17.0 Hydroxy Compounds
17.0 Hydroxy Compounds
17.0 Hydroxy Compounds
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.
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:
Any of the 𝐻 atoms on the carbon marked with an asterisk (*) can be lost alongside the – 𝑂𝐻 group.
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.
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.
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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.
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.
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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:
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.
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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.
𝒑𝑲𝒂
𝒆𝒕𝒉𝒂𝒏𝒐𝒍 16 Increasing
𝒘𝒂𝒕𝒆𝒓 7.0 Acidity
𝒑𝒉𝒆𝒏𝒐𝒍 9.9
𝒆𝒕𝒉𝒂𝒏𝒐𝒊𝒄 𝒂𝒄𝒊𝒅 4.8
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ii) With Sodium Hydroxide
Phenol readily dissolves in sodium hydroxide solution to form an ionic salt.
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).
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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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