Q1.

This question is about NMR spectroscopy.

(a) A compound is usually mixed with Si(CH3)4 and either CCl4 or CDCl3 before
recording the compound’s 1H NMR spectrum.

State why Si(CH3)4, CCl4 and CDCl3 are used in 1H NMR spectroscopy.

Explain how their properties make them suitable for use in 1H NMR spectroscopy.

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(6)

(b) Deduce the splitting pattern for each of the peaks given by the H atoms labelled x, y
and z in the 1H NMR spectrum of the compound shown.

x _____________________________________________

y _____________________________________________

z _____________________________________________
(3)

(c) Suggest why it is difficult to use Table B in the Data Booklet to predict the chemical
shift (δ value) for the peak given by the H atom labelled y.

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(1)

(d) Two isomers of CH3CHClCOCH(CH3)2 each have two singlet peaks only in their 1H
NMR spectra.
In both spectra the integration ratio for the two peaks is 2:9

Deduce the structures of these two isomers.

Isomer 1

Isomer 2

(2)
(Total 12 marks)

Q2.
Which one of the following does not have a singlet peak in its proton n.m.r. spectrum?

A butyl methanoate

B propyl ethanoate

C ethyl propanoate

D methyl butanoate
(Total 1 mark)

Q3.
(a) Ester 1 and Ester 2 were studied by 1H n.m.r. spectroscopy.

Ester 1 Ester 2

One of the two esters produced this spectrum.

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 ppm

Deduce which of the two esters produced the spectrum shown. In your answer,
explain the position and splitting of the quartet peak at δ = 4.1 ppm in the spectrum.

Predict the δ value of the quartet peak in the spectrum of the other ester.

Use Table B on the Data Sheet.

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(4)

(b) Cetrimide is used as an antiseptic.

[CH3(CH2)15N(CH3)3]+ Br–

cetrimide

Name this type of compound.

Give the reagent that must be added to CH3(CH2)15NH2 to make cetrimide and state
the reaction conditions.

Name the type of mechanism involved in this reaction.

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(4)

(c) Give a reagent that could be used in a test-tube reaction to distinguish between
benzene and cyclohexene.
Describe what you would see when the reagent is added to each compound and the
test tube is shaken.

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(3)
(Total 11 marks)

Q4.
Which amine has only three peaks in its proton NMR spectrum?

A Methylamine

B Trimethylamine

C Diethylamine

D Propylamine
(Total 1 mark)

Q5.
Which one of the following pairs of reagents reacts to form an organic product that shows
only 2 peaks in its proton n.m.r. spectrum?

A butan-2-ol and acidified potassium dichromate(VI)

B ethanoyl chloride and methanol

C propanoic acid and ethanol in the presence of concentrated sulphuric acid

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 D ethene and hydrogen in the presence of nickel
(Total 1 mark)

Q6.
Which one of the following has a singlet peak in its proton n.m.r. spectrum?

A ethyl propanoate

B propyl methanoate

C hexan-3-one

D 2-chlorobutane
(Total 1 mark)

Q7.
Which one of the following pairs reacts to form an organic product with only 2 singlets in
its proton n.m.r. spectrum?

A ethene and bromine

B propan-2-ol and acidified potassium dichromate(VI)

C ethanol and concentrated sulphuric acid

D epoxyethane and water in the presence of dilute sulphuric acid

(Total 1 mark)

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Mark schemes

Q1.
(a)
This question is marked using Levels of Response. Refer to the Mark
Scheme Instructions for Examiners for guidance.

All stages are covered and each stage is generally correct and
Level 3 virtually complete.
5-6 marks Answer is communicated coherently and shows a logical
progression from Stage 1 to Stages 2 and 3.

All stages are covered but stage(s) may be incomplete or may

contain inaccuracies OR two stages are covered and are
Level 2
generally correct and virtually complete.
3-4 marks
Answer is communicated mainly coherently and shows a logical
progression from Stage 1 to Stages 2 and 3.

Two stages are covered but stage(s) may be incomplete or may

contain inaccuracies OR only one stage is covered but is
Level 1
generally correct and virtually complete.
1-2 marks
Answer includes isolated statements but these are not
presented in a logical order.

0 marks Insufficient correct chemistry to gain a mark.

Indicative Chemistry content

Stage 1:
1a CDCl3 or CCl4 solvent
1b TMS as reference / calibration / standard / peak at 0 (ppm)
1c Inert (so unlikely to react with the sample allow if inert tied to either TMS or CDCl 3
or CCl4)

Stage 2 CCl4 or CDCl3 as solvent:

2a (Both) have no H (atoms so give no signals in spectrum) tied to either CDCl3 or
CCl4
2b CCl4 non polar (- good solvent for non-polar organic molecules)
2c CDCl3 polar covalent molecule (– good solvent for polar organic compounds)

Stage 3 TMS as reference:

3a (Lots (12) of equivalent H to) give one signal / single environment
3b Signal in an area away from other typical H signals / peak upfield from others
OR
(Low electronegativity of Si shifts) signal right
3c Easy to remove / volatile / low bp
6

(b) M1 x – doublet
1

M2 y – quartet
1

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 M3 z – doublet
Allow similar words eg double, quadruplet
Allow numbers
Allow diagrams with correct numbers of lines
1

(c) H attached to both C-Cl and adjacent to C=O so doesn’t fit with data in table B
1

(d) M1

Allow abbreviated structural formulae

1

M2

1
[12]

Q2.
C
[1]

Q3.
(a) M1 Ester 1
If Ester 2, can score M3 only.
1

M2 peak at δ = 4.1 due to

When marking M2 and M3, check any annotation of

structures in the stem at the top of the page.
1

M3 (δ = 4.1 peak is) quartet as adjacent / next to / attached to CH3

1

M4 Other spectrum quartet at δ = 2.1-2.6 (or value in this range)

1

(b) M1 Quaternary (alkyl) ammonium salt / bromide

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 1

M2 CH3Br or bromomethane
Penalise contradictory formula and name.
1

M3 Excess ( CH3Br or bromomethane)

Mention of acid eg H2SO4 OR alkali eg NaOH loses both M2
and M3.
1

M4 Nucleophilic substitution
Can only score M3 if reagent correct.
Ignore alcohol or ethanol (conditions) or Temp.
1

(c)

Bromine Acidified KMnO4

(penalise Br (Penalise missing

but acid
mark on) but mark on)

Wrong reagent = no marks.

If bromine colour stated it must be red, yellow, orange,
brown or any combination, penalise wrong starting colour.
1

Benzene no reaction / colo no reaction / colour

ur remains / no remains / no (visible)
(visible) change change

Ignore ‘clear’, ‘nothing’.

Allow colour fades slowly.
Allow ‘nvc’ for no visible change.
1

cyclohexene (Bromine) (Acidified KMnO4)

decolourised decolourised
1
[11]

Q4.
C
[1]

Q5.
B
[1]

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Q6.
B
[1]

Q7.
D
[1]

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