17

15.1 Alkanes

17.1 Alcohols
17.2 Phenol

17.1 Alcohols
 Alcohols contain the – 𝑂𝐻 functional group. They are classified into primary, secondary and tertiary:

Examples are:

 In primary (1°) alcohols, the carbon atom that carries the −𝑂𝐻 group is attached to none or one other
alkyl group. In secondary (2°) alcohols, the carbon atom that carries the – 𝑂𝐻 group has two 𝐶 − 𝐶 bonds.
In tertiary (3°) alcohols, the carbon atom that carries the – 𝑂𝐻 group has three C-C bonds.

 Ethanol is the most important alcohol, used as a fuel and for consumption as a beverage. Ethanol can be
produced from fermentation of sugars, and from alkenes:

 Fermentation: At 35 - 40oC and in the absence of air, glucose can be fermented in the presence of
yeast to form ethanol:
𝑪𝟔 𝑯𝟏𝟐 𝑶𝟔 𝟐𝑪𝟐 𝑯𝟓 𝑶𝑯 + 𝟐𝑪𝑶𝟐

A higher temperature can denature the yeast, and a lower temperature slows down the rate of reaction.
This method is cheap and uses renewable resources (sugar cane), hence it is the main process used to
produce a lot of commercial ethanol for fuel and for human consumption.

 Hydration of ethene: When ethene is treated with steam at 300 oC, 60 atm pressure and a phosphoric
acid catalyst, ethanol forms:
𝑪𝑯𝟐 = 𝑪𝑯𝟐 + 𝑯𝟐 𝑶 𝑪𝟐 𝑯𝟓 𝑶𝑯

This process uses a non-renewable hydrocarbon resource and a lot of energy, hence this method is
limited to only when a little pure ethanol is required for some industrial uses.

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Chemical Reactions of Alcohols
i) Combustion
 Combustion reactions of alcohols are exothermic, giving carbon dioxide and water if the air is plentiful:
𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝟑𝑶𝟐 𝟐𝑪𝑶𝟐 + 𝟑𝑯𝟐 𝑶
The exothermic nature of this reaction makes alcohols useful as fuels for internal combustion engines.

ii) With Sodium

 Alcohols react with sodium to give fizzy hydrogen gas and a soluble ionic salt. The reaction is steady and
much slower than between sodium and water:
𝟐𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝟐𝑵𝒂 𝟐𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶− 𝑵𝒂+ + 𝑯𝟐
sodium ethoxide
The salt formed immediately dissolves in the alcohol and is therefore not observed. This reaction, because
it is gentle, is used to safely dispose of small amounts of sodium. Using water to wash away sodium
would not be wise as the reaction is violent.

iii) Dehydration to Alkenes

 When alcohol vapour is passed over a hot aluminium oxide catalyst at 170 ˚C, an alkene is formed. The
alcohol loses the – 𝑂𝐻 group, and an 𝐻 atom from a neighbouring carbon atom.

 Other possible dehydrating agents are concentrated sulphuric acid and concentrated phosphoric acid.
Phosphoric acid is generally preferred to sulphuric acid, as the latter is also an oxidising agent which
tends to oxidise the alcohol to carbon dioxide while it is itself reduced to sulphur dioxide, thus giving
contaminated products.

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  In some cases, two isomeric alkenes form, depending on which 𝐻 atoms have been lost. An example is
the dehydration of buta-2-ol:

these join to form

water and the remaining becomes an alkene

Any of the 𝐻 atoms on the carbon marked with an asterisk (*) can be lost alongside the – 𝑂𝐻 group.

 Cyclohexanol oxidises to cyclohexene:

iv) Substitution of the – 𝑂𝐻 Group

 Alcohols undergo substitution to form halogenoalkanes. The particular reagents and conditions depend
on whether a chloro-, bromo-, or iodoalkane is to be formed:
𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝑷𝑪𝒍𝟓 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝒍 + 𝑷𝑶𝑪𝒍𝟑 + 𝑯𝑪𝒍

 Substitution by a chlorine atom can also be done by heating the alcohol under reflux with sodium
chloride and concentrated sulphuric acid. These two first react to form 𝐻𝐶𝑙 which then substitutes the
alcohol:
𝑵𝒂𝑪𝒍 + 𝑯𝟐 𝑺𝑶𝟒 𝑯𝑪𝒍 + 𝑵𝒂𝑯𝑺𝑶𝟒
𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝑯𝑪𝒍 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝒍 + 𝑯𝟐 𝑶

 Substitution by a bromine atom can be done by heating the alcohol under reflux with sodium bromide
and concentrated phosphoric acid. These two first react to form 𝐻𝐵𝑟 which then substitutes the alcohol:
𝑵𝒂𝑩𝒓 + 𝑯𝟑 𝑷𝑶𝟒 𝑯𝑩𝒓 + 𝑵𝒂𝑯𝟐 𝑷𝑶𝟒
𝑪𝑯𝟑 𝑪𝑯(𝑶𝑯)𝑪𝑯𝟑 + 𝑯𝑩𝒓 𝑪𝑯𝟑 𝑪𝑯(𝑩𝒓)𝑪𝑯𝟑 + 𝑯𝟐 𝑶

 For conversion to iodoalkane, reflux the alcohol in the presence of iodine and red phosphorous:
𝟐𝑷 + 𝟑𝑰𝟐 𝟐𝑷𝑰𝟑
𝟑𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝑷𝑰𝟑 𝟑𝑪𝑯𝟑 𝑪𝑯𝟐 𝑰 + 𝑯𝟑 𝑷𝑶𝟑

 Concentrated sulphuric acid cannot be used to make bromoalkanes or iodoalkanes as the sulphuric acid
would oxidise the halide ion to the halogen.

v) Oxidation
 Primary alcohols can be oxidised by heating them with acidified potassium dichromate (VI) solution.
The product is an aldehyde or a carboxylic acid, depending on whether the reaction is done under reflux
or distillation:

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a) Heat and distil
- Ethanol is heated in a flask to 60 °C;
- At this stage, acidified potassium
dichromate is added in drops;
- Ethanal forms, then boils off to be
condensed and collected.

Reagents: excess ethanol, 𝐾2 𝐶𝑟2 𝑂7 (𝑎𝑞) and 𝐻2 𝑆𝑂4 (𝑎𝑞)

Conditions: heat to 60 °C and distil
Mechanism: oxidation
Observation: orange 𝐶𝑟2 𝑂72− (𝑎𝑞) turns to green 𝐶𝑟 3+ (𝑎𝑞)
Organic Product: ethanal (an aldehyde)

b) Heat under reflux

- Ethanol and excess acidified potassium dichromate
are placed in a flask;
- A reflux condenser is added and the mixture is heated;
- After boiling for some time, ethanoic acid forms. The
solution would have turned green.

Reagents: ethanol, excess 𝐾2 𝐶𝑟2 𝑂7 (𝑎𝑞)

and 𝐻2 𝑆𝑂4 (𝑎𝑞)
Conditions: heat under reflux
Mechanism: oxidation
Observation: orange 𝐶𝑟2 𝑂72− (𝑎𝑞) turns to
green 𝐶𝑟 3+ (𝑎𝑞)
Organic Product: ethanoic acid

Note that an excess of the alcohol favours the formation of aldehyde, while an excess of the dichromate
favours the formation of carboxylic acid.

 Secondary alcohols oxidise in the presence of acidified dichromate to ketones, which resist further
oxidation. Conditions and observations are same as for primary alcohols.
A distillation apparatus is preferred since the ketone is volatile and so can be distilled off as it forms.

 Tertiary alcohols resist oxidation by hot acidified potassium dichromate solution.

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vi) Esterification with Carboxylic Acids
 Alcohols react with carboxylic acids in the presence of concentrated sulphuric acid catalyst to form esters.
The reactions are slow and reversible, and the mixture has to be strongly heated to react.

Reagents: alcohol, carboxylic acid

Conditions: boil for long, using conc. 𝐻2 𝑆𝑂4 (𝑎𝑞) catalyst
Mechanism: elimination/condensation
Observation: sweet smell of ester

The circled atoms split away to form a water molecule.

 The concentrated sulphuric acid serves two key roles:

i) It catalyses the reaction, thus speeding up the process;
ii) It acts as a dehydrating agent. By removing the water formed, equilibrium shifts in favour of a
higher yield of ester.

 Esters are observed by their sweet, fruity smell. They are responsible for the aroma of many fruits,
including pears, strawberries, mangoes and bananas.

 Esters are used as solvents, artificial fruit flavouring and as plasticisers (added to polymers to make them
less rigid).

vii) Acylation
 Alcohols react with acyl chlorides at room conditions to form esters.

Reagents: alcohol, acyl chloride

Conditions: room
Mechanism: addition-elimination ( also called condensation)
Observation: sweet smell of ester

The circled atoms split away to form an 𝐻𝐶𝑙 molecule.

viii) The Tri-iodomethane Reaction

 Alcohols which have the – 𝑂𝐻 group on the second carbon atom, provided they are not tertiary, react
with warm aqueous iodine in sodium hydroxide to form a pale yellow precipitate of tri-iodomethane,
𝐶𝐻𝐼3 .

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 The iodine first oxidises the alcohol to a methyl ketone so that it can give a positive test. The general
overall equation for the reaction is:

R is H, an alkyl or aryl group.

 Ethanol, propan-2-ol, butan-2-ol, pentan-2-ol, etc are examples of other alcohols which have a positive
tri-iodomethane test. Besides the pale yellow colour, tri-iodomethane is also observed by its antiseptic
smell.

17.2 Phenol
 At room conditions, phenol is a colourless crystalline solid, with strong intermolecular hydrogen bonding.

 It dissolves relatively well in water due to its ability to form hydrogen

bonding with water molecules. Solutions of phenol are slightly acidic.

 Phenol is the starting material in the manufacture of many substances

such as plastics, resins, nylon, herbicides and drugs such as aspirin.
Phenol, mp = 41 ˚C
Preparation of Phenol
 The industrial hydrolysis of chlorobenzene can produce phenol:

This process uses a lot of energy and is therefore expensive.

 Phenol can also be prepared from benzene via a series of stages:

Relative Acidity of Phenol, Water and Ethanol

 Aqueous solutions of phenol are weakly acidic due to the reversible protonation in water:

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 Phenol is much less acidic than carboxylic acids, though. For example, phenol does not react with sodium
carbonate or sodium hydrogencarbonate to evolve carbon dioxide, but dissolves readily in sodium
hydroxide. Carboxylic acids react with both sodium hydroxide and sodium carbonate.

 The negative charge on the phenoxide ion is not localised on the oxygen atom, but is spread over the
ring, thus stabilising it against reverse protonation. This makes phenol more acidic than alcohols and
water.

 In alcohols, the alkyl group has a positive inductive effect, pushing electrons towards the – 𝑂 atom,
making it easily attract protons. Hence ethanol is less acidic than phenol and water.

Ethanol Phenol Ethanoic acid

𝑵𝒂(𝒔)   
𝑵𝒂𝑶𝑯(𝒂𝒒) ×  
𝑵𝒂𝑯𝑪𝑶𝟑 (𝒂𝒒) × × 
Key:  = React
× = Do not react
 The 𝑝𝐾𝑎 values also confirm the relative acidity described above:

𝒑𝑲𝒂
𝒆𝒕𝒉𝒂𝒏𝒐𝒍 16 Increasing
𝒘𝒂𝒕𝒆𝒓 7.0 Acidity
𝒑𝒉𝒆𝒏𝒐𝒍 9.9
𝒆𝒕𝒉𝒂𝒏𝒐𝒊𝒄 𝒂𝒄𝒊𝒅 4.8

Chemical Reactions of Phenol

i) With Sodium Metal
 Dry phenol is warmed until molten, and then a piece of sodium metal is added. There is rapid evolution
of hydrogen gas.

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ii) With Sodium Hydroxide
 Phenol readily dissolves in sodium hydroxide solution to form an ionic salt.

iii) With Aqueous Bromine

 The – 𝑂𝐻 group has a positive inductive effect on the benzene ring, making electrophilic substitution occur
readily on the ring without a Friedel-Crafts catalyst and with no heating.

Reagents: phenol, aqueous bromine

Conditions: room
Mechanism: electrophilic substitution
Observation: bromine decolourised and a white ppt forms

 2,4,6-tribromophenol forms as a white precipitate. It is also observed by its antiseptic smell.

iv) With Nitric Acid

 Phenol reacts readily at room conditions with dilute nitric acid to form a mixture of 2-nitrophenol and 4-
nitrophenol, which are observed as a white precipitate.

Reagents: phenol, dilute nitric acid

Conditions: room
Mechanism: electrophilic substitution
Observation: white ppt forms

 Concentrated nitric acid can triple-nitrate phenol at room conditions. As before, a white precipitate is
observed.

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v) Acylation
 Phenol does not form esters with carboxylic acids. Instead, phenol readily forms esters with acyl chlorides
at room conditions:

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 Exam Practice 17 Section A: MULTIPLE CHOICE

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 Question 25 Question 28

Question 29

Question 26

Question 30

Question 27

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 Section A

1. A compound, X, reacts with the product of its own oxidation to form an ester. X could be
A propanal
B propan-1-ol
C propan-2-ol
D propanoic acid

2.

Which line in the table is correct for the types of reaction taking place at①, ② and ③?

3. Which line in the table correctly describes the types of reaction in the following sequence?

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 4. A compound, X, reacts with the product of its own oxidation to form an ester. X could be
A propanal
B propan-1-ol
C propan-2-ol
D propanoic acid.

1. B
2. A
3. C
4. B

Section B
1. The diagram below shows a reaction sequence starting from compound A which is pentan-2-ol (C5H12O).

Compound B can exist as two geometric isomers.

Compound C is pent-1-ene.

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 Compound D is the oxidation product of compound A.
(a) Name and draw the structural formulae for the two geometric isomers of compound B. [2]
(b) Name compound D. [1]
(c) Compound E is a cyanohydrin.
(i) Name the type of reaction occurring when D is converted into E.
(ii) Draw a structural formula for compound E.
(d) Name or draw a structural formula for compound F.

1. a)

b) Pentan-2-one.
c) (i) (nucleophilic) addition.
(ii)

d)

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