CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

Exam-style questions and sample answers have been written by the authors. In examinations, the way marks are awarded
may be different.

Coursebook answers
Chapter 26
Science in context methanoate anion. Therefore ethanoic
acid molecules are more likely to exist
This can be a whole-class discussion after going in the undissociated form, whereas
through the passage on trans-fatty acids, using it methanoic acid molecules are less
to remind learners of the structure of alkenes and likely to exist in the undissociated form.
carboxylic acids, as well as cis/trans isomerism.
2 a because the methanoic acid formed
Give the learners 5–10 minutes to discuss the three would be oxidised to carbon dioxide
questions then ask for answers to the problems (and water)
set. The answers should include the raising of the
b (COOH)2 → 2CO2 + 2H+ + 2e−
melting points of plant oils to make spreadable
(COOH)2 + [O] → 2CO2 + H2O
margarine; the furring of arteries as a result of
a higher than normal proportion of low-density c i to speed up the reaction because
lipoproteins (bad cholesterol) compared with the redox reaction is initially slow
high-density lipoproteins (good cholesterol), before the Mn2+ ions form and act
leading to high blood pressure, strokes and heart as a catalyst
attacks; choose a diet that does not contain a high ii 25 cm3 of 0.0500 mol dm−3
proportion of processed trans-fatty acids. ethanedioic acid, H2C2O4,
( 0.0500  ×  25)
Self-assessment questions contains = 0.00125  moles
1000
1 a CH3CCl2COOH, CH3CHClCOOH, 2 moles of KMnO4 will react with
CH3CH2COOH 5 moles of H2C2O4 so 0.00125
b The electron-withdrawing carbonyl moles of H2C2O4 will react with
group in the ethanoic acid molecule 2
× 0.00125 moles of KMnO4
weakens the O—H bond in the 5
—COOH group, making it more likely 2
Therefore there are 5
× 0.00125
for an ethanoic acid molecule to lose
moles of KMnO4 in 8.65 cm3
an H+ ion than it is for an ethanol
of its solution so the number
molecule. Secondly, delocalisation of
of moles of KMnO4 in 1000 cm3
electrons around the —COO− group
(i.e. its concentration) is:
stabilises the ethanoate ion. This is not
possible in the ethoxide anion formed
when ethanol loses an H+ ion.
( 2
5 )
× 0.00125 × 1000
8.65
moles dm−3
making the concentration of
c Methanoic acid would be the stronger KMnO4 solution 0.0578 mol dm−3
acid, as ethanoic acid has an electron- (to 3 significant figures)
donating methyl group next to the
—COOH group, which does not aid 3 a CH3CH2COOH + SOCl2 →
the breaking of the O—H bond. Also, CH3CH2COCl + SO2 + HCl
once the ethanoate anion is formed b 3HCOOH + PCl3 → 3HCOCl + H3PO3
the methyl group tends to increase the (heat is required for this reaction to
concentration of the negative charge occur)
on the —COO− end of the ion, making c CH3CH2CH2COOH + PCl5 →
it more attractive to H+ ions than a CH3CH2CH2COCl + POCl3 + HCl

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

4 a The carbonyl carbon in an acyl Exam-style questions

chloride carries a greater partial
positive charge than the carbon atom 1 a i ethanol; [1]
bonded to the oxygen atom in an ethanoic acid; [1]
alcohol. This is because it has two
a few drops of concentrated
strongly electronegative atoms (oxygen
sulfuric acid as catalyst [1]
and chlorine) attached to the carbonyl
carbon, compared with just the oxygen ii C2H5OH+ CH3COOH ⇌
atom in an alcohol. CH3COOC2H5 + H2O  [1]
b propanoic acid and hydrogen chloride b i phenol; [1]
c i CH3CH2COCl, CH3CH2CH2Cl, benzoyl chloride; [1]
C6H5Cl warm reaction mixture [1]
ii The hydrolysis of CH3CH2COCl ii C6H5OH + C6H5COCl →
is far more vigorous than the C6H5COOC6H5 + HCl  [1]
hydrolysis of CH3CH2CH2Cl.
iii steamy white fumes (of hydrogen
The hydrolysis of CH3CH2CH2Cl
chloride) given off [1]
needs a strong alkali and heating
under reflux to bring about a c The reactions with acyl chlorides
reaction. The nucleophile is the happen more quickly than the
negatively charged hydroxide ion, reactions with carboxylic acids. [1]
OH−, as opposed to the neutral The acyl chloride reactions also go
water molecule, which is sufficient to completion and do not form an
to hydrolyse CH3CH2COCl equilibrium mixture like the reactions
quickly at room temperature. with carboxylic acids do. [1]
That is because the carbon
[Total: 11]
bonded to the chlorine atom in
a CH3CH2CH2Cl molecule is 2 a H H H
O
not as electron deficient as the
carbon atom in CH3CH2COCl. H C C C C
In CH3CH2COCl the carbon Cl
H H H  [1]
bonded to a chlorine atom is also
attached to an oxygen atom. It b i phosphorus(V) chloride, PCl5 /
has two strongly electronegative phosphorus(III) chloride, PCl3 /
atoms pulling electrons away sulfur dichloride oxide, SOCl2 [2]
from it. Therefore the attack
ii C4H9COOH + PCl5 →
by the nucleophile is much
C4H9COCl + POCl3 + HCl
more rapid. On the other hand,
C6H5Cl, an aryl chloride, will not or
undergo hydrolysis. The p orbitals 3C4H9COOH + PCl3 heat
from the Cl atom overlap with 3C4H9COC1 + H3PO3
the delocalised π electrons in
or
the benzene ring. This causes the
C—Cl bond to have some double C4H9COOH + SOCl2 →
bond character, making it stronger  C4H9COCl + SO2 + HCl  [1]
and more resistant to hydrolysis. iii Chlorine atom withdraws electrons
iii steamy white fumes (of HCl) from the —COOH group [1]
5 a i ethanoyl chloride and ethanol weakening the O—H bond so it is
easier for 2-chlorobutanoic acid to
ii butanoyl chloride and methanol
lose an H+ ion. [1]
iii benzoyl chloride and phenol
iv  Cl
b CH3CH2CONHCH2CH2CH3 + HCl O
H
O  [1]

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

v 2,2-dichlorobutanoic acid /
2,3-dichlorobutanoic acid [1]
vi The hydrolysis of butanoyl
chloride is more vigorous than
the hydrolysis of 1-chlorobutane,
which is more reactive than that
of chlorobenzene.  [1]
This difference between butanoyl
chloride and 1-chlorobutane is
due to the carbon bonded to
the chlorine atom in butanoyl
chloride being more strongly δ+
than in 1-chlorobutane. [1]
This is because in butanoyl
chloride the carbon bonded to
the chlorine atom is also bonded
to an oxygen atom. So the
carbonyl carbon has two highly
electronegative atoms pulling
electrons away from it. Therefore,
the attack by the nucleophile,
H2O, is much more rapid. [1]
Chlorobenzene, C6H5Cl,
will not undergo hydrolysis
(unless subjected to very harsh
conditions). The carbon atom
bonded directly to the chlorine
atom is part of the delocalised
bonding around the benzene ring. [1]
(A lone pair of electrons from the
Cl atom tends to overlap with the
electrons in the benzene ring). This
causes the C—Cl bond be stronger
and more difficult to break, so
hydrolysis is very difficult. [1]
[Total: 13]

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