2.

4 Transition Metals - Formation of Coloured ions – Questions

Q1.
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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___________________________________________________________________

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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)

Q2.
This question is about copper chemistry.

(a)     Aqueous copper(II) ions [Cu(H2O)6]2+(aq) are blue.

(i)      With reference to electrons, explain why aqueous copper(II) ions are blue.

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(Extra space) ___________________________________________________

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(3)

(ii)     By reference to aqueous copper(II) ions, state the meaning of each of the
three terms in the equation ΔE = hv.

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(Extra space) ___________________________________________________

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(3)

(iii)     Write an equation for the reaction, in aqueous solution, between [Cu(H2O)6]2+
and an excess of chloride ions.
State the shape of the complex produced and explain why the shape differs
from that of the [Cu(H2O)6]2+ ion.

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 (Extra space) ___________________________________________________

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(3)

(b)     Draw the structure of the ethanedioate ion (C2O42–).

Explain how this ion is able to act as a ligand.

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(2)

(c)     When a dilute aqueous solution containing ethanedioate ions is added to a solution
containing aqueous copper(II) ions, a substitution reaction occurs. In this reaction
four water molecules are replaced and a new complex is formed.

(i)      Write an ionic equation for the reaction. Give the co-ordination number of the
complex formed and name its shape.

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(4)

(ii)     In the complex formed, the two water molecules are opposite each other.
Draw a diagram to show how the ethanedioate ions are bonded to a copper
ion and give a value for one of the O–Cu–O bond angles. You are not
required to show the water molecules.

 
  

 
(2)
(Total 17 marks)

Q3.
Hydrogen peroxide is used as an oxidising agent in the preparation of transition metal
complexes.

(a)     Consider the following reaction scheme. All the complexes are in aqueous solution.

Reaction 1                                           Reaction 2

[Co(H2O)6]2+       cobalt(II) complex       [Co(NH3)6]3+
H2O2

(i)      Identify a reagent for Reaction 1 and describe the colour change that occurs.

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(3)

(ii)     State the colour of the final solution formed in Reaction 2.

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(1)

(b)     Consider the following reaction scheme. All the complexes are in aqueous solution.

(i)      For Reaction 3, state the colour of the initial and of the final solution and write
an equation for the reaction.

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(4)

(ii)     Write a half-equation for the reduction of hydrogen peroxide to hydroxide ions.

Deduce an overall equation for Reaction 4 and state the colour of the final
solution.

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(4)

(c)     The concentration of a hydrogen peroxide solution can be determined by titration

with acidified potassium manganate(VII) solution. In this reaction the hydrogen
peroxide is oxidised to oxygen gas.

A 5.00 cm3 sample of the hydrogen peroxide solution was added to a volumetric
flask and made up to 250 cm3 of aqueous solution. A 25.0 cm3 sample of this diluted
solution was acidified and reacted completely with 24.35 cm3 of 0.0187 mol dm–3
potassium manganate(VII) solution.

Write an equation for the reaction between acidified potassium manganate(VII)

solution and hydrogen peroxide.
Use this equation and the results given to calculate a value for the concentration, in
mol dm–3, of the original hydrogen peroxide solution.
(If you have been unable to write an equation for this reaction you may assume that
3 mol of KMnO4 react with 7mol of H2O2. This is not the correct reacting ratio.)

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(5)
(Total 17 marks)

Q4.
(a)     Octahedral and tetrahedral complex ions are produced by the reaction of transition
metal ions with ligands which form co-ordinate bonds with the transition metal ion.
Define the term ligand and explain what is meant by the term co-ordinate bond.
(3)

(b)     (i)      Some complex ions can undergo a ligand substitution reaction in which both
the co-ordination number of the metal and the colour change in the reaction.
Write an equation for one such reaction and state the colours of the complex
 ions involved.

(ii)     Bidentate ligands replace unidentate ligands in a metal complex by a ligand

substitution reaction.
Write an equation for such a reaction and explain why this reaction occurs.
(8)

(c)     The frequency, v, of light absorbed by a transition metal complex ion can be
determined using the relationship ΔE = hv. State what is meant by the symbols ΔE
and h. Give three factors which result in a change in the frequency of light
absorbed as a result of the reaction of a complex ion.
(5)
(Total 16 marks)

Q5.
(a)     State the origin of the colour of transition-metal complexes.

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(2)

(b)     Give three changes to a transition-metal complex which result in a change in colour.

Change 1 __________________________________________________________

Change 2 __________________________________________________________

Change 3 __________________________________________________________

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(3)

(c)     You are provided with a 1.00 mol dm–3 solution of iron(III) ions and a visible-light
spectrophotometer (colorimeter). Outline a plan for experiments using this solution
and this apparatus which would enable you to determine the concentration of
iron(III) ions in a solution of unknown concentration.

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(5)
(Total 10 marks)

Q6.
 The characteristic properties of transition metals include complex formation and the
formation of coloured ions.

(a)     Some complex ions can undergo a ligand substitution reaction in which both the
coordination number of the metal and the colour of complex ions change in the
reaction.

Write an equation for one such reaction and state the colours of the complex ions
involved.

Equation ___________________________________________________________

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Colours of complex ions _______________________________________________

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(4)

(b)     The frequency, v, of light absorbed by a transition–metal complex ion can be

determined using the relationship ΔE = hv.

(i)      State what is meant by the symbols ΔE and h.

Meaning of symbol ΔE ____________________________________________

Meaning of symbol h _____________________________________________

(ii)     Give three factors which may cause the frequency of light absorbed to change
when a complex ion reacts.

Factor 1 _______________________________________________________

Factor 2 _______________________________________________________

Factor 3 _______________________________________________________
(5)
(Total 9 marks)

Q7.
(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.

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(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.

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(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.

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(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.

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(5)
(Total 15 marks)

Q8.
(a)     The concentration of iron(III) ions in a dilute solution can be determined by visible
spectrometry. The absorption of light by a number of solutions of iron(III) sulfate,
Fe2(SO4)3(aq), was measured. The results are shown in the table below.
 
Concentration of Absorbance / %
Fe2(SO4)3(aq) / mol dm–3

0.020 2.2

0.040 4.7

0.060 7.0

0.080 9.4

0.100 11.8

(i)      Use these results to plot a graph of percentage absorbance (y-axis) against

concentration of iron(III) sulfate solution on the grid below.
Draw a straight line of best fit.
  
(2)

(ii)     Use your graph to determine the concentration of iron(III) ions in a

solution of Fe2(SO4)3 that has an absorbance of 5.4%.

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(2)

(iii)    Calculate the volume of water that should be added to 100 cm3 of a 0.10 mol
dm–3 solution of iron(III) sulfate to make a 0.040 mol dm–3 solution.
Show your working.

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(2)

(b)     Give one reason why well-water may be more beneficial to health than pure water.

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(1)
(Total 7 marks)

Q9.
Calcium fluoride occurs naturally as the mineral fluorite, a very hard crystalline solid that is
almost insoluble in water and is used as a gemstone.

Tables 1 and 2 contain thermodynamic data.

Table 1
 
Process ΔHο / kJ mol–1

     Ca(s) → Ca(g) +193

     Ca(g) → Ca+(g) + e– +590

    Ca+(g) → Ca2+(g) + e– +1150

      F2(g) → 2F(g) +158

F(g) + e– → F–(g) –348

Table 2
 
Name of enthalpy change ΔHο / kJ mol–1

Enthalpy of lattice dissociation for calcium +2602

fluoride

Enthalpy of lattice dissociation for calcium +2237

chloride

Enthalpy of hydration for F– ions –506

Enthalpy of hydration for Cl– ions –364

Enthalpy of hydration for Ca2+ ions –1650

(a)     Write an equation, including state symbols, for the process that occurs when the
calcium fluoride lattice dissociates and for which the enthalpy change is equal to the
lattice enthalpy.

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(1)
(b)     (i)      Define the term standard enthalpy of formation.

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(3)

(ii)     Write an equation, including state symbols, for the process that has an
enthalpy change equal to the standard enthalpy of formation of calcium
fluoride.

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(1)

(iii)     Use data from the Tables 1 and 2 to calculate the standard enthalpy of
formation for calcium fluoride.

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(3)

(c)     Explain why the enthalpy of lattice dissociation for calcium fluoride is greater than
that for calcium chloride.

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(2)

(d)     Calcium chloride dissolves in water. After a certain amount has dissolved, a
saturated solution is formed and the following equilibrium is established.

CaCl2(s) Ca2+(aq) + 2Cl–(aq)

(i)      Using data from Table 2, calculate the enthalpy change for this reaction.

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(2)

(ii)     Predict whether raising the temperature will increase, decrease or have no
effect on the amount of solid calcium chloride that can dissolve in a fixed mass
of water.
Explain your prediction.
(If you have been unable to obtain an answer to part (d) (i), you may assume
that the enthalpy change = –60 kJ mol–1. This is not the correct answer.)

Effect on amount of solid that can dissolve ___________________________

Explanation ____________________________________________________

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(3)

(e)     Calcium fluoride crystals absorb ultra-violet light. Some of the energy gained is
given out as visible light. The name of this process, fluorescence, comes from the
name of the mineral, fluorite.

Use your knowledge of the equation ΔE = hν to suggest what happens to the

electrons in fluorite when ultra-violet light is absorbed and when visible light is given
out.

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(2)
(Total 17 marks)

Q10.
The concentration of iron(III) ions in a dilute solution can be determined by visible
spectrometry. The absorption of light of a particular frequency by solutions of iron(III)
sulfate of different concentrations was measured. The results are shown in the table
below.
 
Percentage Concentration of iron(III)
absorbance
sulfate / mol dm–3

1.0 7.5 ×10–3

2.5 14.0 ×10–3

5.0 27.5 ×10–3

 7.0 37.5 ×10–3

10.0 54.0 ×10–3

12.0 65.0 ×10–3

(a)     Use these results to plot a graph of percentage absorbance (y-axis) against
concentration of iron(III) sulfate on the grid below.
Draw a straight line of best fit.

 
(2)

(b)     Use your graph to determine the concentration of an iron(III) sulfate solution that
has a percentage absorbance of 14.0%.

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(1)
(Total 3 marks)

Q11.
This question is about some reactions of cobalt compounds.
  

(a)     Give the formula of the complex responsible for the pink colour in aqueous CoCl2
and name its shape.

Formula ____________________________________________________________

Name of shape ______________________________________________________

(2)

(b)     Give the formula of the cobalt-containing compound V and describe its appearance.

Formula ___________________________________________________________

Appearance ________________________________________________________
(2)

(c)     Write an equation for the reaction that occurs when the pink solution is converted
into W.

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(2)

(d)     Give the formula of the cobalt-containing complex in X and state the role of the H2O2
in this reaction.

Formula ____________________________________________________________

Role of H2O2 ________________________________________________________

(2)

(e)     Give the formula of the cobalt-containing complex in Y and explain why this complex
is more stable than the cobalt-containing complex in W.

Formula ____________________________________________________________

Explanation _________________________________________________________

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 (3)

(f)      Identify the cobalt-containing complex in solution Z and explain why its co-ordination
number is different from that in the pink solution of CoCl2

Complex ___________________________________________________________

Explanation _________________________________________________________

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(2)
(Total 13 marks)

Q12.
Transition elements form complex ions with a range of colours and shapes.

(a)     By considering its electron arrangement, state how an element can be classified as
a transition element.

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(1)

(b)     Explain the meaning of the term complex ion.

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(2)

(c)     In terms of electrons, explain why an aqueous solution of cobalt(II) sulfate has a red
colour.

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(3)

(d)     The ligand EDTA4– is shown below.

(i)      Draw circles around the atoms of two different elements that link to a
transition metal ion by a co-ordinate bond when EDTA4– behaves as a ligand.
(2)
 (ii)     Write an equation for the reaction between EDTA4– and a [Co(H2O)6]2+ ion. Use
the abbreviation EDTA4– in your equation.

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(1)

(iii)     Explain why the complex ion, formed as a product of the reaction in part (d)
(ii), is more stable than the [Co(H2O)6]2+ ion.

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(2)

(e)     The diagram below shows part of the structure of haemoglobin.

Haemoglobin contains an iron(II) ion bonded to five nitrogen atoms and one other
ligand. The fifth nitrogen atom and the additional ligand are not shown in this
diagram.

(i)      In this diagram, bonds between nitrogen and iron are shown as N→Fe and as
N―Fe.

State the meaning of each of these symbols.

Meaning of → __________________________________________________

Meaning of ― __________________________________________________
(2)

(ii)     State the function of haemoglobin in the blood.

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(1)

(iii)     With reference to haemoglobin, explain why carbon monoxide is toxic.

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(2)
(Total 16 marks)

Q13.
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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(Extra space) ________________________________________________________

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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)

Q14.
Chlorine can be found in water. One method for the determination of chlorine in water is to
use colorimetry.

A colourless sample of water from a vase of flowers was analysed after the addition of
compound Z as the addition of Z resulted in a purple solution.

Compound W

(a)     Calculate the Mr of Compound W.

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(1)

(b)     Determine the percentage, by mass, of nitrogen in this compound.

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 ___________________________________________________________________

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(1)

(c)     A simplified diagram of a colorimeter is shown below.

(i)      Suggest why it is important that the container for each sample has the same
dimensions.

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(1)

(ii)     Suggest why the coloured filter is used.

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(1)

(iii)    Suggest one reason why a colorimetric method might be chosen in preference

to titration.

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(1)
(Total 5 marks)

Q15.
This diagram represents the energy change that occurs when a d electron in a transition
metal ion is excited by visible light.

(a)     Give the equation that relates the energy change ΔE to the Planck constant h and
the frequency of the visible light v.

Use this equation and the information in the diagram to calculate a value for the
frequency of the visible light, and state the units.
 The Planck constant h = 6.63 × 10−34 J s.

Equation ___________________________________________________________

Calculation _________________________________________________________

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(2)

(b)     Explain why this electron transition causes a solution containing the transition metal
ion to be coloured.

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(2)

(c)     The energy change shown in the diagram represents the energy of red light and
leads to a solution that appears blue.
Blue light has a higher frequency than red light.

Suggest whether the energy change ΔE will be bigger, smaller or the same for a
transition metal ion that forms a red solution. Explain your answer.

Energy change ______________________________________________________

Explanation _________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(2)

(d)     State three different features of transition metal complexes that cause a change in
the value of ΔE, the energy change between the ground state and the excited state
of the d electrons.

Feature 1 ___________________________________________________________

Feature 2 ___________________________________________________________

Feature 3 ___________________________________________________________
(3)
(Total 9 marks)
 Q16.
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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(Extra space) ________________________________________________________

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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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(Extra space) ________________________________________________________

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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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(Extra space) ________________________________________________________

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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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(Extra space) ________________________________________________________

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(7)
(Total 19 marks)

Q17.
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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(Extra space) ________________________________________________________

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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)