7 Transition Elements WS

237
TRANSITION ELEMENTS WS 1
4
1 2 The ions of transition elements form complexes by reacting with ligands.
(a) (i) State what is meant by the terms:
complex, .............................................................................................................................
.............................................................................................................................................
ligand. .................................................................................................................................
.............................................................................................................................................
(ii) Two of the complexes formed by copper are [Cu(H2O)6]2+ and CuCl 42–.
Draw three-dimensional diagrams of their structures in the boxes and name their shapes.
[Cu(H2O)6]2+ CuCl 42–
shape: .............................................. shape: ..............................................
(iii) Platinum forms square-planar complexes, in which all four ligands lie in the same plane as
the Pt atom.
There are two isomeric complexes with the formula Pt(NH3)2Cl 2.
Suggest the structures of the two isomers, and, by comparison with a similar type of
isomerism in organic chemistry, suggest the type of isomerism shown here.
Structures of isomers:
isomer 1 isomer 2
Type of isomerism: .............................................................................................................

[7]
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CEDAR COLLEGE TRANSITION ELEMENTS WS 1

238
5
(b) Copper forms two series of compounds, one containing copper(II) ions and the other containing
copper(I) ions.
(i) Complete the electronic structures of these ions.
Cu(II) [Ar] ..................................................................................................................
Cu(I) [Ar] ..................................................................................................................
(ii) Use these electronic structures to explain why
copper(II) salts are usually coloured,
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
copper(I) salts are usually white or colourless.
.............................................................................................................................................
.............................................................................................................................................
[5]
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239
6
(c) Copper(I) oxide and copper(II) oxide can both be used in the ceramic industry to give blue,
green or red tints to glasses, glazes and enamels.
The table lists the values for some compounds.
compound / kJ mol–1
Cu2O(s) –168.6
CuO(s) –157.3
Cu(NO3)2(s) –302.9
NO2(g) +33.2
(i) Copper(II) oxide can be produced in a pure form by heating copper(II) nitrate. Use suitable
values from the table to calculate the H o for this reaction.
1
Cu(NO3)2(s) CuO(s) + 2NO2(g) + 2 O2(g)
H o = ......................... kJ mol–1
(ii) Copper(I) oxide can be produced from copper(II) oxide.
Use suitable values from the table to calculate H o for the reaction.
1
2CuO(s) Cu2O(s) + 2 O2(g)
H o = ......................... kJ mol–1
Hence suggest whether a low or a high temperature of oxidation would favour the
production of copper(I) oxide. Explain your reasoning.
.............................................................................................................................................
.............................................................................................................................................
[4]
[J’14 P41 Q2]
[Total: 16]
© UCLES 2014 9701/41/M/J/14

Section A
Answer all the questions

240in the spaces provided.
2 1 (a) (i) On the diagrams below, show the outer electron arrangements of the atoms and ions
indicated. (Use the symbol to represent a pair of electrons in an orbital.)
4s 4s 4s
3d 3d 3d
Fe Fe2+(aq) Zn2+(aq)
(ii) Use the above diagrams to explain why Fe2+(aq) ions are coloured, whereas Zn2+(aq) ions
are colourless.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[4]
(b) When concentrated HCl is added to a solution of Cu2+(aq) ions, the solution turns yellow.
(i) State the formula of the species responsible for the yellow colour and name the type of
reaction that has occurred.
.............................................................................................................................................
.............................................................................................................................................
(ii) Ammonia can react as a base or as a ligand.

Describe the colour changes that occur when NH3(aq) is gradually added, with stirring, to
the yellow solution, until the NH3(aq) is in excess.
Identify the three ions or compounds responsible for the new colours.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[7]
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3
(c) When aqueous solutions of KI and K2S2O8 are mixed almost no reaction occurs, but when a
few drops of Fe2+(aq) or Fe3+(aq) are added, iodine, I2(aq), is produced at a steady rate.
(i) Write an equation for the overall reaction.
.............................................................................................................................................
(ii) State the precise role of the iron ions during this reaction.
.............................................................................................................................................
(iii) By means of equations or otherwise, explain why the presence of either Fe2+ or Fe3+ is able
to speed up the reaction.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[3]
[J’14[Total:
P42 Q1]
14]

242
4
32 (a) Complete the electron configurations for Ni and Ni2+.
3d 4s
Ni [Ar]
Ni2+ [Ar]
[2]
(b) The presence of electrons in d orbitals is responsible for the colours of transition element
compounds.
(i) The d orbitals in an isolated transition metal atom or ion are all at the same energy level.
What term is used to describe orbitals that are at the same energy level?
.............................................................................................................................................
(ii) Complete the diagram to show the splitting of the d orbital energy levels in an octahedral
complex ion.
energy
(iii) On the axes below, sketch the shapes of one d orbital from the lower energy level and one
d orbital from the higher energy level.
lower energy level higher energy level
z z
x x
y y
5 [4]
(c) The octahedral complex [Ni(H2O)6]2+ is green. Explain the origin of the colour of this complex.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
..............................................................................................................................................
© UCLES 2014 9701/41/O/N/14 [3]
(d) When NH3(aq) is added to the green solution containing [Ni(H2O)6]2+, a grey-green precipitate,
A, is formed. This precipitate dissolves in an excess of NH3(aq)TRANSITION
CEDAR COLLEGE to give a blue-violet solution,WS
ELEMENTS B. 1
Suggest formulae for A and B and write equations for the two reactions producing A and B.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [3]
243
(d) When NH3(aq) is added to the green solution containing [Ni(H2O)6]2+, a grey-green precipitate,
A, is formed. This precipitate dissolves in an excess of NH3(aq) to give a blue-violet solution, B.
Suggest formulae for A and B and write equations for the two reactions producing A and B.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [4]
[N’14 P41 Q2]
[Total: 13]
5
43 5 due to their partially-filled d orbitals.

Transition elements have characteristic properties
3(a) Transition
(i) Whichelements have characteristic
two elements properties
in the first row due to their
of the d-block havepartially-fi
only onelled d orbitals.
electron in the 4s orbital of
their neutral atoms?
(a) (i) Which two elements in the first row of the d-block have only one electron in the 4s orbital of
their neutral atoms?
.............................................................................................................................................
.............................................................................................................................................
(ii) The d orbitals in an isolated transition metal atom or ion are described as being degenerate.
(ii) The d orbitals in an isolated transition metal atom or ion are described as being degenerate.
What is meant by the term degenerate?
What is meant by the term degenerate?
.............................................................................................................................................
.............................................................................................................................................
(iii) Sketches of the shapes of the atomic orbitals from the d subshell are shown.
(iii) Sketches of the shapes of the atomic orbitals from the d subshell are shown.
In an octahedral complex, the d orbitals are split into two groups at different energy levels.
In an octahedral complex, the d orbitals are split into two groups at different energy levels.
On the diagram below, write an ‘H’ in the box under each of the orbitals at the higher
On the
energy diagram below, write an ‘H’ in the box under each of the orbitals at the higher
level.
energy level.
z z z z z
z z z z z
y y x x yy xx yy xx xx x x
yy yy
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[4] [4]

244
6
(b) The following scheme shows some reactions of Cu2+(aq).
a few drops of NH3(aq)

Cu2+(aq) pale blue precipitate A
concentrated
excess NH3(aq)
HCl
solution of C solution of B
heat with Cu(s)
[CuCl 2]– (aq)
(i) Suggest the formula of each of the following.
A .........................................................................................................................................
B .........................................................................................................................................
C .........................................................................................................................................
(ii) State the colour of the following solutions.
solution of B ........................................................................................................................
solution of C ........................................................................................................................
(iii) Name the type of reaction that occurs when C is heated with copper.
.............................................................................................................................................
Deduce the role of the copper metal in this reaction.
.............................................................................................................................................
[6]
(c) When the solution containing the complex [CuCl 2]– is poured into water, a precipitate of CuCl
is formed. CuCl is white because it does not absorb visible light.
Explain why CuCl does not absorb visible light.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
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245
7
(d) The complex ion [Cr(H2O)6]3+ is coloured because it absorbs visible light. The absorption
spectrum for [Cr(H2O)6]3+ is shown below.
absorbance
400 500 600

violet red
wavelength / nm
Suggest the colour of this complex ion. Explain your answer.
....................................................................................................................................................
.............................................................................................................................................. [2]
[N’14 P43 Q3]
[Total: 14]

246
5
53 The transition element iron is the most abundant element in the Earth’s core.
(a) What is meant by the term transition element?
....................................................................................................................................................
.............................................................................................................................................. [1]
(b) In aqueous solution, iron can form complex ions which contain ligands.
(i) Name the type of bonding that occurs between a ligand and a transition element.
....................................................................................................................................... [1]
(ii) Which of the following species can act as a ligand?

Complete the table by placing a tick ( ) in the appropriate column to indicate whether the
species can act as a ligand or not.
can act cannot act

species
as a ligand as a ligand
NO3–
BF3
H2NCH2CH2NH2
NH4+
[2]
(c) Manganese ions, Mn2+(aq), show some similar chemical properties to those of copper(II) ions,
Cu2+(aq).
Use this information and the Data Booklet to suggest the formula of the manganese species
formed in each of the following reactions. State the type of reaction taking place in each case.
formula of manganese type of

species formed reaction
Mn2+(aq) + NaOH(aq)
Mn2+(aq) + concentrated HCl
Mn2+(aq) + H2O2(aq)
[5]
[N’15 P41 Q3]
[Total: 9]

247
4
4
62 (a) Cobalt is a transition element and forms compounds with oxidation numbers +2 and +3.
2 (a) Cobalt is a transition element and forms compounds with oxidation numbers +2 and +3.
Complete the electronic structures for
Complete the electronic structures for
a cobalt atom, 1s22s22p6.................................
a cobalt atom, 1s22s22p6.................................
cobalt in the +3 oxidation state. 1s222s222p66.................................
cobalt in the +3 oxidation state. 1s 2s 2p ................................. [2]
[2]
(b) (i) In an aqueous solution of cobalt(II) sulfate the cobalt forms complex ions.
(b) (i) In an aqueous solution of cobalt(II) sulfate the cobalt forms complex ions.
What is meant by the term complex ion?
What is meant by the term complex ion?
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
....................................................................................................................................... [1]
(ii) State two chemical properties of cobalt, other than the formation of complexes, that are
(ii) not
State two by
shown chemical properties
a typical of cobalt, other than the formation of complexes, that are
s-block element.
not shown by a typical s-block element.
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
....................................................................................................................................... [2]
(c) Cobalt(II) ions, Co2+2+(aq), show some chemical properties similar to those of copper(II) ions,
(c) Cu (aq).II) ions, Co (aq), show some chemical properties similar to those of copper(II) ions,
Cobalt(
2+
Cu2+(aq).
Use this information and the Data Booklet to suggest the formula of the cobalt species formed
inUse thisofinformation
each and
the following the Data State
reactions. Booklet
thetotype
suggest the formula
of reaction takingofplace
the cobalt species
in each case. formed
in each of the following reactions. State the type of reaction taking place in each case.
formula of cobalt
formula of cobalt type of reaction
species formed type of reaction
species formed
Co2+2+(aq) + an excess of NH3(aq)

Co (aq) + an excess of NH3(aq)
Co2+2+(aq) + OH––(aq)
Co (aq) + OH (aq)
Co2+2+(aq) + S2O82–2–(aq)
Co (aq) + S2O8 (aq)
[5]
[5]
© UCLES 2015 9701/43/O/N/15

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248
5
(d) Some transition elements are present in superconductors. These are materials that conduct
electricity with little or no resistance.
Compound Q is a superconductor and contains 13.4% yttrium, 41.2% barium, 28.6% copper
and 16.8% oxygen by mass.
(i) Show that the empirical formula of Q is YBa2Cu3O7. Show all your working.
[1]
(ii) The table shows the oxidation numbers of yttrium, barium and oxygen in Q.
element oxidation number
yttrium +3
barium +2
oxygen –2
Calculate the average oxidation number of copper in Q.
[1]
(iii) Hence deduce the oxidation number of each of the three copper atoms in Q.
[1]
[N’15[Total:
P43 Q2]13]

249
6
73 (a) Complete the electronic structures of the following species.
Co [Ar] ................................................................
Co2+ [Ar] ................................................................

[2]
(b)
metal ion forms a tetrahedral complex the d orbitals are split into two groups of different
energies.
Complete an orbital energy diagram to show this, indicating the number of orbitals in each
group.
increasing
energy
isolated transition metal ion tetrahedral complex

[1]
(c) Cobalt(II) forms a six co-ordinate complex containing three water molecules and three chloride
ions.
(i) Write the formula of this complex showing the overall charge, if appropriate.
....................................................................................................................................... [1]
(ii) Explain, with the aid of diagrams, how many isomers of the complex in (i) exist.
[2]
(d) Platinum(II) forms a four co-ordinate complex containing two ammonia molecules and two
chloride ions.
(i) Write the formula of this complex showing the overall charge, if appropriate.
....................................................................................................................................... [1]
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250
7
(ii) This complex exists as two isomers.
Draw the structure of these isomers and give their names.
............................................... ...............................................
[3]
(iii) One of the isomers in (ii) is an important anticancer drug.
State which isomer this is and explain why this isomer is effective.
isomer ...................................
reason .................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[2]
(e) Transition metal ions often exist as hexa-aqua complexes in aqueous solution. The reactions
which involve ligand exchange are reversible.
[Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O
(i) Write an expression for the stability constant, Kstab, for this equilibrium. Give its units.
Kstab =
units = ..............................
[2]
(ii) The numerical value for Kstab for this equilibrium at 298 K is 1.20 1013.
Explain how this value relates to the relative stabilities of the two complexes.
.............................................................................................................................................
....................................................................................................................................... [1]
[M’16 P42 Q3]
[Total: 15]
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251
3
82 (a) (i)
the cobalt atom, Co 1s22s22p6 .........................................
the cobalt(II) ion, Co2+ 1s22s22p6 .........................................

[1]
(ii) State the colours you would observe when concentrated HCl (aq) is added to an aqueous
solution of cobalt(II) nitrate, Co(NO3)2.
Give the formulae and geometry of the complexes formed.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [5]
(b) There are two isomers with the formula Ni(R3P)2I2, but only one structure with the formula
Co(R3P)2I2. (R = alkyl, R3P is a monodentate ligand)
Draw diagrams showing the structure of Co(R3P)2I2 and the two isomers of Ni(R3P)2I2.
Ni(R3P)2I2 Ni(R3P)2I2
Co(R3P)2I2
[3]
[J’16 P41 Q2]
[Total: 9]

252
19
9 10 (a) (i)
Fe 1s22s22p6................................... [1]
(ii) In some of its complexes, the Fe3+ ion has only one unpaired electron in its d orbitals.
Using the symbols and to represent electrons of opposite spins, complete the following
this Fe3+ ion.
........ ........
3d energy
........ ........ ........

[1]
(b) A solution containing a mixture of Sn2+(aq) and Sn4+(aq) is added to a solution containing a
mixture of Fe2+(aq) and Fe3+(aq).
Use E o data from the Data Booklet to predict the reaction that might take place when the two
solutions are mixed, and write an equation for the reaction.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
20
(c) Hexaaquairon(III –
,
equilibrium 1, and a deep-red complex with thiocyanate ions, SCN–, equilibrium 2.
[Fe(H2O)6]3+ + F– [Fe(H2O)5F]2+ + H2O equilibrium 1 Kstab = 2.0 105 mol–1 dm3

violet colourless
[Fe(H2O)6]3+ + SCN– [Fe(H2O)5SCN]2+ + H2O equilibrium 2 Kstab = 1.0 103 mol–1 dm3
violet deep-red
(i) Predict and explain the sequence of colour changes you would observe in each of the
following experiments.
A few drops of KSCN(aq) are added to 5 cm3 of Fe3+(aq), followed by a few drops of
KF(aq).
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
A few drops of KF(aq) are added to 5 cm3 of Fe3+(aq), followed by a few drops of
KSCN(aq).
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[4]
(ii) What type of reaction is occurring during the experiments in (i)?

....................................................................................................................................... [1]
.............................................................................................................................................
253
.............................................................................................................................................
A few drops of KF(aq) are added to 5 cm3 of Fe3+(aq), followed by a few drops of
KSCN(aq).
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[4]
(ii) What type of reaction is occurring during the experiments in (i)?
....................................................................................................................................... [1]
[N’16 P42 Q10]
[Total: 9]
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Examinations Syndicate (UCLES), which is itself a department of the University of Cambridge.
© UCLES 2016 9701/42/M/J/16

2
Answer all the questions in the spaces provided.

254
101 Copper is a transition element and has atomic number 29.
(a)
state.
copper atom [Ar] ..............................................................
..............................................................
[2]
(b)
[Cu(H2O)6] l– [CuCl 4]2– 2 O
(i) Name the type of reaction occurring here.
....................................................................................................................................... [1]
(ii) State the colours of these two complex ions.
[Cu(H2O)6] ................................................. [CuCl 4]2– ................................................ [1]
(iii) State the shape of the [CuCl 4]2– ion.
....................................................................................................................................... [1]
(iv) Write the expression for the stability constant, Kstab, for this equilibrium.
Kstab =
[1]
(c) Copper also forms the complex ions [Cu(NH3)2(H2O)4] and [Cu(en)(H2O)4] where en is the
bidentate ligand ethane-1,2-diamine, H2NCH2CH2NH2.
[Cu(H2O)6] 3 [Cu(NH3)2(H2O)4] 2 O equilibrium 1
[Cu(H2O)6] en [Cu(en)(H2O)4] 2 O equilibrium 2
(i) What is meant by the term bidentate ligand?
.............................................................................................................................................
....................................................................................................................................... [2]
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3
(ii) The table lists the values of stability constants for these two complexes.
stability constant, Kstab

[Cu(NH3)2(H2O)4] 7.94 107
[Cu(en)(H2O)4] 3.98 1010
What do these Kstab values tell us about the relative positions of equilibria 1 and 2?
.............................................................................................................................................
....................................................................................................................................... [1]
(d) Nickel forms the complex ion [Ni(en)3] in which it is surrounded octahedrally by six nitrogen
atoms.
(i) Name the type of stereoisomerism displayed by [Ni(en)3] .
....................................................................................................................................... [1]
(ii) Draw three-dimensional diagrams to show the two stereoisomers of [Ni(en)3] .
[3]
[N’16 P41 Q1]
(e) Ethane-1,2-diamine is a useful reagent in organic chemistry.
(i) Explain how the amino groups in ethane-1,2-diamine allow the molecule to act as a
Brønsted-Lowry base.
.............................................................................................................................................
....................................................................................................................................... [2]
(ii) Write an equation for the reaction of ethane-1,2-diamine with an excess of

hydrochloric acid.
....................................................................................................................................... [1]

256
8
114 (a)
Explain what is meant by the term transition element.
....................................................................................................................................................
.............................................................................................................................................. [1]
(b) The following scheme shows some reactions of [Co(H2O)6] .
[Co(H2O)6]2+
excess
OH– (aq) excess NH3(aq)
Cl – (aq)
precipitate A solution of B solution of C
(i) State the formula of each of the following.
A ......................................................
B ......................................................
C ......................................................
[2]
(ii) State the colour of the following solutions.
[Co(H2O)6] .................................................
solution of B ................................................
solution of C ................................................
[2]
[N’16 P41 Q4]
(c) standard electrode potential.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
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2
Answer all the questions in the spaces provided.

257
121 Transition elements are important metals because of their characteristic properties.
(a) Define what is meant by a transition element.
....................................................................................................................................................
.............................................................................................................................................. [1]
(b) (i) For each of the following complexes, state the co-ordination number and the oxidation
number of the transition element present.
co-ordination number oxidation number
[Ni(CN)2(NH3)2]
[CrCl 2(H2O)4]+
[2]
(ii) State the type of bonding that exists between the ligand and the metal ion in these
complexes.
....................................................................................................................................... [1]
(iii) Suggest the structure of [Ni(CN)2(NH3)2] and name its shape.
name of shape ....................................................................................................................

[2]
(c) The complex ion [Cr(H2O)6]3+ can be converted into [CrCl 2(H2O)4]+.
(i) Suggest a suitable reagent for this conversion.
....................................................................................................................................... [1]
(ii) State the type of reaction in (i).
....................................................................................................................................... [1]
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3
(d) The [CrCl 2(H2O)4]+ complex ion shows stereoisomerism.
(i) Name this type of stereoisomerism.
....................................................................................................................................... [1]
(ii) Draw three-dimensional diagrams to show the two stereoisomers of [CrCl 2(H2O)4]+.
[3]
[N’16 P42 Q1]
[Total: 12]

259
12
136 (a) (i) Draw the shape of one of the d orbitals.
[1]
(ii)
Ni 1s22s22p63s23p6 ................................................
Ni3+ 1s22s22p63s23p6 ................................................

[1]
(b) (i) Complete the diagram to show how the presence of ligands around an isolated transition
metal ion affects the energy of the d orbitals.
energy
degenerate
d orbitals
octahedral isolated transition tetrahedral

complex metal ion complex
[1]
(ii) Explain why transition metal complexes are coloured.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
(iii) [Cu(H2O)6]2+ is pale blue but [Cu(NH3)4(H2O)2]2+ is deep purple-blue.
Suggest a reason for this.
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
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260
13
(c) The diagram shows the visible spectrum of a solution of [V(H2O)6]3+.
absorption
blue green red
350 400 450 500 550 600 650 700

wavelength / nm
State and explain what colour the solution is.
colour of solution .......................................................
explanation ................................................................................................................................
.............................................................................................................................................. [2]
(d) (i) 2 O)6]3+ reacts to form a mixture of isomeric octahedral

complexes.
[V(H2O)6]3+ + 2Cl – [V(H2O)4Cl 2]+ + 2H2O
Complete the three-dimensional diagrams to show the two isomers of [V(H2O)4Cl 2]+.
V V
isomer 1 isomer 2
[2]
(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
....................................................................................................................................... [1]

261
14
(e) (i) The complex [V(H2O)6]3+ en 2 NCH2CH2NH2

form a mixture of isomeric octahedral complexes.
[V(H2O)6]3+ + 3en [V(en)3]3+ + 6H2O
Complete the three-dimensional diagrams to show the two isomers of [V(en)3]3+.
You may use to represent en.

N N
V V
isomer 1 isomer 2
[2]
(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
....................................................................................................................................... [1]
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262
15
(f) The reaction of [Ni(H2O)6]2+ with aqueous ammonia produces the complex [Ni(NH3)6]2+.
[Ni(H2O)6]2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq) + 6H2O(l)
(i) Write the expression for Kstab for [Ni(NH3)6]2+.
Kstab =
[1]
(ii) [Ni(H2O)6]2+ also reacts with en to form [Ni(en)3]2+.

The values of the stability constants for the two complexes are shown.
Kstab [Ni(NH3)6]2+ = 4.8 107 mol–6 dm18
Kstab [Ni(en)3]2+ = 2.0 1018 mol–3 dm9
A solution containing equal numbers of moles of ammonia and en is added to [Ni(H2O)6]2+.
State which complex is produced in the larger amount. Explain your answer.
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
(iii) Adding a limited amount of en to [Ni(H2O)6]2+ forms the complex [Ni(H2O)2(en)2]2+.
Suggest the number of possible stereoisomers of [Ni(H2O)2(en)2]2+. Explain your answer.

You are advised to include three-dimensional diagrams in your answer.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
[M’17 Q6]
[Total: 18]

263
6
14 (d) The cyanate ion, NCO–, can act as a monodentate ligand.
(i) State what is meant by the terms
monodentate, ......................................................................................................................
.............................................................................................................................................
ligand. .................................................................................................................................
.............................................................................................................................................
[2]
Silver ions, Ag+, react with cyanate ions to form a linear complex.
(ii) Suggest the formula of this complex, including its charge.
....................................................................................................................................... [2]
[J’17 P41 Q2]
(e) When heated with HCl (aq), organic isocyanates, RNCO, are hydrolysed to the amine salt,
RNH3Cl, and CO2.
RNCO + H2O + HCl RNH3Cl + CO2
A 1.00 g sample of an organic isocyanate, RNCO, was treated in this way, and the CO2 produced
was absorbed in an excess of aqueous Ba(OH)2 according to the equation shown. The solid
BaCO3 precipitated weighed 1.66 g.
Ba(OH)2(aq) + CO2(g) BaCO3(s) + H2O(l)
(i) Calculate the number of moles of BaCO3 produced.
moles of BaCO3 = .............................. [1]
(ii) Hence calculate the Mr of the organic isocyanate RNCO.
Mr of RNCO = .............................. [1]
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8
153 Bubbling air through different aqueous mixtures of CoCl 2, NH4Cl and NH3 produces various complex
ions with the general formula [Co(NH3)6–nCl n]3–n.
(a) (i) Determine the oxidation state of the cobalt in these complex ions.
....................................................................................................................................... [1]
(ii) Name the two types of reaction undergone by the cobalt ions during the formation of these
complex ions.
.............................................................................................................................................
....................................................................................................................................... [2]
(iii) The complex [Co(NH3)4Cl 2]+ shows isomerism.
Draw three-dimensional structures of the two isomers, and suggest the type of isomerism
shown here.
isomer 1 isomer 2
type of isomerism ...............................................................................................................

[3]
(b) (i) What is meant by the term co-ordination number?
.............................................................................................................................................
....................................................................................................................................... [1]
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99
9
(ii)(ii)Complete
Complete thethe
table byby
table predicting appropriate
predicting appropriateco-ordination
co-ordinationnumbers,
numbers,formulae
formulae and
and charges
charges
(ii)for Complete
the the table
complexes C, by E
D, predicting
and F. appropriate co-ordination numbers, formulae and charges
for the complexes C, D, E and F.
for the complexes C, D, E and F.
co-ordination
co-ordination formula
formula charge
charge
complex
complex metal
metalionion ligand
ligand co-ordination formula charge
complex metal ion ligand number
number ofofcomplex
complex on
on complex
complex
number of complex on complex
C C Cr3+
Cr 3+ CN
CN– –
33 –
C Cr3+ CN– 3–
D D Ni2+
Ni H2H
NCH 2CH 2NH 66
H22NCH 2CH 2NH
2+
D Ni2+ NCH 2CH2NH2
2 2 6
E EE Pt2+
Pt 2+
Pt2+ ClCl
– –
Cl – 2–
2–
2–
F FF FeFe
3+ 3+
Fe3+ OO
O C–CO
– –
C–CO
C–CO
– – [Fe(O
[Fe(O 2CCO
[Fe(O2CCO )]
22)33]
2CCO2)3]
2– 22 2 –
2 2
[6]
[6]
(c)(c)
Iron(
(c) III)III
Iron(
Iron( III))forms
formsformscomplexes
complexes in in
complexes inseparate
separate reactions
reactions
separate with
reactionswith both
withboth SCN
bothSCN
SCN– –– ions and Cl––– ions.
ions
ionsand
andCl
Cl ions.
ions.
FeFe
Fe 3+(aq)+ +SCN
3+ 3+
(aq) (aq) + SCN
– ––(aq)
SCN(aq)(aq) [FeSCN]
[FeSCN] 2+2+
[FeSCN] (aq)
(aq)
2+
(aq) equilibrium
equilibrium 1
equilibrium 1
FeFe
3+ 3+(aq) + 4Cl – –(aq) [FeCl 4–]]–(aq) equilibrium
equilibrium 2
3+ – –
Fe (aq)(aq)+ +4Cl
4Cl (aq)
(aq) [FeCl
[FeCl (aq)
4]4(aq) equilibrium 2
(i) (i) Write

(i)Write thethe
Write the expressions
expressions
expressions forfor
for
thethe
the stability
stability
stability constants,
constants,KK
constants, K , ,for
stab
stab
stab
, for these
forthese two
thesetwo equilibria.
twoequilibria.
equilibria.
Include
Include
Include units
unitsunits in your
in your
in your answers.
answers.
answers.
KKstab1 =
Kstab1 = =
stab1
units
units== ..............................
=..............................
..............................
units
KKstab2 =
Kstab2 = =
stab2
units
units = ..............................
units = ..............................
[3]
[3]
(ii)
(ii) An
Anequilibrium
equilibriumcan canbe besetsetupup between
between these these two two complexes
complexes as as shown
shown in equilibrium 3.
(ii) An equilibrium can be set up between these two complexes as shown in equilibrium 3.
[FeCl–44]–]–(aq)
[FeCl (aq) ++ SCN SCN ––
(aq)
(aq) [FeSCN]
[FeSCN] 2+(aq) + 4Cl ––(aq)
2+
(aq) + 4Cl (aq) equilibrium 3
[FeCl 4] (aq) + SCN (aq) –
[FeSCN] (aq) + 4Cl –(aq)
2+
equilibrium 3
Write
Writean anexpression
expressionfor forKKeq3 in terms of K stab1 and
eq3 in terms of Kstab1 and K Kstab2 .
stab2.
Write an expression for Keq3 in terms of Kstab1 and Kstab2.
KKeq3 = ............................................................................................................................. [1]
eq3 = .............................................................................................................................
Keq3 = ............................................................................................................................. [1]
(iii)
(iii) The
Thenumerical
numericalvalues valuesfor forthese
these stability
stability constants
constants are are shown.
shown.
(iii) The numerical values for these stability constants are shown.
stab1 =
KKstab1 =1.41.4 10 1022 KKstab2
stab2 =
= 8.0
8.0 10 10–2 –2
Kstab1 = 1.4 10 2
Kstab2 = 8.0 10 –2
Calculate
Calculatethe thevalue
valueof ofKKeq3
eq3 stating
stating its
its units.
units.
Calculate the value of Keq3 stating its units.
eq3==........................................................
KKeq3 ........................................................ units
units == .............................................................
.............................................................
Keq3 = ........................................................ units = ............................................................. [2]
[J’17 P41 Q3] [2]
[Total: 19]
[Total: 19]
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266
12
12
12
165 (a) 1,2-diaminoethane, en, H2NCH2CH2NH2, is a bidentate ligand.
(i) What is meant by the terms bidentate and ligand?
bidentate .............................................................................................................................
bidentate .............................................................................................................................
bidentate .............................................................................................................................
ligand ..................................................................................................................................
ligand ..................................................................................................................................
ligand ..................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
[2]
.............................................................................................................................................
[2]
[2]
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2]++.
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2] +.
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2] .
Complete the three-dimensional diagrams of the isomers in the boxes.
You may use N N toto represent en.
You may use N N represent en.
You may use N N to represent en.
Cr Cr Cr
Cr
Cr Cr
Cr Cr
Cr
[3]
[3]
[3]
(b) Copper forms complexes with NH3 and en according to equlibria 1 and 2.
(b)
(b) Copper
Copper forms
forms complexes
complexes with
with NHNH33 and
and enen according
according to
to equlibria
equlibria 11 and
and 2.
2.
equilibrium 1 Cu (aq) + 4NH3(aq)
2+
[Cu(NH3)4] (aq)
2+
equilibrium
equilibrium 11 Cu2+(aq)
Cu 2+
(aq) ++ 4NH
4NH33(aq)
(aq) [Cu(NH
[Cu(NH33))44]]2+(aq)
2+
(aq)
equilibrium 2 Cu2+(aq) + 2en(aq) [Cu(en)2]2+(aq)
equilibrium
equilibrium 22 Cu
Cu2+(aq)
2+
(aq) ++ 2en(aq)
2en(aq) [Cu(en)
[Cu(en)22]]2+(aq)
2+
(aq)
(i) Write the expressions for the stability constants, Kstab1 and Kstab2, for equilibria 1 and 2.
(i)
(i) Write
Write the
the expressions
expressions for
for the
the stability
stability constants,
constants, KKstab1 and Kstab2, for equilibria 1 and 2.
stab1 and Kstab2, for equilibria 1 and 2.
Kstab1 =
KKstab1 ==
stab1
units = ..............................
units
units == ..............................
..............................
Kstab2 =
KKstab2 ==
stab2
units = ..............................
units
units == ..............................
[3]
..............................
[3]
[3]
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13
(ii) An equilibrium is set up when both en and NH3 ligands are added to a solution containing
Cu2+(aq) as shown in equilibrium 3.
equilibrium 3 [Cu(NH3)4]2+(aq) + 2en(aq) [Cu(en)2]2+(aq) + 4NH3(aq)
Write an expression for the equilibrium constant, Keq3, in terms of Kstab1 and Kstab2.
Keq3 = ............................................................................................................................. [1]
(iii) The numerical values for these stability constants are shown.
Kstab1 = 1.2 1013 Kstab2 = 5.3 1019
Calculate the value of Keq3 stating its units.
Keq3 = ......................................................... unit = ..............................................................

[2]
[J’17 P42 Q5]
(c) S o values for equilibria 1 and 2 differ greatly, as can be seen in the table. All values are at a
temperature of 298 K.
equilibrium H o / kJ mol–1 S o / J K–1 mol–1 G o / kJ mol–1

1 –92 –60 –74
2 –100 +40
(i) Explain why is so different from .
.............................................................................................................................................
....................................................................................................................................... [1]
(ii) Calculate at 298 K.
= ........................................... kJ mol–1
[2]
(iii) What conclusion can be made about the relative feasibility of equilibria 1 and 2?
Explain your answer.
....................................................................................................................................... [1]
(iv) Using data from the table, suggest a value of H o for equilibrium 3.
....................................................................................................................................... [1]
(v) State the type of reaction that is occurring in equilibrium 2.
....................................................................................................................................... [1]
[Total: 17]

268
8
174 (a) Describe and explain how the density and melting point of cobalt compare to those of calcium.
density of cobalt .........................................................................................................................
explanation ................................................................................................................................
....................................................................................................................................................
melting point of cobalt ................................................................................................................
explanation ................................................................................................................................
....................................................................................................................................................
[3]
(b) Transition metals can form complexes.
What is meant by the term transition metal complex?
....................................................................................................................................................
.............................................................................................................................................. [1]
(c) (i) Cobalt can form the compounds [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br.
These two compounds are structural isomers.
structural isomer.
.............................................................................................................................................
....................................................................................................................................... [1]
(ii) Draw a three-dimensional diagram to show the structure of the ion [Co(NH3)5Br]2+.
Name its shape.
[Co(NH3)5Br]2+
shape ............................................................................................................................ [1]
(iii) State the type of bonding between the cobalt ion and NH3 groups in the [Co(NH3)5Br]2+ ion.
....................................................................................................................................... [1]
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9
(iv) State the oxidation number of cobalt in
) Br]2+
3 5 oxidation number of Co = ..............................
) SO4]+
3 5 oxidation number of Co = ..............................
[1]
(d) Solutions of the compounds [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br can be distinguished from
each other by simple chemical tests.
Assume that any species bonded to the cobalt ion does not react in these tests.
Complete the table with two different tests that could be used to positively identify each
compound. Give the expected observation with each compound.
observation with observation with

test
[Co(NH3)5Br]SO4(aq) [Co(NH3)5SO4]Br(aq)
[2]
(e) The two compounds [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are different colours.
Explain why the colours of the two compounds are different.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
(f)
as heterogeneous or homogeneous.
Complete the table by placing one tick ( ) in each row to indicate the type of catalysis in each
reaction.
heterogeneous homogeneous
Fe in the Haber process
Fe2+ in the I– / S2O82– reaction
NO2 in the oxidation of SO2
V2O5 in the Contact process

[2]
[N’17[Total:
P41 Q4]
14]

270
16
187 (a) Complete the following electronic structures.
2
2s22p6 ..............................
III) ion, Fe3+ 1s22s22p6 ..............................

[1]
(b) Solutions of iron(III) salts are acidic due to the equilibrium shown.
[Fe(H2O)6]3+(aq) [Fe(H2O)5(OH)]2+(aq) + H+(aq) Ka = 8.9 10–4 mol dm–3
Calculate the pH of a 0.25 mol dm–3 FeCl 3 solution.
pH = .............................. [2]
(c) The table shows numerical values of the stability constants for the following equilibrium where
M can be one of the metal ions listed and L one of the ligands which replaces one H2O
molecule.
[M(H2O)6]n+(aq) + L–(aq) [M(H2O)5L](n–1)+(aq) + H2O(l)
metal ion, M ligand, L stability constant, Kstab

Fe3+ F– 1.0 106
Fe3+ Cl – 2.5 101
Fe3+ SCN– 9.0 102
Hg2+ Cl – 5.0 106
(i) What is meant by the term stability constant, Kstab?
.............................................................................................................................................
....................................................................................................................................... [1]
(ii) Use the data in the table to predict the formula of the complex formed in the greatest
amount when
–
and SCN– ions is added to
Fe (aq),
3+
.............................................................................................................................................
3+
and Hg2+ ions is added to
Cl (aq).
–
.............................................................................................................................................
[1]
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17
Ethanedioate ions, –O2CCO2–, are bidentate ligands. The abbreviation ed 2– can be used to represent
ethanedioate ions.
(d) The complex [Fe(ed )2Cl 2]3– can be formed according to the equation shown.
[Fe(H2O)4Cl 2]+(aq) + 2ed 2–(aq) [Fe(ed )2Cl 2]3–(aq) + 4H2O(l)
Write the expression for the equilibrium constant, Kstab, and state its units.
Kstab =
units ..............................
[2]
(e) [Fe(ed )2Cl 2]3– shows geometrical and optical isomerism.
(i) Complete the three-dimensional diagrams to show the three stereoisomers of [Fe(ed )2Cl 2]3–.
You may use –O O– to represent ed .

2–
Fe Fe
isomer A isomer B
Fe
isomer C
[3]
(ii) Give the letters of two isomers of [Fe(ed )2Cl 2]3– which are geometrical isomers of each
other.
....................................................................................................................................... [1]
(iii) Give the letters of the two isomers of [Fe(ed )2Cl 2]3– which show optical isomerism.
....................................................................................................................................... [1]
(iv) Give the letter of the isomer which has no dipole moment.
....................................................................................................................................... [1]
[N’17 P41 Q7]
[Total: 13]

272
11
195 (a) The arrangement of the anions around a cation is called the geometry of the cation; e.g. in
[CuCl 4]2– the geometry of copper is tetrahedral and the co-ordination number of copper is 4.
The geometry of a cation in an ionic compound can be predicted from the ratio of the ionic radii
of the cation and anion involved.
cation radius geometry

anion radius of cation
0.155 – 0.225 trigonal planar

0.225 – 0.414 tetrahedral
0.414 – 0.732 octahedral
Use data from the Data Booklet to predict the geometry of, and hence the co-ordination number
of, the cation for
l,
geometry of Na+ = ............................. co-ordination number of Na+ = .............................
l 2.
geometry of Mg2+ = ............................. co-ordination number of Mg2+ = .............................

[2]
(b) Magnesium(I) chloride, MgCl, is an unstable compound and readily decomposes as shown.
2MgCl (s) Mg(s) + MgCl 2(s)
Use the following data to calculate the enthalpy change of this reaction.
MgCl (s) = –106 kJ mol–1

MgCl 2(s) = – 642 kJ mol–1
enthalpy change = ............................. kJ mol–1 [1]
[N’17 P42 Q5]

273
13
206 (a) transition metal complex.
....................................................................................................................................................
.............................................................................................................................................. [1]
(b) Platinum can form the compound [Pt(NH3)4Cl 2][PtCl 4].
State the co-ordination numbers and the oxidation numbers of the platinum in the two ions of
this compound.
co-ordination number oxidation number
[Pt(NH3)4Cl 2]2+
[PtCl 4]2–
[2]
(c) Draw three-dimensional diagrams to show the structures of the two isomers of [Pt(NH3)4Cl 2]2+.
[2]
(d) Solutions of the compounds [Pt(NH3)4Cl 2]Br2 and [Pt(NH3)4Br2]Cl 2 can be distinguished from
each other by a simple chemical test. Assume that any species bonded to the platinum ion
does not react in this test.
Complete the table with a test that could be used to positively identify each compound. Give
details of expected observations with each compound.
observation with observation with

test
[Pt(NH3)4Cl 2]Br2 [Pt(NH3)4Br2]Cl 2
[2]

274
14
(e) In this question you should consider geometrical and optical isomerism.
What type of isomerism is shown by the following complexes?

You should answer geometrical, optical, both or neither.
octahedral [Co(NH2CH2CH2NH2)2Cl 2]+ .......................................................................................
square planar [Ni(CN)2Cl 2]2– ......................................................................................................
tetrahedral [CuBr2Cl 2]2– .............................................................................................................

[3]
[N’17 P42 Q6]
(f) Many enzymes contain transition metal complexes.
Describe, with the aid of a suitably labelled diagram, how an enzyme catalyses the breakdown
of a substrate molecule.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [3]
[Total: 13]
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7
21 (b) Adding a measured quantity of KCN to a solution of NiCl 2 produces the complex [Ni(CN)2Cl 2]x.
(i) Deduce the overall charge, x, on this complex.
x = .............................. [1]
The complex can exist as two separate isomers with the same geometry (shape) around the
nickel ion.
(ii) State the type of isomerism shown by these isomers.
....................................................................................................................................... [1]
(iii) If bromide ions are present in the solution, the complex [Ni(CN)2Cl Br]x can form.
Assuming that [Ni(CN)2Cl Br]x has the same geometry as [Ni(CN)2Cl 2]x, state the number
of isomers of [Ni(CN)2Cl Br]x that could exist, and draw their structures in the box.
2 Cl Br]x ..............................
structures of the isomers of [Ni(CN)2Cl Br]x
[3]
(c) An aqueous solution of KCN is gradually added to a solution of NiSO4 until the KCN is in
excess. The following series of reactions takes place.
KCN more KCN KCN in excess

NiSO4 C D E
green precipitate yellow solution red solution
The oxidation state of nickel does not change during these reactions.
None of C, D or E contains sulfur.
C contains no potassium.
The K : Ni ratio in D is 2 : 1.
The K : Ni ratio in E is 3 : 1.
Use the information to suggest the formulae of C, D and E.
C ................................................................................................................................................
D ................................................................................................................................................
E ................................................................................................................................................
[3]
[M’18 P42 Q3]
[Total: 15]

276
10
225 (a) (i)
1s22s22p63s2 .................................................................................................................. [1]
(ii) State the two highest oxidation states of chromium commonly seen in its compounds.
....................................................................................................................................... [1]
(b) Six different compounds or complexes, H, J, K, L, M and N, are formed when an excess
of aqueous NH3, aqueous NaOH and concentrated aqueous HCl are separately added to
separate solutions containing Cu2+(aq) or Co2+(aq).
reagent
solution an excess of
an excess of an excess of
concentrated
NH3(aq) NaOH(aq)
HCl (aq)
Cu2+(aq) H J K
Co2+(aq) L M N
(i) State the colours of the following compounds or complexes.
H .........................................................................................................................................
K .........................................................................................................................................
M .........................................................................................................................................
[2]
(ii) Write the formulae of the following compounds or complexes.
L .........................................................................................................................................
N .........................................................................................................................................
[2]
(iii) State the appearance of compound J.
....................................................................................................................................... [1]
[M’18 P42 Q5]
[Total: 7]
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9
235 Copper is a transition element with atomic number 29.
(a) +
ion.
Cu atom 1s22s22p6 ..................................
Cu+ ion 1s22s22p6 ..................................

[2]
(b) Cu+ ions form a linear complex with Cl – ions, which are monodentate ligands.
Draw the structure of this complex and include its overall charge.
[2]
(c) Cu2+ ions exist as [Cu(H2O)6]2+ complex ions in aqueous solution.
Complete a three-dimensional diagram to show the shape of this complex.

Name its shape.
Label and state the value of one bond angle.
Cu
name of shape ........................................

[2]

278
10
(d) When NH3(aq) is added to Cu2+

occur as shown.
dropwise NH3(aq) excess NH3(aq)

[Cu(H2O)6]2+ A B
reaction 1 reaction 2
For each reaction, describe what you would see and write an equation.
reaction 1
observation ................................................................................................................................
....................................................................................................................................................
equation .....................................................................................................................................
reaction 2
observation ................................................................................................................................
....................................................................................................................................................
equation .....................................................................................................................................
[4]
(e) EDTA4– is a polydentate ligand. When a solution of EDTA4– is added to a solution containing
[Cu(H2O)6]2+ a new complex is formed. The formula of this complex is [CuEDTA]2–.
(i) Name the type of reaction occurring here.
....................................................................................................................................... [1]
(ii) Write an expression for the stability constant, Kstab, of [CuEDTA]2– in this reaction.
[1]
(iii) The numerical value of the Kstab of [CuEDTA]2– is 6.3 1019 at 298 K.
State what this tells us about the [CuEDTA]2– complex ion.
....................................................................................................................................... [1]
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11
(f) Ethanedioate ions, C2O42–, can act as a bidentate ligand.
(i) Explain what is meant by the term bidentate ligand.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
(ii) When ethanedioate ions are added to a solution of zirconium ions, Zr 4+, a complex ion
containing four C2O42– ions and one Zr 4+ ion is formed. All four ethanedioate ions act as
bidentate ligands in this complex.
Give the formula of this complex ion and explain why this complex is not octahedral.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
[J’18 P41 17]

[Total: Q5]

280
8
245 Cobalt is a transition element with atomic number 27. Cobalt forms ions with charges of +2 and +3.
Both these ions form complexes.
(a) 2+
ion.
Co atom 1s22s22p6 ..................................
Co2+ ion 1s22s22p6 ..................................

[2]
(b) One Co2+ ion can form a tetrahedral complex ion with four Cl – ions. This complex is blue.
(i) What is meant by the term complex ion?
.............................................................................................................................................
....................................................................................................................................... [1]
(ii) Draw the tetrahedral complex ion formed by one Co2+ ion with four Cl – ions. Your drawing
should clearly show three-dimensional shape, and should include the overall charge on
the ion.
Co
[2]
(iii) Explain why many transition metal complexes are coloured.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [3]
(iv) Using ideas from your answer to (iii) suggest why the colour of the complex formed by one
Co2+ ion with four Cl – ions is blue.
.............................................................................................................................................
....................................................................................................................................... [1]
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281
9
(c) Describe the colour change that occurs when water is added to blue crystals of the
cobalt(II)-chloride complex. Name the type of reaction responsible for this colour change.
colour change ............................................................................................................................
type of reaction ..........................................................................................................................

[2]
(d) Co2+(aq) can be oxidised to Co3+(aq).
(i) Use the Data Booklet to suggest a suitable oxidising agent for this reaction.
....................................................................................................................................... [1]
(ii) Calculate the of this reaction.
= .............................. V [1]
(iii) Write an equation for the reaction between Co2+ and the oxidising agent you chose in
(d)(i).
....................................................................................................................................... [1]
(e) Cobalt(III) forms two isomeric octahedral complexes with the formula [Co(NH3)3(NO2)3]. The
NO2– ion is monodentate.
Complete the diagrams to show the three-dimensional structures of the two isomers and
suggest the type of isomerism shown here.
isomer 1 isomer 2
Co Co
type of isomerism ......................................................................................................................

[3]
[J’18[Total:
P42 Q3]
17]

282

283
TRANSITION ELEMENTS WS 2
7 For
Examiner’s
Use
1 4 (a) The melting point and density of a typical transition element such as iron differ from
those of a typical s-block element such as calcium. Describe and explain these
differences.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
......................................................................................................................................[3]
(b) Suggest a reason why iron forms compounds containing Fe3+ ions as well as
compounds containing Fe2+ ions, whereas calcium only forms compounds containing
Ca2+ ions.
..........................................................................................................................................
......................................................................................................................................[1]
(c) An important ore of iron is siderite, iron(II) carbonate. The first step in converting it into
iron is to heat it in air. When heated in air, both calcium carbonate and iron(II) carbonate
decompose, but in different ways.
(i) Write an equation to represent the thermal decomposition of calcium carbonate.
...................................................................................................................................
(ii) When siderite is heated in air, carbon dioxide is evolved and iron(III) oxide, Fe2O3,
is left.
Construct an equation for this reaction.
...................................................................................................................................
(iii) Calculate how much iron(III) oxide can be obtained by heating 10 tonnes of
siderite.
...................................................................................................................................
...................................................................................................................................
[4]
[N’02 P4 Q4]
[Total: 8]

9701/4 O/N/02 [Turn over
284
12 For
Examiner’s
26 Use
(a) Titanium is an important transition metal. The metal itself is a component of many high-
strength low-weight alloys, and its oxide is used as an opaque agent in many paints
and pigments.
(i) Write out the electronic configuration of the titanium atom.
...................................................................................................................................
(ii) Titanium forms two chlorides. Suggest possible formulae for them.
...................................................................................................................................
[2]
(b) Anhydrous copper sulphate, CuSO4(s), is a white powder that readily dissolves in water.
(i) Describe and explain what is seen when CuSO4(s) is stirred with water.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(ii) Describe and explain the final colour change seen when an excess of NH3(aq) is
added to CuSO4(aq).
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
[4]
[J’03 P4 :Q4]
[Total 6]
9701/04/M/J/03

285
6 For
Examiner’s
34 Use
(a) Explain what is meant by the term transition element.
..........................................................................................................................................
..................................................................................................................................... [1]
(b) (i) How do the atomic radii of the transition elements vary from chromium to copper?
...................................................................................................................................
(ii) Predict, with a reason, the variation in the densities of the transition elements from
chromium to copper.
...................................................................................................................................
.............................................................................................................................. [3]
(c) Complete the following electronic configuration of the Cu2+ ion.
1s22s22p63s23p6 [1]
(d) Copper ions in aqueous solution are pale blue, due to the formation of a complex ion.
(i) Explain what is meant by the term complex ion.
...................................................................................................................................
...................................................................................................................................
(ii) Draw the structure of the complex ion formed in a solution of Cu2+(aq).
[2]
© UCLES 2004 9701/04/O/N04

286 For
7
Examiner’s
Use
(e) When dilute aqueous ammonia is added to a solution of Cu2+(aq), the colour changes
as a new complex ion is formed.
(i) State the colour of the new complex .........................................................................
(ii) Write an equation showing the formation of the new complex.
.............................................................................................................................. [2]
(f) When concentrated hydrochloric acid is added to a solution of Cu2+(aq), the colour
changes to yellow-green. On adding water, the colour returns to pale blue.
Suggest an explanation for these changes.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
......................................................................................................................................[3]
[N’04 P4 Q4]
[Total: 12]
© UCLES 2004 9701/04/O/N04 [Turn over

287
6 For
Examin
4 Use
4 (a) (i) State the electronic configuration of the iron atom.
..................................................................................................................................
(ii) Apart from its electronic structure, state two properties of iron or its compounds
that are characteristic of a transition element.
..................................................................................................................................
..................................................................................................................................
[3]
(b) Acidified solutions of iron(II) salts can be titrated using a dilute solution of potassium
manganate(VII), KMnO4.
(i) Use the Data Booklet to calculate the standard cell potential and to write a
balanced ionic equation for the reaction that takes place during the titration.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Explain why no indicator is required for this titration. What colour change would
you see at the end point?
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[4]
(c) Use the reaction between Fe3+ ions and water molecules to explain the meanings of
the terms ligand and complex formation.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
.................................................................................................................................... [2]
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288 7 For
Examiner's
Use
(d) An important biological molecule containing iron is haemoglobin.
(i) What is the role of haemoglobin in the body?
..................................................................................................................................
(ii) Use your answer to (i) to explain why carbon monoxide is poisonous.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[2]
[J’05 P4 Q4]
(e) In a possible industrial synthesis of ethanol, the complex Fe(CO)5 catalyses the
reaction between carbon monoxide, hydrogen and methanol according to the following
equation.
200 °C
CH3OH + 2CO + H2 –––––→ CH3CH2OH + CO2
300 atm
Describe a test (reagents and observations) that would distinguish ethanol from
methanol.
reagents ...........................................................................................................................
observation with methanol ...............................................................................................
observation with ethanol ............................................................................................. [2]

[Total: 13]

289
6 For
Examiner’s
Use
53 (a) A transition element X has the electronic configuration [Ar] 4s2 3d3.
(i) Predict its likely oxidation states.
...................................................................................................................................
(ii) State the electronic configuration of the ion X3+.
...................................................................................................................................
[2]
(b) Potassium manganate(VII), KMnO4, is a useful oxidising agent in titrimetric analysis.
(i) Describe how you could use a 0.0200 mol dm–3 solution of KMnO4 to determine
accurately the [Fe2+] in a solution. Include in your description how you would
recognise the end-point in the titration, and write an equation for the titration
reaction.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(ii) A 2.00 g sample of iron ore was dissolved in dilute H2SO4 and all the iron in the
salts produced was reduced to Fe2+(aq). The solution was made up to a total
volume of 100 cm3.
A 25.0 cm3 portion of the solution required 14.0 cm3 of 0.0200 mol dm–3 KMnO4 to
reach the end-point.
Calculate the percentage of iron in the ore.
...................................................................................................................................
[8]
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290 For
7
Examiner’s
Use
(c) High-strength low-alloy (HSLA) steels are used to fabricate TV masts and long span
bridges. They contain very low amounts of phosphorus and sulphur, but about 1%
copper, to improve resistance to atmospheric corrosion. When dissolved in nitric acid, a
sample of this steel gives a pale blue solution.
(i) What species is responsible for the pale blue colour?
...................................................................................................................................
(ii) Describe and explain what you would see when dilute aqueous ammonia is added
to this solution.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
[4]
[J’06 P4 Q3]
[Total: 14]

291
6 For
Examiner’s
6 Use
4 The following passage is taken from an A level Chemistry text book.
“In an isolated atom, the five d-orbitals have the same energy. In an octahedral complex ion, however,
the presence of the ligands splits the five orbitals into a group of three and a group of two. These two
groups have slightly different energies.”
(a) Use the following sets of axes to draw the shape of one d-orbital in each of the two
groups mentioned above.
[2]
(b) Explain how the presence of the six ligands, L, in [FeL6]3+ splits the 3d orbitals into two
groups of different energy, and explain whether the two-orbital group or the three-orbital
group has the higher energy.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
......................................................................................................................................[3]
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292
7 For
Examiner’s
Use
(c) The following table lists the colours and energies of photons of light of certain
wavelengths.
wavelength energy of colour of

/ nm photon photon
400 high violet
450 blue
500 lower green
600 yellow
650 low red
The visible spectra of solutions of two transition metal complexes C and D are shown in
the diagram below.
1.4
1.2
1.0
absorbance
0.8 D
C
0.6
0.4
0.2
0.0
300 400 500 600 700
wavelength / nm
(i) A list of possible colours for these complexes is as follows.
yellow red green blue
Choose one of these words to describe the observed colour of each solution.
solution C ............................................ solution D ................................................
(ii) In which complex, C or D, will the energy gap between the two groups of orbitals be
the larger? Explain your answer.
..................................................................................................................................
..................................................................................................................................
[3]
[J’07 P4 Q4]
[Total: 8]

293
6 For
Examiner’s
Use
73 (a) (i) Describe and explain the trend observed in the thermal stability of the carbonates
of the Group II elements.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) By quoting suitable data from the Data Booklet suggest how the thermal stabilities
of
• zinc carbonate and

• lead carbonate
might compare to that of calcium carbonate.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[6]
(b) Malachite is an ore of copper. It contains the following percentages by mass.
copper 57.7%
oxygen 36.2%
carbon 5.4%
hydrogen 0.9%
Malachite reacts with dilute H2SO4 producing a gas B that turns limewater milky and
leaving a blue solution C.
When heated in the absence of air, malachite produces gas B and steam, and leaves a
black solid D. D reacts with dilute H2SO4 to produce the same blue solution C.
Adding iron filings to C produces a pink solid E and a pale green solution F.
(i) Calculate the empirical formula of malachite.
..................................................................................................................................
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294
7 For
Examiner’s
Use
(ii) Suggest the formula of the ion responsible for the blue colour of solution C.
..................................................................................................................................
(iii) Identify the black solid D and calculate the mass of D that could be obtained by
heating 10 g of malachite.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iv) Use data from the Data Booklet to identify the pink solid E and the solution F, and
suggest an equation for the reaction producing them.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(v) What type of reaction is the reaction that produces E and F?
..................................................................................................................................
(vi) Describe and explain what you would see happen when dilute NH3(aq) is added
slowly to the solution C until it is in an excess.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[13]
[N’08 P4 Q3]
[Total: 19]

295 5
83 (a) Explain what is meant by the term transition element. For

Examiner’s
.......................................................................................................................................... Use
..................................................................................................................................... [1]
(b) Complete the electronic configuration of
(i) the vanadium atom, 1s22s22p6 .......................................................................
(ii) the Cu2+ ion. 1s22s22p6 .......................................................................

[2]
(c) List the four most likely oxidation states of vanadium.
..................................................................................................................................... [1]
(d) Describe what you would see, and explain what happens, when dilute aqueous ammonia
is added to a solution containing Cu2+ ions, until the ammonia is in an excess.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [5]
(e) Copper powder dissolves in an acidified solution of sodium vanadate(V), NaVO3 , to

produce a blue solution containing VO2+ and Cu2+ ions.
By using suitable half-equations from the Data Booklet, construct a balanced equation
for this reaction.
..................................................................................................................................... [2]
[J’09 P4 11]
[Total: Q3]

296
8
93 One major difference between the properties of compounds of the transition elements and For
those of other compounds is that the compounds of the transition elements are often Examiner’s
coloured. Use
(a) Explain in detail why many transition element compounds are coloured.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [3]
(b) The following graph shows the absorption spectrum of two complexes containing copper.
blue green yellow red infra-red
[Cu(NH3)4(H2O)2]2+
absorbance
[Cu(H2O)6]2+
400 500 600 700 800 900 1000

wavelength / nm
(i) State the colours of the following complex ions.
[Cu(H2O)6]2+ .................................................................................................
[Cu(NH3)4(H2O)2]2+ .................................................................................................
(ii) Using the spectra above give two reasons why the colour of the [Cu(NH3)4(H2O)2]2+
ion is deeper (more intense) than that of the [Cu(H2O)6]2+ ion.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iii) Predict the absorption spectrum of the complex [Cu(NH3)2(H2O)4]2+, and sketch
this spectrum on the above graph. [6]
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297
9
(c) Copper forms a complex with chlorine according to the following equilibrium. For
Examiner’s
Cu2+(aq) + 4Cl –(aq) [CuCl4]2–(aq) Use
(i) Write an expression for the equilibrium constant, Kc , for this reaction, stating its
units.
Kc = units
...................................................... ......................................................
(ii) The numerical value of Kc is 4.2 105.

Calculate the [[CuCl4] 2–] / [Cu2+ ] ratio when [Cl – ] = 0.20 mol dm–3.
..................................................................................................................................
..................................................................................................................................
[3]
[N’09 P41 Q3]
[Total: 12]

2984
2
10 (a) Describe three characteristic chemical properties of transition elements that are not For
shown by Group II elements. Examiner’s
Use
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [3]
(b) When NH3(aq) is added to a green solution containing Ni2+(aq) ions, a grey-green
precipitate is formed. This precipitate dissolves in an excess of NH3(aq) to give a blue-
violet solution.
Suggest an explanation for these observations, showing your reasoning and including
equations for the reactions you describe.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [4]
(c) Dimethylglyoxime, DMG, is a useful reagent for the quantitative estimation of nickel. It
forms an insoluble salt with nickel ions according to the following equation.
Ni2+(aq) + C4H8N2O2 NiC4H6N2O2(s) + 2H+(aq)

DMG Ni-DMG
A small coin of mass 3.40 g was dissolved in nitric acid and an excess of DMG was
added. The precipitated Ni-DMG was filtered off, washed and dried. Its mass was
4.00 g.
Calculate the % of nickel in the coin.
percentage of nickel = ..................................% [3]

[J’10 P41 Q2]
[Total: 10]
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299
8
11
4 (a) Complete the electronic structures of the Cr3+ and Mn2+ ions. For
Examiner’s
Cr3+ 1s22s22p6 ............. Use
Mn2+ 1s22s22p6 .............

[2]
(b) (i) Describe what observations you would make when dilute KMnO4(aq) is added
slowly and with shaking to an acidified solution of FeSO4(aq) until the KMnO4 is in
a large excess.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Construct an ionic equation for the reaction that occurs.
..................................................................................................................................
[4]
(c) By selecting relevant E o data from the Data Booklet explain why acidified solutions of
Fe2+(aq) are relatively stable to oxidation by air, whereas a freshly prepared precipitate
of Fe(OH)2 is readily oxidised to Fe(OH)3 under alkaline conditions.
relevant E o values and half equations
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
explanation
..........................................................................................................................................
..........................................................................................................................................
[4]
[J’10 P42 Q4]
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300
4
122 (a) (i) What is meant by the term ligand in the context of transition element chemistry? For
Examiner’s
.................................................................................................................................. Use
..................................................................................................................................
(ii) Decide which of the following species could be a ligand, and which could not be.
Place a tick ( ) in the appropriate column.
species can be a ligand cannot be a ligand

OH–
NH4+
CH3OH
CH3NH2
[3]
(b) Read the following description of some reactions of copper(II) sulfate, and answer the
questions that follow.
When 0.1 mol of white anhydrous CuSO4 is dissolved in liquid ammonia at –33 °C,
a deep blue solution C results.
When 0.2 mol of solid NaOH is added to solution C, and the ammonia solvent
allowed to evaporate, a solid residue is obtained.
Heating this residue to 200 °C produces a dark coloured mixture of two solids.
When water is added to this mixture, a black solid D and a colourless solution E are
formed. Neither D nor E contains nitrogen.
Adding BaCl2(aq) to solution E produces a white precipitate F.
Solid D dissolves in HNO3(aq) on warming, without evolution of gas, to give a pale
blue solution containing Cu(NO3)2(aq).
(i) Suggest the formula of the compound contained in each of the following.
solution C ..................................................................................................................
solid D .......................................................................................................................
solution E ..................................................................................................................
white precipitate F .....................................................................................................
(ii) Name the type of reaction that is occurring when D reacts with HNO3(aq).
..................................................................................................................................
[5]
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301
5
(c) (i) Describe what you would observe when a solid sample of anhydrous Cu(NO3 )2 is For
strongly heated. Examiner’s
Use
..................................................................................................................................
..................................................................................................................................
(ii) Write an equation for this reaction.
..................................................................................................................................
[2]
[N’10 P41 Q2]
[Total: 10]

..........................................................................................................................................
..........................................................................................................................................
302
4
13 ..........................................................................................................................................
2 (a) Explain why complexes of transition elements are often coloured. For
...................................................................................................................................... [3] Examiner’s
.......................................................................................................................................... Use
(b) When water is added to white anhydrous CuSO4, the solid dissolves to give a blue
..........................................................................................................................................
solution. The solution changes to a yellow-green colour when concentrated NH4Cl (aq)
is added to it. Concentrating the solution produces green crystals of an ammonium salt
..........................................................................................................................................
with the empirical formula CuN2H8Cl4.
Explain these observations, showing your reasoning.
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [3]
..........................................................................................................................................
(b) When water is added to white anhydrous CuSO4, the solid dissolves to give a blue
solution. The solution changes to a yellow-green colour when concentrated NH4Cl (aq)
..........................................................................................................................................
is added to it. Concentrating the solution produces green crystals of an ammonium salt
with the empirical formula CuN2H8Cl4.
..........................................................................................................................................
Explain these observations, showing your reasoning.
...................................................................................................................................... [3]
..........................................................................................................................................
(c) Copper can be recovered from low-grade ores by ‘leaching’ the ore with dilute H2SO4,
..........................................................................................................................................
which converts the copper compounds in the ore into CuSO4(aq). The concentration
of copper in the leach solution can be estimated by adding an excess of aqueous
..........................................................................................................................................
potassium iodide, and titrating the iodine produced with standard Na2S2O3(aq).
..........................................................................................................................................
2Cu2+ + 4I– 2CuI + I2
I2 + 2S2O32– 2I– + S4O62–
...................................................................................................................................... [3]
When an excess of KI(aq) was added to a 50.0 cm3 sample of leach solution, and the
(c) Copper can be recovered from low-grade ores by ‘leaching’ the ore with dilute H2SO4,
resulting mixture titrated, 19.5 cm3 of 0.0200 mol dm–3 Na2S2O3(aq) were required to
which converts the copper compounds in the ore into CuSO 4(aq). The concentration
discharge the iodine colour.
of copper in the leach solution can be estimated by adding an excess of aqueous
Calculate the [Cu2+(aq)], and hence the percentage by mass of copper, in the leach
potassium iodide, and titrating the iodine produced with standard Na2S2O3(aq).
solution.
2Cu2+ + 4I– 2CuI + I2
I2 + 2S2O32– 2I– + S4O62–
When an excess of KI(aq) was added to a 50.0 cm3 sample of leach solution, and the
resulting mixture titrated, 19.5 cm3 of 0.0200 mol dm–3 Na2S2O3(aq) were required to
discharge the iodine colour.
Calculate the [Cu2+(aq)], and hence the percentage by mass of copper, in the leach
solution.
percentage of copper = ..............................................% [3]

[N’10 P43 Q2]
[Total: 9]
© UCLES 2010 9701/43/O/N/10
percentage of copper = ..............................................% [3]
[Total: 9]
© UCLES 2010 9701/43/O/N/10

303
6
143 (a) On the following diagram draw a clear labelled sketch to describe the shape and For
symmetry of a typical d-orbital. Examiner’s
Use
[2]
(b) Although the five d-orbitals are at the same energy in an isolated atom, when a transition
element ion is in an octahedral complex the orbitals are split into two groups.
(i) Draw an orbital energy diagram to show this, indicating the number of orbitals in
each group.
energy
(ii) Use your diagram as an aid in explaining the following.
• Transition element complexes are often coloured.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
• The colour of a complex of a given transition element often changes when the
ligands around it are changed.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[7]
© UCLES 2011 9701/42/O/N/11
304
7
(c) Heating a solution containing potassium ethanedioate, iron(II) ethanedioate and For
hydrogen peroxide produces the light green complex K3Fe(C2O4)3, which contains the Examiner’s
ion [Fe(C2O4)3]3– . Use
The structure of the ethanedioate ion is as follows.
–
O O–
C C
O O
(i) Calculate the oxidation number of carbon in this ion. ...............................................
(ii) Calculate the oxidation number of iron in [Fe(C2O4)3]3– . ..........................................
(iii) The iron atom in the [Fe(C2O4)3]3– ion is surrounded octahedrally by six oxygen
atoms. Complete the following displayed formula of this ion.
3–
O
O
Fe
(iv) In sunlight the complex decomposes into potassium ethanedioate, iron(II)

ethanedioate and carbon dioxide.
Use oxidation numbers to help you balance the following equation for this
decomposition.
K3Fe(C2O4)3 ...........K2C2O4 + ......FeC2O4 + ......CO2

[5]
[N’11 P41 Q3]
[Total: 14]

305
6
153 For
(a) Complete the following electronic configuration of the Cu2+ ion. Examiner’s
Use
1s2 2s2 2p6 ........................................ [1]
(b) In a free, gas-phase transition metal ion, the d-orbitals all have the same energy, but
when the ion is in a complex the orbitals are split into two energy levels.
(i) Explain why this happens.
....................................................................................................................................
....................................................................................................................................
(ii) How does this splitting help to explain why transition metal complexes are often
coloured?
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(iii) Why does the colour of a transition metal complex depend on the nature of the
ligands surrounding the transition metal ion?
....................................................................................................................................
....................................................................................................................................
[5]
(c) Draw a fully-labelled diagram of the apparatus you could use to measure the E o of a cell
composed of the Fe3+/Fe2+ electrode and the Cu2+/Cu electrode.
[5]
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306
7
For
(d) The E o for Cu2+/Cu is +0.34 V. When NH3(aq) is added to the electrode solution, the Examiner’s
Eelectrode changes. Use
(i) Describe the type of reaction taking place between Cu2+(aq) and NH3(aq).
....................................................................................................................................
(ii) Write an equation for the reaction.
....................................................................................................................................
(iii) Describe the change in the colour of the solution.
....................................................................................................................................
(iv) Predict and explain how the Eelectrode might change on the addition of NH3(aq).
....................................................................................................................................
....................................................................................................................................
[4]
(e) Fehling’s reagent is an alkaline solution of Cu2+ ions complexed with tartrate ions. It is
used in organic chemistry to test for a particular functional group.
(i) Name the functional group involved.
....................................................................................................................................
(ii) Describe the appearance of a positive result in this test.
....................................................................................................................................
(iii) Write an equation for the reaction between Cu2+ and OH– ions and a two-carbon
compound containing the functional group you named in (i).
....................................................................................................................................
[3]
(f) A solution containing a mixture of tartaric acid and its sodium salt is used as a buffer in
some pre-prepared food dishes.
Calculate the pH of a solution containing 0.50 mol dm–3 of tartaric acid and 0.80 mol dm–3
sodium tartrate.
[Ka(tartaric acid) = 9.3 10–4 mol dm–3]
pH = ...............................
[2]
[N’12[Total:
P43 Q3]
20]

307
66
16 For
33 (a) (i)
(i) What
What isis meant
meant by
by the
the density
density of
of aa substance?
substance? For
(a) Examiner’s
Examiner’s
Use
Use
....................................................................................................................................
....................................................................................................................................
(ii) Use
(ii) Usedata
datafrom
from the
the Data
Data Booklet
Booklet to
to explain
explain why
why the
the density
density of
of iron
iron is
is greater
greater than
than that
that
of calcium.
of calcium.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
[3]
[3]
(b) In
(b) In general,
general, reactions
reactions of
of the
the compounds
compounds of
of transition
transition elements
elements can
can be
be classifi
classified
ed under
under
one or more of the following headings.
one or more of the following headings.
acid-base
acid-base
ligand exchange
ligand exchange
precipitation
precipitation
redox
redox
Choose the most suitable heading to describe each of the following reactions, by placing
Choose the most suitable heading to describe each of the following reactions, by placing
a tick ( ) in the appropriate column in the table below.
a tick ( ) in the appropriate column in the table below.
Only one tick should be placed against each reaction.
Only one tick should be placed against each reaction.
ligand
reaction acid-base ligand precipitation redox
reaction acid-base exchange
exchange
precipitation redox
[Cu(H O) ]2+ + 4NH [Cu(NH ) ]2+ + 6H O

[Cu(H22O)66]2+ + 4NH33 [Cu(NH33)44]2+ + 6H22O
[Cu(H O) ]2+ + 4HCl [CuCl ]2– + 4H+ + 6H O
[Cu(H22O)66]2+ + 4HCl [CuCl 44]2– + 4H+ + 6H22O
2FeCl + Cl 2FeCl
2FeCl 22+ Cl 22 2FeCl 33
[Fe(H O) ]2+ + 2OH– Fe(OH) + 6H O
[Fe(H22O)66]2+ + 2OH– Fe(OH)22 + 6H22O
2Fe(OH) + ½O + H O 2Fe(OH)
2Fe(OH)22+ ½O22 + H22O 2Fe(OH)33
CrO + 2HCl CrO Cl + H O
CrO33+ 2HCl CrO22Cl 22 + H22O
Cr(H O) (OH) + OH– [Cr(H O) (OH) ]– + H O
Cr(H22O)33(OH)33+ OH– [Cr(H22O)22(OH)44]– + H22O
[Cr(OH) ]– + 1½H O + OH– CrO 2– + 4H O
[Cr(OH)44]– + 1½H22O22 + OH– CrO442– + 4H22O
[8]
[8]
© UCLES 2013 9701/41/M/J/13

© UCLESCOLLEGE
CEDAR 2013 9701/41/M/J/13 TRANSITION ELEMENTS WS 2
308
7
For
(c) Alloys of aluminium, titanium and vanadium are used in aerospace and marine equipment, Examiner’s
and in medicine. Use
When a powdered sample of one such alloy is heated with an excess of aqueous NaOH,
only the aluminium reacts, according to the following equation.
2Al (s) + 2OH–(aq) + 6H2O(l) 2[Al (OH)4]–(aq) + 3H2(g)
Reacting 100 g of alloy in this way produced 8.0 dm3 of hydrogen, measured under room
conditions.
Calculate the percentage by mass of aluminium in the alloy.
percentage = ........................ %
[3]
[J’13 P41 Q3]
[Total: 14]

309
8
174 (a) (i) Suggest why transition elements show variable oxidation states in their compounds
For
Examiner’s
whereas s-block elements like calcium do not. Use
....................................................................................................................................
....................................................................................................................................
(ii) Calculate the oxidation number of the metal in each of the following ions.
VO2+ .......................................
CrF62– .......................................
MnO42– .......................................
[4]
(b) Explain why transition element complexes are often coloured whereas compounds of
s-block elements such as calcium and sodium are not.
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
[4]
(c) SO2 and MnO4– react together in acidic solution.
(i) Use the Data Booklet to construct a balanced equation for this reaction.
....................................................................................................................................
(ii) Describe the colour change you would see when SO2(aq) is added to a sample of
acidified KMnO4 until the SO2 is in excess.
from ............................................................ to ........................................................

[3]
(d) Describe the observations you would make when NH3(aq) is added gradually to a solution
containing Cu2+ ions, until the NH3 is in an excess.
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
[3]
[J’13 P42 Q4]
[Total: 14]
© UCLES 2013 9701/42/M/J/13


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237

1 2 The ions of transition elements form complexes by reacting with ligands.

(a) (i) State what is meant by the terms:

[Cu(H2O)6]2+ CuCl 42–

shape: .............................................. shape: ..............................................

Type of isomerism: .............................................................................................................

© UCLES 2014 9701/41/M/J/14

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

(i) Complete the electronic structures of these ions.

Cu(II) [Ar] ..................................................................................................................

Cu(I) [Ar] ..................................................................................................................

(ii) Use these electronic structures to explain why

copper(II) salts are usually coloured,

copper(I) salts are usually white or colourless.

© UCLES 2014 9701/41/M/J/14 [Turn over

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

The table lists the values for some compounds.

(ii) Copper(I) oxide can be produced from copper(II) oxide.

© UCLES 2014 9701/41/M/J/14

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

Answer all the questions

(ii) Ammonia can react as a base or as a ligand.

© UCLES 2014 9701/42/M/J/14

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

(i) Write an equation for the overall reaction.

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CEDAR COLLEGE TRANSITION ELEMENTS WS 1

32 (a) Complete the electron conﬁgurations for Ni and Ni2+.

lower energy level higher energy level

43 5 due to their partially-ﬁlled d orbitals.

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CEDAR COLLEGE TRANSITION ELEMENTS WS 1

(b) The following scheme shows some reactions of Cu2+(aq).

a few drops of NH3(aq)

heat with Cu(s)

[CuCl 2]– (aq)

(i) Suggest the formula of each of the following.

(ii) State the colour of the following solutions.

Deduce the role of the copper metal in this reaction.

Explain why CuCl does not absorb visible light.

© UCLES 2014 9701/43/O/N/14

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

400 500 600

Suggest the colour of this complex ion. Explain your answer.

© UCLES 2014 9701/43/O/N/14 [Turn over

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

(a) What is meant by the term transition element?

(ii) Which of the following species can act as a ligand?

can act cannot act

formula of manganese type of

Mn2+(aq) + concentrated HCl

© UCLES 2015 9701/41/O/N/15 [Turn over

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

Co2+2+(aq) + an excess of NH3(aq)

© UCLES 2015 9701/43/O/N/15

CEDAR COLLEGE TRANSITION ELEMENTS WS 1

element oxidation number

Calculate the average oxidation number of copper in Q.

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CEDAR COLLEGE TRANSITION ELEMENTS WS 1