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Demands of A2 Chemistry (Foreword by the Chief Examiner)
An aspect of the new revised specifications is that candidates are required to apply their knowledge
and understanding to a much greater extent than in the old legacy specification.
When devising examinations, two main assessment objectives, AO1 and AO2, are considered. The
weightings for these objectives are shown in the specifications for Chemistry A and they comply with
requirements of the national Science Core Criteria that apply to approved Chemistry specifications
from all Awarding Bodies. An outline of AO1 and AO2 and their relative weightings for the AS and A2
units are outlined below.
AO1
• Recall
• Knowledge and understanding
AO2
• Application
• Unfamiliar situations
In order to deliver the required range of grades with the application emphasis, the A2 examinations
are significantly more demanding than the AS examinations.
The new A2 examinations have a much greater emphasis on application of knowledge and
understanding than in the past and novel questions that require application of knowledge and
understanding will feature in these examinations. A real challenge for both teachers and their
students lies in their preparation for this style of examination. The best candidates usually rise to the
challenge but less able candidates can struggle. It is particularly important that all candidates answer
what they can in the questions, even if they are unable to see the way forwards to a final solution.
It is hoped that this resource will provide a useful stimulus in helping students acquire the skills
required to tackle some of the more demanding problem-solving questions within Organic Chemistry.
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Introduction
These questions have been designed to help students acquire some of the application skills that are
now tested in the A2 examinations, focussing on unit F324, Rings, Polymers and Analysis.
Some parts of these questions assess skills that should be accessible to the majority of students,
whilst others go beyond the demands of the specification or require skills possessed by only the most
able students. These parts are labelled with a ‘**’. The questions may also give ideas to teachers for
resources that they may then develop themselves.
Assessing application
Questions set in examinations will assess AO1 (Recall of knowledge and understanding) and AO2
(Application of knowledge and understanding).
Application in spectral analysis
This type of question is perhaps the easiest to recognise as assessing application. Analysis of
spectra has problem-solving at its heart, using important principles for each type of analysis.
Questions 1–5 in this resource pack provide examples of this type of question, mainly in the context
of NMR spectroscopy.
Application in reaction mechanisms
When assessing reaction mechanisms, a question might require candidates to outline a mechanism
for nucleophilic addition [4.1.2(d)], exemplified by the reaction of NaBH4 with aldehydes and ketones
or electrophilic substitution [4.1.1(d)], exemplified by mononitration and monohalogenation of arenes.
By application, a question could require candidates to outline these types of mechanism with
unfamiliar nucleophiles or electrophiles, which would be provided in the question. This type of
approach is illustrated in Question 6 of this resource pack.
The examples in the specification are there to illustrate the principles of nucleophilic addition and
electrophilic substitution, which could then be applied to other unfamiliar situations. When teaching,
extra examples could be used as extension material but students should be made aware that these
are not necessarily to be learnt. A question could also require an unfamiliar type of mechanism to be
completed using the principle that a curly arrow represents the movement of an electron pair.
Application in synthesis
When assessing synthesis, a question might require a candidate to suggest a multi-step synthesis of
a compound using solely reactions that have been encountered during study of F324. Extra
unfamiliar reagents and reactions could also be provided within a question and these might also be
required in the synthetic route. This approach is also illustrated in Question 6 of this pack.
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Questions
1. Using 13C NMR spectroscopy to distinguish between different substituted arenes.
5. Using 13C NMR spectroscopy and mass spectrometry to identify an organic compound.
This question illustrates some limitations of 13C NMR spectroscopy and shows that, when
combined with another analytical technique, a compound may then be identified.
Useful links
1. Spectral database for organic compounds
http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/cre_index.cgi?lang=eng
This free site is managed by the National Institute of Advanced Industrial Science and Technology
(AIST), Japan. The site contains a range of 13C NMR, 1H NMR, IR and mass spectra for many
organic compounds. It is best to search by molecular formula and to have a working knowledge of
‘old’ names.
2. Spectra School
https://www.le.ac.uk/spectraschool/
This free site, based at Leicester University, is managed by the RSC as part of Spectroscopy in a
Suitcase, a new activity that forms part of the Chemistry for our Future project. This interactive
website provides a variety of resource materials for students and teachers including real 13C NMR, 1H
NMR, IR and mass spectra. The spectra are high quality and it is possible to zoom in on sections that
can prove to be very useful for analysing splitting patterns. Note that chemical drawing packages
such as ChemDraw and ChemDoodle also provide facilities to allow simulation of spectra which could
be used to create homework tasks.
3. OCR community
www.social.ocr.org.uk, a useful place to share teaching resources/ideas. Note that as part of the
International Year of Chemistry 2011, OCR is offering a Kindle for the best GCE Chemistry resource
material posted to the community, see the community pages for more details.
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1. The three isomers, A, B and C below, can be distinguished by 13C NMR spectroscopy.
O2 N NO2 NO2
O 2N NO2
NO2
A B C
Spectra 1–3 are the 13C NMR spectra of the three isomers A–C.
Match each isomer to its spectrum and explain how you made your choice. [6]
[Total: 6]
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2. There are four structural isomers of C4H10O that are alcohols, shown as A–D below.
OH OH
OH OH
A B C D
Spectra 1–4 are the 13C NMR spectra of the four isomers A–D.
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(a) Two of the isomers from A–D can be identified from their 13C NMR spectra but the
other two isomers cannot easily be identified.
• Match the two isomers that can be identified to the correct spectra.
• Explain how you made your choice.
• Explain why the other two isomers cannot easily be distinguished for their 13C NMR
spectra.
[10]
(b) The peak at highest chemical shift in each spectrum is likely to be for the C atom
bonded to the –OH group. It is difficult to predict which peaks are responsible for the
remaining C atoms. It is likely that the closer the C atom to the –OH group, the higher
the chemical shift.
• Using this information, predict the C atoms that are responsible for the peaks in
each of the spectra 1–4.
• Hence predict which spectrum matches the other two isomers.
**
[8]
[Total: 18]
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3. There are four structural isomers of C4H10O that are alcohols, shown as A–D below.
The isomers can be distinguished using 1H NMR spectroscopy.
OH OH
OH OH
A B C D
(a) Spectra 1–3, shown below, are the 1H NMR spectra of the three isomers B, C and D.
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• Match the isomers B–D to the spectra 1–3 and identify the protons responsible for the
peaks in each spectrum.
• Explain any splitting patterns.
[11]
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(b) The 1H NMR spectrum of isomer A is shown below as Spectrum 4. This spectrum is
more difficult to interpret fully than the spectra in (a).
• Analyse this spectrum and explain why it is more difficult to interpret fully.
• In your answer, you should identify the protons responsible for each peak and any
splitting patterns.
*
[4]
[Total: 15]
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4. The three isomers below are members of a family of compounds called dioxanes.
1,4-dioxane
Explain why the spectrum consists of just one peak that is not split.
[1]
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(b) The 1H NMR spectrum of 1,3-dioxane is shown below.
1,3-dioxane
Identify the protons responsible for each peak and explain the splitting patterns.
[3]
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(c) The 1H NMR spectrum of 1,2-dioxane is shown below.
1,2-dioxane
[2]
[Total: 6]
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5. Xylitol is a compound of C, H and O with the molecular formula C5H12O5.
C5H12O5 has many isomers but initial analysis has limited the possibilities to the four
structures below.
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(a) The 13C NMR spectrum reduces the number of possible structures for xylitol.
Explain, with reasoning, which of the structures 1–4 are still possible for xylitol.
[6]
(b) The mass spectrum of xylitol contains fragment ions at m/z = 121, m/z = 91, m/z = 61
and m/z = 31.
[5]
[Total: 11]
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6. Potassium cyanide, KCN, contains potassium and cyanide ions. Although the cyanide ion is
usually shown as CN–, the negative charge is on the C atom:
C N
Nitriles can be converted into other functional groups as in the examples below.
(a) Carbonyl compounds react with aqueous potassium cyanide by nucleophilic addition.
[4]
OH
O
............................ ............................
COOH
[3]
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(c) A chemist intended to synthesise 1-aminobutan-2-ol starting from an alcohol.
**
.........................................................
.........................................................
.........................................................
1-aminobutan-2-ol
[7]
[Total: 14]
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17
Mark Scheme and guidance
Qu. Expected answer Mark
1 (a) Spectrum 1 is isomer C as there are two carbon environments giving two peaks in the
13
C NMR spectrum 9
9 2
(b) Spectrum 2 is isomer A as there are four carbon environments giving four peaks in
the 13C NMR spectrum 9
9
2
(c) Spectrum 3 is isomer B as there are six carbon environments giving six peaks in the
13
C NMR spectrum 9
9 2
Total 6
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Mark Scheme and guidance
3 1
2 3
OH
9
3
D
Spectrum 3 is isomer C 9
There are two carbon environments giving two peaks in the 13C NMR spectrum 9
2 OH 3
1 9
2 2
C
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Mark Scheme and guidance
2 (b)
Total 18
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Mark Scheme and guidance
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Mark Scheme and guidance
Qu. Expected answer Mark
3 (a)
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Mark Scheme and guidance
3 (b) There are five proton environments but there appears to be only four peaks.
The following peaks can be interpreted:
δ = 3.7 ppm: broad OH 9
δ = 3.4 ppm: triplet (δ = 3.4 ppm) for CH2OH adjacent to CH2 9
δ = 0.8 ppm: triplet for CH3 adjacent to CH2 9
The peak at δ = 1.4–1.6 ppm is difficult to interpret. The splitting does not appear to be
sharp and it is the result of two overlapping multiplets for the two central CH2 groups. 9 4
The protons in these two CH2 groups have similar, but not identical, environments.
Total 15
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Mark Scheme and guidance
3
Protons in environment 2 have two protons on adjacent C atoms
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Mark Scheme and guidance
Qu. Expected answer Mark
Total 6
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Mark Scheme and guidance
9
9
9 9
The only structures with three peaks are those with three C environments 9
Total 11
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Mark Scheme and guidance
6 (a)
O
9 H H
O δ− O OH
9
δ+
C R C C N R C C N OH
H3 C H
9 H H
C N
9
4
(b)
OH OH
O
9
KCN(aq) 9
............................ HCl(aq)/reflux
CN ............................ COOH
9 3
(c)
OH 9
K2Cr2O7(aq)/H2SO4(aq), distil 9
.........................................................
O 9
KCN(aq) 9
.........................................................
OH
9
CN
H2/Ni 9
.........................................................
OH
NH2 9 7
Total 14
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