Variableoxidationstates

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Name:
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Variable oxidation states
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Class:
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Date:
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Time: 373 minutes
Marks: 356 marks
Comments:
Page 1 of 84
Q1.
This question is about compounds containing ethanedioate ions.
(a) A white solid is a mixture of sodium ethanedioate (Na2C2O4), ethanedioic acid

dihydrate (H2C2O4.2H2O) and an inert solid. A volumetric flask contained 1.90 g of
this solid mixture in 250 cm3 of aqueous solution.
Two different titrations were carried out using this solution.
In the first titration 25.0 cm3 of the solution were added to an excess of sulfuric acid
in a conical flask. The flask and contents were heated to 60 °C and then titrated with
a 0.0200 mol dm−3 solution of potassium manganate(VII). When 26.50 cm3 of
potassium manganate(VII) had been added the solution changed colour.
The equation for this reaction is
2MnO4− + 5C2O42− + 16H+ → 2Mn2+ + 8H2O + 10CO2
In the second titration 25.0 cm3 of the solution were titrated with a 0.100 mol dm−3
solution of sodium hydroxide using phenolphthalein as an indicator. The indicator
changed colour after the addition of 10.45 cm3 of sodium hydroxide solution.
The equation for this reaction is
H2C2O4 + 2OH− → C2O42− + 2H2O
Calculate the percentage by mass of sodium ethanedioate in the white solid.
Give your answer to the appropriate number of significant figures.
Show your working.
Percentage by mass of sodium ethanedioate ____________________ %

(8)
(b) Ethanedioate ions react with aqueous iron(III) ions in a ligand substitution reaction.
Write an equation for this reaction.
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Suggest why the value of the enthalpy change for this reaction is close to zero.
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(c) Draw the displayed formula of the iron complex produced in the reaction in part (b)
Indicate the value of the O—Fe—O bond angle.
State the type of isomerism shown by the iron complex.
Bond angle _________________________________________________________
Type of isomerism ____________________________________________________

(3)
(d) Ethanedioate ions are poisonous because they react with iron ions in the body.
Ethanedioate ions are present in foods such as broccoli and spinach.
Suggest one reason why people who eat these foods do not suffer from poisoning.
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(1)
(Total 14 marks)
Q2.
Iron forms many complexes that contain iron in oxidation states +2 and +3.
(a) Hexaaquairon(III) ions react with an excess of hydrochloric acid in a ligand

substitution reaction.
Write an equation for this reaction.
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(b) Explain why the initial and final iron(III) complexes in the equation above have
different shapes.
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(2)
(c) Hexaaquairon(II) ions react with an excess of H2NCH2CH2NH2 in a ligand

Draw the structure of the iron(II) complex formed showing its charge.
(2)
(d) Hexaaquairon(II) ions react with an excess of H2NCH2CH2NH2 in a ligand

Which of the following shows the correct change in entropy for a reaction of
hexaaquairon(II) ions with H2NCH2CH2NH2?
Tick (✔) one box.
change in entropy is negative
change in entropy is close to zero
change in entropy is positive
(1)
(e) The percentage of iron(II) sulfate in iron tablets can be determined by titration with
potassium manganate(VII) in acidic solution.
Deduce an ionic equation for the reaction of iron(II) ions with manganate(VII) ions.
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(1)
(f) A student dissolved 1980 mg of iron tablets in an excess of dilute sulfuric acid.
The solution was titrated with 0.0200 mol dm−3 potassium manganate(VII) solution. A
32.50 cm3 volume of potassium manganate(VII) solution was required to reach the
end point in the titration.
Calculate the percentage of iron in the sample of iron tablets.

Give your answer to the appropriate number of significant figures.
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Percentage __________________ %
(4)
(g) State the colour change at the end point in this titration.
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(1)
(Total 12 marks)
Q3.
The table below shows some successive ionisation energy data for atoms of three
different elements X, Y and Z.
Elements X, Y and Z are Ca, Sc and V but not in that order.
First Second Third Fourth Fifth Sixth
X 648 1370 2870 4600 6280 12 400
Y 590 1150 4940 6480 8120 10 496
Z 632 1240 2390 7110 8870 10 720
(a) Which element is calcium?
Z
(1)
(b) Which element is vanadium?
Z
(1)
(c) Justify your choice of vanadium in part (b)
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(d) An acidified solution of NH4VO3 reacts with zinc.
Explain how observations from this reaction show that vanadium exists in at least
Page 5 of 84
two different oxidation states.
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(2)
(e) The vanadium in 50.0 cm3 of a 0.800 mol dm−3 solution of NH4VO3 reacts with 506
cm3 of sulfur(IV) oxide gas measured at 20.0 °C and 98.0 kPa.
Use this information to calculate the oxidation state of the vanadium in the solution
after the reduction reaction with sulfur(IV) oxide.
Explain your working.
The gas constant R = 8.31 J K−1 mol−1.
Oxidation state = _______________

(6)
(Total 11 marks)
Q4.
A student weighed out a 2.29 g sample of impure K3[Fe(C2O4)3].3H2O and dissolved it in
water.
This solution was added to a 250 cm3 volumetric flask and made up to 250 cm3 with
distilled water.
A 25.0 cm3 portion was pipetted into a conical flask and an excess of acid was added.
The mixture was heated to 60°C and titrated with 0.0200 mol dm–3 KMnO4 solution.
26.40 cm3 of KMnO4 solution were needed for a complete reaction.
In this titration only the C2O42– ions react with the KMnO4 solution.
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(a) The reaction between C2O42– ions and MnO4– ions is autocatalysed.
Explain what is meant by the term autocatalysed and identify the catalyst in the
reaction.
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(2)
(b) Select from the list the most suitable substance used to acidify the solution in the
conical flask.
Put a tick (✔) in the correct box.
H 2 C 2 O4
H2SO4
HCl
HNO3
(1)
(c) The reaction between C2O42– ions and MnO4– ions is very slow at first.
Explain why the reaction is initially slow.
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(3)
(d) Write an equation for the reaction between C2O42– ions and MnO4– ions in acidic
solution.
Calculate the percentage purity of the original sample of K3[Fe(C2O4)3].3H2O.
Give your answer to 3 significant figures.
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(7)
(e) A solution of KMnO4 has an unknown concentration.
Describe briefly how colorimetry can be used to determine the concentration of this
solution.
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(3)
(Total 16 marks)
Q5.
A green solution, X, is thought to contain [Fe(H2O)6]2+ ions.
(a) The presence of these ions can be confirmed by reacting separate samples of
solution X with aqueous ammonia and with aqueous sodium carbonate.
Write equations for each of these reactions and describe what you would observe.
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(4)
(b) A 50.0 cm3 sample of solution X was added to 50 cm3 of dilute sulfuric acid and
made up to 250 cm3 of solution in a volumetric flask.
A 25.0 cm3 sample of this solution from the volumetric flask was titrated with a
0.0205 mol dm−3 solution of KMnO4
At the end point of the reaction, the volume of KMnO4 solution added was 18.70
cm3.
(i) State the colour change that occurs at the end point of this titration and give a
reason for the colour change.
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(2)
(ii) Write an equation for the reaction between iron(II) ions and manganate(VII)
ions.
Use this equation and the information given to calculate the concentration of
iron(II) ions in the original solution X.
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(5)
(Total 11 marks)
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Q6.
A student carried out an experiment to find the mass of FeSO4.7H2O in an impure sample,
X.
The student recorded the mass of X. This sample was dissolved in water and made up to
250 cm3 of solution.
The student found that, after an excess of acid had been added, 25.0 cm3 of this solution
reacted with 21.3 cm3 of a 0.0150 mol dm–3 solution of K2Cr2O7
(a) Use this information to calculate a value for the mass of FeSO4.7H2O in the sample
of X.
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(5)
(b) The student found that the calculated mass of FeSO4.7H2O was greater than the
actual mass of the sample that had been weighed out. The student realised that this
could be due to the nature of the impurity.
Suggest one property of an impurity that would cause the calculated mass of
FeSO4.7H2O in X to be greater than the actual mass of X.
Explain your answer.
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(2)
(Total 7 marks)
Q7.
This question explores some reactions and some uses of cobalt compounds.
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(a) Ethanal is oxidised to ethanoic acid by oxygen. The equation for this reaction is
2CH3CHO + O2 2CH3COOH
This redox reaction is slow at room temperature but speeds up in the presence of
cobalt compounds.
Explain why a cobalt compound is able to act as a catalyst for this process.
Illustrate your explanation with two equations to suggest how, in the presence of
water and hydrogen ions, Co3+ and then Co2+ ions could be involved in catalysing
this reaction.
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(4)
(b) In aqueous solution, the [Co(H2O)6]2+ ion reacts with an excess of ethane-1,2-
diamine to form the complex ion Y.
(i) Write an equation for this reaction.
Explain, in terms of the chelate effect, why the complex ion Y is formed in
preference to the [Co(H2O)6]2+ complex ion.
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(3)
(ii) Draw a diagram that shows the shape of the complex ion Y and shows the
type of bond between the ethane-1,2-diamine molecules and the cobalt.
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(3)
(c) Compound Z is a complex that contains only cobalt, nitrogen, hydrogen and
chlorine.
A solid sample of Z was prepared by reaction of 50 cm3 of 0.203 mol dm−3 aqueous
cobalt(II) chloride with ammonia and an oxidising agent followed by hydrochloric
acid.
When this sample of Z was reacted with an excess of silver nitrate, 4.22 g of silver
chloride were obtained.
Use this information to calculate the mole ratio of chloride ions to cobalt ions in Z.
Give the formula of the complex cobalt compound Z that you would expect to be
formed in the preparation described above.
Suggest one reason why the mole ratio of chloride ions to cobalt ions that you have
calculated is different from the expected value.
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(5)
(Total 15 marks)
Q8.
When iodine molecules are dissolved in aqueous solutions containing iodide ions, they
react to form triiodide ions (I3–).
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I2 + I– I3 –
The reaction above between I– ions and S2O82– ions has a high activation energy and
S2O82– ions are only reduced slowly to SO42– ions.
The reaction is catalysed by Fe2+ ions.
(a) Explain why the reaction between I– ions and S2O82– ions is slow.
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(b) Other than having variable oxidation states, explain why Fe2+ ions are good catalysts
for this reaction.
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(c) Write a half-equation for the reduction of S2O82– ions to SO42– ions.
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(d) Construct an overall equation for the reaction between S2O82– ions and I– ions.
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(1)
(Total 4 marks)
Q9.
Iron(II) ethanedioate is another insoluble solid used as a pigment in paints and glass. It
occurs as a dihydrate (FeC2O4.2H2O). One procedure used for the preparation of iron(II)
ethanedioate is outlined below.
Procedure
A 6.95 g sample of hydrated iron(II) sulfate (FeSO4.7H2O) was added to 100 cm3 of water
in a beaker and stirred until all of the solid dissolved. A 150 cm3 volume of 0.20 mol dm–3
sodium ethanedioate solution was added to the beaker. The mixture was stirred until
precipitation was complete. After filtration, 3.31 g of the dihydrate (FeC 2O4.2H2O) were
collected.
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(a) Write an equation for the reaction between iron(II) sulfate and sodium ethanedioate.
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(b) Calculate the amount, in moles, of FeSO4.7H2O in 6.95 g of hydrated iron(II) sulfate.
Show your working.
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(2)
(c) Calculate the amount, in moles, of sodium ethanedioate in 150 cm3 of 0.20 mol dm–3
sodium ethanedioate solution.
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(1)
(d) Calculate the percentage yield of iron(II) ethanedioate dihydrate (Mr = 179.8) formed
in this reaction.
Give your answer to the appropriate precision. Show your working.
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(2)
(e) In this experiment, no side reactions take place, the reagents are pure and the
reaction goes to completion.
Suggest one reason why the yield of iron(II) ethanedioate dihydrate in this
experiment is less than 100%.
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(1)
(f) When dissolved in dilute sulfuric acid, the number of moles of ethanedioate ions in a
pigment can be determined by titration with acidified potassium manganate(VII).
Explain why the titration of a sample of iron(II) ethanedioate would require a different
amount of potassium manganate(VII) than a titration of an equimolar amount of
copper(II) ethanedioate.
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(2)
(Total 9 marks)
Q10.
Transition metal compounds have a range of applications as catalysts.
(a) State the general property of transition metals that allows the vanadium in
vanadium(V) oxide to act as a catalyst in the Contact Process.
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(1)
(b) Write two equations to show how vanadium(V) oxide acts as a catalyst in the
Contact Process.
Equation 1
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Equation 2
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(2)
(c) In the Contact Process, vanadium(V) oxide acts as a heterogeneous catalyst.
(i) Give the meaning of the term heterogeneous.
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(ii) Give one reason why impurities in the reactants can cause problems in
processes that use heterogeneous catalysts.
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(d) The oxidation of C2O42− ions by MnO4− ions in acidic solution is an example of a
reaction that is autocatalysed.
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(i) Give the meaning of the term autocatalysed.
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(ii) Identify the autocatalyst in this reaction.
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(iii) Write two equations to show how the autocatalyst is involved in this oxidation
of C2O42− ions.
Equation 1
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Equation 2
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(2)
(Total 9 marks)
Q11.
Solid iron(II) ethanedioate dihydrate (FeC2O4.2H2O) has a polymeric structure.
Two repeating units in the polymer chain are shown.
Each iron ion is also bonded to

two water molecules. These are
not shown in the diagram.
(a) Name the type of bond that is represented by the arrows.
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(b) In terms of electrons explain how the water molecules, not shown in the diagram,
form bonds to the iron.
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(2)
(c) Predict the value of the bond angle between the two bonds to iron that are formed
by these two water molecules.
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(d) Iron(II) ethanedioate dihydrate can be analysed by titration using potassium

manganate(VII) in acidic solution. In this reaction, manganate(VII) ions oxidise
iron(II) ions and ethanedioate ions.
A 1.381 g sample of impure FeC2O4.2H2O was dissolved in an excess of dilute

sulfuric acid and made up to 250 cm3 of solution.
25.0 cm3 of this solution decolourised 22.35 cm3 of a 0.0193 mol dm–3 solution of
potassium manganate(VII).
(i) Use the half-equations given below to calculate the reacting ratio of moles of
manganate(VII) ions to moles of iron(II) ethanedioate.
MnO4– + 8H+ + 5e– Mn2+ + 4H2O
Fe2+ Fe3+ + e–
C2O42– 2CO2 + 2e–
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(1)
(ii) Calculate the percentage by mass of FeC2O4.2H2O in the original sample.
(If you have been unable to answer part (d)(i) you may assume that three
moles of manganate(VII) ions react with seven moles of iron(II) ethanedioate.
This is not the correct ratio.)
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(5)
(Total 10 marks)
Q12.
(a) Explain the meaning of the terms ligand and bidentate as applied to transition metal
complexes.
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(2)
(b) Aqueous cobalt(II) ions react separately with an excess of chloride ions and with an
excess of ammonia.
For each reaction, draw a diagram to illustrate the structure of, the shape of and the
charge on the complex ion formed.
In each case, name the shape and indicate, on the diagram, a value for the ligand-
metal-ligand bond angle.
(6)
(c) The complex ion formed in aqueous solution between cobalt(II) ions and chloride
ions is a different colour from the [Co(H2O)6]2+ ion.
Explain why these complex ions have different colours.
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(3)
(d) In aqueous ammonia, cobalt(II) ions are oxidised to cobalt(III) ions by hydrogen
peroxide. The H2O2 is reduced to hydroxide ions.
Calculate the minimum volume of 5.00 mol dm−3 H2O2 solution required to oxidise
the Co2+ ions in 9.87 g of CoSO4.7H2O
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(5)
(Total 16 marks)
Q13.
This question is about cobalt chemistry.
(a) Consider the following reaction scheme that starts from [Co(H2O)6]2+ ions.
W, X and Y are ions and Z is a compound.
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For each of the reactions 1 to 4, identify a suitable reagent.
Identify W, X, Y and Z and write an equation for each of reactions 1 to 4.
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(12)
(b) A flue-gas desulfurisation process involves the oxidation, by oxygen, of aqueous

sulfate(IV) ions (SO3 2–) into aqueous sulfate(VI) ions (SO4 2–). This reaction is
catalysed by Co2+ ions in an acidic aqueous solution.
Write an equation for the overall reaction of sulfate(IV) ions with oxygen to form
sulfate(VI) ions.
Suggest why this overall reaction is faster in the presence of Co2+ ions.
Suggest a mechanism for the catalysed reaction by writing two equations involving
Co2+ and Co3+ ions. You will need to use H+ ions and H2O to balance these two
equations.
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(4)
(Total 16 marks)
Q14.
You may find the following electrode potential data helpful when answering this question.
Electrode half-equation Eϴ / V
Cr2O72–(aq) + 14H+(aq) + 6e– 2Cr3+(aq) + 7H2O(I) +1.33
O2(g) + 4H+(aq) + 4e– 2H2O(I) +1.23
Cr3+(aq) + e– Cr2+(aq) –0.44
Zn2+(aq) + 2e– Zn(s) –0.76
Cr2+(aq) + 2e– Cr(s) –0.91
(a) Describe the colour changes that you would observe when an excess of zinc is
added to an acidified solution of potassium dichromate(VI) in the absence of air.
For each colour change, identify the coloured ions responsible and write an equation
for each reaction that occurs with zinc.
In the equations, you should represent the ions in their simplest form, for example
Cr3+.
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(5)
(b) Describe what you would observe when dilute aqueous sodium hydroxide is added,
dropwise until in excess, to a dilute aqueous solution containing chromium(III) ions.
Write two equations to illustrate your observations.

In these equations you should give the full formula of each of the complexes, for
example [Cr(H2O)6]3+.
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(4)
(c) When an aqueous solution containing [Cr(H2O)6]3+ ions is warmed in the presence of
Cl– ions, [Cr(H2O)5Cl]2+ ions are formed and the colour of the solution changes.
Name this type of reaction.
Suggest, in terms of electrons, why the colours of the complex ions are different.
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(3)
(d) The chromium(II) ion [Cr(H2O)6]2+ has different properties from the [Cr(H2O)6]3+ ion.
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Use data from the table above to explain why, in an open container, [Cr(H2O)6]2+(aq)
ions change into [Cr(H2O)6]3+(aq) ions.
Suggest the identity of the products formed in each case when sodium carbonate
solution is added to separate solutions containing [Cr(H2O)6]2+(aq) ions and
[Cr(H2O)6]3+(aq) ions.
Explain why the [Cr(H2O)6]3+(aq) ions behave differently from the [Cr(H2O)6]2+(aq)
ions.
In your answer to this part of the question, equations are not required.
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(7)
(Total 19 marks)
Q15.
An experiment was carried out to determine the original concentration of iron(II) ions in a
solution that had been stored in air. An excess of zinc and acid was added to this solution.
The mixture was then filtered to remove the excess zinc before titration.
(a) Suggest why the zinc and acid were added.
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(b) Explain why it was necessary to remove the excess zinc.
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(Total 2 marks)
Q16.
(a) The iron(II) ions in well-water can be removed by oxidation using potassium
manganate(VII) in alkaline solution. A mixture containing solid iron(III) hydroxide
and solid manganese(IV) oxide is formed. These solid products can be removed by
filtration under reduced pressure.
(i) Draw a diagram of the apparatus used for this filtration. Do not include the
apparatus used to reduce the pressure.
(2)
(ii) An equation representing the oxidation reaction is given below.
3Fe2+(aq) + KMnO4(aq) + 5OH–(aq) + 2H2O(I) 3Fe(OH)3(s) + MnO2(s) + K+(aq)
Calculate the mass, in grams, of KMnO4 required to react with the iron(II) ions
in 1.00 dm3 of well-water that has an iron(II) concentration of 0.225 mol dm–3.
Give your answer to the appropriate precision.
Show your working.
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(3)
(iii) In practice, a slight excess of potassium manganate(VII) is used to treat the

well-water.
Although this treated water is safe to drink, this excess of potassium
manganate(VII) is undesirable. Suggest one reason, other than colour, why
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the excess is undesirable.
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(b) Suggest one reason why the colour of potassium manganate(VII) solution can be a
source of error when using a volumetric (graduated) flask to prepare a standard
solution.
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(Total 7 marks)
Q17.
(a) Use data from the table below to explain why dilute hydrochloric acid cannot be
used to acidify potassium manganate(VII) in a titration.
E /V
MnO4–(aq) + 8H+(aq) + 5e– → Mn2+(aq) + 4H2O(I) +1.51
Cl2(aq) + 2e– → 2Cl–(aq) +1.36
2H+(aq) + 2e– → H2(aq) 0.00
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(2)
(b) Use information from the table in part (a) to determine the minimum volume, in cm 3,
of 0.500 mol dm–3 sulfuric acid that is required for a titre of 25.0 cm3 of
0.0200 mol dm–3 potassium manganate(VII) solution.
Show your working.
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(3)
(c) In each titration using potassium manganate(VII), a large excess of dilute sulfuric
acid is used to avoid any possibility of the brown solid MnO2 forming.
(i) Deduce a half-equation for the reduction of MnO4– ions in acidic solution to
form MnO2.
______________________________________________________________
______________________________________________________________
(1)
(ii) Give two reasons why it is essential to avoid this reaction in a titration
between potassium manganate(VII) and iron(II) ions.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(2)
(d) Potassium manganate(VII) is an oxidising agent.

Suggest one reason why a 0.0200 mol dm–3 solution of potassium manganate(VII)
does not need to be kept away from flammable material.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(1)
(Total 9 marks)
Q18.
An acidified solution of potassium manganate(VII) was reacted with a sample of sodium
ethanedioate at a constant temperature of 60 °C. The concentration of the manganate(VII)
ions in the reaction mixture was determined at different times using a spectrometer to
measure the light absorbed.
Page 26 of 84
(a) Write an equation for the reaction between manganate(VII) ions and ethanedioate
ions in acidic solution.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(2)
(b) By considering the properties of the reactants and products, state why it is possible
to use a spectrometer to measure the concentration of the manganate(VII) ions in
this reaction mixture.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(2)
(c) This reaction is autocatalysed. Give the meaning of the term autocatalyst.
Explain how the above curve indicates clearly that the reaction is autocatalysed.
Meaning of autocatalyst _______________________________________________
___________________________________________________________________
Explanation _________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(3)
(d) Identify the autocatalyst in this reaction.
___________________________________________________________________
(1)
Page 27 of 84
(e) Write two equations to show how the autocatalyst is involved in this reaction.
Equation 1 __________________________________________________________
Equation 2 __________________________________________________________
(2)
(Total 10 marks)
Q19.
When using potassium manganate(VII) in redox titrations with iron(II) ions it is essential
that the reaction mixture is acidified. Normally, dilute sulfuric acid is used.
(a) State why an excess of hydrogen ions is added to the reaction mixture.
___________________________________________________________________
___________________________________________________________________
(1)
(b) State why the acid used must not be ethanoic acid.
___________________________________________________________________
___________________________________________________________________
(1)
(c) Explain why an indicator is not needed in this redox titration.
___________________________________________________________________
___________________________________________________________________
(1)
(Total 3 marks)
Q20.
Due to their electron arrangements, transition metals have characteristic properties
including catalytic action and the formation of complexes with different shapes.
(a) Give two other characteristic properties of transition metals. For each
property,illustrate your answer with a transition metal of your choice.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
Page 28 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(4)
(b) Other than octahedral, there are several different shapes shown by transition metal
complexes. Name three of these shapes and for each one give the formula of a
complex with that shape.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(6)
(c) It is possible for Group 2 metal ions to form complexes. For example, the
[Ca(H2O)6]2+ ion in hard water reacts with EDTA4– ions to form a complex ion in a
similar manner to hydrated transition metal ions. This reaction can be used in a
titration to measure the concentration of calcium ions in hard water.
(i) Write an equation for the equilibrium that is established when hydrated
calcium ions react with EDTA4– ions.
______________________________________________________________
(1)
(ii) Explain why the equilibrium in part (c)(i) is displaced almost completely to the
right to form the EDTA complex.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(3)
Page 29 of 84
(iii) In a titration, 6.25 cm3 of a 0.0532 mol dm–3 solution of EDTA reacted
completely with the calcium ions in a 150 cm3 sample of a saturated solution of
calcium hydroxide.
Calculate the mass of calcium hydroxide that was dissolved in 1.00 dm3 of the
calcium hydroxide solution.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(3)
(Total 17 marks)
Q21.
The table below shows some standard electrode potentials.
E /V
MnO4– + 8H+ + 5e– Mn2+ + 4H2O +1.51
Cl2(g) + 2e– 2Cl–(aq) +1.36
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O +1.33
A student determined the concentration of iron(II) ions in a solution of iron(II) chloride by

titration with acidified potassium dichromate(VI) solution. A second student titrated the
same solution of iron(II) chloride with acidified potassium manganate(VII) solution.
By reference to the table, explain why the second student obtained a greater value for the
concentration of iron(II) ions.
_______________________________________________________________________
_______________________________________________________________________
_______________________________________________________________________
_______________________________________________________________________
(Total 2 marks)
Q22.
Iron is an important element in living systems. It is involved in redox and in acid–base
reactions.
(a) Explain how and why iron ions catalyse the reaction between iodide ions and S2O82–
ions. Write equations for the reactions that occur.
___________________________________________________________________
Page 30 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(5)
(b) Iron(II) compounds are used as moss killers because iron(II) ions are oxidised in air
to form iron(III) ions that lower the pH of soil.
(i) Explain, with the aid of an equation, why iron(III) ions are more acidic than
iron(II) ions in aqueous solution.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(3)
(ii) In a titration, 0.321 g of a moss killer reacted with 23.60 cm3 of acidified
0.0218 mol dm–3 K2Cr2O7 solution.
Calculate the percentage by mass of iron in the moss killer. Assume that all of
the iron in the moss killer is in the form of iron(II).
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
Page 31 of 84
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(5)
(c) Some sodium carbonate solution was added to a solution containing iron(III) ions.
Describe what you would observe and write an equation for the reaction that occurs.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(3)
(Total 16 marks)
Q23.
(a) When a solution containing iron(II) ions is treated with a slight excess of a solution
containing ethanedioate ions a bright yellow precipitate of hydrated iron(II)
ethanedioate, FeC2O4.2H2O, is formed. The precipitate is filtered off, washed with
propanone and then allowed to dry. A typical yield of the solid is 95%.
(i) Propanone boils at 56 °C and is miscible with water in all proportions. Suggest
two reasons why washing with propanone is an effective method for producing
a pure, dry precipitate.
Reason 1 ______________________________________________________
______________________________________________________________
Reason 2 ______________________________________________________
______________________________________________________________
(2)
(ii) By suggesting a simple test tube reaction, state how the filtrate could be tested
to show that all of the iron(II) ions have been removed from the solution. State
what you would observe.
Test __________________________________________________________
Observation ____________________________________________________
(2)
Page 32 of 84
(iii) Suggest one reason why the typical yield of iron(II) ethanedioate is less than
100%.
______________________________________________________________
______________________________________________________________
(1)
(iv) Calculate the mass of hydrated iron(II) ethanedioate, FeC2O4.2H2O that can be
formed from 50.0 cm3 of a 0.50 mol dm–3 solution of iron(II) sulfate when the
yield of the reaction is 95%. Show your working.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(3)
(v) The identity of the precipitate can be confirmed by dissolving it in sulfuric acid
and titrating the mixture with potassium manganate(VII).
Deduce the number of moles of iron(II) ethanedioate that would react with one
mole of potassium manganate(VII) in acidic solution.
______________________________________________________________
______________________________________________________________
(1)
(b) Ethanedioate ions can be used to remove calcium ions from blood plasma.
A precipitate of calcium ethanedioate is formed. Write an ionic equation for the
reaction of ethanedioate ions with calcium ions.
___________________________________________________________________
___________________________________________________________________
(1)
(c) Ethanedioic acid is used to clean marble, a form of calcium carbonate. Suggest one
reason why the reaction between ethanedioic acid and marble stops after a short
time.
___________________________________________________________________
___________________________________________________________________
(1)
(d) Tea leaves contain ethanedioic acid. Suggest one reason why tea drinkers do not
suffer from ethanedioic acid poisoning.
___________________________________________________________________
(1)
Page 33 of 84
(e) Ethanedioic acid is produced by the oxidation of carbon monoxide in a multi-step
process. The equation which summarises the reactions taking place is shown below.
4CO + 4NaOH + O2 + 4HCl → 2H2C2O4 + 4NaCl + 2H2O
Calculate the percentage atom economy for the formation of ethanedioic acid in this
reaction. Show your working.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(2)
(Total 14 marks)
Q24.
(a) State the electron configuration of a Ti(III) ion and that of a Ti(IV) ion. Explain, in
terms of electron configurations and electron transitions, why Ti(III) compounds are
usually coloured but Ti(IV) compounds are colourless.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(5)
(b) Transition metal ions and their complexes can often be identified from their colours.
For each of the following, identify a complex ion responsible for the colour of the
aqueous solution. Restrict your answers to complexes formed from the elements Cr,
Fe, Co and Cu.
A deep blue solution formed in an excess of concentrated aqueous ammonia.
A green solution formed in an excess of aqueous sodium hydroxide.
A yellow–green solution formed in an excess of concentrated hydrochloric acid.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
Page 34 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(3)
(c) An experiment is carried out to investigate the rate of the autocatalysed reaction
between aqueous potassium manganate(VII) and ethanedioate ions in an excess of
dilute sulfuric acid. When these reagents are mixed together, the colour of the
reaction mixture gradually fades. The concentration of the manganate(VII) ions is
recorded at different times using a spectrometer. The temperature of the reaction
mixture is constant.
(i) Give two reasons why the use of a spectrometer is the most appropriate
method for measuring the concentration of the coloured ions in this
experiment.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(2)
(ii) Sketch a curve to show how you would expect the concentration of
manganate(VII) ions to change with time until the colour has faded because
the concentration has reached a very low value. Explain the shape of the
curve.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
Page 35 of 84
______________________________________________________________
(5)
(Total 15 marks)
Q25.
(a) When aqueous ammonia was added to an aqueous solution of cobalt(II) sulfate, a
blue precipitate M was formed. Identify the cobalt-containing species present in
aqueous cobalt(II) sulphate and in the precipitate M.
Cobalt-containing species _____________________________________________
Precipitate M _______________________________________________________
(2)
(b) Precipitate M dissolved when an excess of concentrated aqueous ammonia was

added.
The solution formed was pale brown due to the presence of the cobalt-containing
species P. Identify P.
___________________________________________________________________
(1)
(c) On standing in air, the colour of the solution containing P slowly darkened as the
cobalt-containing species Q was formed. State the type of reaction occurring when
P changes into Q and identify the reactant responsible for this change.
Type of reaction _____________________________________________________
Reactant responsible _________________________________________________

(2)
(d) When potassium iodide was added to the solution containing Q and the mixture was
acidified, a dark brown solution due to the presence of R was formed. On addition of
starch solution the mixture turned blue-black.
Identify R and explain its formation.
Identity of R _________________________________________________________
Explanation _________________________________________________________
(2)
(Total 7 marks)
Q26.
Iron from the Blast Furnace contains carbon. In the steel-making process, oxygen is blown
through molten impure iron. At stages during this process samples of iron are taken and
analysed to determine the remaining carbon content. One method of analysis involves a
redox titration.
At one stage a 1.27g sample of this impure iron was reacted with an excess of dilute
sulphuric acid. All of the iron in the sample was converted into iron(II) sulfate, and
hydrogen was evolved. The solution formed was made up to 250 cm3. A 25.0 cm3 sample
of this solution reacted completely with exactly 19.6 cm3 of a 0.0220 mol dm–1 solution of
Page 36 of 84
(a) Write an equation for the reaction between iron and dilute sulphuric acid.
___________________________________________________________________
(1)
(b) Write an equation for the reaction of iron(II) ions with manganate(VII) ions in acid
solution.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(1)
(c) Assuming that carbon is the only impurity, calculate the percentage by mass of
carbon in the 1.27g sample.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(5)
(d) How would you ensure the reliability of the result obtained in this experiment?
___________________________________________________________________
(1)
(e) Suggest one way in which the reliability of this analysis could be improved.
___________________________________________________________________
(1)
(Total 9 marks)
Q27.
When anhydrous iron(III) chloride is added to water the following reactions occur.
FeCl3 + 6H2O → [Fe(H2O)6]3+ + 3Cl–
[Fe(H2O)6]3+ + H2O → [Fe(H2O)5(OH)]2+ + H3O+
(a) State the type of acidity shown by FeCl3 and by [Fe(H2O)6]3+ in these reactions.
Explain your answers.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
Page 37 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(4)
(b) Explain why the pH of a solution of iron(II) chloride is higher than that of a solution of
iron(III) chloride of the same concentration.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(2)
(c) Transition metals have variable oxidation states. This is an important factor in their
ability to act as heterogeneous and homogeneous catalysts.
(i) Vanadium(V) oxide acts as a heterogeneous catalyst in the Contact Process.

Write equations to show the role of vanadium(V) oxide in this process.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(2)
(ii) In aqueous solution, Fe2+ ions act as a homogeneous catalyst in the reaction
between I– and S2O82– ions. Give one reason why the reaction is slow in the
absence of a catalyst. Write equations to show how Fe2+ ions act as a catalyst
for this reaction.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
Page 38 of 84
______________________________________________________________
______________________________________________________________
(5)
(Total 13 marks)
Q28.
A 0.263 g sample of impure iron, containing an unreactive impurity, was reacted with an
excess of hydrochloric acid. All of the iron in the sample reacted, evolving hydrogen gas
and forming a solution of iron(II) chloride. The volume of hydrogen evolved was 102 cm3,
measured at 298 K and 110 kPa.
The percentage, by mass, of iron in the sample can be determined using either the
volume of hydrogen produced or by titrating the solution of iron(II) chloride formed against
a standard solution of potassium dichromate(VI).
(a) (i) Write an equation for the reaction between iron and hydrochloric acid.
______________________________________________________________
(ii) Calculate the number of moles of hydrogen produced in the reaction.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(iii) Use your answers to parts (a)(i) and (ii) to determine the number of moles of
iron and the mass of iron in the original sample. (If you have been unable to
complete part (a)(ii) you should assume the answer to be 4.25 × 10–3 mol. This
is not the correct answer.)
Moles of iron ___________________________________________________
Mass of iron ____________________________________________________
(iv) Calculate the percentage of iron in the original sample.
______________________________________________________________
______________________________________________________________
(7)
(b) (i) Write half-equations for the oxidation of Fe2+ and for the reduction of Cr2O in
acidic solution, and use these to construct an overall equation for the reaction
between these two ions.
Half-equation for the oxidation of Fe2+
______________________________________________________________
Half-equation for the reduction of Cr2O
Page 39 of 84
______________________________________________________________
Overall equation
______________________________________________________________
(ii) The number of moles of iron in the sample was determined in part (a)(iii). Use
this answer to calculate the volume of a 0.0200 mol dm–3 solution of potassium
dichromate(VI) which would react exactly with the solution of iron(II) chloride
formed in the reaction.
(If you have been unable to complete part (a)(iii) you should assume the
answer to be 3.63 × 10–3 mol. This is not the correct answer.)
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(iii) Explain why an incorrect value for the number of moles of iron(II) chloride
formed would have been obtained if the original solution had been titrated with
______________________________________________________________
______________________________________________________________
(7)
(Total 14 marks)
Q29.
Where appropriate, use the standard electrode potential data in the table below to answer
the questions which follow.
EO/V
Zn2+(aq) + 2e– → Zn(s) –0.76
V3+(aq) + e– → V2+(aq) –0.26
+ 2e- → + H2O(l) +0.17

+ 2H+(aq)
VO2+(aq) +2H+(aq) + e– → V3+(aq) + H2O(l) +0.34
Fe3+(aq) + e– → Fe2+(aq) +0.77
+ e– → VO2+(aq) + H2O(l) +1.00

+ 2H+(aq)
Cl2(aq) + 2e– → 2Cl–(aq) +1.36
Page 40 of 84
(a) From the table above select the species which is the most powerful reducing agent.
___________________________________________________________________
(1)
(b) From the table above select
(i) a species which, in acidic solution, will reduce to VO2+(aq) but will
not reduce VO2+(aq) to V3+(aq),
______________________________________________________________
(ii) a species which, in acidic solution, will oxidise VO2+(aq) to .
______________________________________________________________
(2)
(c) The cell represented below was set up under standard conditions.
Pt|Fe2+(aq), Fe3+(aq)||Tl3+(aq),Tl+(aq)|Pt Cell e.m.f. = + 0.48 V
(i) Deduce the standard electrode potential for the following half-reaction.
Tl3+(aq) + 2e– → Tl+(aq)
______________________________________________________________
______________________________________________________________
(ii) Write an equation for the spontaneous cell reaction.
______________________________________________________________
(3)
(d) After acidification, 25.0 cm3 of a solution of hydrogen peroxide reacted exactly with
16.2 cm3 of a 0.0200 mol dm–3 solution of potassium manganate(VII). The overall
equation for the reaction is given below.
+ 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2
(i) Use the equation for this reaction to determine the concentration, in g dm–3, of
the hydrogen peroxide solution.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(ii) Calculate the maximum volume of oxygen, measured at a pressure of 98 kPa
Page 41 of 84
and a temperature of 298 K, which would be evolved in this reaction.
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
(8)
(Total 14 marks)
Q30.
A 0.0720 g sample of reducing agent R was dissolved in water and acidified with an
excess of dilute H2SO4. The resulting solution was found to react with exactly 18.0 cm3 of a
0.0200 mol dm−3 solution of KMnO4.
In this reaction, 5 mol of R react with 3 mol of KMnO4. The Mr of R is
A 120
B 167
C 240
D 333
(Total 1 mark)
Q31.
The vanadium does not have an oxidation state of +3 in
A [V(H2O)6]3+
B [V(C2O4)3]3−
C [V(OH)3(H2O)3]
D [VCl4]3−
(Total 1 mark)
Q32.
(a) Vanadium(V) oxide is used as a heterogeneous catalyst in the Contact Process.
Explain what is meant by the terms heterogeneous and catalyst and state, in
general terms, how a catalyst works.
State the essential feature of vanadium chemistry which enables vanadium(V) oxide
to function as a catalyst and, by means of equations, suggest how it might be
involved in the Contact Process.
___________________________________________________________________
Page 42 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(7)
(b) The following method was used to determine the percentage by mass of vanadium
in a sample of ammonium vanadate(V).
A solution was made up by dissolving 0.160 g of ammonium vanadate(V) in dilute

sulphuric acid. The ammonium vanadate(V) formed ions in this solution. When
an excess of zinc was added to this solution, the ions were reduced to V2+ ions
and the zinc was oxidised to Zn2+ ions.
After the unreacted zinc had been removed, the solution was titrated against a
0.0200 mol dm–3 solution of potassium manganate(VII). In the titration, 38.5 cm3 of
potassium manganate(VII) solution were required to oxidise all vanadium(II) ions to
vanadium(V) ions.
Using half-equations, construct an overall equation for the reduction of to V2+

by zinc in acidic solution.
Calculate the percentage by mass of vanadium in the sample of ammonium

vanadate(V).
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
Page 43 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(8)
(Total 15 marks)
Q33.
Use your knowledge of the chemistry of transition metals to predict which of the following
will convert [Mn(H2O)6]2+ into MnO
A an acid and a reducing agent
B an acid and an oxidising agent
C an alkali and a reducing agent
D an alkali and an oxidising agent

(Total 1 mark)
Q34.
(a) “The strength of adsorption onto the active sites on the surface of a heterogeneous
catalyst helps to determine the activity of the catalyst.”
Explain how heterogeneous catalysts work, give one example of a reaction

catalysed in this way and discuss why different catalysts have different activities.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
Page 44 of 84
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(8)
(b) Outline a plan of an experiment to determine the percentage of iron present as

iron(III) in a solution containing Fe3+(aq) and Fe2+(aq) ions. You are provided with
zinc, a standard solution of potassium dichromate(VI) and dilute sulphuric acid. Zinc
can reduce Fe3+(aq) to Fe2+(aq).
Write equations for all the reactions that occur. Explain how you would use the zinc
and how you would calculate the final answer.
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
___________________________________________________________________
(7)
(Total 15 marks)
Page 45 of 84
Q35.
Which one of the following would not reduce an acidified aqueous solution of potassium
dichromate(VI)?
A CH3COOH
B Zn
C CH3CHO
D Fe2+(aq)
(Total 1 mark)
Page 46 of 84
Mark schemes
Q1.
(a) Moles MnO4− = 5.30 × 10−4

1
Moles in 25cm3 sample / pipette C2O42− ( from acid and salt)
= 5.30 × 10−4 × 5/2 = (1.325 × 10−3)
1
Moles NaOH = ( = 1.045 × 10−3)

1
So moles C2O42− from acid in 25cm3 sample / pipette
= 1.045 × 10−3 ÷ 2 = 5.225 × 10−4
1
Hence moles C2O42− in sodium ethanedioate in 25 cm3
= 1.325 × 10−3 – 5.225 × 10−4 (= 8.025 × 10−4)

1
So moles C2O42− in sodium ethanedioate in original sample

= 8.025 × 10–4 × 10 (= 8.025 × 10−3)
1
Mass Na2C2O4 = 8.025 × 10−3 × 134(.0) = 1.075(35) g
So % sodium ethanedioate in original sample
1
× 100 = 56.6 % to 3 sig fig

1
The first CE is penalised by 2 marks; further errors are
penalised by one mark each
M2 = M1 × 5/2
M4 = M3 ÷ 2
M5 = M2 – M4 (do not allow if negative and do not allow =
M4-M2)
If no subtraction, max = 5 (M1, M2, M3, M4 and M6)
If incorrect subtraction, max = 6 (M1, M2, M3, M4, M6 and
M7)
M6 = M5 × 10
(M6 can be scored by multiplying M2 and M4 by 10 before
subtraction (giving 1.325 × 10−2 – 5.225 × 10−3 = 8.025 ×
10−3 )
M7 = M6 × 134
M8 = (M7/1.90) × 100 Allow 56.5 – 56.8%
(b) [Fe(H2O)6]3+ + 3C2O42− → [Fe(C2O4)3]3− + 6H2O

1
Page 47 of 84
There are 6 Fe–O bonds broken and then made / same number and type of
bond being broken and made.
1
(c)
Ignore all charges even if wrong
Ignore absence of square brackets
Candidates do not need to show 3D shape
1
90° or 180°
1
optical
1
(d) The ethanedioic acid is only present in small quantities/low
concentration in these foods.

1
[14]
Q2.
(a) [Fe(H2O)6]3+ + 4Cl− ⟶ FeCl4− + 6H2O
1
(b) Cl− is a bigger ligand

1
So only 4Cl− can fit around the metal

Allow fewer Cl− can fit around the metal
1
(c)
M1 for structure of complex
M2 for correct charge
Page 48 of 84
1
1
(d) Change in entropy is positive

1
(e) 5Fe2+ + MnO4− + 8H+ ⟶ Mn2+ + 5Fe3+ + 4H2O

1
(f) Amount of manganate (VII) = 6.50 × 10−4 mol

1
Amount of iron(II) = 3.25 × 10−3 mol

ie M1 × 5
1
Mass of iron = 0.181 g = 181 mg

Allow M2 × 55.8
1
Percentage Fe = 181/1980 × 100 = 9.14(%) 3 sf

1
(g) Colourless to pale pink

1
[12]
Q3.
(a) Y
1
(b) X
1
(c) Jump in trend of ionisation energies after removal of fifth electron
Fits with an element with 5 outer electrons (4s23d3) like V

1
(d) Explanation: Two different colours of solution are observed

1
Because each colour is due to vanadium in a different oxidation state

1
(e) Stage 1: mole calculations in either order
Moles of vanadium = 50.0 × 0.800 / 1000 = 4.00 × 10–2
Extended response
Maximum of 5 marks for answers which do not show a
sustained line of reasoning which is coherent, relevant,
substantiated and logically structured.
1
Moles of SO2 = pV / RT = (98 000 × 506 × 10–6 ) / (8.31 × 293)
= 2.04 × 10–2
Page 49 of 84
1
Stage 2: moles of electrons added to NH4VO3
When SO2 (sulfur(IV) oxide) acts as a reducing agent, it is oxidised to

sulfate(VI) ions so this is a two electron change
1
Moles of electrons released when SO2 is oxidised = 2.04 × 10–2 × 2
= 4.08 × 10–2
Stage 3: conclusion
But in NH4VO3 vanadium is in oxidation state 5

1
4.00 × 10–2 mol vanadium has gained 4.08 × 10–2 mol of electrons
therefore 1 mol vanadium has gained 4.08 × 10–2 / 4.00 × 10 – 2 = 1 mol
of electrons to the nearest integer, so new oxidation state is 5 – 1 = 4
1
[11]
Q4.
(a) A reaction that produces its own catalyst/ one of the products is the catalyst
1
Mn2+
Allow Mn3+
1
(b) H2SO4
1
(c) There is no/very little catalyst at the start OR the reaction

only speeds up when the catalyst is produced
1
Two negative ions (MnO4- and C2O42-) repel

Reference to molecules loses M2
1
The activation energy for the reaction is high / heat is required to overcome the
activation energy
1
(d) M1 5 C2O42-(aq) + 2 MnO4-(aq) + 16 H+(aq) →

10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l)
Ignore state symbols
1
M2 n(MnO4–) = OR n(MnO4-) = 5.28 × 10-4
Page 50 of 84
1
M3 n(C2O42-) = × 5.28 × 10-4 = 1.32 × 10-3
M3 is for M2 × 5/2
If wrong ratio used then can only score M2, M4, M5 and M6
1
M4 n(C2O42– in flask originally) = 1.32 × 10–3 × 10 = 1.32 × 10-2
M4 is for M3 × 10
1
M5 n(K3[Fe(C2O4)3].3H2O) = = 4.40 × 10-3
(Mr K3[Fe(C2O4)3].3H2O = 491.1)

M5 is for M4 ÷ 3
1
M6 Mass of K3[Fe(C2O4)3].3H2O reacted = 4.40 × 10-3 × 491.1 = 2.16 g

M6 is for M5 × 491(.1)
1
M7 % purity = x100 = 94.3 or 94.4%

Answer must be to 3 s.f.
Correct answer scores 6 marks; mark equation separately
Alternative method using ratio by moles:
M5 n(C2O42-) = 4.66 × 10-3 × 3 = 0.0140 moles in 250cm3
M6 n(complex) = 2.29/491.1 = 4.66 × 10-3 moles in 250cm3
M7 % = 0.0132/0.0140 × 100 = 94.3 or 94.4%
1
(e) Make some known concentrations (of the coloured solution

and read the absorbance of each one using a colorimeter)
Ignore addition of suitable ligand
1
Plot a graph of absorbance vs concentration

Not just “plot a calibration curve” / reference to Beer-Lambert
graph is insufficient
Do not allow transmittance in M2
1
Read/compare unknown concentration from calibration curve/graph (and hence the

concentration from the graph)
M3 can only be scored if graph/curve mentioned
1
[16]
Q5.
Page 51 of 84
(a) [Fe(H2O)6]2+ + 2NH3 → Fe(H2O)4(OH)2 + 2NH4+
Allow equation with OH− provided equation showing
formation of OH− from NH3 given
1
Green precipitate
1
[Fe(H2O)6]2+ + CO32− → FeCO3 + 6H2O

1
Green precipitate
effervescence incorrect so loses M4
1
(b) (i) Colourless / (pale) green changes to pink / purple (solution)

Do not allow pale pink to purple
1
Just after the end−point MnO4− is in excess / present

1
(ii) MnO4− + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+
Moles KMnO4 = 18.7 × 0.0205 / 1000 = (3.8335 × 10−4)

Process mark
1
Moles Fe2+ = 5 × 3.8335 × 10−4 = 1.91675 × 10−3
Mark for M2 × 5
1
Moles Fe2+ in 250 cm3 = 10 × 1.91675 × 10−3 = 0.0191675 moles in 50

cm3
Process mark for moles of iron in titration (M3) × 10

1
Original conc Fe2+ = 0.0191675 × 1000 / 50 = 0.383 mol dm−3
Answer for moles of iron (M4) × 1000 / 50

Answer must be to at least 2 sig. figs. (0.38)
1
[11]
Q6.
(a) moles of Cr2O72– per titration = 21.3 × 0.0150 / 1000 = 3.195 × 10–4
1
(Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+ ) Cr2O72-:Fe2+ = 1:6

If 1:6 ratio incorrect cannot score M2 or M3
1
moles of Fe2+ = 6 × 3.195 × 10–4 = 1.917 × 10–3
Page 52 of 84
Process mark for M1 × 6 (also score M2)
1
original moles in 250 cm3 = 1.917 × 10–3 × 10 = 1.917 × 10–2
Process mark for M3 × 10

1
mass of FeSO4.7H2O = 1.917 × 10–2 × 277.9 = 5.33 (g)

Mark for answer to M4 × 277.9
(allow 5.30 to 5.40)

Answer must be to at least 3 sig figs
Note that an answer of 0.888 scores M1, M4 and M5 (ratio
1:1 used)
1
(b) (Impurity is a) reducing agent / reacts with dichromate / impurity is a version of

FeSO4 with fewer than 7 waters (not fully hydrated)
Allow a reducing agent or compound that that converts Fe3+
into Fe2+
1
Such that for a given mass, the impurity would react with more dichromate
than a similar mass of FeSO4.7H2O
OR for equal masses of the impurity and FeSO4.7H2O , the impurity would
react with more dichromate.
Must compare mass of impurity with mass of FeSO4.7H2O
1
[7]
Q7.
(a) Cobalt has variable oxidation states
Allow exists as Co(II) and Co(III)
1
(It can act as an intermediate that) lowers the activation energy

Allow (alternative route with) lower Ea
1
CH3CHO + 2Co3+ + H2O → CH3COOH + 2Co2+ + 2H+
Allow multiples; allow molecular formulae

Allow equations with H3O+
1
O2 + 2Co2+ + 2H+ → 2Co3+ + H2O

1
(b) (i) [Co(H2O)6]2+ + 3H2NCH2CH2NH2 → [Co(H2NCH2CH NH2)3]2+ + 6H2O

2
Do not allow en in equation, allow C2H8N2

1
The number of particles increases / changes from 4 to 7
Page 53 of 84
Can score M2 and M3 even if equation incorrect or missing
provided number of particles increases
1
So the entropy change is positive / disorder increases / entropy

increases
1
(ii) Minimum for M1 is 3 bidentate ligands bonded to Co

Ignore all charges for M1 and M3 but penalise charges on
any ligand in M2
1
Ligands need not have any atoms shown but diagram must show 6
bonds from ligands to Co, 2 from each ligand
Minimum for M2 is one ligand identified as H2N-----NH2

Allow linkage as −C−C− or just a line.
1
Minimum for M3 is one bidentate ligand showing two arrows from

separate nitrogens to cobalt
1
(c) Moles of cobalt = (50 × 0.203) / 1000 = 0.01015 mol

Allow 0.0101 to 0.0102
1
Moles of AgCl = 4.22/143.4 = 0.0294

Allow 0.029
If not AgCl (eg AgCl2 or AgNO3), lose this mark and can only
score M1, M4 and M5
1
Ratio = Cl− to Co = 2.9 : 1

Do not allow 3 : 1 if this is the only answer but if 2.9:1 seen
somewhere in answer credit this as M3
1
[Co(NH3)6]Cl3 (square brackets not essential)

1
Difference due to incomplete oxidation in the preparation

Allow incomplete reaction.
Allow formation [Co(NH3)5Cl]Cl2 etc.
Some chloride ions act as ligands / replace NH3 in complex.
Do not allow 'impure sample' or reference to practical
deficiencies
1
[15]
Q8.
(a) Negative ions repel one another
1
(b) Positive ions attract negative ions in catalysed process
Page 54 of 84
Allow activation energy decreases.
Allow alternative route with lower Ea
Ignore references to heterogenous catalysis.
1
(c) S2O82– + 2e– 2SO42–
Allow multiples including fractions.

Ignore state symbols.
1
(d) S2O82– + 2I– 2SO42– + I2

Allow multiples including fractions.
Allow the correct equation involving I3–
S2O82– + 3I– 2SO42– + I3–
1
[4]
Q9.
(a) FeSO4 + Na2C2O4 → FeC2O4 + Na2SO4
Allow multiples, including fractions.
Allow Fe2+ + C2O42− → FeC2O4
Allow correct equation which includes water of crystallisation.
1
(b) Mr FeSO4.7H2O = 277.9

Allow if shown clearly in the calculation.
Allow 278
1
Moles = 6.95 / 277.9 = 2.5(0) × 10−2
Do not penalise precision but must be to a minimum of two

significant figures.
Allow correct calculation using incorrect Mr.
Correct answer without working scores this mark only.
1
(c) 3(.00) × 10−2
(d) Theoretical mass = 2.50 × 10–2 × 179.8 = 4.50g

as long as 2.50 × 10–2 is the smaller of parts (b) and (c) (M1)
Allow consequential answer from parts (b) and (c).
Allow theoretical mass = (smaller of parts (b) and (c)) ×
179.8
If larger of parts (b) and (c) used, lose M1 but can score M2.
Allow answers based on moles of reactant and product.
1
Yield = 3.31 × 100 / 4.50 = 73.6% (M2)
Page 55 of 84
Award this mark only if answer given to 3 significant figures.
Correct answer without working scores this mark only,
provided answer given to 3 significant figures.
1
(e) Some left in solution / some lost during filtration

Do not allow ‘incomplete reaction’.
Do not allow ‘reaction is reversible’.
1
(f) MnO4− will oxidise the iron(II) ion and the ethanedioate ion
1
MnO4− does not oxidise the Cu2+ ion / larger volume needed for iron(II)
ethanedioate
1
[9]
Q10.
(a) Variable / many oxidation states
1
(b) V2O5 + SO2 → V2O4 + SO3

Equations can be in either order
Allow multiples
1
V2O4 + ½O2 → V2O5

1
(c) (i) In a different phase / state from reactants

1
(ii) Impurities poison / deactivate the catalyst / block the active sites
Allow (adsorbs onto catalyst AND reduces surface area)
1
(d) (i) The catalyst is a reaction product

1
(ii) Mn / Mn ion(s)
2+ 3+
(iii) 4Mn + MnO4 + 8H → 5Mn + 4H2O

2+ − + 3+
Equations can be in either order

1
2Mn + C2O4 → 2Mn + 2CO2

3+ 2− 2+
1
[9]
Q11.
(a) Co-ordinate / dative / dative covalent / dative co-ordinate
Do not allow covalent alone
1
Page 56 of 84
(b) (lone) pair of electrons on oxygen/O
If co-ordination to O2-, CE=0
1
forms co-ordinate bond with Fe / donates electron pair to Fe

‘Pair of electrons on O donated to Feߣ scores M1 and M2
1
(c) 180° / 180 / 90

Allow any angle between 85 and 95
Do not allow 120 or any other incorrect angle
Ignore units eg °C
1
(d) (i) 3 : 5 / 5 FeC2O4 reacts with 3 MnO4–
Can be equation showing correct ratio

1
(ii) M1 Moles of MnO4– per titration = 22.35 × 0.0193/1000 = 4.31 × 10–4

Method marks for each of the next steps (no arithmetic error allowed for M2):
Allow 4.3 × 10–4 ( 2 sig figs)
Allow other ratios as follows:
eg from given ratio of 7/3
1
M2 moles of FeC2O4= ratio from (d)(i) used correctly × 4.31 × 10–4
M2 = 7/3 × 4.31 × 10–4 = 1.006 × 10–3

1
M3 moles of FeC2O4 in 250 cm3 = M2 ans × 10

M3 = 1.006 × 10–3 × 10 = 1.006 × 10–2
1
M4 Mass of FeC2O4.2H2O = M3 ans × 179.8

M4 = 1.006 × 10–2 × 179.8 = 1.81 g
1
M5 % of FeC2O4.2H2O = (M4 ans/1.381) × 100

M5 = 1.81 × 100/1.381 = 131 % (130 to 132)
1
(OR for M4 max moles of FeC2O4.2H2O = 1.381/179.8 (= 7.68 × 10–3)

for M5 % of FeC2O4.2H2O = (M3 ans/above M4ans) × 100)
eg using correct ratio 5/3:
Moles of FeC2O4 = 5/3 × 4.31 × 10–4 = 7.19 × 10–4
Moles of FeC2O4 in 250 cm3 = 7.19 × 10–4 × 10 = 7.19 × 10–3
Mass of FeC2O4.2H2O = 7.19 × 10–3 × 179.8 = 1.29 g
% of FeC2O4.2H2O = 1.29 × 100/1.381 = 93.4 (allow 92.4 to 94.4)
Note correct answer ( 92.4 to 94.4) scores 5 marks
Allow consequentially on candidate’s ratio
eg M2 = 5/2 × 4.31 × 10–4 = 1.078 × 10–3
M3 = 1.0078 × 10–3 × 10 = 1.078 × 10–2
M4 = 1.078 × 10–2 × 179.8 = 1.94 g
Page 57 of 84
M5 = 1.94 × 100/1.381 = 140 % (139 to 141)
Other ratios give the following final % values
1:1 gives 56.1% (55.6 to 56.6)
5:1 gives 281% (278 to 284)
5:4 gives 70.2% (69.2 to 71.2)
[10]
Q12.
(a) A ligand is an electron pair / lone pair donor
Allow uses lone / electron pair to form a co-ordinate bond
1
A bidentate ligand donates two electron pairs (to a transition metal ion) from
different atoms / two atoms (on the same molecule / ion)
QoL
1
(b) CoCl4 diagram

2−
Tetrahedral shape
1
109°28’
1
Four chlorines attached to Co with net 2− charge correct

Charge can be placed anywhere, eg on separate formula
Penalise excess charges
Allow 109° to 109.5°
[Co(NH3)6] diagram
2+
Octahedral shape
1
90°
1
Six ammonia / NH3 molecules attached to Co with 2+ charge

correct
Page 58 of 84
Allow 180° if shown clearly on diagram
CE= 0 if wrong complex but mark on if only charge is
incorrect
(c) In different complexes the d orbitals / d electrons (of the cobalt) will have
different energies / d orbital splitting will be different
1
Light / energy is absorbed causing an electron to be excited

1
Different frequency / wavelength / colour of light will be absorbed /

transmitted / reflected
1
(d) 1 mol of H2O2 oxidises 2 mol of Co 2+
Or H2O2 + 2Co → 2OH + 2Co

2+ − 3+
Mr CoSO4.7H2O = 281
If Mr wrong, max 3 for M1, M4, M5
1
Moles Co = 9.87 / 281 = 0.03512

2+
Moles H2O2 = 0.03512 / 2 = 0.01756

M4 is method mark for (M3) / 2 (also scores M1)
1
Volume H2O2 = (moles × 1000) / concentration

= 0.01756 × 1000) / 5.00
= 3.51 cm / (3.51 × 10 dm )
3 −3 3
Units essential for answer

M5 is method mark for (M4) x 1000 / 5
Allow 3.4 to 3.6 cm 3
If no 2:1 ratio or ratio incorrect Max 3 for M2, M3 & M5

Note: Answer of 7 cm scores 3 for M2, M3, M5 (and any
3
other wrong ratio max 3)

Answer of 16.8 cm scores 3 for M1, M4, M5 (and any other
3
wrong Mr max 3)
Answer of 33.5 cm scores 1 for M5 only (so wrong Mr AND
3
wrong ratio max 1)

1
[16]
Q13.
(a) For reactions 1 to 3 must show complex ions as reactants and products
Take care to look for possible identification on flow chart
Reaction 1
ammonia solution
Page 59 of 84
1
W is [Co(NH3)6]2+
[Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O

Correct equation scores all 3 marks
1
Reaction 2
Allow oxygen, Do not allow air
H 2 O2
1
X is [Co(NH3)6]3+
2[Co(NH3)6]2+ + H2O2 → 2[Co(NH3)6]3+ + 2OH–
Allow 2[Co(NH3)6]2+ + ½O2 + H2O → 2[Co(NH3)6]3+ + 2OH–

Correct equations score all 3 marks
1
Reaction 3
HCl
Do not allow Cl– but mark on
1
Y is [CoCl4]2-
[Co(H2O)6]2+ + 4Cl– → [CoCl4]2- + 6H2O/

Correct equation scores previous mark
[Co(H2O)6]2+ + 4HCl → [CoCl4]2- + 6H2O + 4H+

This equation scores all three marks
1
Reaction 4
Na2CO3 Or NaOH/NH3
Do not allow CaCO3 as a reagent but mark on
1
Z is CoCO3 Co(OH)2/Co(H2O)4(OH)2
1
[Co(H2O)6]2+ + CO32- → CoCO3 + 6H2O [Co(H2O)6]2++ 2OH–→

Co(H2O)4(OH)2+ 2H2O etc
Allow waters to stay co-ordinated to Co. This mark also
previous mark
Or [Co(H2O)6]2+ + Na2CO3 → CoCO3 + 6H2O + 2Na+
Page 60 of 84
Allow Co2+ + CO32- → CoCO3
1
(b) SO32- + ½O2 → SO42-
Allow multiples
1
The activation energy is lower (for the catalysed route)

Or Co3+ attracts SO32-/Co2+ attracts SO32-/oppositely charged
ions attract
1
½O2 + 2Co2+ + 2H+ → H2O + 2Co3+
2Co3+ + SO32- + H2O → 2Co2+ + SO42- + 2H+
Allow these equations in either order

1
[16]
Q14.
(a) Orange dichromate
Allow max 2 for three correct colours not identified to species
but in correct order
1
Changes to purple / green / ruby / red-violet / violet Chromium(III)

(Note green complex can be [Cr(H2O)5Cl]2+ etc)
Do not allow green with another colour
1
That changes further to blue Chromium(II)

Allow max 1 for two correct colours not identified but in
correct order
1
[Cr2O7]2- + 14H+ + 3Zn → 2Cr3+ + 3Zn2+ + 7H2O
2Cr3+ + Zn → 2Cr2+ + Zn2+ /

Ignore any further reduction of Cr2+
1
[Cr2O7]2- + 14H+ + 4Zn → 2Cr2+ + 4Zn2+ + 7H2O

Ignore additional steps e.g. formation of CrO42-
1
(b) Green precipitate

1
(Dissolves to form a) green solution

Solution can be implied if ‘dissolvesߣ stated
1
Page 61 of 84
[Cr(H2O)6]3+ + 3OH– → Cr(H2O)3(OH)3 + 3H2O
Penalise Cr(OH)3 once only
1
Cr(H2O)3(OH)3 + 3OH– → [Cr(OH)6]3- + 3H2O

Allow [Cr(H2O)6]3+ + 6OH– → [Cr(OH)6]3- + 6H2O
Allow formation of [Cr(H2O)2(OH)4]– and [Cr(H2O)(OH)5]2- in
balanced equations
Ignore state symbols, mark independently
1
(c) (ligand) substitution / replacement / exchange

Allow nucleophilic substitution
1
The energy levels/gaps of the d electrons are different (for each complex)
Ignore any reference to emission of light
1
So a different wavelength/frequency/colour/energy of light is absorbed (when d

electrons are excited)
OR light is absorbed and a different wavelength/frequency/colour/energy (of light) is

transmitted/reflected
1
(d) E O2 (/ H2O) > E Cr3+ (/ Cr2+) / e.m.f = 1.67 V

Allow E(cell) = 1.67
1
So Cr2+ ions are oxidised by oxygen/air

Allow any equation of the form:
Cr2+ + O2→ Cr3+
1
With [Cr(H2O)6]2+ get CrCO3

If named must be chromium(II) carbonate
1
with [Cr(H2O)6]3+ get Cr(H2O)3(OH)3 / Cr(OH)3

Allow 0 to 3 waters in the complex
1
and CO2
Can score M3, M4, M5 in equations even if unbalanced
1
Cr(III) differs from Cr(II) because it is acidic / forms H+ ions

1
because Cr3+ ion polarises water

Ignore charge/size ratio and mass/charge
1
[19]
Page 62 of 84
Q15.
(a) To reduce any Fe3+ ions to Fe2+ ions
Allow ‘to ensure that all of the iron present is in the form of
Fe2+ ions’ or ‘to ensure that no Fe3+ ions are present’.
1
(b) Zinc would react with MnO4− / Fe3+ produced in titration

Do not allow ‘would increase titre value’.
Do not allow ‘zinc would react’ without further qualification.
1
[2]
Q16.
(a) (i) Flask with side arm
1
Buchner funnel and horizontal filter paper

Allow Hirsch funnel and horizontal filter paper.
Do not allow standard Y-shaped funnel.
If there is not a clear air-tight seal (labelled or drawn)
between the funnel and the flask maximum 1 mark.
1
(ii) Mr KMnO4 = 158(.0)

1
Mass = 0.225 × 158 / 3 = 11.9 (g)

Lose M2 if no working shown.
Allow consequential mark on an incorrect Mr for KMnO4
1
Precision mark: three significant figures

Allow if mass incorrect.
1
(iii) (Unpleasant) taste

Ignore smell.
1
(b) Difficult to see meniscus / line on graduated flask

Do not allow reference to over filling.
1
[7]
Q17.
(a) Manganate would oxidise / react with Cl−
1
Because Eϴ for MnO4− is more positive than that for Cl2 / 1.51 – 1.36 = +0.15
(V)
Must refer to data from the table for M2.
1
(b) Moles of H+ = 25 × 0.0200 × 8 / 1000 = 4.00 × 10−3
Page 63 of 84
1
Moles of H2SO4 = 2.00 × 10−3 (4.00 × 10−3 / 2)

Allow consequential marking on incorrect moles of H+
1
Volume H2SO4 = 4.00 (cm3) (2.00 × 10−3 × 1000 / 0.500)

Allow consequential marking on incorrect moles of H2SO4
Accept 4 cm3.
8 cm3 scores 2 marks.
Do not penalise precision.
Correct answer without working scores M3 only.
1
(c) (i) MnO4− + 4H+ + 3e− → MnO2 + 2H2O

Allow multiples, including fractions.
1
(ii) Can’t see end point due to brown colour

1
Larger titre (than expected)

Allow the idea that with two reactions can’t make use of titre
in calculations.
Do not allow ‘an inaccurate result’ without qualification.
1
(d) Solution (very) dilute / lots of water

1
[9]
Q18.
(a) 2MnO4– + 16H+ + 5C2O42– 2Mn2+ + 8H2O + 10CO2
For all species correct / moles and species correct but
charge incorrect
1
For balanced equation including all charges (also scores first
mark)
1
(b) Manganate(VII) ions are coloured (purple)

1
All other reactants and products are not coloured (or too faintly coloured to detect)
Allow (all) other species are colourless
Allow Mn2+ are colourless / becomes colourless / pale pink
1
(c) The catalyst for the reaction is a reaction product

1
Reaction starts off slowly / gradient shallow

1
Page 64 of 84
Then gets faster/rate increases / gradient increases
Allow concentration of MnO4– decreases faster / falls rapidly
1
(d) Mn2+ ions

Allow Mn3+ ions
1
(e) MnO4– + 8H+ + 4Mn2+ 5Mn3+ + 4H2O

Allow multiples
1
2Mn3+ + C2O42– 2Mn2+ + 2CO2

1
[10]
Q19.
(a) Stop the formation of MnO2 / Ensures all MnO4– reacts to form Mn2+ / becomes
colourless
1
(b) Weak acid / Does not supply sufficient H+
(c) It is self-indicating / Purple to colourless end-point or vice versa

If colours mentioned they must be correct.
1
[3]
Q20.
(a) Variable oxidation state
1
eg Fe(II) and Fe (III)

Any correctly identified pair
Allow two formulae showing complexes with different
oxidation states even if oxidation state not given
1
(Characteristic) colour (of complexes)

1
eg Cu2+(aq) / [Cu(H2O)6]2+ is blue

Any correct ion with colour scores M3 and M4
Must show (aq) or ligands OR identified coloured compound
e.g. CoCO3)
1
(b) Tetrahedral
1
[CuCl4]2– / [CoCl4]2–
Any correct complex
Page 65 of 84
(Note charges must be correct)
1
Square planar
1
(NH3)2PtCl2
Any correct complex
1
Linear
Do not allow linear planar
1
[Ag(NH3)2]+
[AgCl2]– etc
1
(c) (i) [Ca(H2O)6]2+ + EDTA4– [CaEDTA]2– + 6H2O

If equation does not show increase in number of moles of
particles CE = 0/3 for (c)(ii)
If no equation, mark on
1
(ii) 2 mol of reactants form 7 mol of products

Allow more moles/species of products
Allow consequential to (c)(i)
1
Therefore disorder increases

1
Entropy increases / +ve entropy change / free-energy change is negative

1
(iii) Moles EDTA = 6.25 × 0.0532 / 1000 = (3.325 × 10–4)

1
Moles of Ca2+ in 1 dm3 = 3.325 × 10–4 × 1000 / 150 = (2.217 × 10–3)

Mark is for M1 × 1000 / 150 OR M1 × 74.1
If ratio of Ca2+ : EDTA is wrong or 1000 / 150 is wrong, CE
and can score M1 only
This applies to the alternative
1
Mass of Ca(OH)2 = 2.217 × 10–3 × 74.1 = 0.164 g

M1 × 74.1 × 1000 / 150
Answer expressed to 3 sig figs or better
Must give unit to score mark
Allow 0.164 to 0.165
1
[17]
Q21.
Page 66 of 84
MnO4- will oxidise the chloride ion / reaction of MnO4- and Cl- feasible
Accept converse argument with Cr2O72-
Accept calculations of overall E° values.
1
Larger volume needed

1
[2]
Q22.
(a) 2Fe2+ + S2O82– →2Fe3+ +2SO42–
1
2Fe3+ + 2I– → 2Fe2+ + I2

1
two negative ions repel / lead to reaction that is slow / lead

to reaction that has high Ea
1
iron able to act because changes its oxidation state

allow iron has variable oxidation state
1
With iron ions have alternative route / route with lower

activation energy
1
(b) (i) [Fe(H2O)6]3+ → [Fe(H2O)5OH]2+ + H+
can have H2O on LHS and H3O+ on R

do not penalise further hydrolysis equations
allow high charge density
1
Fe3+ ion has higher charge (to size ratio) (than Fe2+)
1
increases polarisation of co-ordinated water / attracts O

releasing an H+ ion / weakens O–H bond
1
(ii) Cr2O72– + 14H+ + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+
or 6 mol Fe(II) react with 1 mol dichromate

If factor of 6 not used max = 3 for M2, M4 and M5
e.g. 1:1 gives ans= 8.93 to 8.98% (scores 3)
1
moles dichromate = 23.6 × 0.218/1000 = 5.14 × 10–4
moles iron = 5.14 × 10–4 × 6 = 0.00309

M3 also scores M1
1
Page 67 of 84
mass iron = 0.00309 × 55.8 = 0.172
Mark is for moles of iron × 55.8 conseq
Allow use of 56 for iron
1
% by mass of iron = 0.172 × 100/0.321 = 53.7%

Answer must be to at least 3 sig figures allow 53.6 to 53.9
Mark is for mass of iron × 100/0.321 conseq
1
(c) brown precipitate / solid

Allow red-brown / orange solid
Not red or yellow solid
1
bubbles (of gas) / effervescence/ fizz

Allow gas evolved / given off
Do not allow just gas or CO2 or CO2 gas
1
2[Fe(H2O)6]3+ + 3CO32– → 2Fe(H2O)3(OH)3 + 3CO2 + 3H2O

Allow
2[Fe(H2O)6]3+ + 3CO32– → 2Fe(OH)3 + 3CO2 + 9H2O
Use of Na2CO3
e.g. … + 3Na2CO3 → .. + .. + .. + 6Na+
1
[16]
Q23.
(a) (i) Propanone evaporates (or similar)
1
Removes water (from the precipitate)

Accept ‘removes impurities / excess reagents’.
Accept ‘salt insoluble in propanone’.
1
(ii) Add NaOH / NH3 / Na2CO3

1
No green ppt
Accept ‘no visible change’.
Must have correct reagent to score this mark.
1
(iii) Some salt dissolves (in propanone) or some lost in filtration or some Fe2+
gets oxidised (to Fe3+ in air)
Do not accept ‘reaction reversible’ or ‘incomplete reaction’ or
similar.
1
Page 68 of 84
(iv) Moles Fe2+ = 2.50 × 10−2
Accept 2.5 × 10−2

1
Mr of salt = 179.8
Allow 180
Allow if 179.8 or 180 appears in a calculation.
1
Mass of salt = 179.8 × 2.5 × 10−2 × 0.95 = 4.27 (g)

Correct answer with no working scores this mark only.
Allow range 4.2 to 4.3 (g)
1
(v) 1.67 mol or correct ratio of 5FeC2O4 : 3MnO4−
(b) Ca2+ + C2O42− → CaC2O4

Accept multiples.
1
(c) (Insoluble) calcium ethanedioate coats surface

Allow ‘calcium ethanedioate is insoluble’.
Do not allow answers based on ethanedioic acid being a
weak acid.
Do not accept ‘acid used up’ or ‘reaction very fast’.
1
(d) Small amount of tea used or concentration of the acid in tea is low
Accept ‘high temperature decomposes the acid’.
Accept ‘calcium ions in milk form a precipitate with the acid’.
Do not accept ‘do not drink tea often’ or similar.
1
(e) Mass of acid = 180.0 and mass of reagents = 450.0

Accept 180 and 450.
1
(180 / 450 ×100 =) 40.0%

Do not penalise precision.
Correct answer without working scores this mark only.
1
[14]
Q24.
(a) Ti(IV) [Ar]
Or 1s2 2s2 2p6 3s2 3p6
1
Ti(III) [Ar]3d1
Or 1s2 2s2 2p6 3s2 3p6 3d1
Page 69 of 84
1
Ti(III) has a d electron that can be excited to a higher level

Allow idea that d electrons can be excited to another level (or
move between levels)
1
Absorbs one colour of light from white light

Allow idea that light is absorbed
1
Ti(IV) has no d electron so no electron transition with

energy equal to that of visible light
Allow Ti(IV) has no d electrons
1
(b) [Cu(NH3)4(H2O)2]2+
[Cr(OH)6]3–
[CuCl4]2–
(c) (i) Rapid determination of concentration

Or easy to get many readings
1
Does not use up any of the reagent/does not interfere

with the reaction
Or possible to measure very low concentrations
1
(ii) Curve starts with small gradient (low rate)

1
Because negative ions collide so Ea high

1
Curve gets steeper

1
Because autocatalyst (Mn2+) formed

1
Curve levels out approaching time axis

Can score this mark and next one ONLY with simple curve
(that is curve with gradually decreasing gradient)
1
Because MnO4– ions used up

5 max
1
[15]
Page 70 of 84
Q25.
(a) Species [Co(H2O)6]2+
1
Precipitate Co(H2O)4(OH)2
1
(b) [Co(NH3)6]2+
(c) Reaction Oxidation

1
Reactant Oxygen in the air

1
(d) R Iodine
1
Explanation [Co(H2O)6]3+ oxidises I– to I2

1
[7]
Q26.
(a) Fe + H2SO4 → FeSO4 + H2
1
(b) MnO4– + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+
(c) Moles MnO4– in 19.6 cm3

= 19.6 × 0.022 × 10–3 = 4.312 ×10–4
Moles Fe2+ in 25 cm3

= 5 × 4.312 × 10–4 = 2.156 × 10–3
Moles Fe2+ in 250 cm3

= 10 × 2.156 × 10–3 = 2.156 × 10–2
Mass Fe2+ = moles × Ar

Ar = 2.156 × 10–2 × 55.8 = 1.203 g
1
Percentage by mass of carbon

= (1.270 – 1.203) × 100/1.270
= 5.28%
1
(d) Repeat the titration and take an average of the concordant results
1
Page 71 of 84
(e) Analyse several samples from different parts of the molten iron
1
[9]
Q27.
(a) FeCl3 accepts electron pairs from water
1
Hence acts as a Lewis acid

1
[Fe(H2O)6]3+ donates protons

1
Hence acts as a Bronsted-Lowry acid

1
(b) The Fe2+ ion has a smaller charge to size ratio

1
Hence less polarising than Fe3+ or less weakening

effect on O-H bonds
1
(c) (i) V2O5 + SO2 → V2O4 + SO3

1
V 2 O4 + O 2 → V 2 O5
1
(ii) Both ions are negative or ions repel

1
2Fe2+ + S2O82– → 2Fe3+ + 2SO42– Species

1
Balanced
1
2Fe3+ + 2I– → 2Fe2+ + I2 Species

1
Balanced
1
[13]
Q28.
(a) (i) Fe + 2HCl → FeCl2 + H2
(allow ionic formulae)
or Fe + 2H+ → Fe2+ + H2
1
(ii) PV = nRT n = PV/RT

(allow either formula but penalise
contradiction)
1
Page 72 of 84
n=
1
= 4.53 × 10–3 (mol)

(answer must have at least 3 sig. figs. Ignore units)
1
(iii) Moles of iron = 4.5(3) × 10–3 mol

(allow conseq on (a)(ii))
(or = 4.2(5) × 10–3 if candidate uses given moles of hydrogen)

1
Mass of iron = 4.53 × 10–3 × 55.8 = 0.253 g

(mark is for method mass = moles × Ar)
(Mass of iron can be 56)
1
(iv) 0.253 × 100/0.263 = 96.1 % (mark is for answer to 2 sig. figs.)

(allow conseq on mass of iron. E.g. = 90% from
4.2(5) × 10–3 moles of H2 and Fe)
(Do not allow answers greater than or equal to 100%)
1
(b) (i) Fe2+ → Fe3+ + e–
(ignore state symbols)

1
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

1
Cr2O72– + 14H+ + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+
(ii) Moles of dichromate = moles Fe2+/6

= 4.53 × 10–3/6 = 7.55 × 10–4
(Allow conseq, mark is for method (a)(iii)/6)

1
Volume of dichromate = moles/concentration

(= (7.55 × 10–4 × 1000)/0.0200)
(mark is for this method)
1
V = 37.75 (cm3)
(allow 37.7 to 37.8, allow no units but penalise wrong units)
(allow conseq on moles of dichromate)
(if value of 3.63 × 10–3 used answer is 30.2 to 30.3,
otherwise ans = moles Fe2+/0.00012)
(if mole ratio wrong and candidate does not divide by 6,
max score is ONE for volume method)
1
Page 73 of 84
(iii) (KMnO4) will also oxidise (or react with) Cl– (or chloride or HCl)
1
[14]
Q29.
(a) most powerful reducing agent: Zn;
1
(b) (i) reducing species: Fe2+
(ii) oxidising species: Cl2;

1
(c) (i) standard electrode potential 1.25 V;

1
(ii) equation: Tl3+ + 2 Fe2+ → 2Fe3+ + Tl + balanced;

1
correct direction;
1
(d) (i) moles KMnO4 = 16.2 × 0.0200 ×10–3 = 3.24 ×10–4;

1
moles H2O2 = Moles KMnO4 × 5 / 2 = 8.10 × –4;

1
8.10 × 10–4 moles H2O2 in 25 cm3

8.10 × 10–4 × 1000 / 25 in 1000 cm3 = 0.0324 mol dm–3;
1
hence g dm–3 = mol dm–3 × Mr = 0.0324 × 34 = 1.10;

(penalise use of an incorrect H O to KMnO ratio by two
2 2 4
marks)
1
(ii) PV = nRT;
1
hence V = nRT / P
= 8.10 × 10–4× 8.31 × 298/98000;
1
= 2.05 × 10–5;
1
units m3;
(mark consequentially to answers in (c)(i))
(allow correct answers with other units)
(answers to (c)(i) and (ii) must be to 3 significant figures;
penalise once only)
1
[14]
Q30.
Page 74 of 84
A
[1]
Q31.
D
[1]
Q32.
(a) (i) Heterogeneous:- In a different phase to reactants (1)
Catalyst:- Increases reaction rate (1)
Alternative route or route described (1)
Lower Ea (1)
Unchanged at end of reaction (1) Max 4
(ii) Feature:- QoL Variable oxidation states shown by vanadium (1)

Equations V2O5 + SO2 → V2O4 + SO3 (1)
2V2O4 + O2 → 2V2O5 (1)
7
(b) VO2+ + 4H+ + 3e– → V2+ (aq) + 2H2O (1)
Zn → Zn2+ + 2e– (given)
2VO2+ + 8H+ + 3Zn → 3Zn2+ + 2V2+ (aq) + 4H2O (1)

2
Mol KMnO4 = mv/1000 = 0.0200 × 38.5/1000 = 7.70 × 10–4 (1)
Mole ratio MnO4– to V(II) = 3:5 deduced
or equation
5V2+ + 3MnO4– + 4H+ → 2H2O + 3Mn2+ + 5VO2+ (2)
Mol V(II) = 7.70 × 10–4 × 5/3 (1) = 1.283 × 10–3
Mass V = 1.283 × 10–3 × 50.9 (1) = 0.0653 g
% V in sample = 0.06532 × 100/0.160 = 40.8 (1)

6
[15]
Q33.
D
[1]
Q34.
(a) reactants brought together / increased concentration on surface
or increased collision frequency (1)
reactants must be correctly orientated (1)
reaction on the surface (1)
products desorbed (1)
example of a catalysed reaction (not a named process) (1)
Page 75 of 84
a suitable catalyst for this reaction (1)
penalise incorrect second reactions and catalysts
If absorption too weak reactants not brought together (1)

e.g. silver (1)
If adsorption too strong products not desorbed (1)
e.g. tungsten (1)
max 8
(b) Equations:
Cr2O72– +14 H+ + 6 Fe2+→ 6 Fe3+ + 2 Cr3+ + 7 H2O (1)

Zn + 2 Fe3+ → Zn2+ +2 Fe2+ (1)
Method
Titrate measured volume solution against K2Cr2O7 (1)
Reduce same volume solution with zinc (1)
Filter off excess zinc (1)
Titrate total Fen+ using K2Cr2O7 (1)
Percentage Fe3+ = 100 × (titre2 - titre1) / titre 2

or equivalent (1)
7
[15]
Q35.
A
[1]
Page 76 of 84
Examiner reports
Q1.
This was a challenging question with students finding most parts of it difficult.
(a) Only the best students got to the end of the calculation. Many students scored the
first four marks, and some of these then realised that they needed to multiply by ten
because of the dilution used. Very few students appreciated that the amount in
moles of ethanedioic acid had to be taken away from the total amount in moles of
ethanedioate ions to find the amount in moles of sodium ethanedioate. Those
students who did, usually went on to get the right answer.
(b) Students often failed to give a balanced equation; charges on the complex ions
were often incorrect, and many did not give water as one of the products. Many
students understood that the same number of bonds were broken and formed, but
few could also state that they were the same type of bonds. Some stated that the
bond enthalpies were similar, but could not explain why.
(c) Many students struggled to draw the displayed formula; those who got close often
omitted the carbon atoms from the ligand. Most students knew the bond angle, but
some incorrectly gave 120° or 109.5°. The most common incorrect type of
isomerism given was stereoisomerism or cis/trans.
(d) Common answers that did not score here included references to ethanedioate ions
being indigestible, or being so firmly chelated to iron ions already that they were not
free to be absorbed.
Q4.
In part (a) most students could identify the autocatalyst in the reaction however some
students thought that an autocatalyst was a reagent and identified the catalyst as MnO 4–.
Many students correctly identified the acid in part (b). Most students knew that two
negative ions would repel in part (c) but did not link this to high activation energy. Some
students did not state that the reaction was initially slow or would only speed up when the
catalyst was produced. The equation in part (d) was generally well done. Some students
had the correct ratio of reagents but missed charges on the ions or did not produce the
correct amount of CO2. Many students scored the first few marks but then failed to divide
by 3 or multiplied by the wrong Mr. In part (e) many students described a colorimeter and
the absorbance of visible light but did not answer the question as set and hence could not
score the marks. Most students who used a series of concentrations knew that a
calibration curve was used but often did not give correct labels for the axes. Those that
did use a calibration curve mostly scored the last mark. A few very good students drew a
diagram of the graph, with labelled axes, and showed how this would be used to find the
concentration.
Q5.
Most students gave correct observations in part (a) but their attempts at equations were
less successful and often unbalanced. Very few correct answers to part (b)(i) were seen.
The most usual response was to suggest, without any explanation, that the colour change
was from purple to colourless. Part (b)(ii) produced a whole range of responses. Good
students were able to score all 5 marks in impressive style but others lost marks. The
most common mistake was an incorrect equation and the use of an incorrect molar ratio
for moles of iron(II) to manganate(VII). Many students were also unable to calculate the
concentration of iron(II) ions in the original solution from the number of moles of iron(II)
Page 77 of 84
ions in the 250 cm³ flask. A factor of 1000/50 was required but factors such as 1000/250
or 250/25 were common mistakes.
Q6.
Many good answers were seen to part (a) in which full marks were scored. However, most
students used an incorrect ratio for the amount, in moles, of iron(II) that reacts with one
mole of dichromate ions. For these students, the maximum they could score was three out
of a possible five marks. In part (b), many students suggested, correctly, that the impurity
was likely to be a reducing agent but very few went on to explain that the impurity must
react with more moles of dichromate than would the same mass of FeSO4.7H2O.
Q7.
This stretch and challenge question proved testing for many students, particularly parts (a)
and (c). The most frequent mark for part (a) was one out of four for stating that cobalt has
variable oxidation states. Attempts at the two equations were poor. Equations should be
balanced andshould not be half-equations with electrons. Despite the parallel with similar
catalysed systems in the specification, students did not appreciate that the Co3+ ions
would be the oxidising agents, reacting with ethanal and that Co2+ ions would be oxidised
by oxygen back to Co3+. In part (b)(i), weaker students did not know that the chelate effect
is explained by entropy changes and they often, incorrectly, attempted to explain the effect
in terms of the stability of a complex ion with bidentate ligands. Part (b)(ii) was answered
well by most students. Part (c) proved to be very discriminating with only the very best
students scoring more than three out of five marks. The most difficult marks to achieve
were the formula of Z, [Co(NH3)6]Cl3 and an explanation for the difference between the
expected and the given ratio of cobalt ions to chloride ions in the complex. Many students
lost marks because they did not use a correct formula for silver chloride–incorrectly using
AgCl2 or AgNO3. Another common error was to ignore the precision of the data given in
the question and to give the calculated molar ratio to only 1 significant figure whereas 3
significant figures were required, consistent with the data given.
Q8.
Parts (a), (c) and (d) were generally very well answered. In part (b), the most common
wrong answers referred to the catalyst providing a surface for the adsorption of reactants.
Where students did talk about the opposite charges of the ions, they often did not
specifically talk about attraction between these ions
Q9.
The calculations in this Question were well-handled by students. In many cases, the only
mark lost was the final mark in this part (d) for not recording to 3 significant figures. There
were some vague answers given to part (e). To score the mark, the student needed to
mention a specific part of the process which would be responsible for the loss of some of
the product.
In this part (f), some students struggled to explain a redox titration, even though they did
not have to use data from a table of E° values. Very few answers worth both marks were
seen. Many students could not express themselves clearly while many others confused
the two salts. This was one question where students frequently ruined a promising answer
by including some incorrect chemistry. The marking of this question was often very lenient.
Q10.
This question was answered well by most students. The most difficult part was part (d)(iii)
Page 78 of 84
where only the best students were able to write correct equations.
Q11.
This question was answered well by most students. In part (b), a mark was lost by those
students who failed to mention that the electron pair donated to the iron(II) ion by water
was donated by oxygen. Part (d)(i) was the most demanding part of the question but it
was pleasing to find that 37% of students gave the correct reacting ratio of 3:5 for
MnO4–:FeC2O4. Many students tried unsuccessfully to write a balanced equation. The best
students did not attempt an equation. They realised that the reduction of manganate(VII)
ions is a 5–electron change reaction. The oxidation of FeC2O4 is a 3–electron change
reaction. Therefore, the reacting ratio is 3:5. Answers to part (d)(ii) were awarded method
marks and most students scored at least 4 out of the 5 marks available. Some students
lost a mark for an incorrect relative formula mass of FeC2O4.2H2O and some for an
incorrect method of calculating the percentage. Some students who used their own
incorrect ratio obtained in part (d)(i) and those who used the alternative 3:7 ratio given in
the question obtained an apparent mass of iron(II) ethanedioate that was greater than the
original mass. A common error was for students to calculate a percentage with the mass
of the impure compound as the numerator rather than the denominator.
Although question 6(d)(ii) could still be answered and all students were able to access all
of the available marks, we recognise that the alternative ratio given was unhelpful and
caused confusion for some students. We apologise for this and accept that it would have
been better to have provided a different ratio. During marking of this question, senior
examiners identified any student who used the 3:7 ratio. These students’ scripts were then
reviewed by experienced senior examiners and special consideration was given to any
student who had clearly been disadvantaged by using the given ratio.
Q12.
In part (a), the term ligand was usually explained correctly but only 9% of students went
on to explain that a bidentate ligand donates an electron pair from each of two separate
atoms in the ligand. Part (b) discriminated effectively. There was a wide range of marks
with 5% of students scoring zero and about 30% of students scoring full marks. In addition
to making mistakes with formulae and bond angles, weak students continue to lose marks
because they attempt to indicate charges on the ligand or the metal ion of the complex. A
more reliable approach is to indicate only the net charge on the complex ion, preferably
outside square brackets that contain the complex. Most students scored 2 out of the 3
marks available for part (c). The missing mark was usually due to a failure to mention that
the d electron energy levels are different for complexes with different ligands. Good
students usually scored full marks for part (d). Marks lost by weaker students were due to
use of the wrong Mr (often the relative atomic mass of cobalt rather than the Mr for
CoSO4.7H2O) or the wrong reacting ratio for cobalt(II) and hydrogen peroxide.
Q13.
Answers to part (a), a question that required recall of cobalt chemistry, produced a wide
spread of marks. As always, a full identification of reagents was required and many
students lost marks by failing to do so, specifying Cl– (instead of HCl), carbonate (instead
of sodium carbonate) and hydroxide (instead of NaOH). Missing or incorrect charges and
inaccurate formulae were also common eg CoCl4 and Co(OH2). Reaction 1 was well
known. Air was a common insufficient reagent for reaction 2. The equation mark for
reaction 2 was often the missing mark from an otherwise perfect answer. Reaction 3 was
the least well known of the four reactions. Many students did not recognise the blue
solution to be [CoCl4]2– and instead attempted to use an excess of NaOH to give a
cobaltate(II) ion. In reaction 4, NaCO3 and CO3– were common wrong answers. In part (b),
most students gained the first two marks. Although most students attempted the last two
Page 79 of 84
equations, very few were correct. Common wrong answers involved the wrong cobalt
species being used. For example, students tried to oxidise sulfate(IV) ions with cobalt(II).
They did not recognise that an oxidising agent must react with a reducing agent and they
went on with an attempt to reduce cobalt(III) to cobalt(II) with oxygen.
Q14.
In part (a), the equations were usually correct but the colours of the ions were not always
correct and not always identified to an ion. Occasionally the reduction was not continued
as far as chromium(III) and sometimes the reduction was continued, incorrectly, from
chromium(II) to chromium metal. This was not penalised. Answers to part (b) were
generally correct though marks were lost due to careless mistakes where equations were
not balanced with the correct number of hydroxide ions or the correct number of waters
displaced. A significant number of students continued to lose marks by showing a correct
overall charge for a complex with hydroxide ligands but also showing, incorrectly, a
negative charge on the hydroxide ligand.
The type of reaction in part (c) was usually correct but many students did not give a
correct answer to the remainder of the question. Students were asked to suggest why the
colours of the complex ions are different. Many chose to ignore the request to explain the
difference in colour and simply explained why a complex appears coloured. Only the very
best students suggested that the energy gap between the d–electron energy levels must
be different in complexes with different ligands. A surprising number of students stated
incorrectly that the oxidation state of chromium in [Cr(H2O)6]3+ was different from that in
[Cr(H2O)5Cl]2+ and, therefore, the two complexes had different numbers of d electrons. In
part (d), students generally deduced that the chromium(II) ion would be oxidised to
chromium(III) by oxygen but they did not use the electrode potential data correctly to
explain why. It was a very common error to use the data to suggest that oxygen is a better
oxidising agent than chromium(II). In this reaction chromium(II) is the reducing agent. The
last one or two marks of part (d) were often missed. A correct explanation for the
increased acidity of aqueous chromium(III) ions compared with aqueous chromium(II) ions
was only given by the best students.
Q15.
In part (a) and (b) were testing How Science Works questions and only the best students
scored both marks. A number of students were allowed marks for answers which were
either vague, included contradictions or were basically incorrect.
Q16.
(a) (i) The diagram in this part was poorly drawn by the majority of students. Schools
and colleges tended to compensate for errors by generous marking which
often ignored the Marking Guidelines. Diagrams that included a Y-shaped
funnel or omitted the filter paper or which would not be gas-tight or simply
would not work were routinely awarded marks by some teachers.
(ii) The calculation in this part was completed successfully by most students, with
clear and logical working. Many students forgot to convert 11.85 to three
significant figures at the end of the calculation so should have lost the final
mark.
(iii) this part was well answered.
(b) this part posed few problems, though a number of students confused the graduated
flask with a burette.
Page 80 of 84
Q17.
(a) Students usually struggle with questions where data from a table of Eo values is
used to explain a chemical reaction, and this part was no exception. Very few
answers worth both marks were seen. Many students could not express themselves
clearly while many others confused chlorine and the chloride ion. Statements such
as ’manganate(VII) ions have a more positive electrode potential than chloride ions’
and ’chlorine will oxidise manganese(II) ions’ were very common and were often
wrongly credited with a mark. In this question, students frequently ruined a
promising answer by including some incorrect chemistry. Examples included
’manganate(VII) ions have a more positive electrode potential so will reduce chloride
ions to chlorine’ and ’hydrochloric acid was reduced by manganate(VII) ions’. It was
difficult to see how an answer such as ’HCl is not electronegative enough to acidify
KMnO4’ could have been given any marks but it was.
(b) The calculation in this part discriminated well. There were a lot of complete answers
but many students, as expected, forgot that sulfuric acid is a dibasic acid.
(c) (i) The equation in this part must have been unfamiliar to most students but it
proved straightforward.
(ii) In this part, most students appreciated that the presence of a brown precipitate
would obscure the end-point, but the effect on the titre was not widely
understood. Many students made a vague statement that the titre would be
changed, but didn’t explain the change itself.
(d) Most students appreciated the effect of a large volume of water in this part, but
many added that manganate(VII) was a weak oxidising agent in solution so lost the
mark because of the chemical contradiction.
Q18.
The equation required in part (a) is recognised to be discriminating and it proved to be so
with only 34% of students giving a correct answer. Part (b) was a ‘how science works’
question and only 20% of students could explain that a spectrometer can be used
because manganate(VII) ions are coloured but the products of the reaction are effectively
colourless. Some students tried to use a mass spectrometer. Answers to parts (c) and (d)
were pleasing. However, as expected, part (e) proved to be very discriminating and only
the very best students could write balanced equations for the two reactions.
Q19.
Section C continues to prove the most demanding part of the paper, relying as it does on
experience of a wide area of practical chemistry.
(a) This part was very poorly answered with quite a few relying on the need for the
reaction to ’go to completion’ without showing what this meant.
(b) In this part, a surprising number of students thought that the ethanoic acid was an
oxidizing or a reducing agent.
(c) This part was well known though not always well expressed.
Q20.
Parts (a) and (b) were fairly straightforward questions requiring recall of transition metal
chemistry and it is pleasing to report that they were answered well by the majority of
Page 81 of 84
students. It is also pleasing to report that most students gained the mark for part (c)(i). A
correct explanation of the chelate effect in part (c)(ii) was more demanding. Most students
knew, or predicted, that the entropy change is positive but only the best students were
able to explain how and why the disorder increases. Part (c)(iii) proved to be more
discriminating than expected. Only the best students applied the factor of 1000/150
correctly and a surprisingly large number of students did not calculate correctly the
relative formula mass of calcium hydroxide. Some used the Mr for EDTA and some the Mf
for CaOH.
Q21.
This Question proved very demanding as expected. Many candidates provided some Eθ
calculations without any explanation of the significance of the results, and could not be
given any marks. Confusion between chlorine and chloride ion was very common, often
rendering the answer meaningless. A fair number of candidates thought that the oxidation
of chloride ions took place instead of the oxidation of iron(II) ions. Full marks were quite
rare.
Q22.
Each part of this question discriminated very effectively between able and less able
candidates. In part (a) a common omission was a failure to state that iron ions are able to
catalyse redox reactions because they are able to change oxidation state. In this part, the
most usual errors were to give an unbalanced equation for the reaction between iron (II)
ions and persulfate ions and for the reaction between iron (III) ions and iodide ions.
Candidates often used only one mole of iron ions, presumably because they omitted to
check that charges, as well as numbers of moles, should balance. In part (b)(i), most
candidates knew that the increased acidity of aqueous iron (III) ions could be attributed to
their increased charge to size ratio compared with iron (II) ions. However, the reason why
this high charge to size ratio caused an increase in ionisation of the [Fe(H2O)6]3+ was less
well understood. Very few correct equations were seen. Many did not show the release of
one proton into the aqueous solution. They showed incorrectly the formation of
Fe(H2O)3(OH)3 often by reaction with hydroxide or carbonate ions. There were many
good answers to part (b)(ii) with about 40% of candidates scoring full marks. Answers to
part (c) were not so impressive. Although a brown precipitate was usually described,
evolution of a gas was often missing and the difficult equation was not balanced correctly.
Q23.
In part (a)(i), credit cannot be given to candidates who repeat the information from the
question stem, rather than apply this information.
A surprising number could not give a satisfactory test in part (a)(ii). Centres are reminded
that if the candidate chooses an incorrect test reagent the mark for the observation cannot
be awarded. Centres are also reminded that ‘OH-‘or ‘hydroxide’ is not acceptable as a test
reagent, but a correct observation can score the second mark. When required to identify a
test reagent, a candidate must give the full name or formula.
Candidates tended to overlook the practical process in search of an answer to part (a)(iii),
‘incomplete reaction’ being a popular choice.
As at AS, the yield calculation in part (a)(iv) proved to be beyond a large number of
candidates. Many did not attempt the question.
Only a handful of candidates could deduce the mole ratio in part (a)(v).
Many candidates continue to struggle with questions such as part (c), once again unable
Page 82 of 84
to see beyond the observations in a familiar practical activity. Similarly, the application of
logic to everyday chemistry in part (d) defeated many candidates.
The above notes are intended for that small minority of centres experiencing difficulty in
meeting the marking criteria. They must not be allowed to unduly detract from the very
healthy overall picture. Given the pressures on centres to deliver the teaching programme,
this was a very positive first session. Centres are again warmly commended for the
trouble taken to assemble a sample which proved to be easy to moderate. Their efforts
continue to be much appreciated by the moderator team.
Q24.
Part (a) produced a wide spread of marks but many candidates gave good answers.
Amongst the weaker candidates, there appears to be a false impression that the colour of
a compound is caused by emitted light rather than the correct reason that some of the
incident white light is absorbed and the remainder reflected or transmitted. Answers to
part (b) were very disappointing and, as in question 7, showed poor recall of transition
metal chemistry. The ‘How Science Works’ question in part (c)(i) was not answered well.
The most common response was to claim that a spectrometer is ‘more accurate’. This
answer was not given any credit. It would help candidates to answer such questions if
centres were able to demonstrate how a colorimeter can be used in similar experiments. It
was pleasing to see many very good answers to part (c)(ii) where over 50% of candidates
gained four marks or more.
Q28.
This question discriminated effectively between candidates of differing abilities. Very able
candidates scored well in all parts of the question except in parts (b) (ii) and (b)(iii). In part
(a) a surprising number of candidates attempted to write an equation with the Fe ion as a
2+
reactant instead of Fe. Answers to part (a)(ii) were usually correct. In part (a)(iii), many
candidates incorrectly calculated the number of moles of iron by halving the number of
moles of hydrogen. The method for calculating the mass of iron was usually correct but,
although it was allowed, it was disappointing to note that candidates were using an^4 r
value of 56 for iron instead of the value of 55.8, given on the Periodic Table. Answers to
part (a)(iv) usually used the correct method. Answers to part (b) (i) were almost always
correct but the equations involving dichromate(VI) ions were only given correctly by the
best candidates. Very few correct answers to part (b)(ii) were seen. The usual error was a
failure to recognise that six moles of iron(II) ions react with one mole of dichromate(VI)
ions. In part (b)(iii) most candidates did not recognise that chloride ions would be oxidised
by manganate(VII) ions.
Q29.
Although parts (a), (b) and (c) were rather better answered than similar questions on
earlier papers, a significant number of candidates still have problems using redox data.
The calculation in (d)(i) was well done but many candidates lost one mark as, having
calculated the concentration of the hydrogen peroxide solution in mol dm–3, they failed to
convert this to g dm–3 as required by the question. Part(d)(ii) was marked consequentially
to answers determined in (d)(i). Almost all candidates stated the ideal gas equation and
used it correctly but only the best candidates gave correct units for the volume of oxygen
evolved.
Q32.
Although some candidates confused the terms homogenous with heterogeneous, the
terms heterogeneous and catalyst were generally well known and most candidates gave
Page 83 of 84
correct explanations of how, in general terms, a catalyst works. The role of vanadium(V)
oxide in the Contact Process was also well known and many candidates scored full marks
for their answers to part (a). Part (b) proved, as expected, to be more difficult. Many
candidates were able to use half-equations to construct an overall equation for the
reduction of to V2+ by zinc in acidic solution. Almost all were also able to calculate
correctly the number of moles of potassium manganate(VII) used to oxidise the
vanadium(II) ions back to vanadium(V) ions. However, in order to calculate the number of
moles of vanadium(II) in the solution, it was necessary to deduce the mole ratio : V2+.
The best students made this deduction and went on to determine the percentage of
vanadium in the sample. Candidates who failed to make this deduction were able to score
an additional mark if they used the correct Ar of vanadium when calculating the mass of
vanadium in the sample from their value for moles of V2+ in the solution.
Q34.
Most candidates gave good explanation of how a heterogeneous catalyst works and high
marks were scored in part (a). By contrast, few gave a good outline plan for the
experiment to determine the percentage of iron as iron(III) in a solution containing Fe 3+
(aq) and Fe2+ (aq) ions. Most stated correctly that the concentration of Fe2+ (aq) in solution
can be determined by a titration using potassium dichromate(VI) but few clearly stated
that the volumes of both solution would need to be measured. Although most used the fact
that zinc can reduce Fe3+ (aq) to Fe2+ (aq), very few stated that, after the reduction, excess
zinc would need to be removed by filtration. Marks were awarded for correct equations but
many candidates did not give them.
Page 84 of 84

Variableoxidationstates

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_______________________

Time: 373 minutes

Marks: 356 marks

(a) A white solid is a mixture of sodium ethanedioate (Na2C2O4), ethanedioic acid

Two different titrations were carried out using this solution.

The equation for this reaction is

2MnO4− + 5C2O42− + 16H+ → 2Mn2+ + 8H2O + 10CO2

The equation for this reaction is

H2C2O4 + 2OH− → C2O42− + 2H2O

Calculate the percentage by mass of sodium ethanedioate in the white solid.

Give your answer to the appropriate number of significant figures.

Show your working.

Percentage by mass of sodium ethanedioate ____________________ %

Write an equation for this reaction.

Indicate the value of the O—Fe—O bond angle.

State the type of isomerism shown by the iron complex.

Bond angle _________________________________________________________

Type of isomerism ____________________________________________________

(a) Hexaaquairon(III) ions react with an excess of hydrochloric acid in a ligand

Write an equation for this reaction.

(c) Hexaaquairon(II) ions react with an excess of H2NCH2CH2NH2 in a ligand

(d) Hexaaquairon(II) ions react with an excess of H2NCH2CH2NH2 in a ligand

Tick (✔) one box.

change in entropy is negative

change in entropy is close to zero

change in entropy is positive

Calculate the percentage of iron in the sample of iron tablets.

Elements X, Y and Z are Ca, Sc and V but not in that order.

First Second Third Fourth Fifth Sixth

X 648 1370 2870 4600 6280 12 400

Y 590 1150 4940 6480 8120 10 496

Z 632 1240 2390 7110 8870 10 720

(a) Which element is calcium?

(b) Which element is vanadium?

(c) Justify your choice of vanadium in part (b)

(d) An acidified solution of NH4VO3 reacts with zinc.

Oxidation state = _______________

(e) A solution of KMnO4 has an unknown concentration.

(i) Write an equation for this reaction.

(c) In the Contact Process, vanadium(V) oxide acts as a heterogeneous catalyst.

(i) Give the meaning of the term heterogeneous.

(ii) Identify the autocatalyst in this reaction.

Each iron ion is also bonded to

(a) Name the type of bond that is represented by the arrows.

(d) Iron(II) ethanedioate dihydrate can be analysed by titration using potassium

A 1.381 g sample of impure FeC2O4.2H2O was dissolved in an excess of dilute

MnO4– + 8H+ + 5e– Mn2+ + 4H2O

C2O42– 2CO2 + 2e–

(ii) Calculate the percentage by mass of FeC2O4.2H2O in the original sample.

Explain why these complex ions have different colours.

Identify W, X, Y and Z and write an equation for each of reactions 1 to 4.

(b) A flue-gas desulfurisation process involves the oxidation, by oxygen, of aqueous

Cr2O72–(aq) + 14H+(aq) + 6e– 2Cr3+(aq) + 7H2O(I) +1.33

O2(g) + 4H+(aq) + 4e– 2H2O(I) +1.23

Cr3+(aq) + e– Cr2+(aq) –0.44

Zn2+(aq) + 2e– Zn(s) –0.76

Cr2+(aq) + 2e– Cr(s) –0.91

Write two equations to illustrate your observations.

Name this type of reaction.

(a) Suggest why the zinc and acid were added.

(ii) An equation representing the oxidation reaction is given below.

3Fe2+(aq) + KMnO4(aq) + 5OH–(aq) + 2H2O(I) 3Fe(OH)3(s) + MnO2(s) + K+(aq)

(iii) In practice, a slight excess of potassium manganate(VII) is used to treat the

MnO4–(aq) + 8H+(aq) + 5e– → Mn2+(aq) + 4H2O(I) +1.51