Loss Prevention Bulletin 241 February 2015 | 3

Safety review

Hazards of chlorine

Summary
Chlorine (chemical symbol Cl) (CAS: 7782-50-5) is a dense
greenish-yellow gas with a suffocating irritant odour at
ambient temperatures. The elements name arrives from
the Greek word (chloros) meaning greenishyellow. Chlorine is a member of the halogen group;
consequently it is very reactive and a powerful oxidising
agent with the ability to combine with a wide range of
chemical elements and compounds.
Chlorine is very toxic by inhalation and is irritating to the
eyes, respiratory system and skin. In high concentrations,
chlorine can cause serious chemical burns and is highly
corrosive to a wide range of materials, including iron,
aluminium, zinc, etc.
This paper provides a summary of the key chemical
properties of chlorine and its principle hazards, as well
as an outline of the safety precautions that should be
adopted to ensure that the element is used in a safe
manner. The paper also cites and summarises several
accidents that have involved chlorine and the lessons that
can be learned.

Keywords: chlorine, risk control measures, safe

systems of work, hazards.

Introduction
Carl Wilhelm Scheele1 a Swedish pharmacist is credited with
chlorines discovery in 1774. Scheele incorrectly concluded
that chlorine was an oxide of hydrochloric acid and it was not
until much later in 1810 that Sir Humphry Davy confirmed
chlorine was an element.
The gas is extremely poisonous even if inhaled in very
low concentrations; because of this property it is notoriously
associated with the First World War (1914 -1918), where it
was deployed as a chemical warfare agent (bertholite). The
gas, being approximately 2.5 times heavier than air, would
roll along the ground propelled by a gentle wind without it
significantly escaping upwards. Chlorine was later replaced
with more potent agents, such as phosgene and mustard gas.
Chlorine is used extensively to manufacture a wide range
of chemicals and intermediates. Indeed chlorine has the
privilege of having its own distinct chemical industry referred
to as the chloroalkali industry. Some examples for the
uses of chlorine include the manufacture of vinyl chloride,
chlorinated hydrocarbons (e.g. chloroform, dichloromethane,
trichloroethylene, etc.), bleach, etc.

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Over 90% of chlorine is produced from the electrolysis of an

aqueous solution of sodium chloride (brine)2. The remaining
10% of chlorine is generated either by the electrolysis of molten
sodium or magnesium chloride, or via the electrolysis of an
aqueous solution of potassium chloride.
A summary description now follows outlining the production
of chlorine via the electrolysis of brine using the mercury
cell process, originally patented by Hamilton Castner3 in
1892. A stream of purified brine (25.5 % w/v NaCl) at 20oC
flows through a steel trough (0.5-2.0m wide by 7-21m long),
which is lined with either graphite or ebonite (a hard rubber
vulcanite). A very shallow stream of liquid mercury flows in
the same direction as the brine and functions as a cathode.
Graphite blocks (typically, numbering 20-150) acting as anodes
are suspended within the brine at a height of 2mm above the
flowing mercury stream. The arrangement is gas tight and
chlorine is evolved and collected at the anode. At the cathode,
sodium is liberated and dissolves in the mercury to form an
amalgam (alloy) containing typically up to 0.2% sodium by
weight. The amalgam is then transferred to another electrolytic
cell made of iron, where water reacts with the sodium to
generate sodium hydroxide and hydrogen. The mercury is
then recycled back to the production process. The overall
chemical reaction for the electrolysis of the brine solution
proceeds in accordance with the following equation:
2NaCl(aq) + 2H2O (l) Cl2(g) + H2(g) + 2NaOH(aq)

The hazards of chlorine

Chlorine has a suffocating odour and is approximately 2.5 times
heavier than air (density of 3.2 g/l at 0oC and 1 atmosphere).
The gas has a vapour pressure of 5.88 bar (558 kPa) at 21oC.
Under atmospheric conditions, pure chlorine freezes at -101oC
and boils at -34oC. Liquid chlorine is a dense, clear amber
liquid. The gas is sparingly soluble in water (7.3g/l) forming a
yellowish solution, commonly referred to as chlorine water,
containing free chlorine, hydrochloric (HCl) and hypochlorous
acids (HOCl).
Chlorine can be smelled at concentrations of 0.02 0.2
ppm4. Initial exposure to the gas causes burning of the eyes,
nose, mouth and skin. Other common symptoms include:
lacrimation (discharge of tears), rhinorrhea (discharge of
thin nasal mucous); coughing; choking, nausea, vomiting;
headache and dizziness. In addition, exposure to the gas leads
to pulmonary oedema (fluid in the lungs), which often does
not manifest itself for up to 36 hours later5. Gassed individuals
often suffer from hypoxemia (reduced oxygen in the blood).

knowledge and
competence

John M Riddick
Principal Consultant, Risktec Solutions, Canada

4 | Loss Prevention Bulletin 241

February 2015

If liquefied chlorine comes into contact with the skin then

frostbite and chemical burns6 can also be generated.
The following table summarises the acute toxic effects7 in
relation to approximate air concentrations of chlorine.
Concentration
ppm

mg m-3

Signs and symptoms

1-3

3-10

Mild mucous membrane irritation

5-15

15-45

Moderate irritation of the upper respiratory tract

30

90

40-60

115-175

430

1250

Lethal after 30 minutes exposure

1000

2900

Lethal in minutes

Immediate chest pain, vomiting and coughing

Toxic pneumonitis and pulmonary oedema

Note: Concentrations in mg m-3 are approximate conversions from the

corresponding ppm value.

Table 1: Acute toxic effects in relation to approximate air

concentrations of chlorine
The UK Health and Safety Executive (HSE) has established
a short-term exposure limit (15 minute reference period)
Workplace Exposure Limit (WEL)8 for chlorine at 0.5 ppm
(1.5 mg.m-3). (Note: In 2012, the HSE withdrew the long-term
exposure limit because it was concluded that there is no safe
long-term threshold for breathing chlorine.)
Chlorine is classified as a Danger and labelled in
accordance with the new EU CLP Regulations9 with the
following three Globally Harmonized System (GHS)
pictograms:

Precautions to be taken when handling

chlorine
The UK like many other jurisdictions health and safety laws
require consideration of whether hazardous materials can
be eliminated or substituted for substances that present less
risk. In addition, process safety warrants the application of
inherent safety10 principles (i.e. minimise, substitute, moderate
and simplify), where the process safety risks should also
be examined. It may not be possible or indeed practicable
to eliminate the use of chlorine; nevertheless, these
considerations should be fully explored, especially in the early
engineering design stages.
Although chlorine is not combustible, it can support
combustion because it is an oxidising agent. It reacts with
many materials including iron, aluminium, magnesium,
acetylene, rubber, alcohols, phosphorus, boron, etc., often
with violence and heat liberation (exothermic). Since chlorine
is so reactive, authoritative advice should be sought from
specialist publications11, 12.
Advice on the handling of chlorine in bulk, drums and

cylinders is comprehensively documented from bodies

such as the Health and Safety Executive (HSE)13,14 and the
Chlorine Institute15. General safety precautions regarding the
safe storage and use of chlorine are discussed below. Where
chlorine is used on industrial facilities falling under the UKs
Control of Major Accident Hazard (COMAH) Regulations
(i.e. Seveso sites), readers are directed to the HSEs
Hazardous Installations Directorate (HID) Safety Report
Assessment Guide: Chlorine16.
All pipework, vessels and safety equipment (pressure
relief, etc.) must be suitably designed and adequately
maintained to ensure that asset integrity is ensured,
minimising any loss of containment. Where dry chlorine
is handled, pipework can be constructed from seamless
carbon steel or Hastelloy C (not B), or in the case of
flexible hoses, Monel braided hose connections can be
utilised13. Pipework and vessels all need to be designed and
constructed in accordance with ANSI / ASME B31.1 and
BS 5500 Category 1 or equivalent standards respectively. In
circumstances where wet chlorine is handled, construction
can be from ebonite-lined mild steel, reinforced glass-lined,
polyester resins or titanium. Titanium must never be used for
transferring dry chlorine because it is rapidly attacked17. The
use of dissimilar materials for the construction of plant and
equipment is best avoided, or where their use is demanded,
a risk assessment should be carried out.
Liquid chlorine has a high coefficient of expansion and
can generate very high hydraulic pressures (overpressure)
from relatively small rises in temperature. Liquid chlorine
systems may be subjected to hammer blow caused by the
rapid closure of valves and the thermal expansion of the
liquid. The deployment of slow acting valves and inclusion
of surge vessels, coupled with adherence to appropriately
designed standard operating procedures, can help to
prevent this. Lees18 recommends that the design for the relief
volume for chlorine be at least 20% of the line volume. The
pressure relief for each stream should comprise of either two
bursting discs arranged back-to-back, or a single bursting
disc coupled with a pressure relief valve. In either case,
a pressure gauge should be incorporated into the design
located between the two devices18. It is not advisable to
install two relief valves since they are prone to corrosion18. All
pressure relief systems (bursting discs, etc.) and control and
automation devices (e.g. chlorine detectors and alarms) must
be suitably designed, installed, inspected and maintained to
ensure functionality.
Another potential problem faced when handling chlorine is
low temperature embrittlement, since the temperatures can
fall to -34oC (boiling point) due to the cooling effect during
throttling, etc. Appropriate consideration should be given
to the design and materials, as well as the operation of the
facility. If gaseous chlorine is allowed to liquefy in pipework,
then internal corrosion can result and atmospheric moisture
can condense on the outside of pipework leading to external
corrosion.
Bulk chlorine storage vessels should preferably be located
above ground and enclosed with a suitable bund (dike),
with a capacity of 110% of the largest vessel with adequate
freeboard. Where chlorine is stored in drums or cylinders,
it is recommended to store these in a locked chlorine store
sited at ground level. This store should be constructed

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Loss Prevention Bulletin 241 February 2015 | 5

from non-flammable materials that can reflect radiant heat

(sunshine, fire, etc.) and have adequate ventilation and
suitable chlorine detectors coupled to audible and visual
alarms. The store must only be accessible to authorised
personnel and be located at least 5m away from adjacent
flammables. Since there is a potential for the gas to liquefy
in pipework, etc., it is advisable to minimise temperature
difference between the chlorine store and process room,
including associated pipework so as to prevent liquefaction.
Due consideration must be given to safe access and egress,
integrity of lifting equipment, emergency equipment, etc.
Detailed guidance on the safe handling of chlorine from
drums and cylinders, including design and operation of
vaporisers, fume scrubbers, etc., can be found in the HSEs
publication13.
Personnel who use chlorine must be fully trained and
competent in its use and understand what to do in the event
of an emergency, e.g. hose detachment, spillage, fire, on
hearing an alarm, etc. This competency should be supported
by rigorous and up-to-date documented safe systems of
work (e.g. standard operating procedures, permit to work,
etc.) There should be particular emphasis on the protection
of overfilling of vessels19 and ensuring the integrity of all
pipework, etc., through regular inspection and maintenance.
Overarching these risk control measures is adequate
supervision and management review.
The last resort must always be PPE. The risk assessment
must identify the design and standard of PPE that is required.
In the majority of circumstances, using respirators would
be inappropriate, since they do not provide protection for
high concentrations (greater than 10ppm6), or unknown
concentrations of the gas in the atmosphere. Personnel may
be required to wear self-contained breathing apparatus
(SCBA) with a full face-piece operated in a pressure-demand
or other positive-pressure mode, coupled to a clean air
supply from a bottle or piped-in remotely from a safe location
or source. Since chlorine is very irritating to the eyes, eye
protection should be worn, along with impervious protective
clothing, gloves (especially to prevent cold burns when
handling liquid) and appropriate footwear. All chlorine users
are directed to consult the manufacturers or suppliers
Safety Data Sheet (SDS) for specific safety advice on this
matter. The REACH Regulations20 have extended the duty on
manufacturers to provide information on the necessary steps
that are needed to reduce exposure, engineering controls,
PPE, what emergency action should be taken, etc.
Emergency first-aid stations should be strategically
located within the workplace wherever liquefied or gaseous
chlorine is stored and handled. The facility management
team should determine whether a dedicated onsite medical
centre is required or at the very least, establish formalised
communication channels with the local hospital or other
medical facility. If the location is remote or the inventory
of chlorine is sufficiently high, then a greater range of
emergency facilities may need to be established on-site. This
would not only extend to medical personnel and resources,
but also fire-fighting / emergency spillage response
arrangements.
Notwithstanding the above, whenever chlorine is handled
in large quantity, excellent communications and dialogue are
needed with stakeholders, including regulators, emergency

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responders, local communities, etc. This is especially important

in COMAH (Seveso) facilities presenting major accident
hazard risks to both onsite employees and offsite neighbouring
communities. Here, it cannot be stressed the importance for
timely, clear lines of communication and effective onsite and
offsite emergency response planning.

Uses of chlorine
Chlorine is extensively used to manufacture inorganic and
organic chemicals, as well as finding applications in the
utility industry and leisure sector where it is used to sanitise
water supplies used for drinking water and swimming baths
respectively. Some specific uses of chlorine are outlined below.
Vinyl chloride: Vinyl chloride monomer (VCM) is used
to make the polymer polyvinyl chloride (PVC) which has
extremely wide-scale applications.
Metal chlorides: Chlorine is used in the preparation of a
range of inorganic metal chlorides, such as Al2Cl3 and TiCl4,
which are used as catalysts in organic reactions and in the
production of titanium and the pigment titanium dioxide
respectively.
Chlorinated hydrocarbons: The manufacture a number of
useful solvents, including chloroform, 1,2-dichloroethane,
trichloroethylene, perchloroethylene, etc.
Sodium hypochlorite: Free chlorine is generated from
sodium hypochlorite solutions, which are used in
commercial and domestic bleach formulations.

Incidents involving chlorine

An employee dies some hours after being
exposed to chlorine
At 7pm, nearing the end of an evening shift, a process
operator working at a chlorine liquefaction unit was
preparing to bleed off chlorine on a process line in order to
prepare the line for maintenance work. To bleed the line,
the employee opened the valve handle (which indicated
that it was in a closed position) to insert a tube to clear the
chlorine. However, the bleed valve was not completely
closed and the pressure on the chlorine line caused the
cap to blow off, releasing chlorine gas. The worker inhaled
the gas when his airline became trapped on a nearby pipe,
which resulted in his facemask becoming dislodged. He
continued to work and went to a co-workers home at the
end of his shift. Later that evening he was hospitalized but
died the following day at 10am.

Incorrect line connections causes chlorine gas

release
At midday, a chemical technician was working alone
in an iodine recovery plant. The employee was both a
supervisor and a very experienced operator. He was
working on a new plant, setting up a 300 gallon tote and
tank of 32% hydrochloric acid. This was connected to a
transfer pump that was connected to two process tanks

6 | Loss Prevention Bulletin 241

February 2015

located within the plant one of the tanks contained a

solution of 12.5% sodium hypochlorite and the other
38% sodium bisulphite. The acid tank was sited outside
the plant and all tanks were clearly labelled. When the
acid was transferred, a chemical reaction took place with
sodium hypochlorite liberating chlorine gas. The worker
exited the building and was met by a co-worker, who
transported him to the nearby hospital. During the journey
he became unconscious and was immediately placed on
a respirator upon arrival at hospital, but was pronounced
dead later that evening at 8.30pm.

Incorrect assumption leads to three

employees inhaling chlorine gas
Three employees were exposed to chlorine gas after a
tanker truck containing phosphoric acid was mixed with
sodium hypochlorite (bleach). The tanker truck containing
the phosphoric acid was connected to the sodium
hypochlorite nozzle via a hose. The addition of the acid to
the bleach liberated chlorine. The operators had assumed
that both the tankers contained sodium hypochlorite. All
three employees were taken to the hospital for treatment,
but later discharged.

Worker gets burned when changing chlorine

gas cylinder
An operator at a waste water treatment facility was
changing gas cylinders and incorrectly believed the valves
were closed on the cylinder and the distribution manifold.
She loosened the connections on the right cylinder of the
two-cylinder pair allowing chlorine to rapidly escape from
the manifold, which exposed her face to the escaping gas.
She received chemical burns to her eyes, face and nasal
passage. She was admitted to hospital but discharged later
that day.

Conclusion
Chlorine is a very toxic and reactive substance with an
infamous history. However, adopting and maintaining
rigorous risk control measures will promote safe handling. All
personnel, whether they design or operate chlorine handling
systems, must fully understand the hazards associated with
such plant and equipment, comprehend the hazards from
using chlorine and know specifically how to respond in the
event of an emergency. Given appropriately designed and
maintained engineering controls and associated safe systems
of work, gaseous or liquefied chlorine can be confidently
stored and used in a wide range of applications with
acceptable level of risk to all parties concerned.

References
1. Holderness, A., and Lambert, J., School Certificate
Chemistry, Heinemann, London.

2. Thompson, R., (ed.), Modern Inorganic Chemicals

Industry, Royal Society of Chemistry, London.
3. Pauling, L., General Chemistry, Dover Books, New York.
4. OSHA, Occupational Health Guideline for Chlorine, 1978,
US Department of Labor.
5. Chlorine Toxicological Overview, Health Protection
Agency, http://www.hpa.org.uk/webc/hpawebfile/
hpaweb_c/1194947361183, February 2014.
6. NIOSH Pocket Guide to Hazardous Chemicals, NIOSH,
http://www.cdc.gov/niosh/npg/npgd0115.html,
February 2014.
7. International Programme on Chemical Safety (IPCS),
(1996), Chlorine Poisons information Monograph, PIM
947.
8. EH40/2005 Workplace exposure limits Containing the
list of workplace exposure limits for use with the Control
of Substances Hazardous to Health Regulations (as
amended), Health and Safety Executive (HSE), Sudbury,
UK.
9. REGULATION (EC) No 1272/2008 - Classification,
labelling and packaging of substances and mixtures,
amending and repealing Directives 67/548/EEC
and 1999/45/EC, and amending Regulation (EC) No
1907/2006:
http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri
=OJ:L:2008:353:0001:1355:EN:PDF, January 2014.
10. Kletz, T., and Amyotte, P., Process Plants A Handbook
for Inherently Safer Design, 2nd ed., CRC Press,
Abingdon, UK.
11. Brethericks Handbook of Reactive Chemical Hazards, 7th
ed., Elsevier, New York.
12. Saxs Dangerous Properties of Industrial Materials, 12th
ed., John Wiley & Sons, Oxford, UK.
13. Safety advice for bulk chlorine installations, Health and
Safety Executive (HSE), Sudbury, UK.
14. Safe handling of chlorine from drums and cylinders
(second edition), Health and Safety Executive (HSE),
Sudbury, UK.
15. Chlorine Manual, Chlorine Institute, Inc.,
http://www.cl2.com, February 2014.
16. HID Safety Report Assessment Guide: Chlorine, Health
and Safety Executive, http://www.hse.gov.uk/comah/
sragchl/chlorine.pdf, February 2014.
17. Wrongly labelled gasket causes chlorine release, Loss
Prevention Bulletin, April 1989, 086, pp 23-25, IChemE,
Rugby, UK.
18. Mannan, S., (ed.), Lees Loss Prevention in the Process
Industry, Butterworth-Heinemann, New York.
19. Fishwick, T., Distortion of the end of a full drum of liquid
chlorine, Loss Prevention Bulletin, December 2002, 168,
pp 15-16, IChemE, Rugby, UK.
20. Regulation (EU) No 453/2010 amending the REACH
Regulations (Regulation (EC) No 1907/2006 on the
Registration, Evaluation, Authorisation and Restriction
of Chemicals (REACH)), http://eur-lex.europa.eu/
LexUriServ/LexUriServ.do?uri=OJ:L:2010:133:0001:0043
:EN:PDF, January 2014.

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