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Hazardous Materials Incidentsby Chris Hawley
CHAPTER 2: Recognition and Identification
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Chapter 2: Overview• Introduction• Location and occupancy• Placards, labels, and markings• Other identification systems • Containers• Use of senses• Chemical and physical properties• Summary
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HAZMAT Clues (1 of 2)
• It is through recognition and identification (R & I) that you can impact your ability to stay alive.
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HAZMAT Clues (2 of 2)
• Location and occupancy
• Placards, labels, and markings
• Container types• Senses
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Location and Occupancy
• The size of the community does not impact the potential for hazardous materials; every community has hazardous materials – Major transportation corridors – Buildings that store chemicals
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Some Examples• Hardware stores,
hospitals• Auto part supply stores• Dry cleaners• Manufacturing facilities• Print shops• Doctors’ offices• Photo labs• Agricultural supply stores• Semi-conductor
manufacturing facilities• Electronic manufacturing
• Light to heavy industrial• Marine terminals• Rail yards• Airport terminals and
fueling areas• Pool chemical stores• Paint stores• Hotels• Swimming pools• Food manufacturing• Many others
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Placards, Labels, and Markings
• The Department of Transportation (DOT) regulates the movement of hazardous materials (dangerous goods in Canada) by air, rail, water, roadway, and pipeline which can be located in 49 CFR 170-180.
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DOT Placarding (1 of 2)
• Table 1 placards– Require placarding at any amount
• Table 2 placards– Require placarding at 1,001 pounds
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DOT Placarding (2 of 2)
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DOT Hazard Classes (1 of 2)
• DOT has established 9 hazard classes. – Classes 1-8 are specific.– Class 9 is a miscellaneous category.
• Some classes have subdivisions.
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DOT Hazard Classes (2 of 2) • Class 1: Explosives• Class 2: Gases• Class 3: Flammable liquids• Class 4: Oxidizers and organic peroxides• Class 5: Flammable solids, water reactives, and
spontaneously reactive• Class 6: Poisons• Class 7: Radioactives• Class 8: Corrosives• Class 9: Miscellaneous hazards
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Placards• Fixed on the four sides
of a vehicle
• 10 ¾ by 10 ¾ inches
• Provide warning by:– Color– Division number– Name or UN number– Picture
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Labels• Used on two sides of
shipping packages• Affixed near shipping name• 3.9 x 3.9 inches in size• Smaller versions of the
placards• Required for most
hazardous materials packages
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Class 1: Explosives• Division 1.1 – Mass explosion hazard
• Division 1.2 - Projectile hazard
• Division 1.3 - Fire hazard or minor blast hazard
• Division 1.4 – Minor explosion hazard
• Division 1.5 – Very insensitive explosives
• Division 1.6 –Also very insensitive explosives
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Explosives and Fires
• Extremely dangerous
• Withdrawing usually best option
• Consult DOT ERG
• 1988 Kansas City, MO, lost six firefighters to a fire involving explosives.
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Packing Groups• Some materials may not be shipped with
others.
• They have established packing groups.– Packing group I – greatest danger– Packing group 2 – medium danger– Packing group 3 – minor danger
• DOT rules state which materials can be shipped with the various packing groups.
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Class 2: Gases (1 of 2)
• Division 2.1 – Flammable gases
• Division 2.2 – Non-flammable, non-poisonous, and compressed gas– Liquefied gas– Pressurized cryogenic gas– Compressed gas in solution
• Division 2.3 – Poisonous gases
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Class 2: Gases (2 of 2)
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Hazard Zones
• DOT has established hazard zones that signify the amount of toxicity a particular material may present.
• Hazard zones are listed as A-D.• A material listed with “Hazard zone A” is
extremely toxic and presents significant inhalation risk.
• Hazard zone D is also severely toxic, but not as toxic as “A.”
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Class 3: Flammable Liquids (1 of 2)
• Flammable liquids are those that have flash points below 141º F.
• Combustible liquids are those that have flash points above 141º F.
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Class 3: Flammable Liquids (2 of 2)
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Class 4: Flammable Solids (1 of 2)
• Division 4.1 – Flammable solids
• Division 4.2 – Spontaneously combustible materials
• Division 4.3 – Dangerous when wet materials
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Class 4: Flammable Solids (2 of 2)
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Class 5 Oxidizers and Organic Peroxides
• Division 5.1 - Oxidizers
• Division 5.2 - Organic peroxides
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Oxidizers
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Organic Peroxides
• Ability to polymerize
• May be violently reactive or explosive
• May violently rupture container, if contained
• Sensitive to shock, heat, or contamination
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Organic Peroxides
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Class 6: Poisons (1 of 2)
• Division 6.1 – Materials that present a risk to humans during transportation
• Division 6.2 – Microorganisms, or their toxins, that can cause disease
• Has two hazard zones
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Class 6: Poisons (2 of 2)
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Class 7: Radioactive (1 of 2)
• There are no sub-divisions for radioactives.
• There are three labels.– Radioactive I– Radioactive II– Radioactive III
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Class 7: Radioactive (2 of 2)
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Class 8: Corrosives (1 of 2)
• Includes acids and bases
• Capable of causing destruction to humans and metal
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Class 8: Corrosives (2 of 2)
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Class 9: Miscellaneous (1 of 2)
• Present hazard not listed in previous classes– Dry ice– Molten sulfur– Hazardous waste
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Class 9: Miscellaneous (2 of 2)
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Dangerous Placard (1 of 2)
• Placard means mixed load is being carried.
• Load consists of two materials that would require placarding.
• More than 2, 205 lbs. requires dangerous placard and specific hazard placard.
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Dangerous Placard (2 of 2)
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Specific Name Placards
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Primary Placards
• Provides primary hazard and subsidiary hazard.
• Subsidiary hazard does not have class/division number.
• Subsidiary placard is below primary hazard.
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Placard and Identification Numbers
• ID number indicates a bulk shipment.– More than 119 gallons
in one container
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Other Placards and Labels (1 of 3)
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Other Placards and Labels (2 of 3)
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Other Placards and Labels (3 of 3)
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White Squared Placard
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Labels
• Display primary hazard of the package
• May display subsidiary hazard
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Facility Markings: NFPA 704
• Four-tiered system– Health– Fire– Reactivity– Special hazards
• Numerical rating system 0-4
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Ratings
• 4 – Severe hazard
• 3 – Serious hazard
• 2 – Moderate hazard
• 1 – Slight hazard
• 0 – Minimal hazard
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Hazardous Materials Information System (HMIS)
• On containers
• Used by employers to comply with hazard communication regulation
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Military Warning System
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Pipeline Marking System
• Pipeline contents
• Pipeline owner
• Emergency contact information
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Pesticide Markings
• Label signal words– Danger– Warning– Caution
• Pesticide control #
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Containers
• Small, household
• Medium-sized containers
• Large-scale containers
• Fortified containers
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Bottles
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Bags
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Drums• Fiberboard• Fiberboard plastic
lined• Plastic (poly)• Steel• Stainless steel• Aluminum
• Dry, granular• Wetted materials,
slurries• Corrosives• Flammables• Hazardous corrosives• Pesticides or steel
reacting materials
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Drums
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Cylinders
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Totes
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Highway Transportation• Box trucks
– Land sea container (sea box)
• Atmospheric tank truck
• Chemical hauler
• Corrosive tank
• Pressurized tanks
• Inter-modal containers
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Specification Plate
• Located on tank• Provides specific
information on the tank
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DOT 406/MC306 (1 of 2)
• Atmospheric tank truck– Commonly called gasoline tank truck
• 2-5 compartments
• Up to 11,000 gallons
• Aluminum construction
• Elliptical in shape
• Rollover protection
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DOT 406/MC306 (2 of 2)
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Internal Baffles and Bulkheads
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DOT 407/MC307 (1 of 4)
• Chemical workhorse
• Two types– Insulated– Non-insulated
• 2000-7000 gallons (5000 normal)
• Usually one compartment
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DOT 407/MC307 (2 of 4)
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DOT 407/MC307 (3 of 4)
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DOT 407/MC307 (4 of 4)
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Insulated 407/307
• Typically one compartment
• Inner tank surrounded by insulation and outer shell
• Steam lines or heated lines in insulation
• Horseshoe shaped
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Non–Insulated 407/307
• Reinforced rings
• Typically one compartment
• Round in shape
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DOT 412/MC312 (1 of 2)
• Corrosive tank trucks
• Single compartment
• Usually less than 5,000 gallons
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DOT 412/MC312 (2 of 2)
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MC331 (1 of 2)
• Pressurized tank
• Compressed gases
• Up to 11,500 gallons
• Low to high pressure
• Significant BLEVE risk
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MC331 (2 of 2)
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BLEVE
• They pose significant risk to responders.
• Fires involving sealed containers can violently rupture.– Propane tanks are common examples
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Diagram of a BLEVE
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BLEVE Recommendations (1 of 2) • Withdraw immediately in case of rising sound
from venting relief valves or discoloration of the tank.
• Fight the fire from a distance with unstaffed hose holders or monitor nozzles.
• Cool the tank with flooding quantities long after the fire is out.– A minimum of 500 gpm at the point of flame
impingement is recommended by the NFPA.
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BLEVE Recommendations (2 of 2) • If the water is vaporizing on contact, you are not putting
enough water on the tank.– Water should be running off the tank if you are cooling the tank.
• Do not direct water at relief valves or safety devices, as icing may occur which would block the venting material causing an increase in pressure inside the tank.
• The tank may fail from any direction, but avoid the ends of the tank.
• For massive fire, use unmanned hose holders or monitor nozzles. If impossible, withdraw from the area and let fire burn.
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Dangers Associated with BLEVEs
• The fireball can engulf responders and exposures.
• Metal parts of the tank can fly considerable distance.
• Liquid propane can be released into the surrounding area and be ignited.
• The shock wave, air blast, or flying metal parts created by a BLEVE can collapse buildings, or move responders and equipment.
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MC-338 (1 of 2)
• Cryogenic containers
• Vacuum-sealed inner container
• Well insulated
• Low pressure
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MC-338 (2 of 2)
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Tube Trailers• High pressure cylinders
• Contain compressed gas
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Dry Bulk Tanks
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Hot Materials Tanks
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Intermodal Tanks (1 of 2)
• Non-pressure
• Pressure
• High pressure
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Intermodal Tanks (2 of 2)
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Rail Tank Cars
• Increased volume– Up to 30,000 gallons
for HAZMAT
• Limited access
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Types of Rail Cars• Non-pressure• Pressure• Specialized
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Non-pressure Cars (1 of 2)
• Up to 100 psi pressure
• Known as General Service cars
• All piping valves, lines, relief valves on the outside
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Non-pressure Cars (2 of 2)
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Pressure Cars (1 of 2)
• Over 100 psi pressure
• Liquefied gases
• All pipes, valves, and fittings under a protective dome
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Pressure Cars (2 of 2)
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Specialized Rail Cars (1 of 3)
• Trailers of flat car
• Box cars
• Cryogenic cars
• Tube cars
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Specialized Rail Cars (2 of 3)
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Specialized Rail Cars (3 of 3)
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Markings on Rail Cars• Placards
• Dedicated cars labeled
• Specifications on side
• Tank car #
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Bulk Storage Tanks• Underground
• Aboveground
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Gasoline Stations
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Ordinary Tank
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External Floating Roof
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Internal Floating Roof
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Specialized Tanks• Cryogenic tanks
• High pressure tanks
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Senses
• Touch, taste, smell are dangerous tools to use for recognition and identification.
• Sight and sounds are acceptable, but always maintain distance.
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Chemical and Physical Properties
• Follow the science to guide your response.
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State of Matter
• Solid
• Liquid
• Gases
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Temperature• Melting point
• Freezing point
• Sublimation
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Boiling Point• Material turning
to a gas or vapor
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Vapor Pressure
• Indication of vapor production
• Material moves to a gas or vapor
• Measure of the force of the vapors
• 760 mm HG = 1 ATM = 14.7 psi
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Common Vapor Pressures• Water – 25 mm Hg• Acetone – 180 mm
Hg• Gasoline – 300 mm
Hg• Ethyl ether – 440 mm
Hg• Methyl alcohol – 100
mm Hg
• Diesel fuel – 5 mm Hg• Sodium hydroxide – 1
mm Hg @ 2534º F• Sulfuric acid – 0.001
mm Hg• Ethion – 0.0000015
mm Hg• Sarin – 2.1 mm Hg
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Vapor Density
• Relationship with air• Air given value of 1
– Less than 1 rise in air– Greater than 1 stay low
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Specific Gravity• Relationship with water
• Water given value of 1– Less than 1 float on water– Greater than 1 sink
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Corrosivity
• Acids have a value of 0-6.9.
• Bases are 7.1-14.
• Neutral is a pH of 7.
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Common pHs • Water – 7 • Stomach acid – 2• Orange juice – 3• Drain cleaner – 14• Potassium hydroxide – 14• Sulfuric acid – 1• Pepsi – 2• Ammonia - 12
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Chemical Reactivity
• Exothermic– Releases heat
• Endothermic– Absorbs heat
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Flash Point
• Temperature of the liquid when, while being heated, an ignition source is introduced into the vapor/air mixture located above the liquid, causing a flash fire
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Common Flashpoints
• Gasoline – 45º F
• Isopropyl alcohol – 53º F
• Acetone – -4º F
• Diesel fuel – >100º F
• Motor oil 300 – -450º F
• Xylene – 90º F
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Autoignition Temperature
• Material is heated and ignites on its own without the presence of an ignition source.
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SADT
• Self Accelerating Decomposition Temperature– Temperature at which the material will rapidly
decompose• Usually reacting violently or burning
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Flammable Range (1 of 2)
• Lower Explosive Limit (LEL)– Minimum amount in air needed to have a fire
• Upper Explosive Limit (UEL)– Maximum amount in air to have a fire
• Range in between LEL and UEL is the flammable range.
• Fires and explosions occur in the flammable range.
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Flammable Range (2 of 2)
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Toxic Products of Combustion• When most materials burn, smoke is
usually very toxic.
• Even wood, wool, hay, and many other common items present a significant risk.
• Smoke from plastic burning is extremely toxic.
• Respiratory protection should always be worn in the presence of smoke.
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Summary• Hazard classes
• Containers
• Chemical and physical properties