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1.

The diagram below shows a mass spectrometer, which can be used to determine the percentage
abundances of isotopes in an element.

(a)

Explain, in terms of sub-atomic particles, what is meant by the term isotopes.


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(2)

(b)

Describe the role of the following parts of the mass spectrometer.


(i)

Electric field
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(1)

(ii)

Magnetic field
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(1)

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(c)

A sample of the element barium is made up of four isotopes. The data below were taken
from a mass spectrum of this sample.

Mass/charge ratio

% abundance

135

9.01

136

10.81

137

12.32

138

67.86

Calculate the relative atomic mass of the sample, giving your answer to one decimal
place.
(2)

(d)

79

81

The element bromine has two stable isotopes, Br and Br. How many peaks
+
corresponding to Br2 ions would be seen in the mass spectrum of bromine?
Justify your answer.
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(2)

(e)

Suggest another application of mass spectrometry, other than to determine the relative
atomic mass of an element.
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(1)
(Total 9 marks)

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2.

Which of the following features is shown by the mass spectra of propanone and propanal?

propanone

propanal

m/e of the molecular ion

Fragmentation pattern

same

same

same

different

different

same

different

different
(Total 1 mark)

3.

The spectra of the compounds with the formulae CH 3CH(OH)CH3 and CH3CH2CH2OH can be
distinguished by
A

the value of m/e of the molecular ion in the mass spectrum.

the presence of a fragment with m/e = 15 in the mass spectrum.

the presence of an absorption peak due to OH in the infrared spectrum.

the number of peaks in the nmr spectrum.


(Total 1 mark)

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4.

Which of the following has two singlet peaks in its nmr spectrum?
A

Methanal, HCHO

Methanol, CH3OH

Chloromethane, CH3Cl

Dichloromethane, CH2Cl2
(Total 1 mark)

5.

The nmr spectrum of 2,2-dimethylpropane,


A

one singlet peak.

four singlet peaks.

one quartet peak.

four quartet peaks.

, contains

(Total 1 mark)

6.

In the reaction of manganate(VII) ions with reducing agents in strongly acidic solution, the halfreaction for the reduction is

2+

+ 2H2O

2+

+ 4H2O

2+

+ 4H2O

MnO4 + 4H + 3e MnO2 + 2H2O

MnO4 + 4H + 5e Mn

MnO4 + 8H + 3e Mn

MnO4 + 8H + 5e Mn

(Total 1 mark)

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7.

The conditions needed for the E value of the standard hydrogen electrode to be exactly 0 V are
3

1 mol dm solution of hydrogen ions, 1 atm pressure of hydrogen, 25C.

1 mol dm solution of hydrogen ions, 1 atm pressure of hydrogen, room temperature.

1 mol dm solution of hydrogen ions, laboratory pressure of hydrogen, 25C.

0.1 mol dm solution of hydrogen ions, 1 atm pressure of hydrogen, 25C.

3
3

(Total 1 mark)

8.

The electrode potential for a cell can be used to calculate the equilibrium constant for the cell
reaction. This is because

ln E

In E

cell is proportional to lnK

cell

is proportional to K.

cell

cell

is proportional to lnK.
is proportional to K.
(Total 1 mark)

Courier New;OOKHMJ+TimesNewRomanPSMT;Symbol;9.
Brass is an alloy of copper, zinc and,
in some cases, other metals too. There are over 30 varieties of brass for different applications.
The amount of copper in a brass can be found as follows:

A weighed sample of brass is reacted with the minimum amount of concentrated nitric
acid.

The solution is neutralized, a portion of it pipetted into a conical flask, and excess
potassium iodide solution is added.

The iodine produced is titrated with a solution of sodium thiosulfate of known


concentration.

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(a)

The ionic equation for the reaction between copper metal and concentrated nitric acid is
shown below.

2+

Cu(s) + 2NO3 (aq) + 4H (aq) Cu (aq) + 2NO2(g) + 2H2O(l)


(i)

Give the oxidation numbers of the copper and nitrogen in both the reactants and
products.
Copper: from..........................................to..........................................
Nitrogen: from.........................................to.........................................
(2)

(ii)

Write the two half-equations that can be combined to give the ionic equation shown
above.
(2)

(iii)

Explain why the standard electrode potentials for the two ionic half-equations that
you have written give an incorrect value for Ecell for this reaction as described
above.
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(2)

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(b)

The solution produced contains a mixture of zinc ions and copper ions.
(i)

State TWO observations that you would see if concentrated ammonia solution were
to be added, drop by drop, to the solution until in excess.
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(2)

(ii)

Copper ions can be separated from the zinc ions in the solution by adding sodium
hydroxide solution in excess, followed by filtration of the mixture.
Write equations, including state symbols, for the THREE reactions that occur.
Equation 1

Equation 2

Equation 3
(3)

(iii)

Give examples of amphoteric behaviour and ligand exchange, by reference to the


reactions of zinc compounds.
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(3)

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(c)

A sample of Admiralty Brass of mass 3.00 g was treated with nitric acid and made up to a
3
3
neutral solution of volume 250 cm . Excess potassium iodide was added to 25.0 cm
portions of this solution, and the liberated iodine was titrated with sodium thiosulfate
3
3
solution, concentration 0.100 mol dm . The mean titre was 33.10 cm .
(i)

Write the ionic equation for the reaction between thiosulfate ions and iodine.
(1)

(ii)

The equation for the reaction between copper(II) ions and iodide ions is shown
below.
2Cu

2+

+ 4I 2CuI + I2

Hence calculate the percentage by mass of copper in Admiralty Brass. Give your
answer to three significant figures.
(6)

(iii)

When setting up the burette, a student failed to fill the jet of the burette.
Explain the effect that this would have on the value of the first titre.
If this first titre was included in the calculation of the mean titre, what effect would
this have on the value for the percentage of copper in the brass?
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(2)
(Total 23 marks)

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10.

Paracetamol is possibly the most widely used analgesic (painkiller) in the world. It can be made
from phenol as shown below.

(a)

The nitration of phenol in step 1 uses dilute nitric acid at room temperature, whereas the
nitration of benzene requires a mixture of concentrated nitric and sulfuric acids at about
55C.
(i)

Give the mechanism for the nitration of benzene, including the equation for the
reaction that produces the electrophile.
(4)

(ii)

Explain why phenol can be nitrated under much milder conditions than those
required to nitrate benzene.
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(2)

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(iii)

Suggest reagents that could be used for step 2.


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(2)

(iv)

Suggest the name or formula of a reagent that could be used in step 3.


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(1)

(b)

In the nitration of phenol, step 1, two compounds are produced.

These compounds can be separated by steam distillation, since 2-nitrophenol is volatile in


steam but 4-nitrophenol is not.
Describe briefly the technique of steam distillation and give ONE advantage of steam
distillation over normal distillation.
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(3)

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11

(c)

The nmr spectrum of paracetamol is given below. The peaks at 6.7 and 7.4 ppm are due to
the protons on the benzene ring and are both doublets.
Explain why these two peaks are doublets but all the other peaks are singlets.
[There is no need to refer to your data booklet]

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(2)
(Total 14 marks)

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12

11.

More than half of the elements in the Periodic Table are transition elements. Vanadium, element
23, is a typical transition element.
(a)

(i)

Give TWO properties shown by vanadium compounds that are characteristic of


transition metal chemistry, other than variable oxidation state.
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(2)

(ii)

3+

Vanadium(III) ions in aqueous solution exist as [V(H2O)6] .


Draw this ion so as to clearly show its shape. Name the type of bond between the
ligand and the vanadium ion and state the feature of the ligand that enables this
bond to be formed.
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(3)

(b)

Vanadium ions exist in oxidation states from (V) to (II).


(i)

Use your data booklet (page 15) to find the standard electrode (reduction) potential
2+
3+
for the reduction of vanadium(IV), VO , to vanadium(III), V .
...........................................................................................................................
(1)

(ii)

Explain the term disproportionation.


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(2)

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(iii)

Use your answer to (b)(i), and the data below, to calculate E cell for the formation
of vanadium(V) and vanadium(III) from vanadium(IV) in acidic solution. State if
the reaction is feasible under standard conditions and justify your answer.
+

VO2 (aq) + 2H (aq) + e

2+

VO (aq) + H2O(l) E = + 1.00 V

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(2)
(Total 10 marks)

12.

Chlorine has two isotopes with relative isotopic mass 35 and 37. Four m/z values are given
below. Which will occur in a mass spectrum of chlorine gas, Cl 2, from an ion with a single
positive charge?
A

35.5

36

71

72
(Total 1 mark)

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14

13.

The radio waves used in proton nmr


A

must not be absorbed by the sample.

cause electron transitions in the hydrogen atom.

can only be used with organic substances.

cause the hydrogen nucleus to change its spin state.


(Total 1 mark)

14.

This question is about compounds X, C4H10O, and Y, C4H8O.


(a)

Compound X, C4H10O, can be oxidized to compound Y, C4H8O. The infrared spectrum


of X is given below.
Infrared Spectrum of X

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15

What can be deduced about the structures of X and Y using all this information and the
data booklet? Justify your answer.
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(4)

(b)

Below are the nmr spectra of X and Y.


nmr spectrum of X

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nmr spectrum of Y

Use these nmr spectra and your answer to (a) to deduce the structural formulae of X and
Y. Justify your answer and explain why both nmr spectra are consistent with these
structures.
(6)
(Total 10 marks)

15.

The mass spectrum for a sample of a metal is shown below.

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17

The relative atomic mass of the metal is


A

63.2

63.4

63.6

64.0
(Total 1 mark)

16.

Which of the following ions would undergo the greatest deflection in a mass spectrometer?
A

35

2+

35

37

35

37

Cl
Cl
Cl

Cl Cl

(Total 1 mark)

17.

Which of the following values for the mass/charge ratio for singly charged ions would be
present in the mass spectrum of propanal, CH3CH2CHO, but not of propanone, CH3COCH3?
A

15

29

43

58
(Total 1 mark)

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18

18.

(a)

A gaseous sample of an element can be analysed using a mass spectrometer.


(i)

Describe briefly how positive ions are formed from gaseous atoms in a mass
spectrometer.
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(2)

(ii)

What is used to accelerate the positive ions in a mass spectrometer?


...........................................................................................................................
(1)

(iii)

What is used to deflect the positive ions in a mass spectrometer?


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(1)

(b)

The following data were obtained from the mass spectrum of a sample of chromium.

Mass/charge ratio

% abundance

50.0

4.3

52.0

83.8

53.0

9.5

54.0

2.4

Calculate the relative atomic mass of chromium in this sample. Give your answer to three
significant figures.
(2)

(c)

Explain why the four isotopes of chromium behave identically in chemical reactions.
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(1)

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(d)

In which block of the Periodic Table is chromium found?


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(1)
(Total 8 marks)

19.

Buckminsterfullerene is a carbon molecule with formula C60 which can trap metal ions in its
structure. Which of the following compounds of buckminsterfullerene would give a line of
mass/charge ratio at 837.3 in a mass spectrometer?
A

Na4C60

K3C60

Ca3C60

AgC60
(Total 1 mark)

20.

This question is about four hydrocarbons with molecular formulae as shown.


A

C2H2

C3H6

C3H8

C4H10

(a)

Which hydrocarbon has the same empirical formula as its molecular formula?
A
B
C
D
(1)

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21

(b)

Which has a molecular ion in the mass spectrum at mass/charge ratio = 58?
A
B
C
D
(1)

(c)

Which is neither an alkane nor an alkene?


A
B
C
D
(1)

(d)

Which could be 2-methylpropane?


A
B
C
D
(1)
(Total 4 marks)

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22

21.

This question is about magnesium and magnesium oxide.


(a)

Describe the bonding in magnesium and explain why it is a good conductor of electricity.
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(3)

(b)

Draw a diagram (using dots or crosses) for the ions in magnesium fluoride showing all
the electrons and the ionic charges on:
(i)

the magnesium ion

(1)

(ii)

the fluoride ion.

(1)

(c)

Under what conditions does magnesium fluoride conduct electricity?


Explain your answer.
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.....................................................................................................................................
(1)

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23

(d)

The mass spectrum of a sample of magnesium is shown below.

80

re la tiv e a b u n d a n c e %

60

40

20

20

22

24

26

28

m a s s /c h a rg e ra tio

(i)

Use the data above to estimate the percentage isotopic composition of the sample
of magnesium. Hence calculate the average atomic mass of the sample of
magnesium.

(2)

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(ii)

Why do the three isotopes have the same chemical properties?


...........................................................................................................................
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(1)

(e)

(i)

Oceanographers studying plankton found that a sample of seawater contained


3
9
1.20 nanomol dm of chlorophyll, C55H77MgN4O5. (1 nanomol = 1 10 mol)
3

What mass of magnesium would be present in 1.00 cm of this sample of seawater?


Give your answer to three significant figures.

(2)

(ii)

X-ray diffraction can be used to locate atoms or ions in molecules like chlorophyll.
X-rays are scattered by the electrons in atoms and ions. In chlorophyll the atoms of
one of the elements still cannot be located with certainty by this technique.
Suggest which element is most difficult to locate.
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(1)
(Total 12 marks)

22.

(a)

A sample of an element can be analysed to show its isotopic composition using a mass
spectrometer.
(i)

Explain how the sample is ionised.


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(2)

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25

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(ii)

State the TWO properties of the ion that determine the path of the ion through the
magnetic field.
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(2)

(b)

Define relative isotopic mass.


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(2)

(c)

The following data were obtained from the mass spectrum of a sample of chromium.
Relative isotopic mass

Percentage abundance

49.95

4.345

51.94

83.79

52.94

9.501

53.94

2.364

Calculate the relative atomic mass of this sample of chromium.


Give your answer to four significant figures.

(2)

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(d)

Complete the electron configuration of an iron atom, atomic number 26.


1s

2s

2p

3s

3p

3d

4s

(2)
(Total 10 marks)

23.

The formulae of five organic compounds (A, B, C, D and E) containing four carbon atoms per
molecule are shown below:

H 2N C H C O 2H
C H 2C O 2H

C H 3C H 2C H B rC H

N H
CH

C H

C H

C H

C H 3C H

C
C H 3C O N H C H 2C H

(a)

Which formula represents a secondary amine?


Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)

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(b)

Which formula represents compounds which are two geometric isomers?


Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)

(c)

Which TWO of the formulae, A to E, represent molecules with chiral centres?


..................................................
..................................................
(1)

(d)

This part of the question is concerned with compounds A, B, C and D only.


(i)

Which compound would give a cream precipitate when hot silver nitrate is added?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
(1)

(ii)

Which compound would give a purple colour when ninhydrin solution is added?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
(1)

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29

(iii)

Which TWO compounds would react with sodium hydroxide solution?


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(1)

(iv)

Which TWO compounds would react with dilute hydrochloric acid to form salts?
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(1)

(v)

Which TWO compounds react with water, under appropriate conditions, to form
alcohols?
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(1)

(e)

(i)

Name compound E.
...........................................................................................................................
(1)

(ii)

Write the equation for the formation of compound E from ethylamine and another
suitable reagent, using structural formulae.

(1)

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(f)

(i)

Compound A can react with itself to form a dipeptide under appropriate conditions.
Give the structural formula of this dipeptide.

(1)

(ii)

One of the compounds B to E reacts with itself to form an addition polymer.


Write a balanced equation for the formation of this polymer using structural
formulae. State the conditions for this polymerisation.
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(2)

(g)

(i)

Which of the compounds A to E has the least number of peaks in the nuclear
magnetic resonance (NMR) spectrum?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)

(ii)

Justify your answer.


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(1)

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(h)

Which of the compounds A to E would not have an absorption above 3000 cm in the
infrared spectrum?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)

(i)

Which of the compounds A to E would have peaks occurring in pairs in the mass
spectrum? Justify your answer.
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(2)
(Total 18 marks)

24.

Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring ingredients
found in foods. Synthetic vanillin, which is identical to natural vanillin, can be manufactured
from methoxybenzene. One synthetic route is shown below:

SO 3H
O CH

O H
O CH

O H
O C H

O CH

CH O
m e th o x y b e n z e n e

(a)

(i)

2 -m e th o x y b e n z e n e
s u lp h o n ic a c id

2 -m e th o x y p h e n o l

v a n illin

Name the reagent which converts methoxybenzene to 2-methoxybenzene sulphonic


acid.
...........................................................................................................................
(1)

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(ii)

Name the type of reaction which occurs and its mechanism.


...........................................................................................................................
(2)

(b)

After the final stage, in which 2-methoxyphenol is converted to vanillin, the impure
product can be purified by recrystallisation. In this process the solid is dissolved in the
minimum volume of hot water. The mixture is then filtered whilst still hot. The filtrate is
cooled in an ice bath to produce crystals of vanillin. These can be removed by filtration
and dried.
(i)

Why is the minimum volume of hot water used?


...........................................................................................................................
...........................................................................................................................
(1)

(ii)

The impure vanillin may contain soluble and insoluble impurities. Describe how
each of these is removed during recrystallisation.
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(2)

(iii)

How would you check the purity of the vanillin after recrystallisation, other than
by using an infrared spectrometer.
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(2)

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(c)

In order to establish whether or not vanillin had been formed, two infrared spectra were
obtained: a sample of pure 2-methoxyphenol and a sample of the product.
Study the spectra and data below.
In fr a re d S p e c tr u m o f 2 -M e th o x y p h e n o l
100
80
T ra n s m itta n c e
/%

60
40
20
3000

2000
W avenum ber/cm

1000
1

In fr a re d S p e c tr u m o f P ro d u c t
100
T ra n s m itta n c e
/%

80
60
40
3000

2000
W avenum ber/cm

1000
1

Wavenumber / cm
C C Stretching Vibrations
CH Stretching Vibrations
OH Stretching Vibrations
C O Stretching Vibrations

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Arene
Arene
Alcohols and phenols
Aldehydes
Ketones
Carboxylic acids
Esters

1600 1450
3030
3750 3200
1740 1720
1700 1680
1725 1680
1750 1735

34

Comment as to whether any vanillin is likely to have been formed during the process.
Support your answer with relevant evidence.
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(2)
(Total 10 marks)

25.

(a)

(i)

Explain why a water molecule does not have a linear shape.


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(2)

(ii)

State the HOH bond angle in water and explain why it has this value.
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(2)

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(b)

(i)

Draw the boron trichloride molecule, BCl3, making its shape clear. Mark in the
bond angle on your diagram.

(2)

(ii)

Explain why a BCl bond is polar.


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(1)

(iii)

Explain why a BCl3 molecule is non-polar.


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(1)

(iv)

Name the strongest intermolecular force between boron trichloride molecules.


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(1)

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(c)

A compound of phosphorus and chlorine has the composition by mass shown below.
Element

% by mass

14.9

Cl

85.1

Calculate the empirical formula of this compound.

(2)
(Total 11 marks)

26.

Hydrogen peroxide decomposes according to


2H2O2(aq) 2H2O(l) + O2(g)
The reaction is catalysed by solid manganese(IV) oxide, MnO 2.
(a)

Two experiments are carried out under the same conditions except that in one experiment
the manganese(IV) oxide is a fine powder and in the other the same mass of coarse
granules is used.
Which experiment would show the faster rate of decomposition? Explain your answer in
terms of collision theory.
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(2)

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(b)

(i)

Draw a labelled Maxwell-Boltzmann distribution of molecular energies in a


mixture of gases at two different temperatures T1 and T2, where T2 is higher than
T1.

(4)

(ii)

Mark on your graph a suitable value for the activation energy, Ea, for the reaction
between the gases. Use your drawing to account for the increase in reaction rate
with increasing temperature.
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(3)

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(iii)

Use the Maxwell-Boltzmann distribution to explain why a catalyst increases the


rate of a reaction at temperature T1.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)

27.

The following data relate to the thermodynamic changes which occur when Group 2 hydroxides
dissolve in water.
1890 kJ mol

2+

1275 kJ mol

550 kJ mol

Lattice energy of Mg(OH)2

2995 kJ mol

Lattice energy of Ba(OH)2

2320 kJ mol

Enthalpy of hydration of Mg
Enthalpy of hydration of Ba

2+

Enthalpy of hydration of OH

(a)

(i)

Define the term enthalpy of hydration.


...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

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(ii)

Explain why this enthalpy change is always exothermic.


...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(b)

Why is the lattice energy of magnesium hydroxide more exothermic than that of barium
hydroxide?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

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(c)

(i)

Draw a labelled Hesss law cycle to show how the lattice energy and the enthalpies
of hydration are related to the enthalpy of solution of magnesium hydroxide,
Mg(OH)2(s).

(3)

(ii)

Use your cycle and the data to calculate the enthalpy of solution of magnesium
hydroxide. Include a sign and units with your answer.

(2)

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(d)

Use the data to explain how the solubility of barium hydroxide compares with that of
magnesium hydroxide.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 15 marks)

28.

This question is about a compound, A, used as a food flavouring. It has the molecular formula,
C9H8O.
(a)

For each of the following pieces of information, state what can be deduced about the a
structure of A.
(i)

A burns with a very sooty flame.


...........................................................................................................................
(1)

(ii)

A reacts with Bradys Reagent (2,4-dinitrophenylhydrazine) to give an orange


precipitate.
...........................................................................................................................
(1)

(iii)

When A is heated with Benedicts solution, a red precipitate forms.


...........................................................................................................................
(1)

(iv)

A decolorises bromine water.


...........................................................................................................................
(1)

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44

(v)

A is the cis isomer.


...........................................................................................................................
...........................................................................................................................
(1)

(vi)

Use all of the above information to draw the displayed formula of A.

(2)

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(b)

Compound A can be converted to benzoic acid, C6H5CO2H, which is formed as a white


precipitate.
(i)

The precipitate can be purified by recrystallisation, using water as the solvent.


Describe how you would carry out this recrystallisation, explaining the reason for
each step in your method.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(5)

(ii)

How would you check that the purification had been successful?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

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(c)

(i)

Write the equation for the reaction which occurs when solid benzoic acid is added
to sodium carbonate solution. Include state symbols in your equation.

(2)

(ii)

Benzoic acid is slightly soluble in water. Write the equation for the dissociation of
benzoic acid and hence the expression for the acid dissociation constant, K a.

(2)

(iii)

Calculate the pH of a 0.00100 mol dm solution of benzoic acid.


5
3
[Ka for benzoic acid is 6.30 10 mol dm .]

(3)

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(d)

Give the name or formula of an organic compound which, when mixed with a solution of
benzoic acid, forms a buffer solution.

(1)
(Total 21 marks)

29.

Paracetamol can be manufactured from phenol using the reaction sequence below.
O H

O H

O H

S te p 1

S te p 2

N O
A

(a)

O H

S te p 3

N H
C

N H CO C H

P a ra ce ta m o l

Give reagents and conditions for Step 1.


.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

State the type of reaction that occurs in Step 2.


.....................................................................................................................................
(1)

(c)

(i)

Give the name of compound C.


...........................................................................................................................
(1)

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(ii)

Suggest a test and its results for the amino group in compound C.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(d)

(i)

Write a balanced equation for the reaction occurring when paracetamol is boiled
with an aqueous solution of sodium hydroxide.

(2)

(ii)

Would you expect paracetamol to react with sodium carbonate solution? Justify
your answer.
...........................................................................................................................
...........................................................................................................................
(1)

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(e)

(i)

Suggest which types of intermolecular forces exist between paracetamol molecules.


For each type of force give an example of the parts of the molecules involved.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)

(ii)

Suggest a reason why paracetamol is only sparingly soluble in water.


...........................................................................................................................
...........................................................................................................................
(1)

(f)

Suggest which bond gives rise to the broadest absorption in the infrared spectrum of
paracetamol.
State the range of wavenumbers for this absorption.
...........................................................................................................................
...........................................................................................................................
(2)

(g)

(i)

Give the molecular formula of the ion with the highest molecular mass in the mass
spectrum of paracetamol.
...........................................................................................................................
(1)

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(ii)

Suggest the formulae of the ions responsible for the peaks at mass / charge ratios
43 and 93.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(h)

Suggest ONE advantage of using paracetamol, rather than aspirin, as a pain reliever.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 20 marks)

30.

Air is drawn through 10.0 cm of an aqueous solution of vanadium(II) chloride of concentration


3
0.100 mol dm . The colour of the solution slowly changes as oxidation takes place.
The air-oxidised solution is titrated with a solution of acidified potassium manganate(VII) of
3
3
concentration 0.0200 mol dm . The end point is found to be 20.0 cm .
(i)

Draw a diagram of suitable apparatus for carrying out the air-oxidation of the
vanadium(II) chloride solution.

(1)

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(ii)

Complete the half equation for acidified manganate(VII) ions acting as an oxidising
agent.

2+

MnO4 (aq) + ..............H (aq) + 5e (aq) Mn (aq) + ..............H2O(1)


(1)

(iii)

Calculate the number of moles of manganate(VII) ions used in the titration, and hence the
number of moles of electrons removed by the manganate(VII) ions.
3

Calculate the number of moles of vanadium(II) ions in the 10 cm of solution used. Find
the oxidation number of vanadium in the air-oxidised solution given that vanadium(V)
ions are formed in the titration.

(4)

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(iv)

Suggest ONE reason why acidified potassium manganate(VII) is a useful oxidising agent
in redox titrations.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 7 marks)

31.

(a)

(i)

Complete the electron configuration of an aluminium atom.


2

1s .......................................................................................................................
(1)

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(ii)

st

nd

The grid below shows the relative values of the 1 and 2 ionisation energies of
rd
aluminium. Mark on the grid the relative values that you would expect for the 3
th
and 4 ionisation energies of aluminium.

E n e rg y

1 st

2 nd
Io n is a tio n E n e rg y

3 rd

th

(2)

(b)

(i)

Write the half-equation for the oxidation of aluminium metal to aluminium


3+
ions, Al .
...........................................................................................................................
(1)

(ii)

Write the half-equation for the reduction of oxygen gas to oxide ions, O .
...........................................................................................................................
(1)

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(iii)

Combine these two half-equations to produce the redox equation for the reaction of
aluminium with oxygen to form aluminium oxide.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 6 marks)

32.

Iodine and propanone react together in the presence of dilute hydrochloric acid according to the
equation:
)
CH 3 COCH 3 I 2 H
(aq
CH 3 COCH 2 I HI

The rate of reaction can be measured by recording the decrease in the concentration of the
iodine.

The results of four experiments are given below:

Experiment

initial
[CH3COCH3]
3

/mol dm

Sri Lankan School

initial [I2]
3

/mol dm

initial [H ]
3
/mol dm

Rate
3 1
/mol dm s

0.40

0.0040

0.40

1.5 10

0.80

0.0040

0.40

3.0 10

0.40

0.0020

0.40

1.5 10

0.80

0.0020

0.80

6.0 10

55

(a)

(i)

State the order of the reaction with respect to CH 3COCH3, I2 and H . Justify your
answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)

(ii)

Give the value of the overall order of the reaction.


...........................................................................................................................
(1)

(b)

Write the rate equation for the reaction.


Calculate the value of the rate constant and give its units.

(3)

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(c)

A suggested mechanism for the reaction is shown below:


C H 3C O C H

H +
S te p 1

H 3C

C H

I2
S te p 2

C H 3C O C H 2I

O H

Use your answers to (a)(i) to compare the relative rates of the two steps.
Explain your reasoning.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

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(d)

The graph below represents the change in concentration of iodine in Experiment 1 over a
5 minute period.
0 .0 0 5

0 .0 0 4
[I 2 ]
/ m ol dm

0 .0 0 3

0 .0 0 2

0 .0 0 1

0
0

T im e / m in
Add labelled lines to represent Experiment 2 and Experiment 3.
(3)

(e)

(i)

Propanone can also react with iodine to form a pale yellow precipitate of triiodomethane. What other reagent is needed for this reaction?
...........................................................................................................................
(1)

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(ii)

Propanone reacts with lithium tetrahydridoaluminate, LiAlH4, in dry ether.


Suggest which reagent needs to be added to liberate the final organic product.
Draw the full structural formula of this product.

(2)

(f)

State and explain how the n.m.r. spectra of propanone and propanal would differ.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 18 marks)

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33.

In industry, propene is manufactured by the catalytic dehydrogenation of propane at a


temperature of about 450 C.
C3H8(g)
(i)

C3H6(g) + H2(g)

DH = +122 kJ mol

If the pressure is increased, what will be the effect on the yield of propene obtained at
equilibrium? Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(ii)

State why the yield of propene at equilibrium increases with increasing temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)

(iii)

What effect does the catalyst have on the yield of propene at equilibrium?
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 4 mark)

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34.

(a)

Calculate the enthalpy change of atomisation, Hat, in kJ mol , for but-2-ene,


CH3CH CHCH3
CH3CH

CHCH3(g) 4C(g) + 8H(g)

Use the following average bond energies.


Average bond energy
1
/kJ mol
CC

+347

+612

CH

+413

(3)

(b)

The enthalpy changes of atomisation and the boiling points of some alkenes are shown
below.
Alkene

Hat
/kJ mol

Ethene, C2H4

+2260

103.6

Propene, C3H6

+3440

47.3

But-1-ene, C4H8

(i)

Boiling point
/C

6.2

Pent-1-ene, C5H10

+5800

+30.0

Hex-1-ene, C6H12

+6990

+63.4

On the grid below, plot values for the enthalpy change of atomisation (vertical axis)
against the number of carbon atoms in the alkene molecule (horizontal axis).
(One page of graph paper should be provided).

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62

(3)

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(ii)

Explain why these enthalpy changes rise regularly.


...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(iii)

Use your graph to estimate the value of the enthalpy change of atomisation for
but-1-ene.
....................................... kJ mol

(1)

(c)

(i)

Which intermolecular force occurs between alkene molecules?


...........................................................................................................................
(1)

(ii)

Explain why the boiling points increase from ethene to hex1ene.


...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(iii)

There are two boiling points for CH3CH


CH2. Why is this?

CHCH3, but only one for CH3CH2CH

...........................................................................................................................
...........................................................................................................................
(1)

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65

C H 3C H 2C
(iv)

2-methylbut-1-ene,

C H

C H
3

, is an isomer of pent-l-ene.

Predict which of these isomers has the higher boiling point. Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(d)

By considering the intermolecular forces in water, suggest why liquid alkenes do not mix
with water.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 17 marks)

35.

One step in the manufacture of nitric acid is the reaction between nitrogen(II) oxide and oxygen
to form nitrogen(IV) oxide.
2NO(g) + O2(g)
(a)

(i)

2NO2(g)

H = 114 kJ mol

Use the equation to suggest the sign of Ssystem for the forward reaction. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

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(ii)

What is the sign of Ssurroundings for the forward reaction? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(b)

(i)

Write the expression for Kp for this reaction.


What are the units of Kp in this reaction?

Units ..............................................
(2)

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(ii)

Suggest how the temperature and pressure could be altered to make nitrogen(IV)
oxide more economically. Justify your suggestions by considering both yield and
rate.
Temperature
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Pressure
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)

(c)

(i)

What property would allow you to follow the progress of this reaction? Justify your
answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

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(ii)

In a series of experiments, the following results were obtained.


Experiment

[NO(g)]
3
/mol dm

[O2(g)]
3

/mol dm

Initial rate
3 1
/mol dm s

1.0 10

1.0 10

8.0 10

2.0 10

1.0 10

3.2 10

2.0 10

2.0 10

6.4 10

What is the order of the reaction with respect to NO(g)? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

What is the order of the reaction with respect to O 2(g)?


...........................................................................................................................
(1)

(iii)

What is the rate equation for this reaction?

(1)

(iv)

What is the overall order for this reaction?


....................................................................................
(1)

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(v)

Calculate the rate constant, k, for this reaction. Include units with your answer.

(2)

(d)

Suggest why this reaction takes place quickly at room temperature and pressure.
.....................................................................................................................................
(1)
(Total 20 marks)

36.

But-2-enoic acid, CH3CH=CHCOOH, can be converted into 3-oxobutanoic acid,


CH3COCH2COOH in a three step synthesis.

(a)

Step 1

CH3CH=CHCOOH

CH3CHBrCH2COOH

Step 2

CH3CHBrCH2COOH

CH3CH(OH)CH2COOH

Step 3

CH3CH(OH)CH2COOH

CH3COCH2COOH

(i)

Identify the reagents needed for each step.


Step 1 ...........................................................................................................
......................................................................................................................
Step 2 ...........................................................................................................
......................................................................................................................
Step 3 ...........................................................................................................
......................................................................................................................
(4)

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(ii)

But-2-enoic acid exists as two stereoisomers.


Draw these stereoisomers and explain why one does not convert to the other at
room temperature.

......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(b)

Give the structural formula of the organic products of the reaction of


(i)

but-2-enoic acid with an alkaline solution of potassium manganate(VII).

(1)

(ii)

3-oxobutanoic acid with hydrogen cyanide, HCN, in the presence of a trace of


hydroxide ions.

(1)

(c)

3-oxobutanoic acid is a weak acid. The value of its acid dissociation constant, Ka, is
4

2.63 10 mol dm .
(i)

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Give the structural formula of the conjugate base of 3-oxobutanoic acid.

72

(1)

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73

In parts (ii) and (iii) you may use HX as the formula for 3-oxobutanoic acid.
(ii)

Explain how a mixture of 3-oxobutanoic acid and its sodium salt can act as a buffer
solution when a small amount of alkali is added.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)

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(iii)

Calculate the mass of solid sodium 3-oxobutanoate that must be added to 100 cm
3
of a 0.500 mol dm solution of 3-oxobutanoic acid in order to make a buffer
solution of pH 3.80.

(5)
(Total 18 marks)

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37.

(a)

Carboxylic acids react reversibly with alcohols, in the presence of a catalyst, to form an
ester and water.
When 24.8 g of ethane-1,2-diol, HOCH2CH2OH, was mixed with 66.0 g of ethanoic acid,
CH3COOH, in the presence of a catalyst, equilibrium was reached after 80.0% of the
3

ethane-1,2-diol had reacted. The total volume at equilibrium was 90.0 cm .


HOCH2CH2OH + 2CH3COOH

CH3COOCH2CH2OOCCH3 + 2H2O

Write the expression for the equilibrium constant, Kc, and calculate its value. You should
make clear what units, if any, there are for Kc.

(7)

(b)

Ethane-1,2-diol can be made from ethene in a two-stage process. The overall reaction is:

1
C2H4 + H2O + 2 O2 HOCH2CH2OH
1054 g of ethane-1,2-diol was obtained from 560 g of ethene.
Calculate the percentage yield of the process.

(2)

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(c)

Polyesters can be formed from compounds with two functional groups.


(i)

Give the structural formula of a reagent that would react with ethane-1,2-diol to
make a polyester. Draw the structure of the polymer made from this reagent and
ethane-1,2-diol.

(3)

(ii)

Explain whether it would be sensible for protective clothing, made from this
polymer, to be used in an environment where acid spills are likely.
......................................................................................................................
......................................................................................................................
(1)

(d)

Explain why the ester methyl methanoate, HCOOCH3, has a much lower boiling
temperature than its isomer ethanoic acid, CH 3COOH, and why ethanoic acid has a lower
boiling temperature than propanoic acid, C2H5COOH.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(5)
(Total 18 marks)

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79

38.

This question is about the chemistry of methanol, CH3OH.


(a)

(i)

Draw a dot and cross diagram for methanol, showing outer shell electrons only.

(1)

(ii)

Textbooks show the displayed formula of methanol as follows

However, this is not a true representation of the shape of the molecule.


Explain why the shape of methanol is not as shown above.
Label the correct value of ONE bond angle on the displayed formula.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)

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(b)

When methanol burns in a poor supply of air, one of the products is carbon monoxide.
A dot and cross diagram of carbon monoxide is shown below.

(i)

Draw the displayed formula for carbon monoxide. Show the TWO types of bond
which are present.

(1)

(ii)

The length of the bond between carbon and oxygen in methanol is 0.143 nm.
Would you expect the length of the bond between carbon and oxygen in carbon
monoxide to be longer, the same or shorter than this? Explain your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)

(c)

The energy of the bond between carbon and oxygen in methanol (the CO bond) can be
calculated from data on enthalpy changes of atomisation.
(i)

Write an equation, including state symbols, for the atomisation of one mole of
methanol vapour.

(1)

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81

(ii)

Use the data below to calculate the energy of the CO bond in methanol.

standard enthalpy change of atomisation of methanol vapour, H

at

= +2039 kJ mol

energy of CH bond, E(CH) = +413 kJ mol


1
energy of OH bond, E(OH) = +464 kJ mol

(2)

(iii)

Complete a balanced Hess cycle which you can use to calculate the standard

enthalpy change of formation of methanol vapour, DH f.


You should use the value of the standard enthalpy change of atomisation of

methanol vapour, DH at, given in (ii) and the data on enthalpy changes given
below. Write the correct numerical data beside the arrows in the cycle.
Equation
C(graphite) C(g)
O2(g) O(g)
H2(g) H(g)

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Enthalpy change of atomization


1
/kJ mol
+716.7
+249.2
+218.0

82

Use your cycle to calculate the value of DH f for methanol vapour.

(3)

(iv)

Methanol is a liquid at room temperature. Would you expect the standard enthalpy
change of formation of liquid methanol to be more or less negative than the value
you calculated in (iii)? Justify your answer.
................................................................................................................................
................................................................................................................................
(1)

(v)

Methanol is a liquid at room temperature although alkanes with similar molecular


mass are gases.
Draw a diagram to show a bond between two methanol molecules that causes it to
be a liquid at room temperature.
Give the value of this bond angle on your diagram.

(2)
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83

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84

(d)

Methanol can be manufactured in the following reaction.


CO(g) + 2H2(g)

CH3OH(g)

H = 93.3 kJ mol

Decide whether a high or low temperature and a high or low pressure would give the
greater proportion of methanol at equilibrium. Justify your choice in each case.
Temperature ..................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
Pressure .........................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(Total 17 marks)

39.

In the first stage of an industrial process for purifying nickel, carbon monoxide is passed over
impure nickel at 323 K. Gaseous nickel tetracarbonyl, Ni(CO) 4, is formed.
Ni(s) + 4CO(g)
(a)

(i)

Calculate S

system

Ni(CO)4(g)

H = 191 kJ mol

for this reaction given the following standard entropy values.

S
1 1
/J mol K

Substance
Ni(s)

+29.9

CO(g)

+197.6

Ni(CO)4(g)

+313.4

Include a sign and units in your answer.

(2)

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(ii)

Refer to the equation above and comment on the sign of your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)

(iii)

Calculate S

surroundings

at 323 K. Include a sign and units in your answer.

(2)

(iv)

Deduce the direction of this reaction at 323 K. Justify your answer.


................................................................................................................................
................................................................................................................................
(1)

(b)

(i)

Write the expression for the equilibrium constant, Kp, for this reaction.

(1)

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86

(ii)

100 moles of gaseous carbon monoxide is mixed with excess solid nickel at 323 K
in a vessel kept at 1.00 atmosphere pressure. At equilibrium, 1.00 mole of the
carbon monoxide has reacted.
Complete the table below and then calculate the value of Kp at this temperature.
Include the units of Kp in your answer.
Substance

Moles at start

Ni(CO)4

CO

100

Moles at
equilibrium

Partial pressure, peq


/atm

99.0

(4)

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87

(iii)

As Kp has such a small value, suggest THREE ways in which this industrial
process could be improved to increase profitability. Justify each of your
suggestions.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(3)

(c)

The second stage of this process is to recover the nickel from the nickel tetracarbonyl,
Ni(CO)4. By considering your calculations of the entropy changes, suggest how this
could be done. Justify your suggestion.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(Total 16 marks)

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40.

Consider the esterification of the amino acid alanine, which has the formula
CH3CH(NH2)COOH.
CH3CH(NH2)COOH + C2H5OH
(a)

(i)

CH3CH(NH2)COOC2H5 + H2O

Write the expression for Kc.

(1)

(ii)

Using the average bond enthalpies given below, show that enthalpy change, DH,
for this reaction would be calculated as zero.
Average bond enthalpies / kJ mol

CO 358
OH 464

(2)

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89

(iii)

On the basis that DH is zero, state what the effect of increasing the temperature
will be on:
the value of Kc ............................................................................................................
......................................................................................................................
the rate of attainment of equilibrium ..........................................................................
......................................................................................................................
(2)

(b)

Alanine exists as a zwitterion.


(i)

Suggest the structure of this zwitterion.

(1)

(ii)

Suggest why alanine has a relatively high melting temperature.


......................................................................................................................
......................................................................................................................
(1)

(iii)

Using equations, show how alanine can react with both acid and alkali.

(2)

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91

(c)

The alanine molecule is chiral.


(i)

What is meant by the term chiral?


......................................................................................................................
......................................................................................................................
(1)

(ii)

Draw the TWO optical isomers of alanine.

(2)

(iii)

How could the optical isomers of alanine be distinguished from each other?
......................................................................................................................
......................................................................................................................
(1)
(Total 13 marks)

41.

But-1-ene, CH2==CHCH2CH3, can be converted into a polymer.


(a)

Draw the structure of part of the polymer, showing TWO repeating units.

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92

(2)

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93

(b)

The polymerisation of CH2==CHCH2CH3 is exothermic and involves the use of a


catalyst. The diagram below shows the energy profile for this polymerisation using a
catalyst.

Indicate on the profile the activation energy for the catalysed process.
Add another energy profile to the diagram for the polymerisation where a catalyst is not
used.
(3)

(c)

Explain, in terms of activation energy and the collision theory, why the rate of
polymerisation is greater when
(i)

a catalyst is used
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

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(ii)

heat energy is provided to start the process.


...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)
(Total 7 marks)

42.

(a)

During the Haber process, for the production of ammonia, the following reaction occurs.
N2(g) + 3H2(g)
(i)

2NH3(g)

DH = 92 kJ mol

Explain why the rate of a reaction increases with increasing temperature.


......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

(ii)

State, with a reason, the effect of an increase in temperature on the position of the
equilibrium.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

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95

(iii)

State, with a reason, the effect of an increase in pressure on the position of the
equilibrium.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(b)

(i)

Explain how a catalyst increases the rate of a reaction.


......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

(ii)

What catalyst is used in the Haber process?


......................................................................................................................
(1)

(iii)

What is the effect of this catalyst on the position of the equilibrium?


......................................................................................................................
(1)

(c)

Write the equation for the reaction of sulphuric acid with excess ammonia and state a
large-scale use of the product.
Equation .................................................................................................................
Use of product ........................................................................................................
(2)
(Total 14 marks)

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96

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97

43.

In the manufacture of beer, brewers often add small amounts of salts of Group 2 elements to the
water used. These salts influence the chemical reactions during the brewing process.
Two such salts are calcium sulphate and magnesium sulphate.
(a)

A flame test can be used to confirm that a sample of a salt contains calcium ions.
(i)

Describe how you would carry out a flame test.


............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)

(ii)

A positive test results in a brick-red flame colour. Describe the changes that occur
in calcium ions to produce a colour.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(iii)

Impurities in the salt may lead to other colours being observed in the flame.
What metal ion is likely to be present if a yellow flame is seen?
............................................................................................................................
(1)

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98

(b)

Magnesium sulphate can be used in its anhydrous form, MgSO 4(s), or in its hydrated
form, MgSO4.7H2O(s).
An experiment was carried out to find the enthalpy change when hydrated magnesium
sulphate dissolved completely in water.

excess water
MgSO4.7H2O(s) MgSO4(aq) + 7H2O(l)
12.3 g of hydrated magnesium sulphate was added to 100 g of water in a simple
calorimeter and the temperature was found to fall by 1.1 C.

(i)

Calculate the energy change, in joules, that occurred in the experiment, using the
relationship
Energy change (J) = 4.18 mass of water temperature change

(2)

(ii)

Calculate the number of moles of hydrated magnesium sulphate used in the


experiment. Use the Periodic Table as a source of data.

(2)

(iii)

Use your answers to (i) and (ii) to calculate the enthalpy change for the reaction.
Include a sign and units in your final answer, which should be given to 2
significant figures.

(2)
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99

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100

(c)

The enthalpy change as hydrated magnesium sulphate is converted to anhydrous


magnesium sulphate is very difficult to measure. The Hess Cycle below can be used to
find this enthalpy change, Hr.

(i)

Use the cycle to write an expression for Hr using H1 and H2.

(1)

(ii)

Use your expression in (c)(i) and your answer from (b)(iii) to calculate Hr.
Include a sign and units in your final answer, which should be given to 2
significant figures.

(2)
(Total 15 marks)

44.

Phosphine, PH3, is a hydride of the Group 5 element, phosphorus.


(a)

(i)

Draw a dot-and-cross diagram of a phosphine molecule. You should include only


outer shell electrons.

(1)
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101

Sri Lankan School

102

(ii)

Draw the shape you would expect for the phosphine molecule, suggesting a value
for the HPH bond angle.

HPH bond angle .......................................................................................................


(2)

(iii)

Explain the shape of the phosphine molecule you have given in your answer in (ii).
Justify your value for the HPH bond angle.
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(2)

(b)

(i)

Write a balanced equation, including state symbols, for the atomisation of


phosphine gas.
.............................................................................................................................
(1)

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103

(ii)

Use your answer to (i) and the data below to calculate the standard enthalpy change
of atomisation of phosphine at 298 K. Include a sign and units in your answer.

5.4 kJ mol

-1

H at[H2(g)] = + 218.0 kJ mol

-1

H f[PH3(g)]

=+

H at[P(s)]

= + 314.6 kJ mol

-1

(3)

(iii)

Calculate a value for the bond energy of the bond between phosphorus and
hydrogen, using your answer to (ii).

(1)
(Total 10 marks)

45.

This question is about phosphine, PH3, and ammonia, NH3.


(a)

Which compound has the stronger van der Waals forces?


Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
(1)

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104

(b)

(i)

The boiling points of ammonia and phosphine are:


Ammonia
Phosphine

240 K
185 K

Name the intermolecular force responsible for the higher boiling point of ammonia.
...........................................................................................................................
(1)

(ii)

Use displayed formulae to show this intermolecular bond between two ammonia
molecules.
Clearly mark and label the bond angle between the molecules.

(2)
(Total 4 marks)

46.

The equation below shows a possible reaction for producing methanol.

CO(g) + 2H2(g) CH3OH(l)

(a)

H = -129 kJ mol

The entropy of one mole of each substance in the equation, measured at 298 K, is shown
below.

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Substance

S
-1 -1
/J mol K

CO(g)

197.6

H2(g)

130.6

CH3OH(l)

239.7

105

(i)

Suggest why methanol has the highest entropy value of the three substances.
.............................................................................................................................
.............................................................................................................................
(1)

(ii)

Calculate the entropy change of the system, S

system,

for this reaction.

(2)

(iii)

Is the sign of S

system

as expected? Give a reason for your answer.

.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(1)

(iv)

Calculate the entropy change of the surroundings S

surroundings,

at 298 K.

(2)

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106

(v)

Show, by calculation, whether it is possible for this reaction to occur spontaneously


at 298 K.

(2)

(b)

When methanol is produced in industry, this reaction is carried out at 400 C and 200
atmospheres pressure, in the presence of a catalyst of chromium oxide mixed with zinc
oxide. Under these conditions methanol vapour forms and the reaction reaches
equilibrium. Assume that the reaction is still exothermic under these conditions.
CO(g) + 2H2(g)
(i)

CH3OH(g)

Suggest reasons for the choice of temperature and pressure.


Temperature ........................................................................................................
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
Pressure ...............................................................................................................
.............................................................................................................................
.............................................................................................................................
(3)

(ii)

The catalyst used in this reaction is heterogeneous. Explain this term.


.............................................................................................................................
.............................................................................................................................
(1)

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107

(iii)

Write an expression for the equilibrium constant in terms of pressure, Kp, for this
reaction.
CO(g) + 2H2(g)

CH3OH(g)

(1)

(iv)

In the equilibrium mixture at 200 atmospheres pressure, the partial pressure of


carbon monoxide is 55 atmospheres and the partial pressure of hydrogen is 20
atmospheres.
Calculate the partial pressure of methanol in the mixture and hence the value of the
equilibrium constant, Kp. Include a unit in your answer.

(2)

(c)

The diagram below shows the distribution of energy in a sample of gas molecules in a
reaction when no catalyst is present. The activation energy for the reaction is EA.

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108

(i)

What does the shaded area on the graph represent?


.............................................................................................................................
(1)

(ii)

Draw a line on the graph, labelled EC, to show the activation energy of the
catalysed reaction.
(1)
(Total 17 marks)

47.

This question is about the chemical reaction between two gases, oxygen, O 2, and nitrogen
monoxide, NO.
2NO(g) + O2(g)
(a)

(i)

2NO2(g)

Define the term standard enthalpy of formation, DH f.


......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

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109

(ii)

Use the data below to calculate the enthalpy change for the reaction between
oxygen and nitrogen monoxide.

DH f (NO) = + 90 kJ mol

DH f (NO2) = + 34 kJ mol

(2)

(iii)

Construct a reaction profile to represent the reaction in (ii).

(3)

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110

(iv)

On the basis of your calculation in (ii), state why you would expect the reaction to
take place.
..........................................................................................................................
......................................................................................................................
(1)

(v)

Explain why a reaction, which is expected to take place, may actually proceed so
slowly as to appear never to happen.
......................................................................................................................
......................................................................................................................
(1)

(b)

The reaction is reversible and produces a dynamic equilibrium.


2NO(g) + O2(g)
(i)

2NO2(g)

Explain what is meant by the term dynamic equilibrium.


......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(ii)

State, with a reason, the effect on the position of equilibrium of increasing the total
pressure of the system at constant temperature.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

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111

(iii)

Although the reaction is an equilibrium reaction, industrially this and other similar
reactions do not usually achieve equilibrium. Suggest why this is so.
......................................................................................................................
......................................................................................................................
(1)
(Total 15 marks)

48.

(a)

Ammonia is manufactured by the Haber process


N2(g) + 3H2(g)

2NH3(g)

DH = 92.4 kJ mol

The usual conditions for this process are a catalyst of iron, a temperature of 400 C and a
pressure of 200 atmospheres.
Draw, on the axes below, an energy profile diagram for the uncatalysed reaction. Mark
on your diagram the activation energy and the enthalpy change.

E n th a lp y

E x te n t o f re a c tio n ( re a c tio n c o -o rd in a te )
(4)

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112

(b)

(i)

Draw, on the axis below, the Maxwell-Boltzmann distribution that could apply at
400C and mark on your diagram the activation energies for the catalysed and the
uncatalysed reaction.

F ra c tio n o f
m o le c u le s o f
e n e rg y E

E n e rg y
(3)

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113

(ii)

Use your diagram to explain why the reaction is faster in the presence of the iron
catalyst.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

(c)

A mixture of nitrogen and hvdro2en is kinetically stable at 25C but kinetically unstable
at 400C. Explain why this is so.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 13 marks)

49.

(a)

A sample of ammonia was dissolved in water to produce 100 cm of a solution, X.


3
3
3
10.0 cm of this solution was made up to a volume of 250 cm . 25.0 cm of this diluted
ammonia solution was then titrated with aqueous hydrochloric acid of concentration
3
3
0.110 mol dm . 37.10 cm of the acid was required to neutralise the ammonia solution.
Write an equation for the reaction between ammonia and hydrochloric acid, and calculate
the number of moles of ammonia in solution X. Calculate the concentration of solution X
3
in mol dm .
(5)

(b)

The above titration was repeated, but this time the pH was measured throughout the
3
titration until a total of 50 cm of aqueous hydrochloric acid had been added. Carefully
sketch the pH curve you would expect for this titration. Name an indicator suitable for the
titration and use the curve to justify your choice.
(7)

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114

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115

(c)

Suggest a chemical test to confirm the presence of ammonia in solution X.


(2)
(Total 14 marks)

50.

The quality of written communication will be assessed in this question. To gain full marks
you must explain your ideas clearly using equations and diagrams where appropriate.
This question is about the reaction sequence shown below

(a)

Compound A has the composition, by mass, 70.5% carbon, 13.7% hydrogen and 15.8%
oxygen. Show that this percentage composition is consistent with the molecular formula
C6H14O.

(2)

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116

(b)

Deduce the displayed formula for A showing how you used each of the following pieces
of information.
1

Infra-red spectrum.

Mass spectrum.

On dehydration, only a single isomer B can be formed.

(6)

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117

Sri Lankan School

Infra-red spectrum of A.

118

(c)

A simplified mass spectrum of A.

By drawing part of the chain formed from two monomer units, show the structural
formula of the polymer C.

(1)

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119

(d)

Both compounds D and E are chiral and compound E is an isomer of compound A.


(i)

Draw diagrams to show the two optical isomers of compound D and suggest how
they could be distinguished.

..........................................................................................................................
..........................................................................................................................
(2)

(ii)

Give the systematic name for compound E.


..........................................................................................................................
(1)

(e)

Would you expect the conversion of compound D to compound E to be a first or second


order reaction? Justify your answer.
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
(2)

(f)

Name the THREE oxidation products obtainable from compounds A and E.


.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
(2)
(Total 16 marks)

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120

Sri Lankan School

121

51.

Nitrogen and phosphorus are in the same group of the Periodic Table. Phosphorus and hydrogen
form the compound phosphine, PH3, and nitrogen and hydrogen form ammonia, NH3.
(a)

(i)

State the number of bond pairs and lone pairs of electrons in a molecule of
phosphine.
Bond pairs of electrons: ..................... Lone pairs of electrons: ....................
(2)

(ii)

Use your answer to (i) to draw the shape of the molecule and indicate on your
diagram the approximate HPH bond angle that you would expect.

(2)

(b)

The boiling temperature of ammonia is 33 C and that of phosphine 88C.


(i)

List all the intermolecular forces that exist between molecules of ammonia.
....
....
....
....
(2)

(ii)

Explain why the boiling temperature of phosphine is lower than that for ammonia.
....
....
....
....
(2)

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122

(c)

Ammonia forms a dative covalent bond with H ions to form the ammonium ion, NH4 .
(i)

Explain what is meant by the term dative covalent bond.


....
....
(2)

(ii)

What part of the ammonia molecule enables it to form such a bond?


....
(1)

(iii)

State and explain the shape of the ammonium ion, NH4 .


....
(3)
(Total 14 marks)

52.

This question is about phenol and benzoic acid, which are acidic, and benzaldehyde,
which is neutral.

Ka = 1.28 10

(a)

10

mol dm

Ka = 6.3 10 mol dm

Which is the stronger acid, phenol or benzoic acid?


Justify your choice.
.....................................................................................................................................
.....................................................................................................................................
(1)

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123

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124

(b)

Suggest chemical tests, with results, which would distinguish each of these compounds
from the others.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)

(c)

Benzoic acid can be distinguished from benzaldehyde by examining infra-red spectra.


Suggest how the infra-red spectra of these compounds could be used to distinguish
between them. You are not expected to give actual absorption values, but you should
indicate the bonds in the molecules which would give rise to the distinguishing
absorptions.
Benzoic acid ................................................................................................................
......................................................................................................................................
Benzaldehyde ..............................................................................................................
......................................................................................................................................
(2)

(d)

(i)

Write an equation for the dissociation of benzoic acid in aqueous solution.

(1)

(ii)

Write an expression for the dissociation constant of benzoic acid in terms of the
appropriate equilibrium concentrations.
Ka =

Sri Lankan School

125

(1)

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126

(iii)

Calculate the pH of a 0.010 mol dm solution of benzoic acid in water.


You should make the usual two simplifying assumptions.

(3)

(iv)

State ONE of the assumptions that you made in your calculation in (d)(iii).
............................................................................................................................
............................................................................................................................
(1)

(e)

Under suitable conditions phenol reacts with benzoic anhydride, (C 6H5CO)2O, to form an
ester.
(i)

What are the conditions?


............................................................................................................................
(1)

(ii)

Give the name and structural formula for this ester.


Name ................................................................................................................
Structural formula

(2)

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127

(f)

Esters are often used in perfumes.


Suggest TWO properties, apart from smell, which need to be considered for an ester to be
suitable for use in a perfume.
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 19 marks)

53.

Methane, CH4, chloromethane, CH3Cl, and methanol, CH3OH, have molecules with similar
shapes but they have different boiling temperatures.
Compound

(a)

Boiling temperature
/C

Methane

162

Chloromethane

24

Methanol

+65

Draw a dot and cross diagram to show the bonding in chloromethane. You need only
draw the outer electrons of the atoms.

(2)

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128

(b)

Draw a diagram to show the shape of the chloromethane molecule and explain why it has
this shape.

.................................................................................................................................
................................................................................................................................
(2)

(c)

Explain why the boiling temperature of chloromethane is higher than that of methane.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)

(d)

Explain why the boiling temperature of methanol is higher than that of chloromethane.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(3)
(Total 11 marks)

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129

54.

(a)

The acid dissociation constant, Ka for ethanoic acid is 1.80 10 mol dm .


(i)

Write an equation for the dissociation of aqueous ethanoic acid.


......................................................................................................................
(1)

(ii)

Give the expression for the acid dissociation constant, Ka, for aqueous ethanoic
acid.

(1)

(iii)

Calculate the pH of 2.00 mol dm ethanoic acid.

(3)

(b)

When ethanoic acid and propan-1-ol are heated together in the presence of a little
concentrated sulphuric acid an ester is produced.
(i)

Draw the structural formula of the ester produced in this reaction.

(2)

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130

(ii)

Give the name of the ester.


......................................................................................................................
(1)

(iii)

State the function of the sulphuric acid.


......................................................................................................................
(1)

(c)

6.00g of ethanoic acid was mixed with 6.00g of propan-1-ol and 0.00100mol of
concentrated sulphuric acid was added. The mixture was heated under reflux until no
further reaction was detectable. The mixture was then cooled rapidly to room temperature
3
3

and titrated with 1.00 mol dm sodium hydroxide solution. 35.0 cm of the 1.00 mol dm
3
sodium hydroxide solution was required for complete neutralisation.
(i)

Calculate the volume of sodium hydroxide solution that would have been needed if
only the 0.00100mol of concentrated sulphuric acid had been in the flask.

(2)

(ii)

Calculate the volume of sodium hydroxide solution that must have been needed to
react with the ethanoic acid remaining in the cooled mixture.

(1)

(iii)

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Calculate the amount (in moles) of ethanoic acid remaining.

131

(1)

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132

(iv)

Hence, calculate the amount (in moles) of propan-1-ol, ester and water in the final
cooled mixture.

(3)

(v)

Calculate the value of the equilibrium constant under these conditions. The
3
volume of the reaction mixture should be taken as 100 cm .

(2)

(d)

The reverse of esterification is hydrolysis. In experiments to study the hydrolysis of this


ester with aqueous sodium hydroxide, the following data were obtained.
Concentration of
ester
3
/mol dm

Concentration of
sodium
hydroxide
3
/mol dm

0.1

1.0

6 10

0.1

2.0

1.2 10

0.2

2.0

2.4 10

Experiment

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Rate of
reaction

/mol dm
3 1
s
4

133

(i)

Determine the order of the reaction with respect to the:


ester;..............................................................................................................
(1)

sodium hydroxide...........................................................................................
(1)

(ii)

Calculate the value of the rate constant, k, for this reaction including its units.

(3)
(Total 23 marks)

55.

The manufacture of ammonia is an important industrial process based on the equilibrium


N2 + 3H2
(a)

2NH3

DH = 92.4 kJ mol

Explain the meaning of the term dynamic equilibrium.


.................................................................................................................................
.................................................................................................................................
................................................................................................................................
(2)

(b)

Explain why raising the equilibrium temperature results in less ammonia being produced.
.................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)

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134

(c)

State why, despite the lower yield of ammonia, the industrial process operates at about
450C.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)

(d)

How is ammonia removed from the mixture of gases?


...............................................................................................................................
(1)

(e)

(i)

Give the meaning of the term catalyst.


......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(ii)

Draw an energy level diagram (energy profile) for the reaction with and without a
catalyst and use it to explain how a catalyst works.

E n e rg y

......................................................................................................................
......................................................................................................................
......................................................................................................................
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135

(4)

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136

(iii)

State the effect of the presence of a catalyst on the yield of ammonia.


......................................................................................................................
(1)

(f)

Give one large scale use of ammonia.


................................................................................................................................
................................................................................................................................
(1)

(g)

The first stage in the conversion of ammonia to nitric acid involves mixing it with hot air
and passing the mixture over a catalyst.
Complete the equation for the first stage.
.... NH3 +.... O2 .... NO + .... H2O
(1)

(h)

The next stage involves the conversion of NO to nitrogen dioxide, NO by adding cold
air.
(i)

Write an equation for this conversion.


......................................................................................................................
(1)

(ii)

Suggest why the temperature must be lowered at this point.


......................................................................................................................
......................................................................................................................
(1)
(Total 16 marks)

56.

(a)

When solid sodium nitrate is heated with concentrated sulphuric acid the reaction shown
below occurs:

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NaNO3 + H2SO4

HNO3 + NaHSO4

..........

..........

..........

..........

137

(i)

Identify the two conjugate acid-base pairs in this reaction. Write your answer in
the spaces below the equation.
(2)

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138

(ii)

The nitric acid produced is evolved as a gas under these conditions. Explain the
effect of this on the position of equilibrium on heating the mixture in an open
container.
......................................................................................................................
......................................................................................................................
(2)

(iii)

Nitric acid molecules in the vapour phase can be represented as


O

O H

Draw a diagram of the likely shape of this molecule and justify your prediction.

......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

(b)

Dilute sulphuric acid is a strong acid but very concentrated sulphuric acid is weak acid.
Explain the meanings of the terms weak and dilute as applied to acids.
Weak.......................................................................................................................
................................................................................................................................
Dilute.......................................................................................................................
................................................................................................................................
(2)

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139

(c)

Heating solid sodium nitrate, NaNO3, to decomposition requires a temperature of about


550C and produces oxygen as the only gaseous product. Solid magnesium nitrate,
Mg(NO3)2, decomposes on heating at a much lower temperature.
(i)

Write an equation for the decomposition of sodium nitrate.


......................................................................................................................
(1)

(ii)

Relate the ease of decomposition of the two nitrates to the relative sizes and
charges of the cations.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 13 marks)

57.

(a)

Phosgene, COCl2, was used in the First World War as a poison gas. It can be prepared by
reacting carbon monoxide with chlorine.
CO(g) + Cl2(g)

COCl2(g)

DH = 112 kJ mol

1.0 mol of carbon monoxide and 1.0 mol of chlorine were placed in a vessel and heated to
200 C. When equilibrium had been reached, it was found that the total pressure was
1.3 atm and that 85% of the carbon monoxide had reacted.

(i)

Write the expression for Kp.

(1)

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140

(ii)

Calculate the value of Kp, stating its units.

(5)

(iii)

State and explain the effect that an increase in temperature would have on the value
of the equilibrium constant.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(b)

The bond enthalpy of the bonds in carbon monoxide is +1065 kJ mol . The average C
1
1
O bond enthalpy is +360 kJ mol and that of C==O is +743 kJ mol . Use these data to
suggest the number of bonds in carbon monoxide.

(1)

(c)

Both phosgene and ethanoyl chloride, CH3COCl, contain a C==O group. Suggest an
equation for the reaction of phosgene with excess ammonia.
................................................................................................................................
(2)

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141

(d)

The following reactions are those of compounds containing the C==O group. Draw the
structural formulae of the organic products of the reactions between:
(i)

ethanamide and bromine followed by the addition of sodium hydroxide solution,

(1)

(ii)

ethanamide and phosphorus(V) oxide, P4O10,

(1)

(iii)

propanal and hydrogen cyanide in the presence of a trace of alkali.

(1)

(e)

Draw the stereoisomers of the product in (d)(iii).

(1)
(Total 15 marks)

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142

58.

(a)

Benzocaine, C9H11O2N, is an aromatic compound which is used commercially in creams


to alleviate sunburn.
+

Benzocaine reacts with dilute acids to form the ion C 9H12O2N and with ethanoyl
chloride to form C11H13O3N.
When benzocaine is heated under reflux with aqueous sodium hydroxide and the
solution obtained is neutralised, two compounds X and Y are formed.
X has a formula of C7H7O2N and is a solid with a melting temperature of 190 C. It is
soluble in water.
Y is a volatile liquid with a formula C2H6O which gives steamy fumes with
phosphorus pentachloride.
X reacts with sodium hydrogencarbonate solution to give a gas which turns lime water
milky. It also reacts with a solution of sodium nitrite and hydrochloric acid between 0
C and 5 C to produce a substance which reacts with phenol to give an orange
precipitate, Z.

These reactions are summarised as follows.

C 9H

12O 2

H + (a q )

C 9 H 11 O 2 N
B e n z o c a in e

C H 3C O Cl

11

13O 3

1 . N a O H ( a q ) h e a t/r e f lu x
2 . H C l(a q ) u n til n e u tra l
C 7H 7O 2N
X
N a H C O 3 (a q )

C 7H 6O 2N N a

(i)

C 2 H 6O
Y

1 . H N O 2 b e tw e e n 0 C a n d 5 C
2. phenol
o ra n g e p p t. Z

Deduce a structural formula for benzocaine and explain its three reactions shown
above. You may either describe the types of reaction or write the equations for the
reactions.
(6)

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143

(ii)

Write equations for the two reactions of X. Include in your answer the structural
formula of Z.
(3)

(iii)

Explain why substance X has a fairly high melting temperature and why it is
soluble in water.
(3)

(b)

Substance X is a weak monobasic acid and for the purpose of the remainder of this
question you may write its formula as HA.
X has a relative molecular mass of 137, with a pKa value of 4.92 at 25 C.
(i)

Calculate the pH of a solution containing 21.37g of X per dm at a temperature of


25 C.
(4)

(ii)

50.0 cm of this solution was mixed with 50.0 cm of a 0.100 mol dm solution of
sodium hydroxide. Calculate the concentration of the salt of X produced, and the
concentration of the acid X left unreacted.
Hence calculate the pH of the mixed solution.
(4)

(c)

The standard enthalpy change at 25 C for the neutralisation of a strong acid by a strong
1
base is 57.2 kJ mol .
The standard enthalpy change for the ionisation of the weak acid HA in water is
1
+8.3 kJ mol .
(i)

Write the ionic equation for the neutralisation of a strong acid by a strong base and
hence calculate the standard enthalpy of neutralisation of the acid HA.
(3)

(ii)

State and explain how the value of Ka of the acid X and hence the pH of the
solution in (b)(i) would change if the temperature of the solution were increased.
(2)
(Total 25 marks)

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144

59.

Consider the following data for the hydrides of the Group 4 elements.

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element

formula
of
hy
dri
de

boiling
temperat
ure
/K

relative
molecul
ar
mass

carbon

CH4

109

16

silicon

SiH4

161

32

germanium

GeH4

185

77

tin

SnH4

221

123

lead

PbH4

145

(a)

Represent the trend in the boiling temperature with relative molecular mass for these
hydrides.

350
B o ilin g
te m p e ra tu re
/K
300

250

200

150

100

50

50

100

150

200

250

R e la tiv e m o le c u la r m a s s

(2)

(b)

(i)

Account for the increase in boiling temperature as the relative molecular mass
increases.
............................................................................................................................
............................................................................................................................
(2)

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146

(ii)

Use your diagram in (a) to suggest a likely value for the boiling temperature of
PbH4.
............................................................................................................................
(1)

(iii)

PbH4 is actually thermally unstable and unlikely to have the boiling temperature
you have suggested. Suggest why PbH4 is thermally unstable
............................................................................................................................
............................................................................................................................
(2)

(c)

Predict the shape of a molecule of SiH4 and justify your prediction.

.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(d)

(i)

Define the term first ionisation energy.


............................................................................................................................
............................................................................................................................
(2)

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147

(ii)

The successive ionisation energies of silicon are given in the table below.
number of ionisation

ionisation energy/kJ
-1
mol

789

1580

3230

4360

16100

19800

23800

29200

33900

10

38800

11

45900

12

505000

13

235000

14

258000

Use these data to deduce the electronic structure of silicon.


............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(Total 14 marks)

60.

(a)

Propan-1ol, C2H5CH2OH can be oxidised to propanoic acid, C2H5COOH.


(i)

State the names of the reagents necessary for this conversion.


............................................................................................................................
............................................................................................................................
(2)

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148

(ii)

5.67 of propan-1-o1 was oxidised in a reaction with a 64% yield. Calculate the
mass of propanoic acid produced.

(3)

(b)

Propanoic acid is a weak acid. It ionises according to the equation:


C2H5COOH(aq)+H2O(l)

(i)

C2H5COO (aq) + H3O (aq)

DH

= +6kJ mol

State and explain the effect on the position of this equilibrium of:
an increase in temperature;
............................................................................................................................
............................................................................................................................
(2)

an addition of solid sodium propanoate.


............................................................................................................................
............................................................................................................................
(2)

(ii)

How does the addition of sodium propanoate affect the pH of the solution of
propanoic acid?
............................................................................................................................
(1)

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149

(c)

(i)

Sketch, with reasonable accuracy, how the pH changes during the titration of
3
25cm of a weak acid, such as propanoic acid, with sodium hydroxide solution of
the same concentration.

14
12
10
pH

8
6
4
2
0

10

20

30

40

50

v o lu m e N a O H /c m

(ii)

The table contains some data about three indicators.


Indicator

pKind

Acid colour

Alkaline
colour

Bromophenol blue

4.0

yellow

blue

Bromothymol blue

7.0

yellow

blue

Thymol blue

8.9

yellow

blue

State which of these indicators would be best for this titration. Give a reason for
your choice.
Indicator ...........................................................................................................
Reason ..............................................................................................................
...........................................................................................................................
(2)

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150

(d)

The standard enthalpy change of neutralisation of some acids with sodium hydroxide is
tabulated below:
Acid

(i)

DH /kJ
1
mol

Propanoic acid, C2H5COOH

51

Hydrocyanic acid, HCN

12

Hydrochloric acid, HCl

57

Nitric acid, HNO3

57

Why are the values for the enthalpy change of neutralisation of the two strong
acids the same?
..........................................................................................................................
..........................................................................................................................
(1)

(ii)

Why is the enthalpy change of neutralisation of hydrocyanic acid so much less than
that of hydrochloric acid?
..........................................................................................................................
..........................................................................................................................
(2)
(Total 19 marks)

61.

(a)

Some standard enthalpy change of combustion values are listed below:


Substance

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DH /kJ
1
mol

C (graphite)

393.5

H2(g)

285.8

ethane C2H6(g)

1560.0

151

(i)

Define standard enthalpy change of combustion


............................................................................................................................
............................................................................................................................
(2)

(ii)

Complete the following thermochemical equation for the standard enthalpy change
of combustion of ethane.
..C2H6(..)+..O2(..) ..CO2(..)+..H2O(..)

DH

=............................................
(3)

(iii)

Use the data to calculate the standard enthalpy change of formation of ethane.
Draw a Hesss Law cycle as part of your answer.

(3)

(b)

Consider the reaction


C2H6(g) + Cl2(g) C2H5Cl(g) + HCl(g)

DH

= 112.6 kJ mol

This reaction does not proceed at room temperature in the absence of light, but reacts
rapidly when exposed to a bright light. Use these facts to illustrate the concept of
thermodynamic and kinetic stability.
Thermodynamic stability ...........................................................................................
....................................................................................................................................
Kinetic stability .........................................................................................................
....................................................................................................................................
(2)

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152

(c)

Ethane and chlorine react in a homolytic free radical substitution reaction when
exposed to light. The two propagation steps are

H
C H

step 2

(i)

C l

C H

step 1:

C H

C
H

C l

C l

C H

Cl

C l

Cl

Explain the meaning of the term free radical.


............................................................................................................................
(1)

(ii)

Explain the meaning of the term substitution reaction.


............................................................................................................................
(1)

(iii)

Explain the movement of the C-H bond electron pair in step 1.


.........................................................................................................................
.........................................................................................................................
(2)

(iv)

Give an example of a possible termination step in this reaction.


.........................................................................................................................
(1)

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153

(d)

The reaction of ethane with bromine proceeds in a similar way. Given the following
1
average bond enthalpies in kJ mol
CH + 412

HBr + 366

calculate the enthalpy change for step 1 of the reaction involving bromine.

(2)

(e)

The product of bromination of ethane is bromoethane. This reacts with potassium


cyanide in a solution of ethanol and water. The rate of this reaction was studied and the
results are given below.
Experiment

[CN ]/mol dm

[C2H5Br]/mol
3

dm

Initial rate/mol dm
3 1
s

0.060

0.020

1.0 10

0.060

0.040

2.0 10

0.120

0.020

2.0 10

Deduce, showing your reasoning, the rate equation.

(3)

(f)

Two routes can be suggested for the reaction in (e).


Route 1

CN

+ C H 3C H 2B r

H
C H 3
N C .... C .......... B r

C H 3CH 2C N + Br

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154

Route II

C H 3C H 2B r

s lo w

then C H 3 C H

(i)

+
2

C H 3C H
+ CN

fast

+
2

+ B r
CH 3CH 2CN

Explain which route is consistent with the rate equation in (e).


...........................................................................................................................
...........................................................................................................................
(1)

(ii)

This exothermic reaction is catalysed by iodide ions. Draw the enthalpy level
diagram for both the uncatalysed reaction, labelling each clearly.

e n th a lp y

(3)
(Total 24 marks)

62.

(a)

Consider the homogeneous equilibrium


PCl5(g)

(i)

PCl3(g) + Cl2(g)

What is meant by homogeneous equilibrium?


(1)

(ii)

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Write an expression for Kp for this equilibrium including units.

155

(2)

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156

(iii)

Given that PCl5 is 33% dissociated at 700 K and 1.1 atm total pressure, find the
value of Kp under these conditions.
(3)

(iv)

The enthalpy of formation of PCl5(g) is 399kJ mol , and that for PCl3(g) is
1

306kJmol . Find DH for the forward reaction.


(2)

(v)

State and explain the effect on the equilibrium position of this reaction if the
temperature were to be increased.
(2)

(c)

Phosphorus pentachloride also reacts with alcohols, but cannot be used as a definitive
qualitative test for them. Why is the reaction of alcohols with phosphorus pentachloride
not a definitive test?
(1)

(d)

Other phosphorus halides, such as phosphorus tri-iodide, are used to make


halogenoalkanes from alcohols.
Write the equation for the reaction between phosphorus tri-iodide and ethanol.
(2)

(e)

Chloroalkanes can be made from alcohols and sodium chloride in 50% aqueous sulphuric
acid. A similar reaction is unsuitable for the production of iodoalkanes using sodium
iodide. By comparison of the reactions of sodium chloride and sodium iodide with
sulphuric acid, explain why this is so.
(4)
(Total 17 marks)

63.

Sorbic acid has the formula


CH3CH=CHCH=CHCOOH
Together with its potassium salt sorbic acid is used in foodstuffs as an inhibitor of fungal and
mould growth.

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157

Sri Lankan School

158

(a)

Sorbic acid can show geometric isomerism.


(i)

Explain carefully why sorbic acid shows geometric isomerism.


(2)

(ii)

State, with a reason, the number of geometric isomers that sorbic acid has.
(2)

(b)

Sorbic acid and potassium sorbate together form a buffer system.


(i)

What is a buffer system?


(2)

(ii)

Write the chemical equations that are relevant to the functioning of the mixture as a
buffer, and use them to explain how buffering action arises. You may represent
sorbic acid as RCOOH and potassium sorbate as RCOOK.
(5)

(c)

Sorbic acid will react with a solution of bromine in tetrachloromethane.


(i)

Write an equation for the complete reaction of sorbic acid with bromine.
(1)

(ii)

A 7.00g sample of sorbic acid was reacted with a solution of bromine in


3
tetrachloromethane; 125cm of the solution was required. Calculate the
3
concentration of the bromine solution in mod dm .
(4)

(d)

The bromine-containing product from (c)(i) can be reacted with sodium hydroxide in
aqueous ethanol to give a substitution reaction.
(i)

Explain why aqueous ethanol is used as the solvent rather than, say, ethanol alone.
(2)

(ii)

Write the structural formula of the product.


(1)

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159

(e)

Potassium sorbate can function as a soap.


(i)

Explain why this is so.


(1)

(ii)

Soaps are in general made by the alkaline hydrolysis of fats. Write an equation to
illustrate this reaction.
(3)
(Total 25 marks)

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160