Fires

• Fires, explosions & toxic releases

• Organic solvents : most common sources
of fires and explosions in chemical
industry; losses due to fires & explosions
are substantial; 300 million USD 1997
• Engineers must be familiar with
- the fire & explosion properties of materials
- nature of fire & explosion process
- procedures to reduce f & e hazards
 Fire Triangle
• Essential elements for combustion
-fuel
-oxidizer
-ignition source
Fire: When all sides are
Connected.
No Fire: When anyone side is
missing
 Fire
• Fire (combustion, burning): is the
exothermic oxidation of fuel. Part of
energy released is used to sustain
reaction.
• Fuel: solid, liquid or vapor form
• Combustion: always occur in vapor phase
• Liquids are volatized & solids are
decomposed into vapor before combustion
• Vapor & liquid fuels easy to ignite
 Fire
• Fire will not occur if
1. fuel is not present or is not present in
sufficient quantities
2. oxidizer is not present or is not present
in sufficient quantities
3. the ignition source is not energetic
enough to initiate the fire
 Contd.
• Fuels
Liquids: gasoline, organic solvents
Solids: plastics, wood dust, fibers, metal
particles
Gases: acetylene, propane, CO, H2
 Oxidizers
• Gases: O2, fluorine, chlorine
• Liquids: H2O2, HNO3, Perchloric acid
• Solids: Metal peroxides, ammonium nitrite

• Ignition sources: Sparks, flames, static

electricity, heat (elimination or reduction in
ignition sources; preventing flammable
mixtures)
 Fires & Explosions
• Distinction between fires & explosions is
the rate of energy release. Fires release
energy slowly while explosions release
energy very rapidly, typically of the order
of microseconds. Example: automobile
tire; compressed air within tire contains
energy.
• Fires can result from explosions &
explosions can result from fires.
 Flammability Characteristics
• Liquid fuels- Flash point (FP) is major
physical property used to determine fire &
explosion hazard. Determined
experimentally. Open cup & closed cup
• FP: of a liquid is the lowest temperature at
which it gives off enough vapors to form
an ignitable mixture with air
• At FP, the vapor will burn briefly
• Increases with increasing pressure
 Contd.
• Flash point : Open cup FP is few degrees
more than the closed cup; air movements
over the cup may change the vapor
concentration & may increase the exptly
determined flash point
• Fire point: Lowest temperature at which a
vapor above a liquid will continue to burn
once ignited; fire point temperature is
higher than the flash point
 Flash Point (liquids)
• Flash point temperatures for pure
materials correlate well with the boiling
point of liquid
• Flash point for pure components
determined experimentally
• Flash point can be estimated for
multicomponent mixtures if only one
component is flammable and if the flash
point of the flammable is known.
 Flash Point (liquids),contd.
• Flash point temp. is estimated by
determining the temperature at which the
vapor pressure of the flammable in the
mixture is equal to the pure component
vapor pressure at its flash point.
• Methanol has a FP of 54 F and its vapor
pressure at this temp is 62 mm Hg. What
is the flash point of a solution containing
75 % methanol and 25 % water by weight.
 Vapors
• Flammability limits (LFL & UFL): Vapor-air
mixtures will only ignite & burn over a well
specified range of compositions. The
mixture will not burn when the composition
is lower than the lower flammable limit
(LFL); the mixture is too lean for
combustion. The mixture is also not
combustible when the composition is too
rich i.e. above upper flammability limits
(UFL)
 Contd.
• A mixture is flammable only when the
composition is between LFL & UFL.
• Units for flammability limits are volume percent
fuel (percent of fuel plus air)
• Determined experimentally; vapor-air mixtures of
known concentration are added & then ignited.
Max explosion pressure is measured; repeated
with different concns to establish range of
flammability
 Vapor Mixtures
• LFLs & UFLs for mixtures are computed using
Le Chatelier equation

1
LFL mix =
∑ (yi / LFLi)

where LFL i is the lower flammability limit (in

vol%) for component i in fuel and air
y i is the mole fraction of component i on a
combustible basis
n number of combustible species
• Le Chatlier’s eqn is emperically derived
and is not universally applicable.
• The product heat capacities are constant
• The number of moles of gas is constant
• The combustion kinetics of pure species is
independent & unchanged by presence of
other combustible species
• The adiabatic temperature rise at the
flammability limits is same for all species
 Exercise
What is the LFL & UFL of a gas mixture of
0.8 % hexane, 2.0 % methane and 0.5 %
ethylene vol.
Vol. Mole fraction LFL UFL
% on combustible (vol%) (vol %)
Hex. 0.8 0.24 1.2 7.5
Meth. 2.0 0.61 5.0 15
Ethy. 0.5 0.15 2.7 36
Comb. 3.3 Air 96.7 (vol %)
 Exercise (contd.)
1
LFL =
(0.24 /1.2) + (0.61 / 5) + (0.15/2.7)
= 1/0.378 = 2.65 % by vol. total comb.
1
UFL =
(0.24 / 7.5) + (0.61 / 15) + (0.15 / 36)
= 13% by volume total combustibles
Since above mixture contains 3.3 % total
combustibles, it is flammable.
Flammability Limits-dependence
on temperature
• Flammability range increases with
temperature
• LFLT = LFL25 [ 1-0.75 (T-25) / Δ HC]
• UFLT = UFL25[1 + 0.75(T-25) / Δ HC]

Where Δ HC is the net heat of combustion

(kcal / mole)
T is the temperature, C
 Effect of pressure
• Normal variations of atm pr do not have
any appreciable effect on flammability limit
• A decrease in pr below atmospheric can
narrow the flammability range by raising
LFL and reducing UFL until the two limits
coincide and mixture becomes
nonflammable
 Effect of pressure (contd.)
• An increase in pressure above atm can
widen the flammable range by reducing
the LFL and raising the UFL
• Effect is more marked on UFL than LFL
 Flammability Limits
• Pressure has little effect on LFL except at
very low pressures (< 50 mm Hg absolute)
where flames do not propagate
• UFL increases significantly as pressure is
increased, broadening the flammability
range.
• UFLP = UFL + 20.6 (log P + 1)
• P is the pressure, (mega pascals absolute)
• UFL at 1 atm.
 Exercise
• If the UFL for a substance is 11% by
volume at 0.0 MPa gauge, what is the UFL
at 6.2 MPa gauge.
 Addition of Inerts
• Flammability limits affected by addition of
inert gas nitrogen, carbon dioxide or steam
• Carbon dioxide causes a greater
narrowing of flammability range than
nitrogen
• Mixtures can be made non-flammable by
addition of about 30 % of carbon dioxide
or about 40 % nitrogen.
 Exercise
• If the UFL for a substance is 11 % by
volume at 0.0 MPa gauge, what is the UFL
at 6.2 MPa gauge.
Absolute press. P = 6.2 + 0.101= 6.3 MPa
UFLP = UFL + 20.6 (log P + 1)
UFLP = 11 + 20.6 (log 6.301 + 1)
UFLP = 48 volume % fuel in air
 Flammability Limits
• Flammability limits are easily measured;
experimental determination is always
recommended.
• Estimation of flammability limits
• For many hydrocarbon vapors
• LFL = 0.55 CST UFL = 3.5 CST
• CST (stoichiometric concentration of fuel) is
volume % fuel in fuel plus air
 CST contd.
• CST is determined using general
combustion reaction
CmHxOy + z O2 = m CO2 + (x/2) H2O
z = m + (x/4) – (y/2)
units of z : moles O2/moles fuel
 CST
Moles fuel
• CST = X 100
Moles fuel + Moles air
100
=
1 + (Moles air / moles fuel)
 CST Contd.
100
• CST =
1 + (1 / 0.21)(moles O2 / moles fuel)
100
=
1 + (z / 0.21)
 CST Contd.
• Substituting the value of z
0.55 (100)
LFL =
4.76 m + 1.19 x – 2.38 y + 1
3.5 (100)
UFL=
4.76 m + 1.19 x – 2.38 y + 1
 Exercise
• Estimate the LFL & UFL for hexane
C6H14 + z O2 = m CO2 + (x/2) H20
m = 6 x= 14 y=0
LFL = 0.55 (100)/[4.76(6) + 1.19 (14) +1]
LFL = 1.19 volume % (exptl 1.2 volume %)
UFL = 3.5(100)/[4.76(6) + 1.19(4) + 1]
UFL = 7.57 volume % (exptl. 7.5 volume %)
 LOL and UOL
• Lower and Upper Oxygen Limits; percent
fuel in oxygen
• Flammable limits in pure O2 are frequently
used for designing systems to prevent f&e
• In general, most hydrocarbons LOL close
to LFL
• Estimate the UOL for methane
• UFL for methane is 15 vol % fuel in air
• UFLO = 0.21 x 85 = 17.85 %; 62.4% (61%)
 Minimum O2 Concn.
• Minimum oxygen concentration required to
propagate a flame. Below MOC , the
reaction can’t generate enough energy to
heat the entire mixture of gases to the
extent required for self propagation of
flame
• Units: percent moles of oxygen in total
moles (fuel plus air)
 Estimation of MOC
• Explosions and fires are preventable by
reducing the oxygen concentration.
• Basis for ‘inerting’
• If experimental data is not available,
Estimated using stoichiometry of
combustion reaction and LFL
 Estimation of MOC
• Estimate MOC for butane
C4H10+6.5 O2= 4CO2+ 5H2O LFL=1.8 % vol
MOC = (moles fuel/ (moles fuel + moles air))
x (moles O2 / moles fuel)
= LFL (moles O2/ moles fuel)
=(1.8moles fuel/(moles fuel + moles air)) x
(6.5 mole O2 / 1 mole fuel)=11.7 vol % O2
 Estimation of MOC
• MOC = z. LFL
• LOC = [(LFL – CLOCUFL)/(1-CLOC)]
(UFL0/UFL)
• LOC limiting O2 concn (%O2)
• UFLO O2 concn at upper flammability limit
(vol % O2 in air)
• CLOC fitting constant (- 1.11)
 Exercise
• Estimate the LOC for butane (LFL= 1.8%;
UFL = 8.5 %)
 Exercise
• Estimate LFL, UFL and MOC for pentane.
• Estimate the MOC of a mixture of 2 %
hexane (LFL= 1.2 vol %), 3 % propane
(LFL= 2.1 vol %) and 2 % methane (LFL=
5 vol %) by volume.