2.

5 Transition Metals - Variable Oxidation States – Questions

Q1.
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?

X       

Y       

Z       
(1)

(b)     Which element is vanadium?

X       

Y       

Z       
(1)

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

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(1)

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

Explain how observations from this reaction show that vanadium exists in at least
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)

Q2.
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.

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)

Q3.
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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(1)

(b)     Explain why it was necessary to remove the excess zinc.

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(1)
(Total 2 marks)

Q4.
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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 (1)

(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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(1)

(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)

Q5.
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.

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)

Q6.
(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
the excess is undesirable.

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(1)

(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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(1)
(Total 7 marks)

Q7.
(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)

Q8.
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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(1)

(ii)     Give one reason why impurities in the reactants can cause problems in
processes that use heterogeneous catalysts.

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(1)

(d)     The oxidation of C2O42− ions by MnO4− ions in acidic solution is an example of a
reaction that is autocatalysed.

(i)      Give the meaning of the term autocatalysed.

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(1)

(ii)     Identify the autocatalyst in this reaction.

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(1)

(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)

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 (FeC2O4.2H2O) were
collected.

(a)     Write an equation for the reaction between iron(II) sulfate and sodium ethanedioate.

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(1)

(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.
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.

(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.
 
H2C2O4

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)
 Q11.
(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 cm3,
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.

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(1)

(ii)     Give two reasons why it is essential to avoid this reaction in a titration

between potassium manganate(VII) and iron(II) ions.

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(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.

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(1)
(Total 9 marks)

Q12.
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.

(a)     Write an equation for the reaction between manganate(VII) ions and ethanedioate
ions in acidic solution.

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(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.
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(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 _______________________________________________

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Explanation _________________________________________________________

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(3)

(d)     Identify the autocatalyst in this reaction.

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(1)

(e)     Write two equations to show how the autocatalyst is involved in this reaction.

Equation 1 __________________________________________________________

Equation 2 __________________________________________________________
(2)
(Total 10 marks)

Q13.
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.

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(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.

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(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.

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(1)

(ii)     Explain why the equilibrium in part (c)(i) is displaced almost completely to the
right to form the EDTA complex.

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(3)

(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.

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(3)
(Total 17 marks)

Q14.
(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.
(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)

Q15.
(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.

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(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)

Q16.
(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 ______________________________________________________

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Reason 2 ______________________________________________________

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(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)

(iii)    Suggest one reason why the typical yield of iron(II) ethanedioate is less than
100%.
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(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.

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(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.

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(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.

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(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.

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(1)

(d)     Tea leaves contain ethanedioic acid. Suggest one reason why tea drinkers do not
suffer from ethanedioic acid poisoning.

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(1)

(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.

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(2)
(Total 14 marks)

Q17.
(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.
(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).
(8)
(Total 15 marks)

Q18.
Where appropriate, use the standard electrode potential data in the table below to answer
the questions which follow.
 
              Eο/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

(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

and a temperature of 298 K, which would be evolved in this reaction.

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(8)
(Total 14 marks)

Q19.
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

______________________________________________________________

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
potassium manganate(VII).

______________________________________________________________

______________________________________________________________
(7)
(Total 14 marks)

Q20.
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.
(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.

(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.
(7)
(Total 13 marks)

Q21.
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
potassium manganate(VII).

(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)

Q22.
(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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(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.

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(5)
(Total 15 marks)

Q23.
When iodine molecules are dissolved in aqueous solutions containing iodide ions, they
react to form triiodide ions (I3–).
 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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(1)

(b)     Other than having variable oxidation states, explain why Fe2+ ions are good catalysts
for this reaction.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(1)

(c)     Write a half-equation for the reduction of S2O82– ions to SO42– ions.

___________________________________________________________________

___________________________________________________________________
(1)

(d)     Construct an overall equation for the reaction between S2O82– ions and I– ions.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(1)
(Total 4 marks)

Q24.
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)

Q25.
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)

Q26.
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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
 ___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

(Extra space) ________________________________________________________

___________________________________________________________________

___________________________________________________________________
(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).

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
 ______________________________________________________________

______________________________________________________________
(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)

Q27.
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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(2)
(Total 7 marks)

Q28.
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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(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.

______________________________________________________________
 ______________________________________________________________

______________________________________________________________

______________________________________________________________
(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.

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(5)
(Total 11 marks)

Q29.
This question explores some reactions and some uses of cobalt compounds.

(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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
 ___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(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.

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(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.

 
(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.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(5)
(Total 15 marks)