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Edexcel Chemistry Unit 4 Exams Questions

Edexcel Chemistry Unit 4 Exams Questions

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1.

(a) When solid calcium nitrate is heated, brown fumes of nitrogen dioxide, NO
2
, are seen and
the solid remaining after decomposition is calcium oxide.
(i) Write a balanced equation for the thermal decomposition of calcium nitrate.
.........................................................................................................................
(2)

(ii) Describe the changes you would see when cold water is added drop by drop to cold
calcium oxide and give the chemical equation for the reaction.
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
(3)

(iii) State whether barium nitrate will decompose more easily or less easily than
calcium nitrate on heating with a Bunsen burner.
.........................................................................................................................
(1)

(iv) Account for the trend in the thermal stability of the nitrates of the elements in
group 2.
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
(3)

(b) The brown fumes in part (a) are not pure NO
2
but a mixture of N
2
O
4
and NO
2.

N
2
O
4
(g) 2NO
2
(g)
Pale yellow dark brown
A transparent glass syringe was filled with the gaseous mixture of N
2
O
4
and NO
2
and its
tip sealed. When the piston of the syringe was rapidly pushed well into the body of the
syringe, thereby compressing the gas mixture considerably, the colour of the gas became
momentarily darker but them became lighter again.


(i) Suggest why compressing the gases causes the mixture to darken.
.........................................................................................................................
.........................................................................................................................
(1)

(ii) Explain why the mixture turns lighter on standing.
.........................................................................................................................
.........................................................................................................................
.........................................................................................................................
(2)

(iii) Write an expression for the equilibrium constant, K
p
, for this equilibrium.


(1)

(iv) 1.0 mole of N
2
O
4
was allowed to reach equilibrium at 400K. At equilibrium the
partial pressure of N
2
O
4
was found to be 0.15 atm.
Given that the equilibrium constant K
p
for this reaction is 48 atm, calculate the
partial pressure of NO
2
in the equilibrium mixture.


(3)
(Total 16 marks)



2. Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays
fatigue in muscles, thus allowing people to show great strength under stress.
Benzedrine is a pharmaceutical which stimulates the central nervous system in a similar manner
to adrenalin.
CH CH(CH ) NH
2 2 2 3 3
HO
HO CH(OH) CH N
H
CH
Benzedrine Adrenalin


(a) (i) On the structure for benzedrine mark with a (
*
) any asymmetric carbon atom that
causes chirality.
(1)

(ii) Suggest why adrenalin is more soluble in water than is benzedrine.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)

(b) Give the structural formulae of the organic products obtained when benzedrine reacts
with:
(i) an aqueous acid such as dilute hydrochloric acid;

(1)

(ii) ethanoyl chloride in the absence of a catalyst;

(1)

(iii) excess ethanoyl chloride in the presence of the catalyst anhydrous aluminium
chloride.

(2)


(d) It is possible to eliminate a molecule of water from adrenalin which for the purpose of
this question may be represented as R–CH(OH)–CH
2
–NH–CH
3.
Draw the structural
formulae of the two stereoisomers produced.


(2)

(e) The mass spectra of both benzedrine and adrenalin have a peak at a mass/charge ratio of
44. Draw the structure of the species which give these peaks.
(i) in benzedrine;

(1)

(ii) in adrenalin.

(1)
(Total 11 marks)


3. (a) (i) Calculate the concentration, in mol dm
–3
, of a solution of hydrochloric acid, HCl,
which has a pH of 1.13.




(1)


(ii) Calculate the concentration, in mol dm
–3
, of a solution of chloric(l) acid, HOCl,
which has a pH of 4.23.
Chloric(l) acid is a weak acid with K
a
= 3.72 × 10
–8
mol dm
–3
.






(4)

(b) The pH of 0.100 mol dm
–3
sulphuric acid is 0.98.
(i) Calculate the concentration of hydrogen ions, H
+
, in this solution.


(1)

(ii) Write equations to show the two successive ionisations of sulphuric acid, H
2
SO
4
, in
water.
......................................................................................................................
......................................................................................................................
(2)

(iii) Suggest why the concentration of hydrogen ions is not 0.20 mol dm
–3
in 0.100 mol
dm
–3
sulphuric acid.
......................................................................................................................
......................................................................................................................
(1)


(c) Many industrial organic reactions produce hydrogen chloride as an additional product.
This can be oxidised to chlorine by the Deacon process:
4HCl(g) + O
2
(g) 2Cl
2
(g) + 2H
2
O(g) AH = –115 kJ mol
–1
.
0.800 mol of hydrogen chloride was mixed with 0.200 mol of oxygen in a vessel of
volume 10.0 dm
3
in the presence of a copper(I) chloride catalyst at 400 ºC. At
equilibrium it was found that the mixture contained 0.200 mol of hydrogen chloride.
(i) Write an expression for the equilibrium constant K
c
.


(1)

(ii) Calculate the value of K
c
at 400 ºC.






(4)

(d) State and explain the effect, if any, on the position of equilibrium in (c) of:
(i) decreasing the temperature;
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)


(ii) decreasing the volume;
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(iii) removing the catalyst.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(Total 20 marks)


4. This question concerns the three isomers A, B and C, each of which has a relative molecular
mass of 134.
C C
O
H
O
CH
CH CH OH
CH CH CH
CH
2
2
2 2 3
A B
C

(a) The mass spectrum of substance A is shown below. Identify the species responsible for
the peaks labelled 1, 2 and 3.
Peak 1 .........................................................................................................................
Peak 2 .........................................................................................................................
Peak 3 .........................................................................................................................
(3)


(b) The infra-red spectra of two of these substances were also measured.
(i) Use the table and the spectra below to identify which spectrum is that of
substance C.

Bond
Wavenumber
/ cm
–1


Bond
Wavenumber
/ cm
–1

C—H (arenes) 3000-3100 O––H (hydrogen bonded) 3200-3570
C—H (alkanes) 2850-3000 O––H (not hydrogen
bonded)
3580-3650
C==O 1680-1750 C==C (arenes) 1450-1600
The spectrum of substance C is spectrum number ..........................................
(1)

(ii) Give one reason for your choice.
......................................................................................................................
(1)

(iii) Give one other reason why the other spectrum could not be that of substance C.
......................................................................................................................
......................................................................................................................
(1)



100
80
60
40
20
0
R
e
l
a
t
i
v
e

i
n
t
e
n
s
i
t
y
25 50 75 100 125
m/e
1
2
3



100
50
0
4000 3000 2000 1500 1000
Wavenumber/cm
–1
T
r
a
n
s
m
i
t
t
a
n
c
e



100
50
0
4000 3000 2000 1500 1000
Wavenumber/cm
–1
T
r
a
n
s
m
i
t
t
a
n
c
e



(c) State which of the substances A, B and C will react with the following reagents and state
what would be observed.
(i) Bromine dissolved in hexane.
Substance(s) .....................................................................................................
Observation ......................................................................................................
(2)

(ii) A warm ammoniacal solution of silver nitrate.
Substance(s) .....................................................................................................
Observation ......................................................................................................
(2)

(iii) 2,4-dinitrophenylhydrazine solution.
Substance(s) .....................................................................................................
Observation ......................................................................................................
(3)

(iv) Give the structural formula of the organic product(s) obtained in (c)(i).




(1)


(v) Give the structural formula of the organic product(s) obtained in (c)(ii).




(1)
(Total 18 marks)


5. The kinetics of the hydrolysis of the halogenoalkane RCH
2
Cl with aqueous sodium hydroxide
(where R is an alkyl group) was studied at 50 ºC. The following results were obtained:
Experiment [RCH
2
Cl]
[OH

] Initial rate/mol dm
–3
s
–1

1 0.050 0.10
4.0 × 10
–4

2 0.15 0.10
1.2 × 10
–3

3 0.10 0.20
1.6 × 10
–3


(i) Deduce the order of reaction with respect to the halogenoalkane, RCH
2
Cl, and with
respect to the hydroxide ion, OH

, giving reasons for your answers.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)

(ii) Hence write the rate equation for the reaction.
................................................................................................................................
(1)


(iii) Calculate the value of the rate constant with its units for this reaction at 50 ºC.


(2)

(iv) Using your answer to part (ii), write the mechanism for this reaction.






(3)
(Total 10 marks)


6. The reaction between sulphur dioxide and oxygen is a dynamic equilibrium.
2SO
2
+ O
2
2SO
3
AH = –196 kJmol
–1
(a) Explain what is meant by dynamic equilibrium.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(2)


(b) In the table below state the effect on this reaction of increasing the temperature and of
increasing the pressure.
Effect on the rate of the
reaction
Effect on the position of
equilibrium
Increasing the
temperature
Increases
Increasing the pressure
(3)

(c) This reaction is one of the steps in the industrial production of sulphuric acid. The
normal operating conditions are a temperature of 450 °C, a pressure of 2 atmospheres
and the use of a catalyst.
Justify the use of these conditions.
(i) A temperature of 450 °C:
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)

(ii) A pressure of 2 atmospheres:
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)


(iii) A catalyst:
......................................................................................................................
......................................................................................................................
......................................................................................................................
(1)

(d) Give the name of the catalyst used.
..................................................................................................................................
(1)
(e) Give one large scale use of sulphuric acid.
..................................................................................................................................
(1)
(Total 13 marks)


7. (a) What is meant by the term weak acid?
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)

(b) A weak acid, represented by HA, dissociates in water according to the equation:
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A

(aq)
Write an expression for the dissociation constant, K
a
, for HA.


(1)


(c) 25 cm
3
of 1.00 mol dm
–3
aqueous HA, was titrated with 1.00 mol dm
–3
aqueous sodium
hydroxide and the pH measured throughout. The titration curve is shown below.
14
12
10
8
6
4
2
0
10 20 30 40 50
Volume of sodium hydroxide added / cm
pH
3


Use the titration curve to find:
(i) the value of the pH at the end point of the titration.
............................................................................................................................
(1)

(ii) the pH of an aqueous solution of the salt NaA.
............................................................................................................................
(1)

(iii) the value of pK
a
for the acid HA and, hence the value K
a
.
pK
a
...................................................................................................................
K
a
.....................................................................................................................
(2)


(d) Some of the solutions made during this titration would act as buffer solutions.
(i) What is meant by the term buffer solution?
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(ii) Use the titration curve to find:
the range of pH values over which this mixture acts as a buffer;
from .................................................... to ....................................................
(1)
the pH of the most efficient buffer solution.
............................................................................................................................
(1)

(e) Suggest, with reasoning, whether methyl orange or phenolphthalein would be the better
indicator for this titration.
Choice ........................................................................................................................
Reasoning ..................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)

(f) Explain why, as the titration proceeds, the flask becomes warm but not as warm as it
would in a similar titration using 1.00 mol dm
–3
solutions of hydrochloric acid and
sodium hydroxide.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)


(g) A different monobasic weak acid has a dissociation constant of 1.8 × 10


5
mol dm
–3
.
(i) Define pH.
............................................................................................................................
(1)

(ii) Calculate the pH of a 1.00 mol dm
–3
aqueous solution of this acid.






(3)
(Total 21 marks)


8. In the vapour phase sulphur trioxide dissociates:
2SO
3
(g) 2SO
2
(g) + O
2
(g)

(a) (i) Write an expression for K
p
for this dissociation.



(1)


(ii) At a particular temperature, 75% of the sulphur trioxide is dissociated, producing a
pressure of 10 atm. Calculate the value of K
p
at this temperature paying, attention
to its units.





(5)

(b) Solid vanadium(V) oxide, V
2
O
5
, is an effective catalyst for this reaction. State the effect
of using double the mass of catalyst on:
(i) the position of the equilibrium;
............................................................................................................................
............................................................................................................................
(1)

(ii) the value of K
p
.
............................................................................................................................
............................................................................................................................
(1)
(Total 8 marks)


9. (a) (i) Define the term standard enthalpy of combustion.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)


(ii) The values for the standard enthalpy of combustion of graphite and carbon
monoxide are given below:

AH
c
/kJ mol
–1

C (graphite) –394
CO(g) –283

Use these data to find the standard enthalpy change of formation of carbon
monoxide using a Hess‘s law cycle.
C(graphite) +
2
1
O
2
(g) ÷ CO(g)




(3)

(iii) Suggest why it is not possible to find the enthalpy of formation of carbon
monoxide directly.
............................................................................................................................
............................................................................................................................
(1)

(iv) Draw an enthalpy level diagram below for the formation of carbon monoxide from
graphite.




(1)


(b) Natural gas consists of methane, CH
4
. When methane burns completely in oxygen the
reaction occurs as shown in the equation
CH
4
(g) + 2O
2
(g) ÷ CO
2
(g) + 2H
2
O(l) AH
c
= –890 kJ mol
–1

Methane does not burn unless lit.
Use this information to explain the difference between thermodynamic and kinetic
stability.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(4)
(Total 12 marks)


10. (a) An alcohol with the molecular formula C
4
H
9
OH is chiral.
(i) Explain what is meant by the term chiral.
............................................................................................................................
............................................................................................................................
(2)

(ii) Draw two diagrams to clearly represent the optical isomers that result from the
chirality of this alcohol.





(2)


(iii) Explain how you could distinguish between these two isomers experimentally.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(b) Alcohols react with carboxylic acids to form esters.
(i) Write an equation for a typical esterification reaction.
............................................................................................................................
(1)

(ii) Suggest how this type of reaction could be used to form polyesters.
Experimental details are not required.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)

(iii) Suggest, with reasoning, whether a laboratory coat made from a polyester might be
damaged by a spillage on it of hot concentrated aqueous sodium hydroxide
solution.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(iv) Give another type of reagent that could be used to make an ester from an alcohol.
............................................................................................................................
(1)
(Total 13 marks)



11. (a) Methane reacts with steam in a reversible reaction. In industry this reaction, carried out at
a pressure of 30 atm, is used to produce hydrogen for the manufacture of ammonia
CH
4
(g) + H
2
O(g) CO(g) + 3H
2
(g) AH = +210 kJ mol
–1


(i) Define the term partial pressure as applied to a gas mixture.
............................................................................................................................
............................................................................................................................
(1)

(ii) Write an expression for the equilibrium constant, K
p
, for this reaction.





(1)

(iii) State and explain the effect of increasing the total pressure on the position of this
equilibrium;
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(b) State the effect on the value of K
p
for this equilibrium of the following.
(i) Increasing the total pressure.
............................................................................................................................
(1)


(ii) Increasing the temperature.
............................................................................................................................
(1)

(iii) Adding a catalyst.
............................................................................................................................
(1)

(c) There is a theory that methane, CH
4
, constantly leaks from the earth‘s crust. This is not
noticeable on land but at the bottom of a cold sea, such as off the Canadian coast, the
methane is trapped in a solid cage of water molecules.
CH
4
(g) + 6H
2
O(s) [CH
4
(H
2
O)
6
](s)
methane hydrate

At –29 °C the equilibrium pressure of the methane is 101.3 kPa.
(i) Write an expression for K
p
for this equilibrium.




(1)

(ii) Deduce the value of K
p
at –29 °C, stating its units.





(1)


(iii) At 0 °C the equilibrium pressure of methane rises to 2600 kPa. What does this tell
you about the effect of temperature change on the position of equilibrium and
about the enthalpy change for this reaction?
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(iv) Some people have suggested collecting the methane hydrate from the bottom of the
sea and allowing it to warm up to 0 °C on board a ship. Comment on whether this
would be a useful method for collecting methane.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(1)
(Total 12 marks)


12. Ethanoic acid, CH
3
COOH, is a weak acid which can be used, with its salts, to make buffer
solutions.
(a) Explain what is meant by the term weak acid.
....................................................................................................................................
....................................................................................................................................
(1)

(b) Explain what is meant by the term buffer solution.
....................................................................................................................................
....................................................................................................................................
(2)


(c) An aqueous solution of ethanoic acid of concentration 1.00 mol dm
–3
has a pH of 2.8.
Sketch, with care, how the pH changes during the titration of 25.0 cm
3
1.00 mol dm
–3

aqueous ethanoic acid with aqueous sodium hydroxide of the same concentration.
14
12
10
8
6
4
2
0
0 10 20 30 40 50
Volume of alkali added/cm
pH
3

(4)

(d) Indicate on your sketch the portion of the curve where the mixture is behaving as a buffer.
(1)

(e) (i) Write an expression for the dissociation constant, K
a
, for ethanoic acid.


(1)

(ii) Explain how the pKa of ethanoic could be found from the graph.
............................................................................................................................
............................................................................................................................
(2)
(Total 11 marks)



13. In an experiment to determine the rate of the reaction between persulphate ions and iodide ions
in aqueous solution
S
2
O
– 2
8
+ 2I

÷ 2SO
– 2
4
+ I
2

the following data were obtained:
Concentration/mol dm
S O
0.100
0.200
0.200
I
0.100 0.36
0.100 0.72
0.200 1.44
2 8
2–
–3
–3 –1

Initial rate
/mol dm s


(a) (i) Deduce the order of reaction with respect to each of the reagents and hence write
the rate equation for the reaction.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)

(ii) With reference to this reaction state what is meant by the overall order of a
reaction.
............................................................................................................................
............................................................................................................................
(1)

(iii) Calculate the rate constant including units.



(2)


(iv) Explain why the rate equation cannot be written directly from the stoichiometric
equation for the reaction.
............................................................................................................................
............................................................................................................................
(1)

(b) (i) Suggest a suitable experimental technique that would enable you to determine the
rate of the reaction given opposite.
............................................................................................................................
............................................................................................................................
(1)

(ii) Suggest a necessary condition that would help to ensure accurate results.
............................................................................................................................
(1)

(iii) Suggest one advantage or disadvantage of your chosen experimental method.
............................................................................................................................
............................................................................................................................
(1)
(Total 10 marks)


14. (a) The first stage in the manufacture of sulphuric acid is the Contact Process.
2SO
2
+ O
2
2SO
3

At 400 °C the equilibrium constant K
p
= 3.00 × 10
4
atm
–1
. A catalyst of vanadium(V)
oxide is used. In a particular equilibrium mixture at 400 °C the partial pressures of
sulphur dioxide and of oxygen were 0.100 atm and 0.500 atm respectively. Show that the
yield of SO
3
is about 95% of the equilibrium mixture.
(5)


(b) (i) Pure sulphuric acid is a viscous liquid with a high boiling temperature of
338 °C. It has the structure:
O
S
OH
OH
O

Suggest in terms of the intermolecular forces in sulphuric acid why it has such a
high boiling temperature.
(3)

(ii) Sulphuric acid dissolves in water in a highly exothermic reaction
May her rest be long and placid,
She added water to the acid;
The other girl did what we taught her,
And added acid to the water.
Suggest why sulphuric acid must always be added to water to dilute it rather than
the other way round.
(2)

(c) Sulphuric acid dissociates in water according to the equations:
H
2
SO
4
+ H
2
O ÷ H
3
O
+
+ HSO

4

HSO

4
+ H
2
O H
3
O
+
+ SO
– 2
4

The dissociation constant for the first dissociation is very large; that for the second is 0.01
mol dm
–3
at 25 °C.

(i) Calculate the pH of an aqueous solution containing 0.200 mol dm
–3
hydrogen ions.
(1)

(ii) The pH of 0.100 mol dm
–3
sulphuric acid is 0.98. Explain why this is so close to
the pH of 0.100 mol dm
–3
HCl which is 1.0.
(3)


(d) Sulphuric acid is used as the electrolyte in the lead-acid battery found in cars. The
electrodes are made from lead and from lead(IV) oxide. As the cell discharges, the lead
and the lead(IV) oxide are both converted to lead(II) sulphate, and the sulphuric acid
concentration falls.
(i) Use the information above to deduce the two half equations occurring in the lead
acid battery.
(3)

(ii) Hence write an equation to represent the overall process taking place as the cell
discharges.
(1)
(Total 18 marks)


15. (a) Define the following terms.
(i) pH .....................................................................................................................
(1)
(ii) K
w
......................................................................................................................
(1)

(b) Explain the meaning of the term strong, as applied to an acid or a base.
………………...……………….……………………………………………………..
………………...……………….……………………………………………………..
(1)

(c) Calculate the pH of the following solutions.
(i) HCl(aq) of concentration 0.200 mol dm
–3
.



(1)


(ii) NaOH (aq) of concentration 0.800 mol dm
–3
(K
w
= – 1.00 × 10
–14
mol
2
dm
–6
).



(2)

(d) HA is a weak acid with a dissociation constant K
a
= 5.62 × 10
–5
mol dm
–3
.
(i) Write an expression for the dissociation constant, K
a
, of HA.




(1)

(ii) Calculate the pH of a 0.400 mol dm
–3
solution of HA.




(3)


(e) A buffer solution contains HA(aq) at a concentration of 0.300 mol dm
–3
, and its sodium
salt, NaA, at a concentration of 0.600 mol dm
–3
. Calculate the pH of this buffer solution.





(3)
(Total 13 marks)


16. Consider the following equation:
2SO
2
+ O
2
2SO
3

2.0 moles of SO
2
and 1.0 mole of O
2
were allowed to react in a vessel of volume 60 dm
3
.
At equilibrium 1.8 moles of SO
3
had formed and the pressure in the flask was 2 atm.
(a) (i) Write the expression for K
c
for this reaction between SO
2
and O
2
.


(1)

(ii) Calculate the value of K
c
, with units.






(3)


(b) The reaction between SO
2
and O
2
is exothermic. State the effect on the following, if the
experiment is repeated at a higher temperature:
(i) K
c
……………………………………………………………………………..
(1)

(ii) the equilibrium position ....................................................................................
(1)

(c) State the effect of a catalyst on:
(i) K
c
……………………………………………………………………………..
(1)

(ii) the equilibrium position ....................................................................................
(1)

(d) (i) Write the expression for K
p
for the reaction between SO
2
and O
2
.



(1)

(ii) Calculate the mole fractions of SO
2
, O
2
and SO
3
at equilibrium.



(2)


(iii) Calculate the partial pressures of SO
2
, O
2
and SO
3
at equilibrium.



(1)

(iv) Calculate the value of K
p
, with units.



(2)
(Total 14 marks)


17. (a) (i) Explain what is meant by the following terms.
Rate of reaction ………………………………………………………………
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
Overall order of a reaction ................................................................................
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(2)

(ii) Explain why the order of reaction cannot be deduced from the stoichiometric
equation for a reaction.
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(1)


(b) Substitution reactions of halogenoalkanes, can proceed via an S
N
1 or S
N
2 mechanism.
When 1-bromobutane, CH
3
CH
2
CH
2
CH
2
Br, 2-bromobutane, CH
3
CH
2
CHBrCH
3
, and
2-bromo-2-methylpropane, (CH
3
)
3
CBr, are reacted separately with aqueous sodium
hydroxide solution each gives the corresponding alcohol.
(i) Give the mechanism for the S
N
1 reaction between 2-bromobutane and
hydroxide ions.





(3)

(ii) Explain why the product mixture is not optically active.
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(2)

(iii) In an experiment designed to find the mechanism of the reaction between 2-bromo-
2-methylpropane and hydroxide ions the following data were obtained at constant
temperature.
Initial concentration of
2-bromo-2-methylpropane
/mol dm
–3

Initial concentration of
OH

/ mol dm
–3

Initial rate of reaction
/mol dm
–3
s
–1

0.10 0.10
1.2 × 10
–2

0.20 0.10
2.4 × 10
–2

0.30 0.20
3.6 × 10
–2



Use the data to deduce the rate equation for the reaction of 2-bromo-2-
methylpropane with sodium hydroxide solution.
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(3)

(c) Suggest, in outline, a method you could use to follow the progress of the reaction between
a bromoalkane and aqueous sodium hydroxide.
………………………...……………….………………….…………………………..
………………………...……………….………………….…………………………..
………………………...……………….………………….…………………………..
………………………...……………….………………….…………………………..
………………………...……………….………………….…………………………..
………………………...……………….………………….…………………………..
(3)
(Total 14 marks)


18. The pain-relieving drug ibuprofen has the formula
C C CH
CH CH
CO H CH
H H
3 3
2
2 3

(a) A molecule of this compound is chiral. Explain, with the aid of diagrams, how two
optical isomers result from chiral a centre. Identify the chiral centre in such a molecule
and explain how these isomers could be distinguished from each other.
(4)


(b) Compounds A and B, shown below, are used as intermediates in the manufacture of
ibuprofen.
C C C C CH CH
CH CH CH CH
OH CH CH
O H H H
3 3 3 3
2 2
3 3
A B


(i) Suggest how infra-red spectroscopy could be used to identify an impurity in a
sample of ibuprofen which is known to be one of these two compounds.
A table of infra-red absorbencies is given below.
Bond Assignment
Wavenumbers/cm
–1

C-H alkanes
alkenes, arenes
2850 - 2950
3000 - 3100
benzene ring arenes 1450 - 1650
C=O aldehydes, ketones, esters,
carboxylic acids
1680 - 1750
O-H free
hydrogen bonded in alcohols or phenols
hydrogen bonded in carboxylic acids
3580 - 3670
3230 - 3550
2500 - 3300
(3)

(ii) Suggest a simple chemical test which would distinguish between A and B.
(2)

(iii) Treatment of either A or B if heated with a mixture of aqueous sodium hydroxide
and potassium manganate(VII) solution would produce the same compound.
Suggest the structure of this compound.
(2)


(c) A tablet of ibuprofen contains a very small quantity of the drug and the remainder of the
tablet material is unreactive.
In an analysis 50 tablets were reacted with 100.0 cm
3
of 1.00 mol dm
–3
aqueous sodium
hydroxide, an excess. The ibuprofen reacted as a weak acid. When the reaction was
complete, the remaining aqueous sodium hydroxide was titrated with 2.00 mol dm
–3

hydrochloric acid. 25.75 cm
3
of the acid were required for neutralisation.
(i) Calculate the mass, in mg, of ibuprofen in each tablet.
(M
r
for ibuprofen = 206)
(5)

(ii) Calculate the number of molecules of ibuprofen that this tablet represents.
(Avogadro constant h = 6.023 × 10
23
mol
–1
)
(2)

(d) Ibuprofen is almost insoluble in aqueous solutions at pH 3 but if the pH is raised to 8 then
the ibuprofen becomes reasonably soluble. Account for these observations.
(4)

(e) Under the appropriate conditions ibuprofen reacts with ethanol to produce a substance
with a characteristic odour. Identify the functional group in ibuprofen that would react
with the ethanol. Suggest the conditions needed for the reaction to take place and identify
the product.
(3)
(Total 25 marks)


19. Manganate(VII) ions react with ethanedioate ions in acidic solution.
2MnO
4

(aq) + 16H
+
(aq) + 5C
2
O
4
2–
(aq) ÷ 2Mn
2+
(aq) + 8H
2
O(l) + 10CO
2
(g)

(a) In a particular experiment 200 cm
3
of aqueous potassium manganate(VII), KMnO
4
,
of concentration 0.0500 mol dm
–3
were mixed with 50.0 cm
3
of ethanedioic acid,
HOOC÷COOH, of concentration 0.500 mol dm
–3
, and 80 cm
3
of 1.0 mol dm
–3
sulphuric
acid.


(i) Show by calculation that the starting concentration of the manganate(VII) ions was
3.03 × 10
–2
mol dm
–3
.
(1)

(ii) The concentration of the manganate(VII) ions was determined over a period
of time.
Time / s
Concentration of manganate(VII) ions/ mol dm

3

0
3.03 × 10
–2

400
2.98 × 10
–2

800
2.86 × 10
–2

1200
2.75 × 10
–2

1600
1.90 × 10
–2

2000
7.50 × 10
–3

2400
2.50 × 10
–3

Plot a graph of the concentration of manganate(VII) ions against time and from it
determine the initial rate of the reaction and the rate at 1600 s.
(5)


(b) A second experiment was set up involving the same chemicals in the same concentrations
as in experiment 1 but this time some solid manganese(II) sulphate was dissolved in the
ethanedioic acid before the potassium manganate (VII) solution was poured in. The plot
of the concentration of manganate(VII) ions against time is given below:
3.5 × 10
3.0 × 10
2.5 × 10
2.0 × 10
1.5 × 10
1.0 × 10
5.0 × 10
0
–2
–2
–2
–2
–2
–2
–3
0 400 800 1200 1600 2000 2400
time / s

3
c
o
n
c
e
n
t
r
a
t
i
o
n

/
m
o
l

d
m


(i) Determine the order of the reaction with respect to manganate(VII) ions by
considering the time taken for the concentration to fall by half, using the
concentrations at 0, 800 and 1600 s.
(3)

(ii) Compare this graph with the one you plotted in (a) (ii) and give two pieces of
evidence that manganese(II) sulphate is a catalyst for this reaction.
(2)

(c) (i) Carrying out a flame test on potassium manganate(VII) gives a lilac flame.
What does this show?
(1)

(ii) Describe how aqueous sodium hydroxide solution could be used to show that
manganese(II) ions had been produced in the reaction between manganate (VII)
ions and ethanedioate ions in acidic solution.
(2)
(Total 14 marks)



20. Thermochemical data, at 298 K, for the equilibrium between zinc carbonate, zinc oxide and
carbon dioxide is shown below.
ZnCO
3
(s) ZnO(s) + CO
2
(g) ∆H
ο
= +71.0 kJ mol
–1
S
ο
[ZnO(s)] = +43.6 J mol
–1
K
–1

S
ο
[ZnCO
3
(s)] = +82.4 J mol
–1
K
–1

S
ο
[CO
2
(g)] = +213.6 J mol
–1
K
–1


(a) (i) Suggest reasons for the differences between the three standard entropies.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(ii) Calculate the entropy change for the system, ∆S
ο
system
, for this reaction. Include the
sign and units in your answer.





(2)


(b) Calculate the entropy change for the surroundings, ∆S
ο
surroundings
, at 298 K, showing your
method clearly.





(2)

(c) (i) Calculate the total entropy change for this reaction, ∆S
ο
total
, at 298 K.





(1)

(ii) What does the result of your calculation in (c)(i) indicate about the natural
direction of this reaction at 298 K?
Justify your answer.
............................................................................................................................
............................................................................................................................
(1)

(d) (i) Write an expression for the equilibrium constant, Kp, for this reaction.




(1)


(ii) State how you would alter ONE condition to increase the yield of carbon dioxide
from this equilibrium reaction.
Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)


21. Hydrogen peroxide decomposes to form water and oxygen.
H
2
O
2
(aq) ÷ H
2
O(l) +
2
1
O
2
(g)
(a) Suggest a method for following the rate of this reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) The reaction is first order with respect to hydrogen peroxide.
(i) Explain what is meant by the term first order.
............................................................................................................................
............................................................................................................................
(1)

(ii) The overall order of the reaction is one. Give the rate equation for the reaction.

Rate =

(1)


(iii) How would you use a graph of hydrogen peroxide concentration against time to
show that the reaction is first order?
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)

(c) The data in the table show the effect of temperature on the rate of this reaction.
T
/K
Rate
/ mol dm
–3
s
–1

1/T
/K
–1

ln(rate)
293
1.6 ×10
–6
3.41 ×10
–3

–13.3
302
4.2 ×10
–6
3.31 ×10
–3

–12.4
314
14.4 ×10
–6
3.19 ×10
–3

–11.1
323
33.8 ×10
–6
3.10 ×10
–3

–10.3


(i) On the axes below, sketch graphs for two temperatures, T
1
and T
2
, where T
2
is
greater than T
1
, and use them to explain why increasing temperature has a dramatic
effect on the rate of this reaction.

............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(4)


(ii) Plot a graph of ln(rate), on the vertical axis, against 1/temperature, on the
horizontal axis, on the grid below.

(3)


(iii) Use your graph and the equation below to calculate the activation energy, E
A
, for
this reaction.
ln(rate) = constant
R
A
E
(1/T) where R = 8.31 J K
–1
mol
–1

You should include the sign and units with your answer which should be given to
two significant figures.





(3)
(Total 16 marks)


22. (a) Define the term partial pressure.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

(b) If phosphorus pentachloride is heated in a sealed tube the following equilibrium is set up
PCl
5
(g) PCl
3
(g) + Cl
2
(g)

(i) Write an expression for the equilibrium constant, K
p
, for the above reaction.




(1)


(ii) At a given temperature T a sample of phosphorus pentachloride is 40.0%
dissociated, the total equilibrium pressure being 2.00 atm. Calculate the partial
pressures of each of the components of the equilibrium mixture, to three significant
figures. Hence calculate the value of K
p
under these conditions.








(5)

(c) At a higher temperature, T + t, the equilibrium mixture in (b) contains a greater
proportion of phosphorus trichloride and chlorine.
(i) State, with a reason, whether the dissociation of phosphorus pentachloride is
exothermic or endothermic.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(ii) How does K
p
change when the temperature is increased?
......................................................................................................................
(1)

(d) If calcium carbonate is heated in a sealed vessel in the absence of air the following
equilibrium is set up:
CaCO
3
(s) CaO(s) + CO
2
(g)


(i) Write the expression for K
p
for this equilibrium.
......................................................................................................................
(1)

(ii) At 1030 °C the total pressure in the vessel is 16 atm. What is the value of K
p
?
......................................................................................................................
(1)
(Total 12 marks)


23. Propanoic acid is a weak acid which dissociates according to
CH
3
CH
2
COOH(aq) + H
2
O(l) CH
3
CH
2
COO

(aq) + H
3
O
+
(aq)





(a) (i) Indicate, in the space provided below the equation, the two acid/base conjugate
pairs.
(2)

(ii) Write the expression for the acid dissociation constant, K
a
, for propanoic acid.



(1)


(iii) Calculate the pH of a 0.100 mol dm
–3
solution of propanoic acid, for which
K
a
= 1.3 × 10
–5
mol dm
–3
.






(3)

(iv) Calculate the concentration of hydroxide ions, OH

, in this same solution of
propanoic acid. K
w
= 1.00 × 10
–14
mol
2
dm
–6
at the temperature of the solution.







(3)

(b) If sodium propanoate is dissolved in water, the pH of the resulting solution is not 7, but is
near to 8. By writing the equation for the reaction occurring suggest why this is so.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)


(c) A mixture of sodium propanoate and propanoic acid behaves as a buffer solution.
(i) What is meant by a buffer solution?
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(ii) Calculate the pH of a buffer solution that is made by mixing equal volumes of
0.0500 mol dm
–3
propanoic acid and 0.100 mol dm
–3
sodium propanoate.






(3)
(Total 16 marks)


24. (a) In a rate of reaction experiment between two substances, A and B, the overall order of the
reaction was found to be 2. Write three possible rate equations for such a second order
reaction between A and B.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)


(b) At a certain temperature the rate of reaction between nitrogen monoxide, NO, and
hydrogen, H
2
, was investigated. The following data were obtained.
[NO]/mol dm
–3
[H
2
]/mol dm
–3
Rate/mol dm
–3
s
–1

1.0 1.0 0.02
1.0 3.0 0.06
3.0 1.0 0.18

(i) Use the data above to deduce the rate equation for this reaction.






(3)

(ii) Use your answer to (b)(i) above to calculate the value of the rate constant, with
units.





(2)


(c) The investigation described in part (b), above, was repeated, but at a higher temperature,
and the rate of the reactions increased. Explain, in terms of particles, why an increase in
temperature increases the rate of a reaction.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)

(d) State the effect of an increase in temperature on the value of the rate constant, k.
...............................................................................................................................
(1)

(e) Explain the effect of a catalyst on the rate of a reaction.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 15 marks)


25. (a) The equation below shows the reaction which occurs when ammonia is dissolved in
water.
NH
3
(g) + H
2
O(1) NH
+
4
(aq) + OH

(aq)
(i) Explain why water is classified as an acid in this reaction.
..........................................................................................................................
..........................................................................................................................
(1)


(ii) The ammonia is acting as a weak base in this reaction.
What is the difference between a weak base and a strong base?
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(1)

(b) Ammonia reacts with oxygen to form the gases nitrogen(II) oxide and steam.
(i) Complete the Hess cycle below so that ΔH
reaction
can be calculated using standard
enthalpy changes of formation. Include state symbols.

(2)


(ii) Calculate ΔH
reaction
for this reaction using the following data.
ΔH
f
[NH
3
(g)] = – 46.1 kJ mol
–1

ΔH
f
[NO(g)] = + 90.2 kJ mol
–1

ΔH
f
[H
2
O(g)] = – 241.8 kJ mol
–1

Include a sign and units in your answer and give your answer to three significant
figures.






(3)
(Total 7 marks)


26. The reaction between solid barium hydroxide and solid ammonium chloride can be
represented by the equation below.
Ba(OH)
2
(s) + 2NH
4
Cl(s) ÷ BaCl
2
(s) + 2NH
3
(g) + 2H
2
O(l) ΔH
ο
= +51.1 kJ mol
–1

The standard entropies, at 298 K, for the reactants and products are:
S
ο
[Ba(OH)
2
(s)] = + 99.7 J mol
–1
K
–1

S
ο
[NH
4
Cl(s)] = + 94.6 J mol
–1
K
–1

S
ο
[BaCl
2
(s)] = + 123.7 J mol
–1
K
–1

S
ο
[NH
3
(g)] = + 192.3 J mol
–1
K
–1

S
ο
[H
2
O(l)] = + 69.9 J mol
–1
K
–1



(a) Why is the standard entropy of ammonia more positive than the standard entropy of
barium chloride?
....................................................................................................................................
....................................................................................................................................
(1)

(b) Use the values given to calculate the standard entropy change, ΔS
ο
system
, for this reaction.
Include the sign and units in your answer.






(2)

(c) Calculate the standard entropy change of the surroundings, ΔS
ο
surroundings
, at 298 K for
this reaction.





(2)

(d) Use your answers to (b) and (c) to show that this reaction is feasible at 298 K.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(1)


(e) Calculate the minimum temperature, in kelvin, at which the reaction is spontaneous.





(2)
(Total 8 marks)


27. This question is about propanal, CH
3
CH
2
CHO, propanone, CH
3
COCH
3
, and propanoic acid,
CH
3
CH
2
CO
2
H.
(a) Explain why all three compounds are soluble in water.
....................................................................................................................................
....................................................................................................................................
(1)

(b) Propanal and propanone contain the carbonyl group.
State a chemical test for the presence of this group. Give the result of a positive test.
Test ...........................................................................................................................
Result ........................................................................................................................
(2)

(c) Propanal can be distinguished from propanone by its oxidation to propanoic acid.
(i) Name an oxidising agent you would use.
.........................................................................................................................
.........................................................................................................................
(1)


(ii) State the colour change you would observe during the oxidation.
From ...................................................... to ......................................................
(1)

(iii) State how propanone can be distinguished from propanal using infra-red spectra.
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.
.........................................................................................................................
.........................................................................................................................
(1)

(d) A useful test for carboxylic acids is that they will neutralise sodium carbonate solution.
Write a balanced equation, including state symbols, for the neutralisation of sodium
carbonate solution by propanoic acid.




(2)

(e) Give the names of TWO other inorganic chemicals that could be used to make sodium
propanoate from propanoic acid.
....................................................................................................................................
....................................................................................................................................
(2)
(Total 10 marks)



28. A saturated solution of calcium hydroxide, Ca(OH)
2
(aq), has a pH of 9.6.
(a) Write an expression linking hydrogen ion concentration and pH. Use this to calculate the
concentration of hydrogen ions in this solution.




(3)

(b) (i) The ionisation constant for water, K
w
= 1.0 × 10
–14
mol
2
dm
–6
.
Write the expression for K
w
.

K
w
=

(1)

(ii) Calculate the concentration of hydroxide ions in the saturated solution of calcium
hydroxide.



(1)

(iii) Calculate the concentration of calcium hydroxide in the saturated solution.



(1)


(iv) Calculate the solubility of calcium hydroxide in g dm
–3
.
Give your answer to three significant figures.



(1)

(v) Suggest why your calculated value may differ significantly from the value in
chemistry reference books.
.........................................................................................................................
.........................................................................................................................
(1)

(c) An alternative method for finding the solubility of calcium hydroxide is to titrate 100 cm
3

of the saturated solution with hydrochloric acid of concentration 0.00100 mol dm
–3
.
Ca(OH)
2
(aq) + 2HCl (aq) ÷ CaCl
2
(aq) + 2H
2
O (l)
(i) Calculate the pH of the hydrochloric acid.


(1)

(ii) Use your answer to (b)(iii) and the information above to calculate the volume of
hydrochloric acid needed to neutralise 100 cm
3
of the saturated calcium
hydroxide solution.




(3)


(iii) Sketch the titration curve for this reaction.

(2)

(iv) Suggest why phenolphthalein is not a suitable indicator for this reaction.
..........................................................................................................................
..........................................................................................................................
(1)
(Total 15 marks)


29. This question is about the hydrolysis of 2-bromo-2-methylbutane.
C
5
H
11
Br + H
2
O ÷ C
5
H
11
OH + HBr
(a) 15 cm
3
of water was mixed with 15 cm
3
of ethanol. 1.0 cm
3
of 2-bromo-2-methylbutane
was added to this mixture. The conductivity of this mixture was measured and rose from
0 to 200 microsiemens in 600 s.
The experiment was repeated using equal volumes of water and ethanol, with 2.0 cm
3
of
2-bromo-2-methylbutane in the 31 cm
3
of mixture. The conductivity of the mixture rose
from 0 to 400 microsiemens in 600 s.


(i) Explain why the conductivity of the mixture increases during these reactions.
..........................................................................................................................
..........................................................................................................................
(1)
(ii) Why was an ethanol/water mixture used for this reaction rather than water on its
own?
..........................................................................................................................
..........................................................................................................................
(1)

(iii) What is the effect on the rate of the reaction of doubling the concentration of
2-bromo-2-methylbutane?
..........................................................................................................................
(1)
(iv) Deduce the order of the reaction with respect to 2-bromo-2-methylbutane.
..........................................................................................................................
(1)

(v) Explain why this is the order of reaction with respect to 2-bromo-2-methylbutane
and not the overall order of the reaction.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(1)


(b) The table below shows the results from another experiment where a solution of
2-bromo-2-methylbutane is reacted with varying concentrations of hydroxide ions.
A few drops of an acid-alkali indicator are added to the mixture and the time for the
indicator to change to the acidic colour is measured.
[C
5
H
11
Br]
/10
–2
mol dm
–3

[OH

]
/10
–3
mol dm
–3

Time
/s
1.5 0.75 5
1.5 1.50 9
1.5 2.25 14

(i) Calculate the rate of the reaction, in mol dm
–3
s
–1
, for each concentration of
hydroxide ions.





(2)

(ii) What effect does doubling the concentration of hydroxide ions have on the rate of
the reaction?
..........................................................................................................................
(1)

(iii) What is the order of the reaction with respect to the hydroxide ions?
..........................................................................................................................
(1)


(c) When 2-bromo-2-methylbutane reacts with water, or hydroxide ions, the mechanism for
the reaction is the same.
(i) Use your answers to (a)(iv) and (b)(iii) to write the rate equation for the reaction
with hydroxide ions.


Rate =


(1)

(ii) Write a mechanism for the reaction which is consistent with your rate equation.






(2)
(Total 12 marks)


30. (a) Ammonia reacts with water as below:
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH

(aq)
A 0.100 mol dm
–3
solution of ammonia has a pH of 11.13.
(i) Identify the Bronsted–Lowry acid/base conjugate pairs in the equation. Clearly
label which are acids and which are bases.
.....................................................................................................................................
.....................................................................................................................................
(2)


(ii) Draw, on the axes below, a graph to show how the pH of the solution varies as
40 cm
3
of 0.100 mol dm
–3
hydrochloric acid (a strong acid) is added slowly to
20 cm
3
of the ammonia solution.
14
12
10
8
6
4
2
0
10 20 30 40 50
Volume of HCl solution / cm
3
pH

(4)

(iii) Select, from the following list, the indicator which would be the most suitable for
this titration. Give a reason for your choice.
Indicator pK
ind
Range
methyl red 5.1 4.2–6.3
bromothymol blue 7.0 6.0–7.6
phenolphthalein 9.3 8.2–10.0
Indicator: ....................................................................................................................
Reason: ......................................................................................................................
.....................................................................................................................................
(2)


(b) Nitrous acid, HNO
2
, is a weak acid with an acid dissociation constant
K
a
= 4.70 × 10
–4
mol dm
–3
at 4 °C.
HNO
2
(aq) + H
2
O(l) H
3
O
+
(aq) + NO
2

(aq)
(i) Write the expression for K
a
.





(1)

(ii) Calculate the pH of a 0.120 mol dm
–3
solution of nitrous acid.






(3)


(iii) Calculate the pH of a buffer solution made by adding 1.38 g of sodium nitrite,
NaNO
2
, to 100 cm
3
of the 0.120 mol dm
–3
solution of nitrous acid
(K
a
= 4.70 × 10
–4
mol dm
–3
).








(4)

(iv) Suggest why a mixture of nitrous acid and sodium nitrite can act as a buffer
solution whereas a solution of sodium nitrite on its own does not.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 18 marks)


31. In an acidic solution, propanone reacts with iodine as follows:
CH
3
COCH
3
+ I
2
÷ CH
3
COCH
2
I + HI
The rate of this reaction can be followed by removing portions of the reaction mixture at known
times, adding them to a solution of sodium hydrogen carbonate to stop the reaction and then
titrating the mixture with standard sodium thiosulphate solution.
(a) (i) Write the ionic equation for the reaction of thiosulphate ions with iodine in
aqueous solution.
.....................................................................................................................................
(2)


(ii) State which indicator is used in this titration, and describe what you would see at
the end point.
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) Use the following data to deduce the rate equation for the reaction of propanone with
iodine in acidic solution, given that the order with respect to [H
+
] is one.
[CH
3
COCH
3
]
/mol dm
–3

[I
2
]
/mol dm
–3

Initial rate
/mol dm
–3
s
–1

1.0 0.10
3.2 × 10
–3

1.0 0.20
3.2 × 10
–3

2.0 0.10
6.4 × 10
–3

(3)

(c) What is meant by:
(i) order of reaction with respect to a particular reactant
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(ii) overall order of reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)


(d) What does the rate equation in (b) tell you about the involvement of iodine in the rate-
determining step, and hence about the least number of steps in the reaction?
...............................................................................................................................................
...............................................................................................................................................
...............................................................................................................................................
(2)

(e) Sodium hydroxide cannot be used to stop the reaction, because very alkaline conditions
cause another reaction to occur between propanone and iodine.
Write the equation for this reaction.
...............................................................................................................................................
(3)
(Total 14 marks)


32. This question is about the kinetics of the reaction in which ammonium cyanate, NH
4
CNO, turns
into urea, NH
2
CONH
2
, in aqueous solution.
NH
4
CNO(aq) ÷ ΝΗ
2
CONH
2
(aq)
The table below shows the mass of urea, m
t
, which formed at different times in a solution of
ammonium cyanate of known starting concentration.
When the reaction stopped the mass of urea, m
final
, was 20.3 g.
Time / min Mass of urea, m
t
/g m
final
– m
t
/g
0 0 20.3
25 12.5 7.8
50 15.7 4.6
75 17.1 3.2
100 17.5 2.8
150 18.7 1.6
200 19.1
300 20.0


(a) Complete the final column of the table.
(1)

(b) Plot a graph of m
final
– m
t
(on the vertical axis) against time (on the horizontal axis).

(2)

(c) The graph can be used to work out a rate equation for the reaction.
What term in the rate equation for the reaction is proportional to m
final
– m
t
?
……….........................................................................................................................
(1)


(d) (i) Show THREE successive half-life measurements on your graph, and give their
values.
1. ........................................................... 2. ...........................................................
3. ...........................................................
(2)

(ii) Use the half-lives to decide whether the reaction is zero order, first order or second
order. Explain how you decided the order.
Order of reaction ..............................................................................................
Explanation .......................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)

(iii) Suggest a possible rate equation for the reaction.
..........................................................................................................................
(1)

(e) A student thought that water might take part in the rate-determining step of the reaction.
(i) What is meant by the rate-determining step?
..........................................................................................................................
(1)


(ii) The solution of ammonium cyanate used in the experiment initially contained 0.35
moles of ammonium cyanate in approximately 1 dm
3
(55.5 moles) of water.
Is the order you calculated in (d)(ii) an order with respect to ammonium cyanate, or
could it include the water as well? Explain your answer.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(Total 12 marks)


33. When dinitrogen tetroxide, N
2
O
4
, dissociates, the following equilibrium is established.
N
2
O
4
(g) 2NO
2
(g)
(a) State a property which could be measured to follow the progress of this reversible
reaction.
....................................................................................................................................
(1)

(b) Write an expression for the equilibrium constant, K
c
, for this reaction.



(1)


(c) When a sample of 0.0370 moles of gaseous dinitrogen tetroxide is allowed to dissociate at
25 °C in a container of volume 1 dm
3
, 0.0310 moles of N
2
O
4
(g) remain in the equilibrium
mixture.
Complete the table below, and use the data to calculate K
c
for the reaction. Include a unit
in your answer.
N
2
O
4
NO
2

Number of moles at start 0.0370 0
Number of moles in 1 dm
3

at equilibrium
0.0310
K
c
calculation:





(3)

(d) The reaction was repeated at a higher pressure, maintaining the temperature at 25 °C.
(i) How does this increase in pressure affect the amount of nitrogen dioxide, NO
2
(g),
in the equilibrium mixture?
..........................................................................................................................
(1)

(ii) How does this increase in pressure affect the value of K
c
?
..........................................................................................................................
(1)


(e) The reaction was repeated at the original pressure, but the temperature was increased to
75 °C. The value of K
c
was approximately twenty times greater.
How does this information show that the reaction is endothermic?
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(1)

(f) Predict the sign of ΔS
system
for the reaction, giving a reason for your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)

(g) Write the equation for the relationship between ΔS
surroundings
and ΔH for the reaction.



(1)

(h) The magnitude of ΔS
system
for the reaction is greater than the magnitude of ΔS
surroundings
.
Explain why this must be the case.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(Total 13 marks)



34. This question is about the chemistry of benzoic acid, C
6
H
5
CO
2
H.
The scheme below shows some reactions of benzoic acid.


(a) (i) What type of reaction is Reaction 1?
..........................................................................................................................
(1)
(ii) Suggest a reagent which could be used to convert the —CO
2
H group to the
—CH
2
OH group without affecting the benzene ring.
..........................................................................................................................
(1)
(iii) Suggest why the reactant you chose in (ii) does not attack the benzene ring.
..........................................................................................................................
..........................................................................................................................
(1)


(b) (i) Suggest a structural formula for A.



(1)
(ii) Name the type and mechanism of this reaction.
Type ................................................... Mechanism ..................................................
(2)

(c) (i) Give the structural formula and state the name for B.



Name ................................................................................................................
(2)
(ii) Give ONE use for the class of compounds to which B belongs.
..........................................................................................................................
(1)

(d) (i) Give the name for C
6
H
5
COCl.
..........................................................................................................................
(1)
(ii) C
6
H
5
COCl reacts more readily than benzoic acid with ethanol, also forming B as
the product. Explain this difference in reactivity.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)


(e) Hydrogen can add to the benzene ring in benzoic acid, but only under conditions of high
temperature and pressure in the presence of a catalyst. Explain why these severe
conditions are necessary for this addition reaction to occur.
....................................................................................................................................
....................................................................................................................................
(2)
(Total 14 marks)


35. (a) Benzoic acid is a weak acid. What is meant by a weak acid?
....................................................................................................................................
....................................................................................................................................
(1)

(b) Write an expression for the acid dissociation constant, K
a
, for benzoic acid.
(1)

(c) K
a
for benzoic acid has value 6.3 × 10
–5
mol dm
–3
. Use this data to calculate the pH of a
solution of benzoic acid of concentration 0.050 mol dm
–3
.




(3)


(d) In a titration, 40.0 cm
3
of 0.050 mol dm
–3
sodium hydroxide was added from a burette to
20.0 cm
3
of 0.050 mol dm
–3
benzoic acid. Sketch a curve on the grid below to show how
the pH of the solution would change as the sodium hydroxide was added. Detailed
calculations are not required.

(3)

(e) Name a suitable indicator to detect the end-point of this titration.
....................................................................................................................................
(1)


(f) A mixture of benzoic acid and sodium benzoate can act as a buffer solution.
In what proportion must solutions of benzoic acid and sodium benzoate, of the same
concentration, be mixed to produce a buffer solution of pH 4.5?
You may use the equation pH = –log K
a
–log
[base]
[acid]
.
K
a
for benzoic acid has value 6.3 × 10
–5
mol dm
–3
.






(2)

(g) Suggest a salt which would make a buffer solution with pH greater than 7 when mixed
with aqueous ammonia.
....................................................................................................................................
(1)
(Total 12 marks)


36. (a) (i) Use an equation to define the term pH.
.....................................................................................................................................
(1)
(ii) Explain how some solutions can have a negative pH.
.....................................................................................................................................
.....................................................................................................................................
(1)


(b) The concentration of propanoic acid can be found by titrating a sample with standard
sodium hydroxide solution.
(i) Calculate the pH of 0.100 mol dm
–3
propanoic acid at 25 °C; the value of the
dissociation constant for the acid, K
a
, is 1.30 × 10
–5
mol dm
–3
.








(3)

(ii) Sketch with reasonable accuracy the titration curve that you would expect if
25.0 cm
3
of 0.100 mol dm
–3
propanoic acid were to be titrated with 0.100 mol dm
–3

sodium hydroxide solution.
14
12
10
8
6
4
2
0
10 20 30 40 50
Volume of 0.100 mol dm
–3
sodium hydroxide solution/cm
3



(iii) What is the significance of the pH of the mixture when 12.5 cm
3
of sodium
hydroxide had been added to the propanoic acid?
.....................................................................................................................................
(1)
(Total 10 marks)


37. Alanine, 2-aminopropanoic acid, is the simplest chiral amino acid found in nature and is
optically active.
H
C C
O
O H
H N
2
CH
3


(a) (i) Explain the meaning of the term chiral.
.....................................................................................................................................
.....................................................................................................................................
(1)
(ii) How is optical activity detected experimentally?
.....................................................................................................................................
.....................................................................................................................................
(2)
(iii) If alanine is made from propanoic acid the product mixture does not show optical
activity. Explain why this is so.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(b) Alanine reacts with both acids and bases. Give the structural formulae of the compounds
you would expect if alanine reacts with
hydrochloric acid





sodium hydroxide




(2)

(c) Alanine has a high melting temperature of 300 °C, much higher than would be expected
for the structure given at the start of the question.
Draw the structure that is actually present in the solid, and explain why the melting
temperature is so high.






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


(d) Polyamides are made from a diacid dichloride and a diamine; they are condensation
polymers.
(i) Explain the term condensation polymer.
.....................................................................................................................................
.....................................................................................................................................
(1)

(ii) Suggest the structural formula of a diacid dichloride and a diamine that could be
reacted to form a polyamide.





(2)

(iii) Draw sufficient of the polymer chain that would result from the reaction of the
compounds in (ii) to make the structure of the polymer clear.






(2)


(iv) Alanine could be converted to CH
3
CH(NH
2
)COCl which on its own could
polymerise to a polyamide. Draw the structure of the polymer chain showing three
alanine repeating units and all the bonds in the amide links.








(2)
(Total 16 marks)


38. This question concerns the equilibrium
2NO(g) N
2
(g) + O
2
(g) AH = –180 kJ mol
–1

(a) Define the term partial pressure.
............................................................................................................................................
............................................................................................................................................
(1)

(b) (i) Write the expression for K
p
for the above reaction.






(1)


(ii) At 1600 °C and 1.5 atm pressure NO is 99 % dissociated at equilibrium. Calculate
the value of K
p
under these conditions.








(4)

(c) State and explain the effect on K
p
and hence on the position of equilibrium of decreasing
the temperature at constant pressure.
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
(3)


(d) The reaction
Ni(s) + 4CO(g) Ni(CO)
4
(g)
is used to purify nickel.
(i) Write the expression for K
p
for this system.





(1)

(ii) In order to achieve a high equilibrium yield of Ni(CO)
4
should a low or a high
partial pressure of carbon monoxide be used? Explain your answer in terms of K
p
.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)



39. (a) The ester methyl ethanoate reacts with water as follows:
CH
3
COOCH
3
+ H
2
O ÷ CH
3
COOH + CH
3
OH
An experiment to investigate the kinetics of this hydrolysis showed that the concentration
of methyl ethanoate varied as shown in the graph below.
The water in this reaction is not only a reagent but is also the solvent and is therefore in
large excess.
0
0
0.05
0.10
0.20
0.25
0.30
0.35
0.5 1.0 1.5 2.0 2.5 3.0
[ester] / mol dm
Time / hr
–3


(i) Show, under these conditions, that the reaction is first order in methyl ethanoate.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(ii) Explain with a reason whether or not the overall order of reaction must also be one.
.....................................................................................................................................
.....................................................................................................................................
(1)


(iii) Assuming the reaction is first order, use the graph to calculate the rate constant, k.
Include the units in your answer.







(3)

(iv) Suggest a method by which the progress of the reaction could be followed.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(b) The Arrhenius equation
ln k = ln A – E
a
/RT
relates the rate constant k to the activation energy E
a
for a reaction. A is a constant, R is
the gas constant.
(i) Comment on the relative values of the rate constant k at a given arbitrary
temperature T for two reactions, one of which has an activation energy of about
180 kJ mol
–1
, the other of which has an activation energy of about 50 kJ mol
–1
. No
calculation is expected.
.....................................................................................................................................
.....................................................................................................................................
(1)


(ii) Suppose that these two different values of activation energy were for the same
overall reaction at the same temperature. Suggest a way in which the conditions
are different for the two reactions.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 11 marks)


40. Butan-1-ol, a primary alcohol, can be oxidised to form the aldehyde, butanal.
(a) Give the name or formula of an oxidising agent used in this reaction and of the other
reagent required.
Oxidising Agent
.....................................................................................................................................
Other Reagent
.....................................................................................................................................
(2)

(b) A possible by-product of this reaction is butanoic acid, CH
3
CH
2
CH
2
CO
2
H, which is
classified as a weak acid.
Explain what is meant by a weak acid.
Acid ............................................................................................................................
.....................................................................................................................................
Weak ...........................................................................................................................
.....................................................................................................................................
(2)
(Total 4 marks)



41. X and Y are isomers with the molecular formula C
7
H
6
O
2
.


(a) Complete the table with the observations you would make when separate samples of X
and Y are warmed gently in test-tubes with the following solutions.
Solution Observation with X Observation with Y
sodium carbonate
Brady‘s reagent
(2,4-dinitrophenylhydrazine)

potassium dichromate(VI) +
sulphuric acid

(6)

(b) Both X and Y can take part in reactions in which esters are formed.
(i) Complete the structural formula of the ester which forms when X reacts with
methanol.




(1)


(ii) Y reacts with ethanoyl chloride to form an ester.
Draw the displayed formula of ethanoyl chloride.



(1)

(iii) Complete the displayed formula of the ester which forms when Y reacts with
ethanoyl chloride.



(2)

(iv) When X forms an ester with methanol, a catalyst is needed for the reaction to
proceed at a reasonable speed when heated gently.
Name a suitable catalyst for the esterification reaction.
...........................................................................................................................
(1)

(v) Explain why ethanoyl chloride is reactive enough to form an ester with Y at a
reasonable speed without a catalyst and without heating.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(c) The benzene ring in Y reacts readily with bromine in a substitution reaction.
(i) Name the type of reagent which attacks a benzene ring in substitution reactions.
...........................................................................................................................
(1)

(ii) Give the formula of the species which attacks the benzene ring when it reacts with
bromine in a substitution reaction.
.............................................................................................................................
(1)

(iii) Suggest a structural formula for an organic product of the reaction of bromine with
Y.



(1)

(iv) Y reacts with bromine more readily than benzene does. Suggest a reason for this.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 17 marks)


42. 2-bromo-2-methylpropane reacts with aqueous sodium hydroxide as shown in the equation
below.
(CH
3
)
3
CBr + NaOH ÷ (CH
3
)
3
COH + NaBr


A series of experiments was carried out to investigate the kinetics of this reaction.
Initial concentration of
(CH
3
)
3
CBr
/mol dm
÷3

Initial concentration of
NaOH
/mol dm
÷3

Initial rate of reaction
/mol dm
÷3
s
÷1

5.0 × 10
÷4
2.0 × 10
÷2
1.5 × 10
÷4

1.5 × 10
÷3
2.0 × 10
÷2
4.5 × 10
÷4

1.5 × 10
÷3
4.0 × 10
÷2
4.5 × 10
÷4


(a) (i) Give the order of the reaction with respect to
2-bromo-2-methylpropane ...............................................................................
sodium hydroxide .............................................................................................
(2)
(ii) Write the rate equation for this reaction.
...........................................................................................................................
(1)

(b) Use one set of the data to calculate the rate constant for this reaction. Include the unit of
the rate constant in your answer.



(2)

(c) The slowest step of the mechanism is the following reaction
(CH
3
)
3
CBr ÷ (CH
3
)
3
C
+
+Br


Is your rate equation consistent with this information? Explain your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(1)

(d) In another series of experiments, the rate of the reaction was measured at different
temperatures. Complete the missing numbers in the table below.
temperature (T)
/K
1/temperature (1/T)
/K
–1

rate
/mol dm
÷3
s
÷1

ln(rate)
300
3.33 × 10
–3
3.35 × 10
÷4
÷8.00
310
3.23 × 10
–3
7.47 × 10
÷4
÷7.20
320
3.13 × 10
–3
1.66 × 10
÷3
÷6.40
330
3.03 × 10
–3
4.09 × 10
÷3
÷5.50
340 2.94 × 10
–3
9.10 × 10
÷3
÷4.70
350

1.66 × 10
÷2


(2)


(e) On the axes below plot a graph of ln(rate) on the vertical axis against 1/T on the
horizontal axis.

(2)


(f) Use the Arrhenius equation
ln(rate) = constant –
R
E
A
(1/T)
to calculate the value of the activation energy, E
A
, for the reaction.
[R = 8.31 J K
–1
mol
–1
].
Show your working clearly and give your answer to 2 significant figures.





(2)
(Total 12 marks)


43. The equation below shows a possible reaction for producing methanol.
CO(g) + 2H
2
(g) ÷ CH
3
OH(l) ΔH
ο
= ÷129 kJ mol
–1

(a) The entropy of one mole of each substance in the equation, measured at 298 K, is shown
below.
Substance
S
ο

/J mol
÷1
K
÷1

CO(g) 197.6
H
2
(g) 130.6
CH
3
OH(l) 239.7

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


(ii) Calculate the entropy change of the system, ΔS
ο
system
, for this reaction.



(2)

(iii) Is the sign of ΔS
ο
system
as expected? Give a reason for your answer.
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(1)

(iv) Calculate the entropy change of the surroundings ΔS
ο
surroundings
, at 298 K.




(2)

(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 ºC 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) + 2H
2
(g) CH
3
OH(g)
(i) 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)

(iii) Write an expression for the equilibrium constant in terms of pressure, K
p
, for this
reaction.
CO(g) + 2H
2
(g) CH
3
OH(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, K
p
. 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 E
A
.


(i) What does the shaded area on the graph represent?
.............................................................................................................................
(1)
(ii) Draw a line on the graph, labelled E
C
, to show the activation energy of the
catalysed reaction.
(1)
(Total 17 marks)



44. (a) Calculate the pH of a solution of sodium hydroxide of concentration 0.600 mol dm
–3
,
assuming it is a strong base.
The ionisation constant for water, K
w
, is 1.00 × 10
–14
mol
2
dm
–6
.





(2)

(b) Calculate the pH of a solution of ethanoic acid of concentration 0.600 mol dm
–3
.
The acid dissociation constant, K
a
, for ethanoic acid is 1.70 × 10
–5
mol dm
–3
.





(3)

(c) A 100 cm
3
sample of sodium hydroxide of concentration 0.600 mol dm
–3
is mixed with
200 cm
3
of ethanoic acid of concentration 0.600 mol dm
–3
.
(i) Write an equation for the reaction which occurs.


(1)


(ii) Calculate the number of moles of unreacted ethanoic acid remaining in the
resulting mixture.




(2)

(iii) Calculate the concentration, in mol dm
÷3
, of the unreacted ethanoic acid in the
resulting mixture.




(1)

(iv) The mixture which forms is a buffer. Why does the pH of the mixture remain
constant when small quantities of solutions containing H
+
or OH

ions are added?
You may find it helpful to use equations in your explanation.
Addition of solution containing H
+
ions. ...........................................................
.............................................................................................................................
.............................................................................................................................
Addition of solution containing OH

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


(v) The concentration of sodium ethanoate in the mixture is 0.200 mol dm
÷3
. Calculate
the pH of the mixture, using your answer to (iii).
You may use the equation
pH = – log K
a
– log
[base]
[acid]




(2)
(Total 14 marks)


45. Pentanoic acid, C
4
H
9
COOH, is a weak acid with an acid dissociation constant,
K
a
= 1.5 × 10
–5
mol dm
–3
.
(i) What is meant by the term weak in a weak acid?
.....................................................................................................................................
.....................................................................................................................................
(1)

(ii) Write the expression for the K
a
of C
4
H
9
COOH.







(1)


(iii) Calculate the pH of a 0.100 mol dm
–3
solution of C
4
H
9
COOH.








(3)

(iv) On the grid below sketch the change in pH during the addition of 50.0 cm
3
of
0.100 mol dm
–3
sodium hydroxide solution to 25 cm
3
of 0.100 mol dm
–3
pentanoic acid
solution.
14
12
10
8
6
4
2
0 10 20 30 40 50
Volume of sodium hydroxide added / cm
3
pH

(4)


(v) Suggest, with reasoning, a suitable indicator for the titration in (iv).
Indicator pK
ind

Bromophenol blue 4.0
Methyl red 5.1
Thymol blue 8.9
Alizarin yellow 12.5
Indicator .....................................................................................................................
Reason ........................................................................................................................
.....................................................................................................................................
(2)
(Total 11 marks)



46. This question is about the kinetics of the reaction between 2-bromo-2-methylpropane and
sodium hydroxide in a suitable solvent.
(CH
3
)
3
CBr + NaOH ÷ (CH
3
)
3
COH + NaBr
Equal volumes of 0.200 mol dm
–3
solutions of the two reactants were mixed together and
maintained at a constant temperature of 30 °C. The concentration of hydroxide ions was
determined at different times. The results are shown in the table below.
[OH

]
/mol dm
–3

Time
/s
0.100 0
0.071 120
0.052 240
0.035 360
0.024 480
0.018 600

(a) Describe how the concentration of hydroxide ions could be determined during the
reaction.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(3)


(b) (i) Plot a graph of hydroxide ion concentration (vertical axis) against time (horizontal
axis) on the grid below.

(2)


(ii) Mark on your graph TWO consecutive half-lives. Measure their values and write
them below.
First half-life ..........................................................................................................
Second half-life .....................................................................................................
(1)

(iii) What is the order of the reaction? Explain how you used your half-lives to arrive at
your answer.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

(iv) Explain why your answer to (iii) is an overall order.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

(v) Suggest a rate equation for this reaction.
Rate =
(1)

(c) (i) What mechanism is likely to be operating in this reaction? Justify your answer.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)


(ii) Write equations to show the steps involved in your chosen mechanism for this
reaction.




(2)
(Total 13 marks)


47. The reaction between nitrogen and hydrogen can be used to produce ammonia.
N
2
(g) + 3H
2
(g) 2NH
3
(g) ΔH
ο
= – 92.2 kJ mol
–1

Standard entropies are given below
S
ο
[N
2
(g)] = +191.6 J mol
–1
K
–1

S
ο
[H
2
(g)] = +130.6 J mol
–1
K
–1

S
ο
[NH
3
(g)] = +192.3 J mol
–1
K
–1


(a) Calculate the entropy change of the system, ΔS
ο
system
, for this reaction. Include a sign and
units in your answer.





(2)


(b) Calculate the entropy change of the surroundings, ΔS
ο
surroundings
, at 298 K. Include a sign
and units in your answer.





(2)

(c) (i) Calculate the total entropy change, ΔS
ο
total
, at 298 K. Include a sign and units in
your answer.




(1)

(ii) Is this reaction feasible at 298 K? Justify your answer.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

(d) In industry the reaction is carried out at about 700 K using an iron catalyst and high
pressures.
(i) The yield of ammonia produced at equilibrium is less at 700 K than at 298 K, if the
pressure remains constant. In terms of entropy, explain why this happens.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)


(ii) Higher pressures increase the yield of ammonia at equilibrium. Suggest a reason
why pressures greater than 300 atmospheres are not routinely used.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)

(iii) Iron is a heterogeneous catalyst. Explain what is meant by heterogeneous.
...............................................................................................................................
...............................................................................................................................
(1)
(Total 9 marks)


48. Study the reaction scheme below, then answer the questions that follow.


(a) (i) Butanal contains a carbonyl group. State a chemical test for a carbonyl group and
describe the result of the test.
Test .........................................................................................................................
Result .....................................................................................................................
(2)


(ii) An isomer of butanal also possesses a carbonyl group, but cannot be oxidised by
acidified sodium dichromate(VI). Give the structural formula of this isomer and
its name.
Structural formula ..................................................................................................
Name ......................................................................................................................
(2)

(iii) Another isomer of butanal contains a carbonyl group and can be oxidised by
acidified sodium dichromate(VI). Draw the displayed formula of this isomer.




(1)

(b) Compound X is a colourless liquid that smells of pineapples.
(i) To what class of compounds does X belong?
...............................................................................................................................
(1)


(ii) Ethanol, C
2
H
5
OH, reacts with butanoic acid to form compound X. Complete the
diagram below to show the structural formula of X and the other product.





(1)

(iii) Give the name of compound X.
...............................................................................................................................
(1)

(iv) What type of attacking species is ethanol in this reaction?
...............................................................................................................................
(1)

(c) Describe what you would expect to see during Reaction 2.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(1)


(d) Explain why Reaction 4 is far more vigorous than Reaction 3.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(2)
(Total 12 marks)


49. This question is about butanoic acid, CH
3
CH
2
CH
2
CO
2
H.
(a) Butanoic acid can be described as a weak acid. Explain what is meant by weak as used in
this context.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(1)

(b) The acid dissociation constant, K
a
, for butanoic acid is 1.50 × 10
–5
mol dm
–3
.
(i) Write the expression for K
a
.



(1)
(ii) Calculate the pH of a 0.0100 mol dm
–3
solution of the acid.



(2)


(c) A buffer solution can be made by mixing aqueous solutions of butanoic acid and sodium
butanoate.
Explain what is meant by a buffer solution.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(2)

(d) The following equilibrium reactions are present in the buffer solution.
A CH
3
CH
2
CH
2
CO
2
H(l) CH
3
CH
2
CH
2
CO
2

(aq) + H
+
(aq)
B H
+
(aq) +OH

(aq) H
2
O(l)
(i) Which TWO of the substances behave as Brønsted–Lowry bases?
...............................................................................................................................
(1)

(ii) Use the two equations, A and B, to explain how the buffer solution responds to the
addition of a solution containing hydroxide ions.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)


(iii) The pH of a buffer solution is given by the equation
pH = ÷1g K
a
÷ 1g
[base]
[acid]

Using this equation, calculate the pH of a buffer solution made by mixing 100 cm
3

of 0.0100 mol dm
–3
butanoic acid solution with 300 cm
3
of 0.00500 mol dm
–3

sodium butanoate solution.
[The K
a
for butanoic acid is 1.50 × 10
–5
mol dm
–3
.]
(2)
(Total 11 marks)


50. (a) Propanoic acid, CH
3
CH
2
COOH, can be prepared from carbon dioxide and an organic
reagent.
Name this organic reagent and state the conditions for the preparation.
Reagent ........................................................................................................................
Conditions ....................................................................................................................
......................................................................................................................................
(3)

(b) Describe what you would see and write the equations for the reactions of propanoic acid
with:
(i) a solution of sodium carbonate
Observation ........................................................................................................
Equation .............................................................................................................
(2)

(ii) solid phosphorus pentachloride.
Observation ........................................................................................................
Equation .............................................................................................................
(2)


(c) Propanoic acid can also be prepared from propanal, CH
3
CH
2
CHO. State the reagents for
this conversion.
Reagents ......................................................................................................................
(2)

(d) 1-aminobutan-2-ol, CH
3
CH
2
CH(OH)CH
2
NH
2
, is an active ingredient in some deodorant
sprays.
It can be prepared from propanal by the following two-step process.
Step
1
Step
2

CH
3
CH
2
C
H
O

CH
3
CH
2
CH(O
H
)
C
N

CH
3
CH
2
CH(OH)C
H
2
N
H
2


(i) For Step 1
State the reagents and conditions.
............................................................................................................................
............................................................................................................................
Name the type of reaction.
............................................................................................................................
(3)

(ii) For Step 2
State the reagents and conditions.
............................................................................................................................
............................................................................................................................
Name the type of reaction.
............................................................................................................................
(3)


(e) Write the structural formula of the organic product formed when 1-aminobutan-2-ol
reacts with:
(i) ethanoyl chloride, CH
3
COCl




(2)
(ii) hydrochloric acid.



(1)

(f) 1-aminobutan-2-ol exists as two isomers with the same structural formula.
Identify the type of isomerism and draw the TWO isomers, showing clearly the
difference between them.
Type of isomerism .......................................................................................................







(3)
(Total 21 marks)



51. (a) When silver carbonate is heated, it decomposes into silver oxide and carbon dioxide.
Ag
2
CO
3
(s) Ag
2
O(s) + CO
2
(g)
At 227 °C, the value of the equilibrium constant, K
p
, is 1.48 atm.
(i) Write the expression for the equilibrium constant, K
p
.




(1)

(ii) What is the pressure of carbon dioxide gas when silver carbonate is heated to a
temperature of 227 °C in a closed vessel?


(1)


(b) When nitrosyl chloride, NOCl, is heated, it dissociates reversibly into nitric oxide, NO,
and chlorine, Cl
2
, according to the equation
2NOCl(g) 2NO(g) + Cl
2
(g) ∆H = +75.6 kJ mol
–1

(i) Write the expression for the equilibrium constant, K
p
, for this reaction.










(1)


(ii) 1.00 mol of nitrosyl chloride was placed in a sealed container and heated to 500 °C.
Equilibrium was reached when 22.0% of the nitrosyl chloride had dissociated. The
pressure in the vessel was 5.00 atm.
Calculate the value of K
p
at this temperature, stating its units.











(5)

(iii) State the effect of an increase in temperature on the value of the equilibrium
constant, K
p
. Justify your answer.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)


(iv) Hence suggest in which direction the position of equilibrium moves when the
temperature is increased. Justify your answer.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(Total 12 marks)


52. (a) The first step in the esterification of ethanoic acid, CH
3
COOH, by ethanol in the presence
of a small quantity of concentrated sulphuric acid, is the reaction
CH
3
COOH + H
2
SO
4
→ CH
3
COOH
2
+
+
÷
4
HSO


In the space below the equation, identify the two acid base conjugate pairs.
(2)

(b) Ethanoic acid, CH
3
COOH, is a weak acid and dissociates in water according to the
equation
CH
3
COOH(aq) + H
2
O(l)

H
3
O
+
(aq) + CH
3
COO

(aq)
Its acid dissociation constant, K
a
, is
K
a
=
COOH] [CH
] COO ][CH O [H
3

3 3
+
= 1.74 × 10
–5
mol dm
–3
(at 25 °C)


(i) The concentration of a solution of ethanoic acid can be determined by titrating a
25.0 cm
3
sample in a conical flask against a standard solution of sodium hydroxide.
State whether the pH at the end point is less than 7, 7, or more than 7, and hence
name a suitable indicator for this titration.
pH at end point ..................................................................................................
Indicator .............................................................................................................
(2)

(ii) Ethanoic acid is only about 1% ionised in dilute solutions. Its enthalpy of
neutralisation is –55 kJ mol
–1
, whereas the enthalpy of neutralisation of a strong
acid, such as hydrochloric acid, is –57 kJ mol
–1
.
Explain why there is so little difference between these two values.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)


(iii) Calculate the pH of a 0.140 mol dm
–3
solution of ethanoic acid, clearly showing the
TWO assumptions that you have made.
Calculation





Assumptions
............................................................................................................................
............................................................................................................................
............................................................................................................................
(4)

(iv) To 50.0 cm
3
of the solution in (III) , an equal volume of a 0.200 mol dm
–3
solution
of potassium ethanoate was added. Calculate the pH of the buffer solution
obtained.








(3)
(Total 14 marks)



53. (a) Define the terms
(i) Overall order of reaction
............................................................................................................................
............................................................................................................................
(1)

(ii) Rate constant
............................................................................................................................
............................................................................................................................
(1)

(b) In a kinetic study of the reaction
CH
3
I + OH

→ CH
3
OH + I


At a certain temperature the following data were obtained:
Experiment
[CH
3
I]
/mol dm
–3

[OH

]
/mol dm
–3

Initial rate
/mol dm
–3
s
–1

1 0.1 0.1
1 × 10
–5

2 0.2 0.1
2 × 10
–5

3 0.1 0.2
2 × 10
–5


(i) State the order of reaction with respect to CH
3
I and with respect to OH

ions.
Give your reasons.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)


(ii) Write the rate equation for the reaction.
............................................................................................................................
(1)

(iii) Calculate the value of the rate constant for this reaction, stating its units.





(2)

(c) The reaction
CH
3
CH
2
Br + OH

→ CH
3
CH
2
OH + Br


has an S
N
2 mechanism that proceeds through a transition state.
(i) Draw the mechanism, showing the structure of the transition state.






(3)


(ii) Draw a reaction profile for this exothermic reaction. Show the energy level of the
transition state on the profile.






(2)
(Total 12 marks)


54. Persulphate ions, S
2
O
– 2
8
slowly oxidise arsenic(III) acid, H
3
AsO
3
in aqueous solution according
to the equation
S
2
O
– 2
8
+ H
3
AsO
3
+ H
2
O → 2SO
– 2
4
+ H
3
AsO
4
+ 2H
+

- 25 cm
3
of a 1.0 mol dm
–3
solution of potassium persulphate was mixed with 25 cm
3
of a
solution of arsenic(III) acid of the same concentration.
- At timed intervals, small potions of the reation mixture were analysed to determine the
concentration of persulphate ion, [S
2
O
– 2
8
].
The results are shown below.
Time
/ minutes
[
2
8 2
O S
÷
]
/ mol dm
–3

0 1.0
5 0.76
10 0.62
15 0.52
20 0.44
30 0.35


(a) (i) On the grid below, plot a graph of the concentration of persulphate ions against
time.
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0 5 10 15 20 25 30
Time / min
[S O ]
/ mol dm
–3
2–
2 8

(2)


(ii) Draw a tangent to the curve at the point where [S
2
O
– 2
8
] = 0.50 mol dm
–3
and use it
to calculate the slope of the curve at that point. Give your answer to two significant
figures.




Slope: ..............................
(4)

(b) The rate of the reaction at a particular concentration of reactant can be measured from the
slope of the graph at that concentration.
The initial rate, which is the rate when the concentrations of persulphate ions, S
2
O
– 2
8
,
and arsenic(III) acid, H
3
AsO
3
, are both 1.0 mol dm
–3
, was found to be 0.060 mol dm

3
min
–1
.
(i) Use your answer to (a)(ii) to show that the ratio of the initial rate to the rate when
[S
2
O
– 2
8
] and [H
3
AsO
3
] are 0.50 mol dm
–3
is approximately 4:1. Use this ratio to
deduce the overall order of reaction.






(3)


(ii) Suggest TWO rate equations that agree with the order of the reaction that you have
deduced in (i). How could the experiment be adapted to distinguish between these
two rate equations?
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(5)
(Total 14 marks)


55. (a) (i) Give the formula of the ion which causes an aqueous solution to be alkaline.
...........................................................
(1)

(ii) Explain why a 0.1 mol dm
–3
solution of ammonia has a lower pH than a
0.1 mol dm
–3
solution of sodium hydroxide.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)


(b) Using the letters P, Q and R arrange the following in order of increasing pH
de-ionised water 0.1 mol dm
–3
0.1 mol dm
–3
ethanoic acid hydrochloric acid
P Q R

..................................................................
(1)
(Total 3 marks)


56. (a) The distribution of the energy of particles in a gas at temperature T1 is shown below.


(i) On the diagram above, draw the distribution of energy of particles at a lower
temperature, T2.
(2)


(ii) Use the diagram to explain why the rate of a reaction increases with an increase in
temperature.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)

(iii) Explain fully why a catalyst increases the rate of a reaction.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)


(b) The fermentation of glucose is an exothermic reaction and is catalysed by enzymes in
yeast.
C
6
H
12
O
6
(aq) → 2C
2
Η
5
ΟΗ(aq) + 2CO
2
(g)
The reaction is slow at room temperature.
(i) Describe, with the aid of a diagram, an experiment you could do to follow the
progress of this reaction at different temperatures.







................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)


(ii) Would you expect ∆S
system
to be positive or negative for this reaction? Justify your
answer with TWO pieces of evidence.
................................................................................................................................
...............................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)

(iii) Deduce the sign of ∆S
surroundings
. Show your reasoning.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(Total 15 marks)


57. Maleic acid has the structure shown below.

It is a dioic acid and is one of a pair of geometric isomers.
(a) What is the systematic name for maleic acid?
.......................................................................................................................................
(2)


(b) Write the equation for the reaction of sodium hydroxide with maleic acid,
HO
2
CCH=CHCO
2
H, to form disodium maleate (state symbols are not required).



(2)

(c) Maleic acid has two acid dissociation constants with the following values
K
a1
= 1.48 × 10
–2
mol dm
–3
K
a2
= 8.51 × 10
–7
mol dm
–3

(i) Explain why maleic acid has two different K
a
values.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)

(ii) Complete an equation for the first dissociation of maleic acid.
HO
2
CCH=CHCO
2
H
(1)

(iii) Maleic acid is a weak acid. Calculate the pH of a solution of maleic acid of
concentration 0.0100 mol dm
–3
using the value of K
a1
but not K
a2
.






(2)


(iv) Both carboxylic acid groups in maleic acid do dissociate. Suggest how your answer
in (c)(iii) might be affected if you consider K
a2
in addition to K
a1
?
................................................................................................................................
................................................................................................................................
(1)
(Total 10 marks)


58. 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) Ni(CO)
4
(g) ∆H
ο
= –191 kJ mol
–1

(a) (i) Calculate ∆S
ο
system
for this reaction given the following standard entropy values.
Substance
S
ο

/J mol
–1
K
–1

Ni(s) +29.9
CO(g) +197.6
Ni(CO)
4
(g) +313.4
Include a sign and units in your answer.




(2)

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


(iii) Calculate ∆S
ο
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, K
p
, for this reaction.



(1)


(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 K
p
at this temperature.
Include the units of K
p
in your answer.
Substance Moles at start
Moles at
equilibrium
Partial pressure, p
eq

/atm
Ni(CO)
4
0
CO 100 99.0







(4)


(iii) As K
p
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)



59. (a) State Hess‘s Law.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) Methane burns in oxygen.
CH
4
(g) + 2O
2
(g) ÷ CO
2
(g) + 2H
2
O(g)
(i) Calculate the enthalpy change for this reaction, using the bond enthalpies
given below.
Bond enthalpy
/ kJ mol
–1
C – H +435
O = O +498
C = O +805
H – O +464
(3)

(ii) State the name of this enthalpy change.
...........................................................................................................................
(1)

(iii) The value of this enthalpy change, under standard conditions, is –890 kJ mol
–1
.
State the meaning of standard conditions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(iv) Suggest, with a reason, why the enthalpy change calculated in (i) is different from
the standard value quoted in (iii).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(c) Although the reaction between methane and oxygen is exothermic, it does not occur
unless the mixture is ignited.
Use these facts to explain the difference between thermodynamic and kinetic stability.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 14 marks)


60. The weak acid methanoic acid, HCOOH, sets up the following equilibrium in water at 298 K:
HCOOH(aq) + H
2
O(l) H
3
O
+
(aq) + HCOO

(aq)
The acid dissociation constant, K
a
, for methanoic acid at 298 K is 1.78 × 10
–4
mol dm
–3
.


(a) A 0.200 mol dm
–3
solution of methanoic acid has a pH of 2.2 at 298 K.
20.0 cm
3
of this solution is titrated with 0.100 mol dm
–3
sodium hydroxide solution until
excess alkali has been added.
On the grid below, sketch the titration curve you would expect for this reaction.
pH
14
12
10
8
6
4
2
0
10 20 30 40 50 60
Volume of sodium hydroxide solution/ cm
3

(4)

(b) Equal volumes of 0.500 mol dm
–3
methanoic acid and 0.250 mol dm
–3
sodium
methanoate solution are mixed to make a buffer solution.
(i) Define the term buffer solution.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(ii) Calculate the pH of this buffer solution.






(3)

(iii) Explain, with the aid of equations, how this mixture acts as a buffer solution.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 13 marks)



61. 2-bromo-2-methylbutane reacts with aqueous sodium hydroxide in a substitution reaction.
CH
C
3
C H
2 5
Br
CH
3
+ OH
CH
C
3
C H
2 5
CH
3
OH
+ Br
– –


(a) The rate of reaction can be followed by measuring the concentration of 2-bromo-2-
methylbutane at various times.
In one such experiment, a known amount of 2-bromo-2-methylbutane was added to a
large excess of aqueous sodium hydroxide. The following results were obtained.
Time/min
Concentration of 2-bromo-2-methylbutane/mol dm
–3

0 0.96
10 0.61
20 0.38
30 0.24
40 0.15
50 0.10


(i) Plot a graph of the concentration of 2-bromo-2-methylbutane on the y (vertical)
axis against time on the x (horizontal) axis.
1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0 10 20 30 40 50 60
Time / min
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

2
-
b
r
o
m
o
-
2
-
m
e
t
h
y
l
b
u
t
a
n
e

/

m
o
l

d
m

3

(2)

(ii) Show TWO successive half-life measurements on your graph and write their values
below.
First half-life ............................................................
Second half-life ............................................................
(2)

(iii) What is the order of reaction with respect to 2-bromo-2-methylbutane?
Give a reason for your answer.
Order .........................................................
Reason ...............................................................................................................
............................................................................................................................
(2)


(b) When the reaction is repeated using equal concentrations of 2-bromo-2-methylbutane and
aqueous sodium hydroxide, the same results are obtained.
(i) What is the order of reaction with respect to hydroxide ions?
...........................................................................................................................
(1)

(ii) Write the rate equation for the reaction.
...........................................................................................................................
(1)

(iii) Write a mechanism for the reaction which is consistent with your rate equation.








(3)


(c) The reaction between 2-bromobutane, C
2
H
5
CHBrCH
3
, and aqueous sodium hydroxide
proceeds by the same mechanism as in (b)(iii).
Use the mechanism to explain why the reaction of a single optical isomer of 2-
bromobutane produces a mixture that is no longer optically active.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 14 marks)


62. Potassium hydroxide solution, KOH(aq), is used to peel peaches commercially. The peaches are
placed in a 7% solution (7.00 g per 100 cm
3
of solution) for 3 minutes. The peaches are then
washed, cut in half and frozen.
(a) (i) Calculate the concentration, in mol dm
–3
, of the potassium hydroxide solution.


(2)


(ii) Calculate the pH of this solution.
[K
w
= 1.00 × 10
–14
mol
2
dm
–6
]






(2)

(b) The concentration of the potassium hydroxide solution must not fall below
1.00 mol dm
–3
. This is checked at intervals by the titration of 25.0 cm
3
of the solution
with 0.750 mol dm
–3
sulphuric acid.
(i) Write a balanced equation for the complete neutralisation of sulphuric acid with
potassium hydroxide.


(1)

(ii) Calculate the lowest acceptable titration value before more potassium hydroxide
must be added to the solution.



(2)


(iii) Sketch a graph showing how the pH changes when 30 cm
3
(an excess) of 0.750
mol dm
–3
sulphuric acid is added to 25.0 cm
–3
of 1.00 mol dm
–3
potassium
hydroxide.
16
12
8
4
0
–4
0 10 20 30
Volume of 0.750 mol dm sulphuric acid added/cm
–3 3
pH

(4)

(iv) Suggest a suitable indicator to use for this titration. Use your graph to justify your
choice.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(c) Suggest a safety check that should be made before the peaches are frozen. Why is this
check necessary?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 15 marks)


63. One step in the manufacture of nitric acid is the reaction between nitrogen(II) oxide and oxygen
to form nitrogen(IV) oxide.
2NO(g) + O
2
(g) 2NO
2
(g) ΔH = –114 kJ mol
–1

(a) (i) Use the equation to suggest the sign of ΔS
system
for the forward reaction. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

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


(b) (i) Write the expression for K
p
for this reaction.
What are the units of K
p
in this reaction?






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

(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)

(ii) In a series of experiments, the following results were obtained.
Experiment
[NO(g)]
/mol dm
–3

[O
2
(g)]
/mol dm
–3

Initial rate
/mol dm
–3
s
–1

1
1.0 × 10
–3
1.0 × 10
–3
8.0 × 10
–6

2
2.0 × 10
–3
1.0 × 10
–3
3.2 × 10
–5

3
2.0 × 10
–3
2.0 × 10
–3
6.4 × 10
–5

- 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)

(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)


64. This question is about compounds with the molecular formula C
4
H
8
O.
(a) (i) Draw the displayed formulae of TWO isomers, A and B, which are both aldehydes.
Give their systematic names.





A B
Name ....................................................... .......................................................
(4)


(ii) Suggest an instrumental method by which these isomers, A and B, could be
distinguished.
Outline how the results would differ.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(b) Substance C, butanone, is another isomer of C
4
H
8
O.
(i) Name a reagent which results in the same observation when it reacts with all three
isomers, A, B and C.
Reagent .............................................................................................................
...........................................................................................................................
Observation ......................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii) Name a reagent where the resulting observation for C would be different from that
for A and B.
Reagent .............................................................................................................
...........................................................................................................................
Observation with C ...........................................................................................
...........................................................................................................................
...........................................................................................................................
Observation with A and B ................................................................................
...........................................................................................................................
...........................................................................................................................
(3)


(c) (i) Suggest structural formulae for TWO more isomers of C
4
H
8
O, D and E, which are
cyclic and react with sodium to give off hydrogen.







D E
(2)

(ii) Both A and B can be oxidised to carboxylic acids. These acids will then react with
either of the isomers D or E in the presence of a strong acid as a catalyst.
What is the name given to the products of this type of reaction?
...........................................................................................................................
(1)

(iii) For one of the carboxylic acids formed from A or B and one of the isomers D or E,
draw a displayed formula of the product formed when they react together.








(2)
(Total 16 marks)



65. (a) (i) Calculate the pH of 0.050 mol dm
–3
hydrochloric acid.


(1)

(ii) Calculate the concentration of hydroxide ions, in mol dm
–3
, in this solution.
At this temperature, K
w
= 1.00 × 10
–14
mol
2
dm
–6
.






(1)

(b) Phosphoric(V) acid, H
3
PO
4
, is a weak acid, forming the following equilibrium in water:
H
3
PO
4
(aq) + H
2
O(l) H
2
PO
4

(aq) + H
3
O
+
(aq)
(i) Write an expression for the acid dissociation constant, K
a
, for phosphoric(V) acid.





(1)


(ii) Given that a 0.500 mol dm
–3
solution of phosphoric(V) acid has a pH of 1.20,
calculate the value of Ka, stating its units.
Assume that there is no further dissociation of the H
2
PO
4

ion.






(4)

(c) The H
2
PO
4

ion formed when phosphoric(V) acid is added to water can dissociate further
into HPO
4
2–
.
H
2
PO
4

(aq) + H
2
O(l) HPO
4
2–
(aq) + H
3
O
+
(aq)
.................. .................. .................. ..................

(i) In the spaces below the equation, identify the acid base conjugate pairs.
(2)

(ii) Explain why very little dissociation of the H
2
PO
4

ion occurs in solutions of
phosphoric(V) acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(d) The change in pH when 25.0 cm
3
of 0.100 mol dm
–3
phosphoric(V) acid is titrated with
sodium hydroxide solution of the same concentration can be seen on the graph below.
7
6
5
4
3
2
1
10 20 30
pH
Volume of 0.100 mol dm sodium
hydroxide solution added/ cm
3
–3



From the list below, select a suitable indicator for this titration. Justify your choice.
pK
In

bromocresol green 4.7
bromothymol blue 7.0
phenolphthalein 9.3
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)


66. Hydrogen sulphide, H
2
S, is partially decomposed when heated.
2H
2
S(g) 2H
2
(g) + S
2
(g) ∆H = +170 kJ mol
–1
0.500 mol of gaseous H
2
S were placed in a flask of volume 20.0 dm
3
and heated until
equilibrium was reached.
(a) Write an expression for the equilibrium constant, K
c
, for this reaction.




(1)


(b) When equilibrium was established, there were 0.350 moles of hydrogen sulphide in the
flask.
Calculate the value of K
c
at this temperature to two significant figures. State its units.







(5)

(c) The pressure in the reaction vessel was increased. By considering any change in K
c
,
explain the effect on the equilibrium position.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)


(d) State the effect, if any, on the value of K
c
of:
(i) adding a catalyst,
...........................................................................................................................
...........................................................................................................................
(1)
(ii) increasing the temperature.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 11 marks)


67. (a) Explain what is meant by the following terms.
Rate of reaction ...........................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Overall order of a reaction ..........................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(b) Two gases, A and B, react according to the equation
A + 3B AB
3

A series of experiments carried out at 298 K gave the following results.
Experiment Initial
concentration of
A
/ mol dm
–3

Initial
concentration of
B
/ mol dm
–3

Initial rate of
reaction

/ mol dm
–3
min
–1

1 0.100 0.100 0.00200
2 0.100 0.200 0.00798
3 0.200 0.100 0.00399

(i) State the order of reaction with respect to each of the reactants. Justify your
answer.
Reactant A ........................................................................................................
...........................................................................................................................
...........................................................................................................................
Reactant B ........................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(ii) Write the rate equation for the reaction between A and B.
...........................................................................................................................
(1)


(iii) Use the experimental data from Experiment 1 to calculate the rate constant,
including units.








(2)

(iv) Suggest a possible mechanism for the reaction between A and B, leading to the
formation of AB
3
. Identify the rate-determining step.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(c) The rae constant, k, for the reaction in (b) was measured at different temperatures.
The following data were obtained.
log
10
k
T
1
/K
–1

–2.70 0.00303
–3.39 0.00315
–4.09 0.00327
–4.43 0.00333


(i) Plot a graph of log
10
k against
T
1
, on the grid below.
–5.0
–4.0
–3.0
–2.0
0.00300 0.00310 0.00320 0.00330
log k
10
/K
–1
1
T

(2)


(ii) The Arrhenius equation can be written
log
10
k = constant |
.
|

\
|
÷
T R
E 1
30 . 2
a

where R = 8.31 J mol
–1
K
–1
.
A graph of log
10
k against
T
1
has a gradient of
R
E
30 . 2
a
÷
.
Calculate the gradient of the graph and hence calculate the value of activation
energy, E
a
.








(2)
(Total 15 marks)


68. This question is about the reaction between calcium carbonate and hydrochloric acid.
CaCO
3
(s) + 2HCl(aq) ÷ CaCl
2
(aq) + CO
2
(g) + H
2
O(l)
One method of studying the kinetics of this reaction is to measure the volume of carbon dioxide
given off at various timed intervals when using an excess of calcium carbonate.


(a) Suggest TWO other methods for following this reaction. Explain your choices.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) Suggest why the volume of carbon dioxide given off in the first few seconds of the
reaction is an unreliable measure of the initial rate of the reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(c) In an experiment, the following results were obtained.
Time
/ s
Volume of CO
2

V
t
/cm
3

(V
final
– V
t
)
/ cm
3

5 3 85
35 42 46
65 62 26
95 72
125 79
155 84
185 87

(i) What was the final volume, V
final
?
............................................................................
(1)


(ii) Complete the table.
(1)

(iii) To what is (V
final
– V
t
) proportional?
...........................................................................................................................
(1)

(iv) Plot these results on the grid below.
100
80
60
40
20
0
0 100 200
time / s
(V –V )
/ cm
final t
3

(2)


(v) On your graph measure and record THREE successive half-lives. Deduce the order
of the reaction. Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(vi) Give the rate equation for this reaction.




(1)

(vii) What are the units of the rate constant?
..............................................................
(1)


(d) What would you expect the signs of AS
system
and AS
total
to be for the reaction between
calcium carbonate and hydrochloric acid? Justify your answers.
AS
system
..........................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
AS
total
............................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 17 marks)


69. For each of the following reactions, give the names of all of the organic products.
Also give the type or mechanism as indicated for each reaction,
(a) CH
3
CO
2
H + NaOH ÷ CH
3
CO
2
Na + H
2
O
Name of organic product ..........................................................................................
Type of reaction ..........................................................................................
(2)


(b)
O CH
3
+ ICl + HCl
O CH
3
I

Name of organic product .........................................................................................
Type of reaction ......substitution...............................................................
Mechanism .........................................................................................
(2)

(c) CH
3
COCl + 2NH
3
÷ CH
3
CONH
2
+ NH
4
Cl
Name of organic product .........................................................................................
Type of reaction ......substitution...............................................................
Mechanism .........................................................................................
(2)

(d) CH
2
—O—CO(CH
2
)
8
CH
3
CH
2
OH
| |
CH—O—CO(CH
2
)
8
CH
3
+ 3H
2
O ÷ ÷ ÷ ÷ ÷
+
+ (aq) H
CHOH + 3CH
3
(CH
2
)
8
CO
2
H
| |
CH
2
—O—CO(CH
2
)
8
CH
3
CH
2
OH
Names of products .........................................................................................
.........................................................................................
Type of reaction .........................................................................................
(3)
(Total 9 marks)



70. This question is about a compound, A, used as a food flavouring. It has the molecular formula,
C
9
H
8
O.
(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 Brady‘s Reagent (2,4-dinitrophenylhydrazine) to give an orange
precipitate.
...........................................................................................................................
(1)

(iii) When A is heated with Benedict‘s solution, a red precipitate forms.
...........................................................................................................................
(1)

(iv) A decolorises bromine water.
...........................................................................................................................
(1)

(v) A is the cis isomer.
...........................................................................................................................
...........................................................................................................................
(1)


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









(2)


(b) Compound A can be converted to benzoic acid, C
6
H
5
CO
2
H, 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)


(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
–3
solution of benzoic acid.
[K
a
for benzoic acid is 6.30 × 10
–5
mol dm
–3
.]









(3)


(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)


71. Dichloroethanoic acid reacts with pent-1-ene as shown by the following equation:
CHCl
2
CO
2
H(l) + C
5
H
10
(l) CHCl
2
CO
2
C
5
H
11
(l)

(a) Give the name of the product of this reaction and also the name for the new functional
group it contains.
.....................................................................................................................................
.....................................................................................................................................
(2)


(b) In an experiment to determine the equilibrium constant, 1.00 mol of dichloroethanoic acid
was mixed with 2.30 mol of pent-1-ene. The total volume remained at 300 cm
3

throughout. When equilibrium had been reached, it was found that 0.40 mol of
dichloroethanoic acid was left.
(i) List the steps in the experiment you would carry out to determine the concentration
of dichloroethanoic acid present at equilibrium.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)

(ii) Give the expression for the equilibrium constant, K
c
, for this reaction.





(1)


(iii) Complete the table for the number of moles and concentrations at equilibrium.
Substance
Number of
moles at start
Number of moles
at equilibrium
Concentration at
equilibrium
/mol dm
–3

CHCl
2
COOH 1.00 0.40 1.33
C
5
H
10
2.30
CHCl
2
COOC
5
H
11
0
(3)

(iv) Calculate the value of K
c
, and give its units.











(3)
(Total 13 marks)



72. (a) Define the term standard enthalpy of formation.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(b) In the Haber process, ammonia is manufactured from nitrogen and hydrogen as shown in
the equation.
N
2
(g) + 3H
2
(g) 2NH
3
(g)
(i) Use the bond enthalpies below to calculate the standard enthalpy of formation of
ammonia.
Bond
Bond enthalpy / kJ mol
–1

N≡N in N
2

+945
H–H in H
2

+436
N–H in NH
3

+391






(4)


(ii) Draw a labelled enthalpy level diagram for the formation of ammonia in the Haber
process.
Enthalpy

(2)

(iii) State the temperature used in the Haber process and explain in terms of the rate of
reaction and position of equilibrium, why this temperature is chosen.
Temperature .......................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)


(iv) Identify the catalyst used in the Haber process and state what effect, if any, it has
on the equilibrium yield of ammonia.
Catalyst ................................................................
Effect on yield ...................................................................................................
(2)

(v) Explain why it is necessary to use a catalyst in this process.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(c) The pressure used in the Haber process is 250 atmospheres.
(i) State and explain an advantage of increasing the pressure to 1000 atmospheres.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii) Suggest a disadvantage of using a pressure of 1000 atmospheres.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 18 marks)



73. (a) Methanoic acid, HCOOH, is a weak acid. Explain what is meant by the terms weak and
acid.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) Write a balanced equation, including state symbols, for the reaction between aqueous
solutions of methanoic acid and sodium carbonate.
.....................................................................................................................................
(2)

(c) The following equilibrium is set up when methanoic acid dissociates in water:
HCOOH(aq) + H
2
O(1) HCOO

(aq) + H
3
O
+
(aq)

(i) There are two conjugate acid-base pairs in the above equation.
Identify them by completing the sentences below:
Formula of one acid is .......................................................... .
The formula of its conjugate base is .......................................................... .
(1)
Formula of the other acid is .......................................................... .
The formula of its conjugate base is .......................................................... .
(1)

(ii) Write the expression for the acid dissociation constant, K
a
, for methanoic acid.





(1)

(iii) Calculate the pH of a 0.100 mol dm
–3
solution of methanoic acid at 298 K.

[K
a
for methanoic acid is 1.60 × 10
–4
mol dm
–3
at 298 K]






(3)

(d) A buffer solution is made up by mixing equal volumes of 0.100 mol dm
–3
methanoic acid
and 0.400 mol dm
–3
sodium methanoate.
(i) Calculate the pH of the buffer solution obtained.






(3)


(ii) Explain why the pH of this mixture of methanoic acid and sodium methanoate
remains almost constant when a small quantity of an acidic solution, containing
hydrogen ions, or a small quantity of an alkaline solution, containing hydroxide
ions, is added.
In your explanation include equations to show the effect of adding hydrogen ions
and of adding hydroxide ions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(Total 16 marks)



74. One stage in the manufacture of sulphuric acid is
2SO
2
(g) + O
2
(g) 2SO
3
(g)
The equilibrium constant K
p
=
2 2
3
O
2
SO
2
SO
p p
p
×


(a) 10.0 mol of SO
2
and 5.00 mol of O
2
were allowed to react. At equilibrium, 90.0% of the
SO
2
was converted into SO
3
.
(i) Calculate the number of moles of SO
2
, O
2
and SO
3
present in the equilibrium
mixture.





(2)

(ii) Calculate the mole fractions of SO
2
, O
2
and SO
3
at equilibrium.







(1)


(iii) Assuming that the total pressure of the equilibrium mixture was 2.00 atm, calculate
the partial pressures of SO
2
, O
2
and SO
3
at equilibrium.









(1)

(iv) Calculate the value of K
p
.






(2)

(b) The reaction between sulphur dioxide and oxygen is exothermic.
(i) State the effect, if any, on K
p
of increasing the temperature at constant pressure.
...........................................................................................................................
(1)


(ii) Use your answer to (i), and the expression K
p
=
2 2
3
O
2
SO
2
SO
p p
p
×
to explain the effect
on the position of equilibrium of increasing the temperature at constant pressure.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(c) The reaction was repeated at a higher pressure whilst maintaining a constant temperature.
(i) State the effect, if any, of an increase in the total pressure on the value of K
p
.
...............................................................................
(1)
(ii) State the effect, if any, of this increase in pressure on the amount of sulphur
trioxide in the equilibrium mixture.
...............................................................................
(1)

(d) State the effect, if any, of a catalyst on:
(i) K
p

...............................................................................
(1)
(ii) the equilibrium position.
...............................................................................
(1)
(Total 13 marks)



75. (a) What is the formula of the ion found in all acidic solutions?
.....................................................................................................................................
(1)

(b) Which of the following substances would form an acidic solution in water?
A CH
4
B NaOH C HCO
2
H
D NH
3
E HNO
3

.....................................................................................................................................
(2)
(Total 3 marks)


76. When barium nitrate is heated it decomposes as follows:
Ba(NO
3
)
2
(s) → BaO(s) + 2NO
2
(g) + ½O
2
(g) ΔH = +505.0 kJ mol
–1

(a) Use the following data when answering this part of the question.
Substance
Standard entropy,
S
ο
/ J mol
–1
K
–1

Ba(NO3)
2
(s) + 213.8
BaO(s) + 70.4
NO
2
(g) + 240.0
O
2
(g) + 205.0

(i) Explain why:
• S
ο
[NO
2
(g)] is greater than S
ο
[BaO(s)]
...........................................................................................................................
...........................................................................................................................
• S
ο
[Ba(NO
3
)
2
(s)] is greater than S
ο
[BaO(s)].
...........................................................................................................................
...........................................................................................................................
(2)


(ii) Calculate the entropy change of the system, ΔS
ο
system
, for this reaction. Include a
sign and units in your answer.



(2)
(b) Calculate the entropy change of the surroundings, ΔS
ο
surroundings
, for the reaction at 298 K.
Include a sign and units in your answer.
(2)

(c) Calculate ΔS
ο
total
, and explain the significance of the sign for this value.
.....................................................................................................................................
(2)

(d) Calculate the minimum temperature at which the decomposition of barium nitrate should
occur.
You can assume that ΔH and ΔS
system
are not affected by a change in temperature.






(2)
(Total 10 marks)


77. This question is about butanal, CH
3
CH
2
CH
2
CHO, and several related compounds.
(a) What would you see when Brady‘s reagent is added to a sample of butanal?
.....................................................................................................................................
(1)


(b) F, G and H are three isomers of butanal which are each tested with sodium, Benedict‘s
reagent and Brady‘s reagent. The results are shown in the table below.
Key: = positive result
= negative result
Sodium Benedict‘s reagent Brady‘s reagent
F

G

H

Suggest structural formulae for F, G and H.


F


G


H


(3)

(c) An ester with the formula, CH
3
CH
2
CH
2
CO
2
CH
2
CH
3
, is heated under reflux with aqueous
sodium hydroxide.
(i) Give ONE advantage of ―heating under reflux‖, rather than simply boiling the two
liquids together in a beaker.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(ii) Name the ester.
...........................................................................................................................
(1)

(iii) Name the TWO products of this reaction.
...........................................................................................................................
(2)

(iv) What type of reaction is taking place?
...........................................................................................................................
(1)
(Total 9 marks)


78. The reaction between peroxodisulphate and iodide ions occurs as follows:
aq) ( I aq) ( SO 2 aq) ( 2I aq) ( O S
2
2
4
2
8 2
+ ÷÷ ÷ +
÷ ÷ ÷

Initial rates for this reaction can be determined by a method known as an ‗iodine clock‘.
A mixture of potassium iodide, sodium thiosulphate and starch is made up, and a clock started
when a solution of potassium peroxodisulphate is added. When enough iodine has been formed
to react with all the sodium thiosulphate, the excess iodine suddenly forms a blue-black
complex with the starch. At this point the clock is stopped, and the time taken.

(a) In one particular experiment, the volumes of the reactants used were as follows:
Volume of
K
2
S
2
O
8
(aq)
/ cm
3

Volume of
KI(aq) / cm
3

Volume of
Na
2
S
2
O
3
(aq)
/ cm
3

Volume of
starch solution /
cm
3

Volume of
water / cm
3

Time taken
/ s
10.0 10.0 5.0 1.0 14.0 5


(i) The concentration of the sodium thiosulphate used was 0.010 mol dm
–3
. Calculate
the number of moles of thiosulphate ions,
÷ 2
3 2
O S , in the mixture.



(1)

(ii) Iodine reacts with thiosulphate ions as shown below:
aq) ( O S aq) ( I 2 (aq) O 2S aq) ( I
2
6 4
2
3 2 2
÷ ÷ ÷
+ ÷÷ ÷ +
Calculate the number of moles of iodine which had reacted when the clock was
stopped.


(1)

(iii) Calculate the rate of formation of iodine in mol dm
–3
s
–1
.


(2)

(b) Further experiments were carried out and the results are shown below.
Experiment [
÷ 2
8 2
O S (aq)] / mol dm
–3
[I

(aq)] / mol dm
–3
Rate / mol dm
–3
s
–1

1 0.0100 0.0200
2.74 × 10
–5

2 0.0100 0.0400
5.47 × 10
–5

3 0.0300 0.0800
3.28 × 10
–4


(i) What is the order of reaction with respect to iodide ions, I

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


(ii) Deduce the order of reaction with respect to peroxodisulphate ions,
÷ 2
8 2
O S .
Show how you arrived at your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(iii) Use your answers to (i) and (ii) to write an overall rate equation for the reaction.


(1)

(iv) Use the data from experiment 1 to calculate the rate constant for this reaction.
Give the units for the rate constant.


(2)
(Total 9 marks)



79. 10.0 cm
3
of a solution of butanoic acid, CH
3
CH
2
CH
2
CO
2
H, of concentration 0.00660 mol dm
–3
,
was titrated with a solution of aqueous ammonia using a pH probe.
The pH was recorded throughout, and the results were plotted as shown below.
11
10
9
8
7
6
5
4
3
2
1
0
pH
0 10 20 30 40 50 60
Volume of ammonia added / cm
3
X
Y


(a) (i) Using the pH of butanoic acid from the graph, calculate the initial hydrogen ion
concentration.



(2)


(ii) Write the expression for the acid dissociation constant, K
a
, for an aqueous solution
of butanoic acid.



(1)

(iii) Calculate the value of K
a
making the usual assumptions. Give your answer to two
significant figures.



(2)

(b) (i) Write an equation for the reaction between butanoic acid and ammonia. State
symbols are not required.

(1)

(ii) Name the two compounds, apart from water, which are present in the mixture
between X and Y shown on the graph.
...........................................................................................................................
(2)

(iii) What type of mixture is present between X and Y? What evidence is there for your
answer by reference to the graph?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(iv) Explain why it is not possible to carry out this titration using an indicator.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(v) Use the graph to estimate the end-point of the titration. Hence calculate the
concentration of the ammonia solution.


(2)
(Total 13 marks)


80. (i) Define the term enthalpy of hydration, ΔH
hyd
, of an ion.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(ii) The table below gives some information about the sulphates of the Group 2 elements
magnesium and barium.
sulphate lattice energy

/ kJ mol
–1

hydration
enthalpy of cation
/ kJ mol
–1

solubility

/ mol dm
–3

MgSO
4
–2874 –1920 1.83
BaSO
4
–2374 –1360 9.43 × 10
–6

Use the lattice energy and hydration enthalpy values to explain the difference in the
solubility of the two salts.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 6 marks)



81. (a) Sketch the titration curve that you would expect if 25.0 cm
3
of 0.100 mol dm
–3

hydrochloric acid, HCl, is titrated with 40.0 cm
3
of 0.100 mol dm
–3
ammonia solution,
NH
3
.
14
12
10
8
6
4
2
0
10 20 30 40
Volume of 0.100 mol dm
ammonia solution / cm
3
–3
pH

(4)

(b) Using your answer to (a), select a suitable indicator for this titration. Put a tick in the
appropriate box in the table below.
Indicator pK
Ind
( )
thymol blue 1.7
bromocresol green 4.7
phenol red 7.9
phenolphthalein 9.3
(1)


(c) Suggest why there is no suitable indicator for the titration of ethanoic acid with ammonia.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 7 marks)


82. Methanoic acid and ethanol react together to form ethyl methanoate, HCOOC
2
H
5
, and water.
This reaction is reversible and can be allowed to reach equilibrium.
HCOOH(l) + C
2
H
5
OH(l) HCOOC
2
H
5
(l) + H
2
O(l) ΔH = +45 kJ mol
–1

(a) Draw the full structural formula of ethyl methanoate, showing all bonds.





(1)

(b) What type of organic compound is ethyl methanoate?
.....................................................................................................................................
(1)


(c) In an experiment, 3.00 mol methanoic acid, HCOOH, and 6.25 mol ethanol, C
2
H
5
OH,
were mixed together. A small quantity of catalyst was added. The mixture was left for
several days in a water bath to reach equilibrium at constant temperature.
(i) Complete the table.
Number of moles in the reaction mixture
HCOOH C
2
H
5
OH HCOOC
2
H
5
H
2
O
at start of
experiment
3.00 6.25 0.00 0.00
at equilibrium 0.50
(2)

(ii) Write an expression for the equilibrium constant, K
c
, for the reaction.




(1)

(iii) Calculate K
c
for the reaction at the temperature of the experiment. The total volume
of the equilibrium mixture was 485 cm
3
.





(2)

(iv) State and explain whether K
c
for this reaction has units.
...........................................................................................................................
...........................................................................................................................
(1)


(d) (i) The temperature of this equilibrium mixture is lowered.
Explain the effect of this on the value of the equilibrium constant and hence on the
yield of ethyl methanoate.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)

(ii) A student added more catalyst to the mixture.
State, giving a reason, what would happen to the composition of the equilibrium
mixture.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 13 marks)


83. A chemist has synthesised a compound W believed to be

HO CH CH CH C
Cl O
OH


(a) State and explain what you would see if W is reacted with:
(i) sodium carbonate solution
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii) bromine water.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(b) W shows both types of stereoisomerism.
(i) How many stereoisomers of W are there? Briefly explain your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii) Explain why W shows optical isomerism.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(c) Describe how you would show that W contains chlorine.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)
(Total 14 marks)


84. Two gases, A and B, react according to the equation
A(g) + 2B(g) → AB
2
(g)
A series of kinetics experiments performed at constant temperature gave the following results:
Experiment
Initial concentration of
A /mol dm
–3

Initial concentration of
B /mol dm
–3

Initial rate
/mol dm
–3
s
–1

1 0.0500 0.100
1.00 ×10
–4

2 0.0500 0.200
3.92 ×10
–4

3 0.1000 0.100
1.95 ×10
–4



(a) (i) Calculate, showing your working, the order of reaction with respect to A and to B.







(3)

(ii) Write the rate equation for the reaction.
...........................................................................................................................
(1)

(iii) Calculate the rate constant, k, for the reaction in experiment 3, stating its units.
(2)


(b) (i) Explain, in terms of collision theory, why the rate of reaction increases with an
increase in temperature.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(ii) Suggest, with an explanation, the least number of steps which is likely to exist in
the mechanism of the reaction between A and B.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(c) The variation of the rate constant, k, with change in temperature is given by the Arrhenius
equation:
ln k = A
T R
E
a
ln
1
+
|
|
.
|

\
| ÷

where A is a constant.
In a series of experiments performed at various temperatures T to determine the rate
constant, k, for the decomposition of a gas X, a graph of ln k against 1/T gave a straight
line of slope
R
E
a
÷
:
–5
–6
–7
–8
–9
–10
–11
–12
ln k
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034
1
T
/ K
–1



Use the graph to calculate the value of the activation energy, in kJ mol
–1
, for the
decomposition of X. The value of the gas constant R = 8.31 J K
–1
mol
–1
.








(4)
(Total 15 marks)


85. When solid lead(II) sulphate is added to a solution of sodium iodide, the following equilibrium
is established:
PbSO
4
(s) + 2I

(aq) PbI
2
(s) + SO
4
2–
(aq)
The equilibrium constant, Kc, for this reaction may be found by adding an excess of solid
lead(II) sulphate to a known volume of a standard solution of sodium iodide. The mixture is left
to reach equilibrium at a constant temperature, T.
Ice-cold water is added to freeze the position of equilibrium and the mixture is then titrated with
standard silver nitrate solution.
In a typical experiment, excess lead(II) sulphate was added to 50.0 cm
3
of 0.100 mol dm
–3

sodium iodide solution. The whole equilibrium mixture required 31.0 cm
3
of 0.100 mol dm
–3

silver nitrate solution to react with the aqueous iodide ions.
The expression for K
c
for this reaction is
K
c
=
2
2
4
] I [
] SO [
÷
÷



(a) Why is it not necessary to know the mass of the lead(II) sulphate used in the experiment?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(b) Give the ionic equation for the reaction between silver nitrate solution and aqueous iodide
ions to produce a precipitate of silver iodide, AgI.
.....................................................................................................................................
(1)

(c) From the data given above, calculate the equilibrium amounts of the iodide and of the
sulphate ions in solution. Hence calculate the equilibrium concentration of these ions, and
the value of K
c
for the reaction at temperature T, including the units, if any.










(8)
(Total 10 marks)



86. This question concerns the reactions of some compounds of nitrogen.
(a) The ammonium ion reacts with water and behaves as an acid.
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
(i) Identify the TWO conjugate acid-base pairs in the spaces provided.
acid 1 ................................... base 1 ...................................
acid 2 ................................... base 2 ...................................
(1)

(ii) Write the expression for the acid dissociation constant, K
a
, of the ammonium ion.




(1)

(iii) A solution of ammonium chloride has a pH of 5.00 at 25°C.
K
a
for the ammonium ion is 5.62 × 10
–10
mol dm
–3
at 25°C.
Calculate the concentration of this solution. State any assumptions you have made.








(4)


(iv) Use the following table and your answer from part (iii) to suggest a suitable
indicator for the titration of ammonia solution with hydrochloric acid. Justify your
answer.
Indicator pK
In

thymol blue 1.7
methyl red 5.1
phenolphthalein 9.3
...........................................................................................................................
...........................................................................................................................
(2)

(b) Hydrogen cyanide is a weak acid in aqueous solution.
Write an equation to show why aqueous solutions of cyanide ions are alkaline.
.....................................................................................................................................
(1)

(c) Hydrogen cyanide reacts with propanal as follows:
CH
3
CH
2
CHO + HCN → CH
3
CH
2
CH(OH)CN
Propanal is reacted with a solution of potassium cyanide, KCN, containing a little dilute
sulphuric acid.
(i) What type of reaction is this?
...........................................................................................................................
(1)


(ii) Give the mechanism for the reaction.









(3)

(iii) It is important that the pH is neither too acidic nor too alkaline if a good yield of
the product is to be obtained. Explain why this is so.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(d) In an investigation of the kinetics of the nucleophilic substitution reaction between 1-
chloropropane and potassium cyanide in aqueous ethanolic solution, the reaction was
found to be first order with respect to 1-chloropropane and first order with respect to
cyanide ions.
(i) Give the rate equation for the reaction.
...........................................................................................................................
(1)


(ii) Write a mechanism for the reaction that is consistent with this rate equation.









(3)
(Total 19 marks)


87. In the presence of hydrogen ions, H
+
, glucose, C
6
H
12
O
6
, can be oxidised by a solution of
potassium manganate(VII), KMnO
4
, which is purple in colour.
A series of experiments was carried out to determine the rate of reaction and the results are
shown below.
Experiment
Initial
concentration
of C
6
H
12
O
6

/ mol dm
–3

Initial
concentration
of KMnO
4

/ mol dm
–3

Initial
concentration
of H
+

/ mol dm
–3

Rate of
reaction

/ mol dm
–3
s
–1

1 1.0 0.01 0.5
2.0 × 10
–5

2 1.0 0.005 0.5 1.0 × 10
–5

3 0.5 0.005 0.5 1.0 × 10
–5

4 1.0 0.02 1.0
8.0 × 10
–5



(a) Describe how the rate of this reaction may have been measured.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(b) (i) Give the order of reaction with respect to each reactant. In the case of potassium
manganate(VII) and hydrogen ions explain how you arrived at your answer.
Glucose ................................................
Potassium manganate(VII) ...............................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Hydrogen ions ..................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(ii) Write the rate equation for this reaction.
...........................................................................................................................
(1)


(iii) Using the data from experiment 1, calculate the rate constant for the reaction.
Include the units of the rate constant in your final answer.





(2)

(c) Additional experiments were carried out to investigate the effect of temperature on the
rate of reaction.
(i) Complete the missing data in the table below.
Temperature (T)
/ K
1/ temperature (1/T)
/ K
–1

Rate constant ln (rate constant)
295
3.39 × 10
–3
2.88 × 10
–3

–5.85
305
3.28 × 10
–3
1.01 × 10
–2

–4.60
311

1.83 × 10
–2


320 3.13 × 10
–3
4.98 × 10
–2
–3.00
333
3.00 × 10
–3
2.02 × 10
–1

–1.60
(1)


(ii) Plot a graph of ln (rate constant) on the vertical axis against 1/T on the horizontal
axis using the axes below.

(2)

(iii) Use the Arrhenius equation ln (rate) =
T
1
R
E
A
×
÷
+ constant, together with your
graph to calculate a value of the activation energy, E
A
, for this reaction.
Show all steps in your working. Include units in your final answer, which should be
given to two significant figures.
[Gas constant, R = 8.31 J K
–1
mol
–1
]





(2)
(Total 13 marks)



88. Ammonia can be oxidised to form nitrogen(II) oxide and water according to the equation
4NH
3
(g) + 5O
2
(g) → 4NO(g) + 6H
2
O(g) ∆H
ο
= –905.6 kJ mol
–1
.
In industry, the reaction is carried out at 1123 K with a platinum/rhodium catalyst.
The standard entropy of one mole of each substance in the equation, measured at 298 K, is
shown in the table below.
Substance
S
ο
/ J mol
–1
K
–1

NH
3
(g) +192.3
O
2
(g) +205.0
NO (g) +210.7
H
2
O (g) +188.7

(a) (i) Use the values given to calculate the standard entropy change of the system,
∆S
ο
system
, for this reaction. Include the sign and units in your final answer.




(2)

(ii) Is the sign for your value for ∆S
ο
system
what you expected? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(iii) Calculate the entropy change of the surroundings, ∆S
surroundings
, at 1123 K for this
reaction. Include the sign and units in your final answer.




(2)

(iv) Calculate the total entropy change, ∆S
total
, for this reaction at 1123 K. Include the
sign and units in your final answer. You may assume that ∆S
system
is unchanged at
high temperatures.


(1)

(v) What does your answer to (iv) tell you about the extent of the reaction at 1123 K?
Justify your answer.
...........................................................................................................................
...........................................................................................................................
(1)


(vi) An energy profile was proposed to illustrate the effect of the catalyst on this
reaction. The proposal has two errors. Draw a corrected version on the axes below.
Progress of reaction
Energy
Uncatalysed
pathway
4NH
3
(g) +
5O (g)
2
4NO(g) +
6H
2
O(g)
Catalysed
pathway
Proposal
4NH
3
(g) +
5O (g)
2
Energy
Corrected version
Progress of reaction

(2)

(b) The oxidation of nitrogen(II) oxide leads to the following equilibrium
2NO(g) + O
2
(g) 2NO
2
(g)
The number of moles of each gas in a reaction mixture at equilibrium, at a pressure of
1.5atm, was found to be
Substance
Number of moles
at equilibrium
NO (g) 0.025
O
2
(g) 0.025
NO
2
(g) 4.95


(i) Write the expression for the equilibrium constant, K
p
, for this reaction.



(1)

(ii) Calculate the mole fraction of each gas and hence the value of the equilibrium
constant, K
p
, for this mixture. Include units, if required, in your answer.





(4)

(iii) What does your answer to (ii) tell you about the position of the equilibrium?
Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(iv) If the total pressure of the reaction mixture was increased, describe what would
happen to the value of the equilibrium constant, K
p
, and the partial pressure of
NO
2
(g). In each case justify your answer.
Equilibrium constant, K
p
.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Partial pressure of NO
2
(g).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 17 marks)


89. (a) The table below shows the acid dissociation constants, K
a
, of three carboxylic acids.
Acid Structural formula K
a
/ mol dm
–3

Chloroethanoic CH
2
ClCO
2
H
1.3 × 10
–3

Dichloroethanoic CHCl
2
CO
2
H
5.0 × 10
–2

Trichloroethanoic CCl
3
CO
2
H
2.3 × 10
–1


(i) Write an expression for the acid dissociation constant, K
a
, of chloroethanoic acid.


(1)


(ii) Calculate the pH of a 0.0010 mol dm
–3
solution of chloroethanoic acid, making the
usual assumptions.





(3)

(iii) Which acid would have the lowest pH at a concentration of 0.0010 mol dm
–3
?
Use both the data and the structure of the acids to justify your answer. No further
calculation is required.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(b) Chloroethanoic acid, CH
2
ClCO
2
H, reacts with methanol, CH
3
OH, in the presence of a
sulphuric acid catalyst.
(i) Draw the displayed formula and give the name of the organic product formed.
Displayed Formula




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


(ii) What name is given to the functional group formed in this organic product?
...........................................................................................................................
(1)

(iii) What type of reagent is methanol in this reaction? Explain why it is able to behave
in this way and describe how it attacks the chloroethanoic acid.
You may find it helpful to draw a diagram.





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

(iv) How would you convert the organic product of the reaction between
chloroethanoic acid and methanol back into the original compounds?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 15 marks)



90. This question is about ammonia, NH3, which is produced as shown in the following equation.
N
2
(g) + 3H
2
(g) 2NH
3
(g)
(a) Use oxidation numbers to explain why this is a redox reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b) (i) Use the average (mean) bond enthalpy data to calculate a value for the enthalpy
change for this reaction. You are reminded to show all your working.
Bond
Average bond enthalpy
/ kJ mol
–1

N≡N 944
H—H 436
N—H 388






(3)

(ii) The actual standard enthalpy change for this reaction is –92 kJ mol
–1
. Explain why
the value you calculated in (b)(i) is not the same as this.
...........................................................................................................................
...........................................................................................................................
(1)


(iii) At room temperature, a mixture of nitrogen and hydrogen is thermodynamically
unstable with respect to ammonia, but is kinetically stable.
Use the data in (b)(i) and (ii) to help you explain why this mixture is
thermodynamically unstable
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
kinetically stable
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)


(c) The manufacturer of ammonia would like to achieve a high rate of reaction and a high
equilibrium yield of product.
(i) State and explain, in terms of collision theory, TWO ways to increase the rate of
the reaction. An increase in pressure does not alter the rate in this process.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(6)


(ii) State and explain TWO ways to increase the equilibrium yield of ammonia.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 19 marks)



91. Consider the following compounds.
H—C—C—C—C
H
H
H
H
H
H
O—C—H
H
H
O
H—–C—–C—–C—–C
H
OH
H
H
H
H
H
O
C
H
H
H
OH
C—–C—–H
H
H
H
Compound X
Compound Y
Compound Z
C


(a) Name the functional groups present in the three compounds X, Y and Z.
Compound Functional groups present
X
Y
Z
(3)


(b) Compounds X, Y and Z are heated separately with alkaline ammoniacal silver nitrate
solution.
Draw the full structural formula, showing all bonds, of any organic product formed.
If a reaction does not occur, write ‘no reaction’.
Product from X


Product from Y


Product from Z


(3)

(c) Draw the formulae of the organic products formed by the reaction of
(i) X, CH
3
CH
2
CH
2
COOCH
3
, with aqueous sodium hydroxide solution.




(2)


(ii) Z, CH
2
(OH)CH
2
CH
2
CHO, with hydrogen cyanide.





(1)
(Total 9 marks)


92. (a) The equilibrium between hydrogen iodide, hydrogen and iodine was investigated by
sealing hydrogen iodide in glass tubes and heating the tubes at 698 K until equilibrium
was reached.
2HI(g) H
2
(g)+ I
2
(g) ΔH = + 9.4 kJ mol
–1

The glass tubes were cooled rapidly and then opened in a solution of potassium iodide so
that the concentration of iodine at equilibrium could be determined by titration.
(i) Suggest why the reaction mixture was cooled rapidly.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)


(ii) The expression for the equilibrium constant, K
c
, for the above reaction is
K
c
=
2
2 2
HI(g)] [
)] g ( I )][ ( H [ g

One of the tubes was found to contain iodine at a concentration of
5.0 × 10
–4
mol dm
–3
.
Calculate the equilibrium concentration of hydrogen iodide, in mol dm
–3
.
The equilibrium constant, K
c
, for the above reaction is 0.019 at 698 K.





(3)

(b) In a different experiment, 1.0 mol of hydrogen and 1.0 mol of iodine were allowed to
reach equilibrium at 698 K.
H
2
(g) + I
2
(g) 2HI(g)
At equilibrium, 80% of the hydrogen was converted to hydrogen iodide at a total pressure
of 1.1 atm.
(i) Write an expression for the equilibrium constant, K
p
, for the reaction as shown.



(1)


(ii) Calculate the value of K
p
.





(4)

(iii) Explain why, in this case, K
p
has no units.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 11 marks)


93. This question is about propanoic acid, CH
3
CH
2
COOH.
(a) Propanoic acid is a weak acid which dissociates as follows
CH
3
CH
2
COOH(aq) + H
2
O(l) CH
3
CH
2
COO

(aq) + H
3
O
+
(aq)
(i) In the above equation there are two conjugate acid-base pairs.
Identify them by completing the sentences below
Formula of one acid is ......................................................................................
The formula of its conjugate base is .................................................................
Formula of the other acid is ..............................................................................
The formula of its conjugate base is .................................................................
(2)


(ii) Propanoic acid is a weak acid. Explain what is meant by the term weak acid.
Weak
...........................................................................................................................
...........................................................................................................................
Acid
...........................................................................................................................
...........................................................................................................................
(2)

(b) The acid dissociation constant, K
a
, for propanoic acid is 1.30 × 10
–5
mol dm
–3
at 298 K.
(i) Write the expression for the acid dissociation constant, K
a
, for propanoic acid.



(1)


(ii) A solution of propanoic acid has a pH of 3.44 at a temperature of 298 K.
Calculate the concentration, in mol dm
–3
, of the propanoic acid solution. Show
clearly two assumptions you have made.
Calculation:





Assumptions:
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(5)


(c) A mixture of sodium propanoate and propanoic acid acts as a buffer solution.
(i) What is meant by a buffer solution?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii) Calculate the pH of a buffer solution made by mixing 100 cm
3
of 0.0100 mol dm
–3

propanoic acid solution with 300 cm
3
of 0.00500 mol dm
–3
sodium propanoate
solution at 298 K.
[K
a
for propanoic acid is 1.30 × 10
–5
mol dm
–3
at 298 K]





(3)
(Total 15 marks)


94. Name the following organic compound
HCHO
...............................................................................................................................................
(Total 1 mark)



95. (a) Draw the displayed formula of a branched chain ketone containing five carbon atoms.





(2)

(b) Give the systematic name for this ketone.
.....................................................................................................................................
(1)

(c) What is the molecular formula of the alcohol this ketone could be made from?
.....................................................................................................................................
(1)

(d) An alcohol can be converted into a ketone by oxidation with sodium dichromate(VI) and
sulphuric acid.
Explain why refluxing the mixture first, rather than immediately distilling the product
over from the beginning, results in a higher yield of the ketone.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 5 marks)



96. This question is about the reaction between barium hydroxide and ammonium chloride:
Ba(OH)
2
(s) + 2NH
4
Cl(s) → BaCl
2
.2H
2
O(s) + 2NH
3
(g) ΔH = +21.2 kJ mol
–1

(a) Standard entropies of the reactants and products are shown below:
Substance
Standard entropy, S
ο

/ J mol
–1
K
–1

Ba(OH)
2
(s) + 99.7
NH
4
Cl(s) + 94.6
BaCl
2
.2H
2
O(s) +202.9
NH
3
(g) +192.3
Calculate the standard entropy change for the system, ΔS
ο
system
, for this reaction.
Include a sign and units in your answer.




(2)

(b) Calculate the entropy change for the surroundings, ΔS
ο
surroundings
, at 298 K. Give your
answer to 3 significant figures and include a sign and units in your answer.





(2)


(c) (i) Use your answers to (a) and (b) to explain why this reaction is spontaneous at 298
K.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(ii) When these two solids are mixed together in a beaker, no reaction is observed.
What explanation can be given for this, in view of the fact that the process is
spontaneous?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(iii) Apart from heating the mixture, suggest what might be done to encourage the
reaction to take place. Explain why your suggestion is likely to work.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 8 marks)



97. The principal reaction occurring when 2-bromo-2-methylpropane reacts with aqueous sodium
hydroxide is as follows:
CH
3 3 3
C(CH )CH + NaOH CH C(CH )CH
3 3 3
+ NaBr

Br OH
Several experiments were carried out in order to follow the kinetics of this alkaline hydrolysis.
A few drops of phenolphthalein were added to a sample of sodium hydroxide, and, after the
addition of a measured amount of 2-bromo-2-methylpropane, the mixture was vigorously
shaken and a clock was immediately started. The time was taken when the pink colour due to
the indicator disappeared.
This experiment was repeated twice using different concentrations of the two reactants.
All experiments were carried out at the same temperature.
The results are shown in the table below.
Experiment 2-bromo-2-methylpropane
/ mol dm
–3

Sodium hydroxide
/ mol dm
–3

Time /s
A 0.011
8.0 × 10
–4

33
B 0.022
8.0 × 10
–4

16
C 0.022
1.2 × 10
–3

24

(a) (i) Identify the attacking species responsible for this alkaline hydrolysis.
...........................................................................................................................
(1)

(ii) Assuming that the final concentration of sodium hydroxide is zero, calculate the
average rates of reaction in mol dm
–3
s
–1
for experiments A and B.




A ................. mol dm
–3
s
–1
B ................. mol dm
–3
s
–1

(2)


(iii) Deduce the order of reaction with respect to 2-bromo-2-methylpropane. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(iv) By comparing the average rates of reaction between experiments B and C, deduce
the order of reaction with respect to sodium hydroxide.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(v) Write the rate equation for the reaction.
Rate =
(1)

(vi) From your rate equation, suggest how this reaction proceeds by giving a possible
mechanism.




(3)


(b) Explain briefly why 1-bromobutane, an isomer of 2-bromo-2-methylpropane, reacts by a
different mechanism when it is hydrolysed.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)


98. The equation below shows the equilibrium existing between nitrogen, oxygen and nitrogen
monoxide.
N
2
(g) + O
2
(g) 2NO(g)
The equilibrium constant, K
p
, at 298 K is 5.0 ×10
–31


(a) (i) Write an expression for the equilibrium constant, K
p
, in terms of the partial
pressures of the three gases.



(1)

(ii) Why does the value for K
p
have no units?
...........................................................................................................................
...........................................................................................................................
(1)


(b) An equilibrium mixture of these three gases was found to contain nitrogen, at a partial
pressure of 0.87 atm, and oxygen, at a partial pressure of 0.23 atm.
(i) Calculate the partial pressure exerted by the nitrogen monoxide.




(2)
(ii) Deduce the value of the total pressure of the equilibrium mixture of gases.




(1)

(iii) Assuming that the total pressure on the mixture of gases is doubled, what, if any,
would be the effect on the
• partial pressure of nitrogen monoxide
.....................................................................................................................................
.
.....................................................................................................................................
.
• equilibrium constant, K
p
?
.....................................................................................................................................
.
.....................................................................................................................................
.
(2)


(c) Inside a car engine, air (a mixture of nitrogen and oxygen) is drawn in and, under the high
temperatures operating, the value of K
p
increases dramatically.
This increase is also accompanied by an increase in the value of ΔS
total
. Typical values of
K
p
and ΔS
total
are shown in the table below.
Temperature / K K
p
ΔS
total
/ J mol
–1
K
–1

298
5.0 × 10
–31

–580
1500
1.0 × 10
–5

– 96
Although the value of ΔS
system
is unlikely to alter very much, the value for ΔS
surroundings

will change significantly.

(i) At a temperature of 1500 K, ΔS
total
is negative.
Does this mean that the reaction between nitrogen and oxygen cannot occur at this
temperature? Explain your reasoning.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(ii) Why is the value for ΔS
system
for this equilibrium approximately constant when the
temperature rises above 298 K?
...........................................................................................................................
...........................................................................................................................
(1)

(iii) What is the sign of ΔS
surroundings
for an endothermic reaction? Justify your answer.
...........................................................................................................................
...........................................................................................................................
(1)


(iv) Explain why an endothermic reaction results in an increase in the value of ΔS
total
as
the temperature increases.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(d) A student used the value for K
p
at 1500 K to calculate the partial pressure of nitrogen
monoxide inside a working car engine.
Why might the actual partial pressure be lower than the calculated answer?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 12 marks)



99. Calculate the pH of the buffer solution formed by mixing 10 cm
3
of aqueous benzoic acid of
concentration 0.010 mol dm
–3
with 40 cm
3
of aqueous sodium benzoate of concentration 0.020
mol dm
–3
.
For benzoic acid, the acid dissociation constant, K
a
, is 6.3 × 10
–5
mol dm
–3
.
You may find it helpful to use the relationship pH = – log Ka –
[base]
acid] [
log





(Total 3 marks)


100. Compound V, the structure of which is shown below, is found in human sweat.

C C
H
CH
3
C
CH
3
CH
2
CH
2
OH
O

Compound V


(a) Compound V contains two functional groups.
Identify both functional groups and state a chemical test for each. The result of each test
should also be included in your answer.
One functional group in V ...........................................................................................
Test and result .............................................................................................................
.....................................................................................................................................
.....................................................................................................................................
The other functional group in V .................................................................................
Test and result .............................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)

(b) Compound V can be converted into two carbonyl compounds W and X, shown below.

C C
O
H
O
OH
W
CH
CH CH CH
3
3 2 2
C
O
X


(i) Which of the compounds W or X would react when warmed with Fehling‘s
solution to give a red precipitate? Justify your answer.
...........................................................................................................................
...........................................................................................................................
(1)

(ii) Compound W can be reduced in two steps to compound Y of molecular formula
C
2
H
6
O
2
.
Identify Y.
...........................................................................................................................
(1)


(iii) Compound W can be oxidised to compound Z of molecular formula C
2
H
2
O
4
.
Identify Z.
...........................................................................................................................
(1)

(c) The compounds Y and Z react together under suitable conditions to form a polymer.
(i) Draw the structural formula of the repeating unit for the polymer formed.







(2)

(ii) What type of polymerisation reaction occurs between compounds Y and Z?
...........................................................................................................................
(1)
(Total 10 marks)


101. Consider the equilibrium
N
2
O
4
(g) 2NO
2
(g) ΔH = +58 kJ mol
–1

(a) Write the expression for the equilibrium constant, K
p
, for the above reaction.
(1)


(b) (i) An equilibrium mixture contains a mole fraction of dinitrogen tetroxide,
N
2
O
4
= 0.20, and nitrogen dioxide, NO
2
= 0.80. The total pressure of this mixture
is 1.1 atm.
Calculate K
p
at this temperature, stating its units.






(3)

(ii) Calculate the total pressure required to reduce the mole fraction of N
2
O
4
to 0.10.





(3)

(c) (i) What is the effect on K
p
, if any, of raising the temperature?
...........................................................................................................................
(1)


(ii) Use your answer to (c)(i) to explain the effect of increasing the temperature on the
position of equilibrium.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 10 marks)


102. (i) Use the data below to calculate a value for the enthalpy change of solution, ΔH
solution
, for
silver fluoride.
Value
/kJ mol
–1

lattice energy of AgF (s) –958
enthalpy of hydration of Ag
+
(g)
–464
enthalpy of hydration of F

(g)
–506






(2)


(ii) Use your answer to part (c)(i) to suggest whether you would expect silver fluoride, AgF,
to be soluble or insoluble in water at room temperature.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 4 marks)


103. (a) The values of the ionic product of water, Kw, at two different temperatures are shown in
the table below.
Temperature /°C K
w

/ mol
2
dm
–6

25 1.00 × 10
–14

50
5.48 × 10
–14


(i) Write an equation to represent the ionisation of water.
...........................................................................................................................
(1)

(ii) Write the expression for K
w
.
...........................................................................................................................
(1)

(iii) Define the term pH.
...........................................................................................................................
...........................................................................................................................
(1)


(iv) Calculate the pH of pure water at 50 °C.






(2)

(v) Explain why pure water at 50 °C is neutral despite the fact that its pH is not 7.
...........................................................................................................................
...........................................................................................................................
(1)

(b) The pH curve shown below was obtained when a 0.100 mol dm
–3
solution of sodium
hydroxide was added to 25.0 cm
3
of a 0.100 mol dm
–3
solution of ethanoic acid.
14
12
10
8
6
4
2
0
0 10 20 30 40
pH
Volume 0.100 mol dm NaOH / cm
3 –3



(i) What volume of sodium hydroxide solution is required to neutralise half of the
ethanoic acid in this reaction?
Volume added = ..............................................................cm
3

(1)

(ii) Use the graph to determine the pH when the volume of sodium hydroxide you have
stated in part (i) has been added.
pH is .....................................................................................
(1)

(iii) Write an expression for the acid dissociation constant, K
a
, of ethanoic acid,
CH
3
COOH.




(1)


(iv) Use your answers to parts (ii) and (iii) to determine the value of K
a
for ethanoic
acid at the temperature of the titration. Give your answer to two significant figures.






(2)
(c) Phenolphthalein is a suitable indicator for a titration between ethanoic acid and sodium
hydroxide solutions whereas methyl orange is not a suitable indicator.
Explain why this is so.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 13 marks)



104. Ethanal, CH3CHO, can be converted into 2-hydroxypropanoic acid, CH
3
CH(OH)COOH.
State the reagents and conditions needed for each step in this synthesis.
...............................................................................................................................................
...............................................................................................................................................
...............................................................................................................................................
...............................................................................................................................................
...............................................................................................................................................
(Total 4 marks)


105. This question concerns the reaction between nitrogen monoxide and oxygen:
2NO(g) + O
2
(g) → 2NO
2
(g)

(a) In a series of experiments designed to find the rate equation for this reaction, the
following data were obtained. In each experiment the partial pressure of oxygen was the
same.
30
0
25
20
15
10
5
0
0.05 0.1 0.15 0.2
Square of the partial pressure of NO/atm
2
Initial rate/ atm s
–1



(i) What is the order of reaction with respect to nitrogen monoxide?
Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii) A new series of readings is taken with the partial pressure of oxygen doubled.
The gradient of the line doubles.
State, with a reason, the order of reaction with respect to oxygen.
...........................................................................................................................
...........................................................................................................................
(1)

(iii) Hence write the rate equation for the reaction.
...........................................................................................................................
(1)

(iv) State the units of the rate constant.
...........................................................................................................................
(1)


(b) The rate of the decomposition of nitrous oxide
2N
2
O(g) → 2N
2
(g) + O
2
(g)
has been studied at different temperatures. The rate constant k was determined at each
temperature.
The relationship between the rate constant and the temperature T is given by the
Arrhenius equation:
|
.
|

\
|
÷ =
T R
E
A k
1
ln ln
a

where E
a
is the activation energy for the reaction, R is the gas constant, and k is the rate
constant at temperature T.

(i) Given values of k at different temperatures T, what graph would you plot and how
would you use it to determine the activation energy?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii) A plot of the data gave a straight line with gradient – 2.95 × 10
4
K
–1
.
Find the activation energy for the reaction, in kJ mol–1, to three significant
figures.
[The value of R is 8.314 J K
–1
mol
–1
]






(2)


(iii) What is the oxidation number of nitrogen in nitrous oxide, N
2
O?
Put a cross ( ) in the box of the correct answer. If you change your mind about an
answer, put a line through the box ( ) and then mark your new answer with a
cross ( ).
A +2

B +1

C –1

D –2

(1)
(Total 10 marks)


106. Cyanide ions react with 2-bromo-2-methylpropane in the following way:
(CH
3
)
3
CBr + CN

→ (CH
3
)
3
CCN + Br


The rate equation for this reaction is
rate = k[(CH
3
)
3
CBr]

(i) What information does this rate equation give about the mechanism of this reaction?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(ii) Give the mechanism for this reaction consistent with the rate equation.







(3)
(Total 5 marks)


107. The enthalpy change for some reactions cannot be determined directly.
One such reaction is the thermal decomposition of potassium hydrogencarbonate, which in a
closed system at 200 °C is an equilibrium reaction.
2KHCO
3
K
2
CO
3
+ H
2
O + CO
2

However, by determining the enthalpy change for the neutralisation of the two potassium salts
with hydrochloric acid, ΔH for the reaction above can be found. The equations for the
neutralisation reactions are:
K
2
CO
3
+ 2HCl → 2KCl + H
2
O + CO
2
ΔH
1

KHCO
3
+ HCl → KCl + H
2
O + CO
2
ΔH
2

ΔH
1
and ΔH
2
for the neutralisation reactions were determined as follows:
• 30 cm
3
of 2 mol dm
–3
hydrochloric acid (an excess) was placed in a polystyrene cup, and
its temperature measured to the nearest 0.1°C.
• A weighed quantity of the potassium salt (either the carbonate or the hydrogencarbonate)
was added to the acid with rapid stirring, and the temperature measured again when the
reaction was complete.
For the neutralisation using potassium carbonate, the results were as follows:
Amount of potassium carbonate used = 0.0187 mol
Initial temperature = 23.7 °C
Final temperature = 30.1 °C


(a) State Hess‘s Law.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(b) Use the data for the neutralisation of potassium carbonate to calculate the value of ΔH
1
to
two significant figures. Remember to include a sign and units in your answer.
[Assume that the heat capacity of the solution is 4.18 J g
–1
°C
–1
, and that it has a mass of
30 g.]






(3)

(c) (i) Show how the two equations for the neutralisation reactions and their ΔH values
can be combined to find a value of ΔH for the thermal decomposition of potassium
hydrogencarbonate.
Calculate this enthalpy change using your value for ΔH
1
from part (b), given that
ΔH
2
= + 29.3 kJ mol
–1
.





(3)


(ii) Explain why you would need to include the enthalpy of vaporisation of H
2
O(l), in
order to obtain an accurate value of the enthalpy of decomposition of potassium
hydrogencarbonate.
2KHCO
3
(s) K
2
CO
3
(s) + H
2
O(g) + CO
2
(g)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(d) State and explain the effect of a decrease in temperature on the value of the equilibrium
constant for the decomposition reaction and hence on the composition of the equilibrium
mixture.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 10 marks)



108. (i) Draw the shape of a water molecule. Justify your answer.





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

(ii) Water has intermolecular hydrogen bonds, but hydrogen sulphide, H
2
S, does not.
Explain how these arise in water and why they do not occur in hydrogen sulphide.
Give ONE resulting difference in physical properties of water and hydrogen sulphide.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 5 marks)



109. (a) Name the homologous series to which the compound CH
3
CH
2
CHO belongs.
.....................................................................................................................................
(1)

(b) Describe what you would see if a sample of CH
3
CH
2
CHO was warmed with Benedict‘s
solution.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 3 marks)



110. This question is about the reaction of iodine with propanone.
CH
3
COCH
3
(aq) + I
2
(aq) → CH
3
COCH
2
I(aq) + H
+
(aq) + I

(aq)
(a) Suggest, in outline, THREE different methods for following the rate of this reaction.
State which of the reactants or products could be measured by each method you choose.
Method 1
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Method 2
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Method 3
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(b) The reaction is extremely slow at room temperature in the absence of H+ ions as a
catalyst.
Suggest how you would quench the reaction before carrying out a titration method to
determine the concentration of iodine at different times.
Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(c) A series of experiments was carried out, varying the concentrations of the reactants and
the catalyst. The following results were obtained.
Experiment
[CH
3
COCH
3
]
/mol dm
–3

[I
2
]
/mol dm
–3

[H
+
]
/mol dm
–3

Initial rate
/mol dm
–3
s
–1

1 1.00 0.010 0.10
2.8 ×10
–6

2 1.00 0.010 0.20 5.6 ×10
–6

3 1.50 0.010 0.20
8.4 ×10
–6

4 1.50 0.020 0.10
4.2 ×10
–6

The reaction is first order with respect to hydrogen ions, H
+
.

(i) Deduce the order of the reaction with respect to propanone, CH
3
COCH
3
. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(ii) Deduce the order of the reaction with respect to iodine, I
2
.
...........................................................................................................................
(1)

(iii) Hence give the rate equation for this reaction.

(1)


(iv) Which species are involved in the rate-determining step?
...........................................................................................................................
...........................................................................................................................
(1)

(v) Suggest an equation for the reaction between the species in the rate-determining
step.



Explain why this step is likely to take place.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 13 marks)


111. One of the alarm pheromones for ants, compound Q, has the molecular formula C
6
H
10
O.
(a) State what can be deduced about compound Q from each of the following pieces of
information.
(i) Q, C
6
H
10
O, is a non-cyclic organic compound. When saturated it would contain 14
hydrogen atoms.
...........................................................................................................................
...........................................................................................................................
(1)

(ii) Compound Q does not react with sodium.
...........................................................................................................................
...........................................................................................................................
(1)


(iii) One mole of compound Q reacts with one mole of bromine molecules, Br
2
, in the
absence of sunlight.
...........................................................................................................................
...........................................................................................................................
(1)

(iv) Compound Q gives a yellow precipitate with Brady‘s reagent, 2,4-
dinitrophenylhydrazine.
...........................................................................................................................
(1)

(v) When compound Q is warmed with Benedict‘s solution, a red precipitate is
formed.
...........................................................................................................................
(1)

(vi) Compound Q exists in the trans form.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(vii) Given that compound Q is a straight chain molecule with the two functional groups
next to one another, give the displayed formula of Q.





(2)


(b) (i) Compound Q, C
6
H
10
O, can be converted into C
6
H
14
O in two steps.
Give the reagent and any catalyst needed for each step.
Step 1 ................................................................................................................
...........................................................................................................................
Step 2 ................................................................................................................
...........................................................................................................................
(2)

(ii) Name the functional group which would now be present?
...........................................................................................................................
(1)
(Total 11 marks)


112. Phosphorus(V) chloride dissociates as follows:
PCl
5
(s) PCl
3
(l) + Cl
2
(g) ∆H
ο
= + 123.8 kJ mol
–1

Substance
Standard entropy, S
ο

/ J mol
–1
K
–1

PCl
5
(s) + 166.5
PCl
3
(l) + 217.1
Cl
2
(g) + 165.0

(a) (i) Explain why the entropy of solid phosphorus(V) chloride, PCl
5
, is smaller than the
entropy of liquid phosphorus(III) chloride, PCl
3
?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(ii) Calculate ∆S
ο
system
for the forward reaction. Include a sign in your answer.


(1)

(iii) Is the sign of ∆S
ο
system
as you would expect? Fully justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(b) Calculate ∆S
ο
surroundings
for the forward reaction at 298 K. Include a sign and units in your
answer.




(2)

(c) (i) Use your answers to calculate ∆S
ο
total
for the forward reaction at 298 K. Include a
sign in your answer.




(1)


(ii) Comment on the position of equilibrium at 298 K.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(d) In an experiment to investigate this equilibrium, 41.7 g of phosphorus(V) chloride (molar
mass 208.5 g mol
–1
) was heated in a closed vessel at 150 °C until equilibrium was
established. The final pressure was found to be 4.32 atm and 0.15 moles of
phosphorus(V) chloride remained. At this temperature all of the reactants and products
are gaseous.
(i) Give the expression for the equilibrium constant, K
p
, and its units at this
temperature.




(2)

(ii) Complete the table
Substance Moles at start Moles at equilibrium Partial pressure at
equilibrium, p
eq

/atm
PCl
5
(g) 0.15
PCl
3
(g) 0
Cl
2
(g) 0
Total number of moles at equilibrium
(3)


(iii) Calculate K
p
.




(1)

(iv) How would you expect the value of K
p
to change, if at all, if the following changes
were made? Justify each of your answers.
A Only 20.85 g of phosphorus(V) chloride had been used.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
B The temperature had been increased to 250 °C.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 16 marks)



113. Human blood plasma is a buffer solution. It partly owes its buffer properties to carbon dioxide,
produced by respiration, dissolving in the blood for transportation to the lungs.
Carbon dioxide dissolves in water establishing the equilibrium
CO
2
(aq) + H
2
O(l) H
+
(aq) + HCO
3

(aq)
(a) (i) Write the expression for Ka for this equilibrium and give its units.



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

(ii) What is the relationship between pK
a
and K
a
?


(1)

(b) Explain what is meant by a buffer solution.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(c) HCO
3

(aq) can act as an acid or a base.
CO
2
(aq) + H
2
O(l) H
+
(aq) + HCO
3

(aq)
In this equilibrium, decide whether HCO
3

(aq) is acting as an acid or as a base. Give the
reason for your decision.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(d) A sprinter had the pH and total carbonate concentration, [CO
2
+ HCO
3

], of his blood
plasma measured immediately before and after a race. The following results were
obtained.

pH
Total carbonate concentration, [CO
2
+ HCO
3

]
/ mol dm
–3

Before race 7.4
2.52 × 10
–2

After race 7.3
1.98 × 10
–2

The pH of a buffer solution is given by the equation

[base]
acid] [
log p pH
a
÷ = K
For this equilibrium pK
a
is 6.5.


(i) Use this information, together with the data in the table, to calculate
[base]
acid] [
before
the race.





(2)

(ii) The concentration of HCO
3

is 0.0224 mol dm
–3
. Calculate the concentration of
CO
2
before the race.





(1)

(iii) Use your results from (d)(i) and (ii) to complete the table below which will allow
you to compare the results before and after the race.

[base]
acid] [

[HCO
3

]
/ mol dm
–3

[CO
2
]
/ mol dm
–3

Before race 0.0224
After race 0.158 0.0171 0.00270
Two hypotheses have been proposed to explain why vigorous exercise results in an
increase in blood plasma acidity (from 7.4 to 7.3).


Greater muscle activity during a race requires:
either
Hypothesis I the combustion of larger quantities of glucose, resulting in an
increase in dissolved carbon dioxide and hence an increase in
acidity.
or
Hypothesis II partial oxidation of glucose to lactic acid and hence an increase in
acidity.
State, giving your reasons, which hypothesis is favoured by the data and your
calculations.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)



114. The drug ibuprofen can be synthesised from benzene by the route shown below.
H—C—CH
CH
3
2
CH
3
H—C—CH
CH
3
2
CH
3
H—C—OH
CH
3
H—C—CH
CH
CH
3
2
3
C O
CH
3
Step A Step B Step C
CO/ Pd
catalyst
H—C—CH
CH
3
2
CH
3
H—C—CO H
2
CH
3
Ibuprofen


(a) Name the type and mechanism of the reaction in Step A, and suggest a suitable reagent
and catalyst.
Type and mechanism ..................................................................................................
Name of the reagent for Step A ..................................................................................
Catalyst .......................................................................................................................
(3)

(b) Step C is a reduction.
Give ONE reason why lithium tetrahydridoaluminate, LiAlH
4
, is preferred to hydrogen as
a reducing agent in this reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)


(c) A sample of the final product was analysed by combustion. 1.00 g was burnt in oxygen. It
produced 2.78 g carbon dioxide and 0.786 g water.
State the molecular formula of ibuprofen and show that these results are consistent with
it.

















(4)


(d) Ibuprofen can be analysed by instrumental methods. The infrared spectra of ibuprofen
and two other drugs, aspirin and paracetamol, not necessarily in that order, are shown
opposite.
Ibuprofen has the formula
Aspirin has the formula
Paracetamol has the formula
H—C—CH
CH
3
2
CH
3
H—C—CO H
2
CH
3
—O—C
O
CH
OH
3
H—N—C
O
CH
CO H
3
2


(i) Explain, referring to the structure of each molecule, why infrared spectroscopy is
not a good technique to distinguish aspirin from ibuprofen.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(ii) Deduce which of X, Y or Z is the infrared spectrum of paracetamol, giving a piece
of evidence from the spectrum you select.
100
50
0
4000 3000 1500 1000 2000
Wavenumber / cm
–1
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
100
50
0
4000 3000 1500 1000 2000
Wavenumber / cm
–1
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
100
50
0
4000 3000 1500 1000 2000
Wavenumber / cm
–1
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
Spectrum X
Spectrum Z
Spectrum Y



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

(iii) Ibuprofen and aspirin can be distinguished using their mass spectra.
A line at mass/charge ratio 57 occurs only in the mass spectrum of ibuprofen.
Give the formula of the ion which produces this line.
...........................................................................................................................
Suggest the mass/charge ratio of one line which occurs in the mass spectrum of
aspirin but not ibuprofen, and the formula of the species which produces it.
...........................................................................................................................
...........................................................................................................................
(3)
(Total 14 marks)


115. This question involves the following techniques which can be used to follow chemical reactions
in order to investigate their kinetics.
A collecting and measuring the volume of a gas
B colorimetry
C measuring the electrical conductivity
D titration with standard acid solution


Select, from A to D, the technique most appropriate to investigate:
(a) the hydrolysis of 1-bromobutane using hydroxide ions
C
4
H
9
Br(l) + OH

(aq) ÷ C
4
H
9
OH(l) + Br

(aq)
A
B
C
D
(1)

(b) the decomposition of the benzenediazonium ion
C
6
H
5
N
2
+
(aq) + H
2
O(l) ÷ C
6
H
5
OH(aq) + N
2
(g) + H
+
(aq)
A
B
C
D
(1)

(c) the reaction of acidified potassium manganate(VII) with propan-2-ol to give propanone
and manganese(II) sulfate.
A
B
C
D
(1)


(d) the catalytic decomposition of hydrogen peroxide.
A
B
C
D
(1)
(Total 4 mark)


116. 1,2-dibromoethane reacts with potassium iodide dissolved in methanol according to the
equation:
C
2
H
4
Br
2
+ 2KI ÷ C
2
H
4
+ 2KBr + I
2

The rate equation for this reaction is
A rate = k[KI]
2
[C
2
H
4
Br
2
]
B rate = k[KI]
2

C rate = k[C
2
H
4
Br
2
]
D not possible to deduce from this information
(Total 1 mark)


117. For the reaction between sodium bromate(V) and sodium bromide in acidic solution, the rate
equation is:
Rate = k[BrO
3

][Br

][H
+
]
2

When the concentrations of all three reactants are doubled, the rate will increase by a factor of
A 4
B 6
C 8
D 16
(Total 1 mark)



118. This question refers to the following reaction at 298 K:
N
2
O
4
(g) ÷ 2NO
2
(g) AH = + 57.2 kJ mol
–1

S
/J mol
–1
K
–1

N
2
O
4
(g) 304.2
NO
2
(g) 240.0

(a) Calculate AS
system
, in J mol
–1
K
–1
, for this reaction.
A –175.8
B +175.8
C –64.2
D +64.2
(1)

(b) Calculate AS
surroundings
, in J mol
–1
K
–1
, for this reaction at 298 K.
A –192
B +192
C –0.192
D +0.192
(1)
(Total 2 marks)



119. For the equilibrium,
N
2
(g) + 3H
2
(g) 2NH
3
(g)
Which is the correct expression for K
p
?
A
3
2 2
2
3
g)] ( g)][H ( N [
)] g ( NH [

B
g) ( NH
g) ( H g) ( N
3
2 2
P
P P

C
g) ( H
3
g) ( N
g) ( NH
2
2
2
3
P P
P

D
g) ( NH
2
g) ( H
3
g) ( N
3
2
2
P
P P

(Total 1 mark)


120. The expression for Kc for the equilibrium 2SO
2
(g) + O
2
(g) 2SO
3
(g) is
K
c
=
g)] ( O [ g)] ( SO [
g)] ( [SO
2
2
2
2
3

What are the units of Kc in this equilibrium expression?
A mol dm
–3

B mol
2
dm
–6

C dm
3
mol
–1

D atm
–1

(Total 1 mark)



121. For the equilibrium
2NO
2
(g) N
2
O
4
(g) AH = –57.2 kJ mol
–1

which one of the following changes would result in a different value of the equilibrium
constant?
A an increase in temperature
B a decrease in pressure
C an increase in pressure
D an increase in the concentration of NO
2
(g)
(Total 1 mark)


122. Solutions of concentration 0.1 mol dm
–3
of iron(II) ions and silver(I) ions were mixed at room
temperature and allowed to reach equilibrium.
Fe
2+
(aq) + Ag
+
(aq) Fe
3+
(aq) + Ag(s)
Which one of the following statements is true?
A as the equilibrium position was approached, the forward reaction became slower until it
stopped.
B at the equilibrium position, no more Ag(s) reacted with Fe
3+
(aq).
C at the equilibrium position, the rate of the forward reaction equalled the rate of the
backward reaction.
D no Fe
3+
(aq) reacted with Ag(s) until the equilibrium position was reached.
(Total 1 mark)


123. This question concerns four solutions, A to D. They were prepared by mixing equal volumes of
0.2 mol dm
–3
solutions of two different substances. The substances were
A HCl(aq) and NaOH(aq)
B HCl(aq) and NaCl(aq)
C NH
3
(aq) and NH
4
Cl(aq)
D CH
3
COOH(aq) and CH
3
CO
2
Na(aq)


Select, from A to D, the mixture which would:
(a) have the lowest concentration of hydrogen ions
A
B
C
D
(1)

(b) act as a buffer of pH about 5
A
B
C
D
(1)

(c) have a chloride ion concentration of 0.2 mol dm
–3
.
A
B
C
D
(1)
(Total 3 marks)



124. This question concerns the titration of a solution of sodium hydroxide with a solution of
hydrochloric acid. As the titration proceeds the pH of the mixture changes.
(a) What was the pH when 24.95 cm
3
of 1.00 mol dm
–3
NaOH(aq) had been added to 25 cm
3

of 1.00 mol dm
–3
HCl(aq)?
A 3
B 6
C 8
D 11
(1)

(b) What was the pH when 25.05 cm
3
of 1.00 mol dm
–3
NaOH(aq) had been added to 25 cm
3

of 1.00 mol dm
–3
HCl(aq)?
A 3
B 6
C 8
D 11
(1)

(c) Which one of the following indicators would be most suitable to use to determine the end
point of this titration?
pH range
A methyl violet 0–1.6
B universal indicator 3–11
C thymolphthalein 8.3–10.6
D alizarin yellow R 10.1–13.0
(1)
(Total 3 marks)



125. Which one of the following organic compounds does not exist?
A an ester which is a structural isomer of a carboxylic acid C
3
H
6
O
2

B a carboxylic acid which is a structural isomer of an ester C
2
H
4
O
2

C an aldehyde which is a structural isomer of a ketone C
3
H
6
O
D a ketone which is a structural isomer of an aldehyde C
2
H
4
O
(Total 1 mark)


126. This question concerns a proposed two-stage synthetic route to prepare butanamide,
CH
3
CH
2
CH
2
CONH
2

NH
3
Carboxylic acid ÷ Acyl chloride ÷ butanamide

(a) A suitable starting material for this preparation would have the formula
A CH
3
CH
2
CH
2
COH
B CH
3
CH
2
CH
2
CH
2
COOH
C CH
3
CH
2
CH
2
COOH
D CH
3
CH
2
CH
2
CH
2
OOH
(1)

(b) Each stage in the sequence produced a 50% yield of required product. What is the
minimum number of moles of the carboxylic acid which should be used in order to
produce one mole of butanamide?
A 0.25
B 2.00
C 2.50
D 4.00
(1)


(c) Which of the following reagents is needed to convert the carboxylic acid into the acyl
chloride?
A chlorine
B phosphorus(V) chloride
C hydrogen chloride
D ethanoyl chloride
(1)
(Total 3 marks)


127. This question concerns the following compounds containing four carbon atoms.
A Butanoic acid, CH
3
CH
2
CH
2
COOH
B Butanone, CH
3
COCH
2
CH
3

C Propyl methanoate, HCOOCH
2
CH
2
CH
3

D Butanoyl chloride, CH
3
CH
2
CH
2
COCl
Select, from A to D, the compound that

(a) can be made by the oxidation of a primary alcohol.
A
B
C
D
(1)

(b) would be expected to react most rapidly with ethanol.
A
B
C
D
(1)


(c) would have 4 different chemical shifts in its nmr spectrum and a broad absorption
between 2500–3300 cm
–1
in its infrared spectrum.
A
B
C
D
(1)
(Total 3 marks)


128. This question concerns the nucleophilic addition reaction between a carbonyl compound and
hydrogen cyanide, HCN.
(a) Which one of the following carbonyl compounds would produce a racemic mixture?
A CH
3
COCH
3

B C
2
H
5
CHO
C HCHO
D C
2
H
5
COC
2
H
5

(1)


(b) Which of the following best represents the first step of the mechanism for this reaction
with an aldehyde?
A
B
C
D
R
C
H
R
C O
+ –
H
R
C
H
R
C
H CN
O

(:C
C
H
R
C
H CN
O

(:C
C
H
R
C
+
H
OH
H C N +

CN
O
O
O
O
N:)
R
R
N:)



(1)
(Total 2 marks)



129. This question concerns the formation of a polymer.
(a) Which one of the following is a possible formula of the repeat unit of a polymer formed
from ethane-1,2-diol and benzene-1,4-dicarboxylic acid.
A
B
C
D
C
O
O
C O CH
2 2
CH O
O CH
2
CH
2
O C C
O
O
OH
C O CH
2 2
CH O
H
C
OH
O CH
2 2
CH O C C
HO H
OH H
(1)

(b) What type of reaction is this?
A addition
B condensation
C dehydration
D neutralisation
(1)
(Total 2 marks)



130. This question is about the pineapple flavouring used in sweets. It is an ester with the formula
C
3
H
7
COOCH
3
, which can be broken down into butanoic acid and methanol when mixed with
hydrochloric acid.
The following equilibrium is set up:
C
3
H
7
COOCH
3
(l) + H
2
O(l) C
3
H
7
COOH(l) + CH
3
OH(l)
(a) Give the name of this ester.
.....................................................................................................................................
(1)

(b) Why does the ester have a comparatively low boiling point compared to the other three
substances in the equation?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(c) What is the name given to this type of reaction?
.....................................................................................................................................
(1)


(d) Suggest the reasons why manufacturers choose to use the chemically manufactured
pineapple flavouring rather than the natural product and why consumers might prefer to
choose the natural product.
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
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.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)


(e) In an experiment, 10.2 g (0.10 mol) of the ester was mixed with 18 cm
3
of 1.0 mol dm
–3

hydrochloric acid and left until equilibrium had been reached. The hydrochloric acid acts
as a catalyst and contains 18 g (1 mol) of water. At equilibrium, 4.4 g of butanoic acid
was found to be present.
Molar mass of butanoic acid = 88 g; assume the total volume at equilibrium is 30 cm
3
.
Give the expression for the equilibrium constant, K
c
, for this equilibrium and calculate its
value. Explain why it has no units.








.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)
(Total 12 marks)


131. Methane reacts with steam in an endothermic reaction.
CH
4
(g) + H
2
O(g) CO(g) + 3H
2
(g)

(a) State the effect on the value of the equilibrium constant of an increase in temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)


(b) Use your answer to (a) to explain the effect of this change on the position of equilibrium.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 3 marks)


132. This question is about the reaction of magnesium with hydrochloric acid which takes place
rapidly at room temperature.
Mg(s) + 2HCl(aq) ÷ MgCl
2
(aq) + H
2
(g) AH = –467 kJ mol
–1


(a) Rewrite the equation omitting spectator ions.
(1)


(b) Suggest the sign of the following entropy changes for this reaction. Justify each of your
answers.
(i) AS
system

...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii) AS
surroundings

...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii) AS
total

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


(c) A student carried out this experiment at five different temperatures in order to calculate
the activation energy of the reaction. The student‘s laboratory record is shown below.
Method
Clean a strip of magnesium weighing 0.100 g with sand paper. Measure the temperature of
20 cm
3
of 1.00 mol dm
–3
hydrochloric acid in a 100 cm
3
beaker. Add the magnesium ribbon,
stir continuously, and time how long it takes for the magnesium to disappear. Repeat the
experiment at four other temperatures.
Assumption: the initial rate of reaction is proportional to 1/time.
Results
Temperature
/°C
Temperature
/K
1/T
/K
–1

time
/s
1/time
/s
–1

ln 1/time
24 297
3.37 × 10
–3

45 0.0222 –3.81
33 306
3.27 × 10
–3

25 0.0400 –3.22
45 318
3.14 × 10
–3

11 0.0909 -2.40
56 329
3.04 × 10
–3

6 0.1667 -1.79
10 283
3.53 × 10
–3

122 0.0082 -4.80

The Arrhenius equation is ln k = –E
a
/R × (1/T) + constant
ln 1/time is proportional to ln k and so a graph of ln 1/time will have the same gradient as
that of the Arrhenius plot of ln k against 1/Temperature
The student plotted the graph of ln 1/time against 1/Temperature and from this the
activation energy, E
A
, was calculated as + 51.3 kJ mol
–1
.
(i) Suggest the reason for cleaning the magnesium ribbon with sand paper.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(ii) Calculate the number of moles of hydrochloric acid used up when all the
magnesium reacts in one experiment. Hence comment on whether the change in
concentration during the reaction will have a significant effect on the validity of the
assumption that the initial rate of reaction is proportional to 1/time. How would
you overcome this potential error?
[Take the relative atomic mass of magnesium as 24 in this and subsequent
calculations.]
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
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...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(5)


(iii) Use the value of AH and other information given in the question to calculate the
temperature change in an experiment assuming no energy is lost to the
surroundings. Hence comment on whether this change in temperature will have a
significant effect. How would you overcome this potential error?
[AH = –467 kJ mol
–1
.
heat produced = mass × specific heat capacity × change in temperature.
Assume that the specific heat capacity of the solution is 4.18 J K
–1
g
–1
]






...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)


(iv) The most difficult thing to measure accurately is the time it takes for the
magnesium to disappear and the time measured can be up to 2 seconds out.
Assuming this error, calculate the shortest time at 56 °C and the longest time at
10 °C for this reaction.
Complete the table for these times. Plot the two points on the grid below and join
them with a straight line. From the gradient, which equals –E
A
/R, of this line
calculate another value for the activation energy.
Temperature
/ °C
Temperature
/K
1/T
/K
–1

time
/s
1/time
/s
–1

ln 1/time
56 329 3.04 × 10
–3


10 283 3.53 × 10
–3


1/ T(K
–1
)
0.0030 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
–1.0
–1.5
–2.0
–2.5
–3.0
–3.5
–4.0
–4.5
–5.0
l
n
1
/
t



(v) If the reaction mixture is not stirred, the magnesium tends to float on the surface of
the acid.
Suggest how this would affect the measurements of the rate of the reaction.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(vi) Suggest two other improvements the student could do to this experiment to
improve the accuracy or validity of the results.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(vii) If ethanoic acid of the same concentration and at the same temperature is used
instead of hydrochloric acid, explain how the rate would differ.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 24 marks)



133. One step in the production of nitric acid is the oxidation of ammonia.
4NH
3
+ 5O
2
÷ 4NO + 6H
2
O
This is carried out at 900 °C over a platinum-rhodium catalyst and is an example of
heterogeneous catalysis.
Explain in terms of collision frequency and collision energy how the rate would change if the
temperature were increased, and which of these causes the greater effect.
What is the difference between a heterogeneous and a homogeneous catalyst? Suggest one
advantage of using a heterogeneous catalyst in processes such as this.
...............................................................................................................................................
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(Total 6 marks)



134. In moths a pheromone, P, acts as an attractant for the opposite sex. P has the molecular formula
C
7
H
12
O.
What can be deduced about the structure of P from the following information?
(a) (i) 1 mole of P reacts with 1 mole of Br
2
molecules to form a compound with the
formula C
7
H
12
OBr
2
.
...........................................................................................................................
...........................................................................................................................
(1)

(ii) When lithium tetrahydridoaluminate is reacted with P a compound with the
formula C
7
H
14
O is formed.
...........................................................................................................................
...........................................................................................................................
(1)

(iii) P forms an orange precipitate with 2,4-dinitrophenylhydrazine.
...........................................................................................................................
(1)

(iv) When P is heated with Fehling‘s or Benedict‘s solution, the solution remains blue.
...........................................................................................................................
...........................................................................................................................
(1)

(v) P is a Z-isomer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(b) What does the following physical data tell you about the structure of P? Use your Data
booklet where necessary.
(i) The infrared spectrum of P has the following absorptions at wavenumbers above
1600 cm
–1
.
3060 cm
–1

2920 cm
–1

1690 cm
–1

1660 cm
–1

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

(ii) The nmr spectrum does not have a peak corresponding to a chemical shift, o, of
between 9 and 10.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)


(iii) The mass spectrum showed the presence of peaks at mass/charge ratios of 15 and
29, but no peak at 43.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(c) Given that P has a straight chain of carbon atoms in its formula, use the information you
have deduced above to suggest a displayed formula for the pheromone P.




(2)

(d) How could you use a purified sample of the orange precipitate in (a)(iii) to confirm the
formula of P?
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 16 marks)

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