Professional Documents
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(1)
2. (i) Give an equation for the dissociation of propanoic acid and hence an expression for its
dissociation constant, Ka.
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(ii) At 25°C Ka for propanoic acid is 1.30 × 10–5 mol dm–3. Find the pH of a solution of
propanoic acid of concentration 0.0100 mol dm–3. State any assumptions you make.
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(iii)
What does this tell you about the enthalpy of dissociation?
Justify your answer.
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Increasing the temperature of the propanoic acid solution causes the pH to decrease.
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(9)
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(Total 2 marks)
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NT Exampro 1
(ii) The dissociation constant for ethanoic acid is 1.80 × 10–5 mol dm–3. Calculate the pH of
a buffer solution which has a concentration of 0.0150 mol dm–3 with respect to ethanoic
acid and 0.0550 mol dm–3 with respect to sodium ethanoate.
(Total 5 marks)
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6. For the reaction
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(2)
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(b) Liquid oxygen and liquid nitrogen form an ideal liquid mixture. At 70 K the vapour
pressures are 38.3 kPa for N2 and 6.40 kPa for O2. Find the composition of the vapour in
w.
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(3)
NT Exampro 2
(c) Show by means of sketches of boiling point/composition diagrams and a brief comment
why ideal mixtures of liquids of similar boiling temperature are more difficult to separate
by fractional distillation than those with boiling temperatures more widely separated.
(3)
(d) The vapour pressure/composition diagram at constant temperature for a mixture of two
liquids A and B which shows a strong deviation from Raoult’s Law is shown below.
(x(A) = mole fraction of A).
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vapour
pressure
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x(A) = 1 mole fraction x(A) = 0
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(i) Sketch on the axes below the boiling point/composition diagram for this system,
showing the curves for both liquid and vapour.
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boiling
ch
temperature
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(ii) Consider a mixture for which the mole fraction of A is initially 0.75. Use your
diagram to explain what happens when this mixture is fractionally distilled, making
clear the nature of the distillate and of the residue.
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(8)
(Total 16 marks)
NT Exampro 3
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(2)
9. Liquid oxygen and liquid nitrogen form an ideal liquid mixture. At 70 K the vapour pressures
are 38.3 kPa for N2 and 6.40 kPa for O2. Find the composition of the vapour in equilibrium
with a liquid mixture which at equilibrium is an equimolar mixture of the two elements.
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(3)
10.
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Show by means of sketches of boiling point/composition diagrams and a brief comment why
ideal mixtures of liquids of similar boiling temperature are more difficult to separate by
fractional distillation than those with boiling temperatures more widely separated.
ti
(3)
ac
11. The vapour pressure/composition diagram at constant temperature for a mixture of two liquids A
em
and B which shows a strong deviation from Raoult’s Law is shown below. (x(A) = mole
fraction of A).
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vapour
pressure
w.
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NT Exampro 4
(i) Sketch on the axes below the boiling point/composition diagram for this system, showing
the curves for both liquid and vapour.
boiling
temperature
x(A) = 1 x(A) = 0
m
mole fraction
(ii) Consider a mixture for which the mole fraction of A is initially 0.75. Use your diagram
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to explain what happens when this mixture is fractionally distilled, making clear the
nature of the distillate and of the residue.
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(Total 8 marks)
ac
(i) Write an expression for the equilibrium constant, Kc, for this reaction and give
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its units.
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(ii) When 3 mol of hydrogen and 1 mol of nitrogen were allowed to reach equilibrium
in a vessel of 1 dm3 capacity at 500°C and 1000 atm pressure, the equilibrium
mixture contained 0.27 mol of N2, 0.81 mol of H2 and 1.46 mol of NH3.
(4)
NT Exampro 5
(b) Predict and explain the effect of an increase in temperature on:
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(6)
(Total 10 marks)
13.
(b) Write an expression for the dissociation constant, Ka, for NH4+ (aq).
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(c) Calculate the pH of a solution of ammonium chloride of concentration 0.100 mol dm–3
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at 298 K, the Ka value for NH4+ being 5.62 × 10–10 mol dm–3 at this temperature.
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(Total 5 marks)
NT Exampro 6
14. Benzene and methylbenzene may be separated by fractional distillation. Sketch the general
form of the boiling point/composition diagram for such a mixture and use it to explain the basis
on which fractional distillation rests.
b.p. of methylbenzene
temperature
/ºC
m
b.p. of benzene
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0 mole fraction of methylbenzene 1
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(6)
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15. (a) When ethanoic acid is dissolved in water, the following equilibrium is established:
When hydrogen chloride dissolves in ethanoic acid, the equilibrium established is:
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..........................................................................................................................
(1)
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(1)
(b) What is the relationship between the species CH3CO2H2+ and CH3CO2H?
....................................................................................................................................
(1)
NT Exampro 7
(c) The value of Ka for ethanoic acid at 298 K is 1.74 × 10–5 mol dm–3 and for methanoic
acid, HCO2H, it is 1.60 × 10–4 mol dm–3 at the same temperature.
(1)
(ii) Hence calculate the pH of a 0.100 mol dm–3 solution of CH3CO2H at 298 K.
m
(2)
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(d) The pH of a 0.050 mol dm–3 solution of HCO2H is 2.55.
Using this, together with the data in (c) and your answer to (c)(ii):
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(3)
(e) (i) Sketch with reasonable accuracy, on the axes below, how the pH changes during
the titration of 20.0 cm3 of a 0.100 mol dm–3 solution of methanoic acid with 0.050
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12
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10
pH 6
0
0 5 10 15 20 25 30 35 40 45 50 55 60
Volume of NaOH solution/cm3
(3)
(ii) Select using the data below a suitable indicator for this titration. Give a brief
NT Exampro 8
reason for your choice based on the curve drawn in (e)(i).
Indicator pH Range
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(2)
(Total 15 marks)
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16. This question concerns redox behaviour, and the following data will be found useful.
Fe3+(aq) + e–
½Cl2(g) + e–
Fe2+(aq)
Cl–(aq)
MnO4– (aq) + 8H+ (aq) + 5e–
ti ve
Mn2+(aq) + 4H2O(1)
E /V
+0.77
+1.36
+1.52
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(a) In potassium manganate(VII) titrations, the solutions are acidified with dilute
sulphuric acid.
(i) Using the data above, explain why dilute hydrochloric acid is not used for
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this purpose.
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(3)
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(ii) Why is potassium manganate(VII) usually placed in the burette, despite the
difficulties it presents in reading the burette?
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(2)
(b) A test for Mn2+ ions in solution is to react them with sodium bismuthate(V), NaBiO3, in
the presence of nitric acid. A purple colour will develop owing to the formation of
MnO4– ions in the solution. The ionic half equation for the reduction of BiO3– ion is:
NT Exampro 9
(i) Use this half equation and the data above to write an ionic equation for the
oxidation of the Mn2+ ion.
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(2)
(ii) Suggest, qualitatively, how the E value for BiO3– |Bi3+ compares with that for
MnO4– |Mn2+
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(1)
m
(c) An alloy contains iron and manganese only. On warming with dilute nitric acid 2.30 g of
this alloy gave a solution containing iron(III) ions and manganese(II) ions. Treatment of
this solution with excess sodium bismuthate(V) completely oxidised all the Mn2+ ions
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present to MnO4– ions.
The excess bismuthate(V) ions were then completely destroyed and the solution made up
to 250 cm3 with distilled water and thoroughly shaken.
(i) Write the equation for the reaction occurring during the titration.
ac
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(2)
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(5)
(Total 15 marks)
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(a) Write an expression for Kp for this equilibrium, giving consideration to its units.
(2)
(b) When 0.50 mol of I2 and 0.50 mol of H2 were mixed in a closed container at 723 K and 2
atm pressure, 0.11 mol of I2 were found to be present when equilibrium was established.
NT Exampro 10
(i) Calculate the partial pressures of I2, H2 and HI in the equilibrium mixture.
(3)
m
(2)
(c) In an experiment to establish the equilibrium concentrations in (b), the reaction was
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allowed to reach equilibrium at 723 K and then quenched by addition to a known, large
volume of water. The concentration of iodine in this solution was then determined by
titration with standard sodium thiosulphate solution.
(i)
ve
Write an equation for the reaction between sodium thiosulphate and iodine.
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(2)
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(ii) What indicator would you use? Give the colour change at the end point.
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(2)
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(2)
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(Total 13 marks)
18. (a) Hydrogen peroxide reacts both as an oxidising agent and as a reducing agent, depending
on the conditions. Hydrogen peroxide reduces potassium dichromate(VI) in acidic
solution to chromium(III) ions. Hydrogen peroxide will oxidise chromium(III) ions back
to chromate(VI) ions in alkaline solution.
NT Exampro 11
Deduce the overall equation for the reaction between hydrogen peroxide and
dichromate(VI) ions using the data above.
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(2)
(b) In alkaline solution the reaction of hydrogen peroxide with chromium(III) ions is
2Cr3+(aq) + 10OH–(aq) + 3H2O2(aq) → 2CrO42–(aq) + 8H2O(l)
m
This reaction is used to prepare potassium dichromate(VI) from chromium(III) chloride
and hydrogen peroxide in potassium hydroxide solution. The mixture is boiled until it is
bright yellow. Boiling is continued until excess hydrogen peroxide has been destroyed.
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The solution is then cooled, and acidified with ethanoic acid.
ve
Show that this is not a redox reaction.
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(2)
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Suggest how you would know when all the hydrogen peroxide has been destroyed
in the reaction mixture.
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(1)
(iii) Why is it essential to destroy all the hydrogen peroxide in the mixture before it
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is acidified?
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(3)
NT Exampro 12
(iv) Derive the two half equations which together give the overall equation for the
reaction between hydrogen peroxide and chromium(III) ions in alkaline solution.
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(2)
(Total 10 marks)
19. (a) At high temperatures phosphorus pentachloride is a gas which dissociates as follows
m
(i) Write an expression for the equilibrium constant KP for this equilibrium.
(1)
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(ii) At a given temperature 39% of an original sample of the PCl5(g) is dissociated at
equilibrium. If the total equilibrium pressure is 2 atm, calculate the values of the
equilibrium partial pressures of:
PCl5
PCl3
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(4)
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(iii) Hence calculate the value of KP and give its units.
(2)
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(b) Aluminium chloride occurs in the anhydrous state and in the hydrated state. You may
regard the structure of the anhydrous state as having the formula AlCl3. When water is
added to solid anhydrous aluminium chloride, steamy acidic fumes are seen.
ch
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(1)
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(1)
(iii) Explain by reference to the structure of AlCl3 how the first step of this reaction
occurs.
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(2)
NT Exampro 13
(c) (i) When water is added to hydrated aluminium chloride no steamy fumes are seen.
What does this indicate about the bonding in hydrated aluminium chloride?
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(1)
(ii) Hydrated aluminium chloride dissolves in water to give a solution which is acidic.
Suggest an explanation for the fact that the solution is acidic. Give an equation to
illustrate your answer.
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m
…………………………………………………………………………………
(2)
(Total 14 marks)
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20. (a) At high temperatures phosphorus pentachloride is a gas which dissociates as follows
PCl5 (g)
(i)
PCl3 (g) + Cl2 (g)
ve
Write an expression for the equilibrium constant KP for this equilibrium.
ti
(1)
ac
(ii) At a given temperature 39% of an original sample of the PCl5(g) is dissociated at
equilibrium. If the total equilibrium pressure is 2 atm, calculate the values of the
equilibrium partial pressures of:
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PCl5
PCl3
ch
(4)
(2)
(Total 7 marks)
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(3)
NT Exampro 14
(iv) Derive the two half equations which together give the overall equation for the
reaction between hydrogen peroxide and chromium(III) ions in alkaline solution.
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(2)
(Total 10 marks)
m
E /V
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PbO2(s) + 4H+(aq) + SO 24 – (aq) + 2e– PbSO4(s) + 2H2O(1) +1.69
(a)
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Give the equation for the overall cell reaction during discharge.
(2)
ac
(b) (i) State the essential requirement for the rusting of iron in water.
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(1)
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(ii) Explain why corrosion of iron results in deep pitting of the metal surface.
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(1)
(iii) Explain why sheet iron which has been fabricated to a particular shape, sometimes
under high pressure, is more likely to corrode than a single strip of pure iron.
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(2)
NT Exampro 15
(iv) An underground iron pipe is less likely to corrode if bonded at intervals to
magnesium stakes. Give a reason for this. Explain why aluminium would be a poor
substitute for the magnesium.
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(2)
(Total 8 marks)
22. Iron is extracted from its oxides in a blast furnace. Carbon, in the form of coke, is one of the raw
m
materials mixed with the iron ore.
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(a) The reaction between iron(III) oxide and carbon monoxide to produce iron occurs in many
stages; one stage might be represented by the equation
ti ve
Write the expression for the equilibrium constant, Kp, for this reaction.
(1)
(i) Write an ionic half equation for the reduction of dichromate(VI) ions in acidic
em
solution.
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(1)
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(ii) Write an equation for the reaction between dichromate(VI) and iron(II) ions.
…………………………………………………………………………………
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(2)
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NT Exampro 16
(c) A 0.204 g sample of steel was reacted with excess dilute sulphuric acid. The resulting
solution required 27.4 cm3 of 0.0220 mol dm–3 potassium dichromate(VI) solution for
complete reaction.
m
(4)
(Total 8 marks)
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23. (a) Use Brønsted-Lowry theory of acid/base behaviour and acid/base conjugate pairs to
explain how sulphuric acid shows its acidic nature when added to water.
ti ve
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(3)
If the enthalpy of neutralisation ∆Hneut is measured for hydrobromic acid, HBr, or for
em
(b)
nitric acid, HNO3, both with sodium hydroxide solution, the value is –57.6 kJ mol–1; for
the reaction of ethanoic acid, CH3COOH, with sodium hydroxide solution it is –55.2 kJ
mol–1.
ch
(i) Why is ∆Hneut the same for both HBr and HNO3 with NaOH?
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.........................................................…………………………………………..
(2)
(ii) Give one reason why ∆Hneut for the reaction of ethanoic acid with sodium
hydroxide solution is less exothermic than for hydrobromic acid with sodium
hydroxide solution.
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(2)
NT Exampro 17
(c) (i) What is the function of a buffer solution?
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(2)
acid: .........................................................……………………………………..
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base: .........................................................……………………………………..
(2)
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(d) Sulphuric acid is used in the production of soapless detergents.
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(2)
(ii) Briefly indicate the advantages of soapless detergents over soap itself.
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(2)
(Total 15 marks)
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NT Exampro 18
24. Use the following redox potential data to answer the questions that follow
Electrode reaction E /V
m
Fe3+ +e– Fe2+ +0.77
.co
Co3+ +e– Co2+ +1.82
(a) (i) Explain why the reaction of iron metal with dilute, aqueous hydrochloric acid gives
iron (II) chloride and not iron (III) chloride.
ve
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ti
...........................................................................................................................
ac
...........................................................................................................................
(2)
(ii) Suggest how an aqueous solution of iron (III) chloride could be made from iron
em
...........................................................................................................................
ch
...........................................................................................................................
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(3)
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(b) Suggest, in outline, the stages in the rusting of iron, using the data above.
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(3)
(Total 8 marks)
NT Exampro 19
25. (a) (i) Calculate the concentration, in mol dm–3, of a solution of hydrochloric acid, HCl,
which has a pH of 1.13.
(1)
(ii) Calculate the concentration, in mol dm–3 , of a solution of chloric(l) acid, HOCl,
which has a pH of 4.23.
m
Chloric(l) acid is a weak acid with Ka = 3.72 × 10–8 mol dm–3.
.co
ti ve
ac
(4)
(1)
w.
(ii) Write equations to show the two successive ionisations of sulphuric acid, H2SO4, in
water.
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......................................................................................................................
(2)
(iii) Suggest why the concentration of hydrogen ions is not 0.20 mol dm–3 in 0.100 mol
dm–3 sulphuric acid.
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......................................................................................................................
(1)
NT Exampro 20
(c) Many industrial organic reactions produce hydrogen chloride as an additional product.
This can be oxidised to chlorine by the Deacon process:
0.800 mol of hydrogen chloride was mixed with 0.200 mol of oxygen in a vessel of
volume 10.0 dm3 in the presence of a copper(I) chloride catalyst at 400 ºC. At
equilibrium it was found that the mixture contained 0.200 mol of hydrogen chloride.
m
(1)
.co
ti ve
ac
(4)
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(d) State and explain the effect, if any, on the position of equilibrium in (c) of:
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(2)
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(2)
NT Exampro 21
(iii) removing the catalyst.
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(2)
(Total 20 marks)
26. (a) The acid dissociation constant, Ka for ethanoic acid is 1.80 × 10–5 mol dm–3.
m
(i) Write an equation for the dissociation of aqueous ethanoic acid.
......................................................................................................................
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(1)
(ii) Give the expression for the acid dissociation constant, Ka, for aqueous ethanoic
acid.
ti ve
ac
(1)
em
(3)
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(b) When ethanoic acid and propan-1-ol are heated together in the presence of a little
concentrated sulphuric acid an ester is produced.
(i) Draw the structural formula of the ester produced in this reaction.
(2)
NT Exampro 22
(ii) Give the name of the ester.
......................................................................................................................
(1)
......................................................................................................................
(1)
(c) 6.00g of ethanoic acid was mixed with 6.00g of propan-1-ol and 0.00100mol of
concentrated sulphuric acid was added. The mixture was heated under reflux until no
further reaction was detectable. The mixture was then cooled rapidly to room temperature
and titrated with 1.00 mol dm–3 sodium hydroxide solution. 35.0 cm3 of the 1.00 mol
m
dm–3 sodium hydroxide solution was required for complete neutralisation.
(i) Calculate the volume of sodium hydroxide solution that would have been needed if
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only the 0.00100mol of concentrated sulphuric acid had been in the flask.
ti ve
(2)
ac
(ii) Calculate the volume of sodium hydroxide solution that must have been needed to
react with the ethanoic acid remaining in the cooled mixture.
em
ch
(1)
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(1)
NT Exampro 23
(iv) Hence, calculate the amount (in moles) of propan-1-ol, ester and water in the final
cooled mixture.
m
(3)
(v) Calculate the value of the equilibrium constant under these conditions. The
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volume of the reaction mixture should be taken as 100 cm3.
ti ve (2)
(d) The reverse of esterification is hydrolysis. In experiments to study the hydrolysis of this
ac
ester with aqueous sodium hydroxide, the following data were obtained.
Concentration of Concentration of
em
ester;..............................................................................................................
(1)
sodium hydroxide...........................................................................................
(1)
NT Exampro 24
(ii) Calculate the value of the rate constant, k, for this reaction including its units.
(3)
(Total 23 marks)
m
(1)
.co
(ii) Define the term ‘weak acid ’ as applied to methanoic acid, , HCOOH.
….………………………………………………………………………….
….………………………………………………………………………….
The acid dissociation constant for methanoic acid is 1.78 × 10–4 mol dm–3).
ac
(2)
(3)
NT Exampro 25
(iii) a solution of methanoic acid of concentration 0.152 mol dm–3.
(4)
m
(c) (i) What is the principal property of a buffer solution?
.co
….………………………………………………………………………….
….………………………………………………………………………….
(2)
(ii)
ve
The acid dissociation constant, Ka, for ethanoic acid is 1.80 × 10–5 mol dm–3.
Calculate the pH of a buffer solution which has a concentration of 0.105 mol dm–3
with respect to ethanoic acid and 0.342 mol dm–3 with respect to sodium ethanoate.
ti
ac
em
(3)
(Total 17 marks)
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w.
28. (a) Write an expression for Kp for each of the following equilibria, giving the units in each
case.
Kp =
(2)
Kp =
(2)
NT Exampro 26
(b) (i) With reference to the equilibrium in (a) (i), calculate the equilibrium partial
pressures of N2O4 and NO2 at 60 °C and 1.2 atm pressure, given that 81%of the
initial N2O4 is dissociated at this temperature.
(5)
m
(ii) Calculate Kp at this temperature.
.co
ti ve
ac
(1)
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is used in the manufacture of sulphuric acid and uses vanadium(V) oxide as the catalyst.
(1)
(ii) What effect does the catalyst have on the position of equilibrium in this reaction?
….…………………………………………………………………………….
….…………………………………………………………………………….
(1)
NT Exampro 27
(iii) A steel vessel of volume 2.0 dm³ has introduced into it 0.20 mol of SO3, 0.040 mol
of SO2 and 0.010 mol of O2.
By calculation of the apparent value of Kc show that this mixture is not at
equilibrium, and explain in which direction the system will move in order to
achieve equilibrium at a temperature of 800K.
The value of Kc at this temperature is 1.7 × 106 mol–1 dm³.
m
(3)
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(Total 15 marks)
(b) A weak acid, represented by HA, dissociates in water according to the equation:
(1)
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NT Exampro 28
(c) 25 cm3 of 1.00 mol dm–3 aqueous HA, was titrated with 1.00 mol dm–3 aqueous sodium
hydroxide and the pH measured throughout. The titration curve is shown below.
14
12
pH 10
m
6
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2
0
10 20 30
ve 40
Volume of sodium hydroxide added / cm 3
ti 50
............................................................................................................................
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(1)
............................................................................................................................
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(1)
(iii) the value of pKa for the acid HA and, hence the value Ka.
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pKa ...................................................................................................................
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Ka .....................................................................................................................
(2)
(d) Some of the solutions made during this titration would act as buffer solutions.
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
NT Exampro 29
(ii) Use the titration curve to find:
............................................................................................................................
(1)
(e) Suggest, with reasoning, whether methyl orange or phenolphthalein would be the better
indicator for this titration.
m
Choice ........................................................................................................................
.co
Reasoning ..................................................................................................................
....................................................................................................................................
....................................................................................................................................
(f)
ve
Explain why, as the titration proceeds, the flask becomes warm but not as warm as it
ti
would in a similar titration using 1.00 mol dm–3 solutions of hydrochloric acid and sodium
(3)
hydroxide.
ac
....................................................................................................................................
em
....................................................................................................................................
....................................................................................................................................
(3)
ch
(g) A different monobasic weak acid has a dissociation constant of 1.8 × 10– 5 mol dm–3.
............................................................................................................................
(1)
ww
(ii) Calculate the pH of a 1.00 mol dm–3 aqueous solution of this acid.
(3)
(Total 21 marks)
NT Exampro 30
2SO3(g) 2SO2(g) + O2(g)
(1)
m
.co
ti ve (5)
(b) Solid vanadium(V) oxide, V2O5, is an effective catalyst for this reaction. State the effect
ac
of using double the mass of catalyst on:
............................................................................................................................
............................................................................................................................
(1)
ch
............................................................................................................................
............................................................................................................................
ww
(1)
(Total 8 marks)
31. (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
NT Exampro 31
(i) Define the term partial pressure as applied to a gas mixture.
............................................................................................................................
............................................................................................................................
(1)
(ii) Write an expression for the equilibrium constant, Kp, for this reaction.
m
.co
(1)
(iii) State and explain the effect of increasing the total pressure on the position of this
equilibrium;
ti ve
............................................................................................................................
............................................................................................................................
ac
............................................................................................................................
............................................................................................................................
em
............................................................................................................................
(2)
(b) State the effect on the value of Kp for this equilibrium of the following.
ch
............................................................................................................................
(1)
............................................................................................................................
(1)
............................................................................................................................
(1)
(c) There is a theory that methane, CH4, constantly leaks from the earth’s crust. This is not
noticeable on land but at the bottom of a cold sea, such as off the Canadian coast, the
methane is trapped in a solid cage of water molecules.
CH4(g) + 6H2O(s)
[CH4(H2O)6](s)
methane hydrate
At –29 °C the equilibrium pressure of the methane is 101.3 kPa.
NT Exampro 32
(i) Write an expression for Kp for this equilibrium.
(1)
m
.co
(iii)
ve
At 0 °C the equilibrium pressure of methane rises to 2600 kPa. What does this tell
ti (1)
you about the effect of temperature change on the position of equilibrium and about
the enthalpy change for this reaction?
ac
............................................................................................................................
em
............................................................................................................................
............................................................................................................................
(2)
ch
(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.
w.
............................................................................................................................
............................................................................................................................
ww
............................................................................................................................
(1)
(Total 12 marks)
NT Exampro 33
32. Ethanoic acid, CH3COOH, is a weak acid which can be used, with its salts, to make buffer
solutions.
....................................................................................................................................
....................................................................................................................................
(1)
....................................................................................................................................
m
....................................................................................................................................
(2)
.co
(c) An aqueous solution of ethanoic acid of concentration 1.00 mol dm–3 has a pH of 2.8.
Sketch, with care, how the pH changes during the titration of 25.0 cm3 1.00 mol dm–3
aqueous ethanoic acid with aqueous sodium hydroxide of the same concentration.
pH
14
ti ve
12
ac
10
em
6
ch
2
w.
0
0 10 20 30 40 50
ww
(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)
NT Exampro 34
(ii) Explain how the pKa of ethanoic could be found from the graph.
............................................................................................................................
............................................................................................................................
(2)
(Total 11 marks)
33. The following standard electrode potentials will be required in answering this question.
E /V
Zn2+ + 2e– Zn –0.76
m
V3+ + e– V2+ –0.26
.co
SO 24 – + 2e– + 2H+ SO 32 – + H2O +0.17
V3+ V2+
em
(2)
(b) (i) Derive the overall equation for the reduction of VO +2 to VO2+ by zinc in acidic
solution.
ch
............................................................................................................................
............................................................................................................................
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(2)
(ii) Give the formula of the vanadium species that would result if VO +2 ions were to be
ww
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)
NT Exampro 35
(c) Disproportionation requires an atom to have at least three oxidation states.
............................................................................................................................
............................................................................................................................
(1)
+
(ii) Derive an equation for the disproportionation of VO2+ into VO 2 and V3+.
............................................................................................................................
............................................................................................................................
m
............................................................................................................................
(2)
.co
(Total 10 marks)
34. (a)
ve
The bombardier beetle Metrius contractus persuades potential predators to disappear by
firing a boiling mixture of irritants at them. The reaction producing this ammunition is a
redox reaction, H2O2 being the oxidising agent.
ti
The two half-reactions involved are:
ac
OH O E /V
em
+ 2H + + 2e– + 0.70
ch
OH O
H2 O2 + 2H + + 2e – 2H 2 O +1.77
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(i) Write the overall equation for the reaction and show that the reaction is feasible.
(3)
ww
(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) The reaction is highly exothermic; in principle its enthalpy of reaction could be
found by using average bond enthalpies. By a consideration of the structure and
bonding in the compounds involved, suggest why the use of the average bond
enthalpies for C==O, CC, C==C and OH would give a highly inaccurate
answer for the enthalpy of reaction.
(2)
NT Exampro 36
(b) On heating hydrogen peroxide decomposes according to the equation
2H2O2 → 2H2O + O2
The rapid oxidation of hydrogen peroxide was used in World War II to generate steam to
launch the V1 ‘flying bomb’. H2O2 (100 volume) was reacted with acidified potassium
m
manganate(VII) solution.
(i) Write the half-equation for the oxidation of hydrogen peroxide to oxygen, O2.
.co
(1)
–
(ii) The MnO 4 ions are reduced to Mn2+ during the reaction. Derive the overall
equation for the reaction between H2O2 and acidified KMnO4.
(iii)
ve
Suggest in terms of the collision theory of chemical kinetics why 100-volume
ti (2)
hydrogen peroxide (this gives l00 dm3 of oxygen from 1 dm3 of hydrogen peroxide
when it decomposes to water and oxygen) was used rather than the more common
ac
20-volume solution.
(2)
(Total 18 marks)
em
35. (a) The first stage in the manufacture of sulphuric acid is the Contact Process.
ch
2SO2 + O2 2SO3
oxide is used. In a particular equilibrium mixture at 400 °C the partial pressures of sulphur
dioxide and of oxygen were 0.100 atm and 0.500 atm respectively. Show that the yield of
SO3 is about 95% of the equilibrium mixture.
ww
(5)
(b) (i) Pure sulphuric acid is a viscous liquid with a high boiling temperature of
338 °C. It has the structure:
S
O OH
OH
Suggest in terms of the intermolecular forces in sulphuric acid why it has such a
high boiling temperature.
(3)
NT Exampro 37
(ii) Sulphuric acid dissolves in water in a highly exothermic reaction
Suggest why sulphuric acid must always be added to water to dilute it rather than
the other way round.
(2)
m
HSO 4– + H2O H3O+ + SO 24 –
.co
The dissociation constant for the first dissociation is very large; that for the second is 0.01
mol dm–3 at 25 °C.
(i) Calculate the pH of an aqueous solution containing 0.200 mol dm–3 hydrogen ions.
(ii) ve
The pH of 0.100 mol dm–3 sulphuric acid is 0.98. Explain why this is so close to the
pH of 0.100 mol dm–3 HCl which is 1.0.
ti (1)
(3)
ac
(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
em
concentration falls.
(i) Use the information above to deduce the two half equations occurring in the lead
acid battery.
ch
(3)
(ii) Hence write an equation to represent the overall process taking place as the cell
discharges.
w.
(1)
(Total 18 marks)
ww
(i) pH .....................................................................................................................
(1)
(ii) Kw ......................................................................................................................
(1)
NT Exampro 38
(b) Explain the meaning of the term strong, as applied to an acid or a base.
………………...……………….……………………………………………………..
………………...……………….……………………………………………………..
(1)
m
(1)
.co
(ii) NaOH (aq) of concentration 0.800 mol dm–3 (Kw = – 1.00 × 10–14 mol2 dm–6).
ti ve (2)
ac
(d) HA is a weak acid with a dissociation constant Ka = 5.62 × 10–5 mol dm–3.
(1)
(3)
NT Exampro 39
(e) A buffer solution contains HA(aq) at a concentration of 0.300 mol dm–3, and its sodium
salt, NaA, at a concentration of 0.600 mol dm–3. Calculate the pH of this buffer solution.
(3)
(Total 13 marks)
m
.co
37. Consider the following equation:
2SO2 + O2 2SO3
2.0 moles of SO2 and 1.0 mole of O2 were allowed to react in a vessel of volume 60 dm3.
(i)
ve
At equilibrium 1.8 moles of SO3 had formed and the pressure in the flask was 2 atm.
(a) Write the expression for Kc for this reaction between SO2 and O2.
ti
ac
(1)
em
(3)
(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)
NT Exampro 40
(c) State the effect of a catalyst on:
(i) Kc ……………………………………………………………………………..
(1)
(d) (i) Write the expression for Kp for the reaction between SO2 and O2.
m
(1)
.co
(ii) Calculate the mole fractions of SO2, O2 and SO3 at equilibrium.
ti ve (2)
(1)
ch
(2)
(Total 14 marks)
38. (a) The electronic configuration of a cobalt atom can be written as [Ar]3d74s2.
Give the electronic configuratin of the Co3+ ion.
………………...……………….……………………………………………………..
(1)
NT Exampro 41
(b) (i) By reference to the standard electrode potentials given below, suggest a reducing
agent which might reduce aqueous Co3+ ions to cobalt metal. Give your reasoning.
E /V
Zn2+(aq) + 2e– Zn(s) –0.76
Fe2+(aq) + 2e– Fe(s) –0.44
Co2+(aq) + 2e– Co(s) –0.28
Sn2+(aq) + 2e– Sn(s) –0.14
O2(g) + 2H+(aq) + 2e– H2O2(aq) +0.68
Co3+(aq) + e– Co2+(aq) +1.82
m
Suitable reducing agent ..……………………………………………………..
.co
Reasoning ..…………….……………………………………………………..
………………...……………….………………….…………………………..
(3)
(ii)
ve
Suggest two factors that might prevent a reducing agent from being as effective as
the electrode potentials might seem to suggest.
ti
………………...……………….………………….…………………………..
ac
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
em
………………...……………….………………….…………………………..
(2)
ch
………………...……………….………………….…………………………..
(1)
w.
………………...……………….………………….…………………………..
(2)
(Total 9 marks)
NT Exampro 42
39. A compound D, CH3.CH(OH).COOH, may be prepared from C3H7OH by the following series
of reactions.
K 2 Cr 2 O 7 (aq)/H 2 SO 4 (aq)
C 3 H 7 OH C 3 H 6O2
A B
Cl 2 (g)/uv light
m
(i) NaOH(aq)
D C 3 H 5 O 2 Cl
.co
(ii) HCl(aq)
C
(iii) D has a boiling temperature of 186°C whereas C, C3H5O2Cl, boils at 122°C. Draw
ac
a boiling temperature/composition diagram applicable to a mixture of C and D and
use it to show how fractional distillation of a mixture of the two compounds could
produce a sample of D.
(5)
em
(b) Assuming the percentage yield for each step in sequence to be 80%, calculate the mass of
D that could be made from 60 g of C3H7OH.
(3)
ch
(c) An aqueous solution of D of concentration 0.100 mol dm–3 has a pH value of 2.04.
(3)
Ka = 1.3 × 10–5 mol dm–3, would be more exothermic in reaction with aqueous
sodium hydroxide solution of concentration 0.1 mol dm–3.
(2)
(Total 18 marks)
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)
(b) If phosphorus pentachloride is heated in a sealed tube the following equilibrium is set up
NT Exampro 43
PCl5(g) PCl3(g) + Cl2(g)
(i) Write an expression for the equilibrium constant, Kp, for the above reaction.
(1)
m
dissociated, the total equilibrium pressure being 2.00 atm. Calculate the partial
pressures of each of the components of the equilibrium mixture, to three significant
figures. Hence calculate the value of Kp under these conditions.
.co
ti ve
ac
em
(5)
ch
(c) At a higher temperature, T + t, the equilibrium mixture in (b) contains a greater proportion
of phosphorus trichloride and chlorine.
w.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
......................................................................................................................
(1)
NT Exampro 44
(d) If calcium carbonate is heated in a sealed vessel in the absence of air the following
equilibrium is set up:
......................................................................................................................
(1)
(ii) At 1030 °C the total pressure in the vessel is 16 atm. What is the value of Kp?
......................................................................................................................
(1)
m
(Total 12 marks)
.co
41. Propanoic acid is a weak acid which dissociates according to
ti ve
ac
em
(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.
ch
w.
ww
(1)
(iii) Calculate the pH of a 0.100 mol dm–3 solution of propanoic acid, for which
Ka = 1.3 × 10–5 mol dm–3.
(3)
NT Exampro 45
(iv) Calculate the concentration of hydroxide ions, OH–, in this same solution of
propanoic acid. Kw = 1.00 × 10–14 mol2 dm–6 at the temperature of the solution.
m
(3)
.co
(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.
................................................................................................................................
ti ve
................................................................................................................................
................................................................................................................................
(2)
ac
(c) A mixture of sodium propanoate and propanoic acid behaves as a buffer solution.
em
......................................................................................................................
......................................................................................................................
ch
......................................................................................................................
(2)
w.
(ii) Calculate the pH of a buffer solution that is made by mixing equal volumes of
0.0500 mol dm–3 propanoic acid and 0.100 mol dm–3 sodium propanoate.
ww
(3)
(Total 16 marks)
42. (a) (i) A fluoride of phosphorus, Y, contains 24.6% by mass of phosphorus and has a
molar mass of 126 g mol–1. Deduce the molecular formula of Y.
NT Exampro 46
(4)
(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)
(b) (i) Consider the following data, which shows the formulae and boiling temperatures of
the Group 7 hydrides.
m
HF 19
HCl –85
.co
HBr –68
HI –35
Group 7 hydrides.
ti ve
Suggest why hydrogen fluoride, HF, has the highest boiling temperature of the
(3)
(c) When hydrogen fluoride is dissolved in water a solution of a weak acid is formed. Write
ac
the expression for the acid dissociation constant, Ka, for hydrogen fluoride. Calculate the
value of Ka, with units, given that a 0.150 mol dm–3 solution of hydrogen fluoride has a
pH of 2.04.
em
(5)
(Total 18 marks)
ch
43. (a) Consider the following equilibrium, which illustrates one industrial method used to
produce hydrogen:
w.
an expression for the equilibrium constant, Kc, for the system, and use the data to calculate
a value for Kc, with units.
(8)
NT Exampro 47
(b) The following table shows some data for enthalpies of formation, ∆Hf.
Use these data to calculate the enthalpy change for the reaction in (a).
(3)
(c) In practice, the industrial production of hydrogen by this method is conducted at the
m
moderately high pressure of 30 atm, and the high temperature of 750 °C, in the presence
of a nickel catalyst. Suggest why these conditions are used, considering the factors of rate
and yield.
.co
(7)
(Total 18 marks)
ti ve
ac
em
ch
w.
ww
NT Exampro 48