Oxford Cambridge and RSA

A Level Chemistry A
H432/02 Synthesis and analytical techniques

Tuesday 12 June 2018 – Afternoon

Time allowed: 2 hours 15 minutes
* 7 0 1 1 3 9 4 9 8 8 *

You must have:

• the Data Sheet for Chemistry A
(sent with general stationery)
You may use:
• a scientific or graphical calculator

* H 4 3 2 0 2 *

First name

Last name

Centre Candidate
number number

INSTRUCTIONS
• Use black ink. You may use an HB pencil for graphs and diagrams.
• Complete the boxes above with your name, centre number and candidate number.
• Answer all the questions.
• Write your answer to each question in the space provided. If additional space is
required, use the lined page(s) at the end of this booklet. The question number(s) must
be clearly shown.
• Do not write in the barcodes.

INFORMATION
• The total mark for this paper is 100.
• The marks for each question are shown in brackets [ ].
• Quality of extended responses will be assessed in questions marked with an
asterisk (*).
• This document consists of 32 pages.

© OCR 2018 [601/5255/2] OCR is an exempt Charity

DC (ST/CT) 154180/4 Turn over
 2
SECTION A

You should spend a maximum of 20 minutes on this section.

Write your answer to each question in the box provided.

Answer all the questions.

1 Which compound is used as a standard for NMR chemical shift measurements?

A Si(CH3)4

B CDCl 3

C D 2O

D CCl 4

Your answer
[1]

2 Which compound is a secondary amide?

O CH3

A HO C CH2 N

O CH3

B HO C CH2 N

CH3

O CH3

C H3C C N

O CH3
D H 3C C N

CH3

Your answer
[1]
© OCR 2018
 3
3 Which compound does not react with nucleophiles?

A CH3CH2CHO

B CH3CHCH2

C CH3CH2COCH3

D CH3CH2CH2Cl

Your answer
[1]

4 Which structure represents an alicyclic compound?

Your answer
[1]

© OCR 2018 Turn over

 4
5 Which molecule is not planar?

A C 2H 4

B C 2H 6

C H2CO

D HCN

Your answer
[1]

6 What is the number of peaks in the 1H NMR spectrum of HOOCCH2CHOHCH2COOH?

A 3

B 4

C 5

D 6

Your answer
[1]

7 Ethanol can be prepared by different reactions.

Which reaction has the lowest atom economy?

A C6H12O6 → 2C2H5OH + 2CO2

B C2H4 + H2O → C2H5OH

C C2H5Br + H2O → C2H5OH + HBr

D CH3COOC2H5 + H2O → C2H5OH + CH3COOH

Your answer
[1]

© OCR 2018
 5
8 The breakdown of ozone is catalysed by NO radicals.

Which equation is a propagation step in the mechanism for this process?

A NO + O2 → N + O3

B NO + O2 → NO2 + O

C N + O3 → NO + O2

D NO2 + O → NO + O2

Your answer
[1]

9 Which compound could have produced the IR spectrum below?

100

transmittance (%)
50

0
4000 3000 2000 1500 1000 500

wavenumber / cm–1

A CH3CH2OH

B CH3CHOHCN

C CH3COOH

D CH3CONH2

Your answer
[1]

© OCR 2018 Turn over

 6
10 Benzene reacts with an organic reagent in the presence of a halogen carrier to form
phenylethanone.

C
CH3

phenylethanone

Which organic reagent is required?

A CH3CH2OH

B CH3CHO

C CH3COCl

D CH3COOH

Your answer
[1]

11 How many straight-chain structural isomers of C7H15Cl contain a chiral carbon atom?

A 1

B 2

C 3

D 4

Your answer
[1]

© OCR 2018
 7
12 The mass spectrum of (CH3)2CHCH2OH is shown below.

100

80

relative 60
intensity
40

20

0
10 20 30 40 50 60 70 80 90
m /z

Which ion is responsible for the peak with the greatest relative intensity?

A CHCH2OH+

B CH3CH2CH+

C (CH3)2CH+

D CH3CO+

Your answer
[1]

13 Which statement(s) support(s) the delocalised model for the structure of benzene?

1 All carbon–carbon bonds have the same length.

2 The enthalpy change of hydrogenation of benzene is less exothermic than expected.

3 Bromine reacts with benzene less readily than with cyclohexene.

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]
© OCR 2018 Turn over
 8
14 A solid organic compound can be purified by recrystallisation.

Which statement(s) about recrystallisation is/are true?

1 The organic compound is more soluble in hot solvent.

2 The hot solution is cooled before the purified organic compound is collected.

3 The melting point of the purified organic compound is lower than the impure compound.

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]

15 Which of the following could react with the compound below to form a carbon–carbon bond?

H O

C C

Br OH

1 CH3Cl and Al Cl 3

2 KCN in ethanol

3 CH3OH and H2SO4

A 1, 2 and 3

B Only 1 and 2

C Only 2 and 3

D Only 1

Your answer
[1]

© OCR 2018
 9
BLANK PAGE

PLEASE DO NOT WRITE ON THIS PAGE

© OCR 2018 Turn over

 10
SECTION B

Answer all the questions.

16 This question is about reactions of organic compounds containing carbon, hydrogen and oxygen.

(a) A chemist investigates two reactions of alcohol A, shown below.

OH

alcohol A

(i) What is the systematic name of alcohol A?

...................................................................................................................................... [1]

(ii) What is the structural formula of alcohol A?

...................................................................................................................................... [1]

(iii) The chemist heats alcohol A with an acid catalyst to form a mixture containing two
alkenes.

Draw the structures of the two alkenes formed in this reaction.

[2]

(iv) The chemist heats alcohol A with sodium chloride and sulfuric acid.

Construct a balanced equation for this reaction.

Show structures for the organic compounds in your equation.

[2]
© OCR 2018
 11
(b) Compound B, shown below, is refluxed with excess acidified potassium dichromate(VI) to
form a single organic product.

Complete the equation for this reaction.

CH3 H H

H 3C C C C OH + .......... [O]

OH OH H

compound B [2]

(c) The flowchart below shows some reactions of compound C.

In the boxes, draw the organic products of these reactions.

excess CH3OH/H2SO4

Steam
COOH
HOOC H3PO4

compound C

polymerisation

repeat unit of polymer [3]

© OCR 2018 Turn over
 12
17 The general formula of an α-amino acid is RCH(NH2)COOH.

(a) The α-amino acid cysteine (R = CH2SH) shows optical isomerism.

Draw 3-D diagrams to show the optical isomers of cysteine.

[2]

(b) The α-amino acid lysine (R = (CH2)4NH2) reacts with an excess of dilute hydrochloric acid to
form a salt.

Draw the structure of the salt formed in this reaction.

[2]

© OCR 2018
 13
(c) α-Amino acids can react to form proteins.

A short section of a protein chain is shown below.

HO
CH2 H O

CH N C
N C CH

H O CH2
CH2

C
H2N O

A student hydrolyses the protein with hot NaOH(aq).

Draw the structures of the organic products formed from this section of the protein.

[3]

© OCR 2018 Turn over

 14
18 This question is about aromatic compounds.

(a) Phenol undergoes nitration more readily than benzene.

(i) A student carries out the nitration of phenol with dilute nitric acid to produce 2-nitrophenol
and 4-nitrophenol.

A small amount of 3-nitrophenol is also produced.

OH
OH OH

NO2

NO2
NO2

2-nitrophenol 3-nitrophenol 4-nitrophenol

The student thought that 13C NMR spectroscopy could be used to distinguish between
these three nitrophenols.

Explain whether the student is correct.

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

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

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

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

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

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

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

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

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

...................................................................................................................................... [3]

© OCR 2018
 15
(ii) Explain why phenol is nitrated more readily than benzene.

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

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

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

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

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

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

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

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

...................................................................................................................................... [3]

© OCR 2018 Turn over

 16
(b) Methylbenzene reacts with sulfur trioxide, SO3, to form D, shown below.

CH3

O S O

O–
D

The electrophile in this reaction is SO3.

Complete the mechanism for the formation of D.

Show curly arrows and the structure of the intermediate.

CH3

O O
intermediate
S δ+

–
Oδ
CH3

+ H+

O S O

O–
D
[3]
© OCR 2018
 17
19 This question is about the hydrolysis of haloalkanes.

(a) The rate of hydrolysis of a haloalkane depends on the halogen present.

State and explain how the halogen in the haloalkane affects the rate of hydrolysis.

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

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

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

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

.............................................................................................................................................. [2]

(b) Chlorocyclohexane is hydrolysed with aqueous sodium hydroxide.

Outline the mechanism for this reaction.

Show curly arrows, relevant dipoles and the products.

Cl

[3]

© OCR 2018 Turn over

 18
(c) A student hydrolyses a haloalkane, E, using the following method.

• 0.0100 mol of haloalkane E is refluxed with excess NaOH(aq) to form a reaction mixture
containing an organic product F.
• The reaction mixture is neutralised with dilute nitric acid.
• Excess AgNO3(aq) is added to the reaction mixture. 1.88 g of a precipitate G forms.

Organic product, F, has a molar mass of 74.0 g mol−1 and has a chiral carbon atom.

(i) Draw a labelled diagram to show how the student would carry out the hydrolysis of
haloalkane E.

[2]

(ii) Analyse the information to identify E, F and G.

Show your working.

[3]

© OCR 2018
 19
20 Cinnamaldehyde and methylcinnamaldehyde are naturally occurring organic compounds.

CHO CHO

cinnamaldehyde methylcinnamaldehyde

(a) Methylcinnamaldehyde is an E stereoisomer.

Explain this statement in terms of the Cahn-Ingold-Prelog (CIP) rules.

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

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

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

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

.............................................................................................................................................. [2]

© OCR 2018 Turn over

 20
(b) A student plans to carry out some chemical tests on both cinnamaldehyde and
methylcinnamaldehyde.

CHO CHO

cinnamaldehyde methylcinnamaldehyde

(i) Suggest a suitable chemical test to confirm that both compounds contain an unsaturated
carbon chain.

Your answer should include the reagent and observations.

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

...................................................................................................................................... [1]

(ii) Describe a chemical test to confirm that both compounds contain an aldehyde functional
group.

Your answer should include the reagent and observations.

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

...................................................................................................................................... [1]

(iii) Describe a chemical test to confirm that cinnamaldehyde and methylcinnamaldehyde

contain a carbonyl group.

How could the products of this test be used to distinguish between the two compounds?

Your answer should not include spectroscopy.

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

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

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

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

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

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

...................................................................................................................................... [3]

© OCR 2018
 21
(c) The flowchart below shows some reactions starting with cinnamaldehyde.

Draw the structures of the missing organic compounds in the boxes and add the missing
reagent(s) on the dotted line.

excess H2/Ni

OH
CHO
reagent(s): ..........................
CN

cinnamaldehyde

NaBH4 H+(aq)

[5]

© OCR 2018 Turn over

 22
(d)* Methylcinnamaldehyde reacts with iodine monochloride, ICl, by electrophilic addition. The
reaction produces a mixture containing two different organic products.

CHO

methylcinnamaldehyde

The electronegativity values of chlorine and iodine are given in the table below.

Pauling electronegativity value

Cl 3.0
I 2.5

Outline the mechanism, using the ‘curly arrow’ model, for the formation of one of the organic
products and explain which of the two possible organic products is more likely to be formed.

In your mechanism, you can show the phenyl group as C6H5. [6]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

...................................................................................................................................................
© OCR 2018
 23
Additional answer space if required.

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

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

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

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

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

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

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

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

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

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

© OCR 2018 Turn over

 24
21 This question is about aromatic carboxylic acids and their derivatives.

(a) The flowchart below shows some reactions of compound H.

In the boxes, draw the organic products of these reactions.

Na2CO3(aq) NaOH(aq)

C
OH

HO
compound H

Br2

[3]

© OCR 2018
 25
(b) Compound H is used in the synthesis of polymer I, as shown in the flowchart below.

Complete the flowchart by drawing the structure of the acyl chloride and two repeat units of
polymer I, and stating the formula of the reagent(s) required for the first stage on the dotted
line.

C
OH
.........................

HO
compound H

acyl chloride

two repeat units of polymer I

[4]

© OCR 2018 Turn over

 26
(c) A cosmetic product containing four esters, J, K, L and M, is analysed by gas chromatography
and mass spectrometry. The results are shown below.

Gas chromatogram

5.9
J K

4.3
4.2

L
1.0

0 1 2 3 4 5
retention time / minutes

The numbers by the peaks are the relative molar proportions of the compounds in the mixture.

Mass spectrometry

ester m/z of molecular ion peak

J 152
K 166
L 180
M 180

(i) The concentration of ester K in the cosmetic product is 9.13 × 10−2 g dm−3.

Using the results, calculate the concentration, in mol dm−3, of ester M in the cosmetic
product.

Give your answer to two significant figures.

concentration of ester M = .......................................... mol dm−3 [2]

© OCR 2018
 27
(ii) A general structure for esters J, L and M is shown below.

C R
O

HO

Where ‘R’ is an alkyl group.

Use the mass spectrometry results to deduce possible structures for esters J, L and M.

J L M
[3]

© OCR 2018 Turn over

 28
22 The relative molecular masses and boiling points of some fuels are shown in Table 22.1.

Fuel Relative molecular mass Boiling point / °C

hexane 86 69
pentan-1-ol 88 138
heptane 100 98

Table 22.1

(a) Write an equation for the incomplete combustion of heptane.

.............................................................................................................................................. [1]

(b) Explain the difference in the boiling points of the fuels in Table 22.1.

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

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

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

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

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

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

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

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

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

.............................................................................................................................................. [4]

© OCR 2018
 29
(c) Fuel additives are often used to improve the combustion of a fuel.

(i) Compound N is a fuel additive containing carbon, hydrogen and oxygen only.

Complete combustion of 1.71 g of compound N produces 2.97 g of CO2 and 1.62 g of

H2O. The relative molecular mass of compound N is 76.0.

Calculate the molecular formula of N and suggest a possible structure for the compound.

compound N
[5]

© OCR 2018 Turn over

 30
(ii) Solketal has been investigated as a potential fuel additive.

HO O

O
solketal

Solketal is synthesised from propane-1,2,3-triol and a carbonyl compound.

Construct a balanced equation for this synthesis.

Show structures for the organic compounds in your equation.

[2]

(d)* A scientist is researching compounds that might be suitable as fuel additives.

One of the compounds gives the analytical results below.

Elemental analysis by mass:

C: 54.54%; H: 9.10%; O: 36.36%

Mass spectrum:
Molecular ion peak at m/z = 132.0

1H NMR spectrum in D2O

3
1

5 4 3 2 1 0
chemical shift,  / ppm

The numbers by the peaks are the relative peak areas.

When the spectrum is run without D2O, there are two additional peaks with the same relative
peak areas at 11.0 ppm and 3.6 ppm.
© OCR 2018
 31
Use the information provided to suggest a structure for the compound.

Show all your reasoning. [6]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Additional answer space if required.

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

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

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

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

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

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

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

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

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

END OF QUESTION PAPER

© OCR 2018
 32
ADDITIONAL ANSWER SPACE

If additional space is required, you should use the following lined page(s). The question number(s)
must be clearly shown in the margin(s).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Oxford Cambridge and RSA

Copyright Information
OCR is committed to seeking permission to reproduce all third-party content that it uses in its assessment materials. OCR has attempted to identify and contact all copyright holders
whose work is used in this paper. To avoid the issue of disclosure of answer-related information to candidates, all copyright acknowledgements are reproduced in the OCR Copyright
Acknowledgements Booklet. This is produced for each series of examinations and is freely available to download from our public website (www.ocr.org.uk) after the live examination series.
If OCR has unwittingly failed to correctly acknowledge or clear any third-party content in this assessment material, OCR will be happy to correct its mistake at the earliest possible
opportunity.
For queries or further information please contact the Copyright Team, First Floor, 9 Hills Road, Cambridge CB2 1GE.
OCR is part of the Cambridge Assessment Group; Cambridge Assessment is the brand name of University of Cambridge Local Examinations Syndicate (UCLES), which is itself a
department of the University of Cambridge.

© OCR 2018