel not be relied upon for identification of There are several documents avail-
handling oxygen and its mixtures be the mix. If the mixture label and valve able to help design systems and
aware of its hazards and trained in the connection do not comply with the equipment for the safe handling of
use of proper procedures and personal above-mentioned classifications, DO oxygen. They include but are not lim-
protective equipment. The SDS is the NOT use the cylinder until consulting ited to Compressed Gas Association
primary source of hazard data. All with the supplier. NEVER use adapters Pamphlet G-4.4, “Industrial Practices
personnel handling a material should or change connections to accommo- for Gaseous Oxygen Transmission
be thoroughly familiar with the SDS, date the connection of a cylinder to a and Distribution Piping Systems,”
including personal protective equip- system. If a cylinder does not connect and the ASTM International Standard
ment recommendations. easily, do not force; put the cylinder G 88, “Designing Systems for Oxygen
aside, label as to the problem, and Service.” The European Industrial Gas
As mentioned earlier, oxygen mix- contact the supplier. Association and the International
tures are classified, labeled, and valved Standards Organizations also publish
differently. The primary method of From an operating perspective, areas related documents, including IGC Doc
product identification is the label. of possible oxygen enrichment must 13/02/E, “Oxygen Pipeline Systems.”
Mixtures with oxidizing potential will be identified and plans implemented
have a yellow oxidizer hazard class to address these potential hazards. Designing and building these systems
diamond in addition to the green These plans should consider safety requires an intimate knowledge of
nonflammable gas diamond. Do not systems including but not limited oxygen and how it reacts with the
let the presence of the green nonflam- to training, signage, monitoring, and materials it contacts. Basic design
mable label lessen the warning of the ventilation. Systems using mixtures considerations include but are not
oxidizer hazard. of oxygen 5% and greater at high pres- limited to control and avoidance of
sure (greater than 450 psig/30 bar) unnecessarily high temperatures and
should be cleaned for oxygen service. pressures; cleanliness; elimination
Most compressed air systems use of particles; minimization of heat of
compressors that are hydrocarbon- compression; avoidance of friction
lubricated. However, the pressures and galling; minimization of reso-
at which they operate do not pose nance with direct flow paths; use of
reaction problems and cleaning these hardware that has a proven history in
systems is not practical because they oxygen service; minimizing available
are self-contaminating from the fuel and oxygen through materials
compressor oil. However, materials of selection and system volume; antici-
construction and system design re- pation of indirect oxygen exposure
quirements for enriched oxygen con- from system failures; and design of
centrations must go beyond cleaning. systems to manage fires, using tech-
niques such as fire stops and automat-
ic extinguisher systems. The first step
in constructing any system for oxygen
should be to consult your supplier.

6
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