Carbonyl Compounds

A2 Chemistry Unit 4

What functional group do all

carbonyl compounds contain?

What is the aldehyde functional

group?

What is the ketone functional

group?

Name the following

molecules:

Propanal

Propanone

Methylpropan
al

Pentan-3-one

Methanal

Methylbutan
one

Describe and explain the boiling point of

carbonyl compounds, referring to the type
of bonding.
Methanal is a gas and the other carbonyl
compounds are liquid at room temperature.
The molecule are polar, so dipole-dipole forces
as well as van der Waals forces exist between
them. Intermolecular hydrogen bonding is not
possible because neither aldehydes nor ketones
have a hydrogen atom that is sufficiently +.
This causes them to:
Have higher boiling points than alkanes and
alkenes
Have lower boiling points than alcohols

Describe and explain the solubility

of carbonyl compounds in water.
The lower members of both aldehydes and ketones
are soluble in water.
This solubility is due to the hydrogen bonding
between the lone pair of electron in the - oxygen in
the carbonyl compound and the + hydrogen in a
water molecule. Solubility decreases as the number
of carbons increases because the hydrocarbon tail is
hydrophobic.

Describe the smell of carbonyl

compounds.
The lower members of
the homologous series
of aldehydes have
pungent odours.

Ketones have much

sweeter smells than
aldehydes.

Describe the preparation of aldehydes

and give the equation for the
preparation of ethanal.
Aldehydes are prepared by the partial oxidation of
a primary alcohol
Reagents: Primary alcohol
Potassium dichromate (VI) in dilute sulfuric acid
Conditions: Temperature of about 60C
Distil of product as it forms
Observation: Colour change from orange to green
as dichromate (VI)
is reduced to chromium
(III)

Describe the preparation of ketones

and give the equation for the
preparation of propanone.
Aldehydes are prepared by the oxidation of a
secondary alcohol
Reagents: Secondary alcohol
Potassium dichromate (VI) in dilute sulfuric acid
Conditions: Heat under reflux
When reaction has finished, distil off product
Observation: Colour change from orange to green
as dichromate (VI)
is reduced to chromium
(III)

Describe and explain the differences

between aldehydes and ketones with
respect to oxidation.
Aldehydes are readily oxidised whereas
ketones are not.
This is due to the presence of the hydrogen
atom on the C=O in aldehydes which is very
easily oxidised
When an aldehyde is oxidised:

aldehydes with
Fehlings/Benedicts solution and
give an equation involving
Both Fehlings and ethanal.
Benedicts contain copper (II)
complexes.
When
an
aldehyde
is
warmed
with
Fehlings/Benedicts solution it is oxidised. The
solution is alkaline so the salt of the
carboxylic acid is produced.
The blue solution is
reduced
to
a
red
precipitate
of
copper
oxide.
N.B. With ketones there is no reaction and the solution stays blue.

Describe the reaction of

aldehydes with Tollens reagent
and give an equation involving
ethanal.

Tollens reagent is made by adding a few drops of sodium

hydroxide to silver nitrate solution and then dissolving the
precipitate in dilute ammonia.

When a few drops of Tollens are added to the

aldehyde and the mixture is warmed gently, the
aldehyde is oxidised. Because the solution is
alkaline the salt of the carboxylic acid is formed.
The colourless Tollens
reagent is reduced to
give a silver mirror.

N.B. With ketones there is no reaction and the solution stays

aldehydes with acidified

potassium dichromate (VI) and
give an equation involving
ethanal.

When heated with the acidified potassium

dichromate the aldehyde is oxidised to a
carboxylic acid.
The
orange
potassium
dichromate (VI) is
reduced to green
Cr (III)

N.B. With ketones there is no reaction and the solution stays orange.

Describe the reduction of an

aldehyde, including the equation
for the reduction of ethanal.
Reducing agent:
Lithium
tetrahydridoaluminate (III), LiAlH4
The LiAlH4 acts as a source of H- ions which add
on to the + carbon atom at this point the
reactants must be kept dry so it is carried out in
ether solution.
Next, a solution of aqueous acid is added which
protonates the O- formed in the first step.

A primary alcohol is formed.

Describe the reduction of an

aldehyde, including the equation
for the reduction of propanone.
Reducing agent:
Lithium
tetrahydridoaluminate (III), LiAlH4
The LiAlH4 acts as a source of H- ions which add
on to the + carbon atom at this point the
reactants must be kept dry so it is carried out in
ether solution.
Next, a solution of aqueous acid is added which
protonates the O- formed in the first step.

A secondary alcohol is formed.

Why does LiAlH4 reduce carbonyl

compounds but not alkenes?

LiAlH4 is a reducing agent that

reacts specifically with polar bonds.

State and explain the conditions

needed for the reaction between
hydrogen cyanide and a carbonyl
compound.
pH 8 this provides the CN- ion catalyst

Draw the mechanism for the reaction

of hydrogen cyanide and ethanal.

2-hydroxy-propanenitrile

Draw the mechanism for the reaction

of hydrogen cyanide and propanone.

2-hydroxy-2methylpropanenitrile

What is the difference between

the two reactions?

The ketone reaction

happens at a slower
rate.

Describe the mechanism for the

reaction of hydrogen cyanide and a
carbonyl compound.
The lone pair of electrons on the carbon atom
of the CN- ion form a bond with the + carbon
atom in the carbonyl compound.
At the same time, the -electrons in the C=O
group move to the oxygen atom.
The anion formed in the first step removes a
proton from an HCN molecule to form the
organic product and regenerate the CNcatalyst.

Why is it important that the pH

is neither too high or too low?
If it is too low,
there
are
not
enough CN- ions for
the first step.
If it is too high there
are not enough HCN
molecules for the second
step.

Describe and explain the optical

activity of the product when
hydrogen cyanide adds on to a
carbonyl compound.
The product is a racemic mixture of both
enatiomers so it does not rotate the plane
of plane-polarised light.
This is because the carbonyl compound is planar
around the C=O group so the cyanide ion can
attack from above or below the plane.

Describe how carbonyl

compounds react with compounds
containing an H2N- group.
The lone pair of electrons on the nitrogen
atom acts a nucleophile and forms a bond
with the + carbon atom in the C=O group.

A water molecule is then lost and a C=N bond

is formed.

Describe how 2,4dinitrophenylhydrazine can be

used to test for a carbonyl group.
Add a few drops of 2,4dinitrophenylhydrazine to a solution of the
compound.
Simple aldehydes
and ketones give a
yellow precipitate.
Aromatic aldehydes
and ketones give an
orange precipitate.

Give the overall equation for the

reaction between a carbonyl
compound and 2,4dinitrophenylhydrazine.

What type of reaction occurs and

what type of mechanism is it?
Condensation
reaction with the
loss of a water
molecule
Additionelimination

Describe how you can make and purify a derivative

of a carbonyl compound using 2,4dinitrophenylhydrazine.

Explain how this removes

impurities.
In step 2 the derivative will recrystallise but
the impurities will remain in solution.
The third step, washing with cold solvent,
will then rinse of any impurities that did
crystallise.

How can the purified product be

used to identify the original
carbonyl compound?

Find the melting temperature

and compare to known data.

What is the reaction of carbonyl

compounds with iodine in alkali
called?

The iodoform reaction

What type of carbonyl compounds

undergo the iodoform reaction?

Ethanal and methyl ketones

Describe how to carry out the

iodoform reaction, including
observations.
Warm the organic substance with either:
A mixture of iodine and NaOH solution
A solution of potassium iodide in sodium
chlorate (I)
A pale yellow
precipitate
forms
Medical smell

Describe how the iodoform reaction

occurs, including equations.
Sodium hydroxide solution is added to iodine
solution to form iodate (I) ions:

These substitute into the CH3 group next to the

C=O group, forming a CI3C=O group.
The three halogen atoms and the oxygen atom have
an electron-withdrawing effect which weakens
and breaks the -bond between the two carbon
atoms, forming iodoform:

Write the overall equation for

the iodoform reaction.