Raffles Institution

Year 6 H2 Chemistry 2020

An Introduction to the Chemistry of Transition Elements

Note: This Common Last Topic (CLT) will not be examined in 2020 A-Level examination.

1. INTRODUCTION
1.1 The d-block elements
• These elements have atoms in which either the inner 3d, 4d, 5d or 6d subshells are
filling up. Their atoms are characterised by ‘inner building’ of d subshells.
Period
number
1 1s 1s
2 2s 2p
3 3s 3p
4 4s 3d 4p
5 5s 4d 5p
6 6s 5d 6p
7 7s 6d

4f

• We will focus on the first row d-block elements. 5f

• The 3d block contains ten elements, because the 3d subshell contains five orbitals,
each able to accommodate up to two electrons. These elements involve the filling of the
3d orbitals.

• They are all metals and tend to be hard metals compared with the s-block metals.
1.2 Shapes of the 3d orbitals
• There are five d orbitals (i.e. 𝑑𝑥𝑧 , 𝑑𝑥𝑦 , 𝑑𝑦𝑧 , 𝑑𝑥 2 −𝑦2 and 𝑑𝑧2 ) in a d subshell.

𝑑𝑥𝑧 𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2

• These three orbitals have a similar • This orbital also • This orbital consists of a
4–lobed shape. has a 4–lobed dumb–bell surrounded
shape but it has by a small doughnut
• These orbitals have their lobes its lobes aligned shaped ring at its waist
pointing between the axes. along the x and • This orbital is aligned
y axes. along the z axis.

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1.3 Electronic Configurations of the Elements
• The principles that govern the distribution of electrons in the orbitals are:
The Aufbau (building-up) Principle 1s
• Electrons fill orbitals from the lowest energy orbital upwards. 2s 2p
The Pauli Exclusion Principle 3s 3p 3d
• No more than two electrons may occupy a single orbital and, if two 4s 4p 4d 4f
electrons do occupy a single orbital, their spins must be paired.
5s 5p 5d 5f
Hund’s Rule 6s 6p 6d
• Orbitals of a sub-shell (degenerate) must be occupied singly and with
parallel spins before they can be occupied in pairs (with opposite spins).
7s

• Recall from Atomic Structure:

o Electrons occupy the 4s subshell before the 3d subshell.
o When filled, the 4s subshell has a higher energy than the 3d subshell

• Electronic configuration of the first row d-block elements

Element ‘Electrons-in-boxes’ diagram Electronic configuration
3d 4s
21Sc [Ar] 1s2 2s2 2p6 3s2 3p6 3d1 4s2

22Ti [Ar] 1s2 2s2 2p6 3s2 3p6 3d2 4s2

23V [Ar] 1s2 2s2 2p6 3s2 3p6 3d3 4s2

24Cr [Ar] 1s2 2s2 2p6 3s2 3p6 3d5 4s1

25Mn [Ar] 1s2 2s2 2p6 3s2 3p6 3d5 4s2

26Fe [Ar] 1s2 2s2 2p6 3s2 3p6 3d6 4s2

27Co [Ar] 1s2 2s2 2p6 3s2 3p6 3d7 4s2

28Ni [Ar] 1s2 2s2 2p6 3s2 3p6 3d8 4s2

29Cu [Ar] 1s2 2s2 2p6 3s2 3p6 3d10 4s1

30Zn [Ar] 1s2 2s2 2p6 3s2 3p6 3d10 4s2

Two exceptions:
1. Electronic configuration of chromium: 1s2 2s2 2p6 3s2 3p6 3d5 4s1
For Cr, the configuration [Ar] 3d5 4s1 is more stable than [Ar] 3d4 4s2.
3d 4s 3d 4s
[Ar] [Ar]

The electrons occupy the 3d and There is a repulsion between

4s orbitals singly so that the two 4s electrons within the
interelectronic repulsion is same orbital.
minimised.

2. Electronic configuration of copper: 1s2 2s2 2p6 3s2 3p6 3d10 4s1
For Cu, the configuration [Ar] 3d10 4s1 is more stable than [Ar] 3d9 4s2.

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1.4 Electronic Configurations of the Ions
• In the formation of cations, the 4s electrons, which are at a higher energy level than the
3d electrons, are removed first.
• To write the electronic configuration of ions,
Step 1: Write out the electronic configuration of element, filling the 4s orbital first
before the 3d orbitals.
Step 2: Remove the 4s electrons first before the 3d electrons.

Example:

Electronic configuration Electronic configuration

Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2
Cr+ 1s2 2s2 2p6 3s2 3p6 3d5 Fe+ 1s2 2s2 2p6 3s2 3p6 3d6 4s1
Cr2+ 1s2 2s2 2p6 3s2 3p6 3d4 Fe2+ 1s2 2s2 2p6 3s2 3p6 3d6
Cr3+ 1s2 2s2 2p6 3s2 3p6 3d3 Fe3+ 1s2 2s2 2p6 3s2 3p6 3d5

 Exercise 1: Electronic Structure of a d-Block Element (N98/III/1)

The diagram shows the energy levels of various electronic subshells of an atom of a
transition element in the fourth period of the Periodic Table.

What are subshells x and y?

A x = 3d, y = 4s
B x = 4s, y = 3d
C x = 4s, y = 4p
D x = 4p, y = 3d

 Exercise 2
Which one of the following represents the electronic configuration of the +1 ion of an
element with atomic number 29?

A 1s2 2s2 2p6 3s2 3p6 3d9 4s2 C 1s2 2s2 2p6 3s2 3p6 3d10 4s1
B 1s2 2s2 2p6 3s2 3p6 3d9 4s1 D 1s2 2s2 2p6 3s2 3p6 3d10

1.5 The Transition Elements

A transition element is a d-block element which can form one or more stable ions with a partially
filled d subshell.

• Based on the above definition, which first row d-block elements are not transition elements?

Scandium and zinc are not transition elements since they do not form any stable ions with
a partially filled d subshell. They ONLY form Sc3+ and Zn2+ ions respectively that do not
have partially filled d subshell.

Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2
Sc3+ 1s2 2s2 2p6 3s2 3p6 Zn2+
1s2 2s2 2p6 3s2 3p6 3d10

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• The element copper forms Cu+ ion (electronic configuration: 1s2 2s2 2p6 3s2 3p6 3d10) which
has a fully filled d subshell. Is copper a transition element?

Copper is still regarded as a transition element because it can form Cu2+ ion with a partially
filled d subshell.

Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9

2. GENERAL PHYSICAL PROPERTIES

• The first row transition elements are all metals and all elements are remarkably similar in
their physical properties.
➢ they are hard and have high densities
➢ they have high melting and boiling points
➢ they are good conductors of heat and electricity

2.1 Atomic Radius

The atomic radii of the first-row transition elements (in particular, from V to Cu) in Period 4 are
almost constant / relatively invariant.

Element Ti V Cr Mn Fe Co Ni Cu
Atomic radius/nm 0.146 0.135 0.129 0.132 0.126 0.125 0.124 0.128

• In traversing the first-row transition elements, the number of protons increases, and hence,
the nuclear charge increases.
• The number of electrons also increases. Electrons are added to the penultimate 3d subshell.
• The increase in shielding effect, due to an increase in the number of 3d electrons,
offsets the increase in nuclear charge considerably.
• There is only a small increase in the effective nuclear charge and attraction for valence
electrons increases slightly.
• The atomic radii is relatively constant / relatively invariant.
• Some of the first-row transition elements readily form alloys with each other partly because
they have similar atomic radii.

2.2 Ionisation Energies

The first ionisation energies of the transition elements from Ti to Cu is almost constant /
relatively invariant.

The graph below shows the variation of 1st ionisation energies (IE) from Ti to Cu.
1000
800
1st IE/ 600
kJ mol−1 400
200
0
22
Ti 23
V 24
Cr 25
Mn 26
Fe 27
Co 28
Ni 29
Cu

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First IE of transition elements is almost constant / relatively invariant. This is because
• The electron being removed comes from the 4s orbital.
• Across a period, proton number increases and thus nuclear charge increases.
• Electrons are added to the penultimate 3d subshell.
• The increase in shielding effect, due to an increase in the number of inner 3d electrons,
offsets the increase in nuclear charge considerably
• Thus, energy required to remove the first electron is almost constant / relatively invariant.

2.3 Melting Points and Boiling Points

Comparing s-block and transition elements, the melting point of transition elements are generally
higher than the s-block elements in the same period.

s-block elements transition elements

Element K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn

Melting point / C 64 839 1541 1660 1890 1857 1244 1535 1495 1455 1083 420

Boiling point / C 760 1494 2831 3287 3380 2670 1962 2750 2870 2730 2567 907

oC
Reason: Melting Points and Boiling Points of the
elements K to Zn
• The valence 3d and 4s electrons are close in 6000
energy (see Atomic Structure notes).
5000 boiling point
• Thus, both 3d and 4s electrons are
available for delocalisation into the sea of 4000
electrons.
3000
• With a greater number of delocalised melting point
electrons and higher charge density of the 2000
cations, the metallic bonding is stronger in the
1000
transition elements.
0
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn

Explain why the melting point of Ti is higher than that of Ca.

Both Ti and Ca are metals. Ti is a transition element and both its 3d and 4s electrons are available
for delocalisation into the sea of electrons since the 3d and 4s electrons are close in energy. With
a greater number of delocalised electrons and higher charge density of the titanium cations, Ti has
stronger metallic bonding than Ca, which requires more energy to overcome.

2.4 Density

Element Ca Sc Ti V Cr Mn Fe Co Ni Cu

Density /g cm-3 1.54 2.99 4.50 5.96 7.20 7.20 7.86 8.90 8.90 8.92

Comparing s-block and transition elements, the transition elements are generally much denser
than the s-block elements in the same period.
Transition elements have
• smaller atomic size (see Data Booklet) and thus have more atoms per unit volume.
• larger atomic mass
compared to s-block elements. Hence, transition elements have greater mass per unit volume
(i.e. higher density) compared to s-block elements

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Comparing transition elements from Ti to Cu, there is a gradual increase in density.
• The almost constant atomic radius, coupled with increasing relative atomic mass, accounts for
most of this trend.

3. CHARACTERISTIC CHEMICAL PROPERTIES

• Some important characteristic chemical properties of transition elements are listed below and
contrasted against those of s-block elements.

1. The transition elements form compounds 1. The s-block elements form

in which the transition element shows a compounds in which they exist
variety of oxidation states. in a fixed oxidation state.
Examples: Examples:
+2 +3 +6 +1 +1
FeCl2 FeCl3 K2FeO4 KCl K2SO4

2. The transition elements form coloured 2. The s-block elements form

compounds and ions. compounds that are usually white
in the solid state and colourless
Examples:
in aqueous solution.
[CuCl4]2– (aq) yellow
Examples:
[Cu(NH3)4]2+ (aq) dark blue
CaSO4(s) white
[Cr(H2O)6]3+(aq) green
CaCl2(aq) colourless
[Cr(OH)6]3– (aq) dark green
[Cu(H2O)6]2+(aq) blue
[Fe(SCN)(H2O)5]2+(aq) blood-red

3. The transition elements and their 3. The s-block elements and

compounds often show catalytic activity. their compounds show little
Examples: Fe/Fe2O3 or no catalytic activity.
N2(g) + 3H2(g) ⎯⎯⎯⎯→ 2NH3(g)

4. The transition elements show a great 4. The s-block elements show

tendency to form stable complexes. much less tendency to form
stable complexes.
Examples:
[Fe(CN)6]3–(aq), [Cr(OH)6]3–(aq), [CuCl4]2–(aq), Examples:
•
[Fe(SCN)(H2O)5]2+(aq) [Be(OH)4]2–(aq), [Ca(edta)]2–(aq)

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 4. VARIABLE OXIDATION STATES
4.1 Transition elements and variable oxidation states

Compound CrSO4 CrCl3 K2CrO4

Oxidation state of Cr +2 +3 +6

• Why are transition elements able to show variable oxidation states in their compounds?
➢ This is primarily due to the close similarity in energy of the 3d and the 4s electrons,
that both the 3d and the 4s electrons are available for bond formation (ionic or covalent).

• Lower oxidation states

o The lower oxidation states are usually found in ionic compounds.
o For example, Cr ([Ar]3d54s1) can form the Cr2+ ([Ar]3d4) cation by losing one 4s electron
and one 3d electron. This is possible due to the close similarity in the energies of the 3d
and 4s electrons which means that successive ionisation energies increase gradually.
o Comparing the successive ionisation energies of calcium and chromium.
IE / kJ mol–1 1st 2nd 3rd 4th
Ca 590 1150 4940 6480
Cr 653 1590 2990 4770
1. The successive IEs of chromium increase gradually compared to that of calcium which
has a large increase between the 2nd and 3rd IE.
2. There is a large increase between the 2nd and 3rd IE of calcium as the electron
removed is from an inner shell and experiences much stronger attraction, requiring
more energy to be removed.

• Higher oxidation states

o The higher oxidation states are usually found in covalent compounds involving bonding
with electronegative atoms like F and O.
o For example, chromium can exist in a high oxidation state of +6 in CrO42– where it utilises
all its 3d electrons and 4s electrons (a total of six electrons) in covalent bond formation.
This is possible due to the close similarity in the energies of the 3d and 4s electrons.

4.2 Common Oxidation Numbers

• The table below summarises the known oxidation numbers of the elements K to Zn.

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn

4s1 4s2 3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2

+1 +1 +1 +1 +1 +1 +1 +1 +1
+2 +2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6
+7

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 • Highest possible oxidation state
An observation can be made that in general,
highest possible oxidation state = No. of unpaired d-electrons + 4s electrons

Example: Co: [Ar]

No. of unpaired d-electrons = 3, No. of 4s electrons = 2

Maximum oxidation state of Co = 3 + 2 = +5

Some generalisations
(a) From Sc to Mn, the number of available oxidation states for the element increases. The value
of the highest oxidation number for Sc to Mn suggests that in each element all the available
3d and 4s electrons may be used for bonding.
(b) From Mn to Zn, there is a decrease in the number of oxidation states exhibited by the
elements.
(c) The common oxidation states for each element include +2 or +3 or both.
(d) Oxides of elements in low oxidation states tend to be basic as they are ionic while oxides of
elements in high oxidation states tend to be acidic as they are covalent. Using compounds of
manganese as an example,

MnO +2 basic (MnO + H2SO4 ⎯→ MnSO4 + H2O)

Mn2O3 +3 basic
MnO2 +4 amphoteric
MnO3 +6 acidic
Mn2O7 +7 acidic (Mn2O7 + 2NaOH ⎯→ 2NaMnO4 + H2O)

 Exercise 3
N92/4/20 and J99/3/18
Titanium has the electronic structure 1s2 2s2 2p6 3s2 3p6 3d2 4s2.
Which titanium compound is unlikely to exist?

A K2TiO4 B K3TiF6 C TiCl3 D TiO

4.3 Redox systems involving transition metal ions

(a) The relative stabilities of different oxidation states are best understood in terms of standard
electrode potentials.
M3+ + e– ⇌ M2+ E (M3+/M2+)
A more positive E value ⇒ position of equilibrium position lies more to the right i.e.
the +2 oxidation state is favoured over the +3 oxidation state.

Cr3+ + e– Cr2+ E = −0.41 V Electronic configurations

M3+ M2+
Mn3+ + e– Mn2+ E = +1.54 V Cr [Ar] 3d 3 [Ar] 3d4
4
Mn [Ar] 3d [Ar] 3d5
Fe3+ + e– Fe2+ E = +0.77 V Fe [Ar] 3d 5
[Ar] 3d6
Co [Ar] 3d 6 [Ar] 3d7
Co3+ + e– Co2+ E = +1.82 V

(i) Going across the transition elements, there is a general increase in E value.
(ii) There is a decrease in E from Mn3+/Mn2+ to Fe3+/Fe2+.
➢ Addition of an electron to Fe3+ results in a 3d6 configuration, where there is
inter-electronic repulsion between the paired electrons in the same 3d orbital.
Thus, reduction of Fe3+ to Fe2+ is less favoured.

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(b) Aqueous KMnO4 acidified with dilute H2SO4 and aqueous K2Cr2O7 acidified with dilute H2SO4
are common oxidising agents used in laboratories.

MnO4– + 8H+ + 5e– Mn2+ + 4H2O E = +1.52 V

purple very light pink
/ colourless

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O E = +1.33 V

orange green

5. CATALYTIC ACTIVITY

• Transition elements, both in the elemental form and in their compounds, are effective and
important catalysts.
• What is a catalyst?

A catalyst is a substance which increases the rate of a reaction without itself undergoing
any permanent change.

• How does a catalyst increase the rate of a reaction?

A catalyst increases the rate of a reaction by providing an alternative pathway for the
reaction, one with a lower activation energy than that of the uncatalysed reaction.
Consequently more reactant particles have energy greater than or equal to the activation
energy, leading to a higher effective collision frequency and hence a faster reaction rate.
A lower activation energy also results in a larger rate constant, k, and hence a faster
reaction.

• What are the two types of catalysis?

1. heterogeneous catalysis – catalyst and the reactants are in different physical phases
2. homogeneous catalysis – catalyst and the reactants are in the same phase

• Transition elements and their compounds are useful in both heterogeneous catalysis and
homogeneous catalysis.

Transition element
or their compounds Reaction catalysed Type of catalysis
used as catalyst.
V2O5 2SO2(g) + O2(g) ⎯→ 2SO3(g) Contact process Heterogeneous
MnO2 2KClO3 ⎯→ 2KCl + 3O2 -- Heterogeneous
Fe/Fe2O3 N2(g) + 3H2(g) ⎯→ 2NH3(g) Haber process Heterogeneous
Hardening of vegetable
Ni RCH2=CH2 + H2 ⎯→ RCH2CH3 oils (e.g. manufacture of Heterogeneous
margarine)
Electrophilic substitution
FeCl3 C6H6 + Cl2 ⎯→ C6H5Cl + HCl Homogeneous
of benzene
2MnO4– + 5C2O42– +16H+ An example of
Mn2+ Homogeneous
⎯→ 2Mn2+ + 10CO2 + 8H2O autocatalysis

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5.1 Heterogeneous Catalysis

• In heterogeneous catalysis, the catalyst and the reactants are in different phases.
➢ The catalyst is usually in the solid phase and it provides active sites at which the reaction
can take place and the reactants are usually liquids or gases.

• For heterogeneous catalysis to occur, the reactant molecules need to be readily adsorbed onto
the catalyst surface. Such type of catalysis is a surface effect which involves the formation of
weak attractive forces between reactant molecules and the atoms of the surface of the catalyst.

• What are the important features of first row transition elements (and their compounds)
that enable them to function effectively as heterogeneous catalysts?
The availability of a partially filled 3d subshell allows for ready exchange of electrons to and
from reactant molecules, facilitating the formation of weak bonds with the reactant molecules.
- This is due to the availability of 3d electrons for bond formation with reactant molecules or the
availability of low lying vacant orbitals which can accept electron pairs from the reactant molecules.

1. Approach I Approach of reactant molecules

to the catalyst surface
Reactant molecules diffuse towards catalyst surface.
R CH CH2 + H H
2. Adsorption
Reactant molecules become adsorbed onto the active
Ni(s)
sites of the catalyst surface through attractive forces. catalyst
This adsorption leads to an increase in reaction rate
II Adsorption of reactants at the
since catalyst surface
- the bonds within the reactant molecules are H
weakened, thereby reducing the activation energy R C CH2 H H
- the reactant molecules are brought into close
contact with correct orientation for reaction Ni(s)
catalyst

3. Chemical Reaction III Reaction at the surface

This reaction has lower activation energy than the
H
uncatalysed reaction
R C CH3 H

Ni(s)
catalyst

4. Desorption
This is the reverse of adsorption. The product molecule IV Desorption of product
eventually breaks free from the catalyst surface. The
R CH2 CH3
product molecule diffuses away from the surface. The
vacant active sites are now available for adsorbing other
reactant molecules. Ni(s)
catalyst

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5.2 Homogeneous Catalysis
• In homogeneous catalysis, the catalyst and the reactants are in the same phase, either
liquid, aqueous or gaseous.

• Consider a reaction A + B ⎯→ D catalysed by Ct

Uncatalysed reaction: A + B ⎯→ D
Catalysed reaction: Step 1 A + Ct ⎯→ A−Ct
Step 2 A−Ct + B ⎯→ D + Ct
--------------------------------------------------------------
Overall reaction A + B ⎯→ D Energy Profiles for a Catalysed
and an Uncatalysed Reaction
potential
• Typical features of homogeneous catalysis: energy

1. The catalyst (Ct) takes part in the reaction E1

by being converted into an intermediate transition

compound (A−Ct). state 1 transition
state 2

Ea(2)
2. The intermediate compound subsequently
Ea(1)
undergoes reaction to yield the product(s) reactive
intermediate
and the catalyst is regenerated.
reactants
3. The larger activation energy for the
H
uncatalysed reaction is, in this case,
replaced by two smaller activation energies products
for the catalysed reaction.
reaction coordinate

E1 = activation energy of uncatalysed reaction

Ea(1) = activation energy of first step of catalysed reaction
Ea(2) = activation energy of second step of catalysed reaction

• What are the important features of transition elements which enable them to function
effectively as homogeneous catalysts?
1. Their ability to exist in different oxidation states, and
2. The relative ease of conversion from one oxidation state to another.
These features facilitate the formation of, and decomposition of, the intermediate formed
from the transition metal ion catalyst and the reactants.

• Example of homogeneous catalysis

The reaction between peroxodisulfate ions and

Do not confuse the above reaction with the
iodide ions catalysed by Fe2+ or Fe3+. reaction between iodine and thiosulfate.
2S2O32–(aq) + I2(aq) ⎯→ S4O62–(aq) + 2I–(aq)
S2O82– (aq) + 2I–(aq) ⎯→ 2SO42–(aq) + I2(aq)
Relevant E values:
(i) Uncatalysed reaction S2O82– + 2e– ⇌ 2SO42– E = +2.01 V
Fe3+ + e– ⇌ Fe2+ E = +0.77 V
S2O82– (aq) + 2I (aq) ⎯→
–
2SO42–(aq) + I2(aq) I2 + 2e– ⇌ 2I – E = +0.54 V

▪ Since Ecell = 2.01 − 0.54 = +1.47 V > 0 V, the uncatalysed reaction is spontaneous
(thermodynamically feasible) under standard conditions.
▪ However, the uncatalysed reaction involves the collision between negatively charged ions.
The electrostatic repulsion between these negatively charged ions causes the reaction to
have a high activation energy and hence proceeds slowly.

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 (ii) Reaction catalysed by Fe3+ or Fe2+
 Exercise 4
Q1 – Write equations to show how the reaction is catalysed by Fe3+ ion.

Step 1: Fe3+(aq) + I–(aq) ⎯→ Fe2+ (aq) + ½ I2 (aq)

Ecell = 0.77 – 0.54 = +0.23 V > 0

Step 2: Fe2+(aq) + ½ S2O82– (aq) ⎯→ Fe3+ (aq) + SO42– (aq)

Ecell = 2.01 – 0.77 = +1.24 V > 0

▪ The catalysed reaction proceeds via two steps. For each step, Ecell > 0 V indicating that each step
is spontaneous (thermodynamically feasible) under standard conditions.

▪ Each step involves a reaction between oppositely charged ions which have a natural tendency to
attract each other. This lowers the activation energy and enhances the reaction rate.

Q2 – Write equations to show how the reaction is catalysed by Fe2+ ion.

Step 1: Fe2+(aq) + ½ S2O82– (aq) ⎯→ Fe3+ (aq) + SO42– (aq)

Ecell = 2.01 – 0.77 = +1.24 V > 0

Step 2: Fe3+(aq) + I–(aq) ⎯→ Fe2+ (aq) + ½ I2 (aq)

Ecell = 0.77 – 0.54 = +0.23 V > 0

In the above given example, it is expected that other couples involving transition metal cations
would also act as catalysts, as long as their E values were between 0.54 V and 2.01 V.

6. COMPLEXES

6.1 Introduction
One of the most important chemical properties of transition elements is their ability to form
complexes.

This ability is not confined to the transition elements e.g. Al forms the complex ion [Al(OH)4]−,
I forms the tri-iodide complex ion I3− and Pb forms the complex [PbCl4]2−.

• What is a complex?

A complex contains a central metal atom or ion linked to one or more surrounding ions
or molecules (called ligands) by dative covalent bonds. If the species carries an overall
charge, it is called a complex ion.

• What is a ligand?
A ligand is an ion or a molecule which contains at least one atom bearing a lone pair of
electrons which can be donated into a low-lying vacant orbital of a central metal atom
or ion forming a co-ordinate bond (or dative covalent bond), and resulting in the formation
of a complex.

Examples of ligand: Cl–, OH– CN–, H2O, NH3, CO, H2N−CH2CH2−NH2

Based on the definition, ligands act as Lewis bases and the central metal atom or ion they
bond to is a Lewis acid.

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• For complexes, the number of bonds formed with the metal ion exceeds the oxidation state
of the metal ion. For example,
CuCl2 is not a complex. Oxidation state of Cu is +2 and there are 2 bonds.
[CuCl2]− is a complex. Oxidation state of Cu is +1 and there are 2 bonds.

• A complex species may be neutral, cationic or anionic.

Examples Central atom/ion Co-ordination number

Ni(CO)4 Ni 4
neutral complexes
Fe(CO)5 Fe 5

[Fe(H2O)6]2+ Fe2+ 6
cationic complexes
[Ag(NH3)2]+ Ag+ 2

[Fe(CN)6]4– Fe2+ 6
anionic complexes
[CuCl4]2– Cu2+ 4

➢ The co-ordination number of the central metal ion (or atom) is the total number of
co-ordinate bonds that the central metal ion (or atom) formed with ligands.

➢ The net charge on the complex ion is the algebraic sum of the charge on the central metal
ion and the total charge carried by the ligands. For example,

[Ag(NH3)2]+ overall charge of complex ion = (1)(+1) + (2)(0) = +1

[CuCl4]2– overall charge of complex ion = (1)(+2) + (4)(–1) = –2
[Fe(CN)6]4– overall charge of complex ion = (1)(+2) +(6)(–1) = –4
[Fe(SCN)(H2O)5]2+ overall charge of complex ion = (1)(+3)+(1)(–1) = +2

• Summary of terms applied to the [Fe(CN)6]3– complex

N
3- Name of complex ion hexacyanoferrate(III) ion
C
.. Central metal ion Fe3+
N
C.. Ligand CN–
:C N
Fe(III) Type of bond between
Co-ordinate bond
Fe3+ and CN–
N C: ..
C Co-ordination number of
6
N Fe3+ in the complex ion
..
C Co-ordination geometry Octahedral
N

• Salts containing complex ions are known as complex salts (co-ordination compounds).

Complex salt constituent cation constituent anion

[CoCl(NH3)5]Cl2 [CoCl(NH3)5]2+ Cl–
pentaamminechlorocobalt(III) chloride a complex cation a simple anion
K4[Fe(CN)6] K+ [Fe(CN)6]4–
potassium hexacyanoferrate(II) a simple cation a complex anion

-13-
  Exercise 5
Q1 – Determine the oxidation number of the transition metal in each of the following complex
ions:
(a) [Fe(OH)2(H2O)4] (b) K[Cu(CN)2] (c) [CoCl4]–
+2 +1 +3

Q2 –Determine the overall charge of the following complex ions:

(a) [Fe(SCN)(H2O)5] (b) [Ni(NH3)6] (c) [VO3(OH)]
Fe(III) 2+ Ni(II) 2+ V(V) 2–

6.2 Types of Ligands

• Ligands are classified according to the number of co-ordinate bonds that the ligand forms
with the central atom or ion.

Type of ligand Number of co-ordinate 1. The word “dens” means tooth in Latin.
bonds which the
2. A polydentate ligand is one which can form
ligand forms with the more than one co-ordinate bonds with the
central metal ion central metal ion. It has “many teeth”.
monodentate ligand 1 3. The complex ions which are formed between
polydentate ligand >1 polydentate ligands and cations are known as
chelates or chelated compounds from a Greek
1. bidentate ligand 2
work “chelos” meaning “a crab’s claw”, since the
2. tridentate ligand 3 ligand forms a clawing pincer-like grip on the
3. hexadentate ligand 6 metal ion.

Polydentate ligands are also called chelating

agents. The term chelate comes from the Greek
word chela, meaning "crab's claw."

Read more: Chelate - Ligand, Chelates, Ions, and

Molecule - JRank Articles
http://science.jrank.org/pages/1375/Chelate.html#ix
(a) Monodentate ligands zz1ytQ3Spqf
• A monodentate (or unidentate) ligand is one which can form only one co-ordinate bond
with a central metal ion (or atom).

Examples of monodentate ligands: Cl–, OH– CN–, H2O, NH3, CO

Examples of complexes with monodentate ligands: [Fe(SCN)(H2O)5]2+, [CoCl4]2–

(b) Bidentate ligands

• A bidentate ligand is one which can form two co-ordinate bonds simultaneously with
the central metal ion (or atom).
Examples of bidentate ligands:
ethane-1,2-diamine ethanedioate ion 2-hydroxybenzoate ion aminoethanoate ion
(or 1,2-diaminoethane) (oxalate ion) (glycinate ion)
(or ethylenediamine) OH
..
O O .. O
CH2 CH2 C C O- CH2 C
-O C
H2N NH
.. 2 O - H2N
.. O
.. .. .. ..
O

-14-
 Examples of complexes with bidentate ligands:
[Co(H2NCH2CH2NH2)3]3+ [Cr(C2O4)3]3–

O 3

CH2 3+ C
H2 N
.. O
.. O
CH2 C
O
NH
.. 2
H2 C :NH2 C O: :O
H2 C III C
Co O CrIII
H2 N: :NH2 O: :O

CH2 C O
.. ..
H2 N O
CH2 C

(c) Hexadentate ligands

• A hexadentate ligand is one which can form six co-ordinate bonds simultaneously with
the central metal ion (or atom).

Example of a hexadentate ligand: O O

.. ..
-O C CH2 CH2 C O-
ethylenediaminetetraacetate ion
..
• edta4– ion or EDTA4– ion ..
N CH2 CH2 N
• or sometimes just represented by .. ..
edta or EDTA -O C CH2 CH2 C O-
O O

HOOC CH2 CH2 COOH

Note:
.. ..
1. The edta4– ion is formed from N CH2 CH2 N
ethylenediaminetetraacetic acid,
which may be written as H4edta. HOOC CH2 CH2 COOH
H4edta
2. Edta is a useful ligand. It is used in many situations to ‘mop up’ metal ions. For example, it is
▪ added in trace amounts in some foods to prevent metal ions catalysing the reaction that makes fat
rancid.
▪ added to cosmetics to keep minerals and other trace elements from binding with other ingredients
in a cosmetic formulation to prevent deterioration and skin deposition.
▪ added to shampoos, bath foams and other cleansing products to help soften the water

Examples of complexes with edta ligand: [Cu(edta)]2– , [Fe(edta)]–

2
O
O
C

O CH2
O O
C
Cu(II) C O
H2C
N CH2
N
CH2 CH2

CH2 O
C

-15-
6.3 Transition Metal Ions and Complex Formation
• Complex formation
..
Ni2+ + 6 H2O [Ni(H2O)6]2+
metal ion ligand complex ion
Lewis acid Lewis base
(electron pair acceptor) (electron pair donor)

• What are the conditions required for complex formation?

1. the presence of ligands (i.e. species with at least one atom having a lone pair of
electrons) to donate electron pairs to form co-ordinate bonds
2. the presence of a central metal ion (or atom) capable of
(a) attracting the lone pair of electrons from the ligand, and
(b) accommodating the lone pair of electrons in its low-lying vacant orbitals to form a
co-ordinate bond

• Why do transition metal ions show a high tendency to form complexes?

1. The transition metal ions have low-lying vacant orbitals (e.g. 3d, 4s and 4p orbitals)
to accommodate the lone pairs of electrons from the ligands to form co-ordinate bonds.
2. The transition metal ions are relatively small and highly charged. Consequently, they
have relatively high charge to size ratio (charge density) and are able to attract the lone
pair of electrons from the ligands. Their high charge density and hence polarising power,
produces a strong tendency towards covalent bond formation with ligands.

6.4 Aqua Complexes

+
• In aqueous solution, the cations of Group 1 and Group 2 H H
elements are surrounded by water molecules, with the H H
+
O- +
negative ends of dipoles of these water molecules O - -
directed towards the cations. The cations are said to be O H
H Na+
hydrated. - - H
H O
O - +
• The type of interaction between the cations and the water + O
H H H
molecules is that of ion-dipole interaction i.e. +
H
electrostatic attraction between the positive ion and the
negative ends of the dipoles.
3+
OH
.. 2
• In aqueous solution, transition metal ions exist as aqua
complexes. Each oxygen atom of a water molecule H2O:
:OH2
donates a lone pair into a low-lying vacant orbital of the III
Fe
transition metal ion and forms a coordinate bond. In
H2O:
general, aqua complexes are of the form [M(H2O)6]n+, :OH2

where n = 2 or 3. ..
OH2
Solution Cation Complex ions
NaCl(aq) Na+(aq) -
AlCl3(aq) Al3+(aq) [Al(H2O)6]3+(aq)
Cr(NO3)3(aq) Cr3+(aq) [Cr(H2O)6]3+(aq)
FeCl3(aq) Fe3+(aq) [Fe(H2O)6]3+(aq)

-16-
6.5 Acidity of Aqua Complexes
• Why is an aqueous solution of FeCl3 acidic?

In aqueous FeCl3 solution, the Fe3+ ion exists as an aqua complex ion, [Fe(H2O)6]3+.
Due to its high charge and small size, the Fe3+ ion has high charge density and is hence strongly
polarising. It distorts the electron cloud of the H2O molecules bonded to it, weakening the O–H bonds
and enabling these H2O molecules bonded to it to become proton donors. The free water molecules in the
solution act as bases and the following equilibrium is established:

[Fe(H2O)6]3+(aq) + H2O(l) ⇌ [Fe(OH)(H2O)5]2+(aq) + H3O+(aq)

The Fe3+ ion is consequently said to undergo appreciable hydrolysis in aqueous solution. The slight
excess of H3O+ ions in the solution causes the solution to be acidic.

• The aqueous solutions of most transition metal compounds such as CrCl3(aq), FeCl3(aq),
CuSO4(aq) and Co(NO3)2(aq) are acidic.

• An aqueous solution containing either Cr3+ or Fe3+ ions is acidic enough to react with sodium
carbonate to produce carbon dioxide gas together with the formation of a hydroxide
precipitate.

• What happens when Na2CO3 is added to an aqueous solution containing Fe3+ ions?
The following three equilibria are relevant to the Fe3+ ion in aqueous solution:

[Fe(H2O)6]3+(aq) + H2O(l) ⇌ [Fe(OH)(H2O)5]2+(aq) + H3O+(aq) ………..(1)

[Fe(OH)(H2O)5]2+(aq) + H2O(l) ⇌ [Fe(OH)2(H2O)4]+(aq) + H3O+(aq) ………(2)

[Fe(OH)2(H2O)4]+(aq) + H2O(l) ⇌ [Fe(OH)3(H2O)3](s) + H3O+(aq) …………(3)

Upon addition of sodium carbonate, effervescence is observed as the following reaction occurs:

CO32–(aq) + 2H3O+(aq) ⎯→ CO2(g) + 3H2O(l)

The consumption of H3O+ ions causes the equilibrium position of reaction (1) to shift to the right. With
more CO32– ions added, and hence more H3O+ ions removed, the equilibrium position of reaction (2)
and then subsequently that of reaction (3) are also forced to shift to the right. Consequently, a red-
brown precipitate of [Fe(OH)3(H2O)3] (usually written simply as Fe(OH)3) is obtained together with the
evolution of CO2.

Overall: 2 [Fe(H2O)6]3+(aq) + 3 CO32–(aq) ⎯→ 2 [Fe(OH)3(H2O)3](s) + 3 CO2 + 3 H2O

This reaction also occurs for [Al(H2O6)]3+ and [Cr(H2O6)]3+.

-17-
 7. STEREOCHEMISTRY OF COMPLEXES
7.1 Shapes of complexes
The shape of the complex ion depends on the coordination number and nature of the metal ion.
Co-ordination
Shape Examples
number

[Ag(NH3)2]+ [H3N: AgI :NH3]+

2 linear [Ag(CN)2]–
[CuCl2]– [Cl: CuI :Cl]-

NH 2+
.. 3

Ni(CO)4
[Zn(NH3)4]2+ ZnII
tetrahedral
[CoCl4]2–
H3N: : NH3
[Cu(CN)4]3–
..
4 NH3

2+
[Ni(CN)4]2– NC: :CN
square planar [Cu(NH3)4]2+ NiII
[CuCl4]2– NC: :CN

3-
CN
..

NC:
[Fe(CN)6]3– :CN
[Fe(CN)6]4- FeIII
6 octahedral
[Ni(NH3)6]2+ NC: :CN

..
CN

Note:
[Cu(NH3)4(H2O)2]2+ vs [Cu(NH3)4]2+ : both are commonly used and accepted.

7.2 Isomerism in compounds of transition elements

Compounds of transition elements can undergo isomerism. For example, when green crystals of
chromium(III) chloride, [Cr(H2O)4Cl2]Cl·2H2O, are dissolved in water, the following changes occur.

[Cr(H2O)4Cl2]Cl2H2O ⎯→ [Cr(H2O)5Cl]Cl2H2O ⎯→ [Cr(H2O)6]Cl3.

green blue-green violet

The compounds produce different amounts of free chloride ions and hence can be distinguished
by precipitation of the free chloride ion using aqueous silver nitrate.

The complex cations [Cr(H2O)4Cl2]+, [Cr(H2O)5Cl]2+, [Cr(H2O)6]3+ are different even though they
originate from the same ionic compound – chromium(III) chloride

-18-
  Exercise 6
Q1 – N02/17
The anti-cancer drug, cisplatin has the formula PtCl2(NH3)2. In the human body, one of the chloride ions
of cisplatin is replaced by one water molecule.

PtCl2(NH3)2 + H2O ⎯→ [PtCl(NH3)2(H2O)]+ + Cl-

What is the oxidation number of platinum in cisplatin and in the aqua complex? +2

Q2 – N05/1 Q3
Like other transition elements, platinum(IV) Chromium(III) chloride combines with ammonia to
chloride combines with ammonia to form form compound X in which the co-ordination
compounds. The co-ordination number of number of chromium is 6. When solution X is
platinum in these compounds is 6. A formula unit treated with an excess of aqueous silver nitrate,
of one of the compounds contains a cation and only two thirds of the total chloride present is
only two chloride ions. precipitated as AgCl.

What is the formula of this compound? What is the formula of compound X?

A Pt(NH3)3Cl4 B Pt(NH3)4Cl4 A Cr(NH3)3Cl3 B Cr(NH3)4Cl3
C Pt(NH3)6Cl2 D Pt(NH3)6Cl4
C Cr(NH3)5Cl3 D Cr(NH3)6Cl3

8. COLOUR OF COMPLEXES

Transition metal compounds are frequently coloured, both in the solid state and in solution.

• Typical colours for common ions (i.e. with H2O as the ligand) are summarised below.

Aqua Electronic configuration

Colour
Note:
complex ion of the cation 1. Vacant or fully filled d sub-shell is
[Sc(H2O)6]3+ [Ar] 3d0 colourless associated with a lack of colour.
[Ti(H2O)6]3+ [Ar] 3d1 violet
2. Aqueous solutions of Cr3+
[V(H2O)6] 3+
[Ar] 3d 2
green • [Cr(H2O)6]3+ is violet in cold
2+ 3
aqueous solution.
[V(H2O)6] [Ar] 3d violet
• The observed green colour of its
[Cr(H2O)6]3+ [Ar] 3d3 violet / green solutions is due to the partial
2+ 4
replacement of water ligands by
[Cr(H2O)6] [Ar] 3d blue
other ligands, e.g. Cl− or SO42−.
[Mn(H2O)6]3+ [Ar] 3d4 violet • For simplicity, the green solution
is still commonly written as
[Mn(H2O)6]2+ [Ar] 3d5 faint pink
[Cr(H2O)6]3+.
pale violet (lilac) /
[Fe(H2O)6]3+ [Ar] 3d5
yellow 3. Aqueous solutions of Fe3+
[Fe(H2O)6]2+ [Ar] 3d6 pale green • [Fe(H2O)6]3+ is pale violet.
• The observed yellow colour of
[Co(H2O)6]2+ [Ar] 3d7 pink its solutions is due to the partial
[Ni(H2O)6]3+ [Ar] 3d8 green
loss of H+ by a water ligand to
form [Fe(OH)(H2O)5]2+, which is
2+ 9
[Cu(H2O)6] [Ar] 3d blue yellow.
[Zn(H2O)6]2+ [Ar] 3d10 colourless
• For simplicity, the yellow
solution is still commonly written
as [Fe(H2O)6]3+.
•

-19-
8.1 Occurrence of colour

(a) The electromagnetic spectrum

Note: 1 nanometre, 1 nm = 10–9 m

• White light (e.g. sunlight) contains all the wavelengths of light in the visible region of the
electromagnetic spectrum. It can be dispersed into a spectrum of colours, each of which
has a characteristic range of wavelengths.

(b) Coloured objects

• If selected wavelengths of the incident white light are absorbed and other wavelengths
are reflected/transmitted, then the object will appear ‘coloured’. In general, an object
appears coloured because it preferentially absorbs some wavelengths of light in the
visible spectrum and transmits or reflects light that is richer in the remaining wavelengths
of the visible spectrum.

• What determines the observed colour of a coloured object?

The observed colour is the colour due to the combination of wavelengths of visible light
reflected (for opaque objects) or transmitted (for transparent objects).

• The observed colour is usually estimated using the idea of complementary colours.

(c) Complementary colours

650 nm 580 nm
Wavelength range
(nm) Colour Complementary colour orange
400 – 430 violet yellow red yellow
430 – 490 blue orange 700 nm
550 nm
490 – 550 green red 400 nm violet green
550 – 580 yellow violet
blue
580 – 650 orange blue
650 – 700 red green 430 nm 490 nm

Each colour has a complementary colour as shown in the table above. A colour wheel can
be used to help predict the colour that will be seen when absorption occurs in part of the
visible spectrum. Colours directly opposite each other on the colour wheel are called
complementary colours.

-20-
 • Example: A green object
When white light (containing a broad spectrum of all visible wavelengths) passes through
a substance that absorbs red light, the colour observed is green; green is the complement
of red.
transmits all
other wavelengths observed colour
visible light absorbs of light of solution
red light
is green
strongly

• The observed colour is said to be complementary to the colour of light absorbed. Hence
if a compound absorbs light of one colour, we see the complement of that colour.

8.2 Absorption of Light Energy and Electronic Transition

• When light energy is absorbed by a

substance, an electron in the atom or ion of
that substance is promoted from an orbital of
lower energy to one of higher energy.
energy
E absorption
• The atom or ion absorbing the radiation of energy
changes from what is described as its corresponding
ground state to an excited state. to E
ground state excited state
• There can be more than one electronic
transition. The different electronic transitions
involve the absorption of radiation of different
wavelengths (or different frequencies) and if
the absorbed wavelengths are in the
visible region of the spectrum, then the
substance appears coloured.

8.3 Sodium chloride solution

Why is an aqueous solution of sodium chloride colourless?

• Consider the ground state and the excited state of the Na+ ion.
+ +
Na Na
(ground state) (excited state)
1s2 2s2 2p6 1s2 2s2 2p5 3s1

• The excitation of an electron from the lower energy 2p orbital to the higher energy 3s
orbital requires wavelength of light well beyond the range of visible spectrum. Radiation
from the visible spectrum does not provide sufficient energy to promote electrons in Na+
ions to even the lowest of their possible excited electronic states.
Hence NaCl(aq) allows all the incident visible light to be transmitted and appears colourless.

-21-
8.4 Occurrence of Colour in Octahedral Complexes

(a) Crystal Field Theory

• Crystal Field Theory provides a way of determining, by simple electrostatic
considerations, how the energies of the metal ion orbitals will be affected by the set of
surrounding ligands.
• In an isolated metal ion in the gaseous phase, the five 3d orbitals all have the same
energy and are said to be degenerate.
• In an octahedral complex, six ligands L approach the central metal ion M along the x, y
and z axes. This results in electrostatic repulsion between the electrons in the 3d orbitals
and the lone pairs on the ligands, and thus an increase in potential energy. Hence the
energy of an electron in either of the 3d orbitals in a complex of M is higher than in an
isolated M atom.
• 3dx2-y2 and 3dz2 : These orbitals have their greatest electron density along the co-ordinate
axes on which the ligands are situated. Hence electrons in these orbitals are pointing
towards the lone pairs of ligands, and will be repelled by them.

• 3dxy, 3dyz, 3dxz : These orbitals have their greatest electron density in between the co-
ordinate axes. Hence the repulsion between electrons in these orbitals and those of the
approaching ligands will be less compared to electrons in 3dx2-y2 or 3dz2 orbitals.

• Thus the five 3d orbitals are affected differently by the approach of the ligands. The
orbitals are split into two energy levels with an energy gap between them, and the degeneracy
of the five 3d orbitals is destroyed in complexes.

-22-
 Worked Example 1
Using the Cartesian axes, draw and label diagrams to show the d orbitals that the electrons in a
transition metal ion might occupy.
z y z

y z x

x x y

dxz dxy dyz

(in between x and z axes) (in between x and y axes) (in between y and z axes)

dz2
dx2 - y2
(along z axis)
(along x and y axes)

(b) The splitting of the five d-orbitals in octahedral complexes

• In the presence of the ligands, the five 3d orbitals of the central metal ion are split into
two energy levels as illustrated.

The splitting of the

five d orbitals in an
octahedral ligand dz2 dx2-y2
field.
energy Eo

dxy dyz dxz

isolated metal ion ion in octahedral

ligand field

• The resulting small energy gap (i.e. Eo) between the two sets of d-orbitals turns out to
correspond to energies of electromagnetic radiation in the visible region of the
spectrum.

• Transition metal compounds are therefore coloured because radiation in the visible region
of the spectrum is of the right quantity of energy to promote electrons from d-orbitals of
lower energy to one of higher energy (i.e. d-d transitions). The colour observed is the
complement of the colour absorbed.

-23-
• Why is an aqueous solution of NiCl2 coloured?

In aqueous solution, Ni2+ exists as an octahedral complex [Ni(H2O)6]2+.

The presence of the H2O ligands causes the splitting of the five originally degenerate 3d
orbitals in the Ni2+ ion into two sets of slightly different energy levels.
Since the 3d subshell is partially filled (Ni2+: [Ar] 3d8), the electrons from the lower energy d
orbitals can absorb energy corresponding to certain wavelengths from the visible spectrum
and get promoted to the higher energy d orbitals.
Such d-d transitions are responsible for the colour observed in NiCl2(aq). The colour observed
is the complement of the colour absorbed.

L • presence of ligands causes the

S • splitting of the five 3d orbitals into two sets of slightly different energy levels.
P • Since these 3d subshell is partially filled,
E • electrons from the lower-energy d orbitals can absorb energy corresponding to certain
wavelengths from the visible spectrum and get promoted to the higher-energy d orbitals.
(d-d transitions)
C • The colour observed is the complement of the colour absorbed.

8.5 Factors affecting the Colour of Transition Metal Complexes

• The colour of a transition metal complex is dependent on the energy gap (E) between the
two groups of d orbitals. This in turn depends on the following factors.

1. The identity of the metal and its oxidation state (which depends on the number of
d electrons present).
[Cr(H2O)6]2+(aq) [Cr(H2O)6]3+(aq) [Fe(H2O)6]2+(aq) [Fe(H2O)6]3+(aq)
[Ar] 3d4 [Ar] 3d3 [Ar] 3d6 [Ar] 3d5
blue violet pale green lilac

• Compounds of the same element in different oxidation states show different colours.
• [Fe(H2O)6]2+ and [Fe(H2O)6]3+ have different no. of d-electrons and repel the electrons
of the ligands to different extent, thus the energy gap between the split d-orbitals are
different.

2. The nature of the ligands bonded to the central metal ion/atom.

[Ni(H2O)6]2+(aq) green [Cu(H2O)6]2+(aq) blue

[Ni(NH3)6]2+(aq) blue 2+
[Cu(NH3)4(H2O)2] (aq) deep blue

• Different ligands split the d orbitals of the metal ion into two sets of slightly different
energy levels to different extents. Hence different transition metal complexes
absorb different wavelengths of light from the visible spectrum for d-d transitions
(i.e. the promotion of electrons from the lower energy d orbitals to the higher energy
d orbitals).

• Consequently different colours, corresponding to the complements of the different

colours absorbed, are observed for different complexes.

-24-
8.6 Splitting of d-orbitals in Tetrahedral Complexes
The splitting of the
• In tetrahedral complexes, the situation is the five d orbitals in a
reverse of that in octahedral complexes. The four tetrahedral ligand dxy dyz dxz
field.
ligands in tetrahedral complexes approach the energy Et
central metal ion in between the x, y and z axes.
dz2 dx2-y2
• Electrons in the 3dxy, the 3dyz and the 3dxz
orbitals now experience the greatest
electrostatic repulsion from the ligand lone pairs,
so have a higher energy than electrons in the ion in tetrahedral
isolated metal ion
3dx2-y2 or the 3dz2 orbitals. ligand field

9. LIGAND EXCHANGE

9.1 Stability constant

• An aqueous solution of nickel(II) sulfate contains [Ni(H2O)6]2+ ions. When excess aqueous
ammonia is added to this solution, there is a noticeable change of colour because some of the
[Ni(H2O)6]2+ ions are converted into [Ni(NH3)6]2+ ions.

• A ligand exchange reaction occurs and the following equilibrium is established:

[Ni(H2O)6]2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq) + 6H2O(l)

green blue

• The equilibrium constant, Kstab, of the above reaction, taking the concentration of water as
being constant, is

[ Ni(NH3)62+ ]
Kstab = 2+ 6 = 4.8 x 107 mol–6 dm18
[ Ni(H2O)6 ] [ NH3 ]

• Kstab is known as the stability constant for the [Ni(NH3)6]2+ ion. It is a measure of how stable
the [Ni(NH3)6]2+ ion is as compared to the [Ni(H2O)6]2+ ion.

• Definition of Kstab
The stability constant, Kstab, of a complex ion may be defined as the equilibrium constant for
its formation. The greater the value of Kstab, the more stable the complex ion is relative to the
aqua complex containing the same metal ion.

• The large value of Kstab means that:

o The equilibrium position for the above reaction lies very much to the right.
o The [Ni(NH3)6]2+ ion is relatively more stable than the [Ni(H2O)6]2+ ion.
o NH3 is a stronger ligand than H2O.
o NH3 forms a stronger dative covalent bond with the Ni2+ ion.
o There will be replacement of the H2O ligands by the NH3 ligands when excess NH3 is
added to NiSO4(aq) (i.e. a ligand exchange reaction can occur).

-25-
9.2 Ligand exchange in terms of stability constants
The formation of a complex ion can be regarded as a competition between two ligands for the
metal ion. In general, the ligands forming the complex of higher stability constant will replace
those forming the complex of lower stability constant.

(a) Complexes of copper(II) with water and ammonia

Kstab of complexes of copper(II)

complex [CuCl4]2– [Cu(NH3)4(H2O)2]2+ [Cu(edta)]2–

log Kstab 5.6 13.1 18.8
colour yellow deep blue light blue

 Worked Example 2 (N93/2/1a)

(i) Describe and explain what happens when dilute aqueous ammonia is gradually added to an
aqueous solution containing Cu2+(aq).

excess
NH3(aq) NH3(aq) 2+
[Cu(H2O)6]2+(aq) Cu(OH)2(s) [Cu(NH3)4(H2O)2] (aq)
blue solution light blue precipitate deep blue solution

Aqueous NH3 is a weak base which ionizes in water to form OH– ions.
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH–(aq)
An aqueous solution containing Cu2+ ions is blue due to the presence of [Cu(H2O)6]2+ ions.
When dilute NH3(aq) is gradually added, a pale blue precipitate of Cu(OH)2 is first formed
since ionic product of Cu(OH)2 exceeds the Ksp of Cu(OH)2.

[Cu(H2O)6]2+(aq) + 2OH–(aq) ⇌ [Cu(OH)2(H2O)4](s) + 2H2O(l) ……………..(1)

blue solution pale blue precipitate

or Cu2+(aq)+ 2OH–(aq) ⇌ Cu(OH)2(s)

When excess NH3 is added, a ligand exchange reaction occurs and the following
equilibrium is established.

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

blue solution deep blue solution
The equilibrium position of reaction (2) lies very much to the right as the formation of the
more stable [Cu(NH3)4(H2O)2]2+ ion is favourable.

The formation of [Cu(NH3)4(H2O)2]2+ ions results in a decrease in the concentration of

[Cu(H2O)6]2+ and hence decreases the ionic product of Cu(OH)2 to below its Ksp value.
Hence the pale blue precipitate of Cu(OH)2 dissolves to give a deep blue solution of
[Cu(NH3)4(H2O)2]2+.

Note:
1. In this case, there exist two competing equilibria, (1) and (2). Both NH3 and OH– compete to combine
with Cu2+(aq). With a large excess of NH3 (i.e. higher [NH3]), the formation of [Cu(NH3)4(H2O)2]2+ is
more favourable.

2. The following equation is sometimes used to represent the dissolution of the pale blue precipitate upon
the addition of excess aqueous NH3.
Cu(OH)2(s) + 4NH3(aq) + 2H2O(l) ⎯→ [Cu(NH3)4(H2O)2]2+(aq) + 2OH–(aq)

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 (ii) Describe and explain what happens when an aqueous solution of edta is added to the
solution in (i).
When aqueous edta is added to a deep blue solution containing the [Cu(NH3)4(H2O)2]2+ ions,
the colour of the solution lightens considerably as a ligand exchange reaction occurs. The
hexadentate edta ligand replaces the NH3 and H2O ligands to form the more stable [Cu(edta)]2–
ions leading to the formation of a light blue solution. The following equilibrium is established
and the equilibrium position lies more to the right.

[Cu(NH3)4(H2O)2]2+(aq) + edta4–(aq) ⇌ [Cu(edta)]2–(aq) + 4NH3(aq) + 2H2O(l)

The above reaction is entropy favoured as more aqueous particles are formed when the
edta4− ligands substitute the NH3 and H2O ligands. (naq particles = 5 – 2 = +3)

 Worked Example 3

J91/4/1bii Describe and explain what is seen when concentrated hydrochloric acid is added
to a solution of Cu2+ ions in water.
A solution of Cu2+ ions in water is blue in colour due to the presence of [Cu(H2O)6]2+ ions. A
ligand exchange reaction occurs where the Cl– ligands replace the water ligands in the
[Cu(H2O)6]2+ ions to form the more stable [CuCl4]2– ions. The following equilibrium is
established:
[Cu(H2O)6]2+(aq) + 4Cl–(aq) ⇌ [CuCl4]2– (aq) + 6H2O(l)
blue yellow

The presence of both the blue [Cu(H2O)6]2+ ions and yellow [CuCl4]2– ions results in a green
solution.

Addition of more concentrated HCl to the green solution increases the Cl– concentration,
causing the equilibrium position of the above reaction to shift further right. The green solution
turns yellow as more yellow [CuCl4]2– ions are formed.

(b) Complexes of Ag(I):

• One of the fascinating and intriguing demonstrations of different ligands for a particular
cation is outlined in the sequence reactions involving Ag+ shown below.

Note:
Some of the reactions in the sequence
result in the precipitation of insoluble solids.
Being uncharged, they are less readily
hydrated by polar water molecules than the
charged complexes and so they are less
likely to dissolve in water.

Going down the table, the ligands are

increasing in strength and become stronger
competitors for Ag+: H2O < Cl− < NH3 < Br−
< S2O32− < I− < CN− < S2− < edta2−

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 Exercise 7: (J96/IV/22)

(i) [Fe(H2O)6]3+ + 6 CN− ⇌ [Fe(CN)6]3− + 6 H2O

Fe (CN ) 3 − 
 6 

Kstab = Fe ( H O ) 3 +
 CN − 
6
mol-6 dm18
 2 6   

(ii) 1: [Fe(CN)6]3− formed due to the larger Kstab value for the complex.
2: [Co(CN)6]3− due to the larger Kstab value for the Co(III) complex

9.3 Exchange of ligands in haemoglobin

• The body of an adult contains about 4 g of iron, 75% of which is in the form of haemoglobin.
This vital oxygen-carrying constituent of the blood contains iron(II).
• Haemoglobin – red pigment in red blood cells
– acts as a transporter of oxygen in blood
– contains iron(II) which has a co-ordination number of six

Structure:
– The iron(II) exhibits hexa co-ordination.

– Four of the co-ordination sites are taken up by nitrogen

from a ring system called a porphyrin which acts as a
tetradentate ligand. This complex is called ‘haem’.

– Above the plane of this ring is a fifth nitrogen atom,

acting as a ligand. This atom is part of a complex
protein called globin.

– The oxygen molecule may become reversibly bonded

at the sixth site allowing the haemoglobin to carry
oxygen from one part of the body to another.

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– Better ligands than oxygen can bond strongly (almost irreversibly) to the iron(II) and thus
destroy the oxygen carrying capacity of haemoglobin. This accounts for the toxic nature of
carbon monoxide and cyanide ions, both of which are very good ligands.

H2O
O
.. 2 CO
O
.. 2

N: :N N: :N
II
Fe CO
+ O II
2 Fe O22O
+ H
N: :N N: :N

..
N ..
N

9.4 Effect of Ligand Exchange on E values

• Replacement of H2O ligands in an aqua-complex by other ligands can cause large changes in
electrode potential values.

(a) Effect of CN– ligand on the relative stability of Fe(II) and Fe(III)

[Fe(H2O)6]3+(aq) + e− ⇌ [Fe(H2O)6]2+(aq) E = +0.77 V

[Fe(CN)6]3−(aq) + e− ⇌ [Fe(CN)6]4−(aq) E = +0.36 V

• Replacing the H2O ligand by the CN− ligand causes the E value for the Fe(III)/Fe(II)
system to become less positive i.e. Fe(III) becomes more easily reduced and less
oxidising.

• Hence there is stabilisation of the +3 oxidation state of iron relative to the +2 state of iron
by the CN− ligand.

• The positively charged [Fe(H2O)6]3+ ion accepts an electron more readily since oppositely
charged species attract each other naturally. The negatively charged [Fe(CN)6]3− ion does
not accept an electron readily since there is naturally repulsion between similarly charged
species.

How can it be shown experimentally that [Fe(CN)6]3−(aq) is a weaker oxidising agent

than [Fe(H2O)6]3+(aq)?

By reacting both species with KI(aq). Data: ½I2(aq) + e− ⇌ I−(aq) E = +0.54 V

[Fe(H2O)6]3+(aq) + I−(aq) ⎯→ [Fe(H2O)6]2+(aq) + ½I2(aq) Ecell = +0.23 V > 0 V

Since Ecell > 0 V, the reaction is thermodynamically feasible under standard conditions.
Observation: Brown solution of I2(aq) formed.

[Fe(CN)6]3−(aq) + I−(aq) ⎯→ [Fe(CN)6]4−(aq) + ½I2(aq) Ecell = –0.18 V < 0 V


Since E cell < 0 V, the reaction is thermodynamically not feasible under standard
conditions.
Observation: Brown solution of I2(aq) is not produced.

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(b) Effect of NH3 and CN– ligands on the relative stability of Co(II) and Co(III)
[Co(H2O)6]3+(aq) + e− ⇌ [Co(H2O)6]2+(aq) E = +1.82 V
[Co(NH3)6]3+(aq) + e− ⇌ [Co(NH3)6]2+(aq) E = +0.10 V
[Co(CN)6]3−(aq) + e− ⇌ [Co(CN)6]4−(aq) E = –0.80 V
O2 + 4H+ + 4e− ⇌ 2H2O E = +1.23 V
O2 + 2H2O + 4e− ⇌ 4OH− E = +0.40 V

• The E values show that there is stabilisation of Co(III) with respect to Co(II) by the NH3
and the CN− ligands.

• [Co(H2O)6]3+ ions are so strongly oxidising that they react with water to produce oxygen.

• [Co(NH3)6]2+(aq) and [Co(CN)6]4−(aq) are so strongly reducing that they are oxidised by
air.

10. SUMMARY

10.1 Typical reactions undergone by transition metal ions

(a) Precipitation reactions

• Common reagents used: NH3(aq), NaOH(aq)
• See the QA Lecture Notes for details
• Explanation is usually couched in terms of ionic product exceeding Ksp
NH3(aq)
Cu2+(aq) + 2OH–(aq) ⎯⎯⎯⎯⎯→ Cu(OH)2(s)
blue solution pale blue precipitate

(b) Ligand exchange reactions

• Prediction of whether such a reaction occurs is usually based on the given relative stability
constants of the complex ions or the given observations (i.e. colour changes, dissolution
of precipitate, etc.).
• Explanation is usually couched in terms of the relative stabilities of the complexes or the
relative strengths of the ligands.
excess NH (aq)
[Cu(H2O)6]2+(aq) + 4NH3(aq) ⎯⎯⎯⎯⎯⎯⎯⎯→
3
[Cu(NH3)4(H2O)2]2+(aq) + 2H2O(l)
blue solution deep blue solution
conc. HCl
[Cu(H2O)6]2+(aq) + 4Cl–(aq) ⎯⎯⎯⎯⎯→ [CuCl4]2– + 6H2O(l)
blue solution yellow solution
KSCN(aq)
[Fe(H2O)6]3+(aq) + SCN–(aq) ⎯⎯⎯⎯⎯→ [Fe(SCN)(H2O)5]2+(aq) + H2O(l)
yellow solution blood red solution
Na2C2O4(aq)
[Fe(H2O)6]3+(aq) + 3C2O42–(aq) ⎯⎯⎯⎯⎯→ [Fe(C2O4)3]3–(aq) + 6H2O(l)
yellow solution colourless solution
conc. HCl
[Co(H2O)6]2+(aq) + 4Cl–(aq) ⎯⎯⎯⎯⎯→ [CoCl4]2–(aq) + 6H2O(l)
pink solution blue solution

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(c) Redox reactions
• Justification of whether a redox reaction can occur is usually based on E values

2Fe2+(aq) + Cl2(aq) ⎯⎯⎯⎯⎯→ 2Fe3+(aq) + 2Cl–(aq)

pale green solution yellow solution

2Fe3+(aq) + 2I–(aq) ⎯⎯⎯⎯⎯→ 2Fe2+(aq) + I2(aq)

2Cu2+(aq) + 4I–(aq) ⎯⎯⎯⎯⎯→ 2CuI(s) + I2(aq)

cream ppt. brown solution

Cu2+(aq) + Zn(s) ⎯⎯⎯⎯⎯→ Cu(s) + Zn2+(aq)

pink solid
(d) Other reactions
[Cr(H2O)6]3+(aq) + H2O(l) ⇌ [Cr(OH)(H2O)5]2+(aq) + H3O+(aq)

hydrolysis of aqua complex ions reaction with sodium carbonate to give CO2

2CrO42–(aq) + 2H+(aq) ⎯⎯⎯→ Cr2O72–(aq) + H2O(l)

yellow solution orange solution

Cr2O72–(aq) + 2OH–(aq) ⎯⎯⎯→ 2CrO42–(aq) + H2O(l)

orange solution yellow solution

APPENDIX

Rules for Nomenclature of Complexes

The following rules apply to all complexes, whether or not they are derived from transition
elements.

(a) Formulae of Complexes

1. The symbol for the central atom is written first, followed by anionic ligands and neutral ligands in
that order. Example: [Fe(OH)(H2O)5]2+
2. Within each ligand class, the order should be alphabetical in terms of the symbol for the donor
atom of the ligand. Example: [Cu(NH3)4(H2O)2]2+
N is the donor atom in NH3.
O is the donor atom in H2O.
3. Polyatomic ligands, but not monatomic ligands, are enclosed in curved brackets, and the formula
of the whole complex is enclosed in square brackets. Example: [CrCl2(NH3)4]+

(b) Naming of Complexes

1. The cation is always named before the anion.
2. The names of the ligands precede the name of the central atom or ion.
3. The oxidation state of the central atom or ion is shown in Roman numerals in brackets immediately
after its name.
4. Metals forming complex anions are given the word-ending -ate, whereas complex cations and
neutral complexes are given their usual names.
5. Ligands are listed in alphabetical order, the multiplying prefix being ignored.
6. When a number prefix (e.g. di-, tri-) is already included in the name of the ligand, the name of the
ligand is placed in a bracket with the prefix bis-, tris-, tetrakis- instead of di-, tri-, tetra- respectively.
7. Notice that the complex ion names are written as one word, with no spacing between the name and
the oxidation state of the central atom.

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(c) Steps to be taken
Monodentate ligands Polydentate ligands A
1. Identify the ligands H2O aqua en or H2NCH2CH2NH2 ethane-1,2-diamine
(see Box A). NH3 ammine C2O42– ethanedioato
NO nitrosyl edta ethylenediaminetetraaceto
2. Identify the number of CO carbonyl
ligands (see Box B). Cl– chloro
CN– cyano
3. If several ligands are OH– hydroxo Names used for some metals in C
present, list them in NO2– nitro anionic complexes
SCN– thiocyanato
alphabetical order.
Note: prefixes do not Element Name in complex
alter order. B Ti titanate
Prefixes used for V vanadate
4. Name the central monodentate Cr chromate
cation/atom and ligands: Mn manganate
indicate its oxidation Fe ferrate
state using a Roman 2 = di, Co cobaltate
numeral in 3 = tri,
parentheses. Ni niccolate
4 = tetra,
5 = penta, (ASE: nickelate)
For complex cation, Cu cuprate
6 =hexa, etc.
use the name of the Zn zincate
metal. Prefixes used for Ag argentate
For complex anion, polydentate Au aurate
modify the name of ligands:
Al aluminate
the metal to end in
2 = bis, Sn stannate
–ate (see Box C).
3 = tris, Pb plumbate
4 = tetrakis

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