Alkanes

Introduction

Nomenclature of Alkanes

Physical Properties of Alkanes

Preparation of Alkanes

Reactions of Alkanes

 Alkanes are the hydrocarbons of aliphatic row.

Alkanes are hydrocarbons in which all the
bonds are single covalent bonds (-bonds).
Alkanes are called saturated hydrocarbons.
The simplest one, methane (CH4), is also the most
. abundant
All carbon atoms are sp3-hybridized
All bond angles are 109.5

Alkyl groups
Alkyl groups are formed by loss of a hydrogen atom from
the corresponding alkane . General formula of alkyl
group : CnH2n+1
( e.g. CH4 Methane 1 H = -CH3 Methyl group )
Alkyl groups are named by dropping the -ane suffix of
the alkanes and adding the suffix -yl. Methane becomes
a methyl group, ethane an ethyl group, etc.

Unbranched alkyl groups

Nomenclature Of Branched Alkyl

Groups
1. Three-Carbon Groups

- Methylethyl

is the systematic name; isopropyl is a common name.

- Numbering always begins at the point where the group is attached

to the main chain.

Propane
CH3

CH 3-CH2-CH 2-

CH3 -CH

Isopropyl

n-Propyl

Butane
CH3

CH3

CH 3-CH2-CH2-CH2-

CH3 -CH

H2
C

H3 C

C
CH3

n-Butyl

Isobutyl

tert.Butyl

2. Four-Carbon Groups

2. Four-Carbon Groups

IUPAC Nomenclature
IUPAC (International Union of Pure and
Applied Chemistry) names:
1- The unbranched alkanes (homologous
series)
2- Branched alkanes
Suffix of Alkanes added ane

Nomenclature of Alkanes

1. Straight-Chain
Straight-Chain Alkanes
Alkanes
1.
Name
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane

Number of
carbon atoms
1
2
3
4
5
6
7
8
9
10

Structure
CH4
CH3CH3
CH3CH2CH3
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)6CH3
CH3(CH2)7CH3
CH3(CH2)8CH3

Alkanes
Alkanes are molecules(hydrocarbons) that contain
only C-C and C-H bonds.
.Alkanes are either acyclic or cyclic
Acyclic alkanes (not cyclic) have the formula
CnH2n+2 (where n = an integer)

Nomenclature of Alkanes

2. Branched-Chain
Branched-ChainAlkanes
Alkanes
2.
1. Select the longest possible straight chain; this gives the
parent name for the alkane
2. Number the parent chain beginning with the end of the
chain nearer the branched chain
3. Use the number obtained by application of rule 2 to
designate the position of the branched chain
4. When two or more branched chains are present, give
each branched chain a number corresponding to its
position on the parent chain
5. When two or more branched chains are identical,
indicate this by the use of the prefixes di-, tri-,
tetra-, and so on

Nomenclature of Alkanes

1. Select the longest possible straight chain; this

gives the parent name for the alkane
CH3

CH3CH2CH2CH2CHCH3
CH3

methyl hexane- 2

CH3CH2CH2CH2CHCH3
CH2

H3C

H
C
H2C

CH

CH2

CH2

CH3

CH3

CH3

methyl heptane- 3

dimethyl heptane- 3,4

2. Number the parent chain beginning with the end of the

chain nearer the branched chain
-3 -4

CH2 CH3
7
6
5
4
3
2
1
CH3 CH2 CH2 CH CH CH2 CH3
CH3

ethyl-3- methyl heptane-4

Nomenclature of Alkanes

3- Use the numbers obtained by application of rule 2 to

designate the position of the branched chain

In writing the full name the root name is placed last; the substituent
group, preceded by the number indicating its location on the chain, is
placed first.
14

Nomenclature of Alkanes

4. When two or more substituents are present, give each

substituent a number corresponding to its location
on the longest chain.

- The substituent groups are listed alphabetically.

5. When two substituents are present on the same carbon, use

the number twice.

Nomenclature of Alkanes

6. When two or more branched chains are identical, indicate

this by the use of the prefixes di-, tri-, tetra-, and so
on. e.g.

CH3

Nomenclature of Alkanes

CH3 CH2 C
1

CH2 CH2 CH3

CH3

3,3- Dimethyl hexane

CH3
CH3 CH2 CH CH CH2 CH2 CH2 CH2 CH CH3
1

CH3

2,7,8-Trimethyl decane

10

CH3

Nomenclature of Alkanes

7. When two chains of equal length compete for selection as

the parent chain, choose the chain with the greater
number of substituents.

Nomenclature of Alkanes

8. When branching first occurs at an equal distance from

either end of the longest chain, choose the name that
gives the lower number at the first point of
difference.

Nomenclature Of Cycloalkanes
Monocyclic Compounds
1. Cycloalkanes with only one ring:

:Substituted cycloalkanes
1) Number the ring beginning with the substituent first
in the alphabet, and number in the direction that gives
the next substituent the lower number possible.
2) When three or more substituents are present, begin at
the substituent that leads to the lowest set of locants.

Physical Properties Of Alkanes and

Cycloalkanes
1. A series of compounds, where each member
differs from the next member by a constant unit, is
called a homologous series. Members of a
homologous series are called homologs.
2. At room temperature ( 25 C) and 1 atm
pressure, the C1-C4 unbranched alkanes are
gases; the C5-C17 unbranched alkanes are
liquids; the unbranched alkanes with 18 or more
carbon atoms are solids.

Physical Properties of Alkanes

Boiling Point
Point
Boiling
Higher members have
higher boiling points
:Reason
Increase in molecular
mass
Increase in
intermolecular force

Physical Properties of Alkanes

Branched-chain alkanes have lower boiling points than

straight-chain alkanes
molecule is more compact surface area
van der Waals force boiling point

Physical Properties of Alkanes

Melting Point
Point
Melting

Higher members
have higher
melting points
:Reason
Increase in
molecular mass
Increase in
intermolecular
force

Physical Properties of Alkanes

Solubility
Solubility
Alkanes:
non-polar compounds
insoluble in water and highly polar solvents
soluble in non-polar solvents like benzene,
1,1,1-trichloroethane
Density
Density
All alkanes and cycloalkanes have densities less than 1 g
cm3 at 20C.
Petroleum floats on water surface
Alkanes are less dense than water and swim on top of water

Hydrogenation of unsaturated hydrocarbon:

H2C

CH2

Ni or Pd or Pt / H2
200, 300

H3C

CH3

2) From alkyl Halides

B) Hydrolysis of Grignard Reagent

Grignard reagent is an alkyl magnesium halide compound, R-Mg-X
- The Grignard reagent is formed when a solution of an Alkyl Halide
(R-X) is allowed to stand over a metallic magnesium in the presence
of dry ether
- Then Grignard reagent react with water or alcohol to form alkane

CH3CH2Br

2+

Mg

Dry ether

CH3CH2MgBr
Grignard reagent

CH3CH2MgBr

H 3O

CH3CH3

Mg(OH)Br

C) Wurtz Reaction
This is the reaction of two alkyl halides (R-X) with metallic
sodium to give symmetrical alkanes.
The wurtz reaction is a poor method for the preparation of
unsymmetrical alkanes

2 CH3 CH2 CH2 Br + 2 Na

CH3 CH2 CH2 CH2 CH2 CH3

+ 2 NaBr

Preparation of Alkanes
Reforming
Reforming
Reforming is a process in which straight-chain alkanes
are heated under pressure in the presence of a platinum
catalyst. The chains break up and reform to give
.branched-chain molecules

Reactions of Alkanes 29.5

Combustion
Combustion
Complete combustion :
Alkanes react with sufficient oxygen to give carbon dioxide
and water through a complex series of reaction with the
release of a large amount of energy.
General formula:

3n 1
C n H 2 n 2
O 2 nCO 2 n 1 H 2O
2

complete combustion

incomplete combustion
CH3-CH2-CH3 + 4 O2 > CO2 + 2 CO + 4 H2O + heat

Reactions of Alkanes

Chlorination
Chlorination
Methane reacts with chlorine under diffuse sunlight or heating
but not in dark
A mixture of products (CH3Cl, CH2Cl2, CHCl3, CCl4) is
formed with the replacement of hydrogen by one or more
chlorine atom
If methane is
UV light
CH 4 ( g ) Cl 2 ( g ) CH 3Cl( g ) HCl( g )
in excess,
CH3Cl is
CH 3Cl( g ) Cl 2 ( g ) UV
light
CH 2Cl 2 ( g ) HCl( g )
major product
CH 2Cl 2 ( g ) Cl 2 ( g ) UV
light
CHCl3 ( g ) HCl( g )
CHCl3 ( g ) Cl 2 ( g ) UV
light
CCl 4 ( g ) HCl( g )

If chlorine is
in excess, CCl4
is major
product

Reactions of Alkanes

Reaction Mechanism: Free Radical Substitution Reaction

Mechanism of reaction :
1. Chain initiation
homolytic fission of chlorine molecules by heat or light
into two chlorine radicals
Step 1:

Reactions of Alkanes
2. Chain propagation
Step 2:

Step 3:

steps 2 and 3 repeat hundreds or thousands of time due

to formation of the reactive intermediate in each step
chain reaction

Reactions of Alkanes
Further substitution occurs:

Reactions of Alkanes

Reactions of Alkanes

Reactions of Alkanes

3. Chain termination
two free radicals combine to form a neutral molecule
the chain reaction is terminated

Reactions of Alkanes

Example
Write down the reaction mechanism involved in the chlorination
of ethane in the presence of diffuse sunlight.
Solution:
The reaction mechanism is shown as follows:
1. Chain initiation

2.Chain propagation

Answer

Reactions of Alkanes
:Solution

3. Chain termination

Mechanism For the Radical Halogenation of

Methane