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

CH4
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.

3-Methylpentane

2,4.6- Trimethyloctane
(start from right to left)
3-ethyl-2,6-Dimethylheptane
(alphabetically)

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)

Cyclopentane
1-Ethyl-2-metylcyclohexane

1,3 Dimethylcyclobutane

(d)

1-ethyl-3,4dimetylcyclohexane

(3)Name the following compounds

(a) 2,3-dimethylpentane

(b) 3 -ethyl- 3,5 -dimethylheptane

(c) 2,4-dimethylhexane

(d) 4-ethyl-2-methylhexane

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

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

(c) 2,2,3-trimethylpentane

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

PHYSICAL PROPERTIES OF ALKANES

3

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

increases.

increases)

increases

other)

(more
difficult
for
molecules

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

to glide
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 dipole-induced dipole (van der Waals)
forces are present between molecules.
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 point rises with increasing

number of atoms in the molecule.

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:

(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)) .
RCOOH + 2NaOH RH + Na2CO3 + H2O
Carboxylic acid
Alkane
RCOONa + CaO
Sodium carboxylate

RH + CaCO3
Alkane

For example, methane can be prepared from the

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

(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.
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

c. Kolbe's method:
Electrolysis of a concentrated aqueous solution of the
sodium salt of a carboxylic add, for example, sodium
ethanoate
Cathode: 2H+(aq) + 2e- H2(g)
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

Alkanes have relatively low chemical reactivity and
are inert to acids, bases and most other common
laboratory reagents.
.
Hence, alkanes are unreactive towards polar
reagents such as water, H2Oand ammonia, NH3 ,
(not readily attacked by common chemical reagents
which are usually highly polar compounds)

This is because alkanes do not have any unshared pair of

electrons. polar bond, electron-deficient atom or an atom with
an expandable octet
This is because the carbon - hydrogen bond is only slightly
polarised.
Molecules of alkanes also have no unshared electrons to offer
sites for attack by acids.

As such, alkanes react with nonpolar reagents such

as bromine and oxygen under certain conditions.
Why are alkanes inert ?

A reactive site in a molecule usually has one or more

unshared pairs of electrons, a polar bond, an electrondeficient atom or an atom with an expandable octet.
Alkanes have none of these .

The general chemical reactions of alkanes are:

(a) Halogenation
(b) Oxidation

(c) Dehydrogenation

HALOGENATION OF ALKANES
1. At room conditions, alkanes do not react with halogens as the activation energy is too high.
Due to chemical inertness, alkanes do not readily react with halogens in the dark at room temperature.
2.

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(halogen atoms will substitute hydrogen
atoms in the alkanes to form haloalkanes.)
RH + C12 RCI + HCI
For example, CH3CH3 + C12 CH3CH2Cl + HCl
(a) The order of ease of substitution is :
tertiary hydrogen> secondary> primary.
(b) The mechanism is found to be a free radical substitution.

3.

Substitution is a reaction where an atom or a group of atoms in a molecule is substituted

different atom or group of atoms.
Since the reaction takes place in light, it is called a photochemical reaction.
3.
When chlorine (a halogen) is mixed with methane and exposed to sunlight, yellowish-green colour of
chlorine
fades and a steamy acidic fumes of hydrogen chloride is evolved.
CH4(g) + CI2(g) CH3CI(g) + HCl(g)
Further substitution is possible, depending on the amount of chlorine and methane present.
The formation of CH3Cl may be followed by the formation of dichloromethane,CH2Cl2 ,trichloromethane, CHCl3 and
tetrachloromethane, CCI4. A mixture of products is obtained.

CH3CI + Cl2 CH2Cl2 + HCl

CH2Cl2 + Cl2 CHCl3 + HCl
CHCl3 + Cl2 CCl4 + HCI

FREE RADICAL SUBSTITUTION MECHANISM OF CHLORINATION OF METHANE:

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) The mechanism consists of three steps; initiation, propagation and termination.
Initiation
Chain Propagation
Termination
(where products are formed and
(where radicals are removed)
(where radicals are formed)
the radicals are regenerated)
(i) When a mixture of chlorine and alkane
(i) The chlorine radical (or atom)
(i) Thousands of molecules of
such as methane, CH4 is exposed to
formed (possess an unpaired
chloromethane are formed for every
ultraviolet light, chlorine molecules
electron ) is very reactive.
photon of light absorbed.
undergo homolytic cleavage.
It is reactive enough to break the
The yield is due to the chain reaction
(ii) The energy required for homolytic
C-H bond when it attacks the
- steps 2 and 3.
fission of the CI-Cl comes from the light
methane molecule, producing
The reason why the yield is not
absorbed (photochemical homolytic
hydrogen chloride and a methyl
higher is that free radicals can
fission).
free radical.
combine with each other and bring
(iii) As the two chlorine atoms in the bond
CH3 which then combine with CI2, the chain to an end
are identical (the electron pair forming the
molecules to form the product,
-termination steps.
bond are equally shared by the two atoms), chloromethane: CH3C1.
The possible reactions that may
the bond will break homolytically, i.e. one
CH4 + CI HCI + CH3
terminate the chain are as folIows :
electron goes to each chlorine producing
two chlorine atoms, each with one
unpaired electron. Thus, each has an
unpaired electron and is known as a free
(ii) The methyl free radical can
radical.
react with a chlorine molecule to
produce chloromethane CH3 C1,
Initiation: Cl2 CI + CI
(ii) These, or any other termination
and a new chlorine free radical.
steps will remove the free radicals
and bring the chain reaction to a stop.
CH3 + Cl2 CI + CH3Cl
iv) (Methane does not undergo cleavage
because the C - H bond dissociation
enthalpy is 412 kJ mol-1, compared to the
CI - CI bond dissociation enthalpy of 242
kJ mol-1)
It is easier to break the CI-Cl bond (+242
kJ mol-1]) than the C-H bond (+412 kJ mol1
]).
Thus. in the initiation step, only chlorine
radicals are produced although both the

(iii) These two steps, 2 and 3,

enable the reaction to continue.
In step 2, a chlorine free radical is
used up. Meanwhile, in step 3, a
new chlorine free radical is
produced which allows repetition
of step 2.
(iv) Steps 2 and 3 constitute a
chain reaction and are called chainpropagating steps.

(iii) The reaction terminates when

any two free radicals collide.
Termination:
CI. + CI Cl2
CI + CH3 CH3Cl
CH3+ CH3 CH3CH3

chlorine and methane molecules are

exposed to sunlight.
The overall equation for the formation of chloromethane is

: CH4 + Cl2 HCI + CH3CI

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.
(c) Controlled oxidation in limited oxygen and under 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)3CH + [O] ( CH3)3COH
1. Alkanes do not react with air at room temperature but if heated, they burn readily to give carbo
dioxide and water in an exothermic reaction. For example, the combustion of propane:
The exothermic reaction accounts for the use of many alkanes as fuels.
1. Liquid and solid alkanes need to be vaporised first before they burn. For example, liquid is
vaporised in the internal combustion engine before it burns.

~ If the supply of air is limited, the combustion of alkanes is incomplete, producing carbon monoxide and
carbon (in the form of soot) along with partially oxidised hydrocarbons. For example incomplete
combustion of propane:
C3H8(g) + 7/2 O2(g)

3CO(g) + 4H2O(g)

2.
Carbon monoxide is a poisonous gas which bonds to the iron of haemoglobin in the blood i:l
preference to oxygen which could result in death. Hence, all gas burning appliances should be adequately
ventilated
'Combustion reactions can be used to determine the molecular formulae of hydrocarbons.
2' A measured volume of a hydrocarbon is mixed with a large excess of oxygen and the total volume
is noted.
:'1 The mixture is then sparked until combustion is complete.
C After cooling to the original conditions of temperature and pressure and when all the water formed
has condensed, the volume of the remaining gas is measured.
i I The volume of carbon dioxide produced is found from the decrease in the volume after shaking
the yielded mixture with concentrated potassium hydroxide.
e, If the molecular formula of the hydrocarbon is CvHI" the combustion reaction is represented
by the following equation:
.
I

CXHy + (x + 4)02

-7

V + (x + ~)V -7 xv.

xC02 + "TH20

where V = volume

~ Volume of carbon dioxide produced = x(volume of hydrocarbon used) .................................

~ Volume of oxygen used = (x + ~ ) (volume of hydrocarbon used) ........................................... '
2. Thus, the values of x and y can be obtained by solving the two equations abo\e
illcipal component of petrol is an isomer of octane, 2,2,4-trimethylpentane, or more commonly h--=: as
iso-octane .
: ::}:-aw the condensed structural formula of iso-octane .
',"":-ite a balanced equation for the complete combustion of iso-octane .
Test yourself 6 pg 55
I

10

ane is used as a fuel in camping gas stoves. Write balanced equations for the combustion of ~3l1e in
.i plentiful supply of air (oxygen)
'rb a limited supply of air

Example 7
15 cm3 of a gaseous hydrocarbon was mixed with 65 cm 3 of oxygen (excess) and the mixture was sparked. On
cooling to the original conditions of temperature and pressure, the volume measured was 50 cm 3, of which 30
cm3 was absorbed by concentrated potassium hydroxide solution. Determine the molecular formula of the
hydrocarbon .
Solution:
Assume that the molecular formula of the hydrocarbon is C H .

xy

T us, C,Hy + (x + 4)02 ~ xC02 + 2"'H20

Volume of CO2 produced = 30 cm3
Volume of CO2 produced = x(volume of hydrocarbon used) => 30
=x(15)

:.

x=2

Volume of oxygen used = 65 - (50 - 30) = 45 cm3

Volume of oxygen used = (x + ~ ) (volume of hydrocarbon used) => 45 =
(2 + ~)(15)
..

y=4

That is, the molecular formula of the hydrocarbon is C2H4

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
oxide-alumina catalyst.

10 cm3 of a gaseous hydrocarbon was mixed with 100 cm3 of oxygen (excess) and the mixture sparked. On
cooling to the original conditions of temperature and pressure, the volume measured 85 cm 3, of which 20 cm3
was absorbed by concentrated potassium hydroxide solution. Determine molecular formula of the hydrocarbon.

PG 56 TEST YOURSELF 7

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

11

rings (C > 8) behave almost the

same as straight-chained
alkanes.

Catalytic cracking of alkanes

Draw cis and trans isomers of alkenes(propene and butane)
Enantiomers(mirror image)
Calculations on half life, molarity(MaVa = a
MbVb b
pH =-log[H+]

12

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.

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
Asphalt tar

USES OF ALKANES:

13

(a) Most of the alkanes readily burn in excess of air or

oxygen and are usually used as fuels.

14