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1 Alcohols – Introduction
Objectives:
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.
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.
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
Primary alcohols
In a primary alcohol, the carbon with the -OH group has one R group (and
therefore two hydrogen atoms).
Secondary alcohols
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).
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.
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
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.
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
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
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 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 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).
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.