Alkanes

Objectives
• Describe selected chemical reactions of
alkanes
– combustion
– Halogenation
– cracking
• Explain the steps involved in the mechanism
of free radical substitution
– E.g. Methane and chlorine
 Alkanes

• Alkanes are saturated hydrocarbons —each carbon holds

the maximum number of hydrogen atoms).
• Alkanes contain only carbon-carbon single bonds.
• General formula: CnH2n+2 (no rings).
• Since alkanes don’t really have functional groups, they
aren’t very useful in many biologically important
processes.
• Since alkanes undergo combustion easily, they
• are a good source of energy (e.g., gasoline).
• Alkanes also provide the raw materials for the production
of many other more complex substances (plastics, etc.).
 Some Common Alkanes

• Methane, CH₄
– major component of natural gas (~85%), which is produced
by bacterial decomposition of organisms in the absence of
oxygen (marsh gas, cow flatulence).
– burns cleanly, so is useful for cooking.
– odorless — ethanethiol is added to make natural gas leaks
detectable.
• Ethane, CH₃CH₃ (C₂H₆) — a minor component of
natural gas (~10%).
• Propane, CH₃CH₂CH₃ (C₃H₈) — used as an industrial fuel, and
in home heating and cooking.
 Some Common Alkanes

Butane, CH₃CH₂CH₂CH ₃(C₄H₁₀)

– cigarette lighters
– Butane is an unbranched (normal) alkane.
-There is also a branched alkane with the formula
-C₄H₁₀, having a three-carbon chain with a one carbon
group connected to the middle.
– We must give the other isomer a different name:
-CH3CH(CH3)CH3 [or CH3CH(CH3)2] is named 2-
methylpropane).
• – Butane and methylpropane are structural isomers of
each other.
 Physical Properties of Alkanes

• Since alkanes are composed of relatively non polar C—C

bonds and C—H bonds, alkanes are non polar molecules.
• Because they have only weak attractions for each other, they
tend to have lower melting points and boiling points than
other organic compounds of comparable molecular weights.
• The straight chain alkanes make up a homologous series in
which each members differs from a previous member by
having one additional CH2 group. In a homologous series,
the physical properties are closely related and vary in a
systematic way.
 Physical Properties of Alkanes

• Alkanes (nonpolar) are insoluble in water (polar),

and since they are less dense than water, they float(e.g.,
oil slicks).
• Alkanes and other substances that do not dissolve in
water are often referred to as being hydrophobic(“water
fearing”).
• Liquid alkanes of high molecular weight serve as
emollients (skin softeners) to replace oils washed
away by bathing or swimming. Vaseline is a semisolid
mixture of alkanes.
 Alkane Reactions

• Alkanes are the least reactive of all organic

compounds. They do not usually react with
strong acids or bases, or with most oxidizing
or reducing agents.
 Combustion

alkane + O2 CO2 + H2O + heat

• They do, however, burn very easily
in combustion reactions, releasing a
great deal of energy:

• CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) + 212.9 kcal

• C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g) + 488.8 kcal
• 2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(g) +2448 kcal

9
 Incomplete Combustion
• In the absence of enough oxygen for complete conversion to
carbon dioxide, some common waste products are generated
in the incomplete burning of alkanes :
• CH4(g) + 3/2 O2(g) → CO(g) + 2H2O(g)
• CH4(g) + O2(g) → C(s) + 2H2O(g)
– CO, carbon monoxide, is poisonous, colorless, and odorless.
In the exhaust train of most cars, a catalytic converter
converts CO to CO2.
– Solid elemental carbon produces engine deposits; but this
reaction is done to produce lampblack, which is used in some
ink pigments.
 Free radical substitution

• Alkanes in which one or more hydrogen

atoms are replaced by halogen atoms (F, Cl, Br,
or I).
A radical is an intermediate with a single unpaired
electron,
 Formation of Radicals
Carbon radicals are formed by homolytic fission
(cleavage )of covalent bonds using either:

(1) Light ( h)

(2) Heat (Δ)

(3) Radical Initiators (ROOR i.e. peroxides)

 Radical Reactions

Halogenation of Alkanes
• Radical halogenation has three distinct parts.

• A mechanism such as radical halogenation that involves two or more

repeating steps is called a chain mechanism.
• The most important steps of radical halogenation are those that lead to
product formation—the propagation steps.
Radical Reactions—Mechanism
 Selectivity of Radical Formed
• When alkanes larger than ethane are halogenated, isomeric
products are formed.
• All the hydrogens in a complex alkane do not exhibit equal
reactivity.
• Secondary 2º-hydrogens are inherently more reactive than
Primary 1º-hydrogens. Further experiments showed that 3º-
hydrogens are even more reactive toward halogen atoms.
 Example
• Thus, light-induced chlorination of 2-
methylpropane gave predominantly (65%) 2-
chloro-2-methylpropane, the substitution
product of the sole 3º-hydrogen, despite the
presence of nine 1º-hydrogens in the molecule.
 Practice Questions
1. Alkanes react with halogens in a reaction described as homolytic free
radical substitution. Explain what is meant by the terms:
• homolytic
• free radical
• substitution

2.a)Using full displayed formulae, show the four steps involved in the
reaction of ethane with chlorine to give chloroethane. State the type of
reaction involved in each step.
 
b)Show by means of additional steps how this mechanism can account
for the formation of:
• 1,1-dichloroethane
• butane
 Cracking
• Petroleum is a mixture of hydrocarbons formed over millions of
years, primarily from the decay of microscopic ocean-dwelling
plants and animals.
• The resulting crude oil collects in underground pockets in
sedimentary rock.
• Petroleum is separated into different fractions by fractional
distillation.
• Most petroleum products are burned as fuel, but about 2% is used
to synthesize other organic compounds. (That’s still a lot!)
• Over half of all synthetic industrial organics, including dyes, drugs,
plastics, fibers, detergents, insecticides, etc., are made from
petroleum sources
 Fractions from crude oil
Modern separation involves piping crude oil through hot furnaces. The
resulting liquids and vapours are passed into distillation towers:-

B Pt Number of
FRACTION o Uses
C carbons
»Refinery
1-4 Bottled gas, fuels
gas
»Petrol 40 ~8 Fuel for cars
Click to add text Raw material for
110 ~10
»Naptha chemicals and plastics.

»Kerosine 180 ~15 Fuel for Aeroplanes

Fuel for cars and
250 ~20
»Diesel lorries
Fuel for Power
340 ~35 Stations, Lubricants
»Oils and grease
Hot
400+ 40+ Road surfacing.
crude » »Bitumen
 Fractions from Crude Oil
• It is important to realise that the column is hot at the bottom
and cool at the top.
• The crude oil separates into fractions according to weight and
boiling point.
• The lightest fractions, including petrol and liquid petroleum
gas (LPG), vapourise and rise to the top of the tower.
• Kerosine (aviation fuel) and diesel oil, stay in the middle of
the tower
• Heavier liquids separate lower down.
• The heaviest fractions with the highest boiling points settle at
the very bottom.
 Comparison of Fractions
AT THE TOP OF THE COLUMN AT THE BOTTOM OF THE COLUMN
 Short carbon chains  Long carbon chains

 Light molecules  Heavy molecules

 Low boiling points  High boiling points

 Gases & very runny liquids  Thick, viscous liquids

 Very volatile  Low volatility

 Highly flammable  Not very flammable

 Light colour  Dark colour

Petrol comes off near the top of the column. Does Fuel oil comes off near the bottom of the column.
the list above describe petrol? Does the list above describe fuel oil?
 Thermal cracking
 
• In thermal cracking, the bonds are broken using a high temperature (400 –
900oC) and a high pressure (70 atmospheres).

• The high temperatures mean that the molecule breaks near the end of the
chain, giving a high percentage of small alkenes such as ethene.

• Most thermal cracking reactions involve the formation of one of more small
alkane molecules and one alkene molecule. Naphtha (C7 – C14) is usually used
Eg C8H18  C6H14 + C2H4
as the starting material.
H H H H H H H H H H H H H H
H H
H C C C C C C C C H H C C C C C C H + H
C C
H
H H H H H H H H H H H H H H

Eg C6H14  C3H8 + C3H6

H H H H H H H H
H H

H C C C C C H H C C C H + C C C H

H H H H H H H
H H H H
 Catalytic cracking
•  
• In catalytic cracking, the bonds are broken using a high temperature (450 oC,
which is generally lower than in thermal cracking), a slight pressure (slightly
greater than 1 atmosphere), and a zeolite catalyst.

• Catalytic cracking is cheaper and more efficient than thermal cracking as it

uses a lower temperature and pressure.

• The zeolite catalyst favours the formation of branched alkanes and

cycloalkanes, which are widely used in motor fuels. The most important
product of catalytic cracking is 2-methylheptane, which is the major
component of petrol. It also produces aromatic hydrocarbons such as
benzene, which have a variety of uses.
H H
H H H H H C C
H C C C C C H H C C H + 3H2
H H H C C
H H
H H
Eg
A table summarising the differences between thermal and catalytic cracking can is
shown below:

Type of cracking Thermal Catalytic

Conditions High temperature (400 High temperature (450

– 900 oC) o
C)
High pressure (70 atm)
Slight pressure ( > 1
atm)

Zeolite catalyst

Main products High percentage of Motor fuels (ie

alkenes branched alkanes)

Aromatic
hydrocarbons