m


 
 m

 
m Definitions
m Flammability
m Flash Points
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
 d
 
m ôe have been talking about source models for
the release of materials and about dispersion
models if the material is a toxicant.
mAnother concern is a release of flammable
materials where we need to worry about fires and
explosions.
 m


m Most are familiar with the Fire
Triangle.
m In order for a fire to start or be
sustained you need to have a
Fuel, an oxidizer and an
ignition source.
m If one of the three
components is eliminated,
then there will not be a fire (or
explosion)
 m
m Fuel must be present in certain concentrations.
m Typical cases where fuel occur are if there is a leak,
during filling operations, transfer operations, or
excessive dusts.
m Although we often cannot always eliminate these
sources we can help by having good ventilation to keep
vapors from building up.
m Often we locate things out-doors, use grating on floors
so vapors don¶t build up.
   

mOxygen is the most common oxidizer, especially
that found in ambient air.
mFor oxygen, we often use ³inerting´ with nitrogen,
helium blankets over flammable materials to
reduce O2 content below that where you can
have combustion.
 d 

mÔeat is a common ignition source.
m³Ignition sources are free!!!´
mAlthough we can eliminate ignition sources, it is
almost inevitable that an ignition source will be
available if there is a large release of flammable
material that cannot be diluted quickly.
 m



m The fire tetrahedron or fire
pyramid adds a fourth
component²chemical chain
reaction²as a necessity in
the prevention and control of
fires.
m The free radicals formed
during combustion are
important intermediates in the
initiation and propagation of
the combustion reaction. Fire
suppression materials
scavenge these free radicals
   
mCombustion ± a chemical reaction in which a
substance combines with an oxidizer and
releases energy.
mExplosion ± rapid expansion of gases resulting in
a rapid moving pressure or shock wave.
mMechanical Explosion ± due to failure of vessel
with high pressure non reactive gas.
 
 
m Detonation ± explosion (chemical reaction) with shock
wave greater than speed of sound
m Deflagration ± explosion (chemical reaction) with shock
wave less than speed of sound
m 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
 
 
mConfined explosion ± an explosion occurring
within a vessel or a building. Usually results in
injury to the building inhabitants and extensive
damage.
mUnconfined 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.
 
 
m 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.
 m

 
m Definitions
m Flammability
m Flash Point
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
 m  
mFlash Point (FP) ± a property of material used to
determine the fire and explosive hazard. The
lowest temperature of a liquid at which it gives off
enough vapor to form an ignitable mixture with
air.
mNeeds to be determined experimentally.
mDifferent methodsto determine, open cup and closed
cup. Open cup is usually a few degrees higher.
 Ñ m

    
m     
mFlammable IA ± Flash point < 73°F, boiling point < 100 °F
mFlammable IB ± Flash point < 73°F, boiling point > 100 °F
mFlammable IC ± 73°F < Flash point < 100 °F
mCombustible II ± 100 °F < Flash point < 140 °F
mCombustible IIIA ± 140 °F < Flash point < 200 °F
mCombustible IIIB ± Flash point > 200 °F
 Ã 
m  
mFlash Points of mixtures can be estimated only IF one
of the components is flammable. If more than one is
flammable then need to determine experimentally.
mFor mixtures:
mDetermine the temperature at which the vapor pressure of
the flammable in the liquid is equal to the pure component
vapor pressure at its flash point.
 Ã 
m  
mExample
m Methanol FP=54°F, Vapor Pressure @ 54°F is 62 mmÔg
Determine the flash point of a solution that is 75wt% MeOÔ in
water.
Solution:
Since only one component is flammable, can estimate
mixture FP:
Ã 
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X

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ë

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ë

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Ã 
m   
 
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m    
m There is usually a range
of compositions of a
flammable vapor and air
where combustion occurs.
m Too little fuel (lean
mixture) not enough fuel
to burn.
m Too much fuel (rich
mixture) not enough
oxygen to burn
 m    
mTable 6-1 gives upper flammability limits and
lower flammability limits for several common
substances.
mExperimentally determined.
mLFL can be estimated from Flash Point:.
# 
 / 

^^ ë
,
 &
0# 
& 
1 

 Ã 
m    
mIf youhave a mixture of flammable components
you can calculate Lower Flammability Limit of the
mixture LFLmix using Le Chatelier¶s relationship:
*
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     23


 

  
  

 

222 
 2

22
 Ã 
m    
mËou can also calculate an Upper Flammability
Limit of the mixture UFLmix using Le Chatelier¶s
relationship:
*
   ë 


ë*  
m     

 


mTable 6-1gives flammability limits for 25°C and

atmospheric pressure. If you are at a different
temperature you can modify flammability limits
 
ë  + „* ,+
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m     

 
m LFL is not affected by pressure
m UFL does depend on the pressure
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 67  2

m Procedure
m Correct for Temperature
m Correct for Pressure
m Calculate for mixture
 m

 
m Definitions
m Flammability
m Flash Points
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
Ã   
 
Ã
m LFL is based on ³air´ but actually it is O2 that is
important. Often in industry they ³inert´ to dilute
the O2 concentration.
m Below the MOC the reaction cannot generate
enough energy to heat the entire mixture to the
extent required for self propagation.
 Ã
U 6
  U 6
8 
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 6
 96
  6
  
U 6
8
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 6
  

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3
   
   
  

 
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U 6
8
ë 
 6
  
 m

 
m Definitions
m Flammability
m Flash Points
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
 Ã  d 
Ãd
mMinimum energy input needed to initiate combustion
mMost hydrocarbons have low MIE~0.25 mJ
môhereas the ³spark´ from walking across the room is
22mJ (almost 100X too much)
mAgain, we always assume that an ignition source will
exist
mTable 6-2 gives MIEs for some substances
 m

 
m Definitions
m Flammability
m Flash Points
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
   

 
m ôhen gases are compressed they heat up and
can ignite (this is how a diesel engine works, also
the cause of ³knocking´ in gasoline engines)
mThe adiabatic temperature rise is:
´ *
U " ´

" ë
 
  

   2

 m

 
m Definitions
m Flammability
m Flash Points
m Flammability limits
m Mixtures
m Temperature Dependence
m Pressure Dependence

m Minimum Oxygen Concentration

m Minimum Ignition Energy
m Adiabatic Compression
m Ignition Sources
 d 

m Ignition sources are free!!!
m Table 6-3 gives the
results of a study by
Factory Mutual
Engineering Corporation
who studied over 25,000
industrial fires to
determine the source of
ignition.
 d

ôhat is the UFL of a gas mixture composed of 1%
methane, 2% ethane and 3% propane by volume
at 50°C and 2 atmospheres:
Data:
Component Mô Ôeat of Combustion
(kcal/mol)
Methane 16.04 212.79
Ethane 30.07 372.81
Propane 44.09 526.74
  
mProcedure:
mCorrect for temperature
mCorrect for pressure (only for UFL)

mFind for mixture.

  
m Correction for Temperature : UFL from Table 6-1
1
' Y  ^ñ ë ^+ „*
,+ñ +! 4 

  ^+ ë *+ „*
,++! 4 *, ë *

1  ^+ ë *+ „*
,++! 4 , * ë **

  ^+ ë + „*
,++! 4 +
, ë  
  
mCorrection for Pressure (UFL only)
1
'+ Y ^¬ ë ^


&* ¬
*!
U **
¬ U ¬
¬ ë „
   ë  ¬

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mMixture calculation
6):
;6
  
2
6 **

,
 
7
 +

22

mEquation 6-2 for mixtures

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*
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Since total combustibles in air 1+2+3=6 < 18 then

the system is in the combustible range (below
UFL)