6.

FLAMMABILITY, FIRES & EXPLOSIONS

CH4101 Chemical, Biological & Plant Safety

Dr Foo Swee Cheng
 FIRE TRIANGLE
• Elements of fire
Air (Oxygen)
Fuel
Ignition Source
• FIRE
ALL SIDE CONNECTED
• NO FIRE
ANY SIDE MISSING

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 TERMS: Flammability Properties
• Autoignition temperature (AIT)
Self ignition by internal energy (temperature)
• Flash point (FlP): Saturated vapor flammable but
evaporation rate < combustion rate; fire terminated after
initial vapor present consummed
• Fire point (FP): evaporation rate = combustion rate; sustain
fire close to the liquid surface
• Flammable limits
LFL/ LEL: below which not enough vapor to sustain fire
UFL/ UEL: above which not enough O2 to sustain fire
• Combustion energy: Mist/ dust explosions
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 FLAMMABILITY PROPERTIES

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 DEFINITION

• Flash point: the lowest temperature of a liquid that can

give enough vapour to sustain a flash fire

• Fire point: the lowest temperature of a liquid that can

sustain fire above the liquid surface

• Autoignition temperature: Temperature of gas/vapor at

which self-ignition occurs without an ignition source

• Energy of Combustion: Energy released in combustion

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 MEASURING FLASH POINTS OF LIQUIDS

• Methods of experimental measurements

Open cup method
Closed cup method

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 FLASH POINT APPARATUS:
OPEN CUP METHOD

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FLAMMABILITY LIMITS

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 COMBUSTION CHEMISTRY

• Chemical reaction in combustion of methane

Methane reacts with oxygen to form carbon dioxide
and water releasing heat
Stoichiometric: CH4 + 2O2  CO2 + 2H2O
At stoichiometric condition: 2 moles of oxygen is
required to covert 1 mole of methane to carbon
dioxide & water

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STOICHIOMETRIC FUEL/OXYGEN CONCENTRATION
• Combustion of compound: CmHxOy
CmHxOy + zO2  mCO2 + (x/2)H2O
• CmHxOy contains:
m atoms of C  mCO2: m moles of O2 needed
x atoms of H  (x/2)H2O: x/4 moles of O2 needed
y atoms of O  provides y/2 moles of O2
• Oxygen balance: y/2 + z = m + x/4 ; z = m + x/4 – y/2
• Moles of fuel-air mixture for 1 mole of fuel
1 fuel + z Oxygen + (0.79/0.21)z nitrogen = 1 + z/0.21
% of fuel: Cst = 100/(1+z/0.21)
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 FLAMMABILITY LIMITS (1): GASES & VAPOURS
• Experimentally measurements: Confined explosion in vessel
• FL: Depends on T, P, O2/inert gas (N2, CO2, He etc) content
» See eqns 6-4, 6-5, 6-6 & Table 6-2

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 FLAMMABILITY LIMITS (3)
• Estimating flammability limits:
CmHxOy + zO2  mCO2 + (x/2)H2O
z (moles of O2 per mole of fuel) = m + x/4 - y/2
Cst (vol % of fuel in air-fuel mixture) = 100/(1 + z/0.21)
• LFL = 0.55Cst
• UFL = 3.50Cst
• OR

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EXAMPLE 1: ESTIMATE FLAMMABILITY LIMITS

• Estimate the flammability limits of ethylene

SOLUTION 1
• C2H4 + 3O2  2CO2 + 2H2O
• Cst = 100/(1+3/0.21) = 6.542
LFL = 0.55(6.542) = 3.6% (Literature: 3.1%)
UFL = 3.50(6.542) = 22.9% (Literature: 32%)
• Agree well in LEL, but larger discrepancy in UFL
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FLAMMABILITY LIMITS OF VAPOUR MIXTURES

• Le Chatelier equations
ILEL = Σ(Ci/LELi) = 100/LELmix
IUEL = Σ(Ci/UELi) = 100/UELmix
Concentration, Ci is in %
Eqns (6 – 2), (6 – 3)

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 EXAMPLE 2: MIXTURE of FLAMMABLES

• A gas mixture of 30 mole % ethyl ether, 20 mole % ethyl

acetate and 50 mole % nitrogen.
Determine LELFmix & UELFmix
Is the mixture flammable when release?
• Given:
Ethyl ether: LEL: 1.7% UEL: 48%
Ethyl acetate: LEL: 2.2% UEL: 11.5%

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 SOLUTION 2
• Flammable mixture: 30% Ethyl ether & 20% Ethyl acetate
 CFmix = 30% + 20% = 50%
 LEL index: ILEL = ∑(C/LEL)i = 30/1.7 + 20/2.2 = 26.7
 UEL index: IUEL = ∑(C/UEL)i = 30/48 + 20/11.5 = 2.4
 Flammable limits: CFmix/(Flammability index)
LELFmix = (∑Ci)/ILEL = 50/26.7 = 1.9
UELFmix = (∑Ci)/IUEL = 50/2.4 = 21.1
• CFmix > LELFmix : mixture flammable in air

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FLAMMABILITY DIAGRAM

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 EXAMPLE 3: FLAMMABLE ZONE

• Draw the flammability zone for ethylene

• Combustion equation
C2H4 + 3O2  2CO2 + 2H2O
• Flammable limits
LFL = 3.1%
UFL = 32%

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 SOLUTION 3 ethylene

• Draw stoichio line

 100z/(1+z) = 100*3/(3+1) = 75
• Draw air line
• Locate LEL & UEL on air line
• Draw line from LEL point
// to N2 axis to meet the
stoichio line at W

• Connect UEL point to

point W UEL X
75
• Flammability zone
∆(UEL, LEL,W)
Stoichiometric line
LEL
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O2 W N2
 FLAMMABLE ZONES ethylene

• FL in pure O2: see Table 6-2

 LOL: 3.0% A
X
 UOL: 80%
• Flammable zone
 O2 rich zone
A-B-LEL-UEL-A
 O2 poor zone
LEL-W- UEL-LEL
UEL X
75

Stoichiometric line
BX W
LEL
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O2
N2
 INERTING
• Adding inert gas to reduce O2 to below LOC
 General practice: Residual O2 < (LOC – 4)
• LOC: Limiting oxygen concentration
 Max O2 level in fuel that will not support fire
• OSFC: Out-of-service fuel concentration
 Max fuel concentration allowed in the empty vessel when taking
a vessel out of service & before allowing air to enter the vessel.
• ISOC: In-service oxygen concentration
 Max oxygen concentration allowed in the empty vessel when
bringing a vessel into service & before allowing tank filling to
begin.

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 CH4O
EXAMPLE 4: METHANOL (1) B
• CH4O + 1.5O2  CO2 + 2H2O
LOC
• LEL: 7.3 & UEL: 36
• z/(z+1) = 1.5/2.5 = 60%
• LOC: M
 On chart: 10.5
 Table: 10 (Pg 239)
• LOC = zLEL
X
 1.5*7.3 = 11.0
• VP@30oC: 21.9 kPa
• Sat. C = 21.6% M

O2 A N2
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 CH4O
EXAMPLE 4: METHANOL (2) METHANOL
B VP@20oC: 12.3 KPa
Sat. C: 12.2%
• OSFC: A – M – S VP@30oC: 21.9 kPa
Sat. C = 21.6%
 On chart, S: 15.5
 Table: 15.0 (pg304)
• OSFC = LEL/(1 – z*LEL/21)
 7.3/(1 – 1.5*7.3/21)
= 15.3
• VP@30oC: 21.9 kPa X

• Sat. C = 21.6%
x
S OSFC

M
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 CH4O
EXAMPLE 4: METHANOL (3) B

• ISOC: B – M – R
 On chart, R: 11
 Table: 10.8 (pg304)
• ISOC = zLEL/(1 – LEL/100)
ISOC = 1.5*7.3/(1-7.3/100)
ISOC = 11.8
X

O2 A R N2
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ISOC
 FLAMMABILITY & COMBUSTIBILITY
• Flammable materials: give enough vapor to sustain fire at ambient
temperature (e.g. gas & low flash point liquids)
• Combustible materials: give enough vapor to sustain fire after
heated above the ambient temperature (e.g. solids & high flash
point liquids)
• Ambient temperature is not constant & varies with times of day/
seasons/ geographical locations
• Classifications: Legal/ consensus
 International: GHS/ UNDG
 Professional: NFPA/ SPRING/ API
 Legal: OSHA/ SCDF

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 FLAMMABILITY & EXPLOSIBILITY
Vapors, Mists, Sprays
• Excluding explosives, airborne flammable/ combustible vapors, mists &
dusts can cause fires & explosions
 Vapor cloud fire (VCF)/ Flash fire & vapor cloud explosion (VCE)
Cloud concentration > LEL
 Mist/ Dust cloud explosion: µ-size aerosols behave like molecules
Combustible materials with size < 200 µ; through 70 mesh
Mist concentration > LEL/10 with or without vapor presence
Hazardousness: Depends on heat of combustion (Hc), higher Hc
more hazardous
 Spray (Large, size > 600 µ; through 30 mesh): Jet fires

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 DUST CLOUD EXPLOSIONS

• The dust must be combustible and release enough heat when it burns
to sustain the fire.
• The dust must be capable of being suspended in air.
• The dust must have a particle size capable of spreading the flame.
• The concentration of the dust suspension must be within the
explosible range.
• An ignition source must be in contact with the dust suspension.
• The atmosphere must contain sufficient oxygen to support and sustain
combustion.
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FIRE AFTER IGNITION

Northgate
Building fire

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 AFTER FIRE

Tank 912
overfilled
Northgate
Building

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 VCE DAMAGE

Northgate Building

Fuji Building

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 VAPOUR/ DUST CLOUD FIRE & EXPLOSION
• VCF: Flash fire occurs when vapor cloud is ignited in open
areas; produces low explosion overpressure
• VCE: Explosion occurs due to pressure builds up during
vapor cloud fire in confined or congested areas where
flame front moves at supersonic speed; produces high
explosion overpressure
• VCE overpressure produced depends on
Amount of flammable vapor/ dust involved
Degree of confinement
Obstacle density
Type of ignition source
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 FIRES & EXPLOSIONS: Gas & Vapor Release

• BLEVE: Boiling Liquid and Expanding Vapor Explosion

 Liquid vessel heated: e.g. Fire outside vessel
 Pressure > maximum allowable working pressure
 Vessel explosive rupture under pressure
• Mechanical explosion + Rapid vaporization + immediate ignition
 Vapor: Fireball & Liquid: pool fire
• Mechanical explosion + Rapid vaporization + Delayed ignition
 Vapor dispersion: VCE + flash fire

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COMMON FIRE & EXPLOSION ACCIDENTS

• Confined explosions
Within building: 35%
Within process vessels
Air ingress: 16%
Decomposition/runaway reactions: 34%
• Unconfined explosions
Catastrophic vessel failure: 10%
UCVCE: 5%
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 FIRE & EXPLOSION PREVENTION
• Prevention: prevent ignition
 Ventilation: prevent build up of flammable vapor cloud by dilution
 Inerting: reduce oxygen concentration < LOC
 Isolation: Isolate fuel from ignition sources: flame arrestors/
intrinsically safe (low energy)/ explosion proof equipment &
instruments/ prevent intrusion of mobile ignition sources/ prevent
build-up of static electricity
 Cooling/ thermal radiation shielding: Sprinkler systems/ water
curtains
• Mitigation: extinguish the fires
 Sprinkler systems
 Foam systems
 Emergency preparedness/ management systems
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 PREVENTING FIRES & EXPLOSIONS
• Inerting methods
 Vacuum purging: remove vapors or O2 using vacuum, then fill
space with inert gas in cycles
 Pressure purging: pad/inert gas is added under pressure &
purge in cycles
 Sweep-through purging: continuous adding inert gas &
withdrawing mixed vapor simultaneously
• Operation processes need inerting
 Taking tank out of service: OSFC; eqns (7-16) & (7-17)
 Placing a tank into service: ISOC; eqns (7-18) & (7-19)
Conservative: use LOC instead of ISOC

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 STATIC ELECTRICITY
• Charge separation at interfaces
 Helmholtz / Electrical double layer
• http://www.youtube.com/watch?v=QxZ6AWLpnUw&hl=en-GB&gl=SG

–++– –
+
+
–
–+ ––
– + – +
+– –+ + –– +– –
–+– –– – –
+ + +
–
–
–
– Electron
leakage

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STATIC ELECTRICITY: Charge Accumulation Priciples
• Contact & frictional charging
 Conveying belts; Sieving; grinding: Table 7-3; eqn (7-23)
• Double layer charging
 Liquid interface: liquid-solid; liquid-liquid; liquid-gas
 e.g. Liquid through pipe: Streaming current, IS; eqn (7-21)
Charge build-up: Q = ISt ; eqn (7-28)
• Induction charging
 An electrically neutral object approaches a charged object,
making one-side of the object positively and the other side
negatively charged
• Charging by transport
 Settling of charge drops on an object

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 CONTROLING STATIC ELECTRICITY HAZARDS
• Reduce generation: Is (µA) = 10(ud)2
 Limit flow velocity: ud < 0.5 m2/s
• Increase dissipation: increase conductivity of liquid
 Add ions to increase γc , therefore τ decreases
• Prevent accumulation: discharge capacitors formed by equipment
 Tank made of conducting material & Earthing
• Prevent voltage difference: reduce potential differences
 Make voltage between equipment the same: Bonding
• Tank made of conductive material
 Non-conductive tank: very hazardous
Charges of different sign may presence on tanks
Slow charge dissipation

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VAPOR CLOUD EXPLOSION MODELS

• TNT Model
• TNO Multi-Energy Model
• Baker – Strehlow
• CFD: Computational Fluid Dynamics

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 ESTIMATE EXPLOSION ENERGY
• Eex = αW(HC)
Eex = Explosion energy, J
W = Total mass of fuel in the cloud, kg
HC = Heat of combustion on a mass basis, kJ/kg
α = Efficiency factor
Hydrocarbons: 0.04
Highly reactive substances: 0.10
Class 1: α = 0.05 (propane, butane, flammable liquids)
Class 2: α = 0.10 (ethylene, ethers)
Class 3: α = 0.15 (acetylene)
• Typical Eex per unit cloud volume = 3.5(103) kJ/m3
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 TNT MODEL

• TNT equivalent (kg): MTNT = Eex/HTNT

• Where
HTNT = TNT blast energy (5420 kJ/kg)

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 SCALED DISTANCE
• Scaled Distance: Ze or R = R/(MTNT)1/3
R: actual distance from center of explosion to receptor , m

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 TNT MODEL
• Scaled overpressure: Ps = Po/Pa
• Scaled positive phase duration: τd = tp/(W)1/3
• Scaled arrival time: τa = ta/(W)1/3
• Scaled impulse: is = ip/(W)1/3
Po = side-on absolute blast overpressure (Pa)
Pa = ambient pressure (Pa)
R = distance from blast (m)
ip = Potp/2
ta = arrival time (s) Po
tp = positive phase duration (s)
ip = impulse pressure (Pa) Pa tp
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 ALOHA CONSEQUENCE ANALYSIS SOFETWARE
 CAMEO software suite: http://www2.epa.gov/cameo/what-cameo-
software-suite
 Downloading, Installing, and Running ALOHA:
http://www2.epa.gov/cameo/cameo-downloading-installing-and-
running-aloha
 ALOHA is an atmospheric dispersion model
 Evaluating releases of hazardous chemical vapors
 Estimate the downwind dispersion
 Estimate threat zones
Toxic gas clouds
Fires
Explosions
 LEARNING OBJECTIVES

• Able to understand the properties of flammable

substances to prevent fires and explosions
• Able to understand & apply the prevention & mitigation
techniques to control the consequence of fire & explosion
in workplace
• Able to determine the vapor cloud explosion
consequence

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END

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