SM

QUESTIONS

AND ANSWERS
Chlorine Dioxide

ClO2

Dilution
Chlorite water Bleach Acid

Figure 1 — Pump-based system

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What is chlorine dioxide (ClO2)?
Chlorine dioxide is a powerful
oxidizing agent. It is a yellow-
green gas that has a pungent,
chlorine-like odor. As a gas, it is
very soluble with water. Due to
its instability as a gas, it is not
produced and transported in a
gaseous state, but generated at
the application site.
Chlorine dioxide becomes a red
liquid at a temperature of 52°F and
will freeze at –74°F. The liquid
form is unstable and will explode,
the explosion being catalyzed by
bright lights, shocks, or contact
with organics and some inorganics.
For this reason, chlorine dioxide
is never used in the liquid form.
Chlorine dioxide cannot be pur-
chased commercially; it must be
generated on site with extensive
equipment. In water treatment
applications, there are normally
three raw materials: bleach, acid
and sodium chlorite.
Where is chlorine dioxide (ClO2)
used?
Chlorine dioxide is a powerful
oxidizing agent. It has been in use
industrially for approximately
50 years and there are a few
thousand applications in operation
domestically.
Traditional applications include:
• Bleaching textiles, paper pulp,
flour, cellulose, leather, fats and
oils and beeswax
• Purification, taste and odor
control of water
• As an oxidizing agent
• Manufacturing chlorite salts
Why is chlorine dioxide (ClO2)
used in certain applications?
The primary reason is that ClO2
does not have the tendency to
form persistent halogenated
organic compounds. The environ-
mental agencies are concerned
with water containing organic
contaminants or ammonia which,
when treated with chlorine, can
form chlorinated organics or
chloramines. These compounds
are harmful to fish and the envi-
ronment. The compounds of
greatest concern are trihalo-
methanes, chlorinated phenols
and chloramines. The paper
industry has seen the most regula-
tions in this area.
The primary reason chlorine dioxide is used is because
it does not have the tendency to form persistent
halogenated organic compounds.
Why would you not want to use
chlorine dioxide (ClO2)?
Chlorine dioxide is not without
concern. Not only are there
uncertainties related to the health
effects of chlorite and chlorate
ions, but there are also regulations
pertaining to the limits of chlorite
and chlorate because they are
suspected carcinogens. There
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are also additional safety issues
involving the generation of
chlorine dioxide that are
addressed later on.
Why must chlorine dioxide be
generated on site?
Chlorine dioxide is not stable as
a gas. Once the reaction takes
place, it must be used immediately
for any effect since it decomposes
quickly. The only way it can be
obtained directly is in very small
quantities as a frozen hydrate,
which must be shipped and
stored under refrigeration.
How is it generated at the
application site?
There are many ways of produc-
ing chlorine dioxide. Large quanti-
ties of chlorine dioxide (such as
would be required in pulp bleach-
ing in the paper industry) are
generated from sodium chlorate.
For small industrial applications
(those requiring less than a few
tons per day), generation can be
completed in several different
ways, including the reaction of
sodium chlorate (NaClO3) or
sodium chlorite (NaClO2) with
acid.
The most common and efficient
way of generating ClO2 is the
oxidation of chlorite. This is most
easily accomplished by mixing
chlorine with an aqueous solution
of sodium chlorite as shown in the
following equation:
ClO2– + Cl2 → ClO2 + 2Cl–
The chlorine can be either in
gaseous form or prepared from
bleach and acid, normally hydro-
chloric. The end product of the
reaction of chlorine with aqueous
chlorite is an aqueous solution of
chlorine dioxide. The feed point of
chlorine dioxide solution from a
generating unit must discharge
below the water level in a cooling
tower basin or into the recirculat-
ing water piping.
What equipment is necessary?
Specialized equipment designed to
generate chlorine dioxide must be
used due to the safety hazards
involved with the raw materials
and the chemical reaction. Produc-
tion is continuous.
There are two primary designs in
the marketplace today. Each of
these has a generator. A generator
is the chemical reactor that pro-
motes mixing of the precursors to
produce an aqueous solution of
chlorine dioxide.
1. One design uses positive
displacement pumps to push
the precursors together (see
Figure 1).
2. The other design uses an
eductor to pull the precursors
together (see Figure 2).
Eductor
ClO2
Chlorite Bleach Acid
Figure 2 — Eductor-based system
What are the safety hazards?
The chemicals used to create ClO2
and chlorine dioxide present
respiratory problems, corrosion,
fire and explosion hazards. The
safety hazards can be grouped
into the following areas: the
production of chlorine dioxide,
the storage and handling of the
precursors, and misapplication of
the product. There have been
numerous fires and explosions
relating to the storage of the raw
materials and the production of
chlorine dioxide.
Production of chlorine dioxide
Fire and Explosion — Light and
heat must be avoided. Care must
be given to keep the concentration
in air below 10 percent. Chlorine
dioxide gas is explosive when its
concentration in air exceeds 10
percent. An event called a “puff”
is a low intensity explosion that
occurs when there is a decomposi-
tion of dilute chlorine dioxide gas.
3
This reaction, once started, is
exothermic and propagates
quickly. It is usually caused by a
sudden rise in temperature, or the
introduction of reactive impurities
to the chemical process.
As a safety precaution, gaseous
chlorine dioxide should never be
stored or shipped, but should be
produced at the application point
as a dilute aqueous solution.
Several precautions must be taken
when using a positive displace-
ment pump system, since the
probability of generating too high
a concentration of ClO2 is an issue.
Personal Protective Equipment —
Chlorine dioxide is very irritating
at 5 ppm and a concentration of
only 19 ppm can cause human
death. Any chlorine dioxide smell
should be treated as HAZARDOUS!
OSHA has strict exposure limits
that must be adhered to as well.
These include a Permissible
Exposure Limit (PEL), a Short-
Term Exposure Limit (STEL), and
Immediately Dangerous to Life
and Health Limit (IDLH).
All employees who may be ex-
posed should be provided with
gas masks specifically designed
for chlorine-contaminated atmo-
spheres. Employees should be
taught when and how to use
several types of respiratory appa-
ratus provided and how to recog-
nize defects in the equipment.
Periodic practice drills should be
held so that time will not be
wasted in an emergency.
In addition, employees should
wear safety glasses with side
3 mVolts @ 25°C
shields and chemical safety
goggles. Impermeable gloves,
boots and apron or a protective
suit should be worn. 2

2.87
Ventilation — An enclosure and

1.76

1.59
an efficient local exhaust system is

1.49

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1.39

1.15

1.07
the preferred equipment for

0.87
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maintaining the concentration of
chlorine dioxide below the toxic 0

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Storage and handling of the
precursors
Again as a general rule, light and
heat must be avoided.
Acid — Normal safety procedures
must be followed with the acid.
These include secondary contain-
ment, have eyewash and safety
showers in the immediate area.
Employees must wear personal
protective equipment such as
goggles and impermeable gloves
as a minimum.
Sodium chlorite — As a powder,
sodium chlorite is a very strong
oxidizer. If the powder contacts
any oxidizable substance (i.e.,
organics, fabric, paper or wood), a
fire can result. For this reason, it is
normally used as an aqueous
solution. However, the same
issues can be a problem if a spill
of the solution is allowed to dry.
In addition, aqueous sodium
chlorite has the potential to react
with various materials to form
chlorine dioxide. Therefore, it
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Figure 3 — Oxidizing potentials of common oxidants
must be stored away from other Does chlorine dioxide work as a
chemicals, especially acidic biocide?
materials. Some reactions with
Because it is an oxidizer, as long
organic materials can be equally
as you have contact, it will kill
hazardous, resulting in a fire or
bacteria, fungi, algae, spores, and
explosion.
viruses. It is not reactive with
ammonia or amines, so it can be
Misapplication more effective than chlorine. Since
chlorine dioxide exists as a gas in
A knowledge of the properties of solution, it is effective over a
chlorine dioxide along with a good broad pH range.
understanding of the chemistries
involved is important in establish- The chemistry of chlorine dioxide
ing safe, effective applications. in water treatment is not com-
As a general rule, the following pletely understood. While ClO2 is
applies: several times more powerful than
chlorine at low pH (i.e., pH 2-4),
• Chlorine dioxide should not be it has about the same oxidizing
generated into a closed space potential at the pH commonly
• The area must be well ventilated found in water treatment applica-
tions. See Figure 3 for the
• Aqueous sodium chlorite should oxidizing potential of several
never be added directly to any common oxidants. At higher
organic materials pH waters, above 8.0, chlorine
• Aqueous sodium chlorite should dioxide performs better since it
never be allowed to dry out does not dissociate in water like
chlorine.

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 And to summarize, the
Henry's Law Constants disadvantages of chlorine
H (atm) @ 20°C dioxide are?
10000 • More volatile than chlorine and
1000 bromine compounds in water
100
5000 • Expensive to start up and
10 585 operate
59.3 54
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0.5 • Explosion and fire potential
0.1 0.1 0
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Figure 4 — Oxidizing biocide flash off
Chlorine dioxide is volatile. What
does this mean?
Chlorine dioxide is quite soluble
in water. Its solubility in water is a
function of temperature and
pressure. Unlike chlorine, ClO2
does not react with water; it is a
true dissolved gas. And although
it is readily soluble in water, it is
quite volatile and may be removed
from solution with moderate
aeration. In open recirculating
cooling systems, this characteristic
causes its effectiveness to diminish
greatly. This is illustrated in
Figure 4. Chlorine dioxide is over
500 times more volatile than
hypochlorous acid and 1300 times
more volatile than hypobromous
acid. This becomes important as
the water passes over the tower,
most of the chlorine dioxide is lost.
So, what are the advantages of
chlorine dioxide?
• Does not react with ammonia
• Does not react to form haloge-
nated organics
• Effective over a wide pH
• Works very well at high pH
• Destroys chlorophenol com-
pounds (important for taste and
odor control in drinking water
plants)
Does Nalco sell chlorine dioxide?
No, Nalco does not sell chlorine
dioxide systems. Our representa-
tives are trained in water chemis-
try and will be able to assist you.
Your local sales representative
will be able to work with your
system and assist you in selecting
the most appropriate water
treatment package including
corrosion and scale inhibitors and
supplemental biocide programs
whether you choose to use
chlorine dioxide or not.

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