Alkanes

Learning outcomes

Fuels and crude oil

(a) name natural gas, mainly methane, and petroleum as sources of energy
(b) describe petroleum as a mixture of hydrocarbons and its separation into useful fractions by
fractional distillation
(c) name the following fractions and state their uses
(i) petrol (gasoline) as a fuel in cars
(ii) naphtha as the feedstock and main source of hydrocarbons used for the production of
a wide range of organic compounds in the petrochemical industry
(iii) paraffin (kerosene) as a fuel for heating and cooking and for aircraft engines
(iv) diesel as a fuel for diesel engines
(v) lubricating oils as lubricants and as a source of polishes and waxes
(vi) bitumen for making road surfaces
(d) describe the issues relating to the competing uses of oil as an energy source and as a chemical
feedstock

Alkanes
(e) describe a homologous series as a group of compounds with a general formula, similar
chemical properties and showing a gradation in physical properties as a result of increase in
the size and mass, number of electrons of the molecules, e.g. melting and boiling points;
viscosity; flammability
(f) describe the alkanes as a homologous series of saturated hydrocarbons with the general
formula CnH2n+2
(g) draw the structures of branched and unbranched alkanes, C1 to C4
(h) describe the properties of alkanes (exemplified by methane) as being generally unreactive
except in terms of combustion and substitution by chlorine

1
Fuels and Crude Oil

Coal, petroleum (also called crude oil) and natural gas are fossil fuels. They are commonly
used as sources of energy.

Natural gas is mainly composed of methane (about 70-90%) and other short-chain alkanes.

Fractional distillation of petroleum/crude oil

● Petroleum is a naturally occurring mixture of hydrocarbons (mainly alkanes) with different

boiling points.

● Petroleum can be separated (refined) into useful fractions by fractional distillation.

● Petroleum is heated in a furnace and vapourised and hydrocarbons of different lengths

condense at different temperatures.

● Lighter fractions with fewer number of carbon atoms have lower boiling points. They are
condensed and collected at the top of the fractionating column.

● Heavier fractions with a greater number of carbon atoms have higher boiling points. They
are condensed and collected at the bottom of the fractionating column.

oil

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Uses of Petroleum Fractions

Fraction No. of Boiling Point Uses

carbon Range (ºC)
atoms (n)

Petroleum gas 1–4 < 40 Fuel for cooking and heating

Petrol 5 – 10 40 – 75 Fuel for car engines

(Gasoline)

Naphtha 7 – 14 75 – 150 Chemical feedstock (raw material) for

making petrochemicals like plastics and
detergents

Kerosene 11 – 16 160 – 250 Fuel for aircraft engines;

(Paraffin) Fuel for cooking and heating

Diesel 16 – 20 250 – 300 Fuel for diesel engines

in buses, lorries and trains

Lubricating oil 20 – 35 300 – 350 Lubricating machines;

Making waxes and polishes

Bitumen >70 > 350 Making road surfaces and roofing

Alkane Homologous Series

General formula: CnH2n+2

n Name Molecular Formula Displayed Formula

(full structural formula)
1 methane CH4

2 ethane C2H6

3 propane C3H8

4 butane C4H10

3
 n Name Molecular Formula Displayed Formula
(full structural formula)

5 pentane C5H12
6 hexane C6H14
7 heptane C7H16
8 octane C8H18
9 nonane C9H20
10 decane C10H22

Competing Uses of Petroleum

Petroleum is a limited and non-renewable resource.

• generates heat and • 10% (naphtha) used as

electricity petrochemical feedstock
• powers motor • manufacture of plastics,
vehicles and medicines, fertilisers,
industrial activities
90% 10% pesticides and synthetic
rubber
of petroleum used
as fuel
• Petroleum is important as a
chemical feedstock.
• Both of these uses compete for petroleum.
• It is a waste to just ‘burn’
• Hence, there is a need to conserve
petroleum as a fuel.
petroleum in order to extend its supply.

How might we conserve petroleum?

• Reduce the use of petroleum
• Use alternative energy sources such as:
o biofuel
o solar energy
o nuclear energy
• Design power stations and vehicles that use petroleum more efficiently.

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Physical Properties of Alkanes

Name Molecular Mr Melting point Boiling point State Density

formula (oC) (oC) at r.t.p (g/cm3)

methane CH4 16 −182 −162 gas -

Melting and
ethane C2H6 30 −183 −89 gas - boiling point,
density, viscosity
increases
propane C3H8 44 −188 −42 gas -

butane C4H10 58 gas - Flammability

−138 −0.5
decreases

pentane C5H12 72 −130 36 liquid 0.626

hexane C6H14 86 −95 69 liquid 0.659

Physical Property Trend Explanation

Melting and boiling Increases as Mr increase Stronger
points
________________________________
weak intermolecularforces of
_____________
attraction as number of
_____________
electrons increases
Density Increases as Mr increase
Viscosity Increases as Mr increase
Flammability Decreases as Mr increase
Solubility insoluble in water, but
soluble in organic solvents

5
Chemical Properties of Alkanes

Alkanes contain only single covalent bonds and hence, are generally not as reactive as
alkenes. They can undergo combustion and substitution reactions.

A) Combustion

Complete combustion
● Form water vapour + carbon dioxide
● Occurs when there is sufficient oxygen for reaction
Example: C3H8(g) + ___O
5 2(g) → ___CO2(g) + ___H
4 2O(g)
o
3
Incomplete combustion
● Form water vapour + carbon dioxide + carbon (as soot) and/or carbon monoxide
● Occurs when there is insufficient oxygen for complete reaction
o Examples:
▪ 3CH4(g) + 5O2(g) → CO2(g) + 2CO(g) + 6H2O(g)
▪ 2CH4(g) + 3O2(g) → CO2(g) + C(s) + 4H2O(g)
Practice

1) Tick all the reactions that are incomplete combustion.

Incomplete combustion?
C3H8 + 3O2 → C + 2CO + 4H2O
2C4H10 + 13O2 → 8CO2 + 10H2O
C2H6 + 3O2 → CO + CO2 + 3H2O

2) 5 cm3 of an alkane reacts with oxygen in a complete combustion reaction. You may
assume that there is no more oxygen gas remaining at the end of the reaction.

After cooling the mixture to room temperature and passing the resulting mixture of
gases through aqueous sodium hydroxide, the volume of the reaction mixture
decreased by 15 cm3.

Find the number of hydrogen atoms present in 1 molecule of the alkane.

Cocky x 4 02 XC02 Hyo

som isoms
x 3 Avogadro'sLaw ofGases
i C348

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B) Substitution

Substitution reaction: reaction in which one or more atoms of an organic compound is

replaced by one or more atoms of different elements.

X = Cl or Br in general
Reagents: generally Cl2(g) or Br2(l)
Conditions: UV light
Observations: Greenish–yellow Cl2 turns colourless or reddish–brown Br2 turns colourless

● Hydrogen chloride or hydrogen bromide formed is gaseous. They are NOT

hydrochloric acid or hydrobromic acid.

● Generally, rate of reaction of F2 > Cl2 > Br2 > I2 (due to reactivity of halogens)
o However, F2 is so reactive that other side reactions can occur
o I2 is generally so unreactive that it does not react with alkanes under normal
laboratory conditions

Question: What is the role of the UV light in the reactions?

To
break Cl Cl bonds
_________________________________________________________________________
Multiple substitutions

● Since the products can also react with halogens, multiple substitutions can occur. An
example is shown below.

CH4 + Cl2 → CH3Cl + HCl

CH3Cl + Cl2 → CH2Cl2 + HCl

CH2Cl2 + Cl2 → CHCl3 + HCl

CHCl3 + Cl2 → CCl4 + HCl

7
 Question: Explain why the reaction always produces a mixture of chloroalkanes instead of a
pure sample of a particular chloroalkane.

_________________________________________________________________________
collisionsbetweenmoleculesarerandom

Question: Suggest what can be done to obtain chloromethane (CH3Cl) as the main product.

_________________________________________________________________________
Add Cha excess in

Question: Suggest what can be done to obtain tetrachloromethane (CCl4) as the main
product.

_________________________________________________________________________
AddCHC's inexcess

Practice
Catto
How many possible organic products can be formed when ethane undergoes substitution
reaction with chlorine?

24g 12 24sCl HCl

CzHsC Ck CzHall HC
CzHull 42 24 Cl Hel
CzHsclstelz CanClu HCl
Czhacht 12 244s HCl
Callcist 12 2cL HCl

Cahuilla
d
246 ti Ci c
Y f Y H p
H c
y g
c h
c
ci
g
I gI CI

CattsCl g g

ii
H it p
CI
iii
CI CI
a

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 Alkenes

Learning outcomes

(a) describe the alkenes as a homologous series of unsaturated hydrocarbons with the general
formula CnH2n
(b) draw the structures of branched and unbranched alkenes, C2 to C10 and name the alkenes,
ethene to decene
(c) describe the manufacture of alkenes and hydrogen by cracking hydrocarbons and recognise
that cracking is essential to match the demand for fractions containing smaller molecules from
the refinery process
(d) describe the difference between saturated and unsaturated hydrocarbons from their molecular
structures and by using aqueous bromine / liquid halogens / halogens in carbon tetrachloride
(e) describe the chemistry/properties of alkenes (exemplified by ethene) in terms of:
(i) combustion
(ii) addition with hydrogen, steam, hydrogen halides and liquid halogens / halogens in
carbon tetrachloride
(iii) polymerisation (See also Macromolecules)
(f) describe the manufacture of margarine by the addition of hydrogen to unsaturated vegetable
oils to form a solid product
(g) state the meaning of polyunsaturated when applied to food products

9
Alkene homologous series
Atleast double
General formula: CnH2n covalentbond
bet atoms EC
n Name Molecular Displayed Formula
Formula (full structural formula)

2 ethene C2H4

3 propene C3H6

4 but–1–ene C4H8

5 pent–1–ene C5H10
6 hex–1–ene C6H12
7 hept–1–ene C7H14
8 oct–1–ene C8H16
9 non–1–ene C9H18
10 dec–1–ene C10H20

Isomerism in alkenes

Example: isomers for C4H8

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Physical Properties of Alkenes (Generally similar to Alkanes)

Relative Melting Boiling Density State

Molecular
Name Molecular
formula Point / °C point /°C / g cm-3 (at r.t.p)
Mass

ethene C2H4 28 -169 -104 - gas

propene C3H6 42 -185 - 47 - gas

but-1-ene C4H8 56 -185 -6 - gas

pent-1-ene C5H10 70 -135 30 0.63 liquid

Physical Property Trend Explanation

Melting and boiling increases as Mr increase Stronger intermolecular forces between
points molecules as number of electrons
increases
Density increases as Mr increase
Viscosity increases as Mr increase
Flammability decreases as Mr increase
Solubility insoluble in water, but
soluble in organic solvents

Differences in Physical Properties from Alkanes

Melting and boiling point

● Difference: slightly lower than alkanes with the same number of carbon atoms

● electrons than corresponding alkane

Explanation: Each alkene has 2 fewer _____________
with same number of carbon atoms  weaker intermolecular forces between
molecules

o Example: C3H6 (24 electrons) vs C3H8 (26 electrons)

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Production of alkenes

Catalytic cracking of long chain hydrocarbons

at least Ialkene
long chain alkane any combination of alkane, alkene, hydrogen
Alkane
Examples: C18H38 → C6H14 + 6C2H4
Misttenarios
C18H38 → C8H16 + C10H20 + H2

Reagents: long chain alkane Alkenealways

Conditions: high temperature, finely divided SiO2 or Al2O3 catalyst

Purpose of catalytic cracking

1) Produce hydrogen

● For Haber process

● For hydrogen fuel cell

2) Short chain alkenes

● Raw material for making alcohols like ethanol and plastics like poly(ethene)

3) Short chain alkanes

● Short chain alkanes are generally higher in demand than longer chain alkanes

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Chemical Properties of alkenes

Alkenes are highly reactive due to their carbon-carbon double bond (C=C). They can
undergo combustion and addition reactions.

A) Combustion

Complete combustion

● Form water vapour + carbon dioxide

● Occurs when there is sufficient oxygen for reaction
o 6 4
Example: C4H8(g) + _____O2(g) → _____CO 4
2(g) + _____H2O(g)

Incomplete combustion

● Form water vapour + carbon dioxide + carbon (as soot) and/or carbon monoxide
● Occurs when there is insufficient oxygen for complete reaction
o Examples:
▪ C2H4(g) + 2O2(g) → 2CO(g) + 2H2O(g)
▪ C2H4(g) + O2(g) → 2C(s) + 2H2O(g)

B) Addition reactions

Saturated and unsaturated organic compounds

Saturated: Each carbon atom is bonded to 4 other atoms by single bonds (eg alkanes)

Unsaturated: Contains double or triple carbon-carbon bonds (eg alkenes)

Since alkenes are unsaturated compounds, they are able to undergo addition reactions.

General equation for addition reactions

Added

I
x Y across
y

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2A) Addition of hydrogen

Reagents: hydrogen
Conditions: 200 oC, nickel catalyst
unsaturated Alkene Alkane saturated

µ
Ltd H Htt H of of H

Application of addition of hydrogen

● Can be used to convert unsaturated fats to saturated fats, eg hydrogenation of

vegetable oil to form margarine.
unsaturated
o Polyunsaturated vegetable oils contain more than one C=C bond

o The greater the amount of hydrogen added, the more solid the margarine
becomes

o This process increases the melting point of vegetable oil. (See Annex)

vegetable oil H2, Ni catalyst margarine

liquid state (lower m.p.) solid state (higher m.p.)
more C=C bonds 200°C fewer C=C bonds

2B) Addition of bromine

Reagents: Br2(l)
Conditions: in the dark
Observations: Reddish brown bromine turns colourless
Note: Br2 dissolved in inert solvents like tetrachloromethane (CCl4) can also be used

É it
I it Br Br sa H
a
w
a halogensalkane
alkene

Note: Addition of bromine can be used as a distinguishing test for unsaturation, eg C=C
functional group.

14
Question: Why should the addition of bromine to alkene be carried out in the dark?

With UV substitution ofalkane willoccur

_________________________________________________________________________
light
Question: What happens if aqueous bromine is used?

● Same observations will be seen (Br2(aq) can also be used as distinguishing test)

2C) Addition of steam

Reagents: steam
Conditions: 300 oC, 65 atm, H3PO4 catalyst

it It
H c c c n IEEE I EH
H H
I
2D) Addition of hydrogen halides

X = F, Cl, Br, I

Iii
Reagents: hydrogen halides (HX, eg. HF, HCl, HBr, HI)
Conditions: room temperature

SAME

ÉÉ
myptalide
H of y 7
a
ÉÉ I
Question: Draw the 2 possible products formed by propene when it is reacted with HCl.

LEE
I I H
H IL I H H co
y ÉÉ É H
H
dH H
15
2E) Addition polymerisation (covered in macromolecules)

Practice for addition reactions

Which of the following molecules can be formed by addition reactions of alkenes? For the
molecules that can be formed by addition reactions, draw all the possible alkenes that can
form those molecules.

For 2-bromobutane

H
I Eg of H H B

For 1,1-dibromobutance

For 2,3-dibromobutane

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