Hydrocarbons

Alkanes

Learning objectives

Hydrocarbons.
Source of hydrocarbons: Crude oil.
Alkanes:
Representation formulas of alkanes and
isomeric structures.
Characteristic properties of alkanes.
Bonding pattern in alkanes.

Hydrocarbon
A family of compounds composed only of
hydrogen and carbon
Alkanes
Alkenes
Alkynes

*cycloalkanes

Source of alkanes

 Crude oil is the complex mixture of

hydrocarbons i.e. alkanes, cycloalkanes and
aromatic (benzene like) compounds.

How hydrocarbons are processed from

crude oil/petroleum.

Group activity
How to get hydrocarbons from Crude oil
sequence the process

Transportation to oil refining

Oil well
Separation of hydrocarbons
top of fractionating column (low mass / low
b.pt)
fractional distillation unit
Drilling

crude oil processing

1. Drilling: layers of rocks beneath the earth

surface.
2.Oil well: brought on the earth surface
3. Transport to oil refining
4. Process at fractional distillation unit.
5. Separation according to difference in B.pt.
6. Lower mass hydrocarbons collected
nearer the top of fractionating column.

Crude oil/ Petroleum Refining

crude oil is heated in a vessel
connected to the base of a tall
fractionating tower
hydrocarbon vapors pass up
into the fractionation tower and
separate into groups of
compounds according to their
boiling points.
vapors of the most volatile
hydrocarbons those with the
lowest boiling points rise to
the top of the tower where they
condense to liquids and are
drawn off.
hydrocarbon mixtures with
higher boiling points (the less
volatile fractions) condense and
are drawn off from the lower
regions of the tower.

Preparation of Alkanes
Fraction

Boiling
Number of carbon
point range
atoms that the
Major uses
(C)
molecules contain

Fuel gas

< 40

Petrol

14

As gaseous fuel, raw materials for

manufacture of chemicals
Fuel for motor vehicles

40 150

5 10

Kerosene

150 220

10 14

Fuel for aeroplanes, domestic

liquid fuel

Gas oil

220 350

14 25

Fuel for trucks, lorries and

locomotives

> 350

> 25

Fuel for cargo ships and to

generate electricity in power
stations

Lubricating
> 350
oil

> 25

Lubricating oil for moving parts

of machinery

Bitumen

> 25

For surfacing roads and roofs

Naphtha

Fuel oil

> 350

Fuel for manufacture of town gas

Petroleum Fractions
Petroleum is distilled to give a
variety of petroleum fractions
(mixtures of petroleum
hydrocarbons with similar boiling
points)
Fractions contain hydrocarbons
ranging from methane (low boiling,
gaseous component) to very high
boiling, waxy, solid alkanes such
as C60H122 .
feedstock for many drugs, plastics,
synthetic fibers, etc.

Alkanes

contain only carbon and hydrogen atoms

general formula CnH2n+2
have only single bonds
do not have functional groups

can be linear, branched, or cyclic

Straight Chain Alkanes

prefix suffix
# of C Structure
Name
1 CH4 methane
2 CH3CH3
ethane
3 CH3CH2CH3 propane
4 CH3CH2CH2CH3
butane
5 CH3CH2CH2CH2CH3 pentane
6 CH3CH2CH2CH2CH2CH3
hexane
7 CH3CH2CH2CH2CH2CH2CH3 heptane
8 CH3CH2CH2CH2CH2CH2CH2CH3
octane
9 CH3CH2CH2CH2CH2CH2CH2CH2CH3 nonane
10CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
decane

Methane (CH4): The Simplest Hydrocarbon

Remember - carbon has 4 valence electrons,
and can form 4 covalent bonds with other atoms
such as hydrogen
For 1 C and 4 H, there is only one possible way
they can be arranged
H

H
HCH

H
H

Ethane
For a molecule that only contains 2 carbon
atoms and 6 hydrogen atoms, there is only one
possible combination

Propane
For a molecule with 3 C and 8 H atoms, there is
only one possible combination
H H H
HCCCH
H H H

need ball & stick

C4H10
The four carbons can either be in a row or have a
branched arrangement.

straight-chain

branched-chain alkane

alkane

Isomers
structural isomers: compounds with the same
number of atoms and bonds, but in different
arrangements
as the number of carbon atoms increases, the
number of possible alkane isomers grows
rapidly.

How many structure isomers

are possible in pentane

How many structure isomers are

possible in hexane

Number of Possible Isomers of the Alkanes

# Carbons
1 CH4 1
2 C2H 6 1
3 C3H 8 1
4 C4H10
5 C5H12
6 C6H14
7
C7H16
8
C8H18
9
C9H20
10
C10H22
15
C15H32
20
C20H42
40 C40H82

Molecular Formula

2
3
5
9
18
35
75
4,347
366,319
> 62 trillion !

Possible Isomers

Drawing Organic Structures

Structural formula:
Displayed formula
3D display formula
Skeletal formula

Draw structural / display formula

Butane

2-methyl propane

3-D Displayed formula

Propane

3D Displayed formula

Propane

3D displayed formula

Butane

2-methyl propane

Skeletal / Line Structures

Identify the compound

Properties of Alkanes
C1-C4 gases, above C5-C17 liquid, above C17
solid.
colorless
odorless or mild odor
tasteless
nontoxic
flammable

what will happen in terms of

mixing?
(1) If I mix hexane with aqueous
iodine
(2) If I mix hexane with benzene

Physical Properties of Alkanes

Solubility
Solubility

non-polar compounds
insoluble in water
soluble in non-polar solvents like benzene,
1,1,1-trichloroethane

Why alkanes are less reactive?

Physical Properties of Alkanes

BoilingPoint
Point
Boiling

Higher members have

higher boiling points

Reason:

Increase in molecular
mass

Increase in intermolecular
force

Why petroleum floats on water

surface?

Density
Density

All alkanes and cycloalkanes have densities less than 1 g

cm3 at 20C.

Physical Properties of Alkanes summary

Number of
carbon
atom(s)
1
2
3
4
5
6
7
8
9
10

Straightchain
alkane
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane

Density at
Boiling
Melting
20C
(g
point (C) point (C)
cm3)
161
89
42
0
36
69
98
126
151
174

183
172
188
135
130
95
91
57
54
30

At R.T., C1 C4: gases ; C5 C17: liquids ; > C18: waxy solid

0.626
0.657
0.684
0.703
0.718
0.730

Bonding in Alkanes
alkanes contain only non-polar C-C and C-H
bonds
only weak London dispersion intermolecular
forces / vander waals forces are present
recall London dispersion forces are a weak
attraction between molecules.

 Why and where alkanes are used as fuel?

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.
alkane + oxygen gas carbon dioxide + water + heat
General formula:

3n 1
C n H 2 n2
O 2 nCO 2 n 1 H 2O
2

Examples

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

H = -213 kcal/mol

methane

(CH3)2CHCH2CH3 + 8O2 5CO2 + 6H2O H = -843.4 kcal/mol

2-methylbutane

Methane: main component of natural gas and domestic gas

Butane: component of bottle gas

The energy released during combustion

dominates a large part of worlds transport,
industry and domestic heating

Incomplete combustion
In the limited supply of oxygen, alkanes burn to
give CO(g) and carbon particles
7
C 4 H10 ( g ) O 2 ( g ) 2CO( g ) 2C( s ) 5H 2O(l )
2

 Write a balanced equation for the complete

combustion of pentane with oxygen.
C5H12 + 8O2 5CO2 + 6H2O

Heats of Combustion of Representative

Alkanes

Table from Organic Chemistry,

Francis Carey, McGraw-Hill,
1987, p. 58

What are the environmental

issues from burning of fuel?

Cracking
Cracking is the process of breaking down of large alkane molecules
in the heavier fractions of petroleum into lighter fractions of smaller
molecules in the absence of air
e.g. C11H24 C9H20 + CH2 = CH2
C14H30 C8H18 + 2CH2 = CH2 + 2C + 2H2
Catalytic cracking :
in the presence of catalyst, smaller
and highly branched hydrocarbons
formed
Thermal cracking :
in the absence of catalyst,
unbranched chains formed
Cracking tower

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.

Halogenation
Halogenation: the replacement of an alkane hydrogen
by a halogen (usually chlorine or bromine) atom in a
process initiated by heat or light.

ex. complete chlorination of methane

CH4 + 4Cl2 heat or light CCl4 + 4HCl
ex. partial chlorination of methane
CH4 + Cl2 CH3Cl + HCl
note this is another family of
compounds: an alkyl halide (in this
case methyl chloride)

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

UV light

CH 4 ( g ) Cl 2 ( g )

CH 3Cl( g ) HCl( g )

If methane is
in excess,
CH3Cl is major
product

If chlorine is in
excess, CCl4
is major
product

CH 3Cl( g ) Cl 2 ( g ) UV
light
CH 2Cl 2 ( g ) HCl( g )
CH 2Cl 2 ( g ) Cl 2 ( g ) UV
light
CHCl3 ( g ) HCl( g )
UV light

CHCl3 ( g ) Cl 2 ( g )

CCl 4 ( g ) HCl( g )

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

Can Replace Some or All of the Hydrogens

CH3Cl

+ Cl2

chloromethane

CH2Cl2

trichloromethane

+ HCl

dichloromethane

+ Cl2

dichloromethane

CHCl3

CH2Cl2

CHCl3

+ HCl

trichloromethane

+ Cl2

CCl4
tetrachloromethane

+ HCl

Reactions of Alkanes
3. Chain termination

two free radicals combine to form a neutral molecule

the chain reaction is terminated

Halogens & Alkanes

The reactivity of the halogens decreases in the
order: F2 > Cl2 > Br2 > I2
F2
fluorination of alkanes is a violent
reaction and difficult to control; can also result in
C C bond cleavage
Cl2
not very selective, often get mixtures
Br2
more selective than chlorine
I2