15

15.1 Alkanes

15.1 Alkanes
15.2 Alkenes
15.3 Hydrocarbons as Fuels
15.4 Arenes

15.1 Alkanes
Crude Oil and Fractional Distillation
 Petroleum or crude oil is a naturally occurring, toxic, flammable liquid consisting of a mixture of nearly
150 different hydrocarbons of various molecular weights. The hydrocarbons in crude oil are mostly
alkanes (straight chain and branched), cycloalkanes and various aromatic hydrocarbons.

 Petroleum has very little use as a mixture, but the different hydrocarbons in the petroleum have a wide
range of uses. Crude oil is separated into its different components by a process called fractional
distillation, using the fact that they have different boiling points.

 During fractional distillation, the crude oil is passed into a tall tower called a fractionating column. This
is very hot near the base but much cooler near the top.

 The lighter hydrocarbons (methane, ethane, propane and butane) are collected from the top. They are
mainly used as liquefied petroleum gas (LPG) fuel for domestic heating.

 The heavier alkanes from pentane (𝐶5 𝐻12 ) to octane (𝐶8 𝐻18 ) are refined into petrol (gasoline); the ones
from nonane ((𝐶9 𝐻20 ) to hexadecane(𝐶16 𝐻34 ) are used as diesel fuel and kerosene (jet fuel).

 Alkanes of more than 16 C atoms per molecule are solid at room conditions. These are used as lubricating
oil (grease), fuel for ships, candle waxes, polishing waxes, as well as bitumen and tar for road surfacing.
The heavy alkanes are often converted into other, even more useful smaller hydrocarbons by a process
called cracking.

Chemical Reactions of Alkanes

 The C-H bond is non-polar and does not attract either electrophiles or nucleophiles. Hence alkanes are
unreactive towards acids, alkalis or aqueous oxidising agents.

i) Combustion
 Alkanes react with oxygen in air to produce carbon dioxide and water if the oxygen is plentiful. In limited
oxygen, carbon monoxide and soot (unburnt carbon) may also form. Because alkanes are unreactive, the
reactions require heat or a spark to initiate.

 The combustion reactions are highly exothermic, hence alkanes are used as fuels:
𝑪𝑯𝟒 (𝒈) + 𝟐𝑶𝟐 (𝒈) 𝑪𝑶𝟐 (𝒈) + 𝟐𝑯𝟐 𝑶(𝒍); ∆𝐻𝑐 = −890 kJmol−1
𝟏𝟑
𝑪𝟒 𝑯𝟏𝟎 (𝒈) + 𝑶𝟐 (𝒈) 𝟒𝑪𝑶𝟐 (𝒈) + 𝟓𝑯𝟐 𝑶(𝒍); ∆𝐻𝑐 = −2877 kJmol−1
𝟐
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 The general combustion equation for any alkane is
𝒚 𝒚
𝑪𝒙 𝑯𝒚 + (𝒙 + )𝑶𝟐 𝒙𝑪𝑶𝟐 + 𝑯𝟐 𝑶
𝟒 𝟐
ii) Cracking
 Cracking is the breaking down of a long-chain alkane into a smaller alkane and an alkene. There are two
types of cracking: thermal cracking and catalytic cracking.

 Both involve the breaking of 𝐶 − 𝐶 bonds to form smaller molecules. 𝐶 − 𝐶 bonds are weaker than 𝐶 − 𝐻
bonds and so break more easily when heated.
1. Thermal cracking involves using a high temperature (400 – 900 oC) and a high pressure (70 atm).
The high temperatures mean that the molecule breaks near the end of the chain, giving a high
percentage of small alkenes such as ethene. Example:
𝑪𝟖 𝑯𝟏𝟖 𝑪𝟔 𝑯𝟏𝟒 + 𝑪𝟐 𝑯𝟒
2. Catalytic cracking which uses a temperature (450 oC) which is generally lower than in thermal
cracking), a slight pressure (slightly greater than 1 atm), and a zeolite catalyst.
Catalytic cracking is cheaper and more efficient than thermal cracking as it uses a lower temperature
and pressure.

 Thus cracking is important for two reasons:

i) It converts low-demand long-chain alkanes into smaller ones which are more efficient as fuels. For
example, nonane needs 7 times the amount of oxygen needed by methane to burn completely:
𝑪𝑯𝟒 (𝒈) + 𝟐𝑶𝟐 (𝒈) 𝑪𝑶𝟐 (𝒈) + 𝟐𝑯𝟐 𝑶(𝒍)
𝑪𝟗 𝑯𝟐𝟎 (𝒈) + 𝟏𝟒𝑶𝟐 (𝒈) 𝟗𝑪𝑶𝟐 (𝒈) + 𝟏𝟎𝑯𝟐 𝑶(𝒍)

ii) It produces useful hydrocarbons such as alkenes which are not naturally found in crude oil. Alkenes
can be turned into more useful products such as polymers, alcohols, plastics, solvents, etc.

iii) Substitution by Halogens

Reagents: ethane and 𝐹2 / 𝐶𝑙2 /𝐵𝑟2
Conditions: UV light or heat (𝐹2 reacts violently even
in the dark)
Mechanism: free-radical substitution

 The free –radical substitution in reaction occurs in three stages:

1. Initiation: the UV light or heat initiates the homolytic fission of the halogen molecules to form free-
radicals. The reaction is endothermic (bond-breaking):

UV light
𝑪𝒍𝟐 𝑪𝒍 • + 𝑪𝒍 • ∆𝐻 = +242 kJmol−1
The 𝐶𝑙– 𝐶𝑙 bond is weaker than the 𝐶– 𝐶 and 𝐶– 𝐻 bond and hence, is easiest to break.

2. Propagation: the chlorine radicals attack ethane molecules, forming ethyl radicals and 𝐻𝐶𝑙. The 𝐶 −
𝐻 bonds break and 𝐻 − 𝐶𝑙 bonds form, hence the enthalpy change can be deduced.
𝑪𝒍 • + 𝑪𝟐 𝑯𝟔 • 𝑪𝟐 𝑯𝟓 + 𝑯𝑪𝒍
The ethyl radical attacks more chlorine molecules, generating more radicals:
• 𝑪𝟐 𝑯𝟓 + 𝑪𝒍𝟐 𝑪𝟐 𝑯𝟓 𝑪𝒍 + 𝑪𝒍 •
Each time a free radical is consumed, another is generated. This helps propagate the reactions,
leading to more substitution of hydrogen atoms by chlorine:
𝑪𝟐 𝑯𝟓 𝑪𝒍 + 𝑪𝒍 • • 𝑪𝟐 𝑯𝟒 𝑪𝒍 + 𝑯𝑪𝒍
• 𝑪𝟐 𝑯𝟒 𝑪𝒍 + 𝑪𝒍𝟐 𝑪𝟐 𝑯𝟒 𝑪𝒍𝟐 + 𝑪𝒍 •

3. Termination: the reaction stops after some time as any free-radicals formed in previous steps attack
other free-radicals. The reactions are exothermic (bond-forming):
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 𝑪𝒍 • + 𝑪𝒍 • 𝑪𝒍𝟐
• 𝑪𝟐 𝑯𝟓 + 𝑪𝒍 • 𝑪𝟐 𝑯𝟓 𝑪𝒍
• 𝑪𝟐 𝑯𝟓 + • 𝑪𝟐 𝑯𝟓 𝑪𝟒 𝑯𝟏𝟎

The last reaction explains the presence of butane and other alkanes in the products of the free-
radical substitution of ethane.

15.2 Alkenes
Structure and Reactivity of Alkenes
 Alkenes are unsaturated hydrocarbons containing at least a C=C double bond. The atoms around the
C=C bond have a trigonal planar arrangement and the bond angle is 120˚.

 The C=C bond consists of a stronger sigma bond and a weaker pi bond.

 The sigma bond forms by overlap of atomic orbitals directly in between the nuclei of the two atoms. The
pi bond forms by sideway overlap of two p-orbitals above and below the internuclear axis.

 The pi (π) bond in alkenes make the C=C bond a region of high electron cloud density. Therefore, alkenes
are easily attacked by electrophiles. The electrophiles add across the double bond, hence the reactions
are called electrophilic addition. The pi bond breaks by heterolytic fission; the sigma bonds remains
intact.

Preparation of Alkenes
 Alkenes are prepared in industry by the cracking of alkanes.

 In the lab, gaseous alkenes like ethene can be prepared by the dehydration of alcohols. The ethene is
collected over water.

 If ethanol vapour is passed over heated aluminium oxide powder, the ethanol is cracked to ethene and
water vapour:

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 Alternatively, ethanol is heated with an excess of concentrated sulphuric acid catalyst at 170°C. The gases
produced are passed through sodium hydroxide solution to remove the acidic carbon dioxide and
sulphur dioxide produced from side reactions:

Chemical Reactions of Alkenes

i) Addition of Hydrogen

Reagents: ethene and 𝐻2 gas

Conditions: Ni catalyst, heat to 150 °C
Mechanism: reduction/hydrogenation

 Ethene reacts with hydrogen in the presence of nickel catalyst at 150 °C under pressure to produce
ethane:

 This reaction is important in the hydrogenation of vegetable fats to make margarine. An unsaturated
vegetable oil is mixed with a nickel catalyst at 150 ˚C, and hydrogen gas bubbled through. The saturated
product (margarine) has a higher melting point, and is less easily oxidised, hence longer shelf life.

ii) Addition of Steam (Hydrolysis)

Reagents: ethene and water
Conditions: cold conc. sulfuric acid, then warm
Mechanism: hydrolysis

 When an alkene is passed into cold concentrated sulphuric acid followed by steam, an alcohol forms. The
reaction is reversible.

This is a common laboratory method of preparing ethanol. By removing the ethanol from the equilibrium
mixture, a high yield of alcohol can be achieved.

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iii) Addition of Steam (Hydration)

Reagents: ethene and steam

Conditions: conc. 𝐻3 𝑃𝑂4 , 300 °C, 60 atm
Mechanism: hydration

 When alkenes are treated with steam at 300 oC and 60 atm pressure and a phosphoric acid catalyst, the
𝐻2 𝑂 adds across the double bond and an alcohol is formed in a reaction known as hydration:

This is a common industrial method for the production of pure ethanol.

iv) Oxidation by Cold, Dilute Alkaline Potassium Manganate (VII)

Reagents: alkene and 𝐾𝑀𝑛𝑂4 (𝑎𝑞)

Conditions: cold, dilute, alkaline
Mechanism: oxidation (mild)
Observation: purple 𝐾𝑀𝑛𝑂4 (𝑎𝑞) to brown 𝑀𝑛𝑂2 (𝑠)

 A cold solution of potassium manganate (VII) in alkaline solution is weakly oxidising, forming a –diol with
an alkene:

 The [O] is oxygen atom from the oxidising agent. The manganese is reduced from (+7) to (+4) in the
brown 𝑀𝑛𝑂2 (𝑠).

v) Oxidation by Hot, Concentrated, Acidified Potassium Manganate (VII)

Reagents: alkene and 𝐾𝑀𝑛𝑂4 (𝑎𝑞)

Conditions: hot, concentrated, acidified
Mechanism: oxidation (vigorous)
Observation: purple 𝐾𝑀𝑛𝑂4 (𝑎𝑞) to pale pink 𝑀𝑛2+

 With hot, acidified manganate, the C=C bond breaks. The manganese is reduced from (+7) to (+2) in
the pale pink 𝑀𝑛2+ . The products depend on the structure of the alkene.

 Alkenes that are not branched at the C=C bond oxidise to carboxylic acids:

 Branched alkenes oxidise to ketones:

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 A single C atom on one end of a C=C bond converts to a carbon dioxide molecule:

vi) Addition of Hydrogen Halides

Reagents: ethene and 𝐻𝐵𝑟
Conditions: room
Mechanism: electrophilic addition

 Reaction rates increase in the order 𝐻𝐹 < 𝐻𝐶𝑙 < 𝐻𝐵𝑟 < 𝐻𝐼. The 𝐻 − 𝐼 bond is the weakest of the three,
and hence the easiest to break. 𝐻𝐹 reacts very slowly at room conditions.

 Reaction rates also increase as the alkene molecule gets more ‘complicated’:

 Alkyl groups tend to "push" electrons away from themselves towards the double bond. The more alkyl
groups in the alkene, the more negative the area around the double bonds becomes, and the more it
will attracts electrophiles.

vii) Addition of Bromine in Inert Solvent

Reagents: ethene and 𝐵𝑟2 in 𝐶𝐶𝑙4

Conditions: room
Mechanism: electrophilic addition
Observation: reddish-brown bromine decolourised

 When a gaseous alkene is bubbled into liquid bromine in tetrachloromethane at room conditions, an
electrophilic reaction occurs and the reddish-brown bromine is rapidly decolourised.

 For a liquid alkene such as cyclohexene, shaking with liquid bromine in tetrachloromethane at room
conditions causes the reddish-brown bromine to be decolourised:

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viii) Addition of Aqueous Bromine

Reagents: ethene and 𝐵𝑟2 (aq)

Conditions: room
Mechanism: electrophilic addition
Observation: reddish-brown bromine decolourised

 When a liquid alkene is shaken with bromine water (or gaseous alkene bubbled through bromine water)
at room conditions, the reddish-brown bromine is decolourised:

ix) Addition Polymerisation Reactions

 Polymers are long-chain molecules made by joining together many small molecules called monomers.

 For addition polymerisation, the monomers must possess the 𝐶 = 𝐶 bond. During polymerisation, the π-
bond breaks and the monomers join to form thousands of units.

 Examples of polymers are poly(ethene), poly(propene), polystyrene, Teflon, and PVC (poly(vinylchloride)).
Poly(ethene) is not biodegradable, except when it is exposed to UV from sunlight. Hence its disposal
creates an environmental challenge.

Polymer Uses and Properties

 Poly(ethene) General Uses: making plastic materials like shopping

bags, buckets, kitchenware, toys, plastic bottles,
garbage bins, etc.

Properties: low to average melting points (Low Density

Poly(Ethene) - LDPE) and may not not be used for
storing hot substances. HDPE is harder and of higher
melting point.

The polymer units are saturated and have non-polar

bonds, hence they do not react readily. Plastics are
therefore used to store acids, alkalis, oxidising agents,
etc.

 Poly(propene)
General Uses: making garden furniture, stationery,
car interior parts, packaging, straws, etc.

Properties: like poly(propene), this polymer has a

simple molecular structure, with van der Waals’ forces
between the layers.

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  Poly(chloroethene) or PVC General Uses: it is light and water-proof, hence used
to make raincoats and household sewerage pipes and
other pipe applications such as electrical insulation

Properties: PVC can form HCl fumes when combusted.

The C-Cl bond is polar, but most PVC products have
additives called plasticizers to make it biologically and
chemically resistant.
PVC can be recycled.

Detailed Mechanism for the Electrophilic Addition

Reactions of Alkenes
i) Bromine and Ethene
 The 𝐵𝑟 − 𝐵r molecule is non-polar but in the presence of alkenes the electrons of the 𝐶 = 𝐶 bond repel
the bromine bonding electrons to one side of the molecule. This induced dipole makes the bromine
polarised.

 The δ+ end of the bromine molecule becomes electrophilic and attracts to the π-electrons of the 𝐶 = 𝐶
bond. A 𝐶 − 𝐵𝑟 dative bond forms and the 𝐵𝑟 − 𝐵𝑟 bond undergoes heterolytic fission:

carbocation 1,2-dibromoethane

 The curly arrows show the movement of electron pairs, pointing away from the site of electrons. The
second step is fast as it involves reaction between oppositely charged particles.

 This reaction is used as a test for alkenes. The rapid decolourisation of bromine confirms the presence of
the 𝐶 = 𝐶 bond.

 If the reaction is carried out in a solution which has chloride ions or hydroxide ions (in water), these are
smaller and react with the carbocation more readily than does the larger bromide ion. The main products
when bromine reacts with ethene in water or in aqueous sodium chloride are given below:

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ii) Hydrogen Bromide and Propene
 𝐻𝐵𝑟 is already a polar molecule and reacts more readily with ethene, forming bromoethane:

 When propene is used instead of ethene, there are two possible carbocations A and B, resulting in two
possible products X and Y:

 X is the main prodct; Y is the minor product. Alkyl groups have a positive inductive (electron-donating
effect). The presence of two alkyl groups either side of the positive charge in carbocation A statbilises
the ion.

 Markovnikov’s Rule: the H atom from HBr is more likely to attack the C atom which already has more
H atoms bonded to it.

Alternative Mechanism for the

Electrophilic Addition of Bromine to Ethene

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15.3 Hydrocarbons as Fuels
Environmental Considerations
 Combustion reactions of alkanes are highly exothermic, hence their use as fuels.

 Liquid alkanes such as octane must be vapourised before they will burn completely. The reactions have
very low activatioin energy, hence only a spark is needed to initiate the reactions.

 Complete combustion of hydrocarbons gives carbon dioxide and water as products. Incomplete
combustion may produce carbon monoxide and soot (unburnt carbon) as additional products.

 Incomplete combustion occurs when there isn't enough oxygen to allow the fuel to react completely to
produce carbon dioxide and water. This commonly occurs in internal combustion engines of motor
vehicles, in some factory kilns and thermal power plants.

Environmental Pollution
 Virtually all products of combustion – complete or incomplete – have an undesirable effect on the
environment.

a) Carbon Dioxide
 Carbon dioxide is not poisonous and is naturally removed from the atmosphere by plants, but in recent
years enormous quantities of hydrocarbons are being burned, causing carbon dioxide levels to rise
significantly.

 Carbon dioxide is a greenhouse gas, i.e., it prevents the earth’s heat from escaping into space, leading
to gradual rise in global temperature. The phenomena is known as global warming. The result is the
melting of the polar ice caps which is likely to cause severe flooding in the future, as well as serious
damage to some ecosystems.

b) Water Vapour
 Water vapour is also produced in large quantities as a result of combustion of hydrocarbons and is also
a greenhouse gas.

c) Carbon Monoxide
 It binds irreversibly to the haemoglobin in the blood in place of oxygen, and hence reduces the ability of
the blood to carry oxygen causing suffocation and eventually death.

d) Sulphur Dioxide
 Most hydrocarbon fuels contain some sulphur. When the fuel is burned, the sulphur also burns,
producing sulphur dioxide:
𝑺(𝒔) + 𝑶𝟐 (𝒈) 𝑺𝑶𝟐 (𝒈)

 When dissolved in rain water, sulphur dioxide causes acid rain which erodes buildings and structures,
damages crops and contaminates lakes.

e) Oxides of Nitrogen

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 Air contains 79 % nitrogen. The high temperatures inside internal combustion engines cause some of the
nitrogen to react with the oxygen to produce nitrogen monoxide and nitrogen dioxide. These gases
contribute to acid rain and to the photochemical smog.

 A photochemical smog is a mixture of particles formed from the chemical reaction of nitrogen oxides
(𝑁𝑂𝑥 ), ground-level ozone and volatile organic compounds in the atmosphere, in the presence of
sunlight.
It can cause breathing disorders to the elderly and children, leading to lung conditions such as
emphysema and bronchitis. It also causes eye and nose irritation, and compromises the body’s ability to
fight infection.

f) Unburned Hydrocarbons
 Some of the hydrocarbon fuel is vaporised in the engine but escapes before it is burned. Unburnt
hydrocarbons cause cancer if breathed in, and also combine with oxides of nitrogen to produce
photochemical smog.

Reducing Environmental Pollution

a) Flue gas desulphurisation
 A chimney is a structure (usually vertical on a factory building or locomotive) for venting hot flue gases
or smoke from a boiler, stove, furnace or fireplace to the outside atmosphere.
Many factory chimneys contain basic materials such as lime (calcium oxide) to absorb the acidic gases
such as 𝑆𝑂2 and thus prevent them from escaping:
𝑪𝒂𝑶 + 𝑺𝑶𝟐 𝑪𝒂𝑺𝑶𝟑
Further reactions result in the formation of 𝑪𝒂𝑺𝑶𝟒 which is used to make plaster.

b) Catalytic Converters
 Most modern car exhausts are now fitted with catalytic converters. These are designed to convert some
of the more harmful gases present in car exhausts into less harmful ones.

 There are two main types of reaction taking place in a catalytic converter:
i) Conversion of carbon monoxide and nitrogen monoxide into the less harmful nitrogen and carbon
dioxide:
𝟐𝑵𝑶(𝒈) + 𝟐𝑪𝑶(𝒈) 𝑵𝟐 (𝒈) + 𝟐𝑪𝑶𝟐 (𝒈)
ii) Removal of unburned hydrocarbons:
𝟐𝟓
𝑪𝟖 𝑯𝟏𝟖 (𝒈) + 𝟐𝟓𝑵𝑶(𝒈) 𝟖𝑪𝑶𝟐 (𝒈) + 𝟗𝑯𝟐 𝑶(𝒈) + 𝑵 (𝒈)
𝟐 𝟐

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15.4 Arenes
The Benzene Ring
 Benzene is a cyclic hydrocarbon containing six carbon atoms and six hydrogen atoms arranged in a
regular hexagonal shape. Each of the carbon atoms makes three covalent bonds, with the fourth electron
delocalised over the entire molecule.

 The delocalized electrons can be represented as a circle within the hexagonal ring:

 All six C-C bonds have the same length, intermediate between a single and a double length. The
molecular shape is trigonal planar, with bond angle 120˚.

 Any molecule containing the benzene ring can be described as aromatic.

Effect of Delocalised Electrons

 The delocalization of the electrons in benzene makes the molecule more stable than expected for a
molecule with three double bonds. For example, when cyclohexene (one C=C bond) is reduced to
cyclohexane, 120 kJ of energy is released per mole.
Theoretically, if benzene contained three separate C=C bonds it would release 360 kJ per mole when
reduced to cyclohexane, but it releases much less.

Thus benzene undergoes substitution reactions more favourably than it undergoes addition reactions, as
substitution does not disturb the ring.

 The delocalized electrons make the benzene molecule undergo attack by electrophiles. Hence benzene
tends to undergo electrophilic substitution reactions.

Reactions of Benzene
i) Halogenation
Reagents: benzene and 𝐶𝑙2 (𝑔) (𝑜𝑟 𝐵𝑟2 (𝑔))
Conditions: room, Friedel—Crafts catalyst (𝐴𝑙𝐶𝑙3 𝑜𝑟 𝐹𝑒𝐵𝑟3 )
Mechanism: electrophilic substitution
Observation: white fumes of 𝐻𝐶𝑙 (or 𝐻𝐵𝑟)

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 𝐴𝑙𝐶𝑙3 𝑜𝑟 𝐴𝑙
𝑟𝑜𝑜𝑚, 𝑑𝑟𝑦

chlorobenzene

𝐹𝑒𝐵𝑟3 𝑜𝑟 𝐹𝑒
𝑟𝑜𝑜𝑚, 𝑑𝑟𝑦

bromobenzene
 Such reactions are called Friedel-Crafts reactions. They require an electron-accepting catalyst, such as
aluminium chloride, aluminium bromide and iron (III) bromide.

 Iodine has no similar reaction, due to its poor affinity for electrons.

ii) Nitration
Reagents: benzene and 𝑐𝑜𝑛𝑐. 𝐻𝑁𝑂3
Conditions: conc. 𝐻2 𝑆𝑂4 catalyst, reflux at 55˚C
Mechanism: electrophilic substitution

𝑐𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
𝑟𝑒𝑓𝑙𝑢𝑥,
55℃

nitrobenzene

 Reflux refers to the heating of a liquid so that the escaping vapour is condensed and returned to the
liquid.

 Refluxing the above reagents at a higher temperature results in double nitration of the ring. Triple-
nitration of benzene is difficult even at higher temperature.

𝑐𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
𝑟𝑒𝑓𝑙𝑢𝑥,
95℃

1,3-dinitrobenzene

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iii) Alkylation
Reagents: benzene and halogenoalkane e.g. 𝐶𝐻3 𝐵𝑟
Conditions: warm, Friedel—Crafts catalyst (𝐴𝑙𝐶𝑙3 / 𝐹𝑒𝐵𝑟3 )
Mechanism: electrophilic substitution
Observation: white fumes of 𝐻𝐶𝑙 (or 𝐻𝐵𝑟)

𝑑𝑟𝑦 𝐹𝑒𝐵𝑟3
𝑤𝑎𝑟𝑚

methylbenzene

𝑑𝑟𝑦 𝐴𝑙𝐶𝑙3
𝑤𝑎𝑟𝑚

ethylbenzene

iv) Acylation

Reagents: benzene and acylchloride e.g. 𝐶𝐻3 𝐶𝑂𝐶𝑙

Conditions: 50 ˚𝐶 , Friedel—Crafts catalyst (𝐴𝑙𝐶𝑙3 )
Mechanism: electrophilic substitution
Observation: white fumes of 𝐻𝐶𝑙

𝑑𝑟𝑦 𝐴𝑙𝐶𝑙3
50 ˚𝐶

phenylethanone

v) Hydrogenation/ Reduction

𝑁𝑖
180 ˚𝐶, 10 𝑎𝑡𝑚

cyclohexane

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Detailed Mechanism for the Electrophilic Substitution
Reactions of Benzene
i) Nitration
Step 1: an acid-base reaction occurs between concentrated nitric acid and concentrated sulphuric acid. Nitric
acid is a weaker acid than sulphuric acid, and acts as a base by accepting a proton from sulphuric acid:
𝟐𝑯𝟐 𝑺𝑶𝟒 + 𝑯𝑵𝑶𝟑 𝟐𝑯𝑺𝑶− + +
𝟒 + 𝑯𝟑 𝑶 + 𝑵𝑶𝟐

Step 2: The nitronium ion (or nitryl cation) 𝑵𝑶+

𝟐 formed is an electrophile and attacks the delocalised ring. This
forms a short-lived intermediate, in which both the incoming cation and the leaving —H atom are
bonded to the ring. This is the rate-determining step.

Step 3: The delocalised ring then reforms itself by pulling electrons from the C-H bond. The intermediate rapidly
loses a proton to restore the symmetry and stability of the benzene ring. The proton is immediately
picked up by a hydrogen sulphate ion to regenerate the catalyst:

𝟐𝑯𝑺𝑶𝟒− + 𝑯𝟑 𝑶+ + 𝑯+ 𝟐𝑯𝟐 𝑺𝑶𝟒 + 𝑯𝟐 𝑶

ii) Halogenation
 The Cl-Cl bond is non-polar, so a Friedel—Crafts catalyst is needed to polarise it into ions:

 The electrophile formed attacks the benzene ring, forming an intermediate which then forms
chlorobenzene:

The proton is immediately picked up by a hydrogen sulphate ion to regenerate the catalyst:
𝑨𝒍𝑪𝒍−
𝟒 + 𝑯
+
𝑨𝒍 𝑪𝒍𝟑 + 𝑯𝑪𝒍

 Alkylation follows a similar mechanism.

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 methylbenzene

Reactions of Methylbenzene
 The benzene ring in methylbenzene is more reactive towards electrophiles than an ordinary benzene
ring. The positive inductive effect of the methyl group make the ring richer in electrons.

 Methylbenzene undergoes the usual electrophilic substitution reactions of benzene, but using milder
conditions. In addition, the methyl side-group undergoes typical alkyl reactions of free-radical
substitution and oxidation:

i) Halogenation
Reagents: methylbenzene and 𝐶𝑙2 (𝑔)
Conditions: 20 ˚𝐶 , in the dark, 𝐴𝑙𝐶𝑙3
Mechanism: electrophilic substitution
Observation: white fumes of 𝐻𝐶𝑙

𝑑𝑟𝑦 𝐴𝑙𝐶𝑙3
20 ˚𝐶, 𝑑𝑎𝑟𝑘

2-chloromethylbenzene

 Reaction is carried out in the dark to avoid free-radical substitution on the methyl group by the chlorine
in sunlight.

 The actual product is a mixture of the positional isomers, 2-chloromethylbenzene and 4-

chloromethylbenzene.

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ii) Nitration
Reagents: methylbenzene and 𝑐𝑜𝑛𝑐. 𝐻𝑁𝑂3
Conditions: conc. 𝐻2 𝑆𝑂4 catalyst, reflux at 30˚C
Mechanism: electrophilic substitution

𝑐𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
30℃

2-nitromethylbenzene and its positional isomer,

4-nitromethylbenzene

 Triple-nitration occurs by refluxing the mixture at 60˚C:

𝑐𝑜𝑛𝑐. 𝐻2 𝑆𝑂4 2,4,6-trinitromethylbenzene

or TNT, an explosive
60℃

iii) Oxidation of Side-Group

 Any alkyl side-group, no matter how long, oxidises to benzoic acid under the action of hot acidified
manganate solution:

iv) Free-radical Substitution

 In the presence of UV light and sufficient chlorine, free-radical substitution reactions occur on the methyl
side-group forming a mixture of products.

𝐶𝑙2 𝐶𝑙2 𝐶𝑙2

𝑈𝑉 𝑙𝑖𝑔ℎ𝑡 𝑈𝑉 𝑙𝑖𝑔ℎ𝑡 𝑈𝑉 𝑙𝑖𝑔ℎ𝑡

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Inductive Effects of Groups
on the Benzene Ring
 It is possible to bring more than one group on the benzene ring, but the group already present
determines:
- The position where the next group substitutes; and
- How easy it is to bring further groups.

Electron-donating Electron-withdrawing

Structure

Examples of groups −𝑶𝑯, − 𝑪𝑯𝟑 − 𝑵𝑯𝟐 −𝑪𝑶𝑶𝑯, − 𝑵𝑶𝟑 − 𝑪𝑯𝑶

Effect on the benzene ring Electron density increases Electron density decreases
Ease of further substitution Easier Harder
Position of substitution 2, 4, 6 3, 5

 An exception are the halogen atoms, which are electron-withdrawing but are 2,4,6-directing.

 A group has a positive inductive effect on the ring if it “pushes” electrons towards the ring. This makes
the ring more attractive to attack by electrophiles, making further substitution occur more readily.

 A group has a negative inductive effect on the ring if it “withdraws” electrons from the ring. This makes
the ring less attractive to attack by electrophiles, making further substitution more difficult.

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 1. Part of a possible chain reaction mechanism for chlorine reacting with methane is:

Which of the following will not be a termination step in this reaction?

A H• + Cl• → HCl
B Cl• + Cl• → Cl2
C CH3• + CH3• → C2H6
D CH3• + Cl• → CH3Cl

2. The major product in the reaction of HCl with 2-methylpent-2-ene,

is
A 2-chloro-2-methylpentane
B 3-chloro-2-methylpentane
C 2,3-dichloro-2-methylpentane
D 4-chloro-4-methylpentane.

3. The conversion of benzene to monochlorobenzene using Cl2/FeCl3 involves

A nucleophilic addition
B nucleophilic substitution
C electrophilic addition
D electrophilic substitution.

4.

Which species initially attacks the benzene molecule in the above reaction?
A NO3–
B NO2+
C HSO4–
D NO

5. The reaction between chlorine and ethane to give chloroethane is an example of a chain reaction.
Which of the following is a propagation step in this reaction?

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 6.

Which of the following compounds could be X?

7. Bromine reacts with propene to produce 1,2-dibromopropane. A possible intermediate in the reaction is

8. Which of the following represents an initiation step in a chain reaction?

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 9.

Which species initially attacks the benzene molecule in the above reaction?

10.

The above reaction is an example of

A addition
B oxidation
C elimination
D substitution.

11. Which of the following substances could not be a product in the chain reaction between ethane and chlorine?

A HCl
B C2H3Cl
C C2H5Cl
D C4H10

12.

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The two steps in the reaction mechanism shown can be described as
A ethene acting as a nucleophile and Br− acting as a nucleophile
B ethene acting as a nucleophile and Br− acting as an electrophile
C ethene acting as an electrophile and Br− acting as a nucleophile
D ethene acting as an electrophile and Br− acting as an electrophile.

13. Propan-2-ol can be prepared from propane as follows.

Which line in the table correctly describes the types of reaction taking place at Steps 1 and 2?

14. Propene reacts with hydrogen bromide to form two products.

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 Which of the following alkenes does not form two products on reaction with hydrogen
bromide?

A But-1-ene

B But-2-ene

C Pent-1-ene
D Pent-2-ene

1. A
2. A
3. D
4. B
5. D
6. B
7. D
8. A
9. B
10. A
11. B
12. A
13. A

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