THE CHEMISTRY

OF FIRE
 Fire Triangle
Fires Require
 Air (oxygen)
Fuel
Heat
 Air
Air is required as a catalyst
Can be oxygen from the air
OR
From the Fuel itself
 Fuel

For a fire to start

there must be
something to Burn
 Heat

For a Fire to Start,

there must be a heat or
ignition source
TOGETHER, THEY PRODUCE A
CHEMICAL CHAIN REACTION
THAT IS FIRE,

which produces
heat and light.
 Types of Fires
Fires Are Classified
by the type FUEL
they burn.

The 4 Types are

A
B
C
D
Class A Fires (Carbonaceous)
Wood,
Paper,
Plastic,
Rags, etc
Combustible
Material burn and
ash is left behind
 Class B Fires (Oil)
Gasoline,
Oil,
Grease,
Paint, etc
Water not to be
used as oil is
lighter and will
float
 Class C Fires
Electrical Fires and
Gases under fire
Office Equipment,
Motors,
Switchgear,
Heaters,
Gases
ELECTRICITY ITSELF DOES NOT BURN.
IT PROVIDES THE IGNITION TO START A FIRE
 Class D Fires

Metals
 Potassium
 Sodium
 Aluminum
 Magnesium
 PRODUCTS OF FIRE
 SMOKE

 HEAT

 GASES

 FLAME
 BY- PRODUCTS OF FIRE
1. Smoke
• Carbon Di Oxide
• Carbon Mono Oxide
• Hydrogen Cyanide
• Hydrogen Chloride
• Unburnt Carbon Particles
2. Heat - Burn and other physical effects
3. Flames
4. Sound
5. Pressure
• Effect on ears and other limbs
}During Explosion
TERMS & DIFINITIONS
 ATOMS AND MOLECULES
 SMALLEST PART OF A SUBSTANCE
WHICH CAN TAKE PART IN A CHEMICAL
REACTION IS CALLED AN ATOM

 SMALLEST PART OS A SUBSTANCE

WHICH CAN EXIST FREELY IS CALLED A
MOLECULE
 CHEMICAL REACTION
WHEN TWO OR MORE SUBSTANCES
COMBINE TOGETHER TO FORM A
NEW SUBSTANCE OR
SUBSTANCES, IT IS CALLED A
CHEMICAL REACTION
 EXOTHERM REACTION
A REACTION PRODUCES ENERGY, IE
HEAT IS CALLED EXOTHERM
REACTION

FIRE IS AN EXOTHERM REATION BETWEEN

FUEL AND OXYGEN.

NEXT TO HEAT, A FIRE GENERALLY

PRODUCES LIGHT, COMBUSTION GASES AND
SOOT.
 ACTIVATION ENERGY
TO INITIATE A FIRE A CERTAIN AMOUNT OF
ENERGY IS NEEDED.

TAKE A EXAMPLE OF A SIMPLE TEST WITH GASOLINE

AND DIESEL FUEL. A MATCH HAS ENOUGH ENERGY TO
LIGHT THE GASOLINE BUT IN THE DIESEL FUEL THE
MATCH EXTINGUISHES.

IN CHEMISTRY THE ENERGY NEEDED TO

START A REACTION IS CALLED THE
ACTIVATION ENERGY.
 CHAIN REACTION
CHEMICAL REACTIONS NEEDS TO SURMOUNT
ACTIVATION ENERGY BEFORE THE REACTION CAN
TAKE PLACE .

IN A FIRE, THE INITIAL ENERGY SOURCES THAT

CAUSE THE FIRE CAN BE MULTIPLE, E.G. A SPARK,
AN OPEN FLAME, ELECTRICITY, SUNLIGHT, ETC

ONCE THE REACTION IS STARTED, HOWEVER, IT

GENERATES MORE THAN ENOUGH ENERGY TO BE
SELF-SUSTAINING, A CHAIN REACTION OCCURS.
THE ENERGY GIVEN OFF IN EXCESS CAN BE SEEN
AS LIGHT AND HEAT GENERATED BY THE FIRE.
 PYROLYSIS
THE ENERGY LIBERATED IN THE
COMBUSTION PROCESS CAUSES THE
CHEMICAL COMPOSITION OF THE FUEL TO
BREAK DOWN INTO SMALL MOLECULES

 THIS PROCESS IS CALLED PYROLYSIS

THE PYROLYSIS PROCESS CAUSES THE

EVAPORATION OF THE FUEL
 COMPLETE REACTION
MOLECULES EVAPORATE AND REACT WITH
THE OXYGEN IN THE AIR.

COMPLETE COMBUSTION MEANS THAT

JUST ENOUGH OXYGEN MOLECULES
ARE PRESENT, TO OXIDISE THE FUEL
MOLECULES.
 REACTION SURFACE
NEXT TO FUEL, OXYGEN AND ENERGY ONE
SHOULD ALSO NOTE THE MIXING RATIO BETWEEN
OXYGEN AND FUEL.

EXAMPLE, A LOG OF WOOD WILL NOT SUSTAIN A

FIRE IF IT IS LIT WITH A MATCH. AN AMOUNT OF
WOOD SHAVINGS WILL BECAUSE THIS CAUSES A
BETTER MIXTURE BETWEEN FUEL AND AIR,
WHICH FAVORS COMBUSTION.

 LARGER SURFACE OF THE FUEL IN CONTACT

WITH THE AIR CAUSES A GREATER REACTION
SURFACE , WHICH FACOURS COMBUSTION
 INHIBITOR
IN A FIRE A CHEMICAL CHAIN REACTION OCCURS,
RADICALS OF FUEL REACT WITH RADICALS OF
OXYGEN HEAT AND COMBUSTION PRODUCTS ARE
FORMED.

 ADDING A CHEMICAL MOLECULE, WHICH REACTS

WITH THOSE RADICALS WITHOUT SUSTAINING THE
COMBUSTION PROCESS CAN STOP THE FIRE. THIS
CHEMICAL IS CALLED INHIBITOR

THIS PRINCIPLE IS USED IN DRY CHEMICAL

EXTINGUISHERS WICH CONTAIN E.G. POTASSIUM OR
SODIUM BICARBONATE OR IN THE NOW BANNED
HALON EXTINGUISHERS
 CATALYST
CATALYST HAS THE OPPOSITE EFFECT OF AN
INHIBITOR

CATALYST IS A SUBSTANCE, WHICH PROMOTES

THE REACTION (WITHOUT BEING ALTERED OR
USED IN THE REACTION)

E.G. ADDING METAL SHAVINGS TO OIL RAGS AIDS

THEIR COMBUSTION
 IGNITION TEMPERATURE
THE IGNITION TEMPERATURE OF A
SUBSTANCE (SOLID, LIQUID OR GASEOUS)
IS THE MINIMUM TEMPERATURE TO WHICH
THE SUBSTANCE EXPOSED TO AIR MUST BE
HEATED IN ORDER TO CAUSE COMBUSTION
OR FIRE
 FIRE OR FLASH POINT

THE LOWEST TEMPERATURE AT WHICH A

SUBSTANCE CONTINUES TO BURN IS
(USUALLY A FEW DEGREES ABOVE ITS
FLASHPOINT) AND IS CALLED FIRE POINT
OR FLASH POINT

A SPECIFIC IGNITION TEMPERATURE FOR SOLIDS

IS DIFFICULT TO DETERMINE BECAUSE THIS
EPENDS UPON MULTIPLE ASPECTS SUCH AS
HUMIDITY (WET WOOD VERSUS DRY WOOD),
COMPOSITION (TREATED OR NON-TREATED
WOOD) AND PHYSICAL FORM
AUTO IGNITION TEMPERATURE
 AUTO-IGNITION TEMPERATURE IS THE LOWEST
TEMPERATURE AT WHICH POINT A SOLID, LIQUID
OR GAS WILL SELF-IGNITE WITHOUT AN IGNITION
SOURCE.

AUTO IGNITION TEMPERATURE OF SUBSTANCES

EXCEEDS ITS FLASHPOINT.

SUCH CONDITIONS CAN OCCUR DUE TO EXTERNAL HEATING -

A FRYING PAN THAT OVERHEATS CAUSING THE OIL TO
AUTOIGNITE, AN EXHAUST-PIPE FROM A CAR DRIVING OVER
DRY GRASS OR STRAW CAN CAUSE IT TO AUTO-IGNITE- OR
THEY CAN OCCUR DUE TO CHEMICAL OR BIOLOGICAL
PROCESSES - A SILO FIRE CAN OCCUR BECAUSE OF THE
BIOLOGICAL PROCESSES IN HUMID ORGANIC MATERIAL.
 VOLATILITY
VOLATILITY IS HOW READILY A LIQUID
WILL EVAPORATE.

THE VOLATILITY OF A SUBSTANCE IS

CLOSELY LINKED TO ITS BOILING POINT.
THE HIGHER THE BOILING POINT OF A
LIQUID THE HARDER IT WILL BE FOR THE
LIQUID TO EVAPORATE.

THE LOWER THE BOILING POINT, THE

GREATER THE FIRE RISK.
 DEFLAGRATIONN & DETONATION
THE FEROCITY OF AN EXPLOSION
DEPENDS ON THE SPEED OF THE FLAME
IF THE FLAME SPREAD REMAINS LOWER
THAN 340 M/S THE EXPLOSION IS CALLED A
DEFLAGRATION.
IF THIS SPEED EXCEEDS 340 M/S -AND THEY
CAN REACH UP TO 1800 TO 2000 M/S- IT IS
CALLED DETONATION.

THE DIFFERENCE IS BEING FASTER OR SLOWER

THAN THE SPEED OF SOUND, SUPERSONIC AND
SUBSONIC.
 FLASHOVER
IN A COMPARTMENT FIRE THERE CAN COME A
STAGE WHERE THE TOTAL THERMAL RADIATION
FROM THE FIRE PLUME, HOT GASES AND HOT
COMPARTMENT BOUNDARIES CAUSES THE
GENERATION OF FLAMMABLE PRODUCTS OF
PYROLYSIS FROM ALL EXPOSED COMBUSTIBLE
SURFACES WITHIN THE COMPARTMENT.

GIVEN A SOURCE OF IGNITION, THIS WILL RESULT IN

THE SUDDEN AND SUSTAINED TRANSITION OF A
GROWING FIRE TO A FULLY DEVELOPED FIRE.......
THIS IS CALLED 'FLASHOVER'......'

MAIN FEATURE OF A 'FLASHOVER' IS THAT THERE IS

TRANSITION TO A STATE OF TOTAL FIRE
A TIME COMES WHEN THE FLAMES
CEASE TO BE LOCALISED AND
SPREADS TO THE WHOLE
COMPARTMENT VOLUME.

FIRE CHANGES FROM A SURFACE

PHENOMENON TO A VOLUME
PROCESS
 BACKDRAFT
LIMITED VENTILATION CAN LEAD TO A FIRE IN A
COMPARTMENT PRODUCING FIRE GASES,
CONTAINING SIGNIFICANT PROPORTIONS OF
PARTIAL COMBUSTION PRODUCTS AND UNBURNT
PYRO LYSIS PRODUCTS (UNDER-VENTILATED FIRE).

IF THESE ACCUMULATE, THEN THE ADMISSION OF

AIR WHEN AN OPENING IS MADE TO THE
COMPARTMENT CAN LEAD TO A SUDDEN INCREASE
OF THE FIRE.

THIS INCREASE IN FIRE, MOVING THROUGH THE

COMPARTMENT AND OUT OF THE OPENING, IS
CALLED BACKDRAFT
FIRE SPREAD
 FIRE SPREAD
• FIRE SPREADS QUICKLY &
GEOMETRICALLY

• RELEASED HEAT INCREASES

TEMPERATURE IN THE VICINITY

• HIGH TEMPERATURE CAUSES

SELF IGNITION IN OTHER FUELS
 FIRE SPREAD
THE HEAT LIBERATED BY THE FIRE ALSO CAUSES
THE SURROUNDING MATERIALS TO WARM UP. THE
HEAT TRANSFER IS ACCOMPLISHED BY THREE
MEANS, USUALLY SIMULTANEOUSLY:
CONDUCTION
CONVECTION
RADIATION
 CONDUCTION
• DIRECT THERMAL ENERGY TRANSFER
DUE TO CONTACT.
• MATERIALS CONDUCT HEAT AT VARYING
RATES. METALS ARE VERY GOOD
CONDUCTORS WHILE CONCRETE AND
PLASTICS ARE VERY POOR CONDUCTORS,
HENCE GOOD INSULATORS
• NEVERTHELESS A FIRE IN ONE SIDEWALL
OF A COMPARTMENT WILL RESULT IN THE
TRANSFER OF HEAT TO THE OTHER SIDE
OF THE WALL.
 CONVECTION
• HEAT. TRANSFER THROUGH A LIQUID OR
GAS
• CAUSED BY DENSITY DIFFERENCE OF
THE HOT MOLECULES COMPARED TO
THE COLD ONES (eg. BOILING WATER)
• HOT AIR, GASES EXPAND AND RISE.
• CONVECTION NORMALLY DETERMINES
THE GENERAL DIRECTION OF THE
FIRESPREAD.
• CONVECTION CAUSES FIRES TO RISE AS
HEAT RISES
 RADIATION
• ELECTROMAGNETIC WAVE TRANSFER OF
HEAT TO AN OBJECT.
• WAVES TRAVEL IN ALL DIRECTIONS
FROM THE FIRE AND MAY BE REFLECTED
OR ABSORBED BY A SURFACE.
• ABSORBED HEAT RAISES THE
TEMPERATURE OF THE MATERIAL
BEYOND ITS IGNITION POINT, CAUSING
IT TO IGNITE.
FIRE SPREAD- CUBE MODEL
HIGHEST DANGER

LESS LESS
DANGER DANGER

LEAST DANGER
STAGES OF COMBUSTION
 FACTORS AFFECTING FIRE
DEVELOPMENT
 PROVIDING THAT THERE IS SUFFICIENT FUEL
AND OXYGEN AVAILABLE THE FIRE MAY TOTALLY
INVOLVE THE COMPARTMENT.
 THE ITEMS FIRST IGNITED IS SUFFICIENTLY
FLAMMABLE TO ALLOW FLAME SPREAD OVER ITS
SURFACES.
 THE HEAT FLUX FROM THE FIRST FUEL
PACKAGE.
IS SUFFICIENT TO IRRADIATE ADJACENT FUEL
PACKAGES WHICH IN TURN WILL BEGIN TO BURN.
 SUFFICIENT FUEL EXISTS.
 OPEN OR WELL-SEALED COMPARTMENT.
 FLASH OVER
A TIME COMES WHEN THE FLAMES
CEASE TO BE LOCALISED AND
SPREADS TO THE WHOLE
COMPARTMENT VOLUME.

FIRE CHANGES FROM A SURFACE

PHEMENON TO A VOLUME PROCESS
FLASHOVER

FLASH
OVER