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C15.

1 Alcohols – Introduction
Objectives:

 State the general formula of an alcohol.


 Describe how alcohols are classified.
 Describe the physical properties of alcohols.

Ethanol is possibly our oldest social drug as it is derived from the fermentation of
sugars in fruits and so on. It is the alcohol in alcoholic drinks.

 It may, in moderation, promote a feeling of well-being and reduce normal


inhibitions. It is in fact a nervous system depressant (i.e., it interferes with
the transmission of nerve impulses).
 In larger amounts it leads to loss of balance, poor hand-eye coordination,
impaired vision, and inability to judge speed. Large amounts can be fatal.
Excessive long-term use can lead to addiction – alcoholism.
 The ethanol in alcoholic drinks is absorbed through the walls of the stomach
and small intestine into the bloodstream. Some is eliminated unchanged in
urine and in the breath. The rest is broken down by the liver.
 The combined effect of these processes is that an average person can
eliminate about 10 cm3 of ethanol per hour. This is approximately the
amount of ethanol in half a pint of beer, a small glass of wine (125 ml) or a
shot (25 ml of spirits).

The general formula

 Alcohols have the functional group -OH attached to a hydrocarbon chain.


They are relatively reactive. The alcohol most commonly encountered in
everyday life is ethanol.
 The general formula of an alcohol is CnH2n + 1OH. This is often shortened to
ROH.

How to name alcohols

 The name of the functional group (The -OH group) is normally given by the
sulfix -ol. (The prefix hydroxy- is used if some other functional groups are
present.
 With chains longer than ethanol, you need a number to show where the -OH
group is.

 If there is more than one -OH group, di-, tri-, tetra-, and so on are used to
say how many -OH groups there are and numbers to say where they are.

 Propane-1,2,3-triol is also known as glycerol, which may be obtained from


the fats and oils found in living organisms.
Shape

 In alcohols, the oxygen atom has two bonding pairs of electrons and two
tone pairs.
 The C—O—H angle is about 105° because the 109.5° angle of a perfect
tetrahedron is ‘squeezed down’ by the presence of the lone pairs. These two
lone pairs will repel each other more than the pairs of electrons in a covalent
bond.

Classification of alcohols

 Alcohols are classified as primary (1°), secondary (2°), or tertiary (3°)


according to how many other groups (R) are bonded to the carbon that has
the -OH group.

Primary alcohols

 In a primary alcohol, the carbon with the -OH group has one R group (and
therefore two hydrogen atoms).

 A primary alcohol has the -OH group at the end of a chain.

Secondary alcohols

 In a secondary alcohol, the -OH group is attached to a carbon with two R


groups (and therefore one hydrogen atom).
 A secondary alcohol has the -OH group in the body of the chain.

Tertiary alcohols

 Tertiary alcohols have three R groups attached to the carbon that is bonded
to the -OH (so this carbon has no hydrogen atoms).

 A tertiary alcohol has the -OH group at a branch in the chain.

Physical properties

 Higher melting and boiling points than alkanes of similar relative molecular
mass.
 The alcohols with short hydrocarbon chains are soluble in water because
the hydrogen bonding predominates.
 In longer-chain alcohols the non-polar hydrocarbon chain dominates and the
alcohols become insoluble in water.

15.2 Ethanol production


Objectives:

 Describe how ethanol is produced by fermentation.


 Describe the economic and environmental advantages of producing ethanol
by fermentation.
 State what is meant by the term biofuel.
Industrial chemistry of alcohols

 Alcohols are very important in industrial chemistry because they are used as
intermediates. They are easily made and easily convened into other
compounds.
 Methanol is made from methane (natural gas) and is increasingly being
used as a starting material to make other organic chemicals.

Ethanol

 Ethanol, C2H5OH, is by far the most important alcohol. It is used as an


intermediate in the manufacture of other organic chemicals.
 In everyday life it is often the solvent in cosmetics, such as aftershave and
perfumes. It is also used in the manufacture of drugs, detergents, inks, and
coatings.
 It is made industrially by reacting ethene (made from cracking crude oil) with
steam, using a catalyst of phosphoric acid.
 It is also made from sugars by fermentation, as in the production of alcoholic
drinks.
 Beers have about 5% ethanol and wines about 12%. Spirits, Such as gin
and whisky, contain about 40% ethanol – these have been concentrated by
distillation.

Making ethanol from crude oil

 Ethene is produced when crude oil fractions are cracked.

 Ethene is hydrated, which means that water is added across the double
bond.
Making ethanol by fermentation

 During fermentation, carbohydrates from plants are broken down into sugars
and then converted into ethanol by the action of enzymes from yeast. The
carbohydrates come from crops such as sugar cane and sugar beet.
 The key step is the breakdown of sugar in a process called anaerobic
respiration: enzymes from yeast.

 The rate of this chemical reaction is affected by temperature. It is slow at


low temperatures but the enzymes are made ineffective if the temperature is
too high. A compromise temperature of about 35 °C, a little below our body
temperature, is used.
 Air is kept out of the fermentation vessels to prevent oxidation of ethanol to
ethanoic acid (the acid in vinegar).
 Once the fermenting solution contains about 15% ethanol the enzymes are
unable to function and fermentation stops. Ethanol may the be distilled from
this mixture by fractional distillation as its bailing temperature (780C) is less
than that of water (100 °C).

A renewable source of ethene

 Ethene is a vital industrial chemical; it is the starting material for


poly(ethene) and many other important chemicals. Ethene can be produced
by dehydrating ethanol made from sugar, giving a renewable source of
ethene.
 At present ethene is made from crude oil and then converted into ethanol. In
the future it may become more economical to make ethene 1mm ethanol
made by fermentation, see Figure 3.

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15.3 The reactions of alcohols


Objectives:

 State the products when primary, secondary, and tertiary alcohols are
oxidised.
 Explain how the oxidation of a primary alcohol is controlled.
 State what is meant by aldehydes and ketones.
 Describe how a mild oxidising agent can be used to distinguish between an
aldehyde and a ketone.
 Describe what elimination reactions are.
 Describe how alcohols are dehydrated to form alkenes.

Combustion

 Alcohols bum completely to carbon dioxide and water if there is enough


oxygen available. (Otherwise there is incomplete combustion and carbon
monoxide or even carbon is produced.) This is the equation for the complete
combustion of ethanol:
 Ethanol is often used as a fuel, for example, in picnic stoves that burn
methylated spirits. Methylated spirits is ethanol with a small percentage of
poisonous methanol added to make it unfit to drink.

Elimination reactions

 Elimination reactions are ones in which a small molecule leaves the parent
molecule. In the case of alcohols, this molecule is always water.
 The water is made from the -OH group and a hydrogen atom from the
carbon next to the ~OH group. So, the elimination reactions of alcohols are
always dehydrations.

Dehydration

 Alcohols can be dehydrated with excess hot concentrated sulfuric add or by


passing their vapours over heated aluminium oxide. An alkene is formed.
For example, propan-1-ol is dehydrated to propene:

 The apparatus used in the laboratory is shown in Figure 3. Fhosphoric(V)


acid is an alternative dehydrating agent.
Oxidation

 Combustion is usually complete oxidation. Alcohols can also be oxidised


gently and in stages. Primary alcohols are oxidised to aldehydes, RCHO.
Aldehydes can be further oxidised TO carboxylic acids, RCOOH. For
example:

 Secondary alcohols are oxidised to ketones, R^CO. Ketones are not


oxidised further.

 Tertiary alcohols are not easily oxidised. This is because oxidation would
need a C—C bond to break, rather than a C—H bond (which is what
happens when an aldehyde is oxidised). Ketones are not oxidised further for
the same reason.
 Many aldehydes and ketones have pleasant smells.

The experimental details

 A solution of potassium dichromate, acidified with dilute sulfuric acid, is


often used to oxidise alcohols to aldehydes and ketones. It is the oxidising
agent. In the reaction, the orange dichromate (VI) ions are reduced to green
chromium (111) ions.
 To oxidise ethanol (1° alcohol) to ethanal -an aldehyde
 Dilute add and less potassium dichromate (VI) than is needed for complete
oxidation to carboxylic acid are used.
 The mixture is heated gently in apparatus like that shown in Figure 4, but
with the receiver cooled in ice to reduce evaporation of the product.
 Ethanal (boiling temperature 294 K, 21 °C) vaporises as soon as it is formed
and distils off. This stops it from being oxidised further to ethanoic acid.
 Unreacted ethanol remains in the flask.

 The notation [0] is often used to represent oxygen from the oxidising agent.
The reaction is given by the equation:
 To oxidise ethanol (10 alcohol) to ethanoic acid-a carboxylic acid
Concentrated sulfuric acid and more than enough potassium dichromate
(VI) is used for complete reaction (the dichromate(VI) is in excess). The
mixture is refluxed in the apparatus shown in
 Figure 5, Reflux means that vapour condenses and drips back into the
reaction flask.
 Whilst the reaction mixture is refluxing, any ethanol or ethanal vapour will
condense and drip back into the flask until, eventually, it is all oxidised to the
acid. After refluxing for around 20 minutes, you can distil off the ethanoic
acid (boiling temperature 391 K, 1 18 cc), along with any water, by
rearranging the apparatus to that shown in Figure 4.
 Using 101 to represent oxygen from the oxidising agent, the equation is:
 Notice that twice as much oxidising agent is used in this reaction compared
with the oxidation to ethanal.
 Oxidising a secondary alcohol to a ketone
 Secondary alcohols are oxidised to ketones by acidified dichromate. You do
not have to worry about further oxidation of the ketone.

Aldehydes and ketones

 Aldehydes and ketones both have the C^O group. This is called the
carbonyl group,
 In aldehydes H is at the end of the hydrocarbon chain:
 In ketones it is in the body of the hydrocarbon chain;
 Aldehydes are usually named using the suffix -al and ketones with the suffix
-one. So CH3CHO is ethanal; (two carbons) and CH3COCH3 is propanone
(three carbons).

Tests for aldehydes and ketones

 Aldehydes and ketones have similar physical properties but there are two
tests that can tell them apart. Both these tests involve gentle oxidation.
 Aldehydes are oxidised to carboxylic acids (This is the second stage of the
oxidation of a primary alcohol.)
 Ketones are not changed by gentle oxidation.

The Tollens’ (silver mirror) test


 Tollens’ reagent is a gentle oxidising agent. It is a solution of silver nitrate in
aqueous ammonia.
 It oxidises aldehydes but has no affect on ketones. It contains colourless
silver (1) complex ions, containing Ag+, which are reduced to metallic silver,
Ag, as the aldehyde is oxidised.
 On warming an aldehyde with Tollens’ reagent, a deposit of metallic silver is
formed on the inside of the test tube – the silver mirror, see Figure 7. This
reaction was once used commercially for making mirrors.

The Fehling’s test

 The Fehling’s reagent and is a gentle oxidising agent. It contains blue


copper(11) complex ions which will oxidise aldehydes but not ketones.
During the oxidation, the blue solution gradually changes to a brick red
precipitate of copper(1) oxide.
 On warming an aldehyde with blue Fehling’s solution a brick red precipitate
gradually forms.