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Chapter 6

Fires and Explosions

Ref: Chapter 6, D. A. Crowl, J. F. Louvar, Chemical Process
Safety: Fundamental with Applications, 3rd edition,
Prentice-Hall, 2011.

Chemicals present a substantial hazard in the form of fires and explosions.
Ex: combustion of one gallon of toluene can destroy an ordinary
chemistry laboratory in minutes; persons present may be killed.

The potential consequences of fires and explosions in pilot plants and plant
environments are even greater.
Organic solvents are the most common source of fires and explosions in the
chemical industry. Chemical and hydrocarbon plant losses resulting from
fires and explosions are substantial
To prevent accidents resulting from fires and explosions, engineers must be
familiar with the fire and explosion properties of materials, the nature of
the fire and explosion process, and procedures to reduce fire and explosion

Combustion or fire: Combustion or fire is a chemical reaction in
which a substance combines with an oxidant and releases
energy. Part of the energy released is used to sustain the
Ignition: Ignition of a flammable mixture may be caused by a
flammable mixture coming in contact with a source of ignition
with sufficient energy or the gas reaching a temperature high
enough to cause the gas to autoignite.

Autoignition temperature (AIT): A fixed temperature
above which adequate energy is available in the
environment to provide an ignition source.
Flash point (FP): The flash point of a liquid is the 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 flash point generally increases with increasing

Fire point: The fire point is the lowest temperature at which a
vapor above a liquid will continue to burn once ignited; the
fire point temperature is higher than the flash point.
Flammability limits: Vapor-air mixtures will ignite and burn
only 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; that is, when it is above the upper flammable limit
(UFL). A mixture is flammable only when the composition is
between the LFL and the UFL.

Explosion: An explosion is a rapid expansion of gases
resulting in a rapidly moving pressure or shock wave.
The expansion can be mechanical (by means of a sudden
rupture of a pressurized vessel), or it can be the result of
a rapid chemical reaction. Explosion damage is caused by
the pressure or shock wave.
Mechanical explosion: An explosion resulting from the
sudden failure of a vessel containing high-pressure
nonreactive 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.
These are most common and usually result in injury to the building
inhabitants and extensive damage.
Unconfined explosion: Unconfined explosions occur in the open. This type of
explosion is usually the result of a flammable gas spill.
Dust explosion: This explosion results from the rapid combustion of fine solid
particles. Many solid materials (including common metals such as iron and
aluminum) become flammable when reduced to a fine powder.

Boiling-liquid expanding-vapor
explosion (BLEVE):
A BLEVE occurs if a vessel that contains a liquid at a temperature above
its atmospheric pressure boiling point ruptures.
The subsequent BLEVE is the explosive vaporization of a large fraction
of the vessel contents; possibly followed by combustion or explosion
of the vaporized cloud if it is combustible.
This type of explosion occurs when an external fire heats the contents
of a tank of volatile material.
As the tank contents heat, the vapor pressure of the liquid within the
tank increases and the tank's structural integrity is reduced because of
the heating. If the tank ruptures, the hot liquid volatilizes explosively.

Shock wave: An abrupt pressure wave moving through a gas.

A shock wave in open air is followed by a strong wind; the

combined shock wave and wind is called a blast wave.

The pressure increase in the shock wave is so rapid that the

process is mostly adiabatic.
Overpressure: The pressure on an object as a result of an
impacting shock wave.

The Fire Triangle

The essential elements for combustion are fuel, an oxidizer, and
an ignition source.
Fire, or burning, is the rapid exothermic oxidation of an ignited
Two common examples of the three components of the fire
triangle are wood, air, and a match; and gasoline, air, and a



When fuel, oxidizer, and an ignition source are present at the

necessary levels, burning will occur.
This means a 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, and
(3) the ignition source is not energetic enough to initiate the fire.

Common Fuels, Oxidizers and Ignition

sources Process Industry
Liquids: gasoline, acetone, ether, pentane
Solids: plastics, wood dust, fibers, metal particles
Gases: acetylene, propane, carbon monoxide, hydrogen
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

The major distinction between fires and explosions is the rate
of energy release.
Fires release energy slowly, whereas explosions release
energy rapidly, typically on the order of microseconds.
Fires can also result from explosions, and explosions can
result from fires.


Le Chatelier equation for Prediction of

LFL and UFL of mixtures

Where LFLi is the lower flammable limit for component i (in volume %) of
component i in fuel and air,
yi is the mole fraction of component i on a combustible basis, and
n is the number of combustible species.
where UFL, is the upper flammable limit for component i (in volume %) of
component i in fuel and air.


Limiting Oxygen Concentration and lnerting

The LFL is based on fuel in air.
However, oxygen is the key ingredient and there is a minimum
oxygen concentration required to propagate a flame.
This is an especially useful result, because explosions and fires
can be prevented by reducing the oxygen concentration
regardless of the concentration of the fuel.
This concept is the basis for a common procedure called



Below the limiting oxygen concentration (LOC) the reaction
cannot generate enough energy to heat the entire mixture of
gases (including the inert gases) to the extent required for the
self-propagation of the flame.
The LOC has also been called the minimum oxygen
concentration (MOC), the maximum safe oxygen
concentration (MSOC),


Flammability Diagram
A general way to represent the flammability of a gas or vapor is by the
triangle diagram .
Concentrations of fuel, oxygen, and inert material (in volume or mole %)
are plotted on the three axes.
Each apex of the triangle represents either 100% fuel, oxygen, or nitrogen.
The tick marks on the scales show the direction in which the scale moves
across the figure.
Thus point A represents a mixture composed of 60% methane, 20%
oxygen, and 20% nitrogen. The zone enclosed by the dashed line
represents all mixtures that are flammable. Because point A lies outside
the flammable zone, a mixture of this composition is not flammable.
Clearly, any gas mixture containing oxygen below the LOC is not

Flammability diagram for methane at 1 atm and 25 oC


Minimum ignition energy (MIE)

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, the
concentration, pressure, and temperature.


Characteristics of MIE
1. the MIE decreases with an increase in
2. the MIE of dusts is, in general, at energy
levels somewhat higher than combustible
3. an increase in the nitrogen concentration
increases the MIE.


Autoignition Temperature
The autoignition temperature (AIT) of a vapor, sometimes
called the spontaneous ignition temperature (SIT), is the
temperature at which the vapor ignites spontaneously from
the energy of the environment.
The autoignition temperature is a function of the
concentration of vapor, volume of vapor, pressure of the
system, presence of catalytic material, and flow conditions.
It is essential to experimentally determine AITs at conditions
as close as possible to process conditions.

Auto-oxidation is 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

susceptible to this problem.




Liquids with high volatility are less susceptible to autoignition

because they self-cool as a result of evaporation.
Many fires are initiated as a result of auto-oxidation, referred
to as spontaneous combustion. Ex: spontaneous combustion
include oils on a rag in a warm storage area

Detonation and Deflagration

The damage effects from an explosion depend highly on
whether the explosion results from a detonation or a
The difference depends on whether the reaction front
propagates above or below the speed of sound in the
unreacted gases.






Confined Explosions
A confined explosion occurs in a confined space, such as a
vessel or a building.
The two most common confined explosion scenarios involve
explosive vapors and explosive dusts.
Empirical studies have shown that the nature of the explosion
is a function of several experimentally determined
These 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.

1. What are the LFL and UFL of a gas mixture
composed of 0.8% hexane, 2.0% methane,
and 0.5% ethylene by volume?
2. Estimate the LOC for butane (C4HI0).