Lecture 4

Safety Practices in Chemical and

Nuclear Industries
Fire and Explosion

Dr. Raghuram Chetty

Department of Chemical Engineering
Indian Institute of Technology Madras
Chennai- 600 036.

Chemical Industries

Chemicals have become a part of our life for sustaining

many of our day-to-day activities, preventing and
controlling diseases, and increasing agricultural productivity
etc.

An estimation of one thousand new chemicals enter the

market every year, and about 100,000 chemical
substances are used on a global scale. These chemicals
are mostly found as mixtures in commercial products. Over
one million such products or trade names are available.

Chemical Industries

The chemical industrial sector is highly heterogeneous

encompassing many sectors like organic, inorganic
chemicals, dyestuffs, paints, pesticides, specialty
chemicals, etc. Some of the prominent individual chemical
industries are caustic soda, soda ash, carbon black,
phenol, acetic acid, methanol and azo dyes.

The risks associated with the chemical industry are

commensurate with their rapid growth and development.
Apart from their utility, chemicals have their own inherent
properties and hazards. Some of them can be flammable,
explosive, toxic or corrosive etc, and also have the
potential to affect the nearby environment.

Why do organizations have to bother about Safety

In the present global industrial

scenario, for any industry to be
successful, it is essential to
inculcate
safety
culture,
consciousness in health and
environment aspects in each
personnel of an organisation.

The significance of Safety &

Health in chemical industries
has been a vital issue in
achieving productivity and an
edge in the competitive world.

Why do organizations have to bother about Safety

Finance, Human Resources.

Manufacturing and operating

policy.

Societal concerns.

Hazard & Safety

Can cause:

Injury

Death

Damage to equipment/ property

It is practically impossible to completely eliminate all

hazards. Safety is therefore a matter of relative protection
from exposure to hazards.

Hazard & Safety

Safety = freedom from hazards

Maintain a safe work environment

Control unsafe acts and conditions

Ensure operational efficiency

Work Place Hazard

Physical Hazards

Physical agents

falling objects, slips & trips, dangerous machinery,

noise, vibration, electricity, radiation,

Chemical Hazard

solvents, metals,

Work Place Hazard

Biological Hazard

micro-organisms and toxins

Psychosocial issues

ergonomics (design of work place environment)

work stress, violence, bullying

Major Concern in a Chemical Industry

Areas of Concern
1. Dangerous Materials
2. Flammable Gases, Vapours and Dust Hazards
3. Hazardous Chemical Reactions
4. Hazards of Pressure Vessels
5. Hazards due to Instrument Failures
6. Hazardous of Unit Operations
7. Entry in to Confined Spaces
8. Hazards due to Corrosion
9. Working with Pipelines
10. Plant Alteration and Modification

Dangerous Substances
1.

Explosives

2.

Gases

3.

Flammable Liquids/Solids

4.

Oxidizing Substances

5.

Miscellaneous Dangerous Substances

Dangerous substance

What is a dangerous substance?

Dangerous substance includes any substance or

preparation, which because of its properties or the way
it is used could cause harm to people from fires and
explosions.

Dangerous substances include: petrol, liquefied

petroleum gas (LPG), paints, varnishes, solvents, and
dusts which when mixed with air could cause an
explosive atmosphere.

Dangerous substances can be found, in varying

quantities, in most workplaces.

Dangerous substance
What is a dangerous substance?

Dangerous Substances and Explosive Atmospheres

Regulations, 2002 (UK) usually known as DSEAR is a set
of regulations concerned with protection against risks
from fire, explosion and similar events arising from
dangerous substances used or present in the workplace.

Chemistry of Fire

Chemically, fire is a type of oxidation, which is the

combination of oxygen with other substances to produce
new substances.

The rapid oxidation of a fuel evolving heat, particulates,

gases and non-ionizing radiation.

To start fire, the minimum temperature needed to

spontaneously ignite fuel, known as ignition
temperature, must be reached.

Chemistry of Fire

The heat evolved when a substance burns is known as

heat of combustion.

An additional factor, besides the liberation of energy,

needed to explain fire is the rate or speed at which the
oxidation reaction takes place.

Fire
In order to have a fire, two components are
required fuel and an oxidant.
for e.g.

CH4 + 2O2 CO2 + 2H2O

However, the presence of fuel and oxidant is

not sufficient to start combustion; the mixture
must be raised to a high enough
temperature to start the reaction, usually by
a spark or a flame.

Fire

It is possible to have a fuel and an oxidant, but in

proportions such that the process cannot occur
continuously. If the fuel is a small amount of gas
mixed with air and we initiate combustion with a
spark, the small amount of heat produced by
burning might be insufficient to ignite fuel and
continuous combustion fails to happen.

Too much fuel is insufficient oxygen, and once

again the heat produced when a spark ignites
some fuel is not enough to ignite adjacent fuel.

e.g. think of the last time you tried to light

charcoal charcoal was stubborn until... you blew
on it, increasing the oxygen supply.

Fire

Fire or burning, is the rapid exothermic oxidation of an

ignited fuel. The fuel can be in solid, liquid, or vapor form,
but vapor and liquid fuels are generally easier to ignite.

The combustion always occurs in the vapor phase;

liquids are volatized and solids are decomposed into
vapor before combustion.

When fuel, oxidizer, and an ignition source are present

at the necessary levels, burning will occur.

Fire

A fire will not occur if

Fuel is not present or is not present in sufficient

quantities.

An oxidizer is not present or is not present in sufficient

quantities.

The ignition source is not energetic enough to initiate

the fire.

The Fire Triangle

Oxidizers
Liquids
hydrogen peroxide, nitric acid,
perchloric acid
Solids
Metal peroxides, ammonium
nitrate
Gases
Oxygen, fluorine, chlorine

Ignition sources
Sparks, flames,
static electricity,
heat

Fuels
Liquids
gasoline, acetone, ether, pentane
Solids
metal particles, wood dust, fibers, plastics,
Gases
acetylene, propane, hydrogen

Other fuels

Solvents

Paper, boxes, etc.

Plastics

Carpets

Furniture

Waste materials

Common Sources of Ignition

Smoking

Electrical equipment

Heaters

Contractors tools and equipment

Arson

Effective Ignition Source

Open flames: this varies from a lit cigarette to welding

activity.

Mechanically generated impact sparks: for example, a

hammer blow on a rusty steel surface compared to a
hammer blow on a flint stone. The speed and impact angle
(between surface and hammer) are important; a 90 degree
blow on a surface is relatively harmless.

Electric sparks. For example a bad electrical connection or

a faulty pressure transmitter. The electric energy content of
the spark determines the effectiveness of the ignition
source.

Effective Ignition Source

High surface temperature. This can be the result of

milling, grinding, rubbing, mechanical friction in a stuffing
box or bearing, or a hot liquid pumped into a vessel.

Electrostatic discharge. Static electricity can be generated

by air sliding over a wing.

Adiabatic compression. Air is pumped into a vessel and

the vessel surface heats up.

Radiation, Lightning strikes.

Static Electricity

Static electricity is a major

cause of fires and explosions
in many industries.

Generated when a fluid flows

through a pipe or from an
opening into a tank.

Main hazards are fire and

explosion
from
sparks
containing enough energy to
ignite flammable vapors.

Piping Systems - In piping systems

the generation rate and the subsequent
accumulation of static charge are a
function of the flow rate, liquid velocity,
pipe diameter, and pipe length.
Filling Operations - The turbulence
experienced in filling operations,
caused by large flow rates, splashing
or free-falling liquids, greatly increases
the charge accumulation above the
level generated in piping systems.
Filtration - Filters, because of their
large surface area, can generate as
much as 200 times the electrostatic
charge generated in the same piping
system without filtration.

Control of Static Electricity

Bonding

Physically connect two conductive objects together with a

bond wire to eliminate a difference in static charge potential
between them.

Must provide a bond wire between containers during

flammable liquid filling operations, unless a metallic path
between them is otherwise present.

Control of Static Electricity

Grounding

Eliminates a difference in static charge potential

between conductive objects and ground

Although bonding will eliminate a difference in potential

between objects, it will not eliminate a difference in
potential between these objects and earth unless one
of the objects is connected to earth with a ground wire.

Ventilation

Control of Static Electricity

Solvent Transfer

Safety pump

Self closing safety Faucet

Image courtesy: Google Images

Types of Fire

Jet Fire

Pool fire

Flash fire

Fire ball
Image courtesy: Google Images

Definitions

Flash point (FP) of a volatile liquid is the lowest

temperature at which it can vaporize to form an ignitable
mixture in air.

Defined only for liquids at 1 atm. pressure. The flash

point increases with increasing pressure.

Measuring a liquid's flashpoint requires an ignition

source.

At the flash point, the vapor may cease to burn when

the source of ignition is removed.

Definitions

Fire point is the lowest temperature at which liquid gives

enough vapor to maintain a continuous flame; the fire
point temperature is higher than the flash point.

Flammability/Explosive Limit

For each flammable chemical we can

determine limits, concentration of gas or
vapor in air that are at the low or high
extremes of ability to sustain continuous
combustion.
*

There is a lower flammability limit

*
(combustion-lean
limit
mixture),
a
concentration in air, usually expressed as
volume percent (vol%), below which the fuelair mixture dose not sustain continuous
*Upper Explosive Limit
combustion.
*Lower Explosive Limit

Flammability/Explosive Limit

The upper flammability limit (combustiblerich limit mixture) is the highest concentration
of fuel in air that burns continuously.

Such values should not be treated as

absolute physical constant such as melting
point or density of a pure substance, but
rather as guidelines when establishing criteria
for safe conditions.

*
*

For example, flammability limits vary

with temperature, pressure, and
*Upper Explosive Limit
conditions of combustion.
*Lower Explosive Limit

Flammability Limit

Lower flammability limit (LFL):

is the lower end of the
concentration (%) range of a
flammable solvent at a given
temperature and pressure for
which air/vapor mixtures can
ignite.

Outside
this
range
of
air/vapor
mixtures,
the
mixture will not ignite (unless
heated).

Flammability Limit

Upper
flammability
Limit
(UFL):
is
the
highest
concentration (%) of a gas or a
vapor in air capable of
producing a flash of fire in
presence of an ignition source.

Concentration higher than

UFL are "too rich" to burn.

Autoignition Temperature

The autoignition temperature of

a substance is the lowest
temperature at which it will
spontaneously ignite without
an external source of ignition.
This temperature is required to
supply the activation energy
needed for combustion.

Autoignition point of selected

substances in C
Silane
White phosphorus
Carbon disulfide
Diethyl ether
Diesel or Jet fuel
Gasoline (Petrol)
Magnesium
Hydrogen

>21
34
90
160
210
250
473
536

Autoignition Temperature

The temperature at which a

chemical will ignite decreases as
the pressure increases or
oxygen concentration increases.
It is usually applied to a
combustible fuel mixture.
(not to be confused with the
flashpoint, which requires an
ignition source)

Autoignition point of selected

substances in C
Silane
White phosphorus
Carbon disulfide
Diethyl ether
Diesel or Jet fuel
Gasoline (Petrol)
Magnesium
Hydrogen

>21
34
90
160
210
250
473
536

Flammability Limit for hydrocarbons

Hydrocarbon

Formula

LEL in
air
(%)

UEL in
air
(%)

Methane

CH4

5.0

15.0

650

Ethane

C2H 6

3.0

12.4

515

Propane

C 3H 8

2.1

9.5

466

n-Butane

C4H10

1.8

8.4

480

n-Hexane

C6H14

1.2

7.4

275

Dimethyl ether

C 2H 6O

3.4

27

350

Hydrogen

H2

4.0

75

536

Ethylene oxide

C 2H 4O

3.6

100

429

Acetylene

C2H 2

2.5

100

305

Ignition
Temperature,
oC

Vapor/air mixture Concentration Vs. Temperature

A plot of concentration versus temperature shows how several definitions
are related
Boiling Point
Non-flammable region

Vapor Conc. in air

Upper flammable limit (UFL)

Vapor
pressure curve

Flammable region

Lower flammable limit (LFL)

Non-Flammable
region

Flash Point

Temperature

Vapor pressure, temperature diagram shows the relationship among upper

and lower flammable (explosive) limits, flammable and non- flammable
regions, boiling point, flash point and vapor pressure curve.

Explosion

Fire and explosion may be two sides of the same coin

where both are based on a strongly exothermic (heatproducing) chemical reaction, usually combustion in air.

An explosion as opposed to a fire, occurs when the rapid

expansion of gases produces high pressures.

Rapid progression of high pressure and heat result in

explosion.

An explosion is more likely when the fuel-oxygen

mixture is midway between the flammability limits.

Distinction between Fire and Explosion

The major distinction between fires and explosions is the

rate of energy release.

Fires release energy slowly, whereas explosion

release energy rapidly, typically on the order of
microseconds.

Fires can also result from explosions, and explosions

can result from fires.

Distinction between Fire and Explosion

A good example of how the energy release rate affects

the consequences of an accident is a standard
automobile tyre.

The compressed air within the tyre contains energy. If

the energy is released slowly through the nozzle, the
tyre is harmlessly deflated.

If the tyre ruptures suddenly and all the energy within

the compressed tire release rapidly, the result is a
dangerous explosion.

Fire and explosion

FIRE

exothermic, oxidation, with flame

EXPLOSION higher energy release rate

may trigger
each other

pressure or shock wave

EFFECTS

injuries / casualties
property losses
process interruption

Thermal radiation,
asphyxiation, toxic products,
blast, fragments

Required knowledge for prevention

material properties
nature of fire and explosion process
procedures to reduce hazards

Explosion
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.

Explosion

BLEVE (Boiling Liquid Expanding Vapor Explosion): This

is a type of explosion that can occur when a vessel
containing a pressurized liquid is ruptured. Such
explosions can be extremely hazardous.

Vapor cloud explosion: Overpressure caused when a

gas cloud detonates or deflagrates in open air rather than
simply burn, i.e. extremely rapid flame front propagation.

Detonation and Deflagration

Explosion

BLEVE (Boiling Liquid Expanding Vapor Explosion) occurs if a vessel

that contains a liquid at a temperature above its atmospheric pressure
boiling point ruptures.

BLEVE may occur when a pressurized tank, e.g. LPG (as in Mexico
disaster) or partially filled flammable liquid container, is exposed to an
external heat/fire.

If the tank/container cannot resist the increasing pressure it will burst

and the content will be thrown around, mix with air and ignite in a storm
of fire.

Deflagration/ Detonation
Deflagration: An explosion in which
the reaction front moves at subsonic
speed (speed less than the speed of
sound) in the unreacted medium.
Flame propagation velocity, typically
far below 100 m/s, and relatively
modest overpressures, <0.5 bar.

Shock front

The reaction front moves at a speed

less than sound, while the pressure
front moves away from the reaction
front at the speed of sound.

Reaction front

Shock front

Reaction front

modest
overpressure

Detonation: An explosion in which

the
reaction
front
moves
at
supersonic speed (speed greater than
the speed of sound) in the unreacted
medium.
Flame
propagation
velocities, up to 2000 m/s, and
substantial overpressures, up to 20
bars.
Substantial
overpressure

Reaction front moves at a speed

greater than sound, driving shock
front immediately preceding it. Both
front move almost same speed

Explosive atmosphere

An explosive atmosphere is an accumulation of gas, mist,

dust or vapor, mixed with air, which has the potential to
catch fire or explode.

An explosive atmosphere does not always result in an

explosion, but if it caught fire the flames would quickly
travel through it and if this happened in a confined space
(e.g. in plant or equipment) the rapid spread of the flames
or rise in pressure could cause an explosion.

Explosive atmosphere

Knowing the flammability limit and other characteristics of a

chemical allows us to predict the potential for a fire starting.

Check MSDS or the standard diamond shaped hazard code

placed on containers of chemicals (from US), the red upper
quadrant warns of the combustion hazards.

Most organic liquids are flammable, exception being chlorinated

or halogenated hydrocarbon. Industry has been strongly
induced to use chlorinated hydrocarbons as solvents because of
their inability to burn. C-H bond is replaced by more stable C-Cl
bond. CCl4 was commonly used as a fire extinguisher fluid
before its toxic characteristics were recognised.

Definitions

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. The gas is dispersed and mixed with
air until it comes in contact with an ignition source.

Unconfined explosions are rarer than confined

explosions because the explosive material is frequently
diluted below the LFL by wind dispersion.

Definitions

Dust explosion: This explosion results from the rapid

combustion of fine solid particles. Many solid materials
(including metals such as iron and aluminum) become
flammable when reduced to a fine power.

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.

Damage estimation based on Overpressure

Overpressure,
~ kPa
0.5

Damage
Loud noise (143 dB)

Safe distance (probability of 0.95 of no serious

damage below this value)

Windows usually shatter, occasional damage to frame

Minor damage to house structure

6-14

Significant damage to structures (wood and asbestos)

15

Destruction of brickwork house

25

Cladding of light industrial building ruptures, oil tank

ruptures, 50% probability of human fatality

35-50

Nearly complete destruction of houses

Flash point device

The flash point temperature is one of the major quantities

used to characterize the fire and explosion hazard of liquids.
Flash point temperatures are determined using an apparatus
shown below.

Cleveland Open Cup Flash Point Tester

Image courtesy: Google Images

Experimental Determination - Flashpoint

Cleveland Open
Cup Method.
Closed cup
produces a better
result - reduces
drafts across cup.

An open-cup flash point determination

The liquid to be tested is placed in the open cup. The liquid

temperature is measured with a thermometer while a
Bunsen burner is used to heat the liquid.

A small flame is established on the end of a moveable

wand.

During heating, the wand is slowly moved back and forth

over the open liquid pool.

An open-cup flash point determination

Eventually a temperature is reached at which the liquid is

volatile enough to produce a flammable vapor, and a
momentary flashing flame occurs.

The temperature at which this first occurs is called the

flash point temperature.

Note that at the flash point temperature only momentary

flame occurs; a higher temperature, called the fire point
temperature, is required to produce a continuous
flame.

An open-cup flash point determination

The problem with open-cup flash point procedures is that

air movements over the open cup may change the vapor
concentrations and increase the experimentally
determined flash point.

To prevent this, most modern flash point methods employ

a closed-cup procedure.

For this apparatus a small, manually opened shutter

provided at the top of the cup. The liquid is placed in a
preheated cup and allowed to sit for a fixed time period.

The shutter is then opened and the liquid is exposed to

the flame. Closed-cup methods typically result in lower
flash points.

Examples of flash points

Gasoline (petrol) is designed for use in an engine which is

driven by a spark.

The fuel should be premixed with air within its

flammable limits and heated above its flash point, then
ignited by the spark plug.

The fuel should not preignite in the hot engine. Therefore,

gasoline is required to have a low flash point and a high
Fuel
Flash
Autoignition
autoignition temperature.
point
temperature
Ethanol

12.8 C

365 C

Gasoline
(petrol)

<40 C

246 C

Diesel

>62 C

210 C

Jet fuel

>60 C

210 C

Theoretical flash point

Mathematically flash point can be calculated using boiling
point relationship:
2

c/Tb

b(c/Tb ) e
Tf = a +
(1 e c/Tb )2
where,

Tf is flash point in K,
a, b, and c are constants
(provided in Table, next slide),
Tb is boiling point in K

Constants for Tf equation

Constants used in the equation for predicting flash point
Chemical group

Hydrocarbons

225.1

537.6

2217

Alcohols

230.8

390.5

1780

Amines

222.4

416.6

1900

Acids

323.2

600.1

2970

Ethers

275.9

700.0

2879

Sulfur

238.0

577.9

2297

Esters

260.5

449.2

2217

Halogens

262.1

414.0

2154

Aldehydes

264.5

293.0

1970

Temperature and Pressure dependencies

LFLT =LFL25
UFLT =UFL25 +

0.75
(T 25)
H c

0.75
(T 25)
H c

Where Hc is the net heat of combustion (kcal/mole), and T is temperature in oC.

As temperature increases: UFL increases, LFL decreases
Flammability range increases

Pressure has little effect on LFL where as UFL change as follows:

UFL p =
UFL + 20.6(logP + 1)
where P is absolute pressure in Mega Pascal
As pressure increases: UFL increases, LFL mostly unaffected

Calculating LFL/UFL of Mixtures

LFL =

UFL =

1
yi
LFL
i
1
yi
UFL
i

yi = mole fraction of i on combustable basis

Experimental Determination - LFL, UFL

Run experiment at different fuel compositions with air:
Maximum Explosion
Pressure (bar-gauge)

10

8
6

4
2

LFL

0
0

UFL
2

10

Fuel Concentration in air (vol%)

Flammability limits are an empirical artifact of experiment!

Test apparatus for accruing vapor explosion data

TI

Igniter

PI

Pressure (bar-abs)

10

Pmax
8

0
0

50

100

150

200

250

Time (ms)

Typical pressure vs. time data

obtained from gas explosion
apparatus shown in the left.

Experimental Apparatus

Image courtesy: Google Images

Estimation of Flammability limits

Using stoichiometric balance for general combustion

reaction

x
CmHxOy + zO2 mCO2 + H2O
2
z=m+x-y

where z has units of moles O2/mole fuel.

Stoichiometric Conc. [vol%] = Cst
Cst = 21% / (0.21 + z)

LFL = 0.55Cst
UFL = 3.50Cst

Approximate!

Limiting Oxygen Conc. (LOC)

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 especially useful
because explosion and fire can be prevented by reduction
the oxygen concentration regardless of the conc. of fuel.

Below the LOC (Limiting or lowest oxygen concentration

in vol% O2) the reaction cannot generate enough energy
to heat the entire mixture of gases to the extend required
for the self propagation of the flame.
Fuel + z. oxygen Products
LOC z LFL

(Typically 8 - 12%)

Estimate the LOC of butane

The stoichiometry for this reaction is
C4H10 + 6.5 O2 4CO2 + 5 H2O
The LFL for butane is 1.9 % by volume (from literature). From the stoichiometry
LOC

= (moles fuel/total moles) x (moles O2/ moles fuel)

= LFL (moles O2/ moles fuel)

By substitution, we obtain
LOC

= (1.9) * (6.5 moles O2/ 1.0 moles fuel)

LOC

= 12.4 vol. % O2

The combustion of butane is preventable by adding N2, CO2, or even

water vapour until the oxygen conc. O2 below 12.4%. The addition of
water is not recommended because any condition that condenses water
would move the oxygen concentration back into the flammable region.

Flammability Diagram
A general way to represent
the flammability of a gas or
vapour is by the triangle
diagram as shown in the
figure below.
Concentration
of
fuel,
oxygen and inert material
are plotted on the three
axes. Each apex of the
triangle represents either
100% fuel, oxygen or
nitrogen.

Flammability Diagram
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.

Methane Flammability Diagram

Combustion requires fuel and

oxygen
in
the
proper
concentration. Under normal
conditions,
air
contains
approximately 21% oxygen and
79% nitrogen and trace amounts
of other gases.
The diagram shows all possible
mixtures of methane, oxygen,
and
passive
agents
(predominantly nitrogen in the
air).

Nitrogen

The triangle represents the

relationship between fuel,
oxygen, and passive agents
with the total concentration
equals 100%.

Methane Flammability Diagram

The blue (air) line indicates

oxygen
concentration
from
normal 21% (by volume) to 0%.

The red (stoichiometric) line

indicates the ideal mixture of
oxygen and fuel for complete
combustion.

The gray shaded area indicates

the mixtures of methane, oxygen,
and passive agents that will be
flammable.

Nitrogen

The triangle represents the

relationship between fuel,
oxygen, and passive agents
with the total concentration
equals 100%.

Constructing Flammability Diagram

Oxygen

Fuel

Nitrogen

Constructing Flammability Diagram

40% Nitrogen
40% Fuel
20% Oxygen
Oxygen

Fuel

Nitrogen

Constructing Flammability Diagram

1. Draw Air Line
2. Enter LFL & UFL
3. Determine z
4. LOC = z LFL
Oxygen

Nitrogen

Air line represents all

possible combinations of
fuel plus air. The air line
extends from point where
fuel is 0% to oxygen 21%
and nitrogen is 79% to a
point where fuel is 100%,
oxygen 0% and nitrogen
0%. The equation for this
line is
Fuel% = -(100/79) x N2%
+ 100

Constructing Flammability Diagram

5. Add Stoichiometric Line

Stoichiometric line represents all

stoichiometric combinations of fuel &
oxygen
Fuel + zO2 combustion products
where z is the stoichiometric coefficient
for oxygen

Oxygen

Equation for the stoichiometric line is

Fuel% = 100 N2(%) / (1+z)

The
intersection
of
stoichiometric line with the
oxygen axis (in volume %
oxygen is given by)
Nitrogen

100

Constructing Flammability Diagram

5. Add Stoichiometric Line
6. Get Pure Oxygen LFL
and UFL (if available)
LOC
7. Construct curve
UFL

Oxygen

Fuel

LFL

Nitrogen

Diagram
5. Add Stoichiometric Line
6. Get Pure Oxygen LFL
and UFL (if available)
7. Construct curve

LOC

UFL(O2)

Oxygen

Fuel

LFL(O2)
UFL
LFL

Nitrogen

Methane Flammability Diagram

The LOC is also shown in the

figure. Clearly any gas mixture
containing oxygen below the
LOC is not flammable.

The shaded area indicates the

mixtures of methane, oxygen,
and passive agents that will be
flammable. Whereas, point A
represents a mixture composed
of 60% methane, 20% oxygen,
and 20% nitrogen, which lies
outside the flammable zone, a
mixture of this composition is not
flammable.

UFL

LOC = 12 vol% O2

LFL

Methane Flammability Diagram

The shape and size of the

flammability zone on a
flammability
diagram
change with number of
parameters, including fuel
type, temperature, pressure
and other inert species.

UFL

LOC = 12 vol% O2

LFL

Hydrogen Flammability Diagram

Hydrogen Explosion
Deflagration (slow flame;
starting at about 4%)
Deflagration to detonation
transition (DDT)
Detonation (rapid flame,
starting at about 13%)
Total energy maybe same
in detonation but time
scale is smaller

Flammability Diagram for Styrene

Solvents

Organic solvents are the most common source of fires

and explosions in the chemical industry.

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.

Procedures to reduce fire and explosion hazards.

Flammable and combustible liquids

Flammable and combustible

liquids are liquids that can burn.

They are classified, or grouped

as
either
flammable
or
combustible,
by
their
flashpoints.

Generally, flammable liquids

will ignite (catch on fire) and
burn easily usually at normal
working
temperatures.
Combustible liquids have the
ability to burn at temperatures
that are usually above working
temperatures.

Fuel

Flash
point

Autoignition
temperature

Ethanol

12.8 C

365 C

Gasoline
(petrol)

<40 C

246 C

Diesel

>62 C

210 C

Jet fuel

>60 C

210 C

Kerosene

>3872 C

220 C

Vegetable oil

327 C

Biodiesel

>130 C

Flammable and combustible liquids

Under the Workplace

Hazardous Materials
Information System
(WHMIS): flammable
liquids have a flashpoint
below 37C (100F).
Combustible liquids have
a flashpoint at or above
37C (100F) and below
93C (200F).

Fuel

Flash
point

Autoignition
temperature

Ethanol

12.8 C

365 C

Gasoline
(petrol)

<40 C

246 C

Diesel

>62 C

210 C

Jet fuel

>60 C

210 C

Kerosene

>3872 C

220 C

Vegetable oil

327 C

Biodiesel

>130 C

Classification of Flammable Liquids

Flammable liquid refers to any liquid having a flash point below 100 F
(37oC). Such flammables are Class I liquids.
These liquids are subdivided into three classes. The following is an
illustrative list of common flammable liquids:

Class IA
Flash point below 73 F (22C), boiling point below 100 F (37C).
e.g. acetaldehyde
ethyl ether

ethyl chloride

petroleum ether

propylene oxide

pentane

Classification of Flammable Liquids

Class IB
Flash point below 73 F (22C), boiling point at or above 100 F (37C)

e.g. acetone

ethyl acetate

methyl alcohol

benzene

ethyl alcohol

methylcyclohexane

butyl alcohol

gasoline

toluene

Class IC
Flash point at or above 73 F (22C), and boiling point below 100 F
(37C).
e.g. amyl acetate
amyl alcohol

isopropanol
xylene

turpentine

Classification of Combustible Liquids

Combustible liquid refers to any liquid having a flash point at or above

100 F.
Combustible liquids are subdivided as follows:

Class II Flash point at or above 100 F (37C) and below 140 F (60C)
e.g.

acetic acid

camphor oil

methyl lactate

cyclohexane

hydrazine

kerosene

Class III Flash point at or above 140 F and below 200 F (93C)
e.g.

aniline

furfuryl alcohol

phenol

carbolic acid

naphthalenes

pine oil

Classes of Flammable and Combustible Liquids

Hazard

At normal room temperatures, flammable liquids can give

off enough vapor to form burnable mixtures with air. As a
result, they can be a serious fire hazard. Flammable liquid
fires burn very fast. They also give off a lot of heat and
often clouds of thick, black, toxic smoke.

Combustible liquids at temperatures above their

flashpoint also release enough vapor to form burnable
mixtures with air. Hot combustible liquids can be as
serious a fire hazard as flammable liquids.

Hazard

Spray mists of flammable and combustible liquids in air

may burn at any temperature if an ignition source is
present. The vapors of flammable and combustible liquids
are usually invisible, and hard to detect unless special
instruments are used.

Most flammable and combustible liquids flow easily. A

small spill can cover a large area of workbench or floor.
Burning liquids can flow under doors, down stairs
spreading fire widely. Materials like wood, cardboard and
cloth can easily absorb flammable and combustible
liquids.

Fire Flashback

Vapors can flow from open liquid containers. The vapors

from nearly all flammable and combustible liquids are
heavier than air.

If ventilation is inadequate, these vapors can settle and

collect in low areas like sumps, drains, pits and
basements. The vapor trail can spread far from the liquid.

If this vapor trail contacts an ignition source, the fire

produced can flash back (or travel back) to the liquid.

Flashback and fire can happen even if the liquid giving off
the vapor and the ignition source are hundreds of feet or
several floors apart.

TNT equivalent

TNT equivalent is a simple method for quantifying the energy

released in explosions. A typical value for the energy explosion of
TNT is 1120 cal/g = 4686 kJ/kg.

An equivalent mass of TNT is estimated using the following equation:

mTNT =

mTNTis the equivalent mass of TNT

is the empirical explosion efficiency

m is the mass of hydrocarbon
Hc is the energy of explosion of the flammable gas
ETNT is the energy of explosion of TNT

ATEX Directive

ATmosphres EXplosibles

Employers must classify areas where dangerous

explosive atmospheres may occur into zones.

The classification given to a particular zone, and its

size and location, depends on the likelihood of an
explosive atmosphere occurring and its persistence if it
does.

Areas classified into zones (0, 1, 2 for gas-vapor-mist and

20, 21, 22 for dust) must be protected from effective
sources of ignition.

ATEX Directive

Zone 0 and 20 are the zones with the highest risk of an

explosive atmosphere being present.

Equipment and protective systems intended to be used in

zoned areas must meet the requirements of the directive.

Zone 0 and 20 require Category 1 marked equipment,

zone 1 and 21 required Category 2 marked equipment
and zone 2 and 22 required Category 3 marked
equipment.

Where employees work in zoned areas are provided with

appropriate clothing that does not create a risk of an
electrostatic discharge igniting the explosive atmosphere.

Summary

Dangerous substance

Fire triangle: Conditions where fires and /or explosions

can occur.

Explosion: BLEVE, VCE, Detonation and Deflagration

Theoretical and experimental determination of

upper/lower flammability limits, flash point

Flammability diagram

Utilization of inerting to prevent fires/explosions.

Flammable and combustible liquids.