Lecture 8

The alkane series

In Alkanes all of the carbon-carbon bonds are single
bonds, they are also called paraffins and have the
general formula CnH2n+2.
For n = 1, we get the simplest Hydrocarbon which is an
alkane called methane, CH4; for n = 2, C2H6; for n = 3,
C3H8; and so on.
When the carbon atoms are bonded together in a
straight chain with hydrogen atoms completing the four
required bonds to each carbon, we get Straight chainor normal alkanes.
Chemists often use the condensed formula in which
the bonds around each carbon atom in the compound
are not written.
The following table lists the first six straight chain
alkanes with their condensed formula:
Formula

Name

CH4

Methane

C2H6

Ethane

C3H8

Propane

C4H10

Butane

Displayed formula

Condensed formula
CH4

CH3CH3

CH3CH2CH3

CH3CH2CH2CH3

C5H12

Pentane

C6H14

Hexane

CH3CH2CH2CH2CH3

CH3CH2CH2CH2CH2CH
3

Some points concerning this series of alkanes:

- Series is generated by adding CH2 to the previous
member of the series (homologous series)
- Naming: the names of all alkanes end in suffix ane,
and the prefix indicates the number of carbons in the
compound

(Meth

C,

Eth

2C,

.Hept. = 7 C, Oct = 8 C,.ect.).

- Group contains one less hydrogen than the
corresponding alkane is called Alkyl group. In naming
this group the -ane is dropped and -yl is added. For
example, methane becomes methyl; Ethane becomes
ethyl.
Branched-chain alkanes and constitutional
Isomerism

In addition to the straight-chain alkanes (n-alkane),

branched-chain alkanes are possible. For example,
Isobutane (or 2-methylpropane) has the structure:

H H H
H

C C C H
H
H

or

CH3CHCH3
CH3

H
C

CH3CH2CH2CH3

isobutane
(2-methylpropane)

butane

Isobutane. C4H10, has the same molecular formula as

butane, the straight chain hydrocarbon.
Butane and isobutane are constitutional (or structural)
isomers.
Constitutional Isomerism: Compounds that have the
same molecular formula but different structural
formulas.
As butane and isobutane are isomers have different
structures, they have have different properties. For
example, isobutane boils at -12C whereas butane boils
at 0C.
Example : isomers of pentane:
CH3CHCH2CH3

CH3CH2CH2CH2CH3

CH3

pentane
b.p. 36 C

2-methylbutane
b.p. 28 C
CH3
CH3CCH3
CH3

dimethylpropane

2,2-dimethylbutane
b.p. 9.5 C b.p. 9.5C

2,2-

 The number of constitutional isomers increases with the

number of carbons in the series. For example, there are
three isomers of pentane, five of hexane and 75 of
decane (C10H22).
Example VI-1:
Write the condensed structural formula of each of the
following alkanes
H
H C

a.

H H C HH

H H C

H H

H C
H

H H C H H

H C

H
H

b.

Answer:
CH3
CH3
a. CH3CHCHCH3

CH2CH3

CH2

b. CH3CH2CHCH2CH3 or CH3CH2CHCH2CH3

CH3

Cycloalkanes
They have the general formula CnH2n. The smallest
possible ring consists of cyclopropane, C 3H6. Five- and
six-membered rings are most stable.
The following is the first four members
cycloalkane series:

of

the

 Note that in the condensed structural formulas, there is

a carbon atom at each corner and enough hydrogens
are assumed to be attached to give a total of four single
bonds
Reactions of Alkanes
Alkanes

are

unreactive

molecules

at

normal

temperature due to presence of only CC and CH

single bonds. However, we do react alkanes every day
through combustion with molecular oxygen.
Combustion
Alkanes, and other hydrocarbons can be oxidized (by
burning) in the presence of excess molecular oxygen. In
this reaction, called combustion, they burn at high
temperatures, producing carbon dioxide and water and
releasing large amounts of energy as heat.
CnH2n+2

+ O2

CO2

H2O + heat

energy
For example, a propane gas burns according to the
reaction:

C3H8 (g)

+ 5O2 (g) 3 CO2

= -2220kJ/mol

4 H2O (l);

Substitution reactions:
eg. halogenation reactions

Alkanes can also react with a halogen (usually chlorine

or

bromine)

in

reaction

called

halogenation.

Halogenation is a substitution reaction, where a

halogen atom is substituted for one of the hydrogen
atoms in the alkane. The products of this reaction are
an alkyl halide or haloalkane and a hydrogen halide.
This is done by a free radical reaction (homolytical
fission).
Alkyl halides are very useful reactants for the synthesis
of other organic compounds. Thus, the halogenation
reaction is of great value because it converts uncreative
alkanes

into

versatile

starting

materials

for

the

synthesis of desired compounds. This is important in the

pharmaceutical industry for the synthesis of some
drugs. In addition, alkyl halides having two or more
halogen

atoms

are

useful

solvents,

refrigerants,

insecticides, and herbicides. Halogenation can occur

only in the presence of heat and/or light, the general
equation for the halogenations of an alkane as follows,
the R in the general structure for the alkane may be
either a hydrogen atom or an alkyl group

Examples:
If

the halogenation reaction is allowed to continue, the alkyl

halide formed may react with other halogen atoms. When

this happens, a mixture of products may be formed. For
example:
CH4 + Cl2

light

CH3Cl + HCl

+ Cl2

light

CH2Cl2 + Cl2

light

CH3Cl

CHCl3

+ Cl2

light

CH2Cl2 + HCl
CHCl3

+ HCl

CCl4

+ HCl