CHAPTER 2

Hydrocarbon Compounds: Alkane

OUTLINE
 Introduction – Classes of Hydrocarbons

 Structure

 Nomenclature

 Physical properties

 Preparation
 Hydrogenation of alkenes,
 Hydrolysis of Grignard reagents

 Alkane reactions
 Combustion
 Halogenation/free radical substitution & Mechanism

 Sources and uses

Introduction to Hydrocarbons
Hydrocarbons
 Simplest organic compounds
 Contain only carbon and hydrogen

Hydrocarbons

Aliphatic Aromatic
Classes of Hydrocarbons

Hydrocarbons

Aliphatic Aromatic

Alkanes Alkenes Alkynes

Alkanes
 Alkanes are hydrocarbons in
Hydrocarbons
which all of the bonds are
single bonds

Aliphatic H H

H C C H
Alkanes H H
Alkenes
 Alkenes are hydrocarbons
Hydrocarbons
that contain a carbon-
carbon double bond

Aliphatic H H
C C

Alkenes H H
Alkynes
 Alkynes are hydrocarbons
Hydrocarbons
that contain a carbon-
carbon triple bond

Aliphatic H C C H

Alkynes
 Aromatic Compounds

 The most common aromatic

hydrocarbons are those that Hydrocarbons

contain a benzene ring

H
H H
Aromatic

H H
H
Alkanes
 Alkanes are saturated hydrocarbons

 Contain only carbon and hydrogen in their molecules

 General formula of CnH2n+2

 All carbons in alkanes are sp3 hybridized and form only single

bond
Naming of Branched Alkanes –IUPAC
Nomenclature
RULE 1
 Identify the longest carbon chain (not necessary straight) and

write parent name of the compound

CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
CH3 CH2-CH3

Butane Hexane
RULE 2
 Circle the substituent group atom, number the longest carbon

chain making sure the substituent is at lower number

1 2 3 4 3 4 5 6
CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
2 1
CH3 CH2-CH3
methyl
methyl

IUPAC name: IUPAC name:

2-methylbutane 3-methylhexane
RULE 3
 Use prefix in writing the name of No. of Prefix
substituent used
a compound if there is more than 2 di
one substituent 3 tri
4 tetra
H H 5 penta
6 hexa
1 2 3 4
H3C C C CH3

CH3 CH3

2,3-dimethylbutane

Notes: Numbers are separated

by comma
RULE 4
 Arrange substituents according to alphabetical order

 E.g. Bromo > Cyclopropyl > Ethyl > Isopropyl > Methyl

 However, prefixes such as di-, tri-, tetra-, sec-, tert-, are not

considered except the prefix “iso”

RULE 5
 When a compound has two possible longest carbon chains,

select the chain/parent with more substituents

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

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

3-ethyl-2-methylheptane
Cycloalkanes
 Cyclic alkanes are called cycloalkanes

 General formula CnH2n

 Name as the parent alkane but add cyclo-

Cyclopropane Cyclobutane Cyclopentane

Naming of Cycloalkanes
 Name any alkyl groups on the ring in the usual way

CH2CH3 Ethylcyclopentane

 List substituents in alphabetical order and count in the direction

that gives the lowest number

H3C CH3
3-ethyl-1,1-dimethylcyclohexane

CH2CH3
Questions
1. Write structural formulae of C5H12. Label class of C and H
atoms whether 1°, 2°or 3°.
Questions
2. Name the following compounds according to IUPAC
nomenclature.
Questions
3. Write structural formulae of the following alkanes:
Physical Properties of Alkanes
1. Physical State

At room temperature, 25°C and atmosphere pressure, 1 atm:

 Methane, ethane, propane and butane = Gases

 C5-C17 = Liquids

 C18 and above = Solid

Physical Properties of Alkanes
2. Boiling Point

 Generally, boiling point of alkanes increase with higher

number of C or relative molecular mass.

Butane,C4H10 Ethane, C2H6 Methane, CH4

0°C > -89°C > -162°C

 This is because as the size of alkanes (relative molecular mass)

increases, the strength of Van der Waals forces between

molecules increases.
 Isomers of alkanes however have different boiling point due to
branching.

Pentane 2-methylbutane 2,2-dimethylpropane

CH3
H H

CH3 C C CH3 H3C C CH3

CH3CH2CH2CH2CH3
CH3 H CH3

37°C 28.5°C 9°C

 From the above table, boiling point of 2,2-dimethylpropane < 2-

methybutane < pentane
Physical Properties of Alkanes
3. Solubility
 Alkanes are not soluble in H2O because they are non-
polar whereas water is a polar solvent. Besides they
cannot form hydrogen bond with water.

However, it is soluble in non-polar solvents such as ether

and tetrachloromethane because it is non-polar.

Chemical Properties of Alkanes
 Alkanes are LESS reactive compared to alkenes, alkynes , arenes

and others.

 This is because carbon and hydrogen atoms in alkanes have

similar electronegativity values making the C-H bond not polar.

So, alkanes are not attacked by nucleophile and electrophile.

 Besides, alkanes do not have unpaired / unshared electrons to

be reactive towards acids or electrophiles.

 Preparation of alkanes
1. Hydrogenation of alkenes:

H H H H
Pt / Pd / Ni
C C + H2 H C C H
H H H H
Alkene Hydrogen Alkane

Example:
Ni
C2H4 + H2 C 2H 6
Ethene Ethane
Preparation of alkanes
2. Hydrolysis of Grignard reagent (alkylmagnesium halide):

H+
RMgX + H2O RH + Mg(OH)X
Alkylmagnesium
Alkane
halide

Example:
H+
CH3CH2CH2MgCl + H2O CH3CH2CH3 + Mg(OH)Cl
Propylmagnesium Propane
chloride
 Alkane Reactions
1. Combustion
 Complete combustion forms carbon dioxide and water whereas
incomplete combustion forms carbon monoxide or carbon and
water.
 The reaction is EXOTHERMIC

C4H10 13 O2 4CO2 5H2O Complete combustion of butane

2

C4H10 9 O2 4CO 5H2O Incomplete combustion of butane

2

C4H10 5 O2 4C 5H2O Incomplete combustion of butane

2
Alkane Reactions
2. Halogenation
 React with chlorine/ bromine/ iodine gas in the presence of

ultraviolet light or high temperature to form haloalkane or alkyl

halide.
 The mechanism involved is free-radical substitution which C-H bond

is broken and new C-X bond is formed.

CH4 + Cl2 uv CH3Cl + HCl
 Further substitution will result in a mixture of products
uv
CH3Cl + Cl2 CH2Cl2 + HCl
CH2Cl2 + Cl2 uv CHCl3 + HCl
uv
CHCl3 + Cl2 CCl4 + HCl
 The reactivity of the halogens decreases in the following order:

F2 > Cl2 > Br2 > I2

 Bromine reacts with alkanes in the same way as chlorine but at a

lower rate.
 Fluorine is very reactive and difficult to control.

 Iodine is generally unreactive.

 Chlorination and bromination are exothermic.

 Energy input in the form of heat or light is necessary to initiate the

halogenation.
Mechanism of Free Radical Substitution
 Free radical substitution is a chain (series) reaction that involve

in the three step reactions:

i) initiation

ii) propagation

iii) termination
i) Initiation
 The chain is initiated (started) by UV light breaking a chlorine

molecule into free radicals. This process is called photochemical

homolytic fission/cleaveage.

Heat / light
Cl2 2Cl●
ii) Propagation
 These are the reactions which keep the chain going. Radicals are

very reactive. They will react with other molecules to form new
radicals
CH4 + Cl● CH3● + HCl

CH3● + Cl2 CH3Cl + Cl●

 If reaction occurred in the excess of Cl2, mixture of radicals will

be obtained
CH3Cl● + Cl2 CH2Cl2 + Cl●

CH2Cl2 + Cl● CHCl2● + HCl

iii) Termination
 These are reactions which remove free radicals from the system

without replacing them by new ones

 Free radicals can combine with each other and terminate the

propagation process

2Cl● Cl2

CH3● + Cl● CH3Cl

CH3● + CH3● CH3CH3

 Unlike methane and ethane, alkanes with more than two carbon

atoms can form more than one monohalogenation product

based on different classification of carbon atom that given
different IUPAC name.
 The MAJOR product is the most stable product which are:

Alkyl halide 3° > 2° > 1°

Natural Source of Hydrocarbon - Crude Oil
 The major source of alkanes is crude oil or petroleum.

 Petroleum is a liquid mixture of thousands of compounds, most of

them hydrocarbons, which are formed from the decomposition of

ancient plants and animals.
 The petroleum industry is concerned with the separation of the

thousands of hydrocarbon in crude oil to produce useable products.

 The different components in crude oil are separated by fractional

distillation
Fractional Distillation of Crude oil
 Fractional distillation is a separation process based on the

different boiling points of the compounds

 The crude oil is separated into fractions. Each fraction consists of

a mixture of hydrocarbon which boils over a limited range of

temperature

 The table below lists the different fractions obtained from crude

oil
 Fraction Molecular size Boiling point Uses
range / °C

Petroleum gas C1 to C4 <20 Fuel for domestic gas

cookers and for heating

Light petroleum C5 to C6 20 to 60 Organic solvent

Light naphta C6 to C7 60 to 100 Organic solvent

Petrol C5 to C12 40 to 205 Fuel for motor vehicles

Kerosene C12 to C18 175 to 325 Fuel for jet engines

Gas oil/ Diesel C18 to C25 275 to 400 Fuel for diesel engines

Lubricating oil C20 to C34 >400 Lubricants

> C34 For road surfacing and

Bitumen Solid residue
rooling
 Besides being used as fuels, some of these fractions are used to

manufacture thousands of other compounds such as plastics,

detergents, paints, polymers, synthetic rubber and medicines.

 The petroleum fractions are easier to vaporise and are therefore

more useful fuels.

 In the petrochemical industry, the heavier fractions are broken

down into lighter fractions by a process called cracking and

reforming.
Petroleum refining
1. Cracking
 converts high molecular weight hydrocarbons to more

useful, low molecular weight ones

i) thermal cracking (by heat)
ii) catalytic cracking (with the aid of catalyst)

2. Reforming
 increases branching of hydrocarbon chains

 branched hydrocarbons have better burning characteristics

for automobile engines

Cracking
 Cracking is a process where large hydrocarbon molecules (from

crude oil) are broken down into smaller and more volatile
molecules.

 There are two types of cracking, thermal cracking and catalytic

cracking.
Thermal Cracking
 Thermal cracking makes use of high temperature and high

pressure to bring about the cracking process.

Catalytic Cracking
 Catalytic cracking, as the name implies, makes use of suitable

catalysts for the process, which can be carried out at lower

temperature and pressure. The catalysts used are alumina
(aluminium oxide), silica (silicon dioxide) or zeolites.
 Catalytic cracking produces more branched chain alkanes than

thermal cracking.
Reforming
 In reforming process, alkanes are converted to cycloalkanes and

cycloalkanes are converted to arenes in the presence of heat, pressure

and bimetallic catalyst (Platinum / Rhenium or Platinum / Iridium)
 The products are used in petrol and as feedstock for producing a wide

range of organic compounds.