8A
r.1>i
Lanthanides
Actinides
23203808 23!03588 2la02ag1 im 1 -tnoru.,,, ~””‘ U111eqr, N~-‘ll.ti,
Alka li Alkaline Basic
Metals Eortt, l.letal
FIGURE 4.3 A modern version of the periodic table of the elements. [Courtesy of Todd Helmenstine, About Chemistry (2010).]
Elements in the same row of a periodic table are said to belong to the same period. The
periods are numbered on the far left of the table from 1 to 7. There is one period of 2 ele-
ments, two periods of 8 elements, two of 18 elements, and two more periods of 32 elements.
The periodic table of the elements is one of the most powerful icons in science: a single
table that consolidates an array of valuable information. Some version of the table hangs
on the wall of nearly every chemistry laboratory throughout the world. Simply by glancing
ar it, we can observe immediately the atomic number of any element. We can also readily
distinguish among those elements that are metals, nonmetals, and metalloids. In Figure
4.3, the salmon-colored squares contain the symbols of the elements that are metalloids.
They separate the metals from the nonmetals. Generally, the metals are the elements that
fall to the left of the group, and the nonmetals are the elements that fall to the right of it.
The usefulness of a periodic table consists in the manner by which it displays the peri-
odicity, or repetition, in the properties of the elements at regular intervals, In particular,
when we observe the elements as members of the same family, we know that they possess
similar chemical properties, Five families deserve special recognition in this regard. They
are identified by unique names:
period • A horizontal
row on the periodic
table
alkali metal family
The elements of Group
1 A on the periodic
table: lithium, sodium,
potassium, rubidium,
cesium, and francium . 1 Group 1A is called the alkali metal family; its members are lithium, sodium, potas-
sium, rubidium, cesium, and francium. Each metal reacts with water, although lithium re- alkaline earth
acts slowly, Each metal also ignites in air, especially when exposed to a moist atmosphere. family • The elements
In Figure 4.3, the squares designating the alkali metals are colored hot pink. in Group 2A on
the periodic table: .
1
Group 2A is called the alkaline earth family; its members are beryllium, magne- beryllium, magnesium, s1
um, calcium, strontium, barium, and radium. These elements are also chemically reac- calcium, strontium,
tive, bur not nearly as reactive as the alkali metals. They cause water to decompose, but barium, and radium
Chapter 4 Chemical Forms of Matter 115
oxygen family The
elements in Group 6A
on the periodic table :
oxygen, sulfur, sele-
nium, tellurium, and
polonium
halogen family The
elements in Group 7A on
the periodic table: fluo-
rine, chlorine, bromine,
iodine, and astatine
noble gas family • The
elements in Group SA
on the periodic table:
helium, neon, argon,
krypton, xenon, and
radon
molecule • The
smallest neutral unit
of some elements and
compounds, composed
of at least two atoms
nonpolar substance •
Any element or com-
pound having a sym-
metrical distribution of
charges about its center
polar substance • Any
element or compound
having an asymmetrical
distribution of charges
about its center
the rate of decomposition is slow at ambient temperatures. They ignite in the air b
f
. , Ut On!
a ter they have been heated or exposed to an ignition source. In Figure 4.3, the sq Y
designating the alkaline earth metals are colored medium blue. uares
Group 6A is called the oxygen family; its members are oxygen, sulfur, selen·
tellurium, and polonium, each of which is a moderately active substance. In Figur/~•
the squares designating the chalcogens are not uniquely colored as a group. · ‘
Group 7 A is called the halogen family; its members are fluorine, chlorine b
1 h f h
. h . , ro.
mine, iodine, and astatine. These elements are nonmeta s, eac O w ic 1s especial]
reactive. In Figure 4.3, the squares designating the halogens are col~red green. y
Group SA is called the noble gas family; its members are helium, argon, krypton
xenon, and radon. Chemists originally thought that these gases were all inert to chemical
combination and called them “inert gases.” Although some of them, such as xenon, are
now known to form compounds, the noble gases uniquely exist a~ a group of elements
lacking the chemical reactivity observed for all other elements. In Figure 4.3, the squares
designating the noble gases are colored teal.
–
Because thallium compounds are highly toxic, t hey are sometimes commercially available in rodenticides, prod-
ucts that kill rodents . Using the periodic table, answer the following questions:
(al What is the symbol for t hallium?
(bl What are the symbols for the elements immediately adjacent to thallium on the periodic table?
(cl Is thallium a metal, nonmetal, or metalloid?
(dl Provide the symbols of all the elements in the family of which thallium is a member.
(el Identify the group number of t he family of which thallium is a member.
Solution :
(al Thallium is located in the sixth period. Its chemical symbol is Tl.
(b) The elements immediately adjacent t o thallium on the periodic table are mercury and lead, whose symbol
are Hg and Pb, respectively.
(c) Thallium is a metal because it is located to the left of the salmon-colored metalloids on the periodic table
(dl Boron , aluminum , galli um, indium, and thallium are members of the same family of elements.
(el Thallium is a mem ber of the fam ily of elements denoted as 3A.
4 .6 MOLECULES AND IONS
Although the smallest representative particle of an element is the atom, not all uncom·
bined elements exist as single atoms. In fact, only six elements actually exist as single
atoms. They are the noble gases. They are said to be “monatomic.”
Other gases or liquids at room conditions consist of units containing pairs of li ke
atoms. They are called molecules. For example, hydrogen, oxygen, nitrogen, and chl ori ne
are gaseous ~lements as we generally encounter them, each of which is composed
01 3
molecule havmg two atoms. These molecules are said to be “diatomic ” and are symbol·
ized by the formulas H2, 02, N2, and Cl2, respectively. Their structures are illustrated
10
Figure 4.4. Because their charges are symmetrical about their molecular centers, they are
called nonpolar substances.
By contrast, the charges in substances like hydrogen fluoride and w ater a re uonsrm·
metrical about t?e centers of their molecules. These compounds are ca lled polar substances.
a~d a~e s~mbohzed by _the form~as HF and H20, respectivel y. Their structures are pr:
v1ded m ~igure 4.5. Their nature 1s due to the congregation of positive a nd nega ti ve charg
on opposite ends of the molecules.
Chapter 4 Chemical Forms of Matter
TABLE 4.5 Lewis Symbols of Some Representative Elements
FAMILY 1A 2A 3A 4A SA 6A 7A
Li· ·Be· ·B· ·C· ·~· •o• :F’· H·
Na · ·Mg· ·Al· ·S)· ·f ·s• :Cl·
K· ·Ca· ·Ga· ·G~· ·J\s· ·$~· :~r·
Rb· ·Sr· ·1~· :X-
Table 4.5 lists the Lewis symbols of some representative elements important to the
srudy of hazardous materials. Note that a simple way exists for determining the number
of valence electrons for any element of the A family: The number that identifies the A
family on the periodic table is also the number of valence electrons possessed by elements
in that family. For instance, the halogens are located in the family identified as Group 7 A,
and we note from Table 4.5 that each halogen has seven valence electrons.
4.9 IONIC BONDING
Electrons can be transferred from an atom of one element to an atom of another element,
resulting in the formation of positive and negative ions. This phenomenon generally
occurs between the atoms of metals and nonmetals. The ions that form are attracted to
each other by virtue of their opposite charges. Chemists call this electrostatic force of
attraction an ionic bond . The formation of the ionic bond is based on a fundamental law
of nature by which forms of matter with like charges ( +/+ or -/-) repel each other,
whereas forms of matter with unlike charges (+/-)attract.
Many atoms of the elements transfer or accept just the number of electrons that gives
them eight electrons in their outermost atomic orbitals. By transferring only this number
of electrons, these atoms attain the electronic stability of the noble gas nearest to them in
atomic number.
For illustration, consider the ionic bonding in sodium fluoride. From Table 4.5 we
learn that the Lewis symbols of sodium and fluorine are Na • and :f, respectively. When
these two elements combine at the atomic level, an atom of sodium transfers its single
electron to a fluorine atom. By transferring one electron, the sodium atom electronically
resembles neon. By accepting it, the fluorine atom electronically resembles neon. The
atoms become charged; that is, they become ions. The process can be written schemati-
cally as follows :
Na · + :F • —-‘> Na + : F :
The attraction between these oppositely charged ions constitutes the ionic bond that binds
the two ions together.
4.10 COVALENT BONDING
Electrons can also be shared by atoms of identical or different elements to form mole-
cules of elements or compounds. This sharing of electrons is usually between nonmetal
atoms. Atoms of the same nonmetal bond to one another and form molecules of the
element; atoms of different nonmetals bond to one another and form molecules of a
compound.
ionic bond The
electrostatic force of
attraction between
oppositely charged ions
Chapter 4 Chemical Forms of Matter 119
covalent bond A
shared pair of electrons
between two atoms
Lewis structure A
means of displaying the
bonding between the
atoms of a molecule by
the use of dots or
dashes for shared pairs
of electrons
The a toms of nonmetals acquire th eir electronic stability by sharing electro .
h . h mm manner t a t pernuts t em to resemble atoms of the noble gases nearest to them in _a
b F h · h f” atomic ~wn er. or t e atoms m t e IrSt and second periods other than hydrogen, helium
1
. h
mm, and berylliwn, this means sharing a total of eight electrons in their outermost a:o rt_·
orbital. This includes the atom ‘s valence electrons plus those it shares with another at:ic
Hydrogen atoms share only two electrons. One shared pair of electrons between any:·
atoms is called a covalent bond. 0
. Let’s observe how two atoms of hydrogen combine to form a hydrogen molecule. f-{.
1s the Lewis symbol for hydrogen. To achieve the electronic structure of helium, the near-
est noble gas, one hydrogen a tom shares its only electron with the single electron from a
second hydrogen atom. We represent this process as follows:
H · + H · —–> H:
H
The pair of electrons shared between the two hydrogen atoms is a covalent bond. This
manner of representing the hydrogen molecule (H:H) is called Lewis structure.
Two chlorine atoms combine to form a chlorine molecule. :Cl · is the Lewis symbol for
chlorine. To achieve the electronic structure of argon, the neare;t noble gas, each chlorine
atom shares its unpaired electron. This formation of the chlorine molecule from two clllo-
rine atoms can be represented as follows:
: C l• + : C J· —–> : CJ : C J :
Let’s consider next the combination of hydrogen and chlorine atoms. A hydrogen arom
and a chlorine atom can share an electron pair to form a molecule of the substance called
hydrogen chloride. The formation of a hydrogen chloride molecule from a hydrogen atom
and a chlorine atom can be represented as follows :
H· + : CJ · —–> H : C J :
The hydrogen atom shares an electron pair, so its electronic structure resembles that of
helium, whereas the chlorine atom shares an electron pair, so th a t its electronic structure
resembles that of argon.
An atom can also form several covalent bonds with other atoms by simpl y sharing
more than one pair of electrons. For instance, consider the formation of the methane mol-
ecule. This molecule consists of one carbon atom a nd four hydrogen a toms. The Lewis
symbols for carbon and hydrogen atoms are · C · and f-l ·, respectivel y. In the methane mol-
ecule, the carbon atom shares each of its four electrons with the electrons from four
hydrogen a toms, as represented here:
H
· C · + 4 H · —–> H : C : H
H
The sharing of electrons in the methane molecule results in an electronic a rrangement like
that of the neon atom for the carbon atom and an electronic arrangement like that of the
helium atom for each of the four hydrogen atoms.
double bond A cova•
lent bond composed of
four electrons shared
between two atoms
triple bond A cova-
lent bond composed of
six shared electrons
between two atoms
Sometimes, two nonmetallic atoms share more than one pair of electrons . This beha v·
ior is particularly characteristic of carbon atoms and results in the forma tion of multiple
bonds. Two types of multiple bonds exist: double and triple bonds. A double bond con·
sists of the sharing of two pairs of electrons (: :), whereas a triple bond consists of th e
sharing of three pairs of electrons (:::). The name of the element is designated when rbe
pairs of electrons are associated with atoms of the same element, as for exa mple, carbon·
carbon double bond and carbon-carbon triple bond.
120 Chapter 4 Chemical Forms of Matter
H:H :Cl:CI: H:CI:
Hydrogen Chlorine Hydrogen chloride
H
H;¢:H Q::C::Q :C:::O:
H
Metha ne Carbon dioxide Carbo n monoxide
The carbon dioxide molecule consists of one atom of carbon and two atoms of oxygen.
h Lewis symbols for carbon and oxygen atoms are ·C· and ·O· respectively. The forma-
T e of a carbon dioxide molecule from one carbon at~m and’t~o oxygen atoms can be
non II
Se nred as fo ows: repre
·9 · + ·¢· + ·9· – o::c::o
Notice the existence of two pairs of electrons on each side of the carbon atom in the car-
bon dioxide molecule. Each of these shared pairs of electrons is a double bond. By sharing
electrons in this fashion, the carbon atom and the two oxygen atoms all achieve the elec-
tronic arrangement of neon.
The formation of the carbon monoxide molecule from a carbon atom and an oxygen
atom can be represented as follows:
·C· + · O· – :c:::Q:
The three shared pairs of electrons between the carbon and oxygen atoms constitute a
triple bond. Once again, the carbon and oxygen atoms achieve the electronic stability of
the neon atom by sharing eight electrons between them. The Lewis structures of several
other molecules are illustrated in Figure 4.6.
For the sake of simplicity, Lewis structures are usually written by drawing a long dash
to represent the shared pair of electrons. The dots representing all other electrons are
omitted. In this notation, the compounds previously noted can be represented as follows:
H
I
H- H CI – Cl H-Cl H-C- H C=O O=C=O
I
H
Hydrogen Chlorine Hydrogen chloride Me thane Carbon monox ide Carbon dioxide
FIGURE 4 .6 The Lewis
structures of some simple
molecules.
SOLVED EXERCISE 4.3
At ambient conditions nitrogen trifluoride is a gas. It is used to manufacture item s like microchips and flat screen
televisions. ‘
(a) What is the chemical formula of nitrogen trifluoride?
(b) What is its Lewis structure?
Solution:
(a) From Table 4.9, we see that the Greek prefix tri- refers to three . The absence of a prefix fo r ” nitro-
gen” implies that the prefix mono- was dropped for si mplicity. This means that the nitrogen trifluoride
Chapter 4 Chemical Forms of Matter 121
temperature, p. 49
tonne (t), p. 39
vapor, p. 36
vapor pressure, p. 53
volatile, p. 53
volume, p. 36
volumetric thermal•expansion
coefficient p. 60
weight, p. 36
vapor density, p. 47
1+MSM!i
Identify the common properties that characterize solids, liquids, and gases.
Use the factor-unit method to convert measurements expressed in customary units
into their equivalents in appropriate metric units and vice versa.
Describe the concepts of density, specific gravity, vapor density, and vapor pressure
and cite examples of their usefulness to emergency responders.
Convert temperature readings on one temperature scale into their equivalents on the
ocher temperature scales noted in this chapter.
Describe the mechanisms that contribute to the spread of fire from one location to
another.
Convert heat measurements expressed in Beus to measurements expressed in calories
and vice versa.
Use the gas laws to calculate the volume of gases subjected to different temperature
and pressure conditions.
Describe the potential danger associated with the expansion of a heated gas or vapo
r
that is confined in a storage vessel.
Identify the general hazards that emergency responders encounter when exposed to
cryogens.
At first glance, the mere number of hazardous materials is likely to overwhelm the average nonscientist. How is it possible to learn the individual properties of so many substances and recall them under the stressful conditions that often prevail
when lives and property are in jeopardy?
Fortunately, we can associate the hazardous properties of many substances with their
state of matter. We learn, for instance, that all gases possess certain common properties;
on studying the chemistry of gases, we learn to identify these common properties and then
turn our attention later to the features that cause individual gases to be regarded as unique
substances.
In this chapter, we learn about some of the general properties of matter and energy
and how they influence certain phenomena such as the spread of fire . Also, as we review
the properties of matter and energy, we learn how they relate to the issues in fire science.
Specifically, in this chapter we learn how the modes of heat transfer contribute to the
propagation of fire, the reason water often effectively extinguishes a fire, and why gas
cylinders are likely to rupture when their contents are excessively heated.
2.1 MATTER DEF INE D
Each day, we encounter air, water, metals, stone, dirt, animals, and plants. These are the
materials of which our world is made. Scientists refer to them as the different kinds of
matter. When we search for common features among its forms, we note that ordinary
matter possesses mass and occupies space. In other words, matter is distinguishable from
empty space by its presence in it .
matter • Anything that
possesses mass and
occupies space
Chapter 2 Some Features of Matter and Energy 3 5
The qua ntity of
matter possessed by an
object regardless of it s
location in the universe
The force with
whic h a mass is pulled
toward the center of
Earth
The force of
attraction between two
bodies
physic al sta te of
matter • Any form in
which matter is gener-
ally encountered : solid,
liquid, and gas
The capacity
of matter confined
within a tank or
conta iner
solid • Matter that pos-
sesses a definite volume
and a definite shape
li quid Matter that
possesses a definite
volume but lacks a
def inite shape
gas • Matter that pos-
sesses neither a definite
volume nor a definite
shape
The gaseous
form of a substance
that exists as a solid
or liquid at normal
ambient conditions
The concept of mass is closely related to the concept of weight. In our universe, every
form of matter is attracted to all other forms by the force we call gravity. On Earth, the
weight of matter is a measure of the force with w hich graviry pulls it toward Earth’s cen-
ter. As we leave Earth ‘s surface, the gravitational pull decreases until it becomes virtually
insignificant . The weight of matter accordingly reduces to zero, yet the marter still pos-
sesses the same mass as it did on the surface of Earth. For this reason, the expressions
“has a mass of” and ” weighs ” are essentially equivalent on Earth’s surface.
As usually experienced, matter exists in three different for_ms or states of aggregation:
solid, liquid, and gas. 1 These are called the physical states of matter.
Because matter occupies space, a given form of matter is also associated with a definite
volume o r capacity. Space should not be confused with air, because air is itself a form of
matter. Volume refers to the actua l amount of space that a given form of matter occupies.
2.1-A SOLIDS
A solid is the form of matter existing in a rigid state independent of the size and shape of
its container. Consider this book. It retains its shape regardless of its position in space and
does not need to be placed into a container to retain that shape . Left to itself, it will never
spontaneous ly assume a shape different from what it has now.
Solids a lso occupy a definite volume at a given temperature and pressure. We can
squeeze most solids with all our might o r heat or cool them, but their total volume change
is relati vely small.
Certain solid plastics can behave differently from most solid s. Because of their inher-
ent elasticity, they can assume different shapes and vo lumes when squeezed, stretched, or
otherwise manipulated. Solid foams also can behave uncharacteristically, because they
contain encapsulated air.
2 .1-B LIQUIDS
A liquid is a form of matter that does nor possess a characteristic shape; racher, its shape
~ep~nds on the shape of the container it occupies. Consider water within a glass.
The
liquid takes the shape of the glass up to the level that it occupies. If we pour the water into
a cup, the water takes the shape of the cup; or if we pour it into a bowl, the water takes
th_e s_hape of the bowl. Of course, sufficient space must always be available for the warer
wuhm the co~ta1~er; otherwise, the liquid overflows. Assuming that space is available,
howe~er, an~ hqu~d ~ssumes whatever shape its container possesses.
Like sohds, liquids occupy a specific volume at a given temperature and pressure
They rend to maintain a relatively fixed volume when they are exposed to a cha · ·
etther of_ the.se conditions. Liquids and solids are often considered incompressible, b;;.,eu::
the apphcanon of pressure barely changes their volumes When heated 1· ‘d d d h h · · , 1qu1 s o ex pan
muc r:iore t an soh~s d.o, ~ut nor_ nearly to the extent that gases expand. \Y/e revisit th;
expansion of heated l1qu1ds m Section 2.11.
2 .1-C GASES
A gas, or vapor, is anoch_er form _of matter that does not possess a characteristic sha e
and assumes the shape of its co nramer. If a gas or mixture of ases · • • p
a balloon, it assumes the shape of the balloon· or if it is t 7 cl such as air, is put mto
the shape of the tire. ‘ rans erre mro a ure, it assumes
1
0ther physica l sta tes of maner are kn own beside s solid 1· ‘d d
ve ry high temperatures, whereas a fift h state, ca ll ed the B~!~1Ej,~~e . gas. A fourth st~te, plasm a, exists only at
peratures. _Alth_o ~gh we will not encounter materials in th e fo urth //;;1densate, ex1~ts only at very low tem –
ous materials, it. is worthy to note that the sun, other stars, and oth n f I th sta~es during ?ur stud y o~ ha_za rd-
pla sma state. It 1s the predomi nant state of ord ‘n . h’ er o~m s of mtcrga lac n c matter exist m rhe
1 ary matter wit in th e um ve rse.
36 Chapter 2 Some Features of Matter and Energy
Gases also lack a characteristic volume. When confined 10 a container with non-
rigid, flexible walls, the volume that a confined gas occupies dep~nds on its temperatur~
d pressure. When confined to a balloon, for instance, the gas s volume expands an
an ntracts depending on the prevailing temperature and pressure. When confined to a
c~ntainer with rigid walls, however, the volume of the gas is forced to remain constant.
~his property of gases can cause rigid containers to explode, a topic we note later m
Section 2.12. . . . .
The properties of sohds, hqmds, and gases noted in this section can now be used to
formall y define the three states of matter:
1 Matter in the solid state possesses a definite volume and a definite shape.
1 Matter in the liquid state possesses a definite volume but lacks a definite shape.
1 Matter in the gaseous state possesses neither a definite volume nor a definite shape.
2,2 UNITS OF MEASUREMENT
The necessity to measure, and to measure with accuracy, is essential to any kind of scien-
tific or technological endeavor. To measure means to find the number of units in a sample
of something. For instance, when we measure the distance from one point to another
along a wall, we generally determine how many feet, yards, or meters are between the two
points. The foot, yard, and meter are examples of the common units of length.
Two systems of units have survived the test of time: the United States customary
system of weights and measures, and the SI or metric system. The United States is the
only remaining industrialized country that does not exclusively use the SI system. The cus-
tomary system is based on the use of an array of units that appear to have no obvious inter-
relationship, such as inches (in.), feet (ft), yards (yd), miles (mi), ounces (oz), pounds (lb),
pints (pt), quarts (qt), and gallons (gal).
The majority of the world’s population and the worldwide scientific community use a
system that is historically called the metric system of measurement. This system has been
modified so that today, we actually use what is called the 51 system of units, where “SI”
is an abbreviation of the system’s official French name, Le Systeme International d’Unites.
The SI system encourages the use of certain fundamental units from which all other mea-
surements are constructed. These fundamental units are called the 51 base units. Examples
of SI base units are the meter and kilogram, for length and mass, respectively.
Certain prefixes are used in the SI system to denote multiples and fractions of the
units of measurement. Each prefix is a fraction or multiple of the number 10. For example,
when we wish to refer to 1000 meters, we use the word kilometer. The prefix kilo means
1000 times the meter, the SI base unit.
The prefixes listed in Table 2.1 are commonly used in studying the chemistry of haz-
ardous materials. These particular prefixes should be committed to memory. They are
used to measure certain properties of matter, particularly its length, mass, and volume. It
is appropriate to discuss each type of measurement separately.
2.2-A LENG’Jlt
Today, the meter (m) is defined as the length of the path traveled by light in a vacuum in
1/299,792,458 of a second. In ordinary practice, we measure length in the metric system
with_ a metric ruler. By so doing, we discover that one meter is slightly longer than a yard;
spec1fically, one meter equals 39.37 inches (in .).
1 m =
39.37 in.
One meter is equivalent to 100 centimeters (cm) and to 1000 millimeters (mm).
1 m = 100 cm = 1000 mm
customa ry system of
weights and measures
Any unit of weight and
measures based on the
yard and pound and
used in normal com-
merce within the
United States
SI system of units •
Known historically as
the metric system, the
scientific standard of
measurement that
employs a set of units
describing length, mass,
time, and other charac-
teristics of matter
SI base units • The
accepted units of mea-
surement adopted
internationally such as
the meter for length,
kilogram for mass, and
kelvin for temperature
meter (m) • The SI unit
of length in the metric
system of measurement
Chapter 2 Some Features of Matter and Energy 3 7
gram (g) One one-
thousandth of the mass
of 1 kilogram
FIGURE 2.1 The rela-
tionshi p between the inch
and the centi meter. Note
that 1 inch (in.) equals
2.54 centimeters (cm).
TABLE 2.1 Common Prefixes Used in the Metric System
PREFIX SYMBOL MEANING
hecta- h
one hundred (102) times the SI base unit
kilo- k
one thousand (103) times the SI base unit•
deci- d
One-tenth (10-1) of the SI base unit
centi- C
One-hundredth (10-2) of the SI base unit
milli- m
One-thousandth (10-3) of the SI base unit
micro- µ
one-millionth (10-6) of the SI base unit
nano- n
One-billionth (1 o-9) of the SI unit
one-trillionth (1 o-12) of the SI unit
–
pico- p
‘The SI base unit of mass is an exception.
For very large lengths, we use the kilometer (km); once again, 1000 meters is equivalent
to 1 kilometer.
1 km= 1000 m
For very small lengths, we use the micron (µm) . One micron is one-millionth of a meter.
1 µm = 0.000001 m
The relationship between the inch and centimeter is shown in Figure 2.1 . One inch equals
2.54 centimeters.
1 in. =
2.54 cm
2.2-B MASS
The SJ unit of mass is the kilogram. A bit of attention needs to be gi ven to constructing
the multiples and fractions of mass measurements, because this unit of mass already con-
tains a prefix (kilo-). The names of the various multiples and fractions of the unit of mass
are constructed by attaching the appropriate prefix to the word gram (g), not kilogram.
In other words, the gram is used as though it were the SI unit of mass, even though it actu·
ally is not.
One kilogram is equivalent to 2.2 pounds. One gram is approximately the mass of a
peanut.
Three common metric units of mass are the milligram, microgram, and kilogram.
One one-thousandth of a gram is a milligram (mg) ; one one-millionth of a gram is a
microgram (µg ); and 1000 grams is a kilogram (kg).
1 mg= 0.001 g
1 µg = 0.000001 g
1 kg = 1000 g
0 1 2 3 4 5 6 7 8 9 10 r, …… :, ;,;;:~:;~:;, …… , .. ,: .. , ·:’ … , …. , .. :~~:::., .. ,.
.. I”‘ “‘I. I”” … , … , … “‘I .. , …… , .. ,.: … :
0 1 2 3 4
38 Chapter 2 Some Features of Matter and Energy J
1 cubic meter FIGURE 2.2 Because this cube measures 1 meter on each
edge, its volume is 1 cubic meter (m3), the approved SI unit
of volume.
One milligram is approximately the mass of a grain of sand whereas one microgram is
approximately the mass of a fleck of dust, ‘
For relatively large mass measurements, use is made of the metric ton, or tonne (t).
1 t = 1000 kg
To verbally distinguish the ton and the tonne, the latter is pronounced “tunny.”
2.2-C VOLUME
The approved SI unit of volume is the cubic meter (m3). This unit is derived directly from
the SI unit of length and is not a SI base unit itself. We can easily derive the cubic meter by
considering the cube in Figure 2.2, which measures 1 meter on each edge. The volume of
this cube is determined by taking the product of its length, width, and height.
Volume = 1 m X 1 m X 1 m = 1 m3
Using simple arithmetic, the volume of this cube is determined to be 1 cubic meter. Because
it is possible to derive the cubic meter directly from a previously defined unit, it is unnec-
essary to define some other unit as the SI unit of volume.
Although the cubic meter is the approved unit of volume in the SI system, another
unit has been used for many years to measure volume. This unit is the liter (L) . One quart
is slightly less than one liter.
946 ml=
1 qt
Chemists continue to use the liter for measuring volume because its size is so convenient
for laboratory-scale measurements. The cubic meter is comparatively too large.
One liter is equivalent to one one-thousandth of a cubic meter.
1 l = 0.001 m3
If we construct a cube measuring 1 meter on each edge and then divide the resulting vol-
ume into 1000 equal-size cubes, the volume of each small cube is one liter. Imagine further
dividing each liter cube into another 1000 equal-size cubes. These subdivisions are illus-
trated in Figure 2.3. Because the prefix mi/Ii- means one one-thousandth of a unit, the
volume of each of the new cubes is one milliliter (ml).
1 l = 1000ml
Formerly, the milliliter was known as a cubic centimeter (cm3). Although the use of the
cubic centimeter has essentially been phased out in chemistry, it is still used in the medical
field .
t onne (t) The metric
unit of mass equivalent
to 1000 kilograms
liter (L) The volume
occupied by a cube
measuring 10 centime-
ters to an edge
Chapter 2 Some Features of Matter and Energy 39
r
Omnibus Trade and
Competitiveness Act
The federal statute that
enhances the competi-
tiveness of American
industry throughout
international markets
based in part on the
required use of the
metric system
1m
1
1m
1 cubic meter
1 liter
10cm
1
‘<.N. l'll JA"
10cm
1 liter
FIGURE 2.3 The cube on the left measures 1 meter on each edge and has been divided i~to lOOO equal-
size cubes. The volume occupied by each of the smaller cubes is 0.001 c~bic meters, or 1 liter (L). The cube
on the right measures 1 O centimeters on each edge and has been subd1v1ded into 1 _oo_o equal-size cubes.
The volume of the larger cube is 1 liter, and the volume of each smaller cube is 1 milliliter (ml), or 1 cubic
centimeter (cm 3).
2 .2-D GENERAL USE OF THE METRIC SYSTEM IN THE UNITED STATES
In the international community, the United States is the sole industrialized nati_on that has
not officially adopted the metric system. The United States’ nonuse of the metnc system at
one point was contributing to unsuccessful competition in some international ma~kets, To
address this concern, Congress passed the Metric Conversion Act in 1975, Notwithstand-
ing its passage, the act called only for voluntary compliance and accomplished little
change in the manner by which Americans measure the properties of matter.
Then, in 1988, Congress passed the Omnibus Trade and Competitiveness Act, which
mandated the following:
Identified the metric system as the preferred system for U,S. trade and commerce
Required use of the metric system by all U,S. government agencies
Required use of metric units for all federally funded construction projects costing
over $10 million
Required use of metric units for all federally assisted highway construction projects
that began on or after October 1, 1996
This act obligated building and highway construction companies to begin using the metric
system when seeking compensation for work on federally funded projects,
The use of metric units is also evident on warning labels for a variety of products
whose manufacture or use is regulated by agencies of the federal government, especially
when the relevant measurements have been obtained by scientists. For example, a high-
salt (sodium chloride) diet has been linked with ailments like high blood pressure, heart
attacks, and strokes, To warn about these potential ill effects, the FDA requires informa·
tion concerning the dietary content of sodium to be printed on labels affixed to containers
of prepared foods. Three labeling definitions are used to denote the sodium content per
serving: sodium-free, less than 5 milligrams; very low sodium, less than 35 milligrams;
and low sodium, less than 40 milligrams.
Even when the use of the metric system is not specifically mandated, consumer
product manufacturers are printing metric units on labels together with their customary
counterparts, Look at a ~everage can, for instance. Its volume may be listed as 32 fluid
ounc~s (1_ qt) togethe_r with 946 milliliters. All in all, use of the metric system is slowly
creepmg mto the Uruted States and taking us one step closer toward common world-
wide usage.
40 Chapter 2 Some Features of Matter and Energy
2,3 CONVERTING BETWEEN UNITS OF THE SAME KIND
Su ppose we wish to convert between gr~ms and kilograms , pounds and grams, or liters
and ga llons. How do we accomplish this task? Problems like these are best solved by
using a simple procedure called the factor-unit method. Briefly, it consists of the follow-
ing key steps:
1 Identify the desired unit.
1 Choose the proper conversion factor(s).
1 Multipl y the given measurement by the conversion factor(s), being certain to multiply
and di vide numbers and cancel equal units.
Choosing the proper conversion factor is a crucial step to obtaining the correct answer
10 a problem. The conversion factor is a fraction numerically equal to 1 that equates the
quaniiry in the numer~tor to the qua~tity in the denominator. For example, we know
there are 1000 meters m 1 kilometer. Either of the following fractions serves as a correct
conversion factor:
1000 m 1 km
1 km
or
1000m
The factor s are respectively read as follows: 1000 meters per kilometer;
one kilometer per 1000 meters.
Suppose we know the height of Moscow’s Mercury City Tower (at
right ), the tallest building in Europe. It measures 338 .82 meters from
ground level to the top. What is its height in kilometers?
Using the factor-unit method, we simply multiply the given mea-
surement, 338 .82 meters, by a conversion factor that relates meters to
kilometers.
1 km
338.82 m X lOOO m = 0.3388 km
Note that them in 338.82 m cancels with them in 1000 m . Then, divid-
ing 338 .82 by 1000 gives 0.3388 kilometers (to four significant figures) .
Individuals who are experienced in using the metric system simply move
the decimal point from left to right, or vice versa, as the need arises.
Some of the more frequently used metric units and their equivalent
customary counterparts are given in Table 2 .2. These relat10nsh1ps per-
mit us to write conversion factors like the following:
lm
39.37 in.
TABLE 2.2
METRIC UNIT
1m
2.54 cm
1 kg
454 g
946 ml
2.54 cm
1 in.
1 kg
2.2 lb
946ml
1 qt
Common SI (Metric) Units and
Their Customary Equivalents
CUSTOMARY UNIT
39.37 in.
1 in.
2.2 lb
1 lb
1 qt
factor-unit A
procedure for changing
a quantity expressed in
one unit to a quantity
of another unit by mul –
tiplying, dividing, and
arithmetically canceling
numbers and units
conversion factor A
fraction equal to 1 in
which the magnitude
of one unit is related in
the numerator to the
magnitude of another
unit of the same type in
the denominator
Chapter 2 Some Features of Matter and Energy 41
,l .,
I
SOLVED EXERCISE 2.1
. • for use by fire departments and others trained in
A class I standp ipe system contains a 2½-,n ch hose connection . eters
handling heavy fire streams. Express t he equivalent length ,n cent,m . . . . .
. convert 2y, inches into ,ts equivalent length 1n centI-
Solution: We first need one or more_ conversion f actors t~ t the following conversion factor:
meters. Because one inch is 2.54 centim eters, w e can cons rue
2.54 cm
1 in .
. h ( 2 5 inches) into centimeters as follows: Through use of the factor-un it method, w e then convert 2½ inc es or ·
2 .54cm 64 cm 2. 5 lA.. X = ·
SOLVED EXERCISE 2.2
concentration The
relative amount of one
substance mixed or
dissolved in a specified
amount of a second
substance
percentage (%) •The
concentration of a mix-
ture expressed as parts
of a unit in 100 of the
same units
A firefighte r must possess the physical agi lity to easily carry a 60-pound bundle Imm the base to th e top 01 a 148-
foot ladder. Express the bundle mass in kilogram s an d t he length of the ladder 1n meters.
Solut ion: Accordin g to the information in Ta ble 2.2, 1 kg = 2.2 lb, and 1 m = 39.3 7 in. By th e factor-unit
method, a 60-pound bu ndle is equ ivalent to a 27 -kilogram bundle.
60 Ill. x = 27 kg
2.2 Ill.
Furthermore, a 148-foot ladder is equivalent to a 45-mete r ladder.
148 ftx 12 lA.. x _ _ l _m_=45m
1 ft 39.37 1ft.
2 .4 CONCENTRATION
Scientists often measure the amount of a substance as a stated unit in a given mass or
volume of a mixture. This value is called the substance’s concentration. A variety of units
are used by professionals to measure concentration. Emergency responders often use con-
centrations provided by the federal government in DOT, OSHA, and EPA regulations. For
instance, when noting an airborne concentration of hydrogen cyanide at a fire scene, you
may wish to compare it to OSHA’s 8-hour permissible exposure limit in the workplace.
This concentration is 11 milligrams per cubic meter (11 mg/m3).
Concentration is sometimes expressed as a percentage. The word percentage means
parts per hundred. To calculate the percentage of an item in a total, we divide the number
of items by the total number and multiply the product by 100. The percentage is expressed
as a number followed by the percent sign(%) . In chemistry, the concentration of a sub-
stance in a mixture is expressed as either a percentage by mass or a percentage by volume.
In the former instance, we use mass units of the same type, and in the latter case, we use
volume units of the same type. For example, suppose we have 100 grams of a solution in
which 5 grams of table salt is dissolved. The concentration of table salt in the solution is
expressed as 5% by mass. If we have 100 milliliters of a solution in which 5 milliliters of
a substance is dissolved, the concentration of the substance in the solution is expressed as
5% by volume.
42 Chapter 2 Some Features of Matter and Energy
I
heat • The form of
energy transferred
from one body to
another because of
their temperature dif-
ference; energy arising
from atomic or molecu-
lar motion
The
nature of any process
that absorbs heat from
its surroundings
The
TABLE 2.6
f Some Common Liquids as a Function Vapor Pressures o
of Increasing Temperature
TEMPERATURE
WATER (mmHg) ETHANOL (mm Hg)
BENZENE (mmHg)
‘F ‘C
5.6 15
14 -10 2.1
12 .2
27
32 0 4.6
23.6 45
50 10 9.2
43.9 75
68 20 17.5
78.8 118
86 30 31.8
LIQUID
222.2 271 122 50 92.5
167 75 289 .1 666.1
643
760 1693.3
1360
212 100
The evaporation rates of liquids are loosely classified as fast, medium, and slow when
the numerical values are greater than 3.0, between 0.8 and 3.0, an~ less t_han 0.8, res_pec-
tively. Using this subjective system, the evaporation rate of benzene 1s class1fu:d as medmm.
Generally speaking, the vapor of a substance 1s its most hazardous physical form. I’. is
the vapor of a flammable liquid-not the liquid itself- that burns, and 1t 1s a toxic liq-
uid ‘s vapor that causes adverse health effects when inhaled. Clearly, the vapor pressure of
a flammable or toxic substance has a direct impact on its potential fire and health ha z-
ards, respectively.
When a flammable or toxic liquid has a relatively low vapor pressure, little vapor
evolves at the prevailing temperature. It can neither pose a significant fire and explosion
hazard nor an inhalation toxicity hazard. A flammable liquid with a comparatively high
vapor pressure, however, poses a fire and explosion hazard, and a poisonous liquid with
a comparatively high vapor pressure poses an inhalation toxicity hazard.
A flammable or poisonous liquid with a relatively high vapor pressure presents unique
transportation problems. During the course of its transportation, a liquid confined within
a tank or other vessel can increase in temperature by absorbing heat from its surround-
ings. As the temperature of the liquid increases, a considerable volume of vapor is pro-
duced within the tank. This vapor enters the headspace above the liquid and exerts
pressure on the walls of the confining vessel. To retain its integrity, the vessel must be
constructed to withstand this internal pressure during the time that it is used to transport
the liquid.
2.9 HEAT AND ITS TRANSMISSION
Heat is the form of energy associated with the motion of atoms or molecules (Sections 4.4
and 4.6), small particles of which all matter is composed. Heat is manifested when changes
in any of the following occur:
A material’s temperature
The physical state of a substance
The chemical identity of a substance
nature of any process Heat is either absorbed or emitted as these processes occur. When heat is abso rbed,
that emits heat into its the ph_enomenon is called an endothermic process; and when he at is released ro th e sur·
surroundings roundmgs, the phenomenon is called an exothermic process .
54 Chapter 2 Some Features of Matter and Energy
In Section 2.6, it was noted that energy is often d · B · · h h I · d
I
. s. One British thermal un·t B measure m nt1s t erma umts an
ca one 1 , or tu, represents the heat that must be supplied to
· e the temperature of 1 pound of wat 1 d h · • • ra1s , . . er egree Fa renhe1t, specified at the tempera-
e of waters maximum density 39 1°F (3 97°c) • · · rur . . , · • . One calorie, or cal, 1s defmed as the
amount of heat reqmred to raise the temperature f 1 f 1 d c I ·
4 5
15 50c T h . o gram o water egree e sms,
British thermal unit
(Btu) The amount of
heat required to raise
the temperature of
from 1 · to · · ~o. undred fifty-two (252) calories is equivalent to one British
1 pound of water
thermal umt, and 1 calorie 1s equivalent to 4.184 joules.
1 degree Fahrenheit
1 Btu = 252.0 cal = 1055 J
1 cal= 4 .187 J
When_ che_mical reactions occur, the reactants change their chemical identities by
trans~ormmg mto. o~e or more other substances. Thermal energy accompanies these
chemical changes; 1t 1s called their heat of reaction.
calorie The
amount of heat
required to raise the
temperature of 1 gram
of water 1 degree
Celsius
Heat is evolved during a variety of combustion processes such as the burning of gaso-
line, wood, natural gas, and other materials. When these fuels burn, they provide energy
and serve as ~ources_ of heat, power, and light. On the negative side, however, they can occurs
also pose a nsk of fire and explosion. When these materials burn in bulk, they usually
heat of reaction The
energy that is absorbed
or evolved when a
chemical reaction
ignite secondary fires involving nearby materials.
The proper control of the heat emitted during combustion is an extremely important
factor in fire control. Fires continue as self-sustained phenomena only when sufficient
heat is released during combustion to substitute for the input energy initially provided
from an ignition source. Conversely, many fires cannot be extinguished until some means
is undertaken to reduce or eliminate this heat.
Emergency responders also encounter heat as a form of energy in situations having
nothing to do with combustion phenomena. Paramedics, for example, often use instant
heat packs and cold packs when administering first-aid to individuals with muscular inju-
ries. One type of portable pack consists of a pouch of water and a solid chemical sub-
stance: magnesium sulfate for heat packs, and ammonium nitrate for cold packs. When
the separate packs are squeezed, the water commingles with the solids and produces their
solutions. As a magnesium sulfate solution forms, the heat that is evolved may be used to
warm an injury. As an ammonium nitrate solution forms, the heat that is absorbed may be
used to cool an injury.
Heat is always transferred from warm materials to cooler ones. If several materials
near one another have different temperatures, those that are warm become cooler, and
those that are cool become warmer, until they achieve a common temperature. Heat is
transmitted from one material to another or from one spot to another spot by three
independent modes: conduction, convection, and radiation. The nature of each mode
of heat transmission is an important factor associated with understanding how fire
spreads.
2.9-A CONDUCTION
The handle of a metal spoon that has been inserted into hot coffee becomes hot itself. This
transfer of heat between two or more materials in contact-in this case, from the coffee to
the spoon-is called conduction.
Every material conducts heat to some extent. Metals, such as silver, copper, iron, and
aluminum, conduct heat most efficiently; nonmetals, such as glass and air, a re not good
conductors of heat. Materials that are not good conductors are good insulators, because
they delay the transfer of heat.
2·9·B CONVECTION
Beat can also be transferred from spot to spot or even between two or mo_re substances ?Y
the natural mixing of their component parts. This happens when cold milk or cream dis-
conduction The mech-
anism by which heat is
transferred to the parts
of a stationary material
or from one material to
another with which it is
in contact
Chapter 2 Some Features of Matter and Energy 55
I I I convection The mech-
anism by which heat is
transferred by the
movement of a heated
material from spot to
spot
rad iation The mecha-
nism by which heat is
transferred between
two materials not in
contact
perses throughout hot coffee without the use of a spoo~, or when th~ a~r in a room gets
warmer when it is hot outside the room. This transm1ss10n of heat ~1thin a substance or
between substances by means of natural mixing is known as convection.
The circulation of warm air that exits a heat vent into a room is caused by convec-
tion. The popular expression “heat rises” actually means “hot air rises.” As warm air
issues from a heat vent into a room, it rises toward the ceiling. The surrounding cool air
descends to replace the warm air that rose, is heated at the heat vent, an~ then rises
toward the ceiling. In this fashion, warm and cool air exchange to generate a1r currents.
The origin of the convection phenomenon is associa~e~ ‘:”ith ~~e _imp~ct that gravity
has on matter. In zero gravity, convection can occur only if 1t 1s art1fic1ally mduced. When
a substance burns convection moves its combustion products away from the flame to dis-
sipate into the sU:rounding atmosphere; but where zero gravity exists, as in a spaceship
orbiting Earth, the combustion products remain in the immediate area of the combustion
zone, where they quickly extinguish the flame .
2 .9-C RADIATION
Imagine a 200-watt light bulb hanging from a ceiling. When the light is turned on, heat can
be felt when we hold our hands around the bulb. This transfer of heat from the bulb to our
hands cannot be caused by conduction, since the air between the bulb and our hands is a
poor conductor of heat. It also cannot be caused by convection, because hot air currents
rise upward. The heat from the bulb is transmitted by a third means called radiation.
Unlike conduction and convection, radiation occurs even when there is no material
contact between two objects . Heat from the sun radiates through space and warms Earth
and other celestial bodies.
All matter radiates heat at elevated temperatures; that is, it exhibits the phenomenon
called incandescence. When the temperature of a heated object exceeds approximately
932°F (500°C}, the radiation becomes visible. Burning flames , glowing coals, and molten
metal are examples of matter hot enough to radi ate visible light. Hot objects ma y also
radiate energy at lower temperatures, but the energy emitted is generally in the infrared
region of the electromagnetic spectrum, which cannot be observed with the naked eye.
2.9-D SPREAD OF FIRE
The conduction process does not significantly contribute to the sustenance and spread of
a normal fire. Figure 2.9 illustrates that convection and radiation are the modes of hear
transmission primarily responsible for sustaining and sprea ding freely burning fires in the
following ways:
Convection affects the spread of fire by means of the natural movement of hot
and cold air. As hot air rises, heat is transmitted to adjoining materials and initiates
their ignition. Cool, fresh air simultaneously flows inward into the fi re to replace the
hot air, thereby providing the fire with a supply of oxygen.
Radiation affects the spread of fire by transmitting heat, primarily in a lateral di-
rection, from the immediate fire scene to nearby materials. The transmission of radi ant
heat initiates the combustion of these materials.
heat capacity • The 2.10 CALCULATION OF HEAT
amount of heat needed
to raise the tempera-
ture of 1 pound of a
substance 1 degree
Fahrenheit or 1 gram of
a substance 1 degree
Celsius
Two or more substances differ from one another by the quanti ty of hea t required to pro-_
duce a given temperature change in the same mass of each substance. This qu antity at
~eat is called the heat capacity. The heat capacities of some common liquids are p rovided
m Table 2.7. For water, the magnitude of the heat capacity varies as a functi o n o f its cem·
perature, as indicated. The units of heat capacity in the English a nd metric sys tems are rbe
56 Chapter 2 Some Features of Matter and Energy
he events that initiated the war against al-Qaida and other Islamic terrorist groups in
~hich the United States and its allies are now engaged.
During the aftermath of 9-11, emergency responders widely acknowledged the evolu-
tion of a new component of their workload: the necessity to conduct rescue and recovery
work at incidents where hazardous materials were intentionally released to the environ-
ment, Although emergency responders continue to serve the nation by saving lives, prop-
erty, and the environment, they now also must help secure the homeland and preserve our
way of life.
The 9-11 incidents changed the course of world events and drew attention to the
presen~e of a religious ideolo~y th~t promotes terrorism internationally. Islamic
extremists have now expanded mto virtually every civilized country, where they spon-
sor suicide attacks against the local population. The more notorious incidents spear-
headed by radical Islamic terrorists occurred in 2004 when bombings of Madrid’s
commuter trains_ killed 191 people; in 2005, when bombings in London’s. underground
transit system killed 52 people; in 2008, when bombings in Mumbai’s financial dis-
trict killed 166 people; in 2010, when synchronized twin bombings in Kampala
(Uganda) killed 76 people; and in 2011, when a suicide bomb at Moscow’s Domode-
dovo Airport killed 37 people. In each instance, the extremists chose to produce injury
and death by detonating explosives.
Americans have also been attacked by terrorists within our domestic borders. In 2013,
for example, two terrorists, ethnic Chechens, detonated two shrapnel-packed pressure-
cooker bombs within seconds of each other near the finish line of the Boston Marathon.
Now considered the worst terrorist attack on American soil since the events of 9-11, the
lawless deed killed three people and injured over 260.
The nature of hazardous materials did not change since the 9-11 incidents, nor did
the manner in which we respond at hazardous materials scenes; but the 9-11 terrorist
events did spawn a heightened awareness of the unorthodox ways in which hazardous
materials may be used as weapons of mass destruction to intentionally kill and injure vast
numbers of people, cause substantial property damage, and affect economic stability.
They also alerted emergency responders to perform their jobs with an intensified sense of
vigilance by anticipating that the acts may be executed within their communities, espe-
cially during large crowd gatherings.
We begin our study in this first chapter by broadly examining the general features of
all hazardous materials. We also observe how federal statutes aim to eliminate or reduce
the risks associated with the usage, storage, and transportation of hazardous materials,
and how they may assist emergency responders at disaster scenes. Finally, we learn that
allied professionals stand ready to help responders when hazardous materials are involved
in emergencies.
1.1 WHY MUST EMERGENCY RESPONDERS
STUDY CHEMISTRY?
Odds are you have never considered what life would be like without chemistry. If you had,
it would soon be apparent that chemistry affects everything we do. There is not a single
instant during which we are not affected by a chemical substance or a chemical process.
. Chemistry is regarded as a natural science; that is, it is a subject concerned with study-
mg natural phenomena. Specifically, the science of chemistry is the st udy of substances,
their composition, properties, and the changes they undergo. Chemistry concerns itself not
only with substances that occur naturally but also with synthetic substances.
. By understanding the interplay of various substances, chemists have successfully con-
tributed to combating the scourges of hunger, disease, and human deprivation throug hout
the world. By using established methods, chemists aspire to further improve the quality of
chemistry The
natural science
concerned with the
properties, composition,
and reactions of
substances
Chapter 1 Introduction 3
o rgan ic chem istry
The study of the prop-
erties of substances
that contain carbon
in their chemical
composition
inorgan ic chemistry
The study of the prop-
erties of substances
that do not contain
carbon in their chemical
composition
our lives in the future . For instance, during the twenty~first century, ~e anticipate th
chemistry will radically alter the methods used to ~reat sicknesses and ~1sease. a
Chemistry is broadly divided int~ two mam branches: _organic chemistry a
inorganic chemistry. At one time, chemists presumed that certam substances couJd ~c
in the world only if they had originated in living things-plants and animals . These elQsi
stances included sugars alcohols, waxes, fats, and oils, all of which were called or su?.
‘ · · h · 1 f f 1·c · gan1c substances because their origin was believed to require t e vita orce o 11e itself.
In 1828, this hypothesis was disproved when Friedrich Wohler prepared a substa
called urea, a known constituent of urine. Wohler succ~ssfully pr~pare~ urea frorn s:~~
stances having no apparent connection to plants or ammals. This achievement cau
· d f h d · sed chemists to abandon the idea that a vital force was reqmre or t e pro uct1on of cen .
substances. Despite abandonment of the hypothesis, however, the name of this branch
chemistry has been historically retained.
Organic chemistry is now recognized as the study of substances that contain carbo
in their chemical composition. Although some organic substances are actually found i:
living systems, many others have been synthesized that have no known natural counter.
part. The study of organic substances that affect the life process is now regarded as a
subdivision of organic chemistry called biochemistry. By contrast, the study of those sub.
stances that do not contain carbon in their composition is known as inorganic chemistry.
Inorganic substances include aluminum, iron, sulfur, oxygen, table salt, and many others.
To be an effective emergency responder, is it necessary to study organic and inorganic
chemistry? It would be misleading to give the impression that the academic pursuit of
chemistry is essential for achievement of successful careers as firefighters, police officers
and other emergency responders. Nonetheless, the study of hazardous materials by emer’.
gency responders achieves the major objective of enriching their sense of inquiry while
investigating accident scenes at which hazardous materials are implicated. Without the
knowledge acquired from the study of hazardous materials, emergency responders are
severely limited when they must select a course of action during the performance of duty.
1.2 FEDERAL HAZARDOUS SUBSTANCES ACT
The Federal Hazardous Substances Act, or FHSA, was first enacted by Congress in 1960.
Thereafter, it was amended to focus on the protection of users against unsuspecting expo·
sure to hazardous substances contained within consumer products. The statute is adrnin·
istered by the Consumer Product Safety Commission (CPSC) .
One way by which CPSC fulfills its congressional mandate is to require manufacturers
to affix appropriate labeling on the containers of consumer products that contain hazard·
ous substances. This labeling information is directed primarily at consumers, bur it is
potentially helpful to emergency responders and others. At 16 C.F.R. § 1500.121, 1 CPSC
requires the following information to be clearly and conspicuously provided on the labels
affixed to containers of consumer products having hazardous substances as components:
Federal Hazardous
Subst a nces Act The
federal statute that
empowers the CPSC to
protect the public
against unsuspecting
exposure to hazardous
substances contained
within household
products
The name and place of business of the manufacturer, packer, distributor, or seller
The common or usual name or the chemical name of each hazardous ingredient
The signal word DANGER for products that are corrosive extremely flammable, or
highly toxic ‘
The signal word CAUTION or WARNING for all other hazardous products .
The word POISON in addition to the signal word DANGER for the highly roxic
products listed at 16 C.F.R. §1500.129
1R l . . ‘ d l I · -oo 121 e evam citations to 1e era regu at10ns are noted throughout this text. The reference to 16 C.f.R. §l_J · ub·
means T1~le 16 of the Code_ of Federal Regulations, Part 1500, Section 121. The parts are a lso di vid ed inro :
0 05 p_arts,_ which are denoted with capital letters A, B, C, and so on. Readers ma y electronically access all regul arI
cited m this text on the Internet.
4 Chapter 1 Introduction
1 Railroad accidents involving passenger trains or any train accident that results in at
least one fatality or major property damage
1 Major marine accidents and marine accidents involving watercraft
1 Pipeline accidents involving a fatality or substantial property damage
1 Releases of hazardous materials in all forms of transportation
1 Selected transportation accidents involving problems of a recurring nature
The NTSB has investigated numerous accidents and developed factual records and safety
recommendations. Its findings are made public on the Internet and elsewhere.
1.8 INTEGRATED CONTINGENCY PLANS
Although the owners and operators of a facility may be subject to preparing and imple-
menting one or more separate, stand-alone emergency response plans, they may also elect
to consolidate them into a single contingency plan called an integrated contingency plan,
ICP, or one plan.
4
This document sets forth the following goals:
To provide a single integrated plan that consolidates the requirements of multiple
facility emergency response plans
To improve coordination of planning and response activities within a facility and
with public and commercial emergency responders
To minimize duplication
If a facility’s owners or operators elect to prepare an ICP, the document must comply
with the individual requirements of the plans concerned with emergency response activi-
ties mandated by several federal statutes and administered by multiple participating agen-
cies. The following five plans noted in this chapter may be incorporated into an ICP, as
they are needed:
Risk management plan mandated by Clean Air Act regulations (40 C.F.R. Part 68)
Facility response plan mandated by Clean Water Act regulations (40 C.F.R. §§112.20
and 112.21)
Contingency plan mandated by RCRA regulations (40 C.F.R. §§264.52 and 265.52)
Emergency action plan mandated by OSHA regulations (29 C.F.R. §§1910.38)
I Vessel or facility response plan mandated by DOT regulations (49 C.F.R. Part 194
and 33 C.F.R. Part 154, Subpart F)
integrated conti ngency
plan (ICP, one plan)
A single emergency
response plan that
incorporates into one
document the regula-
tory requirements of
the emergency and
contingency plans man-
dated by multiple fed-
eral statutes
Standard formats for the preparation of ICPs have been developed by EPA. This for-
mat may be adopted by facility owners and operators as they integrate multiple plans into
a single plan.
1.9 GLOBAL HARMONIZATION CONCERNING
THE CLASSIFICATION AND LABELING OF
HAZARDOUS CHEMICALS
Over the years, most civilized countries have implemented methods for identifying haz-
ards and classifying and labeling chemical products. In many instances, these methods
vary significantly from country to country. Even within the United States, four federal
authorities-OSHA, CPSC, EPA, and DOT-have the responsibility to warn consumers
that certain products are potentially harmful. Although similarities exist, the agencies’
:j”:–_
61 Fed. Reg. 28642 (June 5, 1966 ).
,., I ; ~ii
United Nations
Chapter 1 Introduction 17
r . . d of classification and labeling have created unneces. inconsistent and confhcnng metho s sary confusion for the public. . I for defining and classifying hazards and
To circumvent this use of mwnp ehsy~e~sd Nations designed the GHS, known fo ,_
communicating hazard informauon,St e ni ; Classification and Labeling of Chemical
mally as the Globally Harmonized _Ystem O f rules with a common format and content
Substances.5 The basis of the ~ystem ths ahset O d f chemical products on warning label
I
GHS The United
Nations system for
defining and classifying
hazards and communi-
cating hazard informa-
tion on labels and
safety data sheets by
means of a common
international format
for worldwide use when classifying t e azar s O s
and Safety Data Sheets. nd OSHA revised their regulations to align with the GH.s,
In the United States, DOT~ . . Ch • I manufacturers are now in th
and EPA and CPSC are studying 1ts adoption. emica c
Process of complying with these regulations. . I ‘f’ · d I b . ‘d b . f greater consistency in the c ass1 icatton an a eltno The GHS prov1 es a aSlS or a . · h k 0
of hazardous chemicals, thus enhancing their safe handh~g and st0.rage m t e wor place
· GHS b dly uses the term to include unique substances, prod-or a consumer-use setting. roa ff d
d h · that could potentially cause harm. It a or s emergency
ucts, adn ot _ethr prepharattons of rapidly identifying the hazard(s) associated with expo-
respon ers wt anot er means bl’ h I h
sure to substances that could cause an unreasonable risk of injury to pu 1~ ea_ t . or the
environment. Its worldwide utilization also provides a means for r~pidly identify~g ~ e
nature of a hazardous material that was manufactured abroad but imported and distrib-
uted in the United States.
GHS communicates hazard information in the three major hazard groups listed in
Table 1.2: physical hazards, health hazards, and environmental ~az~rds. _Most hazard
classes are further subdivided into multiple categories, each of which 1s derived from cri-
teria that are based on the results of prescribed testing procedures. These individual cate-
gories are not of interest here. . .
Inherent in the GHS is information that manufacturers and d1stnbutors of products
affix on the labels to product containers. This information consists of the following:
The product identifier (product name, UN/NA identification number, and DO’f
proper shipping name) 6
Either of the signal words WARNING or DANGER to denote the more and less
severe hazard categories of the product, respectively
One or more hazard statements
One or more pictograms, of which there are two types: GHS pictograms that are dis-
played on the labels of chemical products, and transport pictograms that are dis-
played when the products are transported in commerce
One or more precautionary statements including first-aid instructions
Supplier identification (i.e., the name, address, and telephone number of the manu-
facturer or distributor)
The GHS pictograms associated with the hazards exhibited by chemical products are
displayed in Table 1.2. They are black-and-white, red-bordered, diamond-shaped warn·
ing signs. Multiple pictograms may be displayed on the same container label to warn the
observer of the potential hazards posed by the container’s contents.
The ~rans~ort pictograms are displayed in Table 1.3. They have background colors and
symbols identical to those used on the DOT labels and placards noted later in Figures 6.5
and 6.12, respectively. When a transport pictogram is displayed on a label, the red-bordered
pictogram for the same hazard is not shown.
5
Globally Harm?nized System of Classification and Labeling of Chemical Substances (GHS ), (New York , N’i
and Geneva, Switzerland, 2011), ISBN-13: 978-92-1-117006-l.
6
The nature of the UN/NA identification number and DOT proper shipping name is discussed in Section 6.1.
18 Chapter 1 Introduction
N ,
E:
TABLE 1.2 GHS Pictograms for Labeling the Containers of Hazardous Chemicals
TYPES OF HAZARDOUS MATERIALS REPRESENTED BY
NATURE OF GHS PICTOGRAM GHS PICTOGRAM GHS PICTOGRAM
Exploding grenade Explosives; certain self-reactive substances and mixtures; certain
organic peroxides
–
Flammable gases; flammable aerosols; flammable liquids; flammable Flame
solids; certain self-reactive substances and mixtures; pyrophoric liq-
uids and solids; self-heating substances and mixtures; substances and
mixtures, that, in contact with water, emit flammable gases; certain
organic peroxides
Flame over the letter “O” Oxidizing gases, liquids, and solids
Gas cylinder
Gases under pressure
0
Corrosion Substances that corrode skin and serious eye damage; substances
that corrode metals
Skull and crossbones Certain acute toxicants
Health hazard Carcinogens (substances that cause cancer or are suspected of caus-
ing cancer); respiratory sensitizers; reproductive toxicants; specific
target organ toxicants (single exposure); certain specific target
organ toxicants (single exposure) and target organ toxicants
(repeated exposure); germ-cell mutagens;• aspirants
Exclamation point Certain acute toxicants, skin irritants, eye irritants, skin sensitizers,
¢ and specific target organ toxicants (single exposure)
Environment (aquatic toxicity) Aquatic toxicants
aGerm.cell mutagens are substances that cause a permanent change in the amount or structure of a cell’s genetic material.
Chapter 1 Introduction 19
I TABLE 1 .3 GHS Pictograms for Transporting Hazardous Chemicals
TRANSPORT PICTOGRAM
NAME OF TRANSPORT PICTOGRAM
TRANSPORT PICTOGRAM
NAME OF TRANSPORT PICTOGRAM
TRANSPORT PICTOGRAM
NAME OF TRANSPORT PICTOGRAM
TRANSPORT PICTOGRAM
NAME OF TRANSPORT PICTOGRAM
Explosive 1.1
Explosive 1.6
Flammable
Solid
Poison Inhala-
tion Hazard
Explosive 1.2 Explosive 1.3
Flammable Gas Non-
Spontaneously
Combustible
Material
,,•~:–.
/ ~” ;-,
·, ,,
~ —
Corrosive
Material
Flammable Gas
Dangerous
When Wet
Material
Explosive 1.4
Poison Gas
Oxid izer
Explosive 1.S
Flammable
Liquid
Organic
Peroxide
The hazard and preca utionary statements are respectively coded with numbers pre-
ceded by an Hor P, as relevant, Some representative examples are provided in Table 1.4.
Aside from their use on the labels of chemical products, these statements are also compo-
nents of the “Hazards Information” section of an SDS for a given chemical product,
OSHA’s adoption of the GHS requires each chemical manufacturer, distributor, and
importer to select the appropriate pictograms that describe their produces, The use of the
environmental pictogram is optional because environmental hazards are regulated by EPA ,
not OSHA, Emergency responders may rapidly identify the hazards associated with the
chemical products by looking at their labels and acknowledging the significance of rhe
pictograms ,
When we study the properties of individual hazardous materials beginning in
Chapter 7, GHS pictograms will be displayed with their hazard diamonds (Section 1.1 I)
in the page margin near the point at which a discussion of each haz ar dous material fir5t
begins ,
20 Chapter 1 Introduction
TABLE 1.4
HAZARD CLASS
PHYSICAL
HAZARD GROUP
Explosives (Division 1 .1)
Flammable gases
Flammable aerosols
Oxidizing gases
Gases under pressure
Flammable liquids
Flammable solids
Self-reactive substances
and mixtures
Pyrophoric liquids
Pyrophoric solids
Self-heating substances
and mixtures
Substances and mixtures
which, in contact with
Water, emit flammable
gases
Oxidizing liquids
–
Some Representative Hazard and Precautionary Statements for the
GHS Hazard Classes
HAZARD STATEMENTS
CODE EXAMPLE CODE
H201 Explosive; mass explosion hazard . P201
P210
P202
H220 Extremely flammable gas. P210
P377
H222 Extremely flammable aerosol. P251
P211
H270 May cause or intensify fire; oxidizer. P244
H280 Contains gas under pressure; may
explode if heated.
P410
P403
H224 Extremely flammable liquid and P240
vapor.
P241
P242
P243
H228 Flammable solid. P210
H240 Heating may cause an explosion. P220
H250 Catches fire spontaneously if P222
exposed to air.
H250 Catches fire spontaneously if P335
exposed to air.
P334
H252 Self-heating in large quantities; may P407
catch fire.
P403
H260 In contact with water releases P223
flammable gases that may ignite
spontaneously.
P234
H271 May cause fire or explosion; strong P283
oxidizer.
PRECAUTIONARY STATEMENTS
EXAMPLE
Obtain special instructions before use.
Keep away from heat/sparks/open flames/hot
surfaces. No smoking.
Do not fight fire when fire reaches explo-
sives.
Keep away from heat/sparks/open flames/hot
surfaces. No smoking.
Leaking gas fire : Do not extinguish, unless
leak can be stopped safely.
Pressurized container: Do not pierce or burn,
even after use.
Do not spray on an open flame or other
ignition source.
Keep reduction valves free from grease and
oil.
Protect from sun I ight.
Store in a well-ventilated place.
Ground/bond container and receiving
equipment.
Use explosion-proof electrical/ventilating/
lighting/ .. ./equipment.
Use only non-sparking tools.
Take precautionary measures against static
electricity.
Keep away from heat/sparks/open flames/hot
surfaces. No smoking .
Keep away from clothing/ .. ./combustible
materials.
Do not allow contact with air.
Brush off loose particles from skin.
Immerse in cool water/wrap with wet bandages.
Maintain air gap between stacks/pallets.
Store in a well-ventilated place.
Keep away from possible contact with water,
because of violent reaction and possible flash
fire .
Keep only in original container.
Wear fire/flame resistant/retardant clothing.
(Continued)
Chapter 1 Introduction 21
TABLE 1.4
f ary Statements for the Some Representative Hazard and Precau ion
GHS Hazard Classes (Continued)
HAZARD CLASS HAZARD STATEMENTS PRECAUTIONAR Y STATEMENTS
PHYSICAL
HAZARD GROUP CODE EXAMPLE CODE EXAMPLE
P220 Keep/Store away from clothing/combustible
I
materials.
P280 Wear protective gloves/protective clothingt
eye protection/face protection.
Oxidizing solids H272 May intensify fire; oxidizer. P378 Use for fire extinction.
Organic peroxides H240 Heating may cause an explosion. P411 Store at temperatures not exceeding_ ‘F
L’C).
P410 Protect from sunlight.
Substances corrosive H290 May be corrosive to metals. P390 Absorb spillage to prevent material damage.
to metals
P406 Store in corrosion-resistant/ … container with
a resistant inner liner.
Health Hazard Group
Acute toxicity, oral H301 Toxic if swallowed. P310 Immediately call a POISON CENTER or doctor/
physician.
Acute toxicity, H331 Toxic if inhaled. P271 Use only outdoors or in a well-ventilated inhalation area.
P340 Remove victim to fresh air and keep at rest in
a position comfortable for breathing .
Acute toxicity, dermal H311 Toxic in contact with skin. P361 Remove/Take off immediately all contami-
nated clothing .
Skin corrosion/irritation H314 Causes severe skin burns and eye P350 Gently wash with plenty of soap and water. damage.
Serious eye damage/eye H320 Causes serious eye damage. P305 Rinse cautiously with water for several irritation
minutes
P351 Remove contact lenses, if present and if easy
to do.
P338 Continue rinsing.
Skin sensitization H317 May cause an allergic skin reaction. P350 Wash with plenty of soap and water.
Germ cell mutagenicity H340 May cause genetic defects (Included P281 Use personal protective equipment as in the statement is the route of required.
exposure, if it is conclusively proven
that no other routes of exposure
cause the hazard.)
Carcinogenicity (cancer- H350 May cause cancer (Included in the P313 Get medical advice/attention . causing hazard) statement is the route of exposure,
if known, when it has been conclu-
Reproductive toxicity H360
sively proven that no other routes
of exposure cause the hazard.)
May damage fertility or the unborn
child (Included in the statement are
the specific effect, if known, and the
P405 Store locked up.
route of exposure, when it has been
conclusively proven that no other
routes of exposure cause the hazard.)
22 Chapter 1 Introduction (Co ntinuedi
TABLE 1.4
HAZARD CLASS
PHYSICAL
HAZARD GROUP
specific target organ
toxicity, single exposure
Specific target organ
toxicity, repeated
exposures
Aspiration hazard
Environmental Hazard
Group
Hazardous to the
aquatic environment
(acute hazard)
Hazardous to the
aquatic environment
(chronic hazard)
Hazardous to the ozone
layer
Some Representative Hazard and Precautionary Statements for the
GHS Hazard Classes (Continued)
HAZARD STATEMENTS PRECAUTIONARY STATEMENTS
CODE EXAMPLE CODE EXAMPLE
H372 Causes damage to organ (Included P264 Wash thoroughly after handling
in the statement are the organ
affected, if known, and the route of
exposure, when it has been conclu-
sively proven that no other routes
of exposure cause the hazard.)
H373 May cause damage to organs P260 Do not breathe dust/fume/gas/mist/-vapor/
through prolonged or repeated spray.
exposure. (Included in the state-
ment are the organ affected, if
known, and the route of exposure,
when it has been conclusively
proven that no other routes of
exposure cause the hazard.)
H304 May be fatal if swallowed and P331 Do not induce vomiting.
enters airways.
H400 Very toxic to aquatic life. P273 Avoid release to the environment.
H401 Toxic to aquatic life. P391 Collect spillage.
H420 Harms public health and the envi- P502 Refer to manufacturer/supplier for
ronment by destroying ozone in the
upper atmosphere.
information on recovery/recycling.
1.10 CANADA’ S WORKPLACE HAZARDOUS
MATERIALS INFORMATION SYSTEM
Chemical products are regularly transported across the common borders shared by the
United States with Canada and Mexico. Although Mexico has adopted the GHS for vol-
untary use, Canada was still considering the potential implementation in its workplace
regulations during 2013 . Hence, it is relevant to note here how Canada communicates
information concerning the hazards of chemical products to workers.
In Canada, when a hazardous material is encountered in the workplace, it is referred
to as a controlled product. The Canadian Centre for Occupational Health and Safety, or
CCOHS, regulates certain aspects of the controlled products used by employees through its
Workplace Hazardous Materials Information System, or WHMIS. These regulations
require suppliers to use the symbols for six hazard classes (denoted A through F) when
labeling the containers of controlled products. They also require employers to ensure that
their workers understand the meaning of these symbols and their use on MSDSs and labels.
. The hazard classes of controlled products are depicted by the eight hazard symbols shown
in Table 1.5. The symbols consist of black encircled pictograms on a white background.
Chapter 1 Introduction 23
TABLE 1.5
CLASS OF CONTROLLED PRODUCT
Class A: Compressed Gas
Class B: Flammable and Combustible Material
Class C: Oxidizing Material
Class O: Poisonous and Infectious Material
Division 1: Materials causing immediate and
serious toxic effects
Class D: Poisonous and Infectious Material
Division 2: Materials causing other toxic effects
Class D: Poisonous and Infectious Material
Division 3: Biohazardous Infectious Material
Class E: Corrosive Material
Class F: Dangerously Reactive Material
24 Chapter 1 Introduction
NATURE OF CONTROLLED PRODUCTS . . d
d ases hquef1e
Compressed gases, dis’.olved _gases, an g
by compression or refrigeration
ble of catching fire in the
Solids, liquids, and gases cap:iame under normal work-
presence of a spark or open
ing conditions
f f ‘f they contact Materials that increase the risk o. ,re ,
flammable or combustible materials
Materials that cause death or immediate injury when a
person is exposed to small amounts
Materials that can cause life-threatening and serious
long-term health problems as well as less severe but
immediate reactions in a person who ,s repeatedly
exposed to small amounts
Materials containing an organism that has been shown
to cause disease or to be a probable cause of disease in
persons or animals
Includes caustic and acidic materials that can destroy
the skin or “eat” through metals
Materials that self-react dangerously (e.g., they may
explode} upon standing or when exposed to physical
shock or increased pressure or temperature; materials
that decompose or polymerize vigorously; and materi-
als that react with water to release a toxic gas.
HAZARD SYMBOL
0
@
‘<::::)
@
Al hough they are intended primarily to c · h d · · · h
t ornmurucate azar mformat1on to employees mt e
workplace,
th
e haza
rd
symbols are also useful to emergency responders who encounter con-
trolled products durmg a tra~sportation mishap or elsewhere.
Given th.e dose proxim_ity between the United States and Canada, GHS and WHMIS
information is likely to be cited on th~ labels on chemical products imported from Canada
into the U~ited S
t
ates and exported mto Canada from the United States. The label illus-
trated in Figure. 1.3 pro~ides an e~ample of the manner by which the GHS and WHMIS
convey _hazard mformatton associated with a 35% solution of hydrogen peroxide. The
GHS pictograms a
nd
WHMIS symbols inform the observer that the solution is an oxi-
dizer and corrosive m_aterial. that. damages the skin and eyes upon exposure. GHS also
includes the product identifier, signal word, and hazard and precautionary statements
including f1rst-a1d mstructions.
1.11 NFPA SYSTEM OF IDENTIFYING
POTENTIAL HAZARDS
At the scene of an emergency, how is it possible to identify the potential hazards associ –
ated with the presence of a given hazardous material? The answer to this question is based
on recognizing certain markings that are posted on stationary tanks, exterior building
walls, pipelines, and other fixed facilities at which hazardous materials are stored or used.
The National Fire Protection Association, or NFPA7 uses a procedure that provides a
means for rapidly identifying the relative degree of three chemical properties associated
with a given hazardous material: its health, flammability, and instability hazards. 8 NFPA
implements this procedure by assigning one of five numbers, 0 through 4, to each prop-
erty for a given hazardous material. The numbers in Table 1.6 identify the relative degree
of hazard that corresponds to a relevant property. The number O signifies that the hazard-
ous material at issue does not possess the relevant hazard, whereas the number 4 denotes
that it possesses the highest degree of that hazard.
National Fire Protection
Association (NFPA)
The professional organ-
ization that promotes
and improves fire pro-
tection and prevention
and establishes safe-
guards against loss of
life and property by fire
SOLVED EXERCISE 1.2
Wh en fi refi ghters respond to a fire in a tan k farm , what informati on is im me diately needed to help them effec-
tively fight the fire ?
Solution: When they respond to a fire within a tank fa rm, fire fighters require re~dily accessible and accurate in –
formati on concern ing the hazards of the tank contents. Accordingly,. t he inform~t,on marked on the tanks should
be easily vi sible and legible and should incl ud e th e.nam es of the l1qu 1ds stored w1th1n them, the ir general hazards,
and speci al fi refig hting precautions of which th e f1ref1ghters should be aware . . .
To conve hazard information, NFPA recommends the use of n.umbe’. codes that are marked w1 th1n the top
th d y f d’ d haped symbol pa inted on or otherwise affixed to, the exterior surfaces of storage ree qua rants o a 1amon -s ‘ . d h 1 •
tanks. Be in nin with the left-hand quadrant and proceeding cloc kwise, the number codes enote t . e re at,ve
d gf h lg h fl blt and inst abi lity hazards of the su bstances stored w1th1n each ta.nk . Firefighters
c~~e:;e
0
eac~an~~ b=~::\~ ;~:·a propriate information listed in Table 1 :6. Spedal codes are provided 1n the bot-
t P d Th ‘ b’ t’ pf ·nformation helps fi refi ghters determ ine wh,ch actions to take an d not to tak e om qua rant. ,s com ,na ,on o ,
when they fi rst encounter a fire within a storage tank.
‘N · · · 1 B h Park Quincy MA 022 69- 9101. attonal Fire Protection Assoc1at1on, atterymarc ‘ , C . h © JQl
1 8NFPA 704-2012 , System for the Identification of the Hazards for Emergency Response, opyng t –
(Quincy, MA: National Fire Protection Assoc1at1on) .
Chapter 1 Introduction 25
I
TABLE 16 M&idifl-. !ITU:151′ . F INSTABILITYb IDENTIFICATION 0
IDENTIFICATION OF FLAMMABILITY”
IDENTIFICATION OF HEALTH HAZARD COLOR CODE: YELLOW
HAZARD COLOR CODE: RED
HAZARD COLOR CODE : BLUE SUSCEPTIBILITY TO
SUSCEPTIBILITY OF RELEASE OF ENERGY SIGNAL
TYPE OF POSSIBLE INJURY SIGNAL
MATERIALS TO BURNING Materials that in themselves SIGNAL Materials that will rapidly or 4 are readily capable of detona-
Materials that on very short 4 4 completely vaporize at nor· tion or of explosive decompo-
exposure could cause death mal pressure and tempera· sition or reaction at normal
or serious residual injury ture, or is readily dispers~d temperature and pressures
even though prompt medi- in air, and will burn readily Materials that in themselves cal treatment was given 3
Materials that on short 3
Liquids and solids that can are capable of detonation or
3 be ignited under almost all explosive reaction but require exposure could cause serious ambient conditions a strong initiating source or temporary or res idual injury
that must be heated under even though prompt medi –
confinement before initiation, cal treatment was given
or that react explosively with
water
Materials that must be mod- 2
Materials that in themselves
Materials that on intense or 2 are normally unstable and 2
continued exposure could erately heated or exposed to readily undergo violent
cause temporary incapacita- relatively high temperature decomposition but do not
tion or possible residual before ignition can occur detonate; also, materials that
injury unless prompt medical may react violently with
treatment is given water or may form potentially
explosive mixtures with water
Materials that must be pre- 1 Materials that in themselves Materials that on exposure 1 are normally stable but which 1 heated before ignition can would cause irritation but can become unstable at ele-
only minor residual injury occur vated temperatures and pres-
even if no treatment is give n sures or which may react with
water with some release of
energy but not violently
0 Materials that will not burn 0 Materials that in themselves 0 Materials that on exposure are normally stable, even
under fire conditions would under fire exposure condi-
offer no hazard beyond that tions, and which are not reac-
of ordinary combustible tive with water
materials
asee also Section 3.1-C.
bsefore 1966, NFPA referred to this property as “chemical reactivity.”
Each number is then displayed in the appropriate top three quadrants of the
diamond-shaped diagram in Figure 1.4, called the hazard diamond. Each quadrant of the
diamond is color-coded, beginning with the left-hand quadrant and proceeding clockwise:
blue for the health hazard, red for the fire hazard, and yellow for the instability hazard.
When warranted, the following symbols are displayed in the bottom white-colored quad-
rant of the diamond:
hazard diamond A
diamond-shaped figure
divided into four quad-
rants, each of which is
color-coded for each of
a substance’s three
hazards-health, fire,
and instability-and The letter W with a line drawn through its center (W) to caution firefighters against
marked with a number the application of water
designating the relative The letters CRY to indicate the storage of a cryogen (Section 2.13)
degree of th e hazard The letters OX or OXY to indicate the storage of an oxidizer (Section 11.1 )
26 Chapter 1 Introduction
BLUE
Health
FIGURE 1 .4 four potential hazards of a substance may be
rapidly and simultaneously identified by the use of a color-coded
numeral system on this hazard diamond . Beginning with the
left-hand quadrant and advancing clockwise, the quadrants are
rnlor-coded as follows : blue for the health hazard; red for the
fire hazard ; and yellow for the instability hazard . A number
from O to 4 is entered in each of the top three quadrants con-
sistent wi.th the information compiled in Table 1.6 to identify
the seventy of the health, fire, and chemical reactivity hazards .
Each of several symbols, such as W and/or OXY, may also be
entered. 1n the b?ttom white quadrant to provide additional
hazard 1nformat1on . (Reprinted with permission from NFPA 704-2012,
System for the Identification of the Hazards of Materials for Emergency
Response, Copyright
I The letters AS to i_ndi~ate ~he storage of nitrogen, helium, neon, argon, krypton, or
xenon, e_ac~ of which 1s a simple asphyxiant (Section 10.3-A)
The radiation ha~ar~ symbol, which resembles a three-bladed propeller, or trefoil
(Section 16.3), to md1cate the storage of a radioactive material
The ~ord AC!D or the letters ALK or CORR to indicate the storage of an acid,
alkalme matenal, or corrosive material, respectively.
Only Wand OX are cited by NFPA, but the other symbols have such widespread use that
they are included here.
As noted earlier, beginning in Chapter 7, appropriate GHS pictograms and hazard
diamonds will be displayed in the page margin near the point at which a discussion of
each hazardous material first begins.
1.12 CHEMTREC
The Chemical Transportation Emergency Center (CHEMTREC) serves as a state-of-the-art
communications center that deals with transportation mishaps by reinforcing the effec-
tiveness of specialized emergency response groups and enhancing hazardous materials
transportation security. Within the United States, CHEMTREC may be contacted by
telephoning the following number, which is often posted on cargo tanks, rail tankcars,
and other bulk packaging used to transport hazardous materials:9
CHEMTREC
(800) 424-9300
Companies that list CHEMTREC’s emergency number on their packaging must be regis-
tered with CHEMTREC, and pay an annual fee.
CHEMTREC Formally
known as the Chemical
Transportation Emer-
gency Center, a public-
service hotline for
firefighters, law
enforcement, and other
emergency responders
for obtaining informa-
tion and assistance for
incidents involving haz-
ardous materials
9
For calls originating outside the United States, telephone collect (703) 527-3887. Within Canada, telephone Le
Centre canadien d’urgence transport du Ministere des transports (the Canadian Transport Emergency Centre
of the Department of Transport), or CANUTEC, at (613) 996-6666 . Within Mexico, telephone the Secretar(a
de Comunicaciones y Transportes (Secretariat of Communications and Transportation of Mexico), or SCT, at
52-5-684-1275. These numbers have been widely circulated in the professional literature distributed to emer-
gency service personnel, shippers and carriers, and members of the chemical industry, and they have been further
circulated in bulletins of governmental agencies, trade associations, and similar groups.
Chapter 1 Introduction 27
