Chapter 6

Fires and Explosions

 Chemicals present a substantial hazard in the form of fires
and explosions
◦ combustion of one gallon of toluene destroy an ordinary chemistry
laboratory
• Three most common accidents are fires, explosions, and
toxic releases
• Prevent accidents engineers must be familiar
 The fire and explosion properties of materials,
• The nature of the fire and explosion process
• Procedures to reduce fire and explosion hazards
 Topics, emphasizing definitions and calculation methods for
estimating the magnitude and consequences of fires and explosions
 Essential elements for combustion are fuel,
an oxidizer, and an ignition source
 Elements are illustrated by the fire triangle
 Fire, or burning, is the rapid exothermic oxidation of an
ignited fuel
 Combustion always occurs in the vapor phase
 Ignition source are present at the necessary levels, burning
will occur
 Fire will not occur if
(1) fuel is not present or is not present in sufficient quantities,
(2) an oxidizer is not present or is not present in sufficient quantities
(3) the ignition source is not energetic enough to initiate the fire
• In past controlling fires was reduction in ignition sources

• Current practice is to prevent fires by continuing to eliminate

ignition sources while focusing efforts strongly on preventing
flammable mixtures.
 Various fuels, oxidizers, and ignition sources common in
the chemical industry are
Fuels
 Liquids: gasoline, acetone, ether, pentane
 Solids: plastics, wood dust, fibers, metal particles
 Gases: acetylene, propane, carbon monoxide, hydrogen
Oxidizers
 Gases: oxygen, fluorine, chlorine
 Liquids: hydrogen peroxide, nitric acid, perchloric acid
 Solids: metal peroxides, ammonium nitrite
Ignition sources
 Sparks, flames, static electricity, heat
 Distinction between fires and explosions is the rate of
energy release
 Fires release energy slowly,
 whereas explosions release energy rapidly
◦ order of microseconds
 Fires can also result from explosions, and explosions
can result from fires
 Combustion or fire: Chemical reaction in which a
substance combines with an oxidant and releases
energy
 Ignition: Flammable mixture coming in contact with
a source of ignition gas reaching a temperature
high enough to cause the gas to autoignite.
Autoignition temperature (AIT): Adequate energy is
available in the environment to provide an ignition
source.
Flash point (FP): lowest temperature at which it gives off
enough vapor to form an ignitable mixture with air
At the flash point the vapor will burn but only briefly

Inadequate vapor is produced to maintain combustion

◦ The open-cup flash point is a few degrees higher than the
closed-cup
Fire point: The fire point is the lowest temperature at which
vapor above a liquid will continue to burn once ignited

Flammability limits: Vapor-air mixtures will ignite and burn

only over a well specified range of compositions
 Mixture will not burn when the composition is lower than
the lower flammable limit (LFL)
 The mixture is also not combustible when the composition
is too rich, upper flammable limit (UFL)
 Units are volume percent fuel (percentage of fuel plus air)

 Lower explosion limit (LEL) and upper explosion limit

(UEL) are used interchangeably with LFL and UFL
Explosion: An explosion is a rapid expansion of gases
resulting in a rapidly moving pressure or shock wave.
◦ The expansion can be mechanical
◦ it can be the result of a rapid chemical reaction.
◦ Explosion damage is caused by the pressure or shock wave
Mechanical explosion: containing high-pressure non
reactive gas
Deflagration: An explosion in which the reaction front
moves at a speed less than the speed of sound in
the unreacted medium.
Detonation: An explosion in which the reaction front moves
at a speed greater than the speed of sound in the
unreacted medium
Confined explosion: An explosion occurring within a vessel
or a building, extensive damage
Unconfined explosion:
-Unconfined explosions occur in the open.
-The gas is dispersed and mixed with air until it comes
in contact with an ignition source.
-Unconfined explosions are rarer
Boiling-liquid expanding-vapor explosion (BLEVE):
 Vessel contains a liquid at a temperature above its atmospheric pressure
boiling point ruptures
 Explosive vaporization of a large fraction of the vessel contents, possibly
followed by combustion or explosion of the vaporized cloud if it is
combustible
Dust explosion: This explosion results from the rapid combustion of
fine solid particles
- metals such as iron and aluminium flammable when reduced to a
fine powder
Shock wave:
- An abrupt pressure wave moving through a gas
- A shock wave in open air is followed by a strong wind
- the combination of shock wave and wind is called a
blast wave. process is mostly adiabatic.
Overpressure: The pressure on an object as a result of an impacting
shock wave.
 Liquids: The flash point temperature

Tf is the flash point temperature (K),

a, b, and c are constants provided
Flash points for multicomponent mixtures:

Methanol has a flash point of 54°F, and its vapor pressure at this
temperature is 62 mm Hg. What is the flash point of a solution containing
75% methanol and 25% water by weight?
Solution: for
methanol
 Using a graph of the
vapor pressure versus
temperature, shown in
Figure ,
 the flash point of the
solution is 20.5°C,
Gases and Vapors: Flammability limits for vapors are
determined experimentally in a specially designed
closed vessel apparatus
- Vapor-air mixtures of known concentration are
added and then ignited
- The maximum explosion pressure is measured
Vapor Mixtures
 LFLs and UFLs for mixtures are needed
 These mixture limits are computed using the Le Chatelier
equation:

yi is the mole fraction of component i on a

combustible basis
n is the number of combustible species.
UFLi is the upper flammable limit for component i

Le Chatelier’s equation is empirically derived

What are the LFL and UFL of a gas mixture composed of 0.8%
hexane, 2.0% methane, and 0.5% ethylene by volume
Solution:

Because the mixture contains 3.3% total combustibles,

it is flammable.
In general, the flammability range increases with temperature

ΔHc is the net heat of combustion (kcal/mole)

T is the temperature (°C)

Flammability Limit Dependence on Pressure

Pressure has little effect on the LFL except at very low

pressures (<50 mm Hg absolute)

P (megapascals absolute) and

UFL (volume % of fuel plus air at 1 atm).
 Experimental determination is always recommended
 Flammability limits without experimental data
 Many hydrocarbon vapors the LFL and the UFL are a
function of the stoichiometric concentration (Cst) of fuel

Cst is volume % fuel in fuel plus air

Determined using the general combustion reaction
 Substituting z

Flammability limits as a function of the heat of

combustion of the fuel

ΔHc is the heat of combustion for the fuel (in 103 kJ/mol).
 Flammable limits in pure oxygen are frequently useful for
designing systems
 Prevent fires, combustion in pure oxygen also exhibits a
lower oxygen limit (LOL) and an upper oxygen limit (UOL),


 UOL is the upper oxygen limit (vol. % fuel in oxygen),

 UFL is the upper flammable limit (vol. % fuel in air),
 UFLO is the oxygen concentration at the upper flammable limit
(vol. % oxygen in air),
 CUOL is a fitting constant
 Explosions and fires can be prevented by reducing the oxygen
 Limiting oxygen concentration (LOC)
 LOC has also been called the minimum oxygen concentration
(MOC),
 Maximum safe oxygen concentration (MSOC)
Problem: Estimate the LOC for butane (C4H10)
Solution
The LFL for butane is 1.8% by volume.
From the stoichiometry
 The combustion of butane is preventable by adding
nitrogen, carbon dioxide, or even water vapor until
the oxygen concentration is below 11.7%.
 The addition of water, however, is not recommended
because any condition that condenses water would
move the oxygen concentration back into the flammable
region
 LOC can be estimated using the equation

 CLOC is a fitting constant

 Each apex of the triangle represents either 100%
fuel, oxygen, or nitrogen
 Point A represents a mixture composed of
60% methane, 20% oxygen, and 20% nitrogen.
 The zone enclosed by the dashed line represents flammable
mixture
 The air line represents all possible combinations of fuel
plus air.
 The air line extends from the point where fuel is 0%, oxygen is 21%,
and nitrogen is 79% to the point where fuel is 100%, oxygen is 0%,
and nitrogen is 0%.
 The minimum ignition energy (MIE) is the minimum energy
input required to initiate combustion.
 All flammable materials (including dusts) have MIEs.
 The MIE depends on the specific chemical or mixture,
concentration, pressure, and temperature.
• The MIE decreases with an increase in pressure
• The MIE of dusts is at energy levels somewhat
higher than combustible gases
• An increase in nitrogen concentration increases MIE
 Temperature at which the vapor ignites spontaneously from
the energy of the environment.
 Sometimes called spontaneous ignition temperature (SIT)
 Function of the concentration of vapor, volume of vapor,
pressure of the system, presence of catalytic material, and
flow conditions.

 Process of slow oxidation with accompanying evolution of
heat,
 sometimes leading to auto-ignition 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

Examples
 Oils on a rag in a warm storage area,
 insulation on a steam pipe saturated with certain polymers,
 Filter aid saturated with certain polymers
 Additional means of ignition is adiabatic compression
 Gasoline and air in an automobile cylinder will ignite if the
vapors are compressed to an adiabatic temperature
that exceeds the autoignition temperature
 accidents have been caused by flammable vapors being
sucked into the intake of air compressors
 Adiabatic temperature increase for an ideal gas is
computed from the thermodynamic adiabatic compression
equation

Tf is the final absolute temperature,

Ti is the initial absolute temperature,
Pf is the final absolute pressure,
Pi is the initial absolute pressure, and
γ = Cp/Cv.
• The sources of ignition are numerous; consequently it is
impossible to identify and eliminate them all
• prevent a fire or explosion by ignition from an unidentified
source
• Combinations of sources must also be investigated
• The goal is to eliminate or minimize ignition sources
 Static electricity is generated when mists or sprays pass
through orifices.
 A charge may accumulate and discharge in a spark.
 If flammable vapors are present, explosion will occur.
 Mists and sprays also affect flammability limits.
 For suspensions with drop diameters less than 0.01 mm,
the LFL is virtually the same as the substance in vapor
form
 Mists with drop diameters between 0.01 mm and 0.2 mm
the LFL decreases as the drop diameter increases
 Sprays have drop diameters between 0.6 mm and 1.5
mm, flame propagation is impossible
 Explosion behavior is difficult to characterize
 An explosion results from the rapid release of energy
 Damage from explosion caused by dissipating energy
 A pressure wave propagating called a blast wave
because the pressure wave is followed by a strong wind
 highly explosive materials, such as TNT,
Detonation and Deflagration
 Damage effects from an explosion
 Difference whether reaction front propagates above or
below the speed of sound
 Sound or sonic velocity is a function of temperature only
and has a value of 344 m/s (1129 ft/s) at 20°C
 Detonation, resulting in a reaction front and leading
shock wave that propagates above the sonic velocity.
 Deflagration processes are relatively slow, speed less
than the sonic velocity

Confined Explosions
 A confined explosion occurs in a confined space, such
as a vessel or a building
 confined explosion scenarios involve explosive vapors
and explosive dusts
 Explosion is function of several experimentally
characteristics
 Characteristics depend on the explosive material used
and include flammability or explosive limits, the rate of
pressure rise after the flammable mixture is ignited, and
the maximum pressure after ignition
 Pressure rate and maximum explosion pressure as a
function of vapor concentration.
 The maximum pressure rate does not necessarily occur
at the maximum pressure.
 Pressure data from dust explosion device

 Explosion Characteristics

KG and KSt are the deflagration indexes for gas and dust, respectively
 known energy of a combustible fuel to an equivalent
mass of TNT

◦ mTNT is the equivalent mass of TNT (mass),

◦ η is the empirical explosion efficiency (unitless),
◦ m is the mass of hydrocarbon (mass),
◦ ΔHc is the energy of explosion of the flammable gas
(energy/mass), and
◦ ETNT is the energy of explosion of TNT
 Typical value for the energy of explosion of TNT is
1120 cal/g = 4686 kJ/kg = 2016 Btu/lb
 mTNT, and the distance from the ground-
zero point of the explosion, denoted r.
 Ps is the scaled
overpressure (unit less),
Example: One kilogram of TNT is
exploded. Compute the overpressure
 Po is the peak side-on
at a distance of 30 m from the overpressure, and
explosion.  Pa is the ambient
Solution
The value of the scaling parameter is pressure
determined
  Chemical explosion is generated by the rapid expansion of
gases at the explosion site.
 This expansion can be caused by two mechanisms:
◦ (1) thermal heating of the reaction products and
◦ (2) the change in the total number of moles by reaction.
• Change in the number of moles is small
• Almost all the blast energy must be due to thermal energy
• Heat of combustion is used, but the reaction energy can be
easily computed using standard heats of formation
  Energy is obtained from the energy content of the
contained substance
 Failure of a tire full of compressed air
 Four methods are used to estimate the energy of
explosion for a pressurized gas:
◦ Brode’s equation
◦ isentropic expansion
◦ isothermal expansion
◦ thermodynamic availability
• Brode’s method: Energy required to raise the pressure of the gas
at constant volume
 Isentropic expansion: method assumes that the gas
expands isentropically from its initial to final state

 Isothermal expansion: case assumes that the gas

expands isothermally

 Thermodynamic availability: maximum mechanical

energy extractable from a material as it comes into
equilibrium with the environment.
 The most dangerous and destructive explosions in the
chemical process industries
 These explosions occur in a sequence of steps:
◦ Sudden release of a large quantity of flammable vapor
(vessel, containing a superheated and pressurized liquid, ruptures),
◦ Dispersion of the vapor throughout the plant site while mixing with air,
◦ Ignition of the resulting vapor cloud.

Case: The accident at Flixborough, England VCE.

A sudden failure of a 20-inch cyclohexane line between
reactors led to vaporization of an estimated 30 tons of cyclohexane.
unknown source 45 seconds after the release.
The entire plant site was leveled and 28 people were killed.
 Qualitative studies
(1) the ignition probability increases as the size of
the vapor cloud increases,
(2) vapor cloud fires are more common than explosions,
(3) the explosion efficiency is usually small (approximately 2%)
(4) turbulent mixing of vapor and air and ignition of the cloud

 Methods that are used to prevent

 VCEs include keeping low inventories of volatile, flammable
 Process conditions that minimize flashing
 Analyzers to detect leaks at low concentrations
 Installing automated block valves to shut systems down while the
spill is in the incipient stage of development.
 BLEVEs are caused by the sudden failure of the container as
a result of any cause (commonly is caused by fire)
 A BLEVE occurs when a tank containing a liquid held above
its atmospheric pressure boiling point ruptures, materials are
flammable, a VCE might result;
 Toxic, a large area might be subjected to toxic materials
 For either situation the energy released by the BLEVE, in
considerable damage.
 boiling and burning liquid behaves as a rocket fuel, propelling
vessel parts for great distances
 Only a fraction of the liquid vaporizes
 the amount depends on the physical and thermodynamic
conditions
Most common type of BLEVE is caused by fire
The steps are as follows:
A fire develops adjacent to a tank containing a liquid.
The fire heats the walls of the tank.
The tank walls below liquid level are cooled by the
liquid, increasing the liquid temperature and the pressure
in the tank.
If the flames reach the tank walls or roof where there is
only vapor and no liquid to remove the heat, the tank
metal temperature rises until the tank loses it structural
strength.
The tank ruptures, explosively vaporizing its contents