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
 falling objects, slips & trips, dangerous machinery, …

 Physical agents
 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 Ignition sources
 Solids  Sparks, flames,

 Metal peroxides, ammonium static electricity,

nitrate heat
 Gases

 Oxygen, fluorine, chlorine

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 fuel-
air mixture dose not sustain continuous
combustion. *Upper Explosive Limit
*Lower Explosive Limit

 .
Flammability/Explosive Limit
 The upper flammability limit (combustible-
rich 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
conditions of combustion. *Upper Explosive Limit
*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 Autoignition point of selected
substances in °C
temperature at which it will
spontaneously ignite without Silane >21
an external source of ignition. White phosphorus 34
Carbon disulfide 90
Diethyl ether 160
Diesel or Jet fuel 210
 This temperature is required to Gasoline (Petrol) 250
Magnesium 473
supply the activation energy Hydrogen 536
needed for combustion.
Autoignition Temperature

 The temperature at which a Autoignition point of selected

substances in °C
chemical will ignite decreases as
the pressure increases or Silane >21
White phosphorus 34
oxygen concentration increases. Carbon disulfide 90
It is usually applied to a Diethyl ether 160
Diesel or Jet fuel 210
combustible fuel mixture. Gasoline (Petrol) 250
Magnesium 473
Hydrogen 536
(not to be confused with the
flashpoint, which requires an
ignition source)
Flammability Limit for hydrocarbons

Hydrocarbon Formula LEL in UEL in Ignition

air air Temperature,
(%) (%) oC

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
Vapor/air mixture Concentration Vs. Temperature
A plot of concentration versus temperature shows how several definitions
are related
Boiling Point
Non-flammable region •
Upper flammable limit (UFL)
•
Vapor Conc. in air

Vapor
pressure curve

Lower flammable limit (LFL) Flammable region

•
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 (heat-
producing) 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

injuries / casualties Thermal radiation,

EFFECTS
property losses
process interruption
} 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 Detonation: An explosion in which
the reaction front moves at subsonic the reaction front moves at
speed (speed less than the speed of supersonic speed (speed greater than
sound) in the unreacted medium. the speed of sound) in the unreacted
medium. Flame propagation
Flame propagation velocity, typically
velocities, up to 2000 m/s, and
far below 100 m/s, and relatively
substantial overpressures, up to 20
modest overpressures, <0.5 bar. bars.
Substantial

Reaction front
Reaction front

overpressure

Shock front
modest
Shock front

overpressure

The reaction front moves at a speed Reaction front moves at a speed

less than sound, while the pressure greater than sound, driving shock
front moves away from the reaction front immediately preceding it. Both
front at the speed of sound. 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, Damage
~ kPa

0.5 Loud noise (143 dB)

2 “Safe distance” (probability of 0.95 of no serious

damage below this value)

4 Windows usually shatter, occasional damage to frame

5 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 <−40 °C 246 °C

(petrol)
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 a b
c
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
0.75
LFLT =LFL25 − (T − 25)
ΔH c
0.75
UFLT =UFL25 + (T − 25)
ΔH 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

1
LFL =
yi
∑ LFL
i

1
UFL =
yi
∑ UFL
i

yi = mole fraction of i on combustable basis

Experimental Determination - LFL, UFL

Run experiment at different fuel compositions with air:

10
Pressure (bar-gauge)
Maximum Explosion

LFL UFL
0
0 2 4 6 8 10

Fuel Concentration in air (vol%)

Flammability limits are an empirical artifact of experiment!

Test apparatus for accruing vapor explosion data
10

Pressure (bar-abs)
Pmax
8
TI PI
6

Igniter 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+¼x-½y
where z has units of moles O2/mole fuel.

Stoichiometric Conc. [vol%] = Cst

Cst = 21% / (0.21 + z)

 LFL = 0.55⋅Cst Approximate!

 UFL = 3.50⋅Cst
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. Nitrogen

 The diagram shows all possible The triangle represents the

relationship between fuel,
mixtures of methane, oxygen,
oxygen, and passive agents
and passive agents with the total concentration
(predominantly nitrogen in the equals 100%.
air).
 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.
Nitrogen
 The gray shaded area indicates
The triangle represents the
the mixtures of methane, oxygen,
relationship between fuel,
and passive agents that will be oxygen, and passive agents
flammable. 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 Air line represents all
2. Enter LFL & UFL possible combinations of
3. Determine z fuel plus air. The air line
extends from point where
4. LOC = z LFL
fuel is 0% to oxygen 21%
Oxygen 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%
Nitrogen + 100
 Constructing Flammability Diagram
Stoichiometric line represents all
5. Add Stoichiometric Line
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)
𝒛𝒛
Nitrogen 100
𝟏𝟏+𝒛𝒛
 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)
LOC
7. Construct curve

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
A UFL
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
LOC = 12 vol% O2
outside the flammable zone, a
mixture of this composition is not
flammable. LFL
Methane Flammability Diagram

The shape and size of the

flammability zone on a
flammability diagram A UFL
change with number of
parameters, including fuel
type, temperature, pressure
and other inert species.
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.
Flash Autoignition
 They are classified, or grouped Fuel
point temperature
as either flammable or
Ethanol 12.8 °C 365 °C
combustible, by their
Gasoline
flashpoints. <−40 °C 246 °C
(petrol)
 Generally, flammable liquids Diesel >62 °C 210 °C
will ignite (catch on fire) and Jet fuel >60 °C 210 °C
burn easily usually at normal Kerosene >38–72 °C 220 °C
working temperatures. Vegetable oil 327 °C
Combustible liquids have the Biodiesel >130 °C
ability to burn at temperatures
that are usually above working
temperatures.
Flammable and combustible liquids

 Under the Workplace Flash Autoignition

Fuel temperature
Hazardous Materials point
Ethanol 12.8 °C 365 °C
Information System
Gasoline
(WHMIS): flammable <−40 °C 246 °C
(petrol)
liquids have a flashpoint Diesel >62 °C 210 °C
below 37°C (100°F). Jet fuel >60 °C 210 °C
Kerosene >38–72 °C 220 °C
Combustible liquids have
Vegetable oil 327 °C
a flashpoint at or above Biodiesel >130 °C
37°C (100°F) and below
93°C (200°F).
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 (22°C), boiling point below 100 F (37°C).

e.g. acetaldehyde ethyl chloride petroleum ether

ethyl ether propylene oxide pentane
Classification of Flammable Liquids
 Class IB
Flash point below 73 F (22°C), boiling point at or above 100 F (37°C)
e.g. acetone ethyl acetate methyl alcohol
benzene ethyl alcohol methylcyclohexane
butyl alcohol gasoline toluene

 Class IC
Flash point at or above 73 F (22°C), and boiling point below 100 F
(37°C).

e.g. amyl acetate isopropanol turpentine

amyl alcohol xylene
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 (37°C) and below 140 F (60°C)
e.g. acetic acid camphor oil
methyl lactate cyclohexane
hydrazine kerosene
 Class III Flash point at or above 140 F and below 200 F (93°C)
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:

η 𝑚𝑚 ∆𝐻𝐻𝐻𝐻
mTNT =
𝐸𝐸𝑇𝑇𝑇𝑇𝑇𝑇
mTNTis the equivalent mass of TNT
η 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

 ATmosphères 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.