Using combined spectroscopic techniques to

determine the structure of a molecule

In practice, information from more than one spectroscopic technique is
often used to determine the structure of a molecule. This is best illustrated
using some worked examples.

Worked examples
11.8 The mass spectrum below is for a compound, X, that contains carbon, hydrogen and oxygen. The infrared
spectrum of X has an absorption band at 1725 cm−1.
100
B
80
Relative abundance / %

A
60

40

20

0 77 105 136
0 40 80 120 160
m/z

a What is the relative molecular mass of X?

b Given that X contains two oxygen atoms, suggest the molecular formula for X.
c Identify which group is lost to form the peak marked B.
d Suggest the identity of the species responsible for the peak marked A.
e Calculate the IHD for X.
f Deduce the structural formula of X.

a Using the mass spectrum, the peak at highest m/z value represents the molecular ion – so the relative molecular
mass is 136.
b The only possible molecular formula containing two oxygen atoms that adds up to 136 is C8H8O2.
Two oxygen atoms have a combined mass of 32 and if we subtract this from 136 we get 104. The only other
elements in the molecule are carbon and hydrogen, so we must make 104 from a combination of the masses of
these. Seven carbon atoms gives a combined mass of 7 × 12 = 84, which would require there to be
104 − 84 = 20 hydrogen atoms in the molecule. However, the alkane with seven carbon atoms has only 16
hydrogen atoms, therefore C7H20O2 is not possible
c Peak B occurs at m/z 105. Now, 136 − 105 = 31. So we must think of combinations of C, H and O that add up
to 31. The only possible combination is CH3O, so this group is lost from the molecular ion to produce peak B.
(Note that C2H7 also adds up to 31, but the maximum number of hydrogen atoms for two carbon atoms is six.)
d Peak A occurs at m/z 77. The fragment responsible for this is C6H5+.

11 MEASUREMENT AND DATA PROCESSING 545

 e IHD = 12 × [2c + 2 – h – x + n] for a molecule with formula CcHhNnOoXx, where X is a halogen atom.
The molecular formula is C8H8O2, so c = 8 and h = 8.
IHD = 12 × [(2 × 8) + 2 – 8] = 5
f A benzene ring has an IHD of 4 because it has a ring and three double bonds – so we can conclude that, apart
from the benzene ring, there is one other double bond or ring present.
O H
The peak at m/z 77 indicates that the compound contains a benzene ring substituted
in one position. The loss of 31 mass units from the group suggests that it contains the C O C H
–O–CH3 group. The presence of an absorption band at 1725 cm−1 in the infrared H
spectrum suggests (using Table 11.11) that the molecule contains a C=O group. The
only possible molecule that contains all these elements is:

11.9 An organic compound, Y, is shown by elemental analysis to contain only carbon, hydrogen and oxygen. The
following information about the structure of Y is available:
• mass spectrum: the molecular ion peak occurs at m/z 86
• IHD = 1
• infrared spectrum:
100
% tranmittance

0
3000 2000 1000

• nuclear magnetic resonance spectrum: shows two peaks – one quartet (δ 2.4 ppm) and one triplet
(δ 1.1 ppm)
Determine the structure of the molecule from these data.

Adding up possible combinations of C(12), H(1) and O(16) to make the molecular ion peak at m/z 86
produces C5H10O, C4H6O2, C3H2O3 as possible formulas.
The IHD can be worked out for each of these molecular formulas using
IHD = 12 × [2c + 2 − h − x + n] for a molecule with formula CcHhNnOoXx, where X is a halogen atom. The
IHD corresponding to the possible formulas are:
C5H10O: 12 × [(2 × 5) + 2 − 10] = 1
C4H6O2: 12 × [(2 × 4) + 2 − 6] = 2
C3H2O3: 12 × [(2 × 3) + 2 − 2] = 3

546
 Because the IHD is given as 1, the molecular formula must be C5H10O.
The infrared spectrum has an absorption band in the range 1700–1750 cm−1 indicating a C=O group in an
aldehyde, ketone, carboxylic acid or ester. Because there is only one oxygen atom in the molecule, we can rule
out esters and carboxylic acids because they both have two oxygen atoms in the functional group. Therefore the
compound must be an aldehyde or a ketone.
The NMR spectrum indicates that there are only two different chemical environments for the hydrogen atoms
in the molecule. There are several different isomers that can be drawn for a compound with molecular formula
C5H10O containing a C=O group – but only the two below have just two different chemical environments for
protons:
H H O H H CH3
O
H C C C C C H and H3C C C
H
H H H H CH3

The splitting pattern from the NMR data can be used to distinguish between these two structures:
• a quartet signal indicates the presence of hydrogen atoms adjacent to a C atom with three H atoms attached
• a triplet signal indicates the presence of hydrogen atoms adjacent to a C atom with two H atoms attached.
These two signals together indicate the presence of an ethyl group. This group is present in only the left-hand
structure – so we can conclude that Y is pentan-3-one:
H H O H H

H C C C C C H

H H H H

The NMR spectrum of the right-hand molecule would consist of two singlets because all the hydrogen atoms
have no hydrogen atoms on the adjacent carbon.
As a final check you should use Table 11.14 to compare the chemical shift values given with what you would
expect for pentan-3-one.

Nature of science
Advances in technology have allowed scientists to derive ever more
detailed information about the structure of compounds. Theories of
structure and bonding have developed further as more information has
become available.

11 MEASUREMENT AND DATA PROCESSING 547

 Exam-style questions

1 Rosie carried out an experiment in which she measured a temperature change. Her data are shown in the table.

Initial temperature / °C 18.7 ± 0.5

Maximum temperature / °C 37.6 ± 0.5

The temperature change should be quoted as:

A 18.9 ± 0.5 C 18.9 ± 1.0 °C
B 19 ± 1 °C D 19.0 ± 1.0 °C

2 Aazaish obtained the value 0.002 560 m3 from an experiment. The number of significant figures and decimal places is:
Significant figures Decimal places
A 4 6
B 6 4
C 6 6
D 3 6

3 Molly carried out an experiment to measure the enthalpy change of solution of a salt. In order to calculate a final
value, the following calculation was carried out:
[(50 ± 1) × 4.2 × (20 ± 1)]
1000 × (0.10 ± 0.01)
Quantities without uncertainties can be assumed to be exact. How should the final value be quoted?
A −42 ± 7 kJ mol−1 C −42.00 ± 2.01 kJ mol−1
B −42 ± 2 kJ mol−1 D −42.1 ± 7.1 kJ mol−1

4 Which of the following would be a good method for reducing the random uncertainty in an experiment to
measure the enthalpy change of neutralisation when 50 cm3 of 0.50 mol dm−3 sodium hydroxide reacts with 50 cm3
of 0.50 mol dm−3 hydrochloric acid?
A Insulate the reaction vessel with cotton wool.
B Stir the mixture more rapidly.
C Repeat the experiment.
D Measure out the liquids using a 50 cm3 measuring cylinder instead of a burette.

548
 5 The graph shows the results of a series of experiments to investigate how the rate of the reaction X → Y varies
with the concentration of X.
Rate of reaction / mol dm–3 s–1
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Concentration / mol dm–3

The gradient (slope) of this graph is:

A 2.0 mol dm−3 s−1 C 2.0 s−1
B 0.5 s D 0.5 mol−1 dm3

6 Which of the following would produce only a single peak in the low-resolution 1H NMR spectrum?
A CH3CH2OH C CH3CHO
B (CH3)3CCl D CH2ClCHClCH2Cl

7 Which of the following has an index of hydrogen deficiency of 2?

A C3H6O2 C C4H7N
B C6H6 D C5H8Cl2

8 Which of the following is unlikely be a peak in the mass spectrum of propanoic acid?
A m/z 45 C m/z 74
B m/z 15 D m/z 50

HL 9 The following information is provided about a compound M:

• There is only one peak in the NMR spectrum.

• IHD = 1.
• The molecular ion peak occurs at m/z 56.
• There is only one major band above 1500 cm−1 in the IR spectrum.
Which of the following could be the structure of compound M?
A H2C CH2 C H H H H

H2C CH2 H C C C C H

H H

B H O H D NH2

H C C C H H C C N
H
H H

11 MEASUREMENT AND DATA PROCESSING 549

 conc. H2SO4
alcohol + carboxylic acid ester + water
heat

conc. H2SO4
ethanol + ethanoic acid ethyl ethanoate + water
heat

O H

HL 10 Which of the molecules

H Hbelow will notO haveHa triplet in its NMR spectrum?
H H C C H
conc. H2SO4 O
AH H H C H
C C O H + C C H CH H
C O O H + H H
H H heat heat
C C +H Br H C C H
H H H H H O H H C
H CH C
H Br H H O H
bromoethane
H Br Br H
B D O H
H C C C C H
H H C C H
H H H H
H C C O H

H H

11 Two separate experimental methods were used to determine the value of a particular experimental quantity. Each
experiment was repeated five times. The values obtained from these experiments are shown in the table.

Experiment A B
Trial Value Value
1 49.7 50.6
2 53.2 51.2
3 51.5 51.1
4 52.3 50.8
5 49.2 51.0

The literature value for this quantity is 50.9.

a Explain which set of experimental values is more precise. [2]
b Work out a mean value for each experiment and use this to explain which set of data is more accurate. [3]

12 Yi Jia carried out an experiment to measure a certain quantity. The value she obtained was 56.1 ± 0.5 kJ. The
literature value for this quantity is 55.2 kJ.
a Calculate the percentage error for this experiment. [1]
b The student maintained that any errors could be explained solely by random uncertainties.
Is she correct? Explain your answer. [2]

13 Jerry carried out an experiment to measure the rate of the reaction between Time / s Volume / cm3
magnesium and hydrochloric acid. He did this by recording the volume of
0 0
hydrogen gas collected every 15 s. His data are shown in the table.
15 19
a Plot a graph of these data. [3] 30 33
b Use your graph to determine the initial rate of reaction – include units. [3] 45 44
60 50
75 54
90 56
105 57
120 57

550
14 Certain molecules absorb infrared (IR) radiation.
a IR spectroscopy is one of the techniques that is used to determine the structure of organic molecules.
A student recorded the IR spectrum of a compound, X:

100
% Transmittance

0
3800 3000 2000 1000
Wavenumber / cm–1

The student knew that X was one of the following compounds:

H H H H I
HO C C C C H

H CH3 H H
H H H O II
H C C C C

H H CH3 H
H H H O III
H C C C C
O H
H H CH3
H H H H O H H H IV
H C C C C O C C C C H

H H CH3 H CH3 H H

Deduce which of the molecules is X and explain your choice by reference to the spectrum. [4]
b Explain why NMR is more useful than IR spectroscopy in distinguishing between propanal
and propanone. [4]

11 MEASUREMENT AND DATA PROCESSING 551

 15 The NMR spectrum of propan-2-ol is shown below.

4 3 2 1
Chemical shift (δ) / ppm

a Draw the full structural formula of propan-2-ol. [1]

b Explain why there are three peaks in the NMR spectrum of propan-2-ol. [2]
c The integration trace is shown on the spectrum. Explain what information can be obtained from the
integration trace. [2]
d i Draw the full structural formula of butan-2-ol. [1]
ii State the number of peaks and the relative areas under the peaks in the NMR spectrum of
butan-2-ol. [2]

HL 16 Compounds may be identified using a combination of spectroscopic techniques. The mass spectrum for a
compound, Z, is shown below. Elemental analysis showed that Z contains C, H and O.
100

80
Relative abundance %

60

40

20

0
0 20 30 40 50 60 70
m/z

a Determine the relative molecular mass of Z. [1]

b Work out two possible molecular formulas for Z. [2]
c Deduce the formula of the fragments responsible for the peaks at m/z 31 and m/z 29. [2]
−1
d The IR spectrum of Z shows a strong absorption band at about 3350 cm but no absorptions in the
range 1600–1800 cm−1. Explain what conclusions about the structure of Z can be drawn from these data. [2]

552
 e On the basis of the information above, suggest two possible structural formulas for Z. [2]
f The low-resolution NMR spectrum of Z is shown below.

4 3 2 1
Chemical shift (δ) / ppm

Explain how information from this spectrum can be used to deduce the structural formula of Z
and draw the structural formula of Z. [4]

HL 17 NMR spectroscopy is a very powerful tool in the identification of organic compounds.

a Predict and explain the splitting pattern of the hydrogen atom marked bold in the molecule below. [2]

H H H

H C C C O
H
H H
H C H

b A compound with the formula C4H10O has the NMR spectrum shown below. Draw the structural
formula of the compound and explain your reasoning. [4]

4 3 2 1
Chemical shift (δ) / ppm

11 MEASUREMENT AND DATA PROCESSING 553

 c There are two esters that have the molecular formula C3H6O2. Draw the structural formulas of these
esters and explain the differences between their NMR spectra. [5]
d There are four esters with the molecular formula C4H8O2. Draw the structural formulas of these
esters and explain which will give rise to the NMR spectrum shown below. [6]

4 3 2 1
Chemical shift (δ) / ppm

554
Summary
Measurements are distributed
either side of the mean.
can never be completely
eliminated but their effect can
be reduced by repeating the
experiment.
No figures should be quoted after
the uncertainty.
The uncertainty is in the
last significant figure of the
measured value.
given to one significant figure
precision – how close repeat
readings are to each other
Random uncertainties in analogue instruments
experimental values are – uncertainty is half the
caused by limitations of the smallest division
measuring apparatus and
other uncontrollable factors.
digital instruments – uncertainty
is equal to the smallest division
add absolute add percentage
uncertainties together uncertainties together
adding and subtracting multiplying and dividing
give answer to give answers to
fewest number of fewest number of
decimal places significant figures
UNCERTAINTIES calculations
accuracy – how close measured cannot be reduced
value is to actual value by repeat readings
possible to have great systematic error – introduced
precision but low accuracy due to apparatus or procedure
shifts measured value in existence indicated by
one direction away from percentage error > total random uncertainty
the actual value
|experimental value – accepted value|
percentage error = × 100%
|accepted value|
11 MEASUREMENT AND DATA PROCESSING 555
 Summary – continued
IHD gives the number of
double bond equivalents in
a molecule. For CcHhNnOoXx
IHD = 12 × [2c + 2 – h – x + n]
radio frequencies used
proton NMR
only H nuclei
produce signals
number of peaks gives
the number of different
chemical environments
for H atoms/protons
556
HL
Single crystal X-ray
crystallography
provides a 3-D picture
of a molecule with bond
IR spectroscopy Infrared radiation
lengths and bond angles.
allows identification of
bonds/functional groups
present in a molecule
SPECTROSCOPIC mass spectrometry
TECHNIQUES
HL fragmentation pattern molecular ion peak
chemical shift gives provides information gives the relative
information about about the structure of molecular mass
the environment that a molecule
protons are in
only positive ions
TMS used as a produce a peak in
reference standard the mass spectrum
to set the zero on the
chemical shift scale
integration trace
gives information
about the ratio of
the numbers of H in
each environment HL
splitting pattern gives multiplicity – 1 = number
information about the of H atoms on adjacent C
number of H atoms on
adjacent atom
Topic 11 c Non-linear relationship – as time increases the
temperature increases; as time increases the
1 Set 1 is more precise, because there is less variation increase in temperature per second gets larger
from the mean. 11 a 1.0 cm3 s−1
2 Experiment 2, because this value is closest to the b 17.5–18.4 g A−1
literature value. 12 a 1 c 2 e 4
b 1 d 1
3 Measured Value you should quote
13 B, C, E and G
value ± uncertainty
14 a 2840–3100 cm−1 by C–H
71.7 ± 0.2 71.7 ± 0.2
b 2840–3100 cm−1 by C–H; 3200–3600 cm−1 by
3.475 ± 0.01 3.48 ± 0.01 O–H
0.065 06 ± 0.001 0.065 ± 0.001 c 2840–3100 cm−1 by C–H; 1610–1680 cm−1 by
63.27 ± 5 63 ± 5 C=C
593.2 ± 30 590 ± 30 d 2840–3100 cm−1 by C–H; 2400–3400 cm−1 by
783.28 ± 100 800 ± 100 O–H in COOH; 1700–1750 cm−1 by C=O;
(1000–1300 cm–1 by C–O)
4 a 3 c 4 e 4
b 2 d 3 15 a C2H4O
b C3H8O; C2H4O2
5 a 6.79
c C4H8O; C3H4O2
b 0.000 079 8
d C5H12O; C4H8O2; C3H4O3
c 0.005 00
d 8.25 × 105 16 a CH3+
e 1.78 × 10−3 b CO+; C2H4+
c C2H5+; HCO+
6 0.345 ± 0.001 + 0.216 ± 0.002 = 0.561 ± 0.003 d OCH3+; CH2OH+
23.45 ± 0.03 − 15.23 ± 0.03 = 8.22 ± 0.06 e C3H7+;C2H3O+
0.0034 ± 0.0003 + 0.0127 ± 0.0003 = 0.0161 ± 0.0006 f COOH+; C2H5O+
1.103 ± 0.004 − 0.823 ± 0.001 = 0.280 ± 0.005
g C3H7O+; CH2COOH+; HCOOCH2+
h C6H5+
1.10 ± 0.05 + 17.20 ± 0.05 = 18.3 ± 0.1
17 a 3 peaks; 1 :2 :3
7 Value Percentage uncertainty (%)
b 4 peaks; 3 :2 :2 :1
c 3 peaks; 9 :2 :1
27.2 ± 0.2 0.74
d 5 peaks; 1 :3 :1 :2 :3
0.576 ± 0.007 1.2 e 3 peaks; 3 :1 :6
4.46 ± 0.01 0.22 f 5 peaks; 6 :1 :2 :2 :1
−5 −7
7.63 × 10 ± 4 × 10 0.52 18 a two doublets
8 a The absolute uncertainty is 0.05; the final value b one doublet; one triplet
should be quoted as 9.22 ± 0.05. c one triplet; one quartet; one singlet
b The absolute uncertainty is 0.5; the final value d one triplet; one quartet; one singlet
should be quoted as 86.3 ± 0.5. 19 Using the values in Table 11.14:
9 4140 ± 40 J (assuming that the value for the specific a 0.5–5.0 ppm
heat capacity is exact) b 2.0–2.5 ppm
10 a Linear relationship – as time increases the volume c 3.7–4.8 ppm
increases linearly; not a proportional relationship 20 Multiplicity of peak at δ = 4.0 ppm is 7
b Directly proportional – mass is directly H OH H
proportional to the current H C C C H

H H H

ANSWERS TO TEST YOURSELF QUESTIONS 575