CHAPTER 1 / 1st Week

THE TECHNOLOGY OF FIRE

Introduction

The origin of fire before the dawn of civilization may be traced to an erupting
volcano, or a forest fire, started by lightning. No one really knows where on the earth
surface or at what stage of early history man learned how to start a fire and how to make
use of it. Yet, today, man has had fire as:

 Source of warmth and light

 Protection against enemies
 Cause chemical changes to foodstuffs to be digested to suit man’s body structure
 Provides processes for modifying chemicals into medicine.
 Provide heat to convert wood, metals, and bones into domestic tools or instruments for
aggression

While the application of fire has served man’s needs, its careless and wanton use exact an
enormous and dreadful toll from society in life and property. Hence, man’s understanding
of fire would enable him to develop the technology of prevention and control to a
considerable advanced state. Thus, the scientific study of fire in criminology education is
offered for the first time in SY 1985-86.

1. The Chemistry of Fire

This chapter is intended to present a back ground in Chemistry necessary in

understanding the physical and chemical properties of fire, heat energy sources, heat
measurements and heat transfer.

A. Basic Definitions

1. Technology – is a branch of knowledge that deals with industrial arts and sciences. It is
the application of such knowledge that is used to produce the material necessities of
society.

2. Chemistry – is the branch of science which deals with the study of composition and study
of matter, changes matter undergo, energy involved in a given change and conditions
necessary to bring about changes in matter.

3. Atoms – are fundamental particles of matter. It is the smallest particle of an element that
takes part in a chemical reaction and cannot be further subdivided by ordinary physical
and chemical means. The structure of the atom is conceived to be made of a central core

1
 known as the nucleus that contain proton which is positively charge and neutron which
has no charge. Surrounding the nucleus are principal energy levels where electrons,
which is negatively charged, travel in orbit.

Example: 12 atomic weight

6c atomic number

Proton

6p
6n 2e 4e Electron

Neutron

4. Elements – are pure substances made up of only one kind of atom. Metallic elements are
good conductors of heat and electricity but Non-metallic elements are either poor or non-
conductor of heat and electricity.

5. Molecules – are combinations of two or more different atoms combined in definite

proportions.

Example: N2O, CO2, O2,N2

6. Compounds – are two or more different atoms combined in definite proportions.

Example: Ethyl Alcohol – ( C2H5OH)

7. Atomic Weight of Element – is the relative weight of element as compared to the weight
of an atom of carbon, arbitrarily assigned 12.011.

8. Molecular Weight of a Compound – is the sum of the atomic weight of all atoms in one
molecule of the compound. The subscript in the formula indicates the number of atoms
of that element present, this is expressed in grams, known as gram molecular weight or
mole of the compound.

9. Chemical formula – is an abbreviated way of writing the substance using the symbols of
elements composing the substance and the subscripts of whole numbers to denote the
proportion at which they combine.

Example: Water Formula: H2O

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B. Physical Properties of Matter Related to Fire

1. Specific Gravity – is the ratio of the weight of a solid or liquid substance using the
symbols of elements composing the substance to the weight of an equal volume of
water. In general the higher the specific gravity of a substance the greater amount of
heat is necessary to decompose it.

2. Vapor Density – is the weight of a volume of pure gas composed to the weight of a
volume of dry air at the same temperature and pressure.

3. Vapor Pressure – when a liquid is heated in a liquid container, the molecules in a

liquid state escape to form gaseous molecules, the gas molecules strike one another as
well as the walls of the container and may return to the liquid state. A point of
equilibrium is eventually reached so the number of molecules re-entering the liquid
state. The force exerted by the molecules on the surface of the liquid at equilibrium is
called vapor.

4. Temperature – is the measure of the degree of thermal of agitation of molecules.

Thermometer is the instrument used to measure temperature which can be expressed
in oC (Celcius or Centigrade) oF (Fahrenheit) and oKm (Kelvin or absolute).

5. Boiling Point – is the constant temperature at which the vapor pressure of the liquid is
equal to the atmospheric pressure.

6. Ignition Temperature or Kindling Temperature – is the minimum temperature to

which substance in the air must be heated in order to initiate or cause self-contained
combustion without the addition of heat from outside sources.

7. Fire Point – is the lowest temperature of a liquid in an open container at which vapors
are evolved fast enough to support continuous combustion.

8. Flash Point – the temperature at which a flammable liquid from a vapor –air mixture
that ignites. The minimum and maximum temperature are referred to as the lower and
upper flash point in air respectively.

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C. Chemical Properties of Fire

1. Endothermic Reactions – are changes whereby energy ( heat) is absorbed or is added

before the reaction takes place. This means that the substances formed by the change
contain more energy than the reacting materials.

2. Exothermic Reactions - are those that release or give off energy ( heat) thus they
produce substances with less energy than the reactants.

3. Oxidation – is a chemical change that is exothermic. In connection with the fire

technology, it is simply defined as a chemical change in which combustible material
(fuel) and an oxidizing agent, like oxygen, react.

4. Flames – are incandescent gases. In order to be sustained. It should maintain a high

temperature and a concentration of short-lived intermediate chemical reactants
between fuel and oxidizer. There are different types of flames, categorized as:

4.1. Based on color and completeness of combustibility of fuel.

4.1.1 Luminous Flame – is orange-red, will deposit soot at the bottom of a vessel
being heated due to incomplete combustion of fuel and has a lower temperature.

4.1.2 Non-Luminous Flame – flame is blue forms no soot deposit due to almost
complete combustion of the fuel and has relatively high temperature.

4.2. Based on fuel and air-mixture

4.2.1 Premixed Flame – is exemplified by the Bunsen-type laboratory burner

where the hydrocarbon is thoroughly mixed with air before reaching the flame
zone.

4.2.2 Diffusion Flame – Is observe when gas (fuel) alone is force through a nozzle
into the atmosphere which diffuse in the surrounding atmosphere in order to form
a flammable mixture. The rate at which the fuel and oxidizer are brought together
determines the characteristics of a diffusion flame.

4.3. Base on Smoothness.

4.3.1 Laminar Flame – when a particle follows a smooth path through a gaseous
flame.

4.3.2 Turbulent Flames – are those having unsteady, irregular swirls and eddies.
As physical size, gas density or velocity are increased, all laminar gas flows tend
to become turbulent.

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 D. The Theory of Fire

Fire – is a result of chemical reaction of a fuel (reducing agent) with certain elements
as oxygen or chlorine or fluorine (oxidizing agent). At kindling temperature, this
reaction is known as oxidation.

1. Oxidation Reaction – reactions involved in fires are exothermic. In order for an oxidation
reaction to take place, a combustible material (fuel) and an oxidizing agent must be
present. Fuels include innumerable materials, whether or not a particular material can be
oxidized depends on the chemistry of the materials. For practical purposes, it can be
stated that any substance containing primarily carbon and hydrogen (hydrocarbon) can be
oxidized.

2. Ignition and Combustion – is one of the kinds of oxidation which is the same as actual
burning. It is the rapid oxidation accompanied by heat and light. When the heat,
generated by combustion, becomes sufficient to cause the material has reached its
burning kindling or ignition point.

E. Heat Energy Source

It is important to be familiar with the common ways which heat energy can be
produced since fire prevention and extinguishment are dependent on the control of
heat energy. Among the sources of heat energy are:

 Chemical
 Electrical
 Mechanical
 Nuclear

1. Chemical Heat Energy

Oxidation reaction is exothermic. The sources of this type of heat is the primary concern
of the fire protection engineer.

1.1 Heat of Combustion – the beat of combustion is the amount of heat release during the
complete oxidation where the organic fuel is converted to water and carbon dioxide.
Heat of combustion, commonly referred to as calorific or fuel value depends upon the
kind and members of atoms in the molecules as well as upon their arrangement.
Caloric values are used in calculating fire loading.

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 1.2. Spontaneous Heating - is the process of increase in temperature of a material as a
result of slow oxidation, that is, without drawing heat from its surrounding, until the
ignition temperature results into combustion.

Three conditions that determine whether or not an oxidation reaction will cause
dangerous heating are:

 Rate of Heat Generation

 Air Supply
 Insulating Properties of the intermediate surroundings

1.3. Heat of Decomposition – is the heat released by the decomposition of compounds

requiring the addition of heat for their formation. Compounds formed from exothermic
reaction are often unstable. When decomposition is started by heating these compounds
above critical temperature decomposition continues with the liberation of heat. Cellulose
nitrate “smokeless powder” decomposes with the liberation of dangerous quantities of
heat.

1.4. Heat of Solution – is the heat released when a substance is dissolved in a liquid. Most
materials release heat when dissolved but the amount is usually not enough to have any
significant effect on fire protection.

2. Electrical Heat Energy

Electrical energy produces heat when electric current flows through a conductor or when
a spark jumps on air gap. In a current flow through a conductor, electrons are passed
along from one atom to another within the conductor. Some conductors easily remove the
electrons and are said to be good conductors of electricity as in the case of metals.

2.1. Resistant Heating – is when the rate of heat generation is proportional to the
resistance and square of the current. Bare wire conductors can carry more current than
insulated wires without heating dangerous since the temperature of the conductor
resulting from resistance heating depends on dissipation of heat to the surrounding.
Single wires can carry more current than bundled or closely grouped wires.

2.2. Heat Generated by Lightning – the discharge of an electrical charge on a cloud to

an opposite charge on another cloud or on the ground is called lightning. Lightning
passing between the cloud and the ground can develop very high temperature in any
material of high resistance in its path, such as wood or masonry.

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 2.3. Inductive Heating – Whenever atoms are subjected to electric potential gradients
from external sources, the arrangement of the atom ( or of a molecule of several
atoms) is distorted, with a tendency for electrons to move in the direction of opposite
direction.

2.4. Static Electricity or Frictional Electricity – is an electrical discharge that

accumulates on the surface of two materials that have one brought together and then
separated. One surface becomes positively charge and the other negatively. If the
substance are not bonded or grounded, they will accumulate sufficient electrical
charge so that spark discharge may occur.

2.5. Heat from Arcing – Arcing results when an electric circuit which is carrying
current is interrupted, either intentionally( as by a knife switch) or accidentally (as
when a contact or terminal becomes loosened ).the temperatures of arc are very high,
and the heat released may be sufficient to ignite combustible or flammable material
within the vicinity.

3. Mechanical Heat Energy

Mechanical heat energy is responsible for a significant number of fires each year.
Although there are few notable example of ignition by the mechanical heat energy
released by compression, most fire by this heat source are due to frictional heat.

3.1. Frictional heat – result when mechanical energy is used in overcoming the resistance
to motion when two solids are rubbed together. Any friction generates heat.

3.2. Overheating of Machinery – may cause fires from the heat accumulated from the
rolling, sliding or friction in machinery or between two hard surface, at least one of
which is usually a metal. Ignition sources in this category are heated bearings or rotating
machinery and belts which become overheated due to pulley slippage.

3.3. Heat of Compression is heat released when gas is compressed. This also known as
the diesel effect. The fact that the temperature of a gas increases, the volume of the gas
decreases, has found practical use in diesel engines in which heat of compression
eliminates the use for a spark ignition system. The most plausible explanation for
disastrous explosion aboard two aircraft carriers is compression ignition of an oil-air
mixture in the catapult engines.

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4. Nuclear Heat Energy

The nucleus of an atom are made up of particles bound together by tremendous forces
which can be release when the nucleus is bombarded by energized particles. Nuclear
energy is release in the form of heat, pressure and nuclear radiation. Unstable
(radioactive) atoms spontaneously emit particles or rays from the nucleus of their atom.

4.1. Nuclear Fission – occurs when a subatomic particle called neutron bombards an
appropriate type of nucleus. The nucleus then splits into two lighter nuclei (the fission
products), and at the same time release tremendous amount of energy in the form of
kinetic energy of the fission fragments. In each act of fission, neutrons are emitted and if
one of these is at least captured by another fissionable nucleus, a fission chain reaction
with the continuous production of energy becomes possible.

4.2. Nuclear Fusion – includes all nuclear reaction in which two light nuclei combine to
form heavier nucleus, with the emission of other particles or gamma rays. Some of these
reactions are believed to be the source of energy in man-made devices as in the so-called
“hydrogen bombs”, where two deuterium atom atoms (H2) fused to form Helium (He4).

F. Heat Transfer

The transfer of heat is responsible for the start, as well as the extinguishment of most
fires. Heat is transferred by one or more of the three methods.

 Conduction
 Radiation
 Convection

1. Conduction – is heat transferred by direct contact from one body to another.

Example: Steam pipe in contact with wood transfers its heat to the wood by actual
contact with the pipe as its conductor. Conductance depends on three factors:

1.1. Thermal Conductivity – which is the measure of the rate of flow heat through unit
temperature gradiant. Unit temperature gradiant means that in the direction of heat
flow, the temperature is falling off one degree per unit distance. A typical unit of
thermal conductivity is Kcal/cm/hr/oC.

1.2. Cross Sectional – area normal to the flow path and length of the flow path. The
solution to heat conduction problems takes into consideration the thickness of the
material subjected to temperature with the time constant.

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2. Radiation – is a means of heat transfer when energy travels through space or materials
as waves. Radiant energy waves travel with the speed of light. On arrival at a body
they are absorbed, reflected or transmitted. Visible light consist of wavelength 4x10 -5
to 7x10-5 cm. (violet to red.)

3. Convection – is a means by which heat is transformed by a circulating medium either

gas or a liquid. Heated air expands and rises, and for this reason heat transfer by
convection occurs in an upward direction although heat currents can be made to carry
heat by convection in any direction. Heat generated in a stove is distributed
throughout the room by heating the air by conduction but the circulation of the
heated air through the room to distant objects is heat transfer by convection.

G. Heat Measurement

Heat of a given material is measured by its temperature. A material is conceived to be

made up of minute particles called molecules that are in constant motion. The
temperature of the material is the condition which determines whether it will transfer
heat to or from other materials.

Temperature Unit:

1. Celsius Degree (also called Centigrade). A celsius or centigrade degree ( oC) is

1
the difference between the temperature of melting ice and boiling water at
100
one atmosphere pressure. On the centrigrade scale, the melting point of ice is 0 oC
and the boiling point of water is 100oC.

1
2. Fahrenheit Degree (oF) is the difference between the melting point of ice
180
and boiling point of water at one atmospheric pressure. On the Fahrenheit scale,
the melting point of ice is 32 while boiling point of water is 212.

3. Kelvin or Absolute (oK or oA) is the same scale as the celsius degree but the
melting point of ice is 273 and boiling point of water is 373.

1
There is difference between the melting point of ice and boiling point of
100
water at one atmosphere of pressure.

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 CHAPTER 2 / 2nd Week

COMBUSTIBLE MATERIALS

One of the requirements in the formation of fire is combustible materials which must be
heated to its ignition temperature before it will burn.

SOLID COMBUSTIBLE MATERIALS

A. Wood and Wood-Based Products

Wood is very versatile material which is commonly used for construction,

furniture and interior decoration among others. When the thermal environment is
conductive to a given reaction, they will char, smoulder, ignite and burn. However, wood
and wood-based products can be used for fire protection.

For instance, an insulated plywood-faced wood and wood stud wall will provide a greater
degree of fire endurance than one without insulation.

1. Chemical Composition of wood

The principal component of wood are carbon, hydrogen and oxygen with smaller
quantities of nitrogen, sulphur and other elements. Dry wood is a complex of many
substance but the main constituents is cellulose (C5H10O5)x n. Other chemical
components are lingo-cellulose, lignin, certain sugars, resins, gums and esters of alcohol,
mineral matter (which forms ash when wood is burned) and moisture (H2O).

2. Factors influencing ignition and burning

Characteristics of Wood and Wood Products

2.1. Physical Form: Wood used for kindling are chopped to smaller pieces in order to
speed up burning. Heavier wood logs or timber shows considerable resistance to ignition.
The reason for these observation is that the sizes of the particles are smaller, the ratio of
the surface area to the volume (mass) increases.

2.2. Moisture Content: from laboratory ignition and burning test, it has been shown
that the behaviour of combustible solids of the same size, shape, and chemical
composition will vary with moisture content. The rate of burning is also influence by the
moisture content of the materials.

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2.3. Heat of Conductivity: is a measure of the rate at which absorbed heat will flow
through the mass material. It is the inverse property of insulating. The heat conductivity
of a particular material also plays a major role in its behaviour under fire condition.

2.4. Rate and Period of Heating Influence: the susceptibility of wood and wood
products to ignition. Combustible solids are usually considered less hazardous compared
to flammable vapors at ordinary temperature and atmospheric pressure. Ignition od solid
combustibles usually requires contact between the heat source and the material for a long
period enough to permit release of flammable vapors.

2.5. Rate of Combustion: is markedly influence by physical form of combustible, the

air supply present , the moisture content and other factors but for complete combustion to
proceed, there should be progressive vaporization of the solid.

B. Fiber and Textiles

Almost all textile fibers are combustible. Since textile are an inmate part of daily living-
clothes we wear, carpets, curtains, upholstery, beddings, etc.-there is a high involvement
of textiles in fire.

Factors that influence the Burning of Textiles:

 Chemical Composition of the textile fiber

 The finish of the fabric
 Fabric weight
 The tightness of the weave
 The flame-retardant treatment

1. Chemical Composition

Classification of Fibers According to Composition:

1.1. Natural Fibers

 Vegetables (Cellulosic) as cotton; Kapok (seed fibers); pulp (wood fiber);

coconut coir(nut fiber)
 Animal (protein) as wool (from sheep); silk (from cocoon of silk worm)
 Mineral (inorganic) as asbestos

1.2. Synthetic or Artificial Fibers

 Organic- (the fiber imitates vegetable fibers, divided into cellulosic, as for
example rayon, which is a “reconstituted” cellulose; and cellulose acetate

11
 which is prepared by treating cellulose with acetic acid; non cellulosic
includes rayon.
 Inorganic- like fiber glass and steel

2. Fiber Finish

Is sufficient combustible coating or decorative materials are placed on fabric, this

will support continued flaming. Many synthetic fabrics shrink when exposed to
temperature approaching their melting or decomposition temperatures. When
shrinkage brought the fabric into contact with the skin, the insulating layer of air
is eliminated and the amount of heat transferred to the skin is increase
significantly.

3. Fabric Weight

Affects the rate of combustion at which the textile undergoes. The heavier the
fabric of the same composition, the more considerable resistance to ignition.

4. Tightness of Weave

The closer the fibers are in the weaving of fabrics the more it will minimize the
air spaces between them and thus delay the rate of burning. Limiting oxygen
index (LOI) is a new means of measuring the tendency of a fabric once ignited, to
continue to burn after ignition source is removed. The higher the LOI of the
fabric, the greater the probability that will cease to burn once the ignition
temperature and high LOI can be expected to be safe for clothing and furnishing
since they will not ignite readily and will not continue to burn after an accidenta
source is removed.

5. Flame Retardant Treatments

The effect of chemical treatments in reducing the flammability of combustible

fabrics are varied and complex. Five different ways in which chemicals or
mixtures regard spread of flame and afterglow:

 Chemical or mixture generates non-combustible gases that tend to exclude

oxygen from burning surface.
 Radical and molecules from degradation of the flame retardant chemical
react endothermally and interface with the chain reactions in the flame,
 The flame retardant chemical decomposes endothermally.
 A non-volatile char or liquid is formed by the chemical which reduces the
amount of oxygen and heat than can reach the fabric.
 Finally divided particles are formed that change the combustion reaction.

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C. Plastics

Plastics, other than cellulose nitrate, are classified as ordinary combustibles. They
compromise a group of material consisting mainly of organic substances or high
molecular weight substances. They are solid in the finished state although at some
stage of manufacture plastics can be made to flow into desired shape, usually
through the application of heat or pressure or both.

There are about 30 major classes of plastic or polymer groupings and finished
products aside from which plastics contain plasticizers, colorants, fillers,
stabilizers, lubricants and other special additives some of which are higly
combustible.

LIQUID COMBUSTIBLE MATERIALS

LIQUID – is a state of matter with definite volume but no definite shape. It assumes the
shape of containing vessel. This is because it is characterized by free movement of
molecules among themselves but the molecules do not have the tendency to separate
from one another. It is only slightly compressible and is incapable of indefinite
expansion, unlike a gas.

1. Flammable and Combustible Liquids

Refer to any liquid having a flash point below 37.8 oC (100oF) and having a
vapour pressure not exceeding 40 psia(2068.8 um.) at 37.8 oC. Combustible
liquids are those with flash point at or above 37.8 oC (100oF)

2. Burning Characteristics of Liquids

Since it is the vapors from the flammable liquid which burn, the ease of ignition
as well as the rate of burning can be related to such properties as the vapour
pressure, flash point, boiling point, and evaporation rate. Liquids having vapors in
the flammable range above the liquid surfaceat the stored temperature have a
slower rate of flame propagation .

Flammable and combustible liquid fire and explosion prevention measures

embrace one or more of the following techniques or principles:

 Exclusion of sources of ignition

 Exclusion of air

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  Keeping liquids in closed container or system
 Ventilation to prevent the accumulation of vapour within the flammable
range.
 Use of an atmospheric of inert gas instead of air.
D. Gases

The term “gas” refers to the state of matter which has no definite volume and no
definite shape unless it is confined in a container. It is composed of very tiny
particles called the molecules and these are at constant random motion in a
straight line. They collide against one another and against the walls of the
container and are relatively far from one another.

1. Classification According to Physical Properties

Physical properties of gases are of primary concern of fire protection since these
affect the behavior of gases when they are accidentally release.

From the stand point of fire technology the classes are:

 Compressed gas – is one in which at all normal atmospheric temperature inside its
container, exist solely in the gaseous state under pressure.

 Liquefied gas – is one in which, at normal atmospheric temperature inside its

container, exist partly in the liquid state and partly in the gaseous state and under
pressure as long as any liquid remains in the container.

The pressure is basically dependent upon the temperature of the liquid although
the amount of the liquid also affects the pressure under some condition. A
liquefied gas exhibits a more complicated behavior as the end result of heating.

The net effect is dependent on:

 The gas phase subjected to the same effects as for a compressed gas;
 The liquid attempts to expand, compressing the vapour;
 The vapour pressure of the liquid increases with increasing temperature of the
liquid.

 Cryogenic Gases – is a liquefied gas which exist in its container at temperature far
below normal atmospheric temperature, usually slightly above its boiling point
and correspondingly low to moderate pressure. A cryogenic gas cannot be
retained indefinitely in a container solely in a container design because heat from
the atmosphere, which cannot be prevented from entering the container is
continually tending to raise the pressure to a level which, if continued, could
greatly exceed any feasible container strength.

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2. Classification According to Usage

The primary concern of this method of classification is the relation between

principal use and fire protection. Not only does general industry use this
classification but also standards and codes.

 Fuel Gas – are flammable gases customarily used for burning which air to produce heat
which in turn is utilize as power, light, comfort and process. Most commonly used gases
are natural gas and the liquefied petroleum gas ( butane and propane)

 Industrial Gases – include a large number of gases used for industrial processes as those
used in welding and cutting (oxygen, acetylene); refrigeration (Freon, ammonia, sulphur
dioxide); chemical processing (hydrogen, nitrogen, ammonia, chlorine); water treatment
(chlorine, fluorine), etc.

 Medical Gases – are those used for treatment such as for anaesthesia (chloroform, nitrous
oxide); and respiratory therapy ( oxygen ).

3. Basic Hazards of Gases

For the purpose of systematic evaluation of gas hazards, distinction should be

made by hazards presented by gas when confined in a container and the hazards
when the gas escapes from a container.

 Hazards of Confinement maybe attributed to:

a. Gases expands when heated, and when confined, the heating results in gas release and/or
cause container failure and
b. That the container an exposing fire thus loss in strength of the material of which the
container is made.

 Hazards of Gases

When release from their container vary with the physical and chemical properties of the
gas and the nature of the environment into which they are released. All gases, except
oxygen are hazardous to life if they displace the breathing air. Most odourless and
colourless gases are particularly dangerous as they are not detectable when inhaled.

4. Combustion of Explosions

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 Are among the dangers related to gases. They can be considered as occurring in
the following steps:

 The liquid phase of a liquefied flammable gas or flammable gas in released from its
container, piping or equipment.
 The gas mixes with air.
 With certain proportion of gas and air (the flammable and the combustible range), the
mixture is ignitable and will burn.
 When ignited, the flammable mixture burns rapidly and produces heat at a fast rate.
 The heat is absorbed by anything within the vicinity of the flame and very hot
combustion products.
 If the heated air is not free to expand because it is confined, pressure in the container will
increase.

CHAPTER 3 / 3rd Week

CHEMICALS

A substance maybe considered hazardous not only because they are combustible but also
they are very reactive. They may cause damage to life and properties. On the hazardous
properties, chemicals maybe classified as to:

 Combustibility
 Ability to oxidize other materials
 Reactivity to air and water
 Toxicity
 Radioactivity

Many chemicals process more than one of the enumerated properties. However, the
classification is based on the more predominant hazard.

A. Combustible Chemicals

The chemicals mentioned here are well known combustible chemicals. There are many
others that are combustible. They are not mentioned here since they are not common.

1. Carbon Black ( C )

Carbon black is formed by the incomplete combustion of acetylene or natural

cracking of hydrogen and in absence of air. When it is heated and absorbs oxygen,
slow smouldering may develop.

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2. Lampblack ( C )t

The burning of low-grade heavy oils or resinous or tarry materials with sufficient air
forms lampblack commonly known as soot. It is highly gas absorbent thus is
hazardous, after igniting spontaneously when freshly bagged. When in contact with
drying oils, heat is generated. Lampblack should be thoroughly cooled before bagging
and stored in a cool, dry area away from oxidizing material.

3. Lead Thiocyanate ( PbCNS )

Lead thiocyanate ( lead sulfocyanate ) under goes slow burning and decomposes to
form carbon disulphide which is highly toxic and non-inflammable sulfur dioxide
which has an obnoxious odor and is very poisonous.

4. Peroxides ( O2 - )

Organic peroxides are chemicals widely used in the public industries as well as in
drug and chemical industries. Many organic peroxides can be decomposed on
application of heat or shock or friction. The rate of decomposition is dependent on the
nature of the peroxides and the temperature. They are themselves combustibles and,
as in the case of inorganic peroxides, increase the intensity of fire.

5. Sulfides ( S= )

There are many sulphide salts found in finished products which we get in contact with
everyday such as:

 Antimony pentasulfide readily ignites at ordinary temperature and is hazardous

in contact with oxidizing materials. On contact with strong acids, one of the
products of reaction with Sb2S5 is hydrogen sulfide, highly poisonous, gas that
smells like rotten eggs. Antimony pentasulfide has been used in the
manufacture of safety matches.

 Phosphorus pentasulfide, in the presence of moisture, is exothermic and when

the ignition temperature ( 287o F ) is reached, it burns spontaneously. The
product of combustion includes sulfur dioxide and phosphorus pentoxide
which are both highly toxic. Water and phosphorus pentoxide yield hydrogen
sulfide.

 Phosphorus Sequisulfide is easily ignited and is highly flammable. The

ignition temperature is only 212oF. One of the products of ignition is sulfur
dioxide. It has been used for the manufacture of safety matches.

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  Potassium sulfide and Sodium sulfide are moderately flammable solids. The
oxidation of these compound produce the highly toxic sulfur dioxide. When
made to react with acids, these two sulphides from hydrogen sulfide.

6. Sulfur ( S )

Sulfur at ordinary temperature is an odor less, yellow solid that is not soluble in water
but in carbon bisulfide. In crystalline form, it occurs either as rhombic sulfur that is
stable below 96oC. It occurs in volcanic regions. When melted, melting point of
rhombic is 112oC while monoclinic is 119.25oC. Hydrocarbon impurities present in
the extracted sulfur may undergo combustion and form hydrogen sulfide and sulfur
dioxide.

7. Naphthalene ( C10H8 )

Naphthalene is most often used in the household as an insecticide. It is a while solid

with highly aromatic odor. It sublimes ( soild is converted to gas without passing the
liquid state ) at ordinary temperature. The mixture of naphthalene vapors nad dust
form explosive mixture.

B. Oxidizing Chemicals

In most instances, oxidizing chemicals are not combustible. They are known to be
oxidizing agents because they are sources of oxygen for combustion. They are
increase the ease of ignition of combustible materials and invariably increase in
intensity of burning.

1. Nitrate ( NO3- )

As a fire hazard, inorganic nitrates are not to be ignored because of its wide use as in
the manufacture of fertilizers, food preserves, salt baths, gunpowder and many other
finished consumer products. When heated, nitrates melt to release oxygen which
intensifies fire. In the presence of organic substances that are combustible, the
reaction forms toxic gases of nitrogen.

Among the common nitrates encountered in daily living are potassium nitrate, sodium
nitrate, ammonium nitrate and cellulose nitrate.

2. Nitrites ( NO2- )

Nitrites differs from nitrates not only in the number of oxygen present but also a
more active oxidizing agent since they melt and release oxygen at lower
temperatures. The mixture of a combustible material and nitrites should not be
subjected to hear or flames since explosion may occur.

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3. Inorganic Peroxides ( See Combustible Chemicals )

Barium, Sodium, Potassium and strontium peroxides are non-combustible but in the
presence of water, they react vigorously to form oxygen and heat. If organic
substances or other oxidizing materials are present when the exothermic reaction
takes place, fire likely will occur.

4. Chlorates ( C103 )

Among the most commonly used chlorate is potassium chlorate. This is a white,
odorless crystal that is soluble in water. It is a strong oxidizing agent when heated, it
forms potassium chloride and oxygen. The mixture of combustible materials and
potassium chlorate when heated may ignite or may explode.

5. Dichromate ( Cr2O7= )

Inorganic dichromate that are often used are sodium, potassium and ammonium
dichromate. They are non-combustible. Upon heating, they decompose to form
oxygen, heat and other decomposition products. Hence, in the presence of oxidizing
material, they may cause them to ignite.

6. Hypochlorite ( CIO- )

Better known as bleaching agent are sodium hypochlorite ( also known as chlorox )
and calcium hypochlorite also known as bleaching powder. When heated, they give
off oxygen and when water or acid comes in contact, they form chlorine, chlorine
monoxide and oxygen.

7. Perchlorates ( CIO4- )

Perchlorates have similar chemical properties as chlorates but are more stable. When
added to concentrated sulfuric acid, explosion may occur. Ammonium perchlorate has
a great explosive sensitivity when contaminated with impurities like sulfur, metal
powders and carbonaceous materials. Pure form can detonate if involved in fire.

Potassium, sodium and magnesium perchlorates when mixed with combustible

organic materials or other oxidizable materials form explosive mixtures.

8. Permanganate ( MnO4- )

Inorganic permanganate, especially potassium, sodium or ammonium, are powerful

oxidizing agents. A mixture of permanganate and combustible materials are subject to
ignition by friction or they may ignite spontaneously if an inorganic acid like
sulphuric acid is present.

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C. Unstable Chemicals

Unstable chemicals are those which undergo chemical change very readily on exposure to
air, water, heat, shock or pressure. They may be self-reactive.

1. Acetaldehyde ( CH3CHO )

Acetaldehyde contains the carbonyl group (- C=O ). It undergoes addition reaction with
other compounds. This makes it hazardous in the presence of certain catalysts at elevated
temperature.

2. Ethylene Oxide ( CH2oCH2 )

Ethylene oxide may undergo violent polymerization by action of heat or shock or when
catalysed by anhydrous chlorides; by iron, tin, or aluminium; oxides or iron (rust) and
aluminium, and alkali metal hydroxides. The polymerization reaction is exothermic and
the heat produced may cause polymerization of unreacted ethylene oxide. The vapour
produced may cause detonation. The flammable range of ethylene oxide in air is 30% to
80%.

3. Hydrogen Cyanide ( HCN )

Hydrogen cyanide is a colorless gas that is flammable and very poisonous. In the liquid
or vapour state it has the tendency to polymerize. The reaction is catalyse by alkaline
materials, and since one of the products of polymerization reaction is basic ( NH 3 ), an
explosion may take place.

D. Air and Water-Reactive Chemicals

Some chemicals react violently with air or with water so that from the point of view of
fire protection, they are to be discussed. These reactions are highly exothermic so that if
the chemical itself is self-igniting, burning may take place; if non-combustible, the heat
of reaction may be sufficient to ignite nearby combustible materials.

1. Alkalis ( Caustics ) ( OH- )

Caustic soda (lye) is chemically known as sodium hydroxide while caustic soda is known
as potassium hydroxide. They are the most common bases. These are solid that are very
soluble in water. Caustic are non-combustible but when mixed with water they react with
the evolution of heat. The heat of solution produced maybe high enough to ignite nearby

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 combustible material. One of the products of reaction between caustic and water is
hydrogen gas which in itself is a flammable gas.

2. Anhydrides ( RCO-O-COR )

When two molecules of acid undergo dehydration, acid anhydrides are formed. In turn,
when anhydrides are added to water, acids are formed accompanied by generation of
heat. Organic acid anhydrides are combustible and usually are more hazardous than their
corresponding acids, since their flash points are lower.

3. Charcoal ( C )

Charcoal may react with air at sufficient rate to cause the charcoal to heat spontaneously
and ignite. This is especially true to charcoal made from wood by the retort method. A
newly produced charcoal may readily undergo spontaneous heating than the cold
materials. A greater fire hazard are those freshly made, finely divided charcoal.

4. Coal ( C )

Coal has several allotropic forms. They are anthracite which is mainly used for fuel and
burns with a blue flame; bituminous coal is used for the production of industrial
chemicals aside from fuel; ignite contains some brownish areas where wood has not
completely carbonized; and peat, a most recent coal deposit.

5. Hydrides ( H- )

Most hydrides are compounds of metals and hydrogen. The exothermic reaction of
hydride with water forms a base and hydrogen gas. When exposed to air, the absorption
of moisture may cause ignition.

Among the common hydrides are sodium, lithium, potassium, and aluminium.

6. Oxides ( O= )

Non-metallic oxides and metallic oxides react with water the former produces a base
while the later produces an acid. The reaction evolves enough heat to ignite paper, wood,
or other combustible materials.

7. Phosphorus ( P )

The two allotropic forms of phosphorus rapidly oxidizes in air and spontaneous
combustion takes place. For protection, white phosphorus is stored under water in a
hermitically sealed metal container. Periodic tests should be made to be sure that the

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 containers do not leak. While phosphorus is very poisonous and is very corrosive so it
must not be in contact with the skin.

8. Sodium ( Na )

Is a silvery white solid that is waxy and can be cut with a knife. It has a low density. The
very electropositive element reacts with explosive violence with water forming caustic
soda ( NaOH ) and the inflammable gas – hydrogen. When exposed to air it combines
with oxygen to form sodium oxide. Heat is produced in both reactions. Sodium metal is
stored under petroleum to prevent reaction with air or with water.

E. Corrosive Chemicals

Corrosive chemicals are highly irritants which cause local destruction on living tissues.
They are usually strong oxidizing agents but are separately classified to emphasize their
noxious effect when in contact or when inhaled.

1. Inorganic Acids

The chief hazards of concentrated aqueous solutions of inorganic acids lies in the danger
of leakage and possible mixture with other chemicals or combustible materials.

2. Hydrochloric Acid ( HC )

This acid is commonly known as muriatic acid. With certain electropositive metals like
zinc, iron, tin, aluminium, magnesium, hydrochloric acid form salt and hydrogen gas.
With nitric acid, it forms chlorine gas and nitric oxide.

3. Nitric Acid ( HNO3 )

Nitric acid is used as an etching solution of metals and with sulphuric acid it is a nitrating
agent. As a nitrating agent, it is used in the manufacture of gunpowder and explosives.
When heated in concentrated form, brown fumes of nitrogen dioxide is formed. The
dilute nitric acid when heated produces colories gas of nitrite oxide. Fuming nitric acid
more than 97.5% nitric acid ) when spilled into burning gasoline will detonate.

4. Perchloric Acid ( HNO3 )

In concentration greater than 72% per chloric acid can be extremely dangerous. It is a
strong oxidizing agent and dehydrating agent when heated but at room temperature, it is a

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 strong non-oxidizing acid. The rate of burning of organic substance is greatly increased
by contact with perchloric acid.

5. Sulfuric Acid ( H2SO4 )

Sulfuric acid is colorless, oily liquid often referred to as oil of vitriol. It is a strong
oxidizing agent. With organic substances, it absorbs the water and produces carbon. The
charring is accompanied by the release of heat which may cause ignition. Dilute sulphuric
acid with some metals will produce hydrogen gas. Sulphuric acid produces painful skin
burns.

6. The Halogen ( X2 )

Halogen family (salt-producing ) is the most electronegative group. They include

fluorine, chlorine, bromine and iodine. The chemical activity of these elements decreases
as the atomic number increases. Thus, fluorine is the most reactive and iodine the least
reactive of the naturally occurring members of the family. The first two ( F 2 and CI2O are
fire hazards). They are non-combustible but will support combustion.

F. Toxic Chemicals

From the point of view of fire protection, the toxicity of chemicals is of particular
importance. A fire or explosion may release toxic chemicals and this will subject fire
fighters to a severe life hazard. Where there is a way of eliminating the toxic materials,
protection should be provided for those who are exposed daily to these hazards.

Chemicals during handling can be accomplished in two ways:

 By using the most practical of the methods available of controlling and confining
the chemical so that the toxic chemical cannot be contacted, swallowed or inhaled
in dangerous quantities during normal operations;

 By educating all persons who may be in areas where toxic chemicals are handled
as to the hazards, precautionary procedures to be followed, danger signals and
proper steps to take in case of emergency.

Examples of toxic chemicals have been mentioned in the previous section of these
chapter.

G. Radioactive materials

Radioactive elements and compounds have fire and explosion hazards identical with
those of the same materials that are not radioactive. An additional hazard is due to the
particles and rays emitted by the nucleus of unstable atoms. These radioactive emissions
can cause damage to the tissues and other genetic damage for the generation to come.

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 When fire is produced, vapors and dust (smoke) maybe formed that way contaminate not
only the building of origin but also neighbouring areas which may experience radioactive
fallout. The fire protection of this type is the concern of the nuclear engineer.

CHAPTER 4 / 4rth Week

COMBUSTION PRODUCTS NAD SOME OF THEIR EFFECTS

Combustion is a chemical change which brings about new substances. These products of
Combustion can be divided into four categories:

 Smoke
 Fire Gases
 Flame
 Heat

A. Smoke

Matter made up of very fine solid particles, and condenses vapour as a consequence of
combustion is known as smoke. Frequently, smoke provides warning of fire and
contributes to panic because of its irritating effects. Combustion of common combustible
( as wood ) brings both fire goes that contain water vapor, carbon dioxide, and carbon
monoxide. Due to conditions as insufficient oxygen, compounds like methane, methanol
formaldehyde, formic acid and acetic acid are also present. These gases are less dense
than surrounding air; they rise.

The predominant factors that cause smoke movement in all buildings are:

 The expansion of gases due to the temperature

 The stack effect
 The influence of external wind forces
 The forced air movement within the building

B. Fire Gases

The term “fire gases” refers to gases that remain when the products of combustion are
cooled to normal temperatures. Gases formed by a fire depends on many variables among
which are:

 The Chemical composition of the burning materials.

 The amount of oxygen available for combustion
 The temperature

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Most fuel contain carbon to form the very toxic carbon monoxide when the amount of
oxygen is limited but forms carbon dioxide when there is plenty of supply of oxygen for
burning. Some other gases formed are hydrogen sulfide, sulfur dioxide, ammonia,
hydrogen cyanide, nitrous oxide, nitric oxide, phosgene and hydrogen chloride.

1. Carbon Monoxide ( CO )

The gas is formed by the incomplete combustion of carbon. This is shown in the
reaction below:

Under controlled condition and an excess supply of oxygen, carbon monoxide is

converted to carbon dioxide is indicated below:

2CO-O2-2CO2

The hazard of carbon monoxide is its toxicity. It causes death by asphyxia, it reacts
with haemoglobin (an oxygen carrier of the blood) to form carboxyl haemoglobin
which is 20 times more readily reactive than oxygen. Thus carbon monoxide removes
the oxygen from the blood prevents the disposal of body carbon dioxide through the
lungs.

The following concentration of carbon monoxide and its effects are as follows:

Exposure to CO Effect

0.15% for one hour or Dangerous to life fatal

0.05% for three hours in less than one hour

0.4% or greater causes unconsciousness

1.3% in two or three breaths in two or three breaths and
Will cause death in a
few minutes

2. Carbon Dioxide ( CO2 )

This gas is usually produced in large quantities from fires and high levels of this gas
over stimulates the rate of breathing. This condition, combined with decreased
oxygen and the presence of irritating substances in the fire environment, may cause
the lungs to swell from an excess of liquid. The speed and depth of breathing are said
to be increased 50% by 2% carbon dioxide or 100% by 3% carbon dioxide in air. At
5% breathing becomes labored and difficult for some individuals.

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3. Hydrogen Sulfide ( H2S )

When materials like rubber, skin, hides, wool, hair, silk, and meat, are burned one of
the products formed is hydrogen sulfide. This colorless, highly toxic gas smells like
rotten eggs. Exposure to concentrations of 0.04% to 0.0% for more than one half hour
is dangerous and can cause symptoms of poisoning like dizziness, nausea, intestinal
disturbances and dryness as well as pain in the respiratory system.

4. Sulfur Dioxide ( SO2 )

The colorless gas with irritating, suffocating odor is formed when sulfur and sulfur
containing organic substances like wood, rubber, wool and silk are burned. Sulfur
dioxide causes the eyes to be watery and is irritating to the respiratory tract.
Concentration of about 0.05% are considered dangerous for even a short exposure.

5. Ammonia ( NH3 )

Combustible materials containing nitrogen as silk, wool, feathers, skin, meat, acrylic
plastic, phenolic and melamine resins when burned produce ammonia. It is colorless
gas with strong pungent odor. It is most often used as a heart stimulant, a refrigerant
and a raw materials for the manufacture of fertilizers. Ammonia is highly irritating to
the eyes, nose throat and lungs. Exposure to 0.25% to 0.65% in air for one-half our is
sufficient to cause death or serious injuries.

6. Hydrogen Chloride ( HCI )

Chlorine containing plastic materials will produce hydrogen chlorine when burned.
Polyvinylchloride is one plastic commonly used for electrical conductor insulation,
conduit and piping. Hydrogen chloride is a colorless gas with pungent, very irritating
odor. The inhalation of this gas in concentration of 1,500 ppm ( parts per million) in
air for a new minutes maybe fatal.

7. Hydrogen Cyanide ( HCN )

Relatively large quantities of hydrogen cyanide maybe produced by the incomplete

combustion of nitrogen containing materials such as wool, silk, urethane, polyamide
and acrylics. Hydrogen cyanide is a colorless gas which is highly toxic. Exposure to
0.3% fatal. HCN has a characteristic bitter almond odor and this sometimes warns of
the presence of the gas.

8. Nitrogen dioxide ( NO2 )

The reddish-brown gas nitrogen dioxide is produced during the decomposition and
combustion of cellulose nitrate, ammonium nitrate and other inorganic nitrates. It is
also formed when nitric acid comes in contact with metals or combustible materials.
This gas is extremely toxic.

26
 NO2 tends to anaesthetize the throat so that its presence is not recognized. The toxic
effect is delayed unless the exposure is great.

9. Arcolein ( CH2=CHCHO )

Acrylic aldehyde ( arcolein ) is a highly irritating and toxic gas produced when
petroleum products, fats oils and other common substances undergo combustion.
Concentrations of 1 ppm is tolerable to humans and over 10 ppm are lethal in short
time.

10. Phosgene ( COCI2 )

When a chlorinated compound comes in contact with the flames, phosgene is one of
the products of combustion. Fires involving polyvinylchloride plastics or chlorinated
solvents will produce phosgene. F.A. Patty (5) states that phosgene ordinarily does
not produce a serious health hazard except when ventilation is poor or where large
quantities of chlorinated vapors are involved. Phosgene has been reported as the
cause of death when carbon tetrachloride was used as a fire extinguisher.

C. Flames

Incandescent gases that accompanies rapid oxidation of a combustible material is called

flames. It is considered a distinct products of combustion. The observer can be sure that
there is a fire when flames are present. Burns can be caused by direct contact with flames.

These burns are classified as first degree burns, second degree burns or third degree
burns. First degree burns involves only the outer layer of the skin and are characterized
by abnormal redness, pain and sometimes a small accumulation of liquid. Second degree
burns penetrate more deeply into the skin. The burned area is moist and pink, there are
blisters and usually a considerable amount of subcutaneous fat.

D. Heat

The combustion product mostly responsible for the spread of fire in buildings is heat. The
psychological effect of heat ranges from minor injury to death. Exposure to heat may
result In dehydration, heat exhaustion, blockage of respiratory tract due to fluids and
burns and also increased heart rate. When the intensity of heat goes beyond the threshold
of human tolerance, it is fatal.

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 REFERENCES

HMIJ SCHOOL LIBRARIAN – A BOOK COMPILATION

AUTHORS

PROF. PAZ V. ABIZ AND PROF. DISODADO G. LAPINA

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