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 dont 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
componentchemical chain
reactionas 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 < 73F, boiling point < 100 F

Flammable IB Flash point < 73F, boiling point > 100 F
Flammable IC 73F < 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:
Determine

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.

Mixture Flash Points

Example
Methanol

FP=54F, Vapor Pressure @ 54F 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
sat
P
98.4mmHg
x
0.63
Now need the temperature that corresponds
to this P sat . Use Antoine's equation (Append II)
B
ln P A
C T
T in Kelvin, P sat in mmHg
sat

Mixture Flash Point Example Continued

Rearrange
B
T
C
sat
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 20.21C 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 you

have a mixture of flammable components

you can calculate Lower Flammability Limit of the
mixture LFLmix using Le Chateliers relationship:
LFLmix

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 Chateliers
relationship:
UFLmix

1
n

yi

i 1 UFLi

Flammability Limits Temperature effect

Table 6-1

gives flammability limits for 25C 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 O2
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 O2
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:

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 50C and 2 atmospheres:
Data:
Component
Methane
Ethane
Propane

MW

Heat of Combustion

16.04
30.07
44.09

(kcal/mol)
212.79
372.81
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
Ethane

1
2

0.1667
0.3333

Propane

0.5000

Combustibles 6

Equation 6-2

for mixtures
UFLmix

1
n

yi

i 1 UFLi

Solution Continued
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)