CHEMISTRY AND FIRE BEHAVIOR

DEFINITION OF TERMS

• Fire (Various definitions):

1.Rapid oxidation of matter accompanied by heat or
flame;
2.A rapid chemical reaction that gives off energy and
products of combustion that are very different in
composition from the fuel and oxygen that combine to
produce them;
3.A chemical reaction that occurs, when fuel, air and a
source of ignition are brought together at the same time and
in proper proportions.
• Oxidation – A complex chemical reaction of organic
materials with oxygen in air or other oxidizing agents
resulting in the formation of a more stable compound.
• Organic materials – Substances containing carbon, such as
plant and animal materials. More stable compounds are
simply those with less bound up chemical energy.
• Combustion – A self sustaining process of rapid
oxidation.
• Fuel – Any form of matter capable of burning.
• Heat – A form of energy that raises
temperature.
• British thermal unit (BTU) – The amount of heat needed to
raise the temperature of one pound of water to one degree
Fahrenheit.
• Calorie – The amount of heat needed to raise the temperature
of one gram of water to one degree Celsius.
• Fahrenheit – English unit of temperature with 32⁰ as
freezing point of water and 212⁰ as boiling point.
• Celsius – Metric unit of temperature with 0⁰ as freezing
point of water and 100⁰ as boiling point.
• Vapour pressure – A measure of the tendency of a substance
to evaporate.
• Boiling point – When vapour pressure exceeds atmospheric
pressure. Also when rate of evaporation exceeds rate of
condensation.
• Flash point – The minimum temperature at which a liquid
fuel gives off vapors to form an ignitable mixture with
oxygen in air.
• Fire point – The temperature at which a liquid fuel will
produce vapors sufficient to support continuous combustion
when heated.
• Vaporization – Process by which gases (vapors) are evolved
from liquid when heated.
• Pyrolysis – Process by which gases (vapors) are
evolved from solid when heated.
• Flammable limits (range) – The limits within the
percentage of a substance in vapor state in air will burn
once it is ignited. This is where the fuel vapor in air mixture
is in proper proportions to support combustion.
• Specific gravity – Density of a liquid in relation to water.
This is the weight of the liquid compared to the weight of
an equal volume of water.
• Vapor density – Density of gas or vapor in relation to air.
This is the weight of the gas or vapor compared to the
weight of an equal volume of air.
 THREE (3) ELEMENTS OF FIRE

• Fuel
• Heat
• Oxygen
For a fire to occur, three (3) things must be present at the
same time and in proper proportions; a fuel, a source of
ignition (heat), and a source of oxygen (air or any oxidizing
agent).
 FUEL
• Fuel is the material or substance being oxidized or burned in
the combustion process. In scientific terms, the fuel in a
combustion reaction is known as reducing agent.
• Most common fuels contain carbon along with combinations
of hydrogen and oxygen. These fuels can broken down further
into hydrocarbon-based fuels (such as gasoline, oil, and
plastics) and cellulose-based materials (such as wood an
paper).
• There are also other based fuels that are less complex in their
chemical makeup, including hydrogen gas and combustible
metals such as magnesium and sodium.
• In the combustion process there are two (2) fuel-related
factors:
1. the physical state of the fuel; and
2. its distribution.
• These factors are discussed as follows:
• A fuel may be found in any of the three states of matter:
solid, liquid or gas.
Only gases burn; to burn fuels must normally be in its gaseous
state.
• For solids and liquids, energy must be expended to cause
these physical changes.
• The initiation of combustion of a liquid or solid fuel
require their conversion into gaseous state by heating.
 SOLID FUELS
• Fuel gases are evolved from solid fuels by pyrolysis.
Pyrolysis is the chemical decomposition of a substance
through the action of heat.
• Simply stated, as solid fuels are heated, combustible
materials are driven from the substance. If there is sufficient
fuel and heat, the process of pyrolysis generates sufficient
quantities of burnable gases to ignite.
• Because of their nature, solid fuels have a definite shape
and size. This property significantly affects the ignition of
the fuel.
• Of primary importance is the surface-to-mass ratio of the
fuel. The surface-to-mass ratio is the surface area of the
fuel in relation to the mass.
• Wood is one of the best examples of the surface-to
mass ratio. To produce usable materials, a tree must
cut into a log.
• The mass of the log is very high, but the surface area is
relatively low, thus the surface- to-mass ratio is low.
• The log is then milled into boards. The result of this process
is to reduce the mass of the individual boards as compared
to the log, but the resulting surface area is increased, thus
increasing the surface to mass ratio.
• As the surface area increases, more of the material is
exposed to heat and thus generates more burnable gases by
pyrolysis.
• The physical position of the solid fuel is also of great
importance.
• If the solid fuel is in a vertical position, fire will spread, will
be more rapid than if it is in horizontal position.
• The rapidity of fire spread is due to the increased heat
transfer through the three (3) ways of heat transfer, which
will be explained later.
 LIQUID FUELS
 Fuels gases are evolved from liquid fuels through a process
known as vaporization.
 Vaporization, in scientific terms, is the transformation of a
liquid to its vapor or gaseous state.There must be some
energy input in order to cause this transformation.
 In most cases, this energy is provided in the form of heat.
 A liquid assumes the shape of its container.
 The surface-to-volume ratio of liquids is an important
factor.
 When contained in a container, the specific volume of a liquid
has relatively low surface- to-volume ratio.
 When it is released, this ratio increases significantly as does
the amount of the fuel vaporized from the surface.
• The specific gravity fuel liquid is an important factor in the
degree of hazard of a liquid.
• A liquid fuel with a specific gravity of less than one (1) is
more hazardous that a fuel liquid with a specific gravity of
more that one (1).
• Solubility of a fuel liquid is also an important factor.
• Polar Solvents, such as alcohol, dissolves or mix with
water.
• Hydrocarbons, such as oils or gasoline, do not mix with
water
 HEAT
• Heat is the energy element of fire. It is a form of energy
which may be described as a condition caused by “molecules
in motion”
• When heat, through a source of ignition, comes in
contact with a fuel, the heat (as a form of energy)
supports the combustion process.
 SOURCES OF HEAT
• Heat can be derived from other forms of energies that
results in the ignition of a fuel.
• The five (5) general categories of heat energy are:
1. Chemical Heat Energy
2. Electrical Heat Energy
3. Mechanical Heat Energy
4. Nuclear Heat Energy
5. Solar Heat Energy
 CHEMICAL HEAT ENERGY
• Common types of heat generated as a result of chemical
reaction are:
1.Heat of Combustion – Heat generated by the process of
oxidation of matter. Ex: Flame of a candle.
2.Spontaneous heating – Heating of an organic substance
without the addition of an external heat. Ex: Oil soaked rag
• Heat of decomposition – Release of heat from decomposing
compounds, usually due to bacterial action. Ex: Compost
pile
• Heat of solution – Heat released by the solution of matter
in a liquid. Some acids when dissolved in water, can
produce violent reactions, spewing heat with explosive
force.
 ELECTRICAL HEAT ENERGY
• Electrical heat energy has the ability to generate high temperature that are
capable of igniting any combustible material near the heated area.
• Heat generated by electricity can occur in a variety of ways, such as:
• Resistance heating – Generated by an electrical current passing through a
conductor with a small resistance: Ex: Overloaded circuits.
• Dielectric heating – Action of pulsating a DC or AC at high frequency on
a non conductive material. Ex: Defective micro-oven.
• Leakage current heating – Generated by current leaks to
surrounding combustible materials. Ex: Wires which are not well
insulated.
• Static electricity – Build up of a positive charge on one surface and a
negative charge on the another surface. Ex: Lightning.
 MECHANICAL HEAT ENERGY
• Mechanical Heat Energy is generated in two
(2) ways; by friction and by compression.
1.Heat by friction is created by the movement of two
surfaces against its other.
2.Heat by compression is generated when a gas is
compressed. Diesel engines ignite fuel vapor without a spark
plug by the use of this principle.
 NUCLEAR HEAT ENERGY
• Nuclear heat energy is generated when atoms are either split
apart or combined.
1. Fission is the splitting of atoms.
2. Fusion is the combining of atoms.
 SOLAR HEAT ENERGY

• Solar heat energy is heat transmitted from the sun in the from
of electromagnetic radiation.
• Typically, solar energy is transmitted fairly and evenly over
the surface of the earth and in itself is not capable of starting a
fire. However, when it is concentrated on a particular point,
as through the use of a lens, it may ignite combustible
materials.
 TRANSMISSION OF HEAT
• The transfer of heat from one point or object to another is a
basic concept in the study of fire. Heat is the energy
transferred from one body to another when the temperature
of the two bodies are different.
• Temperature is an indicator of heat and is the measure of the
warmth or coldness of an object based on an standard.
• The transfer of heat from the initial fuel to other fuels in and
beyond the area of the fire origin controls the growth of the
fire.
• Investigators use this knowledge of heat transfer as they
analyze the fire scene and determine the method of heat
transfer from the fuels involved in the ignition to other fuels
in the area of origin.
• Heat moves from warmer objects to those that are cooler.
• The rate that heat is transferred is related to the temperature
differential of the two bodies.
• The greater the temperature difference is between the
bodies, the greater is the transfer rate.
• Heat can be transferred from one body to another in
three (3) ways; conduction, convection, and radiation.
 CONDUCTION
• Conduction is the transfer of heat from one body to
another by direct contact or by an intervening heat
conducting medium.
• It is the point-to-point transmission of heat energy.
• Conduction occurs when a body is heated as a result of direct
contact with a heat source.
 CONVECTION
• Convection is the transfer of heat by the movement of
heated liquids or gases.
• When heat is transferred by convection, there is a movement
or circulation of a fluid (any substance, liquid or gas, that will
flow) from one place to another.
• As with all heat transfer, the flow of heat is from the
warmer area to the cooler area.
 RADIATION
• Radiation is the transfer of heat through the medium of
space or atmosphere.
• It is the transformation of energy as an electromagnetic wave,
without an intervening medium.
• The best example of heat transfer by radiation is the sun’s
heat. The energy travels from the sun through space and
warms the earth surface.
 HEAT CAPACITY
• The heat capacity of a substance, or its thermal capacity, is
that property of a material for absorbing heat with a
consequent temperature rise per unit weight.
• It is measured in terms of heat units necessary to raise the
temperature of the substance to one degree; i.e. BTU or
Calorie.
 SPECIFIC HEAT

• The specific heat a substance is the ratio of the heat capacity

of the substance to the heat capacity of water.
• This value is 1.00 Btu per pound or 1.00 calorie per gram.
• It can be seen that specific heat, heat capacity, and thermal
capacity are synonymous terms.
• The specific heat of various substances vary over a
considerable range.
• This can be seen by the following table:

Substance Specific Heat Substance Specific Heat

Water 1.00 Zinc 0.093
Paraffin 0.694 Iron 0.109
Copper 0.093 Mercury 0.033
• The above table shows that if it takes 1000 Btu of heat from a
fire to raise the temperature of 1000 lbs. of water to 1⁰F, it
only requires a heat input of 109 Btu from a fire to raise the
temperature of 1000 ponds of iron to 1⁰F.

• Conversely, the same relationship holds in lowering substances

1⁰F by removing heat or subtracting Btu’s in order to cool
them to safe temperatures.
 OXIDIZING AGENTS

• The oxygen in air around us is considered as the primary

oxidizing agent.
• Normally, air consists of about 21% oxygen.

• Aside from air there are other oxidizing agents. These are
those materials that yield oxygen or other oxidizing gases
during the course of a chemical reaction.

• Oxidizers themselves are not combustible, but they support

combustion when combined with fuel.
 COMMON OXIDIZERS
• While oxygen is the most common oxidizer, there are
other substances that fall into the category, such as the
following:

1. Bromates 7. Nitrates
2. Bromine 8. Nitric Acid
3. Chlorates 9. Nitrites
4. Chlorine 10. Perchlorates
5. Fluorine 11. Permanganates
6. Iodine 12. Peroxides
 HOW A FIRE WILL START
• For a fire to start, all the three elements, fuel, heat, and
oxygen must come together at the same time and in proper
proportions.
• When a source of ignition (heat) comes in contact with
fuel in air, the heat energy supports the combustion
reaction through pyrolysis or vaporization of solid or
liquid fuels.

• The heat energy from the source of ignition is also necessary

for ignition to occur and for the continuous production and
ignition of fuel vapors or gases.

• The time it takes for a combustion reaction to occur is the

determining factor in the type of reaction that is observed.
• If the fuel is in liquid state, the temperature of the heat
absorbed from the source of ignition must reach flash point
the fuel, at which vapors will start to be evolved from the fuel
but not sufficient enough to support combustion.

• If the liquid fuel continue to absorb more heat energy from

the source of ignition, temperature increases until it reaches
fire point at which vapours produced are already sufficient
enough to support continuous combustion.

• However, for combustion to occur after a fuel has been

converted into vapor or gaseous state, it must be mixed with
air (oxidizer) in proper ratio.

• The range of concentration of the fuel vapor and air is called

flammable limits (range).
FLASH POINTS AND IGNITION TEMPERATURES OF
SELECTED FUEL LIQUIDS

Substance Flash Point Ignition Temp.

Asphalt 400⁰F 905⁰F
Fuel Oil 105⁰F 490⁰F
Turpentine 95⁰F 464⁰F
Alcohol 55⁰F 700⁰F
Gasoline -45⁰F 495⁰F
IGNITION TEMPERATURES OF SELECTED FUELS

Substance Ignition Temp.

Hydrogen 1085⁰F
Carbon 925⁰F
Sulphur Coal 450⁰F
Wood 750⁰F
Kerosene 450⁰F
FLAMMABLE LIMITS (RANGES) FOR SELECTED MATERIALS

Material Lower Upper Flammable

Flammable
Limit (LFL) Limit (UFL)
Acetylene 2.5% 100%
Carbon Monoxide 12.5% 74.0%
Ethyl Alcohol 3.3% 19.0%
Fuel Oil 0.7% 5.0%
Gasoline 1.4% 7.6%
Methane 5.0% 15.0%
Propane 2.1% 9.5%
 THE FIRE TRIANGLE AND

• The fire THE FIRE

triangle is a TETRAHEDORN
graphical representation of fire in the
smoldering mode and incipient free burning mode.
• The fire tetrahedron is a graphical representation of fire
in the flaming mode.
• However, for combustion to occur after a fuel has been
converted into vapor or gaseous state, it must be mixed
with air (oxidizer) in proper ratio.
• The range of concentration of the fuel vapor and air is
called flammable limits (range).
• For many years the fire triangle was used to teach the
elements of fire. While this simple example is useful, it is
not technically complete.
• When a fire becomes free burning, combustion occurs
and the fire is in flaming mode.
• Once the fire is in flaming mode, it can continue when
enough heat energy produced causes the continuous
development of the fire.
• In the flaming mode, there are four (4) components of fire
necessary to continuous combustion process. These
components are:

1. Oxygen (oxidizing agent)

2. Fuel (reducing agent)
3. Heat
4. Self-sustained chemical reaction.
 FIRE DEVELOPMENT
• When the four components of the fire tetrahedron
come together, combustion occurs.
• For a fire to grow beyond the first material ignited, heat must
be transmitted beyond the first material to additional fuel
available.
• In the early development of the fire, heat rises and forms a
plume of hot gas.
• If the fire is in the open (outside or in large building), the fire
plume rises unobstructed and air is drawn into it as it rises.
The spread of the fire in an open area is primarily due to heat
energy that is transmitted from the plume to nearby fuels.
• Fire spread in outside fires can be increased by wind and
sloping terrain that allow exposed fuels to be preheated.
• The development of a fire in a compartment is more complex
than a fire in the open.
• A compartment is an enclosed room or space within the
building. The term compartment fire is defined as a fire that
occurs within such space.
• The growth and development of a compartment fire is
usually controlled by the availability of fuel and oxygen.
• When the amount of fuel to burn is limited, the fire is said
to be fuel controlled.
• When the amount of available oxygen is limited, the
condition is called ventilation controlled.
• Recently, researchers have attempted to describe compartment
fires in terms of stages or phases that occur as fire develops.
 STAGES OF COMPARTMENT FIRES
• The stages of compartment fires are:

1. Ignition
2. Growth
3. Flashover
4. Fully Developed
5. Decay
 IGNITION STAGE
• Ignition stage describes the period when the four
components of fire come together and combustion begins.
• The physical act of ignition can be piloted (caused by
spark or flame) or non-piloted (caused when a material
reaches its ignition temperature as a result of self heating)
such as spontaneous ignition.
• At this point, the fire is small and generally confined in
the material (fuel) first ignited.
 GROWTH STAGE

• Shortly after ignition, a fire plume begins to form above

the burning fuel. As the plume develops, it begins to draw
air from the surrounding space.

• Unlike an unconfined fire, the plume in a compartment is

rapidly affected by the ceiling and walls of the space. The
first impact is the amount of air that is drawn into the plume.
• Because the air is cooler than the hot gases generated by the
fire, the air has a cooling effect on the plume temperatures.
The location of the fuel package in relation to the
compartment walls determines the amount of air that is drawn
and thus the amount of cooling that takes place.
• Fuel packages that are located near walls will draw less air
and will have higher plume temperature.
• Fuel packages located in corners draw even less air and
will have the highest plume temperature.
• This factor significantly impacts the temperature that are
developed in the hot gas layer above the fire. As the hot gas
rise, they begin to spread outward when they hit the ceiling.
This spread continues until the walls that make up the
compartment are reached.
• The depth of the gas layer then begins to increase.
• The temperatures in the compartment during this period are
dependent on the amount of heat conducted into the
compartment ceiling and walls as the gases flow over them,
the location of the initial fuel package, and the resulting air
drawn into the plume.
• Research shows that the gas temperatures decrease as the
distance from the centerline of the plume increases.
• The growth stage continues if enough fuel and oxygen are
available.
• Compartment fires in the growth stage are generally
fuel controlled.
• As the fire grows, the overall temperature in the
compartment increases as does the temperature of the gas
layer at the at the ceiling level.
 FLASHOVER STAGE
• Flashover is the transition between the growth and fully
developed fire stages and is not a specific event such as
ignition.
• During flashover, conditions in the compartment change
very rapidly as the fire changes from one that is dominated
by the burning of the materials first ignited to one that
involves all of the combustibles within the compartment.
• The hot gas layer that develops at the ceiling level during
the growth stage causes radiant heating of combustible
materials remote from the origin of the fire.
• Typically, this radiant heating causes pyrolysis to take
place in the combustible materials in the compartment.
• The gases generated during this time are heated to their
ignition temperatures by the radiant heat energy from the
gas layer at the ceiling.
• Just prior to flashover, several things are happening
within the burning compartment. The temperatures
are rapidly increasing, additional fuel packages are
becoming involved, and the fuel packages in the
compartment are giving off combustible gases as a
result of pyrolysis.
• As flashover occurs, the combustible materials in the
compartment and the pyrolysis gases ignite. The
result is a full-room involvement.
 FULLY DEVELOPED STAGE
• The fully developed stage occurs when all combustible
materials in the compartment are involved in the fire.
• During this period of time, the burning fuels in the
compartment are releasing maximum amount of heat possible
and producing large volumes of fire gases.
• The heat released and the volume of fire gases produced
depend on the number and size of the ventilation openings in
the compartment.
• The fire frequently becomes ventilation controlled; and
therefore, large volumes of unburned gases are produced.
• During this stage, hot unburned fire gases are likely to begin
flowing from the compartment of origin into adjacent spaces
or compartments. These hot gases ignite as they enter a
space where air is more abundant.
 DECAY STAGE
• As the available fuel in the compartment is consumed by the
fire, the rate of heat release begins to decline. Once again the
fire becomes fuel controlled, the amount of fire diminishes,
and the temperatures within the compartment begin to decline.
• The remaining mass of glowing embers can, however,
result in moderately high temperatures in the compartment
for some time.
FACTORS THAT IMPACT FIRE DEVELOPMENT

• As the compartment fire progresses from ignition to decay,

several factors impact the behavior of a fire and its
development within a compartment. These factors are:
• Size, number, and arrangement of ventilation openings;
• Volume of the compartment
• Thermal properties of the compartment enclosures;
• Ceiling height of the compartment;
• Size, composition, and location of the fuel package that is
first ignited; and Availability and locations of additional
fuel packages.
• For a fire to develop, there must be sufficient air available
to support burning beyond ignition stage.
• .
• The size and number of ventilation openings in a compartment
determine how the fire develops within the space.
• The compartment size and shape and the ceiling height determine
whether a significant hot gas will form or not
• The location of the initial fuel package is also very important in
the development of the hot gas layer.
• The plumes of burning fuel packages in the center of a
compartment draw more air and are cooler than those against the
walls or in the corners of the compartment.
 SPECIAL CONSIDERATIONS
• Several conditions or situations occur during
the course of a fire’s development that should be discussed.
These conditions can occur as a fire proceeds through the
stages of growth and development. These conditions or
situations are:
1. Flameover/Rollover
2. Thermal Layering of Gases
3. Backdraft
 FLAMEOVER/ROLLOVER
• The terms flameover and rollover are used to describe a
condition where flames move through or across the unburned
gases during a fire’s progression.
• Flameover is distinguished from flashover involvement of
only the fire gases and not the surfaces of other fuel packages
within a compartment.
• This condition may occur during the growth stage as the hot
gas layer forms at the ceiling of the compartment
• Flames may be observed in the layer when the combustible
gases reach their ignition temperature. While the flames add to
the total heat generated in the compartment, this condition is
not flashover.
• Flameover may also be observed when unburned fire gases
vent from a compartment during the growth and fully-
developed stages.
• As these hot gases vent from the burning compartment into
the adjacent space, they mix with oxygen; if they are at their
ignition temperature, flames often become visible in the layer.

• A flameover will not result in the ignition of target fuels

within the compartment but may result in burn patterns on
walls and other combustible building elements with which the
gases are in direct contact
 THERMAL LAYERING OF GASES

• The thermal layering of gases is the tendency of gases to form

into layers according to temperature. Other terms used to
describe this layering of gases by heat are heat stratification
and thermal balance.
• The hottest gases tend to be in the top layer, while the cooler
gases form the lower layers. Smoke, a heated mixture of air,
gases, and particles, rises. If a hole is made in a roof, smoke
will rise from the building or room to the outside.
• Thermal layering is critical in fire fighting activities. As
long as the hottest air and gases are allowed to rise, the
lower levels will be safer for firefighters. This normal
layering of the hottest gases to the top and out the
ventilation opening can be disrupted if water is applied
directly into the layer.

• When water is applied to the upper level of the layer, where

the temperature is hottest, the rapid conversion to steam can
cause the gases to mix rapidly.
• This swirling mixture of smoke and steam disrupts normal
thermal layering, and hot gases mix throughout the
compartment. This process is sometimes referred to as
disrupting the thermal balance or creating a thermal
imbalance.

• Many firefighters have been burned when thermal layering

was disrupted. Should this condition occur during fire fighting
operations, the investigator could observe uncharacteristic
patterns in the compartment during scene examination.
 BACKDRAFT
• As the fire grows in a compartment, large volume of hot,
unburned fire gases can collect in unventilated spaces. These
gases may be at or above their ignition temperatures but have
insufficient oxygen available for actual ignition to take place.

• Any action during fire fighting operations that allows air to

mix with these hot gases can result in an explosive ignition
called backdraft.
• Many firefighters have been killed or injured as a result of a
backdraft. The potential for backdraft can be reduced with
proper vertical ventilation (opening at highest point).
• Because the unburned gases rise, the building or space should
be opened at the highest possible point to allow them to
escape before entry is made.
• The following conditions may indicate the potential for a
backdraft to occur:
1. Pressured smoke exiting small openings.
2. Black smoke becoming dense gray-yellow.
3. Confined and excessive heat.
4. Little or no visible flame.
5. Smoke leaving the building in puffs or at intervals.
6. Smoke-stained windows.
 PRODUCTS OF COMBUSTION

• Heat
• Responsible for the spread of fire.
• Causes burn, dehydration, exhaustion and/or injury
tonrespiratory tract.
• Flame
• The visible luminous body of burning gas.
• When burning gas is mixed with proper amounts of oxygen,
becomes hotter and less luminous.
• Smoke
• Unburned, finely divided particles of soot.
• Contents vary depending of the exact material that is burning.
• Causes suffocation.
• Fire gases
1.Evolved from fuel during process of
combustion.
2.Most gases evolved are toxic to humans.