Help with Board Question (No Word Count) and Unit Assessment (Word Count Noted On Each Question). APA Format Throughout to include Reference Page.

Board Question

Hydrogen is being used in some areas of the United States, such as in California, as an alternative motor fuel for automobiles. Many people are concerned about the potential damage hydrogen could cause to the environment which is currently limiting its widespread use throughout the world. What are your thoughts about this issue from a socioeconomic, chemical reaction, and safety perspective?

Unit Assessment

QUESTION 1

A company is planning to transport oxygen, chlorine, and phosphorous by train to another city. Identify the labels, marking, and placards that the DOT requires when transporting these elements.
Your response must be at least 75 words in length.

QUESTION 2

Describe some ways that the Emergency Response Guidebook is used when responding to incidents involving the release of hazardous materials.
Your response must be at least 75 words in length.

QUESTION 3

Describe how the chemical characteristics, production methods, uses, and associated unique hazards of hydrogen can affect the safety of an environmental health and safety (EHS) and fire science (FS) professional.
Your response must be at least 75 words in length.

QUESTION 4

A nursing home is installing their own bulk oxygen system due to their large volume of consumption. OSHA regulation 29 CFR 1910.104(b)(2)(iii) requires owners of bulk oxygen systems to provide noncombustible surfacing in areas where liquid oxygen might leak during operation of the system or during the filling of a storage container. If the nursing home provides an asphalt surface in areas where oxygen could potentially leak, will it be in compliance with the workplace regulation regarding oxygen? Explain your answer.
Your response must be at least 75 words in length.

QUESTION 5

Although coal is no longer the favored energy source, U.S. coal mines still produced close to a billion short tons of coal. Detail 5 different forms of coal, including activated carbon, and chemical products and health hazards related to each different form. Describe DOT recommended response actions to incidents involving a release of coal and/or carbon.
Your response must be at least 75 words in length.

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Course Learning Outcomes for Unit II

Upon completion of this unit, students should be able to:

3. Explain the chemistry of common substances
3.1 Explain the chemical characteristics, production methods, uses and associated unique hazards

of oxygen, hydrogen, chlorine, phosphorus, sulfur, or carbon as related to the safety of an
environmental health and safety (EHS) and fire science (FS) professional.

3.2 Identify associated workplace regulations of oxygen, hydrogen, or chlorine.

5. Classify hazardous materials according to Department of Transportation (DOT) classification and
warning systems.
5.1 Identify the labels, markings, and placards that DOT requires when transporting oxygen,

hydrogen, chlorine,

phosphorus, sulfur, or carbon.

5.2 Describe DOT recommended response actions to releases of oxygen, hydrogen, chlorine,

phosphorus, sulfur, or carbon.

8. Apply information resources commonly used in emergency response operations.
8.1 Describe how the Emergency Response Guidebook (ERG) as is used in initial response

actions to hazardous materials incidents.

Course/Unit
Learning Outcomes

Learning Activity

3.1
Unit II Lesson
Chapter 7 Reading
Unit II Assessment

3.2
Unit II Lesson
Chapter 7 Reading
Unit II Assessment

5.1
Unit II Lesson
Chapter 7 Reading
Unit II Assessment

5.2
Unit II Lesson
Chapter 7 Reading
Unit II Assessment

8.1
Unit II Lesson
Chapter 6 Reading
Unit II Assessment

Reading Assignment

Chapter 6:
Use of the DOT Hazardous Materials Regulations by Emergency Responders, pp. 179-217

Chapter 7:
Chemistry of Some Common Elements, pp. 227-267

Unit Lesson

In this unit, we examine the chemical properties of six elements that possess hazardous features that an
environmental health and safety (EHS) and fire service (FS) professional should be aware of. These elements

UNIT II STUDY GUIDE

Chemistry of Some Common
Elements

2

UNIT x STUDY GUIDE

Title

are widely used, which increases the likelihood that they could be involved in unauthorized release incidents
requiring emergency response and/or mitigation efforts. Workplace regulations involving these elements and
Department of Transportation (DOT) labeling and placarding requirements for their transportation are also
covered. These topics are the focus of Chapter 7. We also briefly look at the Emergency Response
Guidebook (ERG) since this is still the most popular reference used for hazardous materials emergency
responses. If you need more background information on DOT regulations, you are encouraged to read all of
Chapter 6 and Appendix C.

Oxygen: When somebody mentions oxygen, the first thing that most people associate it with is air. Normal air
as we all know consists of 21% oxygen and 78% nitrogen by volume. The other 1% consists of argon, with
small trace amounts of inert gases found in the early Earth’s atmosphere, such as helium (Ackerman & Knox,
2011). This oxygen concentration is what supports life as we know it. When the concentration drops to below
19.5%, supplied air or a self-contained breathing apparatus (SCBA) is required. Normally, when humans
breathe out, oxygen levels are in the range of 19%, which is why you can resuscitate an unconscious person
through the means of artificial respiration. OSHA defines an atmosphere containing more than 23.5% as an
oxygen enriched atmosphere, and an oxygen-deficient atmosphere has oxygen content less than 19.5%
(Occupational Safety and Health Administration, n.d.).

Trivia: Although atmospheric oxygen (O2) is constantly being used up by living organisms, oxygen is
replenished by photosynthesis. Scientists estimate that the world’s supply of atmospheric oxygen is
generated by the life process of plants, especially the trees within the huge span of the Amazonian rainforest
in South America (Meyer, 2014).

At ambient temperatures, oxygen is a colorless, odorless, and tasteless gas. Oxygen is commercially
available as compressed gas, cryogenic liquid, or liquid oxygen (LOX). When LOX vaporizes, it becomes
gaseous oxygen, sometimes called GOX.

Oxygen also supports the process of combustion. If the concentration of oxygen is very high, its reaction with
other substances could lead to explosions or detonations. Therefore, great care should be taken in the
storage and handling of gases with high oxygen concentrations. Exposure of an ignitable substance to LOX
increases its rate of combustion. When shippers offer LOX or GOX to be transported, the DOT has certain
labeling and packaging requirements as well as recommendations for responding to a transportation mishap
(Meyer, 2014).

Ozone (O3), an allotrope of oxygen, is a powerful oxidation agent—considerably more powerful than oxygen.
It is used commercially for several purposes such as a microbiocide at drinking water and wastewater plants.
This ozone is produced on purpose by ozone generators. Please note that ozone is also formed (not on
purpose) by the chemical reactions between oxides of nitrogen (NOx) and volatile organic compounds (VOC)
in the presence of sunlight. This ozone is commonly known as ground-level ozone or the “bad ozone” as
inhaling it can trigger or exacerbate a variety of health problems like asthma. Although the presence of ground
level ozone (tropospheric) can be a problem, the presence of ozone in the stratosphere benefits earth’s
inhabitants by reducing the amount of ultraviolet radiation that can reach the earth’s surface.

Hydrogen: Elemental hydrogen (H2) is an odorless, colorless, tasteless, and non-toxic substance. It is
commercially available as both a compressed gas and as a cryogenic liquid. Liquid hydrogen is a good rocket
fuel. In the mid-2000s, compressed hydrogen was being touted as a viable fuel alternative for powering
automobiles, thereby, decreasing dependence on foreign oil for fuel.

When released indoors or into an enclosure where the gas can accumulate, the presence of hydrogen poses
a risk for fire and explosion. For example, hydrogen is released when charging acid-lead batteries indoors.
When released outdoors in a manner that enables the hydrogen to readily dissipate, the likelihood of forming
a flammable mixture is decreased.

Just like oxygen, the DOT has requirements when hydrogen is being transported that shippers have to follow.
When there is an incident involving hydrogen gas, the practical side of responding generally involves
permitting the fire to burn itself out. However, the fire should be monitored to prevent the spread of the fire.
OSHA regulates hydrogen storage locations (Meyer, 2014). They also have placarding requirements.

Chlorine: Elemental chlorine (Cl2) is not found naturally, but chlorine is found on earth to the extent of 0.19%
by mass in a variety of compounds such as sodium chloride, potassium chloride, calcium chloride, and

3

UNIT x STUDY GUIDE
Title

magnesium chloride. In ambient conditions, chlorine exists as a yellow-green gas with a characteristic
penetrating and irritating odor. It is encountered as a gas or a liquefied compressed gas. Chlorine is about 21⁄2
times heavier than air and is highly poisonous when inhaled. This means that a chlorine release will
accumulate in low-lying areas.

Exposure initially causes coughing, dizziness, nausea, headache, and severe inflammation of the eyes, nose,
and throat. Prolonged exposure (> 1 hr) to moderate concentrations could cause the onset of pulmonary
edema, which is the excessive accumulation of fluid within the lungs. OSHA requires employers to limit
employee exposure to a maximum concentration of 1 ppm averaged over an eight-hour workday (Meyer,
2014).

Chlorine is a powerful oxidizing agent and supports combustion of certain elements and organic compounds.
On the positive side, chlorine is used in the production of a wide range of solvents, pesticides, dyes,
bleaching agents, plastics, and other products. Because chlorine poses an inhalation hazard and is very toxic,
the use of proper protective equipment is very important when responding to incidents involving chlorine. Just
like oxygen and hydrogen, shippers have to follow DOT requirements when offering chlorine for
transportation.

Phosphorus: Elemental phosphorus has several allotropes. Two especially important allotropes are white
phosphorus and red phosphorus. Both allotropes are used to manufacture special alloys, rodenticides,
fireworks, matches, phosphoric acids, and metallic phosphides. In the past, both were also used as the active
agents in incendiary bombs.

White phosphorus is a waxy, translucent solid at ambient temperature that has an autoignition temperature of
86° F (Meyer, 2014). Body heat is enough to cause an ignition. Red phosphorus is a dark-red solid consisting
of long chains of P4 tetrahedra, each having an length. Compared to white phosphorus, this red
allotrope is not as reactive. Red phosphorus is not poisonous but could react with water to form the poisonous
gas phosphine.

Sulfur: Sulfur is found in meteorites and also occurs naturally in the vicinity of volcanos and hot springs
(Burke, 2003). Pure sulfur is an odorless solid. Sulfur is one of the world’s most important raw materials and
has a broad use in its elemental form (S) or as one of its compounds in all sectors of the chemical industry. It
is used to produce gunpowder, matches, fireworks, and products manufactured from vulcanized rubber.
Sulfur readily melts under normal fire conditions, thereby, flowing into areas where it can initiate secondary
fires.

For the next unit, we will combine the study of two hazard classes, corrosive and water-reactive/air reactive
materials, so that we can cover all the major hazard classes in this course.

References

Ackerman, S. A., & Knox, J. A. (2011). Meteorology: Understanding the atmosphere (3rd ed.). MA: Jones &
Bartlett Learning.

Burke, R. (2003). Hazardous materials chemistry for emergency responders (2nd ed.). NY: Lewis.

Meyer, E. (2014). Chemistry of hazardous materials (6th ed.). Upper Saddle River, NJ: Pearson.

Occupational Safety and Health Administration. (n.d.). Confined spaces. Retrieved from
https://www.osha.gov/dte/grant_materials/fy09/sh-18796-09/confinedspace

All forms of packaging intended for containerization of a haz-
ardous material is subjected to rigorous testing procedures pre-
scribed by DOT to ensure that they will retain their integrity when
subjected to normal conditions of transportation. There are five
principal tests for each type_ of packaging: drop test; leakproofness
test; hydros_ta_nc test; sta_ckmg test; and vibration test. DOT pub-
lishes the mm1mum reqmrements for compliance with these tests at
49 C.F.R. Subpart M.

A shipper may petition DOT to containerize a hazardous mate-
rial for t~ansport~tion in an unconventional fashion by submitting
relevant mformat1on to demonstrate that the packaging retains its
integrity when subjected to normal conditions of transportation.
When DOT agrees, it assigns the shipper an approved special per-
mit as “DOT-SP-” followed by the assigned special permit number.
The assignment of an approved special permit allows carriers to
legally transport a hazardous material in unauthorized packaging
for a specified period, after which the shipper must reapply for a
new special permit.

6.1-F SPECIAL PROVISIONS

FIGURE 6.2 This intermediate bulk container may
be used to transport sulfuric acid. (Courtesy of Avant

or

Performance Materials, Inc., Center Valley, Pennsylvan ia,
“Packaging Systems: Innovative Design Drives Productivity”. )

DOT identifies certain special provisions that apply to the trans-
portation of unique hazardous materials. Each provision is identi-
fied by a code. We are primarily concerned here only with the provisions that apply
directly to the needs of emergency-response personnel.

When shippers and carriers transport a gaseous or liquid hazardous material that
poses a health hazard by inhalation, DOT requires them to establish its hazard zone. For
gases, the hazard zone is any of the designations Zone A, Zone B, Zone C, or Zone D;
and for liquids, it is either Zone A or Zone B. The greatest degree of health hazard is
posed by exposure to hazardous materials that have been assigned to Zone A.

The code for the hazard zone of a hazardous material that poses health hazard by
inhalation appears in column 7 of the Hazardous Materials Table. When DOT lists any of
the codes 1, 2, 3, or 4 in column 7, shippers and carriers associate them with Zone A,
Zone B, Zone C, and Zone D, respectively.

6.2 THE SHIPPING PAPER
With few exceptions, DOT requires a hazardous material to be properly described for
transportation on a shipping paper. There are several forms of a shipping paper, such as
a shipping order, bill of lading, manifest, railroad waybill, or similar document. Most
resemble the example shown in Figure 6.3, a portion of which we shall use as a template
throughout the remainder of this text. For emergency responders, the information entered
in the section noted as “Shipping Description” is especially important.

6.2-A SHIPPING DESCRIPTIONS OF HAZARDOUS MATERIALS
DOT requires shippers to provide the shipping description of each hazardous material in
a given consignment on the accompanying shipping paper. The shipping description of a
hazardous material is composed in part of a composite listing of the following compo-
nents in the sequence noted.

health hazard by
inhalation The
expression used to
describe the property
of certain gases and liq-
uid vapors that could
cause health problems
when inhaled

hazard zone For pur-
poses of DOT regula-
tions, any of the four
hazard levels assigned
at 49 C.F.R. §§173.11 G(a)
and 173.133(a), respec-
tively, to poison gases
and either of the two
levels (Zones A and B)
assigned to liquids
whose vapors pose a
health hazard by
inhalation

shipping paper The
shipping order, bill
of lading, air bill,
dangerous-cargo mani-
fest, or similar shipping
document issued by a

• “UN/NA” Identification number shipper or carrier as

1

required by DOT at 49
Proper shipping name (including the technical name in parentheses, when applicable) C.F.R. §§172.202,

1 Primary hazard class or division 172.203, and 172.204
Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 179

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No,

-OF Non-Negotiable
BILL OF LADING I Trailer No:

———–lTruck No: I Dispatch/Pro No: Driver: I Date Received: CHAR~ CONSIGNEE
SHIPPER

Name
Name Street Address
Street Address
City, State

City, State Phone

Notify/Contact Phone
Notify/Contact —-

PARTICULARS FURNISHED BY SHIPPER –
Shipping Descriptio~ Primary Hazard

(Identification Number, P~ofer Shipp:~la:;:; Division, and Weight
Class or Division, Subsidiary Hazar (lb)

Units HM
Packing Group)

I Placards Required: I Emergency Telephone: I ERG No.
For hazardous materials transported by vessel : Shipper de- This is to certify that the above-named materials are proper~
clares that the packing/loading of freight containers and/ classified, described, packaged, marked and labeled, and are in
or transport vehicles containing hazardous materials has proper condition for transportation according to the
been carried out in accordance with the provisions of applicable regulations of the Department of Transportation
49 c.F.R. §176.27(c). (49 C.F.R. §172.204).
Signature: Signature: —

LIABILITY FOR LOSS, DAMAGE, ETC. TO GOODS —
Shipper’s attention is directed to Sectio~ 11 on the rever~e side of this Bill of Lading. All goods shall have an agreed release
valuation of S?.10 per pou~d unless Shipper decl?res a h1~he~ value and Carrier accepts that valuation in the space beloW-
For water carnage, see Section 5 on the reverse side of this B111 of Lading:
Shipper’s initials: Higher value: $ per pound Carrier’s acceptance:

ORIGIN DESTINATION

time in : time in : · ion
time out: time out: Received in good order, count and co

nd11

r d-:-a-te-: ———-t-;d-at_e_: __________ _J unless otherwise noted above.

SHIPPER CONSIGNEE
Authorized Signature Date Authorized Signature Date Authorized Signature Date

FIGURE G.3 One form of a shipping paper used in commerce.

180 Chapter 6 Use of the DOT Hazardous Materials Regulations b E Y mergency Responders

,……-
5 bsidiary hazard class or division in parentheses if any

II p~cking group (when applicable) ‘
11 r requires ship~ers to provide this information in English on a shipping paper.
pO p0T also re~uires the t~tal number of packaging units and the total amount of each

dous rnatenal ma consignment to be communicated in the shipping description. The
hazalr umber of units is indicated by such expressions as 4 boxes 17 cylinders 5 steel
ota n b 1 1 t k k d f ‘ ‘ 1 s 3 glass ott es, an true , an so orth. The total amount is typically provided

drum r~ss aggregate mass or volume. Abbreviations are used to express the common units
as a g
1 asurernent. 0 m;OT lists si~ sym?ols in colum_n 1 of the Hazardous Materials Table. When a G is
. d p0T requrres shippers to provide the technical name parenthetically with the hazard-

hste ‘ hi . d . . Wh ous material’s s ppm~ escnption. en a + symbol is listed, the proper shipping name,
hazard class, ~nd_ packing ~roup may _not be altered for any reason. When a D or I is listed,
h proper shipping name is appropriately described for domestic and international trans-

l :Cration, respectively. Finall~, when an A_ or W is listed, DOT regulates the transportation
~/ che given haza~dous material ~nly by aircraft and watercraft, respectively.

When a consignment comprises hazardous materials and other materials whose trans-
orcacion is not regulated _by DOT, the proper shipping descriptions of the hazardous

~acerials must be entered first on the relevant shipping paper, or a contrasting color or an
X in che “HM” col~mn ~an be entered to identify the entries that are hazardous materials.
for example, gasoline, mtrogen, and a flammable solid are listed on the following portion
of a shipping paper before the materials that are not subject to the DOT hazardous mate-
rials regulations. The hazardous materials are specifically identified by an X in the col-
umn headed “HM.”

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SHIPPING NAME,

PRIMARY HAZARD CLASS OR DIVISION, SUBSIDIARY HAZARD WEIGHT
UNITS HM CLASS OR DIVISION, AND PACKING GROUP) (lb)

10 steel drums X UN1203, Gasoline, 3, PG 11 4500
(UN1A1)
40 cylinders X UN1066, Nitrogen, compressed, 2.2 800
(DOT-3AA 1800)
1 steel drum X UN2926, Flammable solids, toxic, organic, n.o.s. (Cloth/Paper 452
(UN1A1) containing 2,4-dinitrophenol), 4.1, (6.1), PG II

4 boxes (UN4D) Advertising materials, paper, n.o.i. 60

1 roll Paper, printing, newsprint 690

12 sets Carbon paper 22

EMERGENCY CONTACT: (000) 000-0000

This example also illustrates that the shipper must provide an emergency-contact tele-
phone number on a shipping paper for each hazardous material within the consignment.
In this instance, there are multiple hazardous materials listed on the same paper, and the
single telephone number applies to all of them. During a transportation mishap, emer-
gency responders secure the shipping paper and provide this number to CHEMTREC.

When providing the shipping description of a hazardous material, shippers must be
aware of other DOT regulatory requirements that are relevant to identifying the given
consignment by a selected mode of transportation. Examples of these regulations are pro-
vided in Table 6.2. They illustrate that emergency-response personnel obtain valuable
information about the nature of a unique hazardous materials consignment from the
information that has been entered on shipping papers.

shipping description
For purposes of DOT

regulations, the follow·
ing minimum informa·
tion for a hazardous
material : proper ship·
ping name (including
the technical name,
when required); hazard
class or division; identi•
fication number; pack·
ing group; total
quantity by mass, vol·
ume, or as otherwise
appropriate; and the
number and types of
packages

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 181

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TABLE 6.2

RELEVAN

&F@fH,01–
T

REGULATION

EXAMPLE {SELECT PHRASES)’
Transportation of a Hazardous Material by All Modes h’ er or carrier transports a hazardous substan .

RQ, UN1052, Hydrogen fluoride, anhydrous, 8, (6.1), PG I
When as Ipp . rt ble q n · ce 1n that exceeds its repo a uan I y in a singl

(Poison – Inhalation Hazard, Zone Cl
an amoun~ letters RQ are included before or after the e
package, t e
shipping

description.

or
UN1052, Hydrogen fluoride, anhydrous, 8, (6.1), PG

I,

RQ (Poison – Inhalation Hazard, Zone Cl When a hazardous material, by chemical interaction with

RQ, UN1428, Sodium, 4.3, PG I (Dangerous When Wet) . r ble to become spontaneously flammable or giv water, Is Ia . . e ff fl mable gases in dangerous quant1t1es, the words
~Dan:rous When Wet” are included with the shipping

description.

UN1831, Sulfuric acid, fuming, 8, (6.1),
When a hazardous material p~s~~sses multiple hazards,
its subsidiary hazard class or d1v1s10~ number~ are entered

PG I (Poison – Inhalation Hazard, Zone B) parenthetically immediately following the primary
hazard class.

UN1760, Corrosive liquids, n.o.s. {Valerie acid), 8, PG I
When a hazardous material is described with an n.o.s. entry
or other generic description in the Hazardous Materials Table,
the shipping description includes the name of the substance
in parentheses.

UN1992, Flammable liquids, toxic, n.o.s. {contains xylene and
When a mixture o,r solution of two or more hazardous

methanol), 3, (6.1 ), PG I
materials described by an n.o.s. entry in the Hazardous
Materials Table is to be transported, the technical names
of at least two components most predominantly contributing
to the hazards of the mixture or solution are parenthetically
entered in the shipping description.

UN1202, Diesel fuel solution, 3, PG Ill
When a mixture or solution of a hazardous material not
listed by name in the Hazardous Materials Table and a non-

or
hazardous material is to be transported, the proper name of

UN1202, Diesel fuel mixture, 3, PG Ill
the hazardous material is entered in the shipping description
along with the word “solution” or “mixture.”

UN1987, Alcohol, n.o.s. (contains 2-octanol), 3, PG Ill
When the name of a hazardous material is not specifically
listed in the Hazardous Materials Table, the entry that most
appropriately describes the chemical class of the material is
used, not its hazard class.

UN2672, Ammonia solutions (with 12.8% ammonia in water), When a concentration range is a component of a proper

8, PG Ill
shipping name, the actual concentration of the hazardous
material, if it is within the indicated range, is used in lieu of
the range. _

UN2789, Acetic acid glacial, 8, (3), PG II (with >80% acid Technic~I and chemical group names may include an .
by mass) appropriate modifier like “contains” or “containing” which is entered parenthetically between the shipping name and the
or hazard class or following the shipping description.
UN2789, Acetic acid, glacial {contain ing more than 80% acid
by mass), 8, (3), PG II

• 49 CF.R. §§172.202 and 172.203.
bNot provided in this table is the unique information that DOT requires in the shippin d • . . . . d’oac·
tlve materials. This information is discussed independently in Sections 13_19_A lS.4

9 d e,stpt,ons of ~rganic peroxides, explo11ves, and ra
1

‘ The component of the shipping description that Is applicable to the regulat i~n Is ‘an_d d.10, respectively. prov, e in blue print.

182 Chapter 6 Use of the DOT Hazardous Materials Regulat ions b E Y mergency Responders

TABLE 6.2 Information Required in Shipping Descriptions

(continued)

e)(AMPLE (SELECT PHRASES)

RO, UN2029, Hydrazine anhydrous, 8, (3, 6.1 ), UN2029,
pG I (Poison)

or
RO, UN2029, Hydrazine anhydrous, 8, (3, 6.1 ), PG I (Toxic)

UN2783, Organophosphorus pesticides, solid, toxic (Ciodrin),
6.1, PG II

or
UN2783, Organophosphorus pesticides, solid, toxic, 6.1, PG 1
(Ciodrin)

RO, UN2199, Phosphine, 2.3, (2.1) (Poison – Inhalation Hazard,
zone Al

or
RO, UN2199, Phosphine, 2.3 (2.1) (Toxic – Inhalation Hazard,
Zone A)

Flammable solids, n.o.s. (sod ium), 4.3, UN 1325, PG 11

UN3082, Hazardous waste, liquid, n.o.s., 9, (contains
trichloroethylene), PG Ill (F001)d

NA3082, Hazardous waste, liquid, n.o.s., (contains toluene
and methanol), 9, PG Ill (EPA ignitabili ty)

or
NA3082, Hazardous waste, liquid, n.o.s., (contains toluene
and methanol), 9, PG Ill (D001)

RQ, UN1621, London purple (contains diarsenic trioxide and
aniline), 6.1, PG II (Marine Pollutant)

or
UN1621, London purple (contains diarsenic trioxide and ani-
line), 6.1, PG II, (Marine Pollutant) RQ
UN1193, Residue: Last conta ined ethyl methyl ketone, 3, PG II

RELEVANT REGULATION

Regardless of the hazard class to which a hazardous material
is assigned, if a liquid or solid material in a package meets .
the definition of a Division 6.1, PG I or II, and the fact that it
is a poison is not disclosed in its shipping name or class entry,
either of the words “Poison” or “Toxic” is entered in the
shipping description.
Notwithstanding the hazard class to which a hazardous
material is assigned, if the technical name of the com-
pound or principal constituent that causes a m~terial to
meet the definition of a Division 6.1, PG I or 11, 1s not
included in the proper shipping name for the material, the
technical name is entered in parentheses in the shipping
description .
For materials that pose an inhalation hazard, either of the
expressions “Poison – Inhalation Hazard” or “Toxic –
Inhalation Hazard” and the applicable words “Zone A,”
“Zone B,” “Zone C,” or “Zone D” for gases or “Zone A” or
“Zone B” for liquids, are entered on the shipping paper
immediately following the shipping description.

If a hazardous material is also a hazardous substance other
than a rad ioactive material, and the name of the hazardous
material does not identify the hazardous substance by
name, one of the following descriptions is entered in
parentheses in the shipping description of the hazardous
material: (a) the name of the hazardous substance;

or
(bl for waste streams, the hazardous waste number;

or
(cl for waste streams that exhibit an EPA characteristic, the
letters “EPA” followed by the characteristic or the EPA
hazardous waste number_d,e

If a hazardous material is also a hazardous substance other
than a radioactive material, and the name of the hazardous
material does not identify the hazardous substance by name,
the letters “RQ” are entered either before or after the ship-
ping description.

The shipping description for the residue of a hazardous
material contained in packaging other than a rail tankcar
may include the words “Residue: Last contained
_____ (name of hazardous material in packaging
before it was emptied) .”

dThe EPA hazardous waste numbers for listed hazardous wastes are prefixed with one of the capital letters F, K, P, or U. The nature of the listed
hazardous wastes is published at 40 C.F.R. §§261.31, 261.32, 261 .33(e) and 261.33(!}.
‘Four EPA characteristics of a hazardous waste are identified at 40 C.F.R. §§261.21-261.24: ignitability (Section 3.2); corrosivity (Section 8.15);
reactivity (Section 5.9); and toxicity (Section 10.1-B). Hazardous wastes exhibiting these characteristics have been assigned the EPA hazardous
waste numbers 0001, 0002, 0003, and D004 through D043, respectively.

(continued)

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 183

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TABLE 6.2

EXAMPLE (SELECT PHRASES) RELEVANT

RQ, UN1052, Hydrogen fluoride, anhydrous, 8, (6.1), PG I When a shipper has been assigned an approved sp . . . h ecIaI
(Poison – Inhalation Hazard, Zone C) (DOT-SP- •• •) permit from DOT to containerize a azardous mat . . h h’ . enaI, an unconventional fashion, t e s 1pp1ng descriptio in
(*** is replaced with the appropriate special permit number) includes the notation “DOT-SP-” followed by the as~ign

special permit number and so located that the notar ed
clearly associated with the description to which the I0n is

REGULATION

exemption applies.

UN2214, RQ, HOT Phthalic anhydride, 8, PG Ill If a liquid hazardous material is to be transported at a
“elevated temperature,” and the fact that it is an elev nt

· I · t d’ I d . th h’ a ed. temperature matena Is no 1sc ose 1n es Ipping n
the word “HOT” immediately precedes the proper ship;~e, . I Ing name of the hazardous matena .

6 cyl (DOT-3AA1 800), RQ, UN1076, Phosgene, 2.3, (8), (Poison
– Inhalation Hazard, Zone A)

The number and type of ~ach nonbu_lk packag_e with its Dor
specification number are included with the shipping

or description.

5 steel drums (UN1 A1), UN1193, Ethyl methyl ketone, 3, PG 11
Transportation of a Hazardous Material by Passenger-
Carrying Railroad or Aircraft

UN1827, Stannic chloride, anhydrous, 8, PG II (Limited When DOT authorizes the transportation of a hazardous
Quantity) material in a limited quantity by passenger-carrying railroad
or or aircraft, the shipping description includes the words

“Limited Quantity” or “Ltd Qty. ”
UN1827, Stannic chloride, anhydrous, 8, PG 11 (Ltd Qty)

Transportation of a Hazardous Material by Cargo Aircraft
UN2363, Ethyl mercaptan, 3, PG I (Cargo Aircraft Only) When DOT authorizes the transportation of a hazardous
(Limited Quantity) material by cargo aircraft, the words “Cargo Aircraft Only”

are entered in the shipping description.
UN2363, Ethyl mercaptan, 3, PG I (Cargo Aircraft Only) When DOT authorizes the transportation of a hazardous
(Limited Quantity) material in a limited quantity by cargo aircraft, the shipping
or description includes the words “Limited Quantity” or “Ltd Qty” in addition to “Cargo Aircraft Only.”
UN2363, Ethyl mercaptan, 3, PG I (Cargo Aircraft Only)
(Ltd Qty)
Nonbulk Transportation of a Marine Pollutant on Water and
Bulk Transportat ion of a Marine Pollutant in All Modes
UN1381, Phosphorus, white, under water, 4.2, (6.1), PG I When a shipper or carrier transports a nonbulk quantity of a
(Marine Pollutant) (Poison) marine pollutant on board watercraft or a bulk quantity of a

marine pollutant by any mode, the words “Marine Pollutant’
are included with the shipping description. –

UN1621, London Purple (contains diarsenic t rioxide and When the name of the component causing a material to be a
aniline), 6.1 , PG II (Marine Pollutant) (Poison) marine pollutant is not evident, the name is identified paren·

thetically in the shipping description.
Environmentally hazardous substance, solid, n.o.s. (Zinc If a marine pollutant is not listed by name in the Hazar~ous
bromide) (Marine Pollutant) Materials Table and it does not meet the defining criteria of

classes 1 through 8, its shipping description is either
“Environmentally hazardous substance, liquid, n.o.s.” or
“Environmentally hazardous substance, solid, n.o.s.,” as
relevant

184 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

– LE (SELECT PHRASES) rABLE 6.2 Information Required in Shipping Descriptions (continued) f’fJ,MP
Q UN30B2, Enviro_ndmentdally h~zardous substances, liquid R , (sodium cyan, e an cupri c cyan ide), 9, PG 111 (Marin~ n-0
1
\ant) (Poison) pol u

T nsportation of a Hazardous Material on Wat .
UNlll5, Ethylbenzene, 3, PG II (flashpoint = 15oC)

UNllg6, Battery fluid, acid, 8, PG II (IM DG Code 1 _ Acids)

sulk Transportation of a Hazardous Material by Railway

UNl962, Ethylene, compressed, 2.1, (DOT-113) (Do Not Hump
or cut Off Car While in Motion) Placarded: FLAMMABLE GAS
(HYDX11111)

UN2214, HOT Phthalic anhydride, 8, UN2214, 111, RQ
(Maximum Operating Speed 15 mph) (LCTX111111)

UN1193, RESIDUE: Last contained et hyl methyl ketone, 3, PG
11 Placarded: FLAMMABLE (ACTX11111)

RQ, UN1076, Phosgene, 2.3, (8), (Poison – Inhalation Hazard,
Zone A) Placarded: POISON GAS (DUPX11111 )9

RQ, UN1075, Liquefied petroleum gas, 2.1, (Noncorrosive)
(CSXTl 111 11)9

Bulk Transportation of Anhydrous Ammonia by Highway

RQ, UN1005, Ammonia, anhydrous, 2.2, (0.2 percent water)
(Inhalation Hazard)

RQ, UN1005 Ammonia, anhydrous, 2.2, (Not for Q and T
tanks) (inhalation Hazard)

RELEVANT REGULATION

When a material designated with an n.o.s. entry in the
Hazardous Materials Table is a marine pollutant, the names
of at least two of the components most predominantly
contributing to the marine pollutant designation are entered
in parentheses in the shipping description .

When a hazardous material possesses a flashpoint equal
to or less than 142°F (61°() and is transported on water, the
flashpoint in degrees Celsius (closed cup) is entered with the
shipping description.

When a hazardous material is designated with an n.o.s. entry
in the Hazardous Materials Table and is not listed in section
3.1.4 ofthe IMDG Code/the applicable IMDG Code
segregation group is entered with the shipping description.

The shipping description of a flammable gas or its residue
contained within a DOT-113 rail tankcar contains an
appropriate notation such as “DOT-113” and the statement
“Do Not Hump or Cut Off Car While in Motion.”

When DOT allows the transportation by ra ilroad of an
elevated-temperature material pursuant to certain
exceptions, the sh ipping description contains an
appropriate notation such as “Maximum Operating Speed
15 mph.”

The shipping description for the residue of a hazardous
material contained in a rail tankcar must include the words
“Residue: Last contained _____ (name of hazardous
material in a rail tankcar before it was emptied).”

When hazardous materials are transported by rail, the
accompanying shipping paper bears the notation
“Placarded: ____ ~” in which the name of the placard
displayed on the railcar is inserted.

When hazardous materials are transported by railway, the
accompanying shipping paper lists the reporting mark and
number9 displayed on the bulk packaging used for
shipment.

When a carrier transports anhydrous ammonia having a
water content equal to or greater than 0.2% by mass in a
DOT Specification MC330 or MC331 tank truck, the shipping
description includes “0.2 percent water” to indicate the suit-
ability for shipping anhydrous ammonia in a cargo tank con-
structed from quenched and tempered steel.

When a carrier transports anhydrous ammonia having a
water content less than 0.2% by mass in a DOT Specification
MC330 or MC331 tank truck, the shipping description
includes the phrase ” Not for Q and T tanks.”

;The International Marit ime Dangerous Goods (IMDG) Code governs the vast majority of the shipments of hazardous materials by water. .
See Section 3.7-A. DUPX and CSXT are the report ing marks of E. I du Pont de Nemours & Company and CSX Transportation Company, respectively.

(continued)

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 185

TABLE 6.2 Tf’ill:SW’illiW’\’IWi’911Wr’k ftl 112 a: a &,¥t.jij.j,i4j,jjijjiQ.1 …..
EXAMPLE (SELECT PHRASES) RELEVANT REGULATION

RQ, UN1005, Ammonia, anhydrous, 2.2, (0.2 percent water)
(Inhalation Hazard)

When a carrier transports anhydrous ammonia or arn
Sol utions relative density less than 0.880 at 15 deg, rnonia , .. . Id eesc· water, the shipping desmptIon me u es the words .. 1 h in tion Hazard” without either of the words “Poison” 0~ }la._ or the designation of a hazard zone. Toxic”

Bulk Transportation of Liquefied Petroleum Gas by Highway

UN1075, Liquefied petroleum gas, 2.1 (Noncorrosive) When a carrier transports liquefied petroleum gas in a 0
Specific~tio~ MC330 .?r MC331 t~n~ true.~. the shipping OT
description includes Noncorrosive (or Noncor”) to ind·

or

UN1075, Liquefied petroleum gas, 2.1 (Noncor) the suitability of transporting noncorrosive liquefied icate
petroleum gas in a cargo tank made of quenched-and.
tempered steel.

Bulk Transportation of Oil by Highway or Railroad
UN1263, Paint-related material, 3, PG Ill (oil) When petroleum oil is transported in packaging having a

capacity of 3500 gal (13,250 L) or more, or when any oil is
transported in packaging in a quantity of 42,000 gal
(159,000 L) or more, the word “oil” is included on the
shipping paper.

hazardous substance
For purposes of DOT

regulations, a substance
listed in Appendix A at
40 C.F.R. §172.101 in an
amount that exceeds its
reportable quantity and
is transported in a sin-
gle package

Let’s consider another example. Suppose a fuel company desires to use a tank truck to
move aviation gasoline from a petroleum storage facility to an airport terminal. DOT
obligates the company to select the particular entry in the Hazardous Materials Table that
most accurately describes the material to be transported. In this instance, the correct selec-
tion is “Fuel, aviation, turbine engine.” This combination of information is properly
entered on a shipping paper as follows:

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SHIPPING NAME,
PRIMARY HAZARD CLASS OR DIVISION, SUBSIDIARY

UNITS HM HAZARD CLASS OR DIVISION, AND PACKING GROUP)
1 tank truck X UN1863, Fuel, aviation, turbine engine, 3, PG I

VOLUME
(gal)
1500

When shippers offer aviation fuel for transportation, DOT requires them to enter only
this description of the commodity on a shipping paper. The selection of any other name
constitutes an illegal entry.

reportable quantity
(RQl For purposes of 6.2-B REPORTABLE QUANTITIES
DOT regulations, the On occasion, the letters RQ are entered with the shipping description of a hazardous
amount listed at 40 material. “RQ” refers to the amount of a hazardous substance that constitutes a report·
C.F. R. §

302
·
4

a
nd 49

able quantity. For the purposes of the Superfund law(Section 1.3-D) any substance li5ted C.F.R. §172.101ofa , f
“hazardous substance” at 40 C.F.R. §302.4 is a hazardous substance, regardless of the amount at issue; but or
within the meaning of the purposes of the DOT regulations, only a substance listed at 49 C.F.R. § 1 ?2JOl,
DOT and CERCLA, the Appendix A, in an amoun~ equal to or exceeding the reportable quantity is a hazard00′.
release of which trig- substance. There are only five reportable quantities: 5000 lb (2270 kg)· 1000 lb (454 kg), gers mandatory notifi- , d us
cation to the National lOO lb (45.4 kg); 10 lb (4.54 kg); and 1 lb (0.454 kg). Examples of several hazar 0
Response Center substances and their DOT reportable quantities are provided in Table 6.3.
186 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

TABLE 6.3 Some Hazardous Sub
Reportable Quantitie

stances and their
s•

HAZARDOUS SUBSTANCE
REPORTABLE QUANTITY

Acetone
Acetonitrile
Ammonia solutions
Asbestos, whiteb

Barium cyanide
cupric cyanide

Chlorine
Chlorobenzene

Dichloromethane
Ethyl methyl ketone

Hydrazine

Hydrogen fluoride, anhydrous

Hydrogen sulfide

Methyl isobutyl ketone

Methyl parathion

Nickel carbonyl

Nitric acid

Phosgene

Phosphine

Phosphorus

Phthalic anhydride

Sodium

Selenium disulfide

Sodium hydroxide

Sodium hypochlorite

Toluene

1, 1, 1-Trichloroethane

Xylene(s)
’40 C.F.R, §302.4 and 49 C.F.R, §172.101, Appendix A, Table 1,
bsection 10.19-A.

POUNDS KILOGRAMS

5000 2270

5000 2270

1000 454

1 0.454

10 4.54

10 4.54
10 4.54

100 45.4

1000 454
5000 2270

1 0.454
100 45.4

100 45.4
5000 2270

100 45.4
10 4.54
1000 454
10 4.54
100 45.4
1 0.454
5000 2270
10 4.54
10 4.54
1000 454
100 45.4
1000 454
1000 454
100 45.4

When a shipper intends to transport a hazardous substance in an amount equal to or
greater than its reportable quantity, DOT requires “RQ” to be entered on the shipping
paper either before or after its shipping description. Suppose, for instance, that a shipper
intends to transport domestically by tank truck 4500 pounds of an aqueous ammonia
solution containing 12% ammonia having a gross weight of 4500 pounds. Although four
shipping descriptions for ammonia solutions are listed in Appendix C, the description
having the identification number UN2672 most adequately describes the commodity,

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 187

I
1, I
11 1,

I II II

‘
I
I

II
II I

11

I
I,’

I
1,

‘
I, I

I,
I
I
I

I I !
i

II ; ;

:
I I
I i

Unt o f an ammonia solution ex t an am o 4 k ” ceed ·
Because the shipper intends to _cransbf; 6.3 as t000 p_o unds (45 g ), RQ” rnus/ ng
the reportable quanti ty listed . in T~ er shipping descnpuon on the accompanying Wabe
included either before or after ,t~, pr f, before the shipping d escnpnon, the complete sl/
b

ill If the shipper elects to enter RQ p.
· d f II w s·

ping descripnon ,s note as o o

SHIPPING NAME, PRIMARY
(IDENTIFICATION NUMBER, SUBSIDIARY HAZARD CLASS OR WEIGHT
HAZARD CLASS OR Dl~IS~~~ PACKING GROUP) (lb)

UNITS HM
DIVISIO , .

. olution (contains 12% ammonia ,n 4500

1 tank X
RO, UN2672, Ammonia s

truck
water), 8, PG 111 — —–

SOLVED EXERCISE 6.1 . E. I. du Pont de Nemours & Company, l_nc. for transportation in a
A shipper offers 2500 pounds of phosgene two h t shipping descript ion does DOT require on the shipping paper)
ra il tankcar marked with the number 111 12. a .
(DUCX is du Pont’s reporting mark.) . ha ardous substance. From this knowledge and the informatio
Solution: Table 6.3 indicates that phosgene 15 a z_ ws · n
listed in Appendix c, the shipping description Is _p rov1deda _s __ 1_01_10 __ · ____________ _

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SHIPPING NAME, PRIMARY
HAZARD CLASS OR DIVISION, SUBSIDIARY HAZARD CLASS OR

DIVISION, AND PACKING GROUP)
UNITS HM

WEIGHT
(lb)

2500

1 cit X
RO, UN1076, Phosgene, 2.3, (8), (Poison – Inhalation Hazard, Zone
A) (Placarded: POISON”G,,A,.S,,) ,(.D,.U,.C •• X .. 11 ._ 1-.:1.=2:..) _ _ _ _________ _

SOLVED EXERCISE 6.2
The following shipping description of a hazardous material is provided on a transportation manifest:

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SH IPPING NAME, PRIMARY
HAZARD CLASS OR DIVISION, SUBSIDIARY HAZARD CLASS OR

UNITS HM DIVISION, AND PACKING GROUP)
1 tankcar X RO, NA3082, Hazardous waste liquid, n.o.s. (contains toluene and

xylene), 9, PG 111 (EPA ignitability) (UTLX42888)

WEIGHT
(gal)

10,000

How is this shipping description useful to an emergency-response team?
Solution: There are at least four pieces of information in this shipping description that are usefu l to emergency·

response personnel:
The notation ” RQ” informs first-on-the-scene responders that the commodity is a hazardous substance, the re-
lease of which could adversely affect public health and the environment. The emergency-response crew should
proceed to darn or dike the area to confine the leak and prevent its widespread release into the environment
The reference to ” EPA ignitability” indicates that the hazardous waste liquid exhibits the RCRA characteri~ic
of ignitability (Section 3.2). This designation informs emergency-response personnel that the hazardous waS

t
e

liquid possesses a flashpoint equal to or less than 140’F (60′ C). Thus, it poses a risk of fire and explosion.
Packing Group Ill indicates that the relative degree of hazard possessed by the commodity is minor. A minor degree
of hazard means that although the material ignites, other groups of hazardous materials are far more hazardous-
In Section 6.7, we shall note that identification numbers direct emergency-response personnel to certain recom·
mended procedures for properly responding to an incident involving the release of th is hazardous waste liquid.

188 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

6.2-C MARINE POLLUTANTS AND SEVERE MARINE POLLUTANTS
DOT regulates the transportation of a variety of environmentally hazardous substances
including marine pollutants and severe marine pollutants, or SMP. These are substances
or mixtures that negatively impact aquatic life or tend ro bioaccumulate in seafood when
released into a waterway. Protection of the marine environment is not an immediate man-
date of DOT; nonetheless, DOT provides a listing of marine pollutants at 49 C. F.R.
S 172. 101 , Appendix B, an excerpt of which is reproduced in Table 6.4.

Marine pollutants that potentially damage the marine environment more severely
than others are called severe marine pollutants. In Table 6.4, severe marine pollutants are
identified wi th the capital letters PP, meaning ” pollution potential,” in the column before
their listing. The listed substances that are nor identified as severe marine pollutants a re
referred to as marine pollutants.

When a substance or mixture is designated as a marine pollutant or severe marine
pollutant, the words “Marine Pollutant” are included parenthetically with its shipping
description. For example, when a glass bottle containing 10 pounds (4 .54 kg) of

pp

PP

PP
PP
PP
PP
PP

TABLE 6.4 Examples of Some Marine Pollutants and Severe
Marine Pollutants•

MARINE POLLUTANT I MARINE POLLUTANT
Anisole lsobutyl isobutyrate

I Barium cyanide lsobutyl propionate
Butanedione Lead acetate
Buty lbenzenes London purple
Butyraldehyde I PP Mercuric oxide
Cadm ium compounds pp Nickel carbonyl
Carbon tetrachloride 1-Octanol
Chlorine pp Phosphorus, white or yellow, dry,

under water, or in solution
Cresols (o-, m-, p-) a-Pinene
Cumene pp Polychlorinated biphenyls (PCBs)
Cupric sulfate Propionaldehyde
1,3,5-Cyclododecatriene n-Propylbenzene
Cymenes (o-, m-, p-) Sodium cyanide, solid or solution
Dichlorobenzene (o-, m-, p-) Styrene monomer, inhibited
Diethylbenzenes 1, 1,2,2-Tetrachloroethane

Epichlorohydrin Tetrachloroethylene

Ethyl acrylate, inhibited 1,3,5-Trimethylbenzene

Ferric arsenate Triethylbenzene

n-Heptaldehyde Turpentine

Hexachlorobutadiene n-Valeraldehyde

lsobutyraldehyde Xylenols

lsobutyl butyrate Zinc bromide
a49 C.F.R. §172.101. Append ix B.

marine pollutant For
purposes of DOT regu-
lations, any substance
denoted in Appendix B,
49 CF.R. §172. 101, and,
when in a solut ion or
mixture of one or more
marine pollutants, is
packaged in a concen-
tration that equals or
exceeds: (1) 10% by
weight of the solution
or mixture for materials
identified in the appen-
dix as marine pollut-
ants; or (2) 1 % by
w eight of the solution
or mixture for mat erials
identified in the appen-
dix as severe marine
pollutants

severe marine
pollutants (SMP)

For purposes of DOT
regulations, any
substance denoted in
Appendix B, 49 CF.R.
§172.101, and indexed
wtth the capital
letters PP

Chapter se o 6 U f the DOT Hazardous Materials Regulations by Emergency Responders 189

dangerous-cargo mani-
fest • For purposes of
DOT regulations, a ship-
ping paper that lists the
hazardous materials
stowed as cargo aboard
watercraft and the spe-
cific locations at which
they are stowed

FIGURE 6.4 When the
driver of a motor vehicle
is at the vehicle’s controls,
DOT requires the shipping
paper to be kept within
immediate reach inside a
holder mounted to the
inside of the door on the
driver’s side of the vehicle.

mercury(Il) oxide is overpacked in a fiberboard ~ox and transported by Watercraft
shipper conveys that the substance is a manne pollutant on the accornp ‘the any1n dangerous-cargo manifest as follows: · g

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SHIPPING NAME, PRIMARY
HAZARD CLASS OR DIVISION, SUBSIDIARY HAZARD CLASS OR WEIG~T

_ ..:_U:_::N::_:IT..:S_ j….’..’.HM::.’..+—-~ Dl:_:Vl::_Sl:.:O::.N,:.:.A.::.N:.::.D..:…PA:….C.:…K_IN_G_G_R_O_U_P)~~—-+-(lb)
Fiberboard x UN1641, Mercury oxide, 6.1, PG II (Marine Pollutant) (Toxic) 10
box (UN6G)

The dangerous-cargo manifest also lists the specific location at which the hazard
· · f h d’ d ous material 1s stowed aboard watercraft. When the na~e o t e commo ity oes not include

the name of the component that causes it to be a marine pollutant, DOT reqwres the shi .
per to parenthetically identify the name of the component. An example is provided ln
Table 6.2.

6.3 LOCATION OF THE SHIPPING PAPER
DURING TRANSIT

During a transportation mishap, where may emergency-response personnel expect to
locate the shipping paper? To avoid any confusion over its location, DOT requires the
shipping paper to be carried on transport vehicles in a specific location. Because it is
important to quickly locate this document when responding to incidents involving the
release of a hazardous material, these requirements are briefly summarized next.

DOT requires the drivers of motor vehicles transporting hazardous materials and
each carrier using the vehicles to clearly distinguish the appropriate shipping paper from
other papers. When the driver is at the vehicle’s controls, DOT requires the shipping
paper to be within immediate reach and readily visible to any person entering the driver’s
compartment. For example, as shown in Figure 6.4, it may be stored in a holder mounted
to the inside of the door on the driver’s side of the motor vehicle. When the driver is not
at the vehicle’s controls, DOT requires the shipping paper to be located either in the
holder or on the driver’s seat inside the vehicle.

When hazardous materials are transported by railroad, DOT requires a member of
the train crew, usually the conductor, to be in charge of the freight waybill that describes

190 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

the wmignments that are transported. This . .
ind1canng the pos1t1on in the tra· f herson also retains the consist, a document
hazardous material. The consist usumllo. eac loaded and placarded car containing a

a Y 1s a comput · h 1· boxcar, and other transport vehicl er pnntout t at 1sts each cargo tank
. e as a separate e t . d’ d , of the tram, or alternatively in desc d. d n ry m ascen mg or er from the front

• . ‘ en mg or er from th f h · b · • • reporting mark (Secnon 3 7-A) and 1 d e rear o t e tram, y Its posmon, · , p acar .
When hazardous materials are t .

carrier to provide a shipping paper d rans,_orte~ by ai~craft, DOT requires the aircraft
The pilot usually retains the h • . escn mg t e consignment to the pilot in command.
destination. s ipping paper m the cockpit until the plane reaches its

When hazardous materials are tra d b
Prepare a dangerous-cargo m •f lnsporte Y watercraft, DOT requires the carrier to am est, 1st or stowag ) d b · · h f the vessel. This document must be co ‘. . . e P an an su mlt 1t to t e master o
vessel’s bridge. On barges it · k . ntamed withm a designated holder on or near the

‘ is ept m the pilot house of the tugboat.

6.4 DOT LABELING REQUIREMENTS
In most instances involving the transportatio of h d · I O ·
h’ t ff ‘b d n a azar ous matena , D T requires

s ippers O a ix prescn e warning labels corresponding to the primary and subsidiary
hazard classes of the material directly to the outs’d f f h k · Th · d 1 b 1 ‘d . . 1 e sur aces o t e pac agmg. e
require a _e_ s are I entifted by the code entries in column 6 of the Hazardous Materials
Table. Add1t1onal labeling requirements for hazard classes 1 and 7 are provided in
Semons 15.4-D and 16.10-B, respectively.

. The DOT labels that shippers affix to packaging containing a hazardous material are
displayed m Figure 6.5 and their names are listed in Table 6.5. Each label is diamond-
sha_ped and color-c~ded to s_ignify a specific hazard class or division and may also include
a pictograph to rapidly s1gmfy the potential hazards of the contents. Each label also bears
the hazard class or division number in its lower corner.

Two points regarding the nature of the EXPLOSIVE labels should be noted:

The uppercase letters that follow the division numbers for the EXPLOSIVE labels
designate the compatibility groups of explosives, whose characteristics are discussed
in Section 15.4-B.
The label at the far right of Hazard Class 1 is the EXPLOSIVE subsidiary label. It is
affixed to packaging when the code listed in column 6 of the Hazardous Materials
Table indicates that the hazardous material has an explosive subsidiary hazard.

DOT requires shippers and carriers to affix the specified labels on the surface of the
package near the spot where they indicate the proper shipping name. For instance, when
shippers and carriers transport gasoline in drums, DOT requires them to affix the
FLAMMABLE LIQUID label to the outside surface of each drum adjacent to the spot
where it is marked “Gasoline.”

When cylinders or other packages have irregular surfaces on which labels cannot
be satisfactorily affixed, DOT allows the labels to be secured on a tag, unless the
packages contain radioactive materials. Because of the irregularity of their surfaces,
gas cylinders are labeled on shoulder tags like that shown in Figure 6.6. When the
tags are embossed on the cylinders, OSHNGHS hazard and precautionary statements
may be cited along with the posting of the relevant transportation pictograms, or
DOT labels.

DOT also requires shippers to affix duplicate labels corresponding to their applica-
ble codes to certain packaging types. Duplicate labels are displayed on at least two sides
or two ends other than the bottom. For multiunit car tanks, they are displayed on each

consist A shipping
document that lists the
location of one or more
locomotives coupled to
one or more railcars
loaded with hazardous
materials as they are
placed, one by one, in a
train, sometimes from
the rear forward

label For purposes of
DOT regulations, any of
several diamond-
shaped and color-coded
warning signs, with or
without a pictogram,
affixed on the packages
of hazardous materials
to identify the specific
hazard class or division
of their contents

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 191

I I

I
If

EXPLOSIVES 1.1 EXPLOSIVES 1.2 EXPLOSIVES 1.3 EXPLOSIVES 1.4 EXPLOSIVES 1.5 EXPLOSIVES 1.S
HAZARD CLASS 3

HAZARD CLASS 2

· · ~ FLAMMABLE NON-FLAMMABLE POISON GAS FLAMMABLE GAS GAS
HAZARD CLASS 4 HAZARD CLASS 5

··· ~ FLAMMABLE SPONTANEOUSLY DANGEROUS OXIDIZER SOLID COMBUSTIBLE WHEN WET ORGANIC PEROXIDE
HAZARD CLASS 6

POISON INHALATION POISON INFECTIOUS
HAZARD SUBSTANCE

HAZARD CLASS 7

RADIOACTIVE
WHITE-I

HAZARD CLASS 8

RADIOACTIVE
YELLOW-II

RADIOACTIVE
YELLOW-Ill

–
1

FISSILE

HAZARD

CLASS 9

CLASS 9

FIGURE 6 .5 DOT requires sh ippers to affix warning labels that identify the rimar . . ·al on
the exterior surface of its packaging. The asterisks in the orange EXPLOSIVE i b I Y and subsidiary hazard classes of a hazardous rnaten 8 01
left blank 1f the explosive hazard is the subsidiary risk associated with the ro~ue; are replaced by the compatibility group (Section 1 SA· ),
words (not shown here on label due to space constraints): “In case of D p · The INFECTIOUS SUBSTANCE label bears the folloWln9 USA

CORROSIVE

Notify Director CDC, Atlanta, GA (800) 232-0124.” amage or Leakage, Immediately Notify Public Health Authority. In

192 Chapter 6 Use of the DOT Hazardous Materials Regulation b s Y Emergency Responders

TABLE 6.5 DOT Warning Labelsa

HAZARD CLASS HAZARD CLASS
OR DIVISION LABEL NAME OR DIVISION

LABEL NAME

EXPLOSIVE 1.1 5.1 OXIDIZER 1.1
EXPLOSIVE 1.2 5.2 ORGANIC PEROXIDE 1.2 – EXPLOSIVE 1.3 6.1 (Inhalation hazard, POISON INHALATION HAZARD 1.3 Zone A or B) – EXPLOSIVE 1.4 6.1 (other than inhalation POISON 1.4

hazard, Zone A or B)
– EXPLOSIVE 1.5 INFECTIOUS SUBSTANCE 1.5 6.2
1.6 EXPLOSIVE 1.6 7

RADIOACTIVE WHITE-I

2.1 FLAMMABLE GAS 7
RADIOACTIVE YELLOW-II

2.2 NON-FLAMMABLE GAS 7
RADIOACTIVE YELLOW-Ill

2.3 POISON GAS 7 (fissile material) FISSILE

3 FLAMMABLE LIQUID 7 (empty packages)b EMPTY

4.1 FLAMMABLE SOLID 8 CORROSIVE

4.2

4.3
149 C.F.R. §172.400.
bsectlon 16.10-B.

SPONTANEOUSLY COMBUSTIBLE

DANGEROUS WHEN WET

9 CLASS 9

end. For a freight container or aircraft unit load device, they are displayed on or near the
closure. The regulations pertaining to use of duplica te labels are published at 49 C.F.R.
§172.406.

When shippers offer for transportation packages containing hazardous materials
authorized solely for transport on cargo aircraft, or when the packages contain net quan-
tities that exceed those a uthorized on passenger-carrying aircraft, DOT requires them at
49 C.F.R. § 172.448 to display the CARGO AJRCRAFT ONLY label in Figure 6. 7 in
addition to any other required labels .

FIGURE 6.6 At 49 C.F.R. § 172.406(b)(2), DOT allows the use of tags to provide both marking and label ing infor-
mation when they are affixed to.the surface of gas cylinders. As required by OSHA/GHS, hazard and precaution-
ary s_tatements are provided on the left of this shoulder tag and the transportation pictogram (or DOT label) is
provi ded on the right. This particular tag is permanently affixed to the outside surface of a propane cylinder. This
shoulder tag provides the required marking information on the left and the warn ing label on the right .

cargo aircraft An
air-transport vehicle
designed solely to
transport cargo but not
paying passengers

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 193

I 1i

448 DOT requ ires
FIGURE 6 .7 At 49 C.F.R. §l;~RCRAFT ONLY label to
shippers to affix the CARG~ d us material packag-
the exterior surface of the azar o ed on
ing when its transportation is solely ~~p~~\he hazard-
board cargo aircraft or the net quant1 _Y n passen-
ous material approved for transportat10~ on the

er-carrying aircraft is exceeded. The printing n e
~ARGO AIRCRAFT ONLY label is black on an ora g

background .

GO AIRCR

SOLVED EXERCISE 6.3 ff h of five fiberboard boxes that contain eight

marking (mark) For
purposes of DOT regu-
lations, a descriptive
name, identification
number, instructions,
caution, weight, specifi-
cation, “UN” marks,
or any combination
thereof required on
outer packaging of
hazardous materials

Identify the label(s). if any, that DOT requ ires a shipper to a ,x to eacder w ater.
1-pound bottles of solid white elemental phosphorus submerged un . dix c w e determine t hat the label codes for white
Solution: By reference to the entry in column 6 of App~n I rh entries mean that DOT requires the shipper elemental phosphorus under water are 4.2 and 6-1, respective y. h es~ ·or surface of each fiberboard box. These
to affix SPONTANEOUSLY COMBUSTIBLE and POISON labels on t e e en ther than the bottoms) of each

box

labels must appear side by side on the surface of two of the sides or ends (o ·

6.5 DOT MARKING REQUIREMENTS
DOT requires several markings, or marks, to be written o~ affixed on packaging contain-
ing a hazardous material when it is offered for transportation. Some markings are written
precautionary statements like the expressions “!NHALATI~N HAZARD” or “MOL-
TEN ALUMINUM”; other markings resemble labels with p1ctograms with or without
written precautionary statements.

There are rwo general types of these markings. The first type, called the specification
marking, is provided by the manufacturer of the packaging. In compliance with DOT regu-
lations, the manufacturer marks certain information on packaging before it is used by ship-
pers or carriers. It usually consists of professionally printed information on an outer
exterior surface of the packaging indicating that the packaging was constructed and tested
in compliance with applicable DOT specifications and standards. The specification mark-
ing also includes the name and address or symbol of the packaging manufacturer or
approval agency and the letters and numerals that identify the standard or specification,
DOT’s requirements relating to specification marking for gases transported in cylinders
and rail tankcars were previously reviewed in Sections 3.3-B and 3,7-A, respectively.

The second type of marking requires shippers and carriers of hazardous materials to
legibly mark certain other information on an outer exterior surface of the packaging
used for shipment. These markings are written in English and are displayed on the pack-
aging, unobstructed by the presence of labels, advertising, and other information. In
particular, DOT requi~es shippers to mark on an outer exterior surface of nonbulk pack-
aging certain informauon published at 49 C.F.R. § 172,301. This information consists of
the ~ame _and address of the shipper and receiver and the proper shipping name and UNI
NA 1dent1ficat1on number of the hazardous material When the p h ‘ · me in
the hazardous materials table is designated by an n s entry DOroTper s _ippinhg_ na s to · · · , requires s 1pper

194 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

mark the outer exterior su f
. h . r ace of the k .
m parent eses immediately folio . Pac aging with the tech .

Some commonly encounr dwmg or below the prope hi meal name of the material
hazardous materials are pro e~e d DOT marking requirem r s f Pmg _name.
through 6.5-M, and Sections ~’5 eO in the sections that im;n~~

0 ~ s~ippers and carriers of
bulk packaging, respectively s· – . \hrough 6.5-W address th: ;ate_y allow. Sections 6.5-A
divisions 1, 6.2, and 7 are n~re~~c,a marking requirements app~qu~tmen~s for nonbuJk and

ater, in Sections 15.4-D 10 2 ca e to azard classes and
‘ · l-D, and 16.10-C, respectively 6.5-A MARKING NONBULK .

PERFORMANCE TEST PFAE CKAGING TO DENOTE
. . ATURES In comphance with global ha . .

49 C FR § 178 503 rmomzation (Secti 1 9)
. : · · · to provide the followin on · ‘ DOT requires manufacturers at
mgs m the presemed sequence on nonbuJk g performance-oriented specification mark-
solid hazardous materials: outer packaging used to transport liquid and

The “un” mark shown in th 1 f . . h’ . I e e t margm (the lo I
Wit ma circ e) or the capital let UN wercase etters u and n inscribed A k . ‘d ters ,

pac agmg I entification code designatin th
from which It was constructed Th· d . g e type of package and the material
letter, and second number in th: Is co e IS a combination of a first number capital
0 f 15 sequence Their si · f · • ‘ ne o the capital letters X y z h. . gm Icance JS provided in Table 6.6.
dard for which the packagi~g ~o: ‘eac fuolflwh,ch designates the performance stan-

a success Y tested as follows·
X For packages meeting PG I, PG II, and PG III res;, .
Y For packages meeting PG II and PG III tests
Z For packages meeting PG IJJ tests only
A designation of t_he spe~ific gravity of liquids, or the mass in kilograms of solids for
which the packaging design has be~n successfully tested without an inner lining ‘
The lette~ S ~or smgle and composite packaging intended to contain liquids, the rest
pressure m kilopascals rounded to the nearest 1 O kilopascals of the hydrostatic pres-
~ure test that the_ pack_aging design type has successfully passed, and for packages
intended to contam sohds or inner packagings
The last two digits of the year during which the package was manufactured
The letters USA indicating that the package was marked pursuant to DOT’s standards
The symbol and identification number of the manufacturer

When the packaging and its contents weigh more than 66 pounds (30 kg), the mark-
ings are applied on an exterior surface of the top and a side of the packaging; otherwise
they appear on the bottom of the packaging. They may be applied on a single line or mul-
tiple lines, and slash marks are generally used to separate the information into sections.
Examples of these markings are provided in Figure 6.8.

Suppose 110 pounds (50 kg) of cupric cyanide is transported within several glass
bottles that are individually cushioned in a fiberboard box. DOT requires the specifica-
tion markings shown in Figure 6.9 to be embossed on an exterior surface of the box, the
majority of which are provided by its manufacturer.

6.5-B MARKING CYLINDERS CONTAINING COMPRESSED GASES
AND LIQUEFIED COMPRESSED GASES

We noted in Section 3.3-B that DOT requires gas cylinders to be marked so as to identify
their service pressures. Jn addition, DOT requires_ gas cylinder~ to be periodically_ tested
and retested to determine their mechamcal mtegnty by authonzed _per~ons. As wah the
service pressures, the results of these testing activities and the 1dent1hcat10n number of the
tester and retester must be marked on the outside surfaces of the cylinders.

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders ‘ 195 j

i!&ii-MH&i-1rwrw:r::w-2m1nw:rear:w:r: · · TABLE 6.6
CODEA.b MEANING

CODE MEANING
woven plastic bag, water-resistant –

1A1 Steel drum, nonremovable head
SH3 –

1A2 Steel drum, removable head
SH4 Plastic film bag

Textile bag, unlined or noncoated
–

1B1 Aluminum drum, nonremovable head
SL 1 –

1B2 Aluminum drum, removable head
SL2 Textile bag, silt-proof

1D Plywood drum
SL3

Paper bag, water-resistant –
1G Fiber drum

SM1 Paper bag, multiwall

1H1 Plastic drum, nonremovable head
SM2

Paper bag, multiwall water-resistant

1H2 Plastic drum, removable head
6HA1

Plastic receptacle within a protective steel drum

1N1 Metal drum, nonremovable head
6HA2

Plastic receptacle within a protective steel crate or box

1N2 Metal drum, removabale head
6HB1

Plastic receptacle within a protective aluminum drum

2C1 Wooden barrel, bung type 6HB2
Plastic receptacle within a protective aluminum crate or

box

2Q Wooden barrel, slack type, removable head 6HC
Plastic receptacle within a

protective wooden box

3A1 Steel jerrican, nonremovable head 6HD1
Plastic receptacle within a

protective plywood drum

3A2 Steel jerrican, removable head 6HD2
Plastic receptacle within a protective plywood box

3B1 Aluminum jerrican, nonremovable head 6HG1
Plastic receptacle within a protective fiber drum

3B2 Aluminum jerrican, removable head 6HG2
Plastic receptacle within a protective fiberboard box

3H1 Plastic jerrican, nonremovable head 6HH1
Plastic receptacle within a protective plastic drum

3H2 Plastic jerrican, removable head 6HH2
Plastic receptacle within a protective plastic box

4A Steel box 6PA1
Glass, porcelain, or stoneware receptacles within a
protective steel drum

4B Aluminum box 6PA2
Glass, porcelain, or stoneware receptacles w ithin a
protective steel crate or box

4C1 Wooden box, ordinary 6PB1
Glass, porcelain, or stoneware receptacles within a
protective aluminum drum

4Q Wooden box, silt•proof walls 6PB2
Glass, porcelain, or stoneware receptacles within a
protective aluminum crate or box

4D Plywood box
6PC Glass, porcelain, or stoneware receptacles within a

protective wooden box

4F Reconstituted wooden box
6PD1 Glass, porcelain, or stoneware receptacles within a

protective plywood drum

4G Fiberboard box 6PD2
Glass, porcelain, or stoneware receptacles within a
protective wickerwork hamper

4H1 Plastic box, expanded 6PG1
Glass, porcelain, or stoneware receptacles within a
protective fiber drum

4H2 Plastic box, solid 6PG2
Glass, porcelain, or stoneware receptacles within a
protective fiberboard box

SH1 Woven plastic bag, unlined or uncoated 6PH1 GlasS, P?rcelain, or stoneware receptacles within a protective expanded plastic packaging

SH2 Woven plastic bag, silt•proof 6PH2 Glass, P?rcela!n, or stoneware receptacles w ithin a
protective solid plastic packaging

‘ 49 c.F.R. §§178.504-178.521.
b49 C.F.R. §§178.522 and 178.523.

196 ency esponders Chapter 6 Use of the DOT Hazardous Materials Regulations by Emerg R

1 = Drum
A= Steel
1 = Tighthead

Year of
Manufacture

Specific Gravity of
Liquid Manufacturer’s DOT Registration Number

Packing Group

Packing Group

(ROI COPPER CYANIDE
UN1587

(al

(bl

From: ___ _ (ii) 4G/Y50/S/09/USA/RA
To:

Country of
Manufacture

Manufacturer’s DOT
Registration Number

Country of
Manufacture

FIGURE 6.9 This outer package is a fiberboard box used as PG II packaging for transporting glass bottles con-
taining copper cyanide, the proper shipping name for cupric cyanide. “RO” must be included with the proper
shipping name, because the reportable quantity for th is commodity is 10 pounds. “4G” is provided in Table 6.6
as the UN identification code for a fiberboard box; “Y” designates the performance standard to determine
whether the box retained its integrity when 50 kilograms of material was contained therein and subjected to
packaging performance tests for Packing Group II; “S” designates that cupric cyanide is a solid; “09” means the
box was manufactured in 2009; and “USA/RA” designates that the box was manufactured in the United States
and marked pursuant to DOT standards by “RA, ” the symbol of the box’s manufacturer. DOT also requires the
shipper to affix the MARINE POLLUTANT mark and POISON labels to the box.

FIGURE 6 .8 Examples of
package identification
markings embossed on
(a) a steel tighthead drum
containing a liqu id
chemical product and
(b) an openhead plastic
drum containing a solid
chemical product.

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 197

I I I

I
I

limited quantity (Ltd
Qty) For purposes of
DOT regulations, the
maximum amount of a
specific hazardous
material for which there
may be labeling or
packaging exceptions

6.5-C MARKING NONBULK PACKAGING CONTAINING
HAZARDOUS SUBSTANCES

When shippers transport a hazardous substance in nonbulk packaging in an amount h
exceeds its reportable quantity DOT requires them to mark the outer exterior surf

I
at

the packaging with the letters’ RQ in _associ~tion_ with the proper shipping name. teth!
proper shipping name does not specifically 1dent1fy the hazardous substance, DOT I
requires them to indicate the name of the hazardous substance on the packaging in pa a so
theses in association with the proper shipping nam~- If more t~an. one hazardous :~~:
stance is contained within the packaging, DOT reqmre~ _them to indicate at lease the two
hazardous substances with the lowest reportable quannnes.

6.5-D MARKING NONBULK PACKAGING CONTAINING HAZARDOUS
MATERIALS THAT POSE AN INHALATION HAZARD

When shippers offer for transportation in nonbulk packaging a hazardous material tha
poses a health hazard by inhalation, DOT requires them at 49 C.F.R: § 172.102.13 1;
mark “INHALATION HAZARD” in association with the proper shipping name and
identification number.

INHALATION
HAZARD

6 .5-E MARKING NONBULK PACKAGING CONTAINING CLASS 6
HAZARDOUS MATERIALS

When a poisonous material is transported within nonbulk plastic packaging, DOT
requires shippers to permanently mark the packaging with the word “POISON.”

POISON

6 .5-F MARKING NONBULK PACKAGING CONTAINING LIQUID
HAZARDOUS MATERIALS OTHER THAN LIQUEFIED
COMPRESSED GASES

When shippers transport liquid hazardous materials other than liquefied compressed
gases in nonbulk packaging, DOT requires them at 49 C.F.R. § 172.312 to assure that the
closure is upward, and that the packages are marked with package orientation markings
on the outer exterior surface of the packaging on two opposing sides with arrows point-
ing in the correct upright direction, as shown in the following illustration:

THIS END
UP

tt
6.5-G MARKING NONBULK PACKAGING CONTAINING A LIMITED

QUANTITY OF A HAZARDOUS MATERIAL FOR SHIPMENT BY
RAIL OR AIR

DOT authorizes the transportation of certain hazardous materials in a limited quaotitY
{Ltd Qty) by passenger-carrying aircraft, rail, or cargo aircraft. DOT provides this auth0-
rization in column (9) of the Hazardous Materials Table published at 49 C.F.R. §172JOl,

198 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

When the tramportation of a hazardous material is authorized in a limited quantity
by rail, DOT requ1res the shipper at 49 C.F.R. §172.315 to mark its package on at least
one side and one e_nd a~ show~ on the left below. When the transportation of a hazardous
material 1s authorized m a hm1ted quantity by passenger-carrying or cargo aircraft, DOT
requires them to mark the package on at least one side and one end as shown on the right.

The top and bottom triangular portions of both markings, their borders, and the let-
ter Y are black and their centers are white.

6.S·H MARKING NONBULK PACKAGING REQUIRING A SPECIAL PERMIT
When DOT assigns a special permit to a shipper to containerize a hazardous material in
an unconventional fashion, it requires the shipper to mark the packaging with the nota-
tion “DOT-SP-” followed by the assigned special permit number.

6.5·1 MARKING NONBULK PACKAGING CONTAINING
HAZARDOUS WASTES

When an RCRA-regulated hazardous waste (Section 1.3-C) is transported in containers hav-
ing a capacity of 119 gallons (450 L) or less, EPA requires the hazardous waste generator to
affix the HAZARDOUS WASTE marking in Figure 6.10 on an outer surface of the containers.

6.5-J MARKING NONBULK PACKAGING OF MARINE POLLUTANTS
OR SEVERE MARINE POLLUTANTS

When shippers intend to transport a marine pollutant or severe marine pollutant by water-
craft in nonbulk packaging, DOT requires them to affix the marine pollutant mark shown in
Figure 6.11 on an outer exterior surface of the packaging along with the following information:

I When the proper shipping name does not specifically identify the name of the marine
pollutant, DOT requires them to indicate the name on the packaging in parentheses
in association with the proper shipping name.

HAZARDo_u_s_1
WASTE

STATE & FEDERAL LAW PROHIBITS IMPROPER DISPOSAL.
IF FOUND, CONTACT THE NEAREST POLICE OR PUBLIC SAFETY

I AUTHORITY OR THEUS. ENVIRONMENTAL PROTECTION AGENCY I
OR THE CALIFORNIA DEPARTMENT OF TOXIC SUBSTANCE/$ CONTROL

GENERATOR INFORMATION:

:~~!es_s __ -_-_-_-_-_-_-_-_-::._-::._-_-_-_-_-_-_-:-c–cPHON=::-, ==========
CITY _________ STATE_ ZIP ____ _

I ~~o./~~NO. ————–1 EPA CA. ACCUMUI.ATION WASTE NO. ____ WASTE NO. ___ START DATE ___ _ I CONTENTS COMPOSmON PHYSICAL STATE I HAZARDOUS PROPERTIES D FLAMMABLE TOXIC I SOLID D LIQUID D CORROSIVE D REACTIVITY D OTHER —-
1, [

I HANDLE WITH CARE! .._ ___ co_NTAINSHAZAR-~oo-u.s .. o_R_TOXI __ C~-

FIGURE 6 .10 When a
container having a capac-
ity of 119 gallons (450 L)
or less is used to transport
hazardous wastes (Sec-
tion 1.3-C), DOT and EPA
require their generators at
40 C.F.R. §262.32 to affix
this HAZARDOUS WASTE
marking on the containers
together with the genera-
tor’s name and address
and the relevant manifest
number.

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 199

I I
11

overpack For pur

–

poses of DOT regula-
tions, an enclosure
other than a transport
vehicle, freight con-
tainer, or aircraft unit-
loading device that i

s

use

d

by a single con-
signor of a hazardous
material to provide pro-
tection or convenience
in handling or to con-
solidate two or more
packages of hazardous
materials

excepted quantit

y

For purposes of DOT

regulations, an auth-
orized amount of a
hazardous material in
certain hazard classes
that may be offered fo

r

transportation in accor-
dance with regulations
published at 49 C.F.R.
§ 173.4

FIGURE 6.11 When a marine pollutant is offered for transp_ortation in nonbulk packaging by watercraft or
bulk packaging by any mode, DOT requires shippers and earners at 49 CF.R: § 17

2322
to poS

t
this MARINE

POLLUTANT marking on its packaging. The pictogram on this DOT marking is identical to t_he GHS Environment
(Aquatic Toxicity) pictogram shown in Table 1.2. It displays a dead tree and dead fish, and is printed in black on a
white background or other contrasting color.

If two or more marine pollutants are contained within packaging, DOT requires shippers
to indicate parenthetically at least the two components most predom_ina~tly contributing
to the marine pollutant designation in association with the p~oper shipping name:
When a nonbulk container is inserted into a transport vehicle or freight contamer for
shipment by watercraft, shippers must affix the MARINE_POLLUTANT marking on
each side and end of the transport vehicle or freight container.
When DOT has not listed a marine pollutant in the Hazardous Materials Table at 49
C.F.R. §172.101 and when the marine pollutant does not meet the definition of any class
1 through 8 material, DOT requires shippers to designate by either of the following class
9 entries, as relevant: “UN3082, Environmentally hazardous substance, liquid, n.o.s., 9,
PG II” or “UN3077, Environmentally hazardous substance, solid, n.o.s., 9, PG ill.”

6.5-K MARKING OVERPACKED NONBULK PACKAGING
To provide protection or convenience in handling hazardous materials, DOT allows a sin-
gle consignor to overpack two or more nonbulk packages on a pellet and secure them by
strapping, shrink-wrapping, or placement in a box or crate. When the overpacked consign-
ment is offered for transportation, DOT requires the consignor at 49 C.F.R. § 173.25(a)(4)
to mark the packaging with the word OVERPACK on an outer exterior surface.

OVERPACK

The packaging must also be marked with the proper shipping name, identification
number, and orientation arrows, when applicable, and be labeled as required for each
hazardous material contained therein.

6.5-L MARKING NONBULK PACKAGING CONTAINING
AN EXCEPTED

QUANTITY

DOT ~!lows hazardous materials in certain hazard classes to be shipped as excepted
q_uant1tres. T~ese are v~ry smaH amounts that a shipper may offer for transportation by a
given mode without being sub1e~ted to DOT’s shipping paper, label, and placard require-
ments. When an excepted quantity of a hazardous material is offered for transportation,
DOT_ requires its shipper at 49 C.F.R. § 173.4(g) to affix the EXCEPTED QUANTITY
marking shown at the top of the following page or on an outer exterior surface of the
packaging. The * and * are used to identify the relevant hazard class/division number
and the name of the shipper or consignee, respectively. The crosshatched border and pic-
togram are red on a white back~round. The lettering for the specific hazard class/division
number and the name of the shipper or consignee are printed in black.

200 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emerge R d ncy espon ers

6.5-M MARKING ~ONBULK PACKAGING CONTAINING ORM-DS
When a material classified as ORM-D is ff d f
Pers to mark its nonbulk packaging . h oh ere or transportation, DOT requires ship-wit t e “ORM D” d . . I d . h. angle. When the package is intend d f hi · . esignat10n pace wit ma rect-
changed to “ORM-D-AIR.” e ors pment by air, the “ORM-D” designation is

[ ORM-D

J

[ ORM-0-AlR

I

DOT requires shippers to mark “ORM” or “ORM DAIR,

, I

I
· d d h . – – , as re evant, on at east one side an one en on t e surface of their packag1·ng or h d on an attac e tag.

6.5-N MARKING ALL FORMS OF BULK PACKAGING CONTAINING
HAZARDOUS MATERIALS

At 49 C.F.R. §1 ‘.2.30_2(a), DOT requires carriers to mark bulk packaging containing a
hazardous material with the relevant identification number on each side and each end if
the packaging has a capacity of 1000 gallons (3785 L) or more, or on two opposing sides
if the packaging has a capacity less than 1000 gallons (3785 L).

6.5-0 MARKING TRANSPORT VEHICLES AND FREIGHT
CONTAINERS LOADED WITH HAZARDOUS MATERIALS
IN NONBULK PACKAGING

When an aggregate gross weight of more than 8820 pounds (4000 kg) of a single
hazardous material in nonbulk packaging is loaded at one facility and is to be trans-
ported in a transport vehicle or freight container, DOT requires the carrier at 49 C.F.R.
§172.30l(a)(3) to mark the transport vehicle or freight container on each side and
each end with the proper shipping name and identification number of the hazardous
material.

When an aggregate gross weight of more than 2205 pounds (1000 kg) of a single
hazardous material in hazard class 6.1, Zones A or B, is loaded at one facility and is to be
transported in a transport vehicle or freight container, DOT requires the carrier at 49
C.F.R. § l 72.313(c) to mark the packaging with the identification number of the material
on each side and each end if the packaging has a capacity equal to or greater than 1000
gallons (3785 L); or on two opposing sides if the packaging has a capacity of less than
1000 gallons (3785 L).

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 201

I elevated-temperatu re material For pur-
poses of the DOT regu-
lations, a hazardous
material that when
offered for transporta-
tion or transported in a
bulk packaging exists as
a liquid at a tempera-
ture equal to or greater
than 212°F (100°C); a
liquid with a flashpoint
equal to or greater
than 100°F (37.8°C) that
is intentionally heated
and offered for trans-
portation or trans-
ported at or above its
flashpoint; or a solid at
a temperature equal to
or greater than 464°F
(240°C)

6.5-P MARKING FREIGHT CONTAINERS CONTAINING FUELED ITEIVJs
To draw attention to the potential for explosive ignition, DOT requires shippe
carriers at 49 C.F.R. § 176.905 to mark freight containers holding a motor veh~:1:nd mechanical equipment with fuel in its tanks. The EXPLOSIVE-MIXTURE marki~r
resembles the following: g

WARNING
MAY CONTAIN EXPLOSIVE MIXTURES

WITH AIR
KEEP IGNITION SOURCES AWAY

WHEN OPENING

6 .5-Q MARKING BULK PACKAGING CONTAINING HAZARDOUS
MATERIALS THAT POSE AN INHALATION

HAZARD

When shippers transport in bulk packaging a hazardous material that poses a health haz.
ard by inhalation, DOT requires them at 49 C.F.R. § 172.102.13 to mark the words
INHALATION HAZARD on two opposing sides of the bulk packaging.

INHALATION
HAZARD

6.5-R MARKING BULK PACKAGING CONTAINING
ELEVATED-TEMPERATURE MATERIALS

The DOT regulations refer to an elevated-temperature material as any of the following:

A liquid at a temperature equal to or greater than 212°F (100°C);
A liquid with a flashpoint equal to or greater than 100°F (37.8°C); or
A solid at a temperature equal to or greater than 464°F (240°C)

When carriers transport bulk packaging containing an elevated-temperature material by
highway or rail, DOT requires them at 49 C.F.R. §172.325 to display the HOT marking
shown below on two opposing sides of the packaging. For example, when they transport
a liquid whose identification number is 3256, they post the following HOT marking
together with an orange panel displaying the liquid’s identification number and a
FLAMMABLE placard:

0 3256
DOT designed the HOT marking as a white square-on-point diamond with black letter-
ing and border.

DOT also allows carriers to post the identification number of the elevated-temperature
material on a HOT marking within a hatched rectangle below the word HOT in_ a whi~e
square-on-point diamond, or at the upper corner of the same square-on-point diarnon ·
For example, a liquid whose identification number is 3256 may be transported with the

202 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

following HOT marking that displays the liquid’s identification number and a
FLAMMABLE placard:

HOT

i_32-56J

6.5-S MARKING BULK PACKAGING CONTAINING MARINE
POLLUTANTS OR SEVERE MARINE POLLUTANTS

When carriers transport a marine pollutant or severe marine pollutant in bulk packaging
by any mode, DOT requires them to affix the MARINE POLLUTANT marking on at
least two opposing sides or two ends other than the bottom if the packaging has a capac-
ity of less than 1000 gallons (3785 L), or on each side and each end if the packaging has
a capacity equal to or exceeding 1000 gallons (3785 L). When carriers transport a bulk
quantity of a marine pollutant or severe marine pollutant in a transport vehicle or freight
container, DOT requires them to mark “MARINE POLLUTANT” on each of its sides
and ends.

6.5-T MARKING EMPTIED BULK PACKAGING THAT CONTAINED
HAZARDOUS MATERIALS

DOT requires at 49 C.F.R. §172.302(d) bulk packaging that has been marked with a
proper shipping name, common name, or identification number to remain marked when
it is emptied unless it is sufficiently cleaned of residue and purged of vapors to remove any
potential hazard, or refilled with a material requiring different markings or no markings,
such that any residue remaining in the packaging is no longer hazardous.

6.5-U MARKING PORTABLE TANKS CONTAINING
HAZARDOUS MATERIALS

When a hazardous material is transported in a portable tank, DOT requires shippers at
49 C.F.R. § 172.326 to mark the portable tank on two opposing sides with the proper
shipping name of its contents. For example, when a solution of a metallic hypochlorite
(Section 11.6) is transported in a portable tank, DOT requires the tank to be marked in
the following manner:

HYPOCHLORITE SOLUTION

6.5-V MARKING BULK PACKAGING CONTAINING CERTAIN
HAZARDOUS MATERIALS FOR SHIPMENT BY HIGHWAY
OR RAIL

When transporting a hazardous material in bulk packaging by highway or rail, DOT
requires carriers at 49 C.F.R. §§ 172.332, 172.334, and 172.336 to identify the identifica-
tIOn number of the hazardous material by displaying it on each side and each end of the

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

I

I

I
I

I

I I

I

203

u

Ii

Ii

TABLE 6.7 ·-•-&•-‘de stabilized (less than 3% water)
Acrolein, stabilized

Hydrogen cyani

Ammonia, anhydrous, liquefied
Hydrogen fluoride

Ammonia solutions (more than 50%
Hydrogen peroxide, ~queous solutions (greater than

ammonia) 1
0% hydrogen peroxide)

Bromine or Bromine solutions
Hydrogen peroxide, stabilized

Bromine chloride
Hydrogen peroxide and peroxyacetic acid mixtures

Chloroprene, stabilized
Nitric acid (other than red fuming)

Dispersant gas or Refrigerant gas
Phosphorus (amorphous)
Ph sphorus white dry or Phosphorus, white, under –

Division 2. 1 materials wa~er or Ph~sphorus white, in solution, or Phosphorus,
yellow dry or Phosphorus, yellow under water or
Phosphorus, yellow in solution

Division 2.2 materials (DOT-107 tank- Phosphorus, white, molten

cars only)
Division 2.3 materials

Potassium nitrate and sodium nitrate mixtures

Formic acid
Potassium permanganate

Hydrocyanic acid, aqueous solutions Sulfur trioxide, stabilized

Sulfur trioxide, uninhibited

•49 C.F.R. §172.330(a)(ii).

bulk packaging across the centers of placards, white square-on-point diamonds, or orange
panels as shown in (a), (b), and (c), respectively, of the following figure:

(a)
(c)

When transporting gasoline, the FLAMMABLE placard is placed adjacent to both the
orange panel and the white square-on-point diamond.

When carriers transport more than one hazardous material separately in compart-
mented portable tanks, cargo tanks, or tankcars, DOT requires them to display identifica-
tion numbers of the hazardous materials on the ends of the tank and on the sides in the
same sequence as the compartments containing the materials they identify.

When shippers transport a bulk quantity of the hazardous materials listed in 7 in a
tankcar by highway or railroad, DOT requires them to mark the key word from the appli-
cable proper shipping name on each side of the tankcar.

6.5-W MARKING BULK PACKAGING DURING OR FOLLOWING
THEIR FUMIGATION

When the lading in a railcar, freight container, truck body, or trailer has been fumigated or
is undergoing fumigation, DOT requires the carrier at 49 C.F.R. § 173.9 to display the
FUMIGANT marking shown in Figure 6.12 so it is observable when a person attempts to

204 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

DANGER

THIS UNIT IS UNDER FUMIGATION
WITH FUMIOANTNAME APPLIED ON

DATE ______ _
TIME ______ _

VENTILATED ON
DO NOT ENTER

FIGURE 6.12 A fumigant is a pesticide that is a
vapor or gas, or forms a vapor or gas on application,
and whose method of pesticidal action is through
inhalation of the gaseous state. DOT regards a rail
tankcar, freight container, truck body, or trailer in
which lading has been fumigated, or is undergoing
fumigation, as a package containing a hazardous
material. DOT requires carriers at 49 C.F.R. §173 .9(c)
to display this FUMIGANT marking in such a manner
that it may be readily observed by a person attempting
to inspect the lading. When a FUMIGANT marking is
displayed, DOT requires carriers to include on the
marking the name of the fumigant, the date and time
of fumigation, and the date on which ventilation
occurred . The printing may be either black or red on a
white background.

enter it or otherwise comes in contact with the fumigated lading. DOT also requires the
carrier to inscribe the technical name of the fumigant and the date and time of its applica-
tion on the face of the marking.

6.6 DOT PLACARDING REQUIREMENTS
DOT requires carriers at 49 C.F.R. §172.504 to display in plain view one or more warn-
ing placards on each side and each end of the bulk packaging, freight container, unit load
device, transport vehicle, or rail tankcar used to transport hazardous materials. These
DOT placards are illustrated in Figure 6.13. The features of the individual placards are
similar to those of the corresponding labels. Both are diamond-shaped and color-coded to
signify a specific hazard class or division and may also include a pictograph.

The following points regarding the nature of DOT labels and placards are relevant:

Although there is a COMBUSTIBLE placard, there is not an analogous label. Furthermore,
although there is an INFECTIOUS SUBSTANCE label, there is not an analogous placard.
The word GASOLINE may be used in lieu of the word FLAMMABLE on a placard that
is displayed on a cargo tank or a portable tank used to transport gasoline by highway.
The words FUEL OIL may be used in lieu of the word COMBUSTIBLE on a placard
that is displayed on a cargo tank used to transport fuel oil that is not classed as a
flammable liquid by highway.
When solely transporting oxygen, carriers may display OXYGEN placards
(Section 7.1 -F) in lieu of NON-FLAMMABLE GAS placards. There is not an analo-
gous OXYGEN label.
As with the EXPLOSIVE labels, the uppercase letters that follow the division designa-
tions for the EXPLOSIVES placards are examples of the designations for the compat-
ibility groups of explosives, whose nature is discussed in Section 15.4-B.

Although shippers and carriers are mutually responsible for the choice of the placards
that are displayed on transport vehicles, the carriers typically bear the responsibility for post-
mg them; i.e., shippers and carriers select the applicable placar~s by _referring to the codes
listed in column 3 of the Hazardous Materials Table, and the earners display them as follows:

Carriers always display the applicable placards when transporting materials whose
hazard classes are listed in Table 6.8, regardless of the amounts transported. For example,
carriers display RADIOACTIVE placards on each side and each end of a motor van used
to transport wooden boxes on which RADIOACTIVE YELLOW-III labels have been af-
fixed , regardless of the amount of hazard-class-? material in the boxes.

fumigated lading A
material in transit or
intended for transpor-
tation, such as grain,
that has been treated
with a fumigant to
destroy rodents, insects,
and germs

placard For purposes
of DOT regulations, a
sign displayed by the
carrier on bulk packag-
ing, freight containers,
transport vehicles, unit
containment devices, or
railcars to rapidly com-
municate hazard infor-
mation relating to the
hazardous material
being transported

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 205

HAZARD CLASS 1

EXPLOSIVES 1.1 EXPLOSIVES 1.2 EXPLOSIVES 1.3 EXPLOSIVES 1.4 EXPLOSIVES 1 ·5 EXPLOSIVES 1.6 EXPLOSIVES
SUBSIDIA~y

HAZARD CLASS 2 HAZARD CLASS 3

•

•

FLAMMABLE NON-FLAMMABLE POISON GAS FLAMMABLE COMBUSTIBLE

GAS GAS

HAZARD CLASS 4 HAZARD CLASS 5

FLAMMABLE SPONTANEOUSLY DANGEROUS OXIDIZER ORGANIC
PEROXIDE SOLID COMBUSTIBLE WHEN WET

HAZARD CLASS 6

POISON

INHALATION

HAZARD
POISON

HAZARD CLASS 7

RADIOACTIVE

HAZARD CLASS 8 HAZARD CLASS 9

CORROSIVE

CORROSIVE CLASS 9

FIGURE 6 _ 1 3 When carriers transport hazardous materials, DOT requires them to post warning placards on their bulk packaging. The placard
at the far right in Hazard Class 1 is the EXPLOSIVES subsidiary placard. It is posted on bulk packaging when the number 1 is listed in column 6
of the Hazardous Materials Table as a subsidiary hazard. The asterisks in the orange EXPLOSIVES placards are replaced by the compatibil ity
group (Section 15.4-B), or left blank if the explosive hazard is the subsidiary risk associated with the product.

Carriers display the applicable placards on the same transport vehicle when they
transport a material whose hazard class is listed in Table 6.9 and when the aggregate
gross mass of the hazardous materials in any one hazard class equals or exceed_s lOO!
pounds (454 kg) . For example, carriers display FLAMMABLE placards on each side an
each end of a rail boxcar used to transport steel drums containing acetonitrile, a flarnrna-
ble liquid, only when their aggregate gross mass equals or exceeds 1001 pounds (454 kg)f

When carriers transport multiple hazardous materials including at least one 0h
whose mass exceeds 1001 pounds (454 kg), they display the applicable placards for eac
hazardous material on the transport vehicle. For example, when carriers transport rnore
than 1001 pounds (454 kg) of acetonitrile with 500 pounds (227 kg) of sulfuric acid, a

206 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

TABLE 6.8 DOT Hazard Classes That Always Require Placardinga

HAZARD • R,AND
ADDITIONAL INFORMATION

CLASS NUMBER DIVISION NUMBE

–
1.1 -1.2
1.3 -2.3
4.3
s.2 (Organic peroxide, Type B, liquid or solid, temperature-
controlled)
6.1 (Inhalation hazard, Zone A or B)

7 (RADIOACTIVE YELLOW-Ill label only)b
•49 c.F.R. §172.504, Table 1.
bsection 16.10-B.

PLACARD NAME

EXPLOSIVES 1. 1
EXPLOSIVES 1.2

EXPLOSIVES 1.3

POISON GAS

DANGEROUS WHEN WET

ORGANIC PEROXIDE

POISON INHALATION HAZARD

RADIOACTIVE

corrosive material, DOT requires them to display both FLAMMABLE and CORROSIVE
placards on each side and each end of the transport vehicle.

When carriers transport one or more hazardous materials in a placarded motor ve-
hicle, DOT requires the operator of the vehicle to have been issued a commercial driver ‘s
license with a hazardous materials endorsement, the standards of which are provided at
49 C.F.R. §383.121. These standards largely require that the driver know the hazardous
materials regulations.

TABLE 6.9 DOT Hazard Classes That Require Placarding Only Under Certain Conditionsa

HAZARD CLASS NUMBER, DIVISION NUMBER,
AND ADDITIONAL INFORMATION PLACARD NAME

1.4 EXPLOSIVES 1.4

1.5 EXPLOSIVES 1.5

1.6 EXPLOSIVES 1.6

2.1 FLAMMABLE GAS

2.2 NON-FLAMMABLE GAS

3 FLAMMABLE

Combustible liquid COMBUSTIBLE

4.1 FLAMMABLE SOLID
4.2 SPONTANEOUSLY COMBUSTIBLE

~-1 OXIDIZER
5.2 (other than organic peroxide, type B, liquid or solid, ORGANIC PEROXIDE
~ mperature-controlled)

1 (other than inhalation hazard, Zone A or Zone B) POISON

~ 2 (None)
8 CORROSIVE
9 CLASS 9
0RM-D (None)
• 49 C.F.R. §172.504, Ta ble 2.

hazardous materials
endorsement • For
purposes of DOT regu-
lations, a recognition by
the U.S. Transportation
Security Administration
that an applicant has
knowledge of the stan-
dards published at 49
C.F.R. §383.121 and is
unlikely to pose a secu-
r ity risk when transport-
ing hazardous materials
in a placarded motor
vehicle

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 207

I
I

Identify the placard(s), if any, that DOT requires a carrier to display on a motor van used to transport six cyli
of compressed fluorine gas, each of w hich weighs 2.5 pounds. nders

Solution: By referring to the entry in column 3 of Appen?ix C, we determin~ that the hazard class fo
pressed fluorine is 2.3 . By referring to Table 6.8, we determine_ tha_t when a earner tra_nsports hazardousr corn.
rial whose hazard class is 2.3, placarding of the t_ransport vehicle 1s always required, irrespective of the arnrnate.
transported . Consequently, DOT requires the earner to display POISON GAS placards on each side and each0Unt
of the transport vehicle. end

s

6.6-A PLACARDING REQUIREMENTS WHEN SHIPPING MULTIPLE
PACKAGES OF MATERIALS WHOSE HAZARD CLASSES ARE
LISTED SOLELY IN TABLE 6.9

When carriers transport multiple nonbulk packages containing materials requiring th
posting of several placards listed in Table 6.9, DOT permits at 49 C.F.R. §172.504 the
display of the DANGEROUS placard shown in the left margin in lieu of the separat:
hazard class placards.

However, DOT prohibits the use of DANGEROUS placards when an aggregate
gross mass equal to or exceeding 2205 pounds (1000 kg) of materials having a single
hazard class listed in Table 6.9 is loaded at a single location. In this instance, carriers are
obligated to display the applicable placards specified in Table 6.10 subject to the follow-
ing conditions:

When the hazardous materials in Table 6.10 are transported by highway or rail,
placards are not required when the transport vehicle or freight container contains less
than 1001 pounds (454 kg) of a hazardous material listed in Table 6.9.

When the hazardous materials are transported in a railcar loaded with transport vehi-
cles .or freight containers, none of which is required to be placarded, placards are not required.

DOT never allows carriers to display DANGEROUS placards in lieu of the required
placards when they transport hazardous materials whose hazardous class or division is
listed in Table 6.8; nor does DOT permit carriers to display UN/NA identification mun-
bers across the center face of any posted DANGEROUS placard.

A carrier loads nonbulk containers of the following hazardous materials into a rail boxcar for delivery frornh
chem ical warehouse to a customer’s plant site: 1500 pounds (682 kg) of acetone, 500 pounds (227 kg) of et_~
mercaptan, 500 pounds (227 kg) of barium cyanide, and 1000 pounds (454 kg) of methyl isobutyl ketone. WhiC
placards does DOT require the carrier to display on the boxcar?

. . cyanide,
Solution: We note from Appendix C that the hazard class codes of acetone ethyl mercaptan, banurn •,15 • aten°
and methyl isobutyl ketone are 3, 3, 6.1, and 3, respectively. The gross aggregate mass of the hazardous rn,arriers
in hazard class 3 is 1500 pounds + 500 pounds + 1000 pounds, or 3000 pounds. Because DOT authorizes ggre·
to display DANGEROUS placards on the boxcar in lieu of the separate hazard class placards only when the a hibits
gate gross mass of the materials in any one hazard class does not exceed 2205 pounds (1000 kg), DOT proh side
the carrier from displaying DAN GEROUS placards and requires the posting of FLAMMABLE placards on eacth 1ess
and each end of the boxcar. The posting of POISON placards is not required since the boxcar is loaded wi
than 1001 pounds (454 kg) of barium cyanide .

208 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

6,6-B PLACARDING FOR SUBSIDIARY HAZARDS

In rhe following
thr

e~ ~ircumStances, DOT requires carriers to display warning placards
to account for a subsidiary hazard in addition to displaying other required placards:

I When carri_ers transport a hazardous material whose subsidiary hazard is 2.3 or 6.1,
DOT reqmres them at 49 C.F.R. §172.505 to display POISON GAS or POISON
INHALATION HAZARD placards, as relevant on each side and each end of the
transport vehicle, freight container, portable tank: unit load device or railcar used for
transportation. This regulatory requirement applies to all hazardous materials that
pose an inhalation hazard, regardless of their unique hazard zones.

1 When carriers transport a hazardous material whose subsidiary hazard is dangerous-
when-wet, DOT requires them to display DANGEROUS WHEN WET placards on
each side and each end of the transport vehicle, freight container, portable tank, unit
load device, or railcar used for transportation.

1 When carriers transport 1001 lb (454 kg) or more of uranium hexafluoride (UF6),
DOT requires them to display CORROSIVE and RADIOACTIVE placards on each
side and each end of the transport vehicle, portable tank, or freight container used
for transportation. This subject is noted again in Section 16.9-D.

When a hazardous material possesses subsidiary hazards, DOT requires carriers to
display multiple placards to account for the subsidiary hazards. However, DOT prohib_its
them from displaying the UN/NA identification number across the center face of a subsid-iary hazard placard.

6.6-C SPECIAL PLACARDING REQUIREMENTS WHEN
HAZARDOUS MATERIALS ARE TRANSPORTED IN
SEPARATE COMPARTMENTED PORTABLE TANKS,
CARGO TANKS, OR TANKCARS

When carriers transport more than one hazardous _material in _separa~e compartme~ted
portable tanks, cargo tanks, or tankcars, DOT ~eqm_res the earner to display the applica-
ble placard on the ends of the tank and on the sides m t~e same sequence as the co~part-
rnents containing the materials they identify. On the sides, the placards are posit10ned
near the location of each compartment as shown in Figure 6.14.

· k · d to transport more than one hazardous material by FIGURE 6.14 When a multicompartment cargo tan is_ u:e lacard corresponding to each hazardous material
highway, DOT requires it s carri er to position the appropna ~p nt. On the two ends, DOT requires the carrier to
on the two sides near the location of each sepa rate comtpa mteaining the materials they identify. This three-Posit’ h . the compartmen s con 1· .

ion t em in the same sequence as I ort gasoline an ethanol and gaso ine mixture, compartment cargo tank is placarded to simultaneou~ ~~r~;:~rd class 3. B~cause these hazardous materials have
and denatured al cohol, each of which DOT designate ost only a single FLAMMABLE placard on each side and
Only a single hazard class, DOT requires the ca mer to p f Transporta tion Washing ton, DC. )
each end of the vehicle . (Courtesy of the U.S. Department O ‘ •

—– DOT Hazardous Materials Regulations by Emergency Responders 209 Chapter 6 Use of the

r

210

6 .6-D SPECIAL PLACARDING REQUIREMENTS WHEN HAZARDOUS
MATERIALS IN CERTAIN DIVISIONS ARE_ TRANSPORTED BY RAIL

. h d us materials in the followmg hazard classes by rail D
When earners transport azar O l 1 d ‘ 01’ . h

49
C FR §l72 510 to post the re evant p acar on a square hav·

requires t em at . • • · tng a
white background and black border:

Division 1.1 explosive materials
Division 1.2 explosive materials
Division 2.3 poisonous gases, Zone A . . . .
Division 6.1 poisonous materials, Zone A, to w~tch Packmg Gro~p I ts asst~ed
Division 2.1 flammable gases when transp~r~e_d ma DOT-113 rail tankcar, tncluding
tankcars containing only the residues of D1v1s10n 2.1 flammable gases.
By requiring the posting of these placards on a whi~e square wit? a black border,

DOT directs a railcar-switching crew to exercise extraordmary precautwn to prevent the
tankcar from being cut off while in motion. These five placards resemble the following:

i—-/ ~ “-

6.7 RESPONDING TO INCIDENTS INVOLVING THE
RELEASE OF HAZARDOUS MATERIALS

When shippers and carriers have correctly complied with the DOT regulations, the UN/
NA identification number of a hazardous material can be readily located during an
emergency-response action by any of the following means:

Listed on a shipping paper as a component of the shipping description of the hazard-
ous material
Marked on the packaging containing the hazardous material
Displayed on bulk packaging within an orange panel or across the center area of a
placard or a white square-on-point diamond
Having located the UN/NA identification number, how may first-on-the-scene respond-

ers use it during an incident involving the release of a hazardous material? The answer to this
question involves consulting the Emergency Response Guidebook (ERG).1 This is a D_~T
manual that primarily provides direction to emergency-response crews during the inittal
phases of a response action. OSHA and EPA require training for emergency responders
regarding ~e use of the ERG at 29 ~.F.R. §1910.120 and 40 C.F.R. Part 311, respective!\

The gwdebook serves as the pnmary reference book for first-on-the-scene personnel.
directs them to a guide, which provides suggested actions that should be considered during rhe
~itial r~sp_onse ph~se of a transportation mishap. When properly implemented, each_ guit~
listed within the gwdebook provides emergency-response personnel with vital inforrnatton .
h · · . 11 d 1 · h · ‘d rial o”‘: to IIlltla . e~ wit ~n 1~c1 en~ involving the release of a unique hazardous mate M·
until more specific informat10n 1s obtamed from the shipper, carrier, manufacturer, or CJ-IE!

1 ln the United States, the Emergency Response Guidebook is pr ‘d d f f h and local sa fe[)

‘

h

· ·
1

· I ·i bl f . ov1 e ree o c arge to state AdJi11o-
aut ont1es. t 1s a so ava1 a e rom private commercial compan ‘ th R h d S · I Programs” C · · d M . ies; e esearc an pec1a D
1stra t1on , Haza r ous atenals Transportation Bureau Us D f T · Washington, C
20590 h US G

. . , • . epartment o ransportation, 0 D
; t e . . overnment Prmtmg Office, Superintendent of D M •t SSOP Washingto ‘ ·

20
402 9328· d h Am . h . . • ocuments, at Stop , enc1es,

– , an t e encan C em1stry Councils Bookstore t (30l) 617 n!Tlenrag
request ISBN 0-16-042938-2. a -7842. From gover

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergenc R d y espon ers

TREC. Each guide provides information on the .
I h) public safety comments for f t- dpote?nal hazards of the situation (fire and hea t , trs respon ers (mmal mstr t. · I h” d vacuation) and emergency respo di . . uc ions, protective cot mg, an e ‘ ‘ nse rect1ons (fire spill O I k d f · d) The Emergency Response Guidebook . . ‘. r ea , an irst at .

ts organized mto the following sections:
YELLOW SECTION, is so called be · h 1

. · of the individual UN/NA idem· f . cause It as ye low-bordered pages. It provides a
hsung . 1 icauon numbers and the hazardous materials having these numbers. A guide number that refers the user to the O

5
• •

1
·d d

1 Th· • range ectton 1s a so prov, e .
is section has blue-bordered pages. It lists alphabetically

the names of the hazardous materials with their cor d. UN/NA “d “f· ·
L”k h y II S . respon mg I enu !Catton

numbers.
1
_ e t e e ow ectton, it provides a guide number that refers the user to the Orange Sectton.

P~GE Sl}CTION This section has orange-bordered pages. It contains 172
indiv1du_al gwde numb~rs, each of which constitutes a two-page summary of information
concernmg the potential hazards of the referenced hazardous material recommended
actions that relat~ to public safety, and _recommended emergency-respon;e actions to be
implemented dunng a transportat10n mishap involving the material in question.

. I . 1:his section has green-bordered pages. It provides initial isola-
tion ~nd _protecnve-act10n distances for small and large spills of hazardous materials that
are highlighted m the yellow and blue sections. “Small spills” refer to the release of the
contents from a smgle, small package (e.g., a small gas cylinder or a drum whose liquid
capacity is 55 gallons [208 L] or less) or a small leak from a large package. “Large spills”
consist of a spill from a large package (e.g., a rail tankcar, a highway tankcar or trailer, or
a ton-container) or multiple spills from many small packages. An exception applies to the
release of chemical warfare agents (Section 13.11 ), for which “small spills” include releases
up to 4.4 pounds (2 kg) and “large spills” include releases up to 55 pounds (25 kg).

The Green Section also provides container-specific guidance for first-on-the-scene re-
sponders relating to the release of the six most common toxic substances transported by rail
or highway. The containers are rail tankcars; highway tank trucks or trailers; multiple ton
cylinders; and multiple small cylinders or single ton cylinders. The toxic substances are chlo-
rine, hydrogen chloride, ammonia, hydrogen fluoride, sulfur dioxide, and ethylene oxide.

The guidebook should always be accessible for immediate use within emergency-
response vehicles, so that responding personnel may locate the appropriate guide number
and implement the recommended actions. DOT also requires shippers and carriers to
have emergency-response information available to workers during all phases of the trans-
portation of a hazardous material. This requirement is often met by having available a
copy of the Emergency Response Guidebook during hazardous material loading, unload-
ing, and transfer operations.

Suppose that information is needed concerning the appropriate response action to be
taken at a transportation incident involving an ini~ially unidentified hazardous material
being transported by motor carrier on a crowded highway. On arnvmg at the scene, pe~-
sonnel note that CORROSIVE placards are displayed on the exterior surface of the vehi-
cle, adjacent to which are orange panels in which the number 1805 is inscribed. On
securing the shipping paper from the driver, personnel also note that a number of items
not regulated by DOT are components of the consignment as well as a hazardous material
having the following shipping description:

UNITS

10 drums
(UNlAl)

HM

X

SHIPPING DESCRIPTION
(IDENTIFICATION NUMBER, PROPER SHIPPING NAME, PRIMARY
HAZARD CLASS OR OIVISION, SUBSIDIARY HAZARD CLASS OR

DIVISION, AND PACKING GROUP)

UN1805, Phosphoric acid solution, 8, PG 111

WEIGHT
(lb)

585

6 U f the DOT Hazardous Materials Regulations by Emergency Responders 211 Chapter se o

. ..,, _ _..

I I I

I
I

I
1,

1: I
J

I
I
I
I
I
I

FIGURE 6.15 Gwde

154

from Emergency Response
Guidebook (Washington,
DC: U.S. Department of
Transportation, 20 7 2),
pp. 246-247. (Counesy of
the U.S. Department of Trans-
portation, Washington, DC.)

··-

GUIDE SUBSTANCES • TOXIC
(NON-COMBUSTIBLE)

AND/OR CORROSIVE ERG2012

154

:
i

y

,;
,.

., ‘ ,.,
HEALTH

TOXIC; inhalation, ingestion or skin contact
Contact with molten substance may cause

with material may cause severe injury or death.
severe burns to skin and eyes.

Avoid any skin contact.
Effects of contact or inhalation may be dela
Fire may produce irritating, corrosive and/a
Runoff from fire control or dilution water m

yed.
rtoxic gases.

ay be corrosive and/or toxic and cause pollution.

FIRE OR ~ LOSIO!!J
Non-combustible, substance itself does not
and/or toxic fumes.
Some are oxidizers and may ignite combusti
Contact with metals may evolve flammable

burn but may decompose upon heating to produce co rrosive

bles (wood, pa per, oil, clothing, el c.).
hydrogen gas.

Containers may explode when heated.
For UN3171 , if Lithium ion batteries are invol ved, also consult GUIDE 147.

1!J11•

CALL EMERGENCY RESPONSE Telephone N
available or no answer, refer to appropriate

umber on Shipping Paper first. If Shipping Peper not
telephone number listed on the inside back cover.
late spill or leak area in all directions for at least 50 meters

As an immediate precauti onary measure, iso
(150 feet) for liquids and at least 25 meters (7 5 feet) lor solids.
Keep unauthorized personnel away.
Stay upwind.
Keep out of low areas.
Ventilate enclosed areas.

PROT! CTIVE CLOTHING
Wear positive pressure self-conta ined breat
Wear chemical protective clothing that is spe

hing apparatus (SCBAI.
cifica lly recommended by the manufacturer. It may provide

little or no thermal protection.
Structural fi refighters’ protective clothing pro
effective is spill situations where direct conta

vides limited protection in fire situations ONLY; it is not
ct with the substance is possible.

EVACUATION
Spill

See Table 1 • Initia l Isolation and Protective A
highlighted materia ls, increase, in the downwi

ction Distances fo r highlighted materials. For non·
nd direction, as necessary, the isolation distance shown

under “PUBLIC SAFETY”.
Fire

lf tank, rail car or tank truck is involved in a fir
consider initial evacuation for 800 meters (1/2

e, ISO LATE for 800 meters (1/2 mile) in all direclions: also,
mile) in all directions.

The orange panel and shipping descri pt
the hazardous material as UN1805 . T

ion provide the UN/NA identification number of
he shipping description also provides the precise
ed within the drums: phosphoric acid solution._
ook, the number 1805 directs the reader to Guide

name of the hazardous material contain
In the Emergency Response Guideb

154, which is reproduced in Figure 6.15. This guide number provides general informatio_n
ant, it notes that the hazardous material is toxic
Responders may then dismiss any concern as to

concerning this substance. Most import
and/or corrosive, but noncombustible.
whether the substance may ignite.

212 Chapter 6 Use of the DOT Hazardous Materials Regulation
s by Emergency Responders

ERG2012 SUBSTANCES • TOXIC AND/OR CORROSIVE
(NON•COMBUSTIBLEI

GUIDE
154

FIR.E
Small Fire
, Dry chemical, CO2 or water spray.
Large Fire

• I

• Dry chemical, CO2, alcohol-resistant foam or water spray.
• Move containers from fire area if you can do it without risk.
• Dike fire-control water for later disposal; do not scatter the material.
fire involving Tanks or Car/Trailer Loads

fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
Do not get water inside containers.
Cool containers with flooding quantities of water until well after fire is out.
Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from tanks engulfed in fire .

SPILL 01) LEAK
ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area).
Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.
Stop leak if you can do it without risk.
Prevent entry into waterways, sewers, basements or confined areas.
Absorb or cover with dry earth, sand or other non•combustible material and transfer to containers.
DO NOT GET WATER INSIDE CONTAINERS.

FIRST AID
Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Do not use mouth-to-mouth method ii victim ingested or inhaled the substance; give anificial
respiration with the aid of a pocket mask equipped w~h a one-wey valve or other proper
respiratory medical device.
Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes.
In case of contact with substance, immediately flush skin or eyes with running water for at least 20
minutes.
For minor skin contact, avoid spreading material on unaffected skin.
Keep victim warm and quiet.
Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed.
Ensure that medical personnel are aware of the matarial(s) involved and take precautions to protect
themselves.

SOLVED EXERCISE 6.6

When a firefighting team arrives at the scene of a highway transportation mishap, they encounter an overturned
moior van bearing POISON INHALATION HAZARD placards on its visible sides and ends. On cautiously examining the van’s interior from a distance they also observe broken boxes to w hich POISON INHALATION HAZARD labels
:~affixed. The boxes are marked “N ickel carbonyl, UN1259,” “INHALATION HAZARD, ZONE A/ and ” MARINE

LLUTANT.” Punctured cylinders of the hazardous material are scattered outside their protective boxes, and

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 213

. r of the van. securing the shipping paper from the d .
. . . t h ve spilled on the underlying fl~o . description of this consignment as follows: river,

their l1qu1d conten s a I t ortion of the shipping
the team captain notes the re evan P

PING DESCRIPTION SHIP PROPER SHIPPING NAME,
(IDENTIFICATION NU~::oR DIVISION, SUBSIDIARY WEIGHT

–

– ~~’.__J ~ ~ -:-:-~P~R~IM~A~R~Y~H~AZA;~RD~C~IV;IS~IO~N0A~NilD( PP

. ed b these first-on-the-scene responders?
What precautionary actions should be implement y . . . . . . . r marking, and placarding 1nformat1on, the team memb
Solution: From the sh1pp1ng description, lab~;n~: ‘d Because the liquid is not confined within its containers
learn that nickel carbonyl is a toxic and ~a~::n ~nd fire. To protect public health and the environm:~·
its vapor poses a pronounced nskffofhin a a d·rect the public from the scene, and prevent entrance of the liqu·d’
they should 1mmed1ately cordon o t e area, 1 . h’ t · I 8 d

1
. E th h the total quantity of this nonbulk s 1pmen 1s on Y poun s, emergency.
into a waterway or sewer. ven oug . f · d b th ‘

I h Id don total enc
apsulating suits with sel -conta1ne rea 1ng apparatus. Only then

response personne s ou · . should they remove the intact boxes from the van and set them aside . For more specific guidance in responding to this incident, CHEMTR_EC should be contacted. _The team mem-
bers should also consult the Emergency Response Guidebook for immediate ass1st~nce. The ident1f1cat1on number
1259 refers the responders to Guide 131 . Here, personnel are_ provided With d_irections s_uch as absorbing the
spilled liquid and eliminating all potential sources of ignition. Guide 131 also provides first-aid information to help
the responders who experience ill effects from inadvertent exposure to nickel carbonyl vapor. –
6.8 REPORTING THE RELEASE OF

A HAZARDOUS SUBSTANCE
At 40 C.F.R. §302.6, EPA uses the legal authority of CERCLA to require persons in
charge of facilities (including transport vehicles) to notify the National Response Center
(NRC) (Section 1.13) when a hazardous substance has been released into the environment
in an amount equal to or greater than its reportable quantity within a 24-hour period. At
40 C.F.R. §110.3, EPA uses the legal authority of FWPPCA to require persons in charge
of facilities to notify the NRC when oil is released into a waterway or when the release of
oil may affect the quality of a waterway based on use of the following criteria:

The discharge causes a sheen or discoloration on the surface of a body of water.
The discharge violates applicable water-quality standards, and
The discharge causes a sludge or emulsion to be deposited beneath the surface of the
water or on adjoining shorelines

Notice to the NRC is also required when oil is released into a waterway or when the
release of oil may affect the quality of a waterway.

In addition, DOT requires at 49 C.F.R. §171.15 that notice be given to the NRC
whenever any of the following circumstances result:

In connection with the release of one or more hazardous materials, at least one of the
following 1s true:

A person is killed.
A person receives injuries requiring admittance to a hospital.

ns Y mergency Responders 214 Chapter 6 Use of the DOT Hazardous Materials Regulatio b E

• •
•

• • •
•
•

The general public is evacuated for 1 hou . r or more.
A ma1or tr~nsport~tion artery or facility is closed or shut down for 1 hour or more.
The operationa_l flight pattern or routine of aircraft is altered.

F~re, breakage, spil_lage, or suspected radioactive contamination occurs .
Fire, breaka_ge, spillage, or suspected contamination involving an infectious sub-
stance (Section l0.21-A) occurs. (Notice of the release of an infectious substance
may be rep?rted to the Centers for Disease Control and Prevention, U.S. Public
Healt~ Service, Atlanta, Georgia, at (800) 232-0124 in lieu of notice to the NRC.)
A marme pollutant is released in a quantity exceeding 119 gallons (450 L) for a liquid
or 882 pounds (400 kg) for a solid.
Even when these criteria are not met, the transportation mishap is so severe that in
the Judgment of the carrier, it should be reported nonetheless. ‘

The notice provided to the NRC includes the following:
The name of the reporter
The name and address of the person represented by the reporter
The telephone number where the reporter can be contacted
The date, time, and location of the release incident
The class or division, proper shipping name, and quantity of the hazardous material
involved in the release, if such information is available
The type of incident and nature of the hazardous material involvement and whether
a continuing danger to life exists at the scene

As previously noted in Section 1.13, the NRC can initially be contacted by telephone
at (800) 424-8802 or, in the District of Columbia, at (202) 426-2675. EPA and DOT
require the submission of a follow-up written report to the following person:

Director, Office of Hazardous Materials Regulations
Materials Transportation Bureau
Department of Transportation
Washington, DC 20590

The informational requirements of the follow-up report are published at at 49 C.F.R.
§171.16.

6.9 TRANSPORTATION SECURITY PLANS
At 49 C.F.R. Part 172, Subpart I, DOT requires carriers to develop and implement a trans-
portation security plan when they intend to transport in commerce the specific hazardous
materials listed in Table 6.10 in quantities that exceed the published values. This requirement
is applicable to carriers who transport the hazardous materials in a motor vehicle, freight
container, or railcar. Its purpose is to assess security risks during the transit of hazardous
materials to deter terrorists and other illegal acts involving them. A copy of the plan must be
made available to the DOT or the Department of Homeland Security upon their request.

At 40 C.F.R. § 172.802, DOT requires carriers to address the following matters in
their transportation security plans:

Personnel Security. Measures confirming information provided by each job appli-
cant hired for a position that involves access to and handling of the hazardous materials
covered by the security plan. This information includes the applicant’s references, employ-
ment history, and immigration status.

Unauthorized Access. Measures addressing the assessed risk that unauthorized per-
sons may gain from access to the hazardous materials covered by the security plan or trans-
pore conveyances being prepared to transport them. Such measures include identification

transportation security
plan For purposes of
DOT regulations, a doc-
ument that addresses
personnel security,
unauthorized access,
and enroute security of
the hazardous materials
identified at 49 C.F.R.
§ 172.800 in amounts
equal to or exceeding
threshold values

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 215

, I

I

HAZARDOUS MATERIAL QUANTITY

Division 1. 1, 1 .2, or 1 .3 materials Any quantity

Division 1 .4, 1 .5, or 1 .6 materials

A quantity requiring placarding

Division 2. 1 materials 792 gal (3000 L) in a bulk cont . _______ …:_ _____ ________________ —“1”::~ – -:-==-=–:-~–……..::.:::_: aIner
Division 2.2 materials with a subsidiary hazard of 5.1 792 gal (3000 L) in a bulk cont · _______ …:_..:..:…:.:..:…..:–=-:=.:.:..:~.:..:=::.:..::….:::..:….:::.:..:…. ___________ i——-:—–……..:::.:::..:. aIner
Materials that pose an inhalation health hazard Any quantity

Class 3 materials in a packaging meeting the criteria for Packing Group I or 11 792 gal (3000 L)

Class 3 and Division 4. 1 materials containing desensitized explosives A quantity requiring placarding

Division 4.2 materials meeting the criteria of Packing Groups I or II 6614 lb (3000 kg) for solids or 792
(3000 L) for liquids in a bulk conta~al

——————————+———–.::..:= in,er
Division 4.3 materials meeting the criteria of Packing Groups I or II A quantity requiring placarding

Division 5. 1 materials in packaging meeting the criteria of Packing Groups I or II;
metallic perchlorates; ammonium nitrate, ammonium nitrate fertilizers, or
ammonium nitrate emulsions, suspensions, or gels

6614 lb (3000 kg) for solids or 792 gal
(3000 L) for liquids

Temperature-controlled organic peroxides, type B, liquid or solid (Section 13.9-A) Any quantity

Division 6. 1 materials other than those that pose an inhalation health hazard 6614 lb (3000 kg) for solids or 792 gal
(3000 L) for liquids in a bulk container

A select agent or toxin regulated by the Centers for Disease Control and Preven-
tion (Section 10.20-A)

Uranium hexafluoride A quantity requiring placarding

•Highway route-controlled quantity” (Section 16. 10-G) of a class 7 hazardous
material
Class 8 materials meeting the criteria for Packing Group I

792 gal (3000 L) in a bulk container

a49 C.F.R. §172.800.

hazardous materials
safety permit • For
purposes of DOT regu-
lations, a document
issued by the Federal
Motor Carrier Safety
Administration that
confers authority upon
motor carriers to trans-
port in commerce the
hazardous materials
identified at 49 C.F.R.
§385.403 in amounts
equal to or exceeding
threshold values

of the measures to be taken that prevent unauthorized persons from gaining acces~ to
shipment when it is stopped. These measures aim to prevent tampering or other il)ega
activity by securing closures of containers and locking them inside their transport vehicles.

Enroute Security. Measures addressing the assessed security risk of shipping ~he haz·
ardous materials covered by the security plan from origin to destination, including shipmen~
stored incidental to their movement. Such measures include identification of the preferre 1
and alternate route plans that the carrier anticipates using during transit and an asse::e;
of how the selected route favors other routes. They also include, when warranted, rest
porting of suspicious incidents or events to local law enforcement officials and the ne~el-
FBI field office and the contacting of local fire department and emergency-rescue perso

6.10 HAZARDOUS MATERIALS SAFETY PERMITS
JoUS . hazar At 49 C.F.R. §385.400, DOT requires motor carriers that transport certain ardous

· I · h” · · d · ·n a hat e matena s wit m interstate or mtrastate commerce to obtain an mamtai . to bat
materials safety permit. To obtain this permit, DOT requires the motor carne! r safetl’
achie~e_d a “~atisfactory” safety rating is~ued e_ither by the Federal _Mot~r ~a:~1~Jace of
Adm1mstrat1on (FMCSA) or the state m which the carrier has its pnncip

216 Chapter 6 use of the DOT Hazardous Materials Regulations by Emergency Responders

‘

Ii / I

I
I

I.
I

TABLE 6.10
Hazardous Materials and Their Quantities Whose Transportation
in Commerce Requires DOT’s Acceptance of a Transportation
Security Plana

HAZARDOUS MATERIAL

Division 1.1, 1.2, or 1.3 materials
Division 1.4, 1.5, or 1.6 materials
Division 2.1 materials
Division 2.2 materials with a subsidiary hazard of 5.1
Materials that pose an inhalation health hazard
Class 3 materials in a packaging meeting the criteria for Packing Group I or 11
Class 3 and Division 4.1 materials containing desensitized explosives

Division 4.2 materials meeting the criteria of Packing Groups I or II

Division 4.3 materials meeting the criteria of Packing Groups I or II
Division 5.1 materials in packaging meeting the criteria of Packing Groups I or 11;
metallic perchlorates; ammonium nitrate, ammonium nitrate fertilizers, or
ammonium nitrate emulsions, suspensions, or gels
Temperature-controlled organic peroxides, type B, liquid or solid (Section 13.9-A)
Division 6. 1 materials other than those that pose an inhalation health hazard

A select agent or toxin regulated by the Centers for Disease Control and Preven-
tion (Section 10.20-A)

Uranium hexafluoride
•Highway route-controlled quantity” (Section 16.10-G) of a class 7 hazardous
material
Class 8 materials meeting the criteria for Packing Group I

•49 C.F.R. § 172.800.

QUANTITY

Any quantity
A quantity requiring placarding

792 gal (3000 L) in a bulk container

792 gal (3000 L) in a bulk container
Any quantity
792 gal (3000 L)

A quantity requiring placarding

6614 lb (3000 kg) for solids or 792 gal
(3000 L) for liquids in a bulk container
A quantity requiring placarding

6614 lb (3000 kg) for solids or 792 gal
(3000 L) for liquids

Any quantity
6614 lb (3000 kg) for solids or 792 gal
(3000 L) for liquids in a bulk container

A quantity requiring placarding
792 gal (3000 L) in a bulk container

of the measures to be taken that prevent unauthorized persons from gaining access to a
shipment when it is stopped. These measures aim to prevent tampering or other illegal
activity by securing closures of containers and locking them inside their transport vehicles.

Enroute Security, Measures addressing the assessed security risk of shipping the haz-
ardous materials covered by the security plan from origin to destination, including shipments
stored incidental to their movement. Such measures include identification of the preferred
and alternate route plans that the carrier anticipates using during transit and an assessment
of how the selected route favors other routes. They also include, when warranted, the re-
porting of suspicious incidents or events to local law enforcement officials and the neare~r
FBI field office and the contacting of local fire department and emergency-rescue personne ·

hazardous materials
safety permit • For
purposes of DOT regu-
lations, a document
issued by the Federal
Motor Carrier Safety
Administration that
confersauthorityupon 6.10 HAZARDOUS MATERIALS SAFETY PERMITS
motor carriers to trans- d s
port in commerce the At 49_ C.F.~. ~3~5.400, DOT_ requires motor carriers that transport cer_tain haz:~~~s
hazardous materials maten_als w1thm mters.tate or mtr_astat_e comm_ erce to obtain and maintam a ~az:

0
have

identified at 49 C.F.R. I f t t -r b h er t matena s sa e y perm, . 10 o tam t 1s permit, DOT requires the motor earn . Safet)’
§385 403 in amounts h d ” • f ,, f • • d . C r1er equa·I to or exceeding ac ieve a sat1s actory sa ety ratmg 1s_sue either by the Federal Motor . ar Jace 0/
threshold values Administration (FM CSA) or the state m which the carrier has its principal P

216 Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders

d

TABLE 6.11
Hazardous Materials and Their Quantities Whose Transportation in
Commerce by Motor Carrier Requires DOT’s Issuance of a Hazardous
Materials Safety Permita

HAZARDOUS MATERIAL QUANTITY
Division 1.1, 1.2, or 1.3 materials More than 55 lb (25 kg)

Division 1.5 materials A quantity requiring placarding

compressed or liquefied natural gas, or other liquefied gas with a 3500 gal (13,248 L) in bulk packaging
methane concentration of at least 85% in bulk packaging (Section 12.5)
Materials that pose an inhalation health hazard and that meet the cri- 1.08 qt (1 L) per package
teria for Zone A (Section 10. 7)
Materials that pose an inhalation health hazard and that meet the cri-
teria for Zone B (Section 10.7)

119 gal (450 L) in bulk packaging

Materials that pose an inhalation health hazard and that meet the cri-
teria for Zones C or D (Section 10.7)

3500 gal (13,248 L)

Class 7 hazardous materials Highway route-controlled quantity (Section 16.10-G)

•49 C.F.R. §385.403.

business. DOT further requires the motor carrier to certify that its security program com-
plies with requirements published at 49 C.F.R. §385.407. In addition, DOT requires
motor carriers to keep a copy of the permit or other document showing the permit number
within the vehicle and provide it to federal, state, or local authorities upon their request.

The issuance of a hazardous materials safety permit confers authority on the motor
carrier to transport in commerce the hazardous materials denoted in Table 6.11 in
amounts exceeding the listed threshold values. It also requires the carrier to prepare and
implement a transportation security plan that complies with the requirements noted in
Section 6.9 and ensures the security of the selected route plan.

Chapter 6 Use of the DOT Hazardous Materials Regulations by Emergency Responders 217

I I
J

I

I I

I I

I I

I
I

I

chlorination A
chemical reaction that
involves the addition of
chlorine to a substance;
the treatment of
contaminate

d

drinking
water to kill the micro-
organisms that cause
dysentery, cholera,
typhoid, hepatitis, and
other diseases

,.,
1 burn when exposed to an atmosphere of h f Elements orher rhan hydr~ge;.:i~~d copper, arsenic, antimony, phosphorus c 10tine.

For exa mple exposure of fme y I . . d ‘and Sul
fur ro chlori1;e causes rhem ro burn with mean escence. ·

Ss(/)
Sulfur

Cu(s) + Clz(g) – CuClz(s)
Chlorine Copper( !!) chloride

Copp~r

2As(s) +
Arsenic

2Sb(s) +
Antimony

Pis) +
Phosphorus

+ IOClz(g)
Chlorine

3Clz(g)
Chlorine

3Clz(g)
Chlorine

6Clz(g)
Chlorine

2AsCl3(s)
Arsenic trichloridc

2SbCl3(s)
Antimony trichloride

4PC13(/)
Phosphorus 1richloride

2S2Clz(/) +
Disulfur dichloride Sulfur tetrachloride

In these instances the chlorine acts as an oxidizing agent.
Chlorine als~ supports the combustion of certain organic co_mpounds. These reac.

tions occur slowly unless the mixture of the compound_ and chlo~me is e~posed to light,
For instance a mixture of elemental chlorine and gasoline vapor ts essennally unreacrive
in the dark, but when the mixture is exposed ro light, the reaction occurs instantaneously.
In such reactions, the light acts catalytically.

When chlorine atoms are incorporated into a compound, the associated chemical
phenomenon is referred to as the chlorination of the compound. This term is also used to
describe the treatment of drinking water and wastewater with elemental chlorine and
chlorine-containing oxidizing agents. When used in this fashion, chlorine acts as a micro-
bicide by killing undesirable microorganisms.

In the United States, there are nearly 60,000 municipal water treatment facilities that
provide drinking water ro over 260 million people. The use of chlorine for treating drink-
ing water saves millions of lives annually from waterborne diseases like cholera and dys-
entery. Notwithstanding this fact, we noted in Section 7.1-I that chlorine is not a totally
effective microbicide, because it does not effectively destroy the Cryptosporidium parvum
bacterium.

When it is dissolved in water, chlorine reacts to form hypochlorous acid, which is
even more powerful than chlorine as an oxidizing agent.

Clz(g) + HzO(/) —> HCIO(aq) + HCl(aq)
Chlori ne Water Hypochlorous acid Hydrochloric acid

During the chlorination of drinking water and wastewater, it is the presence of hypochlo·
rous acid that aids in making chlorine an effective microbicide.

7.3-E WORKPLACE REGULATIONS INVOLVING CHLORINE
When the use of elemental chlorine is necessary in the workplace, OSHA requires employ-
ers to provide thelf workers with respiratory protective gear. When employees are exposed
to a relattvely small amo~nt of chlorine, they should wear goggles and impermeable
gloves, and whenever possible, their activities should be conducted within a fume hood,
When wmking ~n bulk chlorine storage systems, however, employees should wear fully
encapsulanng swts ~nd ~se self-~ontained breathing apparatus.

‘.o avoid or mm1m1ze the ill effects associated with exposure to chlorine, osBA
requires employers to limit employee exposure in th k I aximum chlo· . . . . e wor p ace to a m h

11

rme concentrat10n m air no greater than 1 part ·11· d an 8- 01

kd
per m1 10n, average over

wor ay.

248 Chapter 7 Chemistry of Some Common Elements

FIGURE 7.13 When carriers transport any amount of chlorine in a rail tankcar, DOT requires them to post
POISON GAS placards on each of its sides and to mark CHLORINE and INHALATION HAZARD on two opposing
sides. DOT also requires them to display the identification number 1017 on each side. In this instance, the carrier
chose to display 1017 across the center area of the POISON GAS placards. HOKX 7718 is the reporting mark and
number of Occidental Chemical Corporation, Dallas, Texas . At the time this tank was photographed, DOT did
not require the MARINE POLLUTANT marking to appear on two opposing sides. (Courtesy of the Chlorine
Institute, Arlington, Virginia and Andrew Johnson, iMed Design, Inc., Reno, Nevada .)

7.3-F TRANSPORTING CHLORINE
Chlorine is transported as a liquefied compressed gas in steel cylinders, ton-containers,
cargo tanks, and rail tankcars at 84 psi (580 kPa) at 70°F (21 °C). The ton-container is a
welded tank having a maximum loaded mass of 3700 pounds (1680 kg).

When shippers intend to transport chlorine, DOT requires them to identify it on the
accompanying shipping paper as follows:

UN1017, Chlorine, 2.3, (5.1), (8) (Marine Pollutant) (Poison – Inhalation Hazard, Zone B)

The rail tankcar in Figure 7.13 is an example of a type of bulk packaging used to trans-
port chlorine. DOT requires carriers to display POISON GAS placards and MARINE
POLLUTANT on the tankcar. DOT also requires them to display the identification number
lOl7 on orange panels, across the center area of the POISON GAS placards, or on white
~quare-on-point diamonds, and to mark the expression INHALATION HAZARD on the
ulk packaging. One means of complying with these DOT requirements is noted below:

Chapter 7 Chemistry of Some Common Elements 249

When chlodne is u,n,ported in b”lk by highway oe rail, DOT ,~
display its name on two opposing sides of the tankcar or cargo tank used fes carriers . . d. 1 p or sl.. · to When it is transported by rail, DOT requtres earners to isp _ay OISON GAs ’11P11tent
on squares having a white background and black border (Section 6.6-D). Placari

The DOT-approved tanks and cylinders used for transporting chi .
equipped with fusible plugs designed to melt in the temperature range of 1Ss°r1ne a
(70 to 74°C). The plugs are located on th~ valve just _below t_h~ valve sea:o 16s:;
exposed to the temperatures routinely associated with fire cond1t1ons the · Whe

d h • ‘ rneit- n these plugs permits chlorine to be slowly release to t e environment and p 1ng of reven vessels from rupturing. ts the
DOT also regulates the constru~tio’: and fabri~ation of ra_il tan½cars _and tank t

used to transport chlorine. To maintain the confined chlorine pnmanly in th ~Ucks
state, DOT requires a minimum of 4 inches (10 cm) of insulation about them. Ae liquid
in Section 3 7-A thermally insulated tankcars constructed to DOT specificat· s noted · ‘ Ions h been designed to allow external heat to be slowly transferred to the contents Und ave
normal conditions of transport. When exposed to heat, however, these tanks lo erht~e . . set e mtegnty and rupture. tr

7.3-G RESPONDING TO INCIDENTS INVOLVING
A RELEASE OF CHLORINE

Because elemental chlorine poses an inhalation health hazard, emergency responders
not be too wary when they encounter chlorine during transpo_rtation incidents. In zi~~-
after two freight trains collided in Graniteville, South Carolina, a pressurized tank ‘
ruptured and released more than 9200 gallons (35 m3) of liquid chlorine into the envir~:’.
ment. This sole incident caused the deaths of nine people, the hospitalization of more tha
250 individuals, and the evacuation of more than 5400 people.5 n

When emergency responders are called to a scene at which chlorine tanks or con-
tainers have ruptured or could potentially rupture, it is vital to acknowledge the toxic-
ity hazard associated with elemental chlorine. Because inhaling chlorine may be fatal,
the use of fully encapsulated suits and self-contained breathing apparatus is absolutely
essential.

The responsibilities of a first-on-the-scene team responding to a large spill of chlorine
begin with the immediate isolation and evacuation of all unauthorized persons to a dis-
tance that relates to the amount of chlorine that has been or could potentially be released
into the environment. As initial guidance, 6 DOT recommends the isolation of unauthor-
ized persons 3000 feet (1000 m) in all directions when a release of chlorine from a rail
tankcar, highway tank truck, or trailer is involved; 1250 feet (400 m) from multipl: ton
cylinders; and 800 feet (250 m) from multiple small cylinders or a single ton cylinder. As
additional protection during a large spill of chlorine, DOT also recommends the evacua-
tion of unauthorized persons to a distance ranging from 0.5 mile (0.8 km) to 7+ miles
(11 + km) during day and nighttime hours, respectively, from the same transport vessels.
The latter distances are selected by consideration of the prevailing wind speed [low ( <6 mph, or <10 km/hr), moderate (6-12 mph, or 10-20 km/hr), or high (>12 mph, or 20 km/hr)]for
the relevant type of transport vessel. .

Emergency responders must also identify those who have been exposed to chJrni
f~om leaks ?r ruptured con~a_i~ers. Th~se ~ndividuals should be moved downwind t: k~~t
air where, 1f necessary, artificial respiration can be supplied. They should ~J~o skin
warm with blankets and provided with immediate first-aid attention. To nu01nuze

‘ ·1rnenr, 5David van Sickle, “Acute health effects after exposure to chlorine gas released after a train derai
Amer. J. Emerg. Med., Vol. 27 (2009), pp. 1-7. 35).
6 R . . · 2012), P· Table 3, Emergency esponse Guidebook (Washington, DC: U.S. Department of Transportation,

250 Chapter 7 Chemistry of Some Common Elements

ns Persons exposed to chlorine should remove their clothing and shower thoroughly. bur , · · f ” fo prevent the impairment O _v1S1on, they should irrigate their eyes with flowing water for
a proidmately 30 minutes._ Fmally, they sho~ld be transported to an emergency medical
P ·t·ty fo r follow-up examinat10ns by physicians

fuOI •
An emergen~y response team may be required to examine the physical condition of

a chlorine container or r~il tankcar. Unruptured vessels should be cooled with water as
he ream members pmpoint the specific spots from which chlorine is leaking or could
t orenrially leak . Becau~e containers and transport vessels contain liquid chlorine, it is
~ften the liquid that dnps fro~ valves, fittings, or openings. Liquid chlorine is substan-
. lly more concentrated than Its gas, and when unconfined it readily evaporates. One

ua · ‘d hi · ‘ volume of hqm c . orme evaporates into approximately 460 volumes of gas. Conse-
uently, the immediate area surrounding a chlorine leak becomes a highly toxic envi-

q · h’ d nment wit 111 secon s.
ro Locating a chlo~ine leak_ is not always a simple matter, especially when the gas has
been escaping from its container or transport vessel for some time and the atmosphere is
heavily laden with chlorine. One method of detecting a chlorine leak is based on the
chemical reaction between chlorine and ammonia. These two substances react to form
ammonium chloride and ammonium hypochlorite, each of which is a white solid.

Ammonia Chlorine Water Ammonium chloride Ammonium hypochlorite

The method consists of tying a rag soaked with household ammonia to a broomstick and
rhen passing the stick along the surface of the chlorine container or tank. Ammonia vapor-
izes from the liquid and reacts with the chlorine at the point from which it is escaping. At
this location, a white cloud drifts into the air. By observing the cloud’s formation, the
source of the leak is easily identified. This simple procedure is ineffective when the sur-
rounding atmosphere is heavily laden with chlorine, because under these conditions, the
ammonium compounds are produced virtually throughout the area.

When chlorine is leaking from a tank or container, the exit points must be closed or
sealed. When sealing an opening is impossible or impractical, an attempt should be made
to prevent the further escape of liquid chlorine into the environment. This can sometimes
be accomplished by rolling the vessel so that the opening points upward. Although chlo-
rine gas continues to escape from the opening, the more concentrated liquid remains con-
fined within the vessel.

When emergency responders arrive at the scene of an incident involving the release
of chlorine, specialized equipment should be available for their immediate use. An
essential item is a kit that contains a clamping device to seal a leak at the fusible plug
and a patching device to seal a leak in the cylinder sidewall. They are components of the
so-called Chlorine Institute Emergency Kit “A, ” which is available from several com-
mercial outlets. 7 There are also “B ” and “C” kits for use on ton cylinders and tanks,
respectively.
. To improve the speed and effectiveness of a response action at an emergency involv-
ing the release of chlorine the Chlorine Institute formalized an action known as the
Chlorine Emergency Plan, ~r CHLOREP. Under this plan, the United States and Canada
are divided into regional sectors in which specially trained teams are located. In the event
of an emergency involving the release of chlorine, or when CHEMTREC (Section 1.12) is
contacted, the caller is put into immediate contact with the closest CHLOREP team,
which then oversees the handling of the incident.
,:;:;–_
s~e Chlori~e Institute is a trade association consisting primarily of compa~y repr~sentatives interes_r:d in the
lnei~rod_uct1on, distribution, and use o f chlorine and o~her subst~n~e~ associated with the chlor-alkali industry,

offices are loca ted at 1300 Wilson Boulevard, Arlington, Virginia 22209.

Chlorine Emergency
Plan (CHLOREP) An
action plan for aiding
emergency responders
during incidents
involving the release
of chlorine during
transportation mishaps
or at user locations

Chapter 7 Chemistry of Some Common Elements 251

Convention on
Certain Conventional
Weapons An interna-
tional treaty that aims
to restrict or prohibit
the use of certain con-
ventional weapons dur-
ing warfare, including
those containing incen-
diary agents

White
phosphorus

/!\
PC——~P

TABLE 7.9 MM1411Mii:41hM::ii,IMl·i\4M~
RED PHOSPHORUS

WHITE PHOSPHORUS (AMORPHOUS)

Melting point 111’F {44’C) 1 094 ‘F {590’C) at 43 (4400 kPa) atrn

Boiling point 535’F {280’C) 781 ‘F {416’C) {sublirn ates)
Specific gravity at 68’F {20’C) 1.82 2.34

Vapor density (air – 1) 4.42 4.77

Autoignition point 86’F {30’C) (spontaneous S00’F (260°()
i nition in dry air) g

7 .4 PHOSPHORUS
Elemental phosphorus has several allotropes, two of which are especially import
white phosphorus and red phospho~us. :Vhite ~hosphorus is the un~table form of the:~’.
ment at room conditions. On standmg, 1t acquires a yellow coloration due to the pa . 1 conversion of the white allotrope to the more stable red allotrope. For this reason,
phosphorus is also called yellow phosphorus.

The physical properties of white and red phosphorus are provided in Table 7.9. Their
properties are so strikingly different that we discuss them here separately. Both are used to
manufacture important chemical products such as special alloys (e.g., phosphor bronze)
rodenticides, fireworks, matches, phosphoric acid, and metallic phosphides. In the past’
both were also used as the active agent in incendiary bombs. When dropped from militar;
aircraft, these bombs set fires to objects or caused burn injuries to persons through the
action of flames and heat. The composition of some incendiary bombs containing red
phosphorus was 50% of the incendiary mixture.

White phosphorus has also been used in incendiary bombs to illuminate the battle-
field during nighttime. However, the addition of white phosphorus in munitions is now
regarded as an unwarranted wartime practice, because flaming droplets from exploded
ordnance can become embedded beneath skin and seriously burn civilians.

White phosphorus has also been used in tracer, smoke, and signaling systems. The mixture
of tetraphosphorus hexoxide and tetraphosphorus decoxide produced by the combustion of
white phosphorus possesses the best obscuring power of any known smoke-producing material.

In 1983, many of the world’s civilized countries agreed to ban the use of incendiary
weapons during certain warfare operations by acceptance of the Convention on Certain
Conventional Weapons. Known formally as the Convention on Prohibitions or Restric-
tions of the Use of Certain Conventional Weapons Which May Be Deemed to Be Exces-
sively Injurious or to Have Indiscriminate Effects, it prohibits the use of incendiary
weapons against civilian populations and restricts their use against military targets located
within a concentration of civilians, but it does not restrict the use of incendiary bombs in
illumination, tracer, smoke, or signaling systems.

Although the United States is a signatory to the Convention, it has not ratified the
non use of incendiary weapons on military targets located in civilian-populated areas. _In
2005, during the U.S.-led assault on Fallujah, Iraq, incendiary munitions containing white
phosphorus were used to flush enemy troops from covered positions.

7 .4-A PRODUCTION AND PROPERTIES OF WHITE PHOSPHORUS
White_ phosphor~s is a waxy, translucent solid at ambient conditions. Each of its_ m~;;
cules 1s tetratom1c and has the tetrahedral shape like that shown in the left margin-
these reasons, the chemical formula of white phosphorus is P4 •

252 Chapter 7 Chemistry of Some Common Elements

White phosphorus is industrially prep d b h •
k in an electric furnace Th • _are Y eating calcium phosphate rock with sand

and co e b . 1 Th e principal components of sand and coke are silicon diox-ide and car on, respecnve y. e production of white phosphorus is denoted as follows:
2Ca3(P04)2(s) + 6Si02(s) + IOC(s) -, 6CaSiO3(s) + I0CO(g) + P4(g)

cn1ciulll phosphalt.! Silicon dioxide Carbon Calcium silicate Carbon monox ide Phosphorus

The phos~horuf.Japors are vented from the furnace and condensed under water to pro-
duce a white so 1 . . ..

Because rhe autoigrutwn t~mperature of white phosphorus is on] 86°F (30°C), white
h sphorus spontaneously 1grutes when e d · Th · · y · p o xpose to air. e auto1grut1on temperature 1s so I that body heat can serve as an ig ‘t• T . . • • ow . . ru ton source. 10 reduce or ehmmate the nsk of 1ts taneous combust10n white phos h · d · spon . ‘ P orus 1s store under water or a blanket of rutrogen.

White phosphorus is often _said to possess the offensive odor of a mixture of garlic
and rotten fish, but this comparison is misleading. This specific odor is more likely associ-
ated with the presence of phosphine (Section 9.6-B), a toxic gas slowly produced by the
reaction between phosphorus and cold water.

P4(s) + 6H2O(/) – 3H3PO2(aq) + PH3(g) Phosphorus Water Hypophosphorous ac id Phosphine
The combustion of white phosphorus produces two oxides, tetraphosphorus hexox-

ide and tetra phosphorus decox1de, as follows:

P4(s) + 3O2(g) – P4O6(s) Phosphorns Oxygen Tetraphosphorus hexoxide
P4(s) + 5O2(g) – P4O1o(s) Phosphorus Oxygen Tetraphosphorus dt:coxidt:

As implied by these equations, tetraphosphorus hexoxide and tetraphosphorus decoxide
are the products of incomplete and complete combustion, respectively. Both are white
compounds. Consequently, when white phosphorus burns, billows of dense white, chok-
ing smoke are produced. This luminous dense smoke accounts for the use of white phos-
phorus as a component of military smoke and signaling systems.

Although spontaneous combustion is the principal hazard associated with white
phosphorus, its vapor also is highly poisonous. Prolonged exposure to phosphorus vapor
causes phossy jaw, or phosphorus necrosis, which in the worst instances causes disinte-
gration of the jawbone. In addition, white phosphorus burns the skin and produces
wounds that are extremely painful and slow to heal. For this reason, users must always
handle white phosphorus with gloves.

7.4-8 TRANSPORTING WHITE PHOSPHORUS
When shippers offer solid or molten white phosphorus for transportation in bulk, DOT
requires them to enter the relevant shipping description shown in Table 7.10 on the accom-
panying shipping paper. When the element is molten, HOT markings must be displayed.

DOT requires carriers to display the relevant identification number-1381 or 2447-
on orange panels or across the center area of SPONTANEOUSLY COMBUSTIBLE plac-
ards or white square-on-point diamonds. For example, any of the following may be used
10 display the identification number 1381 on bulk packaging: 1381 1· ~

phossy jaw (phospho-
rus necrosis) The
disfiguring affliction
caused by overexposure
to phosphorus vapor

Chapter 7 Chemistry of Some Common Elements 253

I
I

1j

Red
phosphorus

TABLE 7.10 -wm.;;,1.;.;a;;.;;;.;,;;.140@11, osphorus
WHITE PHOSPHORUS

White phosphorus, solid

White phosphorus, molten

SHIPPING DESCRIPTION

UN1381, Phosphorus, white, dry, 4.2, (G.i)
PG I (Marine Pollutant) (Poison) ‘

HOT, UN2447, Phosphorus, white, molten 4 2 (6.1 ), PG I (Marine Pollutant) (Poison) ‘ · ‘

When white phosphorus is transported in bulk by highway or rail, DOT requir
to display a name such as PHOSPHORUS, WHITE, DRY or PHOSPHORUS e~arriers
MOLTEN on two opposing sides of the transport vehicle used for shipment.’ All l-il’fc,
labeling, marking, and placarding requirements apply. Other

7 .4-C RESPONDING TO INCIDENTS INVOLVING
A RELEASE OF WHITE PHOSPHORUS

White phosphorus generally is burning when first-on-the-scene responders arrive
scene involving its release. Although the fire can be effectively extinguished with w:t a
experts advise firefighters to avoid its use due to the formation of toxic phosphine. lnst/~r,
they recommend the use of dry sand, because it can blanket the element, prevent rei~’.
tion, and minimize the potential exposure to phosphine.

When small quantities of white phosphorus are burning, it is best to segregate them
from nearby combustible materials. This may not be a simple matter, because phosphorus
melts at a relatively low temperature and flows as it burns into nearby low areas. For this
reason, appropriate action should be taken by constructing dams or dikes.

Firefighters responding to incidents involving elemental phosphorus should wear pro•
tective gear and use self-contained breathing apparatus. They should be particularly cau·
tious to avoid inhaling the fumes from a phosphorus fire. Fumes contain particulates of
the phosphorus oxides, which when inhaled, can seriously irritate the nose, mouth, throat,
and lungs.

7 .4-D RED PHOSPHORUS
The red allotrope of phosphorus is a dark red solid whose molecules consist of long chains of
p4 tetrahedra, each having an length. The following example shows only three
interlinked tetrahedra, but this number is generally much larger .

. (t)._.(t)._.(/).
p p p

Due toitS
The chemical formula of red phosphorus is usually denoted as either P or Po:i• d) phos·
structure, red phosphorus is also known as amorphous (unstructur~C) ill an
phorus. It is produced industrially by heating white phosphorus at 482°F (2SO
iron container from which air has been excluded. . al reac·

When compared to white phosphorus, the red allotrope is sluggish in che!lll~ored in
tivity. Small quantities are not spontaneously combustible. They generally are 5

closed containers without an overlying layer of water or nitrogen. bustible,
Bulk quantities of red phosphorus, however, are spontaneously corn ide, ‘f~e

forming a mixture of tetraphosphorus hexoxide and tetraphosphorus deco”

254 Chapter 7 Chemistry of Some Common Elements

II trope combines spontaneously with atmospheric oxygen, but the combustion
red 3. occurs very slowly. When it is stored in bulk the accumulated heat of com-

act10 h b . f th · ‘ · · f d re . n triggers t e urnmg O e entire mass. For this reason, bulk quantities o re
bustl0 h rus are rarely stored.
ph0iedo phosphorus is nonpoisonous, but like the white allotrope, it reacts with water to

Phosphine. /orJll

4.E TRANSPORTING RED PHOSPHORUS 7· hippers intend to transport red phosphorus, DOT requires them to identify it on
Whenc~mpanying shipping paper as follows: the ac

UN1338, Phosphorus, amorphous, 4.1, PG III

\'(/hen red phosphorus is transported in bulk by highway or rail, DOT requires carriers to
display the name PHO~PHORUS (AMORPH_OUS) on_two opposing sides of t~e trans-
port vehicle used for shipment. All other labeling, markmg, and placarding reqwrements
apply.

7.4-F RESPONDING TO INCIDENTS INVOLVING A RELEASE OF RED PHOSPHORUS
Bulk quantities of red phosphorus are unlikely to be encountered, but containers holding
small quantities have been involved in fires. These fires can be extinguished by the appli-
cation of dry sand, foam, or dry chemicals, but not water. Because phosphine is produced
when water is applied to burning red phosphorus, the use of dry sand is advised for fire
exringuishment.

7.5

SULFUR

Elemental sulfur occurs naturally, particularly in countries bordering the Gulf of Mexico
and in Japan, Mexico, and Italy. Sulfur also occurs in minerals and ores too numerous to
mention, in which it is combined with metals and other nonmetals. Sulfur accounts for
0.06% by mass of all the elements found on Earth.

7.5-A PRODUCTION AND PROPERTIES OF SULFUR
Most of the world’s supply of elemental sulfur comes from natural deposits of the element
frequently called brimstone. These deposits are often located near hot springs and volca-
noes. To isolate the sulfur from them, hot water under pressure is pumped into the subter-
ranean brimstone-bearing deposits, whereupon the sulfur melts and is brought to the
surface by an airlift. Brimstone often has an offensive odor because it contains hydrogen
sulfide, a toxic gas having the odor of rotten eggs (Section 10.13-A). Their containers and
tanks must be handled with special care, as the gas can evolve and accumulate in the vent
spaces above the liquid.

By contrast, pure sulfur is an odorless solid. When it is heated at atmospheric
ii~essure, it vaporizes, but the vapor ~an be condensed on~ cold s~r~ace, produci_ng a

Is e dust called flowers of sulfur. It 1s used as a commercial fung1c1de and acancide ect1on 7.5-B).
f T?e solid state of sulfur occurs in numerous allotropic forms, the two most common

~I which are orthorhombic sulfur and monoclinic sulfur. Orthorhombic sulfur is the sta-
phe a_llotrope of solid sulfur at ambient conditions. It is a yellow, crystalline solid whose
te YSrca! properties are noted in Table 7.11. When orthorhombic sulfur is maintained at a
Pa~Perature between 205 and 235°F (96 and 113°C), it changes into a mass of long trans-
ailoent needles composed of monoclinic sulfur. Because monoclinic sulfur is not the stable

trop · I e, 11 s owly changes back into the orthorhombic form.

Sulfur, solid

Sulfur, liquid

flowers of sulfur The
finely divided powder
of elemental sulfur

Chapter 7 Chemistry of Some Common Elements 255

TABLE 7.11
Physical Properties of Elemental Sulfur
(Orthorhombic)

Melting point 248°F (120°()

Boiling point 832°F (445°C)

Specific gravity at 68°F (20°C) 2.07

Vapor density (air= 1) 8.9

Vapor pressure at 475°F (246°C) 10 mmHg

Flashpoint 405°F (207°C)

Autoignition point 450°F (232°C)

Lower flammable limit (as dust)• 0.002 lb/ft3 (35 g/m3)

Upper flammable limit (as dust)• 0.09 lb/ft3 (1400 g/m3)
a The lower and upper flammable limits of sulfur dust vary with ,ts particle size and depth of drspersron.

Both solid allotropes exist as molecules having eight sulfur atoms bonded together in
the puckered-ring arrangement shown below:

Molten sulfur has a highly complex molecular arrangement. Chemists denote it as s
where x is a relatively small but number. The chemical formula of sulfur vap;;
at its boiling point is also represented as Ss, but when the vapor is further heated, the
cyclic arrangement breaks down, and the sulfur molecules assume the formula S,. To
avoid ambiguity, S8 is denoted in this text as the formula of liquid and solid sulfur, a~dS,
is represented as the formula of gaseous sulfur. –

When elemental sulfur is exposed to an ignition source, it first melts and the liquid
sulfur burns with a blue flame before it vaporizes. The combustion produces sulfur diox-
ide, a poisonous gas having a suffocating, choking odor (Section 10.12).

Sg({) + 802(g) – 8S02(g)
Sul fur Oxygen Sulfur dioxide

Elemental sulfur also combines with most metals. For example, when a mixture of
mercury and iron is heated, the elements unite to form mercury(II) sulfide and iron(II)
sulfide, respectively.

8Hg(l) + Sg(/) – 8HgS(s)
Mercury Sulfur Mercury(U) su lfide

8Fe(s) + Sg(/) – 8FeS(s)
Iron Sulfur lron(U) sulfide

Elemental sulfur is likely to spontaneously ignite under the following conditions:
. ·xrure is When flowers of sulfur are dispersed into air a potentially explosive mi . •ry

d d Th . . . . . , . electf!CI pro uce . e spontaneous 1gmt1on of this rruxture is triggered by the sta~ic dust
generated by the movement of the sulfur particles within the air. The potential for_ ah the
explosion may be markedly reduced by electrically grounding the vessel in whic
sulfur is confined.

2 56 Chapter 7 Chemistry of Some Common Elements

FIGURE 7.14 _El_emental sulfur is a constituent of many industrial and domestic products including gunpowder,
matches, insect1c1des, ferti lizers, and vulcanized rubber. When the sulfur burns, it is converted into the toxic gas
sulfur dioxide.

Elemental sulfur reacts with many oxidizing agents. When the mixture is activated,
the resulting heat of reaction is likely to cause the ignition of the residual sulfur. Conse-
quently, all mixtures of elemental sulfur and oxidizing agents pose the risk of fire and ex-
plosion. Every effort should be employed to keep sulfur and oxidizing agents segregated.

7.5-B COMMERCIAL USES OF SULFUR
Sulfur is one of the world’s most important raw materials. There is hardly a segment of the
chemical industry that does not use elemental sulfur or one of its compounds in manufac-
turing or production processes. Approximately 80% of the elemental sulfur produced in the
United States is used as a raw material for the manufacture of sulfuric acid (Section 8.7). As
Figure 7.14 illustrates, sulfur is also used to produce vulcanized rubber products (Section
14.11-A), fertilizers, dyes and other chemical substances, drugs and other pharmaceuticals,
black gunpowder, fireworks, pesticides, and matches.

Elemental sulfur is used as a fungicide (for killing fungi) and an acaricide (for killing
mites and ticks). For agricultural use, it is commercially available as a dust, paste, and
wettable powder. The dust is applied undiluted, but the paste and wettable powder for-
mulations may contain pulverized clay, which deposit and stick to the surfaces of leaves.
They kill by direct contact.

Sulfur is also used as a raw material by the chemical industry to produce other chem-
ical products. For example, elemental sulfur is united with carbon and fluorine to produce
carbon disulfide (Section 13.10) and sulfur hexafluoride, respectively:
1 Carbon disulfide is produced when sulfur vapor is passed over very hot carbon in the

absence of air. The presence of air is avoided to reduce or prevent the likelihood that
carbon disulfide will ignite.

C(s) + S2(g)
Carbon Sulfur

CS2(g)
Carbon disulfide

Chapter 7 Chemistry of Some Common Elements 257 I

n
I
I

I
I
I
I

I
I
I

TABLE 7.12

SULFUR

Sulfur, elemental, solid

Sulfur, elemental, molten

Shipping Descriptions of Sulfur

SHIPPING DESCRIPTION

NA 1350, Sulfur, 9, PG Ill

NA2448, Sulfur, molten, 9, PG 111

or
UN2448, Sulfur, molten, 4. 1, PG 111

Sulfur hexafluoride is the predominant product formed when sulfur comb·
fluorine. tnes With

S8(s) + 24F2(g) —> 8SF5(g)
Sulfur Fluorine Sulfur hexafluoride

It is used as an insulator in high-voltage electrical equipment.

7 .5-C TRANSPORTING SULFUR
When shippers offer sulfur for transportation, DOT requires them to identify the relev
entry in Table 7.12 on the accompanying shipping paper. DOT regulates the transponatio:n;
s~ for domestic and international transportation as a class 9 and a flammable solid, res~.
t1vely. For domestic transportation, DOT notes at 49 C.F.R. §172.102.30 that shippers are
?-ot subject to its labeling requirements if the sulfur is transported in nonbulk packaging, or if
1t is formed in a specific shape like prills, granules, pellets, pastilles, or flakes.

At 49 C.F.R. §172.102.30, DOT also notes that the CLASS 9 placard is not required
on bulk packaging when molten sulfur is transported domestically, as long as the packag-
ing is marked with the identification number 2448 on orange panels, white square-on-
point diamonds, or HOT markings. At 49 C.F.R. § 172.325, DOT also requires the
packaging to be marked with the expression MOLTEN SULFUR.

~-2448 1~~
When molten sulfur is transported internationally in bulk packaging, DOT requires its
carriers to display FLAMMABLE SOLID placards on the packaging. DOT also requires
the HOT marking and the expression MOLTEN SULFUR to be displayed on the packag·
ing. Alternatively, the identification number may be displayed across the center of the
FLAMMABLE SOLID placard, but the HOT marking and the expression MOLTEN
SULFUR are still displayed on the packaging.

7.5-D RESPONDING TO INCIDENTS INVOLVING A RELEASE OF SULFUR
The following practices should be implemented at fire scenes involving burning sulfur:

Firefighters may effectively extinguish sulfur fires by applying water to rbe!Tl :~:i
fog. The fog not only removes heat from the fire scene, but it also avoids the pote
buildup of steam that could cause the hot material to splatter.

258 Chapter 7 Chemistry of Some Common Elements

TABLE 7.13 Physical Properties of Graphite and Diamond

GRAPHITE DIAMOND

~eltin9 point 6606-6687’F (3652-3697′() 6422’F (3550’C)

soilin9 point 7592′ F (4200’C) 8726’F (4830’C)
·re gravity at 68’F (20’C) 2.20-2.35 3.52 speCI I

0.4 density (air= 1) vapor
flashpoint >200’F (>93′ C)

ition point 1346’F (730°C)

1 To avoid inhaling toxic levels of sulfur dioxide, firefighters responding to incidents
involving burning sulfur must wear fully encapsulating suits with self-contained breathing
apparatus. . .

1 Because sulfur readily melts under fire conditions and flows into lower adiacent
eas where it can ignite secondary fires, firefighters must take appropriate action to

:;gregate the molten material from combustible materials by constructing dams or dikes.
1 When firefighters respond to transport incidents involving molten brimstone, they

must understand that hydrogen sulfide may evolve and accumulate in the vent spaces of
the transport vessels. Inhalation of the gas may be deadly.

7.6 CARBON
Elemental carbon occurs naturally as its two primary allotropes, graphite and diamond. 8

It also occurs in soot, coal, coke, charcoal, and carbon black. In these two primary allo-
tropes, the elemental carbon is represented by its chemical symbol, C.

The natural abundance of carbon is only 0.08% by mass on Earth, yet carbon ranks
much higher in terms of importance, because it is a constituent of the compounds needed
by all living organisms for survival.

7.6-A COMMON ALLOTROPES OF CARBON
Neither diamond nor graphite is generally considered hazardous. Each possesses substan-
tially different physical properties, some of which are compared in Table 7.13.

Graphite

(the “lead” of pencils) is a black material that feels slippery, but diamond can be cut and
polished to a crystalline, transparent luster. Although graphite is one of the softest known
substances, diamond is the hardest substance found in nature.

‘There are several other carbon allotopes whose properties are not discussed in this text. In 1962, a one-atom-
thICk sheer of carbon called graphene was first isolated from graphite. Its structure resembles a densely packed
hexagonal honeycomb of carbon atoms. It is regarded as a distinct allotrope of carbon because it possesses a set
of unique properties, even different from those of graphite.

In 1985, the carbon allotrope having 60 carbon atoms per molecule (C6ol was discovered by vaporizing
graphite with a laser. It is called buckminsterfullerene. The name is derived from the observation that its hollow
soccer-ball-shaped molecules resemble rhe celebrared geodesic domes designed by American architect and engi’.
nee, R. Buckminster Fuller. Each c60 molecule is colloquially called a “buckeyball. ” Its symmetry consists of 32
IOterlocking rings (20 hexagons and 12 pentagons) . This geometrical shape is called a truncated icosahedron.
d. \0 1991, the carbon allotrope called a carbon nanotube was discovered. Ir takes the physical form of cylin-
T~ca carbon molecules with at least one end typically capped with a hemisphere of the buckeyball structure.
n, e ~ame 15 derived from irs size, because the diameter of a nanotube is of the order of a few nanometers but
,,:;

1
e sev~ral_millimeters in length. A carbon nanotube exhibits extraordinary strength and is currently finding

u ness in diverse areas including food, cosmetics, electronics, and medicine.

Graphite

Chapter 7 Chemistry of Some Common Elements 259

FIGURE 7. 15 The struc-
tures of two carbon allo-
tropes, diamond and
graphite. In the graphite
structure shown in (a),
planar hexagonal rings
covalently bond to one
another in successive
sheets. In the diamond
structure shown in (b),
each carbon atom is
covalently bonded to four
other carbon atoms in a
tetrahedral arrangement.

‘t::=::=– ~–_y+;;~ : 4fW_:;:s-r :
I I I I I I q i- I 1-o-l II :=ell I I 1- 1 I I I II_.__ ___ I

I I I I
11~ 1
I I I I
I I I I

/–4-_/ :

(a)

I
I
I

(b)

The physical properties of graphite and diamond are linked with the structure f
substances. In the graphite structure shown in Figure 7.15(a), each carbon atom is~ 0 the
to other carbon atoms in planar hexagonal rings joined to one another in succon~ed
sheets. In the diamond structure shown in Figure 7.15(b), each carbon atom is syrn:siv_e
cally bonded to four other carbon atoms in a tetrahedral arrangement. etn-

The diamond structure is produced in nature when carbon-containing materials
subjected to a pressure of approximately 0.8 million pounds per square inch (5.6 milt
kPa) within the hot mantle of Earth, over 75 miles (120 km) below its surface. The hig~~s°
gem-quality diamonds are discovered in ancient volcanic pipes in a greenish rock, kimber’.
lite, in South Africa, Canada, Arkansas, Siberia, and elsewhere.

For decades, scientists and engineers have attempted to produce diamonds in labora-
tories by replicating Nature’s process. Limited success was initially experienced. The dia-
monds produced were small and useful only as low-grade industrial diamonds. They were
too dark in color to be suitable for gemstones. Today, however, significant advances in
producing gemstone-quality diamonds have been made by passing carbon vapor over
diamond seeds inside a vacuum chamber at an approximate temperature of 2000’F
(1093°C). Using this technique, the ability to produce 10-carat diamonds has been mas-
tered.9 By comparison, the largest polished (faceted) natural diamond is the Golden Jubi-
lee Diamond, which weighs 545.67 carats (109.13 g). It is among the crown jewels of the
royal family of Thailand.

At moderate temperatures and pressures, graphite is the stable allotrope of carbon.
On Earth’s surface, diamond converts into graphite at an imperceptibly slow rate. How-
ever, when diamond is heated to approximately 3583°F (1700°C) in the absence of air, it
rapidly converts into graphite.

c(diamond) – C(graphite)

Although graphite and diamond are stable substances at the conditions experienced
on Earth’s surface, both burn in air. The products of their incomplete and complete com·
bustion are carbon monoxide and carbon dioxide, respectively.

7 .6 -B COMMERCIAL USES OF DIAMOND AND GRAPHITE
Diamond companies advertise that a diamond is “a girl’s best friend,” the supre7;
token of love and affection. In many parts of the world, a woman’s acceptance 0

2 20121, pP· 9Lauren K. Wolf and Carmen Drahl, “Carbon Goes Deep,” Chem. Eng. News, Vol. 90 (March 1 ‘
54-58.

260 Chapter 7 Chemistry of Some Common Elements

Jllscone-quali~y ~-amon! fro~ her fiance serves as a formal sign of their betrothal.
Jllscone-quahty 1~mon s pn~arily serve in this exalted role because their dazzling

:rkle is so appeal’.ng. !ndustn~I dia_monds have more mund~ne uses in saw blades
~ed co cut marble, m wire-drawing dies, and in drill bits, grinding wheels, and hack-

v blades.
sa’ Graphite a~d diamond undergo phase changes from solid to liquid carbon at
exceptionally hig~ tempe:at_ures. F~r example, Table 7.13 shows that diamond melts
ar 6422°F (3550 C). This is the highest melting point of any element that occurs

03rura11Y• . Graphite and diamond also possess an important anomalous property when com-
ared with other nonmetals: They are extraordinarily good conductors of heat. If you are

iortunate enough to own _a 5-carat diamond, hold it to the tip of your tongue. The dia-
ond feels cold, because it conducts the heat from your tongue. Diamond possesses the

~ghest thermal ~onductivit~ of ~II s~bstances.
The properoes of ~raph1te give nse to many industrial applications, of which the fol-

lowing are representative:

1 Graphite is molded into crucibles that are used to hold molten steel and other high-
melting metals.

1 Graphite is used to line the walls of furnaces and other vessels where high-tempera-
ture operations are conducted. The graphite protects the underlying metal from melt-
ing or softening.

1 The nose and leading edges of aircraft wings generally are coated with graphite to
protect the underlying metal from the heat of friction generated when the aircraft
travels at high speeds through the air.

I Graphite-based dry powder is an effective fire extinguishing agent on class D fires,
because the carbon conducts heat away from the burning metal.

Carbon in the form of coke (Section 7.6-E) is also used in the chemical and metallur-
~cal industries as a reducing agent. This chemical property is put to use at foundries dur-
ing the production of iron and other metals from their naturally occurring ores.

7.6-C COAL
Almost without exception, all fossil fuels found in nature can be traced to the giant plants
rhac grew during the carboniferous age. Three hundred million years ago, plants grew
much more luxuriantly than they do today. During this period, the dominant plants were
rreeferns, which grew 30 feet (9.1 m) in height with crowns of large, feathery fronds. As
Earth evolved over the subsequent millennia, the remains of the ferns and other plants
ultimately were buried at great depths below the planet’s surface, where intense tempera-
ture and pressure compacted, hardened, and chemically altered them into fossil fuels:
coal, natural gas (Section 12.5), and crude oil (Section 12.13-A). This conversion process
is called the carbonization of vegetable matter. carbonization • The

Coal is a readily combustible black rock whose composition consists of a mixture process of converting
of ca b • d I • d f an organic compound h r onaceous material and organic and inorganic compoun s. t is extracte rom into carbon or a carbon-
t e earth by surface mining as well as from seams that exist in deep, underground containing residue,
natural deposits. In the United States, coal is abundant far more than either natural gas typically conducted
or crude petroleum. Natural sources of coal occur primarily in West Virginia, Pennsyl- under intense tempera-
;ania, Kentucky, and Wyoming. They are also plentiful in areas outside the United ture and pressure
tar,es , especially Australia India and China. On the international scale, China is coal Any black or

coa ‘s . ‘ ‘ rnaior consumer. brownish combustible
In thCeoal _is largely mined to operate factories and power plants that genera_te_ ele_ctricity. rock that formed natu-U d I h I rally by the partial
ated. T n1te States, coal is used as the fuel at 4~0 power p ants w ere e ectnc1ty is gene:- decomposition of plant
rn he worldwide burning of coal at coal-fired power plants accounts for approx1- life at increased pres-

ately 24% of the carbon dioxide found in the atmosphere (Figure 5.6). Coal and other sure and temperature
Chapter 7 Chemistry of Some Common Elements 261

1,

I I

black lung disease
(pneumonoconiosis)
• The lung disease
caused by long-term
inhalation of
coal-mine dust

Federal Coal Mine
Health and Safety Act
of 1969 • The federal
statute that empowers
the Mine Safety and
Health Administration
within the U.S. Depart-
ment of Interior to reg-
ulate health and safety
conditions within coal
mines

rank (grade) Any
class or type of coal dis-
tinguished by its carbon
content and density

fossil fuels are nonrenewable natural resources; once used, only their ash d
products remain. As we continue to advance into the twenty-first century .0 ther b
EPA regulations could trigger a decline in the use of coal for energy prod~ct’ e 11’t’tPaq \
more likely that coal will remain the United States’ primary fuel source for el;on;_ Yet, it~
eration until 2035.10 ctr1city&en~

An underground coal mine itself poses a potentia~y haz~rdous environment. Fi
methane seeps from the coal seams into the surrounding environment where it po arnrnable
of fire and explosion (Section 12.5-A). In addition, the atmosphere of a coal mises the risk
laden with coal dust. When the dust is inhaled over long periods, it causes resp·ne 0 ften is
ea_ses including black lung disease, or pneumonoconiosis. These miners have l;atory dis.
with coal dust, the presence of which severely restricts the exchange of oxygen be: coated
lungs and the blood. Their lungs ultimately become scarred, and they experienc een the
sema, chronic bronchitis, shortness of breath, disability, and premature death The e~Phy.
effec – . · ere 1s nve treatment or cure for those who have contracted black lung disease. no

To limit the amount of coal dust that workers could potentially inhale within .
regulations promulgated pursuant to the Federal Coal Mine Health and Safety~ rtune,
1969, or Coal Act, require mine operators to reduce coal-mine dust within active ct oi
areas to less than 2 mg/m3 of air. Although this regulation produced a decline t0~
number of workers who now contract black lung disease, approximately 1000 Amenr· 1 e

k til ‘ wor ers s l contract the disease annually.
The hazards of coal dust are not limited to its potential health hazards. It is also

readily combustible material. Coal dust ignites readily when exposed to heat, sparks
0
~

other ignition sources. When dispersed in air, its lower flammable limit is greater than
0.05 oz/ft3 (>50 g/m3). Precaution always needs to be exercised by the generators and
users of coal dust to prevent its ignition.

7 .6-D RANKS OF COAL
Coal occurs naturally in several forms, each differentiated from the others by its rank, or
grade. The ranks of coal are determined by the extent to which carbonization has
occurred. Six major ranks of coal are recognized: peat, lignite, subbituminous, bitumi-
nous, semianthracite, and anthracite. As we read from left to right in this list, each rank is
progressively older and denser than those before it. Lignite and anthracite, for example,
have specific gravities of 1.29 and 1.4 7, respectively. Given this wide range, these are
sometimes referred to as soft coal and hard coal, respectively.

Some representative information about the individual ranks of coal is provided in
Table 7.14. Each rank is characterized by its heat content and carbon content. The carbon
occurs both as the element and in the form of numerous compounds that become locked
within the complex structure of coal. The compounds that are volatile evolve from co_al as
it is crushed and pulverized; they burn when their vapors are exposed to an igniu~n
source. Before they ignite, however, a sufficient energy of activation generally mus~
provided to first vaporize and release them from the inner structure of coal. The evo1v\ fl bl h. 1 . . d evo ve heat serves to produce more amma e vapor, w 1ch subsequent y 1gmtes an . the
heat. In this fashion, coal fires are self-sustaining until the flammable compounds in
coal have been entirely exhausted. h ,oal

Table 7 .14 shows that sulfurous compounds also are components of coal. W en
burns, sulfur dioxide is produced. rnains,

After the flammable components of coal have burned, a solid residue or ash r~uJII,
This ash consists of a mixture of the oxides of arsenic, barium, beryllium, boron, ca

10u.s. Energy Information Administration, Today in Energy (March 9, 2012).

262 Chapter 7 Chemistry of Some Common Elements

d

rABLE 7.14 Some Properties of the Different Ranks of Coal

HEAT CONTENT CARBON CONTENT SULFUR CON TNT E

RAllli<0F COAL Btu/lb kJ/kg (%) (%)

5500-8800 13,800-20,500 25-35 0.5-3
peat

7000 16,300 25-35 0.5-3
Lignite
Bituminous

7300-10,000 17,000-23,250 45-86 0.8-5.0

subbiturninous 9000 20,960 35-45
0.6-1.8

sernianthracite 11,500-14,000 26, 700-32,500

cite 14,000-14,500 32,500-34,000 40 0.4-1.9 Anthra

hromium, iron, mercury, thorium, uranium, zinc, and other elements. Although compo-
c enrs of this mixture were formerly ejected as fly ash into the atmosphere from the smoke-
nracks of coal-fired plants, today’s environmental regulations require its capture using
~r-pollution-control equipment. However, there are no federal regulations that address the
uJrirnate fate of the flyash generated during the burning of coal. Most of it ends up in stor-
age near the plants in huge piles, reservoirs, or impoundments.

7,6-E CHEMICAL PRODUCTS OBTAINED FROM COAL
A mixture of volatile gases evolves when coal is heated in the absence of air within a
simple closed assembly like that shown in Figure 7.16. The mixture is called coal gas. It
consists of ammonia, carbon monoxide, hydrogen sulfide, hydrogen cyanide, and meth-
ane, none of which condenses when exposed to the temperature of a cold water bath.
Although coal gas once was used to heat and illuminate homes and other buildings, its use
is now obsolete.

Coal
Gaseous hydrocarbons, ammonia, etc.

(coal gas)

Benzene, toluene,
phenol, etc.

(coal tar)

~:~UR~i7″16 In this laboratory demonstration. coal is strongly heated in the absence of air. In this manner. two
sour ma e or combust ible mixtures are isolated: coal gas and coal tar. When coal is exposed to an ignition
~ chemical components of t hese mixtures ignite and burn .

flyash The mixtu~e of
ultralight, fine particles
generated during the
combustion of coal

coal gas The flamma-
ble and toxic mixture
of gases and vapors
produced when coal is
strongly heated in the
absence of air

coal tar The con-
densed black, viscous
liquid produced by
heating coal in the
absence of air

distillation • A physical
process in wh ich a sub-
stance or group of
substances is separated
from a mixture by heat-
ing the mixture to a
specified temperature
or range of tempera-
tures, thereby convert-
ing one or more
components into a
vapor that is subse-
quently condensed and
collected

Coal gas

Chapter 7 Chemistry of Some Common Elements 263

I
I
I
I

Coal tar

Creosote oil

Coal tar pitch

The heating of coal also produces a viscous liquid called coal tar, a corn .
uct used for waterproofing when sealing roofing or pavements and coating rnercia] Prod
pipelines. It is also used as a binder during the construction of carbon electl!nddergrouh ·

d . roesf ••d pro uct10n of elemental aluminum. or th
Coal tar may be subjected to a separation process called distillation d . e · · h • . , ur1ng 1ht 1s eated within specified temperature randgeshto vap

1
~nze its components ~hich

t ese components are subsequently condense , t e resu ting materials ar · “‘hen
tar distillates. Although the latter term is loosely defined, three distillatee caUed to,

1 · d . sa~ • mze commercially: recog.

The “light” oil is so named because it is a mixture of compounds like be
tion 12.11-A) and toluene (Section 1~.11-~), “”‘.hose densit~es are less than ~~:ne (Sec.
of water; hence, it floats on water. Light 011 boils near 392 F (200°C). density
The “middle” oil boils between 392 and approximate_ly 518°F (200 and 2?0•c .
a raw material from which the chemical industry obtains naphthalene (Secti {” It is
A), phenol (Section 13.2-1), and cresols (Section 13.2-J). on 2-12.
The “heavy” oil boils between 518 and 662°F (270 and 350°C). It cont .
h . d b . a1ns a t racene and other polynuclear aromatic hy rocar ons (Sect10n 12.12-E). A n-

mercially important product produced from heavy coal tar distillate is ere corn.
·1 · 1· · ·d I d ·1 d · 050te 01 , a viscous 1qu1d w1 e y use to preserve ra1 roa cross ties and utility 1 . d d h l · · · bl f 1 · · po es against ecay an to cut asp a t so 1t 1s smta e or app 1cat10n as a road d

f. q roo mg tar.

The viscous residue remaining after coal tar is heated to 662°F (350°C) is called coal tar
pitch. Products made from this residue are used chiefly as sealants and roofing- and road-
paving compounds.

The solid residue that remains when coal and coal tar pitch are heated in the absence
of air is called coke. The heating process is conducted in industrial ovens known as bee-
hives. Coke is the form of carbon used by metallurgists to reduce the ores of arsenic, tin,
copper, iron, zinc, phosphorus, and other elements. It is also used in the steel industry for
reducing the iron oxide in iron ore in blast furnaces.

C(s) + FeO(s) — Fe(s) + CO(g )
Carbon Iron(II) oxide Iron Carbon monoxide

This chemical process is called smelting. A unique form of coke called petroleum coke is
similarly produced when the residues from heating certain crude oil fractions (Section 12.14)
are thermally treated.

7.6-F CHARCOAL AND CARBON BLACK
Charcoal results when wood, animal bones, nut shells, corn cobs, or peach pits are heated
in the absence of air. Most individuals first experience charcoal briquettes when they_fuel
the backyard barbeque, but considerable quantities of carbon are also used industrially
for “adsorbing” undesirable substances from products destined for commercial us~
Adsorption refers to the surface retention of solid, liquid, or gaseous molecules an
should not be confused with the term absorption, a process involving the physical pene-
tration of one substance into the bulk of another one. Charcoal is highly porous bee}~\:
it retains the skeletal cellular structure of the material from which it was made .. for
porosity gives charcoal a very large surface area per unit weight, and forms the basis
its effectiveness as an adsorbing agent.

90
o•C)

Charcoal may also be heated in the absence of air at 1472 to 1652°F (S~O t~ en as
ro produce activated charcoal, or activated carbon. This material often is c os

264 Chapter 7 Chemistry of Some Common Elements

~?£ .;:::i::tr:rmiS 9 t Rn?! :r:w’E:::¥ – -;;- -~ ,,-
bing medium, because its average internal surface area is 284,000 ft

2
~oz

3o ad;’itg). Medic~! per~on~el use activated charcoal as an antidote for the quick
(929 t of potential po1sonmg caused by the consumption of certain drugs and p~s-
rre_ac!lle~t is also used industrially as an adsorbing agent to purify atmospheric _emis-
ric1d:f~orn exhaust stacks by re~u~ing or eliminating the concentration of un~esira?le
s10° es On a smaller scale, 1t 1s used in gas mask canisters and cigarette filter ups

ic gas •
ro” h sarne purpose. . . .
for t;hen coal tar is burned m a furnace with a limited amount of air, a finely divided

f carbon called carbon black is produced. The soot that forms during petroleum
form_o ,ornposed primarily of carbon black. Different grades are available commercially
fires is e distinguished primarily by their particle size. They are used as components of a
rbat ~:r of consumer products including inks, paints, plastics, and tires, belts, and other
n~:sion-resistant rubber products. Carbon black is an ideal component in these products
~ue to its high surface-area-to-volume ratio.

7.6-G CONSUMER PRODUCT REGULATIONS INVOLVING CHARCOAL
To inforrn the public that carbon monoxide is produced when charcoal burns, CPSC
requires charcoal manufacturers to affix the label shown in Figure 7.17 to charcoal pack-
aging. In addition to the written warning, the label contains a pictograph of a grill situ-
ated inside a tent, home, and vehicle. These drawings are enclosed in a circle with an X
through it. They serve to convey the message that burning charcoal in enclosed areas
should be avoided, because deadly concentrations of carbon monoxide could accumulate
and kill the occupants.

7.6-H TRANSPORTING CARBON-BASED PRODUCTS
When shippers intend to transport coal tar distillates, DOT requires them to identify the
distillates on the accompanying shipping paper as shown in Table 7.15. All other labeling,
marking, and placarding requirements apply.

When shippers offer hot coal tar pitch for transportation in a kettle or other bulk
container as an elevated-temperature material, DOT requires them to display the HOT
marking on both sides and ends of the container.

DOT also regulates the transportation of coal dust, charcoal, activated carbon, coke,
and carbon black. DOT requires shippers who offer these products for transportation to
identify it as shown in Table 7.15 on the accompanying shipping paper. For domestic
transportation, DOT allows the use of other appropriate shipping names. All other label-
mg, marking, and placarding requirements apply.

aWARNING CARBON MONOXIDE HAZARD
Burning charcoa l inside ca n
ki ll you. It gives off carbon
m onoxide, w hich has no odor.

NEVER bu rn charcoa l inside
hom es, vehicles o r tents.

FIGURE 7 17 . and back ·a At 16 C.F. R. § _1 500. 14(b)(6), _c PSC requires charcoal manufacturers to affix this label to the front
and use i P nels_ of bags holding charcoal briquettes and other forms of charcoal that are intended for retail sale

n cooking or heating.

coal tar distillate • Any
fraction obtained by
distilling coal tar

creosote oil An oily
liquid obtained from
the distillation of
coal tar
coal tar pitch The
residue remaining after
coal is heated to
approximately 662°F
(350″C) in the absence
of air
coke The final residue
remaining after coal or
coal tar pitch is heated
in the absence of air

smelting A chemical
process used to isolate
an element from its
naturally occurring ore
by reacting the ore
with coke

charcoal The residue
remaining after wood,
animal bones, nut
shells, corn cobs, or
peach pits are heated in
the absence of air

adsorption A physical
phenomenon character-
ized by the adherence
or occlusion of atoms,
ions, or molecules of
a gas or liquid to the
surface of another
substance

activated charcoal
(activated carbon)
• The amorphous form
of carbon characterized
by a high absorptivity
for certain gases and
vapors

carbon black The
finely divided form of
carbon produced when
coal tar burns in a fur-
nace with limited air

Chapter 7 Chemistry of Some Common El ements 265

11

I
TABLE 7.15

Shipping Descriptions of Carbon-Based Che .
Products lllical

CARBON-BASED PRODUCT

Activated carbon
Carbon black

Charcoal
Coal dust

Coal gas

Coal tar distillates

Coal tar pitch

Coke

SHIPPING DESCRIPTION

UN1362, Carbon, activated, 4.2, PG 111
UN1361, Carbon (carbon black), 4.2, PG 11
or
UN1361, Carbon (carbon black), 4.2, PG Ill
UN1361, Charcoal, 4.2, PG Ill

UN1361, Carbon (coal dust), 4.2, PG 11

UN 1023, Coal gas, compressed, 2.3 (2.1)

UN! 136, Coal tar distillates, flammable, 3, PG 11
or
UN! 136, Coal tar distillates, flammable, 3, PG 111
UN3257, Elevated-temperature liquid, n.o.s., 9, PG

111
or
UN3258, Elevated-temperature solid, n.o.s., 9, PG 111
or
UN1999, Tars, liquid, 3, PG II

or
UN1999, Tars, liquid, 3, PG Ill

UN1361, Carbon (coke), 4.2, PG II

or
UN1361, Carbon (coke), 4.2, PG Ill

7 .6-1 RESPONDING TO INCIDENTS INVOLVING
A RELEASE OF COAL

Most fires involving coal may be effectively extinguished with water. When bulk quantities of
coal are burning, it is essential to use a deluging volume of water for the following reasons:

When fires are extinguished only on the surfaces of coal, combustion continues within
the interior of the reserve. Because the liberated heat cannot easily dissipate, the tern·
perature of the entire bulk increases, and the coal erupts into flame once again.
When water contacts coal, coke, or charcoal, the mixture may chemically react to
form carbon monoxide and hydrogen. This is the “water gas” previously no~ed ID
Section 7.2-C. When water gas ignites with in the confinement of a coal IU1ne, it
serves to rekindle coal fires.

7 .6-J UNCONTROLLED COAL FIRES
Uncontrolled coal fires typically are confined to natural coal beds and abandoned coa~
mines. They represent potentially destructive phenomena, not only because they co;;:s
a valuable natural resource, but because they transform landscapes and generat: ro·
of toxic air pollutants-the constituents of coal gas and coal tar. In essence, coal fires pod·

·d h d. · h · d · surrou v1 et econ JtJons t at can cause environmental catastrophes. The resi ents in . haling
ing communities can be swallowed into sinkholes or valleys or be sickened by in
pollutants in the dominant atmosphere, perhaps fatally. ‘

266 Chapter 7 Chemistry of Some Common Elements

When coal fires exist in coal beds, the coal was probably ignited by means of light-
. trikes or spontaneous combustion. A notable example of an uncontrolled fire in a ings . M . . N . 0

1 bed is Burning ount~m in ew South Wales, Australia. This fire has been burning
,oa 6000 years by some eSttmates and is credited as the oldest known ongoing coal fire.
for I the United States, there are at least 112 documented out-of-control underground 0 d 1 . 11 6

·n abandone coa mmes, utmost have been burning “only” for decades. World-
fires

I
th th d f d · · ·

12
Th ·d however, ere are ousan s o ocumented fires in abandoned coal mines. ese wi e, l’k 1 · · · d h

. were most 1 e Y mitiate w en methane (natural gas) seeped from the coal, accumu-fires d’ nf’ d · · h di ·n the surroun mg co me envuonment and ignited· then the burrung met ane !ate . ‘ ‘ ‘ . died the burning of the coal.
kin d d . 1 . · · · h h h Fires burn ownwar in coa mmes, acqumng oxygen from the air t at passes t roug
the fissures in surrounding ro~k. Although attempts are sometimes made to e~tinguish
them, most abandoned coal m~nes a_re ~early impossible to access. Beca_use entering them
. highly dangerous undertaking, firefighters cannot deluge the fires with water. Further-
is \e it is also impossible to starve the fires of oxygen, because the burning coal is exposed
:i~o;t continuously to. new so~rc~s of air f~om the countless borehol_es d~iven into the

rking mines to provide vent1lat1on for miners. Consequently, the fires in abandoned WO , •
coal mines are only rarely extinguished. Many quietly smolder from one generation into
the next.

U I /Au ust2011) pp.60-65. 11 ristin Ohlson, “Earth on Fire,” Discover u Y g World: A,Global Catastrophe,” Int. J. Coal Geo/., Vol. 59 G. B. Stracher, editor, “Coal Fires Burnmg around the
120041, pp, 7-17.

Chapter 7 Chemistry of Some Common Elements 267

do not easily ignite without first being kindled . .
xygen, however, these materials are lik I . · ~hen they have been exposed to hqmd

o I The combustion of meta/,$. Certai: y to ignite spontaneously.
gen The combination of mag • mhet~ls are likely to burn on contact with liquid oX}’ · nesium s avmgs and I’ ‘d f J ·

chemically reactive that these elements explod iqm h oxygen, or examp e, 1s so
parts also react with Jiqu · d e on _contact. T e components of aluminum

pf~~pn This phenomenon 1·s th I oxygefn, especially when the reaction is initiated by
ncao • e reason or avoid ” h f I · · ·

· ded for the storage and ha di ” f . mg t e use O a ummum m eqmpment inten . n mg o cryogenic oxygen.
The combustion of porous materials w; d

f orous materials. When Ji uid O •
0

0

‘ conc~e~e, and_ asphalt are examples 0
P d d di hq xygen contacts them, 1t 1s readily absorbed into their

Pores an pro uces me a t at can be sh k • •
hi h I. “d h .11 d oc -sensitive. An example is an asphalt surface on w c 1qm oxygen as sp1 e . Thi · h . . .

when subjected to a mechanical impact.s oxygen-enr1c ed asphalt may igmte explosively

7.1-D CHEMICAL OXYGEN GENERATORS
Chemical oxygen generators are portable devices that ca b h · II d

d d Th n e c em1ca y actuate to pro-duce oxygen on eman . ey are used in mines and oth 1 · h 1· · d “b”l . • · h h • er p aces wit 1m1te access1 1 -1ry m wh1c t e available oxygen supply may be limited Th d . . . ey were once use to escape
from noXIous or po1so?ous atmospheres, but this practice is now obsolete.

One type of chemical oxygen gener t · f · . . . a or consists o an apparatus with two separate
compartments contammg powdered iron and sodium chlorate, respectively. Oxygen is
generated when these substances are mixed and heated.

Fe(s) + NaC I03(s) —+ FeO(s) + NaCl(s) + 0
2
(g)

Iron Sodium chlorate Iro n(Il ) ox ide Sodiu m chl oride Oxygen

A percussion cap activated by a hammer provides the heat needed to initiate the reaction.
The heat that is evolved by this exothermic reaction permits it to be self-sustaining until
either of the reactants is depleted.

Another type of oxygen generator utilizes the thermal decomposition of an alkali
metal perchlorate. Lithium perchlorate, for example, decomposes when heated as follows:

L iCI04(s) — LiCl(s) + 20 2(g)
Li thium pe rc hl orate Lith ium ch lo1i de Oxygen

The reaction is initiated through use of an igniter that is struck by a firing pin.

7.1-E WORKPLACE REGULATIONS INVOLVING
BULK OXYGEN SYSTEMS

OSHA defines a bulk oxygen system as the assembly of equipment (storage tank, pres-
sure regulators, safety devices, vaporizers, manifolds, and interconnecting piping) that
Possesses an oxygen storage capacity at normal temperature and pressure of more than
13,000 cubic feet (368 m 3) when connected for service, or more than 25,000 cubic feet
(?08 m3) when available as an unconnected reserve.

When bulk quantities of oxygen are stored at the premises of industrial or institutional
co_n~umers, OSHA requires their owners to comply with certain regulations to prevent or
nun1mize the risk of fire and explosion. These regulations pertain to the location of the
system, its elevation, its accessibility to authorized personnel, measures associated with
~eakage from the system, diking, required distances betw~e n the syste~ and nearby expo-
ures, and other safety issues. For exa mple, OSHA reqmres the locat1on of bulk oxygen

st0rage systems to be either outdoor s abovegro und or within a building of noncombustible
~ons~ruction that is adequately vented and use~ fo r tha t y urpose exclusively. The selecte_d
ocat1on must be such that containers a nd a ssoci ated eqmpment are not exposed to electric
Power lines, flamma ble gas lines, or fl amma ble liqu id lines.

chemical oxygen
generator Any
portable device in
which oxygen is
produced upon demand
by chemical reaction

bulk oxygen system
For purposes of OSHA
regulations, the assem-
bly of equipment that
has an oxygen storage
capacity at normal
temperature and
pressure of more than
13,000 cubic feet
(368 m3) when con-
nected for service, or
more than 25,000 cubic
feet (708 m3) when
available as an
unconnected reserve

Chapter 7 Chemistry of Some Common Elements 227

I

I
I

SOLVED EXERCISE 7.

1

t ms to be eith er outdoo rs aboveground or with ‘

OSHA requires the location of bulk oxygen storage sys e d d used tor that purpose exclusive! T rn a build.
ing of noncombustible construction that rs adeq_uately vente an not ex osed to electric ow Y: he selecte
location must be such tha t containers and associated equipment are P . P er lines, flarnrn d
ble or combustible liqu id li nes, or flammable gas lines. Despite

th
e fa~ t::~n~:fl:~ :~ ~h~~~:~~,:nm;ble gas, ‘Nh:;

is the most likely reason OSH A requires bulk oxygen storage syS
t
ems

O
ion.

Solution: The most likely reason OSHA enacted this regulation is to minimi~e a pronounced risk of fire
explosion . Although oxygen is a nonflammable gas, it supports th e com_buS

t
ton of_ many common mater~~d

Because t hese materi als bu rn at increased rates in an oxygen-~nnche? envrronme~t, it rs p~udent to prevent th~
accumulation of oxygen near flammable or combustible materials. This is accomplished by installing bulk oxy e

. h . d’ d f h’ g n
storage systems In t e In Icate as 10n .

OSHA advises the owners of bulk oxygen systems to l~c~te them on ground higher
than flammable liquid storage tanks in nearby storage. When 1~ ts ?ecessary to locate a bulk
oxygen system on ground lower than adjacent flammable hqwd storage tanks, OSHA
requires the owner to provide a suitable means of diking, diversion curbing, or grading such
that in the event of a release from these tanks, the liquids do not accumulate under the bulk
oxygen system. Because flammable liquids burn at increased rates in an oxygen-enriched
environment, it is prudent to prevent their accumulation near the components of a bulk
oxygen system.

To warn workers of the presence of a bulk oxygen system within a workplace, OSHA
also requires its owner at 29 C.ER. §1910.104(b)(8)(viii) to permanently post a placard that

reads as follows:

. -1

OXYGEN

01

NO SMOKING

IQ\ NO OPEN
\:::s, FLAMES

7.1-F TRANSPORTING OXYGEN
When shippers offer GOX or LOX for transportation DOT · h ‘d tify 1·ras
h

· bl . , reg mres t em to 1 en ,
s own m Ta e 7.3 on the accompanymg shipping paper. DOT also requires them to affix
NON-FLAMMABLE GAS and OXIDIZER labels to th 1· d h k ·ng Wh · e cy m ers or ot er pac agt •

. en earner~ transport 1001 pounds (454 kg) or more of GOX or LOX, pOT
reqmres them to display NON-FLAMMABLE GAS I d h b lk k · used P acar s on t e u pac aging

TABLE 7.3 esrnptions of Oxygen and Oxygen Generators Shipping D · ·

OXYGEN

Compressed oxygen

Cryogenic oxygen

Oxygen generator, chemical

Spent oxygen generator, chemical

228 Chapter 7 Chemistry of Some Common Elements

SHIPPING DESCRIPTION

UN 10 72, Oxygen, compressed, 2.2, (5.1)

UN1073, Oxygen, refrigerated liquid, 2.2, (5- 1)

UN 3356, Oxygen generator, chemical, 5.1, PG
11

NA3356, Oxygen generator, chemical spent,
9, pG

111

the shipment; or, in lieu of posting NON-FLAMMABLE GAS placards DOT allows for · 0 YG ‘ carriers to display X EN placards that look like the following:

fhe motor van s_h~wn in Figure 7.3 has been placarded for the transportation of cylinders
d tanks conta1mng both oxygen and nitrogen.

an When carriers transport oxygen within bulk packaging, DOT also requires them to
di play the relevant identification number-1072 or 1073-on orange panels, across the

s ter area of the NON-FLAMMABLE GAS or OXYGEN placards, or on white square-
::point diamonds affixed on each side and each end of the packaging. For example, any
of the following means may be used to display 1072, the identification number of oxygen:

1072

When oxygen is transported in bulk by highway or rail, DOT requires carriers to
display the name OXYGEN on two opposing sides of the tankcar used for shipment.

OXYGEN

DOT requires shippers who transport chemical oxygen generators or spent chemical
oxygen generators to identify them as shown in Table 7.3 on the accompanying shipping

Airgas
Puri:tan
Medical

www.airgas.com

FIGURE 7 .3 DOT auth-
orizes carriers at 49 C.F.R.
§ 172.504(f)(7) to display
OXYGEN placards in lieu
of NON-FLAMMABLE GAS
placards on vehicles used
for the sole shipment of
oxygen in nonbulk cylin-
ders or other containers.
To emphasize that oxygen
is an oxidizer, the back-
ground color of the OXY-
GEN placard is yellow, and
the color of the symbol,
text, hazard class number,
and border is black. When
carriers transport oxygen
and other nonflammable
gases in nonbulk cylinders
or other containers within
the same vehicle, DOT per-
mits them to display NON-
FLAMMABLE GAS placards
or both OXYGEN and
NON-FLAMMABLE GAS
placards on the vehicle.
(Courtesy of Airgas Inc.,
Radnor, Pennsylvania.)

Chapter 7 Chemistry of Some Common Elements 229

I’ I
,11

I I

l I
I

II

allotrope A form
of the same element
having its own unique
set of physical and
chemical properties

· d with an attached means of ini · .
paper. When the generators are eqmppe . b d . tlation l) . . . . l for shipment y emonstratmg th , ().
reqmres their earners to obtam approva . . . . at the h 1 . . . • f reventmg their unintentional a t . Y a ‘
been outfitted with two positive means O P c Uation. 11e

7 .1-G RESPONDING TO INCIDENTS INVOLVING
A RELEASE OF OXYGEN

When oxygen is first released from a storage or transpo~tation ~evice, i~s concentra .
becomes elevated within the immediate area compared to its level m the air. Then s tion
ary fires are likely to occur, especially when the oxygen contacts fuels. An attem;t :~~:d-
be made to combat secondary fires only when they are located far from the area wh Id

f
. • ereth

oxygen is released or when the flow of oxygen rom its contamment vessel can be e . stopped
without exposing personnel to unnecessary nsk.

In the event of a transportation mishap involving the release of oxygen to the en • . d . f h . V1ton.
ment DOT recommends an initial downwm evacuatwn ° unaut onzed person , f h . h f . s toa
distance of at least 0.33 miles (500 m) f~om the sce?e O t e _mis ap. I a ra~ tankcar or
tank truck is involved in a fire, DOT advises evacuat10n to a diSt ance of 0.5 nules (800 m).

7 .1 -H OZONE, THE ALLOTROPE OF OXYGEN
Chemists refer to ozone as an allotrope of oxygen. An allotrope is a unique variation of
an element possessing physical and chemical properties that substantially differ from
those of any other form of the element. Allotropic forms are exhibited by certain ele-
ments that occupy Groups 4A through 6A on the periodic table. The allotropes of four
elements are noted in this chapter: oxygen, phosphorus, sulfur, and carbon.

Ozone is a form of elemental oxygen having three atoms of oxygen per molecule
instead of the usual two; thus, its chemical formula is represented as 03 and its Lewis
structure is represented as follows:

:Q: Q::Q: or 0 -0=0

Ozone is produced when either an electrical discharge or ultraviolet radiation is
passed through oxygen. Although it is reasonably stable at relatively low temperatures,
ozone decomposes rapidly at room temperature; that is, it spontaneously reverts into
“ordinary” oxygen. It is this relative instability that accounts for the fact that ozone is
generally encountered at very low concentrations.

At ordinarily encountered temperatures and pressures, ozone exists as a pale blue gas.
With a vapor density of 1.7 relative to air, ozone is denser than normal oxygen. It P?5~
sesses a pleasing smell in low concentrations, but has an irritating, pungent, “meta~ic
odor at moderate to high concentrations. The fresh, clean, spring-rain smell sometunes
detected around operating electric motors or following a lightning storm usually can be
attributed to the presence of ozone.

Two characteristics are responsible for ozone’s reputation as one of the moSt _h~z-
ardous materials known: a pronounced chemical reactivity and a distinct to~icitl}
0 · f 1 ‘d’ · d b en 1tse · zone is a power u oxi izmg agent-consi era ly more reactive than oxyg en
For example, ozone converts lead sulfide rapidly into lead sulfate, whereas 0 “yg
reacts so slowly with lead sulfide that the reaction is virtually imperceptible.

3PbS(s) + 403(g) 3PbS04(s)
Lead sul fid e Ozone Lead sul fate

. . id inha·
Because ozone 1s a toxic substance, precaution should be undertaken to avo_ une

lation exposure. When it is inhaled, ozone damages the scavenger cells of the iJllill hell
system. These cells, called macrophages, customarily destroy foreign bacteria, but ~ 0se
they are damaged, they are unable to effectively accomplish this task. Individuals W
macrophages have been damaged are more susceptible to contracting diseases,

230 Chapter 7 Chemistry of Some Common Elements

water

7.1-1 COMMERCIAL USES OF OZONE
Ozone is used commercially for several purposes. It is used to bleach undesirable colors
from oils, fats, textiles, and sugar solutions. It is also used as a microbicide at drinking
water and wastewater treatment plants. A microbicide is a substance that kills disease-
causing microorgani~ms. Ozone is an especially effective microbicide. Most importantly, it
is capable of ~est~oymg the parasite Cryptosporidium parvum that is sometimes found in
chlorinated drmkmg water. Chlorine alone does not destroy this parasite (Section 7.3-B).

When water contaminated with Cryptosporidium parvum is consumed, the parasite
causes gastrointestinal diseases that can be fatal. In 1993, for example, consumption of
water in the greater Milwaukee area caused 403 ,000 people to experience stomach
cramps, fever, diarrhea, and dehydration. 1 Moreover, the deaths of 104 people were
attributed to the outbreak of diseases caused by the presence of Cryptosporidium parvum
in their drinking water. Fortunately, such incidents are now rare in the United States and
other developed countries that choose to ozonize their drinking water supplies.

When ozone is used for water treatment, the processes illustrated in Figure 7.4 are imple-
mented. Air is first compressed to separate oxygen and nitrogen. Then, the oxygen is zapped
with electricity to produce ozone, which is passed into less-than-pristine water under pressure.
The ozone reacts with the impurities in the water, thereby killing its constituent microorgan-
isms. The water is then filtered and pumped into the municipal drinking water supply.

The use of ozone is also advantageous for treating wastewater. Ozone converts the
constituent hydrogen sulfide (sewer gas, Section 10.13) into sulfuric acid. At the concen-
tration produced, the sulfuric acid is benign.

3 H2S (s) + 40 3(g) –> 3H2S04(a q)
Hyd rogen sulfid e Ozone Sul furi c ac id

When ozone is used for treating drinking water or wastewater, the process is called ozonation.
Because ozone is unstable and extremely poisonous, it is always synthesized at its

intended point of use in minutely low concentrations. This synthesis is accomplished
“‘.ithin an ozone generator, an apparatus that supplies an ~l_ectrica~ c~rent to oxygen ?r
a1r. The ozone generator shown in Figure 7.5 may be_ fam1h~r to f1re~1g~ters, because 1ts
use often is encouraged within buildings damaged by fire. While the bmldmgs are enclosed
and vacated, ozone produced by the generator o~dizes the com~onents of smoke. 1:his
removes the offensive odors from furni ture, clothmg, and other items damaged by fire.
Ozone generators are also used to produce ozone for removal of musty odors that persist
Within walls and ca rpeting damaged by mold or mildew.

~ , “A mas sive o utbreak in Milwauk ee of Cryptosporidium infection transmitted through
he public wa ter su pply,” N. Engl. ]. Med ., Vol. 33 1 (199 4) pp. 161-167.

FIGURE 7 .4 A simplified
schematic route that
illustrates the production
of ozone from air and
its subsequent use for
producing pure water.

microbicide A
chemical substance
capable of destroying
microorganisms

ozonation The chem-
ical reaction involving
the addition of ozone
to a substance; the
treatment of contami-
nated drinking water to
kill the microorganisms
that cause waterborne
diseases

Chapter 7 Chemistry of Some Common Elements 231

llllllii…….

FIGURE 7 .5 Following
fires and floods, ozone
may be used to decon-
taminate and restore
buildings and their fur-
nishings to their original
or improved condition .
Because ozone is an
unstable gas, it must be
generated for use on
demand. (Courtesy of
Medallion Clean Indoor Air
Solutions of Las Vegas, Las
Vegas, Nevada.)

ground-level ozone
(troposp heric ozone)
The ozone that forms
in the troposphere (the
lower atmosphere)
by photochemically
catalyzed reactions
between voes and the
nitrogen oxides

volati le organic
compounds
(VOCs) Certain
vapors that undergo
photochemical reac-
tions in the atmosphere
to form ozone and
other air pollutants

ea

7.1-J GROUND-LEVEL OZONE
In certain metropolitan regions of the United States, ground-level ozone, or tropospheric
ozone, often is simultaneously present in the air with nitric oxide, nitrogen dioxide
(Section 10.14) and certain substances called volatile organic compounds (VOCs). The
voes are components of the air emissions from petroleum refineries, fuel dispensers,
chemical plants, and other industrial facilities . They typically are regarded as organic
compounds that boil at temperatures less than approximately 392°F (200°C) . Hence, the
substances in gasoline vapor are examples of voes. Figure 7.6 shows that the majority of
the atmospheric voes originate when nonchemical industrial processes are conducted.

The oxides of nitrogen are generated during the operation of automobiles. They are
components of vehicular exhaust and the plumes emanating from the smokestacks of
fossil-fuel-fired power plants. Within the troposphere-or lower atmosphere immediately
above the ground-these oxides react photochemically with the voes to produce ozone,
At ground level where we live and breathe, ozone and the nitrogen oxides often are_

th
e

primary components of polluted air, especially during the daylight hours of summerume,
when ample sunlight catalyzes ozone production.

When the ground-level ozone concentration exceeds approximately 100 ppb, weal
h

er
forecasters declare an ozone alert, which signifies that the ozone concentration in

th
e air

is approaching an unhealthful condition. At this concentration affected individuals-cl . ‘ an
especially the elderly-struggle for breath and feel dizzy. Their eyes, noses, throats, .
1 b

. . d d h · · h. wheez ungs ecome 1rntate , an t ey expenence fattgue, a lethargic feeling, coug ing,
ing, and hoarseness. s

Th
· h 1 · f 1 · h illnesse e m a atton o ow concentrations of ozone is also likely to exacerbate t e o·

f · d. ‘d I uff · f h · · · These pe o m 1v1 ua s s ermg rom eart ailments, emphysema or chronic bronch1tts, . 0d
1 lik I h f

. , pain a
p e are e y to coug more requently and with greater intensity experience cheSt . ked
· · duff ‘ benhn smus congest10n, an s er severe headaches. Short-term exposure to ozone has e 5ed

with premature death, and long-term cumulative exposure has been linked with an increa

232 Chapter 7 Chem istry of Some Common Elements

Nonchernical
industrial
processes

51%

Chemical
industrial
Processes

7%

Fuel
combustion

3%

Transportation
37%

risk of fatalities from respiratory causes This risk ri’ses u t
4

o, f
10

b ·
. t ozon 2 · P o 10 or every pp increase in exposure o e.

7.1-K WORKPLACE REGULATIONS INVOLVING OZONE
When the use of ozone is needed in the workplace, OSHA requires employers to limit employee
exposure to an ozone concentration in air of 0.1 ppm, averaged over an 8-hour workday.

7.1-L ENVIRONMENTAL REGULATIONS INVOLVING
GROUND-LEVEL OZONE

EPA has evaluated the adverse health effects that result from exposure to ground-level
ozone. Using the legal authority of the Clean Air Act, EPA regulates ground-level ozone as
a criteria air pollutant (Section 1.3-A) by setting its primary and secondary national ambi-
ent air quality standards at 0.12 parts per million (235 µg/m 3) as a 1-hour average and
0.079 parts per million ( 157 µg/m 3 ) as an 8-hour average.

On a hot, hum id day, the ozone concentration in urban air can exceed 100 parts per billion . What actions to limit the
adverse health effects associated with breathing ozone should be taken by persons who suffer from emphysema?

Solution: Emphysema is a lung ailment associated with the swelli ng of the alveoli and connecting tissues in
the lungs. Emphysema sufferers cough frequently, experien ce headaches, and have trouble breathing . These ill
effects are exacerbated when they inhale air contaminated with ozone . To limit undue distress when the ozone
concentration exceeds 100 parts per billion, emphysema sufferers are advised to remain in an air-conditioned
environment, avoid heavy work and exercise, and breathe oxygen fro m a portable so urce. –
7.1-M STRATOSPHERIC OZONE
Although the presence of ozone in the troposphere can be a troublewme factor for
maintaining good health, the presence of ozone m the stratosphere prnv1des an excep-
tional benefit to the inhabitants of Earth. Approximately 10 to 19 miles (16 to 30 km)
above Earth’s surface ozone occurs naturally in the region of the stratosphere called the
ozone layer. As sho:n in Figure 7.7, oxygen is bombarded within the stratosphere by
high-energy particles that originate in the sun. The b~mbardment causes s_ome oxygen
molecules to dissociate into their individual atoms (·Q·). The oxygen w1thm the ozone

~ael J 1 ” L O one exposure and mortality,” N. Engl. ]. Med., Vol. 360 (2009 ), erretr et a ., ong-term z
Pp. 1085-95.

FIGURE 7 .6 Ground-
level ozone is produced
when the volatile organic
compounds (VOCs) in the
air react with the nitrogen
oxides discharged in
vehicular exhaust. voes
are contained primarily
within the gaseous dis-
charges of power plants,
motor vehicles, and petro-
leum refineries . (Courtesy
of Un ited States Environmen-
tal Protection Agency.)

ozone layer The
region of the upper
atmosphere that is
especially plentiful in
ozone

Chapter 7 Chemistry of Some Common Elements 233 ‘ lillJJ

I I

ozone hole A thin
spot in the ozone layer
resulting from destruc-
tion of stratospheric
ozone by its chemical
reaction with chloro-
fluorocarbons and
other substances

02
0

3

03 \a, 02 03

03 03
·i:i·

03
10 to 19 mi 02 (16 to 30 km)

02 / Ozone layer

03 03
·i:i·

02 N2
02

02 N2 Lower atrnos h 02 N2 N2 /4 (tropospherei ere 02
N2 N2 N2 02 2

02 02 N2 02 N2 02 02
N2

Earth

FIGURE 7. 7 At the outer edge of the stratosphere is a region c~lled th~ ozone layer, where oxygen is constant!
converted into ozone. The ozone layer prevents much of the suns ultraviolet rad1at1on from reaching Earth. Y
Atmospheric scientists have discovered that in modern times the amount of stratospheric ozone has been deplet
compared with the amount in past times. This depletion allows more harmful ultraviolet radiation to penetrate t ed
Earth’s surface, increasing the instances of skin cancer and cataracts and weakening immune systems. 0

layer exists as a mixture of oxygen atoms and oxygen molecules. These oxygen species
collide to initiate a chemical reaction producing ozone.

0 2(g ) – 2 ·Q·(g)
Oxygen molecule Oxygen atoms

Oxygen mo lecule Oxyge n atom Ozone molec ul e

When molecules of stratospheric ozone absorb low-energy ultraviolet radiation, some revert
to the ordinary form of oxygen. Under normal conditions, the continuous formation and
photodecomposition of ozone compete favorably with one another. This chemical activity
produces a steady-state condition in which the rate at which the stratospheric ozone forms
from oxygen equals the rate at which it undergoes photodecomposition into oxygen.

In the past, the presence of the stratospheric ozone layer has protected Earth, its occupants,
and plant life from overexposure to the harshness of ultraviolet radiation. Today, howevei; the
former use of the halon fire extinguishing agents (Section 5.14), Freon refrigerants, foam·
blowing agents and coolants (Section 12.15), and other halogen-containing compoundsconnn·
ues to adversely affect the environmental quality of our planet. Released into the environment,
these compounds diffuse upward to the ozone layer, where their exposure to ultraviolet ra~·
tion produces halogen atoms. We note more fully in Section 12.15 that these atoms catalyze e
decomposition of ozone and contribute to its overall stratospheric depletion. h •

h . . . b . rosp eric In 1985, atmosp enc sc1ent1sts egan to note a precipitous drop m stra •n
ozone, first over Antarctica and then over the Arctic. The areas of the ozone lar~e1s.
which this thinning of the ozone layer has been observed are referred to as ozoneE oth’s
Due to their existence, more ultraviolet radiation from the sun now penetrates a~ern
atmosphere compared with the amount that reached Earth before 1985. The cf~and
among scientists is that this increased radiation exposure is the cause of certain heat
environmental problems such as the following:

Radi a tion weakens plant life and contributes to lower agricultural outputs.
1

nee of
Radiation may cause climatic changes that could ultimately disturb the baa
aquatic and land ecosystems.

234 Chapter 7 Chemistry of Some Common Elements

1 Th~ overexpos~re to ultraviolet radiation in humans has dramatically increased the
inc1denc~ of skm cance~ a?d cataracts and weakened immune systems.

1 In aquatic systems, rad1at1on harms marine life.

7,1-N ENVIRONMENTAL REGULATIONS INVOLVING
STRATOSPHERIC OZONE

To ensure the conti_nued survival of life on planet Earth, 43 representatives of the world’s
industrialized nat10ns agreed in 1987 to coordinate the control of ozone-depleting
substances by ~hasi?g out their manufacture and use. This agreement, sponsored by
the United Nations, ts known as the Montreal Protocol on Substances That Deplete the
Ozone Layer.

The original Montreal Protocol has now been ratified by 196 nations including the
United States. It banned the parties from producing and consuming most ozone-depleting
substances by January 1, 2010. Even with adherence to the Montreal Protocol, however,
scientists project that it will take until 2050 for the ozone layer to completely recover
from the world’s misuse of these hazardous substances.

Although the United States is a party to the Montreal Protocol, EPA has also used the
legal authority of the Clean Air Act to regulate the manufacture, use, and importation of sub-
stances that deplete stratospheric ozone. Among these substances are methyl bromide, carbon
tetrachloride, 1,1,1-trichloroethane, the halon fire extinguishing agents (Section 5.14), and
certain chlorofluorocarbons (Section 12.15).

7.2

HYDROGEN

Although Table 4.1 shows that hydrogen ranks ninth in natural abundance by mass on
Earth, only traces of this element exist naturally in the free state. Hydrogen is such a reac-
tive element that it is found on Earth only in compounds like water, acids, and hydrocar-
bons. Throughout the entire universe, however, hydrogen is the most abundant element,
72% by mass.

Elemental hydrogen is an odorless, colorless, tasteless, and nontoxic substance. Its
chemical formula is H 2• Although hydrogen exists as a gas at ordinary temperatures and
pressures, the gas liquefies when compressed under a pressure greater than 294 psi
(2030 kPa) and at a temperature less than -390°F (-234.5°C). Liquid hydrogen is
sometimes denoted as LH2.

7.2-A COMMERCIAL USES OF HYDROGEN
Elemental hydrogen is commercially available as both the compressed gas and the
cryogenic liquid. The chemical industry uses it as a raw material for the production
and manufacture of other chemical substances. The petroleum industry uses it to
Process crude petroleum fractions (Section 12.13 -C) during the production of petro-
!eum fuels, and the aerospace industry uses hydrogen as a fuel for propelling rockets
Into space.

Hydrogen is chosen as a rocket fuel by aerospace engineers, because the combustion
of a very small mass produces a prodigious amount of energy (see below). It is within the
aerospace industry that massive volumes of hydrogen are likely to be encountered in stor-
age. For example, at the John F. Kennedy Space Center, Cape Canaveral, Florida, a stag-
gering 800,000 gallons (3000 m3) of cryogenic hydrogen is held in a single storage tank.

For more than half a century, physicists and engineers have also been investigating ways
to successfully develop a thermonuclear reactor, in which the nuclei of hydrogen atoms fuse
and produce heavier nuclei by converting mass into energy. Nuclear fusion is the phenome-
non that powers the sun and other stars; it was also the means used on Earth to detonate the
hydrogen bomb pictured in Figure 7.8. However, the energy released during the detonation

Montreal Protocol
The international
agreement that pro-
vides for phasing out
the worldwide produc-
tion, manufacture, and
use of chlorofluorocar-
bons and other ozone-
depleting substances

Hydrogen gas

LH2

Chapter 7 Chemistry of Some Common Elements 235

FIGURE 7 .8 The explo-
sion o f an experi mental
t hermonucl ear device
(hydrogen bomb) on
Eniw eto k on Oct ober 3 1
19 52 . (Courtesy of Un ited ‘
States Department of Energy.
Nevada Operations Office, Las
Vegas, Nevada.)

of a hydrogen bomb is essentially uncontrolled. To serve as a commercially viable energy
source, self-sustaining fusion reactions must be controlled on a large sca~e. If a thermonu- 1
clear reactor could be successfully developed, hydrogen would most likely become the
energy source of the future. 3 However, serious technical obstacles in achieving a sustainable, I
controlled nuclear power source now exist. Commercialized nuclear fusion is not antici-
pated to begin until late in this century, if at all.

When hydrogen burns in an atmosphere of pure oxygen, the accompanying heatol
combustion is 61,000 Btu/lb (141,790 kJ/kg). This is the most energy for the least mass I
that evolves when any substance burns. This energy is used for launching spacecra& and
cutting and welding metals and glass. Jewelry manufacturers, for example, use the oxyhy·
drogen torch illustrated in Figure 7.9 to craft rings and bracelets made of platinum, a
metal that melts at 3191°F (1755°C). Compressed hydrogen and oxygen are separacelr
stored within steel cylinders and then pressure-fed through tubing into a mixing chamber
within the torch in a 2:1 ratio. This mixture is then discharged from the nozzle, where
combustion of these gases occurs.

3Research relating to the development of a fusion-demonstration reactor is now being conducted in a mula·
national effort called the International Thermonuclear Experimental Reactor Consortium. The United Sra:
European Union, Russia, India, Japan, South Korea, and China are members of the consortium that funds ~- I
project. In 2006, representatives of these seven partner nations agreed to build the plant at Cadarache 1~ ;~;O.
ern France, where 1t ts now under construction and slated to be finished in 2018 and begin operation b) boll<

The underlying technology in demonstrating fusion involves the use of a doughnut-shaped magnen~ “‘
called a tokamak, which confines the hydrogen as it is heated to 180 million degrees. At this superheat “n;.

h h d · I . 1. 0, uuo perature, t e y rogen exists as p asma (see footnote 10 Section 2.1) and its nuclei fuse ro form he iutn, ·u.,
d ff.. h b d .. . . Jhconsofll an. su tctent energy t at c_an e use to generate electnctty. If the mitial tests are successfu , t e

estimates that the construction of a commercial-scale fusion power plant could begin by midcentur)’, bl¥”‘
IhU”dS fu. · … tnota . . n t e _n_1te ta_t~s, _s,on research 1s also underway at a number of government fac1httes, mos eW Me.,i-O-

236 Chapter 7 Chemistry of Some Common Elements
Nattonal lgmt1on Factlity, Livermore, California, and Los Alamos National Laboratory, Los Alamos, N I

_j.

– ~~””””–..LJ.’°3:’::1:~:: Hydrogen Oxygen

FI GURE 7.9 _Hydroge n and oxygen separately enter the mi xi ng chamber of this oxyhydrogen torch from the
right. A 2:1 mixture disch arges from the nozzle at the left at a rate that causes the flame to burn at the tip of
the torch . When this mixtu re is ignited, temperatures rang ing between 3 300 and 4400°F (1800 and 2400°C )
are achieve d.

Hydrogen is also used commercially in connection with the chemical process called
hydrogenation. At elevat~d temperatures and pressures, and generally in the presence of
a catalyst, hydrogen com?mes with certain organic compounds to form commercially use-
ful products. Vegetable 01ls a re hydrogenated, for example, for use as shortening and raw
materials for the manufacture of soaps and lubricants.

Within the chemical industry, h ydrogen is used to produce metallic and nonmetallic
hydrides. Hydrogen combines with elemental sodium, for example, to produce sodium
hydride.

2Na(s) + H2(g) —-+ 2NaH (s)
Sodi um Hydrogen Sodium hydride

Ir is also used to produce compounds such as hydrogen chloride and ammonia .

Hydrogen C hl orine Hydroge n chl o,ide

Hydrogen Nitrogen Ammon ia

7.2-8 HYDROGEN AS AN ALTERNATIVE MOTOR FUEL
In the mid-2000s, there were persuasive reasons for believing that compressed hydrogen
would become a popular fuel for powering automobiles and other surface vehicles . In
particular, the prospective use of hydrogen as a vehicular fuel would reduce air pollution
and our reliance on fossil fuel resources from foreign countries. The use of hydrogen as a
vehicular fuel would truly revolutionize the automotive industry and theoretically pro-
duce a cleaner environment.

In hydrogen-powered automobiles, compressed hydrogen directly replaces the gaso-
line used in gasoline-powered vehicles. It is an example of an alternative motor fuel. In
1984, Daimler Benz first demonstra ted the use of hydrogen to power the Mercedes Benz
280 Te automobile.

hydrogenat ion The
addition of hydrogen
to a substance

alternative moto r
fuel Any of the sub-
stances or mixtures that
can power vehicles as
an alternative to the
use of motor gasoline
or diesel oil

Hydrogen may also be encountered as an alternati ve motor fuel in the form of a
metallic hydride, or metal hydride. A metal powder is generally contained in an alu-
minum cylinder with a pressure-relief valve and a coupling for connecting to a system
for potential use. When hydrogen is charged into the cylinder, it is absorbed into the
metal and p r oduces the corresponding metal hydride. Because the hydrogen is only
loosely bonded to the metal, it is desorbed readily for use upon demand . In this sense, fuel cell Any device
11 Performs similarly to the stora ge and withdrawal of electricity from a battery. that produces electricity

.Although the energy from burning hydrogen may be used directly to power motor
th rough a chemical

v h I react ion between a
d:v” es, hydrogen may also be used indirect!! in the form of fuel cells . These are source fuel and an

ices that produce electricity throu g h a chemica l react10n between a source fuel and oxidizer

Chapter 7 Chemistry of Some Common Elements 237

I I
I I

FI G URE 7 .10 Hydrogen
and oxygen react to
produce energy in a
hydrogen fuel cell. These
reactants are provided to
the cell from external
sources . The flow of
electrons in the cell
produces electricity, which
is the source of power.
When the electricity is
used to power a motor
vehicle, the hydrogen is
regarded as an alternative
motor fuel.

hyd rogen f uel cell A
device that produces
energy by the reaction
of hydrogen and
oxygen

FIGURE 7 .11 At a
hydrogen refueling sta-
t ion, hydrogen fuel is
stored either as a liquid or
a gas under pressure. As
hydrogen fuel is dis-
pensed from the pump,
its pressure typically
ranges from 5000 psig
(34,456 kPa) to 10,000
psig (68,911 kPa).
(Courtesy of Air Products,
Allentown, Pennsylvania.)

e;:-
0

,,., E~
(hydrogen) – • .,

,’
H2 (g) – 2H + (aq) + 2e – Electrodes
H 6

0

! 11lb Air
‘t> – ‘ff (oxygen) ..,

H20 -,.

an oxidizer. The cross section of a hydrogen fuel cell is shown in Figure 7.10. Hydro-
gen fuel cells are manufactured tiny enough to power a cell phone and large enough t
power a car or truck. The reactants in a hydrogen fuel cell are hydrogen and atmos~
pheric oxygen, which react to produce water and energy. The water is discharged t
the atmosphere and the energy is converted into electricity, which powers the vehicle~
Although the sales of vehicles powered by hydrogen fuel cells has annually increased in
the United States, gasoline-powered vehicles are still the most widespread form of
transportation.

The direct use of hydrogen gas for powering motor vehicles is now limited to areas
equipped with hydrogen-refueling stations like the one shown in Figure 7.11. These sta-
tions are primarily located in California, where the current use of hydrogen as an automo-
tive motor fuel is greatest. Each refueling station has equipment from which the hydrogen

238 Chapter 7 Chemistry of Some Common Elements

l is dispensed to customers. At 16 c FR §
3 fue · es retail hydroge n distributors t · · r/ 06 -12, the U.S. Federal Trade Commission

requtrser that resembles the follow·
0

a ix an orange-and-black label on the hydrogen dis pen tng:

HYDROGEN
MINIMUM

98%
HYDROGEN

Th. label identifies hydrogen as the alt •
is 98 ‘¾ by volum Th U S F ernative motor fuel and provides its minimum fuel

ranng as
O

d d e. h’ e · · ederal Trade Commission also requires new-vehicle
manufacturers an use -ve 1cle dealers to affix the 1 b 1 • ‘bl f f h h’

h · ed b h d a e on a v1s1 e sur ace o eac ve 1-cle t at 1s power y y rogen.

7.2-C PRODUCTION OF HYDROGEN
Hydrogen is produced for commercial use by the following methods:

In the firS
t

method, steam is first passed over red-hot coke or coal under high
temperature and pressure. This_ process, called coal gasification, produces a mixture of
gases called water gas, synthesis gas, or syngas. This mixture consists mainly of carbon monoxide and hydrogen.

Carbon monoxide Hydroge n

The hydrogen is isolated from the carbon monoxide, or the carbon monoxide is converted
to carbon dioxide, by passing the water gas with additional steam over a catalyst such as
iron(III) oxide.

Carbon monoxide Water Carbon dioxide Hydrogen

The carbon dioxide in the resulting mixture is passed through an alkaline solution.
The second industrial method of producing hydrogen involves the chemical action

of steam on methane at high temperatures.

Waler Hydrogen Carbon monox ide

The water gas produced by the chemical reaction is treated by either of the methods previ-
ously noted for isolating carbon monoxide-free hydrogen.

Hydrogen is also produced by a multistep, complex reaction between propane and
steam that is denoted by the following overall equation:

C3H 8(g) + 6H2O(g) –> 3CO2(g) + I0H2(g)
Propane Wa ter Carbon dioxide Hydrogen

The carbon dioxide in the resulting mixture is passed through an alkaline solution.
Hydrogen is also produced by the reaction of steam on methanol vapor using a

copper oxide/zinc oxide catalyst as follows:

CH 3OH(g) + H2O(g) –> CO2(g) + 3H2(g)
Meth anol Water Carbon diox id e Hydrogen

Once again, the carbon dioxide is passed through an alkaline solution.

coal gasif ication The
chemical process that
produces a mixture of
carbon monoxide and
hydrogen when steam
is exposed to coal at
high temperature and
pressure

wate r gas (synthes is
gas; syngas) The
mixture of carbon
monoxide and hydro-
gen produced by blow-
ing steam through a
bed of red-hot coke

Chapter 7 Chemistry of Some Common Elements 239
Ii’
I ~

lifting power The
natural ability of a gas
that is less dense than
air to move upwards

TABLE 7.4 Physical Properties of Elemental Hydrogen

Melting point
-434.S’F (-259.2’C)

Boiling point
-423.0’F (-252.8°()

Specific gravity (gas) at 68’F (20’C)
0 .071

Vapor density (air – 1)
0.069

Autoignition point
1058’F (570’C)

Lower flammable limit
4% by volume

Upper flammable limit
75% by volume

Liquid-to-gas expansion ratio
848

7.2-D PROPERTIES OF HYDROGEN
Elemental hydrogen possesses several interesting physi~al properties, some of which
listed in Table 7.4. A notable property is its vapor density-only 0.07 compared w·ih are

1 l”ft’ I a~ Becau~e this value is so low, hy~roge_n posse~s7s a natura I mg po~er or buoyan ·
potential. When expressed in metric uruts, the _lifting power of hydro~en 1s equal to the dJ.
ference in mass between 1 liter of air and 1 liter of hydrogen a~ a given ~emperature and
pressure. At 32°F (0°C) and 14.7 psi (10_1.3 kPa), the mass of 1 hter ?f ~1r 1s 1.2930 grams,
whereas the mass of 1 liter of hydrogen 1s 0.0899 grams; hence, the hftmg power of hydro-
gen in air at this temperature and pressure is 1.2930 g/L – 0.0899 ~~, _or 1.2031 g/L, As
we note in Section 7.2-H, this lifting power once was used to keep dmg1bles aloft.

Another important property of hydrogen is associated with the tiny size of its mole-
cules. Hydrogen molecules are extremely small when compared with other molecules.
They are so tiny that they easily leak through openings such as pipe joints and valve con-
nections. To prevent loss during storage and transport, the steel cylinders, tubes, and
tanks used to hold the compressed gas must be uniquely designed.

Another important property of hydrogen is the relatively high rate at which it diffuses
into the air. When released from a tank or container, hydrogen diffuses into the air more
rapidly than any other substance; that is, at the same temperature, hydrogen moves faster
than other gases or vapors.

Hydrogen is a flammable gas that burns when its concentration in air is between 4%
and 75% by volume. A concentration within this wide range can readily be achieved
when hydrogen is released from its container or tank. Nonetheless, because it dissipates
so rapidly, unconfined hydrogen does not remain in any single area for long.

Hydrogen burns in air to form water vapor.
2Hz(g) + Oz(g) –+ 2H20(g)

Hydrogen Oxygen Water

Given its low vapor density and high diffusion rate, the combustion reaction occurs as
th

e
gas moves upward. Hydrogen burns with an almost nonluminous flame that is especially
difficult to observe during daylight hours.

7 .2-E HYDROGEN AND THE RISK OF FIRE AND EXPLOSION
The physical properties of hydrogen give rise to two potential scenarios relating to its risk
of fire and explosion:

When released indoors or into an enclosure where the gas can accumulate, the pres·
ence of the hydrogen poses a pronounced risk of fire and explosion. . dissi·
When rele_ase? outdoors _or ~n a manner that enables the hydrogen t~ read

1
\ 11 .

pate, the hkehhood that it will form a flammable mixture is comparauvelY sJll

240 Chapter 7 Chemistry of Some Common Elements

.,,— · h h
H drogen diffus es into t e.arr at t e rate of 0.09s in.2/s (0.634 cni2/s) at 32’F (0’C ). What does the magnitude of
i s rate reveal about the likelihood that a fl amm able mixture of hyd rogen and air will be produced under most

1 .d nt scenarios that occur outside building s?
acc1 e
solution: This inform ation indicates that .hydrogen diff uses very rapidly into the surrounding air . In fact, uncon –
fi ned hydrogen ;roves ~ore rapidly into arr than any other gas. Hydrogen is also fl amm abl e over a wide concen-
tration range (4 1/• to.lS 1/o by volume). Because hydrogen does not re main loca lized for long, a flammable mixture
of hydrogen and arr is not 0rd in arr ly produced under most accident scenari os that occu r outside buildings.

Because hydrogen rises in the air, hydrogen-sensing devices often are installed near
the ceilings of enclosures m which hydrogen could be inadvertently released, as from a
leaking storage tank mto a roon:i , These devices activate exhaust fans capable of evacuat-
ing the hydrogen mto the outside air at very rapid speeds. When emergency response
crews are called to such incidents, they should enter the room only after the hydrogen has
been dispelled and its concentration measures less than 4 % by volume,

7.2-F CHEMICAL REACTIONS THAT GENERATE HYDROGEN
Although hydrogen may be encountered in cylinders and storage tanks, it also may be
inadvertently generated as the product of chemical reactions. Certain metals generate
hydrogen by displacing it from water and acid solutions. These displacement reactions
occur at rates that depend on the nature of the metal.

Most alkali metals and alkaline earth metals react with water and acids to produce
hydrogen. Certain other metals react much more slowly with water and acids, Nonethe-
less, these reactions still can pose the risk of fire and explosion, because the hydrogen
produced may absorb the heat of reaction and burst spontaneously into flame.

Many metals possess the capability of releasing hydrogen from acids. For instance,
metallic tin and aluminum displace hydrogen from aqueous solutions of hydrochloric acid
and sulfuric acid, respectively, as follows:

Sn(s) + 2HC l(aq) –> SnClz(aq) + Hz(g)
Tin Hydrochloric ac id Tin(ll ) chlori de Hydroge n

2Al (s) + 3H2S04(aq) –> Al2(S04l3 (aq) + 3Hi(g)
Aluminum Sulfuric acid Aluminum sulfate Hydrogen

The rates at which metals displace hydrogen from water and acidic solutions can be deter-
mined experimentally. When the metals are then arranged by decreasing reaction rates, the
compilation in Table 7.5 is obtained. This arrangement of the metals is called an activity
series. Its significance is summarized as follows:
1 The metals listed at the top of the table are so chemically reactive that they react with

both water and acids.
1 The metals below magnesium release hydrogen from steam and acid solutions , but

not from liquid water.
1 The metals below iron in the series do not displace hydrogen from steam, even when

the temperature is elevated.
1 The metals below lead possess insufficient chemical reactivity to release hydrogen

from either water or acids.

Hydrogen is also displaced by certain metals from solutions of sodium hydroxide.
The common metals exhibiting this chemistry are aluminum, zinc, and lead, but these
reactions occur slowly.

activity series An
arrangement of the
metals in order of their
decreasing ability to
generate hydrogen by
chemical reaction with
water and acids

Chapter 7 Chemistry of Some Common Elements 241

lead-acid storage
battery The collective
group of individual cells
composed of lead and
lead oxide plates and
immersed in a solution
of sulfuric acid having a
specific gravity ranging
from 1.25 to 1.30

TABLE 7.5
Activity series of Some Metals

Metals that react with water to produce Hi

Metals that react with water and acids to produce H2

Metals that react with neither water nor acids to produce H2

7 .2-G HYDROGEN GENERATION WHEN CHARGING
LEAD-ACID STORAGE BATTERIES

Cesiurn

Lithiurn

Rubidiurn

Potassiurn
Bari urn

Sodiurn

Calciurn

Magnesium

Alurninurn

Manganese
Zinc

Chromium

Iron

Nickel

Tin

Lead

Bismuth

Copper

Mercury

Silver

Platinum

Gold

Most of us are familiar with the lead-acid storage battery as the power source in virtu·
ally all motor vehicles, including electric hybrid vehicles. A battery differs from a fuel cell
in that its reactants are generated by chemical action. On the other hand, each fuel-cell
reactant must be continuously provided to a fuel cell from an external source.

A lead-acid storage battery produces electric current by means of two rever~ible
chemical reactions commonly referred to as charging and discharging. A battery is said to
be charged when an outside current has been delivered through it; then, as the batter)’
discharges, it produces electricity by means of chemical reactions involving the subStance’.
that were formed during the charging process. Hydrogen is one of them. When the batte;i
is being charged, bubbles of hydrogen accumulate near the negative plate; simultaneous Y,
bubbles of oxygen accumulate near its positive plate. As they are produced, both gases
dissipate into the atmosphere. . ul·

When banks of lead-acid storage batteries like those shown in Figure 7.12 ar~ s;r Jy
taneo usly charged within an enclosure, however, the concentration of hydrogen is

1
een

to exceed its lower flammable limit. Within an enclosed room, for instance, byd(°!%
rises and concentrates along the length of the ceiling. Because a concentration of on y en·
b I f h d

. ff ‘ . . . d uate v y vo ume o y rogen 1s su 1cient to produce a flammable mixture m air, a eq • s 10
·1 · h Id I b ·d d · · batterie ti auon s ou a w ays e prov, e w1thm rooms containing banks of storage

242 Chapter 7 Chem istry of Some Common Elements

prevent the accumulation of hydrogen and minimize an unreasonable risk of fire and
explosion. OSHA requires the owners and operators of enclosures in which lead-acid
storage batteries are charged to post warning signs like the following:

i ·tMM!il
7.2-H THE HINDENBURG

-BATTERY-
CHARGING AREA

NO SMOKING

Perhaps the best-known incident involving the burning of hydrogen was the destruction
of the German dirigible named the Hindenburg. Although the combustion of diesel fuel

FIGURE 7 .12 This
battery-charging station is
a location at which banks
of individual batteries are
simu ltaneously charged .
Hydrogen gas is produced
during the battery-
charging process . When
the battery-charging
station is located inside a
large ventilated room, the
production of hydrogen is
a relatively small problem,
but when it is located
inside an enclosure, the
hydrogen may reach a
concentration within its
flammable range. Then,
the accumulation of
hydrogen poses the risk
of fire and explosion .
(Photo by Eugene Meyer
and courtesy of Interstate
Batteries of Las Vegas, Las
Vegas, Nevada .)

powered its engines, hydrogen stored in large gas bags held this airship aloft. Germany I
had intended to use the Hindenburg to inaugurate a new era in fast transatlantic travel,
but the airship mysteriously caught fire and exploded while attempting its landing I
approach at Lakehurst, New Jersey. Given the presence of hydrogen onboard, the imrne- 11
diate sentiment linked a hydrogen leak with the burning of the airship. In Section 9.3-D,
we shall examine another likely cause .

The tragedy of the Hindenburg caused Germany and other nations to discontinue the
use of hydrogen as a buoyant gas in airships. Today, helium is used to provide lifting
power in airships, and it is a safer choice because it is a nonflammable gas. It possesses
about 93 % of the lifting power of hydrogen.

Chapter 7 Chemistry of Some Common Elements 243

7 .2-1 WORKPLACE REGULATIONS INVOLVING HYDROGEN
When it is intended for use at manufacturing and processing plants, hydrogen is
encountered as a confined gas within cylinders or storage tanks. The capacif&enerally
tanks used to store hydrogen range from less than 3000 cubic feet (85 m3 ) to ov~:s of the
cubic feet (425 m3 ). At 29 C.F.R. §§1910.103(b)(2)(1)(a)-(d), OSHA regulates th ~5,0oo
tions in relation to the position of buildings and other storage tanks so they a eir loca,

· · d 1 H d re read· accessible to delivery equipment and authonze personne · Y rogen storage tly
must be located aboveground but not beneath electric power lines, and away fro sys.tellls

1

for other flammable gases and flammable liquids. To alert individuals to the pr i1l P1Ping
. . k b 1 esenc this flammable gas, OSHA also requires the tan s to e permanent Y placarded Wi; of

sign that reads as follows: ha

! •

HYDROGEN
FLAMMABLE GAS
NO SMOKING OR

OPEN FLAMES

7 .2 -J TRANSPORTING HYDROGEN
When shippers intend to transport compressed or cryogenic hydrogen, DOT requires
them to identify it as shown in Table 7.6 on the accompanying shipping paper. All label-
ing, marking, and placarding requirements apply.

When hydrogen is transported in bulk by highway or rail, its name must be displayed
on two opposing sides of the tankcar used for shipment. When it is transported by rail in
a DOT-113 tankcar, DOT requires the carrier to display FLAMMABLE GAS placards on
squares having a white background and black border.

To meet demand in high-use areas of the United States, hydrogen is also transferred
by pipeline from production plants to user facilities . For example, hydrogen is supplied to
the petroleum refineries and petrochemical plants located along the coast of the Gulf of

TABLE 7.6 Shipping Descriptions of Hydrogen

HYDROGEN

Compressed hydrogen

Cryogenic hydrogen

Hydrogen in a metal hydride storage system

244 Chapter 7 Chemistry of Some Common Elements

SHIPPING DESCRIPTION

UN1049, Hydrogen, compressed, 2.1

UN1966, Hydrogen, refrigerated liquid, 2, 1

UN3468, Hydrogen in a metal hydride storage
system, 2.1

or
‘d storage UN3468, Hydrogen in a metal hydn e

system contained in equipment, 2.1

or
d ‘de storage UN3468, Hydrogen in a metal hy n

system packed with equipment, 2.1

M )(ico from a supply pipeline that stretches from the Houston Ship Channel to New
o:ieans and connects to a 600-mile (965-km) pipeline network.

2. 1( RESPONDING TO INCIDENTS INVOLVING 7· A RELEASE OF HYDROGEN
AS a practical matter, combating ~n ongoi_ng fire involving hydrogen is rarely success_ful
unless the flow of hydrogen fro~ its cont~1~ment vessel can be stopped withou_t exposing

sonnel to undue nsk. _For this reason, It 1s often best to permit a hydrogen fire to burn
~~hoot interference until t~e fuel is enti~ely exhausted. Because a hydrogen-fueled fire is
JikelY to caus~ secondary fires, appropnate emergency response actions should include

ention of its spread.
prevWhen LH2 ha~ ?~en released, the use of a water fog is generally warranted. It prevents
or reduces the possibility that hydrogen will concentrate in the nearby atmosphere and ignite.

7,3 CHLORINE
Elemental chlorine is not found naturally, but chlorine is found on Earth to the extent of
0.19 % by ma~s in a variety of_compounds including sodium chloride, potassium chloride,
calcium chloride, and magnesmm chloride.

At room conditions, chlorine exists as a yellow-green gas with a characteristic pene-
rrating and irritating odor. It is encountered as a gas and a liquefied compressed gas. The
element is about 2½ times heavier than air and is highly poisonous when inhaled . Several
other physical properties of chlorine are noted in Table 7 .7.

Elemental chlorine should not be confused with solid “chlorine” products used to
treat the water in residential and municipal swimming pools. Although the latter products
frequently are called chlorine, they actually are oxidizing agents that generate chlorine by
chemical action within the pools. Their properties are more appropriately discussed in
Chapter 11.

7 .3-A PRODUCTION AND COMMERCIAL USES
OF ELEMENTAL CHLORINE

For commercial use, elemental chlorine is prepared by passing an electric current through
either molten sodium chloride or an aqueous solution of sodium chloride or magnesium
chloride. When aqueous sodium chloride is used, sodium hydroxide and hydrogen are
simultaneously produced.

2NaCl (aq) + 2H20(/) –> 2Na0H(aq) + H2(g) + Cl2(g)
Sodi um chl oride Wale r Sod ium hydroxide Hydrogen

Chlorine

TABLE 7.7 Physical Properties of Elemental Chlorine

Melting point -150’F (-101′()

Boiling point -30’F (-35’C)

Specific gravity (gas) at 68’F (20’C) 1.56

Specific gravity (liquid) at 6.86 atm 1.41

Vapor density (air – 1) 2.49

Liquid-to-gas expansion ratio 457 .6

Chlorine

Chapter 7 Chemistry of Some Common Elements 245

pulmonary edema
The excessive accumula-
tion of fluid within the
lungs

TABLE 7.8
Adverse Health Effects Associated with
Breathing Chlorinea

TIME EXPOSURE FOR CONCENTRATION

1-8 hr exposure at< 0.5 ppm 1-hr exposure at 0.5-2 ppm

1-hr exposure at 2-20 ppm

1-hr exposure at> 20 ppm

1-hr exposure at 34 ppm

ADVERSE HEALTH EFFECT

No signs or symptoms of adverse effects
Strong odor; slight irritation of nose th ‘ roat eyes • and

Burning of eyes or throat; coughing and cha .
sensations krng

Sense of suffocation;_t~hest padinh; shortness of
breath; nausea; vomI rng; an oarseness

Pulmonary edema; sudden death; bronchos
(closure of the larynx) Pasrn

8 U.S. Army Center for Health Promotion and Preventative Medicine (USACHPPM) T~c_hnical Guide 230, “Environ
mental Health Risk Assessment and Chemical Exposure Guidelines for Deployed Military Personnel” (U.S. Arm~
Public Health Command, June 2010).

Throughout the civilized world, large volumes of elemental chlorine are required
annually for the following commercial applications:

A raw material for the production and manufacture of a wide range of chlorine-
containing compounds used as solvents, pesticides, dyes, bleaching agents, plastics,
refrigerants, and other commercial products
A microbicide for treatment of drinking water and wastewater to prevent waterborne
infectious diseases
A bleaching agent of paper pulp and certain textiles

7 .3-B ILL EFFECTS CAUSED BY INHALING CHLORINE
Exposure to elemental chlorine poses the threat of inhalation toxicity, its principal risk.
The exposure initially causes coughing, dizziness, nausea, headache, and severe inflamma-
tion of the eyes, nose, and throat. Prolonged (>1 hr) exposure to moderate concentra-
tions potentially causes congestion of the lungs, which can give rise to the onset of
pulmonary edema, obstruction of the airways, and painful and difficult breathing. Other
ill effects are listed in Table 7.8.

7 .3-C CHLORINE AS A CHEMICAL WARFARE AGENT
On a somber note, Germany used chlorine during World War I as a chemical warf~re
agent (Section 13.11). The worst incident occurred at Ypres, Belgium in 1915. Taktn7
advantage of ~ts highly pois~nous nat~re, the Germans unleashed the gas as a we~pontie
mass destruct10n. The chlorine was discharged from 5730 pressurized cylinders mt? f
wind, which carried the gas into the trenches. As a poisonous gas with a vapor den5ir_y o
2.49 (air = 1 ), the gas caused mass casualties by maintaining ground-level concentranons
capable of causing death when inhaled. . • h

The reported loss of life at Ypres ranged from 7000 to 15,000 people. The Brttl~e
retaliated by discharging chlorine from 5100 cylinders at German troops during rhe Ba~rd
of Loos. However, meteorological conditions caused the chlorine gas to move back row
the British troops, resulting in 2632 British casualties, including 7 deaths. f oi·

In 1925, the ~eague of Nations too~ first step toward eliminating the ~se eff!cs,
sonous gases dunng warfare between c1v1hzed nations. As a consequence of its

246 Chapter 7 Chemistry of Some Common Elements

130 nations ratified the Geneva Protocol which prohibits the use of chlorine and ver h · 1 ‘ o poisonous gases as c em1ca warfare agents. Known fo rmally as the Proto col for th e
0thr;bition of the Use in War of Asphyxiating, Pois onous, or Other Gases, and of Bacte-
pr~o ;cal Methods ~f Warf~re, it h_as successfully prevented civilized countries from using
r10. g ous gases against their wartime enemies.
poison

Geneva Protocol •
The international
agreement that bans
the use of chemical
weapons against
wartime enemies

SOLVED EXERCISE 7 .4

~ kcar contains 1 ton (0 .9 t ) of chlorine as a liquefied compressed gas . The following informat ion is im-
A. don its exterior surface :
pnnte

PROX28829
DOT-1 0SAS00W

LD LMT
LTWT
NEW

5000 LB
2000 LB
08 97

2273 KG
909 KG

use the data in Table 7. 7_ to ca lculate the approximate volume in cub ic feet of gaseous ch lorine that is generated
when the contents of this tank are suddenly released into the atm osphere during a transportation mishap, and
ascertain how this amount impacts emergency responders when t he wi nd speed is <6 mi/hr (<1 0 km/hr).

Solution: In Section 3 .7-A, we learned that ” LD LMT” and ” LT WT ” are the abbreviations for the load limit and
light weight of a rail tankcar, respectively. Hence, the imprinted information indicates that the tankcar weighs
2000 pounds (909 kg) when empty and may be used to safely transport up t o 5000 pounds (2273 kg) of liquid
chlorine.

using the specific gravity of liquid chlorine in Table 7.7, we calculate the density of t he liquid as follows:

lb
1.41 X 62.4 ft3 = 88 .0 lb/ft3

The volume occupied by 1 ton of liquid chlorine is then calculated to be 22 . 7 cubic f eet:

lb 1 ft3
1 m X 2000tA X 88 _0 lb= 22. 7 ft

3

using its liquid-to-gas expansion ratio, we determine that 22 .7 cub ic feet of liquid chlorine expands to a gaseous
vol ume of 10,388 cubic feet.

22.7 ft 3(11 q uld) X 45 7. 6 = 10,388ft3(gas)
One ton of chlorine per 10,388 cubic feet is equivalent to an undiluted concent rati on in air of 0.19 lb/ft3 , or

3000 parts per million. 4 Because the wind speed is relativel y low, this concentration remains virtually unchanged
du ring the response action. Table 7.8 indicates that the inhalat ion of 34 pa rts per million is likely to cause sudden
death . The inhalation of 3000 parts per million is unquestionably fatal.

7.3-D CHEMICAL REACTIVITY OF CHLORINE
Like oxygen, elemental chlorine is a nonflammable gas capable of supporting combus-
tion. The oxidizing ability of chlorine is apparent from its reaction with hydrogen, which
burns in a chlorine atmosphere to form hydrogen chloride.

H z(g ) + C[i(g) – 2HCl(g)
Hydroge n Chlo,i nc Hydrogen c hloride

,;———-
hA concentration of 0.19 lb/ft3 is converted to its equivalent in part per million through use of the program at

ttp ://www.unitconversion.org .

Chapter 7 Chemistry of Some Common Elements 247