1. Organic compounds are often identified by using more than one analytical technique.

Some of
these techniques were used to identify the compounds in the following reactions.

C3H7Br → C3H8O → C3H6O

A B C

(a) Using H2O as an example, describe what happens, at a molecular level, during the
absorption of infrared radiation.

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

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

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

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

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

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

(3)

–1
(b) The infrared spectrum of B showed a broad absorption at 3350 cm . The infrared
spectrum of C did not show this absorption, but instead showed an absorption at
–1
1720 cm . Explain what these results indicate about the structures of B and C.

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

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

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

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

(2)

1
(c) The mass spectrum of A showed two lines of approximately equal height, one of which
was at m/z = 122. State the m/z value of the other line and explain these observations.

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

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

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

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

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

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

(3)

(d) The evidence in (b) and (c) indicates that each compound (A, B and C) could have two
possible structures. Draw the two possible structures of C.

(2)

(e) Fragmentation of C in a mass spectrometer produced lines with m/z values of 15 and 28,
but none at values of 14 or 29. Identify C and explain how you used this information to
do so.

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

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

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

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

(2)

2
 1
(f) State the number of lines in the H NMR spectrum of each of the structures in (d).

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

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

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

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

(2)
(Total 14 marks)

2. Explain the following observation:

Hydrogen iodide is infrared active whereas iodine is infrared inactive.

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

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

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

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

(Total 2 marks)

3
3. The mass spectra of halogenoalkanes show more than one line corresponding to the molecular
35 37 79 81
ion. This is due to the presence of isotopes such as Cl, Cl, Br and Br.

(a) Analyse the following spectra of halogenoalkanes P and Q and deduce the formula of all
the molecular ion species.

S p e c tr u m o f P
100

80

60
R e la tiv e
abundance /
% 40

20

0
20 30 40 50 60 70
m /z

S p e c tr u m o f Q
100

80

60
R e la tiv e
abundance /
% 40

20

0
0 40 80 120 160 200
m /z
[Source: NIST Mass Spec Data Center, S E Stein, director, “IR and Mass Spectra” in NIST Chemistry
WebBook, NIST Standard Reference Database Number 69, Eds. P J Linstrom and W G Mallard, July 2001,
National Institute of Standards and Technology, Gaithersburg MD, 20899 (http://webbook.nist.gov)]

species in P ..................................................................................................................

species in Q .................................................................................................................

(3)

4
 (b) Predict the m/z values of the molecular ions for the compounds C 2H5Br and C2H4Cl2

C2H5Br ......................................................................................................

C2H4Cl2 ......................................................................................................

(2)
(Total 5 marks)

4. This question is about the three organic compounds involved in the following reaction.

C2H4O2 + C2H6O → C4H8O2 + H2O

W X Y

(a) The infrared spectra of all three compounds showed several absorptions. Describe what
happens on a molecular level when molecules absorb infrared radiation.

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

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

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

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

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

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

(3)

(b) Use the following information about their infrared spectra to deduce which bonds are
present in the three compounds.

–1
All three compounds showed an absorption close to 1200 cm .

There were broad absorptions in both W and X. The one in W was centred around 3000
–1 –1
cm , and in X around 3400 cm .
–1
Compounds W and Y showed absorptions close to 1700 cm .

bonds in W ...........................................................................................................................

bonds in X ............................................................................................................................

bonds in Y ............................................................................................................................

(3)

5
 1
(c) The H NMR spectra of the three compounds were available. State what can be deduced
from each of the following.

(i) The presence of two peaks in the spectrum of W.

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

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

(1)

(ii) The presence of a triplet and a quartet, with areas in the ratio 3:2, respectively, in
the spectra of both X and Y.

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

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

(1)

(d) Use your answers to (b) and (c) to deduce the structures of the three compounds.

W ...........................................................................................................................

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

X ..........................................................................................................................

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

Y ..........................................................................................................................

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

(3)

6
 (e) The infrared spectrum of compound Z, an isomer of Y, is shown below.

100

80

T ra n s m itta n c e / % 60

40

20

3 000 2 000 1 000

–1
W avenum ber / cm

(i) Estimate the wavenumber values of the three most prominent absorptions in this
spectrum and suggest which bonds are responsible for them.

absorption 1 ............................................................................................

absorption 2 ............................................................................................

absorption 3 ............................................................................................

(3)

(ii) Deduce the structure of Z.

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

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

(1)
(Total 15 marks)

7
5. The figure below depicts the visible region of the electromagnetic spectrum and the two regions
nearest to it.

v is ib le
A B

In c re a s in g w a v e le n g th

(a) Name the regions labelled A and B, identify the atomic or molecular processes associated
with each region and compare the energies of the photons involved in these processes.

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

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

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

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

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

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

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

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

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

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

(5)

8
 (b) State, giving a reason, which region (A or B) could be used to

(i) test for metal ions.

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

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

(1)

(ii) obtain information about the strengths of bonds.

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

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

(1)
(Total 7 marks)

6. Compounds A and B are alcohols with the molecular formula C3H8O. The following
information was obtained from a mass spectrum of each alcohol.

A: peaks at m/z = 29, 31, 60

B: peaks at m/z = 45, 60

(a) Deduce the formula of the species responsible for the peak at m/z = 60.

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

(1)

(b) Deduce the formula of the species with m/z = 31.

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

(1)

9
 (c) Deduce the structure of each alcohol.

Structure of A

Structure of B

(2)
(Total 4 marks)

7. (a) (i) Explain why the mass spectrum of 2-chloro-2-methylpropane shows molecular ion
peaks at m/z values of 92 and 94 in the ratio 3:1.

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

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

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

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

(2)

(ii) Suggest the formulas of the species with the following m/z values in this spectrum:

m/z = 77

m/z = 57

(2)

(b) Predict the m/z values of the three main molecular ion peaks in dichloromethane.

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

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

(2)
(Total 6 marks)

10
 1
8. Nuclear magnetic resonance spectroscopy ( H NMR) can be used to identify organic
compounds.
1
(a) Several features of H NMR spectra are helpful in obtaining information about the
structure of a molecule. Outline what can be learned from each of the following:

· the number of peaks in the spectrum

· the ratio of areas under each peak

· chemical shift values (d) of 1.3 and 9.7 ppm

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

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

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

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

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

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

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

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

(4)

11
(b) There are four esters with the molecular formula C 4H8O2. Two of them are shown below.

ethyl ethanoate CH3–COO–CH2–CH3

methyl propanoate CH3–CH2–COO–CH3

1
The H NMR spectra of these two esters, not necessarily in the correct order, are given
below.

S p e c tru m 1

6 5 4 3 2 1 0
C h e m ic a l s h ift / p p m

S p e c tru m 2

6 5 4 3 2 1 0

C h e m ic a l s h ift / p p m

(i) State and explain, in terms of the structures of both esters, the origin of the triplet
and the quartet.

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

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

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

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

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

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

12
 (3)

(ii) Identify the origin of the singlet peak for either ester, and explain why this peak is
not split.

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

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

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

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

(2)

(iii) By referring to the singlet peak, and using information from Table 19 of the Data
Booklet, deduce which spectrum corresponds to which ester, giving a reason for
your choice in each case.

ethyl ethanoate .................................................................................................

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

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

methyl propanoate ...........................................................................................

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

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

(3)

(c) Another ester with the formula C4H8O2 has the structure.

H C O O C H C H

C H 3

1
Predict the number of peaks, and the ratio of the areas under the peaks, in its H NMR
spectrum.

number of peaks ........................................................................................................

ratio of areas ..............................................................................................................

(2)
(Total 14 marks)

13
9. Identify two effects of the absorption of infrared radiation on the bonds in a molecule of carbon
dioxide.

Explain why an oxygen molecule does not absorb infrared radiation.

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

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

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

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

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

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

(Total 3 marks)

10. There are four structural isomers that are alcohols with the formula C 4H9OH.

(a) Explain why the infrared spectra of all four alcohols show very similar absorptions
–1 –1
around 3350 cm and 2900 cm .

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

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

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

(2)

(b) Describe how these alcohols can be distinguished using their infrared spectra.

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

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

(1)

(c) Explain why the mass spectra of all four alcohols show a peak at m/z = 74.

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

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

(1)

14
15
 (d) Suggest the formulas of the fragments formed from C4H9OH with the following m/z
values:

m/z = 57 ......................................................................................................................

m/z = 45 ......................................................................................................................

(2)

1
(e) The numbers of peaks, and the areas under them, in the H NMR spectra of these alcohols
can be used to identify them.

1
(i) Explain why the H NMR spectrum of (CH3)2CHCH2OH has four peaks. Predict
the ratio of the areas under the peaks.

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

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

(2)

1
(ii) Deduce the structure of the alcohol whose H NMR spectrum has two peaks with
areas in the ratio 9:1.

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

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

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

(1)
(Total 9 marks)

11. (a) Describe what occurs at a molecular level when molecules such as carbon dioxide absorb
infrared radiation.

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

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

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

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

(2)

16
(b) Spectra A and B (see below), represent the infrared spectra of two of these compounds:

CH3CH2COOH CH3COOCH3 HCOOCH2CH3

(i) Use Table 18 in the Data Booklet to identify the groups responsible for the
absorption near

-1
1050 cm .....................................................................................................

-1
1750 cm .....................................................................................................

(1)

(ii) Deduce which one of the three compounds produced spectrum A, giving a reason
for your choice.

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

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

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

(2)

(iii) Explain why the other two compounds have similar infrared spectra.

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

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

17
(1)

18
 1
(c) Figures C and D represent the splitting patterns and the chemical shifts shown in the H
NMR spectra of the same two compounds used to obtain spectra A and B.

F ig u re C

12 10 8 6 4 2 0
C h e m ic a l s h ift / p p m

F ig u re D

12 10 8 6 4 2 0
C h e m ic a l s h ift / p p m

(i) State what general information can be deduced from the three different types of
splitting patterns in these spectra.

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

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

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

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

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

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

(3)

19
 (ii) Explain how the chemical shift values close to d 4.1 in figure C and close to d 11.5
in figure D can be used to identify the two compounds. Refer to information from
Table 19 in the Data Booklet in answering this part.

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

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

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

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

(2)
(Total 11 marks)

12. (a) Electronic transitions occur when a molecule absorbs energy from the visible or UV
regions of the electromagnetic spectrum.

(i) Predict the region (visible or UV) in which benzene and nitrobenzene would absorb
energy.

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

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

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

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

(2)

(ii) Explain why CH2=CH–CH=CH2 shows an absorption band at a longer wavelength

than CH2=CH2.

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

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

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

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

(2)

20
 2+ +
(iii) Explain why compounds of Zn and Cu are colourless.

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

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

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

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

(2)

(b) An aqueous solution of copper(II) sulfate is light blue, but when excess ammonia is
added the colour changes to dark blue.

(i) State the formula of the copper(II) complex ions in each of the two solutions.

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

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

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

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

(2)

(ii) Explain why the colour of copper complex solutions is different when different
ligands are present.

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

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

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

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

(2)
(Total 10 marks)

21
13. The structures of four hydrocarbons are shown below.

I II III IV

(i) Identify the compounds that most strongly absorb ultraviolet radiation.

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

(1)

(ii) Identify the compound that absorbs ultraviolet radiation of the longest wavelength, and
explain your choice.

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

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

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

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

(2)
(Total 3 marks)

22
14. Compound A, with the molecular formula C3H6O has this infrared spectrum.

W a v e n u m b e r s ( c m – 1)

(a) (i) Use Table 18 in the Data Booklet to list four classes of compounds that have
–1
absorptions near 1700 cm .

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

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

(1)

(ii) Identify which of the classes listed in part (a)(i) could not have the molecular
formula C3H6O.

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

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

(1)

(b) The mass spectrum of compound A has prominent peaks at m/z = 15 and 29.

(i) Deduce the formula of the species responsible for each peak.

m/z = 15 ..........................................................................................................

m/z = 29 ..........................................................................................................

(2)

23
24
 (ii) Deduce the structure of compound A.

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

(1)
(Total 5 marks)

15. (a) Each of the infrared absorptions A, B and C is produced by one of the compounds I, II
and III. Deduce which compound is responsible for each absorption, and identify the
bond causing the absorption.

I II III
N H 2
O H
H C H 2

C C
C H 3 H

–1
wavenumbers in cm

3500 3300 3100 1800 1700 1600 1800 1700 1600

A B C

Absorption Compound Bond

A
B
C
(5)

25
 (b) Identify which of the absorptions, A, B or C, indicates the greatest amount of energy,
giving a reason for you choice.

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

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

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

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

(2)
(Total 7 marks)

16. The infrared spectra of propanoic acid and methyl ethanoate contain absorptions in
characteristic wavenumber ranges. Using Table 18 in the Data Booklet, identify:

(a) two wavenumber ranges common to both compounds.

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

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

(1)

(b) one wavenumber range found only in the spectrum of one compound.

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

(1)
(Total 2 marks)

26
17. (a) The diagram below represents the principal parts of a double beam infrared spectrometer.

A
B
S
M

D
C

(i) Name the parts labelled A, B, and C.

A: ....................................................................................................................

B: ....................................................................................................................

C: ....................................................................................................................

(2)

(ii) Describe the function of the monochromator, M.

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

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

(1)

(iii) Explain how the detector, D, works.

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

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

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

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

(2)

27
 (b) State and explain what happens to a molecule when it absorbs infrared radiation.

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

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

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

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

(2)
(Total 7 marks)

18. Identify one analytical technique, different in each case, that can be used to obtain the following
information:

Information Analytical technique

Isotopic composition of an element

Functional groups present in an organic

compound
3+
Concentration of Fe ions in industrial waste
waters

(Total 3 marks)

19. Identify one analytical technique, different in each case, which can be used to obtain the
following information about a molecule.

Information Analytical technique

Number of different hydrogen
environments
Types of functional group

Molecular mass
(Total 2 marks)

28
20. An organic compound with three carbon atoms has two structural isomers A and B with the
same functional group. The infrared spectrum of the compound shows a broad absorption at
–1
about 3350 cm .

(a) The mass spectra of the two isomers A and B are as follows.

100

80
R e la tiv e In te n s ity

60

40

20

0
10 15 20 25 30 35 40 45 50 55 60
m /z
Iso m e r A

100

80
R e la tiv e In te n s ity

60

40

20

0
10 15 20 25 30 35 40 45 50 55 60
m /z
Iso m e r B

29
(i) Deduce, giving a reason, the molecular formula of the organic compound.

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

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

(1)

(ii) Deduce the formula of the fragmentation ion responsible for the peak at each of
these m/z values.

isomer A 29 ..........................................................................................

31 ..........................................................................................

isomer B 30 ..........................................................................................

45 ..........................................................................................

(4)

30
 1
(b) The H NMR spectra of isomers A and B are shown below.

Iso m e r A

6 5 4 3 2 1 0
c h e m ic a l s h ift d / p p m

Iso m e r B

6 5 4 3 2 1 0
c h e m ic a l s h ift d / p p m

31
(i) State the formula and function of the compound responsible for the peak at 0 ppm.

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

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

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

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

(2)

(ii) Explain what information about the isomers can be obtained from the number of
peaks and area under each peak.

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

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

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

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

(2)

(iii) Deduce the structural formulas of isomers A and B and give the ratio of peak areas
in each case.

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

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

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

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

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

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

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

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

(4)

32
 (iv) Draw the structural formula of a third isomer C that has the same molecular
formula as isomers A and B but a different functional group. Give the ratio of peak
areas in isomer C.

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

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

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

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

(2)
(Total 15 marks)

1
21. (a) H NMR spectroscopy can be used to obtain information about the structure of
molecules.

State the information that can be obtained from the

(i) number of peaks.

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

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

(1)

(ii) chemical shift.

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

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

(1)

(iii) ratio of peak areas.

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

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

(1)

(iv) splitting pattern.

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

33
 ...........................................................................................................................

(1)

1
(b) The H NMR spectrum of a compound with the formula C4H8O2 exhibits three major
peaks with chemical shifts, areas and splitting patterns given below.

peak
chemical shift / ppm ar splitting pattern
ea

0.9 3 triplet

2.0 2 quartet

4.1 3 singlet

Using information from Table 19 in the Data Booklet, determine the types of proton
present in the molecule.

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

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

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

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

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

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

(3)

34
 (c) Deduce a structure consistent with the information indicated in (b). Explain your answer.

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

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

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

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

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

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

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

(5)
(Total 12 marks)

22. (a) Draw structures for two possible isomers of a compound with the formula C2H4O2.

(2)

35
(b) The infrared spectrum of this compound shows the following absorptions: 2920, 2765
–1.
and 1710 cm Use the information in Table 18 of the Data Booklet to assign each
absorption to a particular vibration.
–1
2920 cm .....................................................................................................................

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

–1
2765 cm .....................................................................................................................

......................................................................................................................................
–1
1710 cm ......................................................................................................................

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

(2)

(c) Deduce the structure from (a) which would demonstrate the infrared absorptions above.
Explain your answer.

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

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

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

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

(2)
(Total 6 marks)

36