Fires and Explosions

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The Fire Triangle
 Fuels:
 Oxidizers – Liquids
– Liquids  gasoline, acetone,
– Gases ether, pentane
 Oxygen, – Solids
fluorine, chlorine
 plastics, wood dust,
 hydrogen fibers, metal
peroxide, nitric
acid, perchloric particles
acid – Gases
– Solids  acetylene, propane,
 Metal peroxides, carbon monoxide,
ammonium hydrogen
nitrate  Ignition sources
 Sparks, flames, static
electricity, heat
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Fires and Explosions
 Definitions
 Flammability
– Flash Point
– Flammability limits
– Mixtures
– Temperature Dependence
– Pressure Dependence
 Minimum Oxygen Concentration
 Minimum Ignition Energy
 Adiabatic Compression
 Ignition Sources
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.
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
Flammability Relationships

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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=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
 Ifyou have a mixture of flammable
components you can calculate Lower
Flammability Limit of the mixture
LFLmix using Le1Chatelier’s
LFLmix  n
relationship: 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
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 6-1 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
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.
Flash Point From Vapor
Pressure
 Most materials start to burn at 50% stoichiometric
 For heptane:
– C7H16 + 11 O2 = 7 CO2 + 8 H2O
– Air = 11/ 0.21 = 52.38 moles air /mole of
C7H16 at stoichiometric conditions
– At 50% stoichiometric, C7H16 vol. % @ 0.9%
– Experimental is 1.1%
– For 1 vol. %, vapor pressure is 1 kPa
temperature = 23o F
– Experimental flash point temperature = 25o F
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Flammability LOC
Limiting O2
Concentration:
Vol. % O2 below
Diagram which combustion
can’t occur
1 Atmosphere
25°C

FLAMMABLE
HEL
MIXTURES

LEL

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Flammability LOC
Limiting O2
Concentration:
Vol. % O2 below
Diagram which combustion
can’t occur
1 Atmosphere
25°C

HEL

FLAMMABLE
MIXTURES

LEL

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Flammable Limits Change
With:

Inerts

Temperature

Pressure

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Effect of Temperature on
Lower Limits of Flammability

L
E
L,
%

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Effect of Pressure of
Flammability
Natural Gas, volume%

HEL

Natural Gas In Air at 28oC

LEL

Initial Pressure, Atm.

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Minimum Ignition Energy
 Lowest amount of energy required
for ignition
– Major variable
– Dependent on:
 Temperature
% of combustible in combustant
 Type of compound

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Minimum Ignition Energy

Effects of Stoichiometry

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Autoignition Temperature
 Temperature at which the vapor ignites
spontaneously from the energy of the
environment

 Function of:
– Concentration of the vapor
– Material in contact
– Size of the containment

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Flammability Relationships
CONCENTRATION OF FUEL

AUTO
IGNITION
MIST
FLAMMABLE
FLAMMABLE REGION
REGION

TEMPERATURE AIT
FLASH POINT AIT
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Autoignition Temperature
Material Variation Autoignition
Temperature
Pentane in air 1.50% 1018 °F
3.75% 936 °F
7.65% 889 °F
Benzene Iron flask 1252 °F
Quartz flask 1060 °F
Carbon disulfide 200 ml flask 248 °F
1000 ml flask 230 °F
10000 ml flask 205 °F
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Autoignition Temperature

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Auto-Oxidation
 The process of slow oxidation with accompanying
evolution of heat, sometimes leading to autoignition if
the energy is not removed from the system

 Liquids with relatively low volatility are particularly

susceptible to this problem

 Liquids with high volatility are less susceptible to

autoignition because they self-cool as a result of
evaporation

 Known as spontaneous combustion when a fire

results; e.g., oily rags in warm rooms; land fill fires
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Adiabatic Compression
 Fuel and air will ignite if the vapors are
compressed to an adiabatic temperature
that exceeds the autoignition temperature

 Adiabatic Compression Ignition (ACI)

 Diesel engines operate on this principle;

pre-ignition knocking in gasoline engines

 E.g.,flammable vapors sucked into

compressors; aluminum portable oxygen
system fires
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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 37/61
More Definitions
 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.
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Classification of Explosions
Rapid Equilibration of High Pressure
EXPLOSION = Gas via Shock Wave

Physical Explosions Chemical Explosions

Uniform Reactions Propagating Reactions

Thermal Detonations Deflagrations

Explosions (Shock Wave) (Normal
Transport)

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Potential Energy

Stored Volumes of Ideal Gas at 20° C

PRESSURE, psig TNT EQUIV., lbs. per ft3

10 0.001
100 0.02
1000 1.42
10000 6.53

TNT equivalent = 5 x 105 calories/lbm

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Deflagration
 Combustion with flame speeds at non-
turbulent velocities of 0.5 - 1 m/sec.
 Pressures rise by heat balance in fixed
volume with pressure ratio of about 10.
CH4 + 2 O2 = CO2 + 2 H2O + 21000 BTU/lb
Initial Mols = 1 + 2/.21 = 10.52
Final Mols = 1 + 2 + 2(0.79/0.21) = 10.52
Initial Temp = 298oK
Final Temp = 2500oK
Pressure Ratio = 9.7
Initial Pressure = 1 bar (abs)
Final Pressure = 9.7 bar (abs)
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Detonation

 Highly turbulent combustion

 Very high flame speeds
 Extremely high pressures >>10 bars

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Pressure vs Time
Characteristics
DETONATION
OVERPRESSURE

VAPOR CLOUD DEFLAGRATION

TIME

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CONSEQUENCES

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Bayway, NJ
H-Oil Incident 1970

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Two Special Cases
 Vapor Cloud Explosion

 Boiling
Liquid /Expanding Vapor
Explosion

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 U V C E
N A L X
C P O P
O O U L
N R D O
F S
I I
N O
E N
D S

 An overpressure caused when a gas cloud

detonates or deflagrates in open air rather than
simply burns.

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What Happens to a Vapor Cloud?
 Cloud will spread from too rich, through flammable
range to too lean.

 Edges start to burn through deflagration (steady state

combustion).

 Cloud will disperse through natural convection.

 Flame velocity will increase with containment and

turbulence.

 If velocity is high enough cloud will detonate.

 If cloud is small enough with little confinement it cannot

explode.
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What Favors Hi Overpressures?
 Confinement  Large Vapor Clouds
– Prevents escape, – Higher probability of
increases turbulence finding ignition source;
more likely to generate
 Cloud composition overpressure
– Unsaturated molecules
– ‘all ethylene clouds  Source
explode’; low ignition
energies; high flame – Flashing liquids; high
speeds pressures; large, low or
downward facing leaks
 Good weather
– Stable atmospheres,
low wind speeds
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Impact of VCEs on People
Peak Equivalent
Overpressure Wind Velocity Effects
psi mph
1 Knock personnel down
2 70
5 160 Rupture eardrums
10 290
15 Damage lungs
20 470
30 670
35 Threshold fatalities
50 940 50% fatalities
65 99% fatalities
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Impact of VCEs on Facilities
Peak
Overpressure Typical Damage
psi
0.5-to-1 Glass windows break
1-to-2 Common siding types fail:
- corrugated asbestos shatters
- corrugated steel panel joints fail
- wood siding blows in
2-to-3 Unreinforced concrete, cinder block walls fail
3-to-4 Self-framed steel panel buildings collapse
Oil storage tanks rupture
5 Utility poles snap
7 Loaded rail cars overturn
7-8 Unreinforced brick walls fail

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Vapor Clouds and TNT
 World of explosives is dominated by TNT impact
which is understood.
 Vapor clouds, by analysis of incidents, seem to
respond like TNT if we can determine the
equivalent TNT.
 1 pound of TNT has a LHV of 1890 BTU/lb.
 1 pound of hydrocarbon has a LHV of about 19000
BTU/lb.
 A vapor cloud with a 10% efficiency will respond
like a similar weight of TNT.
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Multi-Energy Models
 Experts plotted efficiency against vapor cloud
size and … reached no effective conclusions.
Efficiencies were between 0.1% and 50%
 Recent developments in science suggest too
many unknowns for simple TNT model.
 Key variables to overpressure effect are:
– Quantity of combustant in explosion
– Congestion/confinement for escape of combustion
products
– Number of serial explosions
 Multi-energy model is consistent with models
and pilot explosions. 56/61
 B L E V E
O I X A X
I Q P P P
L U A O L
I I N R O
N D D S
G I I
N O
G N
S

 The result of a vessel failure in a fire and

release of a pressurized liquid rapidly into
the fire
 A pressure wave, a fire ball, vessel
fragments and burning liquid droplets are
usually the result 57/61
BLEVE

FUEL
SOURCE

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BLEVE Video Clip

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Distance Comparison
INVENTORY UVCE BLEVE FIRE
(tons)
1 120 18 Distance
2 150 36 in Meters
5 200 60
10 250 90 20
20 310 130 30
50 420 200 36
100 530 280 50
200 670 400 60
500 900 600 100
1000 1150 820 130
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DESIGN for PREVENTION

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Eliminate Ignition Sources
 Fire or Flames  Typical Control
– Furnaces and Boilers – Spacing and Layout
– Flares – Spacing and Layout
– Welding – Work Procedures
– Sparks from Tools – Work Procedures
– Spread from Other Areas jkdj – Sewer Design, Diking,
dkdjfdk dkdfjdkkd jkfdkd fkd Weed Control,
fjkd fjdkkf djkfdkf jkdkf dkf Housekeeping
– Matches and Lighters – Procedures

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Eliminate Ignition Sources
 Hot Surfaces  Typical Control
– Hot Pipes and Equipment – Spacing
– Automotive Equipment – Procedures

 Electrical  Typical Control

– Sparks from Switches – Area Classification
– Static Sparks jkfdkd fjkdjd – Grounding, Inerting,
kdjfdkd Relaxation
– Lightning – Geometry, Snuffing
– Handheld Electrical – Procedures
Equipment

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Inerting – Vacuum Purging
 Most common procedure for inerting
reactors
 Steps
1. Draw a vacuum
2. Relieve the vacuum with an inert gas
3. Repeat Steps 1 and 2 until the desired oxidant
level is reached
 Oxidant Concentration after j cycles:

PL j
y  yo( ) where PL is vacuum level
j PH PH is inert pressure
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Inerting – Pressure Purging
 Most common procedure for inerting
reactors
 Steps
1. Add inert gas under pressure
2. Vent down to atmospheric pressure
3. Repeat Steps 1 and 2 until the desired oxidant
level is reached
 Oxidant Concentration after j cycles:

nL j
y  yo(n ) where nL is atmospheric moles
j H nH is pressure moles
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Vacuum? Pressure? Which?
 Pressure purging is faster because
pressure differentials are greater (+PP)

 Vacuum purging uses less inert gas than

pressure purging (+VP)

 Combining the two gains benefits of both

especially if the initial cycle is a vacuum
cycle (+ VP&PP)

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Other Methods of Inerting
 Sweep-Through Purging
– ‘In one end, and out the other’
– For equipment not rated for pressure, vacuum
– Requires large quantities of inert gas
 Siphon Purging
– Fill vessel with a compatible liquid
– Use Sweep-Through on small vapor space
– Add inert purge gas as vessel is drained
– Very efficient for large storage vessels

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Using the
Flammability
Diagram
1 Atmos.
25°C

FLAMMABLE
MIXTURES

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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

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Double-Layer Charging
 Streaming Current
– The flow of electricity produced by transferring
electrons from one surface to another by a
flowing fluid or solid
– The larger the pipe / the faster the flow, the
larger the current

 Relaxation Time
– The time for a charge to dissipate by leakage
– The lower the conductivity / the higher the
dielectric constant, the longer the time

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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
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Controlling
Static Electricity
GROUNDING

BONDING 72/61
Static Electricity – Real Life

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Explosion Proof Equipment
 Allelectrical devices are inherent ignition
sources

 Ifflammable materials might be present at

times in an area, it is designated XP
(Explosion Proof Required)

 Explosion-proof housing (or intrinsically-safe

equipment) is required

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Area Classification
Class I Flammable gases/vapors present
 National
Electrical Class II Combustible dusts present
Code (NEC) Class III Combustible dusts present but
defines area not likely in suspension
classifications Group A Acetylene
as a function Group B Hydrogen, ethylene
of the nature Group C CO, H2S
and degree of
Group D Butane, ethane
process
hazards Division 1 Flammable concentrations
normally present
present
Division 2 Flammable materials are
normally in closed systems
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VENTILATION
 Open-Air Plants
– Average wind velocities are often high enough to
safely dilute volatile chemical leaks

 Plants Inside Buildings

– Local ventilation
 Purge boxes
 ‘Elephant trunks’

– Dilution ventilation (1 ft3/min/ft2 of floor area)

 When many small points of possible leaks exist

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Summary
 Though they can often be reduced in
magnitude or even sometimes
designed out, many of the hazards
that can lead to fires/explosions are
unavoidable
 Eliminating at least one side of the
Fire Triangle represents the best
chance for avoiding fires and
explosions
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END of PRESENTATION

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