1.

(a)

The enthalpy change for the reaction

CH2=CH2 + H2 CH3CH3
is 120 kJ mol1, whereas that for the reduction of benzene, C6H6, to cyclohexane, C6H12,
is 208 kJ mol1. What may be deduced from the fact that this value is not three times
the first one?
....................................................................................................................................
....................................................................................................................................

....................................................................................................................................
....................................................................................................................................

.co

(i)

State the conditions under which benzene may be nitrated to form

mononitrobenzene.

ve

(b)

(2)

..........................................................................................................................
Both of the reagents that are used to nitrate benzene are usually regarded as acids.
However, in this instance, one of them behaves as a base. Show how this is so.

em
ac
ti

(ii)

..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
Give the mechanism for the nitration of benzene.

(iv)

Explain why benzene tends to undergo substitution rather than addition reactions.

w.

ch

(iii)

ww

..........................................................................................................................
..........................................................................................................................

NT Exampro

(8)
(Total 10 marks)

2.

The enthalpy change for the reaction

CH2=CH2 + H2 CH3CH3
is 120 kJ mol1, whereas that for the reduction of benzene, C6H6, to cyclohexane,
C6H12, is 208 kJ mol1. What may be deduced from the fact that this value is not three
times the first one?
....................................................................................................................................
....................................................................................................................................

....................................................................................................................................
....................................................................................................................................

.co

Consider the following reaction scheme, then answer the questions which follow.

ve

3.

(2)

CH 3

(a)

step 2

OH

step 3

em
ac
ti

step 1

C2 H5

Give the reagents and conditions for steps 1, 2 and 3.

Step 1 Reagent: ................................................................................................

ch

Conditions: .......................................................................................................
Step 2 Reagent: .................................................................................................

w.

Conditions: ........................................................................................................
Step 3 Reagent: ..................................................................................................

(b)

ww

Conditions: ........................................................................................................
(i)

Write an equation for the reaction of compound D with dilute aqueous

sodium hydroxide.

(ii)

What type of reaction is this?

(7)

..........................................................................................................................
(2)

(c)

NT Exampro

Outline briefly how you would isolate a sample of the aromatic product of the reaction in
(b)(i).
2

....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)

CH 3

Give the mechanism for the conversion of

to

Propane-1,2-diol, CH3CH(OH)CH2OH, can be used to manufacture a polymer.

Give the structure of a suitable compound which could react with propane-1-2-diol to
form a polymer.

(b)

Give the repeat unit of the polymer formed and name the type of linkage formed between
the molecules.

(c)

This polymer is not considered to be particularly hazardous to the environment.

Comment on possible reasons for this.

em
ac
ti

(a)

ww

w.

ch

4.

(4)
(Total 16 marks)

ve

.co

(d)

................................................................................................................
................................................................................................................
(Total 5 marks)

NT Exampro

5.

Suggest why polymers such as Terylene soften over a range of temperatures rather than having a
sharp melting point.
......................................................................................................................
..................................................................................................................................
(1)

6.

The characteristic reactions of benzene can be classified as electrophilic substitution reactions.

Select a reaction of benzene which illustrates this type of reaction. Give the reagents and
the equation for this reaction, the conditions under which it occurs and the name of the
organic product.

(a)

.co

Reagent(s): ................................................................................................................
Equation: ...................................................................................................................

ve

Conditions: .................................................................................................................

(b)

em
ac
ti

Name of organic product: ..........................................................................................

(4)

For the reaction selected in (a):

(i)

identify the electrophile;

..........................................................................................................................
(ii)

(1)

give an equation to show its formation;

(2)

give the mechanism for the substitution reaction.

(c)

ww

w.

(iii)

ch

..........................................................................................................................

(3)

Give two specific safety precautions you would need to take in carrying out the
reaction in (a).
....................................................................................................................................
....................................................................................................................................
(2)

NT Exampro

(d)

Give one reaction of the functional group which was introduced into the benzene ring as a
result of the reaction performed in (a). Give the reagents, conditions and equation for this
reaction.
Reagent: ....................................................................................................................
Conditions: ................................................................................................................
Equation: ...................................................................................................................
(3)
(Total 15 marks)

(i)

Under what conditions does this reaction occur?

When excess methane reacts with chlorine, the main product is chloromethane.

.co

7.

(a)

ve

em
ac
ti

8.

Give the mechanism for this reaction.

(4)
(Total 5 marks)

Acyl halides such as ethanoyl chloride, CH3COCl, are useful synthetic intermediates
because they are quite reactive.
Suggest synthetic steps, giving reagents and conditions, by means of which ethanol
could be converted to ethanoyl chloride.

w.

(i)

ch

(ii)

(1)

...........................................................

ww

...........................................................
...........................................................
...........................................................
...........................................................
...........................................................
(5)

NT Exampro

(ii)

Ethanoyl chloride, CH3COCl, reacts violently with water at room temperature,

whereas chloroethane, CH3CH2Cl, reacts extremely slowly with water under the
same conditions. Suggest a reason why CH3COCI is more susceptible to
nucleophilic attack than CH3CH2Cl.
...........................................................
...........................................................
...........................................................
(2)

Ethyl ethanoate CH3COOCH2CH3 can be made either from ethanol and ethanoic acid or
from ethanol and ethanoyl chloride.
Give the equations for the two reactions.

.co

(i)

(b)

...........................................................
...........................................................

ve

(ii)

(2)

Suggest why the reaction with ethanoyl chloride gives a better yield of the ester.

em
ac
ti

...........................................................
...........................................................

(a)

Ethane reacts with chlorine in the presence of ultraviolet light,

(i)

ch

9.

(1)
(Total 10 marks)

What is the function of the u.v. light?

(1)

The reaction gives more than one chlorine-containing organic product.

ww

(ii)

w.

...........................................................

Explain why this is so.

...........................................................
...........................................................
(1)

NT Exampro

(iii)

State the name of one other product formed in this reaction which does not contain
chlorine and account for its formation.
...........................................................
...........................................................
...........................................................
...........................................................
(3)

CH3
+ Cl 2

Methylbenzene reacts with chlorine in the presence of u.v. light in a similar way
to methane:

CH2 Cl

.co

(b)

+ HCl

(ii)

Draw an apparatus which could be used for this reaction

em
ac
ti

(i)

ve

In order for the reaction to take place, chlorine must be passed into boiling methylbenzene
in the presence of u.v. light over a period of time.

(3)

What are the hazards specific to this experiments

ch

...........................................................
...........................................................

w.

Assuming that the organic product from this reaction consists only of
methylbenzene and (chloromethyl)benzene, and that Raoult's Law applies to the
mixture of the two liquids, sketch a boiling-point/composition diagram for the
mixture and use it to show how fractional distillation enables the components of the
mixture to be separated. Methylbenzene boils at 111oC, (chloromethyl)benzene at

ww

(iii)

(2)

179C.

NT Exampro

179 C

111 C

...........................................................

.co

...........................................................
...........................................................

ve

Grignard reagents are useful in organic syntheses where it is necessary to form a new
carbon-carbon bond.
(a)

em
ac
ti

10.

(4)
(Total 14 marks)

Draw a diagram of suitable apparatus, state the conditions and ONE specific safety
precaution for the preparation of the Grignard reagent 1-propylmagnesium bromide,
CH3CH2CH2MgBr, from 1-bromopropane. The following data will be useful.
Substance

Boiling temperature

Flammability

/C

ch

1-bromopropane

low

34.5

very high

(b)

ww

w.

ethoxyethane (ether)

70.8

(7)

Give the names and structural formulae of the organic products obtained when
1-propylmagnesium bromide reacts with:
(i)

ethanal, followed by dilute hydrochloric acid

(2)

NT Exampro

(ii)

carbon dioxide followed by dilute hydrochloric acid

(2)
(Total 11 marks)

This question concerns the three isomers A, B and C, each of which has a relative molecular
mass of 134.

11.

O
CH 2

CH 3

CH 2

CH 2

.co

C
H

ve

CH

CH 2 OH

em
ac
ti

CH
C

(a)

The mass spectrum of substance A is shown below. Identify the species responsible for
the peaks labelled 1, 2 and 3.
Peak 1 .........................................................................................................................

ch

Peak 2 .........................................................................................................................
Peak 3 .........................................................................................................................
The infra-red spectra of two of these substances were also measured.
Use the table and the spectra below to identify which spectrum is that of
substance C.

ww

(i)

w.

(b)

(3)

Wavenumber
/ cm1

Bond

Wavenumber
/ cm1

CH (arenes)

3000-3100

OH (hydrogen bonded)

3200-3570

CH (alkanes)

2850-3000

OH (not hydrogen
bonded)

3580-3650

C==O

1680-1750

C==C (arenes)

1450-1600

Bond

The spectrum of substance C is spectrum number ..........................................

(1)

NT Exampro

(ii)

Give one reason for your choice.

......................................................................................................................
(1)

(iii)

Give one other reason why the other spectrum could not be that of substance C.
......................................................................................................................
......................................................................................................................
(1)

100

.co

60

40

ve

Relative intensity

80

em
ac
ti

20
0
25

50

75

100

125

m/e

ch
w.

50

ww

Transmittance

100

0
4000

NT Exampro

3000

2000
1500
Wavenumber/cm1

1000

10

Transmittance

100

50

2000
1500
Wavenumber/cm1

1000

State which of the substances A, B and C will react with the following reagents and state
what would be observed.
Bromine dissolved in hexane.

ve

(i)

.co

(c)

3000

0
4000

Substance(s) .....................................................................................................

(ii)

em
ac
ti

Observation ......................................................................................................
(2)

A warm ammoniacal solution of silver nitrate.

Substance(s) .....................................................................................................
Observation ......................................................................................................
2,4-dinitrophenylhydrazine solution.

ch

(iii)

(2)

Substance(s) .....................................................................................................
(3)

Give the structural formula of the organic product(s) obtained in (c)(i).

ww

(iv)

w.

Observation ......................................................................................................

(1)

NT Exampro

11

(v)

Give the structural formula of the organic product(s) obtained in (c)(ii).

(1)

(d)

(i)

Give the reagents and the conditions necessary for the preparation of A from
benzene.

Reagents .......................................................................................................
(3)

This is an electrophilic substitution reaction. Write an equation to show the

formation of the electrophile.

ve

(ii)

.co

Conditions ....................................................................................................

......................................................................................................................

(a)

em
ac
ti

12.

(2)
(Total 20 marks)

Three isomers A, B and B have the molecular formula C4H8O.

All three compounds give an orange precipitate with 2,4-dinitrophenylhydrazine reagent.
B and C also give a silver mirror when warmed with ammoniacal silver nitrate solution.

ww

w.

Substance A

ch

Write the structural formulae of A, B and C .

Substance B

NT Exampro

12

Substance C

(3)

(b)

Substance A reacts with the Grignard reagent, C2H5MgBr

Give the equation for the preparation of this Grignard reagent.

(i)

(ii)

State the conditions for this preparation.

.co

..
(1)

ve

..
..

em
ac
ti

(1)

C2H5MgBr reacts with carbon dioxide to form the acid C2H5COOH. This acid can be
converted to propanamide in a two step process.

w.

(c)

Write the structural formula of the product obtained when this Grignard reagent
reacts with substance A.

ch

(iii)

(2)

step 1

ww

C2H5COOH

step 2
C2H5COCl

C2H5CONH2

State the reagent required for each step.

Step 1 .
Step 2 .
(2)

NT Exampro

13

(d)

C2H5MgBr also reacts with ethanal to form substance D, which exists as a pair of optical
isomers.
Draw the structural formulae of these two isomers and use them to explain why
these isomers exist.

(i)

.co

(ii)

(4)

What is the difference in property between these isomers?

..

ve

(i)

Write down the name and the structural formula of the organic compound formed
when substance D is heated under reflux with a solution of potassium
dichromate(VI) in dilute sulphuric acid.

em
ac
ti

(e)

(1)

Name ..

(2)

State the colour of the solution remaining after this reaction.

w.

(ii)

ch

Structural formula.

13.

(a)

ww

..
(1)
(Total 17 marks)

(i)

Give the structural formula of a nitrile, C4H7N, that has an unbranched chain.

(ii)

Primary amines can be made by reducing nitriles. Suggest a reagent that could be
used for this purpose.

(1)

NT Exampro

14

............................................................................................................................
(1)

Draw the structural formula of the amine produced by reducing the nitrile given in
(a)(i).

Draw the structure of an isomer of C4H11N which has a chiral centre in the molecule and
identify the chiral centre.

(c)

(i)

em
ac
ti

ve

(b)

(1)

.co

(iii)

(2)

What feature of an amine molecule makes it both a base and a nucleophile?

(ii)

ch

............................................................................................................................
(1)

Give, by writing an equation, an example of an amine acting as a base.

(1)

Ethanoyl chloride, CH3COCl, reacts with both amines and alcohols.

(i)

ww

(d)

w.

............................................................................................................................

Give the name of the type of compound produced when ethanoyl chloride reacts
with ethylamine, C2H5NH2.
............................................................................................................................
(1)

(ii)

State one of the advantages of reacting ethanoyl chloride with ethanol to make an
ester rather than reacting ethanoic acid with ethanol.
............................................................................................................................
(1)

(e)

Ethanoyl chloride can be made from ethanoic acid.

(i)

Suggest a reagent suitable for this conversion.

............................................................................................................................

NT Exampro

15

(1)

(ii)

Suggest how chloromethane can be converted into ethanoic acid via a Grignard
reagent. (Details of the experimental apparatus are not required.)
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................

............................................................................................................................

An alcohol with the molecular formula C4H9OH is chiral.

(i)

ve

(a)

(4)
(Total 14 marks)

Explain what is meant by the term chiral.

em
ac
ti

14.

.co

............................................................................................................................

............................................................................................................................
............................................................................................................................
Draw two diagrams to clearly represent the optical isomers that result from the
chirality of this alcohol.

(iii)

ww

w.

ch

(ii)

(2)

(2)

Explain how you could distinguish between these two isomers experimentally.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(b)

Alcohols react with carboxylic acids to form esters.

(i)

Write an equation for a typical esterification reaction.

............................................................................................................................
(1)

NT Exampro

16

(ii)

Suggest how this type of reaction could be used to form polyesters.

Experimental details are not required.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)

(iii)

Suggest, with reasoning, whether a laboratory coat made from a polyester might be
damaged by a spillage on it of hot concentrated aqueous sodium hydroxide solution.

............................................................................................................................

.co

............................................................................................................................
............................................................................................................................
Give another type of reagent that could be used to make an ester from an alcohol.

ve

(iv)

(2)

............................................................................................................................

em
ac
ti

15.

(1)
(Total 13 marks)

Consider the following reaction scheme starting from propanone.

I2
NaOH

H+J

CH 3

HCN

O NaCN K

CH 3

ch

CH 3
propanone

Cl

CH 3

CH 3

OH
C

w.

Reagent 2

Reagent 1

CH 3

COOH

ww

Cl

Reagent 3

CH 3

Cl

CH 3

(a)

Br2
NaOH

NH 2
Give the structural formula of:

NT Exampro

17

(b)

.co

Identify:

(4)

ve

Reagent 1: ..................................................................................................................

em
ac
ti

Reagent 2: ..................................................................................................................
Reagent 3: ..................................................................................................................
(c)

(3)

Compounds produced when glucose C6H12O6, is metabolised include:

CH2(OH)CH(OH)CHO
2,3-dihydroxypropanal

CH3CH(OH)COOH
2-hydroxypropanoic acid

Draw the full structural formula for 2,3-dihydroxypropanal.

ww

w.

ch

(i)

CH3COCOOH
2-oxopropanoic acid

NT Exampro

(1)

18

(ii)

Suggest two of these compounds which would give a positive test with
2,4-dinitrophenylhydrazine solution. State what you would see for a positive test
result.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)

Describe a test which would enable you to distinguish between the two compounds
identified in part (ii).

(iii)

.co

............................................................................................................................
............................................................................................................................

ve

............................................................................................................................

16.

(a)

em
ac
ti

............................................................................................................................
(2)
(Total 13 marks)

Pure copper is needed for electrical applications. The purity of a sample of copper can be
found by reacting it with concentrated nitric acid, neutralising the resulting solution and
treating it with excess potassium iodide. Iodine is liberated and this can be titrated with
standard sodium thiosulphate solution. The reactions are:

ch

Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(1)

2Cu2+(aq) + 4I(aq) 2CuI(s) + I2(aq)

(b)

ww

w.

A copper foil electrode from an electric cell weighs 1.74 g. It was made into 250 cm3 of a
solution of copper(II) ions. To 25.0 cm3 of this solution excess iodide ions were added,
and the mixture titrated with 0.100 mol dm3 sodium thiosulphate solution. On average
26.8 cm3 was required. Calculate the percentage purity of the copper foil.
(6)

Copper(II) chloride is used as a catalyst in the reaction of benzenediazonium chloride in

the presence of hydrochloric acid to give chlorobenzene:
+

C6H5N 2 Cl C6H5Cl + N2
The catalytic effect of transition metals or their ions is often attributed to their having
several stable oxidation states. Explain why such states are possible in transition metals
and why they are important in catalysis.
(4)

(c)

(i)

State the reagents and conditions needed to make benzenediazonium chloride from
phenylamine.

(ii)

Explain why the temperature needs to be carefully controlled in the reaction in part
(i).

(2)

NT Exampro

19

(2)

(iii)

Write the equation for the reaction of benzenediazonium chloride with phenol using
structural formulae. Give the conditions under which benzenediazonium chloride
reacts with phenol and state what you would see.
(5)

(d)

Phenylamine is prepared from benzene. Give the reagents and conditions needed for each
of the steps in the conversion of benzene to phenylamine.
(6)
(Total 25 marks)

Write equations to show the reactions of the amino acid alanine, CH3CH(NH2)COOH,
with:

(a)

(i)

.co

17.

HCl

....

ve

(ii)

(1)

NaOH

(b)

em
ac
ti

....
(1)

Explain why alanine has a relatively high melting temperature (290 C).
......
......
(2)

Alanine exists as two optical isomers.

Draw diagrams to show the structures of the two optical isomers.

ww

(i)

w.

(c)

ch

......

(2)

NT Exampro

20

(ii)

Explain how separate pure samples of each optical isomer can be distinguished
from each other.
....
....
....
(2)

(d)

A mixture of isomeric alkenes is obtained when butan-2-ol is dehydrated.

Draw diagrams to show the two structural isomers obtained when butan-2-ol
is dehydrated.

(2)

One of the above structural isomers can itself exist as two different stereoisomers.
Draw diagrams to clearly illustrate these two stereoisomers, and name this type of
stereoisomerism.

em
ac
ti

(ii)

ve

.co

(i)

Type of stereoisomerism ..

18.

(a)

ww

w.

ch

Diagrams

(3)
(Total 13 marks)

Write the structural formulae of the organic products obtained when ethanoyl chloride
reacts with the following compounds. Give the names of these products.
(i)

Ammonia, NH3.
Structure

Name
(2)

(ii)
NT Exampro

Methanol, CH3OH.
21

Structure

Name
(2)

(b)

Bromoethane reacts with magnesium to form the Grignard reagent CH3CH2MgBr.

This Grignard reagent reacts with:

CO2, followed by hydrochloric acid, to form compound A;

water to form compound B;
methanal, followed by hydrochloric acid, to form compound C.

(i)

.co

Compounds A and C react together, in the presence of a suitable catalyst, to

form compound D.
Write the structural formulae of compounds A, B, and C.
B

em
ac
ti

ve

(3)

Draw the full structural formula of compound D.

ww

(ii)

w.

ch

(2)

NT Exampro

22

(iii)

Give the names of compounds C and D.

Name of C .
Name of D .
(2)

(iv)

Identify a catalyst for the reaction between compounds A and C.

(a)

An alcohol, C3H8O, was analysed by low resolution NMR spectroscopy. The spectrum is
given below.

4
ppm

ch

em
ac
ti

ve

.co

19.

(1)
(Total 12 marks)

w.

The chemical shifts of some hydrogen nuclei are given in the following table (where R
represents an alkyl group).
/ ppm

group

/ ppm

0.81.2

ROH

1.06.0

RCH2R

1.11.5

RCH2OH

3.34.0

CHR3

1.5

R2CHOH

3.24.1

group

ww

CH3R

Show that the alcohol must be propan-2-ol.

(2)

(b)

By considering the shapes of the molecules of CH4 and H2O explain why a molecule of
propan-2-ol has bond angles of approximately 109 except in the bond COH where the
angle is approximately 107.
(4)

NT Exampro

23

(c)

Propan-2-ol can be oxidised by an aqueous solution of potassium dichromate(VI)

acidified with dilute sulphuric acid. The two half-equations for the reactions involved are:
Cr2O72(aq) + 14H+(aq) + 6e

2Cr3+(aq) + 7H2O(l)

C3H6O(aq) + 2H+(aq) + 2e
(i)

C3H7OH(aq)

Oxidation of the alcohol takes place. Explain what this indicates about the standard
electrode potentials of the two half reactions. Write the equation for the reaction.
(3)

(d)

(i)

20.

What would you see if the organic product of the oxidation reaction reacts with
iodine in alkaline solution? Write the equation for the reaction.
(3)

State the name of the organic product if propan-2-ol is heated with concentrated
sulphuric acid and classify the type of reaction occuring.
(2)

Draw the structural formula of the organic product that results from heating
propan-2-ol with a mixture of sodium bromide and 50% sulphuric acid.

em
ac
ti

(ii)

(3)

.co

(iii)

An aqueous solution of chromium(III) ions is coloured. Explain the cause of this

colour.

ve

(ii)

(1)
(Total 18 marks)

A compound D, CH3.CH(OH).COOH, may be prepared from C3H7OH by the following series

of reactions.

C 3 H 7 OH

C 3 H 6O2
B

w.

ch

K 2 Cr 2 O 7 (aq)/H 2 SO 4 (aq)

ww

Cl 2 (g)/uv light

(i) NaOH(aq)

(a)

(i)

(ii) HCl(aq)

C 3 H 5 O 2 Cl
C

Identify compounds A, B and C.

(3)

(ii)

Classify the reaction with chlorine.

(2)

NT Exampro

24

(iii)

D has a boiling temperature of 186C whereas C, C3H5O2Cl, boils at 122C. Draw

a boiling temperature/composition diagram applicable to a mixture of C and D and
use it to show how fractional distillation of a mixture of the two compounds could
produce a sample of D.
(5)

(b)

Assuming the percentage yield for each step in sequence to be 80%, calculate the mass of
D that could be made from 60 g of C3H7OH.
(3)

An aqueous solution of D of concentration 0.100 mol dm3 has a pH value of 2.04.

(i)

(3)

Suggest, with reasoning, whether D or propanoic acid, CH3CH2COOH,

Ka = 1.3 105 mol dm3, would be more exothermic in reaction with aqueous
sodium hydroxide solution of concentration 0.1 mol dm3.
(2)
(Total 18 marks)

ww

w.

ch

em
ac
ti

ve

.co

(ii)

Calculate the value of the dissociation constant, Ka, for D.

(c)

NT Exampro

25