LIGAND SUBSTITUTION AND

PRECIPITATION
Specification Points Covered
5.3.1 Transition Elements: Ligand Substitution
(h) Ligand substitution reactions and the accompanying colour changes in the formation of:
○○ [Cu(NH3)4(H2O)2]2+ and [CuCl4]2– from [Cu(H2O)6]2+
○○ [Cr(NH3)6]3+ from [Cr(H2O)6]3+ (see also 5.3.1 j)
(i) Explanation of the biochemical importance of iron in haemoglobin, including ligand substitution involving O2
and CO

Replacement by Similar Sized Ligands

Ligand Substitution Reaction

When a ligand in a complex ion is replaced by
a different ligand.

The exchange of a H2O ligand for an NH3 occurs without a change in coordination
number as the ligands are similar in size. The exchange occurs because NH3 is a better
ligand and forms stronger coordinate bonds than H2O. The shape remains octahedral
after the substitution of these ligands.

Aqueous Copper(II) Ions and Ammonia

Aqueous copper(II) solutions contain the pale blue [Cu(H2O)6]2+ complex.

On adding an excess of ammonia, a dark blue solution is formed:

[Cu(H2O)6]2+ (aq) + 4NH3 (aq) ⇌ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l)

The coordination number is six and does not change. This ligand substitution is said
to be incomplete as only four of the original six ligands are replaced.

When the ammonia is added dropwise, it can be seen that a pale blue precipitate
of Cu(OH)2 is formed in the first step of the reaction. When more ammonia is added,
this precipitate dissolves to form [Cu(NH3)4(H2O)2]2+.

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 Aqueous Chromium(III) Ions and Ammonia
Aqueous chromium(III) solutions contain the violet [Cr(H2O)6]3+ complex.

On adding ammonia, ammonia replaces the water ligands, forming a deep purple
coloured solution in two steps:
1. A grey-green precipitate of Cr(OH)3 is formed when ammonia is added dropwise

2. Cr(OH)3 dissolves in excess ammonia to form [Cr(NH3)6]2+

Overall, this reaction can be shown as:

[Cr(H2O)6]2+ (aq) + 6NH3 (aq) ⇌ [Cr(NH3)6]2+ (aq) + 6H2O (l)

The coordination number is six and does not change. This ligand substitution is said
to be complete as all of the original six ligands are replaced.

Replacement by Larger Ligands

Exchanging the ligand H2O with Cl– will involve a change in coordination number due
to the size difference of the ligands. The coordination number decreases from six to
four because chloride is larger than water, meaning only four Cl– ligands can fit around
the central metal ion. In the example below, the geometry changes from octahedral to
tetrahedral.

Aqueous Copper(II) Ions and HCl

Aqueous copper(II) solutions contain the pale blue [Cu(H2O)6]2+ complex. When
aqueous copper ions are mixed with HCl, the water ligands are replaced by the Cl–
ligands, forming a yellow solution:
[Cu(H2O)6]2+ (aq) + 4Cl– (aq) ⇌ [Cu(Cl)4]2– (aq) + 6H2O (l)

The overall change seen is from a pale blue solution to green, then to a yellow
solution. The green colour is due to the blue and yellow solutions mixing.

EXAM TIP
It is important to remember the colours mentioned in the examples above, and
to be able to write the equations. Focus on understanding how the equations are
derived, as this will make them easier to remember.

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Ligand Substitution in Blood
Every drop of blood contains millions of red blood cells. Red blood cells contain
haemoglobin, a complex protein. Haemoglobin allows red blood cells to transport
oxygen around the body.

The picture below represents haemoglobin. Non-protein groups called haem groups
(shown in red in the diagram) are Fe(II) complexes with one tetradentate and two
monodentate ligands. They have an octahedral shape.

The ligands form coordinate bonds to oxygen molecules when haemoglobin passes
through capillaries in the body.

The Transport of Oxygen in the Blood

1. Oxygen at a high concentration in the lungs can reversibly form a coordinate
bond to the Fe2+ ion in the haem group, substituting a water ligand to form
oxyhaemoglobin

2. Oxyhaemoglobin travels through the bloodstream, transporting oxygen to where

it is needed

3. The concentration of oxygen in surrounding cells is low, so the oxygen is

exchanged for a water molecule

4. The haemoglobin then returns to the lungs and the process repeats

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Carbon monoxide is a molecule formed during incomplete combustion. It binds strongly
to haemoglobin:

Carbon monoxide is a very good ligand, allowing it to bind irreversibly to haemoglobin

to form carboxyhaemoglobin. This makes it toxic because, when inhaled, it reduces
the amount of oxygen that can be transported.

In small doses, carbon monoxide can cause headaches and fatigue. If a large amount
is inhaled, it can cause death by suffocation.

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Specification Points Covered
5.3.1 Transition Elements: Precipitation Reactions
(j) Reactions, including ionic equations, and the accompanying colour changes of aqueous Cu2+, Fe2+, Fe3+, Mn2+ and
Cr3+ with aqueous sodium hydroxide and aqueous ammonia, including:
(i) Precipitation reactions
(ii) Complex formation with excess aqueous sodium hydroxide and aqueous ammonia
○○ For precipitation, non-complexed formulae or complexed formulae, are acceptable e.g.Cu2+(aq) or
[Cu(H2O)6]2+; Cu(OH)2(s) or Cu(OH)2(H2O)4
○○ With excess NaOH, only Cr(OH)3 reacts further forming [Cr(OH)6]3-
○○ With excess NH3, only Cr(OH)3 and Cu(OH)2 react forming [Cr(NH3)6]3+ and [Cu(NH3)4(H2O)2]2+
respectively (see also 5.3.1 h)
Transition Elements: Redox Reactions
(k) Redox reactions and accompanying colour changes for:
(i) Interconversions between Fe2+ and Fe3+
○○ Fe2+ can be oxidised with H+/MnO4– and Fe3+ reduced with I–, Cr3+ can be oxidised with H2O2/OH–
and Cr2O72– reduced with Zn/H+, Cu2+ can be reduced with I–. In aqueous conditions, Cu+ readily
disproportionates
○○ Learners will not be required to recall equations but may be required to construct and interpret redox
equations using relevant half-equations and oxidation numbers (see 5.2.3 b-c)
(ii) Interconversions between Cr3+ and Cr2O72–
(iii) Reduction of Cu2+ to Cu+ and disproportionation of Cu+ to Cu2+ and Cu
5.3.2 Qualitative Analysis: Tests for Ions
(a) Qualitative analysis of ions on a test-tube scale: processes and techniques needed to identify the following ions
in an unknown compound:
(i) Cations: NH4+, Cu2+, Fe2+, Fe3+, Mn2+, Cr3+ (see also 3.1.4 a, 5.3.1 j)

Precipitation Reactions

Precipitation Reaction
When two solutions containing soluble ions
are mixed, forming an insoluble compound.

The insoluble compound formed is the precipitate. Transition metal ions in solution
(metal-aqua ions) often undergo precipitation reactions with bases.

The ionic equations of various transition metals and their observations are highlighted
in the table below. All compounds formed, except Cr3+, are insoluble in excess NaOH.

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 Transition
Equation Observation
Element Ion
Pale green solution forms
a green precipitate with
Fe2+ (aq) + 2OH– (aq) → Fe(OH)2 (s) NaOH
Fe2+
Fe(OH)2 (s) → Fe(OH)3 (s) In air, the green precipitate
turns orange-brown as
Fe(II) is oxidised to Fe(III)
Pale yellow solution
Fe 3+
Fe 3+
(aq) + 3OH (aq) → Fe(OH)3 (s)
–
forms an orange-brown
precipitate with NaOH
Blue solution forms a blue
Cu2+ Cu2+ (aq) + 2OH– (aq) → Cu(OH)2 (s)
precipitate with NaOH
Pale pink solution forms
Mn 2+
Mn 2+
(aq) + 2OH (aq) → Mn(OH)2 (s)
–
a light brown precipitate
with NaOH
Violet solution forms
Cr3+ (aq) + 3OH– (aq) → Cr(OH)3 (s) a grey-green precipitate
with NaOH
Cr3+
Cr(OH)3 (s) + 3OH– (aq) → [Cr(OH)6]3– The precipitate is soluble
(aq) in excess NaOH, forming
a dark green solution

Precipitation Reactions with Ammonia

All of the ions in the table above also undergo precipitation reactions with ammonia.
These reactions are covered in detail in ‘Ligand Substitution Reactions’.

The first step of the reaction is identical to the reactions above.

Transition
Equation Observation
Element Ion
Pale green solution forms
a green precipitate

Fe2+ (aq) + 2OH– (aq) → Fe(OH)2 (s) In air, the green precipitate
Fe2+ turns orange-brown as
Fe(OH)2 (s) → Fe(OH)3 (s) Fe(II) is oxidised to Fe(III)

No further reaction with

excess ammonia

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 Transition
Equation Observation
Element Ion
Pale yellow solution forms
a brown precipitate
Fe3+ Fe3+ (aq) + 3OH– (aq) → Fe(OH)3 (s)
No further reaction with
excess ammonia

Cu2+ (aq) + 2OH– (aq) → Cu(OH)2 (s)
Cu2+
Cu(OH)2 (s) + 4NH3 →
[Cu(NH3)4(H2O)2]2+ (aq)
Mn2+ Mn2+ (aq) + 2OH– (aq) → Mn(OH)2 (s)
Blue solution forms a blue
precipitate
A deep blue solution forms
with excess ammonia
Pink solution forms a light
brown precipitate
No further reaction with
excess ammonia

Violet solution forms

Cr3+ (aq) + 3OH– (aq) → Cr(OH)3 (s)
Cr3+
Cr(OH)3 (s) + 6NH3 (aq) →
[Cr(NH3)6]3– (aq) + 3OH-
a grey-green precipitate
with NaOH
The precipitate is soluble
in excess ammonia, forming
a purple solution

EXAM TIP
You need to know all of the above observations and reactions and you should be
able to recall them in the exam.

Redox Reactions with Transition Elements

A redox titration can be carried out to highlight the redox reaction between iron(II)
and manganate(VII) ions. The half and full equations are as follows:
MnO4– (aq) + 8H+ (aq) → Mn2+ (aq) + 4H2O (l)
Fe2+ (aq) → Fe3+ (aq) + e–
MnO4– (aq) + 8H+ (aq) + 5Fe2+ (aq) → Mn2+ (aq) + 5Fe3+ (aq) + 4H2O (l)

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A similar titration can be carried out to highlight the redox reaction between Fe3+
and I– ions. The full equation is as follows:
2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (aq)
brown pale-green

Iodine is also a brown colour. This can obscure the colour of the Fe2+ ions.

Dichromate ions can be reduced by reacting with zinc. The reaction is shown below.
Cr2O72– (aq) + 14H+ (aq) + 3Zn (s) → 2Cr3+ (aq) + 7H2O (l) + 3Zn2+ (aq)
orange green

Chromium(III) ions can be reduced further with the addition of more zinc to form
a pale blue Cr(II) ion.
Cr3+ (aq) + Zn (s) → Cr2+ (aq) + Zn2+ (aq) + e–

Chromium(III) can be oxidised by adding hydrogen peroxide, H2O2. This requires hot
alkaline conditions. The overall equation is:
2Cr3+ + 3H2O2 + 10OH– → 2CrO42– + 8H2O

Pale blue copper(II) ions can be reduced by reaction with brown iodide ions. The
reaction is shown below. The copper(I) iodide is a red colour.
2Cu2+ (aq) + 4I– (aq) → 2CuI (aq) + I2 (s)

Red copper(I) oxide undergoes a disproportionation reaction when reacted with hot
dilute sulphuric acid, to form orange-brown copper metal and a pale blue copper(II)
salt:
Cu2O (s) + H2SO4 (aq) → Cu (s) + CuSO4 (aq) + H2O (l)

Cu2O is both reduced to Cu and is oxidised to CuSO4.

EXAM TIP
You do not need to remember the full equations in the exam, but you may be
asked to construct them after being given the oxidation states of the species and
any relevant half equations.

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Qualitative Tests for Ions
Qualitative tests indicate whether particular ions are present. However, they do not
indicate how much of a substance is present. They can be carried out in test tubes and
often involve precipitation reactions. To deduce the identity of the compound present,
separate tests need to be carried out for the cations and anions. You have met the
anion tests in the 1st year course.

Tests for Transition Metal Ions

It has already been explained how metal-aqua ions form precipitates when they react
with bases. These precipitation reactions can be used in qualitative tests to identify
the presence of a particular metal-aqua ion. All of the corresponding observations are
detailed above.

You need to know the tests/observations for the following positively charged ions: NH4+,
Cu2+, Fe2+, Fe3+, Mn2+ and Cr3+.

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