Chapter ONE Full PDF

CHAPTER ONE
•01 FIRE INVESTIGATION CASE STUDY

•02 FUNDAMENTALS OF FIRE SCIENCE
TABLE OF •03 FUEL AND COMBUSTION PROCESS

CONTENT •04 THE PHYSICAL CHEMISTRY OF
COMBUSTION IN FIRES
•05 LIMITS OF FLAMMABILITY

SECTION 1
FIRE INVESTIGATION CASE STUDY
HISTORY OF FIRE INCIDENTS
• 9-STOREY GARMENT
FACTOR
» Bangladesh
» 24 Nov 2012
» 112 people kill
» No exterior fire escape
» Not enough exits in the
building
MEC654 // Study Materials by AAR 4

• MGM GRAND HOTEL
» Las Vegas
» Nov 1980/85 people kill
» Fire started at delicatessen
» Partial sprinklers only
» Most victims died of smoke
inhalation
» Smoke spread rapidly through
the building
» Wake-up call to the industry to
improve the fire safety standard

• ROYAL JOMTIEN RESORT
HOTEL
» Thailand/July1997/102 death
» Fire started in kitchen from gas
bottle explosion due to ignition
of a faulty gas cylinder (codes –
gas should be stored outside)
» Door locked to prevent patrons
leaving without settling bills
» Fire stairs not fire rated

• REGENT PLAZA HOTEL IN
KARACHI
» Pakistan/Dec 2016/11 deaths
» No fire exits and alarms
» Smoke detectors not function
» Suffocating smoke kept
circulating within the building
because staff could not be
found to turn of the air-
conditioning system.

• GOTHENBURG DISCO
» Sweden/Oct 1988/63 deaths
» Bodies “piled” at exit, blocking
egress path
» No sprinklers
» Insufficient egress
» Obstructed egress

• SULTANAH AMINAH HOSPITAL
» Malaysia
» 25 Oct 2016/6 deaths
» The fire was caused by a light
capacitor which came into
contact with some combustible
materials lying underneath

FIRE INCIDENTS IN HOSPITAL
• Major fire incidents that took place in several hospitals
in Malaysia
» May 30, 1993: Part of the second floor of the
administration block at the Faculty of Medicine,
Universiti Kebangsaan Malaysia, located next to Kuala
Lumpur General Hospital (now Kuala Lumpur Hospital),
was destroyed in a fire at 2.30am. No one was reported
killed.
» July 8, 1993: A fire broke out at the Neurology Institute
of the same hospital at 2am. Some 190 patients had to be
evacuated. Total loss was recorded at about RM200,000.
in Malaysia
» Jan 16, 1995: Several construction items kept by a
contractor under a staircase were destroyed in a fire that
occurred at the third floor of Universiti Hospital (now
University Malaya Medical Centre).
» May 2, 2007: Power supply tripping in an elevator caused
a small fire on the first floor of the Neurology Ward of
the Kuala Lumpur Hospital (HKL). Some 50 patients and
visitors had to be evacuated.

in Malaysia
» July 30, 2011: A fire broke out at the Mental Patients
Isolation Room of the HKL’s Emergency Department. It
was caused by a mentally-ill patient who ignited a
lighter. The incident occurred at 12.30am, causing the
rapid spread of fire with thick smoke. One person was
reported killed
» Aug 15, 2016: A small fire broke out at a storeroom of
Hospital Sri Kota, Klang. No evacuation of patients or
visitors was carried out. No deaths were reported.
• DARUL QURAN ITTIFAQIYAH
RELIGIOUS RESIDENTIAL
SCHOOL
» Malaysia
» 25 Sept 2017/23 deaths
» The fire started from outside
the door of the hostel, trapping
them in.
» Two gas canisters was
contributed to a bigger cause of
the fire and it spread fast

FIRE INCIDENTS IN SCHOOL (TAHFIZ)
• Major fire incidents that took place in several religions
school
2017
» Jan 13 : A tahfiz student sustained injuries in a fire at the
hostel of Pondok Nurul Iman in Kampung Tanjung Batu,
Nenasi in Pekan, Pahang.
» Jan 16 : The An-Nuur Islamic Education Centre, better
known as Pondok an-Nuur in Pantai Sepat, Kuantan,
Pahang which housed 113 students was razed in a fire.
(This was the second incident after the first in 2006,
which also razed the students’ hostel ).

school
2017
» Feb 7 : A total of 73 female religious school students in
Maran, Pahang were left with just the clothes on their
back when a fire destroyed their hostel.
» Feb 28: Pondok Al-Baghdadi in Tumpat, Kelantan which
accommodated 100 students aged between 15 and 30,
was destroyed in a fire. No casualties were reported.

school
2017
» April 17: Ten residential buildings of Pondok Seri Permai
in Pasir Puteh, Kelantan were destroyed in a fire,
incurring losses estimated at RM161,000.
» April 30: Thirty students of Mahaad Tahfiz Al-Quran Al-
Ismailiyah Mukim Lalang, Banggol Chicha, Pasir Mas,
Kelantan saw their hostel reduced to ashes in a blaze.

school
2017
» April 17: Ten residential buildings of Pondok Seri Permai
in Pasir Puteh, Kelantan were destroyed in a fire,
incurring losses estimated at RM161,000.
» April 30: Thirty students of Mahaad Tahfiz Al-Quran Al-
Ismailiyah Mukim Lalang, Banggol Chicha, Pasir Mas,
Kelantan saw their hostel reduced to ashes in a blaze.

school
2017
» July 3 : The store room of the Al-Islah residential
religious school in Teluk Intan, Perak, which
accommodated 68 students, was destroyed in a fire.
» July 4: The Addiniah Al-Latifiah residential religious
school in Pengkalan Hulu, Perak, which had 66 students,
was destroyed in a fire.

school
2017
» July 30: Two hostel blocks of Maahad Tahfiz Al-Barakah
in Sepang, Selangor which housed 100 male students
were razed in a fire.

school
2016
» Jan 18 : The two-storey building which housed 30
students of Al-Redzuan residential religious school in
Kampung Dato Ahmad Razali, Dengkil, Selangor was
razed in a fire.
» March 7: A total of 60 students of Darul Itqan Al-
Muhammadi residential religious school in Kampung
Batu 40, Sabak Bernam, Selangor lost their hostel to a
fire. MEC654 // Study Materials by AAR 20
school
2016
» March 3: The hostel of Maahad Tahfiz at-Tijarah at Jalan
Bukit Idaman 8, Bukit Idaman in Selayang, Selangor was
among the premises destroyed in a fire.
» May 11 : Madrasah Tahfiz Al-Quran Raudhatul Ulum,
Bagan Selat, in Butterworth, Penang was destroyed in a
fire. No casualties were reported.

school
2016
» June 18 : The hostel of Madrasah Diniah Bakriah Pondok
Pasir Tumboh, which housed more than 50 students was
razed in a fire. No casualties were reported.(According to
the Kelantan Fire and Rescue Department, this was its
second fire-related incident. The first was on July 2016).
» Sept 22 : Maahad Tahfiz Daril Naim in Pangkal Kala,
Melor, Kota Bharu in Kelantan was razed in a fire.

school
2015
» May 6 : The premises that housed the essential items of
the students of Ribat Assyafie residential school in Taman
Murni Perdana, Dungun, Terengganu was destroyed in a
fire.
» May 13: The hostel of Tahfiz Khairul Kalam in Jalan
Kebun, Shah Alam, Selangor which had 26 students was
destroyed in a fire.
school
2015
» July 29 : Three students of Raudhatut Tahfiz residential
religious school in Km2, Jalan Gunung Jerai in Guar
Cempedak, Kedah suffered burns when a fire broke out
at their hostel.
» Aug 28: The hostel of Madrasah Tahfiz Al-Zahra in
Kampung Ladang, Gelang Patah in Johor Baharu, Johor
was razed in fire about 6am.
school
2015
» Oct 21: A fire destroyed 70 per cent of the Al Ummi
religious school in Labuan; however, all of its students
and teachers were safe.

school
2014
» Feb 14 : Seventeen students of Maahad Tahfiz
Muhammadiah, Bukit Rangin in Kuantan, were left
without their two-storey school.

school
2013
» June 15 : A student of Maahad Tahfiz Al-Barakah
(Mantab), Kampung Masjid, Tikam Batu, near Sungai
Petani, Kedah was found burnt to death, and two others
injured when a fire destroyed their hostel.
» July 4 : A total of 81 students of the Kunak religious
school in Sabah lost their belongings when their
temporary hostel for male students was destroyed in a
blaze.
• Major fire incidents that took place in several religions school
2012
» Jan 25 : A hostel for male students at the Sekolah Menengah
Agama Nadzah, Bukit Besar in Yan, Kedah was destroyed in a
fire believed to have been caused by short-circuit. (Fire had
also broke out in 1996 and 2005 at the same school)
» Sept 9 : The second floor of the Assyifa residential religious
school in Kampung Kolam, Kuala Ibai in Terengganu, which
housed 25 students, was destroyed in a fire while the
students performed Zohor prayers at a nearby surau.

school
2011
» Jan 16 : The top floor of the two-storey Maahad Qiraat
Al-Azhar Amal Aimy Zdalifah at Km3, Jalan Sungai
Korok, Sultan Abdul Halim Highway in Alor Setar, Kedah
was destroyed in a fire about 10.50am.

school
2010
» Jan 22 : Sekolah Pondok Lubuk Tapah, Kelantan’s oldest
religious and educational centre was destroyed in a fire.
» July 25 : An eight-year-old student of a private religious
school in Hulu Langat, Selangor was burnt to death in a
1.30am fire.

school
2009
» Jan 1 : A fire which broke out at Sekolah Madrasah Darul
Hikmah in Kota Kinabalu, Sabah left damage estimated
at about RM200,000. However, no casualties were
reported

school
2007
» Aug 7 : Twelve students of Sekolah Menengah Agama
Darul Makmur in Pekan, Pahang, were unable to sit for
an examination after their school building was destroyed
in a fire.
» Sept 22 : A fire destroyed Sekolah Pondok Bandar Hilir in
Teloi, Sik, Kedah, However, there were no casualties as
the incident happened during a school holiday.
school
2007
» Oct 22 : A hostel block which housed 96 students of
Sekolah Nurul Hidayah Al-Quran Maahad Tahfiz Pasir
Puteh, Kelantan was destroyed in a fire.

SECTION 2
FUNDAMENTALS OF FIRE SCIENCE
MATTER, DENSITY, SPECIFIC GRAVITY
• Matter (3 states) • Fundamental property of
» Solid matter
» Liquid
» Gas (vapour) Matter (
 kg m3 )
Water 1000
Mercury 13600
Petrol 750
Air 1.2

MATTER, DENSITY, SPECIFIC GRAVITY
Relative Density = Specific
Possess mass & occupy space
Gravity
mass Density of substance

Density = SG =
volume Density of water
=
m No Units
V
Units : kg m3 or g cm3

GASES & VAPOURS
• Their density is governed by the ideal gas law
PV = RT
P is the pressure in N/m2 or Pa
V is the volumein m3
 is the number of kmols
R is the universal gas constant = 8314 J Kmol.K
T is the temperature in Kelvin
1 P
Therefore,  =
RG T
CONVECTIVE FLOWS
 SG SG
• For gas and vapours At 295K (kg m ) 3
(Hydrogen = 1) (air = 1)
specific gravity (SG) is H2 0.083 1.0 0.07
usually expressed relative CH4 0.66 8.0 0.55
to hydrogen (Because it is Air 1.19 14.3 1.0
the lightest gas) C3H8 1.82 21.9 1.53
CO2 1.82 21.9 1.53
• For hazard applications it is Fire gases
more convenient and 0.292 3.5 0.25
(at 1200K)
informative to express SG
relative to that of air.
CONVECTIVE FLOWS
• Fire are characterised by buoyant flows
» Due to pressure differences arising from density
differences which are the result of temperature
differences
» These pressure differences although small in absolute
terms are responsible for
⊳Drawing air into the based of fire
⊳Expelling hot gases from confined spaces

CONVECTIVE FLOWS
» The stairwell may be regarded as a tank full of hot light
gas communicating at the base with another tank full of
cold gas, i.e the surrounding outside air

CONVECTIVE FLOWS
» Relevant to toxic and flammable gas dispersion, fire
spread and smoke movement due to the fire buoyancy
effects also relevant to building stack-effect to be
discussed later.
Hot Cold
gas
ρH
air
ΔP = PA − PB
h
ΔP = (ρc − ρH ) gh
Tc ρc
A B
Combustion

VAPOUR PRESSURES OF LIQUIDS
• Liquid molecules escape from free surface to form
vapour.
• If the system is closed a state of kinetic equilibrium is
reached.
» Molecules going to vapour state = molecules going to liquid
state
• The partial pressure of the vapour above the surface

reaches a level at which there is no further net
evaporation.
• For a pure liquid this is the saturated vapour pressure, a
property which varies with temperature according to
log(p0) = (-0.2185E/T) +
F
» where p° is the equilibrium vapour pressure in mmHg
and E and F are constants and T is in Kelvin. Values of
these for some liquid fuels are given in the Table below
(Table 1.1, Drysdale, 1995). This equation may be used to
calculate the vapour pressure above the surface of a pure
liquid to assess the flammability of the vapour /air
mixture
Open Container: Closed Container:

Evaporation rate exceed Evaporation rate exceed
condensation rate condensation rate
equilibrium never achieved equilibrium achieved

Table 1: Vapour pressures of organic compounds (Weast, 1974/75)
Temperature range
Compound Formula E F
(C)
n-Pentane n-C5H12 6595.1 7.4897 -77 to 191
n-Hexane n-C6H14 7627.2 7.7171 -54 to 209
Cyclohexane c-C6H12 7830.9 7.6621 -45 to 257
n-Octane n-C8H18 9221.0 7.8940 -14 to 281
iso-Octane 8548.0 7.9349 -36 to 99
n-Decane n-C10H22 10912.0 8.2481 17 to 173
n-Dodecane n-C12H26 11857.7 8.1510 48 to 346
methanol CH3OH 8978.8 8.6398 -44 to 224
Ethanol C2H5OH 9673.9 8.8274 -31 to 242
n-Propanol n-C3H7OH 10421.1 8.9373 -15 to 250
Acetone (CH3)2CO 7641.5 7.9040 -59 to 214
Methyl ethyl ketone CH3CO.CH2CH3 8149.5 7.9593 -48 to 80
Benzene C6 H6 8146.5 7.8337 -37 to 290
Toluene C6H5CH3 8580.5 7.7194 -28 to 31
Styrene C6H5CH=CH2 9634.7 7.9220 -7 to 145
MIXTURE OF GASES OR VAPOUR
• The composition of mixture of gases or vapour may be
expressed in terms of partial pressure (Pi) of the
components, i,
P =  Pi
» P is the total Pressure

• For “ideal solutions” to which hydrocarbon mixture
approximate, Raoult’s law can be used. This sates that
for a mixture of two liquids, A and B,
PA = 
χ A  PA and PB =  
B  PB
» Where PA and PB are the vapour pressures of A and B the

liquid mixture and PA and PB are the equilibrium vapour
pressures of pure A and B given by the previous
equation, and A and B are the respective mole fraction

A B
χA = and  B =
 A +B  A +B
» The molar concentrations A and B can be obtained by

dividing the mass concentrations of A and B by their
respective molecular weights. Care should be taken, as
very few liquid mixtures behave ideally. Guidance can be
found in standard chemical engineering textbooks.

HEAT AND TEMPERATURE
• Heat is energy.
• Energy is the ability to do work
» Can neither be created nor destroy
» Can change from one form to another
• Heat can be produce by:
» Chemical reaction e.g. burning a fuel
» Friction
» Electric current through a resistance
• Heat can be used to do work e.g. steam boiler

• The SI unit of heat is joule (J)
» 1 kilo Joule (kJ) = 1000J
» 1 Mega Joule (MJ) = 1000 kJ
• A common unit of heat is calorie ( 1 cal = 4.18J) one
calorie is the energy required to raise the temperature of
1 g of water by one C.

• Temperature is a measure of the hotness of a body
• Temperature  Heat
• Temperature is measured usually on the Celsius or
Centigrade scale (C).
• The lower fixed point is 0 and it corresponds to the
temperature of melting ice and the upper fixed point is
100 corresponding to the temperature of steam.

• In calculations we used the absolute or Kelvin scale (K).
• On this, zero is the lowest possible temperature and it
corresponds to -273C.
• Therefore,
K = C + 273

HEAT CAPACITY
• Heat energy required to raise the temperature of a body
by 1C (J/ C)
• To compare one substance with another we use Specific
Heat Capacity
• Heat energy required to raise temperature of a unit mass
(1kg) of a substance by 1C (J/kgC)
• Material with low specific heat will heat up faster and
grater hazard.

HEAT CAPACITY
Material Specific Heat (J/(Kg Material Specific Heat (J/(Kg

K) K)
Water 4200 Ice 2100
Iron 460 Earth, rock etc 840
Aluminium 900 Carbon tetrachl 850
Copper 400 Methylated spirit 2400
Mercury 140 Benzene 1720
Glass (ordinary) 670 Glycerol 2560

LATENT HEAT
• Latent heat is the energy needed to convert a substance
from one state to another, e.g
» Liquid to vapour (evaporation) Steam
» Solid to liquid (melting)
Plasma
Water 100°C
F
Enthalpy of system
Temperature
D Gas
E
Phase change Heat
Sublimation >
< Deposition
B C (vapourisation)
Liquid
Temperature will
Phase change remain constant
A (melting) (100C) until all
Solid
Energy Input water evaporate
THE TRANSMISSION OF HEAT
High
Temperatur
e
Conduction
Convection
Radiation Low
Temperatur
e

CONDUCTION
• Heat transfer mode mainly in solid
» Heat from one molecule to next without much molecule
movement
• Ability to conduct heat varies between materials
» Metal: Good conductors
» Non-metallic solids: poor conductors
» Liquids and gases: very poor conductors
• In general
» Good electricity conductors = good heat conductors
» e.g. fire spread due to conduction of heat along a steel
girder
CONDUCTION
Sketch showing how fire

may be spread in a
building due to the
conduction of heat along
an unprotected steel
girder

CONVECTION
• Main heat transfer mode in fluids (liquid and gases)
» When a fluid is heated
⊳It become less dense
⊳It rises, being displaced by a colder and denser fluid (e.g.
chimney)
» Heat energy is carried through the fluid by long range
movement of molecules
• In fire hot gases move upwards and spreads faster in
this direction. Cool air moves in at the base of the fire
helping to decelerate the burning.
» e.g. fire spread through stairwells and lift shafts
CONVECTION
Sketch showing how fire on a

lower floor can spread to upper
floors by convection

RADIATION
• Heat transmission by electromagnetic waves
» In straight lines
» At the speed of light
» Required no intervening medium
⊳e.g. the sun
⊳Heater at high level
• Dominant mode of heat transfer in developed large fires
but also of source of ignition
» e.g. clothes horse
» Ignition due to concentration of sun rays

CONVECTION
Sketch shows how

radiation can cause
nearby buildings to
burn the building being
burned.

SECTION 3
FUEL AND COMBUSTION PROCESS
INTRODUCTION
• For fire protection “fuel” is what is burning
» Mostly solid (but in industry some liquids and gases)
• Flame is the visible oxidation (combustion) of gaseous
material
» i.e. There is no flame unless you have burning gases,
therefore a liquid or solid material can only burn with
flame of it is converted into gaseous fuel
• For burning liquids: the process is normally evaporative
boiling
INTRODUCTION
• For almost all solids chemical
decomposition or pyrolysis is necessary
» To yield products of sufficiently low MW
that can volatilise.
» As this requires much more energy than Combustion
simple evaporation, the surface T of a
Gas
burning solid tends to be high. Evaporative

boiling
» The composition of volatiles released
from the surface of burning solid is Liquid
extremely complex (and important. Can Pyrolysis

be understood by considering the nature
of solid materials.
Solid
POLYMERS
• Solids of significance are polymers materials of high
MW
• Polymers are materials whose molecules consist of long
chains of repeated units derived from simple units
known as monomers through the process of
polymerisation
» Addition Polymers
⊳Formed by direct addition of monomer units to end of growing
polymer chain

POLYMERS
» Condensation Polymers
⊳Involves the loss of a small molecular species (normally H2O)
whenever two monomers link together.
• Cellulose the most widespread of natural polymers in all
higher plants is a condensation polymer of the
monosaccharide D-glucose
• An essential feature of any monomer is that it must
contain two reactive groups or centers to enable it to
combine with adjacent units to form a linear chain.
A A A A A
POLYMERS
• Length of chain depends on conditions
» These can be selected to produce a polymer with desired
properties
» Properties can be changed by branching
⊳By modifying conditions or by small amounts of monomer with
3 reactive groups
A A A A A A A B A A
A A
A A
POLYMERS
⊳Can have effect of producing a cross-linked structure whose
physical & chemical properties will be different from the
equivalent unbranched or slightly branched structure.
» e.g. expanded polyurethane foams
⊳In flexible foams low cross-linking
⊳If high cross-linking (by increasing the proportion of the
trifunctional monomer) rigid foams can be produced

SPONTANEOUS COMBUSTION
• This is a fire caused by a natural heat- producing
process in the presence of sufficient air and fuel
• This reasoning for a fire is often used as an excuse by
arsonists, but rarely occurs in normal conditions.

POLYMERS
For flammability
• High cross-linking = low volatile yield
» Much more of the material forms an involatile
carbonaceous char, thus effectively reducing the supply
of gases to the flame.
» e.g. phenolic resins
» e.g. lignin
⊳The cement that binds cellulosic
structures together in higher plants
giving greater strength and rigidity
to the cell walls

SYNTHETIC POLYMERS
• Two main groups: thermoplastic and thermosetting
» Thermosetting:
⊳Highly cross-linked
⊳Will not melt
⊳Instead decomposed to give volatiles directly from the solid
leaving behind a carbonaceous residue
⊳Good in fire
» Thermoplastic:
⊳Low cross-linking
⊳Will soften and melt
⊳Fire spread may be enhance by failing droplets or the spread
of a burning pool of molten polymer
⊳Bad in fire
THERMAL DECOMPOSITION AND STABILITY
OF POLYMER
• Production of gaseous fuel (volatiles) from solids
involve, thermal decomposition, or pyrolysis of polymer
molecules and the elevated temperatures which exist at
the surface. Whether or not proceeded by melting
depends on nature of materials
• Volatiles comprise a complex mixture of pyrolysis
products, ranging from simple molecules such as
hydrogen and ethylene, to species of relatively high
molecular weight.
THERMAL DECOMPOSITION AND STABILITY
OF POLYMER
• In flaming combustion almost all of the volatiles will be
consumed in the flame
• Under other conditions (e.g. pyrolysis without
combustion following exposure to an external source of
heat or smouldering combustion) the high boiling liquid
products and tars will condense to form an aerosol
smoke at they mix with cool air.

MODEL OF FUEL VAPOUR GENERATION
FROM A SOLID
Plasma
a Sublimation
melting L V
S b Evaporation
Enthalpy of system
I A Gas
O Decomposition
melting Q P
L c + evaporation
Sublimation >
U O
< Deposition
I
Decomposition I Decomposition U
D d Liquid
+ evaporation D + evaporation R
e Decomposition + evaporation
Solid
The initial decomposition may also produce species that can

volatilise directly
MECHANISMS OF DECOMPOSITION
• Unzipping or end-chain scission
» To give high yields of monomer in decomposition
products
» A reverse of the polymerisation process
⊳Direct result of the chemical structure which favours ‘unzipping’, in some
cases to the exclusion of any other decomposition mechanism
⊳No exact equivalent to the ‘unzipping’ process exists in the pyrolysis of
condensation polymers
• Random chain scission
» e.g. pyrolysis of polyethylene in which a completely
random mechanism appears to operate, again as a
consequence of the monomer structure.
• Chain stripping
» Polymer backbone remains intact but molecular species
are lost as they break away from the main chain.
⊳e.g. decomposition of polyvinyl chloride (PVC) which begins to lose
molecular HCI (hydrogen chloride) at about 250C, leaving behind a char-like
residue.
⊳Residue will burn at high temperatures (give much smoke)
⊳Hydrogen chloride is a very effective combustion inhibitor and its early
release will tend to extinguish a developing flame hence PVC has low
flammability

• Cross-linking
» Polymers, which undergo cross-linking during pyrolysis,
tend to char on heating.
⊳This should reduce the amount of fuel available for flaming combustion.
⊳Seldom significant for thermoplastics
» Thermosetting are highly cross-linked in their normal state and it is
likely that further cross-linking occurs during pyrolysis.

THERMAL STABILITY
• Can be quantified by determining how the rate of
decomposition varies with temperature.
» Common assumption: pyrolysis proceeds according to simple kinetic
scheme such that
dm
m = = −k m
dt
» where m represent the mass (or the concentration) of the polymer
and k’ is the rate coefficient

FACTOR AFFECTING THERMAL STABILITY
• Increasing molecular weight strengthens polymer
• Increasing chain branching weekends polymer
• Increasing cross-linking strengthens polymer
• Introducing double bonds in polymer backbone
weakens polymer
• Introducing aromatic rings in polymer backbone
strengthens polymer
• Introducing oxygen in polymer backbone weakens
polymer
IMPORTANCE OF VOLATILE
• Reactivity of constitutes
» Influences flame stabilisation at the surface of a solid
» Controls the rate of burning
• Nature of constitutes
» Determine how much soot
» Control heat radiated to the surroundings and the
burning surface
» Influences the size of fire

IMPORTANCE OF VOLATILE
» Influences the quantity of smoke
⊳Thus volatiles containing aromatic species such as benzene
(e.g. from the carbonaceous residue formed from chain-
stripping of PVC, or styrene (from polystyrene), give sooty
flames of high emissivity.
⊳In contrast or methanol burns with a non-luminous flame,
(volatiles consist entirely of formaldehyde which does not
produce soot).
» Will affect the toxicity of the combustion products
⊳More than 50% of fatalities are caused by the toxic products
⊳The principle toxic species (CO) is produced in all fire
involving carbon based fuel.

SECTION 4
THE PHYSICAL CHEMISTRY OF
COMBUSTION IN FIRE
REGIMES OF BURNING (FLAME TYPE)
• Laminar, premixed
• Laminar, diffusion
• Turbulent, premixed
• Turbulent, diffusion

Laminar, premixed (e.g. Bunsen burner flame)
• Laminar means that the flow streamlines are smooth
and do not bounce around significantly
• Premixed means that the fuel and the oxidizer are mixed
before the combustion zone occurs.
Laminar, diffusion (e.g. candle flame)
• The fuel comes from the wax vapour, while the oxidizer
is air; they do not mix before being introduced (by
diffusion) into the flame zone.
Turbulent, premixed (e.g. Boiler, furnace etc)
• In such systems, the air and fuel are premixed in some
burner device, before reaching the flame zone
Turbulent, diffusion
• Most unwanted fires fall into the category of turbulent
diffusion flames
• Since no burner or other mechanical device exists for
mixing fuel and air, the flame are diffusion type

RATE OF BURNING
• Rate at which fuel is consumed.
• Equated with the rate of supply of gaseous fuel
(volatiles).
• For gas jet flame is independent of combustion
processes.
• For solids and liquids the rate of supply of volatiles
from the fuel surface is directly linked to the rate of heat
transfer from the flame.

RATE OF BURNING
Q F − Q L
m  = g m2 .s
Lv
m  is the mass burningrate per unit area of fuel surface
Q F is the heat flux suppliedby the flame per unit area of fuel surface(kW/m 2 )
Q L is the heat loss expressed a flux throughthe fuel surface(kW/m 2 )

Lv is the heat lrequiredto producevolatiles(kJ/g
For a liquidis the latentheat of evaporation
ENERGY RELEASE IN A FIRE
Q = m A f H C
2
A f is the fuel surface area(m )
H C is the heat of combustionof the volatiles(kJ/g)

 is a factor(  1.0) to account for incompletecombustion

ENERGY RELEASE IN A FIRE
• Energy release rate is the most important single factor
characterising fire behaviour
» From last two Equations, many contributory factors
which together determine Q including properties relating
not only to the material itself (Lv and Hc) but also to the
combustion processes within the flame (which in turn
determine Q"F and ).
» The mass burning Equation emphasises the importance
of the heat transfer terms Q"F and Q"L in determining the
rate of supply of fuel vapours to the flame

THE HEAT OF COMBUSTION (Hc)
• All combustion reactions take place with the release of
energy.
• This may be quantified by defining the heat of
combustion (Hc):
» the total amount of heat released when a unit quantity of
a fuel (at 25C and atmospheric pressure) is oxidised
completely.

• Consider:
C3H8 + 5 O2 → 3 CO2 + 4 H2O
Stoichiometric equation
• Reaction is exothermic (i.e. heat is produce)

• Value of Hc depends on whether water in the products
is in liquid or vapour form:
» Water in liquid form: “gross” Hc (C3H8) = -2220 kJ/mol
» Water in vapour form: “net” Hc (C3H8) = -2044 kJ/mol

• In flames and fires water remains as vapour, therefore it
is more appropriate to use net values of the heat of
combustion.
• Ways of expressing Hc:
» e.g. propane in air
C3H8 + 5 O2 + 5 x 3.76 N2→ 3 CO2 + 4 H2O + 18.8 N2


• Heat of combustion of most common fuels is
approximately constant if expressed in terms of the
mass of oxygen, or air consumed.
Hc,ox  -13 kJ/g of oxygen
Hc,air  -3 kJ/g of air
• If the rate of oxygen consumption can be measured, the

rate of heat release can be estimated
• method adopted by many standard tests based on the
“oxygen depletion calorimetry”.
• Rate of heat release is calculated from the expression:
( 3
)
QC = 0.21− O2 V 10 O2 H C ,OX

» where V is the volumetric flow of air (m3/s). ρO2, is the

density of oxygen (kg/m3) at normal temperature and
pressure, and O2, is the mole fraction of oxygen in the
scrubbed exhaust gases.

• The value selected for H is based on complete
combustion of the fuel to carbon dioxide and water.
• If combustion is incomplete, i.e. carbon monoxide and
smoke particles are formed, the effect on HC.ox will be
small.
» This reasoning rests on the fact that if all the carbon was
converted to CO, the value used for HC.ox would be no more
than 30 % too high. While if it all appeared as carbon (smoke
particles), it could be no more than 20-25 % too low. Given
that these factors operate in opposite directions and that in
most fires the yield of CO2 is invariably much higher than that
of CO. The resulting error is unlikely to be more than 5 %.

• Hc,air  -3 kJ/g of air
» This may be used to estimate the rate of heat release in a
fully developed, ventilation controlled compartment fire
if the rate of air flow is known or can be calculated.
⊳it is assumed that all oxygen is consumed within the
compartment boundaries (discussed more later).
» generally, we can write
1 kg fuel + r kg air → (1 + r) kg products
⊳where r is the stoichiometric air requirement

• Hc,air  -3 kJ/g of air
» The stoichiometric air requirement can be used to
estimate the heat of combustion of any fuel if this is not
known
⊳ Stoichiometric equations can be used to calculate the air
requirements for the complete combustion of any fuel.

EXAMPLE
1. Calculate the heat of combustion of
polymethylmethacrylate (PMMA) which has the
empirical formula C5H802 (identical to the formula of
the monomer.
2. Fully developed, ventilation controlled fire (post-
flashover) in a room with standard size door open.
What is the heat release rate?

THE MECHANISM OF GAS PHASE
COMBUSTION
• Methane will burn in a flame to yield carbon dioxide and
water vapour, according to the reaction
e.g. CH4 + 2 O2 → CO2 + 2 H2O
• Chemical equations such as this define the

stoichiometry of the complete reaction but hide the
complexity of the overall process
» Combustion involves a series of very fast elementary
steps in which highly reactive molecular fragments
(atoms and free radicals) such as H, OH and CH3 take
part.
COMBUSTION
• Mechanism of gas phase
oxidation of methane
(after brown,1975)

COMBUSTION
• The rate of removal of methane depends directly on the
concentrations of free atoms and radicals in the reacting
system.
» This in turn will depend on the rates of initiation
(reaction a) and termination (m, n, p and q),
» but will be enhanced greatly if the branching reaction (e)
is significant,
» this has the effect of increasing the number of radicals in
the system, replacing one hydrogen atom by three free
radicals, as can be seen by examining the fate of the
oxygen atoms by reactions d, g and j (Table 1.15).

COMBUSTION
• In this respect the hydrogen atom is the most important
of the reactive species in the system.
• If other molecules compete with oxygen for H-atoms
then the branching process i.e. the multiplication of the
free radicals is held in check

COMBUSTION
• Species that react rapidly with hydrogen atoms,
effectively replacing them with atoms or radicals which
are considerably less reactive can inhibit gas-phase
oxidation.
» e.g. Chlorine- and Bromine-compounds give rise to
hydrogen halides (HCI or HBr) in the flame. Reactions
such as HBr + H → H2 + Br replace hydrogen atoms with
relatively inactive halogen atoms and thereby reduce the
overall rate of reaction dramatically

COMBUSTION
• For this reason many chlorine- and bromine-containing
compounds (Halons) are found to be valuable for
retardants or chemical extinguishants.
» If the reaction sequence is interrupted as a result of
chemical and physical quenching some intermediate
toxic products could survive and appear in the products

SECTION 5
LIMITS OF FLAMMABILITY
INTRODUCTION
• Although it is common practice to refer to gases and
vapours such as methane, propane and acetone, as
'flammable', mixtures of gases and vapours with air will
only burn if the fuel concentration lies within well
defined limits,
» lower (L) and upper (U) flammability (or 'explosive')
limits

INTRODUCTION
• For methane, these are 5 per cent and 15 per cent
respectively.
» The most extensive review of the flammability of gases
and vapours is that of Zabetakis (1965) which remains
the standard reference.
» It is based largely on a collection of data obtained with
an apparatus developed at the US Bureau of Mines
(Coward and Jones, 1952). Although there are certain
disadvantages in this method, these data are considered
to be the most reliable that are available.

UPWARD VS DOWNWARD FLAME
PROPAGATION
• The limits quoted in the literature (Zabetakis, 1965) refer
to upward propagation of flame.
• Upward propagation limits are slightly wider than the
limits for downward propagation
» differences arise because the buoyant movement of the
burnt gases acts in opposition to the down-ward
propagating flame, creating instability.

UPWARD VS DOWNWARD FLAME
PROPAGATION
• However, the same behaviour can be observed in
unconfined mixtures.
» Following central ignition, flame will propagate
spherically while at the same time the growing volume of
burnt gas will rise, causing distortion. Even in this
situation it is possible to observe upward (and
horizontal) propagation without flame travelling
downwards through a near-limit mixture (e.g., Sapko et
a/., 1976; Roberts et a/., 1980; Hertzberg, 1982).

MINIMUM IGNITION ENERGY (MIE)
• Zabetakis, 1965

• Very small amounts of energy sufficient for ignition of
flammable vapour/air mixtures.
• Figure shows how the minimum spark energy capable of
igniting a mixture varies with composition.
» The minimum on this curve—known as the MIE—
corresponds to the most reactive mixture,
» normally just on the fuel-rich side of stoichiometry

• Possible to design electrical equipment which are
intrinsically safe.
» As no mixture can be ignited by a spark of energy less
than the minimum ignition energy, it is and may be used
in locations where there is a risk of a flammable
atmosphere being formed
» Even the worst fault condition cannot ignite a
stoichiometric mixture of the specified gas in air.

IGNITIBILITY VS FLAMMABILITY
• Limits of ignitability vary with the strength of the ignition
source
• Limits of flammability must be determined using an ignition
source which is sufficiently large to ignite near-limit mixtures.
» However, vary significantly with temperature
⊳flame may propagate in a mixture which is technically 'non-
flammable' under ambient conditions if the ignition source is large
enough to cause a local rise in temperature.
» Thus the criterion for propagation of flame at least half-way
up the flame tube. At this point it is assumed that the flame
will be propagating into a mixture which has not been
affected by the ignition source.
INFLUENCE OF PRESSURE ON FL
• The UFL is effectively controlled by the availability of
Oxygen.
• Increasing the mixture pressure increases the amount of
O2 available (in absolute terms) therefore UFL increases
with increasing pressure
• The LFL is effectively controlled by the amount of fuel
available therefore LFL is insensitive to increasing
pressure

INFLUENCE OF PRESSURE ON FL
• Zabetakis, 1965

INFLUENCE OF TEMPERATURE
• The flammability range widens with increasing
temperature i.e.
» LFL becomes lower and
» UFL becomes higher

CRITICAL ADIABATIC TEMPERATURE AT THE
LOWER LIMIT
• Examination of a wide range of C,H, O-containing fuels
indicates that the adiabatic flame temperature at the LFL
is approximately constant at 1600 K (150 K)
» With the following notable exceptions hydrogen (980 K),
carbon monoxide (1300 K) and acetylene (1280 K)

TEMPERATURE OF FLAMES
• Flame temperature depends on rate of heat release and
rate of heat loss
• Rate of heat release given by
Q = H C AF m  OR Q = H C AF m 
• Rate of heat release and rate of heat loss often difficult

to calculate
LOWER FLAMMABILITY LIMIT
• Adiabatic temperature useful for assessing flammability
limits
• Minimum adiabatic temperature for which flame can
propagate is 1600  100 K
• Not all mixtures of flammable gas & air burn if subjected
to ignition source
• Flammable region bounded by upper & lower
flammability limits
• These limits can be determined quite accurately
FLAMMABILITY DIAGRAMS
• Represent regimes of flammability of combinations of
gases
» such as hydrocarbon, oxygen and nitrogen.
• Record the effects of adding flame suppressants
» useful to a fire protection engineer or a plant operator.
» Such diagrams may be used to decide how spaces
containing mixtures of flammable gas, oxygen and
nitrogen may be inerted safely

Flammability diagram for the
three-component system
methane/oxygen/nitrogen
at atmospheric pressure and
26oC(after Zabetakis,1965).
Points on the line CA correspond
to methane/air mixtures.

Flammability diagram for
CH4/O2/N2 at atmospheric
pressure and 26oC.
The information contained in this
diagram is identical to that
contained in the previous one.
(after Zabetakis. 1965).

Thank You

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CHAPTER ONE

•01 FIRE INVESTIGATION CASE STUDY

TABLE OF •03 FUEL AND COMBUSTION PROCESS

•05 LIMITS OF FLAMMABILITY

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mass Density of substance

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• The partial pressure of the vapour above the surface

Open Container: Closed Container:

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» P is the total Pressure

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» Where PA and PB are the vapour pressures of A and B the

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» The molar concentrations A and B can be obtained by

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Material Specific Heat (J/(Kg Material Specific Heat (J/(Kg

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Sketch showing how fire

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Sketch showing how fire on a

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Sketch shows how

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burning solid tends to be high. Evaporative

extremely complex (and important. Can Pyrolysis

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