IAL Chemistry SB2 Answers Topic17

Topic 17 Transition metals and their chemistry
17A Principles of transition metal chemistry
17A.1 Transition metal electronic configurations

1 (Cr full) 1s22s22p63s23p64s13d5
(Cr abbreviated) [Ar]4s13d5
2 The atom first loses both of its 4s electrons, then two of its five 3d electrons. This
forms the Mn4+ ion with an oxidation number of +4, and an electronic configuration
of [Ar]3d3.
17A.2 Ligands and complexes

1 A ligand needs a lone pair of electrons that it can use to form a dative bond, and
methane has no lone pairs of electrons.
2 It is a complex because there are ligands joined to the metal ion by dative bonds. It is
not a complex ion because the 2+ charge on the metal ion is exactly cancelled out by
the two negative charges on the OH− ligands, so the complex is neutral and has no
overall charge.
17A.3 The origin of colour in complexes
1 Violet light, because yellow and violet are complementary colours, opposite each
other on a colour wheel.
2 The electronic configuration of an aluminium ion is 1s22s22p6, so it has no 3d

electrons that could absorb light from the electromagnetic spectrum.
17A.4 Common shapes of complexes

1 As there are six monodentate ligands around the transition metal ion, the shape is
octahedral. As the overall charge on the complex is 3–, and each ligand has a 1–
charge, then the charge on the transition metal ion must be 3+.
2 As chloride ions are bigger than other ligands, there are four around the central metal
ion, giving a tetrahedral shape. Its name is tetrachloronickelate(II) and its formula is
[NiCl4]2−
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17A.5 Square planar complexes
1 An iodine atom has seven electrons in its outer shell, and each chlorine atom brings
one electron to form the bonds, then adding one for the 1– charge makes 12 electrons.
There are therefore six pairs: four bonding pairs and two lone pairs of electrons,
giving an octahedral distribution. The two lone pairs repel most so they are opposite
each other, giving a square planar shape for the four chlorines around the iodine.
2 (a)
(b) The IFCl3 ion has one F and three Cl atoms, so the only possible
arrangement is for two Cl atoms to be opposite each other and one F and one
Cl to be opposite.
17A.6 Multidentate ligands

1 It cannot act as a bidentate ligand because the two lone pairs of electrons are on the
same atom. It cannot act as a multidentate ligand because the hydrogen atoms do not
have any lone pairs of electrons. It is not a multidentate ligand because it can only use
one of its lone pairs at a time to form a dative bond.
2 [Fe(H2O)6]3+ + 2en → [Fe(H2O)2(en)2]3+ + 4H2O
17B Transition metal reactions
17B.1 Different types of reactions
1 This is only ligand exchange, as one water ligand is replaced by one SCN− ligand.
This causes the overall charge on the complex to decrease from 3+ to 2+, but the
oxidation number of Fe does not change, and there is no change in coordination
number. It being an acid-base reaction can be ruled out.
2 This is ligand exchange because all six water ligands are replaced by ammonia
ligands. It is also redox as the overall charge increases from 2+ to 3+. It is not acid-
base and there is no change in coordination number.
17B.2 Reactions of cobalt and iron complexes
1 [Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O
2 Ammonia is a weak base, so in aqueous ammonia there are many more NH3
molecules than OH− ions.
17B.3 The chemistry of chromium
1 [Cr(OH)6]3− + 6H+ → [Cr(H2O)6]3+
2 The relevant half-equations and Eo values are:

Mn2+ + 2e− → Mn Eo = −1.18 V
Zn → Zn2+ + 2e− Eo = +0.76 V
Adding these together gives:
Mn2+ + Zn → Mn + Zn2+ Eo = −0.42 V
As the Eo value is negative, the reaction is not feasible.
17B.4 Reactions of manganese complexes
1 (a) Percentage by mass of T = 63.18%
n(O) = (36.82 16) = 2.30125 mol

n(T) = (2.30125 2) = 1.150625 mol
molar mass of T = (63.18 1.150625) = 54.9 g mol—1
Hence T is manganese, Mn
(b) [Mn(H2O)6]2+
(c) Q = [Mn(H2O)4(OH2)]
S = MnO2.xH2O
2 (a) [Mn(H2O)6]2+(aq) + 2OH—(aq)  [Mn(H2O)4(OH2)](s) + 2H2O

(b) MnO2.xH2O  MnO2 + xH2O
17B.5 The chemistry of vanadium

V3+ + e− → V2+ Eo = −0.26 V
Sn → Sn2+ + 2e− Eo = +0.14 V
2V3+ + Sn → 2V2+ + Sn2+ Eo = –0.12 V
As the Eo value is negative, tin will not act as a reducing agent in this reaction.
VO 2  H 2O  VO 2   2H   e  Eo = −1.00 V
Cu2+ + 2e− → Cu Eo = +0.34 V
2VO 2  2H 2O  Cu 2  2VO 2   4H   Cu Eo = −0.66 V
As the Eo value is negative, copper(II) ions will not act as an oxidising agent in this
reaction.
17B.6 Reactions of nickel and zinc complexes

1 (a) In each atom the 3d orbitals are filling.
[Note: some texts describe d-block elements as those in which the 3d orbitals
are the last to fill. This is not correct as was explained in Book 1, Topic 2A.3,
page 51. With the elements Sc to Zn, the 4s orbital starts to fill before the 3d].
(b) Nickel forms an ion with a partially filled 3d sub-shell. The Ni2+ ion has the
electronic configuration of [Ar] 3d8
The only ion formed by zinc is the Zn2+ ion. It has the electronic configuration
of [Ar] 3d10. In this ion the 3d sub-shell is completely full.
2 (a) (1s2 2s2 2p6 3s2 3p6) 3d8

(b) The ion will be blue. The spectrum shows that it absorbs in the yellow region
of the electromagnetic spectrum.
(c) (i) Rings drawn around the N and the O−
(ii) They have a lone pair of electrons.
17C Transition metals as catalysts
17C.1 Heterogeneous catalysis

1 Vanadium(V) oxide chemically changes into vanadium(IV) oxide, and back again, so
it does take part in the reaction, even though it is chemically unchanged after the
reaction.
2 4NO + 3O2 + 2H2O → 4HNO3
17C.2 Homogeneous catalysts

1 The autocatalysis reaction involves the conversion between Fe2+ and Fe3+ ions.
Magnesium only forms one ion - Mg2+ so it is not suitable.
2 In alkaline conditions, there would be no H+ ions, which are needed as reactants.

Also, Mn2+ ions would react with alkali to form a precipitate and so would not be
available to act as a catalyst.
Topic 17 Exam Practice
1 D
2 C
3 B
4 C
5 D
6 B
7 B
8 (a) Sc3+ (1s22s22p6)3s23p6 (1).
Ti3+ (1s22s22p6)3s23p63d1 (1).
(b) The ion of a transition metal must have incompletely filled d-orbitals (1).
The Ti3+ ion has this but the Sc3+ ion does not (1).
(c) (Sc(OH)3) +3 (1).
(CaTiO3) +4 (1).
9 (a) A species with a lone pair of electrons (1) that forms a dative bond with a
metal ion (1).
(b) (i) [Fe(H2O)4(OH)2] (1).
(ii) Tetrachlorocobaltate(II) (1).
(c) The 3d energy level splits into two sub-levels with different energy (1).
In the ground state, all the electrons are in the lower energy level (1).
When radiation from the visible spectrum is passed through the solution, some
of the radiation is absorbed (1).
The energy of this radiation excites electrons from the lower to the higher
energy level (1).
The colour of the solution is in the visible spectrum but without the colour
absorbed by the electrons (1).
10 (a) The six water ligands repel each other as far as possible (1)
giving a symmetrical structure with bond angles of 90° (1).
(b) (i) Chloride ions are bigger than water molecules (1).
so only four of them can form bonds with the transition metal ion (1).
(ii) The co-ordination number changes (1).
The oxidation number does not change (1).
(c) (i) Name: diamminesilver(I) (1).
Reagent: Tollens’ reagent / ammoniacal silver nitrate (1).
(ii) Reduction (1).
Silver (1).
(d) Square planar (1).
(1).
(e) (i) It has more than one lone pair of electrons that can bond to a metal ion
(2).
(ii)
(1).
−
(iii) [Fe(EDTA)] (1).
11 (a) Reactant: green solution (1).

Product: green precipitate (1).
(b) Sodium hydroxide (solution) / NaOH (1).
(c) Reaction 3 (1).
Because the oxidation number of Cr changes from +3 to +6 (1).
(d) Yellow to orange (1).
(e) 2CrO 4 2  2H   Cr2O7 2  H 2O(1) .
12 Sulfur dioxide is adsorbed onto the catalyst (1).

The equation for its reaction with the catalyst is V2O5 + SO2 → V2O4 + SO3 (1).
in which the oxidation number of vanadium decreases from +5 to +4 (1).
Oxygen then reacts as follows: V2O4 + ½O2 → V2O5 (1).
in which the oxidation number of vanadium increases from +4 to +5 (1).
Adding these equations together gives SO2 + ½O2 → SO3 (1).

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Topic 17 Transition metals and their chemistry

17A Principles of transition metal chemistry

17A.1 Transition metal electronic configurations

17A.2 Ligands and complexes

17A.3 The origin of colour in complexes

2 The electronic configuration of an aluminium ion is 1s22s22p6, so it has no 3d

17A.4 Common shapes of complexes

17A.6 Multidentate ligands

2 [Fe(H2O)6]3+ + 2en → [Fe(H2O)2(en)2]3+ + 4H2O

17B Transition metal reactions

17B.1 Different types of reactions

1 [Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O

17B.3 The chemistry of chromium

1 [Cr(OH)6]3− + 6H+ → [Cr(H2O)6]3+

2 The relevant half-equations and Eo values are:

17B.4 Reactions of manganese complexes

1 (a) Percentage by mass of T = 63.18%

n(O) = (36.82 16) = 2.30125 mol

2 (a) [Mn(H2O)6]2+(aq) + 2OH—(aq)  [Mn(H2O)4(OH2)](s) + 2H2O

17B.5 The chemistry of vanadium

1 The relevant half-equations and Eo values are:

17B.6 Reactions of nickel and zinc complexes

2 (a) (1s2 2s2 2p6 3s2 3p6) 3d8

17C Transition metals as catalysts

17C.1 Heterogeneous catalysis

2 4NO + 3O2 + 2H2O → 4HNO3

17C.2 Homogeneous catalysts

2 In alkaline conditions, there would be no H+ ions, which are needed as reactants.

11 (a) Reactant: green solution (1).

12 Sulfur dioxide is adsorbed onto the catalyst (1).

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