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Safety related to, storage and use of Chlorine Mainly in small and medium size factories (Technical Paper presented in Safety Seminar at Bharuch-
by Shree H S Dave Deputy Director Industrial Safety & Health)

(A) Important Properties of Chlorine related to Safety

Physical Properties
At room temperature, it is a yellow-green gas with a sharp, burning odor. In liquid phase it is clear, reddish colored liquid.
Under increased pressure or at temperatures below -30 degrees F. or above the threshold quantity of 1,500 pounds Chlorine presents a potential for a catastrophic event.
Specific Gravity = Gas, 2.485 (air); Liquid, 1.467 0/4°C (water) (Heavier than air as gas and water as liquid)
Vapor Pressure = 53.51 psi at 0°C; 112.95 psi at 25°C - Evaporation is total no residue left
Solubility in Water =6.93 lbs/100 gals. (60°F and 14.696 psi)- Minor solubility
Chemical Properties
1. Flammability
Chlorine, gas or liquid, is non-explosive and non-flammable. It is an oxidizer and is capable of supporting combustion. Many organic chemicals react readily with chlorine, sometimes violently.
2. Reactivity
Reactions With Water - Chlorine is only slightly soluble in water.(0.3 to 0.7 percent)
Reactions With Metals - At ordinary temperatures dry chlorine, gas or liquid, reacts with aluminum, arsenic, gold, mercury, selenium,tellurium, tin, and titanium. Carbon steel ignites near 483°F(251°C).
Reactions With Organic Compounds - Chlorine reacts with many organic compounds. Some reactions can be extremely violent or explosive.
It is a highly reacting helogen combining directly nearly all elements hence isolation is the primary requirement for safety.
(B) Exposure to human body and ill effects
Exposure to chlorine can cause immediate burning of the eyes, nose, and throat, warning of potentially hazardous exposure levels. Short-term exposures to chlorine do not often result in long-term health effects. Long-term effects are usually found in people who have had repeated exposures to chlorine causing them to build a tolerance to its irritant effects, making victims unaware of the chemical's presence. Repeated chlorine exposure irritates the lungs, leading to coughing, mucus production, or shortness of breath which can last for months, even years. The very young and elderly, as well as people with known health problems are at increased risk from chlorine exposure.
Common Routes of Chlorine Exposure
Inhalation. The most common way for chlorine to enter the body is through the respiratory system. Chlorine is a respiratory irritant. The gas irritates the mucus membranes and the liquid burns the skin. As little as 3.5 ppm can be detected as an odor, and 1000 ppm is likely to be fatal after a few deep breaths. In fact, chlorine was used as a war gas in 1915.Exposure to chlorine should not exceed 0.5 ppm (8-hour time-weighted average - 40 hour week.)
Signs and symptoms of chlorine inhalation include: rapid, difficult breathing; bluish skin color; wheezing and congestion; cough; nausea and dizziness; burning, irritated throat; swelling or narrowing of the airways; chlorine-induced pneumonia; and possible lung collapse.
Absorption through the Skin.
Chlorine can be absorbed through the skin causing mild to severe burns. Symptoms include: pain, inflammation or swelling, blisters, frostbite, and tissue death.
Absorption through the Eyes.
Chlorine can be absorbed through the eyes causing various problems. Symptoms may include: burning or discomfort, irregular blinking, redness, tearing, involuntary closing of the eyelids, eye burns, eye pain, and blurred vision.
Ingestion. Chlorine may cause tissue injury upon swallowing.
(C)Working safely around chlorine
Containers
Liquid chlorine comes in two types of containers:
- Cylinders with a 68 kg (150 lb.) capacity
- Ton containers with a 907 kg (2000 lb.) capacity
Cylinders and ton containers have fusible plugs designed to melt at 71°C when containers are exposed to extreme heat, such as fire, the plug melts, relieving pressure and preventing the container from rupturing violently.
Storing chlorine - Do and Don'ts
Location Requirement :
q Use signs to clearly identify all areas where chlorine is used or stored. Only qualified personnel are permitted to enter these areas.
q Store chlorine cylinders and containers in a cool, dry, and relatively isolated area, protected from weather and extreme temperatures. If storing cylinders and containers outside, shield them from direct sunlight, unless they are specifically designed for un shaded, outdoor storage.
q Note: Never apply heat to pipes, containers, or container valves unless they have been thoroughly purged of chlorine.
q When storing chlorine containers inside, store the containers in a well-ventilated building, away from any heat sources, such as steam pipes.
q Store chlorine containers on the lowest working level but not below grade.
q Do not store chlorine near busy roadways or anywhere else where vehicles operate. Chlorine reacts with carbon monoxide to produce phosgene, an extremely poisonous gas.
q Store cylinders upright and secure them against falling. Cylinders will discharge vapors when upright and discharge liquid when upside-down.
q Store ton containers on their sides, on steel or concrete supports. The supports should be equipped with trunnion wheels so that, if chlorine leaks from the bottom valve, the container can be quickly rotated with the leak at the top to minimize leakage. Discharge ton containers while they are horizontal, with the two valves in a vertical line (vapour from the top valve, liquid from the bottom).
Housekeeping in Storage place
q Do not store materials that may react violently with chlorine in the same room as chlorine (for example, hydrogen, ammonia, acetylene fuel gases, ether, turpentine, and most hydrocarbons, such as solvents, greases or oils, finely divided metals, and organic matter).
q Store containers with enough room between them to allow for complete accessibility during an emergency.
q Use cylinders and containers on a "first-in, first-out" basis.
q Clearly tag or mark empty cylinders and separate them from full cylinders.
q Note: Never assume a container is empty and therefore non-hazardous even though it may weigh empty.

Handling chlorine - Do and Don'ts
Moving containers
q Handle containers with care while moving or storing them. Do not allow containers to strike objects and do not drop containers.
q Do not use slings or magnetic devices to move chlorine containers.
q Use new gaskets as recommended by the chlorine supplier each time a cylinder or container is connected.
q Follow the chlorine supplier's recommended disposal procedures for leaking containers.
q Do not modify, alter, or repair containers and valves. Only the supplier should carry out these tasks.
Valves
q Ensure that cylinders have valve protection hoods in place when not connected to a system.
q Do not lift a cylinder by its valve protection hood. The hood is not designed to carry the weight of a cylinder.
q Till possible, open valves by applying a steady force to a 200 mm (8 in.) wrench.
q If the valve is very difficult to open, loosen the packing nut slightly. Tighten the packing nut after the valve is opened or closed.
Repair and maintenance
q Employers are responsible for providing written preventive maintenance procedures and written emergency procedures to any person who works on a chlorine system.
q Workers should be familiar with these procedures before carrying out repairs or maintenance on the chlorine system.
q Qualified workers must supervise the cleaning and repairing of chlorine systems.
q The chlorine system must be shut off before cleaning or repairing it, and all piping and other equipment must be thoroughly purged with dry air or nitrogen. Vacuum systems can be purged by drawing the remaining chlorine into the process. Do not weld any part of a chlorine system until it has been purged with dry air or nitrogen.
q After repair or maintenance work and before using the system, the pressurized part of the chlorine system must be pressurized to 150 psi with dry air or nitrogen and tested for leaks by applying soap solution to the outside of joints. Once detectable leaks are repaired, the system must be retested.
Moisture
Chlorine reacts with moisture to form corrosive acids. Every precaution must be taken to keep chlorine and chlorine equipment free of moisture, including the following steps:
q Close pipes, lines, valves, and containers tightly when not in use to keep moisture out of the system. Moisture causes chlorine to rupture steel pipe
q Avoid contact between chlorine and any residual material that drips from the equipment when pipes or lines are being dismantled before repair.
q Dry pipes and lines before use by purging with dry air (air that has a dew point of at least -40°C) or nitrogen.
Foreign material
Pipes, lines, and fittings must have all cutting oils, grease, and other foreign material removed from them before use. Trichloroethylene or other recommended chlorinated solvents may be used; however, take special precautions as required. Never use hydrocarbon or alcohol solvents for cleaning because they can react vigorously with chlorine.
Linseed oil with graphite or white lead, Freshly mixed glycerin and litharge
may be used as a lubricating pipe dope for threaded joints. If Teflon tape is used, all remnants must be removed before joints are remade.
Heat
Because iron and steel will ignite in chlorine at about 230°C (450 - 500°F), all welding or burning must only be done after the chlorine equipment is completely emptied and purged with dry air or nitrogen.
Engineering controls (building design)
specific design and ventilation requirements and guidelines for chlorine systems and storage facilities.
Chlorine enclosure
Consider the following points when designing a chlorine system or storage facility:
q Containers and equipment must be located in a separate enclosure with fire-resistant floors and walls. If possible, chlorine containers should be housed in a room separate from the area where the chlorination equipment is located.
q Chlorine storage enclosures must be designed so that chlorine containers and equipment are located at the lowest level. Work areas should not be located below the chlorine system.
q Storage rooms with floor areas larger than 60 square meters (200 sq. ft.) must have two or more exit doors which must open outwards and should not be self-locking to ensure accessible escape routes.
q Each room or building housing chlorine containers or equipment should have a viewing window at least 30 cm (12 in.) square or larger that will provide a clear view of the container and distribution system.
Ventilation
q A suitable fan, having switch outside the room/ shed providing at least 15 air changes per hour, must ventilate the chlorine storage room.
q Because chlorine gas is much heavier than air and tends to collect at floor level, ventilation fan suction must be located at or near floor level. Air inlets must be located to provide cross-ventilation using outside air.
Administrative controls
Alarm systems
q In case of a chlorine leak or emergency, all factories must have a working alarm that can be heard and seen by workers. A continuous (24-hour) chlorine monitor must be connected to the alarm system. The continuous monitor checks chlorine concentrations in the air and the alarm responds if chlorine concentrations reach a certain pre-set level.
q All the workers and nearby public must be made acknowledge about alarm sounding pattern and actions they are required to take.
Detector tubes
Several systems use detector tubes to give a direct reading of the chlorine concentration. Workers must be properly trained in detector tube use and maintenance. When taking measurements to determine the extent and severity of a leak outside the enclosure, workers must wear appropriate respiratory protection.
Personal protective equipment
Controlling exposure requires strict attention to chlorine exposure limits. Appropriate eye, skin, and respiratory protection are essential. Workers must be familiar with and understand the requirements of their employer's written exposure control program.
Other Equipments required for Leak Control
Emergency kit : It must be having good no rusted condition, and must have all the required components in order. Kit should be easily available any time.
Other Equipments : Whole Body Protection Suit and gloves, Shoes, Breathing apparatus of required types, Helmets, Perfect eye protection spectacles, Dry sand bags etc. are required to be readily available and in usable condition.
Eye protection
When chlorine gas is in the air, safety glasses and face shields will not protect the eyes. Workers in an area that contains a chlorine concentration that may irritate the eyes (for example, greater than 0.5 ppm) must wear eye protection with a tight seal around the eyes or face to prevent chlorine gas entering the eyes. At this concentration, eye protection will be worn with the required respiratory protection.
Skin protection
Emergency response workers who are controlling a serious chlorine leak must have access to full-body protective suits.
Respiratory protection
Outlines of the types of respirators available to protect workers from exposure to chlorine and the limitations of each respirator. Respirator choices must be based on the needs of each individual worksite and the requirements of the employer's written safe work procedures.
Full-face piece respirator with cartridges
A worker must wear a full-face piece respirator fitted with acid gas cartridges during any hazardous work where there is a chance of a chlorine leak. Full-face piece respirators are also appropriate for leak control where tests show the chlorine concentration to be less than 10 ppm (IDLH level).
Full-face piece respirator with canister
Although cartridges are preferable, a worker may use a full-face piece respirator fitted with an air-purifying canister for leak control and repair or maintenance procedures in chlorine concentrations less than 10 ppm.
Notes:
1. When a worker is repairing a leak, cartridges or canisters can only be worn when the chlorine concentration is known.
2. Canisters with an indicator window must be replaced when the material in the window has changed color. Canisters without an indicator window must be replaced after each use. In either case, canisters must never be used after the expiration date stamped on the label.
Half-face piece respirator with goggles
A worker may use a half-face piece respirator with vapour-tight chemical goggles when working on a chlorine system where there is a chance of a small leak. This type of respirator is permitted only when the chlorine concentration is below 5 ppm.
Self-Contained Breathing Apparatus (SCBA)
A worker must use an SCBA when a chlorine leak is suspected and the airborne chlorine concentration is unknown or is measured at more than 10 ppm. A worker wearing an SCBA must not enter a contaminated atmosphere until a second, qualified person is present, also equipped with an SCBA, and ready to perform a rescue. SCBA air cylinders should be refilled every six months or after each use, whichever comes first.
Escape respirator
There are two acceptable types of escape respirators: bite-block respirators and half face piece cartridge respirators fitted with acid gas cartridges. Bite-block respirators must be worn with nose plugs. Escape respirators may only be used for immediate evacuation of the contaminated atmosphere.
Anyone entering a chlorine room for any reason must carry an escape respirator and keep it within arm's reach at all times.
Situation of Chlorine concentration and Respirator choice (for guidance)
Routine work in chlorine room - escape respirator
(If a leak occurs, the concentration will be unknown. Exit room immediately.)
working on chlorine system - half-face piece respirator with tight chemical goggles, or full-face piece respirator (If a leak occurs, the concentration will be unknown. Exit room immediately.)
up to 5 ppm o half-face piece respirator with tight chemical goggles, or o full-face piece respirator greater than 5 ppm up to 10 ppm full-face piece respirator greater than 10 ppm SCBA, when leak occurs, or to enter space (having Chlorine in atmosphere repair) unknown ppm-- always assume to be IDLH level SCBA
Person-check telephone
Employers must establish a check system to ensure the continued well-being of workers who are working alone or at an isolated worksite. Where visual checks are not possible, the check system may require a radio or telephone. Workers who will need to use such a system must be trained in the written procedure.
Emergency equipment
Emergency equipment includes eye wash and shower facilities, first aid kits, and container repair kits. Workers must have immediate access to each of these items and must know how to use them in case of emergency.
First aid in various injuries:
Chlorine inhalation
Someone who has inhaled chlorine may be unconscious, and may have difficulty breathing or may have stopped breathing completely. Assess the victim's breathing:
£ If breathing has stopped, begin artificial respiration and continue until the victim resumes breathing. Pocket masks are recommended for artificial respiration, although the mouth-to-mouth method may also be used.
£ If the victim is having difficulty breathing (for example, gasping or coughing), place the victim in the most comfortable position, usually semi-sitting.
£ If an oxygen therapy unit and trained personnel are available, administer oxygen at a 10-litre flow.
£ Ensure that the victim is transported to hospital in case the victim suffers a delayed reaction in the form of pulmonary edema. Any physical exertion, excitement, or apprehension increases the chance and severity of a delayed reaction. Keep the victim warm and completely at rest. Reassure the victim while waiting for assistance and transportation to hospital.
Unconscious patients
As soon as they resume breathing, always place unconscious patients in the drainage position (on their side, so fluids can drain from the mouth and airways). Never give an unconscious patient anything by mouth.
Skin contact
Skin contact with chlorine can result in severe burns. Before attempting to flush a victim's contaminated skin, make sure the victim is breathing properly. Follow these steps: Assess the victim's breathing and follow the procedure as indicated for inhalation.
q As soon as the victim resumes breathing, flush the victim's contaminated skin and clothing with large amounts of water for 30 minutes.
q Remove all contaminated clothing while flushing.
q Continue flushing until all traces of chlorine have been removed.
q Dress obvious burns with sterile gauze and bandage them loosely. Apply insulated cold packs to help reduce pain.
q Get the victim to hospital.
Eye contact
Eye contact with chlorine (liquid or gas) for even a short period can cause permanent disability. Flushing must begin within 10 seconds. Follow these steps:
1. Flush the eyes immediately with large amounts of running water (preferably lukewarm) for 30 minutes. Hold the eyelids forcibly apart to ensure full flushing of the eyes and eyelids.
2. After flushing has removed all traces of chlorine, cover both eyes with moistened sterile gauze pads and bandage, enough to keep light out.
3. Apply insulated cold packs to help reduce pain.
4. Get the victim to hospital.
Notes:1. Do not attempt to neutralize the chlorine with other chemicals. 2. Do not apply oils, ointments, or medications to the eyes.
What to Do When a Person is Exposed to Chlorine -
q Remove the exposed person(s) to fresh air.
q Call immediately company safety personnel.
q If the victim is not breathing, begin artificial respiration. If the victim is breathing, place in a seated position or lying down with the head and upper body in an upright position. Encourage slow, deep, regular breaths. Have a health professional administer oxygen.
q Keep the person warm and quiet.
q Persons with serious symptoms may need to be hospitalized.
Decontamination Procedures -
q Remove soaked clothing from the victim and double-bag it immediately.
q Flush exposed skin/hair with water for 2-3 minutes; wash twice with mild soap and rinse thoroughly with water.
q Flush exposed or irritated eyes with water/saline for 15-30 minutes. If the person is wearing contact lenses, try to remove them.
What to Do in Case of an Emergency Chlorine Release -
q Follow the procedures laid down in On Site Emergency Plan.
q All persons not engaged in stopping the leak should leave the affected area until normal operating conditions are restored. If the amount of chlorine released is excessive, then special steps should be taken to warn all persons in the path of the fumes.
q Small leaks may be readily located by the use of a squeeze bottle containing ammonia water near the suspected leak (avoid squeezing liquid on the leak). If the container or equipment is leaking, then dense white fumes of ammonium chloride will indicate the exact location of the leak. Approach the leak from the upwind side and since chlorine gas is heavier than air, keep the head above the leak.
q If the leak is in the chlorinating or unloading equipment, the nearest control valve between the chlorine container and the leak should be immediately closed and the chlorine lines emptied to the process. Leaks around a container valve stem can generally be stopped by tightening the packing nut.
q Use emergency kit to stop the leak but only by persons wearing foolproof PPE
q Far as possible use the Chlorine in process using secondary valve of the kit.
q If leakage is not controllable by kit use FRP HOOD and scrub the Chlorine using neutralizing arrangements.
Water should never be applied around a chlorine leak or onto a spill of liquid chlorine..
Apart from the corrosive action caused by the addition of water, the heat supplied by even cold water may cause the liquid in the container or on the ground to vaporize faster. Since the pressure within a container governs the rate of discharge, a leak can be reduced by drawing off gaseous chlorine to the process as rapidly as possible. If the consuming process cannot take the gas rapidly enough, then the chlorine may be absorbed in a solution of sodium hydroxide, soda ash or hydrated lime.
q Notify trained personnel immediately, such as the company's safety team and the local fire department. Untrained persons or those without proper personal protective equipment must not enter areas with high concentrations of chlorine.
q Evacuate people from the hazardous area for at least 500 feet in all directions and have them stay upwind of the chlorine release. They should be sheltered in a building with doors and windows shut and air conditioners turned off.
q Stop/control the source of exposure. If the exposure is from a leaking cylinder, take it outdoors or to an open area until completely drained and contents have evaporated.
q Ventilate potentially explosive atmospheres by opening windows.
q Keep combustibles such as wood, paper, and oil, away from the leak.
q Remove all sources of heat and ignition.
q Refer to Material Safety Data Sheet (MSDS) for more information.

Conclusive Suggestions Based On Experience During Inspections
Accidents in factories using Chlorine are found to be, because of the following reasons which are avoidable by sincere efforts.
Physical reasons
a. Improper storage place and nonscientific unsafe pattern of storage.
b. Insufficient and poorly maintained plant, workplace and equipments including PPE.
c. Not using standard materials like pipes, clamps, spanners etc.
d. Insufficient work force hence Chlorine related processes poorly supervised.
e. Untrained or partially trained workers ( many times ever changing contract workers) engaged in the process.
f. No sincerity towards rehearsal of On Site Emergency Plan and Emergency Control Procedures.
Attitudinal Reasons
g. Implementation of safety laws as a legal must, just for protection against authorities. Hence continuity in implementation not maintained.
h. An attitude to save money against safety compliance.
i. A wrong confidence and belief - No accident took place in past so factory is safe.
j. Poor understanding regarding benefits of implementation of safety laws.
k. Willful ignorance and violation of safety laws.

Some Tips
a. Have a positive attitude for safety, time has changed you must change accordingly for your own at least.
b. Spend sufficient to implementing on safety related requirements- it will prove to be your wise investment.
c. Never allow hazardous work in absence of insufficient trained staff or with untrained work force.
d. Have best of safety equipments and maintain it too, arrange for it's regular and random supervision.
e. Share your experiences and difficulties with near by Chlorine user factory managements. If possible form a Chlorine users club for local area pocket or estate.
f. Introduce some incentive scheme for motivation of safety related activities and attitude of employees.

 



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