Substitutionreactions

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Name:
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Substitution reactions
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Class:
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Date:
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Time: 265 minutes
Marks: 247 marks
Comments:
Page 1 of 57
Q1.
Which statement is correct about this reaction?
[Co(NH3)6]2+ + 3H2NCH2CH2NH2 → [Co(H2NCH2CH2NH2)3]2+ + 6NH3
A The co-ordination number of cobalt decreases.
B The enthalpy change is large and positive.
C The entropy change is large and positive.
D The shape of the complex changes from octahedral.
(Total 1 mark)
Q2.
Solution A contains the compound [Cu(H2O)6]Cl2
(a) State the type of bonding between the oxygen and hydrogen in this compound.
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(1)
(b) State why the chloride ions in this compound are not considered to be ligands.
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(c) An excess of ammonia was added to a sample of solution A to form solution B.
Write an ionic equation for the reaction that occurs when solution A is converted into
solution B and state the colour of solution B.
Equation
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Colour ____________________________________________________________
(2)
(d) Aqueous sodium carbonate was added to another sample of solution A to

form a blue-green solid C.
Identify the blue-green solid C.
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(1)
Page 2 of 57
(e) Reagent D was added to another sample of solution A to form a yellow-green
solution.
Identify reagent D and write an ionic equation for the reaction that occurs
when the yellow-green solution is formed from solution A.
Identity of reagent D
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Equation
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(2)
(f) Explain why colorimetry cannot be used to determine the concentration of

solutions containing [CuCl2]−
In your answer refer to the electron configuration of the metal ion.
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(2)
(Total 9 marks)
Q3.
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)
Page 3 of 57
(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.
Page 4 of 57
Percentage __________________ %
(4)
(g) State the colour change at the end point in this titration.
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(1)
(Total 12 marks)
Q4.
EDTA is a useful laboratory chemical and is found in a wide variety of commercial
products including detergents. It is very soluble in water and is often used in its ionic form
EDTA4− as shown in the diagram below.
(a) EDTA4− can act as a multidentate ligand.
Explain the meanings of the terms multidentate and ligand with reference to the
reaction of EDTA4− with [Cu(H2O)62+](aq) ions to form a complex ion.
Draw on the diagram above a separate circle around each atom that bonds to the
Cu2+ ion in this complex ion.
Multidentate ________________________________________________________
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Ligand _____________________________________________________________
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(3)
(b) Copper(II) compounds may be used as fungicides in vineyards. When used in this
way, copper(II) ions can enter the water supply and cause problems because they
are toxic in high concentrations.
The water supply near a vineyard can be tested for copper(II) ions by forming a blue
aqueous complex with EDTA4− ions. The concentration of this complex can be
determined using a colorimeter.
Outline the practical steps that you would follow, using colorimetry, to determine the
concentration of this complex in a sample of water.
Page 5 of 57
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(3)
(c) The concentration of copper(II) ions, in the sample of water, determined by

colorimetry was 7.56 × 10−5 mol dm−3.
This result was checked by titrating a sample of the water with a solution containing
EDTA4−(aq) ions.
The EDTA4−(aq) used in the titration had a concentration of 1.00 × 10−3 mol dm−3.
Write an equation for the reaction between [Cu(H2O)6]2+ and EDTA4− ions.
Calculate the volume of the EDTA4− solution needed to react with a 25.0 cm3 sample
of the water.
Justify whether this titration will give an accurate value for the concentration of
copper(II) ions. If necessary, suggest a practical step that would improve the
accuracy.
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(5)
(Total 11 marks)
Q5.
Consider the following reaction scheme that starts from aqueous [Cu(H2O)6]2+ ions.
Page 6 of 57
green-blue precipitate
For each of the reactions 1 to 4, identify a suitable reagent, give the formula of the copper-
containing species formed and write an equation for the reaction.
(a) Reaction 1
Reagent ___________________________________________________________
Copper-containing species _____________________________________________
Equation ___________________________________________________________
(3)
(b) Reaction 2
Reagent ___________________________________________________________
Equation ___________________________________________________________
(3)
(c) Reaction 3
Reagent ___________________________________________________________
Equation ___________________________________________________________
(3)
(d) Reaction 4
Reagent ___________________________________________________________
Equation ___________________________________________________________
(3)
(Total 12 marks)
Q6.
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
Page 7 of 57
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.
Page 8 of 57
(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)
Q7.
A desiccator can be used to dry precipitates as shown in the diagram.
Page 9 of 57
(a) Explain briefly how the precipitate in the desiccator becomes dry.
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(1)
(b) Anhydrous cobalt(II) chloride is blue. It is often added to the drying agent to indicate
the amount of moisture in the drying agent.
State the colour change of this cobalt compound that you would observe as the
drying process takes place.
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(1)
(Total 2 marks)
Q8.
(a) Because of the toxic nature of the copper(II) ion, a wide range of alternative anti-
fungal drugs has been developed for use in agriculture. One example is Zineb.
(i) The negative ion in Zineb could act as a bidentate ligand.
On the structure above, draw a ring around each of two atoms that could
provide the lone pairs of electrons when this ion acts as a bidentate ligand.
(1)
(ii) Calculate the Mr of Zineb. Give your answer to the appropriate precision.
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Page 10 of 57
(1)
(iii) Name the functional group formed at each end of the negative ion when all the
sulfur atoms in the structure of Zineb are replaced by oxygen atoms.
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(1)
(b) Zineb has been investigated for harmful effects. Generally, Zineb has been found to
be safe to use in agriculture. It is only slightly soluble in water and is sprayed onto
plants. A breakdown product of Zineb is ethylene thiourea (ETU), which is very
soluble in water. The structure of ETU is shown below.
Determine the percentage, by mass, of sulfur in ETU (Mr = 102.1).
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(1)
(c) Chromatography is a technique used to show the presence of a small amount of

ETU in Zineb.
Outline how this technique is used to separate and identify ETU from a sample of
Zineb powder.
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(4)
(Total 8 marks)
Page 11 of 57
Q9.
In its reactions with transition metal ions, ammonia can act as a Brønsted–Lowry base
and as a Lewis base.
(a) Define the term Lewis base.
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(1)
(b) Write an equation for a reaction between aqueous copper(II) ions ([Cu(H2O)6]2+) and
ammonia in which ammonia acts as a Brønsted–Lowry base. State what you would
observe.
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(2)
(c) Write an equation for a different reaction between aqueous copper(II) ions
([Cu(H2O)6]2+) and ammonia in which ammonia acts as a Lewis base but not as a
Brønsted–Lowry base. State what you would observe.
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(2)
(d) An excess of dilute ammonia solution is added to an aqueous solution containing

iron(II) ions in a test tube that is then left to stand for some time.
State and explain what you would observe.
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Page 12 of 57
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(4)
(e) Diaminoethane (H2NCH2CH2NH2), like ammonia, can react as a base and as a

ligand.
(i) Write an equation for the reaction that occurs between an aqueous solution of
aluminium chloride and an excess of aqueous diaminoethane.
Describe the appearance of the aluminium-containing reaction product.
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(3)
(ii) Write an equation for the reaction that occurs between an aqueous solution of
cobalt(II) sulfate and an excess of aqueous diaminoethane.
Draw a diagram to show the shape of and bonding in the complex product.
Write an equation for the reaction that would occur if the complex product of
this reaction were allowed to stand in contact with oxygen gas.
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(5)
(Total 17 marks)
Q10.
This question is about copper chemistry.
(a) Aqueous copper(II) ions [Cu(H2O)6]2+(aq) are blue.
Page 13 of 57
(i) With reference to electrons, explain why aqueous copper(II) ions are blue.
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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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(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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(3)
(b) Draw the structure of the ethanedioate ion (C2O42–).

Explain how this ion is able to act as a ligand.
Page 14 of 57
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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)
Q11.
Complexes containing transition elements have a wide variety of uses including acting as
dyestuffs like Prussian Blue.
Page 15 of 57
Cisplatin is a platinum-based chemotherapy drug used to treat various types of cancers. It
was the first member of a class of anti-cancer drugs that react with DNA in tumour cells.
Cisplatin is prepared from K2PtCl4 according to the following scheme.
All the reactions shown are reversible.
(a) Name the type of reaction occurring in all four steps of the scheme.
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(b) Explain why an excess of potassium iodide is used in Reaction 1.
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(c) (i) Write an equation for Reaction 1.
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(1)
(ii) Calculate the percentage atom economy for the formation of K2PtI4 in Reaction
1.
Show your working.
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Page 16 of 57
(2)
(d) In Reaction 3, silver nitrate solution is added to improve the yield of product.
(i) Write the simplest ionic equation for the reaction of iodide ions with silver
nitrate.
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(1)
(ii) Suggest why addition of silver nitrate improves the yield of product from
Reaction 3.
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(1)
(e) Suggest two reasons, other than poor practical technique, why the overall yield of
cisplatin in this synthesis may be low.
Reason 1 ___________________________________________________________
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Reason 2 ___________________________________________________________
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(2)
(f) The cisplatin formed in Reaction 4 is impure. Outline how the impure solid is purified
by recrystallisation.
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(3)
(g) Platinum compounds are highly toxic.
(i) State why cisplatin is used in cancer treatment despite its toxicity.
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(1)
(ii) Suggest a suitable precaution that should be taken by medical staff when
using cisplatin.
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Page 17 of 57
(1)
(Total 15 marks)
Q12.
(a) Some metal ions are toxic to humans. A substance that can be used to treat such
poisoning contains the ion EDTA4–.
EDTA4– forms very stable complexes with metal ions. These complexes are not
toxic.
(i) Write an equation for the reaction of EDTA4– with aqueous copper(II) ions,
[Cu(H2O)6]2+.
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(1)
(ii) A solution containing EDTA4– can also be used in a titration to determine the
concentration of metal ions in solution.
A river was polluted with copper(II) ions. When a 25.0 cm3 sample of the river
water was titrated with a 0.0150 mol dm–3 solution of EDTA4–, 6.45 cm3 were
required for complete reaction.
Calculate the concentration, in mol dm–3, of copper(II) ions in the river water.
Show your working.
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(2)
(b) The determination of the concentration of copper(II) ions in a single sample of river
water gives an unreliable value for the copper(II) ion pollution in the river.
Give one reason why this value is unreliable.
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(1)
(c) Silver complexes can be used to identify a particular organic functional group.
Give one example of a silver complex that can be used in this way and state the
organic functional group it identifies.
Silver complex _______________________________________________________
Organic functional group _______________________________________________

(2)
(Total 6 marks)
Q13.
Aqueous metal ions can be identified by test-tube reactions.
For each of the following, describe what you would observe.
Page 18 of 57
Write an equation or equations for any reactions that occur.
(a) The addition of aqueous sodium carbonate to a solution containing

[Fe(H2O)6]3+(aq) ions.
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(4)
(b) The addition of aqueous sodium hydroxide, dropwise until in excess, to a solution
containing [Al(H2O)6]3+(aq) ions.
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(4)
(c) The addition of dilute aqueous ammonia, dropwise until in excess, to a solution
containing [Cu(H2O)6]2+(aq) ions.
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(4)
(d) The addition of concentrated hydrochloric acid, dropwise until in excess, to a

solution containing [Cu(H2O)6]2+(aq) ions.
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Page 19 of 57
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(2)
(Total 14 marks)
Q14.
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+
H 2 O2
(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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(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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Page 20 of 57
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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)
Q15.
The scheme below shows some reactions of copper(II) ions in aqueous solution.
W, X, Y and Z are all copper-containing species.
Page 21 of 57
(a) Identify ion W. Describe its appearance and write an equation for its formation from
[Cu(H2O)6]2+(aq) ions.
Ion W ______________________________________________________________
Appearance _________________________________________________________
Equation ___________________________________________________________
(3)
(b) Identify compound X. Describe its appearance and write an equation for its
formation from [Cu(H2O)6]2+(aq) ions.
Compound X ________________________________________________________
Appearance _________________________________________________________
Equation ___________________________________________________________
(3)
(c) Identify ion Y. Describe its appearance and write an equation for its formation from
X.
Ion Y ______________________________________________________________
Appearance _________________________________________________________
Equation ___________________________________________________________
(3)
(d) Identify compound Z. Describe its appearance and write an equation for its
formation from [Cu(H2O)6]2+(aq) ions.
Compound Z ________________________________________________________
Appearance _________________________________________________________
Equation ___________________________________________________________
(3)
Page 22 of 57
(e) Copper metal can be extracted from a dilute aqueous solution containing copper(II)
ions using scrap iron.
(i) Write an equation for this reaction and give the colours of the initial and final
aqueous solutions.
Equation ______________________________________________________
Initial colour ____________________________________________________
Final colour ____________________________________________________

(3)
(ii) This method of copper extraction uses scrap iron. Give two other reasons why
this method of copper extraction is more environmentally friendly than
reduction of copper oxide by carbon.
Reason 1 ______________________________________________________
Reason 2 ______________________________________________________
(2)
(Total 17 marks)
Q16.
Ethanedioic acid is an important industrial chemical with a number of uses.
Ethanedioate ions, C2O42–, act as bidentate ligands with transition metal ions.
(a) Write an equation for the ligand substitution reaction of an excess of ethanedioate
ions with aqueous cobalt(II) ions.
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(1)
(b) The table below shows some standard electrode potentials.
E /V
Fe3+(aq) + e– → Fe2+(aq) +0.77
2CO2(g) + 2e– → C2O42–(aq) –0.49
Use E values from the table to explain why an iron(III) complex is not formed
when solutions containing ethanedioate ions and iron(III) ions are mixed.
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(2)
(Total 3 marks)
Page 23 of 57
Q17.
Which one of the following reactions in aqueous solution has the most positive change in
entropy?
A [Cu(H2O)6]2+ + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 4H2O
B [Cu(H2O)6]2+ + 4Cl− → [CuCl4]2− + 6H2O
C [Cu(H2O)6]2+ + EDTA4− → [Cu(EDTA)]2− + 6H2O
D [Cu(H2O)6]2+ + 2H2NCH2CH2NH2 → [Cu(H2NCH2CH2NH2)2(H2O)2]2+ + 4H2O

(Total 1 mark)
Q18.
Consider the reaction scheme below and answer the questions which follow.
(a) A redox reaction occurs when Cu(NO3)2 is decomposed by heat. Deduce the
oxidation state of nitrogen in Cu(NO3)2 and in NO2 and identify the product formed by
oxidation in this decomposition.
Oxidation state of nitrogen in Cu(NO3)2 ___________________________________
Oxidation state of nitrogen in NO2 _______________________________________
Oxidation product ____________________________________________________
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(3)
(b) Identify and state the shape of the copper-containing species present in solution A.
Page 24 of 57
Shape _____________________________________________________________
(2)
(c) (i) Identify the pale blue precipitate B and write an equation, or equations, to
show how B is formed from the copper-containing species in solution A.
Identity of precipitate B ___________________________________________
Equation(s) ____________________________________________________
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(ii) In what way does the NH3 behave as a Brønsted–Lowry base?
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(3)
(d) (i) Identify the copper-containing species present in solution C. State the colour
of this copper-containing species and write an equation for its formation from
precipitate B.
Identity ________________________________________________________
Colour ________________________________________________________
Equation ______________________________________________________
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(ii) In what way does the NH3 behave as a Lewis base?
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(4)
(e) Identify the copper-containing species present in solution D. State the colour and
shape of this copper-containing species.
Identity ____________________________________________________________
Colour _____________________________________________________________
Shape _____________________________________________________________
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(3)
(f) The oxidation state of copper in [CuCl4]3– is +1.
(i) Give the electron arrangement of a Cu+ ion.
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(ii) Deduce the role of copper metal in the formation of [CuCl4]3– from the copper-
containing species in solution D.
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(2)
Page 25 of 57
(Total 17 marks)
Q19.
(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.
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(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.
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(4)
(ii) Bidentate ligands replace unidentate ligands in a metal complex by a ligand

Write an equation for such a reaction and explain why this reaction occurs.
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Page 26 of 57
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(4)
(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.
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(5)
(Total 16 marks)
Q20.
(a) State what is meant by each of the following terms.
(i) Ligand ________________________________________________________
______________________________________________________________
(ii) Complex ion ___________________________________________________
______________________________________________________________
(iii) Co-ordination number ____________________________________________
______________________________________________________________
(3)
(b) Using complex ions formed by Co2+ with ligands selected from H2O, NH3, Cl–,
and EDTA4–, give an equation for each of the following.
(i) A ligand substitution reaction which occurs with no change in either the co-
ordination number or in the charge on the complex ion.
______________________________________________________________
Page 27 of 57
(ii) A ligand substitution reaction which occurs with both a change in the co-
ordination number and in the charge on the complex ion.
______________________________________________________________
(iii) A ligand substitution reaction which occurs with no change in the co-ordination
number but a change in the charge on the complex ion.
______________________________________________________________
(iv) A ligand substitution reaction in which there is a large change in entropy.
______________________________________________________________
(8)
(c) An aqueous solution of iron(II) sulphate is a pale-green colour. When aqueous

sodium hydroxide is added to this solution a green precipitate is formed. On
standing in air, the green precipitate slowly turns brown.
(i) Give the formula of the complex ion responsible for the pale-green colour.
______________________________________________________________
(ii) Give the formula of the green precipitate.
______________________________________________________________
(iii) Suggest an explanation for the change in the colour of the precipitate.
______________________________________________________________
______________________________________________________________
(4)
(Total 15 marks)
Q21.
(a) Give one example of a bidentate ligand.
___________________________________________________________________
(1)
(b) Give one example of a linear complex ion formed by a transition metal.
___________________________________________________________________
(1)
(c) Write an equation for a substitution reaction in which the complete replacement of
ligands in a complex ion occurs with a change in both the co-ordination number and
the overall charge of the complex ion.
___________________________________________________________________
(2)
(d) Write an equation for a substitution reaction in which the complete replacement of
ligands in a complex ion occurs without a change in either the co-ordination number
or the overall charge of the complex ion.
Page 28 of 57
___________________________________________________________________
(2)
(e) When a solution containing [Co(H2O)6]2+ ions is treated with a solution containing
EDTA4– ions, a more stable complex is formed. Write an equation for this reaction
and explain why the complex is more stable.
Equation __________________________________________________________
Explanation ________________________________________________________
___________________________________________________________________
(3)
(Total 9 marks)
Q22.
(a) State what is meant by the term co-ordinate bond.
___________________________________________________________________
___________________________________________________________________
(2)
(b) Define the terms Brønsted–Lowry acid and Lewis acid.
Brønsted–Lowry acid _________________________________________________
Lewis acid __________________________________________________________

(2)
(c) State what is meant by the term bidentate ligand.
___________________________________________________________________
___________________________________________________________________
(2)
(d) State how the co-ordination number of cobalt(II) ions in aqueous solution changes
when an excess of chloride ions is added. Give a reason for the change.
Change in co-ordination number _________________________________________
Reason for change ___________________________________________________
___________________________________________________________________
(2)
(e) Suggest why the enthalpy change for the following reaction is close to zero.
[Co(NH3)6]2+ + 3NH2CH2CH2NH2 → Co(NH2CH2CH2NH2)3]2+ + 6NH3
___________________________________________________________________
___________________________________________________________________
(2)
Page 29 of 57
(f) Deduce the formula of the compound formed when ethane-1,2-diamine is treated
with an excess of hydrochloric acid.
___________________________________________________________________
(1)
(Total 11 marks)
Q23.
Which one of the following statements about the reaction below is false?
[Cu(H2O)6]2+ + EDTA4− [Cu(EDTA)]2- + 6H2O
A [Cu(EDTA)]2− is a more stable complex than [Cu(H2O)6]2+
B Both [Cu(H2O)6]2+ and [Cu(EDTA)]2− are octahedral complexes.
C There is an increase in entropy when the reaction occurs.
D There is a redox reaction.

(Total 1 mark)
Q24.
Which one of the following statements is true?
A A blue solution containing the ion [CoCl4]2− turns pink when added to an excess of
water.
B A purple solution is formed when chlorine is bubbled into aqueous sodium bromide.
C A yellow precipitate is formed when aqueous silver nitrate is added to aqueous

sodium chloride.
D A green solution containing the ion [CuCl4]2− turns blue when added to an excess of
concentrated hydrochloric acid.
(Total 1 mark)
Page 30 of 57
Mark schemes
Q1.
C
[1]
Q2.
(a) Covalent
Do not allow dative covalent or coordinate (covalent)
1
(b) Cl(-) not donating lone pair (to Cu(2+))
Cl(-) does not form a coordinate/dative bond (to Cu(2+))

Allow without charges but penalise incorrect charges
Cl−/it is bonded ionically (to Cu2+)
1
(c) [Cu(H2O)6 ]2+ + 4NH3 → [Cu(NH3)4(H2O)2 ]2+ + 4H2O

1
Deep blue / Royal blue / Dark blue (solution)

1
Allow combination of:
[Cu(H2O)6 ]2+ + 2NH3 → [Cu(H2O)4(OH)2 ] + 2NH4+
[Cu(H2O)4(OH)2 ]+ 4NH3 → [Cu(NH3)4(H2O)2 ]2+ + 2H2O +
2OH−
Do not penalise missing square brackets
Ignore initial colour of Cu2+ (aq)
(d) CuCO3 or copper carbonate

Penalise incorrect oxidation state
Allow correct formula for basic copper carbonate
1
(e) HCl/ hydrochloric acid

Ignore concentration
Allow soluble chloride salt
Also allow any reagent which leads to a change in colour of
solution due to a change in ligands (e.g. NH2CH2CH2NH2) or
change in oxidation state (e.g. SO2 ) and associated correct
equations.
1
[Cu(H2O)6 ]2+ + 4Cl− → [CuCl4]2− + 6H2O

[Cu(H2O)6 ]2+ + 4HCl → [CuCl4]2− + 6H2O + 4H+
Mark independently
1
(f) (3)d10 or has full (3)d (sub) shell/orbital
Page 31 of 57
Penalise incorrect principal quantum number
1
It is colourless/cannot absorb (frequencies of) visible light

Ignore clear
1
[9]
Q3.
(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
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
Page 32 of 57
(g) Colourless to pale pink
1
[12]
Q4.
(a) Multidentate − EDTA can form many / six dative bonds with central cation.
1
Ligand − lone pair (on N or O of EDTA) can form dative bond with copper(II) ions.
1
6 circles drawn on EDTA4− structure − 2 × N and 4 × −O

1
(b) Calibrate a colorimeter / produce a calibration curve.

1
By testing the colorimeter with solutions of copper-EDTA complex of known

concentration.
1
Add excess EDTA salt to the sample.

1
(c) [Cu(H2O)6]2+ + EDTA4− ⟶ [Cu(EDTA)]2− + 6H2O

1
Amount of copper(II) = (25.0 × 7.56 × 10−5) /1000 = 1.89 × 10−6 mol

1
Volume of EDTA4− = (1.89 × 10−6 / 0.001) × 1000 = 1.89 cm3
This is too small to be accurate.

1
Dilute the EDTA4− solution / use larger volume of river water.

1
[11]
Q5.
(a) Reaction 1
General principles in marking this question
Square brackets are not essential
Penalise charges on individual ligands rather than on the
whole complex
Reagent and species can be extracted from the equation
Ignore conditions such as dilute, concentrated, excess
Reagent must be a compound NOT just an ion
Equations must start from [Cu(H2O)6 ]2+ except in part (b)
Mark reagent, species and equation independently
ammonia (NH3) (solution) / NaOH

1
Page 33 of 57
[Cu(H2O)6]2+ + 2NH3 → [Cu(H2O)4(OH)2] + 2NH4+ /
[Cu(H2O)6]2+ + 2OH- → [Cu(H2O)4(OH)2] + 2H2O

Do not allow OH– for reagent
Product 1, balanced equation 1
Allow either equation for ammonia
2
(b) Reaction 2
Ammonia (conc / xs)

1
[Cu(H2O)4(OH)2] + 4NH3 → [Cu(H2O)2(NH3)4]2+ + 2H2O + 2OH−

Note that the equation must start from the hydroxide
[Cu(H2O)4(OH)2]
2
(c) Reaction 3
Na2CO3 / any identified soluble carbonate / NaHCO3

Do not allow NaCO3 or any insoluble carbonate but mark on
1
[Cu(H2O)6]2+ + CO32- → CuCO3 + 6H2O
OR [Cu(H2O)6]2+ + Na2CO3 → CuCO3 + 6H2O + 2Na+
OR 2[Cu(H2O)6]2+ + 2CO32- → Cu(OH)2.CuCO3 + 11H2O + CO2
OR with NaHCO3
[Cu(H2O)6]2+ + HCO3− → CuCO3 + 6H2O + H+

2
(d) Reaction 4
HCl (conc / xs) / NaCl

Allow any identified soluble chloride
1
[Cu(H2O)6]2+ + 4Cl- → [CuCl4]2- + 6H2O

2
[12]
Q6.
(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
Page 34 of 57
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

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)
Page 35 of 57
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]
Q7.
(a) Water in the gaseous state from the precipitate absorbed by drying agent
OR
Water vapour from the precipitate absorbed by drying agent

Allow ‘water vapour reacts with drying agent’.
Do not allow ‘absorb water’ without qualification.
1
(b) (Blue to) pink / pink colour observed

1
[2]
Q8.
(a) (i) Two rings only around nitrogen or sulfur
Lose this mark if more than 2 atoms are ringed.
Do not allow two atoms at the same end of the ion.
1
(ii) 275.8
Accept this answer only. Do not allow 276
1
(iii) Carboxylate / COO–
Allow salt of carboxylic acid or just carboxylic acid.

1
(b) (32.1 / 102.1) = 31.4%

Do not penalise precision but do not allow 1 significant
figure.
1
(c) Zineb is mixed with a solvent / water

Max=2 if M1 missed
1
Use of column / paper / TLC

Lose M1 and M2 for GLC
1
Appropriate collection of the ETU fraction
Page 36 of 57
OR Appropriate method of detecting ETU
Allow ETU is an early fraction in a column or collecting a
range of samples over time, lowest retention time / travels
furthest on paper or TLC (allow 1 mark for having the longest
retention time in GLC).
1
Method of identification of ETU (by comparison with standard using

chromatography)
If method completely inappropriate, only M1 is accessible
1
[8]
Q9.
(a) Electron pair donor
Allow lone pair donor
1
(b) [Cu(H2O)6]2+ + 2NH3 Cu(H2O)4(OH)2 + 2NH4+
(Blue solution) gives a (pale) blue precipitate/solid

M2 only awarded if M1 shows Bronsted–Lowry reaction
1
(c) [Cu(H2O)6]2+ + 4NH3 [Cu(H2O)2(NH3)4]2+ + 4H2O

Allow formation in two equations via hydroxide
1
(Blue solution) gives a dark/deep blue solution

If (b) and (c) are the wrong way around allow one mark only
for each correct equation with a correct observation (max
2/4)
M2 only awarded if M1 shows Lewis base reaction
1
(d) (Start with) green (solution)

1
Green precipitate of Fe(H2O)4(OH)2 / Fe(OH)2 / iron(II) hydroxide

Do not allow observation if compound incorrect or not given
1
Slowly changes to brown solid

Allow red-brown ppt
Allow turns brown or if precipitate implied
Can only score M3 if M2 scored
1
(Iron(II) hydroxide) oxidised by air (to iron(III) hydroxide)

Allow Fe(OH)2 oxidised to Fe(OH)3 by air / O2
Ignore equations even if incorrect
1
Page 37 of 57
(e) (i) 2[Al(H2O)6]3+ + 3H2NCH2CH2NH2 2Al(H2O)3(OH)3 + 3[H3NCH2CH2NH3]2+
For correct Al species

1
For correct balanced equation
Allow equation with formation of 3[H2NCH2CH2NH3] + from 1
mol [Al(H2O)6]3+
1
White precipitate
1
(ii) [Co(H2O)6]2+ + 3H2NCH2CH2NH2 [Co(H2NCH2CH2NH2)3]2+ + 6H2O

1
Complex with 3 en showing 6 correct bonds from N to Co

Ignore charge
Accept N – N for ligand
Ignore incorrect H
If C shown, must be 2 per ligand
1
Co–ordinate bonds (arrows) shown from N to Co

Can only score M3 if M2 correct
1
4[Co(H2NCH2CH2NH2)3]2+ + O2 + 2H2O 4[Co(H2NCH2CH2NH2)3]3+ 4OH–
For Co(III) species

1
For balanced equation (others are possible)
Allow + O2 + 4H+ 2H2O
If en used can score M4 and M5 only
If Cu not Co, can only score M2 and M3
Allow N2C2H8 in equations
1
[17]
Q10.
(a) (i) absorbs (certain frequencies of) (white) light / photons
not absorbs white / u.v. light
1
d electrons excited / promoted

or d electrons move between levels / orbitals
d electrons can be implied elsewhere in answer
1
the colour observed is the light not absorbed / light

reflected / light transmitted
allow blue light transmitted
penalise emission of light in M3
1
Page 38 of 57
(ii) ΔE is the energy gained by the (excited) electrons (of Cu2+)
allow:
• energy difference between orbitals / sub-shells
• energy of photon / light absorbed
• change in energy of the electrons energy lost by
excited electrons
• energy of photon / light emitted
1
h (Planck's) constant
1
v frequency of light (absorbed by Cu2+(aq))

do not allow wavelength
If energy lost / photon lost / light emitted in M1 do not
penalised light emitted
1
(iii) [Cu(H2O)6]2+ + 4Cl– → [CuCl4]2– + 6H2O

note that [CuCl4–]2– is incorrect
penalise charges shown separately on the ligand and overall
penalise HCl
1
tetrahedral
1
Cl– / Cl / chlorine too big (to fit more than 4 round Cu)
allow
water smaller than Cl–
explanation that change in shape is due to change in
co-ordination number
1
(b)
allow:
• ion drawn with any bond angles
• ion in square brackets with overall / 2- charge shown
outside the brackets
• ion with delocalised O=C–O bonds in carboxylate
group(s)
1
lone pair(s) on O– / O
allow position of lone pair(s) shown on O in the diagram
even if the diagram is incorrect.
1
Page 39 of 57
(c) (i) [Cu(H2O)6]2+ + 2C2O42– → [Cu(C2O4)2(H2O)2]2– + 4H2O
product correct
1
equation balanced
1
6
note can only score M3 and M4 if M1 awarded or if complex
in equation has 2 waters and 2 ethanedioates
1
octahedral
If this condition is satisfied the complex can have the
wrong charge(s) to allow access to M3 and M4 but not M1
1
(ii)
ignore charges
diagram must show both ethanedioates with correct bonding
ignore water
1
90°
allow 180°
mark bond angle independently but penalise if angle
incorrectly labelled / indicated on diagram
1
[17]
Q11.
(a) (ligand) substitution
Allow ‘ligand exchange’.
1
(b) To displace the equilibrium to the right

To ensure reaction goes to completion.
1
To improve the yield

Allow ‘to replace all chlorines’.
1
(c) (i) K2PtCl4 + 4Kl → K2Ptl4 + 4KCl

Allow correct ionic equations PtCl42− + 4l− → Ptl42− + 4Cl−
Allow multiples and fractions.
1
Page 40 of 57
(ii) = (780.9) ×100 / (415.3 + 664)
Working must be clearly shown.
Allow one mark for correct relationship even if Mr values are
incorrect eg using values from ionic equation.
1
= 72.4
Allow 72%
1
(d) (i) Ag+ + I− → AgI

Ignore state symbols even if incorrect.
This equation only.
1
(ii) Stops the reverse reaction / equilibrium displaced to the right

1
(e) Number of steps in the process

Allow ‘equilibrium may lie on the reactant side’ / side
reactions / isomer formation.
1
Losses at each stage of the synthesis

Equilibrium losses or practical losses or yield not 100% for
each step.
1
(f) Minimum amount of hot solvent

Accept ‘small’ for minimum.
Accept water.
1
Cool / crystallise
1
Filter
1
(g) (i) Small amounts are more likely to kill cancer cells rather than the patient
1
(ii) Wear gloves / wash hands after use

Ignore masks.
Apply the list principle if more than one answer.
1
[15]
Q12.
(a) (i) EDTA4− + [Cu(H2O)6]2+ → [Cu(EDTA)]2− + 6H2O
1
(ii) (Mol EDTA = (6.45/1000) ×0.015 = )9.68 ×10−5 mol Cu(II)

1
Conc. Cu(II) = ((9.68 ×10−5) / 0.025 =) 0.00387 mol dm−3
Page 41 of 57
Correct answer without working gains M2 only.
1
(b) Samples may not be consistent throughout the river

OR
Concentration may vary over time
Ignore comments on technique.
1
(c) [Ag(NH3)2]+
Accept name eg diamminesilver(I) ion.

1
aldehyde
Allow CHO.
1
[6]
Q13.
(a) Brown ppt/solid
1
Gas evolved/effervescence
1
2[Fe(H2O)6]3+ + 3CO32– → 2Fe(H2O)3(OH)3 + 3CO2 + 3H2O

Must be stated, Allow CO2 evolved. Do not allow CO2 alone
Correct iron product (1) allow Fe(OH)3 and in equation
Balanced equation (1)
2
(b) White ppt/solid

1
Colourless Solution
Only award M2 if M1 given or initial ppt mentioned
1
[Al(H2O)6]3+ + 3OH– → Al(H2O)3(OH)3 + 3H2O

Allow [Al(H2O)6]3+ + 3OH– → Al(OH)3 + 6H2O
1
Al(H2O)3(OH)3 + 3OH– → [Al(OH)6]3– + 3H2O

Allow formation of [Al(H2O)6–x(OH)x](x–3)– where x = 4,5,6
Allow product without water ligands
Allow formation of correct product from [Al(H2O)6]3+
1
(c) Blue ppt/solid

1
(Dissolves to give a) deep blue solution

Only award M2 if M1 given or initial ppt mentioned
1
Page 42 of 57
[Cu(H2O)6]2+ + 2NH3 → Cu(H2O)4(OH)2 + 2NH4+
Allow [Cu(H2O)6]2+ + 2NH3 → Cu(OH)2 + 2NH4+ + 4H2O

Allow two equations: NH3 + H2O → NH4+ + OH–
then [Cu(H2O)6]2+ + 2OH– → Cu(OH)2 + 4H2O etc
1
Cu(H2O)4(OH)2 + 4NH3 → [Cu(H2O)2(NH3)4]2+ + 2OH– + 2H2O

Allow [Cu(H2O)6]2+ + 4NH3 → [Cu(H2O)2(NH3)4]2+ + 4H2O
1
(d) Green/yellow solution

1
[Cu(H2O)6]2+ + 4Cl– → [CuCl4]2– + 6H2O

1
[14]
Q14.
(a) (i) Ammonia
If reagent is missing or incorrect cannot score M3
1
Starts as a pink (solution)

1
Changes to a yellow/straw (solution)

Allow pale brown
Do not allow reference to a precipitate
1
(ii) (dark) brown

Do not allow pale/straw/yellow-brown (i.e. these and other
shades except for dark brown)
1
(b) (i) Ruby/red-blue/purple/violet/green

Do not allow red or blue
If ppt mentioned contradiction/CE =0
1
Green
If ppt mentioned contradiction/CE =0
1
[Cr(H2O)6]3+ + 6OH– → [Cr(OH)6]3– + 6H2O

1
Formula of product
Can score this mark in (b) (ii)
1
(ii) H2O2 + 2e– → 2OH–
Page 43 of 57
2[Cr(OH)6]3– + 3H2O2 → 2CrO42– + 8H2O + 2OH–
Allow 1 mark out of 2 for a balanced half-equation such as

Cr(III) → Cr(VI) + 3e–
or Cr3+ + 4H2O → CrO42– + 8H+ + 3e– etc
also for 2Cr(III) + 3H2O2 → 2CrO42– (unbalanced)
2
Yellow
Do not allow orange
1
(c) 2MnO4– + 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2

if no equation and uses given ratio can score M2, M3, M4 &
M5
1
Moles MnO4– = (24.35/1000) × 0.0187 = 4.55 × 10–4
Note value must be quoted to at least 3 sig. figs.

M2 is for 4.55 × 10–4
1
Moles H2O2 = (4.55 × 10–4) × 5/2 = 1.138 × 10–3
M3 is for × 5/2 (or 7/3)

Mark consequential on molar ratio from candidate's equation
1
Moles H2O2 in 5 cm3 original

M4 is for × 10
1
= (1.138 × 10–3) × 10 = 0.01138
Original [H2O2] = 0.01138 × (1000/5) = 2.28 mol dm–3
(allow 2.25-2.30)
M5 is for consequentially correct answer from (answer to
mark 4) × (1000/5)
Note an answer of between 2.25 and 2.30 is worth 4 marks)
If candidate uses given ratio 3/7 max 4 marks:
M1: Moles of MnO4– = 4.55 × 10–4
M2: Moles H2O2 = (4.55 × 10–4) × 7/3 = 1.0617 × 10–3
M3: Moles H2O2 in 5 cm3 original
= (1.0617 × 10–3) × 10 = 0.01062
M4: Original [H2O2] = 0.01062 × (1000/5) = 2.12 mol dm–3
(allow 2.10 to 2.15)
1
[17]
Q15.
(a) W is CuCl42–
1
Page 44 of 57
Yellow-green/yellow/green
Not necessary to indicate solution
Do not allow precipitate/solid
1
[Cu(H2O)6]2+ + 4Cl– → CuCl42– + 6H2O

Allow + 4HCl → 4H+
1
(b) X is Cu(H2O)4(OH)2
Allow Cu(OH)2/copper hydroxide
1
Blue precipitate/solid
Ignore shades
1
[Cu(H2O)6]2+ + 2NH3 → Cu(H2O)4(OH)2 + 2NH4+
Allow any balanced equation/equations leading to this

hydroxide or Cu(OH)2
But must use ammonia
1
(c) Y is [Cu(NH3)4(H2O)2]2+
Deep/dark/royal blue solution

QoL
1
Cu(H2O)4(OH)2 + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2H2O + 2OH–
Accept equation for formation from Cu(OH)2

1
(d) Z is CuCO3
Allow copper carbonate
1
Green solid/precipitate
Allow blue-green precipitate
1
[Cu(H2O)6]2+ + CO32– → CuCO3 + 6H2O

1
(e) (i) Cu2+(aq) + Fe(s) → Cu(s) + Fe2+(aq)

Allow hydrated ions
State symbols not essential but penalise if wrong
1
Blue
Do not allow description of solids
1
Green
Page 45 of 57
Allow yellow/(red-)brown/orange
1
(ii) Any two correct points about copper extraction from two
of these three categories:
Any relevant mention of lower energy consumption

Do not allow reference to electricity alone or to temperature
alone.
Any relevant mention of benefits of less mining (of copper ore)

Allow avoids depletion of (copper ore) resources
Less release of CO2 (or CO) into the atmosphere

Not just greenhouse gases. Must mention CO2 or CO
Max 2
[17]
Q16.
(a) 3C2O42− + [Co(H2O)6]2+ → [Co(C2O4)3]4− + 6H2O
Accept multiples.
Equation must have cobalt(II) hexaaqua ion.
1
(b) Ethanedioate ion reduces iron(III) ion or

iron(III) ion oxidises ethanedioate ion
Allow answer using equations.
1
(CO2 / C2O42−) more negative than (Fe3+ / Fe2+) or

(Fe3+ / Fe2+) > (CO2 / C2O42−)
or e.m.f. positive or cell voltage = +1.26
1
[3]
Q17.
C
[1]
Q18.
(a) oxidation state of N in Cu(NO3)2: +5;
1
oxidation state of N in NO2: +4;

1
oxidation product: oxygen;

1
(b) copper-containing species: [Cu(H2O)6]2+;

1
shape: octahedral;
1
Page 46 of 57
(c) (i) precipitate B: Cu(H2O)4(OH)2 or Cu(OH)2 or name;
1
equation: [Cu(H2O)6]2+ + 2NH3 → Cu(H2O)4(OH)2 + 2NH4+
OR
NH3 + H2O → NH4+ + OH–
and
[Cu(H2O)6]2+ + 2OH– → Cu(H2O)4(OH)2 + 2H2O;

1
(ii) NH3 accepts a proton;

1
(d) (i) identity: [Cu(NH3)4(H2O)2]2+;

1
colour: deep blue;

1
equation:
Cu(H2O)4(OH)2 + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2H2O + 2OH–;

1
(ii) NH3 is an electron pair donor;

1
(e) identity: [CuCl4]2–;

1
colour: yellow-green;
1
shape: tetrahedral;
1
(f) (i) Is2 2s2 2p6 3s2 3p6 3d10 ;

1
(ii) role of Cu: a reducing agent;

1
[17]
Q19.
(a) Ligand: -
atom, ion or molecules which can donate a pair of electrons to a metal ion.
1
co-ordinate bond:- a covalent bond

1
in which both electrons are donate by one atom

1
(b) (i) Two correct complex ions

1
Page 47 of 57
Balanced equation
1
Two correct colours

2
(ii) Complex with a bidentate ligand

1
Balanced equation
NB en not allowed as a ligand unless structure also given
1
More molecules/ions formed

1
Increase in entropy
1
more stable complex formed

1
Max 2
(c) ΔE; energy absorbed by electron, ground to excited state (QoL)

1
h; Planck’s constant or a constant

1
Change in
Oxidation state
1
Ligand
1
Co-ordination number
Apply list principle to incorrect additional answers
1
[16]
Q20.
(a) (i) An atom, ion or molecule which can donate a lone electron pair
1
(ii) A central metal ion/species surrounded by co-ordinately

bonded ligands or ion in which co-ordination number
exceeds oxidation state
1
(iii) The number of co-ordinate bonds formed to a central metal ion

or number of electron pairs donated or donor atoms
1
(b) (i) Allow the reverse of each substitution
[Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O
Page 48 of 57
Complex ions
1
Balanced
1
Allow partial substitution
(ii) [Co(H2O)6]2+ + 4Cl– → CoCl + 6H2O
Complex ions
1
Balanced
or H2O or NH3 or C2O by Cl–

1
eg. (iii)
Complex ions
1
Balanced
1
Allow all substitution except
(i) NH3 by H2O
(ii) more than 2Cl– substituted for NH3 or H2O
eg. (iv)
Complex ions
1
Balanced
or H2O or NH3 by and or by

1
(c) (i) [Fe(H O) ]

2 6
2+
(ii) Fe(OH) or Fe(OH) (H O) where x = 0 to 4

2 2 2 x
(iii) Fe is oxidised to Fe or Fe(OH)

2+ 3+
3
By oxygen in the air

1
[15]
Q21.
(a) C2O42– or H2NCH2CH2NH2 (1)
1
Page 49 of 57
(b) [AgCl2]– or [Ag(CN)2]– or [Ag(NH3)2]+ (1)
1
(c) e.g. [Co(H2O)6]2+ + 4Cl– → [CoCl4]2– + 6H2O

Correct complex species (1), Balanced (1), Only allow if species correct
2
(d) e.g. [Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O

Correct complex species (1), Balanced (1), Only allow if species correct
2
(e) Equation: [Co(H2O)6]2+ + EDTA4– → [Co(EDTA)]2– + 6H2O (1)

Explanation: More molecules on right hand side (1)
Entropy increases (1)
3
[9]
Q22.
(a) A shared electron pair or a covalent bond (1)
Both electrons from one atom (1)
OR when a Lewis base reacts with a Lewis acid
Mark points separately
2
(b) Brønsted-Lowry acid: A proton or H+ donor (1)

Not H3O+
Lewis acid: A lone or electron pair acceptor (1)
2
(c) Two atoms or two points of attachment (1)

Each donating a lone electron pair (1)
OR forms 2 (1) co-ordinate bonds (1)
OR donates two (1) pairs of electrons (1)
2
(d) Change in co-ordination number: 6 to 4 (1)
Reason for change: chloride ligands are larger than water ligands (1)
2
OR greater repulsion between chloride ligands
DO NOT allow chlorine or Cl
(e) Same number (1), and same type of bonds (1), broken and made
2
(f) ClNH3CH2CH2NH3Cl (1)

OR (NH3CH2CH2NH3)2+ 2Cl–
Allow C2H10N2Cl2 and NH3ClCH2CH2NH3Cl
1
[11]
Q23.
D
[1]
Page 50 of 57
Q24.
A
[1]
Page 51 of 57
Examiner reports
Q1.
D was the commonest incorrect response; presumably the presence of only 3 ligand
molecules in the product meant that some students did not realise that the cobalt still has
a co-ordination number of 6. 73.9% of students did, however, give the correct response.
Q2.
(a) 63.7% of candidates answered this correctly.
(b) Students usually answered this correctly (71.2%); a common incorrect answer was
that chloride ions did not have lone pairs.
(c) The colour of the solution formed was better known than the equation; many
students could not give a correct ionic equation and [Cu(NH3)6]2+ was a common
incorrect product.
(d) 78.1% of candidates answered this correctly.
(e) This part was generally answered well, with 59.4% of students gaining at least one
mark. Hydrochloric acid was often given as the reagent; chlorine was the most
common wrong answer. Equations were often unbalanced. A common incorrect
product was CuCl4−
(f) Students could often state that the electronic configuration was d10, but the effect on
electron transitions was less well known. Students often failed to realise the
importance of visible light being absorbed. Some students scored the mark by
stating the complex was colourless.
Q5.
This question was answered well and students of all abilities were able to score a
reasonable number of marks. The most common errors were to give wrong overall
charges for some of the complex ions and a failure to give a complete name or formula for
the reagent. In part (b), some students lost the equation mark because an aqueous
copper ion rather than the hydroxide precipitate was used as the starting material. Part (c)
was answered least well. Some students did not recognise that the green-blue precipitate
was copper carbonate and many who did were unable to give a correct formula for sodium
carbonate.
Q6.
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
Page 52 of 57
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.
Q7.
In this part (a) tested students on a relatively unfamiliar piece of apparatus. Unfortunately,
this was one of the less well-marked questions in the Written Test. The specific phrases
underlined in the Marking Guidelines were often ignored. A mark was often awarded for an
answer that did little more than restate the question.
Q8.
(a) In part (i), most students were able to identify two appropriate atoms in the structure,
but the ionic nature of Zineb resulted in many students failing to calculate its Mr
correctly in part (ii).In part (iii) proved to be demanding too, ester being the most
common error.
(b) The simple calculation in this part proved straightforward for most students.
(c) This part highlighted the difficulties students face when applying theoretical ideas.
Many students ignored the specific references to Zineb and ETU and wrote at length
about the theory of chromatography. It was not uncommon to see long answers that
did not specify the type of chromatography to be used, or make any mention of
Zineb or ETU. Students were similarly reluctant to use the information in the
questions to predict the outcomes for this particular separation. Such non-specific
answers received few marks. A significant number of students chose gas
chromatography, and even then could not make any use of the information at hand.
Q9.
Parts (a) and (b) were usually correct. Part (c) proved to be more difficult than part (b).
Weaker students gave an ammine complex with six rather than four ammonia molecules
and the charge of the ammine complex was often incorrect. Part (d) was very
discriminating. Only the best students identified the initial green precipitate as a form of
iron(II) hydroxide and went on to explain that this would be oxidised to a brown solid by
oxygen in the air. Part (e)(i) was set as a ‘stretch and challenge’ question and it proved to
be so. It was disappointing to find that only a very few students could draw a parallel with
the reaction in part (b) and hence predict that aluminium hydroxide would be formed. Part
(e)(ii) was very discriminating; most students could gain some credit but only the very best
students were able to gain four or more marks out of the five available. Only about 2% of
students were able to write a correct equation for the oxidation of the cobalt(II) complex.
Q10.
A similar question to that in part (a)(i) has been asked on several occasions. It is,
therefore, disappointing to find that candidates continue to lose a mark for the same error.
Weaker candidates continue to insist that the blue colour of copper (II) sulfate solution is
due to emission of blue light. They should understand that the blue colour is due to
transmission of light remaining from white light after other colours have been absorbed. In
part (a)(ii) about one third of candidates scored full marks. The most common error was
either to confuse h and ν or to state that ν represents the wavelength of light. Parts (a)(iii)
and (b) were answered well. Part (c)(i) proved to be much more challenging and only 28%
of candidates scored full marks. One common error was to give a wrong charge for the
Page 53 of 57
complex ion [Cu(C2O4)2(H2O)2]2–. Usually either the final 2- charge was missing or an
additional 2- charge was shown on the C2O4 ligands within the square brackets. The
other common error was to suggest a co-ordination number of four for the complex ion.
Part (c)(ii) was a testing question so it was pleasing to note that 35% of candidates scored
full marks.
Q11.
(a) While most candidates scored the mark in part (a) only the best candidates scored
both marks in part (b). Many candidates could not clearly explain the changes in an
equilibrium reaction.
(b) While most candidates scored the mark in part (a) only the best candidates scored
both marks in part (b). Many candidates could not clearly explain the changes in an
equilibrium reaction.
(c) The equation in part (i) proved quite demanding but most candidates had a good
appreciation of atom economy in part (ii), though mathematical slips were quite
common.
(d) (i) Most candidates scored the mark for the ionic equation in this part, the
presence of spectator ions was the usual error.
(ii) Answers to this part were disappointing. Most candidates explained what
happened in the reaction, rather than addressing the improvement. Many
answers that had little relevance to the question were incorrectly awarded a
mark.
(e) Many candidates had little awareness of the practical consequences of a multi-stage
process in this part. There was a tendency for candidates to repeat themselves and
for the centre, incorrectly, to award two marks.
(f) A surprising number could not give a satisfactory description of recrystallisation in this
part. Far too many candidates described completely different techniques. Centres
need to exercise some common sense in this type of question. For example, a
candidate cannot be awarded a mark for filtration or recrystallisation if a solution
was not prepared or if the candidate melted the mixture.
(g) (i) In this part many candidates described how cisplatin works rather than
addressing the balance of factors when using a toxic drug.
(ii) The safety factor in this part was well known.
Q12.
(a) While most candidates were able to write a correct equation in part (i), many
struggled with the mole calculation in part (ii). The usual error was in scaling for the
final volume.
(b) Some candidates continue to have difficulty with questions such as this part, once
again being unable to see beyond the possibility of an error in the analysis itself.
(c) Many centres were too generous in the first part of this part, awarding a mark for
Tollens’ reagent or silver nitrate in ammonia.
Q13.
Page 54 of 57
The general standard of answers to this question was very disappointing. It was clear to
examiners that a large majority of students could not recall what should be observed and
what happens in the various reactions given. In part (a), only 8% of candidates scored full
marks. Examiners hoped that candidates would understand that the action of carbonate
ions on a metal ion with a 3+ charge always leads to a hydroxide precipitate and evolution
of carbon dioxide gas, but most candidates were unable to give a full answer. In part (b)
most candidates suggested either the formation of a hydroxide precipitate or a complex
[Al(OH)6]3– (or [Al(OH)4]–) ion but only the best candidates knew that one would be formed
first followed by the other. The same sort of responses were common in part (c) with only
the best candidates explaining correctly that a blue hydroxide precipitate would be
followed by a deep blue solution containing [Cu(H2O)2(NH3)4]2+ ions. Answers to part (d)
were more often correct.
Q14.
This question also proved to be discriminating. In questions similar to part (a), candidates
may need to be reminded that when the question asks for a description of the colour
change, the colours of the initial and final solutions are required. Part (b)(ii) proved to be
very demanding. Only 3% of candidates scored all four marks. Most candidates did not
recognise that the equation should start with the [Cr(H2O)6] 3– ion and even when they did,
they could not usually write a balanced equation for the reaction with hydrogen peroxide.
Most candidates made a reasonable attempt at part (c) and the average score for this
question was about half marks. However, only about 7% of candidates scored full marks.
The most difficult mark to gain was for the reaction equation. The second most difficult
mark was the final one awarded for a correct conversion of moles of hydrogen peroxide in
5 cm3 of the original solution into a concentration.
Q15.
This question proved to be much more difficult than the other transition metal question.
Many candidates were not able to describe the appearance of W, X, Y and Z and were
also unable to write correct, balanced equations for the reactions. In part (a) the colour of
the [CuCl4]2- ion was not well known. In part (b), the colour was sometimes given but
without the physical state. A 'blue solid (or precipitate)' was required for the answer. To
give just 'blue' was not accepted as a correct description of the appearance of X. Many
candidates gave an equation using OH- ions. The correct answer required the use of
ammonia in a single equation or as part of two equations where the OH- ion was formed
by reaction of ammonia with water. Answers to part (c) were rarely correct. Only the best
candidates answered the question correctly and showed formation of the
[Cu(H2O)2(NH3)4]2+ ion from X, the hydroxide precipitate. The chemistry in part (d) was not
well known. Answers to part (e)(i) were of a higher standard but in part (e)(ii), very few
candidates could give two correct environmental reasons. Many candidates referred to
scrap iron even though the question specifically asked for reasons other than the use of
scrap iron.
Q16.
(a) Many candidates failed to score the mark in this part, an incorrect charge for the
complex being the usual error.
(b) Answers to this part were disappointing. Most candidates had some idea of the
answer but could not explain themselves clearly. Many centres awarded marks for
answers that made little sense.
Q18.
Page 55 of 57
Most candidates deduced correctly the oxidation state of nitrogen in NO2 but rather less
correctly determined the oxidation state of nitrogen in Cu(NO3)2- Many failed to identify the
oxidation product as oxygen with CuO being the most common incorrect answer. Part (b)
was generally well answered but identifying the precipitate B as copper(II) hydroxide, in
(c)(i), proved more difficult. Many candidates failed to give an equation, or a pair of
equations, showing the role of ammonia in the formation of this precipitate and lost a
mark. Most stated correctly that ammonia is a proton acceptor in answer to (c)(ii) but
many failed to correctly identify the copper-containing species in solution C as
[Cu(NH3)4(H2O)2]2+ with [Cu(NH3)6]2+ being the most common incorrect answer. The colour
of this complex was generally well known but only the better candidates were able to write
a correct equation for its formation. The role of ammonia as a Lewis base was generally
well known but the formula and colour of the copper-containing species, [CuC4l]2–, present
in solution D, were less well known. Part (f) proved to be particularly testing and only the
better candidates gave a correct electronic arrangement for a Cu+ ion and correctly
identified copper metal as the reducing agent in the formation of [CuCl4]3–.
Q19.
The term ligand was generally defined correctly but rather than define the term co-
ordinate bond many candidates described how such a bond is formed. Most candidates
gave a correct equation for a ligand substitution reaction in which both the co-ordination
number of the metal and the colour change. Marks were lost by candidates who gave
complex ions with charges missing or incorrect. The colours of ions were generally well
known. Complex ions formed with bidentate ligands were less well known and answers
were only accepted if the formula of the bidentate ligand was given. Most candidates gave
good explanations for why this type of substitution occurs. A general statement that the
symbol ΔE in the relationship ΔE = hV means ‘enthalpy change’ was not accepted and a
more precise answer linking the energy of the light absorbed to electron excitation was
required. A surprisingly large number of candidates gave an incorrect meaning for h most
commonly stating it to be the frequency of the light absorbed. The three factors which
result in a change in the frequency of light absorbed were well known with even the
weaker candidates often scoring full marks.
Q20.
Although part (a) was generally well done, a significant number of candidates lost marks
as their definitions were imprecise. This was most notable in section (iii) where candidates
who stated that the co-ordination number was the number of ligands co-ordinately bonded
to the central metal ion lost a mark as this statement is only correct if the ligands are
unidentate. The ligand substitution reactions in part (b) were generally well done.
Candidates should be reminded that although it is necessary to use the charges on
ligands when deducing the overall charge on the complex ion, these charges should not
be included in the formula of the complex. The answer to (b)(iii) was not, as a significant
number thought, an acid-base reaction. Most candidates understood the chemistry
required in part (c) but some lost a mark as they failed to state that the oxidation of iron(II)
to iron(III) was caused by oxygen in the air.
Q21.
Parts (a), (b), (c) and (d) were well answered by most candidates. Although most also
gave a correct equation in part (e) many failed to explain the stability of the complex in
terms of the change in the number of molecules when the complex is formed and the
consequent increase in entropy during the reaction.
Q22.
Page 56 of 57
Many candidates stated correctly in part (a) that both electrons are supplied by one atom
when a co-ordinate bond is formed but some lost a mark when they failed to state that the
bond formed is a covalent bond. Part (b) was also well answered with only the weaker
candidate failing to score full marks. The term bidentate ligand was generally well
understood although some candidates found difficulty expressing their answer. Part (d)
was similarly well answered. By contrast neither part (e) nor part (f) were well done.
Although there were some excellent answers to part (e), many candidates failed to
recognise that the same number and the same type of bond were being broken and made
when ammonia ligands are replace by ethane-1, 2-diamine. Some candidates gave
incorrect answers based on entropy rather than enthalpy change. Although most
candidates would have been able to state that each of the nitrogen atoms in ethane-1, 2-
diamine had a lone electron pair only the very best realised that (NH3CH2CH2NH3)2+2Cl-
would be formed when it reacts with an excess of hydrochloric acid.
Page 57 of 57

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_______________________

Time: 265 minutes

Marks: 247 marks

[Co(NH3)6]2+ + 3H2NCH2CH2NH2 → [Co(H2NCH2CH2NH2)3]2+ + 6NH3

A The co-ordination number of cobalt decreases.

B The enthalpy change is large and positive.

C The entropy change is large and positive.

D The shape of the complex changes from octahedral.

(c) An excess of ammonia was added to a sample of solution A to form solution B.

(d) Aqueous sodium carbonate was added to another sample of solution A to

Identify the blue-green solid C.

(f) Explain why colorimetry cannot be used to determine the concentration of

In your answer refer to the electron configuration of the metal ion.

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

Write an equation for this reaction.

(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.

(a) EDTA4− can act as a multidentate ligand.

(c) The concentration of copper(II) ions, in the sample of water, determined by

Copper-containing species _____________________________________________

Copper-containing species _____________________________________________

Copper-containing species _____________________________________________

Copper-containing species _____________________________________________

(i) Write an equation for this reaction.

(i) The negative ion in Zineb could act as a bidentate ligand.

Determine the percentage, by mass, of sulfur in ETU (Mr = 102.1).

(c) Chromatography is a technique used to show the presence of a small amount of

(a) Define the term Lewis base.

(d) An excess of dilute ammonia solution is added to an aqueous solution containing

(e) Diaminoethane (H2NCH2CH2NH2), like ammonia, can react as a base and as a

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

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

Cisplatin is prepared from K2PtCl4 according to the following scheme.

All the reactions shown are reversible.

(b) Explain why an excess of potassium iodide is used in Reaction 1.

(c) (i) Write an equation for Reaction 1.

(g) Platinum compounds are highly toxic.

Silver complex _______________________________________________________

Organic functional group _______________________________________________

For each of the following, describe what you would observe.

(a) The addition of aqueous sodium carbonate to a solution containing

(d) The addition of concentrated hydrochloric acid, dropwise until in excess, to a

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

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

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

Initial colour ____________________________________________________

Final colour ____________________________________________________

(b) The table below shows some standard electrode potentials.

Fe3+(aq) + e– → Fe2+(aq) +0.77

2CO2(g) + 2e– → C2O42–(aq) –0.49

A [Cu(H2O)6]2+ + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 4H2O

B [Cu(H2O)6]2+ + 4Cl− → [CuCl4]2− + 6H2O

C [Cu(H2O)6]2+ + EDTA4− → [Cu(EDTA)]2− + 6H2O

D [Cu(H2O)6]2+ + 2H2NCH2CH2NH2 → [Cu(H2NCH2CH2NH2)2(H2O)2]2+ + 4H2O

Oxidation state of nitrogen in Cu(NO3)2 ___________________________________

Oxidation state of nitrogen in NO2 _______________________________________

Oxidation product ____________________________________________________

Copper-containing species _____________________________________________

Identity of precipitate B ___________________________________________

(ii) In what way does the NH3 behave as a Brønsted–Lowry base?