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which of the following could represent the change in the concentrations of X and Y with time,
starting with a mixture of both X and Y? Equilibrium is reached at time t eqm.
(Total 1 mark)
2.
(a)
In the catalytic converter of a car engines exhaust system, the following reaction occurs.
2NO(g) + 2CO(g)
N2(g) + 2CO2(g)
H = 745 kJ mol
State the effect, if any, on the position of equilibrium if the temperature is lowered.
Give a reason for your answer.
Effect.................................................................................................................
Reason...............................................................................................................
...........................................................................................................................
(2)
(ii)
The gases from the engine are not cooled before entering the converter. Explain
why this is so.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
State the effect, if any, on the position of equilibrium if the pressure on the reacting
gases is increased. Give a reason for your answer.
Effect................................................................................................................
Reason...............................................................................................................
...........................................................................................................................
(2)
(b)
Nitrogen monoxide, NO, is formed when nitrate ions, NO 3 , in acidic solution are
reduced by silver metal.
(i)
In NO...............................................................................................................
In NO 3 .............................................................................................................
(2)
(ii)
Balance the half-equation for the reduction of nitrate ions, NO 3 , in acidic solution.
(iii)
Write the half-equation for the oxidation of silver metal, Ag, to silver ions, Ag .
(1)
(iv)
Hence deduce the full ionic equation for the reaction between silver metal and
nitrate ions in acidic solution. State symbols are not required.
(2)
(Total 13 marks)
3.
(Total 1 mark)
4.
3
3
3
(Total 1 mark)
5.
Which of the following solutions, when mixed, would make a buffer with pH more than 7?
A
6.
2NH3(g) H = 92 kJ mol
7.
CH2=CHCl(g) + HCl(g)
H = +51 kJ mol
Which of the following would result in an increase in the equilibrium yield of chloroethene?
A
8.
Ethanoic acid can be manufactured by the following reaction, which is carried out between
150 C and 200 C.
CH3OH(g) + CO(g)
(a)
CH3COOH(g)
A mixture of 50.0 mol of methanol and 50.0 mol of carbon monoxide reaches equilibrium
at a pressure of 32.0 atm. At 175 C, the equilibrium partial pressure of ethanoic acid is
22.2 atm.
(i)
Write the expression for the equilibrium constant in terms of pressure, K p, for this
reaction.
(1)
(ii)
(iii)
Calculate the value of Kp for this reaction at 175 C. Include a unit in your answer
and give your answer to three significant figures.
(2)
(b)
Another sample of 50.0 mol of methanol and 50.0 mol of carbon monoxide was allowed
to reach equilibrium at the same pressure of 32.0 atm, but at a lower temperature. 93.6%
of the methanol was converted at equilibrium.
(i)
Complete the table below to show the number of moles of each species in the
equilibrium mixture.
CH3OH
Number of moles at
start
50.0
CO
CH3COOH
50.0
Number of moles at
equilibrium
(2)
(ii)
(iii)
(1)
(c)
How, if at all, does the addition of methanol to the equilibrium mixture affect the
following? Justify your answers.
CH3OH(g) + CO(g)
(i)
CH3COOH(g)
(ii)
(d)
In industry, catalysts are used even though they are often expensive.
State and explain ONE benefit to the environment resulting from the use of catalysts in
industrial processes.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 13 marks)
9.
A titration was carried out to measure the concentration of ethanoic acid in a sample of
3
vinegar. 25.0 cm of a vinegar solution was titrated with a solution of sodium hydroxide,
3
concentration 0.250 mol dm . The concentration of the ethanoic acid in the vinegar
3
solution was found to be 0.125 mol dm .
(i)
14
(ii)
Write the expression for the acid dissociation constant, Ka, for ethanoic acid.
(1)
(iii)
(iv)
When half the ethanoic acid is neutralized, the concentration of the remaining
ethanoic acid equals the concentration of the sodium ethanoate which has formed.
What is the pH of the mixture at this point? Justify your answer.
pH.....................................................................................................................
Justification.......................................................................................................
...........................................................................................................................
(2)
(v)
On the axes below, sketch the titration curve for this reaction when 30 cm of the
3
sodium hydroxide is added to 25.0 cm of the vinegar solution.
(3)
10
(vi)
The only indicators which were available for this titration were methyl yellow (in
ethanol) and thymolphthalein. Explain which indicator is more suitable for this
titration and why the other is unsuitable. You will need to refer to your data
booklet.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b)
In the food industry, ethanoic acid is described as an acidity regulator, additive number
E260.
Ethanoic acid can neutralize alkalis. What substance could be mixed with ethanoic acid
so that it regulates pH as a buffer in foodstuffs?
.....................................................................................................................................
(1)
(Total 13 marks)
10.
The electrode potential for a cell can be used to calculate the equilibrium constant for the cell
reaction. This is because
ln E
In E
cell
is proportional to K.
cell
cell
is proportional to lnK.
is proportional to K.
(Total 1 mark)
11
11.
Magnesium nitrate, Mg(NO3)2, decomposes when it is heated. One product is the brown gas,
nitrogen dioxide.
(a)
(i)
Write an equation for this reaction. State symbols are not required.
(2)
(ii)
(b)
(c)
Scientists have found that the bonds between nitrogen and oxygen in the nitrate ion are all
the same length. Is the students suggestion supported by this evidence? Explain your
answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
12
(d)
Nitrogen dioxide gas can dimerize to dinitrogen tetroxide, N2O4, a very pale yellow gas,
as shown in the equation below.
2NO2(g)
(i)
N2O4(g)
H = 58 kJ mol
What would you see when an equilibrium mixture of these gases is warmed gently?
Explain your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
13
(e)
Use the distributions to explain why gases react faster when the temperature is increased.
.....................................................................................................................................
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)
14
12.
PCl5(g)
Which of the following is true when the total pressure of the system is increased at constant
temperature?
Value of Kp
decreases
decreases
unaltered
increases
decreases
increases
unaltered
unaltered
(Total 1 mark)
13.
(Total 1 mark)
14.
Why does phenolphthalein, which is colourless in acidic solutions, turn pink in alkaline
solutions?
A
(Total 1 mark)
15
15.
At equilibrium, the reaction from left to right and the reaction from right to left have
stopped.
(Total 1 mark)
16.
17.
A solution of a weak acid cannot be titrated with a weak base using an indicator to find the endpoint because
A
(Total 1 mark)
16
18.
Iron and steam at high temperature react in a closed vessel to give an equilibrium mixture
3Fe(s) + 4H2O(g)
Fe3O4(s) + 4H2(g)
Kp
A
Kp
B
Kp
C
D
PH 2
PH 2O
PFe 3 O 4 PH42
PFe3 PH42O
PH42
PH42O
K p PH42
(Total 1 mark)
19.
at 100 C, water has a higher concentration of hydrogen ions than of hydroxide ions.
(Total 1 mark)
20.
(a)
(i)
Define pH.
.............................................................................................................
(1)
(ii)
17
18
(b)
Ethanoic acid is a weak acid with an acid dissociation constant, K a, of value 1.75 10
mol dm at 25 C.
(i)
(ii)
pH of 0.00100 mol dm
solution
pH of 0.000100 mol dm
solution
Hydrochloric acid
3.0
4.0
Ethanoic acid
3.9
4.4
19
(c)
Orange marmalade usually contains sodium citrate as a preservative. Together with the
fruit in the marmalade, it forms a buffer solution which, at a suitable pH, inhibits mould
growth.
(i)
(ii)
What is the substance in the fruit that produces a buffer with sodium citrate?
...........................................................................................................................
(1)
(iii)
Explain how a buffer solution works using this system or any other of your choice.
Support your explanation with equations.
...........................................................................................................................
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(4)
(Total 15 marks)
20
21
21.
Hydrogen is used in very large quantities as a fuel, as a reducing agent, and in the production of
ammonia. Hydrogen is manufactured by steam reforming of methane from natural gas. Two
reactions are involved, both being in equilibrium in closed systems.
(a)
Reaction I
CH4(g) + H2O(g)
Reaction II
CO(g) + H2O(g)
H = 42 kJ mol
Write the expression for the equilibrium constant, Kp, for reaction I.
(1)
(b)
State and explain the effect, if any, on the value of Kp of increasing the pressure on
the reaction.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
Explain, in terms of your answers to (a) and (b)(i), why an increase in the pressure
leads to a decrease in yield in reaction I.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
22
(iii)
(c)
PCO 2 PH 2
PCO PH 2 O
(d)
Carbon dioxide and hydrogen are separated by washing the gas with potassium carbonate
solution to give potassium hydrogencarbonate solution, leaving hydrogen in the gas
stream. Potassium carbonate is expensive and is regenerated by heating the potassium
hydrogencarbonate and liberating the carbon dioxide.
(i)
23
(ii)
(e)
Although industrial processes are often discussed in terms of equilibria, they are rarely
allowed to reach equilibrium.
Suggest why, apart from insufficient reaction time, this is so.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 12 marks)
22.
In the equilibrium below, what effect would the changes described have on the system?
2H2S(g) + SO2(g)
(a)
3S(s) + 2H2O(g)
H is negative
Increase in temperature
A
(b)
Decrease in pressure
A
24
23.
Iodine can react with sodium hydroxide solution to form NaIO3(aq), according to the equation
below.
3I2(aq) + 6NaOH(aq) 5NaI(aq) + NaIO3(aq) + 3H2O(l)
Which of the statements about the reaction is false?
A
24.
2+
In the reaction between Ag (aq) ions and Fe (aq) ions, what would be the effect of increasing
+
the concentration of Ag (aq) ions?
+
2+
3+
Ag (aq) + Fe (aq)
Fe (aq) + Ag(s)
3+
3+
3+
3+
(Total 1 mark)
25.
2+
(Total 1 mark)
25
26
26.
Almost two thirds of the worlds ethanoic acid is made using the following equilibrium reaction,
with the aid of an iridium complex as a catalyst.
CH3OH(l) + CO(g)
CH3COOH(l)
DH = 135 kJ mol
Which of the following changes in conditions would increase the equilibrium yield of ethanoic
acid?
A
increase pressure
decrease pressure
increase temperature
add a catalyst
(Total 1 mark)
27.
2NH3(g)
[ NH 3 (g)] 2
A
[ N 2 (g)][H 2 (g)] 3
PN 2 ( g) PH 2 ( g)
PNH 3 ( g)
P 2 NH 3 ( g)
PN 2 ( g) P 3 H 2 ( g)
PN 2 ( g) P 3 H 2 ( g)
P 2 NH 3 ( g)
(Total 1 mark)
27
28.
2SO3(g) is
[SO 3 (g)] 2
2
Kc = [SO 2 (g)] [O 2 (g)]
mol dm
mol dm
dm mol
atm
6
1
(Total 1 mark)
29.
N2O4(g)
DH = 57.2 kJ mol
which one of the following changes would result in a different value of the equilibrium
constant?
A
an increase in temperature
a decrease in pressure
an increase in pressure
28
30.
Solutions of concentration 0.1 mol dm of iron(II) ions and silver(I) ions were mixed at room
temperature and allowed to reach equilibrium.
2+
Fe (aq) + Ag (aq)
3+
Fe (aq) + Ag(s)
as the equilibrium position was approached, the forward reaction became slower until it
stopped.
at the equilibrium position, the rate of the forward reaction equalled the rate of the
backward reaction.
no Fe (aq) reacted with Ag(s) until the equilibrium position was reached.
3+
3+
(Total 1 mark)
31.
This question concerns four solutions, A to D. They were prepared by mixing equal volumes of
3
0.2 mol dm solutions of two different substances. The substances were
A
29
(b)
(c)
32.
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 of 1.00 mol dm NaOH(aq) had been added to 25 cm
3
of 1.00 mol dm HCl(aq)?
A
11
(1)
30
(b)
What was the pH when 25.05 cm of 1.00 mol dm NaOH(aq) had been added to 25 cm
3
of 1.00 mol dm HCl(aq)?
A
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
01.6
universal indicator
311
thymolphthalein
8.310.6
alizarin yellow R
10.113.0
(1)
(Total 3 marks)
33.
This question is about the pineapple flavouring used in sweets. It is an ester with the formula
C3H7COOCH3, which can be broken down into butanoic acid and methanol when mixed with
hydrochloric acid.
The following equilibrium is set up:
C3H7COOCH3(l) + H2O(l)
(a)
C3H7COOH(l) + CH3OH(l)
31
(b)
Why does the ester have a comparatively low boiling point compared to the other three
substances in the equation?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(c)
(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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(4)
32
(e)
In an experiment, 10.2 g (0.10 mol) of the ester was mixed with 18 cm of 1.0 mol dm
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.
3
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)
(Total 12 marks)
34.
(a)
CO(g) + 3H2(g)
State the effect on the value of the equilibrium constant of an increase in temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)
33
(b)
Use your answer to (a) to explain the effect of this change on the position of equilibrium.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 3 marks)
35.
This question is about the reaction of magnesium with hydrochloric acid which takes place
rapidly at room temperature.
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
(a)
DH = 467 kJ mol
34
(b)
Suggest the sign of the following entropy changes for this reaction. Justify each of your
answers.
(i)
DSsystem
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
DSsurroundings
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
DStotal
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(c)
A student carried out this experiment at five different temperatures in order to calculate
the activation energy of the reaction. The students laboratory record is shown below.
Method
3
Clean a strip of magnesium weighing 0.100 g with sand paper. Measure the temperature of 20 cm of 1.00 mol
dm
hydrochloric acid in a 100 cm 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
1/T
time
/s
1/time
45
0.0222
3.81
25
0.0400
3.22
11
0.0909
-2.40
3.04 10
0.1667
-1.79
3.53 10
122
0.0082
-4.80
Temperature
/C
Temperature
/K
/K
24
297
3.37 10
33
306
3.27 10
45
318
3.14 10
56
329
10
283
/s
ln 1/time
35
36
Suggest the reason for cleaning the magnesium ribbon with sand paper.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
37
(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)
38
(iii)
Use the value of DH 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?
1
g ]
...........................................................................................................................
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(4)
39
(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.
0 .0 0 3 0
1 .0
1/T
1
/K
Temperature
/ C
Temperature
/K
56
329
3.04 10
10
283
3.53 10
0 .0 0 3 1
0 .0 0 3 2
1 / T (K 1)
0 .0 0 3 3
0 .0 0 3 4
0 .0 0 3 5
time
/s
1/time
1
/s
ln 1/time
0 .0 0 3 6
1 .5
2 .0
ln 1 / t
2 .5
3 .0
3 .5
4 .0
4 .5
5 .0
40
(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)
(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)
41
36.
42
37.
(Total 1 mark)
38.
positive
negative
39.
The standard electrode potential for the electrode system based on the equation below is
+1.51 V.
2+
Mn (aq) + 4H2O(l)
changing the concentration of Mn (aq) would cause a change in the electrode potential.
2+
2+
(Total 1 mark)
43
40.
DHr
DSsystem
DSsurroundings
DStotal
(Total 1 mark)
41.
Methanol can be vigorously oxidised with an acidified solution containing dichromate(VI) ions,
2
Cr2O7 , to form methanoic acid and chromic(III) ions.
(a)
What are the oxidation numbers of carbon in methanol and methanoic acid?
Methanol
Methanoic acid
A
+1
+2
+1
+2
2
(1)
(b)
How many moles of methanol react with one mole of dichromate(VI) ion, Cr 2O7 ?
A
3
(1)
(Total 2 marks)
44
42.
(a)
(i)
[Ar] .........................................................................................................
2+
[Ar] .........................................................................................................
(1)
(ii)
2+
Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6] , clearly showing its
shape.
(1)
(iii)
Give the equation for the complete reaction of hydroxide ions with a solution of
hexaaquairon(II) ions.
(1)
(iv)
State what you would see if the product mixture in (iii) is left to stand in air.
...........................................................................................................................
...........................................................................................................................
(1)
45
(b)
2+
+ 2e
Fe
E = 0.44 V
Define the term standard electrode potential with reference to this electrode.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(ii)
Explain why the value of E suggests that the iron will react with an aqueous
2+
solution of an acid to give Fe ions and hydrogen gas.
...........................................................................................................................
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...........................................................................................................................
...........................................................................................................................
(2)
(iii)
State why E values cannot predict that a reaction will occur, only that it is
possible.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 10 marks)
46
43.
The first stage in the manufacture of sulphuric acid is the combustion of sulphur.
The following equation shows the reaction taking place when the standard enthalpy of
combustion of sulphur is measured.
S(s) + O2(g) SO2(g)
Define the term standard enthalpy of combustion.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
47
(b)
In the second stage of the manufacture of sulphuric acid, sulphur dioxide is oxidised to
sulphur trioxide as shown in the following equation:
2SO2(g) + O2(g)
(i)
2SO3(g)
H = 196 kJ mol
(ii)
State and explain the effect, if any, of increasing the temperature on the equilibrium
yield of sulphur trioxide.
...........................................................................................................................
...........................................................................................................................
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(2)
48
49
(iii)
State and explain the effect, if any, of an increased pressure on the equilibrium
yield of sulphur trioxide.
...........................................................................................................................
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(2)
(c)
The following equation represents the overall reaction for the manufacture of sulphuric
acid from sulphur, oxygen and water.
2S(s) + H2O + 3O2 2H2SO4(l)
Use the data below to calculate the enthalpy change for this reaction.
Substance
Hf
/ kJ mol
H2O (l)
286
H2SO4 (l)
814
(2)
(Total 13 marks)
50
44.
2NO2(g)
H = +58 kJ mol
Write the expression for the equilibrium constant, Kp, for the above reaction.
(1)
(b)
(i)
(3)
(ii)
Calculate the total pressure required to reduce the mole fraction of N 2O4 to 0.10.
(3)
(c)
(i)
51
(ii)
Use your answer to (c)(i) to explain the effect of increasing the temperature on the
position of equilibrium.
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(2)
(Total 10 marks)
45.
(a)
The values of the ionic product of water, Kw, at two different temperatures are shown in
the table below.
Temperature /C
Kw
2
/ mol dm
(i)
25
1.00 10
14
50
5.48 10
14
(ii)
(iii)
52
(1)
53
(iv)
(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 solution of sodium
3
3
hydroxide was added to 25.0 cm of a 0.100 mol dm solution of ethanoic acid.
14
12
10
pH
8
6
4
2
0
10
20
V o lu m e 0 .1 0 0 m o l d m
30
3
N aO H / cm
40
3
54
(i)
(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, Ka, of ethanoic acid,
CH3COOH.
(1)
55
(iv)
Use your answers to parts (ii) and (iii) to determine the value of Ka 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)
46.
(a)
Define the term standard electrode potential, making clear the meaning of standard.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
56
57
(b)
(c)
(ii)
Use the following information to derive the equation for the disproportionation of
hydrogen peroxide.
Calculate E
cell
H2O2
E = + 0.68 V
2H2O
E = + 1.77 V
O2 + 2H + 2e
H2O2 + 2H + 2e
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
58
(iii)
Explain why your answer to (ii) does not necessarily show that hydrogen peroxide
will disproportionate under standard conditions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 9 marks)
47.
(a)
(i)
Explain, in terms of kinetic factors, why the mixture is heated for a significant
amount of time.
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
59
(2)
60
(iii)
Suggest why butan-2-ol, which is only partially miscible with water, is much more
soluble in concentrated hydrochloric acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iv)
Why is the organic layer shaken with dilute sodium carbonate solution?
...........................................................................................................................
...........................................................................................................................
(1)
(v)
(vi)
How would you heat the mixture safely? Explain your choice of method.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
61
(b)
SN1
C H 2C H
H 3C
C H 2C H
B r
H 3C
H
C H 2C H
H 3C
+ :B r
H
C H 2C H
+ :O H
H 3C
SN2
O H
H O :
C H 2C H
H 3C
C H 2C H
B r
H O
C
H
C H 2C H
H O
B r
H 3C
C
C H
+ :B r
62
Explain which one of these mechanisms is consistent with the lack of optical activity in
the product mixture.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(c)
(ii)
CH3CH(OH)CH2CH3 CH3COCH2CH3 + 2H + 2e
Write the ionic half-equation for the reduction of dichromate(VI) ions, and hence
derive the overall equation for the oxidation of butan-2-ol.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
63
(iii)
The IR spectra of butan-2-ol and of the organic product from its oxidation with
dichromate(VI) ions are given below.
S p e c tru m o f b u ta n -2 -o l
T ra n s m itta n c e /%
100
50
0
4000
3000
2000
1500
W a v e n u m b e r/c m
1000
500
T ra n s m itta n c e /%
100
50
0
4000
3000
2000
1500
W a v e n u m b e r/c m
Bond
Wavenumber/cm
1000
500
Bond
Wavenumber/cm
CH (alkanes)
28503000
CO (alcohols,
esters)
10001300
CH (alkenes)
30003100
OH (hydrogenbonded alcohols)
32303550
C=O (aldehydes,
ketones, carboxylic
acids)
16801750
OH (hydrogenbonded carboxylic
acids)
25003300
64
What evidence is there from the spectra that the reaction in part (ii) has occurred?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d)
If a solution of barium ions is then added to this solution, solid barium chromate,
BaCrO4, is precipitated; it is sparingly soluble in water, so the equilibrium given
below also exists in the solution
2+
BaCrO4(s)
Explain what happens to the pH when the barium ions are added.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
65
(ii)
48.
PCl3(l) + Cl2(g)
H = + 123.8 kJ mol
(a)
(i)
Substance
Standard entropy, S
1 1
/ J mol K
PCl5(s)
+ 166.5
PCl3(l)
+ 217.1
Cl2(g)
+ 165.0
Explain why the entropy of solid phosphorus(V) chloride, PCl 5, is smaller than the
entropy of liquid phosphorus(III) chloride, PCl3?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
Calculate S
system
(1)
66
67
(iii)
Is the sign of S
system
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b)
Calculate S
answer.
surroundings
for the forward reaction at 298 K. Include a sign and units in your
(2)
(c)
(i)
total
(1)
(ii)
68
69
(d)
Give the expression for the equilibrium constant, Kp, and its units at this
temperature.
(2)
(ii)
Moles at start
PCl5(g)
Moles at equilibrium
Partial pressure at
equilibrium, peq
/atm
0.15
PCl3(g)
Cl2(g)
(iii)
Calculate Kp.
(1)
70
(iv)
How would you expect the value of Kp 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)
49.
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
CO2(aq) + H2O(l)
(a)
(i)
Write the expression for Ka for this equilibrium and give its units.
Units ........................
(2)
(ii)
(1)
71
(b)
(c)
In this equilibrium, decide whether HCO3 (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 + HCO3 ], of his blood
plasma measured immediately before and after a race. The following results were
obtained.
pH
/ mol dm
Before race
7.4
2.52 10
After race
7.3
1.98 10
[acid]
[base]
72
(i)
[acid]
[base]
Use this information, together with the data in the table, to calculate
before
the race.
(2)
(ii)
(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.
[acid]
[base]
Before race
After race
[HCO3 ]
3
/ mol dm
[CO2]
3
/ mol dm
0.0224
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).
73
or
Hypothesis II
State, giving your reasons, which hypothesis is favoured by the data and your
calculations.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)
50.
This question is about ammonia, NH3, which is produced as shown in the following equation.
N2(g) + 3H2(g)
(a)
2NH3(g)
74
75
(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
NN
944
HH
436
NH
388
(3)
(ii)
The actual standard enthalpy change for this reaction is 92 kJ mol . Explain why
the value you calculated in (b)(i) is not the same as this.
...........................................................................................................................
...........................................................................................................................
(1)
76
(iii)
77
(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)
78
(ii)
State and explain TWO ways to increase the equilibrium yield of ammonia.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 19 marks)
51.
(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)
H2(g)+ I2(g)
H = + 9.4 kJ mol
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)
79
80
(ii)
The expression for the equilibrium constant, Kc, for the above reaction is
[ H 2 ( g )][I 2 (g )]
Kc =
[ HI(g)]2
(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.
H2(g) + I2(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, Kp, for the reaction as shown.
(1)
81
(ii)
(4)
(iii)
52.
82
(ii)
Propanoic acid is a weak acid. Explain what is meant by the term weak acid.
Weak
...........................................................................................................................
...........................................................................................................................
Acid
...........................................................................................................................
...........................................................................................................................
(2)
(b)
The acid dissociation constant, Ka, for propanoic acid is 1.30 10 mol dm at 298 K.
(i)
Write the expression for the acid dissociation constant, Ka, for propanoic acid.
(1)
83
(ii)
Assumptions:
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(5)
84
(c)
(ii)
(3)
(Total 15 marks)
85
53.
(i)
POCl3(g)
H = 153.6 kJ mol
Suggest how you would adjust the temperature and pressure to increase the yield of this
reaction. Justify your answer in each case.
Temperature ...............................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Pressure ......................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(ii)
State the effect of the adjustments you propose in part (i) on the rate of the reaction.
Temperature ...............................................................................................................
.....................................................................................................................................
Pressure ......................................................................................................................
.....................................................................................................................................
(2)
86
(iii)
On the axes below, sketch the energy profiles of the reaction in (c)(i) with and without a
catalyst. Label the profiles.
E n e rg y
R e a c tio n p a th
(2)
(Total 6 marks)
54.
The equation below shows the equilibrium existing between nitrogen, oxygen and nitrogen
monoxide.
N2(g) + O2(g)
2NO(g)
(a)
(i)
31
Write an expression for the equilibrium constant, Kp, in terms of the partial
pressures of the three gases.
(1)
87
(ii)
(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)
(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, Kp?
......................................................................................................................................
......................................................................................................................................
(2)
88
(c)
Inside a car engine, air (a mixture of nitrogen and oxygen) is drawn in and, under the high
temperatures operating, the value of Kp increases dramatically.
This increase is also accompanied by an increase in the value of Stotal. Typical values of
Kp and Stotal are shown in the table below.
1
Kp
Temperature / K
Stotal / J mol K
31
580
96
298
5.0 10
1500
1.0 10
Although the value of Ssystem is unlikely to alter very much, the value for Ssurroundings
will change significantly.
(i)
(ii)
Why is the value for Ssystem for this equilibrium approximately constant when the
temperature rises above 298 K?
...........................................................................................................................
...........................................................................................................................
(1)
(iii)
What is the sign of Ssurroundings for an endothermic reaction? Justify your answer.
...........................................................................................................................
...........................................................................................................................
(1)
89
(iv)
(d)
A student used the value for Kp 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)
90
55.
Calculate the pH of the buffer solution formed by mixing 10 cm of aqueous benzoic acid of
3
3
concentration 0.010 mol dm with 40 cm of aqueous sodium benzoate of concentration 0.020
3
mol dm .
5
For benzoic acid, the acid dissociation constant, Ka, is 6.3 10 mol dm .
log
[acid]
[base]
(Total 3 marks)
91
56.
Hydrogen gas is manufactured by passing methane and steam over a heated catalyst.
CH4(g) + H2O(g)
CO(g) + 3H2(g)
H = +206 kJ mol
a higher pressure
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(ii)
a higher temperature
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(iii)
a catalyst.
.....................................................................................................................................
(1)
(Total 5 marks)
92
57.
(a)
Sketch the titration curve that you would expect if 25.0 cm of 0.100 mol dm
3
3
hydrochloric acid, HCl, is titrated with 40.0 cm of 0.100 mol dm ammonia solution,
3
NH .
14
12
10
pH
8
6
4
2
0
10
20
V o lu m e o f 0 .1 0 0 m o l d m
a m m o n ia s o lu tio n / c m 3
30
40
(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
pKInd
thymol blue
1.7
bromocresol green
4.7
phenol red
7.9
phenolphthalein
9.3
( )
(1)
93
(c)
Suggest why there is no suitable indicator for the titration of ethanoic acid with ammonia.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 7 marks)
58.
Methanoic acid and ethanol react together to form ethyl methanoate, HCOOC 2H5, and water.
This reaction is reversible and can be allowed to reach equilibrium.
HCOOH(l) + C2H5OH(l)
(a)
H = +45 kJ mol
Draw the full structural formula of ethyl methanoate, showing all bonds.
(1)
(b)
94
(c)
In an experiment, 3.00 mol methanoic acid, HCOOH, and 6.25 mol ethanol, C2H5OH,
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)
C2H5OH
HCOOC2H5
H2O
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, Kc, for the reaction.
(1)
(iii)
Calculate Kc for the reaction at the temperature of the experiment. The total volume
3
(2)
(iv)
95
96
(d)
(i)
(ii)
59.
Brass is a widely-used alloy that contains copper and zinc. There are many varieties of brass
with different compositions.
In the volumetric analysis of the composition of brass, the first step is to react a weighed sample
of the alloy with nitric acid. This gives a greenish-blue solution.
(a)
The following standard electrode potentials are needed for this question:
2+
Zn + 2e
2+
Cu + 2e
NO3 + 2H + e
Zn
Cu
NO2 + H2O
E /V
0.76
+ 0.34
+ 0.81
97
(i)
Use the half equations given above and the values of E to calculate the standard
electrode potential for the reaction between zinc and nitric acid and derive the
equation.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
Suggest why zinc does not produce hydrogen with nitric acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
If the greenish-blue solution is diluted with water it turns light blue and contains
hydrated copper(II) ions.
Name the light blue complex ion and draw its structure so as to show its shape.
Name .................................................................................................................
Structure:
(2)
98
(iv)
(b)
The light blue solution from (a)(iii) is then neutralised, and reacted with an excess of
potassium iodide solution.
The following standard electrode potentials are needed:
2+
Cu + e
I2 + 2e
(i)
Cu
2I
E /V
+ 0.15
+ 0.54
Use these E values to explain why you would not expect the following reaction to
occur.
2+
(ii)
Explain why, in practice, the reaction in (i) does occur and iodine is liberated.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
99
(iii)
When the precipitate formed in the reaction in (i) is filtered off and then dissolved
in concentrated aqueous ammonia, a colourless solution is produced.
Suggest the formula of the cation in this solution.
...........................................................................................................................
(1)
(iv)
If the colourless solution from (iii) is left to stand in air for some time, it turns blue.
State why this is so, naming the reactant responsible for the change.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(c)
In a determination of the composition of a sample of brass, 1.50 g of the alloy was treated
3
to give 250 cm of a neutral solution of copper(II) nitrate and zinc nitrate.
3
Excess potassium iodide solution was added to 25.0 cm portions of this solution, and the
3
liberated iodine titrated with 0.100 mol dm sodium thiosulphate solution. The mean titre
3
was 16.55 cm .
2+
(i)
State which indicator you would use for the titration and the colour change seen at
the end point.
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
Explain why the indicator is not added until the reaction is nearly complete.
...........................................................................................................................
...........................................................................................................................
(1)
100
101
(iii)
(5)
(Total 22 marks)
60.
When solid lead(II) sulphate is added to a solution of sodium iodide, the following equilibrium
is established:
PbSO4(s) + 2I (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.
3
In a typical experiment, excess lead(II) sulphate was added to 50.0 cm of 0.100 mol dm
3
3
sodium iodide solution. The whole equilibrium mixture required 31.0 cm of 0.100 mol dm
silver nitrate solution to react with the aqueous iodide ions.
The expression for Kc for this reaction is
2
[SO 4 ]
2
Kc = [ I ]
102
(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 Kc for the reaction at temperature T, including the units, if any.
(8)
(Total 10 marks)
103
61.
(ii)
Write the expression for the acid dissociation constant, Ka, of the ammonium ion.
(1)
(iii)
(4)
104
(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
pKIn
thymol blue
1.7
methyl red
5.1
phenolphthalein
9.3
...........................................................................................................................
...........................................................................................................................
(2)
(b)
(c)
105
(ii)
(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 1chloropropane 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)
106
(ii)
Write a mechanism for the reaction that is consistent with this rate equation.
(3)
(Total 19 marks)
62.
The main reactions involved in the conversion of synthesis gas to methanol in both methods are
CO(g) + 2H2(g)
CO2(g) + 3H2(g)
CH3OH(g)
CH3OH(g) + H2O(g)
H = 91 kJ mol
H = 49 kJ mol
Compare the old and the new methods by considering their operating conditions.
Discuss ONE advantage of the old method and THREE advantages of the new method. Justify
your answers.
(i)
107
(ii)
63.
Ammonia can be oxidised to form nitrogen(II) oxide and water according to the equation
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
H = 905.6 kJ mol .
S / J mol K
NH3 (g)
+192.3
O2 (g)
+205.0
NO (g)
+210.7
H2O (g)
+188.7
108
(a)
(i)
Use the values given to calculate the standard entropy change of the system,
S system, for this reaction. Include the sign and units in your final answer.
(2)
(ii)
system
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(iii)
Calculate the entropy change of the surroundings, Ssurroundings, at 1123 K for this
reaction. Include the sign and units in your final answer.
(2)
(iv)
Calculate the total entropy change, Stotal, for this reaction at 1123 K. Include the
sign and units in your final answer. You may assume that Ssystem is unchanged at
high temperatures.
(1)
109
(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.
P ro p o sa l
U n c a ta ly s e d
p a th w a y
E n e rg y
4 N H 3(g ) +
5 O 2 (g )
4 N O (g ) +
6 H 2O (g )
C a ta ly s e d
p a th w a y
P ro g re s s o f re a c tio n
C o r r e c te d v e r s io n
E n e rg y
4 N H 3(g ) +
5 O 2(g )
P ro g re s s o f re a c tio n
(2)
110
(b)
2NO2(g)
(i)
Substance
Number of moles
at equilibrium
NO (g)
0.025
O2 (g)
0.025
NO2 (g)
4.95
Write the expression for the equilibrium constant, Kp, for this reaction.
(1)
(ii)
Calculate the mole fraction of each gas and hence the value of the equilibrium
constant, Kp, 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)
111
112
(iv)
If the total pressure of the reaction mixture was increased, describe what would
happen to the value of the equilibrium constant, Kp, and the partial pressure of
NO2(g). In each case justify your answer.
Equilibrium constant, Kp.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Partial pressure of NO2(g).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 17 marks)
64.
(a)
The table below shows the acid dissociation constants, Ka, of three carboxylic acids.
(i)
Acid
Structural formula
Ka/ mol dm
Chloroethanoic
CH2ClCO2H
1.3 10
Dichloroethanoic
CHCl2CO2H
5.0 10
Trichloroethanoic
CCl3CO2H
2.3 10
Write an expression for the acid dissociation constant, Ka, of chloroethanoic acid.
(1)
113
(ii)
(3)
(iii)
(b)
Draw the displayed formula and give the name of the organic product formed.
Displayed Formula
Name .................................................................................................................
(3)
114
(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)
115
65.
(a)
(b)
In the Haber process, ammonia is manufactured from nitrogen and hydrogen as shown in
the equation.
N2(g) + 3H2(g)
(i)
2NH3(g)
Use the bond enthalpies below to calculate the standard enthalpy of formation of
ammonia.
Bond
+945
+436
NN in N
HH in H
NH in NH
+391
(4)
116
(ii)
Draw a labelled enthalpy level diagram for the formation of ammonia in the Haber
process.
E n th a lp y
(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)
117
(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)
(c)
(ii)
118
119
66.
(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)
(i)
.......................................................... .
.......................................................... .
(1)
.......................................................... .
.......................................................... .
(1)
(ii)
Write the expression for the acid dissociation constant, Ka, for methanoic acid.
120
(1)
121
(iii)
(3)
(d)
A buffer solution is made up by mixing equal volumes of 0.100 mol dm methanoic acid
3
and 0.400 mol dm sodium methanoate.
(i)
(3)
122
(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)
123
67.
2SO3(g)
2
p SO
3
(a)
2
p SO
p O2
2
10.0 mol of SO2 and 5.00 mol of O2 were allowed to react. At equilibrium, 90.0% of the
SO2 was converted into SO3.
(i)
Calculate the number of moles of SO2, O2 and SO3 present in the equilibrium
mixture.
(2)
(ii)
(1)
124
(iii)
Assuming that the total pressure of the equilibrium mixture was 2.00 atm, calculate
the partial pressures of SO2, O2 and SO3 at equilibrium.
(1)
(iv)
(2)
(b)
125
2
p SO
3
(ii)
p 2 p O2
Use your answer to (i), and the expression Kp = SO 2
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 Kp.
...............................................................................
(1)
(ii)
State the effect, if any, of this increase in pressure on the amount of sulphur
trioxide in the equilibrium mixture.
...............................................................................
(1)
(d)
Kp
...............................................................................
(1)
(ii)
126
127
68.
(a)
(b)
B NaOH
E HNO3
C HCO2H
.....................................................................................................................................
(2)
(Total 3 marks)
69.
Y
X
5
4
3
2
1
0
0
10
20
30
40
V o lu m e o f a m m o n ia a d d e d / c m
50
60
128
(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, Ka, for an aqueous solution
of butanoic acid.
(1)
(iii)
Calculate the value of Ka 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)
129
(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)
70.
(a)
(b)
130
PCl5(g)
PCl3(g) + Cl2(g)
131
(i)
Use the values of enthalpy of formation given to calculate H for the forward
reaction.
Hf /
kJ mol
PCl5(g)
399
PCl3(g)
306
(1)
(ii)
Explain, with reasons, the effect that raising the temperature would have on the
composition of the equilibrium mixture.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
Other than by changing the temperature, suggest how the amount of PCl 5 present at
equilibrium could be increased. Give a reason for your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 8 marks)
71.
(a)
(i)
132
(1)
133
(ii)
(1)
(b)
Phosphoric(V) acid, H3PO4, is a weak acid, forming the following equilibrium in water:
H3PO4(aq) + H2O(l)
(i)
Write an expression for the acid dissociation constant, Ka, for phosphoric(V) acid.
(1)
(ii)
134
(4)
135
(c)
The H2PO4 ion formed when phosphoric(V) acid is added to water can dissociate further
2
into HPO4 .
H2PO4 (aq) +
..................
(i)
H2O(l)
..................
HPO4 (aq) +
..................
H3O (aq)
..................
In the spaces below the equation, identify the acid base conjugate pairs.
(2)
(ii)
Explain why very little dissociation of the H2PO4 ion occurs in solutions of
phosphoric(V) acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
136
(d)
The change in pH when 25.0 cm of 0.100 mol dm phosphoric(V) acid is titrated with
sodium hydroxide solution of the same concentration can be seen on the graph below.
7
pH
10
20
30
V o lu m e o f 0 .1 0 0 m o l d m 3 s o d iu m
h y d ro x id e s o lu tio n a d d e d / c m 3
137
From the list below, select a suitable indicator for this titration. Justify your choice.
pKIn
bromocresol green
4.7
bromothymol blue
7.0
phenolphthalein
9.3
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)
72.
E /V
3+
Fe (aq) + e
Fe (aq)
2+
+0.77
Cl2(aq) + 2e
2Cl (aq)
+1.36
Mn (aq) + 4H2O(l)
2+
+1.51
(a)
(i)
Use the data to explain why dilute hydrochloric acid is not used to acidify
solutions of potassium manganate(VII).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
138
(ii)
(b)
(i)
The ionic equation for the oxidation of iron(II) ions by manganate(VII) ions in
acidic solution is
2+
2+
3+
(1)
139
(ii)
Patients suffering from iron deficiency are often prescribed tablets containing
hydrated iron(II) sulphate, FeSO4.7H2O.
Some tablets, of total mass 6.00 g, were dissolved in distilled water and made up to
3
3
200 cm in a volumetric flask. 25.0 cm portions of this solution were titrated
3
against a 0.0200 mol dm solution of acidified potassium manganate(VII). The
3
mean titre was 20.10 cm .
Calculate the percentage of hydrated iron(II) sulphate in the tablets.
1
(5)
(c)
E /V
2+
Pb(s)
Pb (aq) + 2H2O(l)
Pb (aq) + 2e
PbO2(s) + 4H (aq) + 2e
(i)
2+
0.13
+1.46
140
(1)
141
(ii)
A single cell in a car battery has an e.m.f. of 2.00 V. Suggest why this value is
different from the answer calculated in (i).
...........................................................................................................................
...........................................................................................................................
(1)
(Total 11 marks)
73.
Iron is produced from the ore haematite, which contains iron(III) oxide.
Some standard enthalpies of formation are given below.
Compound
(a)
(i)
Hf / kJ mol
Fe2O3 (s)
822
CO (g)
110
CO2 (g)
394
Write the equation for the complete reduction of iron(III) oxide by carbon
monoxide.
Calculate the enthalpy change for this reaction.
(3)
142
143
(ii)
H = +492 kJ mol
Explain whether the reduction process in (i) or (ii) is more likely to occur.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(b)
Fe3O4(s) + 4H2(g)
At 600 C, a mixture of iron and steam is allowed to reach equilibrium. The equilibrium
partial pressures of hydrogen and steam are 1.6 atm and 1.2 atm respectively.
(i)
Write the expression for the equilibrium constant, Kp, for the reaction. Calculate its
value and state the units.
(2)
144
(ii)
State the effect, if any, on the value of Kp when the temperature is increased.
Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(c)
When an iron nail is left in a test tube of water containing a little phenolphthalein, it starts
Z
Y
Write the half-equations for the reactions taking place in regions X and Y.
Name the green precipitate that forms in region Z.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
145
(d)
Anhydrous iron(III) chloride is made by passing dry chlorine gas over heated iron. It is
formed as a dark red covalent gas with formula Fe 2Cl6 and has a similar structure and
reactions to aluminium chloride.
Draw a diagram to show the structure of the Fe2Cl6 molecule. Label the types of bonding
present.
State the shape around each iron atom.
(3)
(e)
3+
ions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
146
147
74.
The Hess cycle below can be used to estimate the enthalpy change of formation, DHf, of the
unstable gaseous compound with the formula HOCl(g).
+ 6 6 7 k J m o l 1
H O C l(g )
G a s e o u s a to m s o f th e e le m e n ts
H
+ 5 8 9 k J m o l 1
E le m e n ts in th e ir s ta n d a rd s ta te s
(a)
(i)
Insert formulae, with state symbols, into the appropriate boxes, to show the correct
quantities of each element.
(1)
(ii)
Use the cycle to calculate a value for the enthalpy change of formation, H f
[HOCl(g)].
(1)
148
(iii)
Assuming that the HO bond energy is +464 kJ mol , calculate a value for the O
Cl bond energy.
(1)
149
(b)
(i)
Draw a dot and cross diagram for the HOCl molecule showing outer electrons
only.
(2)
(ii)
150
(c)
2HOCl(g)
What effect, if any, would an increase in pressure have on the proportion of HOCl(g) at
equilibrium? Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 9 marks)
75.
(a)
CHCl2CO2C5H11(l)
Give the name of the product of this reaction and also the name for the new functional
group it contains.
.....................................................................................................................................
.....................................................................................................................................
(2)
151
(b)
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)
152
(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
3
/mol dm
CHCl2COOH
1.00
0.40
1.33
C5H10
2.30
CHCl2COOC5H11
0
(3)
(iv)
(3)
(Total 13 marks)
153
76.
2SO3(g)
(b)
(i)
State the conditions of temperature and pressure used industrially for the
manufacture of SO3.
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
Justify the choice of temperature for this reaction in terms of yield and rate.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
154
(iii)
The yield of products would be greater if a higher pressure were to be used for the
reaction.
Suggest a reason why a higher pressure than you have given in (i) is not used.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(c)
(i)
Calculate H for the forward reaction, given the enthalpies of formation below.
Hf / kJ mol
SO2(g)
297
SO3(g)
395
O2(g)
(2)
(ii)
(d)
(i)
155
(ii)
Draw an enthalpy level diagram to show the reaction profiles of the uncatalysed
and catalysed reactions.
(3)
(iii)
(e)
Suggest why the sulphur trioxide produced is passed into concentrated sulphuric acid
rather than water to form sulphuric acid at the end of the process.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 18 marks)
156
77.
The weak acid methanoic acid, HCOOH, sets up the following equilibrium in water at 298 K:
HCOOH(aq) + H2O(l)
The acid dissociation constant, Ka, for methanoic acid at 298 K is 1.78 10 mol dm .
(a)
20.0 cm of this solution is titrated with 0.100 mol dm sodium hydroxide solution until
excess alkali has been added.
On the grid below, sketch the titration curve you would expect for this reaction.
14
12
10
pH
8
6
4
2
0
10
20
30
40
V o lu m e o f s o d iu m h y d ro x id e s o lu tio n / c m
50
60
(4)
157
(b)
Equal volumes of 0.500 mol dm methanoic acid and 0.250 mol dm sodium
methanoate solution are mixed to make a buffer solution.
(i)
(ii)
(3)
158
(iii)
Explain, with the aid of equations, how this mixture acts as a buffer solution.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 13 marks)
78.
(a)
159
(b)
When a metal is placed in a solution of its ions, the electrical potential set up between the
metal and the solution cannot be measured without using a reference electrode. Explain
why this is so.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(c)
E /V
2+
Zn (aq) + 2e
0.76
2+
Fe(s)
0.44
Sn (aq) + 2e
2+
Sn(s)
0.14
O2(g) + 2H2O(1) + 4e
4OH (aq)
+0.40
Fe (aq) + 2e
(i)
Zn(s)
Write an overall equation for the first stage in the rusting of iron.
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
160
(iii)
Use the E values above to explain why zinc is used in preference to tin for
preventing corrosion of steel car bodies.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(Total 10 marks)
79.
(a)
The elements from scandium to zinc belong to the d-block. Some, but not all, of these
elements are transition elements.
(i)
(ii)
Which of the elements, from scandium to zinc inclusive, are in the d-block but are
not transition elements?
...........................................................................................................................
(1)
(b)
(i)
2+
Mn
2+
and Mn
2+
ions below.
[Ar] ..............................................................................................................
2+
[Ar] .............................................................................................................
(1)
161
(ii)
2+
3+
ions, but Mn
2+
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(c)
Draw a diagram to show the three-dimensional structure of the [Fe(CN) 6] complex ion.
(2)
(d)
162
163
(e)
Ammonium vanadate(V), NH4VO3, reacts with dilute sulphuric acid to form a solution
+
Write an ionic equation for the reaction of the anion in NH4VO3 with dilute
sulphuric acid.
...........................................................................................................................
(1)
(ii)
(iii)
Addition of zinc to the solution containing VO2 ions causes the colour to change
from yellow to green then to blue, followed by green again and finally violet.
State the formulae of the ions responsible for each of these colours.
The first green colour
...............................................................................
...............................................................................
................................................................................
(3)
(Total 16 marks)
164
80.
Write the ionic equation to show the disproportionation of the chlorate(I) ion. Use
oxidation numbers to explain the meaning of the term disproportionation in this reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(b)
Domestic bleaches are dilute solutions of sodium chlorate(I). The amount of ClO ions in
a sample can be found by reacting it with excess acidified potassium iodide solution.
ClO + 2I + 2H I2 + Cl + H2O
The iodine produced is then titrated with standard sodium thiosulphate solution.
3
10.0 cm of a domestic bleach was pipetted into a 250 cm volumetric flask and made
up to the mark with distilled water.
3
A 25.0 cm portion of the solution was added to excess acidified potassium iodide
solution in a conical flask.
3
This mixture was titrated with 0.100 mol dm sodium thiosulphate solution, using
starch indicator added near the end point.
3
(i)
Give the colour change you would see at the end point.
...........................................................................................................................
...........................................................................................................................
(1)
165
(ii)
The equation for the reaction between iodine and thiosulphate ions is
2
2S2O3 + I2 S4O6 + 2I
Calculate the amount (moles) of chlorate(I) ions in 1.00 dm of the original bleach.
(5)
(iii)
Use the equation below to calculate the mass of chlorine available from 1.00 dm
of the original bleach. Give your answer to 3 significant figures.
(1)
166
(c)
Sodium thiosulphate can be used to remove the excess chlorine from bleached fabrics.
2
+ 10H + 8Cl
(d)
Starch-iodide paper can be used to test for chlorine. It contains starch and potassium
iodide.
Explain the reactions taking place when a piece of damp starch-iodide paper is put in a
gas jar of chlorine. State what you would see.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 14 marks)
167
81.
(i)
(1)
(ii)
Draw a dot and cross diagram for propene. You should show outer shell electrons only.
(1)
(Total 2 mark)
82.
One step in the manufacture of nitric acid is the reaction between nitrogen(II) oxide and oxygen
to form nitrogen(IV) oxide.
2NO(g) + O2(g)
(a)
(i)
2NO2(g)
H = 114 kJ mol
Use the equation to suggest the sign of Ssystem for the forward reaction. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
168
(ii)
What is the sign of Ssurroundings for the forward reaction? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b)
(i)
Units ..............................................
(2)
169
(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)
170
(ii)
[NO(g)]
3
/mol dm
[O2(g)]
3
/mol dm
Initial rate
3 1
/mol dm s
1.0 10
1.0 10
8.0 10
2.0 10
1.0 10
3.2 10
2.0 10
2.0 10
6.4 10
What is the order of the reaction with respect to NO(g)? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
(1)
(iv)
171
(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)
83.
(a)
When silver carbonate is heated, it decomposes into silver oxide and carbon dioxide.
Ag2CO3(s)
Ag2O(s) + CO2(g)
(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?
172
(1)
173
(b)
When nitrosyl chloride, NOCl, is heated, it dissociates reversibly into nitric oxide, NO,
and chlorine, Cl2, according to the equation
2NOCl(g)
(i)
2NO(g) + Cl2(g)
H = +75.6 kJ mol
Write the expression for the equilibrium constant, Kp, for this reaction.
(1)
174
(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 Kp at this temperature, stating its units.
(5)
(iii)
175
(iv)
Hence suggest in which direction the position of equilibrium moves when the
temperature is increased. Justify your answer.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(Total 12 marks)
84.
(a)
The first step in the esterification of ethanoic acid, CH 3COOH, by ethanol in the presence
of a small quantity of concentrated sulphuric acid, is the reaction
+
CH3COOH + H2SO4 CH3COOH2 + HSO 4
In the space below the equation, identify the two acid base conjugate pairs.
(2)
(b)
Ethanoic acid, CH3COOH, is a weak acid and dissociates in water according to the
equation
CH3COOH(aq) + H2O(l)
176
(i)
(ii)
177
(iii)
Assumptions
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(iv)
(3)
(Total 14 marks)
178
85.
(a)
(i)
[Ar].................................................................................................
2+
[Ar].................................................................................................
(2)
(ii)
2+
(1)
(iii)
Give the equation for the complete reaction of sodium hydroxide solution with a
solution of hexaaquairon(II) ions.
......................................................................................................................
(1)
(iv)
State what you would see if the product mixture in (iii) is left to stand in air.
......................................................................................................................
......................................................................................................................
(1)
(v)
Give the equation for a reaction in which iron metal is used as a catalyst.
......................................................................................................................
(1)
179
(b)
2+
+ 2e
Fe
E = 0.44 V
Define the term standard electrode potential with reference to this electrode.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(ii)
Explain, with the aid of an equation, why the value of E suggests that iron will
2+
react with an aqueous solution of an acid to give Fe ions and hydrogen gas.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(iii)
State why E values cannot predict that a reaction will occur, only that it is
possible.
......................................................................................................................
......................................................................................................................
(1)
180
(c)
Use the following standard electrode potentials to explain why iron(III) iodide does not
exist in aqueous solution.
Fe
3+
+ e
I2 + 2e
Fe
2I
2+
E = +0.77 V
E = +0.54 V
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(Total 15 marks)
86.
(a)
Step 1
CH3CH=CHCOOH
CH3CHBrCH2COOH
Step 2
CH3CHBrCH2COOH
CH3CH(OH)CH2COOH
Step 3
CH3CH(OH)CH2COOH
CH3COCH2COOH
(i)
181
(ii)
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
(1)
(ii)
(1)
(c)
3-oxobutanoic acid is a weak acid. The value of its acid dissociation constant, Ka, is
4
2.63 10 mol dm .
(i)
182
(1)
183
In parts (ii) and (iii) you may use HX as the formula for 3-oxobutanoic acid.
(ii)
Explain how a mixture of 3-oxobutanoic acid and its sodium salt can act as a buffer
solution when a small amount of alkali is added.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
184
(iii)
Calculate the mass of solid sodium 3-oxobutanoate that must be added to 100 cm
3
of a 0.500 mol dm solution of 3-oxobutanoic acid in order to make a buffer
solution of pH 3.80.
(5)
(Total 18 marks)
185
87.
(a)
Carboxylic acids react reversibly with alcohols, in the presence of a catalyst, to form an
ester and water.
When 24.8 g of ethane-1,2-diol, HOCH2CH2OH, was mixed with 66.0 g of ethanoic acid,
CH3COOH, in the presence of a catalyst, equilibrium was reached after 80.0% of the
3
CH3COOCH2CH2OOCCH3 + 2H2O
Write the expression for the equilibrium constant, Kc, and calculate its value. You should
make clear what units, if any, there are for Kc.
(7)
(b)
Ethane-1,2-diol can be made from ethene in a two-stage process. The overall reaction is:
1
C2H4 + H2O + 2 O2 HOCH2CH2OH
1054 g of ethane-1,2-diol was obtained from 560 g of ethene.
Calculate the percentage yield of the process.
(2)
186
187
(c)
Give the structural formula of a reagent that would react with ethane-1,2-diol to
make a polyester. Draw the structure of the polymer made from this reagent and
ethane-1,2-diol.
(3)
(ii)
Explain whether it would be sensible for protective clothing, made from this
polymer, to be used in an environment where acid spills are likely.
......................................................................................................................
......................................................................................................................
(1)
(d)
Explain why the ester methyl methanoate, HCOOCH3, has a much lower boiling
temperature than its isomer ethanoic acid, CH 3COOH, and why ethanoic acid has a lower
boiling temperature than propanoic acid, C2H5COOH.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(5)
(Total 18 marks)
188
189
88.
(a)
(i)
Draw a labelled Hesss Law cycle for the dissolving of solid calcium hydroxide in
water, and use it and the data below to calculate the lattice energy of calcium
hydroxide.
H/ kJ mol
2+
1650
460
16.2
(4)
(ii)
State and explain the trend in solubility in water of the Group 2 hydroxides.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
190
(b)
The dissolving of sparingly soluble calcium hydroxide in water can be shown by the
equilibrium reaction
Ca(OH)2(s) + (aq)
2+
H = 16.2 kJ mol
(ii)
(c)
When concentrated sulphuric acid is added to solid calcium chloride, one acidic gas is
given off.
When concentrated sulphuric acid is added to solid calcium bromide, three gases are
given off.
Identify the three gases given off in the reaction with calcium bromide. Explain why only
one gas is given off in the reaction with calcium chloride.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
(Total 18 marks)
191
192
89.
In the first stage of an industrial process for purifying nickel, carbon monoxide is passed over
impure nickel at 323 K. Gaseous nickel tetracarbonyl, Ni(CO) 4, is formed.
Ni(s) + 4CO(g)
(a)
(i)
Calculate S
system
Ni(CO)4(g)
H = 191 kJ mol
S
1 1
/J mol K
Substance
Ni(s)
+29.9
CO(g)
+197.6
Ni(CO)4(g)
+313.4
(2)
(ii)
Refer to the equation above and comment on the sign of your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
(iii)
Calculate S
surroundings
(2)
193
(iv)
(b)
(i)
Write the expression for the equilibrium constant, Kp, 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 Kp at this temperature.
Include the units of Kp in your answer.
Substance
Moles at start
Ni(CO)4
CO
100
Moles at
equilibrium
99.0
(4)
Sri Lankan School
194
195
(iii)
As Kp has such a small value, suggest THREE ways in which this industrial
process could be improved to increase profitability. Justify each of your
suggestions.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(3)
(c)
The second stage of this process is to recover the nickel from the nickel tetracarbonyl,
Ni(CO)4. By considering your calculations of the entropy changes, suggest how this
could be done. Justify your suggestion.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(Total 16 marks)
196
90.
A step in the Contact Process, for the manufacture of sulphuric acid, is the catalytic oxidation of
sulphur dioxide:
2SO2(g) + O2(g)
2SO3(g)
DH = 196 kJ mol
If sulphur dioxide and oxygen are heated to a temperature of 450 C and at a pressure of 2 atm
in the presence of a catalyst of vanadium(V) oxide, a dynamic equilibrium is reached in which
about 98 % of the sulphur dioxide is converted into sulphur trioxide.
(a)
(i)
(ii)
State the effect on the percentage of sulphur dioxide converted, if extra oxygen is
added to the system in equilibrium.
......................................................................................................................
(1)
(iii)
State the effect on the percentage of sulphur dioxide converted, if the catalyst is
removed from the system in equilibrium.
......................................................................................................................
(1)
(b)
Use your understanding of kinetics and equilibria to justify the temperature used to obtain
an economic yield in the manufacture of sulphuric acid.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(4)
(Total 8 marks)
197
91.
Ka = 1.5 10 mol dm .
(i)
(ii)
(1)
(iii)
(3)
198
(iv)
On the grid below sketch the change in pH during the addition of 50.0 cm of
3
3
3
0.100 mol dm sodium hydroxide solution to 25 cm of 0.100 mol dm pentanoic acid
solution.
14
12
10
pH
8
6
4
2
10
20
30
V o lu m e o f s o d iu m h y d ro x id e a d d e d / c m
40
50
(4)
(v)
pKind
Bromophenol blue
4.0
Methyl red
5.1
Thymol blue
8.9
Alizarin yellow
12.5
Indicator ................................................................................................................
Reason ...................................................................................................................
...............................................................................................................................
(2)
(Total 11 marks)
199
92.
Consider the esterification of the amino acid alanine, which has the formula
CH3CH(NH2)COOH.
CH3CH(NH2)COOH + C2H5OH
(a)
(i)
CH3CH(NH2)COOC2H5 + H2O
(1)
(ii)
Using the average bond enthalpies given below, show that enthalpy change, DH,
for this reaction would be calculated as zero.
Average bond enthalpies / kJ mol
CO 358
OH 464
(2)
200
(iii)
On the basis that DH is zero, state what the effect of increasing the temperature
will be on:
the value of Kc ............................................................................................................
......................................................................................................................
the rate of attainment of equilibrium ..........................................................................
......................................................................................................................
(2)
(b)
(1)
(ii)
(iii)
Using equations, show how alanine can react with both acid and alkali.
(2)
201
202
(c)
(ii)
(2)
(iii)
How could the optical isomers of alanine be distinguished from each other?
......................................................................................................................
......................................................................................................................
(1)
(Total 13 marks)
203
93.
The reaction between nitrogen and hydrogen can be used to produce ammonia.
2
N2(g) + 3H (g)
2NH3(g)
H = 92.2 kJ mol
= +191.6 J mol K
= +130.6 J mol K
= +192.3 J mol K
S [N2(g)]
S [H2(g)]
S [NH3(g)]
(a)
system,
(2)
(b)
surroundings,
(2)
204
(c)
(i)
total,
(1)
(ii)
(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)
205
206
(iii)
94.
(a)
(i)
(ii)
(b)
The concentration of propanoic acid can be found by titrating a sample with standard
sodium hydroxide solution.
(i)
(3)
207
(ii)
Sketch with reasonable accuracy the titration curve that you would expect if
3
3
3
25.0 cm of 0.100 mol dm propanoic acid were to be titrated with 0.100 mol dm
sodium hydroxide solution.
14
12
10
8
6
4
2
0
(iii)
10
20
30
40
3 s o d iu m h y d ro x id e s o lu tio n /c m
V o lu m e o f 0 .1 0 0 m o l d m
50
3
95.
N2(g) + O2(g)
DH = 180 kJ mol
208
(b)
(1)
(ii)
(4)
(c)
State and explain the effect on Kp and hence on the position of equilibrium of decreasing
the temperature at constant pressure.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
209
210
(d)
The reaction
Ni(s) + 4CO(g)
Ni(CO)4(g)
(1)
(ii)
96.
(a)
(i)
Define the term standard electrode potential, making clear the meaning of
standard in this context.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
211
(ii)
(b)
Mn
H2O2
+0.68
2H2O
+1.77
MnO4 + 8H + 5e
O2 + 2H + 2e
H2O2 + 2H + 2e
(i)
2+
E /V
+1.52
+ 4H2O
Derive the equation for the reaction between hydrogen peroxide and
manganate(VII) ions in acidic solution and use E values to show that the reaction
is feasible.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(ii)
212
(iii)
Derive the equation for the disproportionation of hydrogen peroxide and explain, in
terms of oxidation states, why it is a disproportionation reaction.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 12 marks)
97.
The industrial processes involved in the production of poly(chloroethene) are summarised in the
flow chart:
ethane ethene 1,2-dichloroethane chloroethene poly(chloroethene)
(a)
(i)
(1)
(ii)
Explain why conditions of high pressure are less favourable for ethene production.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(b)
Draw a labelled diagram of an ethene molecule, showing the electron density distribution
in the s and p bonds between the carbon atoms.
(2)
Sri Lankan School
213
214
(c)
Give a chemical test which would distinguish between ethane and ethene.
State the result of your test with ethene.
Test ..............................................................................................................................
Result ...........................................................................................................................
(2)
(d)
98.
(a)
H = -129 kJ mol
The entropy of one mole of each substance in the equation, measured at 298 K, is shown
below.
(i)
Substance
S
-1 -1
/J mol K
CO(g)
197.6
H2(g)
130.6
CH3OH(l)
239.7
Suggest why methanol has the highest entropy value of the three substances.
.............................................................................................................................
.............................................................................................................................
(1)
215
(ii)
system,
(2)
(iii)
Is the sign of S
system
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(1)
(iv)
surroundings,
at 298 K.
(2)
(v)
(2)
216
(b)
When methanol is produced in industry, this reaction is carried out at 400 C and 200
atmospheres pressure, in the presence of a catalyst of chromium oxide mixed with zinc
oxide. Under these conditions methanol vapour forms and the reaction reaches
equilibrium. Assume that the reaction is still exothermic under these conditions.
CO(g) + 2H2(g)
(i)
CH3OH(g)
(ii)
(iii)
Write an expression for the equilibrium constant in terms of pressure, Kp, for this
reaction.
CO(g) + 2H2(g)
CH3OH(g)
(1)
217
(iv)
(2)
(c)
The diagram below shows the distribution of energy in a sample of gas molecules in a
reaction when no catalyst is present. The activation energy for the reaction is EA.
(i)
(ii)
Draw a line on the graph, labelled EC, to show the activation energy of the
catalysed reaction.
(1)
(Total 17 marks)
218
99.
(a)
NH3(aq) + H2O(l)
(ii)
Draw, on the axes below, a graph to show how the pH of the solution varies as
3
3
40 cm of 0.100 mol dm hydrochloric acid (a strong acid) is added slowly to
3
20 cm of the ammonia solution.
14
12
10
pH
8
6
4
2
0
10
20
30
V o lu m e o f H C l s o lu tio n / c m
40
50
(4)
219
(iii)
Select, from the following list, the indicator which would be the most suitable for
this titration. Give a reason for your choice.
Indicator
pKind
Range
methyl red
5.1
4.26.3
bromothymol blue
7.0
6.07.6
phenolphthalein
9.3
8.210.0
Indicator: ......................................................................................................
Reason: .........................................................................................................
......................................................................................................................
(2)
(b)
Ka = 4.70 10 mol dm at 4 C.
HNO2(aq) + H2O(l)
(i)
(1)
220
(ii)
(3)
(iii)
(4)
221
(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)
100. The concentration of iron(II) ions in a solution can be found by titration with standard
potassium manganate(VII) solution. In the reaction iron(II) ions are oxidised to iron(III)
ions.
If a solution contains both iron(II) and iron(III) ions, the concentration of each ion can be
found by:
titrating samples of the original solution with standard potassium manganate(VII) solution
reacting samples of the original solution with zinc and dilute sulphuric acid and then titrating
with the same potassium manganate(VII) solution.
The following standard electrode potentials are required:
E /V
2+
+ 2e
Fe
2+
+ 2e
Fe
3+
+e
Zn
Zn
0.76
Fe
0.44
Fe
+
2+
MnO4 + 8H + 5e
+ 0.77
Mn
2+
+ 4H2O
+ 1.51
222
(a)
(i)
Use suitable E values to show that both iron(II) and iron(III) ions in solution
should react with zinc to give iron metal.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(ii)
In practice the reaction produces only iron(II) ions and no iron metal.
2Fe
3+
+ Zn 2Fe
2+
+ Zn
2+
(b)
(i)
Derive the ionic equation for the reaction between iron(II) ions and
(ii)
State what you would see as iron(II) ions in solution are titrated with potassium
manganate(VII). How would you detect the endpoint of the titration?
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
223
(c)
A solution containing both iron(II) and iron(III) ions was titrated with 0.0200 mol dm
3
potassium manganate(VII) solution, 18.20 cm being required.
Another portion of the same volume of the same solution was reacted with zinc, and then
3
titrated with the same potassium manganate(VII) solution; 25.30 cm was required.
What mass of zinc had reacted?
(5)
(d)
(i)
(ii)
3+
2+
and
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 20 marks)
224
225
101. When dinitrogen tetroxide, N2O4, dissociates, the following equilibrium is established.
N2O4(g)
(a)
2NO2(g)
State a property which could be measured to follow the progress of this reversible
reaction.
....................................................................................................................................
(1)
(b)
Write an expression for the equilibrium constant, Kc, for this reaction.
(1)
(c)
Number of moles in 1 dm
at equilibrium
N2O4
NO2
0.0370
0.0310
Kc calculation:
(3)
226
(d)
How does this increase in pressure affect the amount of nitrogen dioxide, NO 2(g),
in the equilibrium mixture?
..........................................................................................................................
(1)
(ii)
(e)
The reaction was repeated at the original pressure, but the temperature was increased to
75 C. The value of Kc was approximately twenty times greater.
How does this information show that the reaction is endothermic?
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(1)
(f)
Predict the sign of Ssystem for the reaction, giving a reason for your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(g)
Write the equation for the relationship between Ssurroundings and H for the reaction.
(1)
227
228
(h)
The magnitude of Ssystem for the reaction is greater than the magnitude of Ssurroundings.
Explain why this must be the case.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(Total 13 marks)
102. Crude oil is a mixture of compounds including members of the homologous series of alkanes. It
is used to manufacture fuels, such as petrol, and petrochemicals, such as buta-1,3-diene.
(a)
(b)
One of the reactions in the catalytic converter in the exhaust system of a car engine is
2NO(g) + 2CO(g)
N2(g) + 2CO2(g)
DH = 745 kJ mol
This reaction converts two poisonous gases into two harmless gases. The temperature in
the catalytic converter is high.
(i)
State, with a reason, which way the position of the equilibrium would shift if the
temperature were lowered.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
229
(ii)
The gases from the engine are not cooled before entering the converter.
Explain why this is so.
......................................................................................................................
......................................................................................................................
(2)
(c)
(1)
(ii)
230
(iii)
Predict the structural formula of the organic product of the reaction of buta-1,3diene with an excess of an alkaline solution of potassium manganate(VII).
(2)
(Total 11 marks)
(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, Ka, for propanoic acid.
(1)
Sri Lankan School
231
232
(iii)
(3)
(iv)
(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)
233
(c)
(ii)
(3)
(Total 16 marks)
104. (a)
(i)
(ii)
Draw the shape of a molecule of compound Y. Show the values of the bond angles
on the diagram.
(3)
(iii)
Compound Y was converted into the ion PF6 . Draw and name the shape of PF6
and suggest a value for the bond angles.
(3)
234
(b)
(i)
Consider the following data, which shows the formulae and boiling temperatures of
the Group 7 hydrides.
Group 7 hydride
Boiling temperature/C
HF
19
HCl
85
HBr
68
HI
35
Suggest why hydrogen fluoride, HF, has the highest boiling temperature of the
Group 7 hydrides.
(3)
(c)
When hydrogen fluoride is dissolved in water a solution of a weak acid is formed. Write
the expression for the acid dissociation constant, Ka, for hydrogen fluoride. Calculate the
3
value of Ka, with units, given that a 0.150 mol dm solution of hydrogen fluoride has a
pH of 2.04.
(5)
(Total 18 marks)
105. (a)
Consider the following equilibrium, which illustrates one industrial method used to
produce hydrogen:
CH4(g) + 2H2O(g)
CO2(g) + 4H2(g)
container of volume 4 dm . At equilibrium, 2.0 moles of hydrogen, H2, had formed. Write
an expression for the equilibrium constant, Kc, for the system, and use the data to
calculate a value for Kc, with units.
(8)
235
(b)
The following table shows some data for enthalpies of formation, DHf.
Substance
DH f /kJ mol
CH4(g)
76
H2O(g)
242
CO2(g)
394
Use these data to calculate the enthalpy change for the reaction in (a).
(3)
(c)
106. This question is concerned with alkenes including ethene and buta-1,3-diene,
CH2 = CHCH = CH2.
(a)
(i)
The typical reactions of alkenes are addition reactions, for example their reactions
with bromine.
Explain why the reaction of ethene with bromine is described as an addition
reaction.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(1)
(ii)
Why should this reaction be carried out in the absence of sunlight or ultra-violet
radiation?
..........................................................................................................................
..........................................................................................................................
(1)
236
237
(iii)
Explain how, in this reaction, the bromine molecule is able to act as an electrophile,
even though it is normally non-polar.
(2)
(b)
(i)
(2)
(ii)
238
(c)
It has been suggested that cyclohexene, another alkene, could be made by a reaction
between ethene and buta-1,3-diene.
Using molecular formulae, the reaction could be represented by the equation
C2H4(g) + C4H6(g)
(i)
C6H10(l)
H = 200 kJ mol
(1)
(ii)
Decide whether high or low temperature and pressure would give the higher
proportion of cyclohexene at equilibrium. Justify your choice in each case.
Temperature .....................................................................................................
..........................................................................................................................
Pressure ............................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(Total 10 marks)
239
Write an expression linking hydrogen ion concentration and pH. Use this to calculate the
concentration of hydrogen ions in this solution.
(3)
(b)
(i)
14
mol dm .
Kw =
(1)
(ii)
(1)
(iii)
(1)
240
(iv)
(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 .
(1)
(ii)
Use your answer to (b)(iii) and the information above to calculate the volume of
3
hydrochloric acid needed to neutralise 100 cm of the saturated calcium
hydroxide solution.
(3)
241
(iii)
(2)
(iv)
108. In the Ostwald process for the production of nitric acid, ammonia is oxidised at 900 C over a
platinum/ rhodium alloy catalyst according to the equation:
4NH3(g) + 5O2(g)
4NO(g) + 6H2O(g)
(i)
242
(ii)
State with a reason the effect of an increase in pressure on this equilibrium system.
....
....
....
(2)
(b)
The mixture obtained from the catalyst chamber contains excess oxygen.
Write the equation for the further reaction that occurs on cooling this mixture.
....
(1)
(ii)
Show, by means of an equation, how the product in (b) (i) is used to make
nitric acid.
....
(2)
(c)
(i)
(2)
243
(ii)
Use your diagram and any necessary explanation to show how the presence of a
catalyst leads to an increase in reaction rate at the same temperature.
....
....
....
....
....
....
(4)
(Total 12 marks)
109. (a)
pH .....................................................................................................................
(1)
(ii)
Kw ......................................................................................................................
(1)
(b)
(c)
(1)
244
(ii)
14
mol dm ).
(2)
(d)
(1)
(ii)
(3)
245
(e)
A buffer solution contains HA(aq) at a concentration of 0.300 mol dm , and its sodium
3
salt, NaA, at a concentration of 0.600 mol dm . Calculate the pH of this buffer solution.
(3)
(Total 13 marks)
2SO3
3
2.0 moles of SO2 and 1.0 mole of O2 were allowed to react in a vessel of volume 60 dm .
At equilibrium 1.8 moles of SO3 had formed and the pressure in the flask was 2 atm.
(a)
(i)
Write the expression for Kc for this reaction between SO2 and O2.
(1)
(ii)
(3)
246
(b)
The reaction between SO2 and O2 is exothermic. State the effect on the following, if the
experiment is repeated at a higher temperature:
(i)
Kc ..
(1)
(ii)
(c)
Kc ..
(1)
(ii)
(d)
(i)
Write the expression for Kp for the reaction between SO2 and O2.
(1)
(ii)
(2)
247
(iii)
(1)
(iv)
(2)
(Total 14 marks)
111. (a)
(b)
(i)
Zn(s)
0.76
2+
Fe(s)
0.44
2+
Co(s)
0.28
2+
Sn(s)
0.14
Zn (aq) + 2e
Fe (aq) + 2e
Co (aq) + 2e
Sn (aq) + 2e
+
O2(g) + 2H (aq) + 2e
3+
Co (aq) + e
2+
H2O2(aq)
Co (aq)
+0.68
+1.82
248
249
(ii)
Suggest two factors that might prevent a reducing agent from being as effective as
the electrode potentials might seem to suggest.
.......
.......
.......
.......
(2)
(c)
(i)
(ii)
250
112. (a)
A mixture of hydrogen iodide, hydrogen and iodine (all in the gaseous state) establishes
dynamic equilibrium if a constant temperature is maintained.
2HI (g)
(i)
H2 (g) + I2 (g)
H = +9.6 kJ mol
(ii)
(iii)
The reaction is catalysed by metals such as gold and platinum. How, if at all, would
the proportion of hydrogen iodide present at equilibrium change if the reaction
were to be catalysed? Justify your answer.
............................................................................................................................
............................................................................................................................
(1)
251
(b)
Part of an energy profile for this reaction is shown below. It is not intended to be to scale.
the products;
labelled arrows to indicate the activation energies of both the uncatalysed and
catalysed reactions.
(4)
(Total 9 marks)
113. Thermochemical data, at 298 K, for the equilibrium between zinc carbonate, zinc oxide and
carbon dioxide is shown below.
ZnCO3(s)
ZnO(s) + CO2(g)
H = +71.0 kJ mol
1
S [ZnO(s)] =
+43.6 J mol K
S [ZnCO3(s)] =
+82.4 J mol K
252
(a)
(i)
Suggest reasons for the differences between the three standard entropies.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(ii)
system
(2)
(b)
surroundings,
(2)
253
(c)
(i)
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)
254
(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)
114. The reaction in the Haber Process that is used to produce ammonia is a homogeneous dynamic
equilibrium:
N2(g) + 3H2(g)
(a)
2NH3(g)
DH = 92 kJ mol
dynamic equilibrium;
............................................................................................................................
............................................................................................................................
(2)
(ii)
homogeneous.
............................................................................................................................
(1)
(b)
Give, with a reason in each case, the effect of the following on the position of the
equilibrium above:
255
(i)
an increase in pressure;
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(ii)
an increase in temperature.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(Total 7 marks)
115. (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
CH4(g) + H2O(g)
(i)
CO(g) + 3H2(g)
DH = +210 kJ mol
(ii)
Write an expression for the equilibrium constant, Kp, for this reaction.
256
(1)
257
(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 Kp for this equilibrium of the following.
(i)
(ii)
(iii)
Adding a catalyst.
............................................................................................................................
(1)
(c)
There is a theory that methane, CH4, constantly leaks from the earths 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.
CH4(g) + 6H2O(s)
[CH4(H2O)6](s)
methane hydrate
258
(1)
(ii)
(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)
259
(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)
116. Ethanoic acid, CH3COOH, is a weak acid which can be used, with its salts, to make buffer
solutions.
(a)
(b)
260
(c)
14
pH
12
10
8
6
4
2
0
10
20
30
40
50
V o lu m e o f a lk a li a d d e d /c m 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, Ka, for ethanoic acid.
(1)
(ii)
Explain how the pKa of ethanoic could be found from the graph.
............................................................................................................................
............................................................................................................................
(2)
(Total 11 marks)
261
262
117. (a)
O H
E /V
+ 2H
O H
+ 2 e + 0 .7 0
O
H 2O
(i)
+ 2H
+ 2e
2H 2O
+ 1 .7 7
Write the overall equation for the reaction and show that the reaction is feasible.
(3)
(ii)
The beetle makes use of an enzyme catalyst in the reaction. Explain in general
terms how catalysts increase the rate of a chemical reaction using a graph of the
Maxwell-Boltzmann distribution of molecular energies.
(5)
(iii)
(b)
263
264
(c)
(i)
(ii)
2+
The MnO 4 ions are reduced to Mn during the reaction. Derive the overall
equation for the reaction between H2O2 and acidified KMnO4.
(2)
(iii)
118. (a)
The first stage in the manufacture of sulphuric acid is the Contact Process.
2SO2 + O2
2SO3
4
265
(b)
(i)
O H
O H
Suggest in terms of the intermolecular forces in sulphuric acid why it has such a
high boiling temperature.
(3)
(ii)
(c)
HSO 4 + H2O
H3O + SO 4
The dissociation constant for the first dissociation is very large; that for the second is 0.01
3
mol dm at 25 C.
(i)
(ii)
The pH of 0.100 mol dm sulphuric acid is 0.98. Explain why this is so close to
3
the pH of 0.100 mol dm HCl which is 1.0.
(3)
266
267
(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)
119. Ammonia reacts with oxygen, in a reversible, exothermic reaction, as shown in the equation
below. This is the first stage in the manufacture of nitric acid.
4NH3(g) + 5O2(g)
(a)
(i)
4NO(g) + 6H2O(g)
State and explain the effect of an increase in pressure on the position of this
equilibrium.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(ii)
State and explain the effect of an increase in temperature on the position of the
equilibrium.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
268
(b)
(i)
State and explain the effect of an increase in pressure on the rate of the reaction.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
(ii)
State and explain the effect of an increase in temperature on the rate of the
reaction.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
(c)
(i)
Name the catalyst used in the reaction, during the manufacture of nitric acid.
..........................................................................................................................
(1)
(ii)
269
(iii)
120. (a)
(b)
HA(aq) + H2O(l)
H3O+(aq) + A(aq)
(1)
270
(c)
25 cm of 1.00 mol dm aqueous HA, was titrated with 1.00 mol dm aqueous sodium
hydroxide and the pH measured throughout. The titration curve is shown below.
14
12
pH
10
8
6
4
2
0
10
20
30
40
V o lu m e o f s o d iu m h y d ro x id e a d d e d / c m
50
3
(ii)
(iii)
the value of pKa for the acid HA and, hence the value Ka.
pKa ...................................................................................................................
Ka .....................................................................................................................
(2)
271
(d)
Some of the solutions made during this titration would act as buffer solutions.
(i)
(ii)
to ....................................................
(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
3
would in a similar titration using 1.00 mol dm solutions of hydrochloric acid and
sodium hydroxide.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)
272
273
(g)
mol dm .
Define pH.
............................................................................................................................
(1)
(ii)
(3)
(Total 21 marks)
(a)
(i)
2SO2(g) + O2(g)
(1)
274
(ii)
(5)
(b)
Solid vanadium(V) oxide, V2O5, is an effective catalyst for this reaction. State the effect
of using double the mass of catalyst on:
(i)
(ii)
122. (a)
275
(ii)
Give the expression for the acid dissociation constant, Ka, for aqueous ethanoic
acid.
(1)
(iii)
(3)
(b)
When ethanoic acid and propan-1-ol are heated together in the presence of a little
concentrated sulphuric acid an ester is produced.
(i)
(2)
(ii)
(iii)
276
277
(c)
6.00g of ethanoic acid was mixed with 6.00g of propan-1-ol and 0.00100mol of
concentrated sulphuric acid was added. The mixture was heated under reflux until no
further reaction was detectable. The mixture was then cooled rapidly to room temperature
3
3
and titrated with 1.00 mol dm sodium hydroxide solution. 35.0 cm of the 1.00 mol dm
3
sodium hydroxide solution was required for complete neutralisation.
(i)
Calculate the volume of sodium hydroxide solution that would have been needed if
only the 0.00100mol of concentrated sulphuric acid had been in the flask.
(2)
(ii)
Calculate the volume of sodium hydroxide solution that must have been needed to
react with the ethanoic acid remaining in the cooled mixture.
(1)
(iii)
(1)
278
(iv)
Hence, calculate the amount (in moles) of propan-1-ol, ester and water in the final
cooled mixture.
(3)
(v)
Calculate the value of the equilibrium constant under these conditions. The
3
volume of the reaction mixture should be taken as 100 cm .
(2)
(d)
Concentration of
sodium
hydroxide
3
/mol dm
0.1
1.0
6 10
0.1
2.0
1.2 10
0.2
2.0
2.4 10
Experiment
Rate of
reaction
/mol dm
3 1
s
4
279
(i)
sodium hydroxide...........................................................................................
(1)
(ii)
Calculate the value of the rate constant, k, for this reaction including its units.
(3)
(Total 23 marks)
123. This question is about Group 7 of the Periodic Table - the halogens.
The standard electrode potentials for these elements are given below.
Electrode reaction
1
2
1
2
1
2
1
2
F2 + e
Cl2 + e
I2 + e
+1.36
+1.07
Cl
Br
I
/V
+2.87
Br2 + e
+0.54
280
(a)
(i)
(ii)
State which element or ion in the table above is the strongest oxidising agent.
......................................................................................................................
(1)
(b)
The standard electrode potentials for chromium(III) changing to chromium(II) and for
chromium(VI) changing to chromium(III) are given below.
Cr
1
2
3+
+e
Cr2 O7 + 7H + 3e
(i)
Cr
2+
Cr
3+
7
2
H2O
= 0.41V
= +1.33V
On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III).
......................................................................................................................
(1)
(ii)
On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III) but not to chromium(VI).
......................................................................................................................
(1)
281
(iii)
124. (a)
When solid sodium nitrate is heated with concentrated sulphuric acid the reaction shown
below occurs:
(i)
NaNO3 + H2SO4
HNO3 + NaHSO4
..........
..........
..........
..........
Identify the two conjugate acid-base pairs in this reaction. Write your answer in
the spaces below the equation.
(2)
(ii)
The nitric acid produced is evolved as a gas under these conditions. Explain the
effect of this on the position of equilibrium on heating the mixture in an open
container.
......................................................................................................................
......................................................................................................................
(2)
(iii)
O H
282
Draw a diagram of the likely shape of this molecule and justify your prediction.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(b)
Dilute sulphuric acid is a strong acid but very concentrated sulphuric acid is weak acid.
Explain the meanings of the terms weak and dilute as applied to acids.
Weak.......................................................................................................................
................................................................................................................................
Dilute.......................................................................................................................
................................................................................................................................
(2)
(c)
283
(ii)
Relate the ease of decomposition of the two nitrates to the relative sizes and
charges of the cations.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 13 marks)
125. The reaction between sulphur dioxide and oxygen is a dynamic equilibrium.
2SO2 + O2
(a)
2SO3
DH = 196 kJmol
(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
Increasing the
temperature
Increases
(3)
Sri Lankan School
284
(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)
(e)
285
286
126. (a)
(i)
(1)
(ii)
(4)
(b)
(1)
(ii)
Write equations to show the two successive ionisations of sulphuric acid, H 2SO4, in
water.
......................................................................................................................
......................................................................................................................
(2)
287
288
(iii)
Suggest why the concentration of hydrogen ions is not 0.20 mol dm in 0.100 mol
3
dm sulphuric acid.
......................................................................................................................
......................................................................................................................
(1)
(c)
2Cl2(g) + 2H2O(g)
DH = 115 kJ mol .
0.800 mol of hydrogen chloride was mixed with 0.200 mol of oxygen in a vessel of
3
volume 10.0 dm in the presence of a copper(I) chloride catalyst at 400 C. At
equilibrium it was found that the mixture contained 0.200 mol of hydrogen chloride.
(i)
(1)
(ii)
(4)
289
(d)
State and explain the effect, if any, on the position of equilibrium in (c) of:
(i)
(ii)
(iii)
127. (a)
(i)
Draw dot and cross diagrams to show the electronic structure of the ammonia and
of the boron trifluoride molecules. Hence deduce their shapes and suggest values
for the HNH and FBF bond angles in these molecules.
(5)
290
(ii)
Explain, in terms of the intermolecular forces involved, the variation of the boiling
temperatures of the Group 5 hydrides listed below.
Hydride
Boiling Temperature/ K
Ammonia, NH3
240
Phosphine, PH3
183
Arsine, AsH3
218
Stibine, SbH3
256
(5)
(b)
When ammonia and boron trifluoride are mixed, an addition compound, H3NBF3, is
formed.
(i)
Suggest how the nitrogen-boron bond forms between the two molecules in the
addition compound.
(1)
(ii)
Suggest how the HNH and the FBF bond angles would change when the addition
compound forms.
(2)
(c)
One of the early rocket fuels was hydrazine. It burns in oxygen as follows:
H2NNH2(g) + O2(g) N2(g) + 2H2O(g)
4
Bond
Bond
enthal
py
/kJ
1
mol
Bon
d
Bond
enthalp
y
/kJ
1
mol
NH
+388
O==O
+496
NN
+944
HO
+463
(4)
(Total 17 marks)
291
292
128. (a)
Benzocaine reacts with dilute acids to form the ion C 9H12O2N and with ethanoyl
chloride to form C11H13O3N.
When benzocaine is heated under reflux with aqueous sodium hydroxide and the
solution obtained is neutralised, two compounds X and Y are formed.
X has a formula of C7H7O2N and is a solid with a melting temperature of 190 C. It is
soluble in water.
Y is a volatile liquid with a formula C2H6O which gives steamy fumes with
phosphorus pentachloride.
X reacts with sodium hydrogencarbonate solution to give a gas which turns lime water
milky. It also reacts with a solution of sodium nitrite and hydrochloric acid between 0
C and 5 C to produce a substance which reacts with phenol to give an orange
precipitate, Z.
C 9H
12O 2
H + (a q )
C 9 H 11 O 2 N
B e n z o c a in e
C H 3C O Cl
11
13O 3
1 . N a O H ( a q ) h e a t/r e f lu x
2 . H C l(a q ) u n til n e u tra l
C 7H 7O 2N
X
N a H C O 3 (a q )
C 7H 6O 2N N a
(i)
C 2 H 6O
Y
1 . H N O 2 b e tw e e n 0 C a n d 5 C
2. phenol
o ra n g e p p t. Z
Deduce a structural formula for benzocaine and explain its three reactions shown
above. You may either describe the types of reaction or write the equations for the
reactions.
(6)
293
(ii)
Write equations for the two reactions of X. Include in your answer the structural
formula of Z.
(3)
(iii)
Explain why substance X has a fairly high melting temperature and why it is
soluble in water.
(3)
(b)
Substance X is a weak monobasic acid and for the purpose of the remainder of this
question you may write its formula as HA.
X has a relative molecular mass of 137, with a pKa value of 4.92 at 25 C.
(i)
(ii)
50.0 cm of this solution was mixed with 50.0 cm of a 0.100 mol dm solution of
sodium hydroxide. Calculate the concentration of the salt of X produced, and the
concentration of the acid X left unreacted.
Hence calculate the pH of the mixed solution.
(4)
(c)
The standard enthalpy change at 25 C for the neutralisation of a strong acid by a strong
1
base is 57.2 kJ mol .
The standard enthalpy change for the ionisation of the weak acid HA in water is
1
+8.3 kJ mol .
(i)
Write the ionic equation for the neutralisation of a strong acid by a strong base and
hence calculate the standard enthalpy of neutralisation of the acid HA.
(3)
(ii)
State and explain how the value of Ka of the acid X and hence the pH of the
solution in (b)(i) would change if the temperature of the solution were increased.
(2)
(Total 25 marks)
294
129. (a)
(ii)
5.67 of propan-1-o1 was oxidised in a reaction with a 64% yield. Calculate the
mass of propanoic acid produced.
(3)
(b)
(i)
DH
= +6kJ mol
State and explain the effect on the position of this equilibrium of:
an increase in temperature;
............................................................................................................................
............................................................................................................................
(2)
(ii)
How does the addition of sodium propanoate affect the pH of the solution of
propanoic acid?
............................................................................................................................
295
(1)
296
(c)
(i)
Sketch, with reasonable accuracy, how the pH changes during the titration of
3
25cm of a weak acid, such as propanoic acid, with sodium hydroxide solution of
the same concentration.
14
12
10
pH
8
6
4
2
0
10
20
30
40
50
v o lu m e N a O H /c m
(ii)
pKind
Acid colour
Alkaline
colour
Bromophenol blue
4.0
yellow
blue
Bromothymol blue
7.0
yellow
blue
Thymol blue
8.9
yellow
blue
State which of these indicators would be best for this titration. Give a reason for
your choice.
Indicator ...........................................................................................................
Reason ..............................................................................................................
...........................................................................................................................
(2)
297
(d)
The standard enthalpy change of neutralisation of some acids with sodium hydroxide is
tabulated below:
Acid
(i)
DH /kJ
1
mol
51
12
57
57
Why are the values for the enthalpy change of neutralisation of the two strong
acids the same?
..........................................................................................................................
..........................................................................................................................
(1)
(ii)
Why is the enthalpy change of neutralisation of hydrocyanic acid so much less than
that of hydrochloric acid?
..........................................................................................................................
..........................................................................................................................
(2)
(Total 19 marks)
130. (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)
298
(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 N2O4 and NO2.
N2O4(g)
Pale yellow
2NO2(g)
dark brown
A transparent glass syringe was filled with the gaseous mixture of N 2O4 and NO2 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)
299
.........................................................................................................................
(1)
300
(ii)
(iii)
Write an expression for the equilibrium constant, Kp, for this equilibrium.
(1)
(iv)
1.0 mole of N2O4 was allowed to reach equilibrium at 400K. At equilibrium the
partial pressure of N2O4 was found to be 0.15 atm.
Given that the equilibrium constant Kp for this reaction is 48 atm, calculate the
partial pressure of NO2 in the equilibrium mixture.
(3)
(Total 16 marks)
(a)
(ii)
State, with a reason, the number of geometric isomers that sorbic acid has.
301
(2)
302
(b)
(ii)
Write the chemical equations that are relevant to the functioning of the mixture as a
buffer, and use them to explain how buffering action arises. You may represent
sorbic acid as RCOOH and potassium sorbate as RCOOK.
(5)
(c)
Write an equation for the complete reaction of sorbic acid with bromine.
(1)
(ii)
(d)
The bromine-containing product from (c)(i) can be reacted with sodium hydroxide in
aqueous ethanol to give a substitution reaction.
(i)
Explain why aqueous ethanol is used as the solvent rather than, say, ethanol alone.
(2)
(ii)
(e)
(ii)
Soaps are in general made by the alkaline hydrolysis of fats. Write an equation to
illustrate this reaction.
(3)
(Total 25 marks)
303