THE CHEMISTRY OF COMBUSTION

CHEM4351
University of Belize
LEARNING OUTCOMES:

¡ What is a Fire
¡ Fire Dynamics
¡ Phases of Burning
¡ Stages of Fire Development
FIRE DYNAMICS

• An exothermic combustion reaction:

• 𝐹𝑢𝑒𝑙 + 𝑂𝑥𝑦𝑔𝑒𝑛 → 𝐶𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 + 𝑊𝑎𝑡𝑒𝑟
• Sometime incomplete combustion, CO not CO2
• Produce heat and light (flames)
• Useful
• Destructive
FIRE INVESTIGATION

“Fire scene investigation: In its broadest sense involves the

identification, recovery, examination and interpretation of evidence
related to a fire scene or a gas (vapour) phase explosion, together
with post fire/explosion damage to provide a determination (where
possible) of the area(s) of origin of the fire/explosion, the most likely
ignition mechanism involved and the mechanism by which a
fire/explosion may have developed and spread”

UK Code of Practice, 2021

CAUSES OF FIRES
Smoking Materials,
Fire/Candles,
Human error Poor Housekeeping,
Children

Electrical,
Accidental Technical
Fire

Mechanical (friction),
Gas leaks

Spontaneous
Natural combustion,
Lightning
Deliberate
CAUSES OF FIRES
History, Vandalism,
Juveniles Disorder

Frequency, Common
Pyromaniacs
methods
Accidental
Fire
Race, Religion, Group,
Grudge
Revenge, Reprisal
Deliberate

Financial Bankruptcy, Insurance

Racial, Political,
Terrorism Religious, Urban

Conceal a crime,
Evidence destruction
destroy records
FIRE INVESTIGATION AIMS

• Where did the fire start?

• How did the fire start?
• How did the fire develop and spread?
• Was the fire accidental or deliberate?
FIRE DYNAMICS

• Fire Dynamics is the study of how fires start, spread and

develop.
• In order to understand how fires can start and develop we must
have an understanding of:
• Basic physical and chemical properties of matter
• How materials are affected by energy such as heat
• How properties of matter are determined and what the limitations are in
application to the ‘real world’.
PHASES OF BURNING

Faraday (and others) postulated two phases in the burning

There are clearly two
different kinds of action—one process :
the production of the vapor,
and the other the combustion 1. Vapour production
of it—both of which take
place in particular parts of 2. Combustion of the produced vapours
the candle.
e.g. Methane:
CH4 + 2O2 à CO2 + 2H2O
Michael Faraday (1791 – 1867)
STATES OF MATTER

¡ Solids: Particles held closely together by chemical bonds.

¡ Liquids: Particles held together by weaker intermolecular forces.
¡ Gas: Particles move independently of each other and have overcome the
intermolecular forces.
¡ Vapor: a material in the gas phase which can be condensed.
VAPORIZATION
Vapourization:
• Liquids exposed to air evaporate -
molecules escape the surface.

• Temperature à Gas molecules.

• Equilibrium reached in closed system – saturation of vapour, Equilibrium vapour pressure:

no net evaporation.

• Gas-phase molecules exert pressure on remaining liquid à

“vapour pressure”

• Heat of vaporization – energy/heat required for the phase change

Liquid molecules
Gas molecules
 VAPORIZATION

• A direct measure of the

760 torr = 1 atm
volatility of the liquid. (boiling point)
• Determined by molecular weight,
chemical structure and temperature.
• Temperature à
• Evaporation à
• Vapor pressure
• Vapour pressure changes at different
temperatures for a given material.
PHASE CHANGE

• Phase changes occur when there is a

change in temperature or pressure in • AB and AC:
a system
• Vapour pressure effect

• Represents equilibrium between liquid and

gas (AB) or solid and gas (AC)
• Triple point (A): all phases are in equilibrium

• Critical point (B): liquid and gas phases

indistinguishable from each other
VAPOR DENSITY

• Vapour density dictates how a Compound Vapour density

vapour once released in air will Hydrogen 0.07
behave. Methane 0.55
Acetylene 0.90
• Vapour density of air is 1 Carbon monoxide 0.97

• <1 vapour will diffuse upwards Methanol 1.10

through air Propane 1.51

Butane 1.93
• >1 vapour will diffuse Diethyl ether 2.60
downwards through air Petrol 3-4
FLASH POINT AND FIRE POINT

• Temp. > Flash point: Liquid fuel Material Flash point oC

Closed cup
produces ignitable mixture in air.
Petrol - 43
• Temp > Fire point: Sufficient Diesel >62
vapour that it would ignite and Kerosene >38-72
remain lit if ignition source
present.
Combustible liquid:
• Flash point typically quoted as 37.7 > X < 93.3 oC

it’s the tipping point. Flammable liquid:

< 37.8 oC
• Fire points are roughly 10°C Highly flammable liquid:
above the flash point. <32 oC
FLAMMABILITY LIMITS
100 % 0%
No flame,
• Mixtures of air and vapours too little oxygen
will combust when within
Upper
particular ranges of gas:air explosive/ Limited combustion
around ignition source
flammability
• Below lower limit not enough gas limit (UEL)
Flame as soon as
• Above upper limit not enough oxygen ignition is applied
Lower
Lower % Upper % explosive/
flammability
Hydrogen 4.0 75.0
limit (LEL)
No flame,
Methane 5.0 15.0
too little gas
Petrol 1.4 7.6
0% 100 %
Gas Air
PHASES OF BURNING
• Faraday (and others) postulated two phases in the burning process :

Liquid
1. Vapour production
Solid

2. Combustion of the produced vapours

e.g. Methane:
CH4 + 2O2 à CO2 + 2H2O
PHASE 1 –VAPOR PRODUCTION

• Pyrolysis – a solid or liquid undergoes thermal degradation into

smaller volatile components in the absence of oxygen or other
oxidants.

• Typically occurs between 500 – 800°C

• 3 levels :
100°C – 300°C: Thermal degradation
300°C – 500°C: Mild Pyrolysis

>800°C: Vigorous pyrolysis

TO CHAR OR NOT TO CHAR?

• Char: “partially burn so as to blacken the surface”

CHAR PATTERNS IN FIRE INVESTIGATION

• Wood is a common material found in buildings

• Char patterns on wood are often the most notable burn patterns following a
fire
• Attempts made by fire investigators to estimate burning duration based on
depth of char

• Ventilation affects charring, making interpretation complex

• Presence of an ignitable liquid may affect burn/char patterns

PYROLYSIS: MATERIAL DOES NOT CHAR

• Pyrolysis products released as gases which can readily combust.

• Gaseous substances react with each other and oxygen à large amount of heat à
more pyrolysis and combustion à Reaction (fire) becomes self-sustaining and
maybe even expanding

• Temperature of pyrolysis depends on the material

• General thermoplastic plastics shrivel and melt away from the source of heat as
they pyrolyse.
PYROLYSIS: MATERIAL CAN CHAR

• E.g. Wood
• Pyrolysis products either remain inside the material or are released as gases.

• 2 main pyrolysis pathways:

• T < 300°C – Char forming, initial formation of dehydrated cellulose to produce CO2 and
H2O leaving a backbone of carbon as char (H2 easier to remove than C) followed by highly
exothermic pyrolysis reaction
• T > 300°C – Tar forming producing gaseous mixtures which readily combust
CELLULOSE

• Linear chain of hundreds / thousands of D-glucose units

• Primary structure in plant cell walls
• 90% of cotton
• 40-50% wood

• Wood: Cellulose
• ~25% hemicellulose
• ~50% cellulose
• ~25% lignin
Decomposition
Lignin
order
 exothermic
Tar Flammable
Endothermic COMBUSTION
Levoglucosan Gases/vapours
> 300oC

Cellulosic
Flammable
material gases/vapours
Exothermic oxidation
Endothermic
C,CO2,H 2O
< 300oC CHAR
etc
PYROLYSIS OF CHAR FORMING MATERIALS

Pyrolysis starts in thin layer at the surface of wood.

Char layer forms and deepens as pyrolysis
penetrates wood.
Char burns from surface to
produce ash.
Speed of pyrolysis layer through wood determines
burning rate.
Char has low conductivity à
insulating layer slowing pyrolysis.
PYROLYSIS OF CHAR FORMING MATERIALS

• Charring rate depends on moisture content, density and heat flux.

• Some extremely severe charring can be found, due to a combination of
radiant heat flux and ventilation effects.

• Burn patterns may look like a “liquid pour pattern” but are not.
• Non charring materials are generally better heat conductors and pyrolysis occurs
faster.

• Pyrolysis is an endothermic process… it requires heat

CHAR FORMING MATERIALS

• Poylvinylchloride Polyurethane

• Some plastics can also char

• Some thermoplastic materials capable of supporting a rigid char
because the polymer chains cross link at high temperatures.
PHASES OF BURNING

• Faraday (and others) postulated two phases in the burning process :

Liquid
1. Vapour production
Solid

2. Combustion of the produced vapours

e.g. Methane:
CH4 + 2O2 à CO2 + 2H2O
PHASE 2 – COMBUSTION
• Complex exothermic reaction between oxygen and a gaseous fuel, producing
heat and various chemical products.
• Complete combustion, to CO2 and H2O is difficult.
• Partial combustion products are also generated.
• If combustion occurs in air, also get nitrogen oxides produced (at high
temperatures >1500°C).

CH4 + 2O2 CO2 + 2H2O

2CH4 + 3O2 2CO + 4H2O
N2 + 2O2 NOx
• Combustion in solids is normally preceded by pyrolysis
PHASE 2 – COMBUSTION

• Most efficient combustion when fuel air mixtures at stoichiometric

concentrations Fuel Stoichiometric concn
(%)
Methane 9.5
Butane 3.1
Kerosene 0.9
Ethanol 6.5
Petrol 1.7
Hydrogen 29.6
Acetylene 8.4
• Fuel air mix and temperature of fire will have an effect on the residues
present.
COMBUSTION – LIQUID POOLS

• Combustion of liquid pools occurs at the surface where oxygen is available

• Remaining liquid in the pool cools the solid below and can protect the surface from
the effect of heat.
• Liquid pool fires can burn off the liquid and leave the underlying surface largely
unaffected by the fire.
• An ignitable liquid pool on wood may only burn for around 1 min and produce only
surface scorching or very shallow char
• Alternatively, liquid pool fire may spread beyond the pool
EFFECT OF PETROL ON FIRE

Laminate Vinyl Polypropylene

carpet
 COMBUSTION – SOLIDS

• Generally requires initial input of energy for pyrolysis.

• Energy must be sufficient to break chemical bonds in solid and release gaseous
materials.
• Energy provided as heat energy, which is well defined for different
circumstances.
• Combustion process highly influenced by mechanisms of heat transfer.

• 3 main types: Smouldering, Glowing, Flaming

SMOULDERING COMBUSTION

• Slow, low temperature, flameless burning, porous fuels

• Rate of burning ~ 0.1 g/s
• Oxygen can diffuse through porous surface and produce exothermic
reactions within the char.
(If material can char, surface is sufficiently porous and no flames)

• Combustion reaction sustained and smouldering front moves through the

material, producing ash.
(If sufficiently high internal heat production and small heat loss)

• Transition to flaming combustion can occur

(If reaction rate high enough and conditions for ignition)
GLOWING COMBUSTION

• Material appears red with a faint blue glow as CO is oxidised to CO2

• Rate of burning ~ 0.1 to 100 g/s
• Low porosity or rate of volatilisation too low to maintain a flame
• Oxidation of surface can occur if temperature ~ 600°C from external
heat.
FLAMING COMBUSTION

• Rate of burning ~ 100 g/s

• Stream of gases emitting radiant energy at a particular
wavelength (depending on the combustion chemistry).

• Some emitted radiation visible as glowing portion of fire.

• Flames are a mixture of oxygen and hydrogen, carbon monoxide and
the gaseous products of the fuel.

• Oxygen available à Flame temperature

(Higher than for same fuel in normal atmosphere)
FLAMING COMBUSTION

Diffusion flames : fuel and

oxygen transported from
opposite sides of the
reaction zone (flame) due
to concentration differences
- Ficks Law

Premixed flames : fuel and oxygen mixed by a mechanical device

prior to combustion.
CHARACTERIZATION OF CANDLE FLAMES

Hamins et al.
LAMINAR AND TURBULENT FLAMES

• Laminar flames: Single flames. e.g. candle

In inner portions of the flame, combustion may not

be complete and soot (carbon within the flame) is
formed. This migrates to the edge of the flame
where it is consumed producing an orange/yellow
coloured flame.

• Turbulent flames: large flames that can be considered as

lots of tiny laminar flames all trying to reach a stoichiometric
mixture. e.g. a fire
FIRE DEVELOPMENT
May be conductive,
Typically from convective or radiative
air,
ventilation
needed Three essential
components required to
sustain a fire, if any are
removed the fire will
extinguish.

Generally hydrocarbon containing material

• To sustain a fire, fuel and oxidiser must interact in a self sustaining exothermic
chain reaction called combustion.
HEAT

• Heat energy: • Heat capacity (c):

• Vibration of molecules • Heat required to raise temperature
• Can initiate/support chemical by 1 Kelvin
changes/changes of state • Units: J/K
• Energy transfer due to difference in • Depends on substance and mass of
temperature material
• Units: Joules (J) • i.e. Water, specific heat capacity:
• Rate of heat energy transfer, 4200 J/(kg·K)
units:J/s
• 1 J/s = 1 W
ENTHALPY

• The change in enthalpy (DH), accounts for the heat flow in a process
at constant pressure.
• DH < 0 Exothermic reaction (heat outputted)
• DH > 0 Endothermic reaction (heat gained)
• Combustion of methane: CH4 +
2O2 àCO2 + 2H2O
DH = -890 kJ
Exothermic reaction
HEAT TRANSFER – CONDUCTION
• Movement of heat via
movement of adjacent
molecules in a solid.
• Good conductors – most
metals - Ag, Cu.
• Bad conductors (insulators)
- most liquids and gases

Heat
THERMAL CONDUCTIVITY
• Heat flow through unit Material Thermal conductivity at
°25 C (W/(m.K))
thickness, due to unit
Air 0.024
temperature gradient under
Paper 0.050
steady state conditions.
Wood 0.130
• Units: W/(m.K) PTFE (Teflon) 0.250
• High thermal conductivity à Water 0.580
faster heat transfer Concrete 1.050
• Temperature dependent - Glass 1.050
materials become more Steel 46.000
conductive as temperature Aluminium 250.000
increases. Copper 401.000
Silver 429.000
HEAT TRANSFER – RADIATION

• Emission of electromagnetic
waves in the infra red and
visual frequencies
• In all directions
y µ x4
HEAT FLUX DENSITY

• Rate of heat energy transfer through a surface per unit area (W/m2)

Radiant heat flux Observed effect

(kW/m2)
1.0-1.5 Direct sunlight
4.5 Blistering of skin after 30 sec exposure
16 Blistering of skin after 5 sec exposure
20 Some cellulosic materials ignite - onset of
flashover in a typical residential room
29 Wood ignites spontaneously
40 Flashover
100-170 Post flashover burning
STAGES OF FIRE DEVELOPMENT
¡ Initiation (ignition) and free burning ¡ First stage is initiation (or ignition) and free
burning

¡ Release of volatiles
¡ Growth period
¡ Ignition of volatiles
¡ Generation of heat (mainly convective)

¡ Flashover ¡ Early fire growth including plume development

¡ Post flashover and steady burning

¡ Smouldering
STAGES OF FIRE DEVELOPMENT
• Solids: pyrolyse to produce vapours
• Liquids: expose to temp. > flash point
• Mix of vapours and air within flammability limits
• Suitable ignition source in the immediate vicinity of sufficient energy and
duration
• Vapour and the ignition source must come into contact with each other.
• Ignition temperature can vary for a particular material depending on the
circumstances.
STAGES OF FIRE DEVELOPMENT
Open
flame

Explos-
Embers
ion

Cause
of fire Natural
Auto-
pheno-
ignition
menon

Friction Electri-
cal
STAGES OF FIRE DEVELOPMENT

• Ignition temperature: lowest temperature at which

combustion begins and continues in air.
(Not fixed and will change with amount of oxygen)

• Auto-ignition temperature: initiation of combustion by heat, without

spark or flame.

• Minimum ignition energy: lowest energy an electrical spark can

initiate a propagating flame in a given mixture of a gas or vapour.
Measure of the ease of ignition.
EXAMPLES
Material Auto-ignition Fuel Auto-ignition
temperature (°C) temperature (°C)
Cellulosic natural 255-400 Acetone 465
fibres (cotton, linen Ethanol 363
etc.)
Methanol 385
Protein natural 570-600
fibres (wool, mohair Petrol (low octane) 280
cashmere etc.) Kerosene 210
Acrylic 460-560 Linseed oil 206
Nylon 450-570 Diethyl ether 160
Paper 230
Polyethylene 350
Polystyrene 455-495
SELF HEATING

• Source of heat is chemical reactions within the material itself.

• Requirements:
• Chemically reactive material
• Adequate availability of oxygen (fuel must be porous)
• Big enough pile of material
• Sufficient time for reaction to occur.
• Exothermic reaction generates heat, and if not dispelled as fast as it
is made, heat can build up in a fuel mass and raise temperature.
SELF HEATING

• Examples:
• Polymerization of fatty acids (oxidation of the fatty acids across the double bonds) in a
matrix of cellulose materials (eg linseed oiled rags)
• Enzyme induced oxidation in large masses of certain materials (e.g. hay)
• Oxidation of carbonaceous materials in large quantities (e.g coal and charcoal).

• Temperature of the environment is critical.

• External heat source not required, but critical ambient temperature (CAT) related to the
size of the pile is required.
• Larger pile à lower external temperature required for spontaneous ignition.
• Some materials ignite below room temperature if big enough pile
FIRE PLUMES
Buoyant
flame
• Non reacting zone – Buoyantly Ceiling
rising column of hot combustion jet flow
products (smoke particles) and
unburned vapour. Intermittent
flame

• Reacting zone – fuel vapours

released as the fuel burns
(persistent and intermittent flame).
Persistent
flame
• Air is entrained (sucked into) the
fire plume as combustion occurs.
STAGES OF FIRE DEVELOPMENT
Initiation (ignition) and free
burning
Growth period:
• Heat (mainly radiant), heats other
Growth period
combustibles and fuel packages
• Build up of hot gas layer, smoke
Flashover filling
• Increase in fuel packages involved in
Post flashover and steady fire = more radiative heat
burning • Increase in heat flux
• Smoke escaping, venting
Smouldering
STAGES OF FIRE DEVELOPMENT

Initiation (ignition) and free • Flashover:

burning
• Every combustible exposed to
thermal radiation in an enclosed
Growth period space rapidly and simultaneously
ignites
Flashover • Fire reached critical heat flux
• Ventilation becomes an issue
Post flashover and steady
burning

Smouldering
HEAT RELEASE RATE (HRR)

• Heat release rate: kW (kJ/s)

• Amount of energy a burning object releases per unit time.
• Most materials, HRR changes with time as its chemical and
physical properties and the availability of oxygen changes.
• HRR is derived from testing, not a fundamental property.
• Measured by calculating burning rate (mass loss rate) –
weighting the fuel as it burns
.
Q Heat release rate (kW/s)
.
m Mass loss rate (kg/s)
DHc,eff Effective heat of combustion (kJ/kg)
HEAT RELEASE RATE

2 bar electric heater

2 kW = 2000 W Burning car
8 MW = 8000 kW
Candle = 200 candles
= 800,000 candles
10 W
MAXIMUM HEAT RELEASE RATE

Item Max rate of heat release(kW)

Smouldering cigarette 0.005
Lighted match 0.050
Plastic waste bin 13-150
Burning bin 100
Upholstered chair 150-700
Cotton mattress 40 - 970
1.9L pool of camping fuel 900-1000
Christmas tree (dry, 6-7ft) 1000-2000
Sofa 250-3000
Wardrobe (68Kg, plywood) 3500
 Flashover

FIRE DEVELOPMENT Post-flashover

Growth Decay

Heat
release
rate
(kW)
Ignition of
second
fuel item
Total energy is
area under curve

Time
Ignition of
first fuel item
FLAME TEMPERATURES

• Flashover: upper gas Metal Melting points

temperature > 500°C, floor (°C)
temperature ~500°C Lead 327
• Peak fire temperature in room Aluminum 660
fires (governed by ventilation Brass 950
and fuel supply)
Copper 1083
~ 1200°C max
Cast iron 1300
• Typical post flashover room fire:
Steel 1510
800 – 1000°C
BURNING DURATION

• Length of time fuel in a compartment would be expected to burn

• Linked to fuel loading assuming no ventilation issues

• Assuming constant HRR – fire will consume fuel mass at a constant
rate
• Mass of material burned per second and amount of fuel present
will provide an estimate of burning duration.
BURNING RATE

• Dependent upon:
• Chemistry of the material and how it responds to pyrolysis or
smoldering
• Shape: surface area available to combust compared to total mass.
• Building construction
• Geometry of the fuel relative to the impinging heat flux.
 EFFECT OF GEOMETRY

• Unconfined flaming fire:

• Plume rises vertically until gases cool and disperse

• Confined flaming fire:

• Hot gases rise until barrier (e.g. a ceiling) reached
• Plume and jet of hot gases spread out along barrier

• Restricted flames:
• Location close to a wall or corner restricts free air entrainment into the flame or
plume.
• This lengthens the flame and increases the temperature in comparison to an
unrestricted flame.
FUEL LOAD AND VENTILATION

• Pre flashover fires – Fuel controlled

• Fire damage predominantly controlled by location of fuel.
• Heat flux from fuels burning in specific locations creates burn patterns near those
locations.
• Area of lowest burn and deepest char may indicate where fire has burnt longest.

• Post flashover fires - Ventilation controlled

• Fire damage is predominantly controlled by location of ventilation.
• Sites of lowest burning and deepest char may be distant from the fire’s origin.
• Fuel gases everywhere, burn most effiicently where sufficient oxygen.
FLAME SPREAD

• Ventilation from outside compartment of fire à volatile hot gases emerge from
opening allowing heat transfer to pyrolyse new fuel.
• Flame extension occurs along these gases, giving ignition source to
pyrolysed gas/air mixture.
• Fire can spread rapidly to the rest of the building through suitable
pathways by flame extension.
• Fires spread upward as hot gases rise & heat potential fuels
• Fires may spread downwards if structural collapse or an ignitable liquid
penetrates to floor below.
• At the end of corridors, any unburned volatiles burn as a plume extending
out as they become exposed to air.