City University

Faculties of Marine Science & Agriculture

Organic Chemistry

 
Lecturer: Mr.Abdirashid Adam Isak
M.Sc. in Pure Chemistry
 CHAPTER 3

Unsaturated Hydrocarbons
 Unsaturated Hydrocarbons
 Definition:
 Hydrocarbons in which all the valencies of
carbon atoms are not fully utilized by
single covalent bonds are known as
"unsaturated hydrocarbons". 
They contain at least one double or triple
bond in their structure.
 Classification of Unsaturated
Hydrocarbons

 Unsaturated Hydrocarbons can be

classified into Alkenes and Alkynes
 Alkenes
 Alkenes are open chain unsaturated hydrocarbons in which a
carbon-carbon bond is a double covalent bond.
   GENERAL FORMULA:            CnH2n
 Where, n=number of carbon atoms and n is greater than 1.
 They are very reactive organic compounds due to the presence
of double BOND. They are also known as "OLEFINS”.
 Trigonal shape around C with the double bond.
 The simplest of Alkenes is C2H4 Ethene.
TABLE 2.1
 The first two members of alkenes are:

Common Name: Ethylene

IUPAC Name: Ethene

Common Name: Propylene

IUPAC Name: Propene

Bonding and Geometry of Two-Carbon Molecules
 Alkenes (Continued…)

 The double bond of alkenes is shorter and

stronger than the single bond of alkanes.
 The double bond makes alkenes more
reactive than alkanes.
 Many naturally occurring biological
compounds contain the double bond found
in alkenes.
Alkenes (Continued…)
Naturally Occurring Alkenes

Alkene Function
β-Carotene Orange pigment in
carrots and potatoes
Limonene Scent of citrus fruits
α-Pinene Scent of pine trees
Fatty acids, Biologically important
cholesterol compounds
Naturally Occurring Alkenes
Physical Properties of Alkenes

1) First three members are gases, while C5 to C15

are liquids and higher members are solids.

2) They are insoluble in water.

3) They have characteristic smell and burn with
luminous flame.
 Physical Properties of Alkenes
TABLE 2.2

Name Formula Molar Mass BP, °C Density, g/cm 3

ethene CH2=CH2 28 -104 0.52
propene CH2=CHCH3 42 -47 0.59
1-butene CH2=CHCH2CH3 56 -6 0.59
1-pentene CH2=CH(CH2)2CH3 70 30 0.64
1-hexene CH2=CH(CH2)3CH3 84 64 0.68
1-heptene CH2=CH(CH2)4CH3 98 93 0.70
1-octene CH2=CH(CH2)5CH3 112 122 0.72
1-nonene CH2=CH(CH2)6CH3 126 146 0.73
1-decene CH2=CH(CH2)7CH3 140 171 0.74
IUPAC Nomenclature of Alkenes

1) Choosing the main chain ：

The longest one containing the double bond
2)
Numbering:
From the end nearest the double bond and
use the first number of the double bond to
locate it
3)
Naming
The name
: of alkene ends in
 Write theExamples
IUPAC name of each of the following:

CH3- C CH2 2-methyl-1-propene

CH3
CH3- CH2- CH-CH CH- CH3 4-methyl-2-hexene
CH3

CH3- CH CH-CH-CH3 4-methyl-2-pentene

CH3

CH3-CH2- C CH
CH 2
-
-CH – CH3 3,6-ethylmethyl-3-heptene
C2H5 CH3
(Continued…)
(Continued…)
(Continued…)
 (Continued…)

Pay attention to the number of the substituent

only if you get the same number for the
functional group in both directions.
 Exercise
Write the IUPAC name of each of the following:

1 CH3- CH- CH2 -CH2- CH CH2

CH3
CH3- CH- CH-CH CH- CH3
2
CH2 CH2
CH3 CH2
CH3
CH3- CH C -CH2-CH3
3
CH3
CH3 CH2-C CHC-
2 CH3

C2H5 CH3
4
Structural Formula of Alkenes
 Learning Check:
Draw the structure for each of the
following

 3,4-dimethyl-2-pentene
 3-ethyl-2-methyl-1-hexene
 3,4-bromoethyl-3-heptene
Learning Check
Name each, using cis-trans prefixes when needed.
Br Br
A. C C
H H

CH3 H
B. C C
H CH3

CH3 Cl
C. C C
H Cl
Unsaturated Hydrocarbons

Reactions of Alkenes

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
31
 Reactions of Alkenes
There are four addition reactions we will study,
summarized in table 3.2
TABLE 3.2
Reactions of Alkenes (Continued…)

 A) Addition reactions:
 1) Hydrogenation: Addition of hydrogen
to an unsaturated molecule

Heat-
 Hydrogenation of Oils
Adding H2 to double
bonds in vegetable
oils produces:
 Compounds with higher

melting points.
 Solids at room

temperature such as
margarine,
soft margarine,
and shortening.
2) Halogenation
 Alkenes easily add halogen molecules
Addition of Halogens (Continued…)
 3) Hydrohalogenation
Alkenes react with hydrogen halides (HCl, HBr etc.) to form
halogenoalkanes. The reaction occurs at room temperature and
pressure. e.g.
H H H H
C=C + HBr H–C–C–H
H H H Br

C2H4 + HBr  CH3CH2Br

ethene bromoethane
 Hydrohalogenation (Continued…)
What happens in hydrohalogenation reactions?
Again, think about where atoms of a hydrogen
halide end up.

H Cl
CH3 CH CH CH3 + HCl CH3 CH CH CH3

H
+ HBr

Br
 Markovnikov’s Rule
 When an unsymmetrical alkene undergoes
hydrohalogenation, the H in HX adds to the carbon
in the double bond that has the greater number of
H atoms .
H Cl
CH3 CH CH2 Does not form

CH3 CH CH2 + HCl

C with the most H
Cl H
CH3 CH CH2 Product that forms
4) Hydration
 Addition of water to an alkene
Hydration (Continued…)
When hydration occurs with a double bond that has an
unequal number of H atoms,
 The H atom bonds to the C in the double bond with
the most H.
 The OH bonds to the C in the double bond with the
fewest H atoms.
OH H
H+ │ │
CH3─CH=CH2 + H─OH CH3─CH─CH2
(1H) (2H)
Learning Check
Write the product for the hydration of each of the
following:
H+
1. CH3─CH2─CH=CH─CH2─CH3 + HOH
CH3
│ H+
2. CH3─C=CH─CH2─CH3 + HOH

H+
3. + HOH
Learning Check
Write the products of each reaction

A. CH3 CH CH2 + Cl2

CH3 CH CH CH3 + HOH H+

B.

Pt
C. + H2
 B) Combustion

 Alkenes burn in air with luminous

flame and produce carbon dioxide,
water vapour and heat.

C2H4 + 3O2 → 2CO2 + 2H2O + Heat

Polymers
Polymers are
 Large, long-chain molecules.
 Found in nature, including cellulose in plants,
starches in food, proteins and DNA in the body.
 Also synthetic such as polyethylene and
polystyrene, Teflon, and nylon.
 Made up of small repeating units called
monomers.
 Made by reaction of small alkenes.

45
C) Polymerization
 Is the process of simple units combine
to form large molecules.
 Monomer : Simple unit
 Polymer : Large molecule
 n(CH2 = CH2) → [- CH2 - CH2-]n
Ethylene (Monomer) Polyethylene (Ploymer)
 Polymerization
 In polymerization, small repeating units called
monomers join to form a long chain polymer.
H H H H H H
C C + C C + C C
H H H H H H monomer unit repeats
Ethylene monomers
H H H H H H
chain continues C C C C C C chain continues
H H H H H H
n
Polyethylene
 Polymers from Addition Reactions
TABLE 2.3
Common Synthetic Polymers

49
 Use of Alkenes
 Ethylene is used:
 For the manufacture of polyethylene, a plastic
material used for different purposes.
 For artificial ripening of fruits.
 As a starting material for a large number of
chemicals of industrial use such as glycols
(antifreeze), ethyl halide, ethyl alcohol, etc.
Exercise
 1) Write equations for the reaction
between CH3CH=CHCH3 and each of the
following:
 H2 with (Ni catalyst)

 Br2

 H2O with (H2SO4 catalyst)

 Alkynes
 Alkynes are unsaturated hydrocarbons in which a
carbon-carbon bond is a triple covalent bond.
   GENERAL FORMULA:           CnH2n-2
Where, n=number of carbon atoms and n is greater
than 1.
 Linear shape around C with the triple bond.
IUPAC Name:
 The simplest of Alkynes is C2H2 Ethyne.
Common Name: Acetylene
 Physical Properties of Alkynes

1) They are colourless, odourless, except

acetylene which has a garlic like odour.

2) The first three members are gases at

room temperature, while next eight members

are liquids and higher members are solids.

 Physical Properties of Alkynes

3) The melting points, boiling points and

densities increase gradually with the increase

in molecular masses.

4) They dissolve readily in solvents like ether,

benzene and carbon tetrachloride.

IUPAC Nomenclature of Alkynes
1) Choosing the main chain ：
The longest one containing the triple bond
2)
Numbering:
From the end nearest the triple bond and
use the first number of the triple bond to
locate it
3)
Naming
The name
: of alkyne ends in
Naming Alkynes (Continued…)

Alkyne IUPACCommon
HC≡CH ethyne acetylene
HC≡C─CH3 propyne

Br

H3C CH C C CH3 4-Bromo-2-pentyne

5 4 3 2 1

cycloheptyne
 Examples
Write the (Continued…)
IUPAC name of each of the following:

CH3 -CH – C CH 3-methyl-1-butyne

CH3
CH3- CH2- CH-C C- CH3 4-methyl-2-hexyne
CH3

CH3- C C-CH-CH3 4-methyl-2-pentyne

CH3

CH3-CH2- C CH
C - CH – CH3 5,6-ethylmethyl-3-heptyne
C2H5 CH3
 Exercise
Write the IUPAC name of each of the following:

CH3 -CH – C C –CH3

CH3
–CH3
CH3- CH2- CH-C C- CH2
CH3

CH3- C C-CH-CH2–CH3
CH3

CH3-CH2-CH - C C- CH - CH – CH3
CH3 C2H5 CH3
 Draw the condensed
structural formula for
2-methyl-3-hexyne.
STEP 1 Draw the main chain of carbon atoms. For
3-hexyne, there are six carbon atoms in the chain, with a
triple bond between carbons 3 and 4,
C─C─C≡C─C─C

STEP 2 Number the chain and place the substituents on

the carbons indicated by the numbers.
CH3

C─C─C≡C─C─C
1 2 3 4 5 6
Basic Chemistry Copyright © 2011 Pearson Education, Inc.
 Solution (continued)
STEP 3 Add the correct number of hydrogen
atoms to give four bonds to each C atom.

CH3

CH3─CH─C≡C─CH2─CH3
1 2 3 4 5 6

2-methyl-3-hexyne

Basic Chemistry Copyright © 2011 Pearson Education, Inc.

Exercise:
Draw the structure for each of the following

 4-methyl-2-pentyne
 3-ethyl-4-methyl-1-hexyne
 2,5-bromoethyl-3-heptyne
Reactions of Alkynes
 A) Addition reactions:

 Alkynes undergo addition reactions

like alkenes but add two molecules
of the reagent instead of one.
 Initially alkenes are formed and
then alkanes.
1) Hydrogenation
 Alkynes react with hydrogen in the
presence of catalysts like Ni, Pt or Pd.
 H–C C-H + H2 Heat Ni
CH2 CH2
Ethyne Ethene

Heat-
 2) Halogenation
 One or two molecules of halogens can be added to alkynes
giving dihalides and tetra halides respectively.
 H–C C-H + Br2 CH CH
Ethyne
Br Br
1,2-dibromoethene

Br Br

Br Br
1,2-dibromo 1,1,2,2-tetrabromoethane
 B) Combustion
 Ethyne when burnt in air or oxygen
produces carbon dioxide, water vapour
and heat.
 The reaction is highly exothermic and
the resulting oxyacetylene flame is used
for welding and cutting of metals

2C2H2 + 5O2 → 4CO2 + 2H2O + Heat

Acetylene
C) Polymerization
 Conversion of acetylene to benzene:
 When acetylene is passed through a
copper tube at 300°C, it polymerizes to
benzene:

300°C
3C2H2 Cu-tube

Acetylene
Benzene
 Use of Alkynes
 Ethyne is used:
 In oxyacetylene torch which is in turn
used for welding and cutting metals.
 For the preparation of alcohols, acetic
acid and acetaldehyde.
 For the manufacture of polymers like PVC.
 For ripening fruits.