ALKANES

Alkanes or paraffins are saturated aliphatic hydrocarbons, that is, they contain only carbon-hydrogen (C-H) and
carbon-carbon (C-C) single bonds.
The general formula of alkanes is CnH2n+2, where n is the number of carbon atoms in one molecule or RH (where R
represents the alkyl group CnH2n+1)
Number
of carbon
atoms
1
2
3
4
5
6
7
8
9
10
11
12

Prefix

Name

MethEthPropButPentHexHeptOctNonDecUndecDodec-

Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane

Molecular
formula
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22

Condensed Structural formula

CH3
CH3 CH3
CH3 CH2 CH3
CH3 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2CH2 CH2 CH2 CH3
CH3 CH2CH2 CH2 CH2 CH2 CH22 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3

ALKYL GROUPS
An alkyl group is derived from an unbranched alkane molecule by removing one hydrogen atom from the end carbon
atom of the alkane.
The symbol R is used to represent an alkyl group, CnH2n+1
Alkyl groups are named by dropping the suffix -ane from the parent alkane and adding the suffix -yl.

Alkane
Methane

Name of alkyl group

Methyl

Ethane

Ethy

Propane

Propyl

Isopropane

Isopropyl

Butane

Butyl

Isobutane

Isobutyl

Pentane

Pentyl

Condensed formula

QUESTIONS

ANSWERS

1. Write the IUPAC names for the following alkanes.

(a)

(b)

(c)

(d)

2. Write the IUP AC names for the following alkanes.

(a)

(b)

NAMING CYCLOALKANES
Alkanes having one or more rings of carbon atoms are called cycloalkanes.
1. Give the names for the following cydoalkanes
(a)

(b)

2. Name the following cydoalkanes

(a)
(b)

(c)

(3)Name the following compounds

(a)

(b)

(c)

(d)

(d)

(4)Draw the structural formula of the following compounds.

(b) 2,4-dimethylpentane
a) 2-methylhexane

(d) 2,2-dimethyl-S-ethyloctane

(c) 2,2,3-trimethylpentane

PHYSICAL PROPERTIES OF ALKANES

1.
Molecular

Physical

formula

states

Solubility

point
water

CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C18 onwards

Colourless

Almost

gases

insoluble

Colourless
liquids
Colourless

Melting

Boliling

Density

Viscosity

increases

Combustibility

point

ethanol/ether

readily soluble

increases

Increases

Increases

but solubility

(attractive

(attractive

(molecules

decreases as

van der

van der

are

molecular

Waals

Waals

closer to

weight

forces

forces

each

molecules

increases.

increases)

increases

other)

to glide

(more
difficult
for

decreases
(as larger
molecules
burn with a
sootier flame
due to the
increase
percentage
of carbon).

or flow)

solids

2. The normal alkanes from C1 to C4 are colourless gases; C5 to C17 are colourless liquids; and from C18 onwards are
colourless solids at room temperature and pressure.
3. The alkanes are almost insoluble in water, but readily soluble in ethanol and ether, the solubility diminishing

with increase in molecular weight.

4. Generally, when the number of carbon atoms increases, the attractive van der Waals forces between the
molecules increases.
This causes
(a) the melting point and boiling point to increase
(b) the density to increase because the molecules are closer to each other
(c) the viscosity to increase because it is more difficult for molecules to glide or flow
(d) the combustibility to decrease as larger molecules burn with a sootier flame
due to the increase percentage of carbon.

Normal (unbranched) compound

Branched compound

The normal (unbranched) compound always

has the highest boiling point.

Branched isomers have lower boiling points and lower density.

Generally, the greater the branching, the lower is the boiling point.
As branching increases, the alkane molecule becomes
more spherical in shape and thus, has a smaller surface
area available for intermolecular attractions.
Small, compact and symmetrical molecules
As the surface area decreases, contact between adjacent molecules
decreases as well.
As a result, the strength of the instantaneous dipole induced dipole forces
decreases and hence, the boiling point decreases
But branched isomers have higher melting points.
The boiling point of 2,2-dimethylpropane is the lowest since it has the
most branching and the least surface area

More spread out and more easily polarised

Hence, a larger molecular surface area
allows greater contact between molecules and
gives rise to higher dispersion forces.

The boiling point of n-pentane is the

highest because a straight chain isomer has
the greatest surface area where two
molecules can touch each other along the
length of the chain. Hence, the van der
Waals forces are greater
The melting point of a substance depends on the arrangement and packing of the molecules in the crystal lattice.
The melting point of 2,2-dimethylpropane is the highest among the three isomers because it is more spherical in
shape and hence, can be packed as close as possible in the lattice.

PHYSICAL PROPERTIES
BOILING POINTS
The boiling point of alkanes is lower than
of other organic compounds.

Alkane molecules have low polarity, i.e. only weak instantaneous dipoleinduced dipole (van der Waals) forces are present between molecules.

The boiling point rises with increasing

number of atoms in the molecule.

As the number of electrons in the molecule increases (with increasing

number of carbon atoms),
the strength of these attractive forces also increases. More energy is
needed to break these forces the molecules when boiling.

The boiling points of unbranched alkanes

show a regular increase with increasing
number of carbon atoms in the molecules.

MELTING POINTS
The melting point of alkanes also
increases with an increase in the number
of carbon atoms.
However, the increase is not as regular as
that observed for the boiling points
because the ability of molecules to pack
into ordered patterns of solid changes as
molecule size and shape changes.
There is an alternation as one progresses
from an unbranched alkane with an even
number of carbon atoms to the successive
one with an odd number of carbon atoms .
MELTING POINTS
However, if only the melting points of
alkanes having odd number of carbon
atoms are plotted, a smooth increase is
shown.
This trend is also true for alkanes having
even number of carbon atom
Alkanes with even number of carbon
atoms pack more closely in the solid
state.
Hence, the attractive forces between the
molecules are greater resulting in higher
melting point.

DENSITY
Alkanes are the least dense of all groups of organic compounds and have densities less than water.

SOLUBILITY
Alkanes are almost insoluble in water because of their low polarity and their inability to form hydrogen .
However, liquid alkanes are miscible with each other.

PREPARATION OF ALKANES
1. Alkanes are usually prepared through the catalytic reduction of alkenes.
An alkene is converted to an alkane when passed with hydrogen over nickel heated at 200 - 300C .

Ethene

Ethane

2. Other methods of preparation are:

(b) Wurtz reaction
(The Wurtz reaction gives good yields only for even
numbered carbon alkanes of high molecular weights).
In a Wurtz reaction, an ethereal solution of an alkyl halide
is treated with sodium to form an alkane.

(a) decarboxylation of a carboxylic acid or its salt

(not a useful general method for the preparation of
alkanes)
When a mixture of a carboxylic acid (or its sodium
salt) is heated with a soda lime (a mixture of
calcium oxide and sodium hydroxide), carbon
dioxide is eliminated.
The process is known as decarboxylation.
( heating the anhydrous sodium carboxylate salt
with soda lime (a mixture of sodium hydroxide and
calcium hydroxide)) .

2RX + 2Na R - R + 2NaX

For example,
2CH3CH2Br + 2Na CH3CH2CH2CH3 + 2NaBr

Wurtz reaction: The action of sodium on alkyl halide in

ether.
2R-X + 2Na ~ R-R + 2NaX
For example,
2CH3-1 + 2Na ~ C2H6 + 2NaI

RCOOH + 2NaOH RH + Na2CO3 + H2O

Carboxylic acid
Alkane
RCOONa + CaO
Sodium carboxylate

RH + CaCO3
Alkane

c. Kolbe's method:
Electrolysis of a concentrated aqueous solution of the
sodium salt of a carboxylic add, for example, sodium
ethanoate

For example, methane can be prepared from the

decarboxylation of sodium ethanoate.
CH3COONa + 2NaOH CH4 + Na2CO3 + H2O
Note:

Cathode: 2H+(aq) + 2e- H2(g)

[The alkane produced has less carbon atoms

compared to the original carboxylic acid or
carboxylate salt used.
Benzene can also be prepared from the
decarboxylation of sodium benzoate.
C6H5COONa + 2NaOH C6H6 + Na2CO3 + H2O

Anode : 2CH3COO-(aq) C2H6(g) + 2CO2(g) + 2e-

However, other sodium salts decompose to form

various products. Hence, this is not ,a useful
general method for the preparation of alkanes sinse
the separation of the products is usually difficult. ]
CH3CH2COONa + NaOH C2H6 + CH4 + H2
(44%) (20%) (33%)
+ Unsaturated compounds

CHEMICAL PROPERTIES OF ALKANES

The general chemical reactions of alkanes are: (a)
1. Alkanes have relatively low chemical
Halogenation
reactivity and are inert to acids, bases
(b) Oxidation
and most other common laboratory
(c) Dehydrogenation
reagents.
2. This is because alkanes do not have any
unshared pair of electrons. polar bond,
electron-deficient atom or an atom with
an expandable octet. Hence, alkanes are
unreactive towards polar reagents such
as water, H20 and ammonia, NH3'
3. As such, alkanes react with nonpolar
reagents such as bromine and oxygen
under certain conditions.
Halogenation of alkanes:
(a) At room conditions, alkanes do not react with
halogens as the activation energy is too high. In the
presence of ultraviolet light. heat (around 4000C) or
catalysts, alkanes react with halogens such as
chlorine and bromine to form haloalkanes or alkyl
halides.
RH + C12 ~ RCI + HCI
For example,
CH3CH} + C12 ~
CH3CH2Cl + HCI
(b) Markovnikoff found experimentally that the
order of ease of substitution is tertiary hydrogen>
secondary> primary.
(c) The mechanism is found to be a free radical
substitution.

Free radical substitution:

(a) A free radical is a chemical species which
possesses an unpaired electron. (b) Free radicals are
formed in two general ways:
(i)
through homolytic cleavage of
bonds: A - B ~ A. + B.
(ii) by reaction of molecules with other free radicals:
A - B + C ~ A. + B - C
(c) Homolytic cleavage of sigma bonds can be made
to occur using heat or light (photolysis) .
(d) Free radicals formed in these ways are most
often the precursors that generate other free radicals.
Most free radicals are very reactive and usually
cannot be isolated
(e) Halogenation at a saturated carbon atom is a
typical example of free-radical substitution.
Although a functional group can be introduced into
a molecule, it is often difficult to control the
position and extent of reaction.
When a mixture of chlorine and alkane such as
methane, CH4 is exposed to ultraviolet light,
chlorine molecules undergo homolytic cleavage.
Methane does not undergo cleavage because the C H bond dissociation enthalpy is 412 kJ mol-I,
compared to the CI - CI bond dissociation enthalpy
of 242 kJ mol-I.
Initiation:
Cl2 -t CI + CI.
The chlorine free radicals or chlorine atoms formed
possess an unpaired electron and are highly reactive.
These radicals then collide with methane molecules
to produce methyl free radicals, CR which then
combine with CI, molecules to
form the product, chloromethane: CH) C1.

"
Propagation: CH4 + CI. -t HCI + CH).
CH,. + Cl2 -t CI + CH3CI
The reaction terminates when any two free radicals
collide.
Termination: CI. + CI -t CI,
CI + CH). -t CH)CI CH). + CH3 -t CH3 CH)
10. The overall equation for the formation of
chloromethane is
CH4 + Cl2 -t HCI + CH,CI
llH =
-96 kJ mol-I
This free-radical chain reaction usually yields a
mixture of products such as CH,CI" CHCl) and
CCI4. However, a good yield of monohalogenated
methane can be obtained if the quantity of chlorine
used is much lower than that of CH4 .

Oxidation of alkanes
(a) At room conditions, alkanes
do not react with oxygen.
(b) All alkanes readily burn in
excess of air or oxygen to form
carbon dioxide and water.
y
y
C,Hr + (x + 4)02 -t xC02 +
TH20
(c) Controlled oxidation in
limited oxygen and under

14. Dehydrogenation
(a) Alkanes can lose hydrogen when heated at a high
temperature in the presence of a catalyst to form carbon
black (used in the manufacture of rubber tyres, black
paints and black shoe polish) and alkenes.
(b) Many alkenes can be manufactured by high temperature
dehydrogenation processes, using a chromium oxidealumina catalyst.

various conditions, leads to

different products such as acids,
mixed ketones and alcohols.
(d) Oxidising agents such as
potassium permanganate readily
oxidise a tertiary hydrogen atom
to a hydroxyl group.
(CH3))CH + [0] -t (CH)))COH
Cycloalkanes, CI1H2n
(a) Cycloalkanes exhibit similar
chemical properties as alkanes,
such as free radical substitution
and oxidation.
Br + HBr
(b) However, cycloalkanes with
smaller carbon rings such as
cyclopropane may be more
reactive due to the angle shain in
the compound. Larger sized
rings (C > 8) behave almost the
same as straight-chained alkanes.

Crude Oil as a Source of Energy

and Chemicals
1. Crude petroleum contains alkanes (straight and
branched chains, from CI to C40), cycloalkanes
and aromatic hydrocarbons. Natural gas consists
chiefly of the first six alkanes.
2. Except for the low-boiling hydrocarbons, no
attempt is made to separate the individual
hydrocarbons. The crude oil is fractionated by
continuous distillation into four main fractions,
i.e. petrol. kerosene, heavy oil and lubricating
oil.

10

Fraction

Approximate
composition

Boiling
point (0C)

Use

Light petrol
Petrol
Kerosene
Heavy oil

C5 - C7
C6 - CII
CI2 - CI6
CI3 - CIS

20 - 100
70 - 200
200 - 300
> 300

Solvent
Motor fuel
Lighting
Fuel oil

Lubricating oil

CI6 - C20

> 300

Grease, vaseline

CIS - C22

> 300

Paraffin wax

C20 - C30

Bitumen

C30 - C40

> 300
> 300

Lubricants
Pharmaceutical
preparations
Candles, waxed paper

USES OF ALKANES:
(a) Most of the alkanes readily burn in excess of air or
oxygen and are usually used as fuels.

11

Asphalt tar