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GOVERNMENT OF INDIA

DEPARTMENT OF ATOMIC ENERGY


HEAVY WATER BOARD ( CO )
MUMBAI

PUBLISHED
BY
COMPILED
BY
SAFETY, SAFETY ENGINEERING & PUBLIC AWARENESS GROUP
HEAVY WATER BOARD (MUMBAI)

2008

CONTENT

S.N. TITLE

PAGE NO.

Introduction

History

Uses of chlorine

Occurrence

Physical & Chemical Properties

Toxic Properties

Health Hazards

Fire & Explosion Hazards

10

Construction Details & Safety features of

12

chlorine tonner
10

Material of Construction

15

11

Safety in a. Storage of a tonner / cylinder

16

b. Handling of a tonner / cylinder


c. Loading & unloading of tonner
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Monitoring & measurement of chlorine

21

13

Controls for chlorine leaks

22

a. Engineering Controls
b. Administrative Controls
14

Emergency measures & first-aid

24

15

Case Studies

28

16

List of Suppliers

31

17

Annexure

32-37

INTRODUCTION
In 2002-2003 the total chlorine production in our Country was 1.478 million tons
(worldwide production approx. 44 million tons). Out of this approximate 0.875
million tons was liquefied and transported to various destinations in the country.
With the transportation of liquid chlorine over long distances the hazards are no
longer confined to the place of its manufacture, storage and use but are spread all
over the country.
One of the greatest hazards associated with the use of chlorine is its familiarity due
to its common use. It is often forgotten that it is potentially dangerous. The
shipment of liquid chlorine in bulk from manufacturer to consumer involves
various handling operations, in which the principal risks are common. These are
attributable due to its toxicological character, physical properties, and chemical
reactivity.
The filling, possession, transport and importation of chlorine is governed by Static
& Mobile Pressure Vessel (Unfired) Rules. In case the quantity of storage exceeds
10 MT then the statutory requirements specified under MSIHC Rules are required
to be adhered.

HISTORY:
Chlorine was discovered by Karl Wilhelm Scheele, a Swedish chemist, in 1774.
Scheele thought that chlorine was an oxide of murium, or hydrochloric acid. He
did not, however, establish chlorine as an element. In 1810, chlorine was named
and classified as an element by Humphrey Davy. It was named after the Greek
word chloros, which means pale green.
Chlorine has also been used during World War-I. It was first introduced as a
weapon on April 22, 1915 at Ypres by the Germans. The results of this weapon
were disastrous because gas masks (canister) were not invented at that time. But,
some compounds of chlorine are more dangerous and have replaced chlorine gas
on the battle field. They are phosgene, chloropicrin, Lewsite, and mustard gas.
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USES OF CHLORINE
Although chlorine is highly toxic and hazardous in nature, at the same time it is
very useful for mankind and has become indispensable. It is used for disinfecting
drinking water, bleaching of textiles and paper, manufacture of insecticides,
pesticides and weedicides, pharmaceuticals, synthetic rubber, P.V.C./Plastics,
refrigerants, industrial solvents, rocket fuels and treatment of cooling water.
Owing to its strong oxidizing properties, chlorine is very effective in destruction of
bacteria, viruses, primitive life forms and algae. These properties are used very
widely today in the treatment of water for power stations and for drinking water
supplies. A small residue of chlorine is also left in the water to retain the necessary
antiseptic or fungicidal properties.

OCCURRENCE
The Natural Abundance of Chlorine: Chlorine's abundance is in igneous rock
which makes up 95% of the Earth's atmosphere. The most frequently seen form of
chlorine is in sodium chloride, NaCl, found in seawater.
Chlorine is never found in a free state; it combines with almost all elements.
Basic Properties of Chlorine
Atomic Mass

35.453

Atomic Number

17

Melting Point

-101 oC

Boiling Point

-34.6 oC

Density in natural state 1.56 g/cm3

Isotopes of Chlorine
Nominal Mass Accurate Mass % Natural Abundance
35

Cl

34.968

75.77

37

Cl

36.965

24.23

These two isotopes have been used to define the atomic weight of chlorine to be
35.3. These isotopes have the same chemical properties, but, their masses are
different.
There is also a radioactive isotope of chlorine, including 36Cl.

The Structure of Chlorine

This is the structure of a chlorine molecule. The shared atoms are equidistant form the
atoms. Therefore, each atom has the same relationship for the shared atoms.

Chlorine is a member of the halogen family and group 17. It has seven valence
electrons. It consists of 17 protons, 18 neutrons, and 17 electrons. Its electronic
configuration is the following:
1s2 2s2 2p6 3s2 3p5
Because the element has only seven electrons in its outer shell, the atom is
unstable and will seek to find an element to combine with. All elements want to
have 8 valence electrons to secure stability.
How is chlorine made?
Chlorine is produced by electrolysis of brine solution (common salt dissolved in
water).
Essential by-products are caustic soda (sodium hydroxide (NaOH)) and hydrogen
(H2).

PHYSICAL AND CHEMICAL PROPERTIES


Physical state
Colour
Smell
Molecular Weight
Boiling Point ( Liquefying )
Melting Point
Specific Gravity (Water = 1)
Density
Vapour Pressure, at 20oC
Critical Temperature
Critical Pressure
Latent heat of vaporisation
Heat of reaction with NaOH
Solubility

Volumetric Expansion

Relative density
Fire / explosion hazards

Incompatibility

Corrosivity

Gas as well as liquid however, chlorine is a gas at ambient


temperature
Chlorine gas is Greenish yellow in colour
Liquid chlorine is a clear, amber colored liquid
Characteristic & suffocating
70.9
- 34. 6C (1 atm)
-101oC
1.41 (liquid)
3.209 g/l (1 atm, 0C)
3.617 atm (0C).
144 C
77.1 bar absolute
63.2 kcal/kg
348 kcal/kg
Chlorine is soluble in alkalis and only slightly soluble in water,
approximately 1 percent at 9.4C. The solubility decreases with
rise in temperature up to the boiling point of water at which it is
completely insoluble. Below 9.4C chlorine hydrate known as
Chlorine-ice (Cl2.8H2O), may crystallize
One volume of liquid chlorine when vaporized will yield about
457.6 volumes of gas at 0 deg. & one atm. Pressure.
It expands about 0.15 % in volume for every F increase in
temperature
Chlorine is about 2 times heavier than air. It seeks lowest
level in the building / area where it leaks.
Neither liquid nor gaseous chlorine is explosive or flammable,
but both react readily with many organic substances, usually
with the evolution of heat and, in some cases, resulting in
explosion. Chlorine is also capable of supporting combustion of
certain materials.
 May cause fire & explosion with gasoline & petroleum
products, turpentine, alcohol, acetylene, hydrogen, ammonia,
sulfur and finally divided metals.
 Chlorine will attack some form of plastic, rubber & coatings
Liquid chlorine attacks and dissolves P.V.C at ambient
temperature.
Dry chlorine is not corrosive; however, it is strongly corrosive
when moisture is present. Reacts slightly with water forming
weak solution of HCl and HOCl
H2O + Cl2

HCl + HOCl
That why moist chlorine is corrosive to most metals
1. At ambient temp. dry Cl2 reacts with Al, As, Au, Sn, Ti and
Hg
2. It reacts with steels, Fe, Cu, Pb, Pt, Ag & Ni on heating above
120oC
3. At certain temp, Cl2 reacts spontaneously with H2 to form
HCl. This occurs slowly in dark but explosively in sunlight or at
more than 2500C.
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Reactivity
a. With metals
 Dry chlorine reacts with aluminium, arsenic, gold, mercury, selenium,
tellurium, tin and titanium
 At certain temperatures potassium and sodium burn in dry chlorine
 Carbon steel ignites at temperatures above 250C
b. With other elements Chlorine reacts with most elements under specified
conditions. Mixtures of chlorine and hydrogen composed of more than 5 percent
of either component may react with explosion. It reacts with ammonia, alkalis and
alkaline earth metal hydroxides.
c. With inorganic compounds Chlorine has great affinity for hydrogen and as
such, removes hydrogen from some inorganic compounds to form hydrochloric
acid. It reacts with ammonia and ammonium compounds to form various mixtures
of chloramines and under proper conditions nitrogen trichloride which is
explosive. Chlorine reacts readily with lime and caustic soda to form hypochlorite
which is well-known bleaching agents.
The following chemical reactions take place between chlorine and lime or caustic
soda:
2Ca(OH)2 + 2Cl2 + 2H2O = Ca(OCl)2.4H2O + CaCl2
2CaO + 2Cl2 + 4H2O

= Ca(OCl)2.4H2O + CaCl2

2NaOH

= NaOCl +NaCl + H2O

Cl2

These reactions are important because lime and caustic soda solutions are used for
handling chlorine leaks. Chlorine reacts with moisture to liberate nascent oxygen
and form hydrochloric acid.
d. With organic compounds Chlorine reacts with organic compounds to form
chlorinated derivatives and hydrogen chloride. Some of these reactions,
particularly those with hydrocarbons, alcohols and ethers may become explosive.
Gaseous chlorine, wet or dry, may be used with hard rubber equipment at normal
temperatures and pressures. However, neither soft nor hard rubber can be used
with liquid chlorine.
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TOXIC PROPERTIES (PPM OF Cl2 GAS IN AIR):


Concentration
0.02 0.2 ppm
0.5 ppm
1.0 ppm
3.5 ppm
4.0 ppm
5.0 ppm
15 ppm
30 ppm
40-60 ppm
50 ppm
137 ppm/ 1 h
1000 ppm

Effect
Order of threshold
TLV - TWA(ACGIH), Nasal Irritation & Coughing
STEL
Least amount for detectable odour
Threshold of irritation
Noxiousness, impossible to breathe
Least amount causing irritation of throat
Least amount causing cough
Amount dangerous in - 1 hour
Concentration dangerous, for even short exposure
IHL-RAT LC 50 (Lethal Concentration Inhalation)
Fatal even if the exposure is brief

TLV (Threshold Limit Value): Concentrations of air contaminants in the working


environment to which all workers are exposed repeatedly day after day without
adverse effect. Normally, it is the TWA concentration in ppm or gm/m3 for a normal
8 hour work day or 40 hour workweek.
STEL (Short Term Exposure Limit): It is defined as a 15 minutes time weighted
average exposure, which should not be exceeded at any time during a workday even
if the 8 hours time weighted average is within the TLV. STEL should not be > 15
minutes and not more than four times per day with an interval of 60 minutes.

PHYSIOLOGICAL EFFECTS OF CHLORINE


Chlorine gas is classified as a respiratory irritant. When a sufficient concentration
of chlorine gas is present in the atmosphere, it will irritate the mucous membranes,
the respiratory system and the spine. Relatively small amounts of chlorine can be
detected because of characteristic odour of the gas. Significant amounts cause
irritation of eyes, coughing and laboured breathing. If the duration of exposure or
the concentration of chlorine gas is excessive, it will result in general excitement
of the person affected and followed by restlessness, throat irritation, sneezing and
copious salivation. In extreme cases, the difficulty in breathing may increase to the
point where deaths can occur due to suffocation, or lung tissues may be attacked
resulting in pulmonary edema. Persons afflicted with asthma, bronchitis and other
chronic lung conditions or irritations of the upper respiratory tract should not be
employed in areas where chlorine is handled. Chlorine produces no cumulative
effects and complete recovery occurs from mild exposures.

HEALTH HAZARDS
General Chlorine gas is primarily a respiratory irritant. The characteristic
penetrating odour of chlorine gas usually gives warning of its presence. At higher
concentration it is visible as greenish yellow gas.
Acute Local Chlorine gas exposure to the skin is not much irritating or
corrosive for short time. Splashes of liquid chlorine on the eyes, skin and clothing
may cause immediate irritation, chemical burns and severe damage to body
tissues.
Acute, Systemic Chlorine gas is extremely irritating to the mucous membranes,
the eyes and the respiratory tract. If the duration of exposure or the concentration
of chlorine is excessive, it will cause restlessness, throat irritation, sneezing and
copious salivation. In extreme cases, lung tissues may be attacked resulting in
pulmonary edema. The physiological effects of various concentrations of chlorine
gas are shown in table above.
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Chronic (Local and Systemic) Chlorine gas produces no known cumulative


effects. A concentration of 1 ppm of chlorine gas may produce slight symptoms
after several hours exposure, but careful examination of workers exposed daily to
detectable concentrations reportedly has shown no chronic systemic effects. Local
chronic effects have not been clinically demonstrated. Sensitization has not been a
problem with chlorine. It has been observed that prolonged exposure to
atmospheric chlorine concentration of 5 ppm results in disease of bronchi and a
predisposition of tuberculosis while lung studies have shown that concentration of
0.8 to 1 ppm cause permanent, although moderate reduction in pulmonary
function. Acne is not unusual in persons exposed for long periods of time to low
concentrations of chlorine, and is commonly known as chlorance Tooth enamel
damage may also occur.

FIRE & EXPLOSION HAZARDS


 Flammable gases & vapor will form explosive mixture with Cl2
 Reacts explosively to form explosive compounds with many common
chemicals specially acetylene, turpentine, ether, NH3, fuel gas, hydrocarbon, H2
& finally divided metals, saw dust & P
 Vapor is heavier than air. Local heating of steel equipment a Cl2-Fe fire may
develop.
 Container may burst if exposed to more 95 0C, due to rise in pressure above
design value.
 Chlorine reacts spontaneously with hydrogen slowly in the dark but explosively
in sunlight or at high temperatures, to form hydrogen chloride. This is very
important during manufacturing of chlorine by electrolysis. The lower
explosive limit of hydrogen-chlorine mixtures varies from 3.1 to 8.1 percent,
depending on pressure and other variables.
 Hot chlorine gas from electrolytic cells, may sometimes crystallize as chlorine
octahydrate (Cl2.8H2O) due to sudden cooling and clog the pipe lines resulting
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in hold up of the gas in the pipe lines and allied equipment. This will cause
back pressure inside the cells and escape of chlorine into air or into the
hydrogen chamber resulting in explosion
 Since liquid chlorine increases considerably in volume when evaporated,
hydrostatic rupture in containers, pipe lines and other equipments may occur
due to build up of excessive pressure. Particularly, the danger due to pressure
build up in a heated cylinder can lead to an explosion.

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CONSTRUCTION DETAILS OF CHLORINE TONNER


1

Design pressure

19.9 kg/cm2 (This is the vapour pressure of liquid


chlorine in equilibrium with its vapour at 65oC)
The pressure on a container is not a measure of the
amount of liquid chlorine in the container but is
only a function of its temperature. A container
having 900 kgs or 1 kg of liquid chlorine will have
the same pressure at a given Chlorine temperature

Design temperature

650C (India is a tropical country)

Capacity

900 kg. The volume of liquid chlorine in a container


becomes greater as its temperature increases. All
containers when filled, have about 12% free space at
68F, it is reduced to less than 8% at 100 F.
Because of this characteristic chlorine containers
should be handled with care and never be heated.

Code of design

BS:1500-1958 art II (Class I Vessel)

Corrosion Allowance

3.0 mm.

Joint Efficiency

95%

Radiography

Full

Stress Relief

Yes

Filling Ratio

1.19

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Gross weight

1,500 kgs ( Filled with liquid chlorine)

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Colour of Paint

Golden yellow

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Supports

Allowance for thermal expansion / contraction over


design temp. range

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Branches

Dimensions to be limited to minimum required,


particularly liq. Lines.

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Approval

Petroleum & Safety Organisation, Dept. of


Explosives, Govt. of India, Nagpur
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SAFETY FEATURES OF A TONNER


The various safety measures related to Chlorine Tonners Design and Use are:
a) Concave Ends: The design of the concave heads is especially significant from
the safety angle. Due to accidental overfilling and subsequent warm-up of
liquid chlorine to ambient temperature, an excessive internal pressure may
develop and then one or both the concave ends will partially reverse. This
increases the container volume (some more space is created for the liquid
chlorine to expand) and at the same time gives visual notice so that this
abnormal situation is corrected (the container should be emptied immediately
in such case) and a possible hazardous or fatal situation is averted. In case of
convex ends, the failure will result in bursting of toner directly (without any
such warning) thereby endangering the personnel around.

b) Valve protection hood: This protects the valves from any accidental damage
during loading/unloading and transportation of toners.
The ton container is equipped with two identical valves near the centre of one
end. Each valve connects with an ejection pipe fitted inside the container. Ton
container in a horizontal position and with valves in a vertical line delivers gas
from the upper and liquid from the lower valve.
A cylinder has one valve at the top for drawing chlorine as liquid or gas.
Cylinders deliver chlorine gas when in an upright position, and liquid in an
inverted position. A steel removable cap is provided for the protection of the
valve.

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c)

24 hours storage after filling for observation: During this period liquid
chlorine attains ambient temperature and the pressure in the container is
10Kg/cm2 (during summer months) or 6 kg/cm2 (during winter months). This
should be checked before the containers leave the factory.

d)

Limitation of filling: 900 Kgs. liquid chlorine filling in the tonner: The
quantity of liquid chlorine to be filled in a tonner is dependent on its water
capacity.
Quantity of liquid chlorine (Kgs.) = Water capacity (1) X Filling density
(kg/l) = Water capacity x 1.19
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Filling density means the ratio of weight of liquefiable gas allowed in pressure
vessel to the weight of water that the vessel will hold at 150 C.
Generally the water capacity of tonners in our country is 760 liters.

MATERIAL OF CONSTRUCTION
1. Mild steel is suitable for dry chlorine handling.
2. Fiber reinforced plastic is commonly used for wet chlorine. However,
ebonite lined mild steel& rubber lined vessels and pipes are also suitable for
wet chlorine. Titanium is also suitable for wet chlorine.

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SAFETY IN STORAGE
STORAGE OF TON CONTAINERS
 Toner shall be kept in cool, dry & relatively isolated area protected from
weather and extreme temperature changes
 Tonner shall be kept under cover, should not be exposed to the Sun
 Ventilation should be sufficient to prevent accumulation of Cl2 vapors
 No welding/gas cutting work should be done near the place of storage
 Due to high expansion ratio, danger of pressure build-up is there. Hence, they
should be kept away from direct source of heat
 Floor should be maintained dry where container / cylinders are stored. Failing
which the container will be externally corroded and its life will be reduced
 Toner shall be kept on their sides on rollers, a few inches above floor. They
should not be stacked or racked more than one high
 Keep enough room between the containers so that they are accessible in case of
an emergency
 Store Cl2 in areas where there is no contact with such a material with which it
reacts.
 Storage area shall be constructed of non-combustible materials
 Keep inventory as low as possible
 Filled & empty containers should be stored separately. Even if the container is
empty, valve outlet caps and valve protection hoods should be in place.
Provision must be made to permit inspection and facilitate prompt removal if
any leak occurs.
 Chlorine should be used on FIFO (first in -first out) basis because valve
packing can harden during prolonged storage and may cause leakage when
containers are finally used
 The storage area should be separate from the area where other compressed gas
cylinders / containers are stored.

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Storage of cylinders
Cylinders should be stored in an upright position.
They should be secured to prevent from falling over.
Full and empty cylinders should not be stored together.
The storage area should be dry, well-ventilated, clean of trash, and protected
from external heat sources (steam pipes, etc). Sub-surface areas should be
avoided for storing chlorine cylinders.

The valves on cylinders and ton containers should be protected by a stout metal
cap securely attached to the cylinder body. This cap should always be kept in
place on all containers in storage and at all times except during use of chlorine

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Handling of cylinders & tonners


1 Cylinders should never be lifted by holding through metal cap. The manila rope,
wire ropes or slings, chains or magnetic devices should not be used for lifting
cylinders. Unloading platforms should preferably be at truck or car-bed level.
The ton container should be handled with a suitable cradle with chain slings in
combination with a hoist or crane having at least 2 metric tonnes capacity.
2 Cylinders and ton containers being trucked should be carefully checked,
clamped, or otherwise suitably supported to prevent shifting and rolling. They
should not be permitted to drop, and no object should be allowed to strike them
with force. They should not project beyond the sides or ends of the vehicles in
which they are transported.
3 Use of Chlorine
a. From Cylinders Cylinders normally should be emptied in the gas phase,
standing secured in an upright position. Connection of containers
discharging liquid to a manifold is not recommended.
b. Ton-containers set in a horizontal position, with the valves in a vertical
plane, deliver gas from the upper valve and liquid from the lower valve.
When emptied in the liquid phase, a vaporizer should normally be used.
4 The flow of chlorine-gas from any chlorine container depends on the internal
pressure which in turn depends on the temperature of the liquid chlorine.
Discharge rates may, however, be increased by forced circulation of roomtemperature air around the container.
a. If the gas discharge rate from a single container will not meet demand
requirements, two or more container may be connected to a manifold and
discharged simultaneously, or a vaporizer may be used. When discharging
through a manifold, care shall be taken that all containers are at the same
temperature, particularly when connecting a new container to the manifold.
If there is a difference in the temperature of the liquid chlorine, it will be
transferred by distillation from the warm to the cool container, and the
cooler container may become completely filled with liquid. If this should
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occur and the container valve remains closed, hydrostatic pressure may
cause bursting. For this reason, extra precautions shall be observed when
closing valves of containers connected to a manifold. Connection of
cylinders or ton containers discharging liquid chlorine to a manifold is not
recommended.
5 A flexible connection between the container and the piping should be used;
annealed copper tubing (9.5 mm outside diameter 0.889 mm wall), suitable
for 35.2 kg/cm2 service is recommended. A clamp and adapter connector is
preferred; if a union connector is used, the threads on the connector shall match
the valve outlet thread. (Valve outlet threads are straight threads, not standard
taper pipe threads.) A new gasket (lead) should be used when making a
connection.
6 Valves should be opened counter-clockwise with square box wrench not over
152 mm long. If the valve is difficult to open, the packing nut may be struck
with the heel of the hand, no other implements should be used.
7 Tonner/cylinder valves should not be used as controlling valve for flow of
liquid/gas. Separate valve should be provided at the source of consumption for
regulating the flow.
8 When chlorine is being absorbed in liquid, a barometric leg should be provided
to prevent suck-back of the liquid into the container when it becomes empty.
BAROMETRIC LEG
A suck back of process liquid can occur whenever Chlorine gas is injected into
the process liquid if there is a loss of pressure on the supply side. This
condition occurs if the supply container is emptied or if the chlorine supply is
interrupted. This suck back of liquid results in internal corrosion in the
Chlorine containers thereby decreasing their life. This can be prevented by
installing a suitably designed BAROMETRIC LEG in the system. In systems
working at atmospheric pressure, the height of the Barometric Leg should be
h = 34/d ft

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where d is the density of the liquid (water or liquid used) in gm/cc (in case
there is a change in the density of the process liquid during Chlorination
reaction then the lowest value of density should be taken into consideration).
9. Always empty ton containers on scale, in order to know at all times the amount
of Chlorine in the container. The pressure in container is not a measure of the
amount of Chlorine in the container. The pressure varies with the temperature
of Chlorine gas. At any given Chlorine temperature, the pressure on the
container holding one Kg and 900 Kgs Chlorine will be the same.
As soon as the container is empty, the valve should be closed and the lines
disconnected. The outlet cap should be applied promptly and valve protection
hood attached. The open end of the disconnected line should be plugged to
keep atmospheric moisture out of the system.
10 OTHER FACTORS
a. TEMPERATURE
Liquid chlorine expands about 0.15 % in volume for every F increase in
temperature this factor is very significant in handling chlorine in pipelines,
since liquid chlorine trapped in length of pipe subjected to a rise in
temperature can easily build up enough hydrostatic pressure to rupture the
pipe.
b. OVERFILLING
Over filled containers can also fail for the same reason.

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LOADING / UNLOADING OF CONTAINERS


A permanent system should be installed for loading/unloading of containers;
a) Manually operated Chain pulley block. They should be provided with suitable
slings, lifting beams and hooks etc.
b) In the absence of above, a platform with a ramp will also serve this purpose.

MONITORING & MEASUREMENT


As soon as there is any indication of the presence of chlorine in the air,
immediate action should be taken to locate the leak:
a. This is best done with the help of aqua Ammonia. Tie a cloth to the end of a
stick; soak the cloth with aqua ammonia and hold it close to the suspected
area. A dense white smoke of Ammonium Chloride develops which will
reveal the point from which the Chlorine is escaping.
b. Use of detector tube
Principal: Detector tubes have base impregnated with ortho-toludiene whereby
this turn in yellow color on exposure of chlorine present in ambient air.
Cl2 + O-toludiene (Colourless) Reaction product (yellow colour)
Appearance of dark colour indicates high concentration of chlorine. Bromine,
chlorates and nitrites give error.
c. Use of portable chlorine monitors.
Principal: The portable monitors have amperometric sensors and contains gel
filled electrochemical sensor mounted in area where chlorine monitoring is
required. Sensor is covered with membrane that is permeable to halogen family
chemicals notably chlorine. Any chlorine present in ambient air will flow
through permeable membrane & initiate ampherio-metric activity within
sensor. A platinum electrode & silver anode are joined vai salt bridge circuit.
With low voltage applied constantly across the electrode, contact with chlorine
gas generates a flow of current that is instantly measured & displayed on
electronic control unit. Operating ranges are 0 2 ppm & 0 20 ppm.
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CONTROLS FOR CHLORINE LEAK

ENGINEERING CONTROLS
a. Local exhaust ventilation system should be provided.
b. Proper access for maintenance and inspection
c. The storage shall be preferably located in open air.
d. Online monitoring devise (chlorine monitors) shall be installed in storage area
to get early warning alarm.
e. The low lying areas, trenches and drains near storage / handling areas shall be
avoided.
f.

Periodic & regular inspection to detect corrosion

g. The tonner / cylinder storage area shall be located such that there is no air
intake for the ventilation system of buildings like control rooms etc & fumes
can spread to other areas.
h. Care to be taken against possible damage from flooding
i.

Minimum distance 25 m from public roads and main railway lines

j.

Provision of emergency lighting

k. Adequate storage space for emergency equipment (gas canisters, breathing air
sets, & other PPEs) should be provided in a safe location to be readily
available.

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ADMINISTRATIVE CONTROLS
a. Operator selection: Trained operator should be deployed.
b. Operating instructions: Detailed operating instructions and procedure for
unloading the tonner and use of Cl2 shall be displayed in operating area.
c. Training: Periodic training should be conducted for both new and old
employees to keep them conscious and informed of the hazards. Periodic
emergency exercises and instruction regarding location, purpose and use of
personal protective equipment, safety showers, eye fountains, chlorine
emergency kit, first aid box, etc. be a part of periodic training. They should
be told to report to proper authorities immediately in case of any leakage for
abnormal condition.
d. Monitoring & Surveillance: Containers, piping and equipment should be
checked for leaks daily. If a leak is detected it should be reported and
immediate steps taken to correct the conditions.
e. Availability of emergency equipments: Eye wash fountain cum safety
shower, BA set & Cl2 emergency kit shall be available promptly
f. Pre-placement medical examination: It is recommended for all new entrants
and follow-up medical examinations at suitable intervals for all workers
handling chlorine

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EMERGENCY MEASURES
General wherever chlorine is handled a potential risk is involved and a serious
emergency might suddenly and unexpectedly occur. Emergency situations should
be anticipated, emergency action plans should be established and persons trained
to counteract emergencies, if any.
Handling Leaks Chlorine leaks always get worse unless they are corrected
promptly. Chlorine leaks should be investigated by authorized, trained personnel
equipped with suitable gas masks. If the leak is extensive an effort should be made
to warn all persons in the path of the gas. Chlorine is heavier than air; therefore
persons should be instructed to keep above and upwind or perpendicular to wind
direction prevailing.
a. Water shall never be used on a chlorine leak as it always makes the leak worse
due to the corrosive effect. In addition, heat supplied by even the coldest water
to a leaking container causes liquid chlorine to evaporate faster. A leaking
container shall not be immersed or thrown into a body of water as the leak will
be aggravated due to the corrosive effect and the container may float when
partially full, allowing gas evolution and dispersion at the surface.
b. Equipment and Piping Leaks If a leak occurs in equipment in which chlorine
is being used, the supply of chlorine shall be shut off and chlorine which is
under pressure at the leak shall be disposed off safely.
c. Leaks around valve stems usually may be stopped by tightening the packing nut
or gland. If this does not stop the leak, the container valve shall be closed and
the chlorine, which is under pressure in the outlet piping, shall be disposed off.
If a container valve does not shut off tight, the outlet cap or plug should be
applied. In case of a valve leak on a ton-container, the container shall be rolled
so that the valves are in a vertical plane with the leaking valve on top; so that
gaseous chlorine leaks & not the liquid.
d. If practical, the pressure in the container should be reduced by removing the
chlorine as gas (not as liquid) to process or a disposal system. In some cases it

24

may be desirable to move the container to an isolated spot where it will do the
least harm.
e. In case of chlorine leaks all exhaust mechanisms should be turned on
immediately. BA sets & other PPEs should be located outside the probable area
of contamination so that it will be possible to reach them in emergency.
f. As a regular part of chlorine storage and use, provisions shall be made for
emergency disposal of chlorine from leaking cylinders or ton-containers. One
vessel should always be kept empty as to allow transfer the content in case of
emergency.
i) Chlorine may be absorbed in solutions of caustic soda or soda ash, or in
agitated hydrated-lime slurries. Caustic soda is recommended as it absorbs
chlorine more readily.
ii) A suitable tank to hold the solution should be provided in a convenient
location. Chlorine gas should be passed into the solution through an iron
pipe or rubber hose properly weighted to hold it under the surface; the
container should not be immersed.
g. Display of MSDS will help as ready reckoner during emergency.
h. Chlorine Emergency Kits It is advisable for the consumers to purchase
chlorine leak arrest kit and to train employees in their use. These kits may be
used to stop most of the leaks in a chlorine cylinder, ton container etc. (Ref.
annexure)
i). In Case of Fire In the event of fire, chlorine containers should be moved
from the fire zone immediately. If chlorine containers cannot be moved, water
should be applied to cool them provided no chlorine is escaping.

25

FIRST-AID
General All minor accidents and also report any sickness should be reported.
Any one overcome by or seriously exposed to chlorine gas should be removed at
once to uncontaminated area.
Inhalation If breathing has not ceased, the patient should be placed on his
back, with head and back elevated, and kept warm, using blankets, if necessary.
Rest is essential.
i. If breathing apparently has ceased, artificial respiration shall be started
immediately. A physician shall be called immediately. If oxygen-inhalation
apparatus is available, oxygen should be administered immediately.
ii. Adequate oxygenation should be maintained, and any drugs for shock treatment
should be given only by a physician. Milk may be given in mild cases as a
relief from throat irritation. Nothing should ever be given by mouth to an
unconscious patient.
iii. Skin and Clothing If liquid chlorine or chlorinated water has contaminated
skin or clothing, the emergency shower shall be used immediately. Skin areas
should be washed with large quantities of soap and water. No attempt shall be
made to neutralize chlorine with chemicals. No ointment shall be applied for 24
hours. Contaminated clothing should be removed immediately.
iv. Eyes If eyes have been affected with liquid chlorine or high concentrations
of chlorine gas, they shall be flushed immediately with running water for at
least 15 minutes. (No attempt shall be made to neutralize with chemicals). No
oils or oily ointment should be used unless prescribed by an eye specialist.
v. Ingestion The swallowing of liquid chlorine is extremely unlikely. However,
if a person has swallowed chlorine and is conscious, he should immediately be
made to drink copious amounts of lime water, milk of magnesia, or fresh water
if the others are not readily available. Sodium bicarbonate shall not be given.
The victim may be expected to vomit spontaneously, but no attempt should be
made to induce vomiting. A physician shall be called immediately.

26

First-Aid Equipment All employees should be given comprehensive


instructions on the use of first-aid equipment mentioned below;
a. Eye wash fountain cum safety shower should be available at convenient
locations and they should be properly maintained.
b. Oxygen administration apparatus should be available in the central control
room, first-aid center. Trained persons shall be available all the time.
c First-aid boxes Distinctly marked First-Aid boxes shall be provided in
readily accessible positions like control rooms. These should not contain
anything except the prescribed medical appliances and requisites. A list of
contents should be fixed inside the box. A sufficient number of persons should
be imparted effective training in First-Aid.
General Principle
All individuals who have developed symptoms as a result of an acute
overexposure to chlorine gas by inhalation should be placed under the
supervision of qualified health care personnel.
There is no known specific antidote for acute chlorine exposure. Prompt medical
assessment and supportive measures are necessary to obtain good therapeutic
results.

27

Case study No.1


Chlorine Tonner Explosion

In a large factory producing Chlorine, Hydrogen, Caustic lye, Caustic Flakes,


Chloroform, Methylene etc. an accident of Chlorine Tonner Explosion took place
on 5th Sept 2002 at about 11 A.M.
Incident: In the filling section of the plant, liquid chlorine is filled at 11 kg./cm2
pressure. Filling was started in tonner no. GC 1606 88. This tonner had come from
Anugrah In Organic, which manufactures monochloro acetic acid. After sometime,
operation checked the temperature of the tonner from the outside, with his hands.
Operator felt it hot. He immediately stopped the filling operator and tonner was
removed from the filling line and with help of crane, he took it to the neutralization
bay for neutralization purpose. While taking to the neutralization bay, the tonner
exploded on the hanging position.
Cause of the incident: Due to the chemical reaction between chemicals inside the
tonner pressure inside the tonner tremendously increased and exploded the tonner
in the hanging position and there was liquid spray splash but no chlorine leakage.
The spray contained mono chloro acitic acid.
Area & persons affected: Due to the explosion, atmosphere in the plant became
fumming and because of the splash of the chemicals which were inside the tonner,
24 workers who were working of the filling section, nearby and passing by this
area were affected and out there workers, 4 workers expired.
Action to be taken for non repetition of such incident:
Empty chlorine tonner received back, be sent to tonner preparation section for
evacuation of gases of tonner, valves / spindle checking.
Before filling and during filling, weight of tonner, physical condition and
temperature be kept under watch.
Use of BA set or face mask while filling.
Chlorine monitors should be installed at different locations.

28

Case Study No.2


In a public water works, chlorine gas leaked from Chlorine tonner on 7-10-2003 at
17.45 hrs.
Incident: Chlorine gas leaked at about 17.45 hrs. Contractor Supervisor was on the
job noticed the leakage. He immediately informed the Supervisor of filtration Plant.
He rushed to the site at 18.00 hrs. And checked the tonner, connection etc. and
noticed the leakages of Chlorine gas from valve spindle. He immediately called the
fire brigade. Fire-brigade personnel came to site and tried to close the leakages of
Chlorine gas. However it could not be controlled. At last, they pushed the toner in
the alkali pit. At night (01-30 hrs.) after ensuring that chlorine gas has been emptied
out from the tonner; the tonner was taken out from the pit and placed at a safe
place.
Cause of the incident: Leakage of chlorine gas from valve spindle of the tonner.
Area and persons affected: People residing in nearby area were affected due to

leakage of chlorine gas and 74 people were hospitalized.


Action taken for non-repetition of such incidents:

1. Emergency kit for chlorine shall be provided and kept.


2. FRP hood shall be provided around chlorine tonner to restrict leaked gas from
spreading around.

3. Two nos. of self-breathing apparatus shall be provided and workers shall be


given periodical training to handle it safely in case of emergency.

Case Study No.3


At Madras on 9th February 1971
Incident: Chlorine from a cylinder was used for chlorination of swimming pool
water regularly in a college campus.
Cause & consequences: Cylinder was found to have two holes on the body
Area and persons affected: 200 students got affected

29

Case Study No.4


At Bombay on 13th December 1973
Incident: Two chlorine cylinders kept inside the heap of scrap material in an
abandoned chemical factory released the gas when involved in a fire.
Cause & consequences: Improper storage & bursting of cylinders due to fire.
Area and persons affected: 7 fireman and 89 residents of surrounding locality got
affected.

Case Study No.5


At Madras on 22nd March 1974
Incident: Valve of one of the chlorine cylinder got damaged while unloading from
the truck.
Cause & consequences: Cylinders valve cap was not provided.
Area and persons affected: 1 killed and 41 injured.

Case Study No.6


At Aleppy, Kerla, on 23rd April 1981
Incident: A Czechoslovakian cylinder meant for CO2 after getting proper
clearance but one of its valves was not changed to suit chlorine. When gas started
leaking through it, the cylinder was shifted to drain duct so that the gas will get
dissolved in water. Gas gushed out from one hole in the cycle neck and spread to
nearby ladies hostel.
Cause & consequences: Cylinder was kept in water; the body got corroded very
fast thus causing heavy leakage. .
Area and persons affected: 3 killed and 154 injured.

30

Case Study No.7


At Kolkatta 16th February 1990.
Incident: Chlorine from a 100 kg cylinder kept in a small factory in a congested
locality started leaking during mid-night and spread over the nearby area.
Cause & consequences: Cylinder was badly corroded..
Area and persons affected: 04 killed and 87 injured.

LOCAL EXHAUST VENTILATION

LIST OF SUPPLIERS
S.

Name of supplier,

Address of supplier

Phone Number

No.

M/s

Chlorination

Engineers & Manufacturers, Unit

022 - 25967882

Systems

No. 4104, 4th Floor,


Bhandup Industrial Estate,
Pannalal Compound,
Bhandup (West),
Mumbai 400078

S M Polymers

Office 4B/8, Om Sudama Arts,

022 - 25368908

Kalwa, Thane - 400605


3

Banaco

A/702, Sagittarius, Divya Park,

022 - 39516813

Technologies Pvt. Off Marve Road, Malad (West),

Ltd.

Mumbai - 400095

Pennwalt Limited

D-221, M.I.D.C., T.T.C, Thane


Belapur Road, Nerul,
Navi Mumbai 400706.

31

022 - 27632503

Annexure-I

VAPOUR PRESSURE CURVE OF CHLORINE

32

Annexure-II

33

Annexure-III

USE OF CHLORINE EMERGENCY KIT

34

Annexure-V

USE OF CHLORINE EMERGENCY KIT

35

Annexure-VI

BAROMETRIC LEG

36

Annexure-VII

LOCAL EXHAUST VENTILATION

37