CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: WORKBOOK

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

Workbook answers
Chapter 30
Exercise 30.1
a i Type of chromatography
paper chromatography
gas-liquid
chromatography (GLC)
thin layer
chromatography (TLC)
high-performance liquid
chromatography (HPLC)
Stationary phase
water absorbed onto
cellulose
liquid (long-chain alkane)
absorbed on support
silica / aluminium support
non-volatile liquid
absorbed on support
Mobile phase
organic liquid or mixture of
solvents, sometimes aqueous
gas such as N2, H2 or He
organic solvent
polar liquid, e.g. methanol

ii TLC can be used to separate different
types of plant pigments (colourings).
A mixture of plant pigments is placed
on the solid stationary phase of the TLC
sheet. A solvent such as heptane is used
as the mobile phase. As the solvent runs
up the sheet, the pigments separate. This
is because pigments with more polar
molecules have a greater attraction for
the polar solid used as a stationary
phase. The more polar the molecules are,
the slower they travel up the sheet. This
allows separation from molecules that
are less polar and dissolve more easily in
heptane.
b The mixture to be separated is injected into
the carrier gas and the time noted. The
gas flows through a long tube containing
a long-chain hydrocarbon supported on
silica (stationary phase). As the gas moves
through the tube, components, which are
less soluble in the stationary phase, move
further, while those that are more soluble
are in equilibrium with the stationary phase
for longer. The compounds leave the tube
at different times. The time taken between
injection and detection is called the retention
time.
distance
c i Rf (0.42) = = 30 × 0.42 = 12.6 cm
30 cm
ii By comparing with known Rf when run
under identical conditions / by running
suspected compound at the same time to
see if they finish at the same level.
iii Takes shorter time to run / can use smaller
samples.
d All the components in the mixture must be
completely separated. Detector must respond
equally to the different components.
e Approximate % = 22%
Exercise 30.2
a A. When placed in a strong magnetic field …
E. 1
H nuclei behave like tiny magnets and
line …
H. … themselves up with or against the field.
D. When the correct frequency of radiation
is absorbed, the nuclei …
B. … ‘flip’ from being lined up with the
magnetic field (lower energy) to …
G. … being lined up against the magnetic
field (higher energy).

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: WORKBOOK

C. The size of the energy gap varies with the ii

environment in which the 1H nuclei are
placed and so …
I. … different frequencies give different
NMR peaks corresponding …
F. … to different radio frequencies emitted
when the proton returns to the lower
energy level.
b i 3 H attached to C in CH3 group
2 H attached to C in CH2 group
2 H attached to N in NH2 group
ii 6 H attached to C in 2 CH3 groups
1H attached to C in CH group
2H attached to C of CH2
iii 3 H attached to C in CH3 group attached
to CO
3 H attached to C in CH3 group attached
to CH2
2 H attached to CH2 group
c i It is inert and volatile and all CH3 groups
in same environment
ii Chemical shift
d A = ethanal CH3CHO
Aldehyde (aliphatic) at δ = 10.0 (1 H attached)
Splitting 1 peak 2 peaks 3 peaks 4 peaks
pattern (singlet) (doublet) (triplet) (quartet)
relative 1 1:1 1:2:1 1:3:3:1
intensities
of splitting
pattern
iii SN, SN, SN
SN, SN, NS
SN, NS, NS
NS, NS, NS
The magnetic effects in the −CH3 groups
are transmitted to the neighbouring
−CHO proton so they absorb four different
frequencies, so there are four signals.
f The NMR spectra for most compounds are
recorded for the compound dissolved in a
solvent. The solvent used in an NMR spectrum
causes signals (peaks) which can interfere with
the interpretation of the spectrum. The use
of deuterated solvents such as CDCl3 reduces
the interference because it gives a signal
which corresponds to triplet peaks at 79 ppm.
Modern NMR spectrometers can take account
of this signal so that a standard such as
tetramethylsilane is not necessary.
Exercise 30.3
a −NH2 / −NH−

CH3 group attached to carbonyl group at δ = b The absorption frequencies overlap, so you
2.3 (3 H attached) cannot be sure which group is responsible.

B = ethanol CH3CH2OH c i −OH + D2O ⇌ −OD + HOD

−OH group at δ = 5.5 (1 H attached) ii −NH− + D2O ⇌ −ND + HOD

CH3 group at δ = about 1.4 (3 H attached) d i The deuterium atoms do not absorb in the
same region as protons.
−O─CH2─R group at δ = about 4.0 (2 H
attached) ii Compare the non-deuterated spectrum
with the deuterated one.
e i −CH3 splits into three because there are
two 1H atoms on the −CH2− group next to If some of the original peaks disappear, they
it. were the −OH or −NH− groups present
in the sample.
−CH2− peak splits into four because there
are three 1H atoms on the −CH3 group e i 2 C atoms in 2 −CH3 groups attached
next to it. to −CH2−

−OH group is not split because of 1H 1 C atom in −CH2− group attached to −CH3
exchange with other alcohol or water
molecules.

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ii 3 C atoms in 3 −CH3 groups attached to CH c Quartet / 4 peaks near δ = 10 [1]

1 C atom in CH group attached to due to 3 protons on adjacent CH3 group. [1]
3 −CH3 groups
Doublet / 2 peaks near δ = 2 [1]
iii 1 C atom in CH3 group attached to CO
due to 1 proton on adjacent CHO group. [1]
1 C atom in CO group
Use of n + 1 rule: 3 + 1 = 4 (or 1 + 1 = 2) [1]
1 C atom in CH2 group attached to CO
and CH2 IGNORE: comments on heights of peaks

1 C atom in CH2 group attached to NH2  [Total: 12]

f A: R−CO−R present at δ just over 200 Question 2

CH3 attached to a C group between 0 and 50 a distance of spot from baseline  [1]
(1 peak because groups are equivalent) distance of solvent front from baseline
This peak is double the one at 200 because b i Solid phase that the mobile phase passes
there are 2 CH3 groups. over or through during chromatography [1]
2 CH3 groups and 1 CO suggests the formula ii The solvent which moves over the
is (CH3)2CO stationary phase. [1]
B: CH3− attached to −CH2− group gives c Place spot of compound / ibuprofen on base
one peak line and dip (bottom of) chromatography
−CH2− attached to OH group gives the second sheet into solvent [1]

They are the same height because there is 1 of Allow solvent to run up the stationary phase
each type of carbon. until solvent has nearly reached the top [1]

There is 1 CH3 and one −CH2 − attached to an Visualise spot with locating agent or
OH group. ultraviolet light  [1]

So formula must be CH3CH2OH. d i A = solvent front, B = base line [1]

ii Allow values between 0.31 and 0.33 [1]
g i 4 peaks, CH3−CO, CH3CH2−,
−CH2−CH3, CH3−CO iii Separation depends on the differences in
attraction between the stationary phase
ii solvent peak
and each compound [1]
and on the relative solubility of each
Exam-style questions compound in the mobile phase. [1]
In non-polar solvents, all three
Question 1 compounds will not dissolve well [1]
a 15 = [CH3] +
[1] all 3 compounds do not move because
they do not dissolve in the mobile phase
28 = [CO]+ [1] (so not separated well) / all 3 compounds
77 = [C6H5]+ [1] do not move because the attractive
forces between them and the stationary
105 = [C6H5CO]+ [1] phase are too strong to allow good
b Peak at 1680 to 1750 indicates a ketone separation. [1]
(possibly aryl ketone) [1] 1
e idea of area of triangle = (base ×
height)  2 [1]
Several weak peaks at 3000–3300 indicates an
arene [1] 1
theobromine = (7 × 27) = 94.5 (mm2)
2
Peaks at 700 / 750 indicate arene ring with 5 1
carbons [1] and caffeine = (12 × 33) = 198 (mm2)
2

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: WORKBOOK

(allow: 90–99 for theobromine and 194 Stationary phase is a long-chain hydrocarbon
to 202 for caffeine)  [1] supported on silica (in long tube). [1]
% caffeine = 198 / (94.5 + 198) = 67% [1] Idea of equilibrium between the ‘solutes’ in
the stationary and mobile phases. [1]
 [Total: 15]
Components which are less soluble in the
Question 3 stationary phase move further (or reverse
argument). [1]
a Shift at 10 = aromatic aldehyde CHO
connected to benzene ring [1] The time taken between injection and
detection / retention time is measured. [1]
Shift just before 8 = 3 H attached to C6H5 [1]
Retention time values compared with
Shift at just before 8 = possibly OH attached retention times of
to benzene ring [1]
known substances under identical
Shift at 4 = 3 H attached to CH3O− group [1] conditions. [1]
b The mixture is injected into a carrier gas  [Total: 10]
which is the mobile phase. [1]

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