Fires and Explosions

Fires and Explosions

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

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
 Introduction
 We have been talking about source models for
the release of materials and about dispersion
models if the material is a toxicant.
Another concern is a release of flammable
materials where we need to worry about fires and
explosions.
 Fire Triangle
 Most are familiar with the Fire
Triangle.
 In order for a fire to start or be
sustained you need to have a
Fuel, an oxidizer and an
ignition source.
 If one of the three
components is eliminated,
then there will not be a fire (or
explosion)
 Fuel
 Fuel must be present in certain concentrations.
 Typical cases where fuel occur are if there is a leak,
during filling operations, transfer operations, or
excessive dusts.
 Although we often cannot always eliminate these
sources we can help by having good ventilation to keep
vapors from building up.
 Often we locate things out-doors, use grating on floors
so vapors don’t build up.
 Oxidizers
Oxygen is the most common oxidizer, especially
that found in ambient air.
For oxygen, we often use “inerting” with nitrogen,
helium blankets over flammable materials to
reduce O2 content below that where you can
have combustion.
 Ignition Sources
Heat is a common ignition source.
“Ignition sources are free!!!”
Although 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.
 Fire Tetrahedron
 The fire tetrahedron or fire
pyramid adds a fourth
component—chemical chain
reaction—as a necessity in
the prevention and control of
fires.
 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
 Definitions
Combustion – 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.
 Explosions
 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
 Explosions
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.
 Explosions
 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.
 Fires and Explosions
 Definitions
 Flammability
 Flash Point
 Flammability limits
 Mixtures
 Temperature Dependence
 Pressure Dependence

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
 Flammability
Flash 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.
Needs to be determined experimentally.
Different
methods to determine, open cup and closed
cup. Open cup is usually a few degrees higher.
 National Fire Protection Association
Flammability classification
Flammable IA – Flash point < 73°F, boiling point < 100 °F
Flammable IB – Flash point < 73°F, boiling point > 100 °F
Flammable IC – 73°F < Flash point < 100 °F
Combustible II – 100 °F < Flash point < 140 °F
Combustible IIIA – 140 °F < Flash point < 200 °F
Combustible IIIB – Flash point > 200 °F
 Mixture Flash Points
Flash 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.
For mixtures:
 Determinethe temperature at which the vapor pressure of
the flammable in the liquid is equal to the pure component
vapor pressure at its flash point.
 Mixture Flash Points
Example
 Methanol FP=54°F, Vapor Pressure @ 54°F is 62 mmHg
Determine the flash point of a solution that is 75wt% MeOH in
water.
Solution:
Since only one component is flammable, can estimate
mixture FP:
Mixture Flash Point Example Continued
Raoult's Law
P  xP sat
P 62mmHg
P  
sat
 98.4mmHg
x 0.63
Now need the temperature that corresponds
to this P sat . Use Antoine's equation (Append II)

ln  P   A 
sat B
C T
T in Kelvin, P sat in mmHg
Mixture Flash Point Example Continued
Rearrange
B
T sat
C
A - ln P
From Appendix II
A is 18.5875
B is 3626.55
C is -34.29
3626.55
T  34.29  293.36 K
18.5875  ln  98.4 
T  20.21C  68.4 F
Flammability Limits
 There is usually a range
of compositions of a
flammable vapor and air
where combustion occurs.
 Too little fuel (lean
mixture) not enough fuel
to burn.
 Too much fuel (rich
mixture) not enough
oxygen to burn
 Flammability Limits
Table 6-1 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 youhave a mixture of flammable components
you can calculate Lower Flammability Limit of the
mixture LFLmix using Le Chatelier’s relationship:
1
LFLmix  n
yi

i 1 LFLi

LFLi is flammability limit for component i

yi is mole fraction of i on combustible basis
n is the number of combustible species
 Mixture Flammability Limits
You can also calculate an Upper Flammability
Limit of the mixture UFLmix using Le Chatelier’s
relationship:
1
UFLmix  n
yi

i 1 UFLi
Flammability Limits – Temperature effect

Table 6-1gives 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
 Fires and Explosions
 Definitions
 Flammability
 Flash Points
 Flammability limits
 Mixtures
 Temperature Dependence
 Pressure Dependence

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
Minimum Oxygen Concentration
(MOC)
 LFL is based on “air” but actually it is O2 that is
important. Often in industry they “inert” to dilute
the O2 concentration.
 Below the MOC the reaction cannot generate
enough energy to heat the entire mixture to the
extent required for self propagation.
 MOC
 Moles Fuel   Moles O 2 
MOC    
 Moles Fuel & Moles Air  Moles Fuel 
 Moles O 2 
MOC  LFL  
 Moles Fuel 
Need to balance stoichiometry
Cm H xO y  zO2  mCO2  x H 2O
2
x y
z m 
4 2
 Moles O 2 
z 
 Moles Fuel 
 Fires and Explosions
 Definitions
 Flammability
 Flash Points
 Flammability limits
 Mixtures
 Temperature Dependence
 Pressure Dependence

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
 Minimum Ignition Energy (MIE)
Minimum energy input needed to initiate combustion
Most hydrocarbons have low MIE~0.25 mJ
Whereas the “spark” from walking across the room is
22mJ (almost 100X too much)
Again, we always assume that an ignition source will
exist
Table 6-2 gives MIEs for some substances
 Fires and Explosions
 Definitions
 Flammability
 Flash Points
 Flammability limits
 Mixtures
 Temperature Dependence
 Pressure Dependence

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
 Adiabatic Compression
 When gases are compressed they heat up and
can ignite (this is how a diesel engine works, also
the cause of “knocking” in gasoline engines)
The adiabatic temperature rise is:
 1
 Pf 
T f  Ti  
 Pi 
T and P absolute
 Fires and Explosions
 Definitions
 Flammability
 Flash Points
 Flammability limits
 Mixtures
 Temperature Dependence
 Pressure Dependence

 Minimum Oxygen Concentration

 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
 Ignition Sources
 Ignition sources are free!!!
 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.
 In Class Problem
What 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 MW Heat of Combustion
(kcal/mol)
Methane 16.04 212.79
Ethane 30.07 372.81
Propane 44.09 526.74
 Solution
Procedure:
Correct for temperature
Correct for pressure (only for UFL)

Find for mixture.

 Solution
 Correction for Temperature : UFL from Table 6-1
Eq. 6-4  UFLT  UFL25 1  0.75(T  25) / H c 
Methane UFL50  15 1  0.75(25) / 212.79   16.32
Ethane UFL50  12.5 1  0.75(25) / 372.81  13.13
Propane UFL50  9.5 1  0.75(25) / 526.74   9.84
 Solution cont.
Correction for Pressure (UFL only)
Eq. 6-5  UFLP  UFL  20.6(log10 P  1)
 101kPa   MPa 
P   2atm      0.202 MPa
 atm   1000kPa 
UFL2 atm  UFL1atm  20.6(log10 (0.202 MPa )  1)
UFL2 atm  UFL1atm  6.290
UFLMethane  22.61
UFLEthane  19.40
UFLPropane  16.13
 Solution cont.
Mixture calculation
Mixture Vol% Mol frac Comb
Methane 1 0.1667
Ethane 2 0.3333
Propane 3 0.5000
Combustibles 6
Equation 6-2 for mixtures
1
UFLmix  n
yi

i 1 UFLi
 Solution Continued
1
UFLMixture   18.0vol %
0.1667 0.3333 0.5
 
22.61 19.40 16.13

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

the system is in the combustible range (below
UFL)