Faculty of Chemical Engineering

Universiti Teknologi MARA

Fires and Explosions:

CGE653
Health, Safety and Environment -
Part I
 Learning objectives
1. Describe the nature of fires and explosions.
2. Define the fire triangle and explain how to use it to
prevent flammable mixtures.
3. Characterize the flammability of gases, liquids, and
dusts.

CGE653
Health, Safety and Environment -
4. Estimate flammability parameters for mixtures.
5. Draw a flammability triangle diagram and apply it.
6. Identify the types of fire.
7. Describe the effects of fire on people.
8. Estimate the effects of fire on people using Probit equation.
Source: Chemical Process Safety: Fundamentals with Applications (3rd Edition)
(International Series in the Physical and Chemical Engineering Sciences) 3rd Edition, pp:
239 -264
by Daniel A. Crowl (Author), Joseph F. Louvar (Author)
INTRODUCTION

Health, Safety and Environment -

CGE653
 Three most common
chemical plant accidents
FIRES

CGE653
Health, Safety and Environment -
This Photo by Unknown Author is licensed under
CC BY

This Photo by
EXPLOSIONS This Photo by Unknown Author is licensed
under CC BY-SA

Unknown
Author is
licensed under
CC BY-SA-NC

TOXIC RELEASES
 CAUSES
LIVES LOST AND INJURY PROPERTY AND EQUIPMENT DAMAGE

CGE653
Health, Safety and Environment -
ENVIRONMENTAL POLLUTION BUSINESS CONTINUITY
 What engineers need to know?

To prevent accidents resulting from fires

and explosions, engineers must be

CGE653
Health, Safety and Environment -
familiar with:
• The fire and explosion properties of materials
• The nature of the fire and explosion process
• Procedures to reduce fire and explosion hazards
 Fire

Oxidisers: Fuels:
Gases: oxygen, fluorine, Liquid: gasoline, acetone,
chlorine ether, pentane
Liquids: hydrogen peroxide, Solids: plastics, wood dust,
fibers, metal particles

CGE653
Health, Safety and Environment -
nitric acid, perchloric acid
Solids: metal peroxides, Gases: acetylene, propane,
ammonium nitrite hydrogen

Ignition sources:
Sparks, flames, static electricity, heat

Remove any side of the triangle,

and the fire will be extinguished.
 Fire
• So, fire will not occur if:
 Fuel is not present or is not present in sufficient
quantities
 An oxidiser is not present or is not present in sufficient

CGE653
Health, Safety and Environment -
quantities
 Ignition source is not energetic enough to initiate the
fire

 Robust control
 Prevent flammable mixtures rather than elimination or
reduction in ignition source.
 The combustion process
• Fire or combustion is a chemical reaction in which a
substance combines with an oxidant and heat is
released (exothermic oxidation).

CGE653
Health, Safety and Environment -
• Combustion always occurs in the vapour phase.
• Liquids are volatised and solids are decomposed into
vapour upon heating – if the concentration of vapour
is high enough, it forms a flammable mixture with the
oxygen of the air.
• If this flammable mixture is heated further to its
ignition point, combustions starts.
Combustion Behavior – Most Hydrocarbons

CGE653
Health, Safety and Environment -
Smoke and fire are very visible!

Slide courtesy of Reed Welker.

Combustion Behavior – Carbon Disulfide

CGE653
Health, Safety and Environment -
No smoke and fire, but heat release rate just as high.

Slide courtesy of Reed Welker.

 Combustion Behavior – Methane

CGE653
Health, Safety and Environment -
Methane burns mostly within vessel, flame shoots out of vessel.
 Combustion Behavior – Dusts

CGE653
Health, Safety and Environment -
Much of the dust burns outside of the chamber.
 Distinction between fires and
explosions
• The major distinction is the rate of energy release.
• Fires release energy slowly, whereas explosions
release energy rapidly (in the order of microseconds).

CGE653
Health, Safety and Environment -
• Fires can also result from explosions, and explosions
can result from fires.
DEFINITIONS

Health, Safety and Environment -

CGE653
 Definitions
• Combustion: Chemical reaction in which a
substance combines with an oxidant and releases
energy. Part of the energy release is used to
sustain the reaction.

CGE653
Health, Safety and Environment -
• Ignition: Caused by a flammable mixture coming
in contact with a source ignition with sufficient
energy.
• Auto-Ignition Temperature (AIT): Temperature
above which adequate energy is available in the
environment to provide an ignition source.
 Definitions
• Flash Point Temperature: Temperature
above which a liquid produces enough
vapor to form an ignitable mixture with air.
• Defined only for liquids at 1 atm.

CGE653
Health, Safety and Environment -
pressure.
• Fire point: Lowest temperature at which a
vapor above a liquid will continue to burn
once ignited. Usually higher than the flash
point.
 Definitions
LFL: Lower Flammability Limit
Below LFL, mixture will not burn, it is too lean.
UFL: Upper Flammability Limit

CGE653
Health, Safety and Environment -
Above UFL, mixture will not burn, it is too rich.
Defined only for gas mixtures in air.
UNITS: volume percent in air
Can also define flammable limits in pure oxygen:
LOL and UOL:
UNITS: volume percent in O2
 Definitions
Limiting Oxygen Concentration (LOC): Oxygen
concentration below which combustion is not
possible, with any fuel mixture.
Expressed as volume % oxygen.

CGE653
Health, Safety and Environment -
Also called: Minimum Oxygen Concentration (MOC)
Max. Safe Oxygen Concentration (MSOC)
Possibly others…
FLAMMABILITY

Health, Safety and Environment -

CGE653
 Flammability Relationships
Saturation Vapor Pressure Curve

Vapor pressure / concentration

UFL
Flammable
Liquid

CGE653
Health, Safety and Environment -
Auto-ignition zone
Gas
LFL

Flash Point AIT: Auto Ignition Temp

Temperature  Ambient Temperature
Figure 6-2
 Flammability limit
• Flammability limits for vapours are determined
experimentally.
• For a mixture, LFL and UFL are computed using Le

CGE653
Health, Safety and Environment -
Chatelier equation:
1
LFL mix = n
yi …………………………………(6.2)
∑
i =1
(LFL)i
Where,
LFLi is the lower flammability limit for component i (in volume %)
yi is the mole fraction of component i on a combustible basis
n is the number of combustible species
Flammability limit

1
UFL mix = n …………………………………(6.3)
yi
∑ (UFL)i

CGE653
Health, Safety and Environment -
i =1
Example 6-2
What are the LFL and UFL of a gas mixture composed of
0.8% hexane, 2.0% methane, and 0.5% ethylene by
volume?
Is the mixture flammable?

CGE653
Health, Safety and Environment -
Solution to Example 6-2
Volume% Mole fraction on LFL (vol%) UFL (vol%)
combustible basis
Hexane 0.8 0.24 1.2 7.5
Methane 2.0 0.61 5.0 15.0

CGE653
Health, Safety and Environment -
Ethylene 0.5 0.15 2.7 36.0
Total Combustible 3.3
Air 96.7

Use eq 1.1, LFLmix = 2.65% by volume total combustible

Use eq 1.2, UFLmix = 13.0% by volume total combustible

Because the mixture contains 3.3% total combustible,

its is flammable.
Flammability limit behavior:
Temperature dependence
As temperature increases:
UFL increases, LFL decreases
--> Flammability range increases
0.75 100CP

CGE653
Health, Safety and Environment -
LFLT= LFL25 − (T − 25 )= LFL25 − (T − 25 )
∆H c ∆H c

0.75
UFLT = UFL25 + (T − 25) Equations 6-4, 6-5
∆H c
Approx. for many
T : oC hydrocarbons

∆H c : kcal/mole, heat of combustion

Flammability limit behavior:
Pressure dependence
As pressure increases:
UFL increases
LFL mostly unaffected

CGE653
Health, Safety and Environment -
UFLP = UFL + 20.6 * (logP + 1) (6-6)

P is pressure in mega-Pascals, absolute

No theoretical basis for this yet!

Pressure and temperature effects on flammability limits are poorly

understood – estimation methods are poor.
 Estimating flammability limit
• Estimate without experimental data
• For many hydrocarbon vapours, the LFL and the UFL
are a function of the stoichiometric concentration (Cst)
of fuel:

CGE653
Health, Safety and Environment -
LFL = 0.55Cst …………………………………(6-7)

UFL = 3.50Cst …………………………………(6-8)

Where,
Cst is volume % fuel in fuel plus air
 Estimating flammability limit
• The stoichiometric concentration for most organic
compounds is determined using the general
combustion reaction.

CGE653
Health, Safety and Environment -
x
C mHx O y + zO 2 → mCO 2 + H2O
2

O2 Balance gives you

y x x y
+z=m+ OR z=m+ −
2 4 4 2
Where z has units of moles O2/mole fuel
 Estimating flammability limit
• Additional stoichiometric and unit changes are
required to determine Cst as a function of z.
moles fuel
Cst = × 100
moles fuel + moles air

CGE653
Health, Safety and Environment -
100
=
 moles air 
1+  
 moles fuel 
100
=
 1  moles O 2 
1+   
 0.21  moles fuel 
100
=
 z 
1+  
 0.21 
Estimating flammability limit
x y
z=m+ −
4 2

Substituting z and applying equations 6-7 and 6-8

CGE653
Health, Safety and Environment -
0.55(100 )
LFL = ………………………….(6-10)
4.76m + 1.19 x − 2.38 y + 1

3.50(100 )
UFL = ………………………….(6-11)
4.76m + 1.19 x − 2.38 y + 1
Example 6-4
Estimate the LFL and the UFL for hexane, and compare the
calculated limits to the actual values determined
experimentally.

CGE653
Health, Safety and Environment -
 Solution to Example 6-4
• The stoichiometry of hexane combustion is:
x
C6H14 + zO 2 → mCO 2 + H2O
2

CGE653
Health, Safety and Environment -
m=6
x = 14
y= 0
From eq 6-10, LFL = 1.19 vol%
From eq 6-11, UFL = 7.57 vol%
Compare these values with those in the flammability
data table…. (LFL = 1.2 vol%; UFL = 7.5 vol%)
Estimating flammability limit
• Flammable limits can also be in pure oxygen
• LOL = lower oxygen limit
Oxygen concentration at
• UOL = upper oxygen limit the upper flammable
• Units = % in oxygen limit (vol. % oxygen in
air)

CGE653
Health, Safety and Environment -
UFL 100 − CUOL (100 − UFLO )
UOL = 6-14
UFLO + UFL 1 − CUOL

Fitting constant = -1.87

Example 6-5
Estimate UOL for methane.
From data table, the UFL is 15.0 vol. % fuel in air.

Assume a basis of 100 moles of gas mixtures.

15 moles → methane

CGE653
Health, Safety and Environment -
85 moles → air

Air contains 21% oxygen

Moles of oxygen = 85(0.21) = 17.85 moles of oxygen
∴UFLO = 17.85%

Substitute all values in Equation 6-14. Answer = 62.4%

 Estimating LOC
• LFL is based on fuel in air.
• However, oxygen is the key ingredient and there is a
minimum oxygen concentration required to propagate

CGE653
Health, Safety and Environment -
a flame.
• Fires and explosions can be prevented by reducing the
oxygen concentration regardless the concentration of
fuel.
• This concept is the basis for a common procedure
called inerting.
 Estimating LOC
• Below the LOC, the reaction cannot generate enough
energy to heat the entire mixture of gases to the
extent required for the self-propagation of the flame.

CGE653
Health, Safety and Environment -
• LOC is estimated by using the stoichiometry of the
combustion reaction and the LFL.

LOC = z(LFL ) ………………………….(6-15)

Example 3
Estimate the LOC for butane (C4H10)
 Solution to Example 3
• The stoichiometry of hexane combustion is:
C 4H10 + 6.5O 2 → 4CO 2 + 5H2O

CGE653
Health, Safety and Environment -
• The LFL for butane = 1.8%

LOC = 6.5(1.8) = 11.7% O 2

Flammability Diagram
Upper limit in 100
pure oxygen
Air Line
Flammability 20 80
Zone A

CGE653
Health, Safety and Environment -
40 60

60 40
Lower limit in
pure oxygen
80 UFL 20

MOC
100 LFL 0
0 20 40 60 80 100

Nitrogen
 Flammability Diagram
Useful for:
• Determining if a mixture is flammable.
• Required for control and prevention of flammable
mixtures

CGE653
Health, Safety and Environment -
Problems:
• Only limited experimental data available.
• Depends on chemical species.
• Function of temperature and pressure.

Flammability diagram can be approximated.

Flammability Diagram - 1
(1) Fuel + (z) Oxygen ---> Products

0 100
60% Fuel,
25% 25% Oxygen,
15% Nitrogen
60%

100 0
0 15% 100
Nitrogen
Flammability Diagram - 2
(1) Fuel + (z) Oxygen ---> Products
0 100
Air Line, all combinations of
fuel + air

CGE653
Health, Safety and Environment -
UFL
Flammable % Fuel in Air
LFL
100
0 100 0
Nitrogen
Flammability Diagram - 3
Air line always extends

FROM: Fuel: 0%, Oxygen: 21% Nitrogen: 79%

CGE653
Health, Safety and Environment -
TO: Fuel: 100%, Oxygen: 0%, Nitrogen: 0%

Equation for this line:

Fuel = -(100/79) Nitrogen + 100

 Flammability Diagram - 4
(1) Fuel + (z) Oxygen ---> Products
0 100 CH4 + 2 O2 --> Products
𝑧𝑧
100 z=2

CGE653
Health, Safety and Environment -
1 + 𝑧𝑧
𝑧𝑧
100 (6-19)
1+𝑧𝑧

Flammable
100 0
0 100
Nitrogen
Flammability Diagram - 5
Stoichiometric line always extends from:

FROM: Fuel: 100/(1+z),

Oxygen: 100z/(1+z)

CGE653
Health, Safety and Environment -
Nitrogen: 0%

TO: Fuel: 0%,

Oxygen: 0%,
Nitrogen: 100%

Equation for this line:

Fuel = (100 – Nitrogen)/(1+z)

Flammability Diagram - 6
(1) Fuel + (z) Oxygen ---> Products
0 100
LOC

CGE653
Health, Safety and Environment -
UFL

Flammable LFL
100 0
0 100
Nitrogen
 Approximation of the
flammability zone – Method 1
1. Draw flammability limits in air as
points on the air line.
2. Draw flammability limits in pure
oxygen as points on the oxygen
scale.

CGE653
Health, Safety and Environment -
3. Use Equation 6-19 to locate the
stoichiometric point on the oxygen
axis, and draw the stoichiometric
line from this point to the 100%
nitrogen apex.
4. Locate the LOC on the oxygen axis,
and draw a line parallel to fuel axis
until it intersects with the
stochiometric line. Draw a point at
this intersection.
5. Connect all the points shown.
TYPE OF FIRES

Health, Safety and Environment -

CGE653
 Hydrocarbon releases
 Hydrocarbon releases in the petroleum
industry are either gaseous, mists or liquids
and are either atmospheric releases or

CGE653
Health, Safety and Environment -
pressurised.
 Gas and mist releases are considered more
significant since they are readily ignitable.
 The cause of release can be from corrosion,
erosion, equipment wear, metallurgical defects
or human errors.
 Gaseous releases
 There are a number of factors that determine the
release rate and initial geometry of a hydrocarbon
gas release.
 The most significant is whether the gas is under

CGE653
Health, Safety and Environment -
pressure or released at atmospheric conditions.
 If released under atmospheric conditions, the gas
will either rise or fall depending on its vapour
density and will be directed in the path of the
prevailing wind.
 The atmospheric releases, if ignited, will burn
relatively close to the source point.
 Gaseous releases
 The pressurised gas is released as gas jet and
depending on the nature of the failure may be directed
at any direction.
 The released hydrocarbon gas/vapour will generally

CGE653
Health, Safety and Environment -
produce a vapour cloud.
 The cloud, if not ignited will eventually disperse in the
atmosphere.
 Initially escaping gases are above the UFL but with
dispersion and turbulence effects they rapidly pass into
the flammable limits. If not ignited and given adequate
distance they will eventually disperse below the LFL.
 Mist or spray releases
 Spray and mists release generally behave like a gas
or vapour release.
 The fuel is highly atomised and mixed with air.

CGE653
Health, Safety and Environment -
 Spray or mists can easily be ignited, even below the
flash point temperature of the material involved,
since mixing of the fuel with the air has already
occurred.
 Liquid releases
 Liquid releases can be characterised by either being
contained, allowed to runoff or spread.
 If they are highly volatile, dissipation by
vapourisation may occur when the vapourisation

CGE653
Health, Safety and Environment -
rate equals the spread rate.
 Depending on the viscosity, they will form into a
“pool” of liquid – the higher the viscosity the longer
it will take to spread.
 Most liquid fires are relatively easy to contain and
supress while gas fires are prone to explosion.
 Ignition Sources

Health, Safety and Environment -

CGE653
Types of hydrocarbon fire

•Jet fire
•Pool fire

CGE653
Health, Safety and Environment -
•Flash fire
 Jet Fire
• A jet fire is the combustion of material emerging with
significant momentum from a source under pressure,
e.g. a flammable liquid or gas is ignited after its
release from a pressurized, punctured vessel or pipe.

CGE653
Health, Safety and Environment -
• The pressure release generates a long flame which is
stable under most conditions.
• The duration of a jet fire is determined by the release
rate and the capacity of the source.
• Flame length increase directly with flow rate.
 Jet Fire

Health, Safety and Environment -

CGE653
 Pool Fire
• A pool fire is the combustion of flammable vapor
evaporating from a layer of liquid at the base of the
fire.

CGE653
Health, Safety and Environment -
Pool of liquid
 Pool Fire
• It occurs on ignition of an accumulation of liquid as a
pool on the ground or on water or other liquid.
• A storage tank fires are usually treated as pool fires.

CGE653
Health, Safety and Environment -
• A steadily burning fire is rapidly achieved as the vapor
to sustain the fire is provided by the evaporation of
the liquid by heat from the flames.
• Pool fire are less dangerous to human life than flash
fire.
• However, their longer duration results in greater
structural and equipment damage.
 Pool Fire

Health, Safety and Environment -

CGE653
 Flash Fire
• Flash fire is a combustion event with little or no
overpressure.
• As the name implies, it proceeds in a very fast time

CGE653
Health, Safety and Environment -
scale until the fuel is consumed.
• As fuel gas is released into air, typically its
concentration is very high near the release point and
it is not well mixed in the air. If the gas ignites at that
time, generally the result is a flash fire.
• Flash fires consume escaping fuel so it is not available
for further mixing in air.
 Flash Fire

Health, Safety and Environment -

CGE653
EFFECTS

Health, Safety and Environment -

CGE653
 Effects of Fire on People
• The main hazards present from large open fires are
due to heat radiation.
• A first degree burn

CGE653
Health, Safety and Environment -
 At a mild level causing reversible reddening, erythema.
 No blisters are formed and only the epidermis is affected.
 The skin usually reverts to normal within 24 hours.
• A second degree burn
• Is characterized by formation of blisters.
• The blister depth may be shallow with only the surface layer
of the skin damaged.
• In more severe cases the whole of the dermis is damaged.
 Effects of Fire on People
• A third degree burn
 Is a deep burn characterized by the destruction of the skin
layers and part of the subcutaneous tissue.
• The thermal radiation effects on people depend upon

CGE653
Health, Safety and Environment -
the length of time the people are exposed to a
specific thermal radiation level.
• Longer exposure durations, even at a lower thermal
radiation level, can produce serious physiological
effects.
 Degree of burn

Health, Safety and Environment -

CGE653
 Effects of Fire on People
• Burn or deaths are a direct consequence of the
intensity of the radiated heat flux from the fire and
the exposure time.
• To determine the number of burns and deaths, the

CGE653
Health, Safety and Environment -
term “thermal radiation dose” is employed.

D = t eff (q ' )4 / 3 ………………………….(1)

Where
D = thermal radiation dose (W4/3 s.m-8/3)
q’ = heat flux (W/m2)
teff = person’s exposure time to the heat flux
 Effects of Fire on People
• The exposure time of a person to a fire depends upon
several factors:
 The type of fire
 The position of the person in relation to the fire
 The time he takes to react and how he reacts when he

CGE653
Health, Safety and Environment -
realises the event, as well as parameters like his age and
physical conditions.
• The exposure time of a person in the case or fire balls and
flash fires is actually equal to the duration of the fire (< 1
min).
• In case of pool fires and jet fires, the duration of the fire is
longer and the person’s exposure time to the radiated
heat flux depends upon the time he takes to react and run
away.
 Effects of Fire on People
• The exposure time, teff (s) is usually taken as equal to
the sum of an initial reaction time plus the time
required to reach a safe point
xo − r
t eff = tr +

CGE653
Health, Safety and Environment -
………………………….(2)
u
Where
tr = reaction time (= 5 s)
xo = the distance between the flame and the position where the
intensity of heat flux is lower than 1 kW/m2
teff = person’s exposure time to the heat flux (s)
r = the distance of the person from the surface of the flame (m)
u = the escape velocity taken as 4 m/s
 Probability of Injury or Death

• In order to estimates the effects from fires, dose-

response curves are usually employed.
• Dose-response relations have been created from

CGE653
Health, Safety and Environment -
experimental or field data for various parameters like
thermal radiation, overpressure, heat, noise,
concentration of toxic gases etc.
• The most widely used method today is the method of
Probit functions.
Probit equation

Y = k1 + k 2 lnV

CGE653
Health, Safety and Environment -
Where:
Y = Probit Variable
k1 and k2 = constants
V = Causitive Variable
Probit for the effects of fire

Effect k1 k2 V

CGE653
Health, Safety and Environment -
1st Degree Burn -39.83 3.0186 Thermal radiation dose (D)

2nd Degree burn -43.14 3.0186 Thermal radiation dose (D)

Death -36.38 2.56 Thermal radiation dose (D)

 Percentage
Conversion of Probit to

Health, Safety and Environment -

CGE653
 Example 1
Find the percentage of people that suffer 1st degree
burn, 2nd degree burn and death from an exposure to
thermal radiation dose of 9,000,000 W 4/3 s. m-8/3 .

CGE653
Health, Safety and Environment -
Solution
Probit Equation
Y = k1 + k 2 lnV
 Effect k1 k2 V

Solution
1st Degree -39.83 3.0186 Thermal radiation
Burn dose (D)
2nd Degree -43.14 3.0186 Thermal radiation
burn dose (D)
Death -36.38 2.56 Thermal radiation
dose (D)
1st degree burn:
Y = −39.83 + 3.0186 lnD

CGE653
Health, Safety and Environment -
2nd degree burn:
Y = −43.14 + 3.0186 lnD
Deaths:
Y = −36.38 + 2.56 lnD
Solution
4/3 -8/3
For D = 9,000,000 W sm
1st degree burn:

CGE653
Health, Safety and Environment -
Y = 8.51
2nd degree burn:
Y = 5.20
Deaths:

Y = 4.61
 Percent Affected
From probit-percentage conversion table

Percent Affected (%)

CGE653
Health, Safety and Environment -
1st Degree Burn 100

2nd Degree Burn 58

Deaths 35
Summary
• Fire triangle
• Difference between fire and explosions
• Flammability
• Liquid

CGE653
Health, Safety and Environment -
• Flash point
• Fire/ Ignition point
• Vapour/ Gases
• LFL
• UFL
• Flammability diagram
• LFL
• UFL
• LOC
Summary
• Pool fire
• Jet fire
• Flash fire
• Effects of fire on people

CGE653
Health, Safety and Environment -
• Usage of Probit for the probability of injury or death