DEPARTMENT OF CHEMICAL ENGINEERING
Motilal Nehru National Institute of Technology Allahabad
Allahabad – 211 004, U.P (India)
Terminologies
Dust Explosions - This explosion results from the rapid combustion of fine
solid particles. Many solid materials become very flammable when
reduced to a fine powder.
Confined explosion – an explosion occurring within a vessel or a building.
Usually results in injury to the building inhabitants and extensive damage.
Unconfined explosion – an explosion occurring in the open. Usually
results from spill of a flammable gas spill. These explosions are rarer than
confined since dilution occurs.
Ignition - start of the burning process
Auto ignition temperature - T such that mixture can self-ignite
Flash Point - lowest temperature at which the liquid will volatilize enough
vapor to form an ignitable mixture
Fire point - lowest T at which vapor above a liquid will burn
Flammability limits - burning occurs between LFL and UFL (LEL and UEL)
Shock wave - pressure wave moving through a gas
Overpressure - P as f(shock wave)
Terminologies
Combustion/ fire – a chemical reaction in which a substance combines
with an oxidizer and releases energy.
Explosion – rapid expansion of gases resulting in a rapid moving pressure
or shock wave.
Mechanical Explosion – due to failure of vessel with high pressure non
reactive gas.
Detonation – explosion (chemical reaction) with shock wave greater than
speed of sound.
Deflagration – explosion (chemical reaction) with shock wave less than
speed of sound
BLEVE (Boiling Liquid Expanding Vapor Explosion) – when liquid is at a
temperature above its atmospheric boiling point. Vessel ruptures –
flammable liquid flashes and results in a fire/ explosion
VCE (Vapour Cloud Explosion) - an explosion occurring outdoors
beginning with the unplanned release of a large quantity of flammable gas
or vaporizing liquid which ignites following the formation of a cloud or
plume of pre-mixed fuel and air.
Caution…! Fire or Explosion?
Fires: release energy slowly
Explosions: rapid release of energy
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The Fire Triangle
• Fuels:
• Oxidizers – Liquids
– Liquids • gasoline, acetone,
– Gases ether, pentane
• Oxygen, fluorine, – Solids
chlorine
• plastics, wood dust,
• hydrogen peroxide, fibers, metal particles
nitric acid, perchloric
acid – Gases
– Solids • acetylene, propane,
• Metal peroxides, carbon monoxide,
ammonium nitrate hydrogen
Ignition sources
Sparks, flames, static
electricity, heat
• FIRE is the rapid oxidation of a material in the exothermic chemical
process of combustion, releasing heat, light, and various
reaction products.
FIRE • Slower oxidative processes like rusting or digestion are not included
by this definition.
• Fire is hot because the conversion of the weak double bond in
molecular oxygen, O2, to the stronger bonds in the combustion
products carbon dioxide and water release energy.
FLASH FIRE JET FIRE POOL FIRE
It is characterized by high The pressure of release generates Fires in the open will be well
temperature, short duration, and a long flame, which is stable under ventilated (fuel-controlled), but fires
a rapidly moving flame front. most conditions. within enclosures may become under-
ventilated (ventilation-controlled).
A flash flame may take the form of
jet flame on reaching the spill Pool fires may be static (e.g. where the
point. pool is contained) or 'running' fires.
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Physical Properties Key Factor of Flammable
1. Boiling Point
2. Vapor Pressure
3. Flash Point
4. Auto ignition
5. Enthalpy of Combustion (ΔHc)
6. MIE
7. Density
8. Conductivity of material
9. Size of material
Environmental Properties Key Factor of Fire
/ Explosion
1. Operational Parameter (Pressure, Flowrate, Temp, etc)
2. Lay-out of unit process/equipment
3. Installation (congested, confined, etc)
4. Source of heat (open fire, conductive heat, static electric, etc)
5. Metrological condition (Wind speed, direction, etc)
6. Leakage dimension (bore, rupture, hole, etc)
Impact of Fire & Explosion
1. Breakage the molecular bond
2. Heat Flux / Heat Radiation
3. Poisonous Gas
4. Blast Wave/Shock Wave
5. Debris trajectory/projectile
Ignition Sources of Major Fires
Source Percent of Accidents
Electrical 23
Smoking 18
Friction 10
Overheated Materials 8
Hot Surfaces 7
Burner Flames 7
…
Cutting, Welding, Mech. Sparks 6
…
Static Sparks 1
All Other 20 10/61
Liquid Fuels – Definitions
Flash Point : lowest temperature at which a flammable liquid
gives off enough vapor to form an ignitable mixture with air
Auto-ignition Temperature: lowest temperature at which a
volatile material will be vaporised into a gas which ignites
without the help of any external flame or ignition source
Flammable Liquids (National Fire Protection Association)
– Liquids with a flash point < 100°F
3
Combustible Liquids (NFPA)
– Liquids with a flash point 100°F
Note: On the NFPA diamond label, a fire hazard
rating of 3 or 4 denotes a flammable liquid.
Vapor Mixtures – Definitions
Flammable / Explosive Limits
– Range of composition of material in air which will burn
UFL – Upper Flammable Limit
LFL – Lower Flammable Limit SAME
HEL – Higher Explosive Limit SAME
LEL – Lower Explosive Limit
Measuring these Limits for Vapor- Air Mixtures
– Known concentrations are placed in a closed
vessel apparatus and then ignition is attempted
FLAMMABILITY RELATIONSHIPS
AUTO
IGNITION
CONCENTRATION OF FUEL
FLAMMABLE REGION
FLAMMABLE REGION
MIST
FLASH POINT
TEMPERATURE AUTO AIT
IGNITION
Flammability Characteristics
of Liquids and Gases
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Flammability Limits
Above table gives upper flammability limits
and lower flammability limits for several
common substances.
Experimentally determined.
LFL can be estimated from Flash Point:.
vapor pressure at flash point
LFL =
760 mmHg
Determine vapor pressure using Antoine Equation
Mixture Flammability Limits
If you have a mixture of flammable components you can calculate
Lower Flammability Limit of the mixture LFLmix using Le Chatelier’s
relationship:
1
LFLmix = n
yi
LFL
i =1 i
LFLi is flammability limit for component i
yi is mole fraction of i on combustible basis
n is the number of combustible species
UFLmix of mixtures of several combustible gases can be calculated
using Le Chatelier’s mixing rule for combustible volume fractions, yi:
1
UFLmix = n
yi
i =1 UFLi
Flammability Limits – Temperature
effect
Above table gives flammability limits for 25°C and
atmospheric pressure. If you are at a different
temperature you can modify flammability limits
LFLT = LFL25 (1 − 0.75(T − 25) / H c )
UFLT = UFL25 (1 + 0.75(T − 25) / H c )
H c is heat of combustion for component
T is in C
Flammability Limits – Pressure
effects
LFL is not affected by pressure
UFL does depend on the pressure
UFLP = UFL + 20.6(log10 P + 1)
P is in MPa absolute
Procedure
– Correct for Temperature
– Correct for Pressure
– Calculate for mixture
Problem
Q1. A gas mixture composition by volume is given
on the following table. Calculate the LFL and
UFL of a gas mixture ? Whether the mixture is
flammable or not?
Explosion occurrence step
Explosion
Physical Chemical
Explosion Explosion
1. Overpressure 1. Runway reaction
2. BLEVE - Fireball
3. UVCE/CVE
Explosions….
Fire
– A slow form of deflagration
Deflagration
– Propagating reactions in which the energy transfer from the
reaction zone to the unreacted zone is accomplished thru
ordinary transport processes such as heat and mass
transfer.
Detonation / Explosion
– Propagating reactions in which energy is transferred from
the reaction zone to the unreacted zone on a reactive
shock wave. The velocity of the shock wave always
exceeds sonic velocity in the reactant.
Classification of Explosions
EXPLOSION = Rapid Equilibration of High Pressure Gas via
Shock Wave
Physical Explosions Chemical Explosions
Uniform Reactions Propagating Reactions
Thermal Detonations Deflagrations
Explosions (faster than the speed (slower than the speed
of sound) of sound)
Impact of VCEs on People and Facilities
The VCE will result in overpressures
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Damage due to Overpressure
The VCE will result in overpressures
Peak Damage Type Description
overpressure
0.30 bar Heavy Damage Major damage to plant equipment
structure
0.10 bar Moderate Damage Repairable damage to plant
equipment & structure
0.03 bar Significant Damage Shattering of glass
0.01 bar Minor Damage Crack in glass
Boiling Liquid Expanding Vapour
Explosion (BLEVE)
It is caused due to loss of containment of liquid above its
normal boiling point at the moment of its failure.
BLEVE is a type of fireball in which a mass of liquefied
flammable gas initially at a temperature above its boiling
point is released suddenly and ignites immediately.
Static Electricity
Sparks resulting from static charge buildup
(involving at least one poor conductor) and
sudden discharge
Household Example: walking across a rug
and grabbing a door knob
Industrial Example: Pumping
nonconductive liquid through a pipe then
subsequent grounding of the container
Dangerous energy near flammable vapors 0.1 mJ
Static buildup by walking across carpet 20 mJ
Controlling - Static Electricity
Reduce rate of charge generation
– Reduce flow rates
Increase the rate of charge relaxation
– Relaxation tanks after filters, enlarged
section of pipe before entering tanks
Use bonding and grounding to prevent
discharge
Controlling - Static Electricity
GROUNDING
BONDING
Explosion Proof Equipment
All electrical devices are
inherent ignition sources
If flammable materials might
be present at times in an
area, it is designated
Explosion Proof Required
Explosion-proof housing (or
intrinsically-safe equipment)
is required
Area Classification
Class I Flammable gases/vapors present
Class II Combustible dusts present
National Electrical
Code (NEC) defines Class III Combustible dusts present but
not likely in suspension
area classifications Group A Acetylene
as a function of the Group B Hydrogen, ethylene
nature and degree Group C CO, H2S
of process hazards
Group D Butane, ethane
present
Division 1 Flammable concentrations
normally present
Division 2 Flammable materials are
normally in closed systems
