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Fire Behavior and Chemistry

Fire Safety Management

SAFM 534
Ken Tennant, Adjunct Faculty
List and describe the elements of the fire triangle
and fire tetrahedron.
Explain the physical and chemical changes of matter
during the combustion process.
Identify and explain the methods of heat transfer,
products of combustion, and the self-sustained
chemical reaction of fire.
List and explain the different classes of fire.
Discuss the stages of compartmentalized fire
Describe the methods used to control and extinguish
fires of each class.
Course Element 2

Safety Managers must have an

intermediate knowledge of fire
behavior and chemistry.
Fire is a living and breathing thing?
Managers must promulgate and oversee measures to
reduce or eliminate the risk of fire by preventing heat
sources from combining with fuel. While such a
description may seem elementary, it is the fundamental
backbone of all prevention programs.

Society depends on the good use of fire in many ways. We

use it to heat or homes and buildings, in many
manufacturing processes, and to cook and provide light.
Keeping fire in a controlled environment requires the use
and understanding of the combustion process. Fire is also
an enemy of the environment, and can cause devastating
destruction to life and property when control and
prevention measures fail. A manager must realize and
have knowledge of how fire behaves in different physical
settings such as in an open floor factory or in a
compartmentalized storage area.
Overview Cont.
The measures and systems in place to detect and
extinguish fires are critical components of a fire
control plan. There are many systems, agents, and
other measures to control or extinguish a fire that
will be later investigated in another learning module.

This module will examine the chemical and physical

changes of fuels when different control measures
are used to control fire. You should expect to spend
an extended amount of time on the reading
assignments and breakout learning videos to fully
grasp fire behavior and chemistry.
Science of Fire
Fire is part of basic physical chemistry involving a heat
producing chemical reaction between a fuel and oxidizing
agent (oxygen). The study of the other factors that influence
the spread and behavior of fire is fire dynamics.

A proper fire safety management plan will include the

prevention measures to reduce the risk of ignition sources
reaching fuels. If a fire would occur, a fire safety
management plan must include early detection and
suppression with the appropriate measures and agents.

While you can find several varied definitions of fire, it is an

exothermic chemical reaction called combustion that
releases energy in the form of heat and light. Combustion is
considered to be a rapid oxidation process since oxygen is
rapidly combining with a fuel source when burning.
Flaming combustion, what we think of
when we see fire, requires a vapor or
gaseous fuel to oxidize with available
air. Combustion can occur in oxygen
concentrations as low as 14%, although
15-16% is needed for visible flaming. In
most cases, solid fuels have to be heated to
give off ignitable gases, and liquid fuels
need to be heated to give off ignitable
vapors. Air is 78% Nitrogen, 21% Oxygen,
and 1% other gases.
Fire Triangle
In free air, combustion will always
have plenty of oxygen to support the
chemical oxidation process. The smoke
and flames visible from a fire are
byproducts of combustion. Water
vapor, carbon soot, and other gases
such as Carbon Monoxide, Hydrogen
Cyanide, and Carbon Dioxide are
common in smoke. For many years,
the Fire Triangle symbolically
illustrated the three elements needed
to support combustion: Heat (Ignition
Sources), Fuel, and Oxygen. Take
away any one element of the triangle,
and the combustion process stops.
Fire Tetrahedron
A more accurate
illustration is to add a
fourth side and call it the
Fire Tetrahedron. This
illustration adds the self-
sustaining chemical
reaction taking place
between the oxidizer and
the reducing agent (fuel).
Fuels (Reducing Agents)
Scientifically defined, fuel is a reducing agent. But
we know it in everyday life as any material or
substance that when oxidized, can produce flaming
or smoldering combustion. Fuels are normally found
in 3 physical states:

Fuels can also be organic and inorganic. Organic

fuels contain carbon, and most inorganic fuels are
gases or combustible metals. As stated above, fuels
must be in a gas or vapor form to burn.
Solids are the most abundant of any
fuel available in ordinary environments.
Gases and vapors from solids are
produced by a chemical process call
Pyrolysis. Pyrolysis is the thermal or
chemical decomposition of a substance
through the action of heat.

For example, as wood is heated it first

releases water vapor as the drying
process begins. As further or continuous
heat is applied, combustible gases and
carbon are released through
decomposition. If enough heat and
temperature is applied, the gases will
begin to burn freely.
Candle Chemistry
The chemical process of a candle burning
represents the basic chemistry found in all
The surface to mass ratio of a solid will
affect the decomposition process and
govern how easy or difficult something is to
ignite. The orientation of solid fuels also
contributes to the decomposition process. A
wood 2x4 board will burn much faster if it
is positioned vertically rather than
Liquid fuels normally take on two forms that a safety
manager must be readily familiar with: Flammable
and Combustible Liquids.

Liquid fuels must first be vaporized where they

overcome the normal atmospheric pressure. Heating
a flammable or combustible liquid will help to
vaporize the fuel into a vapor state. The Flash Point
of a liquid is the lowest temperature at which a
liquid releases sufficient vapors to ignite. Flammable
liquids have flash points below 100F or 38C, and
Combustible liquids give off vapors above 100F or
38C. Most flammable and combustible liquids are
lighter that water.
Liquids Cont.
The Specific Gravity of a liquid fuel is its comparison
to water. Water is assigned a Specific Gravity of
1. Fuels with a specific gravity of less than 1 will
float on water. It is difficult to extinguish flammable
or combustible liquids with ordinary water. Most
often, a fire will be spread around rather than
A safety manager would need to be aware of
facilities that store or process flammable or
combustible liquids, and what measure are in place
to control a possible fire. The solubility of a fuel is
also important as hydrocarbon fuels such as gasoline
and oil will not mix with water, while Polar solvents
such as alcohol will mix and dilute in water.
Gases are the most dangerous fuels to handle and
store because they are already in a state required for
ignition. The Vapor Density of a gas is it's relation to
normal atmospheric air. Gases such as methane are
lighter than air and will rise, and liquefied petroleum
(propane) will sink.

A safety manager must be familiar with product

labels, warnings, and definitions of flammable gases.
Some gases such as Propane and Acetylene are in a
liquid state while under pressure, and then will
expand at high rates when released. These gases
present a higher degree of hazard due to the
expansion rate.
Flammable or Explosive Limits
Once fuels are in a vapor or gas state, they
must also be in a proper concentration in
relation to the normal presence of oxygen.
The range in which a fuel is either rich or
lean is called the flammable or explosive
range. The range has 2 extremes...
LEL-UEL cont.
the LFL (Lower Flammable Limit)
where below this threshold gases and
vapors are too lean to burn, and
the UFL (Upper Flammable Limit)
where gases above this given
threshold are too rich to burn.
The ranges are also referred to as
LEL and UEL.
Types of Heat Energy

Heat can come from several

sources. The most common forms
of heat energy are:
A safety manager most often will be
concerned with electrical, mechanical, and
chemical heat sources. Two forms of
ignition common to combustion are Piloted
and Autoignition. Piloted ignition occurs
when a gas or vapor encounters an
external heat source with sufficient
temperature and energy to start
combustion. Autoignition occurs without
sparks or open flames when a fuel surface
is heated beyond the flash point and piloted
ignition temperature.
Exothermic Reaction
Chemical heat energy is heat that is
released from an exothermic
reaction. A type of chemical heat is
heat of combustion. Another form of
chemical heat is from self-heating or
spontaneous heating. This occurs
when a material increases in
temperature without the addition of
external heat. Spontaneous ignition
may occur when a material is
insulated and cannot dissipate heat.
It also must have an adequate
supply of oxygen to support
combustion. The rate of heat
production from the reaction must
enough to raise the material to its
autoignition temperature.
Spontaneous Sources

A safety manger must be aware of

some of the most common
materials that may self-heat:
Organic Fertilizers,
Linseed Oil,
Vegetable and Animal Fat Oils.
Other heat sources

Mechanical heat energy can be

produced by friction, cutting,
compression, etc.
Electrical heat energy can be
produced by resistance heating of
energized conductors, over-current,
or overload heating of appliances or
equipment, arcing of conductors,
and sparks from short circuits.
Heat Transfer

Once a fire starts, the transmission

of heat to other objects causes fire
growth. Heat can be transferred by
3 common methods:


Conduction is when another fuel or

object is in direct contact with a
heat source. A fire burning under a
steel beam may cause other
combustible objects in contact with
the beam to be heated.
Convection is the transfer
of energy in the form of a
buoyant plume upwards from
the burning fuel to cooler
areas and surfaces. A fire will
spread through a vertical
shaft rather quickly due to
convection. A fire safety
management plan must
address the protection of
vertical chases and shafts in
Radiation is the transmission of energy
through electromagnetic waves, and is the
most destructive and fastest way a fire
spreads during the growth and fully
developed phase. Feeling the heat of a
large bonfire while standing nearby is a
good example of heat transferred through
Classification of Fires

Fires are classified by the types of

fuels that make up the primary
reducing agent. The classification
of a given fuel will determine what
type of agent or method is best
used to control or extinguish a
fire. Portable fire extinguishers are
classified by this way so they are
readily usable for the appropriate
type of fire.
Class A Ordinary Combustibles

Class A fires are the most common

and involve ordinary combustibles
such as wood, paper, plastic,
etc. Cooling the fuel with water is
the most effective way of
extinguishing a Class A fire.
Class B Flammable Liquids

Class B fires involve flammable or

combustible liquids and gases. Dry
chemical agents found in portable
fire extinguishers, water based
firefighting foam, and CO are
common methods to extinguish
Class B fires.
Class C Electrical Equipment

Class C fires involve energized

electrical equipment. Once de-
energized, the equipment would
most likely be considered a Class A
fuel, however, until de-energized, a
dry-chemical or other non-
conductive agent must be used to
extinguish this type of fire.
Class D Combustible Metals
Class D fires involve combustible metals such as
magnesium, aluminum, sodium, etc. These fuels
are very difficult to try to extinguish or
control. Some special dry powder agents (not dry
chemical) such as Super D, G Plus, and Met-L-
X are effective on combustible metal fires.
Some combustible metals can explode or react
violently with water. A Safety manager must be
aware of the locations and quantities of all
combustible metals.
Class K Cooking Media

Class K fires involve oils and

greases from commercial cooking.
Application of Class K agents causes
Saponification, which turns oils and
fats into foam.
Stages of Fire Growth
A fire within a compartment or building will
develop much different than a fire in open
air. Building features such as walls,
ceilings, floors, doors, etc. will affect the
spread of fire. Four stages of fire
development are commonly recognized in
Fire Dynamics. A fire safety management
plan with proper control features will
hopefully detect, control, and then
extinguish a fire in an early stage.
Incipient Stage
Incipient Stage is the when
the fuel first comes in
contact with an ignition
source. A trash can fire in an
office break room would be
an example of an incipient
fire. Temperatures and heat
release are not significant
enough to cause rapid fire
growth. A simple dry
chemical or pressurized
water fire extinguisher will
extinguish the fire.
Growth Stage
Growth Stage occurs when convection begins to form
plume of hot gases that reach the ceiling or other
obstruction. These gases will spread latterly across the
ceiling to cooler areas. At this point it would be too
dangerous for an untrained person to use an extinguisher
to control the fire. A sprinkler head in a properly operating
sprinkler system should activate during this state of fire.
A flame rollover may occur when unburned smoke and
gases accumulate at the ceiling layer and ignite as they
reach ignition temperature. Extreme amounts of radiation
are given off from the ceiling layer to other objects in the
room or compartment.
Eventually, all combustible objects will reach their ignition
temperature and ignite. This point in the growth stage is
called Flashover, and all objects in the compartment
simultaneously ignite.
Growth Stage Cont.
Fully Developed Stage
The Fully Developed Stage begins once all
combustibles in the compartment or room
are burning. If not controlled by separation,
ventilation, or suppression, a fully
developed fire can rapidly spread and
quickly destroy a building. All three
methods of heat transfer are at high levels
during the fully developed stage.
Extinguishment at this stage is only
accomplished by trained firefighters using
hose streams or master streams.
Neutral Plane of Ceiling Gases
Fire Control
A Fire Safety Management Plan must include control
measures. Once prevention programs fail, and a
heat source contacts fuel, a fire must then be
detected, controlled and extinguished. Fire control
measures may be automatic or manual. Fire
behavior and growth can be effectively controlled by
one of several measures:

Lowering temperature of the burning fuel

Removing the fuel
Separating the fire from other available fuel packages
Lowering the oxygen concentration
Interrupting the self-sustained chemical chain
Automatic Fire Sprinklers
Standard Time-Temperature Curve

Fire-resistive barriers are evaluated in a

testing furnace by exposure to a fire
whose severity follows a time-varying
temperature curve known as the standard
time-temperature curve.

The standard time-temperature curve is

tabulated in NFPA 251, Fire Tests of
Building Construction and Materials,
Figure 6-6A.
Standard Time-Temperature Curve

The curve was adopted by the American

Society for Testing and Materials (ASTM)
in 1918 and has been the basis of almost
all fire-resistance testing ever since.
Standard Time-Temperature Curve &
the Effect of Ventilation
The burning rate of fully developed fires
may depend upon the:

Available fuel surface area or

On the air available for combustion.
When ample air is available, the burning
rate of a fire depends upon the exposed
surface area and on the properties of
the combustible itself.
Standard Time-Temperature Curve &
the Effect of Ventilation

When a fire cannot get sufficient air to

maintain the burning rate associated with
fuel-surface-controlled combustion, it will
burn at a ventilation-controlled rate.
Standard Time-Temperature Curve &
the Effect of Ventilation

The burning rate for fully developed fires

in ordinary combustibles to which air is
supplied through broken windows or a
doorway is approximated by:

R=0.62AoHo1/2 (lb/min)
Ao=the opening in sq ft
Ho=the height of the opening in ft
Standard Time-Temperature Curve &
the Effect of Ventilation

Overall a considerable ventilated area is

required for a fully developed fire to burn
at a fuel-surface-controlled rate.
Important Definitions

Celsius: is 1/100 the difference between

the temperature of melting ice and boiling
water at 1 atmosphere pressure
Important Definitions

Fahrenheit: is 1/180 the difference

between the temperature of melting ice and
boiling water at 1 atmosphere pressure.
Important Definitions

Joule: the energy expended when unit

force (1 Newton) moves a body through
unit distance (1m).
Important Definitions

Watt: a measure of power, or the rate of

energy flow. One watt is equal to one Joule
flowing per second. The rate of heat
release from a fire can be expressed in
kilowatts or megawatts-units that are
familiar to the electrical engineer.
Important Definitions
Thermocouple: a pair of wires of
different metals connected to each other
at one end. The other ends are connected
to a voltmeter.

When the sensing end is at a different

temperature from the voltmeter, a voltage
is set up, and the magnitude depends in
part upon the temperature difference
between the two ends. The voltmeter can
be calibrated to give readings in degrees of
Important Definitions

Calorie: the amount of heat required to

raise the temperature of one gram of water
one degree Celsius.
Important Definitions
British Thermal Unit: the unit of
measurement used in measuring heat

One Btu is the amount of heat required to

raise the temperature of one pound of
water one degree Fahrenheit. It is usually
compared to the amount of heat released
from one match.
Important Definitions
Ignition Temperature: The minimum
temperature required to initiate or cause
self-sustaining combustion independently
of the heating or heated element under
specified environmental conditions.
Important Definitions
Ignition temperatures: are commonly
reported as the autogenous ignition
temperature, auto ignition temperature
(AIT), or spontaneous ignition temperature
Important Definitions
Combustible: any material that does not
comply with the definitions of either
noncombustible material or limited-
combustible material, and has a flashpoint
equal to or greater than 100 degrees
Fahrenheit. (NFPA Standard)
Important Definitions

Flammable: capable of burning and

producing flames, and has a flashpoint
less than 100 degrees Fahrenheit and a
vapor pressure not greater than 40 psia.
(NFPA Standard)
Important Definitions
Flash Point: The minimum temperature
of a liquid at which sufficient vapor is
given off to form an ignitable mixture
with the air, near the surface of the
liquid or within the vessel used.
Important Definitions
Fire Point: the lowest temperature of a
liquid in an open container at which
vapors evolve fast enough to support
continuous combustion. The fire point is
usually a few degrees above the flash

Arthur E. Cote, P.E., ed., Fire Protection

Handbook 20th Edition. National Fire
Protection Association Quincy,
Massachusetts, 2008

Della-Giustina, Daniel E. The Fire Safety

Management Handbook. CRC Press, 2014