Reactions

of Hydrocarbons and
Aromatic Compounds
 Focus on the Environment
Combustion

Alkanes have no functional group, so they undergo

few reactions.
Combustion is an oxidation–reduction reaction
(Section 5.4).

In the combustion reaction, alkanes burn in the

presence of 𝐎𝟐 gas to form 𝐂𝐎𝟐 and 𝐇𝟐 𝐎 .

The products, 𝐂𝐎𝟐 + 𝐇𝟐 𝐎, are the same, regardless

of the identity of the alkane that undergoes
combustion.
 12.8 Focus on the Environment
Combustion (2)

CH( +2 O, CO, + 2 H, O + energy

-./01
methane
(natural gas)

2(CH8 )8 CCH, CH(CH8), +25 O,

-./01
16 CO, + 18 H, O + energy

isooctane
(high-octane component of
gasoline)
 12.8 Focus on the Environment
Combustion (3)

If there is not enough 𝐎𝟐 to react, incomplete

combustion may occur, and carbon monoxide
(CO) is formed instead of carbon dioxide (𝐂𝐎𝟐 ).

2CH( 2 CO
+ 3 O, + 4 H, O + energy
methane -./01 carbon monoxide

Carbon monoxide is a poisonous gas that binds to

hemoglobin in blood, thereby reducing the
amount of 𝐎𝟐 that can be transported to cells.
 12.9 Halogenation of Alkanes

The reaction of an alkane with a halogen (𝐂𝐈𝟐 or

𝐁𝐫𝟐 ) is called halogenation.

The reaction forms an alkyl halide (RCl or RBr)

and a hydrogen halide (HCl or HBr).

Halogenation is a substitution reaction, an atom is

replaced by another atom or group of atoms.
 13.6 Reactions of Alkenes (1)

Alkenes undergo addition reactions wherein new

groups X and Y are added to the alkene.

One bond of the double bond is broken and two

new single bonds are formed.
In an addition reaction, the weak bond is broken and two new strong single bonds are formed.
Alkenes react with hydrogen (H2), halogens (Cl2 and Br2), hydrogen halides (HCl and HBr), and
13.6 Reactions of Alkenes (2)
water (H2O). These reactions are illustrated in Figure 13.4 with a single alkene starting material.

One bond is broken. Two single bonds are formed.

H H
H2
H
Hydrogenation
metal catalyst H
H
cyclohexene H

H
X2
X
Halogenation
(X = Cl or Br) X
H
H
HX H
Hydrohalogenation
(X = Cl or Br) X
H
H
H2O H
Hydration
H2SO4 OH
H
 13.6 Reactions of Alkenes (3)
A. Addition of Hydrogen—Hydrogenation
Hydrogenation is the addition of 𝐇𝟐 to an alkene.

The metal catalyst (usually palladium—Pd) speeds

up the rate of the reaction.

The product of hydrogenation is an alkane.

 13.6 Reactions of Alkenes (4)
A. Addition of Hydrogen—Hydrogenation

The metal catalyst provides a surface that

binds both the alkene and 𝐇𝟐, which speeds
up the rate of reaction.
 13.6 Reactions of Alkenes (5)
B. Addition of Halogen—Halogenation
Halogenation is the addition of halogen (𝐗 𝟐) to an
alkene.

𝐗 𝟐 is usually 𝐂𝐥𝟐 or 𝐁𝐫𝟐 .

Halogenation occurs readily and does not

require a catalyst.
The product of halogenation is a dihalide.
 13.6 Reactions of Alkenes (6)
B. Addition of Halogen—Halogenation
 13.6 Reactions of Alkenes (7)
C. Addition of Hydrogen Halides—
Hydrohalogenation

Hydrohalogenation is the addition of HX (HCl or

HBr) to an alkene.

The product of hydrohalogenation is an alkyl halide.

 13.6 Reactions of Alkenes (8)
C. Addition of Hydrogen Halides—
Hydrohalogenation
 13.6 Reactions of Alkenes (9)
C. Addition of Hydrogen Halides—
Hydrohalogenation
If the reactant is an asymmetrical alkene, two
possible products can be formed in theory.

These two potential products are constitutional

isomers.
 13.6 Reactions of Alkenes (10)
C. Addition of Hydrogen Halides—
Hydrohalogenation

To determine which of the two products will

actually form, we use Markovnikov’s rule.

Markovnikov’s rule states that the H atom of

H–X will bond to the less substituted C atom
in the C=C double bond.

This means the C in the double bond with the

most H’s will bond to the H atom of H–X.
 13.6 Reactions of Alkenes (11)
C. Addition of Hydrogen Halides—
FIRST PAGES Hydrohalogenation
UNSATURATED HYDROCAR

CH3 H H H H H
C C + HCl CH3 C C H or CH3 C C H
H H Cl H H Cl
C2 C1 C2 C1
propene 2-chloropropane 1-chloropropane

only product

ample, the addition of HCl to propene could in theory form two products. If H adds
rbon (labeled C1) and Cl adds to the middle carbon (C2), 2-chloropropane is formed
o the end carbon (C1) and H adds to the middle carbon (C2), 1-chloropropane is form
of HX to an alkene.

13.6
addition of HX to an Reactions of Alkenes (12)
unsymmetrical alkene, the H atom bonds to the less substi
on atom—that is, the
C. carbon that has more H’s to begin with.
Addition of Hydrogen Halides—
Hydrohalogenation
carbon (C1) of propene has two hydrogens while the middle carbon (C2) has
n. Addition puts the H of HCl on C1 since it had more hydrogens (two versus
h.
CH3 H H H
C C + H Cl CH3 C C H
This C has only 1 H H H Cl H
so the Cl bonds here.
This C has 2 H’s so the H bonds here.

E PROBLEM 13.6
duct is formed when 2-methylpropene [(CH3)2C CH2] is treated with HBr?

s
 13.6 Reactions of Alkenes (13)
D. Addition of Water—Hydration

Hydration is the addition of water to an alkene.

Hydration requires a strong acid, 𝐇𝟐 𝐒𝐎𝟒.

The product formed by hydration is an alcohol.

 13.6 Reactions of Alkenes (14)
D. Addition of Water—Hydration
se of a great deal of energy. Although ethanol can also be formed by the fermentati
drates in grains and potatoes, much of the ethanol currently used in gasoline and so
13.6 Reactions of Alkenes (15)
om the hydration of ethylene.
D. Addition of Water—Hydration
ation of unsymmetrical alkenes follows Markovnikov’s rule.
If the reactant is an asymmetrical alkene, the
addition of H2O to an unsymmetrical alkene, the H atom bonds to the less substitu
product
on atom—that will be
is, the carbon determined
that bybegin
has more H’s to Markovnikov’s
with.
rule.
CH3 H H H
C C + H OH CH3 C C H
H2SO4
This C has only 1 H H H OH H
so the OH bonds here.
This C has 2 H’s so the H bonds here.

EM 13.18
ohol is formed when each alkene is treated with H2O in the presence of H2SO4?

CH3
CH CHCH3 b. CH3CH2CH CH2 c.
 13.7 Focus on Health and Medicine
Margarine or Butter? (1)
Butter is made up of saturated fatty acid chains.

A diet rich in saturated fatty acids is widely

considered to be unhealthy.

Scientists have attempted to produce alternative

versions of butter (margarine) with similar taste
and properties, but with some C═C double bonds
(that is, unsaturated fatty acid chains).
 13.7 Focus on Health and Medicine
Margarine or Butter? (2)
Most naturally occurring unsaturated fatty acid
compounds are liquids at room temperature.

To make the desired butter alternative, we need a

compound that is a solid at room temperature.

This is done by partially hydrogenating

unsaturated fatty acid compounds.

This process allows only a few C═C double bonds

to remain on the chain, making a solid fatty acid
that is not naturally occurring.
13.7 Focus on Health and Medicine
Margarine or Butter? (3)

Unsaturated vegetable oil

• two C=C’s
• lower melting
• liquid at room temperature

Partially hydrogenated oil

in margarine
• one C=C
• higher melting
• semi-solid at room temperature

© The McGraw-Hill Companies, Inc./Jill Braaten, photographer

 13.7 Focus on Health and Medicine
Margarine or Butter? (4)
Some partial hydrogenations leave trans double
bonds on the fatty acid chain.

Trans fatty acids are very similar in shape to

saturated fatty acids.

Trans fatty acids are widely considered to be just

as unhealthy as saturated fatty acids.

Nutritionists agree that a healthy diet consists of

very few saturated or trans fats.
13.7 Focus on Health and Medicine
Margarine or Butter? (5)
 13.9 Aromatic Compounds (1)
Aromatic compounds are compounds that
contain a benzene ring.

Each C is trigonal planar (that is, 𝟏𝟐𝟎𝐨 bond

angles), making benzene a planar molecule.
 13.9 Aromatic Compounds (2)

Each of these representations has the same

arrangement of atoms, but different locations of
electrons.
These are resonance structures, and neither is the
true structure of benzene.

The actual structure is a combination of both

resonance structures, called a hybrid.
 13.9 Aromatic Compounds (3)
In this hybrid structure, all three electron pairs in
the double bonds are delocalized in the six-
membered ring.

This can be drawn as a circle inside the hexagon.

Delocalization gives benzene added stability

compared to other unsaturated hydrocarbons.
 13.9 Aromatic Compounds (4)
Aromatic hydrocarbons do not undergo the
addition reactions that characterize alkenes.
 13.10 Nomenclature of Benzene Derivatives (1)
A. Monosubstituted Benzenes
To name a benzene ring with one substituent:
• Name the substituent first
• Then add the word benzene at the end
13.10 Nomenclature of Benzene Derivatives (2)
A. Monosubstituted Benzenes

Some monosubstituted benzenes have common

names.
 13.10 Nomenclature of Benzene Derivatives (3)
B. Disubstituted Benzenes

1,2-Disubstituted benzene 1,3-Disubstituted benzene 1,4-Disubstituted benzene

ortho isomer meta isomer para isomer
13.10 Nomenclature of Benzene Derivatives (4)
B. Disubstituted Benzenes

If there are two groups on the benzene ring and

they are different, alphabetize the two substituent
names.
13.10 Nomenclature of Benzene Derivatives (5)
B. Disubstituted Benzenes

If one of the two substituents is part of a

common root, then name the molecule as a
derivative of that monosubstituted benzene.
13.10 Nomenclature of Benzene Derivatives (6)
C. Polysubstituted Benzenes

Number to give the lowest possible numbers

around the ring.
Alphabetize the substituent names.

When the substituents are part of common roots:

• Name the molecule as a derivative of that

monosubstituted benzene

• Put the common root substituent at C1, but

omit the “1” from the name
13.10 Nomenclature of Benzene Derivatives (7)
C. Polysubstituted Benzenes

Assign the lowest set of numbers.

Alphabetize the names of all the substituents.

4-chloro-1-ethyl-2-propylbenzene
13.10 Nomenclature of Benzene Derivatives (8)
C. Polysubstituted Benzenes

Name the molecule as a derivative of the common

root aniline.
Assign the 𝐍𝐇𝟐 group to position 1 and then assign
the lowest possible set of numbers to the other
groups.
2,5-dichloroaniline
 13.10 Nomenclature of Benzene Derivatives (9)
D. Aromatic Compounds with More than One Ring
 13.11 Focus on Health and Medicine
Aromatic Drugs, Sunscreens, and Carcinogens (1)
Some common drugs that contain benzene
rings are:

(top): ©McGraw-Hill Education/John Thoeming, photographer; (middle):

©Rob Walls/ Alamy; (bottom): ©Picture Partners/Alamy
 13.11 Focus on Health and Medicine
Aromatic Drugs, Sunscreens, and Carcinogens (2)
A common sunscreen used contains benzene:

A common environmental pollutant that is a

potential carcinogen has several benzene rings:
13.13 Reactions of Aromatic Compounds (1)
Aromatic compounds undergo substitution
reactions primarily.
Substitution is a reaction in which an atom is
replaced by another atom or group of atoms.

Substitution of H by X keeps the stable aromatic

ring intact.
13.13 Reactions of Aromatic Compounds (2)
A. Chlorination and DDT
In chlorination, a Cl atom substitutes for a
hydrogen atom on the benzene ring.

The pesticide DDT is formed by a

chlorination reaction.
(Dichlorodiphenyltrichloroethane)
13.13 Reactions of Aromatic Compounds (3)
B. Nitration and Sulfa Drugs

Benzene reacts with nitric acid (𝐇𝐍𝐎𝟑 ) in the

presence of sulfuric acid (𝐇𝟐 𝐒𝐎𝟒) to form
nitrobenzene.

Substitution of a nitro group (𝐍𝐎𝟐 ) for a

hydrogen is called nitration.
13.13 Reactions of Aromatic Compounds (4)
B. Nitration and Sulfa Drugs

Sulfa drugs, such as the antibacterial agents shown

below, are formed by the nitration reaction.
 13.13 Reactions of Aromatic Compounds (5)
C. Sulfonation and Detergent Synthesis
In sulfonation, benzene reacts with 𝐒𝐎𝟑 in the
presence of 𝐇𝟐 𝐒𝐎𝟒 such that a 𝐒𝐎𝟑 𝐇 group
substitutes for a hydrogen atom on the benzene ring.

The synthetic detergent

shown is a product of
sulfonation.