Unit 4 Rates, equilibria and further organic chemistry

Chapter 7 Carbonyl compounds

1 Both compounds contain the C=O carbonyl group. Aldehydes have an H atom bonded to the carbonyl carbon
atom, but ketones do not.

2 The ketone isomers are:

H3C

CH3
H 3C

CH2CH2CH3

CH2

CH2

CH3

H3C

CH

CH3

3 The preparation of propanal from propan-1-ol is an oxidation reaction. The target product, propanal, is more
easily oxidised than the starting reactant, propan-1-ol, so the aldehyde must be boiled off as it is made. The
temperature must be high enough to boil off the propanal (i.e. above the boiling point of propanal) but not so
high as to boil off any propan-1-ol (i.e. below the boiling point of propan-1-ol). This means that the reaction
temperature must be kept between the two boiling points.
e

Aldehydes can be oxidised further to carboxylic acids. This subsequent reaction does not affect the preparation of
ketones from secondary alcohols, as ketones are not oxidised by acidified potassium dichromate.

4 Ethanal contains a oxygen atom in the CHO group. This can form hydrogen bonds with the + hydrogen
atoms in water. The remainder of the molecule is a CH3 group. Although CH3 is hydrophobic, the energy
released by the formation of the hydrogen bond more than compensates for the lack of attraction between the
non-polar hydrocarbon group and water molecules.
Pentanal has a oxygen atom, but it also has a bulky hydrophobic C4H9 group, and so insufficient energy is
released from hydrogen bonding to make pentanal soluble in water.

H
+

H3C

O
represents a hydrogen bond
H +
O
H

5 All three substances have similar numbers of electrons in their molecules. Butanone, CH3COCH2CH3, has 40
electrons and butan-1-ol, CH3CH2CH2CH2OH, and pentane, C5H12, each have 42. This means that the intermolecular induced dipole (dispersion) forces are almost the same between the molecules in all three substances.
Butan-1-ol has a + hydrogen atom as well as a oxygen and so it can also form hydrogen bonds between its
molecules. The other compounds cannot form intermolecular hydrogen bonds as they do not have any +
hydrogen atoms. This means that the intermolecular forces are the strongest in butan-1-ol and it has the
highest boiling temperature.
Butanone is polar and so, unlike in the non-polar pentane, permanent dipoledipole, as well as induced dipole,
forces exist between molecules. This makes the total strength of intermolecular forces greater in butanone than
in pentane.

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Chapter 7 Carbonyl compounds

H
O

CH2(CH2)2CH3

+
H

CH3(CH2)2CH2

H3C

CH2CH3

+
C

Butanone

Butan-1-ol

CH2
CH3CH2CH2CH2CH3

(CH2)2

Pentane

CH3
e

Butan-1-ol: hydrogen bonds plus the weaker dispersion forces

Butanone: dispersion forces and the very weak permanent dipoledipole forces
Pentane: only the dispersion forces
A general rule for the relative strengths of intermolecular forces is:
hydrogen bonds > dispersion forces > permanent dipoledipole forces
The exception is molecules such as I2 that have a very large number of electrons. The dispersion forces are so strong that
iodine is a solid at room temperature, whereas the hydrogen-bonded water is a liquid.

6 a CH3COCH3 + HCN CH3C(OH)(CN)CH3

b The nucleophile that attacks the + carbonyl carbon atom is a CN ion. HCN is a very weak acid (Ka =
4 1010 mol dm3), so there are too few CN ions in the solution for the reaction to happen at a noticeable
rate. If a little alkali is added, some of the HCN molecules are deprotonated to form CN ions and the
reaction takes place.
e

The second step of the reaction is when the O group in the intermediate removes a proton from an HCN molecule. This
regenerates CN ions, which act as a catalyst in this reaction.

C
H3C

then

H 3C

H3 C

O
H3C

H
O

H3C

H+

H 3C

OH
C

C
H3C

H3C

8 The answer is that the product CH3C(CN)(OH)CH3 is not chiral, as there are only three different groups on
the central carbon atom.

9 The product is chiral, CH3C(CN)(OH)C2H5, but butanone is planar at the attack site. This means that the CN
nucleophile can attack from either above or below the plane. The result is an equal mixture of the two
enantiomers. Therefore, there is no effect on the plane of polarisation of plane-polarised light.
e

In this mechanism, a nucleophile attacks a planar starting material whereas in an SN1 mechanism the nucleophile
attacks a planar intermediate.

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Chapter 7 Carbonyl compounds

10 a

H
C

H3C

CH2

O2N

NO2

Observation: a yellow-orange precipitate

b CH3CH2COOH
e

If you are asked to give the structural formula, you must draw the COOH group in full:
O
CH2

H3C

C
O

Observation: the orange potassium dichromate(VI) would turn to a green solution of Cr3+ ions
e

You must give the colour before and after for observations such as this and the next two reactions. You do not need to
identify the coloured product unless specifically asked.

c CH3CH2COONa+
e

The formula CH3CH2COONa is acceptable (unless you are asked for the structural formula), but drawing a covalent bond
between the oxygen and the sodium is not:
O
CH3CH2C
O

Na

Observation: warming the reactants causes the blue Fehlings solution to turn to a red precipitate (of
copper(I) oxide)

d CH3CH2COONH4 or CH3CH2COONH4+
Observation: on warming, a silver mirror would be seen on the side of the test tube

e No reaction
Observation: the solution would stay colourless
e

Ethanal is the only aldehyde that undergoes the iodoform reaction.

11 a Y is either an aldehyde or a ketone as it forms a yellow precipitate with 2,4-dinitrophenylhydrazine.

However, it did not reduce Fehlings solution, so it is not an aldehyde. Y is a ketone with four carbon atoms
and so it is butanone.
As X was oxidised to a ketone, it must be a secondary alcohol. It has to be unbranched because the oxidation
product is butanone, so X is butan-2-ol. The structural formulae are:
X CH3CH2CH(OH)CH3
Y

O
H3C

CH2

C
CH3

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Chapter 7 Carbonyl compounds

The formula for X does not need to be written out in full as the question asks for only the structural (not the full
structural) formula and the compound does not have any double bonds. Y must be drawn so as to show the double bond
between the carbon and the oxygen.

b X contains the CH3CH(OH) group and reacts to form a yellow precipitate of iodoform, CHI3. Y contains a
CH3C=O group and also gives a yellow precipitate of iodoform.

c CH3CH2COCH3 + 3I2 + 4NaOH CHI3 + 3NaI + CH3CH2COONa + 3H2O

e

This is a difficult equation to derive and balance. If you remember that only half the iodine ends up as iodoform, this
means that there must be 3NaI on the right. The organic product is sodium propanoate, so 3 + 1 = 4 NaOH are needed on
the left.
If you cannot remember anything about the equation, just write down CHI3 and the sodium salt of the acid with one
fewer carbon atoms on the right and you will get 1 mark at least.

d Z is also oxidised to a carbonyl compound. Since this is then oxidised by Fehlings solution, it must be an
aldehyde and Z must be a primary alcohol:
CH3CH2CH2CH2OH and (CH3)2CHCH2OH
Butan-1-ol

Methyl propan-1-ol

12 The product of the reaction of CH2=CHCH2CHO with:

a LiAlH4 followed by hydrolysis is CH2=CHCH2CH2OH
b H2 and a platinum catalyst is CH3CH2CH2CH2OH
e

Only the polar C=O group is reduced by lithium tetrahydridoaluminate(III). Both groups are reduced by hydrogen in the
presence of a suitable catalyst.

13 Preparation of butanone from butan-2-ol:

I

Butan-2-ol is added to a solution of potassium dichromate(VI) and sulfuric acid in a round-bottomed flask.

A reflux condenser is then fitted and the flask heated for 15 min, using a water bath or an electric heater.

The flask is allowed to cool and the apparatus reassembled for distillation.

The flask is heated again, using a water bath or electric heater, and the liquid that boils over between 78C
and 82C is collected.

If very pure butanone is required, the distillate can be dried over anhydrous calcium chloride and redistilled,
collecting the fraction that boils over between 78C and 82C.
(a)

Water out

(b)

Thermometer
Still head
Water out
Condenser

Butan-2-ol +
potassium
dichromate
in dilute
sulphuric acid

Water in
Mixture of
butanone
and unreacted
butan-2-ol
Roundbottomed
flask
Electric heater
Heat under reflux

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Round-bottomed
flask
Electric heater

Distillation with addition of reactant

Water in Open
beaker

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Chapter 7 Carbonyl compounds

14 a A nucleophile is a species that uses its lone pair of electrons to form a covalent bond with a + atom in
another molecule.
Oxidation occurs when a species loses one or more electrons. It occurs when an atom in a species increases
its oxidation number.

b (i) Ethanal and hydrogen cyanide react in a nucleophilic addition reaction.

e

The lone pair of electrons in the CN ion acts as a nucleophile and forms a bond with the + carbon atom in the C=O
group.

(ii) Ethanal and Fehlings solution react in a redox reaction ethanal is oxidised and the copper(II) complex
in Fehlings solution is reduced.
e

Ethanal is oxidised to ethanoate ions and the copper(II) complex is reduced to copper(I) oxide.

(iii) Ethanal and 2,4-dintrophenylhydrazine react in an addition/elimination reaction which can also be
called a condensation reaction, as a simple molecule, H2O, is lost from the two reactants.
CH3CHO + H2NNHC6H3(NO2)2 CH3CH=NNHC6H3(NO2)2 + H2O
e

The route is:

G

The lone pair of electrons on the N of the NH2 group attacks the carbon atom in the C=O group as the
2,4-dinitrophenylhydrazine adds on.

Water is then eliminated.

15 The substance is a ketone. The identity of this ketone can be found by recrystallising the orange precipitate,
drying it and then measuring its melting temperature. This value is then compared with those in a data source
of the melting temperatures of the 2,4-dinitrophenylhydrazine derivatives of ketones.

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