Help with Board Question (No Word Count), Unit Essay. APA Format Throughout to Include Reference Page.

Board Question

According to the American Petroleum Institute (API), hydraulic fracturing (fracking) and horizontal drilling are unlocking vast U.S. reserves of oil and natural gas found in shale and other tight-rock formations. This fracking technology for the United States means security, economic growth, and jobs. Critics, however, are against fracking, pointing out environmental impacts such as groundwater pollution and putting people at risk of serious illnesses. What are your thoughts on this controversy?

Unit VI Essay

Your company has been contracted to assess and cleanup a site that previously had a manufacturing facility for an organochlorine pesticide (i.e., aldrin, chlordane, dieldrin, eldrin, or heptachlor). You are tasked with shipping these wastes off-site to a treatment, storage, disposal facility (TSDF) for disposal.

Review the information found in the 16-point GHS SDS for at least two of the organochlorine pesticides detailed in this question. Describe how you would prepare for transport of these materials and ensure proper shipping documentation based on DOT regulations (hazard class, descriptions, labels, markings, and placards). Describe the importance of having these regulations in place when transporting hazardous materials.

Describe the chemical properties, uses, and ill effects that first responders, such as EHS and FS professionals, may encounter upon arrival to the site discussed in this assignment. Summarize the information found in the SDS and explain how that information prepares EHS and FS professionals to assess and mitigate workplace hazards related to organochlorine pesticides.

Your essay must be at least one page in length. You are required to cite the relevant SDS in your response as well as at least one other sources. All sources used, including the textbook, must be referenced. Paraphrased and/or quoted materials must have accompanying citations in APA format.

OHS 3640, Interactions of Hazardous Materials 1

Course Learning Outcomes for Unit VI

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

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

transporting hazardous organic compounds.
5.2 Describe the importance of having regulations for transporting hazardous organic compounds.

6. Determine strategies for dealing with chemical properties of specific types of hazardous substances.

6.1 Identify the chemical properties, uses, and ill effects associated with common hazardous
organic compounds as related to the tasks and safety of an EHS & FS professional.

9. Examine widely used hazardous material classification and labeling systems.

9.1 Interpret the new 16-point format requirement of the new Global Harmonized System of
Classification and Labeling of Chemical Substances (GHS) Safety Data Sheet (SDS) as it
relates to organochlorine pesticides.

9.2 Utilize the new GHS SDS to assess and mitigate workplace hazards related to organochlorine
pesticides.

Course/Unit
Learning Outcomes

Learning Activity

5.1

Unit VI Lesson
Chapter 12 Reading
Chapter 13 Reading
Unit VI Essay

5.2

Unit VI Lesson
Chapter 12 Reading
Chapter 13 Reading
Unit VI Essay

6.1

Unit VI Lesson
Chapter 12 Reading
Chapter 13 Reading
Unit VI Essay

9.1

Unit VI Lesson
Chapter 12 Reading
Chapter 13 Reading
Unit VI Essay

9.2

Unit VI Lesson
Chapter 12 Reading
Chapter 13 Reading
Unit VI Essay

Reading Assignment

Chapter 12:
Chemistry of Some Hazardous Organic Compounds: Part I, pp. 466-527

UNIT VI STUDY GUIDE

Chemistry of Some Hazardous
Organic Compounds

OHS 3640, Interactions of Hazardous Materials 2

UNIT x STUDY GUIDE

Title

Chapter 13:
Chemistry of Some Hazardous Organic Compounds: Part II, pp. 533-600

Unit Lesson

In this unit, we will study the chemistry of some hazardous organic compounds. Organic compounds are all
around us. They are the building blocks and end products of a wide variety of many commercial products
such as rubber, fuels, pharmaceuticals, cosmetics, detergents, coatings, and agrichemicals. As useful as they
are, organic compounds have inherent hazardous properties of which environmental health and safety (EHS)
and fire science (FS) personnel must be aware. For example, organic compounds are usually flammable and
some are toxic.

Chapters 12 and 13 in your textbook focus on more simple organic compounds. In a subsequent unit, we will
study the more complex forms of organic compounds that include polymers and explosives. Note: To better
understand this unit, refer to the textbook to see the structural formulas of the various organic compounds as
they are not easy to present in a Word document. There is also a short PowerPoint presentation attached in
the Suggested Reading that illustrates structures of organic compounds.

CHAPTER 12: Chemistry of Some Hazardous Organic Compounds: Part I

What are organic compounds?

 Organic compounds have one or more carbon (C) atoms in their chemical makeup or structure. Some
examples are methane (CH4), carbon monoxide (CO2), and polychlorinated biphenyls (PCBs).

 Carbon atoms can share electrons with other non-metallic atoms, such as carbon disulfide (CS2) and
methane (CH4). When carbon shares electrons with a hydrogen atom, the resulting compound is
known as a hydrocarbon. Most organic compounds are hydrocarbons (HC).

 Carbon atoms can also share electrons with other carbon atoms. In this case, their sharing can be by
single bond (C-C), double bond (C=C), or triple bond (C≡C) (Meyer, 2014).

Hydrocarbons (HC) are divided into the following:

 Aliphatic hydrocarbons do not contain aromatic or aromatic-like structures (the simplest aromatic HC
is benzene).

 Aromatic hydrocarbons contain a benzene ring; aromatic does not necessarily reflect odors, but
denotes specific chemical and physical properties (Pine, 1987).

A benzene ring has six carbon atoms with three double bonds. The structural formula is shown below:

Structural formula of a benzene ring
(Jynto, 2010)

OHS 3640, Interactions of Hazardous Materials 3

UNIT x STUDY GUIDE
Title

ALKANES and CYCLOALKANES

Alkane is a hydrocarbon with a single bond. The bond could be with hydrogen (C-H) or with another carbon
(C-C). Refer to Table 12.1 on page 471 in our textbook for the simple alkanes and their names. The general
chemical formula for alkanes is:

CnH2n+2 where n = non zero integer.

Example: Propane has three carbons, so n=3; therefore, the number of H is 8 (Meyer, 2014). Propane can
then be written as C3H8 or as shown below:

Cycloalkanes are alkanes arranged in a cyclic ring (single bonds). The general formula is CnH2n. See page
472 of your textbook for the illustration of some examples such as cyclopropane and cyclobutane. Alkanes
and cycloalkanes are known as saturated hydrocarbons since the four bonding electrons of each carbon atom
are shared with the bonding electrons of four other atoms; bonds are stronger/more stable compared to the
double or triple bonds (which we will cover later in this unit) (Meyer, 2014).

Common system of nomenclature: Molecular and structural formulas of the alkanes and cycloalkanes are
discussed on pages 470-471 of your textbook. It is a straight-forward discussion, so read them to get a
foundation of how to name organic compounds and write their formulas.

IUPAC system of nomenclature: IUPAC (International Union of Pure and Applied Chemistry) has
established some rules on naming the more complex organic compounds to ensure uniformity (Meyer, 2014).
The rules for each type of organic compound are listed in the textbook with examples. Familiarize yourself
with them so you can identify most organic compounds that you encounter in practice.

Alkenes, dienes, trienes, and the cyclos: These HCs have double bonds that are considered as
unsaturated HCs (more reactive than the saturated HCs) (Meyer, 2014). Alkenes have the general formula of
CnH2n+2. Cycloalkenes have the general formula of CnH2n-2. Just like with the alkanes, there are also rules in
naming them (see page 477 in your textbook). In the names, the prefix depends on the number of carbon
atoms, and the suffix is ene.

Alkynes: Alkynes have one or more triple bonds, also considered unsaturated HCs (Meyer, 2014). Their
general formula is CnH2n-2. The simplest alkyne is C2H2 known as acetylene. If we are to follow the IUPAC
system, the other name for acetylene is ethyne (two carbon atoms with a triple bond).

Common aliphatic HC: Now that you understand the basics, some common organic compounds that may be
encountered in your daily work or life are listed below and covered in the textbook. These are all very
flammable gases, so shippers are required to follow DOT regulations during their transport.

 Methane is the simplest aliphatic HC (CH4); it is the primary constituent of natural gas, also landfill
gas. It is an odorless gas which is why commercially mercaptan (garlic or rotten egg smell) is added
so it can be detected if there is a leak.

 LPG (liquid petroleum gas) is propane and butane or a mixture of both.

 Ethylene (ethane) and propylene (propene) are simple alkenes (double bonds).

 Acetylene, as mentioned earlier, is the simplest alkyne (triple bond) (Meyer, 2014).

AROMATIC HC

Benzene, Toluene, and Xylene (BTX): These are commonly encountered aromatic HCs; see Table 12.12 on
page 496 of your textbook for a list of their physical properties. They have commercial uses but may impact
worker’s health if their vapors are inhaled. BTX are considered volatile organic compounds. Years ago, when

Structural formula of propane
(NEUROtiker, 2009)

OHS 3640, Interactions of Hazardous Materials 4

UNIT x STUDY GUIDE
Title

underground storage tank regulations first came out, there were a lot of leaking underground tanks found,
mostly from gasoline stations. The contaminants of most concern, which also served as indicators of a
gasoline leak, were BTX. Benzene is a known human carcinogen (Meyer, 2014).

Polynuclear Aromatic HCs (PAHs): The only PAH that is of commercial importance is naphthalene (Meyer,
2014). For the most part, PAHs are formed as products of incomplete combustion. Specific PAHs are
identified when a sample media is analyzed (considered semi-volatile organic compounds). Examples: PAHs
are adsorbed in soot from fires, exhaust from diesel fired engines have PAHs, and landfill leachates could
also have PAHs.

There are also firefighting concerns with PAHs. Firefighters are vulnerable to airborne PAH exposure at fire
scenes and potentially from the idling of diesel fueled fire trucks at the firehouse. For air quality and health
reasons and more importantly to comply with the US Environmental Protection Agency (EPA) rules, some fire
departments that use diesel fueled fire trucks have already upgraded or retrofitted their engines with air
pollution control equipment. This helps to reduce diesel particulate emissions. Due to potential power loss
issues, the EPA (2012) granted relief for fire engines and ambulances from these retrofit requirements.

PETROLEUM AND PETROLEUM PRODUCTS

Hydrocarbons are generally associated with petroleum. Petroleum (crude oil) is a complex chemical mixture
of thousands of organic compounds that are mainly hydrocarbons (Meyer, 2014). Crude oil is found in
subsurface rocks, the depth of which varies depending where in the world it is located. When crude oil is
extracted, water and gas are also produced. The natural gas is processed at gas plants to break it down into
methane (natural gas), propane, butane, and natural gasoline. The crude oil is processed at refineries
resulting in gasoline, diesel, and kerosene products with which we are all familiar. In all production processes,
starting from crude oil extraction from the ground to the transportation of the various products by trucks or
pipelines to storage and use, there is the potential for exposure and emergency incidents. This is why EHS
and FS professionals are needed.

Hydraulic fracturing (fracking): An oil and gas development process that has recently gained popularity as
well as controversy is hydraulic fracturing. This process involves injecting water under high pressure into
bedrock formations to increase oil and/or gas flow to a well (United States Geological Survey, 2014). For
additional information, visit http://www.usgs.gov/hydraulic_fracturing/. Its recent use is in the extraction of
natural gas from shale (sedimentary rock). Most of you have probably heard of the Marcellus Shale—this is
the largest known reservoir of natural gas, found underneath sizeable portions of West Virginia, New York,
Ohio, and Pennsylvania (Meyer, 2014). This is why there is a lot of fracking being conducted on the east
coast.

Other HCs: The textbook also discusses chlorofluorohydrocarbons (CFCs) and polychlorinated biphenyls
(PCBs), which I am sure you are all familiar with. You are required to read about these organic compounds for
this unit.

CHAPTER 13: Chemistry of Some Hazardous Organic Compounds: Part II

In this chapter, we will cover the various classes of organic compounds and get familiar with their structures,
their properties, and precautions in handling them. These compounds and their general chemical properties
can be identified by knowing their functional groups. Their functional groups as well as their general formulas
are listed in Table 13.1 on page 535 in your textbook. Depending on your job, it may be beneficial to
memorize the functional groups and classes.

Alcohols: The general formula is R-OH, where R is the arbitrary alkyl or aryl group and OH (hydroxyl) is the
functional group (e.g., CH3-OH methyl alcohol or methanol). Simple alcohols such as methanol, ethanol, and
isopropanol produce soot-less flames when they burn; this presents a problem when fighting fires involving
them.

Ethers: The general formula for simple ethers is R-O-R’ where R and R’ are arbitrary alkyl or aryl groups and
–O- (oxy) is the functional group (e.g., CH3-O-CH2CH3 methyl ethyl ether). Ethers are highly volatile and
flammable liquids and pose fire and explosion hazards. They can react with atmospheric oxygen to produce
peroxo-organic compounds.

http://www.usgs.gov/hydraulic_fracturing/

OHS 3640, Interactions of Hazardous Materials 5

UNIT x STUDY GUIDE
Title

Aldehydes and ketones: Their functional group is called carbonyl (see the textbook for the illustrations of
these organic compounds). The simplest aldehyde is formaldehyde. If you have done biology
experiments/projects in high school, formaldehyde was used to preserve frogs and other specimens. A
solution of formaldehyde that is commonly used as a disinfecting, sterilizing, and embalming agent is formalin.
Formaldehydes are also released from equipment exhaust stacks during combustion of organic compounds
such as natural gas.

Acetone (also propanone or dimethyl ketone) is the simplest ketone. Other known ketones are methyl ethyl
ketone (MEK) and methyl isobutyl ketone (MIBK). These ketones are water soluble but highly flammable.

Other organic compounds: Other classes of organic compounds that you should be familiar with are esters,
organic acids, peroxo-organic compounds, and amines.

The following are used as chemical warfare agents:

 nerve agents,

 vesicants,

 blood agents, and

 choking agents

References

Environmental Protection Agency. (2012). EPA grants relief for fire trucks and ambulances. Retrieved from
http://www.epa.gov/otaq/highway-diesel/regs/420f12025

Jynto [Username]. (2010, August). Structural formula of a benzene ring [Image]. Retrieved from

https://commons.wikimedia.org/wiki/File:Benzene-2D-full.svg

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

NEUROtiker. (2009, June). Structural formula of propane [Image]. Retrieved from

https://commons.wikimedia.org/wiki/File:Propan_Lewis.svg

Pine, S. (1987). Organic chemistry (2nd ed.). New York, NY: Mc-Graw-Hill.

United States Geological Survey. (2014). Introduction to hydraulic fracturing. Retrieved from

http://www.usgs.gov/hydraulic_fracturing/

Suggested Reading

Click here to access a PowerPoint presentation covering the basics of organic chemistry.
Click here to access a PDF version of this presentation.

The U.S. EPA maintains a webpage describing natural gas and their position on gas extraction. Links to
other resources such as the U.S. EPA final report on hydraulic fracturing on drinking water resources can
be found on this page.

Environmental Protection Agency. (2012). Water: Hydraulic fracturing. Retrieved from

http://water.epa.gov/type/groundwater/uic/class2/hydraulicfracturing/wells_hydrowhat.cfm

https://online.waldorf.edu/CSU_Content/Waldorf_Content/ZULU/EmergencyServices/OSH/OSH3640/W14Cc/UnitVI_Presentation.ppsx

https://online.waldorf.edu/CSU_Content/Waldorf_Content/ZULU/EmergencyServices/OSH/OSH3640/W14Cc/UnitVI_Presentation

http://water.epa.gov/type/groundwater/uic/class2/hydraulicfracturing/wells_hydrowhat.cfm

OHS 3640, Interactions of Hazardous Materials 6

UNIT x STUDY GUIDE
Title

The U.S. Geological Survey provides a summary of the technology of hydrofracking or using water using
high pressure to develop oil and gas wells. There are links to several assessment and resources that can
be found on this page.

United States Geological Survey. (2014). Introduction to hydraulic fracturing. Retrieved from

http://www.usgs.gov/hydraulic_fracturing/

http://www.usgs.gov/hydraulic_fracturing/

Interactions of Hazardous Materials

This presentation was prepared to provide some

background or refresher notes on selected and limited

topics in basic organic chemistry that may be of help

for the chemistry portion of the OSH 3640 course.

Your textbook is needed for some parts of this

presentation.

Intro to Organic Chemistry
Prepared by:

Dolores Gough, P.E.

George Gough, P.E., CSP

Basic Features of Atoms

Atom: smallest particle of an element; composed of smaller

particles known as electrons, protons, neutrons

Electrons: negative particles responsible for reactivity; charge of

–

1

Protons: positively charged particles; charge of +1

Neutrons: neutral particles; no charge

P+ N

e –

–

Protons and neutrons reside within the nucleus.

Electrons reside in designated regions surrounding the nucleus

called atomic orbitals.

Electron

Nucleus

Carbon has four (4) electrons in the outer shell that need to bond for stability.

Carbon can also share electrons with other carbon atoms to form the following

types of carbon bonds:

C – C (single bond)

C = C (double bond)

C Ξ C (triple bond)

Organic Chemistry – chemistry of compounds containing
one or more carbon atoms. However, the hydrogen atom is
almost always present in these compounds (shown in next slide).

6 P

6 N

–
–
–
–

–
Atomic Structure of Carbon

–

Carbon electron sharing with Hydrogen: Hydrogen has one (1) electron in its outer shell that

can share with the C to form covalent bonds. However, C needs to share all 4 electrons in its

outer shell. Example: If all four electrons were shared with H, CH4 is formed.

H

H C H or CH4 (methane)

H

1 P

0 N

Atomic Structure of Hydrogen

–

Hydrocarbons (HC) are compounds whose molecules consist of only
carbon and hydrogen atoms.

Carbon – Carbon Single Bond:

• Alkanes: have general formula of CnH2n+2 where n = number of carbon atoms

• Example: Butane has 4 carbons, all single bonds as shown:

H H H H

I I I

I

H – C – C – C – C – H C4H10 (see Table 12.1)

I I I I

H H H H

• Cycloalkanes: same as alkane but the first and last C are linked (closed).

In naming them, just add “cyclo” to the alkane name. (Examples – see Sec. 12.2-B)

Cyclobutane
( http://commons.wikimedia.org)

Cyclohexane

http://commons.wikimedia.org

Organic Chemsitry Graphics retrieved from http://commons.wikimedia.org

Carbon = Carbon Double Bond:

• Alkenes or Olefins: have general formula of CnH2n
• Example: Butene has 4 carbons and at least 1 double bond

H H H H

I I I I

H – C – C = C – C – H or H – C = C – C – C – H

I I I I I I I

H H H H H H H

C4H8

Carbon Ξ Carbon Triple Bond:

• Alkynes: have general formula of CnH2n-2
• Example: Butyne has 4 carbons and at least 1 triple bond

H H H H
I I I I

H – C – C Ξ C – C – H or H – C ΞC – C – C – H

I I I I

H H H H

C4H6

General Properties/Characteristics:

Alkanes (paraffins or saturated HC): relatively stable to chemical

reactions. Low molecular weight alkanes are gases or

liquids, high MW are solids.

Alkenes (olefins ): unsaturated HC because they don’t have the

maximum number of atoms each carbon is able to

accommodate; physical properties are closely

related to those of the corresponding alkanes

Alkynes (unsaturated HC): physical properties similar to those

of alkanes and alkenes

IUPAC System of Nomenclature

IUPAC (International Union of Pure and Applied Chemistry – used

for naming complex hydrocarbons)

When a hydrogen atom is removed from an alkane, the resulting

group is called alkyl group or alkyl substituent. See Table 12.2 (page

472) for common alkyl substituents.

Rules for naming an alkane (pages 472-473)

1 2 3 4 5

Example: CH3 – CH2 – CH – CH2-

CH3

I

CH3

3-methyl pentane

Methyl (one carbon)

IUPAC SYSTEM (cont.)
Rules for naming alkenes (1 double bond), dienes (2 double bonds),

tienes (3 double bonds) & “cyclos”

1 2 3 4 5

Examples: CH3CH = CHCH2CH3 2- pentene

1 2 3 4

CH2 = CH – CH = CH2 1, 3 – butadiene

Rules for naming alkynes (pages 479-480)

1 2 3 4 5 6

Examples: CH3CH2C Ξ CCH2CH3 3- hexyne

1 2 3

CH Ξ CCH3 1- propyne

Aromatic Hydrocarbons

Regarded as compounds whose molecules are composed of

one or more special rings of carbon atoms

Benzene – simplest aromatic hydrocarbon

C6H6

http://commons.wikimedia.org

Other common aromatic compounds:

• Toluene (or methylbenzene)

• Xylene

1,4 dimethyl benzene

(para-xylene)

1,3 dimethylbenzene

(meta-xylene)

1, 2 dimethylbenzene

(ortho-xylene)

http://commons.wikimedia.org

http://commons.wikimedia.org http://commons.wikimedia.orghttp://commons.wikimedia.org

Organic Chemistry Graphics retrieved from http://commons.wikimedia.org

Polynuclear Aromatic Hydrocarbons (PAHs)

Two or more mutually-fused benzene rings per molecule (when a pair of

carbon atoms is shared and the bond between them)

Examples:

•Naphthalene (C10H8): colorless solid having odor of mothballs; poses

chronic respiratory hazard to humans; exposure is llinked with onset of

cancerous growths.

• Anthracene (C14H10): component of coal-tar.

http://commons.wikimedia.org
http://commons.wikimedia.org
Organic Chemistry Graphics retrieved from http://commons.wikimedia.org

Functional Groups
In a hydrocarbon, one or more hydrogen atoms may be substituted with

another atom or group of atoms. This atom or group of atoms is called the

functional group, and this group determines many of an organic compound’s

characteristic chemical properties. It identifies an organic compound as alcohol,

ether, aldehyde, etc.

There are over 100 functional groups; some of the important ones are covered

in the book and listed in Table 13.1.

Let us take some examples:

Functional group: hydroxyl (-OH)

Class of organic compound: alcohol

General formula: R-CH2-OH

Functional group: oxy (-O-)

Class of organic compound: ether

General formula: R-O-R’

where: R and R’ are arbitrary alkyl or aryl substituent

Alcohols
•Organic compounds derived by substituting one or more hydrogen

atoms in hydrocarbon molecule with hydroxy group (-OH)

•General chemical formula of simple alcohol is R-OH

Examples: H

I

Methyl alcohol H – C – O – H or CH3OH

(methanol) I

H

OH CH3
1 2 3 I 4 5 / 6

3,5 dimethyl 3-hexanol CH3 CH2 C CH2 CH

I

\

CH3 CH3
methyl methyl

Ethers
• Organic compounds that are highly volatile, flammable liquids

• Produce organic peroxides by reacting with atmospheric oxygen

catalyzed by light

• Highly reactive, potentially explosive

• General formula is R-O-R’

Example:

Diethyl ether CH3CH2 – O – CH2CH3
(ethyl) (ethyl)

Aldehydes and Ketones

\

• Both contain the carbonyl group C = O
/

• Aldehydes – have carbonyl group located at end of chain of carbon

atoms O
II

R – C – H

• Ketone – has carbonyl group located at nonterminal position

within chain O
II

R – C – R’

Examples of aldehyde: formaldehyde or methanal (CH2O);

acetaldehyde or ethanal (CH3CHO;

2-propenal or acrolein (CH2=CHCHO)

Examples of ketone: acetone or 2-propanone (CH3COCH3)

methyl ethyl ketone or 2-butanone

(CH3COCH2CH3)

Organic Acids

• Organic compounds containing the carboxyl group (-COOH), so

they are also called carboxylic acids. They are weak acids,

inherently corrosive, and water-soluble with characteristic odors.

• General formula is R – COOH

• In the IUPAC nomenclature, the suffix – oic acid is used to

designate carboxylic acids; but when the functional group (-COOH)

is connected to a cyclic structure, – carboxylic acid becomes the

appropriate suffix.

• Examples:

Methanoic acid (or formic acid): H COOH

Ethanoic acid (or acetic acid): CH3 COOH

Propanoic acid (or propionic acid): CH3CH2 COOH

connected to cyclic structure:

2- hydroxybenzene carboxylic acid (or salicylic):

o-HOC6H4 COOH

Peroxo-Organic Compounds

• Organic hydroperoxides, organic peroxides

• Many compounds unstable

• Used to induce polymerization, process

essential to production of plastics

Meyer (2014)

Meyer (2014) Chemistry of Hazardous Materials. (6th ed). NJ: Pearson

More details and other common

hazardous organic chemicals

are in the textbook.

Reference

Meyer, E. (2014). Chemistry of Hazardous Materials. (6th ed.). Upper Saddle River, NJ:

Pearson.

Organic chemistry graphics retrieved from http://commons.wikimedia.org

f

518

Fi-Hii&@M·llli’,I ~:~:: : ~: Chloroflu orocarbons II CFC OR HCFC OESIGN.::A:CTl.::CON::.._,__:C;__H<:-:M_IC:-::CAL N_A_M::-< :::-:-:-:-----,M_ OlECULAR FOR,_, CFC-11 Tnch lorofluoromethane I ~

I

CFC-12 Dic hlorod1fluoromethan e

CFC-13 Chlorotr1f luorom ethane

CFC-21 I Dichlorofluoromethane
I

CFC-113 / 1, 1,2-Trichloro- 1,2,2-trifluoroethane

I
CFC-tt4

1

1.2-Dk hlo co-1, 1,2,2-l etca fl uo,oelhaoe

HCFC-22 ! ChlorodifJuo ro methane

I
HCFC-123

1 2, 2-D,chloco -1, 1, 1-Jciflu o,oethao e

HCFC-124
2-Chtoro-1, 1, 1,2-tetraflu oroethane

HCFC-1 23a
1,2-Dichloro-1, 1,2-trifluoroethane

HCFC-134a
1,1 ,1,2-Tetrafluoroethane

Chapter 12 Chemistry of Some Haz ardous Organic Compounds: Part I

I Cl – ~ – CI
I
f

f
I

ci- c- 0
I
f

f
I

CI – C-

F
I

f

H
I

CI – C- Cl
I
f

f
I

CI – C- H
I
f

f f
I I

CI – C- C- F
I I
Cl Cl

f f
I I

CI – C- C- CI
I I
f f

Cl f
I I

CI- C-C- F
I I
H f

f H
I I

F- C-C-F
I I
f Cl

f f
I I

CI -C – C- CI
I I
f H

f H
I I

F- C- C-F
I I
f H

,\!though the CFCs served well fo r thi s b’ .
J(SirJb le featu res: They are among th e mostco~e !nation of pu rP? ses, they also have less

greenho use ga se s. The global warm ing po ~t ozone-depleung subs1ances, an d th ey
;;;01 5310 to 11 ,000 over a 20-year ti me ~:::n~ia~::

3
1he comme rcialized CFCs ~anges

arrnosphe re se.riuu ~ly exace rbates st rat ospheric ~zon u;e the. presence of CFCs m .ou

r

tn1·1ronmemal1Sts view positively th e restriction in thei; w:~i1:~~.~;e ::n~~~~t~r:a rm1n g,

12,15-A HOW THE CFCs DESTROY STRATOSPH ERIC OZONE
The CFCs are extre mely stable compounds – h
. . -long enough to be transported h Wit atmo_spheri c lifetime s of hundreds of
;~~: the ozone la yer, hig h levels of u:~r~i·~o~:~::~fa~:nc ozone l~yer. W~en their va~ors
simpl~ r subs rnnces.

14
The ~FC mol ec ul:s absorb cer: ~: c1:~:l:n~~h:oof :~:”:if1~::i1; ,~~ r.idiauon fr<:>m th e su n, .which ca uses their ca rbon-<:hl orine bonds to rupture res ultin in

the produ_cu?n of chlonne atoms, When a chlorofluoromethane molec ul e absorbs ul~ra –
i·iol et rad1at1on, for exa mple, chl orine atoms are produ ced.

CF,,Cl, – n(g) — CF~C1, -n- r (g) + :i:”J ·(g)
A chlorofluomcaroon A chlorofluonx:artxin r.ld1cal Ch l;nnc ~tom

When these c~lo rine atoms are exposed 10 ozone molec ul es in th e ozone la ye r, the y react
by the following three-step process:

0 3(g) + :c’l· (g) – CIQ·(g) + o2Jg)
0 1.onc Chlonnc atom Chl onnc n10no.1.1de O,)gc n

md1cal

Ch!onnc1r10110,1de 010111:
nidic:il

CIO !(g) —-1- :¢) ·(g) + 02(8)
Chl onncd10 , 1de Chlonncatom O.1. }’gcn

The first two steps of t hi s process result in the destruction of ozone. The actual ozone-
destroying agent s are the chlorine atom and chlorine monoxide radical. The cumulative
impact of th ese reactions in the upper atmosphere caused ozone holes to form, through
which ultraviolet radiation could penetrate and travel into the lower atmosphere.

To protec t the integ rity of the ozone layer, the member cou ntri es of the Unit ed Nations
have banned the production of CFCs through implementation of the Montrfol Protocol
(Section 7.1-N ). In the Uni ted States, EPA has used the authori ty of th e Clean Air Act to
ind ependently ban rhe use of chlorofluorocarbons as refrigerants, foam-bl owing agents,
an d aeroso l propellants. Furthermore, the CPSC has used th e authority of the Federal
Hazardous Substances Act ro ban the use of consumer products containing a CFC propel-
lant. The impact of the combination of the se actio ns has led to the reduction or di sa ppear-
ance of virt ually all CFCs from the commercial ma rketpl ace.

12,15-B HYDROFLUOROCARBON S AND
HYDROCHLOROFLUOROCARBONS

When the use of chlorofluorocarbons was banned, chemical manufacturers sought 10 fi.nd
envi ronment all y friendly replacements for use as refr igeram s, coolants, and foa~,-blo~\’. mg
agents, Two groups of such transitional CFC replacements substances were 1dennf1ed:

J. Molina and F. S. Rowland , ~siratospheric sink for chloron uorome1hu1es: Chlorine atom-ca1al yied
des tru ction of omn e,” Nature, Vol. 249 (1974 ), pp. 810-812.

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 519

r

/1
I/’

I
I
I

/I

hyJro/lll orocarbons, or H FCs , and hydrochlo ro{lu orocarbo11s, or H CFC.s . HF
cu/es hai·t onl y C- 11 and C- F bonds. bu1 H CFC molrcu/es have C- H , C- 1-. :inJ llloJ,.
bonds. Examples of subs tances 111 th ese two gro ups arc datluoromc rh ane and chloro2 ‘(‘J
romC’ than e, respt,crn•cl y. n~o.

F
I

H-C- H
I
F

(Hf’C. l~ J

F
I

F- C-H
I

Cl
Chlon.xl 11l uon ,mc1hJnc

(l tCrf’ 221

Jnirial scientific research s uggesred ch a~ mos t HFCs a nd H C FCs were desrro, d .
a rmosphere ar low a/rirudes and did not s1gnificanrly diffuse upward to the oz~~e t ‘.ht
Wh en rh is initial information could no r m:-_corrobo r:it ed, however, 190 counrrieso:~:
United Nations agr~d through rhe Montreal Protocol to phase o ur rhe product
use of aH HCFCs ocher than rho se used as refrig erants by 20 15. T he protocol ter:~;

1
~

che production of all HCFCs by 2030.
Sever:il HCFCs have a/read~ been specifica lly banned by EPA for use as refrigerant

gases, coo/anrs, and foam-blowing age nt s. Fo r examp le, HCFC – 14 J b (1, l -dichlor0- i.
fluoroethane ) was banned in 2003, and H CFC- ~42b ( l -ch loro- 1, 1-difl uoroethane) and
HCFC-22 (chlo rodifluoromet hanej were banned m 20!0 although EPA pe rm its rhtir uS(‘
in tq uipmenr manufacrured before 2010. Sevtral HCFCs ?1a y be used as EPA -approi·(l!
halon subsriru res (Section 12. 15-C) for now. The production and use of rhe HFCs h,n t
nor ye r been resrricred.

The HFCs and HCFCs are nor only ozone-depleting subs tances; they are also gretfi •
house gases. The global w:i rming potential of th e co mm on H FCs and HCFCs rangts from
43 ro 12,000 and 273 ro 5490, respectively, over a 20-yea r rime period (Sec tion 5.8).

Several HCFC replacements have betn sugges ted by chemica l manufacrurtrs, indudmg
J, J, I ,3,3-penufluoropropane and the hydrofJuoroolefins (HFO), 2,3,3,3-reuafluoroproprne
trans-1,3,3,3-tetr:afluoropropene, and Jrans- l -chloro–3,3,3-tritluoropropene. EPA apprm·td
the use; of I, J, 1,J,3-penrafluoropropane as a refrigerant, coola nr, and foam-blowing agenc
and 2,3,3,3-rerraalluoroproptne as an auromoti\’e air-conditioni ng refrigera nt.

F H F
I I I

F- C- C-C- H
I I /
F H F

J.J . J_l.J PcniJ nuorop rop.:mc
(llfC.2.i5J)

F H
\ I
C= C
I \

I-I CF1
1ran.r·I.JJ.J. TctrJnuorop rofl(“nr

(lff0-123~,~,

F F
I I

Cl l2= C -C- F
I
F

2.3.3.J-Tcu,, nuorop,o~nc
WFQ . 123.i)f)

C/ H
I /
C= C
I \

H CF3
1ranJ-I-Cl!roro-J.J.l. tnfluoroprop,.•nr

(Hl’0- 1233 ,d)

In 2011, auromake rs first bega n to consider replacing HFC-1J 4a wit h HF0-123 4yf
as rh e air-condiri?ning fl~id in new-model ca rs. Although HFO – l 234yf has a GWP of 4
over a JOO-yea r nm e homon, .rh e autom.:1kers used ir ro replace HFC-l34a , which ha~ ~

?f 1_430 o~e~ rhe same rime horizon. Howe ve r, rh e use of HFO-l234yf as an~ir·
c

nd
u,omng fluid 1~ not p roblem-free: Ir is a flammable gas, causing au tomak ers ro b(

cinc ern ed
th

ar l~ak mg HFO- J2 34yf may ca use a fir e during a head-on collision, f ur·
t ermo re, when mh aled at elevated concentrations, HFO – l 234yf causes as ph rx iarion
and central nervous sysrem disorders.

520 Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part J

12,15-C SUBSTITUTE~ FOR THE HALON FIRE-EXTINGUISHING AGENTS
A firs t noted 1n Sec11on ) . 14, H:i lon l 30 J (b
bs 0111oc h!orod iflu orometh :i ne) once W~re ro

1
mot~ifl uoromc tha nc ) and Hal on 1211

( r r11pk s of brom of111 orocarbo”s or BFCs popdu ; r fi re extmguis hm g age nt s. The y arc
~:pect1vel y. As pre,·io usly noted, ‘clean Atr’ ~:t r/~'[~od,lorofli. oroca r~o11s, o~ BC FCs ,
ducuon and manu fa cture in Janua ry 1994 . g lions banned the,r Ame ncan pro-

Et\::: r~itc:~”;~r t~,\~i~ ~i !n umber of co~mercia! fire C’Xtinguishing agC’ ms that
:~e s~bs1iruu agenrs are subj « r 10 n::r:;_r::e~;~~

1
;s~: fo: .nonres1dent ial uses onl r,

ozone .nor contribute as,s~s n’.ficant [y to global warmm~ as
(ol!owmg: HCFC- l~ J f-,–di chloro-l ,1,1 -trifl uoroethane ), HCFC- 124 (2-chro ro -1 I I l .
lt’tr.1fluoroethan~), I lalotron I, HFC- 227ea, HFC-236fa , and Nov« l2 J0. ‘ ‘ ·-

F F F FF F F F F
I I I l I I 1 1 I F-y-y -y-F F-r-r- ~ -?-?-F F -C-Cl-1 ,-C- F
F 1-1 F F F O C F1 F } – }

U,! .: .J~ ;~J~~~~~e~•opropan~ I , J. l,].2.-l.5,S.5-Non:~~~~tn
1
~~~-thi 1._ 3 ~ntano~c 1.1.1.2-3 :i:;g;~:~:tirrorane

Ha lotron I co~sim of a th ree -component propne1ary blend based on HCF C- 123. It is
most commonly d1schargC’d as a Streamin g agent. Following use, it do es not lea,·C’ a resi•
du e. Halo tron I ha s hecn approved by the U.S. Coast Guard as a halon substi rut e fo r
maritime application onbo3rd w:itercraf1.

The Federa l Avia tion Adminis trat ion has :ipproved HFC-22 7ea and HFC-236fa
35 fire-e xtinguis hing age nts to replace Halon 1211 . The agent s may be used not onl y onboard

Jircra ft , but 3lso on re sc ue and firefighting \’e hicles. Ai rbus uses onl y HFC-236fa, but
Boeing uses both J-IFC-227ea and HF C-236fa.

12.15·0 STORING OZONE-DEPLETING SUBSTANCES
Owoc-depleting sub stances, including the CFCs, HFCs, and HCFCs, are s1ill likely to be
encountered toda y wit hin storage conta iners and tanks, especia ll y at facilities 1hat rece1 vtd
an exemption from EPA or those th3t nt3i ntain, repair, or dispo se of refr ige rat ion and air-
co nd itioning equipment. When an ozo nt-depleti ng substance is stored, EPA regulations
requ ire it s ow ners 10 mark their comaincrs and tan ks wi th 3 warning statement that reads
as fo llows: “WAR NING: Contains !or manufactured with, if app licable] [insert name of
substance /, a subs tance which harms public health and en vironment by destroying ozone
in the uppe r atm osphere.” For exa mpl e, at 40 C.E R. S82. 106, EPA requires ow ners of
HCFC-22 to mark their co nt aine rs and tanks of chlorodifluoromethane as fo ll ows:

CONTAINS CHLORODIFLUOROMETHANE (HCFC-22),
A SUBSTANCE WHICH HARMS PUBLIC HEALTH AND
THE ENVIRONMENT BY DESTROYING OZONE IN THE

UPPER ATMOSPHERE

Thrs statement serves 10 assist first-on-the-scene responders who encounter .ozon e- de~leting
imb scances in storage. To pro tect r.he environment, they n~t~ s~era;;e ~:~:a~::t,~e:’~~~ht:
pre \•~n.t th e rupture of these con~ame rs and t~nks; fo\~

1
~:n ‘tur; doe~ occur, eme rgency

prodigious volume of water durmg an. ongomg fire. confinepthe contaminated water fo r
res ponders should implement appropriate measu res to
su bsequent co ll ection.

Chapter 12 Chemistry of Some Hazardous Or ganic Compounds: Part I 521

I I
11

522

ii·+l&ilfflih’ t1ons of Some ReprMen tatt\le CFCs,
CFC. HFC. OR HCFC —- –
Bromotr,fl uorom,thane

I-ChJoro-l,l

—–
l-Chforo-1,2,2, 2-tetraffuoroethane

Chlorotriffuoroethane

1, 1,1,2-Tetraf!uoroethane

1,1,1-Triffuoroethane

SHIPPING OESCRIPTJON

UN1009, Bromotrifluoromethane,
2 2

—.._

” UN1009, Refrigeran1gasR-1Js1, 2.2
UN2~ 1, 1-ch/~ifluoro~ne~,
M • . J

—i UN2517,Refn~as ~ J~
~
1
NT021, 1-Chloro-1,2,2,2-tetraffuoree~

UN1021, Refrigerant gas R-124, 22

l UN1022, Ch lorotr ifluorom ethan~
Jo,

UN1 022, RefrigerantgasR -1 3,2.2

UN3l5 9, 1,1,1,2-TetrafJuoroethane, 22

UN3l 59, RefrigerantgasR-134a,22

/ UN2035, 1,1,1-Trifluoroethane,comp~
( M ‘

/ UN2035, Refrigeran1gasR-143a, 2.1

12.15•E TRANSPORTING CFCs, HFCs, AND HCFCs
When shippers offer a CFC, HFC, or HCFC for transportation, DOT requires rhem ro
idenrify th e appropriare commodity on an accompanying shipping paper rit hf’r by usmg
irs IUPAC name or .. Rcfrigeram gas R-Ut.\”)’Z, .. where rhe meaning of the suffix WX)’l wa

5
nored ea rlier. Some examples of the shipping names for several represe nrarive CFCs, HFCs,
and HCFs are provided in Table 12.18.

Wh en carriers transport CFCs, HFCs, or HCFCs by highway or rai l, DOT requirf’!
them to display the wo rds “Dispersant Gas” or ” Refrigerated Gas” on two opposing
si des of th e rransporr ,,chid e.

12. 16 POLYCHLORINATED BIPHENYLS I
Th e polychlorinated biphenyls, or PCBs, are th e chlorinated derivat ives of rh e complex
hydrocarbon biphenyl, which ha s rh e fol lowing molecular sr ru cture:

00
There are 209 strucruraJ isomers of th e PCBs, each of which ha s t~e chemical ~ormu~
C11 l·lxCI; , where x ranges from Oro 9, and y equals JO – x . Approximately 130 ,some d
we re components of rh e PCB products manufactured and marketed throughout the worl
from the J 930s through most of rh e l9 70s

Ar ordinary ambient conditions, produ~ts containing PCBs usuall y are viscous, sricky
liquids. faen ar ele va ted temperatures, rheir individual componenrs are nonflam~J ble,
inc redibly stable compounds that can be heated ro th eir res pective boiling poin ts with~ur
undergoi ng decomposirion or bu rsting into flame. This combin:irion of prop erries

Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part I

fo rmerly was considered ideal fo r implcmentin cen . .
high 1en1pcrarurcsand fi re resistance. g ain mdustnal practices that required

In ihe 1960s, however, 1hc PCBs first be
c0n

1
t t _e PCB.s are extraordinarily ~tabl e

udies also showed tha t PCB exposu re co !d n ent, th:1t 1~, they arc pe rS/5tent. The
s~Jor:1cne (J disfiguring skin condition that u ca~lse cancer, bmh defects, liver damage,
; m these stu dies, we also learned that rese~ es severe acne ), 1mpotenc~, and death.
r~oepror tissues o~ th e thymus, lungs, sp];;:,e ~;::;;1:\i~he PCB_s mig rate into \’anous
ll’here they are primarily re ta ine d or bioaccumufate~ ‘in t~r, brain; muscle, ~nd t~sc es,
rdease from th e fatty ti ss ues has been linked with a . ef body~ fat. ,!heir ~wod1c
and bin h ~bnormal~ties. For example, children who :::;::x~:;~r: ~~~ 1

1
~:\sd~sr°; t~:

during _their mo
th

er 5 pregnancy often are born with reduced motor ski ll s and sbort• term memories.

Tod;\ w~ ~o~\’ kno\~ that PCBs ca use ph ysiologica l d1s~ rdm by mimick ing the
action° t e O Y s own orm_one! or by inttrfering with their norma l functions. Hor-
mones ar e subs tance_s ~~creted m minute quamities by th e endocrine glands, the organs
rha r com r~l such 3Ctn·it,es as growth , development, metabolism, and reproduc tion. When
Jbsorbed 1~to the bod)’., th e PCBs like th ese hormones, sending false signals that
interfe re _with th~ bo?y s normal aCt1vn1es. Th ey are exampl es of endocrine disrupters.
Gi\·en tlus ~o mbmatron of ad\’e rse properties, PCBs are rnnked by epidemiologists as
huma ncarcm oge ns.

12.16-A USE OF Pees IN ELECTRICAL EQUIPMENT

I

from approximarely 1930 10 1977, product s conta ini ng PCBs were ma rketed for com-
mercial utilization within crrtJin types of electrical equ ipment such as tran sformers, vol t-
age regubtors, circui t brrakrrs, capaCl tors, motors, electroma gn ets, reclosers, cables, and
fluo rescent light ballasts. They were also mJnufactured as hea t-tran sfe r, hydraulic, lubri-
cating, and cutt ing fluid s. PCBs were al so used to manufacture carbonl ess copy paper, and
,hey were incorporated as constituents in certain plastic, paint, wax, and rubbe r prod ucts.
ln all th ese instances, the purpose of the PCBs was primarily to provide these commercial
products wit h a greater degree of fire resistance.

Beca use PCBs pose an unreaso nable risk to public health and the enviro nment, EPA
ba nn ed th ei r rnanufo cr ure, sal e, impo rt , and distribution in 1978 by using the legal
amho nt)’ of TSCA. The rele vant rrgulations are published at 40 C.F.R. S76l et st_q.
Al though th eir producrion and manufacture is ba nned. in the United States, _EPA pe rm its
1he in definite use of PCBs in systems that werr opera11ng before 1978, albe11 under spe•

hormont • Ach emlcal
subst;mceproduced ln
minute amounts by an
endocrine gland and
carried through the
bloodstream to target
organsoragroupof
cellsofthebody,where
it regulates growth,
reproduct ion, and
other biological
funct iom

duct lessgland,sucha1
theadrenal,lhyro id.
and pituitary glands,
that secretes fluids
directly Into the gen•
eralcirculatorysystem
t nd ocr ln e dls rupttr

compound that
mim ic.saho1moneor
Interferes with hormonal
actionwhenlngested
into the body

cific regularory conditions. Even today, PCBs can be lega lly used in a “toiallr enclosed dlt !t ct ric fl uid • The
man ner,” th at is, within equipm ent that ha s bee n designed Jnd consti:ucted.so as t~ ens_ure fluid used in cenain
rhat no human or environmental ex posu re to rhem occurs, When th1 s eqUt_Pme!it is wi th_ types of electrical
drawn from service or repaired, EPA requires rep lacement of the PCB flmd wuh a non- ;~~r:~~t~~~tt~ease
PCB-co nt ain ing alternati ve producr. II I d One type can arcing and serve as a

An e!ecrri ca l transfo rmer is an example of a tota Y e~c osc . S}’S tem. · · heat-transfer med ium
ohen be observed near the tops of electric po!~:ft is a sr:ir dev:::tc~v~~:~s~~~~::nh~s t~ PCB transform er . For
transfe ~ elec trica l energy _ betwee n ci rcuits ~f winli~enst ovroc:~r~f a metal suc h as copper. purpom of TSCA regu-
magnet1c core around which there are s:vera .

1
• h g ·mmersed in a flu id within a tank. lations. a transformer

This assembly of co re ~nd cur rcnt- c~ r~m;;,c~l~~~s :s :: :ncrease che resistance of the unit :~~:~n~i:~
1
~;~~~:~id

The pu~pose of _th e fluid, ca ll ~d a d1t e~-rransfe; medi um. Large numbers of sue~ trans- nated bipheny(s at a
to susramcd arcing and to se n e as a e? d by municipal uti lity companies. concentration equa l to
fo rme~s a_re loca ted at elccrricJI sub:atr~~fa~:~:,r~PA defines 3 PC~ transformer a1 40 or meed in g 500 parts

Wuhm rh e contex t o( rh ee;;~t : :~rain s PCBs at a concentrnnon of 50 0 pamper per million
C.F. R. S761.3 as a rr.rnsform . H dous Organ ic Compou nd s: Part I 523

Chapter 12 Chemistry of Some azar

II

524

min e r a l o il transform e r
•AA@’lectrie.tl trani-
former conta in ing
m ineral oil as ,ts

million o r g reater. A 1ypical PC B tra nsfor me r co nta ins approxuna td ,
( 1500 LJ of fluid with a PCB concen tra tion of approximately 50 % to 60; -io ga l] 0n
bu r a forge PCB tran sform er may hold .as much as .1000 ga llo _ns (7500 L) ~f ; ~\:lurr.r’.
The remaining 40 ro 50 % cons ists of d1J ue nt s, a m ixture of tn c hlo ro bcn ze ne a nd tl 111d,
chlor obe nu ne iso mers. rt r;i.

die le-ctr,c fl u ,d

PCB-

The vasr majoriry of t~nsfo~mer~ m se_n •ice r~~y were m.:mufactured with the int
using mineral oil as thetr d,electrJc flwd. Mm eral 0 1] 1s a pe troleu~-based o il, and th etii ot
an- called mineral oil transformers. Alt.hough PCBs we re ne ve r intentionally add/se lln1tl
minera l oil used in these transformers, the oil ohen became conraminared with PC d to ~
workers conducted routine equipme nt mai ntenance .on both tran sformer ty pes ll~tn”/itn
sa me hoses and pumping e~u.ipn_1ent. EPA ~efine~ a unn a_s a PCB-00 pares pe r m1Jl1o n. A non -PCB transtorrn,r t
unit contairung PCBs at a concentration equal fO or less than 50 ppm.

no n-PCB transform er
• For purposes of TSCA
regu lations, a trans-
former who~ d ielectric
fluid cont,1ins polychlo-
rin ated biphenyb at a
concentr•tion equal to
or less than SO parts

1 2. 16-B PCBs AND FIREFIGHTING
AJrho ugh PCB fluids do no r rea dily burn, rh ~y may ignite ~i th’.n. an ene rgized lransformrr
whe n high-energy arcing, elt”CTrica l o~e rl oadmg, o r s~ort-c1rcumng occu rs. These fires arr
characterized by la rge amounts ~f 01/y, blac~ s’:>o t rn r?e _accompanying smoke plumr
Wh en the energized transformer 1s loca ted wnh m a buildrng, t he soo t and PCB va ·
travel w’irh the smoke p lu me throug h ve nti lat ion sha fts, building ductwork , and

0
:,~

per m illion

open-constr uctio n areas.
Today’s fi refighters respond ra rely fO PCB tra nsfo rmer fires, but beca use rh r scn·ict

lifetime of a transforme r is 40 to 85 years, such an action is not ou tside the real m of possj.
bi /i ry. Firefighters are faced with an unwa r ra nted heal th risk when they are exposed to Ulf
smoke from these class C fi res. To red uce the ma gnitude of the ri sk, EPA req uires the O\\n• 1
ers of the PCB transfonners to prominent ly affix the ML ma rk ing shown in figure 12. IOso
that it is easily read by firefighting person nel who respo nd to an electrical-eg uipmem fur.
EPA requires the Ms marking shown in Figu re 12. 10 to be affixed ro PCB eq uipmcm 1hJr
can not accommo date rh e larger ML ma rking. EPA a lso imposes mandatory reponing
requiremenrs ar 40 C. F. R. S76 1.30 to ens ure that the Na tiona l Respo nse Cemer (S«tion
l . 13) is contacted immedia tely on the occ urrence of an accid enra l fire in vo lvi ng PCBs.

EPA also imposes reporting req uiremenrs on the owners of facili ties tha r still use dee·
trical eg uipmenr conta in ing PCBs. Fo r exa mpl e, EPA req uires the registration of PCB
transform ers, incl uding o ur-of-service transforme rs held in sro rage fo r reuse. Fir e depart·
ment pe rso nne l should identify the location of th ese tra n sfo r mers with in thc- ir area of
jurisdiction an d p lan a response actio n in case of an accide nta l PCB release.

When PCBs unde rgo incomp le te com bustion during t ransfo rm er a nd o th er electrical·
equipme nt fi res, they p rod uce the highl y toxic compo un ds ca lled polychl orina ted dibenzo,
fura~s and !’°lychlorinated dibenzo-p-diox.ins (Section 13.4-B). D uring electrica l-equipm ent
fires mvoJvmg PCBs, these subs tances a lso may be re leased into th e enviro nment. Firefight·
ers should b_e especia lly wa ry when co mbat ing elec trica l equi p m ent fires, beca use exposurt
co rhese toXJ~ substa nces could ca use long-term ill effec ts. Rega rdl ess o f the magnitude of
the fi r e, fU”ef1g hrers shou ld always wea r self-conra in ed brea thing a p pa ra t us to elimin:lfeor
red uce th e potenrial for expos ure to these s ubstan ces. Pub lic h ea lth ca n also be effec ri\·dr
p rotected by constru cting suitable d iki ng, d ive rsion cu r bi ng, or g ra di ng to confint th e
sp read ?f ~ese conra rn ina nrs and prevenr th ei r d ra inage into sco rm sewe rs.

1
~ fi re im•? lvi ng elec trica l equi pme nt is no c th e o nl y type d urin g whi ch PCBs, polr·

c hl orm ated d1 benzofura ns, a nd polyc hl o rina red d ibe n zo-p- d iox ins m ay be rde.ase~-
Before 197 7, PCBs we re components of some p rotecrive and decorative pain rs, \’armshes,
lacg u~rs, sealanrs, ad hesi\•es, ca ulk ing, and s im il a r co nstru ction p rod ucts. Some of th ,m
co nramed 5 % to 30% PCBs. Altho ugh th ese products were used severa l decades ago, ,he

Chapter ‘2 Che mist ry of So me Hazardo us Organic Co mpou nds: Part r

CONTAINS

IPolvchl ~ ,S~B~ph,oy1, 1 ~ ;s:\.~ Atox,cenv1ronmentelconte
special hendl,ng and disposa7l~ent r~qulrlng

” ;;~~~t~o;~~
1
CtRm7~n1t~l:~~~1~g~~r:

” Jnf?rmetroncontact the nearest US E p
Off,ce. . . ·.,A, ~

~ U lo 5case of ecc,den1 or sp,11, cell toll free the · · Coast Guard National Response Cente r: ~,
800–424-8802 ‘-.

Also ~,

~~(“”

f lGURE
12

–
1

0 The~e two EPA markin gs are calle d the M t and M, markings, respective ly Th ey differ on ly by the,r wording and s,ze The
le tters and strip ing on both mark,ngs are b

1
acl:. on a yellow backg round and ,nclude the warn ing CAUTION CONTA> NS PC Bs and instruct,ons

to be 1mpiemented m t he event of a PCB re’ease The M, mark ing also ,nd udes the telephone number of the Nat,ona! Response Center
Th e TSCA regu lat ,on at

4
0 C FR § 76 1 4 5 requires a mar king to be affixed to PCB transformers and PCB capaotors 1n seMce and PC B ,terns

con:a ,n1ng or contam inated w ,th PCBs •n storage for disposal when t ~ PCB concentrat,on 1s eq ual to or greater than so parts pe r m,llton
The regulation a lso requires t he marl:.1ng to be aff,xed to all doors or accesses leading from the outermost door 10 the door 1mmed 1ately
,K(USin gthePC8umt

PCBs st ill remain in surface coa tings, joint sealams around wi ndows, caulk ing between
maso nry pane ls, and elsew here. As fir es occ ur in the buildings in whic h these PCB-
conia in ing prod ucts we re once app li ed or used, the PCBs and the ir incomplete comb us-
tion products a re re leased into th e environment.

12 .1 6-C THE AD VERSE IMPACT ON THE ENVIRONMENT
CAUSED BY

PCBs

Why are PCBs regarded as ult ra- haza rd ous substa nces? The answe r to th is qu estion is
linked wi th th e ho rrifi c impac t they could have not only on pub lic hea lth but also on a
wide segme nt of 1he en vi ronm ent. The wo rst PCB-conta mina ted site in the United Stales
1s a 200· mile stretc h o f the H udso n River in New Yor k nort h of Alba ny. An estimated
1.3 mi ll io n po un ds (-0.6 million kg ) of PCBs was all eged ly dwnped inro th e rive r by an
el«rrica l•transfo rmer man ufactu rer from 1947 to 1977.

The adve rse envi ro nm ent al impact fro m expos ure to PCBs is li nked wilh its passage
from anima l co ani ma l. W hen PCBs are co nsu med by a n ani mal th at is then e~ten by
anot her anima l, th e PCBs pass progressively through the food chain: worms to. f.’ sh and
birds; fis h to birds; and birds and fis h to mamma ls. T his process is ca lled biomagnif1catlon,
or bioamplification, beca use the PCBs increasi ngly concentrate .3~ t hey pas~ up_ th e f~od
chain, T he PCBs may th ereby affec t the we ll -bei ng of many ind1 v1dual ~pec1es, md ~dmg
humans who co ns ume fi sh or mea t co ntami nated with ~CB~. 1n th e Unned States a ~ne,
EPA has id ent ified 703 bod ies of water where hea lt h adviso ri es have been posted to \\arn

peo ple against consumi ng PCB• ridhde ~ ~i_s~. d fis h ? The answer to th is questio n ce nte rs
H?\\’. do PCBs affect tl1~ hea lt \’:rc;::~med PCBs become sexuall y dysfunct ional.

on rhe1 r immu ne syste ms. Fis h who 3 • • the m to experience a reduced
The fe ma le fis h a re born wi th immature ova ri es causing

blomag n ifi catlon
(bloampliflca tio n) • The
retention of a sub·
stance in human and
animatt lssuesat
Increas ingly higher con•
centratlonsasthesub·
stance passes through
success ive leve ls of the
food cha in

Chapter 12 Ch emistry of Some Haza rd ous Org anic Compounds: Part I 525

I r l
r I
I

526

PCBs

. , Boch fish and birds who ha\’e con.sumed PCBs experience &row
ab1l1cy to s;aw~. amnent. In birds, these pr~ble_ms m~lude _cggs_hell thinning, lowtb iJld
r:~~:i:~:(‘d::eased egg hatching, deformi’.1cs m the JU\’emle birds that doernerg:;rtgg

s and reduction in their growth and surv1\•a l rates. . . . °Ill
gg i-he em·ironmentol impacr from exposure to PC~s 1s especia ll y ev ident in

3
u

an ·sms Within the ocean hierarchy, for example; killer whal~s are :ontarninareJ it!(
~lBs :c c~ncenrr.uions higher than chose obse~\’Cd m other marine anunals ~a use ~th
arc at the top of the food chain. Although herrmg may ca rry PCBs_ ac an average conceey
trarion of onl)’ 1 part pe r million, the seals _rhat eat chem may conta in 20 parts per miUi n.
and the killer whales that ear cheseconcam1nated seals may have PCB level~ a~ highasi~
am r million. The male killer whales carry r_he P~Bs throug?our th eir li ves, but tbt

imal::periodicaJ/y rid these pollutants from their bodies by passing them to thc-ir call-~
This couJd explain why the mal es live_ on_ly half as long as the females, and wh>• ITld~~
calves die within Se\’eral months of their birth.

12.16-0 FDA REGULATIONS INVOLVING PCBs
Because PCBs have become an unavoidable co~rami~ant in the environment, FDA pu ~
lishes the following tolerance limits for PCB residues m foods , at 21 C.F. R. Sl09JO:

1.5 ppm in milk (fa t basis) .
I.5 ppm in manufactured dairy produm (fa r basis)
3 ppm in poultry /fa t basis )

: g:J :~ ll:J:hed animal feed for food -producing an imals {ot her than feed concrn-
trares, feed supplements, and feed premixes) . . . .
2 ppm in animal feed components of anima l ongm, mcl ud mg fis hmet1 l and orher by.
products of marine origin and in anim_al fe e~ concentrates, feed suppl emc-ms, and
feed premixes intended for food-prod ucing an_1mals
2 ppm in th e edibl e portio ns of fis h and she llfrsh
0.2 ppm in in fant and junior foods

12. 16-E TRANSPORTING PCBs
Whe n shippers offer polychlori na ted biphenyls for transportation , DOT re~uires them 10
identify th e PCBs on an accompany ing shipping paper as one of the follow mg:

UN2315, Polychlorinatcd biphcnyls, liquid, 9, PG II (Marine Pollutant )
UN2315, Polychlorinated biphen yls, solid, 9, PG 11 (Ma rine Pollutant)

DOT also requires them to affix CLASS 9 labels on its packagi ng.
When bulk quantit ies of PCBs a re transport ed, DOT requires th e ide nti fication

number 2315 to be on displayed on orange panels or white squa re-on- point diamonds
on th e packaging. DOT do es not require CLASS 9 placards to be displayc-d on rhr
transpon vehicle.

When shippe rs offer a PCB-conraining electrica l unit including a PCB-co nt amina_tcd
transformer fo r tra nspo rtatio n, EPA requires th em to affix the app rop ri ate marking
shown in Figure 12.1 0 on the unit when it is transpo rt ed. EPA requires this mark in~io~
affixed on an elec trica l unit e\•en when the fluid has been drained from it, as the umr 1YP1•
cally contains residual PCB fluid.

12. 17 ORGANOCHLORINE PESTICIDES
The organocl~lorine pesticides arc chlorina ted organic compo und s rhat fo rmers form:rl!
used as insecticides. Mose are chlorina ted hydrocarbons like the PCBs. Also lik e rhe PCB,,
rhey are exrremelr sta ble subs rances that do not biodegrade in the environment. fnSrcad,

Chapter 12 Che mis try of Some Hazardo us Orga nic Compounds: Pa rt 1

formrr use has resulted in their bioaccum ! • h
,neir 1 5 e<:ics, ultimately causing their dem u ation 1 ~ough the food web in diff~rcnr 3

”
1
”

13
a~oc hl orine pcsueides to osc- 3 su m.· or_ drc_lme in numbers. EPA now considers

ihe o~ health and the environm!t Cons bstant1al ~1sk of causing a negative impact on
num

3
1 4_8 ) to their potential · f equemly, it does not issue FIFRA registrations

~~~~

1

~ 1~ 1erda ll y, o_r their u_se is~~nug ~~~::~\~te~;:h:h~:i::CJt~:~~:.are either unavail-
Jn 200hl,1

th
.e Um te~ -~atiobns_ also took action on banning or severely limiting 1he use

of orga noc orme p~mc, es Y _implementation of 1he international treaty known 3s the
Stockholm Convention on Pe~istent Organic Pollutants, or the POPs Treaty. The POPs
are a group _of

th
e

13
moSt persi 5t ~nt, toxic substancc-s tht1t pose a threat to human health

and rhe environment, The grou~ is i~f”posed of aldrin, chlordane, dieldrin, endrin, hep-
r.1chlor, hexachlorob~nzene, Mi_rex_ ‘ , To xapbeneTM, DDT, PCBs, the polychlorinated
dibentofura ns and dibenzo-p-~io_xms, and hexabromocyclododecane (Section 14.2-A ).
The first nin e membe rs of this listing are organochlorine pesticides. Ahhough it is doubt –
ful that eme rgency responders would ever encoumer them, this brief introduction is pro-
rided here to emp ha size that some toxic subsiances are considered so ultra-haza.rdous
tha t rhei r production, ma nufac1ure, and use must be regulated.

Stock holm Con vention
on Pers istent Organic
Polluta nts (POPs

Nillt ionstrHtythat
bans or lim its the
worldwideu~of
nineorganochlorine
pest icides, P

Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part I 527

580

1- ‘¾ h I and other additi ves is another popular blend. Biomass-based d’ to .) o er ano _ · . . te5’1 a
ma y be mixed wtth petroleum-based di esel ml. . . . . IS()

At 16 C.F.R. S306. l2, the U.S. Federal Trade Comm1ss1on requires b1odiesel dis t

r

rors co affix on their di spensers, as rel evant, a blue-and-black or orange-and-black libu

.

rese mbling those shown here: a~l

The blue-and-black labels characterize either a ~iodi ~se\ fuel ?r a biomass-based die-
sel blend, and the orange-and-black labels cha_ra~tenze e1~her a b1om~ss~based diesc::I fue\
or 3 biomass-based diesel blend. The comr~uss1on requires these d1stmctively colored
labels to highlight and distinguish their chem1cal natures. _ .

The blue-and-black biodiesel blend label shown here IS affixed specifica lly 10 dispen,.
ers of B20 biocliesel blend havmg a b1od1esel concentration that ranges from 5% to lO o/,
by volume. Biodiesel blends with 5% or les.s ~iodiesel or b~omass•base~ diesel arc cxcmp~
from this labeling requirement. The comm1ss1on also requires new-vehicle manufacturers
and used-vehicle dealers to affix the relevant label on a visible surface of each vehicle

10 identify the manner by which it is powered.

13.7-E TRANSPORTING ESTERS
When shippers offer an ester for transportation, DOT requires them ro provide the rele-
vant shipping description on an accompanying shipping paper. Some examples of scvm!
representative esters are listed in Table 13.18.

When they transport a flammab le ester whose name is not provided in the Hazardous
Materials Table at 49 C.F.R. 5172.101, DOT requires them to identify the commodicy
generically on a shipping paper as either “UN3272, Esters, n.o.s ., 3, PG TT ” or “UN3272,
Esters, n.o.s., 3, PG Ill.” The generic shipping description includes the name of the spe-
cific ester entered parenthetically. DOT also requires shippers and carriers to comply with
all applicable labeling, marking, and placarding requi rements .

When carriers transport biodiesel fuels, they must identify the commodity on th~
shipping paper in the following manner, as relevant:

For biodiesel blends equal to or less than B5: NA 1993, Diesel fuel, 3 PG Ill,
UN1202 , Diesel fuel, 3, PG lll , or UN1202, Gas oil, 3, PG Ill.

For biodiesel blends over B5:NA1993, Diesel fuel solution, 3, PG !TI, UN1202,
Diesel fuel solution, 3, PG Ill, or UN1202, Gas oil solution, 3, PG TI!.

ihhiiUI Shipping Descriptions of Some Representative Esters
ESTER

Ethy l acetate
SH IPPING DESCRIPTIO

N

lsopropyl propionate
Methyl formate
Methyl propionate
n-Propyl acetate
Pro pyl formates

UN1173, Ethyl acetate, 3, PG I

I

UN2409, lsopropyl propionate, 3, PG II
UN1243, Methyl forma te, 3, PG I
UN1248, Methyl propionate, 3, PG n
UN1276, n-Propyl acetate, 3, UN1276, PG II
UN1281, Propyl fo rmates, 3, PG II

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

13,8 AMINES
the amines :1re organic derivati ves of am . .

in one two or three alkyl or I mania , that is, compounds whose molecules
cfon~;u\:ls ar~ R- NH2, R2NH, and :i g:o~ps bo~ded to ~ nitrogen atom. Their general
or 3 , ere R 1s an arbitrary alkyl or aryl group.

H H

I I

R- N R- N
\ \

R
I

R- N
\
R

amine Any organic
compound whose gen-
eral chemica\ formu\a is
R- NH 2, R2NH. or R3N,
where R is an arbitrary
alley! or aryl group

H R
for exai:riple, the amines whose molecules have one, tv.•o, and three methyl groups bonded
to the mtrogen atom are the compounds whose structures follow:

H
I

CH 3- N
\
H

TH

‘

CH3-~

CH ,
Mcth yl:im1nc Di mcth) laminc Tn mcth) l:lffilne

They are synthesized industrially from ammonia and methanol in the presence of an alu·
minum oxide catalyst at 842°F (450°C) .

+ NH3(~)
Meth:mol Ammom3

CH 3NH2(.g)
t.. leth) l:lrn mc

(CH3l,NH
D1 mc1hylamine Tnmc th ) l:lnunc

Table 13.19 provides their physical properties, which reflect the fact that the primary risk
associated with them is fire and explosion. The incomplete combustion of amines pro•
duces nitric oxide, carbon monoxide, and water vapor, and complete combustion pro•
duces nitrogen dioxide, carbon dioxide, and water vapor.

The simple amines generally are used by manufacturing and process indust ries as
coagulants, flocculating agents, corrosion and rust inhibitors, bactericides, and fungi·
cides. In the pharmaceutical industry, they are used to manufacture drugs, and in the
chemical industry, they are used to manufacture dyes and other substances.

The simplest amines can pose a health risk because their inhalation causes serious eye,
nose, and throat irritation. The more complex amines usually are flammable and corro•
sivc liquids. The nature of their corrosivity is linked with the similarity in chemical behav•
ior that the amines share with ammonia.

ifrliiiiti Physical Properties of the Simple Amines
METHYLAMINE DIMETHYLAMINE TRIMETH YLAM INE

Melting point -137’F (- 94″() -134′ F (-92′ 0 -179″F (-117 ‘ 0

Boiling point 21’F (- 6′ C) 4S ‘ F(7 ‘ 0 39’ F(4’C)

Specific gravity at68°F
(20′()

0.69 0.68 0.66

Vapor density (air – 1) 1.08 1.65 2.0

Flashpoint 34′ F(l’C) – SB’ F (-SO’ () 8 to 18°F (- 13 to -8°C)
374′ F (190″() Autoignition point 806′ F(430’C) 755′ Fl402′ 0

2.8% by volume 2% by volume Lower flammable limit 4.9% by volume
Upper flammable limit 20 .7% by volume 14.4% by volume

11 .6% by volume

Mtthylamine and
Dimtthylami ne

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 581

rr

‘

/1/
l

1

582

Trimethyl•min • Some amines are biologic:1/ly important .com pou.nds. Some, like doparnine and
aline, are among rhe subsrances char trans mit nerve nnpulses. adrtn.

Mcotine

Dop.:umne
·H2-Anunocrh)l )tx-n,cne- 1.1•d10!

h OH
HO-v-tH- CH2- NH – c H,

Adfl.”nlh nc, or Epm<."phnnc -'• [l - Hydro, y-2 -(11 1C lh)fon1 1no)c-1h)[ j

bc-n lC IIC· l.2 d1ol

Dopamine is produced naturall y in the brain and is responsible fo r the feeling of de-sirr
loss of appetite, and inability to sleep. These symptoms are commonly associated WJ1b
‘”falling in love.” . k l7

Se\’eral aromatic amines are const1ruents of tobacc~ s’.no e. Un~oubtedly the best
known is nicotine, th e primary stimulant rhar ca uses add1ct1on ro smoking and accelerat(S
rhe rates ar which che carcinogens in toba~co smoke ca _use ~ancer. Two other aroma tic
amines in tobacco smoke are ~-naphth ylamine and 4-a mmobiphenyl.

Nu:-otine
J.( 1-.\leth)lpyrrolldmc -2-yl}p~nd1ne

oo-NH2

P-NJphthyl.1m1nc
(2-N:iphth)bnunc)

O-OKH1
•l -,\nunotiiphcn;I

Nico tine is th e only constituent of tobacco that has commercial va lu e. Its poison•
ous narure {LDso = 55 mg/kg in rats ) is the basis for its use as a potent insecticide.
However the insecticidal use of nicotine in th e United States wil l cease in Janua q·
2014. Usi ng the aurhoriry of TSCA, EPA then ~ill ~erminare the. lega l production and
use of nicotine, due in large part to rhe nega nve impact that ltS release has on the
environment.

The inha latio n of ~-naphrhylamine and 4-aminobiphen yl in tobacco smoke is
regarded as the primary cause of human bladder cancer. Research scudies 18 revea l rh a1
smokers are four rim es more likely than nonsmokers to develop bladder cancer. BrcauSt
they cause cancer of rhe urinary bladder in humans, these aromatic amines are ranked H
human carcinogens. . .

Diamines are compounds ha ving two amino groups per molecule. The dramm es
putrescine and cadaverine ha ve especia ll y foul odors.

Pmn:sc1ne
(l.4- Bu1 .1ni:d 1:u111 nc)

C1da1cr111c
( 1.5·Pcru anl’dt:uninc J

Their combined stench is evident in deca yi ng flesh. Cadaver dogs are trained to der«t
th e odor when searching for human remains. Both are poisonous liquids without com·
mercial value.

1
; Rcp_on of t~c Surgcon _Gcna:I, ~How To bacco S~ok c Causes Disea se: The ~iology and Behal’i~ra\;~; ~’.

Sm okmg-Am1but.1 ble Dtse J se. U.S. Ce nrers fo r D1 se rn: Conrro! and Prevention, Ar!antJ, Georgia (
978-0-16- 08 40 78 -4). •
18

Ne.1J D. Freeman et al. , ~Associ a1 ion between smoking and ri sk of bladder cancer :imong men and women,
]. Amer. Med. A51oc., Vol. 306 (20 1 I ), pp. 793-896.

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

Anoth er diamin; b~nzidi~e, which formerly was used by homicide detecti ves ro
,erif)’ the presence o oo at cnme scenes.

H2N-O-ONH2

l:ltn11dmc
-i.4 ‘ -D111mnob1phCn)I

An enzyme in blood causes be~zidi~e to oxidize, thereby fo rming a blue-colored deri va-
ri\•e. Like seve.ra l or.her aromat1~ am_mes, benzidine is a human carcinogen. Although for-
merly used w,de_ly _m the chemical industry to produce certain dyes, its commercia l use
now is severely hmued.

Several means are used for naming amines. The simplest amines are known by their
common n:1me s. They are identified by naming th e alk yl or aryl group bonded to the
nitrogen atom, followed by the suffix -amine. The names of rhc simpl est ami ncs-methyl-
amine, dime1hylamine, and trimeth ylamine-are examples. Although di- and tri- are used
to name two and three identical groups bonded to a nitrogen atom, respecti vely, che pre-
fixes bis and tris, instead of di and tri, arc used when complex amino groups are compo-
nents of a formula.

Ami nes may also be named as aminoalkancs, alkylaminoa lk anes, and dialkylamino·
a!kanes. A number is used to show the position of the amino group along the carbon-
carbon chain. For example, the compounds whose formula s are CH1CH2CH2NH2,
(CH3)CH- NH2, and (CH 3)iCH- NHC H3 are then named as follo ws:

CH1- CH – NHCH 3 • I
CH3

l -Annnop rop1ne 2-Aminopropanc 2·/1 1c Lh)llminoprop;mc

In the IUPAC system, amines are named by replacing the -e i~ the name of ~he alkane
with -amine. A number is again assigned to show rhe position of th~ ammo group
along the cha in. The prefix N- (i n italics ) is used ro design_are the bon~mg of an alk~l
or ar yl substitueni on the nitrogen atom. Then, the subsmuenis are !1Sted alpha~ett-
ca ll y regardless of whether the y are bonded to the nitrogen atom or along the cham of
carbon atoms.

CH3CH2- ~ H -CH2CH2CH3

NHCH1

CH 3

N·Ethy l.J-hc.,.1na11 11 nc

CH3- ~- CH2C H2CH 3

CHi
N.N•Dimcth ylpropan.1rn1nc

. . d h !amine or more commonly, aniline; ics The simplest aromatic amme ts name P e~y ‘ h • the chemical formul as
chemical formula is C6 H5-N ~ 2• The su stancesd ~~~ethy laniline and N,N-
C6 Hs-N HCH 3 and C6Hs-N (CH1l2 are name
dimethylaniline, respectively.

REGULATIONS INVOLVING THE SIMPLE AMINES
13.SaA W_ORKPLA~E r in the workplace, OSHA requir_es e~pl~yers, to
~h.en the simplest ammes are prese~e following ma xi mum concen1r~t1ons m a1_r, a\er-
l1mn employee exposure to them at t . IO parts per million; d1met hylanu~e,. 10
aged over an 8-hour workday : mer hylamine, ‘ll’on· ethylamine, 10 parts per m,lhon;

B11nzldin

11

pans per million; trimeth ylamine, .1 O parts per mi 1 ‘

and aniline, 2 part s per million (skm). . f S me Hazardous Organic Compounds: Part II
Chapter 13 Chemistry o 0 583

N-nitro w mine Any
organic compound
whose mo ll!CI.J les have
a nitroso group bonded
to the nitrogen atom
ofan am ine

13 .8-8 N -NITROSAMINES
The N-nitrosamines are compounds w h?se ~ o lecu~es ha v~ a nitroso group (-~==O
bonded to an amine nitrogen :.1tom. The ahph:.1nc N-mtrosanunes have the followin
era! chemical formula , where R and R ‘ are arbitrary alkyl o r aryl groups: ggen.

R
\
N- N = O
I

R’

These compounds are produced when nitrous acid react s with those amines who
molecules have only one hydrogen atom bonded to the nitrogen atom. As pre\’ious

;;

noted in Section 11.15, when cured meat products are consumed, the sodium nitritt
used during the curing process reacts with stomach acid to produce nitrous acid, which
in turn reacts with th e proteins contained in all meat products to produce
N-ni trosamines. This issue is potentiall y problematic because these compounds art
probable carcinogens.

. Several N-nitrosamines have been detected in tobacco smoke at concentrations much
higher than those detected in cooked bacon and ocher cured meat products. 19 Included
among them are the following:

CH,
\.
N-N= O
I

Cl-1 3

\
N-N= 0
I

N

O c – c 1-1, n1, CH , – N- N=o
II I

CH 3 CH 2CH,
,\’· “•=od,rn..•th:,lam,m.• \’-Nnru~octh}lmelh) la,mnc

0 013
•H1\ · 1′ klh }l •N-n1t ro~!lm1nol •I•
O ·pynd )ll • l -burnnonc (N :-.K J

T~ese nitrosamines are produced during the fermentation curing and burning ol
:~da:;i·v!e::1~s;xt:e:edmay contribute to the cance_rs experie,nced b/ tobacco smokers
human carcinogen~ to second hand smoke, N•mtrosamines are considered probablt

EPA ha s noted that N-nitros · I f ‘d
used for cooling, lubricatin a d amme~ may a so . orm when meralworking flui_ s_are
and other machining O era~~n n corrosi~n or ru~t mhibition during grinding, pol1 ~h1_ng,
or similar substances r!ix with st.h:;e N-_n1trosammes are pro?uce~ when mer~lli~ mtrH C5
rese?tative compound used in me e tuids .. The c?mplex am1_ne dierhan?lam~ne 1s a r~~-
N- rmrosodiethanolamine is produc:~.workmg fluids. When 1r react s with m1rous act ,

HOCH2C~ 2 HOC J·h CH J

r- H(f) + H NO ]:(r1 q) – 0 I + H_,0(/l
H0CH2c 1-12 1 – N = ()

D1ethanol.1m,ne HOC H 2C~2 ,\ ‘ 11rou,ar ,d
p . .V-,” nru,oJir1h:inol :11mul’ W 31a

E A used us aurhoriry under TSC \
sure to N-nitrosamines when mer:r . ~~a:~~u~e or eliminate the potential for human ~x~:·

ming work required the use of fluids conr::uni g

584 Chapter 13 Chemistry of 5
ome Hazardous Organic Compounds: Part II

.1inin es. Al 40 C. F.R. §747.115, EPA prohibits th e mixing of metallic nitrites or simi lar
subsrn nces with metalworking fluids and requires all conta iners of metalworking fluid s
dimi buted in commerce to be labeled as follows:

WARNING !
Do Not Add Nitrites to This Metal-working Fluid Under

Penalty of Federal Law
Addition of Nitrites Leads t o Formation of a Su bstance

Known to Cause Cancer
This Product is Designed t o b e Used without Nitrites

EPA requires this label to be affixed to the containers with such co nspicuousness that the
warni ng statement is read and understood by 1he ordinary indi\’idua l under customa ry
condi 1ions of purchase and use.

13.8-C METHAMPHETAMINE
.\lcthamphetamine is a controlled sub sta nce, i.e., an illegal drug that can sti mulate or dull
an individual’s se nses and become addictive when used repea1edl y over time. As a legiti•
mace drug, it is prepared in pharmaceutical laboratories b y reacting meth ylaminc with
pheny\•2-propanone in the prese nce of a reducing agent.

+ O cH,-c- cH,(I)
– II

0
~klh}l:umnr Ph cn} l-2-prop:monc l\k1h:imphc t3.m1nc

N•M rth) 1- 1-phrn) lprop:i.n.::~-am,nc

Physicians generally presc rib e methamphetamine for use as a stimulant.
Aside from its legitimate production, methamphetamine is produced for use by drug

abusers, who refer to it as speed, splash, crystal, or mcth. The unlawful production usu –
all y involves the reduction of the legal drugs, ephedrine or pse udoephedrine (both decon·
ges1ants), with flammable solvents and other ha za rdous materials.

Clandestine laboratories used co produce methamphetamine can represent extremely
dangerous settings. Emergency respon se personnel who encounter them must take special
prese rvation meas ures because the illicit production of any controlled substance is a crim•
inal activity. These measures are accomplished in major cities. by Methamphet~mine
Response Teams whose respo nsibilities include the proper collection of relevant evidence
from the crime scenes for use when the drug producers are prosecuted .

13. s. o TRANSPORTING AMINES
When shippers offer an amine for transpo rtation, DOT requires them to provide the r_el-
cva.nr shipping description on a shipping paper. Some examples for s~ve ral repr~sentat1vc
anunes are listed in Table I 3.20. When shippers offer for transportanon ~n anune whose
name is not listed at 49 C.F.R. S 172.101 , DOT requires them to detcrm1~e ~hether t_he
c.0 mmodity is solely corrOsivc, or corrosive and flam~ab~e – Then, the sh1ppmg d~ scnp-
tion of the commodity is provided generically on th e shtppmg p~per that a~compan1es .the
shipn1ent. DOT also requires shippers and carriers to co mpl y wnh a ll applicable labelmg,
IT\arking, and placarding requirements.

Met hamp heta mine

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 585

r

organic hydropu ox-
ide Arly derivat ive of
hydrogen perox ide in
wh ich one hydrogen
atom in the H1O2 mol-
ecu le has been subni-
tuted with an alky l or
aryl group; any mem –
ber of a class of organic
compounds having the
generalchem icalfor-
mula H-O—o-R,
where Risanarbitrary
alkyloraryl group

orga nic pero xi de A
derivative of hydrogen
peroxide in which both
hydrogen atoms in the
H202 molecule have
been substituted with
alkyl or aryl groups;
any organ ic compound
whose general chemica l
formula is R-0—0-R ‘,
where R and R’ are
arbitrary alkyl orary l
groups; for purposes of
DOT regulat ions, an

i/.\,iiifUIUJil·Ml/.i:N.\4%&,iJWJ,i@;;:;qf
:~ii~: ——C:~:;;’;;:;;~N;,.°-;:.°;:;,:,:~~ –
“o;”e1”,,’-,,-m,-ine——–,l;;uN;;;1~,s~,,-;o;;;;,;;;;thyla~
N,N•Diethylan iline UN2432, N,N•Diethylaniline, 6.1, PG Ill

Dimethylam in e (anhyd rous) UNt032, Dimethylamine, anhydrous,
2
,
1

Ethy lam ine UN1036, Ethylam in e, 2.1

HeJ1.amethylenetetramine UN1328, Hexamethylenetetramine, 4.1, PG
111 Methylam fne, anhydrous UN1061, Methy)amine, anhydrous, 2.1

Trlmethylam ine, anh ydrous UN1083, Trimethylamine, anhydrous, 2.l

13.9 PEROXO-ORGANIC COMPOUNDS
Peroxo-organic compounds are ei rh er organic hydroperoxides or organic peroxides.
They respectiYe! y differ by the substitution of one or borh of rhe hydrogen atoms in lht
H20 1 molecule with alkyl or aryl groups (R and R ‘ ), Consequenrly, their chemical formu –
las are R- 0 – 0 – H and R-0-0-R’, respective ly.

The simplest organic hydroperoxides arc idenrified by the name of th e alkyl or aryl
group bonded to the H- 0 – 0 – group foll owed by th e word hydroperoxide. Exampl~
are tert-buryl hydroperoxide and isoprop ylbenzene hydroperoxide, whose chemical for-
mulas are (C i-1 3);-C-0 – 0H and C6HJ-C{ CH 1)1-0 – 0H, respectively.

CH;
I

CH ,- C – 0 -0H
I

CH,
l<'rt-ButJlh)(lropcrox.Je

Cl-1 3

nr-1 – 0 – 0 H
V CH~

lsoprop)’lbcnlcnc h}dropcrox1(lc
(Cunic nch)Jropcm ,1 d,•)

The simplest organic peroxides are identified by the names of the alk yl or aryl groups
bonded ro the -0-0- group followed by 1he wo rd peroxide. Whe n 1he alky l or arJ l
group is the same (R :c R ‘ ), rhe name of th e gro up is preceded by the prefix di. Examples
are diacery l peroxide and di-tert-buryl peroxide, whose chemica l fo rmu las are (CJ-1 3C0~!2
an d !(CH3)3-C- b02, respectively.

0 0

// \\

CH3- C\ F-C Hi
0-0

CI-IJ C/-h
I I CH ,- c – o- o- c – rn,
I I

CH, CH,
organ ic compound con-
ta in ing oxygen in the
biYalent -0-0- struc –
tureandthatmaybe
considered a deriYat ive
of hydrogen perox ide
in which one or more
of the hydrogen atoms
have been replaced by
organic rad icals

D1Jrcl)lpcro,1de 01 -1rr1-b u1 )1pcro,i;k

Di-tert-butyl peroxide is a substance sometimes added in /ow co ncentra tio n to diesel 011
,o im pro,·e irs ceiane number (Scc;ion 12.13-F). er, c·
. Some commercia ll y •mporranr peroxo-organic compounds are perkerones, P
ids, a

nd
pereS

t
ers. These substances are oxidized ac id s ket~nes a nd es ters, resp ec·

,ivelr. The peracid~ ‘.” usuall r named br insen ing the ~refix pe:, or peroxy-, befor:
rh, name of ,he ox ,d,zed acid, The common perncids have from I to 4 carbon a,omd

t~lecfullel. F~r examp le, perpropionic acid, or peroxypropionic acid, is the compoun
586 H t e

O Owing molecular str ucture:
Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part IJ

0
//

C1!1CH~ -~

0 – 011
Perpropiomcacid

(f’crpropano,c11e,dJ

The perketones co~m~nly are named by inscning the word peroxide after the name of
rhe ketone from which Jt .wa~ produced. These substances generally contain multiple fu nc –
tional groups, one of which JS the peroxide group, as illustrated by the following molecu-
lar struc tu res of ethyl methyl ketone peroxide and cyclohexanone peroxide.

1 H2CH3 1 H2CH3
1-10 – 0 – c – o – o – c – o – ott

I I
CHJ CH3

8″(2 -h)JropcrrJ\~ -1t,-but) l)ptro \1de
( Elh)l 11 \C’lh)l l ctone pcro~ 1(k)
(~frlh)l<·th)llctoneperoMdcJ

l -ll)dro~)-l ‘-h)d ropcro,)d1c}’Clohc ,)1 ptro\i(lc
{C}clohc.unorx,pcro\1(lc)

A perester often is identified by inserting the term peroxy before the name of alk yl or aryl
group that is bonded to th e carboxyl group, as in tert-burylperoxybenzoate.

0
CH3 1:fi

CH3-{- o – 0 1 Q
CH3

,tn• Bul)lpcro , )bcn 1t:\1tc

Sometimes, however, th e peres1er is named as a dialkylperoxydicarbonate, whose general
chem ical formula is th e following:

0 0
// \\

R- 0 – C C- 0 – R
\ I
0-0

For example, when R is 1he isopropyl group, !CH3)2 CH- , the peroxyester is na med dii so•
propylperoxydicarbonate.

11-1 , f ~\ TH,
C/-1 3-CH – 0-C, r – 0 – CH- CH3

0 – 0
o, 150prop) lp,.:ro.\)d1c.ubonat~

The peroxo-organic compounds are commonly_ employed ~~sr:;/~i::i::!~n!uJ;~; :;
~aw materials i~ sy_mhetic processes. P~roxo-~::a::d~~::~nd manufacture of plastics.
induce polymenzatton, a process essenttal to p d’tions peroxo-organic compounds
Althoug h they are either liquids or solids at room con -1 te

0
;ganic solvent. These solve nts

ohen are enc.o_umered dissolve~ in water~~:: a~~:;~:;marure the rm al decomposition.
serl’e to srab1hze peroxo-orgamc ~om~\und ~ are flammable substances, they are also

Althoug_h .the perox?•?rgam~ con en within th ei r molecular stru~rures. \yhe? the y
Powe rful ox1d 1zers c?ntammg acuve OX}!rr their own combustion. Thi s com~m~uon of
bu rn , p~roxo-organic ~ompo unds sup~ced risk of fi re and explosi_on. When 1gruted, the
Propert ies pos7s a pamcul arly P;~~o~urn furiously and more intensely than other
Pe roxo-orgamc compounds

O
. f S Hazardous Organic Compounds: Part 11 587 Chapter 13 Chemistry o ome

I I
I

J ‘I

defl.tgr~tion The
ch~1ca l prOQSs du ring
wh1chaS1Jbstance
bvms 1ntensety instead
of detona ting

F1 GURE 13.S This la be l
affix .. -dtononbv!kcon-
tainers ol d1t>Pnzoy1 per-
OXldecompheswrth
OSHA’s regulations pvb-
lished at 29 C FR.
§19101200(f}

co mbustible sub stances. This burning pheno menon is ca ll ed deflagration S f
energv 1s gene rated du ring deflag ration to enable the burn in g to proceed and u fic1rn1
with~ut the mp ut of ad d itiom1I energy fro m another source. An exampl e is illu:t::~~~~tr
the fo ll owing equauon: hi·

[(Cl·IJh-C-bO1(s) ,.. 9O1 (gl – 3CO~(g l -r- 5CO{g) + 9l·l:O(g J
Di-,trr bUt) l pt” n>~1,k 0 \}g1.”n C:u-bon d10 , 1J;.- Ca rbo n mollO \IJc \\ itcr

Most peroxo-orga nic compounds are un stable. When exposed to a n igni tio
th ey are just as likely to unde~go rapid , autoaccel erated d ecomposi tion as they arent:~tr,
Some are so sens iti ve to fr1ct1on, heat, or shoc k 1hat they can not be safely handl ed t·
maintained at low tem~racures a~d diluted \_vi1_hin a n inert so lid ~at erial or solvent~:
thermorc , orgamc peroxides are sk m and ere 1rm_ams and are very like ly to caust &asrroin.
tesunal prob lems when swa llowed. Th ese po1enually hazardou s features are illustrat d
the label affixe-d w co nta iners of d1be-nzoy l peroxide and prov ided in Figure 13.5. e on

0 0

O < ;co 0-0 DIBENZOYL PEROXIDE

UNJ104, Organ ic perox ide type C, solid

DANGER
Heatingmayca useafire.

Keep away from heat/sparks/open llam eWlot surfaces. No smoking.
Keep/Store away from clothing/combusti ble mate rials. Keep only
inorigin alconta ine r. WearprotectivegloveS/protect ivec loth ing/eye
protecti oNface protection. Store at temperatures not exceed ing
104 “F 140 “Cl. Keep cool. Protect from sunlight. Store away from
o~her materials. Do not eat , drink, or smoke when using this prod uct.
Di spose of cont ents/container in accordance with state end federa l
envir onmental regulations.

FIRST-AID INSTRUCTIONS:

IF SWA LLOWED: Immed iately call POISON CENTER or doctor.

IF IN EYES: Rinse caut iously with water for seve ral minutes.
~e~ove contact lenses, if present, and easy to do. Cont inue
rinsing . Immediately ca ll POISON CENTER or doctor .

:k~~~~~::~:, ‘. mmed iat ely all contaminated clothing.

ReadSafetyOataSheetbefore use.

MvCom~•nv
My Stroer

“‘YTaw,, _1,1yS111tOOOOQ
Tt lel)l,001 1000)0000000

588
Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part

11

l l ,9-A TRANSPORTING PEROXO -ORGANIC COMPOUNDS
Jl(fore

3
pcroxo-organic com~und ma y be offe red for tran spona1ion, DOT requ ires its

mJnufac curer or ol
h

c~ responsible _party to lest a sampl e of the subs1ance usi ng prescr ibed
procedures to derermm_e wh ether 1t decompo~s under th e tempera1ure cond i1io ns likely
10 be= enco ~nrercd during tran sportauon. At 49 C.F.R. Sl 73. 2i (f), DOT prohibits the
transportation of a package when the test ing data revea l that 1he substance is likel y to
deco mpose at a self: acceleratlng decomposition temperature , or SADT, of 122•F (50°C)
or Im, or polyn~enze at a temperature of 130•F (54°C) or le ss , wit h an evolution of a
dJngerous quanmy of heat or gas.

When shippers prepare th_e shipping descript io n of a peroxo-organic compound, the y
con sul! the Hazardous Materials Table and the Organic Peroxides Table published at 49
C. F.R. SS 1~2.101 and 17~.22$, re_spe~ively. DOT docs not disti nguish between organic
b}droperox1des and orgamc peroxides m the haz.ardous mat erial s regula1ions. For DOTs
purposes, each is referenced as “organic peroxide.”

The shippmg desc riptions of organic peroxides are li sted generically in 1he Hazardou s
~late- rial s Table. Several exampl es are provid ed m Append ix B. Each \isling denotes a type
of orga nic peroxide and its slate of maner (liquid or solid ). Th ere are se,·en organic per-
oxi de types, each of whic h is de signated by a capital letter A throu gh G, which collectively
fo rm a continuum of decrea si ng ha zard. Thei r features are noted in Tabl e 13.21.

The types of the generic peroxo-organic compounds no ted in the Hazardous Materia ls
Tab le refer only to types A through F. As no1ed ea rli er, DOT prohibits the transportation of
1rpe A organic peroxi des. Some table entries include the word s “temperature-controlled:·

The lener G appears in column I of the Ha za rdous Material s Table fo r each proper
shi pping name of an organic peroxide. As noted in Section 6.2-A, this signifies that the
tec hnical name of th e- organic perox id e mu st be enter ed in parentheses in its shipp ing
desc ripti on, This name is included in th e shi pping infomtation provided in th e Organic
Peroxides Tabl e, an exce rpt of which is provided in Table 13.22.

iil!IIMI Genen c “types of Organi c Pero xid es•
TYPE

Type A

Ty pe B

Type(

TypeD

TypeE

Type F

Type Gb

ID EN TI FYING FEATU RES

Can detonate or rapidly defl agrate as packaged for transport . The transportation of
typeAorganicperoxidesi,proh ibiledbyDOT
Ne itherdetona1esnordeflagrate1rap idlywhencorrectlypackagedfort ransportatlon,
butcanundergoatherma\ exp los ion
Ne itherdetonatesnordeflagratesrapld\y whencorrect lypackagedfortransportation
andcannotundergoatherma!exploslon
Detonates only part ially, but does not deflagrate rap idly, and i1 no~ affect~ heat
when confined; or doei not detonate, dellagrates slowly, and maniferts no -v ‘.olenl
effectifheatedwhenconfined,ordoesnotdetonateordel!agrateandmamfestsa
med ium effect when heated under confinement
Ne ither detonates nor deflagrates and manifests either a low or no effect when heated
under confinement

Will not detonale in a cavitatedd state:, w~! ~~te~::~,~::t:o::;1, sho’NS no effect when
heatedunde rco nfin emen!,an mani ei

•~9 C.f.R. §173 .128. n•t lon requirements for organic per ox loes ,I It Is “ther•
~A fype G orga11 lc peroxide Is oot subject to D0!’11”:1: erature 11 122’f (W’C) or nigher !or a 110-pouod (SO- kg)
m11t,, st able,” I.e ., Its 1elf•acce ler at l119 drcom~,~~;:ct e;;s!ic:s of ly~ G other tha11 therm•I mblhty and requires

~:~~e~:;~r: rie:1::!:: :~•: :;~1t:~periturHontro\led org~olc peroxide.

u!lf-accele rating
decom position
temp eratu re (S AOT)
The lowe1ttempera-
ture at wh!chaperoxo-
organ ic compound In a
typical package under •
goesself•accelerating
decompositi on that
cauiesthepackageto
rupture

Chapter 13 Chem istry of Some Hazardous Organ lc Compounds: Part II 589

r
l’. i

i
i 0 :,, e:c sc

z
0
~:’fl ;;
~i~e . ;; io~
8

7 G ”
<

” ” z
3 <

11

5 ~I ” .
z

I 0 fi ;i I i,N !i~ 1’i v V 0
8

I I ll aa I 8 E “~ z l
~z

I
590

Ii:

~I is
I

;;

:’l .
2

h 8 8 I~ v T V 0
I

lg/~
/i z z

.
I

\’\1hen s hipp ers prepare the sh .
DOT requ ire s them to pro vi de th

1
Pjing desc np1ion of a perox .

1Jt ntif)’ th~ name of 1hc spec ifi c ; 0 r~;~:~~g~~eric shipping desc r~~~:gn~”;:r: ~~~~~~;1f•
concc~trallo n o~ the concentration range of the ;red for transporranon , and include th~
follow ing sh 1pp1_ng_ description when they tran s uh st3″ CC. For example, shippers use the
io) 1 peroxide wuhm a pla stic -lined cardboard h::1 50 pounds ( 110 kg ) of 80 % dilx-n-

UNITS HM
1 boi (UN4G)

SHIPPING 0E SCft1PTION
J~:~l~ci=N NUMBER, PROPER

CLASS OR DJV~s~;~~~=S~D~O
HAZARD CLASS OR DIVISION , ANO

PACKING GR OUP)
UN_3012, o ,g~nic ~type 8
SO ii d, _s.2,(1), PG ll (d ,benzoyl .
pero K1de, pane,80 %)

– ~ T (1~
50

When s hippers of fe r for transpo rt a tion a O .
te mpt’ramre and eme rgency temper:i t u;e a re 1i:C~ i:o~~rs:inic compound w~ose con_t rol
Tabk, DOT requ ires them to include t he se tern t’rarur umn 7 of _the_ Organic Pe rox ides
in the following ex:imple: P es on th e sh1ppmg p:ipe r :is shown

UNITS

2 boKeS
(UN4G)

SHIPPING DESCRIPTION
{IDENTIFIO.TION NUMBER, PROPER
SHIPPING NA.ME , PRIMA. RY HA.ZARO

ClASS OR DIVISION, SUBSIDIARY
HAZARD ClASS OR DIVISION , ANO

~_ C_KI_NG~ G~R~OU~PJ._ ___ ~ WEIGHT(1b)
UN3115, Organ ic peroKlde type O, l iqu id, 60
temperat u re-

When ~hippe rs offer a pcroxo -org:mic compou nd for trans porta ti on , DOT requires
them to affix an O RGAN IC PEROXID E label to its p:i ck:igi ng. In ce rtai n ship men1 s, :in
EX PLOS IVE label is also requi red. DOT :i lso requires shi ppers !O ma rk eac h pac kage
contain ing a peroxo-o rgan ic co m pound w it h th e fo ll owing infor ma tion:

• Name a nd address of t he s hippe r and its receiver
Th e proper s hip ping name

• Ident ifica t io n number of th e commodirr
• Ap pl icab le specifications, inst ructions, and preca utio ns

In addi tion, whe n s hi p pe rs o ffer the packagi ng fo r rra nspo_n atio n by aircra_fc, ~OT
requi res t h e m co affix the KEE P AWAY FR OM H EAT h:ind lmg ma rk shown m Figure
13.6 o n the packaging.

W hen wa rra nt ed , DOT requ ires carrie rs to post O RGANIC ~ERO:

Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part 11 591

FIGURE 13. 6 When
Pddage,s conta ining \@lf.
l’N

— —– ——— — —–
Keep away from heat

13 . 9 – B STORING PEROXO·ORGANIC COMPOUNDS

As a gene ral policy, manufacturers of peroxo-o rganic compounds advise their cusromm
to store limited quantities of thes e compounds in a segregated area at a temperature Im
than their emergency temperature.

13 . 9 -C IDENTIFYING CONTAINERIZED PEROXO –
ORGANIC COMPOUNDS

The hazards of pe roxo-organic compounds may be read il y d et ermined. by obsernng th~
GHS pictograms that OSHA reqmres manu facture rs, distributors, a nd unporters to affix
on container label s. There are two typ es:

The exploding-bomb pictogram is posted on product labels when the conta inm
hold any type A and cenain type B mganic pernxides. . h Id mi,i a

The fl a me pic1ogram is p os ted on product label s when the co nt ainers o
type B organic peroxides a nd all t yp e C, D, E, and F organic peroxides.

OSHA doe, nor ,equi,e o,ganic pecoxide man ufacrum,, disr,iburocs, and imp_~,«~ ‘°
affix a GHS pi ctogram on the labels of containers ho lding type G organic pcrox1 es.

13 . 9 – D RESPONDING TO INCIDENTS INVOLVING A
RELEASE OF PEROXO- ORGANIC COMPOUNDS

Emergency responders identify the pr ese nce of peroxo-organic compounds al tr;ui sPortl·
tion mis ha ps b)’ obse rving any of the following:

The number 5.2 a s a compo nen1 of a proper s hipping de sc ription of a haza rd ous

;i;e~:~~; ~~hZX~rtr;;OX/0 £ and ,he numbec 5.2 on )’e ll ow a nd rcd l,bd;
~i;x:::~:~~l~,~~~n;EROXID E and rh e numbec 5.2 on yellow a nd ced placa

. . ids their fi res Because man )’ o,gan1e comp0<1nd, ace fla~m able gases o, fl.imm.iblc l,q~" ',his"·"'""" fought using the genera l technique s noted 111 Sections 3.5 and 3.8. Howe '

592 Chapter 13 Chemistry of Some Hazardous Organic Compounds : Part It

J,,s ,,o, mdinaci ly a ppl y ‘
0

fices i”‘ol,iag

nd
ergo the~mal decom~osition before the fires are exunguish;d. The gencr-

31[y recomm_end ed pra ct ice fo _r fighting fires invo lving peroxo-organic compounds is to implement e11 hcr of th e following proc edures;

1 Use unmanned monitors to cool th e area where these reactive mater ial s arc stored and assur e that fi re doc s not reach them.

When a fire ha s engulfed the immediate area wh ere pe roxo•organic compounds are
located, evac uate all personnel and do not combat the fire.

13.9-E TERRORISTS ‘ MISUSE OF PEROXO-ORGANIC COMPOUNDS
At least two peroxo-o rganic compounds have been activated by terrorists to achieve their
ev il ac1s: triaceton e peroxide, or TATP, and hexamethylen e triperoxide diamine, or
HMTD. Th ese com pounds are not used commercia ll y due to their sensitivity to shock,
friction, a nd heat. Nonethele ss, terro ri sts produce them by the acid -catalyzed union of
h)d rogen peroxide with acetone and he xameth ylenetetranune, respectively.

The mo lecular formulas of TATP and HMTD contain three peroxo groups, as shown below:

T11 a,,·1or.: mp;.-ro”,k (TATI’)
13 6,6,9,9.~k~3!1Wlh~ 1· 1.2 .~.5 .7,8 h.,~~O.~OC)dvnon:uw,

CJ-h – 0 – 0 – CH , I . . \
N \ CH2- 0 – 0 – CH2;N

CH2-0-0-C H2
f k,amc\h) kill.’ mpcm, 1<.lc <.l,;im,nc (11).ffO)

J ,S ,9•12 , 1 J. fl nal1\a• 1.6.() 1a.,;ib1qdv\4 4 4Jtctr:iJcca””

Te rrori sts have clandestinely produced and used, or attempted to use, TATP and HMTD.
The following 1errorist events uc well acknowledged: ,

. the United States onboard an aircraft ca r-• In December 200 I, ~ hi!e tr~ve l.m; ;:rrorist called the “shoe- bombe r” ane~pted
t)ing 197 people from Pans to Miam,\on of the explosi\’C penta ery thritol tetramtratc
to use TATP to accele ra te _ the detonal d a blend of TATP and PETN within the so les of
(Sec tion 15. 12 ). The terromt had pac\~ fli hi attendam and passengers before he could his shoes but wa s overtaken by an ale g
success fully ac 1i vate the mixture. ed b four terrorists responsible for the London

• TATP and (poss ibly ) l-L\1TD werep us k.i y he unstable substance and chemical explo-
,ra osi r bombing, on Jul y 7, 2005 (p. ~;’°~~”~gt~e nuxMe insid_e Lo~doa”_s bus and undec;
s11es \\’llhm backpacks, the terr_o.r1 st:f TATP were subsequentl y identified tn the apanmen
ground subw.iy sys tem. Quannues . .

u~d by one of the 1errorists. nnected with an attempted terrorist plot
1
.
11

• TATP and HMTD probab ly. were co 1, sou ,ht to bomb multiple trans- Atl a~nc
1\ugust 2006 during which terrorisis allered) Eng~nd. The terrori sts intended to bring
Passengec ;er; bound fo, th e Unite d St:;1: , ‘;.::,d within rh,i, hand lurge. ~:/:;~;:
liquid, onboa,d rh, planes in ,~ate; i~emined. British aurhocirtl wm x~::;:’;h,i, plaas.
of ,hes, liquids ha, nem been cm ~s irnro” befoce they wece a e ‘° ‘ . ouod sc Part II 593
te rro rists’ plans and captured

th
e co ~hapter

13
Chemistry of Some Hazardous Organic. Comp

I
I

I

ii

594

In September l006, TAT P was identified dur ing the arrest of seven suspected trr.
rorisrs in Vollsmose, Denmark. . “f .

During Sep tember 200 7, TATP was a lso 1dent1 1ed during the a rres t of eigh, s
peered terrorists in Copen hagen, Denmark. . . . lb,

Also during September ~007, Ger ma n anuterrori_st forces foi led p_lans initiated bi
three German te rrorist s who ai med to bomb the U.S. a irbase at Ramste in as Well as th’
U.S. and Uzbek consubtes in Germany. Th~ Ge rma _n force~ unc overed more than

16
e

pounds (?2 7 kg ) of 3 35 % _hyd roge n peroxide solution , wh ich the ter rorists presumab~
intended to use for production of TATP. . . . .

On Chris tmas Day 2009, a Nige rian citi ze n w1th co~ nect1ons r_o Muslim exirernisti
anemp ted to detona~e a mixtu re of TATP a~d pentae rythnto l tctra nnrate while travel tng
on a flight to De troit from Amsterdam. Fl1g_ht art~ndants and passen_ger~ thwarted his
activity, Because a packet of TATP was se~v n mto his underwear, th e N1gen:in sometirnr;
is referred to as the .. Underwea r Bomber.

l-LVITD was identified as an ex plosive component of a bomb that an al -Qaeda terr .
isr intended to activate at Los Angeles International Airport on New Year’s Eve 1999/2 ~
The terrorist’s acti vi ti es were thwarted. He is known as the Millennium Bomber, ·

13. 10 CARBON DISULFIDE
Carbon disul fide is a colorl ess, wa ter-insoluble, and highly volat il e liqu id who se chemical
form ul a is CS 2. Whereas pure carbon di sulfide ha s a pleasant odor, the industrial grades
of carbon di sulfide ge nerall y are yellow and exhibit c:ibbagelike odors. Some other phrsi •
ca l properties of carbon di sulfi de are li sted in Table 13.23.

Carbon disulfide usuall y is prepared by reacting methane with vaporized sulfur at
1200’F (650’C).

2CH,(g ) , Sg(g) – 2CS,(g) + >H ,S(g)
\lc1 hanc Sulfur Carbond isulfidc H}drogcnsulfidc

The compound is used commercially as a solvent and as a raw material for the manufuc•
t ure of viscose rayon, cellophane, and other textiles.

Bec:iuse its fla shpoint is -22° F ( -30°C), carbon disulfid e is a highly flammabl e liq•
uid. Its flammabl e range ex tends from I % to 44 % by volume, and its vapor is 2.6 times
heav ier th a n air. The a utoi gnition point of carbon di sulfide is extremely low, 212°F
( 100°C), and th e igni ti on of its vapo r may be initiated by exposure to :i hot steam pipe or

ihl!i•hl Physical Properties of Carbon Disulfide
Melt ;,g po;o, , – 169 ‘ F (-112 ‘ ()
Soiling po int 1 IS “F (46 °( )
Specificgrav1ty at68″F (20 °() 1.26 ——-

Va po r dens ity (a ir = 1) —–t””2-.6–

~V•:::p:::o’-:-‘ -‘°-‘”-‘°- ‘-‘ -68_’ F_12_0_’ C_) –~~-1300 m_ m_ H_ g ____ _
F_la_sh_po_'”‘– _ t:’22 °F (- 30°()

~ oint 212~ 1oo•cJ
Lower flammable limit

Upper flammable limit

Eva porat ion rate (ether :,i- ±
–

1% by volume
.44% by volume
1.6

Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part II

30 eteccric li ght bulb loca ted 3 co nside rab le dis1ance away. This combin:11ion of properties
,ons1itutCS cause for grave ;{;hncern to firefi ght ers who id entify ca rbon di sulfid e ac an
emergency res ponse sce ne. en bulk quami1ies of carbon di sulfid e are encountered,
they usually ~re _stored under water to r~duce their potent ial to ignite.

Sulfur dioxide and car bon monoxide fo rm as products of incomplete combustion
\\’hen carbo n disulfide burns.

2CS2(g) + 50 2(g) –. 4S0 2(g) + 2CO(g)
Carbon dt~ulridc O,}l;tn Sulfurd10~1..Jc Carbon mono”dc

To protect against. inhaling th e~e toxic subs1a nces, th e use of se lf-contained breathing
appara tu s is ess~nual when fir e~1g ht~rs respond to major fires invol vi ng carbon disulfid e.

The inhalation of carbon d1sulf1de va por also is harmful. The repea ted inhalation of
rhe vapo r dama ges the liver and kidneys and permanently affects th e central nervo us sys•
cem, The prolonged co ntact of carbon di sulfide with th e skin also is harmful, as the liquid
is abso rbed throu gh the skin. In th e worst case, th e absorption is fatal.

13.10-A W ORKPLACE REGU LATIONS INVOLVIN G CARBON DISULFIDE
When carbon disulfid e is present in th e workplace, OSHA requires wo rkers to limit
em ployee exposure to a maximum vapor co nce ntration of 20 parts per million, averaged
oi·er an 8-hour workday.

13.10-B TRANSPORTING CARBON DISULFIDE
When shippers offer carbon disulfid e for transportation, DOT req.uire~ them to describe
the substance o n a shipping paper as follows: UNI 131, Carbon d1 sulf1de, 3, (6. l ), PG l.
DOT also requires shippers and carriers to comply with all applicable label ing, marking,
and placarding requirements.

13.11 CHEMICAL WARFARE AGENTS
Some substances a rc so highly tox ic to humans that th eir use dur ing wartim~ can injure,
incapacir:1t e, or ca use mass ca sualti es among 1he enemy. The y are called_chem1ca\ ~arfare
agents, Thei r use has been scorned by many co~mries; nonetheless, their production, use,
and stockpiling have occurred due to mutual mistrust and fear. . .

Chemica l warfare agents are primarily liquids that can be sealed mto ca~1sters or
charged into mi ssile wa rh eads or other ex plosive devices. Beca use they vapon~e when
released into che atmosphere, these substances readily provide a let hal_ concen~rauon.

In 1997, the Uni ted Nations spea rheaded attempts to create th e 1nternauo.nal tr eaty
known as rhe Chemical weapons Convention. Kno”‘.~ formally as the Co nv~nuon on the
Prohibition of the Development, Production, Stockp1lmg, and ~se of Ch~~1_cal Wear;s
~nd on their Destruction, it prohibits ~he d~velopment, pr~~~~:1~:• :~i~t~1~~•r::~;

0 mg retention transfer or use of chemica l \\:1rfare agents. . . g h’
tre~ty including ‘the U~ited States. Its watchdog agenc y is the Organf1zat10n for the P~o t·
b·,· ‘ f Ch . I ”’// or OPCW but the U.S. Department o Commerce regu ates 11011 o enu ca I capons, ,

0 722 its activities in the United States at I_S ~. F.R. S\7 ~ I· h Ch mica l Weapons Convention
Asi de from the directives noted m its .forma k u!

1
e, t f eh e ical weapons and declare in

als? .req uires it s sig natorie_s ~o d_emoy theif s~:cm~~eie~ c~ u~:ries that have acknowledged
Writing th e quamit)’ remammg m them . O t . d S th Korea have totally eliminated
pos_scssi ng chemical. wea pons, Al~anias Indthaav: de~l~oy cd 62.5% and 89.8 % o f their
their arsenals. ~uss1a and t.he ~mted

1
~~\om lete di sposa l by 201 s and 2023. In the

dec_lared stock piles, r:spect1 vel~, ~nd P e fat ultimate di sposal ac sites in Pine Bluff,

ch e mka l warfare
A nerve agent,

vesicant. blood agent.
or other substance that
can inflict harm or
cause mass casualties
among exposed
ind ivi duals
Ch emical Weapo ns
Con ve ntion A Un ited
Nations’ treaty that
proh ibits the develop •
ment. production ,
acqu isit io n, stockp iling,
retention , transier, or
use of chemical warfare
agenu

United Stares stockpil es remain m storag
Ark ansas· lO~ele Uta h; and Umatilla, Oregon. . d . p rt

11 ‘ ‘ Chapter 13 Chem istry of Some Hazardous Orgamc Compoun s. a 595

r nerve agen t • Achem-ic alwarfareage ntthat
canadverselyaffe

1/li!iiRI
Melting point

Bo ilin g po int

13.11-A NERVE AGENTS
Nerve agents are vola tile organofl~1orophosphorns co mpounds o f which the follo\\”1n
mole<"ubr srructures are representative: g

CH3 F
I I

p
I/ I

O CH- CH ,
I
CHi

Sann. GB. or O -l ~oprop~ I
niethylphosphononuonJ3h:

CN 0
I I

p
// I

CH 3-N O- CH2CH 1
I
CH3

l3bun.or Elh)lN.N-d 11m:th)lphosphoro:llTl 1dOC-)3Rldatc

0
II

CH,- P- 0 ~
I
F

C)clo,;,_1nn, or O-C}clohc,ylmc1hylfluoropt1oi.~~

CH \ ?-CH2CH J
p

# I
0 S-C H2CH2-~ – CH(Oi1h

CH(CH3J,
VX Jgc nt , or O -Eth) l-S-(:?-d1Mprop)!Jnu~h)’IJ.

rncth)lpho s ph ono1h1olatc

These formulas are simi lar to those of organophosphoru s pesticides (Section 10.201,
although the latter sub sta nce s are not fluorinated.

Ne rve agents are fairly simple to synt hesize from re adily available raw materials. For
this rea so n, law enfo rcement authorities are sensitive to the fact that they could easi ly b(
ob tained and used by terrori sts as weapons of ma ss destruction.

The physical properties of sa rin, cyclosarin, CF, ta bun, GA, and VX are noted in
Table 13 .24 . These data illustrate that th e va pors of nerve agents are much heavier than
air. Consequemly, when the liquid agems are initially rel eased from their comainm, their
vapors seek out low-lying areas. Sarin is the most volati le of th em, and VX is the most
lethal. Aside from thei r potential use as chemical wea pons of mass de struction, th e nene
agents may also be used by te rrorists to contaminate water and food supplies.

Nerve agents generall y cause their ill effects by rwo mechanisms: inhalati on 3nd
abso rp tion thro ugh the ski n. The initial exposure often occu rs by penetration of the
::agent’s vapor through th e eyes. Once in 1he bod y, 1hey interact w i1h substances th3t cause
the nerves 10 transmit impulses to nearb y mu scl es. This action para lyz es the muscl es ,
whic h in turn , causes convulsions, resp iratory faiJure, and immediate de::ith.

Ne rve gases were produced by Nazi Ge rman y but neve r used against its enemies.
Toward the end of World Wa r II, U.S. troops seized at lea st 4100 pounds ( 1900 kg ) of ihe
nerve gas tabun and brought it 10 the United Srates for sa fekeeping . Pursuant IO the ter~
of lhe Chemica l Weapons Con ve ntion, the stockp ile was fina ll y incinerated in 201 I-six
decades afrer the end of the war.

Physical Properties of Some Nerve Agents

I SARIN CYCLOSAR IN TABUN
-69•F (-5 7°() -2 2°F (- Jo•ci -sS” F (-so·o
316 “F(1S8 ‘ C) 462°F (239°() 464°F (240°()

Specific gravity at 68′ F (20″( ) 1.11
1 1.12

1.07
Vapordensity(air \) 14.86 i s.63
Vapor premHe at 68′ F (20 ‘ 0

6.2 9.2 —
1.48mmHg 0.044 mmHg 0.03 7 mmHg

• 0,00044 mmH 9

596 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

During the Cold War, the U.~. mi li1ary produced and stockpiled sa rin, but neve r used
ir. By co ntra st, the use of c~em,cal warfare agents in weapo ns of ma ss des truction ha s
been used in co nt empo rary times as noted by the following:

lraq _used 1he _n~rv e a_gent sa rin in i1 s war against Iran during 19 84- 1988, as well
as agai nst ,rs own cittze~s_m 1988. An est im ated 5000 people we re killed and anm her
65,000 sic kened. I~aq ratified th e ~rticles of the Chemica l Weapons Convention in 1995.

In 1995 , sann ~ -as released m 1he Tok yo subway system by members of Aum Shin-
nkyo, a Japanese reli gious movem ent. The rel ease caused the dea th s of 13 perso ns and
sickened ar least 1000 other individuals.

In 2013, France and England reponed fo rensic evidence 1hat confirmed the use of sa rin
gas as a weapon of ma ~ des_trucrion by Syria against its own citizens in the ongoing civil war.
An attack near th e capita l city of Damascus killed approximately 1400 civilians.

13.11 -B VESICANTS
vesicants are chemical wa rfare agents 1hat blister skin and damage the eyes, mucous
memb ranes, and respiratory tracts of 1he exposed enem y. The besr known is m11stard gas ,
3

yellowish brown, oily liquid ha ving a faint odor of garlic or mustard. Its chemical name
is 2,2 ‘-dichloroethyl sulfide.

CICH2CH2-S-CH2C H2Cl
2.2′- Dichlorotlh)lsulfide

\~ luS!:ird gas )

~Ius1ard gas may be pou red on the ground, sprared into rh e air, or loaded into artillery
shells and dropped from planes to serve as a chemical weapon of mass de struction.

The grisl y success of mustard gas as a vesicant is due in part to irs high vapor density
of 5.4 (air = I ). The va por hovers for a relativel y long period :it ground leve l. The vapor
subsequently contacts the moisture on the skin and in the eyes or lungs and produces cor·
rosive hydrochloric acid.

v@sl cant A chemical
warfare agent that can
blister the skin and
other body tissues of
wanimeenemies

ClOJ
2
c H

2
– S- CH2CH2Cl(g) + 2H20 (IJ – HOCH2CH2 – S- CH2CH20H(g) + 2HCl(g)

Prolonged exposure of mu stard gas to the eyes ca uses 1emporary blindness. When it is
inhaled, mustard gas may cause cancer of the re spiratory tract. .

The use o f mustard gas by Germany against enemy troops_ during ~o rl.d \Y/ar l 1s
well documented. Discharged as a liquid, its vapor moved m th e d,_recuon of th e
wind along th e surface of th e ground and into 1he trench e_s ,~here soldiers were seek•
ing a leve l of protection against live artillery. It was w~thm th e trenches r~at the
deadl y vapor inflicted th e maximum harm ~n ~nsuspe:ung :roops. Ap prox1matcl~
400,000 Briti sh and French soldiers lost their li ves during \\:orld War I from expo

sure~oo:~~~a~~g;~· tons (5455 t) of mustard gas produ~ed f~r use by th~ U.S. military
still remains in storage, mainly in Utah. Destruction of this ves1canr began rn_ 2006.

Second- eneration ves icants include the compo und s known ,as _ the nitrogen 111′.1s-
tards. Thesegcom ounds are similar in molecular structure to 2,2 -d1chlo roethyl sulfide
in that an am inopnitro en atom replaces the sulfur atom. :”here are three wcl l_- known
ni trogen mustards: me~hyl bi s( 2-chloroethy l)amine, ethyl b1s(2-chloroerhyl)a m1n e, and

tr is(2-c hl oroethyl)amine.

CH 3

C!CH2C H2- – CH2C H2Cl
\klh)I h1~(2 •c hloroo:: th)l)J.!ll111C

TH, CH3
ClCH2C H2-N – CH2CH2CI

Eth\ l b1>(2•chlorue lh)l)Jlll1″C
ins\2 °Chloroe1hyl),um11<:

· Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part 11
597

blood age nt • A chem .
ical warfare agent that
can interfere with a
wart ime enemy’s utili-
zat ion of oxygen

choki n g age nt • A
chemical w a rfare agent
that can damage the
respiratory passage–
ways of wartime ene-
m ies so severely that
they choke

These compounds arc liquids wh ose vapors arc especial\ )• heavy [v
5 .9, 5.4, and 7. 1 (air= l ), respecti ve ly,! Alt hough the nitrogen mustar~~:Jens1 t1 e~ ,,
du~cd and w ~rc a \’ailable fo r use by Germany and the A ll ies, neither side use:en Pr~
vcs1cancs durin g World War II. thelll ,1

1 In 201 1, s hells filled with mustard gas we~e identi~ied b y rebel fighte rs .:it two .
cenrr:il Libya. The shells al\eged~y were supplied .to Libya b y lr~m. Whether th e ttcs1n
was ordinary mu stard ga s or a nitrogen mustard 1s unknown. es ica n

1

13 .11 -C BLOOD AGENTS

Blood agents ace highly volatile chemical wacface age nts that can cause seizures, res
tory failure, and cardiac a rrest upon mhalatton exposure. An example of a blood Pira .
hydrocyanic acid. In Section I 0.11 -F, we noted that hydrogen c yanide in hibits th agent

1
1

ti vc utilization of oxygen at the cellular level. e eff~.

13 .11 -0 CHOKING AGENTS

Choking age~ts are chc~ical war~are ag~nts that cause the br.onchial passageways of
exposed enemies to constrict upon mhalauon. Involuntary c hoking and suffocation ihcn
follow, and prolonged exposure may cause the onser of pulmonary edema. The most com.
mon exam ples of cho king agents are elemental chlorine, phosgene, diphosgene, and chloropicrin.

0
II

Cl ,….. C …_ CI
Pho, gcnc

(C.irbonO l ) Chlondc )

0
I/

CI- C Cl
\ I
0 – C – CI

I
Cl

D1phos~cnc
t T n chl oromc 1hylc hl oroform.:itc)

Cl
I

C I- C – NO,
I •

Cl
N1trotnc htoromc:1h.ine

(C hl oro p1c n n )

During World Wa r 1, ch lorine a nd phosgene were r espo n sible for numerous casualties on both sides.

13 .11 – E RESPONDING TO INCIDENTS INVOLVING THE
RELEASE OF A CHEMICAL WARFARE AGENT

Imagine how gruesome it must be to encounter a scene at which a c hemica l warfare agent
ha s been dispersed! Mass casualties are lik ely to appea r everywhe re . The sur\’ivors anx•
ious ly seek medical ancntion from health care personnel, who a lso arc anxious th at iheJ’
wi ll be exposed to the causative agent. .d.

The major job of the first-on -the-scene responders may be restricted to provi ing
calm a nd ordec to the prevailing pa~demonium and delivering immed i_are help;;.:;:;,
p eople who we re fortunate to su rvi ve the ordeal. Thereafter, these first-on t

1 responders should quick ly move the exposed individuals to an agent-free environmen
while wea rin g fully e ncapsu lated suits and breathing air from self-co n tained so.urc: ~
Ther must also encourage exposed individuals 10 quickly remove their co~;:;;~~m-
clorhmg and physically was h any exposed areas wit h soap and w~ter. To _\n special
p lete r emova l of the age nr , experts recommend was hin g rlu ee times, g iv g ders
attention 10 shampooing the ha_ir, to w hich r_he agent m ay cling. Eme rgcnc; r:’.~~r.,,,.,
a ls o must collec t th e conrammated clothing and sea l 1t wJthm bags 0 disposition.

598 Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part II

It is onl y afier th e victims have be
1 med ica l ,m ention is gi \’en by health-ca;; c~;rd etel y deco~t~minated tha1 approp ria1e

re:;pirators, gi ven an amidote designed to ~ount/rs. The .v1ct1ms should ha ~•: acce ss to
wh ich the y were exposed, and ntonitored at a hea~~~t/he 1m~~ct of th e spec1f1c agem to

Emergenc y responders mus, a lso tend to the dec~/:e facilit y for at least 24 hours ..
a propriate directions for removing clothi d s d. T~e l~al coroner can prov1~e
t~nsferral to the local morgue. ng an decontaminating corpses befo re their

13 .12 LACRIMATORS

As noted in Section I0.
9

-A, lac rim ~tors are substances that cause 1he ercs to involuntarily
tear ~lose upon expo_Sure. Th~1r use by 1he military during warfare usually is limited
to acuv.1ues such .as clearing enemies from tunnels. More commonl r, lacrimarors are dis-
persed m the en~ironmem by la w enforcement personnel during civilian disputes to con-
trol mobs and discourage unlawful acts without resorting 1

0
the use of firearms. During

their use, lacrimators render the recipients 1emporarily incapable of resistance or flight.
They are commonly known as riot-control agents, or tear gases.

Riot-control agems are used defensively to control the action of ac1ivists and troops
by temporarily impairing their vision and causing them to chok e and breathe painfully. h
is the temporary aspect that causes the use of lacrimators by authorized individuals to be
considered humane. Exposure to riot•comrol agents can be a particularly irritating expe-
rience for recipients, especia ll y within confined spaces.

Some represemati\’e molecular formulas of lacrimators arc shown here:

5t H I CJ-h = C • I
CHO

Ac: rolc ,n. or 2-Pro~nal

o-i-c1,,c1

BrC H2-~( CH3
0

lh omo:.c..-100,:

u -Ch loroJcetophcoone ,.. Chlorob,:, n1) hdcoc malonon1tnl c
o. -Uronm,) kn<· {Macri fCS g:i, )

Lacrimators have been ex tensively used during warfare since at least Wor ld Wa~.I, wh~n
the German army dispensed benzyl bromide at Ru~sian ~nd Fre?ch troops . . mce t .,~
1960s, CS gas a lso has ~een used wor1d;,ide

1
~~

0
~l~c~;;h~~ci:~~:•:;t~:t~:;.ssive assa i

ams. The gas is c harged mto cans as a i° s\~i~ are personal self-defense agents . The
The lacrimators used by the gene ra ·s an extract derived from Capsirnm pepper

most commo n of th em is pepper spr~y, w
1
1
~-~ ·droxy- 3·methoxyphcnyl )methrl\nonan-plants. The principal component 15 N,- _( }

amide, known more commonly as capsaicin.

0 H – NH – C- (CH2),1- CH = CH – CH(C l-l ,h C H3- 0 C 2 II 1-1 0 0
-“·I ( + H) Jro, ) .J- ,i1et;~:J~;~~)l)ni,:th~ l]n()nanJm ,d,·

. the ungcnt, hot taste of jalapefi~, habafie_ro ,
It is the compound mainly respo~

1
si
1
bl::~~eir ri1s and sreds, as well as the d1scomforung

carenne, and chili peppers, especi, Y

lsobutvrlc
11:ld

r lot-cont rol agent(te-ar
gas)• Any substance
that rap idly can pro-
duce sensory Irritation
or a disabling physical
effect among exposed
individuals

p erson al self-d ef en se
agent • Anytemporar •
ilyincapacit ing
substance

Chapter 13 Chemistry of Some Ha zardous Organic Compounds: Part II 599

r

incendiary agent Any
substance used during
warfare to intentionally
set fire to objects or
cause burn injury to
exposed enemies
through the action of
flames or heat

napalm An alumi-
num triglyceride that
produces a jellylike mix-
ture with gasoline for
use as an incendiary
agent during warfare

feeling rhar results from irs use as a personal self-defense agent. Capsaicin is also the
active ingredient of certain analgesic ointments including Capzasin-HP, a medication
capable of reducing or eliminating mild arthritic and other pains.

For use as a personal self-defense agent, oleoresin capsicum is generally dissolved in a
solvent to which a dye has been added and charged into an aerosol can. To affect inca-
pacitation, the user dispenses it by aiming the discharge directly into an attacker’s face.
The dye helps police identify the attacker. The topical application of capsaicin to skin
surfaces causes irritation, pain, prolonged sneezing, and coughing. When sprayed into the
eyes, the pain and inflammation are especially severe.

Pepper spray can be used effectively in several ways. Women can use it to incapacitate
aggressive or violent assailants; postal workers can use it against attacking dogs; police
can use it to disperse unwieldy crowds; and park rangers can use it to ward off bears and
other wild animals. Although the purchase of pepper spray by the general public is legal ,
most states have enacted laws that restrict the manner of its use.

13.13 NAPALM
Substances called incendiary agents are used during warfare to intentionally initiate fires.
The use of white phosphorus in incendiary bombs, and triethylaluminum in flamethrow-
ers, was previously noted in Sections 7.4 and 9.4, respectively.

Several materials have been developed to thicken petroleum products for their poten-
tial use as incendiary agents . The first incendiary agent of this type was called napalm. It
consisted of a mixture of aluminum compounds made from several rriglycerides found
naturally in coconur oil. The compounds were aluminum naphthenate and palmitate,
which denotes the origin of the name.

Napalm rhickens gasoline until a mixture containing approximarely 4% napalm by
volume is produced. The resulting material is jellylike in consistency. When napalm or a
napalm-like substance is used as the active agent in firebombs, an explosive substance
triggers the burning of the gasoline, jet fuel, or kerosene. When these firebombs are acti-
vated, massive fireballs often are produced.

For conducting military activities, the use of fuel thickened with napalm is associated
with results that are provided by few other materials. Napalm increases the range of
flamethrowers, imparts slower-burning properties compared with gasoline alone, adds a
clinging feature, and causes the burning flames to move around corners and rebound off
walls and other surfaces. Its use during warfare can psychologically affect the enemy.

Upgraded versions of the napalm formulation now have been produced. Modern ver-
sions consist of jet fuel , kerosene, or benzene thickened with a polystyrene-based gel. Dur-
ing World War II and the Korean and Vietnam conflicts, napalm formulations were used
as incendiary agents in firebombs and portable and mechanical flamethrowers. The burn-
ing of napalm controlled the extent of unwanted vegetation and routed the enemy from
hiding places within jungles and other densely vegetated terrains.

Today, however, most countries have agreed to limit the use of all incendiary weapons
if it is likely to adversely affect civilian populations. The Convention on Certain Conven-
tional Weapons (Section 7.5) effectively limits the future use of napalm and napalm-like
incendiary agents. Because the United States did nor ratify this protocol, the U.S. military
continues to use incendiary agents in warfare. For example, during the initial advance
into Baghdad in 2003, U.S. pilots dropped napalm-like incendiary bombs called Mark 77
firebombs on Iraqi troops; later, these firebombs were again used during an arrack on an
observation post at Safwan Hill, a location near the Iraq-Kuwait border.

600 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

CHAPTER

caurti!SYOfDrlgerwerk AG & Company
KGiAtubeck.

iNW#

I

absolute alcohol, p. 545
al536

akohollc cirrhosis, p. 543
alcoholic hepatitis, p. 543
alcoholicproof,p. 541
aldehyde, p.

564

amine, p. 581
bioditsel blend, p. 579
biodiesel fuel, p. 579
biofuel,p. 544
biomass-based diesel, p. 579
blood agent, p. 598
blood alcohol concentration
(BAQ,p.

542

ctllulosic ethanol, p. 544
chemical warfare agent, p. 595
Chemical Weapons Convention, p. 595
choking agent, p. 598
composite wood product, p. 567
crtsol,p. 55

0

ddlagratlo n, p. 588

13
Chemistry of Some Hazardous
Organic Compounds: Part

II

denaturant, p. 545
denatured alcohol, p. 545
epoxide, p. 553
ester. p. 575
esterlflcation, p. 575
ether, p. 553
ethylene glycol alkyl ether, p. 557
fatty acid, p.

578

fatty liver disease, p. 543
fennentatlon, p. 540
fetal alcohol syndrome, p, 543
fire retardants, p. 562
flex-fuel (flexlbl.-fuel) vehlcle (FFV),
p. 540
formalin, p. 567
functlonal group, p. 534
glycol (dlol), p. 547
grain alcohol, p. 541
halogenated ether, p, 559
incendiary agent, p. 600
ketone, p. 564

napalm, p. 600
nerve agent, p. 596
N-nltrosamine, p. 584
organic hydroperoxide, p. 586
organic peroxide, p. 586
oxygenate, p.

556

personal self-defense agent, p. 599
phenol, p. 549
phenolic compound, p. 548
phthalate, p. 576
plasticizer, p. 577

L

po1ychlorinated dlbenzofurans (PCDF),
p. 560
polychlorinated dlbenzo-p-dioxins
(PCDD), p. 560
riot-control agent (tear gas), p. 599
self-accelerating decomposition
temperature (SADT), p. 589
self-reactive material, p. 567
triglyceride, p. 578
veslcant, p. 597
wood alcohol, p. 538

533

fu nct!on algroup •

i ·iA,M!I
Associat< ,h, physical and heahh haz.irds of ,he organic compounds~ chapter with the information provided by their ~azard diamonds and GH.s ;

1

;t 15

Memorize the functiona l group t~at cha racteri zes akoho.ls, ethers, ald ehydesograrns_
ke tones, organic aci ds, esters, ammes, and peroxo-orgamc compound s. ‘
Memorize and apply the rub fo r_ naming simple alcohol~, ethers, aldehydes,
ketoncs, organic acids, esters, ammes, and peroxo-orga~te compounds.
Identify the adverse health effects that res ult from abus ing the use of alcoholic
beve rages. . . ,
Describe the most practical means of extmgu1shmg bulk ethanol fi res.
Identify the risk associated wit h encounterin~ an elevated concentrati on of
peroxo–organic compounds within th e containers used to store ethers,
Identify the haza rdous properties of the halogenated ethers, including the P(I)f
PCDDs, PBDFs, PBDDs, and PBDEs, and identify the most likel y ways by whic~’
emergency respo nders are likely to be exposed to the m. .
Identify the locations at which emergenc y responders are likely to encounte

r

formald,hyd,.
Identify the genera l nature of the labels required by the U.S. Federa l Trade
Commission on biodies el dispen se rs when types of this mat erial are provided to
customers for potential us e as alternative moto r fuels.
Identify the labels, markings, and placards that DOT requir es on packaging of th e
organic compounds noted in this chapt er, especia lly organic peroxides, and the
transport ve hicles used for their shipment.

Chemists have learned from experience that organic compounds ca n be cl assified into famili es according to their common mol ecular features. For exa mple, we noted in Chapter 12 that alkanes, alkencs, and alkynes are chemical fam ilies
because each of their members has at least one carbon-<:arbon single, double, and triple bond, respectivel y. These structural similarities are primarily responsible for the reactions that are noted by the members of each family.

Certain organic compounds arc composed of molecules in which one or more of their
carbon atoms are bonded directly to an oxygen atom. Depending on the nature of 1hc
chemical bonding, these compounds arc called alcohols, ethers, aldehydes, ketoncs,
organic acids, esters, or peroxo•o rganic compounds . Other orga nic compounds, called
ami nes, arc composed of molecules in which the carbon atoms covalently bond to a nitrogen
atom. In this chapter, we study the hazardous characteristics of some representati ve mcm•
hers of each fami ly.

13.1 FUNCTIONAL GROUPS
One or more hydrogen atoms in the molecular structure of a hydrocarbon may be sub!iti·

The atom or group of
atoms in the molecules
of a substance that
ch aracterizes its
chemical beha vior

tuted with another atom or group of atoms. When this substitution occurs, a new organic
comp~und is produced. The atom or group of atoms that substitutes for the hydrogen
atom 1s an example of a functional group, because it represents the location on 1hc mo\·
ecule at which chemical reactions often occur. Mukiple functional groups are components
of complex molecules.

The functional groups that are components of the molecular structures of the ~ 1
common organic compounds are listed in Ta ble t 3. 1. The group of atoms as sociated wilh
each class of organic compound should be memo rized. The alkencs, a!kynes, and halog:
nated hyd ro~arb ~ns were introduced in Chapter 12; we st udy the other classes of orgaruc
co mp ounds m this chapter.

534

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part

11

(LASS OF ORGANIC COMPOUND GENERAL FORMULA FUNCTIONAL GROUP

,A\ltene \ r C= C, carbon-

Alltyne
Hal ogenated hydrocarbon

Alcohol

Ether

Ald ehyde

Ketone

Carboxylicacid

Ester

Amine

Hydroperoxide

Peroxide

I \
R” R'”

R-C=.( -R’

R-CH 2- X ..
I

R- CH- X ..
I

R- C-X
I ..

R- CH z-OH ..
I

R- CH – OH ..
I

R.- C-

OH

I ..

R-0-R’

R- C-R’

i
p

R- C
\
OH

0
II

R-C

‘o-R’
R-NHi
R- NH-R’
R-N – R’

I ..
H-0-0-R

R- 0-0-R’

•R, R’, R”, and R- ar ~ arb itr ary alkyl oraryl 1ubstltutnU.

<=c, carbon-

-01–1,hyd roryl

– O-,ox:y

– C-,carbony\

” 0
? -c
\
0 – , carboryl

0
I -c
‘o- .carbo ry1

– NH2,amino

H-0-0-, hydrope roxyl

-0-0-,peroxyl

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 535

f
I
r

I I

11 11′ 111 I
/I I I/

I
I

I
536

SOLVED EXERCISE 13. l

a /coho/ • Any organ ic
compound whose mo /-
KY ies conta in at least
one hydroxyl (- O H)
g roup

~~~:~’::~~7o.~:.~9; ::,=~~,~~~ monoethyl eiher acetate ,n a categ ory 2 flammab1t hQll(! 7″-i
0

‘ CHiCH 1-0-CHiCH2-C
b – CH3

USt’ Tablt 13 1 10 1den11fy tht’ functron a! gro ups 1n th,s molecule

Solutlon: Tat,/e J 3 I ind,ures th at the molKules of ethyle ne glycol mo noe th y! e t her acetate ha v!’ on
aadoo,o,yg,oop ~ I

13.2 ALCOHOLS l
Alcohols are organic compounds deri ved hr substituting o ne o , mor e hydrogen at .
a hydrocarbon molecule with the hydroxyl group (- O H ). Thus, 1he genera l chemi;r;;m
mula of the simplest alcohols is R- O H, where R is the fo rmula o f a n arbitrary alkyl:
aryl group.

When one hydrogen atom is substi tuted wi th th e hydroxyl gro up in molecules of m(tha
and ethan e, the r~ulting compounds are methyl alcohol and ethyl alcohol, respectively. oe

H H 1-l
I I I

J-1 -C- OH H- C- C- OH
I I I

H H H
Mi:-!h)Ja lrnhoJ Elh}·J 11JcohoJ

These are th e commo n nam es of rhe t.vo simplesr alcohols.
In rh e I UPAC system , th e simple a lco hols are na med by repl acin g th e -e in the name

of th e co rresponding alkan e with -o/; hence, the compounds having the formulas CHJOH
an d CH 3 CH20 H a re a lso nam ed methan ol and et han o l, re sp ec tively.

To name more co mpl ex alcohols, it is necessa ry to indica te th e position of the
hydroxyl group by a number immediately precedin g th e name of th e alcohol. We use the
following rules:

Locate rhe Jong es r chain of ca rbon aroms th a t contains rhe hydro xy l group.
Consec utivel y number them so that th e lowest possib le number is ass igned to the car·
hon atom to which the hydroxyl group is bonded.

These rul es are applied in the following examples:

I 2 J
CH3-rH – CH3

OH
2·f-‘ropan o l

I 2 J 4
CH3-TH – C!-12- CH3

OH
2-Bu t.Jnol

I 2 J 5
CH3- Cl·J- C H2- CH – CH2

I I
OH C H3

.J -,\lc1 hy l -2 -pcn r:mol

When one or more hydroxyl groups are present in a molecular structure, th e co rr;
spo nding compound so metim es is named as a hydroxy deriva ti ve of th e p a rent com~un ·
The number of hydroxyl groups in th e srrucrure is indicated by the use of mono·, dt-, /fl·,
a nd tetra-, a_s relevant, fo r I, 2, 3, and 4, re specti vel y. When two or three hyd r~ xy~!r~~~
are present ma molecular s trucrure, the co mpou nd may a lso be named as a diol

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

..r,,;., •••• i–i-i®,116 · ru:::ewwnm@t

METHANOL

Melting po int -144 ‘ F (-98′ () ~1::~F~~ 114′ 0
soihngpoint 149’ F(65″C)
sped f,cgrav;tyat68 “F(20 “C)

0 .79

v, pordensity(air .. 1)

Vdp0r pressure at 68″F (20 ‘ () 98 mmHg

F/ashpo int(withoutwater) S4 “F(12’C)
{with15%waterbyvolume)
(with24 % waterbyvolume)

Autoignit ion po int

Lower flammabl e l imit

lJpper f lammable li m it

867’F(464′ Q

6%by

volume

36.5 % byvolume
fvaporat ionrate(ether=l) 5.2

174″F(79″O

0.79

1.59

SOmmHg

S4″F(12 ‘ Q
68′ F(20’ Q
97 ‘ F(l6’ Q

79)’f(423 ‘ 0

3.3%byvolume

19% byvolume
7(appro~ imate )

ISOPROPANOL

-128″f (-89″C)
180′ F(82″ C)

0 .79

207
33 m mHg
S3 ‘ f(12 ‘ Q

7SO’ f(399 ‘ 0

2.3% byvolume
12.7%byvolume

Heatofcombus-ti on
9

74
0 8tu/lb (22,700 ~J/ltg) 12,800 Btu/lb (29,7001,;;Jlkg) 14,200 Btu/lb (33,000 k.J/kg)

rC”s pectivdy, of th e parent compound. The following exa mpl es il lustrate the use of th ese
rules for nami ng alcohols with multiple hydroX}•l groups:

0 1-1 OH
I I

Cll 1- Cl-l~- CH2- c;: – c 112- Cl·l 3 CH3- ~ H- CH-r-CH2- CHJ
Oil OH OH

_1,1 -D,h) dro,) hnane
( l k.ul’l\’ – 1,J -d,olJ

2,4.4-Tn h)dro., )hnane
i Htunc -2.4.4-tno l)

6-0H
l.2 ,3-Tn h)Jro., ) bt: n1’nc

(Bcnr.cnc- 1.2,J -tn o\)

Ta bl e 13.2 li sts some ph ysica l properties of three simple alipha1ic alco hols: methanol,
ethanol, and isopro panol. T hese data in dica te that when exposed to an ignilion so urce,
th eir vapors easily burn . Fi re and ex plosion are co nsi dered their primary risks. Becaus.e
oxvgen is a lrea dy a componenl of their molecular struc1ures, these alcohols predonu –
na~ tl y produce th e prod ucts of complete combustion when they burn.

CH30H (g) + 20 2(g) — C02(g) + 2H20 (g )
~k thanol Carbon d,o , ,Je

CH3CH20H (g) + 302(8) -, c~~~~~:!ide + ) H,:~~;)
E1h ano l O:>. )!,’.,.-n

2(Cl·l 3)2- CHOl-l (g) + 90 ~(g) — C:r~:~!!,dr + SH’~~~~)
h o prop:mo l 0:>.)g..- n

. bustion prod uces soo t-less flam es tha1 are
W~cn alipha_tic alcohols burn, th et~V~oe: methanol, eth anol, and isopropanol bur_11,

nearl y 1mpercep t1ble to th e naked eye. le blue and vi rtuall y invisible. This absence _of \’\~-
~or exa mp le, 1he flan:ies produced are pais characi eri stic of the burning of ot her ahphauc
rble flames and parucu!ate matt er also s in th ei r molecula r si ru ctures. Bec~use a~c~ho\
co mpound s th a t contarn o~ygen atomd e •e firefight ers o ft en encounter unique d1fficul –
flames cannot be det ected with th e nake > ‘
ties when combating fir es involving th em. . S Hazardous Organ ic Compounds: Part II

Chapter 13 Chemistry of ome
537

r
I
I

SOLVED EXERCISE 13.2

:t

0

~1;!\:C~:.;~d~;tthanol and ethanol burn 1n air? How does the absence ofseot aHeq’

Solution: Methanol and ethanol a,e e)(olmplts of orgam< compounds whose molecu les conti io aa0,non to caibon and hydrogen dtoms TM o,:,-gen 1s used together with the a~ailable a1orni l'I v.nN'I methanol and etl'lal'!OI b!.lll Methanol and ethanol burn predominantly by complete c o~ produce cart>on a OXJ~ uistl’ad of carbon monOXJde and soot Because flames are v,s1bly I e.
m nute particulates of matter are heated ro incandescence, the absence of soot cau~s the flam es on.} ,,.,%\
the combusnon of~ s,mple alcohOls to be llE’arly imperceptible ,j(:CO/l1Pilttr419

1•·1&i·t;iiii\ihiffl
Name tne alcohol whose molKUlar structtJre appears belov.’

OH (H 3
I I

Cr! r CH – ( H_;( Hi( Hr CH – CH ;

Solution: Fi m,duetothepresenceofth e hydro):)’l groupin the mol ecular structure, 111se’lldent thatthe
pound IS an alcohol Because the longest chain of ca rbon atoms con ta inin g the hyd roxyl group has sei~n CQtn.
atoms, this compound Is a hydroxy denvat1ve of heptane To name the alcoh ol, the -e ending in h,p~
;~~c~a~~o~:1~:Z~\~~~/i\:”~ the chain are consecutive ly numbered beg rnnmg at the end of~

The SC(‘O!ldary risk associated wi rh meth l .
11 hcn as little as 0.06 pi~t (3_0 ml) of meihan;~~ i~ posed by its ingestion. Death may occur
to cause th_e onse~ of optJC diseases, including retinaf~ted. Lesse r amounts have ~n knO\;°
r l!!’C\’crsible blmdness. The toxicity of m th I . ~ma, th~t further lead to either parual

~rn1a1ion into the toxic metabolic b)”·p rod e a;o is directly linked with its stepwise trans-

CH 10H (aq)

\l c1 lunol

ucts ormaldeh yde and formic acid.
0

‘ H -~(a,1)
H

0

‘ H -~(aq)
OH

Foml3.IJ.,hJdo: Fonn1cx,J

Although th e fo rmaldehyde is prod~ced by metabolism in the live r, it travels in the blood-
scream throughout the body to various organs incl d’ h . f
! · ate accumulation of form · ·d h u ing t e _retin a o the eyes, where 1he

u n~e production of formic t e onsec _of optic diseas es.
II bo the metabolism of methanol also causes the pH

of ~e blood, norma Y ~t 7-~•-t_o decline. lt is this condition, called acidosis, that causes
1·1cr1ms of mcr hanol poisomng mmally to hypcn·e milatc and ultimately to suffer disorders
of th~ ce~tral nerl’Ous syStem. ~esc symptoms arc similar to those associated with ethanol
intox1ca uo~. Therea_fter, the vicums of methanol poisoning experience blurred vision and
dccrea~d rnual acuity. Absent treatment, these indi\·iduals may lose their sense of sight.

9H TH1 ~~——————-_Jlliiliilililliliiillilll

wood alcohol • The
common name for
methanol produced by
heatlngwood in the
absence of air

CHr CH- O-!i( H,CHi- CH -CH 3 .At !6( FR §1500 14(bJ(4), CPS( requires mamrfacturers to mar\:. the labe’sa ffu.~to consumerproducts con-
1 2 3 • 5 6 7 tH11ng methanol with the sl:.ull-and-trossbones sym bol, the signal W04’ds DA’,GfR and POi~ON, and tl-ie foJ low-

Because the hydroi,;yl group Is bonded to the ca,bon atom numbered 2, and a methyl group Is bond!d 10 ltie
carbon atom numbered 6, tt,e compound Is named 6-methyl -2-heptanol

13.2-A METHANOL
At room conditions, methanol is a colorless, water-soluble, and highly vo lati le liquid, Jr
formerly was called wood alcohol, a term that acknow ledges it as a constituent of thr
mixture that results when wood is strongly heated in the abse nce of air.

In the United States, methanol is manufactured ma inly by the high-tempera1urc, high-
pressure hydrogenation of carbon monoxide in the presence of an appropriate catalyst.

CO(g) + 2H , (gl – CH30H (gJ
Caibon mono~1dc H}Jrogtn Mc1hanol

It is also manufactured by the incomplete combustion of narural gas.
2CH ,Cg) + O2(g) – 2CH 1OH(g)
\ fcth.lne Mc1 hanol

In dustrially, methanol is used as a polar sol\’cnt for shellac and gu ms; as a raw ma terial
for the m~n_ufa:ture of acetic acid and forma ldeh yde; and directly as an antifreeze, aw
craft fucl~mJecnon flu id, windshield washer fl uid, automobile raci ng fuel, heat sourer for
chafing dishes, and component of me than ol fuel cells

Fire and explosion arc considered th e prima ry ~isks associa ted with methanol. hs
complete combus tion is represe nted as follows:

2CH30H(g) … 302(g) — 2C01(g) -t-
\klh.inol

Carbondiuwk

r
ir,g phram VAF OR HAftWUL, MAY SE FATAi. OR CAUSE SU”.DNESS If SWAlLOWEO. and CA~~OT BE MADf.
NC\ i’O,SONO US. What is the mO’St plaus1b:e reason CPSC requ res this 11i format100 to be marked on com um er
prod1.1CtScontaIningmethanol?

SolYtlon: As first noted 1n ~ on 1 2, to forewam the publl( of the presence of haza rdovs substal’\Ces m a
consumer product. CPSC comp!ls its manulactu1ers to label the product with cena·n mformat,oo Incl ud,ng advi-
‘>Of’/ war,nrngs and m1t1al precautionary statements tha t Iden t,fy the product’s pl’mc,pal hazards The most tog,ca l
rta1on tnat CPS( ta~es this pos1t,on with regard to consumer products conta,nmg methanol 1s that death and
blindness could result from the,r Ingestion CPS( Is congrm, onarty mandated to provide special phram on tne
labfl1 ofconsumerproductsconta1ning methanol so thatthepubl c 1sadequatelya’enedtoavo,ddrink,ngthem
These CPSCreq u1 rementsarenotedon the label d•solayed 1n Section13 2-B

13.2-B CONSUMER PRODUCT REGULATIONS INVOLVING METHANOL
Because death and blindness may re sult from the ingestion of methanol, 1he U.S. Con-
sume r Product Safety Commission requi res that the label affixed to meihanol containers
include the following statements:

“‘”” ‘””””
VAPOR HARMFUL

MAY BE FATAL OR CAUSE BLINDNESS IF SWALLOWED
CANNOT BE MADE NONPOISONOUS

538 Chapter 13 Chemistry of Some Ha zardous Orga nic Compounds: Part 11
Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 539 I

1
11

I

fltx•fu tl (fleJ1iblt-futl)
w:hid t (FFV) • Any
mot or Vf’hic!I!: that has
been S!)Kia lty d esigned
to use gasolinl!: blended
With ml!:tNnol or
eth anol as its fu el

ft rm tnt.lltion • The
enzymat ically con-
u oll ed, a nal!robic
conve rsion o f sugar
into an a lcoh ol

Ethanol

13.2-C METHANOL AS AN ALTERNATIVE MOTOR FUEL
:\kthanol is poten u::illy useful as an alt erna ti\’e motor fuel in either of th e follow in

M S5 . a blend of 85 % methanol and 15 % gasoline by ~olume, is used in
5

g Wal’i:
built c:irs and tr uc k~ c:illed ~ex-fuel n”hicles. A flex-fuel (flexible-fuel) vehicle, :;1a!ry.
an automobile speciall y designed to use blc-nds of gaso lin e and met h:i.nol or ethanol~’ 1$
as th e M85 an d E85 fu els. UCh

PW:e met hanol, called M /00. can be used as the fuel in some heavy.duty truc k
and tr.msn buses. ;

At 16 C. F.R. 5306. 12, the U.S. Federal Trade Commissio n requ ire s retail rn~ha
d1St n buto rs to affix the orange- and-black label show n bel ow on met hanol di spenS(rs: nol

MINIMUM
85%

METHANOL

In th is instance, the label identifies th e fu el as M85 and pro vi des the minimum methJ
nol concl!ntration as 85 % by volum e. The U.S. Federal Trade Commission also req
new- vehicle _manufacturer~ a nd used-vehicl e dealers to affix thi s label on a visible su~;:
o f each M8:, -powered \·eh1cle.

When compa red to the combustion of motor gasoline, th e combustion of MIOO p
duces fe wer to xic ~llucants. F_unh ermore, the use of M l00 in tran sit buses produc~:
far lesser concentration of particulate matter compared to th e use of diesel oi l. For thrst
reaso ns, methan ol is considered an env ironmentall y fri endl y fuel.

When compared to motor gasolin e, methanol is also safer to use as a fuel because it is
more difficult to _ig nite .. The info rma_tion in Table _13.2 demonstrat es that methanol pos•
sesses a substanoall y higher fla shpoint than gasoline. [The average fla shpoint of motor
gaso line is – 45″F (-43 °C).]

Nonetheless, th e he:H of combustion of methanol is less than ha lf that of gasoli ne:
974_0 Btu/lb (22,700 kj/kg ) compared to 20,400 Btu/lb {4 7, 300 kj/kg ). Conseq uentl)’,
vehi cles powered by me thanol require more frequ ent refueling than tho se powered br
petrol eum fuel.

. Because methanol is water-soluble, fires in vol vi ng M 100 can be effectively extinguished
wit h water. However, fi res in vo lving M85 cannot ht extinguished with wat er alone. Expem
reco ~mend th e us e of alcoh ol-resi stant aqu eou s-film -forming foam (AR -AFFF )
(Section 5. 12- C) 10 extinguish fires that are fueled with M85.

13 .2-D ETHANO L
Ethanol is al so _a colorle.ss, water-soluble, highly volatile liquid. As th e most commonly
encoun tered actJ\’e consmuenr of beer, win e, and th e so-called ‘” hard liquors,., ethanol ha s
bee n 3 staple of 1he human di et throughout reco rded history. Some archeologists specu·
late th at be verages were produced b}’ fermentation as ea rl y as l00,000 years ago, when
our human ance~ tors were first spreading out of Africa.

The pr?ducnon of ethanol in wine, champagne, and various brandies is accompl ished
~y ;;~;~~~~nf

th
i;uga~ naturall y pre ~ent in ripe fruits. For example, the e1ha~ol in winr

dioxid e c y me?nng th e sugar m grapes; when the wine is charged wHh car bon
h ‘ h~mpa gne is produced; and when the ethanol is di stilled from ferm ented

pea cEt~ ~~~[
1
i~~~s~:::~:; and other _frui~s, brandies are produced. r·

ated by the enzymatic coni~n ~umpuon is al so p~oduced by fermenting 1he sug;US ~en\
540 rst on of the starches m corn potatoes barley r)’e, and \\hea

Chapter 13 Chemistry of Some Haza rdous Organic Compounds: Part II ‘ ‘ ‘

7 lfl101dUIIS
11 w,vsdrinkat
low-risk levels

do not drink
atall

3ln10adults
drlnk1tlevals
lhllputthem

1trl1kfor
a1cohollsm,

llverdlsease,1nd
oth1rproblems

The ethanol in beer is P.roduced by ferment ing malted barley; in whiske y by ferment ing
com, b~rley, or wheat; •~ ~·odka by ferm enting potato mash; and in gin is produced by
fermenun~ rye. B~a use II LS pro~uced br ferment ing cereal g.rains, the ethanol present in
beers, whiskeys, g1~, and vodka 1s sometim es called grain alcohol.

The concent ~atton of ethanol in alcoholic be,·erages frequently is expressed by use of
the term alcohohc proof. In the seve?teenth century, peop le believed that sp irits resided in
bererages that caused t_he p~ychoact1ve effects experienced by individuals who consumed
them.~ proce_dure demed m England to test for the presence of these spirits consisted of
preparing a mixture of gunpowder and a sampl e of the liquor bei ng te sted. If the gunpow-
der ig~ited after t~: alcoho l had burned away, the event was regarded as “proof” or con-
firmatmn that spmts wer~ ~ctuall y present. If the gunpowd er did not ignite, th e action
was taken to mean that spmts were absent. In reality, the liquor had been diluted with so
much water it could not burn.

The percentage by volume of ethanol in an alcoholic beverage is defined as half its
3lcoholic proof. Thus, alcoholic beverages containing 90% and 95 % ethan ol by volume
arc 180-proof and 190-proof solutions, respectively.

Indi viduals o ften enjoy alcoholic beve rages, either alone or wh en socializing with
friends and family, When the Nationa l Institutes of Health survey ed 43,000 adults, 1 they
determined that 28 % of chose studied placed themselves at a health risk by drinking 100
much alcohol. The result of their investigation is illustrated in Figu re 13.1. Assuming that
firefighters act simi larly to th e adults survere d in this stud y, over 280,000 firefighters ma y
b( drinking too much akoho l.2

Wh en individuals consume an alcoholic beverage, the ethanol is absorbed into the
bloodstream, after which it is metabolized primarily in the liv er and removed from the
bod y. The rat e of absorpt ion is faster than the rate of metabolism. An estimat e of the
amount of alcohol that has been absorbed into th e bloodstream ca n be approximated
wi th an instrument lik e th e one shown in Figure 13.2.

The metaboli sm of ethanol invol\’es the stepwi se oxidation to acetaldehyde and acetic
aci d.

CH,CM10 H(aq)

E1 h:m.il

0
I

Cl-!3- C(aq)

I
H

Areul,kh )ok

1
·R~thinkmg Dr inking: Alcohol ~n d You r HcJlth” (Wishmgton, DC: U.S. Dcpm me111 of Health and Human

~n-1ccs,NIHP ublica1ion No. 10•J770,20 10),p. I.
· In 2000, the numbe r of cJrce r and active vol unteer fi refi ghters alone in ~he Amerka n cme rgcn~y rt’!opoll~
community was 1,05 4,000. [Ari. N. Houser, Brian A. Jackso n, Jamn T. 8.t rus . and D. J. Pmr~on, Emergency
Re1pond~ r Injuries and Facahties• (Arli ngcon. Virginia: Rand Science ~nd T~hno logy, 2004). ]

FIGUR E 13.1 Alco nol
u5ebyAmer1canadults,
aged1Byears or o’der
(Courtesy ofNat!OflJl/nsr~
M l’S of HN/lf>, Wit~”1g /on,
DCUS ~1or
HHlth ard Hurn.nServ:cts
0 0 10))

gr.ai n a ko hol • The
common name o f etha –
nol produced by the
fermentation of gra in

a lco holic

A

measure of the vo lu me
of ethanol !nan alco •
ho li cbeverage ; in the
Un ited States, tw ice the
percentage of ethanol
by volu me

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 541

r
I
I

lrli 11

FI Ci URE 13.l Ths
Alc-o!e-st7110m«n.ne ,s
.!SOnof
emanol ,n me b.OOC In
1007. S..preme Coun
;,f tne State cf New !e™!y
ri.i~dmdt tn.sl”act)j r,.e
~dessu’fioen:~re’1 –
a!J,’e•l’acJ”1gstha1may t,e
aCl”‘t:edinto eviderce
c!unng atNlorhe-.wig
wrtho.:ttne ne-ed forthe
tesnmol’yof an eme ri.
WIU,es5l(o,,,r,a-.foft::Jrlger-
“”””AG,llC/Tlo,tyKGd.4.

‘-“””

blood akohol co ncen•
trati on{ BA Q • The
rat ioofthevolumeof
ethanol to total blood

When more alcohol is ingested than the li ver is capable of metabolizing in a cimei)’ fash-
ion, the blood alcohol concentration, or BAC, increases,

When ethanol is consumed, it acts sim ultan eo usly as a brain st imulant and a ceniral
nervous system depressant, The sti mu.bcion is responsible for the pleasurable, euphoric,
and deinhihiting effects commonly associa ted with drinking alcoho l, whereas the deprcs·
sion accounts for the anxiery, te nsio n, and dulling of normal cognitive and mo1or pnr

volume
542

cesses. When alcoho li c beverages are co nsumed, individual s expe rience physical,
behaviora l, and speec h changes. The me rabo lic by-product aceta ld ehyde is responsi b!e for
these unpleasant physiological effects (including the dreaded hangover ), but it is easicri_o
measure rhe ethanol rat her th an th e acera ld ehyde in the cons um er’s blood. It is for th 15
reason that an in di vi dual’s behavior is routinely co rrelated wit h an individual’s blood
alco hol concentration.

At eleva 1ed alt itudes, a person has ro breathe hard er to ge l a mpl e oxygen int o tht
blood; a~d w~en alcoholic beverages are drunk at high altitudes, th e alcohol is ~bsor~
more qui ckl r mto the bloodstream. These phenomena cause a person to experience
effm~ of consu ming alco hol faste r when compa red ro drinking the sa me amount at lower eleva t1 ons.

Ind ividua ls wirh blood alcohol concentrations between 50 and 150 mg/dL, or berwctn
0.05 % and 0. 15% by vo lume, rypica!ly expe ri ence a complete Jac k of coo rdination. fOnc

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Pa rt II

I
J~~:rr~~ t ; )n::t~~Ov:~:~/~~e;~• ~1~::

1
s~a~!sa ~•~er.] This condit10:1 prevents thern from s.ifcl r

:~ununt leg.ii lm1it abo\·e wh ic h a (Xrson’ IS pr:~ii~;do; 0,08 1/o , ha s bttn selected as the
JI th is BA C, brakmg, s1eenng, lane changing, jud lent rorn dn_v.mgon ~oadways, ~ecause
l ed s1gmficanrl y. ,\-lost countries other h gn • and abiUty 10 dmde attention are

Jf ros ‘¼ as the threshold fo r est bl” h / an ihc United Stat es have selected 50 mgtd L,
or i-10\1:•much alcohol is Mtoo rn:c~Mtg egall>: whethcr a dri1·er is intoxicated.

be ·. Alcoholic beve rages should be consumed onl y in
moderation- tween one and t_hree ~rmks pn day. The rcixared consumption of alcohol
1ha l le.1ds ro d~unk_c:nness negatt~ely im pacts not only the lives of individua l drinkers but
the Jives of ~hetr f~ie nd s a.nd family as well. Bmgc drinking, the indisc riminate consump –
uon of mu lt iple dnnks m.re5f~ne immed iately after the other-can cause death wi1hin a
/c11• short hours of th e drinkers attempt IO discover am usement. This high -risk practice is
dearly a dange rous for m of recreation.

Btca use alcohol consumption dulls the senses and causes reflex es to be slugg ish,
emergency re sponders who consu me alcohol in amounts be yond mode ration cannot
expecl to pe rfo ~n~ ro ih e bes, of th_cir ability. Emergency responders serve thei r communi –
ues brst by avoiding alc~ hol or drm_king only in moderation. As a general practice, e1·ery-
one should choose to drink responsibly at all times.

13.2-E ILL EFFECTS CAUSED BY ALCOHOL ABUSE
!nd11·iduals who co nsume alcohol in relat ively large amounts over long periods of time
often become addic1ed to alcohol. As alcoholics, they usually develop one or more alcohol-
rdared li1·er diseases, of wh ic h th ere arc three independent types:

Fatty liver disease, the build-up of ext ra fat in 1he liver. The drinkers exhibit no
unique symptoms, but 1he disease ceases to exist wh en they abst:iin from the conti nued
use of alco hol.

Alcoholic hepatitis, the swelli ng of th e liver. Dr inkers do not always exhibit symp-
toms, but when 1hey occur, th e symptoms incl ud e nausea, vomiti ng, tenderness in the
abdome-n, an d jaundice (:i ye ll owish ness of the sk in). Again, the di sease disa ppears when
the drinker s cease 10 cons ume alcohol.

Alcoholic cirrhosis, a disease in which normal liver tissu e is replaced by scar tissue.
!t 1s ca used by the dea th of li1·er cells and is ch aracte ri zed by infbmmacion, pain, and
jJundice. Because alco holic cirrhosis causes se rious impairment of the liver’s biological
fu nction, it can be fa tal.

Studies3 have also link ed alco hol abuse with mouth, larynx, esophagus, liver, an d
breast cance rs. Althoug h it is uncl ear how et hanol causes the onset of these cancers, th.e
prevailing 1heory is th at metabolic acetaldehyde damages cellular DNA so severely th:i t 11
1s unabl e to repair itself.

Etha nol also enhances the ca nce r-causing effects of oth er ca rcinogens, particubrly those
fo un d in tobacco smoke. The American C:inccr Institute warns that freque~t co nsumptio n_ of
alcoho l by a habitual smoker leads to as much as a l?O-fold incre:isc in. the nsk for contra~mg
mouth, tra cheal, or esophagea l cancers compared wi th peop le who neither smoke n_or dnnk.

Pregnant women and women who plan to become pregnant sho~ld be especia ll y wary
of consumi ng alcoholic beverages, beca use alco hol may cause their offsp.ring t_o subse-
quen tl y experience mental disabilities, physical deflcienci~s, and oth er b1~ th d1 sorder~.
Prena tal ex os ure 10 alcoho l inju res the neurological func~1on of _a de\·~lop.mg fe, _us, ul.u-
lT\ately caus~n a red uct ion in the child’s inte ll ectual pote nu al fo r its cnure !•fc. This af~1c-
1i on is know n !s the fetal alcohol syndrome. The acetaldehyde formed dunng metabolism
JN E. Allen rr al ~~!oder ate ~kohol mtJke 3nd c~nce r mcidence m women,• / . Null. Ca 11. /11s1 .. Volume I OI
12009/,p p.1 96-·j oJ.

fo tty l!vtrd lsc asc •
The disease associated
withan increaseoffat
in the liver

The swelling of the
livercausedbythe
m1suseofalcohol

a lcoho li c cirr ho si s • A
potent ially fatal liver
d isease resulting from
the misuse of alcohol

fc ta l a l

Chapter 13 Chemistry of Some Hazardous Organ ic Comp ounds: Part II 543

biofu@I • Any alterna-
tive motor fuel pro-
duced in who le or in
part from domest ic
farm crops (such as
corn kernels or soy-
beans) or crop residues,
nonedible plant parts
(such as wood, grass,
switchgrass, or algae),
or municipal or forest
wastes

cel/ulosic @thanol
Ethanol produced from
algae, cornwaste,
switchgrass, and other
nonedible parts of
plants

is re,spons ible for th e onset of feral alcohol syndrome, because it crosses the place ntal h
rier J nd accumulates in the !n·er of the fetus. . . ar.

To apprise ihe public of the potential dangers as~oc tared wnh alcoh ol cons urnPtio
the Alcohol and Tobacco Ta x and Tra de Bureau requires at 27 C. F.R . Sl 6.2t la~lin n,
all alcohol conramers wi th th e hea lth -warn in g message shown here: &of

GOVERNMENT WARNING
According to the Surgeon General, women should not dnnk alcoholic

beverages dunng pregnancy because of the nsk of birth defects

Consumption of alcohohc beverages 1mparrs your ability to dnve or
operate machinery, and may cause health problems

Posting of this la bel has been required on a!/ alcohol comamers sold m th e United Siaies
since Nove mber J 8, l 98 9. . .

f\”orwit.hsranding the combina tion of adverse effects associated with th e consumpt ion o(
alcohol research studies also re\·eal that moderate drinking by mature adults may contribute
co pre\’~nting hea n arracks, rega rd less oft.h e nature of r_he alcoholi~ beverag e co nsum«f. For
example, one srudi4 ill ustrates tha t individuals who drmk alcoho!rc bc vera_ges three tirnrsa
week experience approximately one-third fewer heart attac ks th a n nondrink ers, Th is m.iy
mea n chat drinking a smal1 am ount of alcohol each da y may be beneficial to one’s he1Jth;
nonetheless, che reco mmended guid el in e has alwa ys been to drink in moderation.

13.2-F INDUSTRIAL-GRADE ETHANOL

Aside from its use in alcoholic beverages, ethanol is also widel y us ed for various ind us•
trial purposes. Manufacturing and process industries use large volumes of ethanol, most
typically as a polar sofrent in toiletries, cosmetics, pharmaceuticals, and surfa ce coat·
ings; a raw material in the manufacture of other substances; and as an oxygenate in
vehicular fuels.

Erhanol is sometimes produced for industrial us e by the acid-catalyzed vapor-pha se
reaction berween ethylene and water.

CH1= CH1(s ) + H10 (s) CH3CH10H (g)
Water Elhanol

Industrial-grade ethanol can also be produced from corn. The production o( co.m-
based ethanol involves fermenting th e sugar generated during the enz ymatic con version
of the search in corn. First, corn kernels are ground into flour and slurried with wat er;
~hen, enzym es are added to the mixture to convert the starch into sugar; and final!)’,_ )’e~S!
‘~ added to hasten the conversion of the sugar into ethanol, which subsequencl )’ JS ~i s-
nlled from the mixture. Modifications of this process were used by moonshiners dunng
Pr~hibirion ! 1920 to 1933 ). In Brazil, rhe ethanol made from sugarcane is solely uS!d as
a b1ofuel (without any gasoline ).

. Industrial-grade ethanol is also produced from variou s cellulosic materials incl~ding
SWJtchgra ss (a perennial warm-season grass native to N orth America ), wood residues
from the foresr producrs industry, algae, and other nonedible parts of plants. When P”.;
duced solely from these cellulosic sources for ultimate use as a biofucl, the erhan°\

1 called cel/u/oslc ethanol, When mixed with a petroleum-ba sed fuel , cellulos1c t rhan
Ji.as been used successfully to fuel ground-based vehicles, as well as air• and watercraft.

_’Jea, ;fr, K. P,;_” ,I., “Loag-r«m alcohol eom,mpr;o, ;, rd,r;
00

ro , 11<,om ,ad wd;o"" "'" m;;,;; Ir)' among

5
urvJ11o r5 o_f myoc 3rdia l infa rction: rh e heah h pro fe§ sionals fo ll ow- up,” Eur. Hort. J. I !DO/: J0. J09J/eurheartJ/e hs047).

544 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Pan II

Two fo rms of ind ustria l-grade ethanol are avai lable commerci all y:
1 Absolute alcohol is .ethano l th at co ntains no mo re than

1
% wat er.

Denatured alcohol •s a_n a.qu eous so lu tion consisting of approx imatel y 95 % eth ano l
h)’ vo lume.’° whi ch a hqu_id ca ll ed a denaturant has been ad ded to impede 11s use as
an alcoholic he \’crage or Lnrernal human med ici ne. Only certai n subs tances may be
added to eth:rn ol as de natura nts. Th ey are pu blished by th e Alcohol 1ind Tobacco Tax
and Trade Bu reau at 2 7 C. F.R. S19. I 005. The prese nce of the dena tu ra nt may cause
ethanol to be not only unpalat abl e bu t al so poisonous. Dena tured alcohol is intended fo r use prima n ly as a solve nt.

13,2-G ETHANOL AS A BIOFUEL

To reduc e fo reign oil im ports and greenh ouse gas emissio ns, the U.S. Co ngress has o\’er-
haul ed the nation’s energr policies through th e introduction of a bio fu els prog ram 1ha t
rl.’q uires th e blending of a biofuel int o gaso lin e. Und er th e mandate of the Energy Ind e-
pe nd ence an~ Sec ur itr ~c t of 2007, refine.,ri es, blend ers, and im porters now are res ponsi-
ble fo r blending 36 b1ll1on gaVy { 14 X 10 m3/ y) of bio fu els into veh ic ul ar fuel s br 20 22.
Gil’en rhi s manda te, it is apparent that th e dema nd fo r bio fuel use in U.S. vehicu lar fu els-
mdud ing ethan ol use-is ce rta in to subscant iall r increa se.

ln compliance wi th th e intent of th e Energy Independence and Security Ac t of 200 7,
etha nol is used as a biofue l in the United States when producing th e foll owing types of
1·eh icular fu els:

ElO, a blend of IO % ethattol attd 90% gasoline by volume. ElO ma y be used as
an add iti ve th e fuel in any motor \’chicle manu factured in 200 0 and earli er wit hout engi ne
modification. Because mos t petro leum fuel s used in the United States now contain 10 %
ethanol as an additiv e, th ey are co rrec tl y denoted as ElO motor fuel s.

E15, a blend of 15 % etliattol and 85% gasoline by volume, EIS may be used as
the fuel in li ght-duty motor ve hicl es, sport-utility vehicl es, an d fle x-fu el ve hicles manu –
fac tured in 200 I or later witho ut engi ne mod ification. However, motorcy cl es, boats,
snow mobiles, sc hool buses, deli very trucks, off-road equipment such as lawnmowers, and
chai nsaws cannot use E 15 wi thout causi ng them to malfunc1ion. To ass ure that customers
are aware of the potentia l problems when purcha sin g El 5, EPA requir es EIS distributors
to affix the follo win g label to di spensers:

~5
Up to 15% ethanol

Use only in .
• 2001 and newer passenger vehicles
• Flex-fuel vehicles

Don’t use in other veh lcles, boats, or
I owered equipment. It may cause

~::~;::nd is prohibltfil by federal law,

;:i b~o lute alcoh ol •
An eth an ol solution
containing no mor e
than 1% wate r

denat ured alcohol•
An et hanol solut ion
(9S% etha nol!S %
wate r) that is unfit
fo r con sumption asa
beverage due to t he
intent ional add it ion
of ade natu rant

de natura nt • Any
tox ic or noxious sub•
na ncel ist@dat27 C.F.R.
§19. l00S t hat isadded
t o ethanol to make it
unpa lat ab le

I IS C½ gasoline by 110 /ume. E85 ma)’ also be
E85, a blend of 85 % etl~anol a~:’ . , 0°01 and later )’ears. These cars and trucks Used as a bi ofu el in fle x-fuel vehrcles bur t ‘” – . . I 545

Chapter 13 Chemistry of Some Hazardous Organic Compounds. Part I

1 ha\·e sensors ro adrus t the n nung of spark plugs and_ fuel in jectors so tha t t ht• t’n i smoot hly rega rdless of the foci’s e th a nol co nce nrrauo n . . . g ne “% Ar 16 C.F. R. SJ06. l2 , the U.S. Federal Trade Comm1 ss10~ req uires retail di str” to affix. the fo ll owing o range-a nd-black label on the alcohol dispen ser: 1but0ri
MINIMUM

95 %
ETHANOL

This specific label identifies the f~el as El 00 and provide~ r~e minimum :rhano! cone
rration as 95 % by volume. As wHh methanol, rhe c~mn11 ss1on also_ ~equires ntw-,•elii~·
manufacturers an d used -vehicle _dealers to attac h this _label on a v1S1b/e surface of eac;
E85-powered vehicle. Ethanol with a denar_ur?nt only, 1s referred to _as £ 100. AJrhough it
is a\·ailable commercially, ElOO ha s only limited use as an alternative motor fuel in~
Uni ted States.

The sole use of ethanol as a biofuel is nor free of problems, several of which are noir,d
below:

Ethanol has onJy abo ut 66 % of rhe energy content of ga soline. Consequent!
use in \’ehicula r fuels red uces mileage per gallon compared to th e sole use of motor:;:
line or diesel oil.

Etha nol absorbs moisture from th e air, causing :orrosion within pipelines. To noid
cfos problem, ethanol is now transported solely by ra1 I ranks, barges, and tank trucks to
regional fuel terminals or gasoline-blending rack s.

The ethanol produced from corn diverts the use of corn throughout th e agricultur;i/
and /ives rock indusuies and can contribute to the rise in ce rtain food prices.

The ethanol produced from corn requires large amounts of pesticides and fetti J.
izers, e.ach of which requires the us e of petroleum fue ls for their production.

The ethanol produced from corn hampers the technologi ca l development of ed.
lulosic ethan ol and its commerci alization.

The soa ring demand for ethanol in the United Scares ha s res ulred in an incrmdn
transportation incid ents involving ethanol. For exa mple, in 2009, rhe derailment of a
Canadian Na tional Railway Company freight train in Cherry Valley, IHinois resu lted in the
explosion and burning of the ethanol contained in 13 tankcars. 5 The train consisted of 1
locomoti ves and 114 cars, 75 of which contained a roral of 2,158,724 gallons (8 J69m 3)of
ethanol. Nineteen tankcars, all containing ethanol, derailed.

13.2-H EXTINGUISHING ETHANOL FIRES
Fire and explosion are considered the primary risks associated with ethanol. The combus·
tion process, which at times can be near/)’ imperceptible, is represented as follows:

CH, CH, OH(g) + 3O,(g l – 2CO2(g l + J H,O(g)
Elh.lno/ Oxrncn Carbonil10 ,1 il_. Wmn

Because ethanol is a water-sol uble substance, rhe use of water on fires fueled br ethJ·
no/ should bring them under control. However, the fla shpoi nt dara in Table 13.2 rercal
rliat even when ethanol is diluted with water ro produce a solution containing 24 % ware~

5
Ra ilwJ y i\ ccidcm Report, ~Dmilmem ofCN Fteighr Train U7069 1- l 8 with Sub sequ enr Hnardo~s .\lartnt

Rdca ~ and Fire, Che rry Valley, ll!inois, June 19, 2009,” NTSIVRi\R -12/0 I, P820 J 2-91630 I (~’a;h1ngton, D
N J t1onJ/ Transporra rion Safery Board, 2012 ).

546 Chapter 13 Chemistry of 5ome Hazardous Organic Compounds: Part JI

solution is still flammable . From a pra 1 1~~mgms h a non bulk e1hanol fire, but it is
11

; 1t1~:l vicwp~int,_ the so le us e of water ma y
e; re,• eals th at when water alone is used { 10 ex rmgu 1sh a bulk ethanol fire. Test•
1:sS: l J 15 need ed 10 extinguish the fire. In mo:;

1
~

51
ulk ci~a.no!_ fi re, ? subst ~nt1 al volume

Lre chis vo lume of warer avai labl e for use at a fir::::~:r 15 simpl y 1mprac11cal to alwa )’S
Expe rts concur that among the firefightin f h.

I the use of alcohol -resistant aqu e .fl f oa_ms t at are now commercially ava1l –
Jb 1~~s best to exti nguish a bulk etha~~~ f\r: · ~rmmg foam (AR -AFF F) (Section 5 .. 12 -C ) str

.nt out that the firefighti ng profession n · owever, th ~se ex perts are also quick to
:re effec tively th an AR-AFFF. ctds an economical foa m thar performs even

13.2-1 ISOPROPANOL
There are two ~ropyl alcoh~ls, n-p~opyl alcohol and isopropanol. Bo1h are commercially
1mporrant, but isopropanol is used m larger \’Olum e. Jsopropanol is also known as isopro-
pyl alcoho l and 2-propanol. Most people recognize it as rhe most commonl y encountered
alcohol after etha nol. The formula of isopropano! is 01

3
– CII – OH .

I
Cl1 3

In the ~hcmica! indus try, isopropanol is manufactured by th e acid-catal yze d vapor•
phase reacnon between propene and water.

Cll 3CH= CH~(g) + l·l20(g) -… (C H3)1 – CIIOH (8)
l’ropc””-‘ WJ1e1 bopmp;uiol

lsoprop:wol is used in many wa ys. In th e chemical industry, large vo lumes are needed
fo r the productio n of hydrogen peroxide (Section 11.5), acetone (Section 13.5-C ), and
ot her substa nc es. Mose people recognize it as the ma in constituent of rubbing alcohol, a
60% to 70% solution (with methanol and e1hanol ) that is appli ed ex1ernally to th e skin
10 relie\’e muscle and joint pains. As it evaporates, it cools ::ind soot he s th e skin at the
point of co nta ct. lsopropanol is also used as a gasoline additive, where it serves ::is an
oxygenate and “deicer.” In the latter case, it dissolves water in the fuel line, lsopropanol
1> also used as a solvent for m::iny lotions, oils, and other commercial products.

Although rhe major hazard associated with isopropanol is 1he risk of fire and explo-
sion, the liquid is also :l poison. The consumption of isopropanol causes permanent dis-
abling illnesses, and when consumed in excess, it causes death, Ingested isopropanol
metabolizes primarily to aceton e.

13. 2-J GLYCOLS
Glycols are diols whose molecules have rwo hydroxyl gr~ups on adjacent ~arbon atoms.
Gl)·co/s may be produced by oxidizing alkenes and hydr::iung the alke ne oxide. For exam-
ple, ethylene glycol is produced as follows:

0
2cH 2= CH2(c) + 0 1cc 1 — 2df2-‘cH2(g)

E1hyknc Eth}k nc 0~ 1Jc

0
c~ -C H1(8) + H20(gJ —

E!h)knco,1J.e Waler Elh)lcncglycol

Ar room temperature, et hylene glycol and other simple glyco ls are sli ghtly viscous liquids
tha r are completely miscible in water.

g lyco l(d iol ) I Any
compound whose
molecules have two
hydroxyl groups
bonded to adjacent
carbon atom!

Ethylent glycol!
Propyl1n1glyeol

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 547

r
I I

phe noli c com p ou nd •
Any o rgan ic compound
whos e molea.il es have
at least one hydroxyl
group of atoms directly
bonded t o a benzene
rin g

Phenol

The two m ost commonly enco~ mercd ~lycol ~ -‘ _re cth ylen(.” g lyco l a nd prop ·le
co l. These co mm o n nam es are derived by 1dent1fym g the a lk ent: portion of ne &!}-
oxide us ed to synthesi ze the m fo ll owed by 1he word glycol. 1 e alken,

CH: – CH,2(8)
‘o ,

\\’,u~r

Cl-l3- C~l -;=H2(g) + H 20 (g)
0

Prop)kr>eo’l.ule W:iw r

HO – C H ~_Cl-12 – 0!i(R)
Eth)knc g!)~o l
( 1.2- [th,:m~1.l ,o l)

CH3-y11- CJl ~-OH(g)
OH

l’1 op) kne ~l~col
( 1, 2 Prop,m,.:,hol )

~thylene glyco l and pr ~pyle~e oxide used ~s liquid antifreeze agents in cooling and h~t-
mg sys tems. An ulcrav1olet -li ght-sensmve d ye 1s normally added to glyco ls iniended f
as a mifr~ze agents to help loca te hairline cracks in radiators. Ethylene glycol is also =t
hyd raul ic brake fluids, deicing fluids for a ircra ft and airport runwa ys, and as

3
solven in

paints and printer’s in~s. Propylene glycol is ofte~ the _so lvent used in certain medicati~~
that arc intended co be mhal ed or rubbed on the skm . It 1s also used as a raw material fonhe
manufac ture of certain polyes ter re sins.

The human body respo nds ini tially in a similar fa shion when increasing amount s of
either e thanol or eth ylene gl yco l is ingested; i. e., the consumers become intoxicated. lnd i.
viduals may be tempt ed co drink eth ylene glycol to experience the same “high” that they
could obtain from drinking alcoholic beverages. You ngsters are attracted co ethylene g!y•
col beca use it ta stes sweet. H oweve r, when it is ingested, ethylene g lycol acts as a toxic
s ubstanc e by destroying tissues and up setting th e normal pH o f the blood. In adult s, the
ingestion of as Little as 0.2 pint ( t 00 ml ) ma y cause death.

The toxicity of et hylene glyco l is directly linked wi1h its tran sformation into toxic
m e tabo lic by-products. The metabolis m of ethylene g lyco l occurs within th e liver and
invol ves the ste pwise o xidation ro fou r toxic m e tabolit es : glycoa ld c h yde , glycolic add,
g.l yox al ic acid, and oxa li c acid.

HO – C H1CH~-OH(aq)

E111)k negl)Col

0
\\
C – C H2- 0 l·l (aq)
I

l·J
Gl) co:i ldt’l1 )

0 0
\\ II
C – C(aq)
I \

H OH
Gl) O\ a li cacu.l

0 ,
HO – CH ,-C{oq)

• I
OH

0 0
\\ //
C – C(oq)
I \

HO Oil
O ulicncul

Following the initial ingestion of et hylene glycol, victims expe rience in eb ri at!on, ~ut ~•
the metabolism progre sses, th e acids ca use extensive ce llular damage, espcc1a ll y in\ e
kidney s. The victims ex perience th e sy mptoms of acidosis, which includes hypen·: :~:
~ion a nd di so rders of the centra l nervo us sys tem. In severe ca ses of ethy lene g_ly~ ol ~s who
mg, th e substa nce ca uses the o nse t of h y pocal~emi_a (Section 8. t t -.B). Jnd 1v1d~• 3

0
emer·

dem o nstrat e the symptoms of ethy le ne glyco l poisoning should be quickly ru she t
gency facilities for amidota l tr ea 1menc.

13 .2 -K PHE N OL

The phenolic compounds arc regarded as derivativ es of ben ze ne in which one or n~~:
h yd rogen atoms have bee n su bstituted w ith the h ydrox yl group of awms (- OH ).

548 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

n, pkst phen o lic compoun d is itself c:illed phe
I

b . . :: c6H ,OI I. no ‘ or car ol1 c acid . Its chemi cal formula
0-0H

c~H,- 0 – is nam~~ the phenoxy group.
At room condltlons, phe~o l is a colo rl ess to wh it e-pink crystalline solid that often dark-

(OS to red upon exposu_re ~o light. Because phenol readily absorbs atmospheric moisture, it is
3Jw encou nt ered as a ltqutd. h has the sweet acrid odor characteris tic of disinfectant s.

Ahho~gh phenol c.a n be di still ~d from the middle coal-tar dist illate (Section 7 .6-C), it
gene rally 1s produce~ m the chemical industry using othe r raw mat erial s. The dominant
production metho~ m ~olves d~omposition of cumene hydroperoxide by a rwo- step
process. Cumenc ts first ox 1d12:ed using a ir to cumene hydroperox ide, which th en is
decomposed into phenol and acetone.

o-CH (C H3)i(/)
lsopm p)ll’<'nicnc

lCumcnc)

Cunl<.°ne h~Jropcru, 1Jc

+ 0 1(8) _ o-C(CH, >,- 0-0H(I)

Ph<: nol

h oprup jlll)dror,ro, idc
\Cijl!XIIC l\)dropc,rn.,_,dc)

An organ ic
compoundwhoie
molecul eihaveone
hydroxyl group (-OH)
bonded directly to the
benzene ring

Thi s production method is eco nomically desirable, because th e coproduct acetone is also
a comme rcially important chemical product.

Phenol is an important industria l substance, because ii is the raw mat erial from which
a number of derivativ es and phenolic resins are manufactured. Phenolic derivative s are
also used in surgical anti se ptics and other germicidal solutions. Phenol itself was the first
surgical antiseptic. A so lution of one part phenol in 850 parts o.f w~t er by mass prevents
the multiplication of certain bacteria; for this reason, phenol denvauves are common con-
~tit uent s of mouthwashe s, gargles, and sprays.

So me important physical properties of phenol :1re provided in Table 13.3. Thes~ data
show that phe nol burns, but its fla shpoint is fairly elevated: ~75° F (79°C). For thi s rea-
son phenol genera ll y doc s not pose th e risk of fire and explosm~. . d .

‘W hen dissolved in water, phenol dissociates into hydrogen ions and phcnox1 e ions,

m,sing the ph,nolo-solut io:~~ be acidic. o-o·
(s) H .. ((U/) + (oq)

Phcnr-! ll)JTO);CIIIOll Phcno\\dc1un

. • 11 when it contacts ex posed skin, mucous
Th us, phenol is a cor ro sive m3 ~en 3 l, es~:c~s/ dilut e solutions of phenol with soap and
me mbranes, a nd th e e)’es. Plasnc surgeo d artial -thicknes s con1rolled burn of
vege~ab \e oil for chemical faci~I peel.s to ~::du~:e~:lar facial pigmentation.
predictabl e ~cpth wh ~n remov111g wnnt:: is absorbed into the body by all rout es of exP<:1-

Phenol ts also poisonous. A_lrhoufg \eva ted co ncentrations of phenol through the ski~
sure, the ingestion and a~ so rpuon °1 i~ airs liver and kidn ey function and profound\)’ can be especiall y damag111g. Pheno P sed indi\’iduals often experien~e coma an~ ma)
d(stu rbs the cent ra l ne ~\’ou s system~ ~::rmal LD so is 630 mgfkg (rabb11 s), phenol is also
die from res piratory fai lure. Becaus
conside red a sev ere skin irritant, . f Some Hazardous Organic Compounds: Part II

Chapter 13 Chemistry o
549

Ufl ol • Any of the
three methylated
denvativMofpheno l

Md,i!iiiiM!M¥:114·i06MESJ.i::@,.4Jfuil
PHENOL I o-CRESOL m-CRESOL P.CRESOl

Me lt ing point j , 04•F (40 ‘ 0 I SS ‘ F (3 1°C) 54″F (12 “Cl 9S”F (ls •q
Boiling po int 358″F (181 “C) )76 “F(191 “C) 397″F (203 “() 396’ F(202″Q
Speoficg rav1ty a t 107 105 1.03 1.04
68″F (20″C)

Vapor density 3.24 3.7 3 .7 3.7
(air = 1)

Vapor pressure at 0.357 mm Hg
68″F (20 ‘ Q

OJm mHg <1 mmHg <1 mmHg

Flashpo int 1 175 “F(79″C) 202 ‘ F(94″C) 202°F(94 ‘ Q
Auto ignit ion point 1319″F (715 “() I 11 l0″F (599 “() 1038″F (559 “() 1038’ F (559 ‘ Q

Lower fla mmable 1.5% by volume 1 35 % b y
limit vol ume

Upper flammab le
fim it I
Evaporation rate
(ether: !)

13.2 -L CRESOLS

1.06%by
volume

1.06%by
volume

1.35 % @J02 “F 1.4% 0302 ‘ F
(150 “() (150 ‘ 0

>400 >S00

o-Cresol

A commercially important group of phenols is 1he hydroxy de ri vatives of toluene, callM
cresols. There are three isomeric cres ol s, named o-, m-, and p-cresol.

p-Cruol

6°” 6°”

550

o- Cresol m-Cn:sol p·Cn:.wl

Their mix ture is called cresylic acid. The ph ys ical properties of 1he cresol isomers are
included in Table 13 .3.

In the chemical industr)’, the cresol isomers generall y are isolated as a mixture from
th e middle coal-tar distillate (Section 7. 6-C), aft er which the mixture is subjected to frac·
tional di stillation to separate the individual isomers. o-Cresol boils at 376°F (191″CI;
thus, it easil y separates from a mixture of the other two isomers, which boi ls at approxi·
matel y 394°F (20 I °C). This mixture of 111- and p-c resol is chemica ll y treated with an acid
to produce compounds that can be isolated mo re eas ily. Of the three isomers, the P•isorntr
is mos t imponant commercially.

When individuals are exposed to the cresol isomers, the y are likely to experienc~~~
same ad ver se health effects as those noted for exposure to phenol. For example,
phenol and rh_e cresols impair liver and kid ne y function and disturb the cenrral ne_r

1

:~0~;

sys tem when mges red or absorbed through th e skin. The cresols :ire more corros i
skin than phenol. The dermal L0 50 (o-, 111 . , and p- ) is 30 1 mg/kg (rabbits).

13.2 -M WORKPLACE REGULATIONS INVOLVING ALCOHOLS
When me th anol and ethanol are used in the workplace, OSHA requires employers to 1:
emplo yee e~p_os urc to a maximum \’apor co ncentration of 200 pan s per mil lion and J
parts per m1ll10n , respective ly, averaged over 311 8-hour wo rkda y.

Chapter 13 Chemistry of So me Hazardous Organic Compounds: Part
11

When phenol and th e cresols :ire used in th e workplace, OSHA requires employers to
hrni t employee ex posure by dermal contact to a maximum concent ra tion of 5 parts per
millio n, averaged ove r an 8-hour workday.

13,2 -N TRANSPORTING ALCOHOLS
When shippers offer an alcohol for transportat ion, DOT requires them to emer the rele-
1,anr shipping description on an accompan ying shipping paper. Some examples for sever.ii
represenmive al_cohols :ire .pro vided i~ Table 13.4. DOT also requires shippers and carri-
ers 10 comply w11 h all applicable labelmg, marking, and placarding requirement s.

When shippers offer for transportation an alcohol wh ose name is not listed at 49 C.F.R.
§172.10 1, its shipping description is identified genericall y as “U N1987, Alcohols, n.o.s., 3,
PG!,” “UNl987, Alcohols, n.o,s., 3, PG 11,” “UN198 7, Alcohols, n.o. s., 3, PG III,”
-UN!986, Alcohols, flammable, toxic, n.o. s., 3, PG I,” “UN l 986, Alcohols, flammable,
toxic, n.o. s., 3, PG II ,” or “UNt 986, Alcohol s, flammable, toxic, n.o.s., 3, PG Ill.” DOT
requires the shippi ng desc ription to include the name of the specific compound entered par-
enthetically. For instance, shippers describe a shipment of 1-octanol in PG lll packaging as
follows: “UN 1987, Alcohols, n.o.s. {contains 1-octanol ), 3, PG lll (Marine Pollutant ).”

ifri!IUI Shipping Desrnpt1ons of Some Representative Alcohols
ALCOHOL OR GROUP THEREOF

Alcohol ic beverages

A!lyla!cohol

Creso!s, fi quid

Cmols,soli d

Ethanol

lsopropanolorlsopropylal cohol

Methanol (international transportation)

Methanol (domestic transportati on)

Phenol, molt en

Phenol.solid

Phenol solu t ions
n-Propanol

SHI PPI NG DESCRIPTION

UN306S, Alcohol ic beverage~, 3, PG II
o,
UN3065,Alcoholicbeverages, 3, PG!II

UN1098,Allyla1cohol,6.1, (3), PG l(Poison –
lnhalationHazard,ZoneB)

UN2076, Cresols.liquld, 6.1, (8), PGI l(Poison)
(Marine Pollutants)

UN2076, Creso ls, solid, 6.1, (8), PG II (Poison)
(Marine Pollutants)

UN1170, Ethanol, 3, PG II

” UN1170, Ethylalcohol,3, PG l1
” UNl 170. Ethanol ~olutions, 3, PG II
” UNl 170, Ethyl alcohol solutions, 3, PG II
UN1 219, lsopropanol.3, PGII

” UNl l \9, lsopropylalcohol, 3, PG II
UN1230, Methanol. 3, (6.1), PG II (Poison)

UN12 30, Methanol, 3, PG II
UN2312, Phenol, molten, 6.1, PG II (Poison )

UN1671, Phenol, sol id, 6.1, PGll (Po ison)
UN2821, Phenolsolutions, 6.1. PGll (Po ison )

UNlZJ4, n-Propanol, 3, PG II

~rNI ZJ4, Propylalcohol, 3, PG II

m-Cresol

Chapter 13 Ch emistry of Some Hazardous Organic Compounds: Part II 55 1

I

37t>:,

SOLVED EXERCISE 13.5

:;:a~,ppe~ ot’er gaso:,ne anc ethanol for trat’lioorta1,on wittm, separate com panmented cargo lan~i bi

::: ::: ::w:a~:~g~;er~~•:r;~~; :;r~;:~~ sh,pp,ng Pd!)erl
Sol u ti on :

C•I ~.~; ~::~e~~~•;:~Giz;::: ~i’ a: /~s~r;;i,ons on tne accomoa nyog
(b) ~:~:=, ~a~:: ~:~~~:i/ ~~~1:81~::;~:d01~ :~~r:1: ::;~:~! ~~nc:rgo

t;mk., DOT requ,re!i the earner t o d1Sola y the 1den11f1ca1,on numbers 1203 and 1170 on the ,
11
~t

tank and on the sides in the s.ime ~ qu ence as the companments conta ,n, ng the matenals tht-, K!en!;
They may bt d1Sp!<1y~ w,th,n e,ther 01 angt panels er white SQuare-on-point d,amonds an each si~ a-.;i NCh end of the tank near the FLA"'1 MABLE pla ca rd, but 11 ,s Im oro;:ier t o display the two numbtriacr

011 thecer,terareaofasngleplacard

•1·/i?i·!Piilifiifll

552

BPA

‘Mt’lt’fl Y!,ppers offu for transpo,tatJOn EIO and ESS in ~pa1a1e cargo tan ks , what sh, pp1ng desc11ptrons\.llo,J(j
be entered on the accompanying shlpo.ng pa p!trs ?

Solution; E 10 and E85 are mooures of gasoline and not more t han 10% and 85% ethanol by volum,, 1~-
tJ~ly We see rn Append~ C that when these mIXt1Jres are offe1ed for t ra nsportat

13.2-0 BISPHEN0L A
Whe n phenol r eacts w ith ac e ton e , r he produ c t pre dominantl y produc ed is P,P”·
isopropylidene diph enol, more common ly known b y t he p roduct name Bisplmwl A, or
BPA. The pro ducrion reactio n is cata lyzed by anh yd rou s h ydro gt’n chlo r ide .

Cl h 0 011 + Clh -C-Cl·I ~ –. -0 1-00 II ( ) + JH )(tl 2 t;:l ,1 (.(.’J HO C · J -0 I
C H ~ Phenol

li 1sphc-nul,\

Bi sph e nol A is use d a s an inte r m ediate in th e p o lymer in d u stry to m a n u foctur t _c-PoX~
res ins (Secti o n 14.7) used in th e produ c t io n and m anufocr ure of elect r ica l, elecir~nic,~
s p.orrs -s afery e quipment. ‘.he epo xy resins are a lso used as pro tec t ive co_ati ngs in~t~t”u~tnJi
mrlk, an d be ve r ~ge ~o ntame rs, baby bott les, .. s ipp y cups, ~ and m u nicipal and ~:I hralth
water tank s. ft 1s t h is latr ~r comb ina t io n of uses rhat ha s give n ri se to po~e n ci rs of the
concerns , because BPA re sidue s leac h fr o m th ese coati ngs a nd become cons rnu c- n_ d
contents. W hen th e foo d s, bev t” r a ges, and wat e r arc cons u mt’d , BPA is :i lso ingtstc
unknowi~gl y. . . , r ustd

10 . BPA
1
~ also use d as a c o lo r-d tve lopcr that is coated on therma l- imag in g P•1P:i

15
ri sk

pnm c re dit -ca rd ?nd ca s h- regis ter recei pt s. The workers w ho hand le 1hese rec P
expos ure to th t” B1 s ph enol A via absorption throu g h th e s kin.

Chapter 13 Chemistry of Some Haz ardous Organic Compounds: Part II

Th: we ig ht o f scie nt ific l”Vidcnce indica te s that BPA adversely affects huma n health .
Studies sho w

th
a t adult ex posure to low concentrations of BPA can causl” an inc rease in

the r,ue s of proSlatc an~ brea5r can~ers, ~eproducrive abno rmaliti es , lowered sperm co unt ,
,
3 rly onset ~f puberty m f: r~alcs, insuhn -dcpcndem diabe1e s, obes ity, heart d isea se, and

neu robe haviora ~ a~normahtiC’ s. OihC’ r St udies7 a lso indica1e that BPA ma y cont ribute to
3dolescc nt oberny m expose d child ren.

Whe n inge st C’~ , be haves as an e ndocrine di srupte r \Section 12. 16) by pre venting
estrogen from acting m tts customary way. Es1rogen is a hormo ne that normally promotes
and regulat es t he d evdopme nt of fema le charattC’ristics.

In recogni tion of th is c~mbination of adverse information, chemica l m:inufac1urers volun –
rarily ceased the use of BPA m baby bott les and Msippycups” in 2009, but FDA did not ban thC’
pr.tctice until 20 12. Funhennore, to avoid food poisoning and sho rter shelf-!h·es, manufactur-
ers in the food and be \·erage industry a re eage rly seeking to find a repl:icemem fo r thC’ BPA now
ustd to coat containers. Several Sta tes now prohibit the sale of products intended for use by
mf:tnts and toddlers when 1he BPA concentration in thei r contai ners exceeds specified valu es.
C.an:ida also ha s ba nned the impon, sale, and ad\·errisi ng of baby bonles that contain BPA. In
ihe Uni ted States, ho weVC’t; FDA has rejected a pl ea to ban the use of BPA in food packaging.

13.3 ETHERS
An ether is any organic compound whose molecules ha\’e o ne or more oxygen atoms bridged
betwee n two alkyl or ary\ groups. The simple eth ers have the gC”n era l che mi ca l fo r mula
R- 0 – R’ , where R and R’ a re the formulas of arb itrary alkyl or ary l groups. In t he chemica l
and petrol eum industry, the simpl e et hers a re used as soh·ents and oxygC” nat es, respectively.

A special group of e t hers is 1he epo xl des . The molecu les of t hese compounds hav e an
oxyge n atom bond ed to two carbon atom s, eac h of whi ch is a lso bonded to each other.
Th fir general chemica l fo rmula fo llows, where R and R’ ar c arbi1rary alkyl o r ary\ groups
or hydroge n atom s:

0
/ —R – CH – CH – R’

!n the che mical ind ustry, epoxides typica ll y are used as reactant s for the pre paration of

othe~h sub st ances. f h s’ mpl e eth ers are dete rmi ned by alp habetically nming the
e common names o t e

I
f Bowed b . the word et her .

names of the alk yl o r a ryl groups ~anded to th e_o7f~~n::~;CI~ -0-Cl~\,Cl-1
3

is named
For ex:impl e, the compoun~ havmg thC’ che micaand R’ is the : , hyl grouP. Th e s imple st
(t hy] methyl e1her. H e re, R is th: meihyl groupe whose formula is c

6
H.,-0-CI-\

3
• Thi s

,1 hcr ha vin ~ a sing le ar yl group is th e su;~~n~e name ,rniso/e.
co mpound 1s most frequent ly encountere d \c la cing t he -y/ suffix of the relevant alkyl

In the IUPA C system, e_the rs are name ~u b~titut ed a\kan e. Thu s, et hyl meth yl ether
! ~~u:n~:~~ ~~?~aa;:d n: 1::

1
;;x~:~:~~:ra~~ amethoxybenzene, res pective ly.

Q-o-rn,
cH 3- Q – CH 2CH 3

Elh)lmclh)lc1hcr
1~k1ho , }cth:t11t)

An 1..olc
(Me1ho,)bcnlCM)

ethtr • My organic
compoundwtiosegen-
eral chemkalformula is
R-0- R’ , wtiere R and
R’ representarbitrary
alkyl orarylgroups

epoxid e • My organ ic
compound whose mol •
eculesh a11etwocarbon
atoms bonded toan
oxygen atom and to
eactiother as a three·
membered ring

B’ heno\ A concenlrauon wuh medk:11 d,sordcrs and llborJrof}’
‘ l.1,n A. L.1ng ct al., ~Aswc1auon of unnu:< ,s~ol. JOO (200S ), pp. \JOJ-l3 \0. . Bis hcno\ A conc.-nfra• t:~~r~~t~:~:~~~:~~:!~~~~•:.r~:i:~:: :n~ Blu1m~J • ;:~;~~•;; (20~2 ), pp . 111 !- I I 21 . r1on .1nd obe\ity ptev.1 1rncc ,n ch1l

Chapter 13 Chemistry o 553

554

An (‘ poxid(‘ is usuJII )’ n:im cd as an alkcne oxide or e~o xyalk a n(‘ , In the laiter insta n
numb(‘rS ar(‘ used to id enti fy thi:- carbon atoms to whic h the oxygen atom is b Ct,
Th ese methods of nomencl ature arc illustrated in the examples that follow: Ondtd.

0 /’ CH2- CH – CH1
Prop) !~nc o,1Jc:-

(l.2 Er,o,)piup.111c1
Hu1cnto,i..lc

(l,2Cpo\)but.ln~I

13 .3-A REACTIO NS OF ETHERS WITH ATMOSPHER IC OXYGEN
The primary hazard associated with most ethers is that th.ey are highly rnlatile, flammabl
liquids; henc(‘, the y constitut(‘ dangerous fire a~d explosio n hazards. Ethe rs are also
ardous substances because they produce potent1ally unstabl e peroxo-organic compounds
(Section 13.9 ) by slowly reac ting with atmos pheric oxygen. For example, th e followin
(‘qua.tions illustrate successive reactions that occur between diethyl ether and oxygen: &

CH 1CH2- 0 – CH2CH3(/)
D1c1b}lc1hc:r

CH1CH2- 0 – CH2C H2- 0 – 0H (s)
1-ELht> ~}c lh) ! h)Jropron ,dc

–, CH3CH2- 0 – 0 – CH2CH3(s)
D1c1h>l~r’011dc

2-Ethoxyethyl hydroperoxide and diethyl peroxide arc examples of peroxo-organic com•
pounds that di:-compose at explosive ra tes.

The eight ethers having the fo llowing molecular formulas are the most vulnerable to
forming peroxo-organic compounds:

CH 1CH1-0-CH1CH1
Dlcth}ltthtr

CH1-0 – CH2C H2- 0 – CH 1
Elb)k11egl)tol d1mclh)lt1hc:r

/G l)mcl

C.JH9- 0 – CH= CH1
8u1}t•mylc1her

CH1-OI – O – CH – CH 1
I I Q 0 1 CH 1 CH3

Dmr.prop) l,·thcr Trtr:lh)

CH3- 0 – CH2CH2- 0 – CH~CH~- O- Clli
D11’1h~lcne ~l}C0ld 1111e 1h) I c1hcr

(D, gl)lnc:)

CH2= CI-I – 0 – G l = CH:

. Th ese ethers ar e popular polar solvent s. To warn users of th ei r potential reactil’iry
wnh

0
:

followmg on ether containers:

PROPERLY DISCARD 30 DAYS
AFTER OPE NING OR

AFTER ONE YEAR IF UNOPENED

T~e c~emical reac1i~n s between ethers and oxygen arc ca tal yzed by light. C~ns~
;~:~;J•b\ est~:~~ a;thrchh pe~oxo-organic compounds arc formed may be ef~ecr;\eh~

g c et ers 111 metal cans or brown glass boules tha1 preHn

Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part II

pcnemnion of light. Because th e per.oxo-organic compounds are produced slowly, ethr rs
that were purchased years ago are likel y to be more susceptibl e to decomposition when
,omp~red

10
r~ose

th
at were rece.ntly purch.ased. Bttause ethers ar(‘ .al so vrry volatile, the

orgaruc peroxide ~ concen~rate wnhm the final residu:il volume of th e liquid, Henc e, the
nsk of an ex~losive reaci~on may be grea1er in e1her com.ainers containing small liquid
residurs than m fullcomamers.

Safety en~ineers recommend storing ethers in a cooled, darken(‘d room and marking
ihe date recei.vrd an~ the date fir st opened on a label affix ed to th eir containi:-rs. An
example of this label 1s shown be low:

13.3-B OIETHYL ETHER
Diethyl ether is a colorless, water-soluble, flammable, and highl y volat ile liquid. In the chem1-
ol industry, it is produced by th e dehydration of ethanol using concentrated sulfuric acid.

2CH1CH20 H(I) – • CH3CH~- 0 – CH2CIIJ(f) + H~O(/J
Eth.l!!t>l Dicth)ll’1hc:r

On inhalation, the vapo r of diethyl ether acis on the body as a short-lived muscle relax•
ant. Owing to this feature, it once was .a well -known inhalation anesthetic. A generation
ago, the odo r of diethyl ether was commonplace in the surgical rooms of medical clinics
and hospitals, where it was known simply as ether. The use of ether allowed surgeons to
perform surgical operations while the patient was unconscious. However, tht patient’s
reco1·ery from exposure 10 ether was slow and unpleasant. Anesthesiologists now ge ner-
all y select al1erna.tives to et her. Todar, you are unlikely to detect the odor of ether in a
cl inic or hospital, but likely to dete<:t i1s odo r when using an automotive starting fluid during cold weather.

The physical properties of diethy l ct hrr are provided in Table 13.5. The low flashpoim,
wide flammable rnnge, and relatively high \’apor. dr~sit)’ attest ~o the fla?U11abl~ nature ~f
diethyl ether. As demonstrated by the experimi:-nt m Figure 13.1, tts vapor 1s heavier than air.

MiliiiilW Ph ysica l Prope rti es o f Die thyl Eth e r
Melting point

Boil ing po int

Spec ifi cgravityat68″F(20′ C)

Vapordensity(air = 1)
Vaporpressureat68″F(20′ 0

Flashpoint

Autoignit ion point

Lower flammable limit

Upper flammable limit

Evaporationrate(ether::: 1)

– 1B9’F(-12l”O

94’F(34′ C)

0 .7\

2.SS

442mmHg

-49 ‘ F(-4S’ Q

320′ F{160′ C)

1.85%byvolume

48% byvolume

1.0

Dl1thyl1thtr

Chapter 13 Chem lstry of Some Hazardous Organic Compounds: Part II 555

Methyltert-
bvtyl ether

oxygt nate • A veh icu-
lar fueJ additive that
promote:s complete
combustion of the fu el
and generates lesser
amounts of carbon
monoxide and other
pollutants compared to
the amounts produced
wh en the fuel burns
w ithout the add iti vl!’

Euca lyptol

FIGU RE 13 _3 In rn,s labora1ory ,lfustratwn, a cloth 1s saturated wrth d,ethyl etner and placed at 1he top endc11
a1roughthathasbt’enar1 angt”data4S•angle 6ecausetht ether hasavapor den s1tyof lSS (a1t,.l ),1trn~
down the uough, replacing the a,1, un1,1 ,t ,,aches the lighted candle Th en, the vapo r 1gn1tes and flas~ up lht
trou ghto thefuelsou rce

Diethyl e ther burns wnh th e production of a virtua ll y invisible , pal e blue flame and
no accompa nyi ng soo t.

CH3CH2-0 – CH~CHJ(_e) “”f'” 60 2(g ) -4CO!(g ) + 5H 2O(g)
Dreth) l ctho:r o,,i;cn Carbo nd1 0 ,1Jc \\ ;uc ,

The presence of oxygen in th e molecular structure of die [h yl e th e r accounts for 1he l’irn.i-
a lly imperceptible flame assoc ia red w ith irs combus t ion.

13.3-C METHYL t ert-BUTYL ETH ER
.\.-!ethyl tert-butyl et her, o r MTBE, wa s first introduce d in th e U.S. fuel market in 1995 io
boost th e oxygen co nt ent o f gasoline, becau se it ha s an antiknock raring of 11 6.

fHJ
CH1 – 0 – C – Cli3

I
CH ,

Mcth)Jrnt-bu!)lrihrr
t1rrr -8uro,,,11C’rh~nc1

.\1TBE fo rm erl y was a major organic co mpound manufactured in the United States. It im
u~ d as a n oxygenate so that gasoline b urn ed more cleanly and produ ced less carbon mon·
oxide when compa red ro che petroleum fuels conraining non oxyge nated antiknock agerm.

In 1996, MTBE wa s id enrified as a low-level comami nam of a drinking water sour,c
in Santa Monica, California. Its o r igin was Jink ed w ith lea king unde rg round gasoline 5ior·
age tanks. Sanra Monica was obliged to close 7 of its J J municipal groundwat er well >.

Even at ver y low concentration s (40 µg/L ), th e prese nce of MTBE causes w:itrr ;0
s mell and ta sre fou l. To ens ure that drinking wa ter s uppli es are si multaneou s ly pala’.J ~ r
_and unlikel y t~ have harmful constituems, EPA pha se d out irs use as _a gasol~n_e ad~:~
foda y, MTBE 1s no longe r a componem of rh e exis tin g pool of ga so line addml’CS ,

o n a scientific review of available dara , EPA a lso concluded that MTBE ca uses cancerwh rn
ir is consumed in high doses; hence, it is classified as a probabl e h uman ca rcinogen.

13 .3-0 EUCA LYPTOL

556

_Eucalyptol is an oily_ liq uid produ c ed by euca lyp t us tre es, whe re it concentrates primarily
in the leaves. It pro vides the u ees with th ei r unique camp ho r- lik e fragra nce.

Chapter 13 Chem istry of So me Hazardous Organic Compounds: Part JI

Fucalyptol is a cyclJC e t her d es pne ihe u.sc of th e suffix: -o/ in its common name . Its
ridrr red name 1s l ,J,J -1r1me1h yl-2-ox:abicyclo[2.2.21ocrane.

~O, CH,

WcH1
1.1.3 Tnrncihyl 2oub,,), lo[! 21)0.. l;ine

( Euc-1-l )lllO! I

It h.1s ,1 bo iling po int of 176.5°F (3 49. 7°C) and a fl.1shpoin1 of 120• F (49″C).
Althou g h e ucalypt~s trees we re not inirially indige nou s to the United States, they are

nonet heless abundant Ill south ern California and Hawaii. When exposed to an igni1ion
sourer , th eir outer bark ignites readily, especially during dry, ho t weath r r and droughts.
The hr.11 of combust io n vapo r izes the e ucalyprol, and the ir leaves become ablaze wi1h
fi re. Secondary fires are initiated readi ly in ne.1rby ho mrs and uncul!iv:ited land s. Fires
10 \·olvi ng eucalyptu s trees a re occasionall y so difficul1 to ex:1inguish that fi refighte rs
rq;a rd ch em as major hazards and have di sco uraged their use in landscaping.

13 .3•E ETH YLENE GLYCOL A LKYL ETH ERS
Tor ethylene glycol alkyl ethers are co mpounds ha ving th e fo ll ow ing ge neral chemical
formula, in which R is an a lk yl group, R” is a hyd rogen atom or alkyl group, and n is a
no nuro in tege r:

R – (O – CJ·l 2CH! ),,-O- R’

Th ese compou nds a rc commerciall y known by the 1rade names Cellosofve and Carbito{.
Exam ples a re not ed in Tab le 13.6.

Th e simp le ethy lene glrcol alk yl ethers gene r:illr :ire refe rred to by th ei r common
na mes, which are obtained hr in dicating th e nat ure of R and R’ and the val ue of 11. Whrn
n = I, 2, and 3, m o 11 0•, di-, and tri- are used to respe clillely designate th e numb er o f
– O- Cl-!2C I 12- chains, a lth o ugh 111011 0- ma y be used only to :ivoid ambiguity. The

ldAiiiW Some Ethylene Glycol Alkyl Ethersa
COMMERCIALNAME _ f-“CH.:,Ec:M:::ICA:::Lc.:N:::AM:”E’:-::-:;::::::;-::;;::;-::;—jl-;c::;HE;::M::;ICA;::;;LF;;:0

0
RM;-::U::;LA;;;—~

Buty l Ce Uosolve Ethyl ene glycol monobuty l eth tr, or C..H<1- 0-CH1CH1-0H 2-butoxyethanol

eth ylene gl ycol al ky l
Any organic

compound whoie gen-
era l chemical formul a is
R-< O-CH1CH1)~- 0 - R", where R !s an alkyl group, R" lsahydrogen atom or alkyl group, andn l1 a nonzero integer

Ethyl1n1glycol
monomethylether

Carb 1tolsolvent Olethyl eneg!ycolmonoe th~leth er HO- CHr–CH1-0- CH1CH1 – 0 – C4H ~

Ct!lo1olvesol vent

O,butyl Cel losolve

O,glyme

Eth yleneglycolmo noethyleth er,or
2-ethoxyethanol

Ethyleneglycold,buty l ether, or
1,2 -dibutoxyethane
Diethy leneg lycold im ethylether,o r
l -methoxy-2 -(2 -methoxy)-ethane

Dimethyl Ce llosolve, or Ethylene glycol dimeth yl ether, or
monoglyme 12-dimetho•yethane
Methyl Celloso lve E;hyfene glycol monomethyl ether, or Cl-l1-0 – Cl-l1Cl-l 1-0H

= = —-g ‘ •=m•~th~O~”J~,t~ha~oo~I ;,;;;;:;;;;c;;;;;~-rCOH;;:, -::Co-c;::ciH¥iC1-1i- 0 – CH i CH 2- 0 – CH1CH z-O- CH1 rr”1 glyme Triethylene glycol dimet hyl ether, or
2, s,8.11-t etraoxadodecane

Chapter 13 Chem istry of Some Hazardous Organ ic Compounds: Part II 557

II

55 8

prefLxes mono- and dt – are also used to desig nate the nu mber (one or tv,o) of the
alk ,·I gro up. For e1h ylrne gl)col dt mec hy l eth er (o r monoeth yle ne glycol din, ech I s.i ltlt
R ;; nd R :i re name-d -Jimrth yJ- and n is I; fo r dieth yl ene glyco l di meth yl ether k ether),
are named -J 1me thyl- :ind II is 2; and fo r tr ieth ylene glycol dinier hyl eth er, R ~nd ~ d R
again named -Jime th yl- and 11 1s 3. . •re

Jn rhe- ruPACS)-s tem, R or R’ are namrd w11h the oxygen atom from the rthera lk
J.C., CHrO 15 named me thoxy; CH30·l~-O- is named etho xy; et c. Then, the se~h>f:
glycol ethe rs arc named as deriva ti ves of alkanes, alcoho ls, or ethers, as appropriate.

The ethylene glycol alkyl ethu s :ire- widdy used through o ut a va riety of cornm
ind ustries. For c-xa mple, mono_ech ylen e glycol ~i~i eth yl ech ~r is u_scd as a solvent an; r:;~
compo nent of rl ec1 rolyu solu ttons fo r sealed l1th1um bam nes; d1 eth ylcn e gl ycol dirncth
eth er is used as a so lve nt for priming ink s; and meth ylene gl ycol dimeth yl cthcr is a c )l
poncnt of brake flu ids. Th ese 1hrec ethyl cnc gl ycol alk yl eth ers :i.rc al so call ed ni onog/):~·
digfyme, and tnglyme, mpt”Ctivcl y, because – O-CH2Cl-l1- is a co mponent of th ei r fo r’.
mulas one, rv.•o, and three times. Othcr eth ylene ~lycol alk ~I c1h c~s a re al so mgred icnrsin
commerc ial produet s l1k c surface coatin gs, adhcm•es, clea ning fluid s, and consumer paint
stri ppers. All are fl amma ble liquids.

Th e eth ylen e gl ycol alkyl ethers arc produced by reactin g eth ylene oxide wi,h an
appropriate alcohol. Fo r exampl c, ethylene glycol monoethyl ether is producrd by react •
ing ethylene oxide and eth yl alcohol in thc presence of an a ppropriate c:11alysr. It is pro-
duc ed as a mixrure of mon o·, di- , and tri cthyl cne glyco l monoc th yl ethers, each of which
is isolated from th e O[her two by fractional di stillation .

Eth)knco \ 1J~
t- CH3CH~0H – CH 1C l·l2-0 – CH2Cl·l 20II

[th;irx:,j [ lh)l~~g)) COl mono,.•1h) I C!hr;r

+ CH3CH2-0 – CH1CH2- 0 – Cil1Cl!~OII
D:elh)knc glicol monoc lh)I e1h<-1

+ Cll3CH1-0 – CJ-l2CH2- 0 – G i2C H2-0 – Cl-l2C H20H
Tr,1·1h)lcrio:glJco! monU1.” lhJ l r 1he1

Several eth r lenc glyco l alk yl ethers are known reproductive toxins 8 \’ia sk in absorp·
ti on a nd vapor inhalation . Pregnant women appear to be especiall y vuln erable to thei r
ad\’erse health risks, becau se th ey ma y experience mi scarriages after inhalation exposure.

To emphasize the ill effects potentially posed to an exposed pregnant woman and her
unbo~n child h)’ the eth ylene glycol alk yl ethers, manufacturers include the foll owing
warning statemems on the labels of their commercial products:

W,-ii@@Mi May Cause Harm to the Unborn Child
13.3 -F TRAN SPORTING ETHERS

When s.hip.pers offe.r any ether for tran sportation, DOT requi res rhem to enter the rd e·
vam sh1ppmg descnp1ion on an accompanying shipping paper. Examples fo r m ·er:11 rep-
resen1:1m~ ethers ar~ pro\•ided in Table 13.7. DOT also requires shippers and carriers to
compl y wrt h ~II applrcab le labeling, marking, and placarding requirements. .

When shippers offer for tr.in sportation a f1ammable ether othe r than those h5red .at 4? C.F.R. Sl?l.lOJ , DOT requires th em to identify the commodity gencric:i. ll y on 3 sh ip·
pm~ paper as.eithcr .. UNJ27J, Eth ers, n.o. s., 3, PG II” or ” UNJ271, Ethe rs, n.o.s, J, PG
Ill. In both instances, th e shippin g descriprion includes the name of the sprcific ether entcred parenth etical ly.

! Brya n D. l·fardm , “Rtp roduct ion tox1rny of the gl rcol rthm,· Tox,co /ogy, Vol. 27 ( 19831. PP · 9 1- 101 .
Chapter 13 Chemistry of Some Hazardous Organic Compounds : Part

11

w11112tniu·:1wwmw11::1-

Oi~d,y l ethe r

o11sopropyl ether
1,1.oimethoxyeth ane

1,2•01met hoxyeth 11 ne

Dimethyl ethe r

o,oxane

Mt thyl ttn•buty l ether

Tetri hydrofuran

Ffriiiiii

\ SHIPPlNGDESCRIPT!ON

– ~ 222, An1~o lt, 3, PG 1U (M,1rint ?; u~t )–
UN115 5, 0 itthyl tt.htr. 3, ?G I
0,

!
1

UN115S,Ethyltth er, 3,?G ! __ _

UN \ 159, 0 il\O propy let htr, 3, PG t

UN2377, l . l •D,methoxyethan e, 3, PG 11

UN22S2, 1,2·Dimttho,:yeth,1 ne, 3. PG !t

UJ\11033 , Dimtthyl tthtr, 2 1

UN\\6S. D1oune. 3, PG II

UN2398, Mt thyltt n •blltylelher,3, PG II
UN20S6. Tt trahydrofuran, 3, PG II

Sh1ppmg Dtscnpt1ons of So mt Rt prese ntat1ve
Ethylene Glyco l Meth yl and Ethyl Ethe rs

HHYlfNE GLYCOL METHYL OR ETHYL ETHER SHIPPING DESCRIPT IO N
Ethyl ene glycol diet hyl eth er

Ethylene glycolm onoethylether

E!hyleneglycolmonomethylether

UN1153, Et hyle ne glyco1d,ethy l ethe,. 3, PG II

UN1153. Ethy leneglycold iethyl ether. 3, PG \11

UN1171 , Ethyl eneglycol monoethy l ether,3.
PG !II

UNl 188. Ethy lene glycol monomethyl ether, 3.
PG III

When shippers offer a gl rcol ether for transportat ion, DOT requ ire s them to identify
the subsl3nce on a shipping paper. Examples for the ethy len e gl ycol me1hyl ~thers and
rth ylene gl)·col eth yl e1hers arr listed in Table 13.8. Once again, all DOT labelmg, mark –
ing, and placard ing rcquiremcms apply.

13.4 HALOGENATED ETHERS
A halogenated ether is an organic compound whose mol ec ules. contain the – 0 – group
an d in which at least one hydrogen atom has been rcplac_ed wnh a halogc~ atom: The
halogenated el hers of importance 10 eme rgency res ponders mc)ud ~ the following: ep_ichlo-
rohydrin; the polychlorinaicd dibenzofurans and dibenz~-p-d1o~m s; the polybrommated
d1hf nwfu rans and dibenzo-p-dioxins; and th e pol ybromma ted d1phenyl ethers.

13,4-A EPICHLOROHYORIN . . .
In terms of chemical reactivity, the chlorinated cpoxidc known as cp1chlorohydnn is one
of the more versatile halogrnated ethers.

0
cr.i”1-‘cH – CH1

Cl

Epic hl omh) Jnn
(t-Chlum-13 ~po •} r ror.111e\

A.nyha!ogenated
derivat ive of an ether

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part n 559

r

!! 11 ‘I I , I
N

I I
I

Bislchloromnhyl /

“”ff

po lyc hlo rlna ted dibe n-
zo fu ran (PCDF) Any
chlorinated der il,ative
ofd1benzofuran
polychlori na ted
dibenzo-p–dio.io:in
(PCDD) Any chlori –
nated der ivat ive of
d ibenzo -p-d ioxin

MH=l’i!&M Physica l Properties of Ep1chlorohydr,n
Melti n9po1n t _

Boiling po int -+ 242 0~•q _
Specificgr av ityat68 ‘ F(20″Cl 1· 18
Vapordens ,ty(a ir 1) l .28

Vapor pressure at 68’F (20°C) 12.5 mm Hg

Flashpo int 88 “F(31 “C)
.~,~,o’.’.’:;g’.’.’.:oC,”‘-, o-,–:, ,—:0,—–,1 -;;,.~,.;,, ~,.;;,.;;;:;.Cl –
,=,=- “‘,”’11,”m”‘m-“,,’-,,-::1im- ,-,–, —–,…3~.8;;;¾ by volume
Upper flammab le hm1t 21 % by volume
Evapor.it,onr

Although ch em ises use epic hlorohydrin fo r ~ va riety _of purpos es, its main industrial use is
associared wirh the production of e poxy resins (Section 14. 7 ).

Epichlorohydrin is a volatile co lorless liquid. ~me of its ~~man~ physical prop.:rnn
a re noted in Tabl e 13.9. These data indicate that epichlorohydnn is a highly flammabl e liq-
uid. In addition, the vapor of epichlorohydrin is highl y poi so nous wh e n it is i~haied. Rept.11rd
exposures of moder.ire concentrations ma y cause pulmonary ede ma (Sec~1on 7.3- B). Upon
contact, the liquid acrs as a corrosive materia l that abso rb s through the skm. lARC cla ssifin
it as a probable huma n ca rcinogen.

The combina ti on of these haza rdous prop e rti es is e vident from it s DOT shipping
desc ription: UN202 3, Epichlo roh ydrin, 6. 1, (3), ~G II (Poi so n ) (Ma r.inc Po llutant ). When
epic hloroh ydrin is tra nsported, shippers and carriers mu s t co mpl y wnh all DOT labthng,
marking, and placarding requirements.

13.4-8 POLYCHLORINATED DIBENZOFURANS
AND DIBENZO-p -DIOXINS

The polychlorinated dibenzofurans a nd dibenzo-p-dioxins a r e, respecti vely, th e chlon·
nared derivatives of dibenzofu r:rn and dibe nzo-p-dioxin. Th ese latt e r s ub srnnces ha\e
m o lecul es composed of two benzene rings linked to each other by on e and MO oxygen
atoms, respect ively.

01bc rll O p •d lO \IO

Th e ca r bo n atoms are numbe red 3S shown from I to I 0. . I ·
Th e polychlorinated dibe nzofurans and dibenzo-p -dioxin s a re designated co ll ecfl\C)

as PCDFs an d PCDD s, re spectivel y. Their general mo lecular s tru ct ures :u e as fo llow s:

Cl ~ CI ,
0

560 Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part 11

Pol}ch lonll.ll cd d,fx- n1ofv r:m,
l’ol }ch lon n., tcd J 1bc n10-r• diu ~ins

Jn che~~ s; r;~:~~~~r~;1::~~;1~:~~:r~:ers, and_ th ~ ~ines dra\~~ from Cl ~ and Cly 10 th e ben –
1.r ne r, g h d ai an) a\atlable pos11 1on. Us in g th e ind icated nun1 –
l-(- ring s)’Ste~i, I e

17
cornpo un~ s ch lorina ted at least at the 2 3 7 and 8 posi uon s are of

the great es t mt e rc
5t

, because epidemiologists assoc iate th em :vi;h relativel y high degree
0fwxi rny. .

Thrre are 135 polychlonnated d1benzofura n iso mers an d 75 polychlorinared dibenzo –
p-dioxin isomers. A~iong th em, the PCDF an d PCDD ha ving the follo wing molecular
,ir ucmres have the hi ghe st degree of tox ici t y:

Cl~o De Cl cc,, V ooV cc,,
Cl~,M’C<

! , ~.7, 8-T~trac hJoro,;1,t,cniofu~ 2_\ 7.a-Tctl”Joe hlomJ,bcn,o-p-J,o ~,n

2.3 ,7,8- Tetrachloro dib enzo-p- diox in is commonly denoted as dio:rn1, o r 2,3,7,8-T CD D,
bu t the fi rst name is c hemica ll y imprecise.

The PCDFs and PCDDs were neve r imentionally manufactured as co mmercia l prod –
ucts, bu t they were ge ne rated as unwant ed by-products during cen:.i n uncontrolled incin-
er.ition, paper pulp bleac hing, and chemica l manufac turi ng operations. The latter incl ud ed
the production and manufacture of trich lo rophenol , letrac hlorophenol, pentachlorophe-
nol, and 2,4,5- t ric hl oro phenoxyacetic acid.

Interes t in dioxin was first stimulated by public health offic ial s wh en th e substance
was identified as a trace contaminant in herb ic ides form e rl y used by th e U.S. m ilitary
du ring th e Vie tn a m Connict. Se\·era l color-coded herbicides were use d as defoliant s to
dea r jungle ter rai n, strip 1he Viet Cong of cover, and destro y enemy c rop ~. Among_ th:m
was Agent Orange , a 50:50 mixture of 2,4 -dichl o rophen_oxyacetic ac id and ~10×1~-
con 1aminated 2,4,5 – trichlo ropheno xyace ti c acid. 2,4 -D1 chlorophcn oxya cet1 c acid
an d 2,4,5- tri chlo ro ph e noxyacetic acid are co mmonly kn ow n as 2,4 -D and 2,4,5-TP,
rrspecrively.

2,-1 -Di~hlorup~mn)OCCIIC oc,d
12.-1 -0,

Cl

cr-Q 0-CH,-c!’. 1/ OH
CC

!A.5 Tnchl-:,rup~ no~),=h•· a.:ul
12.-1.5 -TPJ

Brtween 1962 a nd 1970, the U.S. Air Force sp rayed ap~roximately 18 million ga ll o ns
(68, 100 m l) of Agent Orange on vcge t~t i_o_n in so u;\: ,~~ev;:m:;1d to the dioxin in Agent

The milit ary pe rso nnel a nd loca l _c~ vih~n s w h The ex ~ure in Vieinam veteran s, fo r
Orange subsequ e ntly contra~ted hor_nfi c d~ s~a:;-four ca:rs· soft-tissue sa rcoma; non –
exa mpl.e,. has bee n linked wit~ ~he _mc ep_ti ond chron ic lym ph~c ytic leukemia. The expo-
Hodgkm s lym p homa; ~ odgki ~ s d isease, a of res ira ro ry cancers (lung, bronchi, lar ynx ,
su re has a lso been associated with th e o~sr m ·elo~a, as well as a numbe r of noncance r-
and t~ac hea ), p ro s tat e canc~r, an~ m.ulti~/anJ , e

2
diabe tes.’1

ous ai lm e nt s including Pa rkin so n s di sea ea r r~’:,e lim ited so lely ro those pe rso nn el \\’~ o
Th.esc adv e rse health effec ts do not esti\·e ev id ence associa tes th e ex posure with

were di rectl y exposed to Agent O range. gg

‘ ‘ . . , ,md A tu t Or,mge – Ht.i /tl, Effects of Herb1e1dts Uud ;., V1 t hr.i,u Na11onal Ac,1Jcmy of Sc,cncc s, \ tter,ms f,
(~’Hhi ngton, DC: NationJl Ac,1dc mies l’rc,s,

19
I. . f H ardous Organ ic Compounds: Part II

Chapter 13 Chemistry o Some az 561

r;;- I

fire retarda nt • An
add itiV!tOcommerc ia!
products that promotes
rHistance toburning

serious birth defe.cts in th eir offspring. In particula r, th is evidence ~inks Agent Oran
expo sure with the inception of spina bifida, a c~nge~1t~.b1rth d~ ~ect, tn vete rans’ chi ld1!
v.’. ho were born after a pa rent servc-d on acnve t~ty m ietnam.

Altho u h the Viemam Conflict occu rred dunng the_ 1960s a~d early l 970s, expos
10 th e PCDis and PCD Ds is possible even today, es pec1~1ly ro hr~fighrers. As first no:
in S«tion 12. , 6-A, these subs tances are genera ted durmg ce rt ain d~c trical- rqu iprntnt
fires; and in S«-rion 14 .6, we will note th at th ey ar~ a lso genera t~d durmg _residemial and
other fi res 35 produm of the incomplete co mbu su on of po ly(vmy l chloride ) (PVC) and
simJla r plastics. Under chesc circu mscanccs, exposure to the PCDFs a nd PCDOs may ?Ost
a pronounced healr h risk ro the firefighters who_ respond to them.

IARC h.is ranked dioxi n as a hu ~an carcinogen. h ran~ s- th e PCDDs and PCDfs
whose molecu les have ch lorin e atoms m the 2, 3, 7, and 8 posmons as probab lt’ carcino-
gens. To avoid adverse health effec1s fro m dioxin cxposur_e, EPA desig nates 6.4 ftm ro-
grams ptr kilogram of _b?dy wcig_~~ as th ~ acceptable daily dosage for hum ans. (Oct
femrognim is one quadnlhonth (10 ) of a gra m.)

13.4 -C POLYBROMINATED DIBENZOFURANS
AND DIBENZO-p ·DIOX INS

The polybrominated dibenzofurans and dibenzo_-p-dioxins, or PBD_Fs and PBDD s, resPtt-
tivcly, are rhe polybromi nat ed de_rivativ~s of d1 bc nzofuran and _d1benzo -p-dioxin. Tht)
once we re incorporated into certa in pl astK product s to se rve as fire retardants.

Po!)bmm,na1rddiben1ofo r-Jn, Pol)brom1n J1cdd1 1:>cnm 1,-d10,m,

Here agai n, ., and y are intege rs, and th e lin es drawn from Br.r and Br, to th e btnzm
rings rep resent bond s at an y availab le position. Li ke th e PCDFs and PCDD s, thm m
135 PBDFs an d 75 PBDDs.

When they are exposed to hea t, the PBDFs and PBDDs undrrgo th ermal decomposi –
tion an d produce bromine atoms. These bromine atoms consum e the fr ee r:idi ca!s pro-
duced when polymers decompose a nd 1hereby retard the deve lopment of fire.

Research st ud ies on animals 11 re vea l that th e PBDFs and PBDDs disrupt th e normal
biological fu nction of th e 1hyroid and sex hormones. Th ey also damage developing brain ;,
impai r moto r skill s and mental abilities, weaken th e immune system, a nd a irer bone struc-
rure. Although these st ud ies ha~·c not bee n performed on humans, scien ti sts fear thJt
expos ure to th e PBDFs :ind PBDDs may similarl y affecl the human organi sm.

Like the PCDFs and PCDD s, th e compounds ass ociated with elevated to xicities att
1hose whose molecules are brominated in at least the 2, 3, 7, and 8 positions. The st
PBDFs_ and PBDDs are rega rded as probabl e carcinogens. .
. It is assumed that em erge ncy responders are at ris k from exposure to pol yb rominated

dibenzofurans an d ~ibcnzo-p-dioxins. During fire s, pla stics containing bromina1ed fir~
retardants und ergo incomplete co mbustio n an d rel eas e low concentrations of PBDFs an
~B D_Ds to rhc surround ings. Th e in halation of chese substances can potentially sub1rct
f1rC”f1ght ers and othe rs 10 an unwarranted hea lth ris k.

10
Jdf John~ n. E11111ro 11. Sci. Trcb ,m/., \’oJ. JO ( 19 96 ) 19 3

A

562
~!:,~: ~~j\~~~l:~r;;d Cheng-~ ~un Lee, “Polybro~ i~~ted D; hfn w -p-dioxms Jnd 01 bc n,ofurJ n! : L,trri-.:ri

stsim ent, &rmo11. HrJ!tl, /’m p,ct., Vol. 101 (1994 ), pp . 265 – .!74 .
Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part ti

13 _4.o POLYBROMINATED DIPHENYL ETHE RS
fhe pol ybrommared dipheny l ethers, or PBDEs, are rhe polybromina ted deri,•aflVeS of
diphen )’l ether, whose chemical formu la is Cb! \1 O- Ct> l 15.

Hr• Br,
Pol)broIT11nltf .Jd1 1)Nn)I Uhcr.,

( PBD&J

In this general molecular structur e, x and )’ are integers less rh an 5. There are 209 isomers
of the PBD Es.

Like rh e polybrominated dibenzofurans and dibe nzo-p-dioxins, th e PBD Es fo rmerly
we re manufactured for inco rpo ration as fire reta rdants imo the polymers used to make
wpers and carpet padding and automobile and furniture cus hioning. When used commer-
cially, they often were m:inufactured as mixtures of rh e pcma-, octa-, and dttabromodi –
phcnyl ethers. The pcntabromodiph enyl ether isomers, collectively ca ll ed the penta- group,
once were formulated as fire retardants into the polyurethane foam med in uphols1ery.
Al.a popul:ir were the octabromodiphenyl ether isomers and dernbromod1phcny l eth er, all
of which once were used in the housings fo r business machines and electrical a ppl iances.

U.S. production and manufacture of the PBDEs ceased in 2004 whe n tesn confi rmed
ihe presence of 1hese compounds in human serum and breast milk . Nonethe less, despite
their nonproduction, stockpil es of these compounds we re fo rm ulated into U.S. produ cts
afte r 2004. C:irpcts, bl:inkets, upholstery, fabrics, :ind oth er items manufacmred before
and after 2004 remain in U.S. homes. It is prudent to assume that firefig h1ers are exposed
to the PBD Es wh en they battle house fires. Decabromodipheny l et her is th e so le com-
pou nd among the PBD Es that is still imported into the Uni ted States.

The concern about PBDEs is th e ris k posed by expos ure to chem. Although resea rch
studies linking adve rse heal th effem with PB DE expos ure in humans are ongoi ng, animal
expos ure ha s shown to cause ch e ri sks previously not ed for exposure to PB DFs ,md
PRDDs. The av:1i l:1ble information suggests that PBD Es may cause ncu rodevelo pmental
problems, endocrine disruption, :ind cancer. Epidemiologists rank them :is probable human

carctir~:~ shown th at exposure to PBD E-lade n dust was th e key means by wh~ch
household c:u s acquired high levels of ce rta in PBDEs. The cats suffe red from ove ractn•e
1h)·roi ds. Altho ugh hype r1h yroidism is treatabl e in borh cais and humans, th e health
concern has focu sed on yo ungs ter s who are jus1 as likel y as cats to be ex posed 10 th e
PBDEs in normal hou se hold du st. Unlike adults, the y crawl on carpeted fl oo rs and
chew blankets. Pruden t parents ma y red uce the risk of ch ild _expos ure ~o PBD Es b~ ~re-
quently v:1cuuming carpets, 1.aundering blankets, and cleanmg other Items contammg
th

es~~:;~~~:r:::t:,rc considered major env iro nmental conrnmin~nts not onl y in th e
general U.S. pop ulation but al so in :inimals. PBD Es en_m _th e environm ent when th e
products in wh ic h the y wer e incorponred arc either m~men~ ed as compo nents ~f
muni~i p:1 1 wa ste or buried in landfi ll s. The im?act of th~1r env1 7~h:e~t:~ ~~e:~nnc~~:
rsptc1ally worrisome for rh e sur vival of the ammals at c e top O

I
d ‘. ‘

1
Arc1 ic pola_r b~a rs. Tes ts show t~at PBDE conce~~:

5
t~oc:smar~u~~:~i:~~:~~if;

1
::~h ;;.

btars 1han m nnged se:i ls or Arcuc fo xes, brc~~~s continu e~o survive in th e wi ld may
pass from prey to predator. Wh eth er th esc an b h f PBDEs and other bromi-
well be connected with internation:11 efforts to :i nt e use 0
nated fire retardant s.

Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part 11 563

II

13.5 ALDEHYDES AND KETONES
&ldehyde • AAy
organ1C compound
~general chemical

Aldehydes and ketones are org;m1 c compounds whosr molecules coma 111 th e- carbo”JI

group of atoms (b= O). In aldehydes, the carbonyl group is locatrd at the end of a chain of

carbon atoms, j hereas in keconrs it is located at a nonterminal position within th lta
Thus. aldrhydes an d kecones have the fol low ing general chemica l formula s, wher:~ a:

0

‘ fomiula is R-s
H

where Ris anarbitrary
a!lcylor arylgroup

ktt one • Any organic
compound whose gen-
e~J chem1al formula is
R-C-R’, where Rand

I
0

R’ rep,e-sentarbitrary
allcyt or aryl group~

R’ are arbitrary alk yl or aryl groups.
0

//
R- C R- C- R’

I
H 0

A n iihleh) de A ~ttonc

Naming A ldehydes . _
In che common symm, an alde hyde is na~1~d by_ c?mbmmg th e wo rd aldehyde with the
prefix of che name of the acid to whi ch it 1s ox1d1zed. The alde hydes ha vi ng one f\\·
three, and fo ur ca rbon acorns pe r molecule _are nam ed formalde~yde, aceta ldeh rd:, p:
pionaldeh yde, and n-buryraldehyde, res pect1 \’ely, becau se the y o xidize to formic acid, ac~
cic acid, propionic acid, and 11-buryric acid, res pectivel y.

In the IUPAC sys[em, an aldehydr is ll.lmed by replacing th e -e in 1he name of the com,.
sponding hydrocarbon with -al. The position of the carbonyl carbon atom does not have to

bt

designa ted.. because ic is always loc.:ired on a termi nal ca rbon atom. The aldehydes haiingone,
t’A·o, three, and fou r carbon aroms per molecule are then named methanal, ethanal, prop.3 ru(,
and bucanal, respccti1·ely, by replacing the -e in methane, ethane, propane, and butane wi1h-aJ.

O O O 0
II II I/ I/

H- ~ Cl·h – C\ CH3CH1-~ CH3Cl·l1CH2-~
11 II H H

Fo rmaldt h)dc.•
(\lelrul!ll )

Atel~llle h)d~
(f lll:inal j

Prop10 1U1lck-hJdc,
/l’roparul )

nBu!Jmldl’h}’de
(/lutam1.I )

The simplest aromatic aldeh yde is called benza ldehyde. Its chemica l fo rmula is C6Hs-CH0.

06”
Nami ng Ketones
In the common sys tem, a ketone is named by alpha betica ll y id entifying the alk yl or 3rJ 1
groups of wh ic h rhe substance is composed. Th us, 1he compound havin g rhe formulJ
CH1 -~ -CH1CH~Cl l 3 is properl y named meth yl 11 •prop yl ketone.

0
In the IUPAC sysrem, a keto ne is named by replaci ng th e -e in rhe name of rht’ corrt-

sponding hydrocarbon wit h -one; thc-n , rh e chain of continuous carbon atoms is num·
berrd so as co assign th e smallest possible number to ihe carbonyl group. Henct’, ih c
fUPA C name for methyl 11-propyl ketone is 2-pencanone.

564

I 2 J 4 5
CH 3-~- CH1CH2CI-J3

0
~lc!h) I ~-r rop) l l t10ne

11 -l ‘cll!JMOI\<'/

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

The keione whose formula is C6 Hs-~- CH. 1 is named methyl phen)’l knone, but it is also
~n-0\111 commonly as ace top henone. O

o~-Cil1
0

\ !u hi !phc n) lle111ni:
(l\cc1oi,,-,..noneJ

_______________ _J ____ _

tJs,ng the 1UPAC system. name tile CO!l’IPOUnd hal’l ng the follow,ng cond~d formula

CH1CH1- j – p-1cn1CH
0 (H 1

Solurion : By exam 1na1,o~ of Table 13 1. we determ,n, ti1at the function.ti g-oup reprmnted as -(, ,s tl’ie
urbcn)’I group l/\”1en •t ,s bonded to nonterminal carbon atoms, the cll’bonyl grouo charactenzes tne class of
0,gal”II{ compounds called ketones To name a ketone using !ht! IUPAC system, wt consecuti,e,y riumber each
carbonatom 1nti1e lon9estcontinuouscha,nolcarbon a:omsthat ton ta.nsthtcarbonyl9roup , btg,nn.n9at tht!
,rni of u,e cha ,n nearer to the carbonyl group By so d0in9, we Sef that th IS parucular ketone Is the parent com-
p,ound, 3-nexanor:e . Th is name 1s den11eO by replac,ng the -e wsth ,n hexane, the ahne hav,r19 s,x carborl
i 1Cll’5permolecule

t 2 l 4 S &
CH~Ch1-j- ~H- C”11CH i

0 CH 3

Thtfi. we 1dent1fy the methyl group on tht ca1bon atom numbtred 4. so me compound’s correct IUPAC name ,s
4-n’tthyl- 3- hexanone .

111s ,ncorrect to number the longe11 chilln of continuous cafOO!l atoms from nght to !eh as fol’cr,.,,,s, because
oh.9nernumbe1(4)wouldthenbeas~gne dtothecarbonylgroup

i 5 4 l 2 1
CHp,1-; – 7 H- CH 1CH ,

0 (H3

13.S·A FORMALDEHYDE
The simplest ald ehyde is formaldehyde, or merhanal. It s chemical formula is I-I CHO.

0
//

H- C
I
II

Forma ldehyde is a colorle ss, flammable g~ s at room cond~tion\ih:~ h~;l~::.”~~:~
ir rit a1ing odor detrctab le al concentracio~s as low as par p

important ph ysical properties are provid~~
1
~ .!:b!~:~ ~l~~ react with each other and pro-

In the pre ~ nce of water vapor, forma e ) Th ‘ b tance has an inddinite composi-
duce a so lid substance called paraformaldeh)’dhe. is su :s from approx imately 8 to 100.
rion. It s ch emical fo rmul a is HO{CJ-120 ),.H, w ere II ra ng

0
//

11H-C(~) ..-
1
H

Fo nnal,kh) lk
Par:iform:.Jd<:h) JC

Water

Chapter 1l Chem istry of Some Hazardou~ Org anic Compounds: Part II 565

r

,I
/I

P1r11fonn. Fonn1t• illi!iili·I 1/d1hrd1 d1hrd1 Ph ys ica l Prop erties of Fonnaldehyde
Me ltmgpoinl –+-134 ‘ F~

Bo,h ng po_ ;_”‘- —:-:-:=:-::——r:,-]’ F (~C)
Spec1 fic gr,rntyat68″F (20′ C) 082

Vapordermty(a ir., 1) 108

1.3 ~

1 147 ‘ F (64″C)

Fomu1ll n (i:ont.ining
20%mtth1n 0 1J

Vapo r pressure,t68 “F (20″Cl

Fl,uhpoint

Auto ignit1on po1nt —–+1-‘°-‘ ‘_F_(430~
Lower flammab le hmit 7.0% by volume
Upper flamma ble hmlt 73% by volume

fkcause formaldehyde is_ a self-reactive materia l, the gas is unavailable commercial!
How~ver, formaldehyde 1s so lubl~ m water :ind alcohol, produc~ng colo rl ess, corrosii
:~u:i’;::~-1~~~: ~:~~:~a\;:;r with 1he for maldehyde concentrarion. These solutions arr
. The liquid called fo rm alin is an aqueous solu ri_on ~f forrnaldehyde com.iining approx•
1mately 40% w3ter 3nd 5 % to 12% meth3nol. h is w1dd)’ used 3S a dis infect ing, sttri[iz.
ing, and emb3Jming 3gent. A formalin solution con raining 37% water and 15 % mrrha llOI
flashes ar 122°F (50°C). whereas an aqueous solution of formaldehyde without methanol
flashes ar 185°F (85°CJ and is corrosive.

For indusrri3I use, formaldehyde may be genera ted as 1he gas from paraformJldeh)·dr
andsym-trioxane:

Paraforma!dehyde consists of severa l form:ildehyde units bonded one to anorher i.~
a shorr chain. It s formula is HO- J-(CH1J,1-0-I-H, where II equals 8 or more. W’li en 11
1s mildly heared, paraformaldehyde decomposes into formaldehyde and water.

0
//

HO – f- (CH:).-0 -J- H(s) 11 H -C(i:) + H20(g)
I
H

Parafonn.1/dch)de Form.1ldc h)dc

sym-Trioxane is a combustible solid having :i cyclic mol ecula r structure. Whtn
mixed with a strong acid, sym-trioxa ne decomposes into formaldehyde.

CH,
/ ‘ 0 0

I I (s)
C(!blH2

0
q

311 – C(g )
I
I)

«m-Tno.\.1 rr Formaldt’hy,Jc

Aldehydes ofte n are produced as incomplete combustion products when organic sub-
stances burn wirhin confined areas. Materia ls that produce formaldehrde upon iheir
incomplete combust ion incl~de tobacco, wood, diesel oil, kerosene, n:irur~! ga_s, and et~;
nol. Aldehydes are the maJor cla ss of organic compounds conrained in d1esel-engi
exha ust, with formaldehyde being the most abundant among them.

i\-l~st ptr~ons fi~st e.ncounter fo~maldehyde while studying th~ anatomy of frogs; ~:
focal pigs ~unn~ their h!gh schoo l biology classes. Formalin so lunon s once were ,uStortJ•
P.re serve biological specim ens. Although rhey are still used in che United Statts b} rn
cians as tmbalming agen1s, their use as biocides in the European Union now is banne-d ,

566 Chapte r 13 Chemistry of Some Hazardous Organic Compounds: Part II

The bulk uf 1ht formaldeh)·de produced · h . .
for production of forma ld ehyde-deri ved ~:,~n~ied States 1s used ~s a raw material
mJtertals :ire manufactured. Prolonged exposi ,f rom which bu1ld111g-con st_ructio~
dentia l :ind commercia l bmldmgs construct re_ to ormaldehyde ma y occur mside res1-
wo0 d prod ucts, e~pecially when the buildi ed, insulated, or_ furni shed wnh com posite
]kcausemobile homes often are constructed ~~;;r;

0
newly_ builr and mfrequemly \’ented.

of formaldehyde may Ix especially prominent inside ~t~Ltt wood products, 1he presence
Formaldehyde leaches from composite wood produ~1 s, especiJIJy part icleboard in

11hich urea -formaldehyde was u~d as the adhesh·e to bind the wood pieces. Some specific
sources of th ese products are the following:

I ~~~~i~ng:nd bathroom cabinetry and furniture, shd\’ ing, coumertops, flooring, and

1 Glues and adhesives !hat were used to bind wood pieces and fragments into particle-
board, hardwood pl ywood, and fiberboard composites

1 Foaminsulation
1 Synthetic padding and carpets

s@!f,r u ctivt mal@rlill •
Forpurpo1e10IDOT
regula11ons,amaterial
that l1th@rmallyun11a•
bltaridcanund@rgoa
ltronglyexoth@rmic
decompos1t1oneven
wjthoutth@partlcipa-
tionofatmospheric
oxyg@n

fo rmahn • Asolutiori
offormaldehyd@ in
watuand/ormethanol

Figure 13.4 shows 1hat low concentrations of formaldehyde often leach from these ~~~~~1~:
0
;~~1:ehyde

sources into the surroundi ng en\’ironmem. These concemrations increase when the doors or urea-formaldehyd@
and windows of a mobile home are shu t forextensi\·e periods. The rate of relt’ase decreases reiin
as 1he age of th es~ produc1s increases and is dependent on the prevailing temperature and
humidity, Formaldehyde is releast”d into the air at its maximum ra1 e when 1emperaturr
and humidity are elevated.

Consumers ma)’ avoid their exposure to formaldehrd e in presse d-wood products by
buring only those labeled U.L.E.F., or ultra-low-emitting formaldehyde; N.A.F., or no-
3dded formaldehyd e; or C.A.R.B., or California Air Reso urces Board. C.A.R.B. refers to
specific stale of California standards that compel manufac1urers to limit the formalde-
hrde emiss ion levels in composite wood products.

FIGURE 1]A Fonnalde·
hydega1 escapes s!owly
from thefollow,ng con-
struct1on sources k1tchen
an dbathroomcab,netry
andfu rn 11ure, g!ue ano
ac!hes, ves used tobmd
wood panrdesm panode-
bwrd. hardwood ply-
wood. and fi berboard,
fo am,nsulatron, and 1yn-
thet,cpa dd ,n g an dca r•
pet,ng WMnam obtle
home ,snewlycon-
s1ruct~ . unver11ed, or
heavi ly1mula:ed.the 1nie•
nora,rcon1a1maneie-
vate d formaldeh~de
concentra1,on,wh 1ch.
when1nha! edby115 0W.1·
panu. maycal/lethem to
exper,en<:eresp,ratoryd,1· comfortan dotherhulth prob 1ems

Chapt er 13 Chem istry of Some Hazardous Organic Compounds: Part II 567

I I

568

bt

8/liiiiiii Adverse He alth Effe cts Associated with Breathin g Formaldehyde’
FORMALDEHYDE
CONCENTRATION
INAJR(PPM)

0.1–0.5

0.6–1 .9

2.0-5.9

6.0-10.9

11-50

;:,,50.0

:>100.0

SYM PTOMS

I Nasal and eye irrit at ion, neurological effects, in creased risk of anhm allergies . aa nd.lor
Nasal and eye irritat ion, eaema, change in pulmonary funct ion

Nasa l, eye, and throat irr itat ion, eczema, or skin irritat ion, change in Pulmona
function r,

Nasal. eye, throat and sk in irritation, headache, nausea, discomfort Jn breath.
ing, cough

Nasal, eye, and sk in irritation, nasal ulceration, change in pulmonary function,
sible liver dysfunction, testicular effects, nasal tumors, red uced survival (in an~

Possible pulmonary edema, pneumonitis, and possible death bloody nasaJ
discharge, pu lmonary edema (in animals)

Death probable

•Agency For TOJ: lc Substa nce: & Disease R!Q1my, Forma ldehyde (Washington, DC. U.S. DepartmMt of Hukh irrd
Human Service:, 2008) .

Exposure to formaldehyde can be wo rrisome, since inhalation causes the ill effrcrs
noted in Table 13. 11. Furthermore, forma ldehyde is a well -known human carcinogen.
Toxicological studies ha\•e linked forma ldeh yde inha lation with the onser of upper•lta ct
cancers, especially naso pharyngea l and sinonasa l cancers. Embalmers comprise a group
that is especially vulnerable, because the y typica ll y contract myeloid leukemia and rare
cancers of the nasal passages and upper mouth. 12

13 .5-B WORKPLACE REGULATIONS INVOLVING FORMALDEHYDE
When forma ldehyde is present in the workplace (such as anatomy and pathology la bora•
ro ries), OSHA requires emplo yers at 29 C.F.R. S 1910.1048 to limit employee exposure to
a maximum concentration of 0.75 part per million in air, averaged over an 8·hour work-
da y, with a ceiling limit of 2 parts pe r million. The NIOSH recommended exposure limit
is 0.016 part per million with a ceil ing limit of 0.1 pa rt per mi llion, and the short•rerm
exposure limit is 2 parts per million over a 15-minute period. These exposure limits are.so
low that those who rour inely use forma lin have been encouraged to select an altern a[Jl’e
substance that accomplishes th e same task.

At 29 C.F.R. SI910.1048(e)( I ), OSHA also requires employers ro establish regular,d
areas when the concenrrarion of airborne forma ldehyde exceeds the rim e-weighted average
va lue (0.75 part per million ) or the short-term exposure limit (2 parts per million ), a~d ro
post all entrance and accessways with warni ng signs tha t bear the fo llowing information:

• •t·V@a;•
FORMALDEHYDE
IRRITANT & POTENTIAL

CANCER HAZARD
AUTHORIZED PER SO NNEL ONLY

;::’!~ H:s:~f:a;: ct ~~-,h•Mo~ality from lymphoh~ma ropoiet ic malignanc ic-s an d brain cancu amongtmbJlm·
P

O
ma e ydc , f. Natl. Gm ccr /115fs f,, Vol. 95 {2003), pp. 16 15- 1623.

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part
11

OSHA al so requires fo rma lde hyde•conrami nat d I d b . . labded :i s follow s: e aun ry to e pl ace d 111 a plasuc bag and

P. •t·HMaaj
fORMALDEH Voe.
CONTAMINATED

CLOTHIN G.
AVOID INH ALATION

AND SKIN CONTACT.

Ali formaldehyd e-contaminated laundry must be cleaned through use of a specia li zed
commercia l laund ry service.

13.5-C ACETONE
The si mplest ketone is ca ll ed aceton e, propanone, or dimeth yl ketone. Its chemical for-
mula is (Cl-13)c0=0 .

Acc lO!lc:

Jr is a colorless, water-soluble, and hig hl y vo latile liqu id with a sweer odo r.
The data in Table 13.12 indicate that acetone and ot her simple ketones pose the risk

of fi re and ex plosion. When they burn, carbon dioxide and water vapor are th e product s
of combu stion.

(C H,)2- C- O(g) + 402(g) – JC02(g) + lH20 (g)
1\ c.-1on,· Carbond 10 \lde W:nrr

ifriiiiii
Meltin g point

Boiling point

Specificgravityat68°F
(lO’ C)

Vapordensity(a ir = 1)
Vaporpressureat68 ‘ F
(lO”CJ

Flashpoint

Autoignition point

Lower flammable limit
Upper flammable limit

Evaporation rate
(ether= 1)

Physical Pro pe n,es o f Ace tone, Methyl Ethyl
Ket one, a nd Methyl lso bu tyl Ketone

M ETHYL
METHYL ETH YL ISO BUTY L KET ONE

AC ETONE KETONE(MEK) (MIBK)

– 137°F(-94″C) -124″F(-87 “C) -l21 ” F (-8S”Q

133′ F (56°C) 175°F(Bo•q 243 °F (117 ‘ C)

0.79 0.81 0.80

l .O l .5 3.5

181.lmmHg 71 mmHg 15.7mmHg

0°F (-18 ‘ () 20″F( – 7″C) 73 “F(2 3” Q

1000″F(538″C) 960″F(515 “C) 860″F (460 ‘ ()

3% byvo1ume 2%byvolume 1.4% byvolume

13 %byvolume !O% byvolume 7.SV.byvolume

1.9 l .7 5.6

Acetone

Chapt er 13 Chemistry of Some Hazardous Organic Compounds: Part II 569

I I
11

I I I Ii

I
570

MEK MIBK In the chemical ind ustry, acetone is manufa cc~red by several methods, As
11 in Section 13.2-K, acetone is produ ced rogerher wnh p~enol by the decomposfrio0t’1J

Dlacety/

cumene hydropero x. ide. Jr is also produce d coge ther w.1th hydrogen peroxide b llof
1 oxida tio n of isopropanol. The m.ost co_mmon method of production, ho\\-:

1
‘.ht

involves rh e caralyuc dehydrogenation of 1sopropanol. t~

(CHih- G l – OH(gl __. CH,-~- Cll !(g) “t- H2(g)

0
lsoprop.11101 Acc1011c H}drugcn

Acetone is largely utilized commercially as a _polar sol venr in varnishes, lacquers
paints, fi ngernail polish remo ver, and acetyle.ne. rr is also used as a raw material for

1
~

manufacrure of meth yl merhacrylare, meth yl ,so buryl ketone, and other substances.

13 .5-D OTHER KETONES
Ocher commercially imporranr kerones have physical properties similar to ihos e f
acetone. Two are eth yl meth yl ketone (or, incorrect.ly, methyl eth yl keton e) and meih:J
isoburyl ketone.

rn,-c- rn,rn,
II
0

E1hylmeth)ll,: tollc.’
Meth)lc-th)ll etone

(2· Butano rie)

CH, – C -CH 2-CH – C ll 3
II I
o rn,

h ubul)lm(•lh)lket oM
Mc th}l1 >0bu1 yJlcr ont·

(4-,\klh)l •2-p,:-m:mo,~)

Jn commerce, th ey are known more widely by their ac ronyms, MEK and MIBK, respC\’.•
ti\·ely. Borh are flammable , water-soluble, highly volatile liquids at room conditions.
They formerl y were encountered as constituents of solvent mixtures, especiall)’ solvtm-
based paints.

Several commercially important kerones containing multiple ca rbonyl groups alsom
known. The compound called diacetyl is a volarile, high ly flammable yellow liquid whost
molecules have two carbonyl groups. They are bonded to rhe two nonterminal car bon
aroms that provide a chain of four carbon atoms. Its IUPAC name is 2,3-butanedione.
(Nore that rhe -e in the name of the alkane is not dropped when naming a dion e.)

CH,-~-~- CH1
0 0

Drncc t) I
l’.!.3- 8u 1t111cd1oncJ

Diaceryl once was used as a butter-flavoring agem and an aroma carrier in food produc ts
like microwa ve popcorn umil it became apparent that the inhalation of elevated concen·
trarions of its \·apor could cause the rare lung disease bronchiolitis obliterans, .known
c~lloquially a.s popcorn lung. Workers exposed to relatively high concentratJons of
diacetyl experience shor_mm of brearh, coughing, fatigue, and ultimately death. _Pop

13.5-E TRANSPORTI NG ALDEH YDES AND KETONES

When shippecs ofb •~ aldehyde o, keionc for transportarion, DOT req uires them ~o
enter the relevanr shipping description on an accompanying shipping paper. Some exa
pies for several represemarive aldehydes or kerones are listed in Table 13.13. When -‘~e
name of an aldehyde or kerone is not listed in Table 13.13 or the Hazardous Marena s

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part
11

iliiiiHI Shi pping Descripti ons of Some Re pre sen t ative Ald ehydes and Ke-tones
ALDEHYD E, KETONE,
OR THE IR SOLUTIONS

Acetaldehyde

Acetone

Benzaldehyde

Butyraldehyde

cycloheJ1:anone

Ethyl methyl ketone

Formaldehyde solutions (flammable)

Formaldehydesolutions(l0-24.9%
formaldehyde)•

Formaldehyde so lutions (;;. 2S %
formaldehyde)

Methylcydohexanone

Methyl isobutyl ketone

Paraformaldehyde

Propiona ldehyde

‘ Forshl pm , ntbyalr.

I SHJPPJNG DESCRI PTION
UN 1089, Aceta ldehyde, ], PG 1
UN!D90, Acetone, 3, PG U ——

UN1990, Benzaldehyde, 9, PG IU

UNl 129, Butyraldehyde, 3, PG II (Marine Po llutant)
UN1915, Cyclohuanone, 3, PG 111
UN1193, Ethyl methyl ketone, 3, PG ti

UNl193, Methyl ethyl ketone, 3, PG 11

UNl 198, Formaldehyde solutions, flammab le, 3, PG Ill
UN3334, Aviation regu !ated liqu id, n.o.s
(formaldehyde), 9

NA3082, Other regulated substances, liquid, n.o.s.
(formaldehyde),9, PGUI

UN2209, Formaldehyde solutions, 8, PG Ill

UN2997, Methylcytlohexanone, 3, PG II

UN124S, Methyl i5obutyt ketone, 3, PG II

UN2213, Paraformaldehyde,4.1, PG Ill

UN127S, Prop ionaldehyde, 3, PG II (Marine Pollutant)

Table at 49 C.F.R. S 172.101, its shipping description is identified generically. DOT also
requires shippers and carriers to comply with all applicable labeling, marking, and plac-
arding requirements.

13.6 ORGANIC ACIDS
In Section 8.2-8, we learned that organic acids, or carboxylic acids, are compounds whose

0
11

-COO H In molecules of the organic molecules possess the group of atoms, -~ , or ·

OH n ox , en atom in the e,arboxyl group. The
a~ids, a hydro~en a~om is bonded as sho,~n !Oi~s co)! ounds having one carboxyl group
simplest orgamc acids are monocarbo:’}’hc acb. ‘ fk I or aryl group Ne xt are th e di –
and the formula R- COO H, where R IS an r l~rary and three c~rboxyl groups,
and 1ricarboxylic acids, whose molecu es a,•e w

respectively. . . . .fied b their common historical names: formic
The simple orgamc acids are idenn f h >’1 the IUPAC sysiem the y are named by

acid, ~cetic acid, propion!c acid, and :of t~:t c~r~esponding alkane ,~irh -oic_ acid. When
replacing the terminal -e m th e ~ame alon

3
chain of carbon atoms is des ignated by a

necessary, the position of a sub 5muent
I

g is assigned th e number 1.
number. The carbon atom in the carboxy grotu3pCh mistry of Some Hazardous Organic Compounds: Part II

Chapter e 571

I

II 11
I /I ;
1 ‘/ I

.;1 572

The orgamc acids ha\·ing_from one to four carbon arorns per molecule arc-
111 manl y cncoumered. These acids are named as follows: Ost c

0
lll-

0
//

11-C
I
OH

0
//

ClliCl l ,-C

Fomucac,J
( \l”thano,ca..,J)

,\ce1,cx1d
(E1hano1cac1J)

– I
01-1

Prop1on1c ~c,d
1PropJno1cru;,d)

0
//

CH1CH 1CH~- c . – – \
11-Bu1ync:i.:,d

( B ui.mo1 c ac1d )

OH
0
//

0 13- 7 11 -~
Cl-!3 01!

lsobu t}n cacid
(2 -,\k1h ) lp ropano1cll.1d1

They are colorless, wa ter-sol uble liquids with characteristic odors. Formic acid .
aci d; and p r~pio~ ic acid h~ve pu~genr bur not disagreeable odo rs, ‘_Y hereas n-buryri;:~~
and 1sobutyric acid ha ve highly disagreeab le odors. Low concenrrarions of isoburyric cid
are constituents of hum an perspiration and feces.

ifri!IMM PhysJCal Properties of the Simple Organ,c Acids
FORMIC ACI D ACETIC ACID PROPJONJC AQ D

Melting po int 47″F{8.2°Q 61 °F(l7°C) – 8″F(-22″C)
Boiling po int 101 °F(213″C) 244″F(118″C) 286″F(141″C)
Specific gravity at 68 ‘ F (20°() 1.22 1.05 0.99
Vapor dens ity (air= 1) 1.59 2.1 2.56
Vapor pressure at 68 °F (20 “0 44.8 mmHg 11 mmHg 3mmHg
Flashpoint 156″F(6 9″C) 109°F(43″C) 130″F(54′ Q
Auto ign it ion point 1114°F(60 1″C) 800’ F (426°() 9SS”F(513°C)
Lower flamm able limit 18% by volu me 4% by vo lu me 2.9%byvolume
Upper flammable limit 57% byvolume 16% by volume
Evaporation rate (ether = 1) ,,

11.0

/ n- BUTYRIC ACID ISOBUTYR/C ACID
Melting point

18″F(-8″C) -S l” F ( 47°()
Bo ilin g po int

327°F (164 “C) 309″F(153” C)
Spe cific gra vityat68′ F(20″C) 0.96 0.949
Vap ordensity(air = 1) 3.0 3.04
Vapor pressure at 68°F (20 °() 0.84 mmHg 1.5mmHg Flashpoint

151 “F(66°C) 132″F(SS”C) Autoign ition po int
846″F(452″C) 824″F(439″C) I Lower flammable lim it
2% by volume 2% by volume Upp er fla mmabl e limit
10% by volume 10% by volume I

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part IJ

The simple organic acids are weak ‘d
v,·hen dis~olved in wa~er. ~!though corr~;ii_,,;~~1:?1~g that th ey only partially ionize
005 so luuons of formic ac id, acetic acid, pro ion ‘s t primary hazard of most aque-
bili t)’ 1s regarded as the primary ha zard f P lc acid, a_nd 11-butyric acid, flamma –
burn, these acids produce the products con~entrated 1so?uty ric acid. When the y
noted in Section 8.13-C that ca rbon dio;id:

0

3
~~ ~,~e combumon. For instance, _i t w~s

burns. When they are diluted with Water the ~ter ~re producc:-d when acetic acid
are nonflammable. ‘ orga ni c acids do not “aporize, and thu s,

The simplest aromatic acid is named be,
1

· •

la C6H5-CO OI-I. Benzoic acid a d • od~orc ac,d. It is a white so lid ha”ing the for.
mu n its s ium salt ha,·c:- the structures shown:

B~n1 01c a.::,d
SoJ1umbcnlo.itc

Sodium benzoatc i~ identified on th e labds of many food containers
10

indicate its pres•
ence as a presc rvanve and ant im icrobial agent.

13.6-A THE FORM YL, ACETYL, AND BENZOYL GROUPS
The formyl, acetyl, and be11zoy/ groups are derived from formic acid acetic acid and
benzoic acid, respective ly. Thei r molecular structures are represented as ‘follows: ‘

0 0 0 // // o-t 11 – C CH1 – C I I 0 – 0 –
Foml)l gl\}l)p A,~i~I ~1oup lknlO)lgro up

These groups are encou nt ered in many compo und s. Acetyl chloride (Section 9.9·C) and
benzoyl chlor ide, fo r instance, are 1he compou nd s having the fo rmul as CHrCOCl and
C~ H5-COCI, respect ively,

Acc L)IChlond~

Formyl chl oride is unknown, When chemists anempt IO prepare it, ca rbon monoxide and
hydroge n ch lorid e a rc produced instead, The ~ce ryl and benzoyl groups are co mmon
compo nents of peroxo-o rganic compounds (Semon 13.9).

13,6-B PER FLUOROO CTANOIC ACI D .
Per flu oroocta noic ac id is better known by its ac ronym PFOA. It is the totally fluorinated
de ri va ti ve of octa no ic acid.

0
//

CF3CF2CF2CF !CF2CF~CF2 –
0 11

l’~rfluorooctal’lf’IC acid

Chapter 13 Chem istry of Some Hazardous Organ ic Compou nds: Part 11 573

574

nds are ofte n associa ted with perfluo roocta noic acid: amrn
perfl:::::.~=~~;t~:~ perfluorooctane suJfonate, eac h of whi c h is denoted as APF~ ~:~
PFOS, respectively.

0
//

CF 1-(CF2)6 -~
o-

Ammoruump,:-r0uorooc1″’10Jtl.”

NH.i …

0
I

CF3 -(CF2h – S – 0 1-1

” 0
Pl·rlluorooct.onl.’sullon.itt”

PFOA fo rmerly was used as an esse nt ial processing aid du~ing the manufacture of
fluoro lymers like Teflon (Section 14. 10-A) a nd as a surfactant .m aqueous-fi lm-form1 n
foam Ce extinguishers (Section 5. 12-B). The PFOAs were also widely use~ to impan fire~
resistance and oil-, stain-, grease-, and warer-rep~llence to ca~pet s, textiles, and PaPtc
They we re also used ro make a low-fric t ion :oa1mg for bearmgs, gears, and wcaponi
components. PFOA was used to provid e nonsnck surfaces on cookware and waurpr0of,
breathable membranes for clothing. Conseque~cly, the PFOAs have been widely used f0r
decades Lfl dozens of commonly used commercial products :

Although there is no ev id ence that nor~al us e of nonstick Teflon coo kw~re is dirttt]y
harmful, scientists note rhat when Teflon 1s hea te~ t? temperatures exceedmg approxj.
mately t000°f (600°C ), the perfluoroocta noic ac id 1s release?. Exposure co it may h(
harmful wh en indi vi duals heat Teflon cookware to th ese very high tempera.cure s.

In the late 1990s EPA first ra ised concern that PfOAs had been identified on a wide-
spread basis in sa mpies of blood withdrawn tron:i virr~ally all Americans. The blood of
approximately 95 % of the Ame ri can populac10n 1s be li eved to contam at least a trace of
PFOA. EPA also notes that these compounds persist in the envi ronment and bioaccum u-
lare within the fatty tissues of animals.

Research srudies 13 indicate that anima l exposure to PFOA can cause severa l types of
tumors and neonatal death and may ha ve toxic effects on the immune, li ve r, and endo-
crine systems. This finding was so startling that many major Amer ican PFOA manufac-
turers vo luntaril y ceased their production of this subs tance . In 2005, EPA repomd that
additional studies performed on laboratory animals Hnked PFOA exposure wich theonm
of breast, testes, pancreas, and liver cancer. Based on the resuhs from these studi es, PFOA
is now regarded as a probable human carcinogen. EPA has asked PFOA manufacturers 10
phase ou r the production of rhis substance.

In 201 I , studies 15 conducted on humans revealed thar c hildr en wit h high blood levels
of PFOA and PFOS attain puberty la ter in life when compared co the norm. Elevated !e1·•
els of PFOA we re associated with ch e onset of delayed puberty in girls on ly, w hereas ele-
vated levels of PFOS were linked to the onset of delays in both boys and gi rl s.

13 .6 -C TRANSPORTING ORGANIC ACIDS
When shipper.s ~He r an organic acid for rransporcacion, DOT require s them ro enter the r
el_evanr d ~scripuon on a shipping paper. Some examples of several representative organic

acidt ar~ hsted i.n Tabl e I ~. 15. DOT also requ ires shippers and carriers to comply with aU
app ica le labeling, marking, and placarding requirements.

. .1
nd

~ lct~~er T. SJ \’ itz, Mf pidc:miologi,; cvid en,e on the he.11th effect of pc: rnuoro octano ic l .ci
15M. J. Lopez-Esp mosa ,..•, al· MA· .”‘ ~onmc:n1.1 l Pr o ic,;t io n Agenc y, 2005 ).
IPFOS) with ag,.. of pu ~riy ~•( 1 ~~OCll;’.

0~ o f pcrnuorooctano k J cid WFOA ) and pcrnuorooc-rane sulfon.air
pp. 8 160-8 166. cu rcri iv ,rig ricar 3 c:hem k .il p lJ nr. M Em1iro 11, Sd. Tulmol., Vol. 45 120ll l,

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

iJJhiii?W Shipping D~cn pt1ons of So me Re prese ntative Organic Acid~
fORM OF ORGANIC ACID OR ITS SOLUTION

A80 % ac id by man)

Acetic ac id solutions, conta in ing 50-8o% acid by mass

A

formi c ac id with more than 85 ‘1e acid by man

isobutyricacid
-s«alsoTable 8.18.

SHIPPING DESCRIPTION •

~~2789, Acet ic ac id. glaci al , 8. (3), PG II

UN2789, Acet ic aci d solutions. 8. (3), PG ll

UN2790. Acet ic aci d lOlut,on, 8, PG II

UN2790. Acet ic aci d solut ion, 8, PG Ill
UN 1779, Formic acid , 8, (3), PG II

UN2529. lsobutyrlc ac,d, 3, (8). PG Ill

When shippers offer for transportati on a liquid organic acid whose name is not list ed
ar 49 C.F. R. S 172. 101 for transpo rtation, DOT requires chem 10 identify rhe commodity
gener icall y .as .”UN~2.65, Cor~osive liquid, acidic, organic, n.o. s., 8, PG l, ” MUN3265,
Co rro sive hqwd, ac1d1c, organ1C, n.o. s., 8, PG II,” or MUN3265, Corrosive liquid, acidic,
organic, n.o. s., 8, PG Ill. ” The shipping de sc ription includes the name of th e s pecific
organic acid entered parenthetically.

13.7 ESTERS 0
//

An ester is an organic compound ha vi ng che gen eral chemica l formula R – C . It is
the: su bstance that res ult s when an organic acid reac ts with an alcohol. b- R’

0
//

R – C + R’ – OH
\
OH

An alcohol

0
Ii

R – C + H20
\
o – u:

Water

This type of chemical reaction is ca ll ed esterification.
Esters are mo st commonly denoted by th ei r IUPAC names. In the IUPAC system, an

es ter is named by changing the -ic suffix of the organic acid to -ate, preceded by the name
of the alky l o r ary•I group of the alcohol used to produce it. In other words, the R ‘ group
is named fir st followed by the name of the acid with -ic acid replaced by -ate.

The si mple es ters are colorless, highly vo lati le, and nammable liquids that are only
partially soluble in water. Many possess pleasant, fruity odors. for example, the com-
pounds responsible for the odors of pineapples, banana s, and apples are et ~yl butyrate,
isoa myl acetate, and ethyl-2-methylbutyrate, res pectivel y. Several syn thetic esters arc
adde d to foods as flavoring agen1s.

0
//

CH3Cli ,C H,- C

0
//
0
//

C il , -CJ-1- C l-l,-C
I – \

u t er Any organic
compound whose gen –
eral chemical formula is

0 ,,
R – \ where R and

0 – R”
R’ represent arbitrary
alkyl or aryl groups

este r ificatlon The
process of producing an
ester by the react ion of
an organic acid with an
alcohol

. – \
O – C H2C H3

E thyl bu l}rat~

Cl-13-~
O – CH~C l-1 2-c;: H – Cl-1 3

Cl-1 3
lso:,ro}lac<"Ll1C

C l-h 0 – Cl·l ~CII J
Ethyl-J -nwlh),lbul)rJU:

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 575

i I
Ethyt acetate

phth alate • Any ester
of o-. m-, or p-phthalic
add

OEHP

1/liiiiiii
Meltmg pcmt -119 ‘ F (-84’ ()

B01l1 ng po int ~ 7″_£) =———
Specific gravity at 6B “F (20 “C) 0.90 – —-

Vapordens ity (air =l ) – 304 — – —-
v-,-po- ,-.-,.-,.,~,.- ,-, -68-,F-(l-0′-Q—–~,:c, -m-m:CHg– =——–:
Flashpo int I 24″F (-4.4″() ——–
Auto ign,tion point , 800″F (427 “Q ——

Lower flammab le limit 2.18% by vo lume ——–
Upper flammable limit 9% by volume —–
Evaporation rate (ether:: 1) 2.7 ——

13.7-A ETHYL ACETATE
Eth yl acetare _is a con:imonly _encounrered constit~enr of nitrocellulos~•based lacquers and
other prorect1 \’C coacmgs. Ir 1s produced by reacting et hanol and acetic acid .

0 0
// // Cl·l3CH10H (aq) . CJ-1 3- ~ (aq ) C H 3-~(aq ) + H20 (/J
OH O – CJ·l1CH.1

Eth:mol Ace t1cnc1J Ethy l~<. dJ1 C W a1ct

Ethyl acetate is a colorless liquid with a pleasing, fragrant odo r. As reflected by the dai.a in
Table 13. 16 , it poses the risk of fire and explosion. When ethyl acetate burns, carbon
dioxide and warer vapor are the products of combustion.

0
//

Cf-1 1-~(g) + 501(g) – 4C01(g ) + 411 20 (g)
O – CH2CH3

Elh)lln• IJtr: o ~)gcn Cu1 bond1o ~Hk

13 .7-B DI(2-ETHYLHEXYL) PHTHALATE
The phthalates are es ters of 1,2-, 1,3-, and 1,4-benzcnedicarboxylic acid, common!t·
called o-, m- , and p-phrha lic acid. The esrers o( o-phrhalic acid are co mmerc ially impo~·
ram. Their chemica l form ula general! y is represented as foll ows, where Ra nd R’ are arbi·
trary alk yl or aryl groups:

0 0
// \\ R-O-b-0-R’

T he indi\’idua! phthalates are identified by naming R an d R, followed by rhe word phrli; j
late. The commercially important pht.halates include di-n-buryl phrhalare (DBP), benz~
b~tyl ph1halate (BBzP), di (2-ethylhexyl ) phthalatc (DEHP), diisononyl phthalare (D:::1′. duso~ecyl phthalare (DIOP), and diisoocty l phthalatc (DIOP ). They are produc
reacting o-phtha lic acid wir.h appropriare alcohols.

576 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part u

DH~P is. rcp_re se nra rive of th e conimerci
1 o-p hih:ihc :1C1d wuh 2-i:-thylhexanol. 3 phthalates . Ir is produced by re:icting

COO H

A ‘f H~C ll ] 0 COOH (I) lC1! 1-(CH1h- CII – Cl·i
1
0H (/J

DEf:P i~ a c~mponem of various rubbe r and other polymeric form ul ations in which
it> fu_ncuon. ts to increase t~e flexibility and toughness of the related products. When used
in this fashion, the DEHP 1s called a plasticizer. DEHP is 1he most wide!>· used plasticizer
for 1he ma~ufacrure of products .~ade from the polymer poly(\’inyl chloride).

DEi-IP •.s _also used as a plast1c1~er wi1h ce rtain explosi\’es, where its presence provides
the malleab,ltty that allows explosives to be molded into shapes and safely handled with-
out detonating prematurely.

DEHP is also a compo nent of Certain cosmetics, where its function is to facilitate 1he
addition of pleasant-sme ll ing substa nces to shampoos, soaps, lotions, and deodorants.
The prese nce of a ph1halate ester in the composition of perfumes and nail polishes also
pro\’ides them with an adhering or clinging quality.

When DEHP is used to manufacture plasticized products, it is mixed with the poly-
mers but only loose!)’ bonds wit h th em. Hence, i1 is capable of leaching from the prod-
um. Persons often encounter DEHP unknowingly while searching 10 buy a new car.
DEHP slowly vaporizes from the vinyl upholsiery and provides the “new-car smell~ in
vehicles whose windows and doors ha 11e been kept closed.

In animal and human studies, 16 health concerns have been ra ised 011er the impact of
th e DEHP that leaches from plasticized medical products such as intravenous bags, dialy-
sis tubing, and sy ringes. When blood is stored in DEHP -p la sticized bags, for example, the
phrha late ester leaches from the plastic and di ssol11es in the blood. Then, patients unknow-
ingly receive DEHP during blood infusions. The prevailing _fear is that phthalates are
endocrine disrupters that may interfe re with de11elopmem. Animal exposure to D~HP ~as
bten shown ro interfere with normal kidney and li\’er function and c~use phys1olo~1cal
abnormalities in the reproductive systems of th e animals, especially th eir male of~spnng,

Whether ph1halates can int erfere with the hormon es generated by hum ans 1s a con-
troversia l topic FDA initially concluded that patient exposure~ to DEHP g~ne~lly ~;e
well below th e levels expected IO cause adverse effects, ah~ough tt do~s con~e e I atdc \

dl sent a special population at mcreasc ns dren, especially infants a~d-tod ers.’ may rep: :iew th e FDA proposed voluntary restric-
from expos ure. In recognition of th1 s guaTde b ‘ t women and newborn infants.
tions on th e use of DEHP-pl~sticized_ :~v!:~.~ce: t:;:~:te the absence of DEHP.
The FDA also proposed labeling medic d DEHP DBP and DBP at concentrations

In 2008 , the CPSC permanently ban~~d ticle in;e nded for use by children 12
excerding 0.1 % in any children’s to~ :n:t

1
h:~:~a~:s, DIDP, DINP, and DIOP, also have

)’ears of age and rounger. Three addiu P

A sub-
stance, such as a
phthalateester,which
whenadded inapre-
mib~amounttoa
po!ymericformulation,
facilitates processing
and provides flexib ility
and toughness to the
end product

• Washingt on, DC: U.S. Dcpanm ent of HeJ lth and HumJn ” ·Tox1cologk al Profile of Dieth )’ !hcxrt PhibJl.ttc (

Sr rv ice~f, 2002. Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part II 577

r

/1 1 /1 I

i
i I
I

I !I /!

fa tty add • AAy car-
boxylicacidderived
from the tr iglycerides
present in an imal and
vegetable fats and oi ls
trig lyceride • Anytri-
enerofglycerol, usu-
ally produced by
react ing glycerol with
fatty acids

Unseedoil

111,111.;,eI11il411Miiili+Ma::a;
COMMON NAME CHEMICAL FORMULA.:’.,__ ___ _

Stear1cacid

Pa lm1ticac1d
0/eicacid

linoleicacid
a -linoll!nrcacid’

CH1(CHz)1′-COO H
j c1-11((Hz) 1CH=< H{CH2),_COO H

CH 3((H1), CH=CH CH2CH=CH((Hz)-,CO OH

Palm oil
Olive oil

Soybean oil

1:: ;~:u;::~:::1;~~~~::~~;-~~~~;~c:;~;r!~~;: !i°1~!s~:;,~~=t~;~~;a;~:/:;:r:~~,::~ i1
In a llnu1 fash iOI\ the compounds actualfy u 111 as w – , nd t”ns· gtometr lca l Isom ers. Nature prodU

1
11-

.artu/al walls c.itJSlng arter loscleros!s-narrowlr,g of the arter ies . The t rlgfyce rides of the 11ans isomeri of u !ht
rated fmy ad ds are co!/oqu l1lly called 1/itnI fits . Their presence In the diet has b~n lmpliciled with tilt~>
ofardlovasculardlsorders. 0nSn
‘ Nutrll lomsts assert that linolt1c ac ,d and a-!lnofen/c aci d are des ir able components of one’s diet beca\/le tilt
lmport1ntforgrowthandbfa lnfunct lonand~/p10/owe r trlglycerldesandcho!esterol. YMt

been temporarily prohibited, pending further study and re view, The Europc.’.ln P.’.lr/iamtnr
also banned the use of certain phtha late es rers, including DEHP, in children’s toys and
child-care items like pacifiers and reerhing rings .

13.7-C LINSEED OIL
Li~ se~d _oil is a clear to ye llowish oil ob tained from rhe seeds of rhe fla x plant Lmum
11s1ta t1ss1m11m /Section 14.5-A). The oil is a mixture of the triesters of l ,2,3-propanetriol,
an alcohol commonly known as glycerol. The trieste rs of glycerol are produced nat w.UJ’
when ~ ycerol reacts with long-chain sa turated and unsatu rated fatty acids. Some repre-
sentative ex amples of fatty acids are provided in Table 13.17.
form:~: triesrc r of glycerol is called a triglyceride. It ha s 1he following ge neral chemio!

H 0
I 4

H- C- 0 – C- R’
I p

H- C- 0 – C- R”

I 1?
H- C- 0-C- R”‘

I
H

Here , R’, R” and RN’ are alk I lk l bo
atom~ /usua/1 ~ ~,; even number), Y or a eny groups that possess from 12 ro 22 c:H n

Lm seed oil ,s a mix ture of the tri I •
g yce nd es of the fo ll owing fatry acids:

The sa tura ted fatt y acids pa lmiti .d o
The monounsarurated f ‘ .d c .:i~ r (~7¼) and srearic acid (3.4%-4,6 %)

578

The doubl y unS.’.llurateda;ry ac, ? ol~1c ac id ( 18.5%-22.6 %)
The triply un sa turated o• ttylac~d, /1~0/eic acid ( 14.2 %- 17%)

rno emc acid (5 1.9%-55_2%)
Chapter 13 Chemistry of Some Haza d

r ous Organic Compounds: Part II

.i,1tho 11 gh it was formerly used extensivel y as • . . •
.” seed oil h:is declined se rious! since ea rn er m paints and va rni shes, thi s use

ofhn ( ff . d y the 19)0s. Tod ay, linseed oil is used mainly to
palish th ~ surh ace O d ur~iture ~n mher commercial products made from wood. It is also
~std dunng t _e ~ro ucoon ~n man~facture of linoleum fl oo rm g.

Lm secd 011 15 c_omme rc.,a!ly available in tv,10 fo rm s: raw and boiled Howeve r th e
tspression bo’.led lms~ed oil ~s _a misnomer because linseed oil docs not ·boil. The :erm
rders co raw lm ~eed _ml ~ontammg additi\·es ihat acceleraie dry ing.

A~ linseed oil dnes, ltS_ con 5t it u~nrs ~\•aporare, Unless the heat of vapo rization dissi-
pates mco th e atmo~phere, He_m_s m~1st wnh linseed oil are likel r to bu rn . Co tton rlgs and
other por

6
°
6

11 ~ mahrerials contdammg lmseed oil are prone to undergo spomaneous combus-
tion. H_o yisrs . av e cause many domestic fir es by fai lmg to follow precautions when
disca rding these it ems.

13.7-D BIODIESEL FUEL, BIDDIESEL BLENDS,
AND BIOMASS-BASED DIESEL FUELS

Siofucls ha\’C” become popular sub stitutes for petroleum•ba sed diese l oi l for the fol lowi ng
reaso ns:

Thei r comparatively lower cost
I Chemical compatibility with hoses and other accessories ne eded for storage and

delivery
A comparativel y lower risk of fire and explosio n
Lesse r amou ms of s~oke, VOCs, ca rbon mon ox ide, and sulfur dioxide (none ) pro-
duc ed on comb ustion. (The NOx concentra tion remain s unc hanged in the
emi ss ions.)

Three types of biofuels are used to power diesel-ope rated vehicles and equipment:

Biodiesel fuel is an alternative mo1or fuel produced from naturall y occurring fats and blod!esel fu el Ally
oils derfred from plants and animals includ ing olive oil, soybean oil, coconut oil, cotto nseed alternative motor fuel
oil, peanut oil, tallow, rapeseed oil, and canola oil. Recycled restaurant grea se, poultry fats, produced by bio!og i-
tallow, .’.lnd oth er rendered fats also are used to produce biodiesel fuel. The biodiesel fuel ::~:; ~~;7rii~~~{e~~dn~s
produced from soybean oil is most commonl y encountered in the United Stares. Ir has a cc- in plant and an imal fau
1ane number of 47. The biodiesel fuels produced from rapeseed oil and canola oil are more and oils into the ir fatty
commonly encou ntered in Europe. They have cetane numbers of approximately 54. acid methyl or ethyl

The manufact urers of biodiesel fuels treat th e fat-and-oi l feeds1ocks with met hanol or erters
ttha nol. During thei r trea tment, 1he fony acid triglyce rides are converted into mixtures of
methyl or ethyl fatry ac id esters.

When biodiesel fuel has nor been blended with other fuels , it is called B100. It ge ner•
all y is encountered onl)’ during its production, transporta ti on, or stora ge. Bl 00 possesses
a va riable flashpoint that depends upon th e chemical composi ti on of the biofuel. None·
the!ess, the fla shpoint is always greater th an 200°F {93.3°C ); hence, B100 is an OSHA
category 4 flammab le liquid, or an NFPA class lt!B combustibl e liquid. blo ditsel bl end • Any

Biodiesel blend is an alternative motor fuel consistin g of a mixture of biodiesel and :i;~~~nftl
bio mass-based diesel fuels. biodiesel and biomass•

Biomass-based diesel is an alternative motor fuel produced from the remai ns of based diesel fuels
recent ly li vin g plants or animals (i.e., grea se and rendered tall ow and other animal fat s), biomass-based
but the y are not chemicall )’ treated. diestl Any biofuel

Biodiesel fuel is also encountered as a mixture with pe1roleum-based fuel s, but it is f;;~~~~:~~:a~~;pe•
not then regarded as ei ther a biodiesel blend or a biomass-based diesel. Fo r example, the resources, but that does
blend known as 820 is a mixture of 20% biod iesel fuel and 80 % petrol eum-based diesel not consist of a miJCtu re
oil. It is used b th e ·ry of San Francisco to fuel i1s entire fleet of diesel-o perated ve hicl es of the esters of fatty
from amb ul an:es to : :reer-sweepers. A mixture of Diesel #1, Diesel #2, or JP-8 wi th 7.7% acids

Chapter 13 Chemistry of Some Haz ardo us Organic Compounds: Part II 579

12
= • .

I

. 7 ~, Chemistry of Some Hazardous Organic Compounds: Part

1

,c,–1\ ‘ -= –>~,
– I l

!W tJi m – ‘ ~ i I

Courtesy of Eugene Meyer.

i:iW4iUA
acute mye/ogenous leukemia, p. 498
aliphatic hydrocarbon, p. 469
alkane, p. 470
alkene (olefin), p. 476
alkenyl group, p. 47

7

alkylate, p. 507
alkylation, p. 506
alkyl group (alkyl substituent), p. 472
alkyne, p. 479
allyl group, p. 477
antiknock agent, p. 507
aplastic anemia, p. 498
aromatic hydrocarbon, p. 469
aryl substituent (aryt group), p. 496
asphalt, p. 506
asphalt kettle, p. 506
aviation gasoline, p.

508

benzyl group, p. 496
biomagnification
(bioamplification), p. 525
boilover, p. 504
bottled gas, p. 488
BTX, p. 496

carbon-carbon double bond, p. 468
carbon-

466

•:. ‘ –
:·

carbon-carbon triple bond, p. 468
catalytic uacking, p. 483
cetane number, p. 510
chlorofluorocarbon (CFC), p. 516
common name, p. 470
common system of nomenclature, p. 470
compressed natural gas (CNG), p. 486
condensed formula, p. 470
cracking, p. 483
crude petroleum (crude oil;
‘”crude·), p. 503
cydoalkane (naphthene), p. 471
cydoalkene, p. 476
degreaser,p. 515
dehydrogenation, p. 492
dielectric fluid, p. 523
diene, p. 476
diesel oil (diesel fuel, gas oll), p. 505
endocrine disrupter, p. 523
endocrine gland, p. 523
ethyl group, p. 472
fractional distillation
(fractionation), p. 504
Freon (Freon agent), p. 517
geometrical isomerism, p.

478

halogenated hydrocarbon (alkyl h,1llde,
aryl halide), p. 573
heating oll {fuel oil), p. 5

11

heavy naphtha, p. 504
heterocydlc compound, p. 500
hormone, p. 523
hydraulic fracturing (tracking), p. 483
hydrocarbon, p. 469
hydrotreatment, p. 510
IUPAC name, p. 473
IUPAC system of nomenclature, p. 473
kerosene, p. 505
knocking, p. 507
light naphtha (ligroin), p. 504
line marker, p. 484
liquefied natural gas (LNG), p. 486

liquefied petroleum gas (LPG), P· 487

lubricating oll (lubricant), p. 505
methane hydrate, p. 483
methanogenesls. p. 482
methyl group, p. 477
methylene group, p. 472
mid-grade gasoline, p. 509
mineral oll transformer, p. 524

motor gasoline, p. 508

n•tur”I gas, p. 480
non-PCS transformer, p. 524
ll”propYI group, p. 472
octant number (octane rating), p. 508
organization of Petroleum Exporting
countries (OPEC), p. 503
ortho· (o-), meta- (m·), and
~f,l· (p-), p. 495
,ca-contaminated transformer, p. 524
pCB transformer, p. 523
pttrothemkal, p. 513
petroleum coke, p. 573

iMii,10¥5

petroleum distillate, p. 504
petroleum gas, p. 504
petroleum products, p. 503
petroleum refinery, p. 5o3
phenyl group, p. 496
polynuclear aromatic hydrocarbon
(PAH),p. 499
premium-grade diesel oil, p. 517
premium-grade gasoline (supreme and
su~r unleaded), p. 509
rtformation,p. 497
regular-grade diesel oil, p. 511

regular-grade gasoline (regula

r

unleaded), p. 509
saturated hydrocarbon, p. 470
sour crude, p. 510
Stockholm Convention on Persistent
Organic Pollutants (POPs treaty), p. 527
structural Isomerism, p. 470
thermal uacking, p. 483
trlene, p. 476
unleaded gasoline, p. 510
unsaturated hydrocarbon, p. 476
vinyl group, p. 477

Associate the physical and health hazards of the organic compounds noted in this
chapter with the information provided by their hazard diamonds and GHS
picrograms.

I Discuss the manner in which a carbon atom covalently bonds to nonmetallic atoms
including other carbon aroms.

I Describe the nature of carbon-carbon single bonds, carbon-carbon double bonds,
and carbon-carbon triple bonds.

I Describe the chemical bonds that exist in molecules of the hydrocarbons.
I Illustrate that most hydrocarbons have structural isomers but only those with carbon-

carbon double bonds have geometrical isomers.
Memorize and apply the rules for naming simple alkanes, cycloalkanes, alkenes,
dienes, trienes, cycloalkenes, cyclodienes, cyclocrienes, and alkynes.
Describe the nature of the line markers required by DOT to identify the approxi-
mate loca tions of natural gas and petroleum transmission pipelines.
Identify the types of liquefied petroleum gas that are available for commercial use as
bottled gas.

1 Identify the general nature of the labels required by the U.S. Federal Trade Commis-
sion on compressed natural gas and liquefied petroleum gas dispensers when these
substances a re provided to customers for potential use as alternative motor fuels.

1 Describe generally the manner in which acetylene is containerized in steel cylinders
fo r storage and transportation.

1 Name the simple aromatic hydrocarbons and their derivatives when provided with
their molecular structures and vice versa.
Identify the most common ways by which emergency responders are likely to be
exposed to polynuclear aromatic hydrocarbons (PAHs). . .
Identify the petroleum products that are produced by the fracuonation of crude
petroleum. .

1 Provide the molecular structures of the halogenated hydrocarbons havmg one and
two carbon atoms per molecule and provide acceptable names for them.
Identify the primary risks assoc iated with exposure to the halogenated hydrocarbons

havin? one and two carbon atoms per molecule. hi rofluorocarbons.
Describe the molecular nature of the most common c 0
Identify the principal ways in which chlorofluorocarbons and related substances

Were formerly used · d k f
I Describe the nature. of the markings that EPA requi res on conramers an ran so

ozone-depleting subsrances.
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 467

I
_I/

carbon-

carbon-ca rbon double
bond Two shared
pairs of electrons
between two carbon
atoms

carboo-

Describe rhe mokcul~u srruccures of the polychlorinated biphenyls (PCBs)
Identify the primary reason ih~t PCBs are “? longer manufactured in the United
ldenrify the locations in a typical commumty where emergency responders are ~t•””
ro encounter PCB transformers. . k~i)’
Describe the nature of rhe markings that EPA requ ires on PCB-containing dectri
(‘QUipment. . caJ
ldenrify che labels, markings, and placards 1hat DOT requires on packa .
organic compounds noted in this chapter and the transport vehicles use~1? of th~
shipmenr. or their

0 rganic compounds are constituents of many commercial products in I d’ ing and motor fuds, solvents, plastics, resins, fibers, su rface coatings cu f 1_ng h~,. textiles, and explosives. The fact 1hat they are used so widely undersc~~:sr:i:rants,
to srudy them in some derail. netd_

1\,lany org:mic compounds of commercial interest are flammable gases or fla
liquids. ft is hardly surprising t_o !ear~ that many organic compounds are burning w~:~bk
a.re encountered at cra~~rtanon m1sha~s an~ other emergency scenes. Although the t ry
rial for fire and explosion 1s generally their primary hazard, exposure to o rganic co Po en.
may also pose a heahh risk. Prolonged exposure to certain organic compounds mPound.s
variety of acute and chronic health effects that includes damage to the liver, kidn~~ a
hean; depression of the central nervous system; and the onset of cancer, ‘ d

This chaprer is an introduction to the study of organic compounds and the propcnj f
hydrocarbons and halogen.ated hydrocarbo~s that are commonly encountered commerC:u0,.
Chapters 13, 14, and 15 discuss the propemes of more complex organic compounds. )

12.1 WHAT ARE ORGANIC COMPOUNDS?
The molecules of all organic c_ompounds have one common fearu re: the presence of one or
more carbon atoms. In most mstances, the carbon atoms share electrons with other non•
metallic atoms. As shown by their molecu lar structures in Figure 12.1, methane, carbon
tetrachloride, carbon monoxide, and carbon disulfide are exa mples of o rganic compounds
having molecules in which the ca rbon atoms are bonded ro other nonmetallic atoms.

Carbon atoms can also mutually share electrons with other ca rbon atoms. When the
molecular structures of such compounds are examined, we fi nd that two carbon atoms
can share electrons to form any of the following: carbon-

Figure 12.2 illustrates the bonding in molecules of erhane, ethylene, and awylcne,
each of which has two carbon atoms. Molecules of erhane have carbon-carbon single
bonds, molecules of ethylene ha\’e carbon-carbon double bonds, and molecules of actt) ·
lene have carbon-carbon triple bonds.

H
I

H-C- H
I

H
\1ethlnc

Cl

I

CI – C- C

I
I

Cl
Carbon 1u r..1Chlomk

Cas o

C.lrt,011 niono\1dc Cnrbond1 ,u lfi dc.-

FIGURE 12 · , A carbon atom may share 1ts electrons with the electrons of hydrogen chlorine, orygen. anoi~·
fur The com pounds that resul1 from this electron sharing are methane, carbon tetrachlor,de, carbon mon-OJ.oe
and carbon d,sulf,de, respectively

468 Chapter 12 Chemistry of Some Hazardous Organ ic Compounds: Part J

I

– c- C-
1 I

H H

I I

H- c- C- H

I I

H H

– c ase-

H- CasC- H

: ,~~URE 12 ·2 Two carbon atoms may share their
form ~~ns in lone of three ways, resulting ,n the
carboni~n ° ,carbon-carbon s,ngle bonds. carbon-
bo d Oub.ebonds, andcarbon-

a,oms.fhe compoundsthatresult are ethane ethene
(ethylene), and ethyne (acetylene), respect,v~ly

The cova lent bonds between carbon atoms i h l
nds may be linked into chains · I d’ n t e mo ecules of more complex organic

~0111~u arbon skeleton of the follow·’ me u mg I branched ch~ins, or into rings. Consider
~~s;a\ :ncd (b): mg two mo ecules noted m the following ill ustrarion

– C- C- C- C- C- c – – c – c – c-c-c- c –
1 I
C C

l•l lb)

In (a), the carbon atoms are bonded to one anorher in a continuous chain, whereas in (b),
the carbon atoms are bonded to one another in a branched pattern. This means that car-
bon atoms bond n_ot only_to other carbon atoms in long chains bur also ro groups of other
carbon atoms as side chains attached to the main chain.

Aside from being bonded t~ other carbon atoms, each carbon atom displayed in either
a straight- or a branched-cham manner is typically bonded to one o r more atoms of
hydrogen, oxygen, nitrogen, sulfur, or a halogen. For instance, when the ca rbon atoms in
[he compound having the carbon skeleton (a) are bonded to hydrogen atoms, the molecu-
lar structure of the compound is written as follows:

H H H H H H
I I J I I I

H-C-C-C- C- C- C- H
I I I I I I
H H H H H H

When che ca rbon atoms in (b) are bonded to hydrogen atoms, the molecular structure of
rhe compound is written as fo llows:

H H H H H H
I I I I I I

H- C-C-C- C- C- C- H
I I I I I I H H H H
I I I I
H- C- H H- C- H

I I
H H

There arc many orga nic compounds that consist of continuous or branched chains of
carbon atoms. The actu:i l number of such compounds appears to be virtua lly unlimited.
More than 6 mill ion organic compounds are already know~. . .

\Y/e begin the study of organic compounds by exammmg the simplest group, the
hydroca rbons. These are compounds whose molecules ar~ composed of only ~ar~n and
hydrogen atoms. All hyd rocarbons are broadly divided mto two _groups: aliphatic and
aromatic hydrocarbons. Aliphatic hydrocarbons are nona~omanc hydrocar~on;-
aro_matic hydroca rbons are a group of.compounds_chara;;~:::~:/r~~s~:;~r/~n u~~re
their molecular structures: They conram benzene rings.
detail in Section 12. 11.

compound whose mol-
ecules are composed
solely of carbon and
hydrogen atoms

aliphatic hydrocarbon
Any compound com·

posed of molecules
having only carbon and
hydrogen atoms that
are not arranged in
benzeneorabenzene-
likestructure

aromatic hydrocarbon
Any compound whose

molecules are composed
solely of carbon and
hydrogen atoms, at
leastsomeofwhlchare
structurally similar to
benzene

Chapter 12 Chemistry of Some Haza rdous Organic Compounds: Part I 469

–,

I I
I
I

s::::tin

a lltane • AAy hydrocar-
bon having molecules
in which the carbon
atoms are bonded
wlely as carbon-carbon
single bonds (C–C) or
(C-H) bonds

Sil tur.at~ hydrocarbon
Any hydrocarbon

having molecules that
are composed solely of
C-< and C-H bonds

structural isomer-
ism • The phenomenon
associated with com-
pounds whose mole-
cules have the same
atoms but differ in the
manner in which the
atoms are structurally
arranged

common system of
nomenclature • The
system used historically
for the naming of
organic compounds

common name The
historical name for an
organic compound

condensed formu la
• The formula of a
compound in wh ich
symbols of the atoms
are written ne1rt to the
symbols of the atoms
to which they are
bonded and in wh ich
dashes are omitted or
used only in a limited
fashion

12.2 ALKANES AND CYCLOALKANES
An alkane is a hydrocarbon in whose molecules the carbon atoms are bonded cit
hydrogen atoms or to other carbon atoms solely by means of carbon-carbon si

1
htr I()

The general chemica l formula of an a lkane is C,,H2,,~1, where II is a non:z;g e.boni.h.
When the number of carbon atoms is only I, the n~mber of hyd~ogen atoms i~ ~~:c&tt
responding compound is n:imed methane. Its chem1ca l_formula 1s Cl-14. When the nu c0r.
of carbon atoms is 2, _the num_ber of hydro~en atoms 1s 6. T he cor responding comPo~~r
is named ethane, and us chemica l formula 1s C2. H6- lld

The alkanes are called saturated hydrocarbons, because the four bonding cl
each carbon atom are shared with the bonding electrons of four othe~ atoms. The~~:n~~f
to be saturated with hydrogen. Several examples of the alkanes having from

00
. d

carbon atoms are noted in Table 12.1. Their names and formulas should be mem~~~~gh1

12.2-A FORMULAS OF THE ALKANES
The molecular st ructures liste~ in Table 12.1 are straight~ch~in ar~angements for tilt
alkanes having from one to eight carb?n atoms, but beg1nnmg wuh butane, several
branched-chain arrangements ma y be written as well._ Buta~e molecules have four carbon
atoms per molecule, which can be represented by their Lewis structures as follows:

H H H H H H H
I I I I I I I

H-C-C-C-C- H H- C- C- C- H
I I I I I I I
H H H H 7 7

H-C- H
I
H

In the first structure, the fo ur carbon atoms are bonded to one another in a continuous
chain. In the second structure, only three carbon atoms are bonded in a continuous chain.
The fourth carbon atom is bonded co the carbon atom in the middle of the chain.

Because there are two correct ways to write molecular st ructures for the formula
C; H 10, they represent two distinct compounds. To distinguish them by name, 1he com-
pound having the ca rbon atoms bonded in a continuous chain is called n-butane, whmas
the compound with the branched structure is named isobutane.

The phenomenon associated with two or more compounds that have the same molC\-
ular formula but different structural arrangements of t heir atoms is ca ll ed structural
isomerism. One way by which strucrural isomers are identified is with an 11- (for “nor-
mal” ) in front of the name of the compound that contains a continuous chain of carbon
atoms, and iso- (meaning ” the same”) in from of the name of the compound that hasa
methyl group (CH3-) bonded to a carbon atom next to the terminal (end) carbon a1om.
This system generally is referred to as rhe common system of nomenclature, and thr
names of the compounds are called common names.

. Ahhough a m?lecular structure may be written for a ny alkane, it ge nera lly is conve-
nient to condense It by simply writing the symbols of rhe atoms next to the symbol ofihr
carbon arom to which they are bonded. When writing the formula for an alkane, the S)’m·
bols of rhe hydrogen atoms are written next to rhe symbols of the carbon atoms to which
they are bonded. The formulas derived in this manner are called condensed formulas.
For example, the condensed formulas for 11-butane and isobutane are noted here:

CH3CH2CH2

CH3

\11-Butanc) CH3-y H-CH3

Cl-1 3
1~obu1:rnc

470
Condensed fo rmulas convey the same bonding information as the more complete Lewi>
strucrures, bur rhe dashes are either entirely omitted o r used only in a limited fashion.

Chapter 12 Chem istry of Some Haza rd ous Organic Compounds: Part
1

• ·HlfaCUM,.;;;;,;p.;; · u·ennv::·nw::IJVEle:w·w ·,01::r
N.AME
t,-1ettiane

Utiane

propane

Butane

Pentane

Hexane

Heptane

Octane

Nonane

Decane

MOLECULAR FORMULA LEWIS STRUCTURE
CH,

I
C2H6

C1Ha

Ci.H10

CsH12

C6H14

C1H16

CsH,a

C10Hn

I
H
I

H- C- H
I
H

H H
I I

IH- C-C – H I I H H
I H H H I I I

H-C-C- C- H
I I I
H H H

H H H H H H
l \ \ I 1 I

H-C- C- C- C-C-C- H

I I I I I I \ HHHHHH
\

HHHHHHH
1 I I I l 1 l H- c- c- c- c- c- c- c-H
l \ \ \ I l \
HH HHHH H

I HHHHHHHH
I I I I I I I I H- c- c- c- c-c-c- c-c-H
\ I I I 1 I \ I
H H H H H H H H

HHHHHHHHH

\ CONDENSED FORMULA

I CH,

\ CH ,CH,CHa

I CH ,CH,CH ,CH,
\ CH ,CH ,CH ,CH, CH a

I I I I I I I I I
H- C- C- C- C- C- C- C- C-C-H

I I I I I I I I I I H H H H H H H H H

I

12.2-B FORMULAS OF THE CYCLOALKANES cydo,lkano (oaphthml
I . I f h lkanes in which the fi rst and last carbon atoms • Any hydrocarbon
_t IS possible to write formu as o_r t ea . d h other in a cyclic arrangement. whose molecules ar
in a cont inuous chain are chemically hnkel hto the petroleum industry, they are composed of a eye.lie
These compounds are ca lled cycloalka~es , ah: ~l~~n::, the cyc\oa\kanes are saturated ring of carbon-

hydrocarbons. h . t oi Some Hazardous Organic Compounds: Part I 471 Chapter 12 C emts ry

r
I

I

~I

alkyl group {alkyl
substituent} • Any
grou p of atoms having
the general chemical
formu la C,,Hz,, . 1
obtain@d by rem~ving
a hydrogen atom from
the formu la for an
alkane

methyl group • The
designation for the
group of atoms CHr

ethyl The des-
ignation for the group
of atoms CH1CHr

n-propyf The
designation for the
group of atoms
CH3CH20·!z-

The general chemica l. formula of th e cyd o:ilkanes is C,, 1-12,, . C hemists narne th
placing the prefix C)’clo- m from o f the name of the parent hydroca rbon. Thus, th:rn ti,
plest cyd oaJkanes are cydopropane, cyclobutane, cyclo pentanc, and C}’clohexane s1rn.

Sometimes the str_u~tural ~ormulas for cyclopropanc, cyclo burane, and cyclo~en
are represented by wrirmg a mangle, square, and pentagon ~or C.3 H6, C.d-fs, and C ;anr
respectivel y. The structural formu la of cyclohexane (C6 H 1.z) 1s represented by tv,, s 1,,
fo rmula s called its boat and chair co,rformations. 0 unique

6 0 8
C)dopropant· C)clobutafll.’ C)clop,:nt:an,: (bo.111 C)cloh,.,~an”

(d1.11r1

In chis text, the chair conformation solel y is used to represent cyclohexane.

12 .2-C THE IUPAC SYSTEM OF NOMENCLATURE
When a hydrogen atom is remo ved from an alkane, the resulting group is ca lled an alk

1 group, or alkyl substituent. Their general chemical formu la is C., H zn+ 1• The most fa mir.
iar examples are the meth yl group, et hyl group, and n-propyl group.

– Cl·l-i – C/-l2CH3 – CJ·l2CH2CH3
\kth)lgtou11 Eth)lgroup ,, . Prop)l group

The names of che common alk yl subsriruems arc provided in Table 12.2 .. These names and
their molecular formula s should be memorized.

MH/iifW Some Common Alkyl Substltuents
NAM E• I CHEMICA

L

FORMULA
Methyl

Ethyl

n-Propyl

lsopropyl
– – —r-‘ -:C-CH2CH1CH3, or C3H0,-_________ _

CHrfH- , or (CH3)1CH-
CH3

-,-“·-,-•u_tyc-l;——–rl – cH2CH2CH2CH1, Of(4H_, -___ _
Jsobutyl CH3

I
– CH2 rH, or (CH 3)iCHCH2 –

CH3
sec-ButyJb

tert-Butyl b—-

CH3 7-, or(CH3lJ C –
n-Pentyl’ —-

– CH2CH2CH,CH2CH1, or(5H11- —
%e alkyl group~ a re named by replacing !he -ane suffix ~ ent hydrocarbon w!th -yf. . If it is

:~~~r~i:~;o;h~or 7ahi~~na : ,~~’.1~~~~1P:~m~;~~1 :~et:~1~:r~~~r:~:~. si; c~ns~~~~;;~e;~: J · and ~
bonded to three carbon atoms, ,1 Is ten la ry (!ert-).
‘Also called n•am~I.

472 Chapt er 12 Chemistry of Some Hazardous Organic Compounds: Part 1

Although the simple h)’drocarbons genera lly f
he complex hydroca rbons are difficult to name :;~nr\~~r:d to by 1hei r common names, 1

To o vercome this hurdle, a second S}’stem f g
I

ommon system of nomenda –
1~re. le and systemat ic . It was adopted b the 1~ nom:nc anire_was devised that is both
~~:rnistry (IUPA C) an? is called the 1J’PAC sy;~~:t~~n~~~:;n of Pure and Applied
org;i nic compounds deri ved from the use of this sys1em are calledc:~~~~-n:~e;ames of

In the IUPAC syStem, the following rules apply to the naming of alkancs fr~m their molecular structures:

1 Locate th~ longeSt chain of carbon atoms in the structure. This is called the ” main
chain .• , It is not necessary ~hat the main chain be written horizontal!}’ to be continuous.

1 Assign numbers consecut1vely to each carbon atom in the main chain starring from
the end that gives _1~e alkyl substituents attached to rhe chain the smaller numbers.

1 Designate the posmon of each subsciruent

by the number of the carbon atom along

the main chain to whic h it is attached.

1 Name the subs1itu~nts alphabetically (ethyl before methyl, and so on) and place the
names of rhe subsutuents as prefixes on the name of the main chain,

1 If several substituents occur in the same compound, indicate the number of identical
groups by the use of the following prefixes before the name of the substituent: di- for
rwo identical groups, tri- for three identical groups, tetra- for four identica l groups,
and so on. The prefixes di, tri, tetra, sec, and tert are ignored when alphabetizing the
substituents, but the prefixes iso and cycfo are not ignored.

The use of these IUPAC rules of nomenclature is illustrated in Table 12.3.

FiH!ifii Examples of Using the IUPAC Rules for Naming Alkanes When Their Chemical Formulas Are Known
A.LKAN E

3-Methylheptane

2,2-Dimethylbutane

2.4-Dimethylhexane

l Ethyl-4-isopropylheptane

5-Ethy l-2,S-d imethylheptane

CHEMICAL FORMULA

CH3CHi-TH- CH 1

CH,
I

CH,
I
CH,
I
CH,

CH,
I

CH3- T- CH2CH 1

CH3

CH3-TH- CH2-TH- CH3

CH 1 TH2
CH3

CH3

CH3-tH-TH- CH2CH, CH1

CHJCH2-CH-CH; CH3

CH2CH1

CH CHi – t- CH2CH2- TH -CH1 1
~HJ CH i

IUPAC system of

internationally recog-
nized system used to
name organic
compounds

name of an organic
compound derived
from use of the IUPAC
synemofnomenclature

. of Some Hazardous Organic Compounds: Part I Chapter 12 Chemistry
473

r
f
r ,~
I

474

SOLVED EXERCISE 12.1
Using the IUPAC sys1em. name the -,11:ane having the fol/ow,ng condensed formula

(H1 -CH -CH2-fH – CH1 -CH1

(Hi TH;
CH

Solution: :t ~den;,~:hr:~~l:s’~hn;;~~~~~~;~~~; ~a~:~1:;~50f ~e::~:•:;~~~~51~:~c;;i~~;n c~
~::.~:,, of ~h’:7dngest chan rtot~

I 2 J • S 15
(HJ-7H-CH2-7H-CH;-CH1

(/-13 y”Hz
CH;

we see that me methyl group 1s bonded 10 the carbon atom numbered 2, and the ethyl group is bonded ID
carbon atom numbt’f’eo’ 4 Because tne a•~yt substituents are named ,n alphabetical order, the comPCIIJnd !l::.
rectly named 4~thy1•2-methy/hexane

bt

0ai:; ;:~:~t:~~;~~~1~~t~~n°~~;,~b; :c:
methyl group and 3 for the ethyl group) Hovvever, 11 Is correct to number the longest chain of carbo., atoms ~
e1therofthtfol/owmg ways

1 J 4 5 6
CH3 – fH-CH1-;H-CH1 -CH1

1CH3 y”H1
CH;

2 l •
(H3 – CH -CH1 – CH – CH1 -Cr-13

I I
1CH3 5(H1

I
6CH1

The use of erthtrof these numbenng schemes also g;ves 4″(‘thy1•2-methylhexane as the correct name of this coml)CUIO’

SOLVED EXERCISE 12.2

7hf’ detalled analysis of a commercial rubber solvent proV1des the followin9 approximate chemical compos1oon

f•) 50% by volume 1s a m1lCture of 2,3.0imethylbutane, 2,3-dimethylpentane. and 3,3-dimethylpenlil~.
(bJ 30% 1s a mixture of 2.2-d,metnylbutane, 3•methylpentane, 2,2-dimethylpentane, methylcydoptntarit,

methykydoheXc1ne, 1.2-d,merhylcyclopemane, n-hexane, and n-heptane. and
lcJ 20% 1s a mlXtlJre of n-butane, n-pentane, and 2,4–dimethylhexane
wr1tethechemrcalf°’mulaforeachsubsr.ance

Solution: The solvent’s corutrtuents have the following condensed formulas
(;ii) CH1 CH1

I
(H3- ·H – (H -(H3

13-0’TTE’l)bu1,1r,e

CH;
I

f””H (H “(-(H1(H,

CH;
JO

fH3 fH1
CH3-CH-CH-CHzCH3

l J-0,melh)lperi\Jne

Chapt er 12 Chemistry of Some Hazardous Organic Compounds: Part J

(b) 1H’
CH1-1 (H1(’13

CH;
ll-O”>eth)-h;1,T<1"('

CH,
I

CHJ-1-CH1CH;CH1

CH;
22-ome1n,per,t.:me

~CH;

w ethykyclohex<1ne

(d ( H3(HzCH1CH3
n-8U!.!f11′

CH3- TH-CH2 ~ 1H – CH;(H3

CH3 CH1
1 4-0memy!he.>..lne

T'”‘l
(H3(H2-(H -CH1CH1

J-~•etn~•oenwne

0-cH,
lv’ethylcycloperu~ne c/·

1.2-0,methtcyi;loPtnt~-ie

CH3CH1CH1CH1CH;
n–Pe<11.dne

12.2-D TRANSPORTING A LKANES AND CYCLOA LKANES
When shippers offer an alkane or cycloa lkane for transportation, DOT requires them to
encer the relevant shipping description on an accompanying shipping paper. Some exam-
ples for severa l rep resentative alkanes and cycloalkanes a rc lis ted in Table 12.4. DOT also
req uires shippers and carriers to comply with all applicable labeling, marking, and plac-
arding requi rements.

Fhiiifii Sh1ppmg Oesrnpttons of Some Representative Alkanes and Cycloalkanes
ALICANE OR CYCLOALKA NE

SHIPPING DESCRIPTION

Butan,

Cyclohexane

Ethane

Methane, compressed

Methane, cryogen ic

Natural gas, compressed

Natural gas, cryogenic

Petro leum gases, liquefied

Propane

UN1011, Butane, 2.1

UN1145, Cydohexane, 3, PG

II

UN1035, Ethane, 2.1

UN1971 , Methane, compres~d, 2.1

UN1972, Methane, refrigerated liquid, 2.1

UN1971, Natural gas, compressed, 2.1

UN1972, Natural gas, refr igerated liquid, 2.1

UNl075, Petroleum gases l iquefied, 2.1
o,
UNl075, Liquefied petroleum gas, 2.1

UN1978, Propane, 2.1

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 475

r
I
I
I

Iii i11 i’ ii/ I
1/111/ I 1-il I

alkene (olefin) • Any
hydrocarbon h.JVing
molecules tha t contain
a t le,1.st one carbon–
carbon double bond
(C=O

unw1uro1 tedhyclrocar-
bon • Any hydro-carbon
whose molecules con-
tam at least one carbon–
carbon double bond o r
tnple bond
(C=C orC=C)

cyclo.alhne • Any
afkene w hose carbon
;, toms are bonded to
each othe r in a cyclic
fash ion

12.3 ALKENES, DIENES, TRIENES, CYCLOALl

Hydroca rbons whose mol« ules conram one or more carbon-<:a rbon double bon called alkenes, or olefins. Beca use the molecular structure o f each alkene is defi,

1

ds ~,r

hvdrogen acorns rdarive ro 1he molec ular structure of the corresponding lk en1 tn
alkew.-s .:i re sai d ro be unsaturated hydrocarbons. Like the cycloalka.nes, the arke~;e, the
the general chenucal formula C,.H_,:,, . s h.. it

The simples t alkene is _n:1med ethe_ne, or more.~o~monl y, ethylene. Its molecular
mula is C:H.i , and 1rs Lewis structure 1s the fo/lo\\ rng. for

H H
I /
C= C
I \

H H

The presence of the carbon–car’;><>n double bond i_n the str~cture restricts the moverneni
o f the atoms about the bond. This means that the six atoms m the ethylene molecule lie in
the !>.:lme plane.

T~ere are also alken_es in which rhe first and last carbon atoms in a continuous chain
a re jo rned to each o th~r rn a cyclic arrangement . They are ~ailed cyclo~lkenes. Their gen.
era.J chemical fo rmula 1s CM H;M – ; . They are named by placing the prefix cyclo- in front of
the na me of the parent alkene. The three simplest cycloalkenes are cydobutene, crdopen.
rene, and cyd ohexene. Their chemical formula s often are represented by using appropn-
a re geometrical designs as shown here:

0 0
CJcloOOtcoc C)clopen1,:nc C).: lohc., cnc

diene • Any hydrocar-
bon w hose mo lecu les
have two carbon-
c<11rbon do uble bonds

The molecules of alkenes can also have multiple carbon-carbon double bonds. When
rhey ha ve rn•o and three double bonds, the compounds a re called dienes and trients.
respectively.

triene Any hydrocar-
bon whose molecule s
have three carbon-
ca rbon d ouble bonds

12.3-A STRUCTURAL ISOMERISM IN ALKENES
Ethene and propene do not ha ve structural isomers. For example, rhe condensed formulJ
for propene ca n be correctly represented in eith er of the following wa ys:

Bec:iuse either formul:t 1s 1hc other one turned around end for end, it is a rcpre~ntJt!On
of rh e same substa nce.

Howe\·er, we ca n write the fo llowing rhree condensed formula s for the strncrurnl JSO·
mers of 1he alkene having the formu la C.~ 1-18,

ln the fi rst two fo rmula s, th e ca rbo n atoms are displayed in a co ntinuous chain. Tht
molecu la r s tructures differ o nly by the position of rhe carbon-carbon double bond.
Th e ih ird fo rm ula differs in rha1 ch c carbon atoms arc bonded to one anoth(‘r in a
b ra nched p ::m crn.

476

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

3 B NAMING ALKENES. DIENES TRJE
12. • cvcLoO1ENEs, ANO CVCLOTRIEN~:s. cvc toALKENes,

niisrs use rhc -e11e suffix to name alkenes C
~ : members of the a lkene series are named. et~:1~:qu::11: , in ihe IUPAC system, the fi r~t
~ 111111011 names arc ethylene, propylene, butylene, a:y~;~~u:; ~e::r~v~rntene. Their

I~ the IUPAC S)’Stem, n~t only is _the -ene suffi x used to identfr,, an aik.ene but the
ros1non °1f

the dou~ct bood m tlhk r- mam cha in of its molecules also is indicated .• The fol-
lo”1ng rues are use o name a enes:

I Consec_ud~ely number rhe car~on atoms in the main chain of continuous carbon atoms
b)’ begrnmng at the e~d that 1s ~ie~rer the double bond. The carbon-carbon double
bond must alwa_y~ be included withrn the main chain of continuous carbon atoms.
]odr,1care the pos1t10n of the carbon-carbon double bond by the appropriate numerical
pre 1x.

~:s~:~~ec~~~/t:s!’.~~:~tei:t
0

~l~~~’.tuent by the number of the carbon atom along

For example, the compounds having the fo rmulas CH2::CHCH2CH3and CH3CJ !=Cl /C l I; ue named I -butene and 2-butene, respectively. The compound having the formula CH2 =T-CH3
CH ,

1s named isobutenc, isobutylene, or 2-merhylpropene. The name used exclusively in com-
merce is isobutylene.

When dienes and trienes are named, the positions of rhe carbon-carbon double bonds
are denoted with appropriate numbers, and diene or trie11e is used as rhe relevant suffix .
The following examples illustrate the naming of a diene and a triene:

CH2=CI I – C!-l = CH2 CH3-CH= CH – G i = CH – CH= CH~
l .3• 1lurnd1cne I J.S. fkpt.1tncrn:

An alkrl derivative of a cycloal kene, cyclodiene, and cyclotriene is named by using
one or more numbers to identify the location of the alkyl group relative to the location of
the double bond. For example, the compounds designated by the following molecular
srructures are named 1-meth ylcyclopentene and 3-met hylcyclopentene;

o-Cll3 o-Cl-13
1-,\lc th)k} , lop,:n tene

The atoms in the carbon-carbon double bond of a cydoalkene are always numbered I
~nd 2. Consequently, as 1he name of a q ‘cloalkane, methylqdopentene may be preceded
only b)’ a 1-, 3-, or 4-.

Finall>·, just as there arc a lkyl groups, there are also alkenyl groups: The three
most common ly encou ntered alkenyl groups are the methylene group , vinyl group,
and allyl group .

,\klh)kn,·,ruup Vin)l grnup ,\ll ) l group

Ahhough the vinyl and ally! groups :ire basc_d on alkenes, th;a~:~y~~:~~~~: ;i3k:~
1
~ ,~

conrain a carbo n-carbon double bond because It h_as ~~l~ro:~ic com ounds such as the
groups are used in the common system to name sunp g P
chlorinated derivat ives of methane, ethcne, and propene,

CH::Cl2 CH2=CH – CI CH2=CH – CH~- Cl
M clh)lcncchlonJc
(D1chlornn1elh.1ncJ

V1n~l chl0n

noncycl ic group of
atoms having either
the formula – CH1- or
t he general chemical
formula C,,H~,
wheren .- 2

methytene group • The
designation for the
group of atoms -CHi –

vlnyl The des-
ignation fo r the group
of atoms CH1=CH-

desig-
nation for the group of
atoms CH1= CH-CHi-

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 477

L

r
I

/1

111 1/ II

I
478

geometnQI lsomuism
• The phenomenon
assoeiatedwith
compounds whose
moleculeshawthesame
atoms but d iffer in the
manner in which they
are spatia lly bonded
about a carbon-carbon
double bond

12.3-C GEOMETRICAL ISOMERISM IN ALKENES
The relari\’e rigidiry of the ~arbon~arbon double bon~ leads to a new kind of iso .
call ed geometrical isomerism. This phenomenon anses when 1he two substicu:erisll!
atoms are different on each c-jrbon arom that makes up the ca rbo n-ca rbon d b n1s or
for ex.ample, nrn Lewis srruc1ures can be written for 2•butene as follows: ou le bond.

\H3
c-c
I I

H CH;
muis-2-Buicnc

\HJ 5=’·!3
c-c
I I

H H
ru-2-Butcnc

These structures illusrrate that a hydrogen atom and a methyl grou p are bond d
carbon atom in the carbon-ca rbon double bond. Because they are bonded toe th~o ~ach
carbon atoms in each Lewis structure, they do not rep resent structural isomer . mt
arrangement of their atoms differs in space. When two compounds have the sa~ )Ct th(
tural formula but differ by the spatial arrangement of their atoms, they are ca ll:dst:
metrical isomers. g

Geometrical isomers are named by using either of the prefixes trans- or ds- m .
on the opposite and same side. oft.he carbon-carbon double bond, respectively. ‘A/;~;~
~~:~cs:e~~c:,p~;i:i~. geometrical isomers of 2-butenc are named trans-2-butene and tis-

SOLVED EXERCISE 12.3

Us,ng the IUPAC system, name the alk:ene having the fo llowing condensed formula

CH1CH2-~ – CH1

CHiHz

Solution: First, 1dentrfy the longest continuous chain of carbon atoms that contains the carbon-

4 1 2 1
CH3(Hz – 7 =CH2

( H3CH1

Th,s means that the compound 1s a dem•at1ve of 1-butene The ethyl group is bonded to t he carbon atom num-
be,ed 2 The compound then is correctly named 2-ethyl-1-butene f’,Ne do not ass ign a number to each carton :om from the left to the r,ght of the longest chain, because then the carbon atoms in the carbon-carbon cloub’t nd

would be numbered 3 and 4 We always ass,gn numbers to the carbon ato ms so that the smclle< numbtri are assigned to the carbon a1oms in the carbon-

12
·3·D TRANSPORTING ALKENES, DIENES, TRIENES, CYCLOALKENES,

CYCLODIENES, AND CYCLOTRIENES
:hen ship~ers offer an a lkenc, diene, t ricne, cycloa lkenc cydodicne or q •dotricnc for
acc~:;;~~~/:;~h~O: re~uires them ro corer the releva~t shipping :description °~ ;:
listed in Tab[ 12 Pf Jcj per. Some examples for se\•era l representarn·e compound h
applicable lab:lin · ~a ! also requires ~hippcrs and carriers to compl)’ with all or er

g, rkrng, and placarding requirements
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I .

iHifii
ALKENE, DIENE, TRIENE,
OIi CYCLOALKENE

sutadlenes, stabilizeda

1-Buteneb

, 11.2-Buteneb

u,1ns•2•Butene~

1,s,9-Cydododecatriene

cycloheptatnene

cyclohexene

Cydopentene

o,i1obutylene, isomeric
compounds’

Ethylene

Hexadienes

1-Hexene

1-Pentene

Propylene

Shipping Descript f
Dienes, Tnenes, a~~~;1::i;;:~::presentat1ve Alkenes,

SHIPPING DESCRIPTION

UN1010, Butadienes, nabilized, 2.1
UN1012, Butylene,2 .1

UN1012, Buty1ene,2.1

UN1012, Butylene, 2.1

UN2S18, 1,5,9-Cyclodode<:atriene, 6.1, PG Ill (Marine Pollutant) UN2603,Cycloheptatriene, 3, PGII

UN2256, CycloheJ1.ene, 3, PG II

UN2246, Cyclopentene, 3, PG II

UN2050, Diisobutylene, i1omeric compounds, 3, PG 11

UN1962, Ethylene, 2.1

UN2458, Heudienes. 3, PG 11

UN2370, 1-Hl’Jl.ene,3, PG II

UN 1108, 1-Pentene,3, PG I

UN1077, Propylene, 2.1

‘ Pi.or to. the ir shipment, OOT requires the addit ion of a subnance to 1,2· arid 1,3-butadiene to lnhiblt their aui:o-
l)O!ym,nzat lon and thereby promote th, lr stab111 zatlon (Sl’alon 14.]).
1Fo1pu1posesofOOTregulat lom, t-butene, c/1-2-butene, and tram•2·butenearede1lgnated “butyl, ne •
‘ for purposes of DOT regulat ions, dllsobutylene refers to .i, mhctuf t of the compounds 2,4,4-tr lmtthyl-i-pentene
,lld2,4,4-trimethy l-2-pentene.

12.4 ALKYNES
Hrdrocarbons having one or more ca rbon-

The simplest member of the a lkyne series has the fo rmula C21-12• It is named ethync in
the IUPAC system, but it is known more generally as acetylene, its common na me. The
Lewis structure of acetylene is denoted as fo llows:

In the common system, alkynes are named as dcriva1ives of acetyle~c . If an alkyne is
represented by either of the general fo rmulas R-C=C- H or R-C=C-R , the correspond-
ing compound is named by identifying the alkyl groups, Ra nd R’ , in their formulas. Thus,
the derivatives of acetylene having one and two methyl groups are named mcthylacerylcne
and dimethylacety lenc, respectively.

,\kth) l~CCI) k m: Dunc th) l:iccl~ knc

In the IUPAC system the alkynes are named by replacing the -ane or -~ne suffi~ o.n
the associated alkanc or ~lkene, respectively, with th~ s:~:l::·rh: ~~a7nc~~::t~~f~:

1
~~

Used lo indicate the position of the carbon-ca rbon tnpl . h 1 1 f 1 tinllous ca rbon atoms. Consider the two alkync isomers havrng t c mo ecu ar ormu a

bon whose molecules
have at least one
carbon-

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 479

II

!I

G H ., . The compound n;uned 1_-butyne is the isomer in whic~ the carbon-<'arho bond is loc.ued between a terminal ca rbo n atom a nd the one munediatel d " n tr% The compound named 2 -buryne is the C~ H6 isomer in w hich the carbo~..:;:bent10

1
l

bond 1s located ben\·een the rwo nonternunaJ carbon atoms. on trip]r

H – C .:; C – CH~CH1 CH3- C =: C – CH ,
l -BUl)OC ! -HUt)nc

Although an alkyne may have structura l isomers, it do~s nor have geometrical is
In the IUPAC system, the alk ynes are named by usmg the following rules: oniers.

Con~ utively number the carbon ~toms i~ the main chai_n of cominuous carbo
by beginning at the end of ~e cham ~ at_ 1s neare~ the ~1ple bond. The carbo 11 :uorns
crip!e lxmd must_ ~ways be rnc_luded within the main cha_m of continuous carbo~rbo.i
Indicate the posmon of the triple bo~d by the appropriate numerical prefix. tOJn.i

by the number of the carbon atom along

SOLVED EXERCISE 12.4

natu ra l gas • The
flammable gas-
primar ily consis-ting
of methane-formed
in nature by the
decomposition of
an imal and plant life

Using the IUPAC system, name the a11cyne having the following condensed formula

CH3-CH – CHi -C :C -H
CH,
CH,

Solution; F1m. determine that the longest continuous cham of carbon atoms containing the carbon-cafbon a-,.
p!e bond has so,; carbon atoms This s,gn1fi1.”S that the compound ts a derivat ive of 1 •he)(}’ne. Next, ass ign numOI!~
to the carbon atoms from the right to the left and then downward. The two carbon atoms 1n the carbon-urb.:iti
tnp!~ bond are &,en nuMbered 1 and 2, respectively

‘ 3 2 1 CH3-1H-CH2-C=-C-H
sSHi
6CH3

Becaus~ the methyl group 1s bonded to the carbon atom numbered 4, the compound 1s correctly namt~ 4-methyl-1–hexyne

12.5 NATURAL GAS (METHANE)
The simple aliphatic h ydrocarbon s are flammabl e gases. They are most common])’
encoumered as domestic and industrial fuels. The simplest of rhem is methane, whose
chemical formula is CJ-Li. Methane is the primary constituent of natural gas, roug~l)’
70% by volume. The chemica l industry uses narural gas as both a feedstock and an tn·
plant energy source.

N atural-gas-fired power plants are used co produce electricity. T hese plants no,~’ prof
duce approximately 25 % o f the electricity used by Americans . A lthough the operat’.0 ” ~ .
narural-gas-fired power planis is not pollution -free it is a more en vi ronmentally fn~nd )
practice when compared to the operation of eithe; coal-fi red or oil-fired power plant~
figure 12.3 illustrates char natural-gas fired power plants produce less poll ution 30
fewer greenhouse gases.

The ~merican elect ric utilit y industry’s swi tch from the use of coa l to n~cu r~~~~’.
substantia ll)’ reduced the atmosphe r ic carbon dioxide concentration during ~

480 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part t

!’.:r~i:~ed~;\~:::tit~;/~;~;~tbon dioxide emi ssions from energy genera tion in 20 l2

~-!_ethane COnSti_tutes IO% to I~% of the greenhouse gases linked to global warming. As
noted m Table 5.3, ICs_global wa rming potential m·er a 20-year time period is 72. This GWP
rtflects that metha,~e 1s much more potent as a greenhouse gas than carbon dioxide.

Pure methan: is an odorless, colorless, tasteless, and lighter-than•air gas. Some of its
phrsica l properties are provided in Ta_ble 12.6. Although odorless, when natura l gas is
encountered by emergency respon~ers, tt usually possc:ssc:s a slighdy offensive smeU caused
b)· the presence of sulfurous organic compounds that have been added imentionally

10
assist

!)(l’SOnnel attempting to detect gas leaks.
As shown by the data in Table 12.6, when methane is mixed with air, it burns at con-

ccnm1cions between approximately 5% and 15% by volume, producing a slightly luminous
f\lme and relea sing 958.1 Btu/ft3 (39,820 kjlm3) to the surroundings. Fire and explosion
JTC its primary ha za rds.

Methane can pose a health hazard as an asphyxiant (Section 10.3-A). Individual s
who inhale the gas for a prolonged period lose consciousness because they are denied suf•
ficienc oxrnen. Prolonged exposure constitu1es a direct threa t to life by suffocation.

~·lethane occ urs primarily in nature as a result of the decay and alteration of animal
and plant remains deep below Earth’s surface. Consequently, it often accompanies nearby
deposi ts of crude petroleum (Section 12. l3-A ), which forms by the same mechanism.
~!ethane is a lso abundant in the atmosphere within coal mines, where it is called ~fire-
dJmp. When the mud a t the bottom of stagnant pools, swamps, and rice paddies is dis-
turbed, methane bubbles ro the surface. Here, it is called .. marsh gas.”

1/li!ifiW Physical Properties of Methane
Melting point
801lingpoint

Specificgravityat68°F (20°C)
Vapor density (air= 1)

Flashpoint

Autoignition point

lower flammable limit
Vpper flammable limit
Heat of combus-tion [32′ F (O”C) and 1 atm}

-297°F(-183″C)

– 25B’ F(-161°()
0.42
0.553
-366″F (-221 ‘ C)
999′ F(537’ C)

5¾ byvolume
15% byvolume
958.1 Btu/ttl (J9,8201dlm3)

1
U.S. Energy lnforma1ion Admmistration (WJshington, DC).lO!J. . H dous Organlc Compounds: Part l

Chapter 12 Chemistry of Some azar 481

nr ll.S-A METHANE IN THE ATMOSPHERE OF COAL _MINES Sec 7 6 C mechwe 1s one of se,·eral constHucms of coal 1:sr1~~;~10t~~ ~reda:o; )C’eps from seams 1nro the surrounding enclose “·here ir ~ccumubres and pose:; a senous risk of fm: and explosion The of merhane 15 onlv $ % to l5% by volume m :m E\en a small spark can
/I

I
/1

1
482

m1-th.1nogenu i:s • The
biological production
of methane by anaero-
bic bacteria

World\\ rdc.-. thousands 0 ( coal miners are killed annually, en herd
flammable merh3.Ile ignm:s \\ irhm a mme, or b} subsequently breathing

hC’rc of carbon monoxide formed when methane and other gases burn
~e Umrc.-d Srates. using the Jeg.:il au rhonty of the Coal Act {Section , e \
Safer} and Health Admiruscraaon (MSHA), a dumon of the U.S Department of ln1,}1nr
regulates health and s.ifecy conditions m coal m111es b) means of man dator} standard 1~

Safety standards withm mines address the reduction o f methane and other gases s.
guard ag:unsc the porennahry of ha zardous incidents mvolvmg the presence of metba To
carbon monoxide, and ocher gases w1chm enclosed mmes, the owners and operaton IJt,
coal mmes are required at 30 C F.R 575 330 .. co provrde ven nlatton /within minesJ ;f
dilute, render harmless, and to carry away flammable, explosive, noxio us, and har~
gases, dusts, smoke, and fumes. ” . . . .

ln 2010, the fui!ure co _comply “.”uh this re~ulaaon conmbured to the ~eadliesr c~
mine accident ~x~rienced m the Unued ~tares smce ~970. An earth-sha~er~n~ explosiOQ
occurred withm severa l tunnels of a mm~ l~c~ ted m Beckley, West Virginia. Expen\
concl uded char it was triggered by t~e 1gnmo~ of accum ul_ar~d methane and coal
du st. 2 As a consequence of the explosion, 29 mmers lost their li ves, 19 from carbon
monoxide poison ing.

12 .5-B METHANE PRODUCTION BY THE DECOMPOSITION OF
ORGANIC MATTER

Methane is also produced when bacteria decompose organic wastes by means of rh~
anaerobic process called methanogenesis. H ence, methane is the prima ry conscitumi
of landfill gas and mamma lian flatulence. Ir is also produced by ca rde and other rumi-
nants as rhey digest cellulose-like foods such as grass and s traw. The culprit in thts!
foods is actua lly Jignin (Section 14.5-A), a gro up of complex compo unds that exist in
and berween plant cdJ walls and provide che plant with its rigidity. The ruminanrs arc
unable to easily digest Jignin . The process requires the help of rnicroflora inhabiring
cheir guts. Methane is produced as these microflora degrade the lignin , and the rumi-
nants belch ir into che atmosphere.

There are 1.8 billion ru minants worldwide. On average, a si ngle cow exhales 634
quarts (600 L) of methane into the air daily. EPA has estimated that approximately 25%
of the methane in the air originates with th e belching of livesrock. As amusing as this mJ )’
fuse appea.r; the production of methane by livestock has become a serious matter. This fact
has caused agricultural scientists to test ways of altering the volume of methane rhar li1·~-
srock produce, primarily by providing ruminants wi th dietary adjustments.

The belching of livestock is no r the o nly uncharacteristic way in which the a1mos·
pheric methane concentration increases. For example, m ethan e has also been locked in
the permafrosr in Siberia since th e last ice age, 10,000 yea rs ago. The wa rming of plantt
Earth has caused the Siberian permafrost ro thaw and slow ly release its methane inrorhe
atmosphere. 3 Scientists estimate that approximately 9% o f the met han e emissions into rhe
atmosphere originate in the Arcric tundra.

;1. DJ ~irt McAtcu, Upper Big BrJnch, Report ro the Gov(‘rnor (,\by 20 11).
NJfJ/Ja ShJkhova er al.. ~Extemi\·e methane ven ting to thr :irmo;phcrr from scdimrnts of rhr Uir SibtnJn

Arctic Shelf,~ SC1enu, Vol. 327 (20JOJ, pp. 1146-1250.

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

11
_s-C INDUSTRIAL SOURCES OF

METHANE

l he v;t~d ~;~;;:~~::
1
;~:~s8j~r~~;aie\yblS_ trillion cubic fm {~0.7 1 1113 ) of natura l gas

Jllnu,i >·14’% coming from Canada a
1
i:do ~:~~ed from do~1estic _sources, wit h anot her

1
!1e ~etroleum and coal by a process ca lled ,;:: k~~/

11;:1::e, !~a,;k~~so
~LiCed when rn~;~:;;1:icc:ah{k~~oca rbons arc subjected to hig~ tempcr~;ures under r::od· ~;~: •~;f!~i~~e
rrJ te press,urelyt·,c c,acking ) g ) or relativel y low tempera tures in 1hc presence of a associated with break.-

nlrst (ca a . • ing down larger,
C’J • ;,Ja1ur;il gas gcnera_lly is recri:ved from underground, porous reservoirs where it has :~:;~;d:~:a;~~e ~:t

umulatrd for cenlunes. There 15 a vase wealth of natu ral gas\ rid “d b · 1 k d ecules into simpler and
~;densr rock deep beneath Earth’s surface where it often is d~·~ icu~\:’rc~:i:~~- t~c lighter molecules
niiddk of t~e la Sr dtcadef th, rc was serious concern chat America would experience a
shortage in its su pp ies O natur_a l gas. However. drillers perfected a method to extract
nJt11rlll gas from shale_. T he retne~a l method is certa in to boost U.S. gas production for
Jrc;1drs to coi:ne, and 15 based 0 ~ imp_le~enting a process called hydraulic fracturing , or
fracklng . During the pr~css, dnllers IOJ CC- t a mi xture of water, sand, and chemical prod-
ucts under pressure deep into the ground to break up the shale rock forma, ions and nearly
impenetrable sa nds to create channels from which the entrained natural gas (and crude

rroleum ) may be recovered.

crackingproceuaccom·
plished by the applica-
tion of heat

cracking process accom·
plished lnthepresence
of a catalyst

pe Shale is a fine-grained sedimenta ry rock composed mostly of clay and mud . Shale-rich
regions exist in the Appalachian sect ion of the northeastern Uni1ed States, as well as in
Trxas and North Dakota. The la rgest known reservoi r of natural gas in the United States
is J geologic format ion known as the Marcel lus Shale. It underlies siza ble portions of
Wes[ Virginia, New York, Ohio, and Pennsylva nia. The natural gas within thi s one shale
may be as much as 490 trillion cubic feet (14,000 km3).s

Natural gas is a lso ava ilable off U.S. shores beneath the seafloor. The U.S. Depa rt-
mrnt of Interior estimates that the outer continental shelf holds 420 trillion cubic feet
(1 2 trillion m3) of unrecovered natural gas, which, if tapped, could heat America n homes
for the next 80 years. Although scientists perceive a benefit in harnessing this resource

h~d raulicfracturing

that involves pumping
water laced with sand
and chemical products
deep underground at
high volumes and pres-
sure to extract natural
gas entrapped in shale

for future use by humankind, activists fear that em•ironmenta l havoc would be wreaked
b)· drill ing operations that occur offshore in ultradeep waters.6 Marine microorganisms
produce approximately 4% of the methane that ultimately reaches che ocean surfaces
and becomes a constituent of the atmosphere.

The prevailing pressure below the sea noor is approximately 30 times the atmospheric
norm. Under these condi tions, meth:m e and water molecules coexist in a unique fas hion:
The metha ne mo lecules are trapped within “cages” composed of 5¾ water molecules.
.\fany cages link together co form white crystals that physically resemble ice. Each unit of
the substance, ca ll ed methane hydrate, is represented by the formula CHr5.75 H2O (s ).
.\!ethane hydra te is stabl e under pressure, but when brought to the ocean’s surface, its
units collapse and the methane wafts into the atmosphere.

‘U.S. Energy Information Administration (\Vashing1on, DC), 20_13. . . , .
Jfor rwo major reasons, hrdraulic fracturing h.u become a subJcct of mten!te cn\·1ronment.1.I scrut~ny. First, the
chemical products used in [he process include canccr-uusing substances whose rele.ise 1mo the environment has
nrgl tirdy impacted the quality of the groundwater in the regions where the proces!.CS are_conduct~d. Scc?nd,
hydraulic fractur ing nor only dislodges natural gas but also compounds of toxic metals hke arsenic, banum,
chromium, and zinc, :ill of which are natural components of shlle. The fea r is that 1hesc compounds could le.1th
1n10 1heground111arer andtainritfor fu turegcnerations. . . , ,
10ffshorc drilling fo r natural gas and crude petroleum i~ als~ ~otenml!y replete w11h adHrse cm ironmental
constqucnces. In 2010, the explosion of an offshore drilling ng m the Gu~f of iM~~~:~e:~u~d t;:xt;:\~~)~! i.~
1rorkcrsand the rele,1sc ofn:1turalfasandcrudepetroleumthroughamassivcppe Id be. pp d Tl h
m1lh~n cubic feet ( J .62 million m _) o~ narural gas was flared ::~=!~rt~;h~~~~/:1~xico, :~:r: 1~ e;~an~::~
rluging oil_ flowed 10ward the barrier islands, marsh~ , and_ be and threatened coastal touri~m in four states.
1rg1onal wildli fe, shut down large areas of commcmal fishing,

m1-thane
Ice-encrusted natural
gas located in porous
rock in the arctic
tundra under the
permafrost and in the
deep-ocean sediments
of the continental slope
and ocean floor

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 483

line marbr • An
aboveground sign ind i•
eating the appro~ mate
location of a natural-
gas-transmiu ion
pipeline

\lt th me h ·dr.m deposits :ire fo und not on_ly below ocea~ flo~rs, bur also I.Jnd
• ‘ . } ·h he climaie is especiall y cold. 1Vla1or discoveries f er th,

r~~~~r~::.t~~a;o:n; :~ ~J.isk.i and Si beria.
0 rncthJ~r

l~.S-D NATURAL GAS TRANSMISSION BY PIPELINE
Throughout many of rhe lower 48 states, large \’Ol~m~ of nar~rral gas ~re directly trans~
irom pffl’Oleum fidds or refineries by a network ~f p1peli~es _until they ~lunately are dis1nbt’r~
ro individual homes. apamnenr complexes~ busmess bu1ldmgs, chenuca l plants, and na;r~
g:is-fired power pbnts. Approximate-!y 60 ¼ of U.S. households use natural gas 10 Pri/~-
the heat on rhe kitchen stovetop a~d ~o fi re_ the_ home _furnace, water hearer, and clothes d ‘.cit

As it moves through tr::msnuss1on pipelines, n.~rural_ ga~ gradua ll y loses its Pres?~t
:rnd \’elocit-y. To o,·ercome these problems, the ~as 1_s penod1cal!y pa~sed through a llu~rt
ber of compressor stations located along the p1p~lm~. At each s~at~on, tu rbines reco Ill-
press the natural gas to increase rhe ra1e at wh1:h it moves wuhm the pipeline I.Jn7i
rt”aching the nexl compressor station . The longest smgle network of natural-gas-iran _ 1
sion pipelines in the United States srre1ches a distan~c of over 13,000 miles (20,909 sk:· during \\’hich it passes through 100 compressor s1a uons. ‘

When utility and construction workers and emerge~cy r:spo1~ders check for the l)Os-
sibility of pipeline damage or interfe rence, t~ey m_ust quickly 1d~nufy the location of naru.
ral gas pipelmes. Firsr, rhey generally spot signs li ke the followmg:

HIGH PRESSURE
NATURAL GAS PIPELINE
SHORE DIGGING IN THE VICINITY,
(All YOUR LOCAL GAS COMPANY

(000) 000 0000

Second, ar 49 C. F.R. S 195.410, DOT requires a line marker like that shown in (a) of Figure
12.4 to be posted ar regular intervals along a pipeline, at road and railroad crossings, and a,
aU aboveground facilities. The line marker idenrifies 1he approximate location of both
abo\’eground and underground pipeline right-of-ways. Its pos ting is intended to al~n

,., lb/ le/ (di
FIGURE 12A To alert workers and emergency responde1s of the presence of a natural-gas-transm1ss-on p.ptl ‘it
DOT requires the ~ng of line markers along a pIpe l1ne 1oute (al ,5 a hne mark.er posted near roads, ra•lroad>.
and alcng pipeline nght-of-ways It contains the wo1d WAl!~iNG followed by any of the words PlPEU\ E, GAS ,
P-PEU”,,f , or ~.t.ATURAL GAS PIPEU/\;E, the name of the opera tor, and the telephone number at which theoper~O

I’

may be reached at all times The line mari:er colors are yellow. black, and red (b) Is an aerial ltne mark.er for~ of
by ~ lots of pipeline patrol planes. (c) is a p1pelrne casing vent. and (d) Is a parnted metal or plastic post The
defacing, damaging, removing, or destroying any type of pipeline marker 1s a federal cnme

484 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part r

r\·ers 10 exerci se caution. Line markers d . .
0

~ ‘ ipd ine, nor do they provide the pressure :f~~: mdicate the exa~t la:cat ion ?r d_epth of
ih Pl ine markers arc posit ioned as fo llows: natural gas movmg m the p1pelme,

• The line marker for aboveground i 1· •
S((llon 3cce~si blc to the public. p pe mes is placed and maintained along each

The hnc marker fo r underground pi r · 1 . . roJd, ra ilroad, and waterway crossings. pe mes 15 Paced m nght-of-way areas :ind at

l\amf~~~:;;~:n~:~~:~cn t~-lin:s themselves ~ y represcm hazards due ro leaks caused
b)’ narur:i

1
. ‘ Y . iggmg and excavauon, surface corrosion, and other 1rou-

bl C-S• In ihc U~1ted States, ap~roximacely half of them, 250,000 miles (402 000 km) are steel
Of casr-ir~:a~~~/~~~c~::~

111
::~il~~d~,~ore 1~70. Pri_or to their_ installation, chcy

1
wer_e not

generally . P ,1th anticorros1on protemon, nor were they equipped
,rith auwmattc shut-off valves. Consequently, when they rupture, the release of narural gas
ofttn must be stopped manually. Because many pipelines 1hat were installed four and five
d”‘-1des ago _no~ arc badly corr?d~d, they could rupture catastrophically at an)’ 1ime.

These pipelines resembl~ t~ckm~ ti~e bombs, as noted during the past decade when
ruptured natura l•gas-transmission pipelines released massive fireba lls resembling BLEVEs
(Stction 3.8-A)._ In ~010, for example, the rup1ure of a segment of a 30-inch•diameter
pipelin~ i_n a resi?enrial area ~f ~an Biuno, California caused the release of approximate!)’
47,6 m1!11on cubic fee t.(1.4 million m l of natura l gas 101he environment.’ The gas ignited
and burned for 95 nunutes before a public utility employee could operate the manual
vah·es 1ha1 stopped the gas flow. The pipeline segment had been ins1alled in 1956 and
nearb)’ segments had been insta lled in 1948. The fi re caused eight fata lities and num;rous
injuries as well as the destruction of 38 homes and heavy damage to another 70 homes.
Emergency responders cou ld only attack the secondary fi res ignited by the blaze.

The rupturing of a main transmission pipeline is not the sole hazard associa1ed with
ddi\·ering natural gas to the spot where it is needed. Before it is distributed 10 furnaces
and appliances within buildings, natural gas first mea nders within pipelines that were
placed through shafts and ceilings, under floors, and around gas boilers. When the pipe-
lines dcmiorate, crack , or are otherwise damaged, narnral gas leaks from them into the
5Llrrounding environment, where it ma)’ accumulate and pose the risk of fire and explo-
sion. The detection of 1hese leaks is the responsibility of the local gas utility company, but
firefighters usuall y are asked to assist in accessing areas and preventi ng explosions.

Lea king natural gas may be initially identified by its odor, a hissing or roaring sound,
discolored vegetation surrounding the pipeline, or wa1er or dirt blowing into the ai r.
However, when leaks of natural gas originate from buried pipes, the odorant may adsorb
10 particulates of the surrounding soils. Consequently, odor alone should never be used to
determine the source or intensity of natural gas leaks.

A more practical method for detecting natural gas leaks involves 1he use of monitors 1hat
c.in be aimed at a buried pipeline ro detect a natural gas leak or assess where a buried pipeline
was accidentally damaged during an excavarion operarion. To detect the location of t~e leaks,
emergency responders aim them from a safe distance within buildings at suspect areas hke holes
or vents monitor the methane concentration, and assess whether the area may be safely accessed.

Na;ural-gas-distribution pipelines appear to be buried al~o~t evel)’\vhere in residen-
tial areas, nor just beneath 1he surface of streets an? al_leys. F1rcf1ghter_s often accompany
gas company employees to scenes at which these ptpdme~ have been_ madverrently dam-
aged during a routine landscaping or other soil•excavau_on operauon. Da~age to the
pipeline may cause a natural gas leak that has the potem.ial to produce service outages,
evacuations, ignition, property da mage, injur)’, or loss of life.

·P1pdme Accidenr Report ~sJn Bruno, California, Narural Gas Pipeline Explosi~n and Fire, Septe~bcr 9, 2010,~
NTSB No. PAR-I !-0 I, PBzot l-916501 {Washington, DC: Narional Transpon.11LOn Safety Board, _QI I).

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 485

I I

/I
I

I

I
! 1

1
I

I I

II ///

/1

To r~uce or dimin:ire the occu~rence of such incidents, local gas cornpanies and 1
ordinances often require the fo llowing: OcaJ

Contact the local g3s company befo re staning 10 excavate.
W:iit until a tr:J.ined cechnici:rn fro m the company has flagged the location of the
line (usually within less rh:m 24 hour~). P1 Pt.
Mai ntain tht’ pipeline m:uks and avo1d.1heJlagg_ed areas when excavating.
Contact the company again if 1he pipeline is acc1~entally damaged during

311
ex

tion operation 50 that che dam:ige can be profess1?n_ally as~essed. Even a tnino/a1•a-
or scr:iping of the pipeline may cause future leaks tf It rem,uns unrepaircd. d~nt

A narurnl gas pipeline ma y be loc:ued near a sewer line. Whe1~ the pipeline is
aged, 3 leak of natural gas may percolate through th~ ~ubsurface sod and enter the :~-
sysrcm. Then, bubbles of natural gas arc obser\’ed mmg through standing Water on ~Cr
surfuce or even in toiler bowls. Th~ odor of natural. gas may als~ be detected when Usi!e
a rooter device ro clear an obstrucuon or blockage m the sewer line. g

When a natural gas /e::ik is ~ppa rent or s_uspccted. anywhere, gas companies recolll-
mend rhar indi\’ iduals comply w1th the fo llowing practices:

Leave the ::irea immedia1ely by foot and leave the doors open.
Do nor light a march, start or srop an engine, .u~e a telephone, turn light switches or
appliances on or off, or perform any other act1v1ty tha t may generate a spa rk.
Warn others to sray away from the scene.
Contact 91 J or the gas company from a distance of at least 1000 feet (300 m) from
the leak.
Do nor ammpr ro extinguish a natural gas fi re, but ca ll the fire depanmenc.
Do nor arrempt to opera te pipeline valves.

Gas companies also recommend that residents and workers know the location of tht
incoming natural gas shutoff valves into rheir homes and other bui ldings so this inforllt.1-
tion can be rapidly conveyed ro firs t-on-the-scene responders when necessary.

12.5-E BULK SOURCES OF METHANE
compr@s~ natural gas Aside from its transference by pipeline, natural gas is also transported as compressed
(CNG) • Methane as a natural gas, or CNG, and the cryogenic fluid ca ll ed liquefied natural gas, or LNG.

liq ue fi PdnattJra l gas

cryogenic liquid

comprened gas Compressed natural gas is an alternative motor fuel whose use to power American
motor vehicles has been strongly encouraged since at least the mid-2000s. When com-
pared ro motor gasoline, CNG is a desirable \’ehicular fuel, nor only because its com-
bustion provides a high hea r value but because fewer volatile organic compounds
(Figure 7.J-J ) are components of rhe vehicle ‘s exhaust. Given this positive environmen-
tal outlook, compressed natural gas has been chosen by severa l America n municipali-
ries fo r fueling an entire fleer of buses, raxi cabs, refuse trucks, and other city-owned
vehicles. Businesses, too, like United Parcel Service, use CNG instead of diesel oil to
power rh eir su rface vehicles. When vehicles are powered wi th CNG, the fuel is stmd
in cylinders located in the trunk area, under the side panel of a va n or school bus, on
the frame, or in rhe bed of a truck.
. During rhe first decade of the rwemy-firsr century, it first became popular ro transport

liquefied narural gas over long distances in large, cylindrical ra nks on speciall y construcwl
refrigerated ships. Transporting LNG is more cost-effecri ve compared ro transporting
CNG. As noted ea rlier in Table 2.10, when methane is cooled ro -258°F (-161°CJ, tht
liquid volume is reduced ro 11650th of its gaseous volu me. By cooling natu ra l gas to 3
temper:ru~e equa l to or less rhan this value, the gas is converted into LNG.

LN.G is no_w transp~rted from foreign plants in Nigeria , Trin idad, and Tobago IO
domemc pons rn the Urnted Stares. Ir then is transported on land by mea ns o( refrigrrated

486 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part
1

k irucks, del ivered ~o r~gasification terminals wh . . _
iJrl d as [he gas by p1pchne to its destin::it’ 1 . ere rt ts convened to CNG, or crans-insula.red ranks. ion. t is ::i lso stored until needed in double-

When shippers transfer CNG by pipeline
able gases) br any means, DOT requires a;:; ~a;ion C;’\JG o r LN? (or othc.r flam-

addition of ethyl mercaptan, thiophane, or amyi ~e·rf};::25 tha t it be odomed by

Eth)I mcn:~ptan
( l ,2-Eth.:ln

?M1-7H2
Cl·h CH, “-/ .

Thioptunc
CTcu-ahydroth1or~ncl An1) l mercap1ao

(Pcnune1h10IJ

These sulfurous 0.rg:inic compounds ha ve such offensive odors that their detection is help-
ful when attempting to locale gas leaks.

A.t 16 C.F.R. S306.ll, the U.S. Federal Trade Commission requires retail disrribuwrs
103ff1x a black-and-orange label that resembles the following on CNG dispensers:

MINIMUM
90%

METHANE

This label identifies compre~sed natural g::is as the alternative mowr fuel and provides the
minimum methane fuel raung as 90% by volu me. The commission also requires new-
\’chide manufacturers and used-vehicle dealers to affix the label on a visible surface of
each vehicle powered by CNG.

12,6 LIQUEFIED PETROLEUM GAS
Most people are first introduced to propane or n-butane as the substances used to fuel a
backya rd barbeque grill. As noted ea rlier, propane and n-butane are alkanes having the
chemical formu las C3Hs and C4H 10, respectively. The liquid mixture of these simple
hydrocarbons is called liquefied petroleum gas, or LPG. Although largely produced as a
fuel, its constituents also are used as propellants in aerosol ca ns.

There are three types of LPG: a propane/butane mixture, commercial propane, and
commercia l butane. The propane/butane mixture consists of approximately 60% propane
and 40% butane by volume; commercia l propane is approximately 92% propane; and
commercia l butane is approximately 85% 11-butane. Although the main constituents of
LPG arc propane and n-burane, sma ll amounts of ethane, cthene, propene, butene, isobu-
1ane, isobutene, and isopentene also may be present. For commercial use, LPG is generally
isola ted as a by- product from the rectifiers used for treating natural gas.

At most ambient conditions, propane and n-butane are colorless, odorless, and tasteless
gases, bur DOT and OSHA require the addition of an odorant to each type so that leaks
may be easily detected. Additional phrsical properties of propane and n-butane are noted in
Table 12.7. These data show that when propane and n-butane burn, they evolve af amount
of heat rnnging from 2550 Btu!&’ (101 ,000 kjlm3) to 3200 Btu/&’ (133,000 kJ/m ). Conse·
quentJy they are highly desirable as domestic and industria l fuels.

Th; data in Table 12.7 also show that propane and n-burane readily liquefy under
modera1e pressure. Hence, when pressurized in steel cylinders, each of the three ~ypes of
LPG exists as a liquefied compressed gas. These data also sho””.’ t~at_ 11-burane liquefies
near the freezing point of water. Consequently, i1s use

0
as a fue l 1s ltm1ted when the tern•

perature of the surroundings is colder than 31 °F (-0.5 C).

liquefled petroleum

three compressed
commercial products
consisting of a mixture
of liquefied propane
and butane

LPG

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 487

r Md,iiifMM!Mi4\G,Hi:14i:i#hbi~ PROPANE fl•BIJTA.NE
-30S”F(-187″Q

~M~,tu~o~g~poE'”~’=~~~~;;=======t~–4~9•~,(~–4~5’~C)c========~~-t”t6″F(-13a,q ~oiling point ll ‘ F (-O.s•q
Spec1ficgravityat68″F(20’ C) O.SB 0.6Q

Vapordensity(air = 1) l ,52 2.04

:_:Fl•::•h~po::i”:::’–,———t,;;-l;;;S6~•F,,(-;ol;,;-04’C) _ _ _ _ T”;_;::,76’F(-&o-q
Autoignit ion point 874″F (468″0 761’F (40s•o
Lower flammable limit 2·2″ by volume 1.9¾ by volurn,
Upper flammable limit 9.5% by volume 8,5% by volun,,
Heat of combustion 25S0Btu/tt’ 3200Btutftl
l32″F (O”Q and 1 atmJ (lOl,OOO kJ/m 3) (133,00o kJlrn~

LPG and its constituents pose a health hazard as an asphyxiam (Section
10

J-A
Individuals who inhale them for a prolonged period lose ~onscio~sness because th;y a!~
denied sufficient oxygen. Prolong7d exposure to LPG or either of its constituents P0Sts a
potentia l threa t to life by suffocation.

SOLVED EXERCISE 12.5

bottled gas•Broadly,
any gai stored under
pressure in a portable
gas cylinder, but more
speclficalJy, propane,
butane, ora propane/
butane mixture stored
under pressure in a
portable gas cylinder

wtry 1s propane generally mo,e iuitab1e than butane for fueling mobile appliances and heaters during very told
weather7

Solution: Jt1s thegasteus state of a fuel tha11gn11tsand burns The data m Table 12 7 1nd1catethat propal’l!~i
gas at temperatur~ equal to or greater than -49°F {-45°( ), whereas butane 1s a gas at temperaturtS equal

10
er

greater than 31°!={- 0 s•o These facts severely !1m1t the use of butane as a fuel rn cold climates because 1t/ffllL’ll
hquJd There are few areas of the wci1d where ttmperatures colder than -49°F (-45°() are expenenced; c~
quently, propanegenerallyismoresuitablethan butane forfuehng mobileapp/1ancesandheaters

12.6,A BOTTLED GAS
The commercial types of LPG usually are shipped under pressure by motor or rail tankcar
from peuoleum gas wells and refineries to filling stations, where they are transferred into
a bulk storage tank. Distributors then transfer them into horizontal or vertical dispensers
from which they are further dispensed into far smaller portable, thick-walled cylinder;
and tanks. The contents then are said to be “bottled” and the gas is commonly referred to
as bottled gas. The gas cylinders and tanks are convenient to deliver to rural areas ~nd
ocher locations where natural gas cannot be supplied economically by pipeline. They art
always stored outdoors, because local codes and ordinances prohibit indoor storage.

Ca re muse be exercised in storing porrable LPG tanks. When it is rapidly subjected to
incense heat, they can rupture. The rank may also be struck by lightning or be exposed ro
another ignirion source. In these instances, the rank contents immediately ignite as a fire-
ball as they expand into the atmosphere.

LPG is also transported by 1ruck to fill permanently installed tanks. These ranks are
always situated ar prescribed distances from homes and other major buildings and con·
nected by means of copper tubing to appliances and furnaces loca1ed indoors. .

The largest volumes of LPG are found at LPG-fi lling stations, which arc loca_re~ in
virtuall y every major city. Ar these fi lling stations, the LPG genera ll y is contained within ~
bulk storage tank having a maximum capacity of less rhan 90,000 gallons (340 m3).

488 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part 1

12_6.e LPG AS AN ALTERNATIVE MOTOR FUEL
G c.in also be usC’d as an altC’rnativC’ motor fu I

1
.

t~iurrd as the world’s fi rst LPG.fuC’ led car. t” • n l008, Hyundai’s Eltmtra was manu-
At 16 C.F.R. S306. l2, the U.S. Fedrral Trade Co ..

coaffLx orange-and-black labels on their LPG dispense:~:~:~u~~:,~:’~-~~t~’.~t~~;~:ors

MINIMUM
90%

PROPANE
MINIMUM

90% PROPANE
2% BUTANE

Tht~e labds identify the’ a_lternative m~tor fuel as liquefied petroleum gas and provide the
rni n1mum perce~tage 6> ,olume as 90¼ propane (on the left ) and 90% propane and 2%
buiane (on the nght ). T~e U.S. Federal Trade Commission also requires new-vehicle man-
ufacturers and used-vehicle dealers to affix the label on a visible surface of each vehicle
ihar is powered by LPG.

~ at s~1al actions should foef1ghtei-s implement when r~pond1ng to the SCffie of a car crash rnvotv1ng a LPG-,~:ed l’th1cle?

Solution: Once the vehicle has been slilb1hzed and secured aga nrt movemfflt, f1rdightm should f1m a’.>Certam
t>iatrt 1spoweredby lPG Thenatureof thevehicular futl mayberead1lyiden11fiedbylocat1ngthelabelaffaed
to the ve hicle Having determined that the vehicular fuel 1s LPG, fim-on-the-scene re~nder; should then tum
U1egas cy11nder valvehandle tothe “oft• postt10n and~archfOfs1gnsoffutlleakmgfromrupturedconneC11on
fttngs andhnes. F1ref19hter;shouide)(ljngu1snallnearby firesandremoveaUpotent1alsourcesofheat The use
offlaresshouldbeavo1dE’dalthoughnonsparkingmarbr;orconesmaybeusedtocordonoffahazardzone
1,1os1 1mportantl~. firefighters should bear m mmd that when LPG cyl,nders are exl)OS@d to 1nteme heat, they wlll
r11 Pture and catastrophically releasE’ th!’1r contents to W ffi..,ronment as a BLEVE (Sectlon 3 8-Al This s1tua11on
snouldbeavoidedatallcosts

Ethylene Propylene

12.7 ETHYLENE AND PROPYLENE
Ethylene and propylene, or erhene and propene, respectively, arc 1he common names of
the simplest alkenes. As noted earlier, their chemical _formulas a~e CzH4, or CH2=CHi,
and C3H6, or CJ-1 3- CH=Cl-11, respectively. The physica l ~rop_em_es of ethylene and pro-
pylene are provided in Table 12.8. The tabulated infor~atton m~1ca~es that ethyl.en~ and
prop)•lene pose the ri sk of fire and explosion when either gas 1s discharged within an
enclosed area, . h II

Ethylene and propylene are produced in the United St~tes 1~ larger amoum
1
s t an a f

. I . d h e used primarily for the manu acture o other subsrnnces. In the chem1ca 10 u.Stry, t ey d
14 6

_
8
·) b t they are also used as

polyethyle~e and polypropylene (Semons .14.6-f ~~er ch.emic~l ~rodum .
raw materials fo r the manu fac~ure of a van~ryl :nJust . For example, in the agricultural

Ethylene is also used outside the chemtca . ry
field, it is used as both a plant regulator and an herbicidr: . .

I b hastening the uniform npen mg of apples,

i
I Ethylene performs as a plant re~u at~r .Y . h siimulation of seed germination and

bananas, berries, figs, tomatoes, and Citrus ruits, t e d Organic Compounds: Part I
Chapter 12 Chemistry of Some Hazar ous 489

1.3·

Butadiene

MhiiiA=IMi&SWU:44\.tl-i§ ;~
ITHYLENE ~ YLENE ·

Meltingpoint -272″F(-169″C) , -30~ (
-ies•o – 1ss”F <-104"Cl _54.F l-1s•o

Boiling point

Specificgravityat68′ F(20″C)

Vapor density (air “‘ 1)

Flashpoint
Autoignition point

Lower flammable limit

Upper flammable limit

Heatofcomburtion
[32″F WO and 1 atmJ

0.001 o.s,
1.0

-2 l3″F (- 135’0

842″F(4SO’ C)

3.1 % by volume

32% by volume

21 ,600Btu/lb
(50,JOO kJ/kg)

sprouting; the curing of robacco leaves; the_ production of flowers in pineapples; and the
normal thinning of flowers, leaves, and frun from trees as they mature.

Ethylene performs as an herbicide by controlling the spread of wirchweed in corn,
cotton, peanut, and soybean fields.

Ethylene and propylene can pose health hazards as asphyxiams, Individuals who inhale
either gas for a prolonged period lose consciousness because rhey are denied sufficient oxygen
Prolonged exposure ro these gases poses a potential threa t ro life by suffocation.

12.8 BUTADIENE
l ,3·Buradiene is a colorless, highly fla mmable gas wirh a mild gasoline•like odor. Its phys•
ical properties are provided in Table 12.9. The gas often is manufactured ar petroleum
refineries by rhe dehydrogenation of l·burene and 2·burene.

CH, CH,CH =CH,(g) – CH2= CH – CH = CH,ig) + H,(g)
1-BUl)nt

CH3CH2=CHCH3(g) – CH2= CH- CH = CH,ig) + H1(gJ
1-Hut~ ne

I .J -Bul:tdiene

l, l-Hu1ad1me

1-l)Jrogcn

H)drogcn

Md=l!ifii Physical Properties of 1,3-Butadiene
Melting point
Boiling point

– 164°F (-109″C)

Specificgravity at 68″F(20°q
23’f (-4 .7′ ()

1.88
Vapordensity(air: 1)
Flashpoint

1.97

Autoignition point
-105’F(-76’C)

Lower flammable limit
804″f (429′ ()

Upper flammable limit
2% by volume

11.5% by volume

490 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

J-But;id iene is 3 \’Cry reactive substance h
I,! for molecule, to fo rm pol)’buradiene ·(S e~en reacts Spontan eously with itself, mole-

;~>eis mixed \\’. ith ;in inhibitor during its pro~:~~i~~ 4· 11 ·B). To prevent the reaction, the
Conunerc1ally, the product is ca lled but d’ · .

11 often is transferred from production planr: b;n;~:~~:~ut. use_ of the numerical prefixe~.
cal pbnts where the gas is used to manufacture va ri P1~elines to nearb_y petrochem1-
auiomobilc 1ir~s, a~pl ia nce pans, pipes, and synthetic ~:r1; pes of S)’ntheuc rubbers fo r

I J-Bu1ad1ene 1s produced as a product of h • ·
prod~m, wood, and tobacco. Individuals who 1\,: ~~’:,mp;’.” combusti~n of. proleum
i1•hkh butadie_ne is produced or ~sed are more likely ~ha~nt~: ~:anre~:I ustn: laat~:ans ;:
brea1he butadicne. B_eca.u~e butadiene is formed during the incomplete ::bustion of
petroleum ~roducts, individuals who routinely breathe 1•ehicular exhaust are also at risk
of contracting can_cer. In the ‘-:0 rkplace, OSHA requires employers to limit emplorce
exposure tokad maximum butad1ene concentration of I pan per million, al’eraged O\’er an 8-hourwor ay.

When individua ls breathe 1,3-butadiene, thev experience nausea ere nose and
throat irritation, h.eada~he, and decre~sed blood pre.ssure and pulse rate. Long:term ; xpo-
>ure to 1,3-but:diene increases the r_1sk of .com~acting stomach, blood, and lymphatic-
srs1em cancers. Based on these studies, ep1dem1ologists rank 1,3-butadiene as a human carcinogen.

Beca use 1,3-butadiene is one of several carcinogens formed during the incomplete
combustion of tobacco,

9
smokers are exposed to 1,3-butadiene when they inhale tobacco

smoke. Beca use it is highly reactive, scientists beiie1·e that the substance poses by far a
more significant cancer risk to smokers and individuals exposed to secondhand smoke
compared to the other carcinogenic components of tobacco smoke.

12.9 ACETYLENE
Acetylene is the simplest alkyne and the sole member of this class of compounds that has
commercial importance. As noted earlier, its chemical formula is C2,H

11
or H-0:=C-H.

The physical properties of acerylene are pro\’ided in Table 12.10.

ifrjjjij/,; Physical Properties of

Acetylene

Me lting point
Soiling po int

Specif ic gravity at 68″F(20″C)
Vapor density (air= 1)
Flashpoint
Autoignition point
Lower flammable limit
Upper flammable limit
Heat of combustion [32″F (0°C) and 1 atmJ

Sublimes
– 118’F{-83°C)
0.91
0.899
O’ F(-18°()
635′ F(335″C)
3%byvolume
82%byvolume
12018tu!ft3 (49,900kJ/m3)

IN. Sarhiakumar et al., ~Mortality from cancer and other causes of dea1h among syn1hc1ic rubbtr workers/

fcmp. bwiro11• Med., Vol. 55 (1998),pp. 230-Z!:;kt C.Ot1~$ DiseJu: Tl,e Biology arrd Btli~l’i~ral Bas is ~:

Acetylene

Repon of th~ Surgeon Gener3l, Horii TobaccoD~scase Control and Pm·enrion, Atlama, Georgll (_0\0) (ISB.
S111okmg-A11, ib 11tab/e Distase, U.S. Centers for

IJ: 978-0- 16-084078-4). . f 5 e Hazardous Organic Compounds: Part I Chapter 12 Chemistry o om 491

I
I
I””

7

I
‘I
I _,_

I I
I

dehydrogenation • A
chemical process
typically conducted
at a h igh temperature
and pressure and
during which molecular
hydrogen is removed
from a compound

In the United States, acerylene is produced mamly by cracking natural gas.

~C H..i(g ) – C2H 2(g) -,.. -~H i (g)
ACtl ) kne

In this instance, the cracking involves dehydrogenation. Although pure acct ·le .
colorless gas with an etherea l odor, industrial-grade acetylene can be fo ul-s > 1/e 1s a noted in Section 9.7-8, industrial-grade acetylene sometimes is produced by ~Tl~ ing. As
ca lcium carbide. Because calcium carbide generally is contamina1ed with ca]~ rolyzing
ph.ide, the foul-smelling phosphine is simultaneously produced. ciurn Ph0s-
. Acetylene is an _innarely unstable substa.nce, decomposing a~ a n explosive ra te i
;~

0
~1:;:;.cs when 1r has been compressed m excess of approx1macely 2 atmosphe::

The decomposition is especially likely when the comp ressed acetylene has been sub· d
to thermal o r mechanical shock. Jecte

Nor only is acetylene flammable and innatel y unstable, but it a lso reacts with c .
pounds containing the copper(!) ion, especially in moi st air. The product of this chem~~
reaction is copper(I) acetylide, which when dry, can decompose explosively.

H -C:= C – H(g) + Cu * (s) – H -C=C -Cu(s) + H ~(aq)
Acct)kne Copper(I J1on Coppcr(l) ;Kclyhdc Hy

To reduce or eliminate the po1 en tial for this explosive reaction, welders and other indi-
viduals who work with acetylene avoid using copper fittings or tubing on arnrlene
cy linders.

When spa rked , a mixture of acetylene and oxygen burns with an intensely hot
name, reaching temperatures as high as 5400°F (2982°C), This combustion proms
yields 21 ,400 Btu/lb (49.9 kJ/g), which is put to use when we lding and cutting steel and
cladding meta ls.

Careless welding practices have caused many major fires. Heat that is sufficient to
weld steel is capable of triggering the ignition of many other commonly encoummd
f1ammable materials. When acetylene is used to generate heat fo r welding, the risk that
its hea r of combustion will be transmitted to nearby f1ammable materials should alwap
be acknowledged.

To counteract its potential decomposition, a special method is employed co safd)’
compress. ~nd store acetylene within steel cylinders. Thi s procedure rakes advantage of
the solub1hty of acetylene in acetone. One volume of acetone dissolves approxim;m\y
25 volumes of acety lene at 1 atmosphere (101.3 kPa ) and 300 volumes at 12 atmos·
pheres ( 1216 kPa ). By di ssolvi ng acetylene in acetone, gas manufacturers increase ihe
amoun~ th~c may be safely compressed in cylinders by means of the three-step p~ocess
sho~\’n 111 Figure 12.5. First, they pack the cylinders with a porous medium consisnng_of
3_ m~xture of mo_nolithic fille r and ba ls3 wood. Then , they satu rate this mediu~ wi th

liquid ~ce~one. Fi ~ally, they charge acetylene at a presc ribed pressure into the cyhnders.
~v here 11 di~solves m the acetone. As acetone solutions, acetylene typically is compret~
m sreel ~y lmders of various sizes whose volumes range from 9.9 cubic feet (0.28 m )t
390 cubic feet ( 11.04 ml) .

Acetylene poses_ a health hazard as an asphyxianr. Indi vid uals who inhale acecykr
fur a prolon~ed .period lose consciousness because they a re denied sufficient oxyg~n ir,
:1L~:r:::lti:~:1rat1on. Prolonged exposure to the gas poses a potenri:d threat to hft }

492 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part 1

Removable metal cap

Acetylene capacity
appro1uma1ely –
275 ft3 at 250 PSI – _ –
and70•F – _
(21 “C) ~- _ _ _

°§§

12!j3115~}
~er11~dlametsl’_

FIGURE 12.5 Th1~cut•
awayof an acetytene cyl-
•nder 1l\umate\ 1ts unique
lea:ures Themonolith,c
Mlerorbalsawood 1sa
porous materi al that is
chargedw1lhacetone.
into which the acetylene
subsequently d,~!>Olvu

Monolithic filler
or balsa wood

12.10 TRANSPORTING THE SIMPLE GASEOUS
HYDROCARBONS

When shippers offer acetylene, butadiene, ethylene, methane, or propylene for transportation,
DOT requires them to identify 1he chemical commodity as shown in Table 12.11 on an
accompanying shipping paper. All labeling, marking, and placarding requirements apply.

illliifiii
HYDROCARBON

Acetylene
Butadiene
Butane
Ethylene

liquefied petroleum gas

Methane, compressed

Methane, cryogen ic
Propane

Propylene

Shipping 0e’.icnpt1ons of the Simple Gaseou’.i Hydrocarbons

SHIPPING DESCRIPTION

UN1001 , Acetylene, dissolved, 2.1

UN1010, Butad!ene, stabil ized, 2.1

UN1011. Butane, 2.1

UN1962, Ethylene,2.1
UN1075, Petroleum gases liquefied, 2.l
o,
UNl075, Liquefied petroleum gas, 2.1

UNl971, Methane, compressed, 2.1

UNlgn, Methane. refr igerated liquid, 2.1

UN1978, Propane, 2.1
UN1077, Propylene, 2.1

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 493

494

DOT also requi res the issuance of a ha za rdous i:naterials sa fety permit (Section
t tor carriers before they transport methane as either a compressed gas or

3
. 6.101

1~: ~ wi,h , me

When LPG is transporr~d in a DOT Specification_ M _330 or 33 J tank truck, Do
requires ca rriers ro d~tm~me wher_her. the com~o?uy 1s corrosive and 10 indicate thT
appropriate information m the shtppmg ~esmp110~ _as ~n .. e of the _following: “RQ•
UN I075 Liqudied petroleum gas, 2.1 , (Non-corrome), RQ, UNI075 Pe,

1
,

ga~, liq~efied, 2.1 (Noncor),” or “RQ, UN1075, Liquefie_d petroleum gas, i..
1
(~::~l!J

Q and T ranks).” Noncorrosive LPG may be transported m tank trucks thac hav
constructed from a special steel that is “quenched and tempered,” or “Q and T.” e

When a Oammable gas is transported in bulk by highwa y or rail, its name m br
displayed on two opposing sides of the rankcar used fo r shipment. When it is transt
by rail in a DOT-113 rankcar, DOT requires their carriers to di splay FLAMMABLEo~~
placards on squares having a white background and black border. S

When shippers offer nonbulk ~uantities of unodorized LPG fo r transponarion, DOT
requires them to mark the packaging NON-ODORIZED or NOT ODORJZED near th
spot where the proper shipping name is marked. e

12.11 AROMATIC HYDROCARBONS
The word aromatic suggests that aromatic hydrocarbons are compounds possessing
fragrant odors. The odors of some simple aromatic hydrocarbons actually are fragra nt
bur otherwise, this perception is misleading. Aromatic hydrocarbons are regarded ,;
compounds whose molecules are composed of one or more special rings of carbon
a1oms. These compounds are typified by the substance ca ll ed benzene, the simplrn
aromatic hydrocarbon. Its chemical formula is C6H6. Although the molecular structure
~f benz~ne ~a )’. be represented by either hexagon shown on the left in the following
illustrauon, u 1s more commonly represented by a hexagon wit h a circle inside, as
shown on rhe right:

00 0
Aromatic and aliphatic hydrocarbons thus are differentiated by rhe fact that rhe

~olecular struc~ures of aromatic hydrocarbons have one or more hexagonal benzrne
nngs, usually with side chains, while the molecular structu res of a liphatic hydrocarbom
do not. Hereafter, the molecular structure of benzene wi ll be represented by the hexagonal st

ructural formula with the inscribed circle. Ir is called the benzene ring. Although thr
symbols of

th
e carbon atoms are nor written as part of the hexagon it is always under· st

fd
th

ac a carbon atom occupies each corner of the hexagon wher; i1 is bonded to rwo
ot er carbon atoms and a hydrogen atom. ‘

Wh~n any one of the six hydrogen atoms in benzene is substituted with a methJ”I
rh:”!t~’.,:T;:;~~~t ;;:~i”‘”I’.’ is called methylbenzene, or more commonly, roloe~
as follows: uene is C61 l s-CH3, and its molecular structure 1s represent

o-CH,
When two hydrogen atoms in th b h I upl,

the resulting compound h h h e . enzene molecule arc substituted with met r
position the methyl grou;: itn ~~re:m~~:r formu la C6H.1-(Cl-!3b Bec?use it is poss1~1:r~~

Ch . 1 fercm ways on the benzene nng, three mu apter 12 Chemistry of Some Hazardous Organic Compounds: Part I

6-· ·6 .6 6-. ¢
onho B

isomers for the formula C6!—Li-(CH3)i exist. These three compounds are the struc1ural iso-
mers of dimethylbenzene, or xylene. Their molecular structures are written as follows:

OCH,
l .2-0111ic lh ) lbi:n1cn~

\o- X)lcnc)
!.J-Dn!lelh) lt-enun~

(m•X)kllC)

¢
CH,

l ,-l-D1n1c1h)!lll:n1.cnc
IJ>·X)lcnc)

In the common system of nomenclature, the prefixes ortho- (o-) , meta- (m-) and
para- (p-) are employed to identify disubstituted benzenes. Ortl,o- means “str~ight
3head,” meta- means “beyond,” rind para- means “opposite.” In commerce, the isomeric
mixtures of xylene arc sometimes referred to as either .. xylene” or “xylene(s)” with total
disregard for their isomeric distinctions.

The simplest dcri\’atives of an aromatic hydrocarbon are compounds in which a sin-
gle alkyl substituem has replaced a hydrogen atom on the benzene ring. These compounds
are named by identifying the substituem followed by the word “benzene.” For example,
the compounds having the fo llowing molecular structures are named ethylbenzene and
11-propylbenzene, respectively.

Eth) lbcnmll:

O CH,CH,CH3
n- l”rop) lben~<' nc

When two substituenrs have replaced two hydrogen atoms, their loca tions on the
benzene ring must be identified. The molecular structures of the three compounds in Fig-
ure 12.6 illustrate two arbitrary substituents, A and B, positioned on the benzene ring. B
is located in the ortho-, meta-, and para- positions relative to the position of A. When
naming the disubstituted benzenes, 1he italicized letters o-, m-, and p- are used as prefixes
to identify 1he location of one substituent relative to the other one. When one of the two
substituenrs is a methyl group, the compound often is named as a derivative of toluene as
1hown br the following examples:

p•Elh) ltolutn~ o•hobUl}l!olucnc

ortho- (o-), meta- (m•).

prefixes used to name
disubnituted benzenes
inthefollowing man-
ner: ortho-referstothe
subnitution of the
hydrogen atoms
bonded to adjacent
(the first and second)
carbon atoms on the
benzenering;meta-
referstotheir subnitu-
tion on the first and
third carbon atoms;
and para-refers to
their substitution on
the first and fourth car-
bon atoms

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 495

t1 1
11

l:1

des,gn.i tion for the
benzene rmg when 1t b;
namedasasubrutuent
on another molecule
(C.,H~-l

d6ignationforthe
seven-carbon atom unit
coruittingofcombined
phenyl methylene
groups (Ci;H5CH2- J

aryl group {aryl

the phenyl or benzyl
group of atoms.
obtained by removing a
hydrogen atom from
thechemiu t formulas
of benzene and tolu-
ene, i.e ., C.H,- and
4 HsCHz-, respectively

BTX The collective
name given to ben-
zene.toluene, and the
xylene Isomers

illiiifiN

In the IVPAC srstcrn, when rwo or more alk)·I groups arc bonded to the
rhe resulrmg hydrocarbon 1s named by hsrmg the al kyl groups alphabcucally
mg the first group with a I . Each of 1hi: six ca rbon atoms in the benzene ruig
bered from t 10 6. Two exampli:s that illustrate the use of this rule for
deriv:rn,·es of aromatic hydrocarbons are shown next:

I-Bh)l•2 nprup) lbcnLtnc I bol’ll!}I l ,, prup) lbcM~n~

Aromat ic hydroca rbons sometimes arc named by ident ifyi ng th e C H
C6 H;CHr groups of aiom:;. Cb! I;- and C6H5CI Ir arc called the phenyl :nd
benzyl group, respectively. They are examples of aryl groups, or aryl substituents. nd

-0 -CH,-0
A~n, }I group

Thus, the compounds having the following molecular s1rucrures are named phen}·lrth
1 ene and dibenzylacerylene, respecti1·ely. ) ·

01 tx-n,} llCcl)l~,1,:

12.11-A BENZENE, TOLUENE, AND XYLENE(S)
Benzene, toluene, and xylene are the three mos! commonly encountered aromatic h)·dro-
carbons. They arc sometimes referred to collectively by the acronym BTX, Benzene, to]u.
ene, and xylene(s) are colorless, water-insoluble, highly 1•olacile liquids. Some importam
ph)•sical properties of benzene, toluene, and xylene{s) are provided in Table 12.12. Their

Physical Properties of Benzene, Toluene, and the lsomem Xylenes

BENZENE TOLUENE / o-XYLENE m•XYLENE I p-XYLENE
Meltingpo,nt 41 ‘ F(S4″C) j -139′ F(-95′ C) ( -15′ F(-26′ C) – 54″F(-48′ C) 55′ F(13’ C)
_,,_m~,,~po_;_”‘—–i-c.:.:l116″F_1s_o·c_1_~/-” _’ ‘_F1_111 °c) / 291 ‘F(1 44’Cc-J-t-,-.,-.,-1,-,,-.,-1-,1-,-so–,-11″‘JS:-:’O-
specificgravityat68’ F(20·O 0.88 / 0.87 1 0.90 0.87 ! 0.B6
Vapordensity(air= 1} -~,-;, -;;_, —-“-:-, .:-‘, —lt’l:::.,::__–+3′.::_7::___ ___ l;._:l’.:.7::__ __
Vapor prern.ire at 68′ F (20′ 0 ‘ 75 mmHg I 22 mmHg 8 mmHg 8 mm Hg ) 9 mmHg
Flashpoint l 2’ F (- 11 ‘ Q ) 40′ F(4.4″() / gO’ F(32,C) B4′ F(29,C) Bl ‘ F(27’ Cl _

Autoignitionpoint ~ ‘ F(S62′ 0 I 997′ F(Sl6′ C0 867″F(464′ C) 982′ F{528″C) ) 984’ F(S29’Cl
Lower flammable limit , 1.4¾ byvolume j 1.4%by,ol”me I.O”by,ol”me ‘ · ” ,. ” 1.1% by volume I l . l¾byvolurl’.t
_Upper flammable limit 8% by volume I 6.7% by volume I 6.0% by volume 7.0% by volume I 7.0% by vo~
Evaporat lonrate. (ether= l) J_!.s ) 4.5 I 9.2 9.2 I 9.9
Heatofcombustoon 18 184Btu/lb 18200 -7 -r —
[32′ F(O’C)and 1 atmj (4i300kJ/kg) {4i3ooet~’lb 18,400Btu/lb , ,8,4008tu/lb j 18,400Btulibl

• ‘ J/kg) (42,B00kJ/kg) (42,800kJ/kg) (42,B00kJ/kg

496 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

Aashpornts. flamm,1b!c ranges, and heats of combust1
l>soci:11ed with them is fire and explosion. Their comb on mdica1e 1hat the primary nsk
Jucr ion of smoky ~arncs consistmg of particulate maustion 1s characterized by the pro-
l”‘Jynucle:1r aromatic hydrocarbons (Section ll . \2-C) a~:~r~o which the cancu-causing

Benzene, rolu.ene, and xylene are manufactured b , ·
c:1i:ilrnc reforman~n of alkyl cycloalkanes at hi h tc Y_se\eral procrsses mcludmg the

J chrmJCal reacuon involving the refo m g f mpcrature and pressure. Reformation
~tha substances. It .almost alwa)’S occurs rwi~~gt:c sr;;tl~cules into different molecules of

When naphtha 1s suhiccted to the conditions of c~u tan~ous loss o~ hyd.rogcn.
C}·doolkanes arc converted 1mo compounds within the 8~tic uforma uon, 11.s constit~cm
il!U>m1te reformation reactions that result in the production of t.:~~~~:l~~~::\:~~ :~.;~::~

Q-rn,1,1 Q,,1 + 311 ,,”
~ CH1(g)

~ CH1(g)
CH3

1,J.LJ ,n~ th)IC)dohruoc

lol u,: ,.._,

0-CH,lol +

CH ,
11 X}kno.· ll)dmi;co

In the che~1ical industrr, P-xyle.ne is the most commercially important xylene isomer.
h competes with naphthalene (Section 12. 12-A) as 1he raw material needed to manufac-
ture phthalic a~ydri~e, a substance widely employed for the production of certain resins
and pol}·esters mcludmg poly (ethylene 1erephthalate) (Sec1ion 14.2-B ). Table 12.12 shows
that the. boiling points of m• and p-xylene are very similar. This similarity permits them-
and p- isomers ro be sepa rated from 1he o• isomer. The isomeric mixture is heated to
rnporize its components within two temperature ranges; then the vapors are condensed
~nd i~dependently collected, Fina.lly, the p- isomer crystallizes as a sol id, which allows its
1solmon from m-xylene by fi hratlon.

Although benzene once was a popula r industrial solvent, it is no longer widely used
fo r this purpose because workers’ exposure to benzene vapor caused 1hem to contract
acute mrelogenous leukemia and aplastic anemia (Section 12. 11-B). Following thi s dis-
covery, indust rial employers turned 10 using toluene and xylene as replacement solvents.

Notv.•ithstanding that worker exposure poses the risk of contracting cancer, the BTX
group of compounds still is used by the chemical industry in substantia l quantities as a
raw material for the manufacture of other organic compounds. For example, benzene is
used to produce ethylbenzene and isopropylbenzene.

Q 1, 1 + CH! = CH2(g)
O CH,CH3(g)

ll cn,cn~ Et h) krn., 1:Jh)lbc:nl<'hC

olg) + CH3CH= CH~(g1
O CH(CH,1,(g)

lkntc ne Pml’,’nc
hoprop)lt’<'nune

1Cum,.-~1

chem ical react ion in
which certain sub•
stances art reformed
intod,fferent
substances.often
a

81nzen1

Tolu1n1

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 497

I
I’ ii

I

//
1

11

1,/1 —-

Xylenefs)

.acute~logenous
Jeukem J.a • Thecancer
of the blood that
dl!V! fops inwh1te
blood cell.s. often ,mo-
ci.ated with chronic
v:posuretobenzene

.apl.asti t ,1neml.l • A
bonemarTOw injury,
often associated with
v:posure to benzene

d · transported commemally in nonbulk and bulk
Con~i~c;a~T:\~:1;

1

1::i~~ 0?101uene and xylene _form~rly were used as container\
sol1·e1u•b.1sed paints and other coatings, adhesives, mks, and
con1emporary umes, EPA regulations h.1vc- reduced the use o

comfo1~:~; ~
0

: 1~~~: i;:1:~~:·nal nrc-

12.11-B ILL EFFECTS CAUSED BY INHALING BTX VAPOR
Among thC’ simplC’st hydrocarbons,. bC’nzene y~ses rhe most_ serious health risk whrn I!$
vapor is inhalc-d. Short•term effects include d1zzmess, confusion, ?nd asphyx_iation . .\fore.
on:r. in humans, benz~ne is a well-known hemo- and neurotox1cant; tha t is, when hen.
zenC’ vapor is inhaled, rt negari1·ely affe:cs the ~lood and the central ne~vous systems.

Exposure 10 benzene is also assocwted wi_th t~e potential onset m humans of fo~r
types of leukemia (cancer of the blood-formmg tissues and ?rgans )_, one of which 11
acute myelogenous leukemia, a generally _fa tal cancer durmg which the ininiaturr
white blood cells in the bone ma rrow rnulnply uncontrol!a bly . • \1ost blood cells arc
manufacturc-d in the bone marrow. Myelogenous leukem!a usually develops after a
latency period of approximately 15 y~ars. ft~ onset_ us~a_lly 1s

1
accompanied by a second

illness known as aplastic anemia, dunng wh1ch_an rndividua ~ s _bone marrow is irm-m.
ibly injured. The presence of white blood cells m the blood 1s importan t, because thcst
cells fight infection in the body. Consequently, even with treatment, individuals wbo
have contracted benzene-induced acute ~yelogenous leukemia often are more suscepti-
ble 10 infection and have a poor prognosis for full recovery.

Because benzene exposure by humans is dearly linked with the onset of cancer, ep 113(.
miologists d :mify ir as a human carcinogen. EPA estimates that a lifetime exposure to 4
parts per billion benzene in air results in one additional case of leukemia in a population
of 10,000 exposed individuals.

Exposure ro toluene and xylene is nor linked wi th the onset of cancer. Howem, rht
inhalation of their vapors irritates the respiratory system and depresses the ccntnl nrr-
1·ous system. Initially, the inhalation of toluene and xylene vapors causes dizziness ar.d
nausea, and long-cerm inha lation can have a narcotic impact on the body. The long-term
inhalarion of toluene can also be addictive. This dangerous practice, colloq uially known
as glue sniffing, im•olves \’Oluntarily inhaling the toluene vapor emitted by certain ~ut
products like hobby glue. People who regularly practice glue sniffing risk injury to the ha,
hearr,and lungs.

12.11·C WORKPLACE REGULATIONS INVOLVING
THE BTX HYDROCARBONS

OSHA publishes regulations at 29 C.F. R, SS 1910. 1028 and 1910. 1000 that aim to pro·
tect ;orkers fro~ exposure to ben_ze~e, toluene, and xylene.
toluen;~a~le!~:::(:~Isl~~~~s\~~ limit employee exposure to airborne vapors of benzene,

• (he maximum benzene \’apor concentration has been established at I pa~t per mil·
t:~~~;~:;z~::.over an 8-hour workday. This va lue reflects the cancer-causing poten·

The ~ximum tolut’ne vapor concentration has been established at 200 parts per nul·
mn, a\eraged over an 8-hour workday

The maximum xylene vapor concentra;ion has been establi shed at 100 pa rts per nul·
ion, averaged over an 8-hour workday,

498 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

iHlifiii Shipping Descnptions of Some Representative Aromatic Hydrocarbons
,AROMATIC HYDROCAR BON
OR GROUPS THEREOF

senzene

~e
fthylbenzene

150propylbenzene

n-P1opylbenzene

Toluene

Xy lenes

SHIPPING OESCRIPTION

UN1114, Benzene, 3, PGII

UN2049, Oiet hylbenzene, J, PG 111 (Marine Pollutant)
UN117S, Ethylbenune, 3, PG 11——

UNl9 l B, lsopropylbenzene, 3, PGtll(MarinePollutantl
UN2364, n-Propylbenzene, 3,PG lll (Marine Pollutant)
UN1294, Toluene, J,PG II

UN1307,Xylenes,3,PG II

UN1307, Xylenes, 3, PG m

When benzene is present in the workplace, OSHA requi res employers to establish
rtgulated areas where th~ c_oncemration of benzene 1·apor exceeds the permissible expo-
sure limit of l part pe~ million as a ti~e-weighted average limit, or 5 parts per million as
an a\·erag~ conct’nt~auo~ over a 15-mmute period. OSHA also requires employers to post
the followmg warmng sign at the entrances to these regulated areas:

12.11·D TRANSPORTING AROMATIC HYDROCARBONS
When shippers offer a simple- aromatic hydrocarbon or any of its dc-rivati\·es for transpor-
mion, DOT requires them 10 enter the relevant shipping description on an accompanying
shipping paper. Some examples for several reprcsentati\·e aromatic hydrocarbons are
listed in Table 12. 13. DOT also requires shippers and ca rriers to comply with all appli-
cable labeling, marking, and placa rding requiremen1s.

12.12 POLYNUCLEAR AROMATIC HYDROCARBONS
There are more than 500 substances commonly called polynuclear aromatic hydrocarbons, or
PAHs. The simplest members of this class of compounds are a group of structurally similar
h)·droca rbons whose molecules consist of two or more mutually fused benzene rings .
~Murually fused” means that the benzene rings sha re a pair of carbon atoms and the bond
between them. The PAH having rwo mutually fused benzene rings is called naphthalene. The

~··’~ “‘””~ ‘”‘•~ ·-
Anthrocenc Pt>cnamhr-:nc

polynudear aromatic
hydrot.1rbon (PAH)

aromatic hydro-
carbon whose mole-
cules have two or more
mutuallyfusedben-
zeneorother rings

i\Jf}hl hllrnc
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 499

I
I I

‘1// 1,

~l
I I I
I II I ;
I L 500

hettrocydicrompound

Thc- molecules of tbC’ PAHs rna)’ also hJl’C’ four•, fi\’e- . s1_x-. or SC’ \’l’n •member nn
The molccu!c-s of some PAH d e r J\’3 Cl\ ‘C’S consist of bc-nu nc ~mgs fused lo cycloprntc &s.
(C H-) a nd other rings. The molC”cules of some PAH den va11 ves ma y cont:iin a n)I
nu ro C’n or oxygt n arom (that is. J rrnrogen or OX’}’grn a tom subsrnmes for a ring C3r~
aromf. ThC’ submmccs whose molecules possess one or more rmg •Homs other than car
bon :m:· caJ/C”d heterocydic compounds. . . ·

All Pr\Hs are solid compounds ar_ roo~1 temperature. Although ~nd1v_1d uaJ PAI-ts ha1·
bttn isobtrd and ch:i racreriu d, th t’1r mr~rures a re of co ncern pnman/y as haia rdo~c
mJtl” rials. T~ey_dC”compo~e only slowly rn simpler subsrnnces; hence, once produced,

1
~

tend ro remam m the em·1ronmrnt.

• Any compound who~
molKUh!sconu 1non,
o, morermg.aroms
oth~ thancarbon

N1phthalana 12.12-A NAPHTHALENE
t\°aphrha!ene is the only PAH of commercial imporrancr. h is a whi1e to colorless solid
generally described 35 h3ving rhe odor of mothballs. Ah hough ?.i phrh . .ilrne once Wai t/ir
main constiruenr of 3 consumer produc~ u_sed as m~thb~lls,_ this spt”C1fi~ us~ is now dis.
couraged. As noted m Section 12.1 J-A, 1r 1s used pri_m.:mly m the chrmical mdusrry asJ
raw mareri:11 for thr m:inufacture of phth3!1c :inhydnde.

12.12-B SOURCES OF THE PAHs
,\fany processes 3ssoci.1red wuh rhe incomple_te combustion o_f organ_ic materials generate
mixtures of PAHs. Hence, many manufacwnng and process mdus~nes often sptw PAHs
from their smokestacks inro the air. PAHs are also dissolved consrnu_encs of coal tar and
coal tar distillares, crude ~trolrum, and certain petroleum fractions mcluding heavy die-
~ , fuel , hearing oils, motor oil, heavy naphtha, and asphalt. They are also components of
the emissions and residues associated wirh the burning of coa l, diesel oil, wood, wbacco
and pear. They are e\·en found m minute concentrations on bread crus1s, burnr toast, and
the burnt surfaces of meats cooked on barbecue grills at high temperatures.

Beca use PAHs are widely sc,m ered throughout the environment, they are frequend)’
identified in samples of media collected from different sources. For examplr, the)’ m
idenrified as consriwenrs of lake srdiments and the particulate matter of 1obacco smokr.
In the former instance, the presrnce of the PAHs is traceable ro the previous use of coaltar
forsealingpavemenrs.

The most common sou rces of the PAHs are diesel-engine exha ust and the smoh
generated during rhe burning of wood, tobacco, and coal. Typically, they are adsorbed
ro the consri1uenr soot particulates generated during combustion. Because many hea l’)•
duty truck s, buses, and moving equipmen t are diesel-powered, the PAHs produced dur·
ing their use become components of the environmenrs into which their exhaust 11
discha rged. This is a matter of significant concern wh en the exhaust is inadequate! )’
venred from enclosures.

During incomplete combus tion processes, PAHs are produced simultaneously with
soot by a multisrep mechanism similar to that depicted in Section 5. 11. \'(ihen simplr
hydrocarbons are heated ro high temperatures, molecular fragments-such as fm
r~dicals-are produced. These fragments undergo reactions that result in the produc-
uo~ of new molecules. Th e_ original molecules a nd their fragments dehydrogenm
•:~ile ~he new m_olecules s!m1!arly fragment, amalgamate, and conti nu e 10 dehyd~oge-
n e. ‘1hen deh}drogenar10n ha s occurred ro irs maximum extent , all that remains 11
soot or carbon black.

12.12-C ILL EFFECTS CAUSED BY INHALING PAHs

is~ complex m’.xt~re of_p~rricubte ma Her and gaseous com(:°u~d;
h g oxide, carbon dmx1de, mtnc oxide nitrogen dioxide sulfur dioxitk,

me, ane, nzene, phenol. 1,3-buradiene, acro!c.-in, and the
1

vapors of several i~dividual PAJ-1;.
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part

1

n,e p;i rncubte mailer co~~iSts mainly of soot to which the PAHs and orher compounds have
JJsort-ed, \'{lhr:n they arc inhaled, the soot aggr:iva1es chronic respiratory problems.

Jnh.11:won exposure ro soot and crrta in ind1v1dual PAHs has also been linked with the
onset of lung, and catdmva~cular dysfunction. Morem·er, massi,·e numbers of mutated
crl!s emerge in t_he bronchia l passageways and bladders of indi \·idua\s who regularly
inha le d1esel•eng_1~e exhaust, thereby causing lung and bladder cancer. 10.11 For this rea-
son, soot is class1f1ed as a known human carcinogen.

The U.S. Department of Health and Human Services has concluded that exposure to
JI ]east 15 PAHs causes the emergence of malignant tumors at the s11e of contact. The
010Jecu1Jr structures of these compounds are provided in Figure 12.7. These 15 com•
p0unds are among c_he substances th.It the scientific community now suspecrs of niggering
he onstt of cancer tn humans. 1

As previously no~ed, the particulate matter of tobacco smoke is also a source of PAHs,
especially the following: benz(a]anthracene, benzolb]fluoranthene, benzo[,lfluoramhene,
benz[ k ]fluoranthene, benzo[a ]pyrene, dibenz[a,h Jamhracene, dibenzo[a, llpyrene,
indenoP,2,3-c,d]pyrene, 5-methylchrysene, and 7H-d1benzo[c,g]carbazole_l 2 These com-
Pounds arc not cons~ituents of native tobacco le,n·cs but form when the tobacco undergoes
1ncomplrte co_mbust1on. They are suspected of collectively contributing to the onset of the
canctrs experienced by tobacco smokers and individuals expo~d to secondhand smoke.

12.12-D PAHs A ND FIREFIGHTING
Among modern-da y occupational settings, career-oriented firefighters are a major group
of individuals most vulnerable to routinely inhaling PAHs. Fircfighms arc unwtttingl )·
exposed to PAHs in at least the following ways:

Firefighters are repeatedly exposed to airborne PAHs adsorbed to soot particulates
ar1·inually every fire scene.

Firefighters are also exposed to PAHs adsorbed to soot p:miculates in enclosed
areas where diesel engines operate. Such areas include firehouses, where diesel-power
equipment is regularly serviced and maintained and fire trucks idle for immediate use.

These repeated exposures to soot and the cancer-causing PAHs could constitute the basis
for long-term health concerns for firefighters. Scientists denote soot and diesel engine
exhaust as human carcinogens.

To protect firefighters against inhaling diesel-engine exhaust, the enclosed areas of
firehouses should be \’entilated using a local exhaust ventilation system. As a general
polic)’, the idling of vehicles inside the firehouse should be avoided.

SOLVED EXERCISE 12.7

Wh!n em,ned from the exhaust p,pe of an 1dl,ng fire engine, d°’s the el”.haust tend to corxentrate in the IO’Ner
i;r upperreg1onsof an endosed f1 rehouse?

Solution: Becausedese!–eng,needldust is honerthan the temperature oftl1esuriound,nga1, ttrisestothece, l.ng
or ooders1aeof theroofmanendosedf,rehouse Becausetheexhaustconcentratesnearthece,lmg,exhaustfarn
UIOuId be located In the upper regions of ari enclosed firehouse to vent the exhaust to the outside environment

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 501

I

I
I I I

‘1 I
J/11 , Nn l

I

FIGURE 12.7 Based on
1nlorMa:ionfromtheUS
D~rtmt’f’II0fHeal1hand
HumanServ-ces. 15PAHs
are h~tlyto c.-iu}e CJncer
rn ~hum<1ns Tht-y ar! p,oduc~ dunng the lll(Omple~combustionof ~ . petroieum,coal, andtobacco, andare c=utuentsofdiesel- ffll>SS1on&naustandcoal
1M The1rmo!ec1Jla1wuc-
turesshowtna11heydre
comp’vccom~unds
CO!’ISIStlngofmutUdlly
f\Mdbenztnenngs
D1benzf.1,h)acnd1ne,
d’benz{d,Jj.Kr,d,ne.and
7H-0:benzc[c.g/carbazole
are~,cPAHs,
meanmg mat tne,r
mole’CUl.arnructureshave
a n,ttogenat0minpldCe
ofanngcart>ona:om
~tl’l~11!h
tli!O\ U.S°’P,lrtrnffltof
HNlll’ln:ll-!JJmM1SeM::1’S,
f’utihcHNlttlSerw:t. N.JTIOl’lal
lo«ciogyP,ogram. ~,o,
to.n;:e Part.Nol’lliC.vohna,
1011 )

BOkno”nJ,BA

lkn.io(l]f!uor.1mhc:nc
Al wJ.no,.nti B[A] F

O,bcn1[0,1larnd, nc
Aho l no”·n as DB /a.J]AC

D,t:,,.-n,c,fll.r)p)rtne
Al’Wlloo”n as D8/a.tlP

,,,,__ 11

‘vV
D1bcn10[0.flp)m11:

Aho l ll0\\na,D8[a,()P os
dil>:n1ofd1J1,f,hl) }tr1C

&ruo(/J)f!~or.1n11’t

Bc:n.wja]P)l~OC
AJ.-o)./1()\

D1 lx-n1/

D1bcnLO[i1Ji)p} ICIIC
Also l no\\n as D8 [ll,11 /P

lmkll0/1.!J rd)p)rt-nr
,\l,o lnu .. n aslP

502
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

lknrnl;/fll>Ol’.11\lhc,-_,
Al w l no11na~ R[J)f

“”” C(XY N I N v-
D,ticn,[11.lr/.w;nJ,~

Alw lno” n as DU[a.h)AC

SE #
N
I
II

711 -D, bt-nw k.JIIC:irh.uok
Aholno”O.l$71Hllt fr,,JC

D10Cn10[11,1Jp}rl’f’ll.’
Alsolno\\na, Dll [o.1JP

5-1′. lel h)lrhf)-Cll£’
Abo l no”na,5-,\IC

12, 12·E WORKPLACE REGULATIONS INVOLVING THE PAHS
,\hhough a ?emussible t’~p?sure li_mit for diesel-engine exhaust has not bt-en publisht”d by
OSHA ~r !\IOSH, the _li~11ts for tts gaSt>ous constituents are available. In this rexc, rhe
ptrmiss1blt> expoSl’.re h~its for carbon monoxide, ni tric oxide, nirrogt”n dioxide, and
sulfur.dioxide a.re ~is~ed m Table 10.2. OSHNNIOSH’s publication of permissible expo·
,ure limits for individual PAHs as limited to naphthalene, amhracent”, benzo[aJpyrt’nt’,
chrysene, pht’nanchre~e~ and pyrent- r apor. For naphthalene, the permissi ble exposurt’
hrrur is 10 parts per millmn (50 mg/m ), averaged over an 8-hour workday- for the mher
pi\Hs listed here, the \’alue is 0.2 mg/m3, a\’eraged O\’er an 8-hour workda;.

12,13 PETROLEUM AND PETROLEUM PRODUCTS
Tht word petroleum is deri\’ed from the Greek pt tra, meaning “rock ., and Latin o/eum
meaning “oil.” The name “rock oil” is reminiscem of humans· earlie;t contacts with thi;
rna teriJ l: a liquid that oozt”d from fissures in rocks,

12, 13-A THE NATURE AND NATURAL ORIGIN OF CRUDE OIL
Perro!eum is a highly complex mixture consisting of many thousa nds of organic com-
pounds, approximately 75% of which are h)·drocarbons, each of whose molecules ha s
from 3 co 60 ca rbon atoms. The actual number of indi\’idual hydrocarbons in petroleum
has been estimated to bt” be-tween 50,000 and 2,000,000. Petroleum occurs naturally det”p
b(low Ear1h’s surface in certain art’as around the world. Wells are drilled through rhe rock
to 1he oil-bea ring stratum, through which the petroleum is then pumped co the su rface. In
1h1s fo rm, it is called crude oil, crude petroleum, or “crude.” In the United Stam, major
oil fields are located in Texas, California, Louisiana, Oklahoma, and Alaska, from which
crude oil is transporied in tankers or transferred by pipeline, to plant sites known as
petroleum refineries, where it is treated to produce petroleum products.

Although the mechani sm by which crude oil fo rmed in the earth is open to some
dtbate, most scientists belie\’e that it originated from the partial decomposition of animals
and plants (zooplankton and algae) chat li\•ed millions of yt”ars ago, Because geological
forces caused the position of Earth’s crust co change ovt’r the passing millennia, tht’se
ancient organisms were buried at grt’at depths. Thei r decomposition resulted from the
enhanced temperature and press ure at tht’se depths.

Both crude oil and natural gas formed when the remains of anciem organisms decom-
posed , Crude oi l formed when the temperature was approximatdy 150°F (76°C), whereas
natural gas fo rmed when the temperature rose to approximately 200°F (93°C). Scientists
~timate that approximately 13.0 pounds (5.9 kg) of crude oil resulted from the decompo-
mion of 98 tons (89 t) of prehistoric matter.

A group of 14 Middle Eastt’rn and South American countries now controls a largt”
portion of the world’s supply of crude oil through a ca rtel callt”d the Organization of
Petroleum Exporting Countries, or OPEC. This organization ext’rts comrol O\’er the sup-
pl)’ of crude oil b)’ voluntarily restra ining production in order to stabili~e its price. Bttause
the United Sta tt”S has an insatia ble tbirst for petroleum products, considerable efforts are
now ongoing to shed U.S. dependence on foreign sources of crude oi l by replacing tbem
wirhalternati\•es.

uude oil (crude petro-
leum; The
comple)(chemicalmi)(-
turethatformsfrom
naturally occurring bio-
mauinsubsurface rock
formations under high
temperatureandpres-
sureconditionsover
geological time

fa cility engaged
primar ily in producing
on a commercial scale
gasoline, kerosene,
fuel oils, lubr!canu,
and other products
through fractionation,
alkylation, cracking,
blending, and other
processes

petroleum product
• My petroleum-based
fuel such as gasol ine,
jetfuel,kerosene,and
heating oil, nonfuel
like asphalt and lubri-
cants, andpetrochemi-
cals likeethane,
propane, andbutane

Organization of
Petroleum E)(porting
Countries {OPEQ • The

12.13.9 FIGHTING FIRES INVOLVING CRUDE PETROLEUM
Crude pmolt”um is a highly flammable liquid, because its fl ashp~in~ rang.es fro~ 20 to ~:~;;

0
w,~~s~~~~ec-

?O’F (- 7 10 32°C). Firt’s in\’olving this material ha\’e oc~urre~ at oil f.ield~, 10 transit, ~ur- and unify common oil-
ing pipeline transfer, and during storage. Ca pping burning oil wells ts a JOb fo r_s~i~lly marketing policies
!rained t’X perts, but regular firefighters ha\’e also been ca ll~d on_to combat fi rt’s mvo\\’mg among member
crude oil at storage faci lities and during transfer and 1nns11 acc1dt”nls, countries

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 503

I’

l1

I
I

,non associated with
theupulsionofcrude
oil and the production
of steam during a fire
withinacrudeoil stor-
ageunk.

fBctlonatlon (fractional

cm of separating mul-
tiple components of a
mixture based on the
different boil ing points
ofitsconstit\Jenu, dur-
ing which thl! vapon
arecollectedats~i-
fied temperatures or
withinspecifiPCltem-
peraturerangMand
subsequentlycon-
densedto liquidsand
collected

fractionofcrud epetro-
leumobtainedbythe
vaporizatlonofitscom-
ponentswithina spe.
cifictempera turerange
followed by its
condensation

eous fraction of crude
petroleum that does
not condense at room
temperature,consist ing
ofmethane,ethane,
propane.and butane

lightnaphtha (llgrolnJ
•The most volatile
fract ion of crude
petroleum

petroleum fraction of
crude petroleum often
used as the feedstock
fortheproductionof
gasoline

Alt hough small crude oil fires can be extinguished ~sing a del ugi ng volu
most e:..-pem rrcommend the use ?f a~u~us film-for~1111g foam (AFFF) (Sec~~no~ ~·~ltt,
as the most practical means of ex~111gu1shmg a crude oil fi re ms1d.e a bulk storage ta.n tBI
ihese incidents, the use of water ,s recommende~ soldy for coolmg purposes. Water • In
peiroleum are immiscible hquid~, and petroleum 1s less dense than water. When di~ha all(!
on a peirolewn fi re, the water smks w the bottom of the storage tank, where it sen]~
a separare la rer and serves no useful purpose. iS

Furthennore, the presence of a water layer at. 1he bottom of a bulk storage tank
a sp~ial concern fo r firefighters when combating a petroleum fi re. Although hpo5cs
occurs at the t3nk’s surface, wher~ flammable vap~r is emme~, t~e accompanyingth~~re
combustion can be slowly transmmed b~ convect1~n and rad1at1on through the Under:
ing petroleum to the water lay~r- Absorp110~ of th~ mte.nse heat causes the temperature ~
the petrolcwn and the underlymg water ~o nse until ~l11matel y, the water boils. Thewatti
vapor then forces its w~y upward, pus~mg the b~rnmg petroleum_ up and over ihe walls
of the storage rank. This phenomenon 1s appropm1ely called a bo1lover.

When a crude petroleum fire occurs !nside a storage rank, e:ery attempt should bt
made to extinguish the fi re before the boilover occurs. The bummg, froth ing petrolt
rhac spills outside 1hc storage tank has. been kno~•n ~o flow substantial distances from:
tank, triggering numerous secondary fires. The firefighte rs who combat these fi res should
be particularly wary, as the flowing, burning petroleum cou ld overtake unsuspecting fi
fighters in its pathway. They must also anempt to confine water runoff to pm·tnt
ad\·ersc impact on 1he environment and limit the department’s liabi lity. n

12.13-C FRACTIONATION OF CRUDE PETROLEUM
One of the major operations occurring at petroleum refineries is 1he fractional isolation of
the substances in crude petroleum. The process is ca lled fractionation, or fractlonal disti~
lation, and is accomplished by heating the crude wi1hin precstablishcd temperature rangtS
until its components vaporize. The vapors of these compounds then arc condensed mto
liquids and collected in separate receivers. They arc referred to as petroleum distillatu .

. A single petroleum fraction may be used directly as a commercia l petroleum product,
or 1t may be stored until it can be further processed. Bulk volumes of pe1roleum prodllCIS
are tra nsported to major distribution centers, whe re th ey often are s1ored in rnulriplr
tanks in a tank farm.

The fractions most commonly isola ted during the fractionation of crude pcrroleum
arc represented in Figure 12.8. They consist of the fo llowing:

A gaseous mixture of methane (65% to 90%), ethane, propane, and butane. Tlus
fraet1on, called petroleum gas, separates from crude petroleum at a 1emperarure bdow
i0°F (21 °CJ. It is recovered and used directly as a feedstock for 1he production of othrr
substances, or its components can be isolated to produce petroleum products such ll
bottled gas.

A liquid mixture consisting mainly of alkanes a,id cycloalkanes IJaving from j 10
_11. carbon a~o~s per molecule. This fraction, ca lled light naphtha or ligroin, genera l!)’
is isob red w11hm the boiling point range 158 to 284oF (70 tO I 40oC). At one rime, light
~::~:~a

0
7~; ~:e~ directly. as th~ fuel ~ormerly k~own as straight-nm gasoline. ~owew~

because it co~tai aphtha is no\~ considered env1ronmcmall y undesirable fo r di.reel ust,
ihe Clean Ai r A;t a~ mu~h ~s 3 ¾, benzene by volume. (In 1995, using its authori ty under
I%.) Toda Ii ht ‘n PA h~lled the benzene content in petroleum produc1s to bs thJn
toluene, an~ le x ,]:~~t?a IS used :is the f~dstock either for the production of benzen_~:

d I } isomers by ca talytic refo rmation, or fo r the production of elh)
ene ~\ :i:~::::~::tc. cracki.ng. Jl

rb Sfing mamly of alka11es and cycloalkanes having from 7 to

504
ca o11 atoms per molecule. This fraction, called heavy naphtha, is generally isolated w11hrn

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

Gaseous
<70"Ft <:21~) hvdroca1bon1

Kerosene

Diesel oil

>&98″ft>J70″C) Lubricating oil

Residue

Methane
Uquefiedpetroleum
gas(LPGI
Llghterfuel

Stralght•rungasolln•

Motor gasoline
Jet fuel

Tractor fuel
Jetfuel
Heating fuels

Diesel fuel
Heat1ngfue\1

Crankcaseolls
Hydraulic fluids
Transmission fluids

Asphalt
Pe11oleumcoke

FIGURE 12.8 Some
prodvctsden~~bythe
lract1onat,onofcrude
petro!eum LJ quefed
pet1oleum ga~(LPG)1s
marketed 1ntheformthat
come-sd,rectlyiromlr’e
ds11llat,on 1ower. butthe
otherlract,onsrequ1re
furthe1relmemtntto
remove undesirable com
ponenis,m~tnotably,
benzenearidwlfurous
andnitrogenoo\com-
pounds Theiehnement
proctsses1ncludevacuum
d1st1lla1Jon. ca1alyt1c
reform mg,hydrocrad.lflg,
andcatalyticcrack,ng

1hc boiling point range 284 to 392°F (140 to 200°(). It typicall)· is used as the feedstock for
1he production of motor gasoline. The production of gasoline involves catalytic cracking,
during which hydrocarbons having from 7 to 11 carbon atoms per molecule arc produced.
Thi~ fmtion is also the feedstock for the production of toluene. ;i:i~~nc~~d~np:~%’.rac-

1 A liquid petrole,mt product consisting of a/kanes and cycloalkanes having from leum often usl?d as a
9 lo 16 carbon atoms per molecule. This fraction, called kerosene, is often isolated tractor futl. jet fuel,
within the boili ng poim range 302 to 527°F ( 150 to 275°(). Kerosene has been used as and heating fuel in
the fuel in space heaters, portable cooking stoves, and water heaters and is suitable as a space heaters
hght sou rce when burned in wick-fed lamps. Todar, kerosene is used primaril)’ fo r the dlMel oil {diesel fuel ,
production of jet fuels. gas A fraction of

Ptr :,:ie~~;~d ;~::7r::,~~::::;’1:~ a;i!s?ic~~t:~;;:, l~~:t:go~:s 1~tu!~a~~ :~s:r::~ ~~~f~~Z:i~!;!ing
within the boiling point range 392 10 698°F (200 to 370°(). In addirion to carbon and diesel engines
h1·drogen atoms, the molecules of the component hydrocarbons may co~rai_n sulfur or lubricating oil (lubricant)
rritrogen atoms. Diesel oil is blended with additives and used to heat buildi~gs and 10 1 Any fraction of
power passenger cars pickup and heavy-duty 1rucks, buses, ships, and certa in types of peooleum oil 1hat is
hcal’y equipment. Mo;e than 50% of the passenger cars now used ~y Europeans, and more capable of producing a
than 90% of rhe ca rs in Italy alone are diesel•powered. In the United States over the past !~~a’::\ :,a~~~i~~e
drcades, the use of diesel-powered passenger vehicles has fluctuated. . metal parn. so that

1 A liquid to semisolid fraction composed 0( polynuclear aromatic hydroror!’ons when used. It redum
havi11g from 30 to 45 carbo11 atoms per molecule. This mixture of compounds ry_p1cally the fr iction generated
1, isolated at temperatures above 698°f (370°(). The products p~oduced fron., 1h1s f~c- between bearing
hon arc broadly called lubricating oils, or lubrlcants. h typically 1s blended wtth various surfam

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I SOS

f I/

I I
I
I I ii

I II/
506

performance.” addmvcs, corrosion inh1birors, and dcterg~ncs and ihen US(‘d as crank
otl or hydraulic flrnd. Ir 1s also 1he feedstock from wh1Ch other motor and t;isi:

asp/ult • The dark
brown-to·b!ackcement-
hke residue that
remains when crude
petroleum is refin ed,
usu•Jly combined with
m1ner•!maner

Jubricanng oils are produced. Typically, this fraction JS hydrotreated and
other cherrucal prOCC’SS(‘S ro remo\’e its undesirable coi:nponenrs-metals, to
sulfur-and then blended tO achieve a Sj>fi:ified viscostf}’, srabilif}•, and lubricit
they are used, Jubncating oils produce an oily film that coats the surfaces of movi~~ :’11
paru, thereby reducing friction and wear. iii

The solid residue of the di~tillation process,, The fractionation residue is cal)
asphalt, a mixture of compounds with molecules hav111g 40 or more carbon atoms As td
igni tes at approximately 400°F (204°C). fr is used commcrciall~ as a componen~ llult
rective coating, waterpro_ofing, and a~hesive products. Befo_re ns u_se for paving~ r:0-
airfield runwa y, and roof mg construction, hot asphal~ often 1s held tn crucibles, asph•!
kettles, and porra_ble tank trucks. DOT regulates Its transporcarion as an clevatt’d.
temperature material.

uphaftkettle • Any
vessel or container used
to process,. treat. hold
for heating. or dispense
flammable or combus-
tible roofing materials
intheformof viscous
liquids

alkyJation • Any peuo-
leum rdining operation
!nvofvingthecombina-
tionofanalkane
(u1ual/y isobutane)and
ana!kMe,throughthe
control of temperature
andpreswre inthe
pre:sMceofanaa d
catafynandresutting
lntheproductionofa
branched

The hydrocarbons that are ~omponents of pttroleum fractions arc primarily com.
pounds having carbon-carbon smgle bonds, but not carbon-carbon double bonds
carbon-carbon triple bonds. Prior to their treatment, diesel oil, lubricating oils, and o,
phalt usually contain sulfurous or nitrogenous compounds in addition to the polynuc]:
aromatic h)·drocarbons.

12.13-D CHEMICAL TREATMENT OF PETROLEUM FRACTIONS
The nature of the processing and chemical treatment operations cond ucted al mosi petro-
leum refineries is noied in Table 12.14. One process is alkylation . This chemical reacnon
produces a branched-chain hydrocarbon by the chemical union of an alkanc and an alkrnc.
AJkylation generally is conducted in the presence of either sulfuric acid or hydrofluonc
acid, borh of which act catalytically. The product of 1hc alkylation reaction is called an

ifriiiiiii Ma1or Treatment Processes Conducted at Petroleum Refmenes
Thermal cracking and cata• 1 The breaking down of large hydrocarbon molecules into i:malltr
lytic cracking of the con- hydrocarbon molecules by the application of heal or the Ult of Cili·
stituentsofpe1ro!eum lysls
fract ions
Alkylation

lsomerization

Catalytic reformation

Steam cracking

Catalytichydrotreatment

Hydrocracking

The application of heat or pressure to produce a branched-

The rearrangement of a hydrocarbon molecule ha11ing a given num·
her of carbon atoms to produce another molecule having the same
number of carbon atoms

The reforming of alkyl cycloalkanes into aromatic hydrocarbons (e g.
methylcydohexane – toluene) by passing the 11apor of a petro-
/eum fract /on over certain catalysts at h1gh tempera1ure and pressurt

The production of ethylene, propylene, and the butane isomers. from
:he ethane, propane,andbutane, respectively, in natural gas by react·

, mgthelatterwithstearn

The P_rocessing of a petroleum fraction with hydrogen .10 remoi·e su~
fur, nitrogen, heavy metals, and other impurities from its compontfl

The processing of a petroleum fract ion with hydrogen at high pres·
sure and temperature to con11ert complex hydrocarbons into
smaller ones for use as componenu in gasoline and other fuels

Chapter 12 Chemistry of Some Hazardous Organic Compounds; Part
1

alkyi’::~ B;~:,:~;;~:~~sl)~~:~~:~l: oft~n are prcseni at petroleum refineries in bulk stor•
J!t The ~10s1 ~ommon alkylate prod:i~e~t~n~;:nd pose a fi re and explosion hazard.
JS()O(l:Jl/e, but t_his nan~e is ~crua\ly a misnom: r. Th;’;;r~leu~ mdustr)~ 1s commo~!y called
It 15 producc-d mdustrially m massive amounts from rh~/’1:1e 15 2’7,4-mnmh)lpcmane.
isobu1ene in the presence of a strong acid catalyst. mica] union of 1sobutane and

CH,
CHi- r H- CHj(g ) + Clh ::c t – CH,f/.’)

Cl l3

CH 1 1-l
I I

Cl-l 1- C- CH1- ~ – C!i1(II

1-.ob,.i cnc
CH1 CH3

, __
fr 15 also produced by the catalytic co~version of 1sobmene to diisoburylene (foomoie “c
Table 12.5), followed by hyd rogenation. ‘

CH1
I –

K H1::cC- Cl-1 1(!1)

hobll1rnc

r H1 ‘f!h CH 1 CH 1
CH3-r – CH~- C= CH~(£l + CH 1 – ‘f-CH : C- CH,(gl

CH 1 Cl\3
!.J .-1 Tn11″‘ lh) I 1 JX” ntcnc 1.J ,J Tnmc,h) l- ~•P,:nlclll:

/
CH1 H
I I

2CHi – r – c H~- ‘f-CH’1,gJ
CH1 Oh

L !.~ fo mc1h)lr,,..ntlnc
· 1-.00..tJni:”

Aside from producing 1rimethr lpen1anes, alkylation reactions also produce
d1methylhexanes and other branched-chain alka nes. These compounds are desirable
additives in gaso line, because the)’ improve the completeness of its combustion. In
rheir absence, the phenomenon called knocking occurs. This term refers to the “putt•putt”
noises, i.e., audible pings, sputtering, and rattling, that are generated as the fuel burns
wuhm the engine. Fuel additives that reduce the intensity of this knocking are called
antiknock agents.

;i, lkyfo te • Any
branched

knocking • Thenoises
associat,dwithth,
incomplete combustion
of a petroleum fuel,
,sptcia\lylnintemal
combustion engines

pflroteumtu,l additi11e
thatreducesorelimi•
natesthenolsesgentr-
atedwithin a
combustion chamber
when the fu el burns

SOLVED EXERCISE 12.8

n-Tnde

CH1CH2CH1C H1CH1C H2CHiCH1(Hp•-1iCH1CH2CH,(91 –
n-lrC<'Cdoe

CH3CH1CH1C H1CH2CH1CH2CHi(g’ • CH2 :(HzCH1·9. c..01~ H
t>-Octi!Oi’ P,OO<'f'

I/Jha tpe11oleum1reatmentprocess lsrepresentedby th,schem1calconvers,on?

Sotutlon: The eQuation represents an exam.pie of “crac~ing, ·ba ~””t~~u
9
~~: :•~;~ ~’.:t;::: w:::;~

large hydrocarbon molecule 1s decompmed into ~mailer ones Y ,, .
in911toacatalyst

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 507

I I

I

ii
I

)II/

II I

i/11 I
I 1/. 111

1111/

111/.11

/H

t II I 11

Motor
guoline

motor guoline •The
comptexm1xtureof
hydroc.arbonscom-
monlyusedasafuel
for small veh icles

aviation gasolint • The
complex mixture of
hydro~rbonsthathas
been blended with
additwesforuseasa
fuel inaviationrecipro-
catingengines

octane number{octane

thatmeasurestheresis•
tanceofagasol ine
blend to knocking
when burned in an
engine, based on its
comparison with the
burningofamixtureof
n-heptaneand
2,2,4-trimethylpentane

12.13-E GASOLINE .
The following general cypes of g.,so/mc are produced at petroleum refrncries;

• Motor gasoline, the fuel primJnly produced by treating the hravy naphtha fracti
,ind b/C’nding ic wit.h oxygrnm·s (Sl-ct1on 13.2-F) and orhcr pcrformancr additii·et It~
us(‘d mainly IO (ud passtng(‘r cars Jn.d small 1rucks. .

Aviation gasoline. [he fud primarrl~ produced b} tn:a.r111g t~e kerosrn(‘ fraction
db! d ng ir with d(‘icmg mhibitors (to ehmmaft the form:mon of 1cc) and man)· o•h

;;rfor:a~ce addim·es. It 15 ustd ma_mly to fuel a.~rcraft. Thr, terms .. aviat_ion ga>0Ji~~
and .. Jet fuel~ normally art differentt:ll_td 111 wda) s Jarg?n h) the r_n,mne_r m which th~•
art inrtnded for ust. Aviation gasol~n(‘ ts us_rd to power aircraft (‘ngm.es w1_1h spark plugs,
where.is JO:-t fuel 15 us(‘d 10 pow.:-r Jtt turbme engines. Je_t fuels :ire .1dennfled by na rnts
like JP-4, JP-7. and JP-8, wh(‘re ~JP~ i_s rhe acronym for Jet propulsron :ind the terrru ‘1.i]
number designates a sprdfic composJtton.

The chemical composition of petroleum fuels varies, _nor only in differt’nt parts of rbr
world bur also at different times of rhe year. The ehem1cal co111pos1t1on of a given furl
produced at a refinery can even change dai ly. There are numerous constituent compo-
nems of both moror gasoline and aviation gasoline, but most are branched-chain alkants.
Hrdrorrea ring and hydrocracking com’trl ihe unsaru~ared hydrocarbons in the p,:,rroleum
fraction used for rheir production into branched-cham alkanes, thereby yielding alhnts
having 7 to J I carbon atoms per molecuJe in motor gasoline and 9 to l 6 ca rbon atom;
per mo/,:,cule in aviation gasoline :ind jer fuel. These furls arc flammable liquids that po.t
the risk of fire and explosion.

The different commercial types of gasoline are distinguished by 1h c-i r inheum
octane numbers. The octane number, or octane rating , is a represrntation of thi
antiknock properties of a fuel under laboratory or rest conditions. Ocrane numbers
of zero :ind 100 are arbitrarily assigned ro n- hepra ne (a hig h “k nockc-,~ ) and
2,2,4-rrimerhylprntane (a low “knocker”). respectively. Heptane is an undc-sirablt
fuel, becausr it causes engine knocking as it burns in a combustion chamber, bur
2,2,4-rrimt rhylpenranr /”isoocta neM) is a desirab le fuel, bec,1use its combustion don
nor cause engine knocking.

CH3CH2CH2CH2CH2CH~CH,i
n lkpll,ie

Ocla.itnumb,:r : 0

CH1 Cl-11
I

CH1-f- nl2 – CH – Cf-lJ

Cl-I;
2.2.4-Tnnwth) lp,;01:mc
Oc1,mc nu111bcr ” 100

T~e octane _numb~r of a gi\·en fuel is determined by compa ring its knocking v.~rh the
knock’.ng of va rious mix rum of 11-heptane and 2,2,4-trimech r lpentane. When a sample of
a fuel 15 found by ttsting to knock like a mixture of 85 parts 2,2,4-rrimerhylpt’ntane and
15 parts 11-hep1ane, rho:- fuel is assigned an octane number of 85.
meth~~::ocrane rating of gasoline is commercia ll y measu red by 1he fo llowing tll’O

h Th_e Research_Octane Number, or R or RON, is dererrn ined by using a sampkof
r e g_a~ohne as fuel 10 a trn engine wirh a variable compression ratio under conrrolltd
:~;i;:::\:nf~e~;mparing rhe results using mixtu res of 2,2,4- rrimcrhylpenrane and

508

ing ,~el~~~~to; ~c::ne Nt~mber, or~ or MON, is determined in a similar ~~nnet u;·
and variable i:~rion ti:i~;~me, bur wuh a prehe.:ned fuel mixtu re, higher engmesp« ·

The expression R + Mil is called rhe antiknock index.
Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

f here are three common gradfs of motor gasoline:

1 ,tegularf•g
8
•
2
ade gasoline. also call.:-d regular unleaded, \\ h1ch has a minimum ocrane

rJringo
1 Mid-grade gasoline, which hJs an octan.:- raung gre.1.ter rh.1n or equJI tO 88 and lrss

thMiorequal to 90
1 Premium-grade gasoline, also call(‘d supreme and super unleaded which ha s :m

antiknock mdex (R + .\1/2) grr.1.ter th.1.n 90 ‘
Byconrrast. rhe mdi\·idual iypes of a\•1a11ongasol1nr ha1·.:- 1:1r}’mg octane numbtrs, but all
Jceorer 100.

At srrvic~ sra~JOns, cusro~ers ma y d1spensr 1he1rehoict’ of grad.:- from fuel pumps like
rhos.:- ~ho1~·n 111_ Figure 12.9 directly i_nro motor vehicle. A ytllow label r.:-scmbling rhe
followmg is affixed to c:-ach pump ro tdrnt1fy the minimum octane rnting and rhe expres-
sion /R + M)/2 MET! 10D:

MINIMUM OCTANE RATING
(R + M)/2 METHOD

re9ular•9ro1de g~so1ine
(itgul.trun! t aded)
• Thegr.tdeofgaso!ine
h.tvingamlnimum
octane rating of 81

mid-gr.tde gasoline

having an octane rat ing
greater than or equal
to88and less than or
equal to90

premium•grade gaso-
line (supreme. super
unlu ded) • Thegrade
of gasoline having an
.tnt1knock index greater
than90
JP-4 JP-5 93

Thelart” ,s rhe mrngc of rhe ,cse,,ch ocrm ,umbe,'”d rhc mo10,ocra1,enumbe,.

fl(iURE 11 .9 The d,fferent grades ol gasol,ne fuels a·e d,ffe·enuted by the:’. ooane num~rs. wh•ch are estab-
llhed by subJectmg a gaso line samo’e to test CO’ld1t1ons that ascerta n how we,1,t ~nocb when 1gnrted 1n a com-

1 IJl.st~ chamber At these fuel mos, regular, mid-grade, and prem,um gasoline fuels Mv,ng octane numbers o
87, 89, and 91 respectively ar~rowied forsa’e As reou, red t:y u S federal Trade Comm,~•on regulations at 16
C FR §30612: the octilne ~umbers are pnnted on labels in tilac~ on a ye’1ow background (CQl.l’1eSyoif!¥’)e~)

Chapter 12 Chemistry of Some Hazardous Organ ic Compounds: Part I 509 I

r unlud~g•so!lne notconta,n • h.•ad
compoynd svch as
tetr•~yllead,
formerly an addtt,ve
tha t functioned iitS an
an1ilo:.nock.tg~t

Diewloil

All ty~ of gJ.solmt sold in the Umred States smcc 1975 are referred to as lln le
gasoline. meamng ihar they do ~ot coma m rccrnn,iechyllead, wraechyllcad, or oihe, idtt1
b.iSN addmres. Using the aurhomy of thf’ Clran Air_Act, EPA ban nrd /Cid
USt’ of 1~.id compounds 111 gasolmt> to protoct a_utom?t1 ve Ca13 lyt
rivail!”d by !rad and to a\·oid the unnecess.1ry dispersion of le:id throughout the c

As previously notrd 111 St’CtlOII 5.8-A, ro reduce the vol ume of carbon
operating mocor i•t-hlcles emit to the atmosph: re, the federal governm(‘nt is rrquir in
bJ· 2016 and 2025, the flem of auto co~1pa111(‘S must a1•erage 3!.5 mi/gal (15 krnf1.g1h.i1 54.5 mi/gal (23 km/L), rrspecti1·dy. This almost doub/(‘s roday s average of 27 5

~nd
( 11. 7 km/L). . 11’~1

12.13-F DIESEL OIL
Diesd oil is the furl used ro powrr diesel engines in cenain vehicles and mach ‘ .
flashpoinr ranges from I JO to 190″~ (43 to 8.S”C). In the United States, dicsrl 0:~;;~r:
duced from the fraction .of crude 011 that rrfine~s call sour crude. Because this fractiori
conrains sulfurous and mtrogenous compoun_ds, II mu~t be trea1~d to reduce or elimi~ie
the sulfur :md nitrogen content to comply with todays Clean Arr Act standards. Tha

11 accomplishrd by hydrogenation. The process, cal!e_d hydrotreatment, produce’!
3

dits(I
oil consisting of alkanes, cycloalkanes, and ~romanc compoun~ s. During hydrotr~ting,
0e sulfur and nirrogrn atoms are com•erted mto hyd rogen sulfide and ammonia, resptt.
CJvely, and removrd from the fuel.

U1Jdeo,l orthefraction
thereof that contains
sulfurous and nitroge-
nous compounds

petroleum refin ingpro-
cessthatupgradesthe
quality of petroleum
fractlonsbyusing
hydrogen to reduce or
elimlnatetheirnitrog-
enousandsu/furous
content and to convert
alkenestoalkanes

Umreatrd and hydrorreated diesel oi l are sometimes referred to as heavy diesel oJ
and light diesel oil, mprcrively. The combustion of untreated dirscl oil yields a SOOI}·
smoke consisting of particuk11es to which polynuclea r aromatic hydrocarbons adsorb.
As notrd in Section 12.12-C, the production of this plume poses a risk 10 public health
and the environment, brcause inhalation rxposu re to PAHs is linked with the dndop-
ment of malignant tumors in the lungs. The combustion of ligh t diesel oil yieldi an
emission that contains fewer pollutants. To comply with the Clean Ai r Act standard
established fo r finr particulate matter (Section 10.9-D), the American diesel indusm·
brgan changing from heavy 10 light diesel oil in the mid-2000s. Today, light diesd o~
is thr ma in fuel used in diesel-powered vehicles that arc dri ven on U.S. roadways.

The different commercial types of light diesel oil are ra red by a system similar to th{
octane-numbrr syste m used for raring different t)’pes of gasoline. For diesel oils, n 11
cal/rd the cetane number. Whereas the octane number meas ures the abi lity of a gaso-
line fuel to reduce engine knocking, the cetane number gauges 1he case with which l
diesel fuel auroignites when it is compressed in a cylinder of a diesel engi ne without a
spark plug.

cetane
parameterthatmea-
suresthecombus-tlon
qualityofdieseloildur-
ing iu compression
ignition

Cetanr is the common name for n-hexadcca ne, an alkane having the formula C10H;.i.
For tesr purposes, the cerane number of 2,2,4,4,6,8,8-hepramcthylnonane and crtane arr
arbitrarily set ar 15 and I 00, respectively.

fH1 y’·l3 THJ y 1·! 1
CM1-y-CH2-r – CH1- CH – CH2 – y – CH 1

CH3 Cl·h CH3
2.2.~A,6.8.S. /kpu 1nc1 ll}lnon~ 11e

C,·1.incnumOCr “” 15

CH3CH2CH2CH2CH2CH~CH2CH2CH2CH2CH2c 1-12c H2CH2CH:CH3
11 1ln.ide(J.Oc(C,·1anl’f
C, 1:vic nu111bcr 100

510 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part
1

[‘he crtJnl’ numhcr of a diesel fuel is deiermmrd in
irs! ,ngines. . specia l \·anablc-comprcss1on-ratio

Generally, d1esc- l engines operate well h h
1,crween 40 :md 55. The 1wo diesel fud t . w en f e diesel ful’I has a Cl’tanc number
egular-grade diesel oil and premlum-gra~~l’~I ava;la_blr c~mm~rcially arc rcfe rrcd to as

:ng from 40 to 60 and 45 ro 50, respectively. ese oil, whrch hne cctane numbers ra ng·

12.1 3-G HEATING OILS
5ome petroleum produces are useful as heating ·1 Th
~tion, followc-d by blrnding with specified additii•: 1 ~ore? ;re produced by framon-
naphtha often are proccssed to produce hcatin, ~i ls eit~c/!’• diesel f~el and h~avy
11•11h’.n a narr?wcr d1s1illarion range or by adding! spe~ified amo~m~e;::~~1;rs
fracuons until thc frna! blcnd possesses de’i irable ignirion temperatures and ~eat (Btu)
values. These pro?ucts used as fuels in home furnaces and boilrrs for focroril’s ,
apartm~n t anfd offi~e buildings, schools, and Stram-powered vessels, as well as for thl’
grner:1 non o clrctr1c 1ty.

Six grades of heating oils are commercially recognized in the United States, each des-
ignated by the words Fuel Od followed b)’ a number from I to 6. The grades are com-
postd o~ hrdrocarbo.ns _ha~i_ng 14 to 20 carbon atoms per molecule and arc commercially
d1snngu1shed by their 1gnmon temperatures, rach progrcssh·ely increasing in the range
from 444 °F (229°C). CO 7~5°F (407•q, In the United States, Fuel Oil No. 2 is the most
commonly used hea tmg 01I.

12.13-H TRANSMISSION OF CRUDE PETROLEUM
ANO PETROLEUM PRODUCTS BY PIPELINE

Crude oi l is f~eq uenrly transfer~ed by a nerwo~k of pipelines from.oil fields imo stor:1gr
tJnks where 1t awau s processmg. In the Umted Siate’i , approximately 55,000 mi les
(88,500 km ) of transmission pipelines transfcr crude oil from spot to spot. Similarly, all
t)’pes of pe1roleum products arc regularly transferred by pipelinr from refinrries into stor-
ase tanks awaiting an end-use.

A single pipeline used co transfer crude oil or a pet roleum product may be either
aboregrou nd, underground, or both. Portions of the 799-milc ( 1242-km) Trans-A laska
Pipeline System pm·iously notrd in Section 10. 15 are both located underground and ele-
1ated alxll’eground. The pipeline is used to transfer hot crude ml from the oil fields in Prudhoc
BJ)’ to Valdez, the northernmost ice-free American port. The crude oil then is transported
m bulk by ca rgo ships 10 the west coast of the United States, from wherr it is again trans-
ferred by pipeline to refineries.

At 49 C.E R. S 195.410, DOT requires the posting of line markers like thosr shown in
Figure 12.4 co indicate the approximate location of petroleum-transmission pipelines.
Like the line markers used for locating natural-gas-transmission pipelines, the line mark-
ers for abol’eground petroleum-transmission pipelines must be placed along each section
1ocared in an area accessible to the publ ic and post(‘d along right-of-ways and at road,
railroa d, and wa1crway crossings. .

A major lea k of crude petroleum or a petroleum product from a petrolrum-transn~1s•
1ion pipeline constitutes a major fi re and explosion hazard , and may also ca_use a ma1or
tnvironmcnra l disa ster. Jn 2010, a failed valve was the cause of a ca tastrophic leak fjom
the trans-Alaska pipeline that resulted in the release of over !00,000 gallons (378 m_ ) ~f
cnrde oil to the environment. The oil was collected in a containment system from which LI
was thereafte r retrieved. A ma jo r disaster associated with the lea k wa_s a.\’Crted onl y
btcausr the prevailing temperatu re was 50 cold that the oil w:1s unable IO 1g111te.

Htatlngoi15

regular-grade ditsel oil
• Oitsel oil ha~1ng a
cetanenumberranging
from40to60

premlum-grade dlesrl
having a

cetanenumbrrranging
from4Sto50

heating oil • Anyprtro-
leumd,stillateused
direalyorasa blend to
fuelfurnacesandboll-
ersmresidences,large
building1, andf11ctories

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 511

Comider chi: following Lewis srructures of rhe chlonnated dem·.Jtn•es of mrthJnr;

H – C-Cl

\fi:1 h)IChlomk
(Chloro,…..1h~ll

H H T’
CI – C – CI CI – C – CI Cl – C – c1

I I I
H Cl CJ

\k!h)knc d1Jondc
(O,,hlorortl<'lhancJ

Chlmofonn
(Tnchlonimc,th;,ncJ

C.lroOnt~lr;ichl

From lefr to right, each structure iden~ifies an organic compound in which one, f’.l·c
three, and four hydrogen atoms, resprcuve(r, have been substituted with c~!orine Jfoni~
These compounds are known mamly by thc1.r common ~a mes: methyl chloride, methylcr~
ch loride, chloroform, and carbon tetrachloride, rcspcct1velr, ,

ln the IUPAC system, the halogen atoms arc named as substJt~cnts ~f the compound h.ii.
ing the longest continuous chain of carbo~ atoms. _As first noted m Section 5.14, thr haKlgr:l
atoms are named as substitucnrs by rcp!acmg the -me suffix on the name of the halogen llit&
-o. The number of halogen atoms is indica ted by the use of mo110-, d,- , tn-, tetra -, and !O
forth, for one, rwo, three, four, or more atoms of rhc same halogen, respectively. Henct, tit
IUPAC names of rhc chlorinated derivatives of methane are chloromethane (rhe mono-~
is droppro), dichloromethanc, trich/oromethanc, and retrachloromethane.

•M’frliliHifiifll

5 14

1hr ma1or compooent 1n the fore suppressant k/’IOWTl as Pyro•Chem FM-200 1s 1. 1, 1,2,3,3,3-heptafluorOl)l”Ofl””f –
Show how th,s name 15 used to determine the mo!Ku1ar formula for tli1s substance

Sollltion: The name of this fire suopressant md,cates that 1r 1s a fluonnated derrva t1ve of propane, whostcher-.-
cat formuta 1s C3H1 The use of ~ta If\ 1he name of the lire suppressant means that seven of the e,ght Jtyc;~
atomsm propane have be-en replaced with f!uonneatoms The notation ” 1, 1, 1,2,3.3,3″ 1denul,,s prw~~wr.:-
hydro;,n atoms a!Qrlg tne three-

FF F
I ‘ F- C-C – C- F

I I I
F H f

Th,s formula may bt conde~ to CF3-

The molecular s1rucrures and names of several chlorinated derivat ives of erhant arr
noted below:

CHJ- CH1CI
Chloroc-1h;ii-1,· l.f -D,chlonx1h.mc 1.2-Dichloroc th:rnc

C! – CI-I – CH1CI
CJ

Cl – CH – 0 1- CI
I I

Cl Cl

Cl

Cl
I

c 1- C- CH3
I

Cl
Ll,1 -TnchloroclhlM

I
CJ – C – Gl2CI

I
Cl

l , l .2•Tnchlora.-1hanc I. J.~ .l Tclr.l( ~/,,nicttun,•

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I
I. J, ),J TCIIJChl,)rOclh:lllC

The molecu lar structures and names of the ch lo ri nated derwaU\’es of ethenc- arc
nottdnes t:

Cl II

\ I
C,: C
I I

11 I!

Cl Cl
I I
C= C
I I

fl H
‘ “I~ D,chl<1rocth,n,:

Cl Cl
\ I
C= C
I \

Cl II
Tn,hloror-thrn,:,

Cl H
I I
C= C
I I

II Cl

Cl Cl
\ I
C= C
I I

Cl Cl
Tr1r:1..hlon:,e1hrnc

Cl II
I I
C C
I \

Cl II

Each of these simplc chlorinated hydrocarbons is a colorless, wa1cr-insoluble, high! )’
,·obrile liquid/ most a_re nonfl~mmable. For decades, this combination of physica l propcnies
vns the rechmcal basis fo r their popular use by many manufacmring :rnd process industries.
for ex:t mplc, trichloroerhene, 1,1 , l -trichloroethane, and l ,1,2.2-tt1rachloroethane were
once popular industrial degreasers. These liquids were used to cff«tively clean oil, grease,
\\’as, and other undesirable material from metallic, textile, and glass surfaces. Ca rbon
rmachloride once was m ed as a fire-extinguishing agent. Methylene chloride forme rly
was widely used as an aerosol, and is still used as a solvent. Tetrachloroethenc, also ca lled
pmhloroethylene and perc, is still used as a popular dry-cleaning agent in many stat es,
although in southern Ca lifornia, its use is illegal in new and upgraded facilities.

Whtn inhaled, the vapors of rhese simplr chlorinated hydrocarbons can ca use cancer.
Furthermore, when released to the environment, 1hcy deplete s1ra1ospheric ozone. One by
ont, the simple chlorinatcd hrdrocarbons ha ve been replaced in the modern world with
othtr substances that perform as well for a specific purpose but do not cause cancer or
deplete stratospheric ozone. Chemical companies are still actively sea rching for substances
10 replace tetrachloroerhene as an economical dry-cleaning agent because 1hc days of its
ust are probably numbered. One nonhazardous agent that has been chosc-n for this pur-
post is a mixture of banana and orange ex1rae1s.

12.14-A ILL EFFECTS CAUSED BY INHALING THE VAPORS
OF THE SIMPLE HALOGENATED HYDROCARBONS

When the vapors of the halogenated methanes and etha nes are inhaled at relativelr low
conccmrations, the)’ usually cause lighthcadcdness, dizziness, and fatigue. However, when
they arr inhaled at concentrations above their permissible exposure limits, they ca use a
lowering of consciousness that can be life-threatening.

Inha lation exposure co the v.ipors of the following halogenated hydrocarbons causes
cancer in laboratory animals: bromodichloromethanc, carbon 1etrachloridc, chlo roform,
1,2-dichloroethane, hexachloroethane, mc-thylene chloride, tetrachloroethene, tet rafluo-
roNhene, and trichloroethene. EPA classifies trichlorocthene as a human carcinogen, 13
bur the ocher halogenated hydrocarbons in this list generally are ack nowledged to be
probable carcinogens,

12.14-B TRANSPORTING THE HALOGENATED HYDROCARBONS
When shippers offer a halogen.ired hydrocarbon for 1r::mspor1?tion, _D~T requires them
to enrer th e rel evant shipping description on a n accompanying s~1pp1~g paprr. Some
CX3 mples for severa l representative ha logena1ed hydrocarbons arc listed m Table 12. 16.

IJ “Toiucologica l Review of Tr ichloroethykne~ (EPA/6J5/R•09/0IIF) IWash1ng1on, DC: U.S. Em·lronmrnul
Prot«:t,onAgency, 1011),

deg re<1str•Any organic compound used as a solvent to remove grease and oil from surfaces

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 515

I I

Ml’thylene
chloride

chlorofluorocarbon
(CFq • Any compound
whosemoteculesare
composed solely of
carbon, chlorine, and
fluor ine atoms

8/Hiliiii Shipping Desmpbons of Some Representative Halogenated Hydrocarbons
HALOGENATED HYDROCARBON
OR GROUPS THEREOF

Al\ylchloride

Carbon tetrachlo ride

Chlorod 1fluoromethane

SHIPPING DESCRIPTION

UNllOO, Allylchlor1de, 3, (61), PG~ )——

UN1846, Carbon tetrachloride, 6.1, PG II (Marine Pollutant)(Po.
UNI0l8, Chlorod1fluoromethane, 22
o,
UN101 8, Refr igeratedgasR-22, 2.2

=Chcclo-,o-;-fo-,m—–r;;;UN:;-;1;;888;;-,;;Ch;;loroform, 6.1, PG 111 (Poison) —-
Chlorotnfluoromethane UN1022, Chlorotrifluoromethane, 2 2

o,
UN1022,Refrigeratedgas R-13, 2.2 0,,-:-,_=-0,-:-,,,–,0,-0,-::lh-.,:-,—T, ~UN;;,;;,.,,_-;-,_;–;,_o;;:,,:;;hl;;:o,=o,:;;,,;:.,;:,,-;,-;_ ,;;c;;-,,—-

~,,~,-,-,oo-, ccdi~lh,-lo,~,d~,.—,~U~N~ll”~~. ,~lh~,,=eo~,d;;ic:;;h,=o,~,d~,. ,3,o,pc~,~, —-
Methyl bromide

Methyl chloride

Methylene chloride

1,1,2,2-Tetrachloroethane

Tetrachloroethylene

1,1,1 -Trichloroethane

Trichloroethy!ene

UN1062, Methyl brom ide, 2 l (Poison • Inhalation Hazard, ZOlltQ
I UN1063,Methylchloride,2.I —

o,
UN1063, Refr igeratedgasR-40, 2.1

UN1593, Dichloromethane, 6.1, PG 111 (Poison)

i UN1702, 1, 1,2,2-Tetrachloroethane, 6 1, PG II (Poison) (Marint
I Pollutant) UN1897, Tetrachloroethylene, 6.1, PG Ill (Poi1on) (Marine PolliJtanu

UN2831, 1, 1, 1-Trkhloroethane, 6 1, PG Ill (Poison)

i UN1710, Trichloroethylene,6.1, PG Ul(Poison)
•E1hytenedl(hlo1ide.tnd\,2-d1(hloroeth•ne.t1esynonym1.

DOT also requires shippers and carr iers to comply wi th all applica ble labeling, marking,
and placarding requirements.

12.15 CHLOROFLUOROCARBONS AND THEIR
RELATED COMPOUNDS

A special grou p of halogenated hydroca rbons are the chlorofluorocarbons, or CFCs. Their
molecules contain only carbon, chlorine and fluorine atoms. They fo rmerly were impor-
tant commercial compounds, but for reasons soon to be discussed, their use has bttn sharply cunailed worldwide.

The commercially important chlorofluoroca rbons used in the past were primw!r
members of the following classes of substances:

• Chloroflitoromethanes, These compounds have the gene ral chemical formulJ
CF ,Cl,._., where x and 11 are whole numbers less than 4.

• Chlorofl,mroetha11es. These compounds have the general chemical formula C2F~Clr,•
where x and II arc whole numbers less than 6.

As a class of organic compounds, the chlorofluoroca rbons are relatively inert su~·
stances. They readily vaporize at room temperature. Although many are nonflammJb r gases, some are flammable.

516 Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I

Thr chlorofluorocarbons typically were pre db
commercially available chlorinated hydroca.rbo~~r;or !’ react ing h}drofluoric acid w11h a
romethanes was prepared from carbon tetrachloride as fu

1
:~.:; a mixture of chlorof\uo-

KCllg) -i- JHI·(/) –. CCl~F2(g) .,. CChF(~) .._ JHCUg)
c,rt,.:,nlctl’3<.hlon,k ll)fen

The two chlorofluoroca rbons were then separated by disullation.
Some examples of the CFCs and ‘.heir related compounds, hydrofluorocarbons and

h)drochlorofluorocarbons, are n~ttd in Table 12.17. Aside from their chemical names
they ar~ .also k~own by com.merc1a\. names as CFC-u,xy:, or R-wxy~, where w, x, )’, and
, are d1g1ts derived from their chemical formulas as follows:

w ,.. the number of carbon-carbon double bonds per moll!CU!c
x ,.. the number of carbon atoms per molttule minus one
y =- 1he number of hydrogen atoms per molecule plus one
z – the number of fluorine atoms per molecule

When w, x, y, or l i.s zero, the digit is omitted. For example, 1u, :t, )’, and z fo r the ch!o-
rof\uoroc~ rbon having the formula CFC\3 are 0, 0, 1, and I, respec1ively. It is denoted
commerctally by the product names CFC· 11 or R-11. Usmg the \UPAC sys1em, n is named trichlorofluoromethant’.

Sometimes, it is necessary to distinguish between two or more structural isomers of
the chlorofluoroethanes in their commercial names. The compound within a group of
these isomers having the smalles1 atomic mass difference on each of the two carbon atoms
is denoted without a letter. A lowercase a, b, c, or dis appended to WX)’Z to differentiate
1he isomers as their masses diverge from this difference.

As individual compounds and blends thereof, the chlorofluoroca rbons once were
widely used for the following purposes:

I Refrigerants and coolants in residential and commercial refrigemion and air-conditioning
equipment, including refrigerators, frttZers, dehumidifiers, water coolers, ice machines, and
air-conditioning units (including automotive air-conditioning units). The CFCs were first
commercially introduced into the U.S. market in 1931 as safe ahernati\·es to the flammable
and toxic substances then in common use fo r cooling: methyl chloride, sulfur dioxide, and
ammonia, In commerce, they arc known ooUea:ively as Freons, or Freon agents.
Cleaning fluids fo r electric, precision electronic, and photographic equipment and for
maintaining aircrah . _ .

I Foam-blowing agents by extruded-polystyrene (Section 14.2-Al and n~1.d-poly’.1rethane•
foam man11faciurers (Section 14.9). Because the CFCs ha\’e low ~oihng points, the}’
readily vaporize when mixed with hot plastics. The bubbles of t.h~1r vapors caustd the
plastics to expand until the)’ resembled frothy mi>:tures that sohd_1fied as foams. These
foams were 1hen marketed commercially as insulat10.n and packaging.
~erosols for dispensing cons~lfller products containenzed inr m:t:~::· :~F~ t~r~
is ~lieved ro have. releas~ m.to the. aun~_phere fal~~te te~s to ·de fixed amoums.
refrigeration and alf-rondmomng uruts, v. hich use c .. rs b~ .

1
cu

When mixed with rthylene oxide, sterilizers of heat-sens’.t1vc reu·sa· e osp1t_a appara s.
A general inhalation anesthetic in hospitals and ,·ctermary chmcs, espmally the com-
pound known commercially as halothanc, or fluothane.

Cl F
I I

Br-C-C- F
I I
H F

2-Hmmo-!-chloro-1. 1.1 tn!lu~tlunc
i l\l llllhJl’lc)

T1trachl010•
1th1n1

t
Carbon

t1tr.chlorid1

Fr, on(freon ag,nt,)
• Thetrademarkofany
chlo1ofluo1ocarbon,
hydrochlorol luorocar-
bon, and hydrofluo10-
carbon used a1 a
foam-blowing agent or
refr igerant

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 517