S6 CHEM 19/APR/2022

THE TRANSITION ELEMENTS

Introduction
 Transition elements are those that occur in either the 𝑑 − or 𝑓 − blocks in the
Periodic Table.
 In this topic, we shall only consider the chemistry of d-block elements that
stretch from scandium to zinc (i.e. the first d-block series of elements).
 Thus, some important definitions are:
 A transition element is one with a partially filled 3d subshell/3d sub energy
level/3d orbitals in any of its stable oxidation states as well as the
uncombined/atomic state.
 A d-block element is one with the outermost electrons filled in the d-
subshell/d-sub energy level/d-orbitals.
 The general electronic configuration of the elements that stretch from Sc to
Zn is in the form [𝐴𝑟]3𝑑 𝑥 4𝑠 2 or [𝐴𝑟]4𝑠 2 3𝑑 𝑥 ; where x=1-10 and [Ar] is the argon
core; 1s 2 2s2 2p6 3s 2 3p6 .
 The elements in the first d-block series of elements and their electronic
configurations are shown in the table below:

Element Symbol Atomic number Electronic configuration

Scandium Sc 21 1s2 2s2 2p6 3s 2 3p6 4s2 3d1
Titanium Ti 22 1s2 2s2 2p6 3s 2 3p6 4s2 3d2
Vanadium V 23 1s2 2s2 2p6 3s 2 3p6 4s2 3d3
Chromium Cr 24 1s2 2s2 2p6 3s 2 3p6 4s1 3d5
Manganese Mn 25 1s2 2s2 2p6 3s 2 3p6 4s2 3d5
Iron Fe 26 1s2 2s2 2p6 3s 2 3p6 4s2 3d6
Cobalt Co 27 1s2 2s2 2p6 3s 2 3p6 4s2 3d7
Nickel Ni 28 1s2 2s2 2p6 3s 2 3p6 4s2 3d8
Copper Cu 29 1s2 2s2 2p6 3s 2 3p6 4s1 3d10
Zinc Zn 30 1s2 2s2 2p6 3s 2 3p6 4s2 3d10

Note:
The anomalous behaviour of Cr and Cu is due to the extra stability of the
half-filled and fully filled 3d sub energy levels respectively than neither fully
filled nor half-filled 3d sub energy levels.

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Ions formed by transition elements

 Transition elements form ions by losing electrons first from the 4s sub energy
level rather than the 3d sub energy level.
Reason:
The 3d sub energy level electrons closer to the nucleus repel the 4s sub energy
level electrons even further away from the nucleus. The electrons in the 4s sub
energy level are less strongly attracted by the nucleus than the electrons in the
3d sub energy level. Thus, the electrons in the 4s subshell are lost before the
electrons in the 3d subshell during ion formation.
For example;
Cu …3d10 4s1 forms Sc …3d1 4s2 forms Cr …3d5 4s1 forms
𝐶𝑢+ …3d10 𝑆𝑐 + …3d1 4s1 (rare) 𝐶𝑟 + …3d5 (rare)
𝐶𝑢2+ …3d9 𝑆𝑐 2+ …3d1 (rare) 𝐶𝑟 2+ …3d4
𝑆𝑐 3+ …3p 6
𝐶𝑟 3+ …3d3
𝐶𝑟 4+ …3d2
𝐶𝑟 5+ …3d1
𝐶𝑟 6+ …3p6
Zn …3d10 4s 2 forms
𝑍𝑛2+ …3d10 4s1 (rare)
𝑍𝑛2+ …3d10

Note:
(a) The definition of the term transition elements excludes:
(i) Atomic copper, Cu and copper(I) ion, 𝐶𝑢+ (in compounds); since their
3d sub energy levels are fully filled.
(ii) Scandium(III) ion, 𝑆𝑐 3+ (in compounds); since the 3d sub energy level
is empty/vacant.
(iii) Atomic zinc, Zn and Zinc(II) ion, 𝑍𝑛2+ (in compounds); because both
have fully filled 3d sub energy level.
(b) The elements Sc and Zn are however, included amongst the first series
of transition elements:
(i) Because their compounds chemically resemble those of the
transition metal compounds.
(ii) To complete the series of ten elements which corresponds to the
filling of the 3d sub shell.

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 Atomic radius the elements in the first transition series

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Atomic 21 22 23 24 25 26 27 28 29 30
number

Atomic 0.144 0.132 0.122 0.117 0.117 0.116 0.116 0.115 0.117 0.125
radius
(nm)

1st I.E 632 661 648 653 716 762 757 736 745 908
(kJ
mo𝒍−𝟏 )

Activity 1
(a) Plot a graph of atomic radius against the atomic number of the elements.
(b) Explain the shape of your graph.
(c) Comment about the first ionization energies of the elements.

 The outstanding features of the transition elements (d-block elements) which

differentiate them from the elements in the s-block and p-block elements are:
The d-block elements:
 form compounds/ions in variable oxidation states. For example; copper forms
compounds/ions in +1 and +2 oxidation states while, calcium forms
ions/compounds in only +2 oxidation state.
 form complexes/complex ions.
 form coloured compounds/ions. For example; iron(II) ions/compounds are
generally green and iron(III) ions/compounds are generally
brown/yellow/reddish brown. The s-block and p-block elements form
compounds which are white and in aqueous solution, their soluble salts are
colourless.
 and their compounds are catalysts. For example; 𝑀𝑛𝑂2 is used as a catalyst
in the decomposition of hydrogen peroxide; finely divided iron is a catalyst in
the Haber process (synthesis of ammonia) and so on.
 form interstitial ‘compounds’ with non-metals with small atomic radii. The
non-metals include; hydrogen, boron, carbon and nitrogen.
 and many of their compounds are paramagnetic.

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 Activity 2:
Give reasons for each of the following observations.
(a) Zinc is a d-block element but not a transition element.
(b) Copper is a transition element.

THE GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS

 Transition elements and their compounds have a number of characteristics as
outlined below:
1. All are typical metals. Thus, they exhibit the usual physical properties
common to all metals. For example; make sound when hit, conduct
electricity and heat and so on.
2. Their boiling and melting points are generally much higher than those of
the s-block elements (in the same period).
For example:

Variation of melting point across the first transition series

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 21 22 23 24 25 26 27 28 29 30
number
Melting 1400 1680 1917 1890 1247 1535 1490 1452 1083 420
point
(˚C)
Boiling 2730 3260 3450 2642 2100 3000 2900 2730 2600 906
point
(˚C)

Activity 3:
(a) Plot a graph of melting point against the atomic number of the
elements.
(b) Explain the shape of your graph.
(c) Explain each of the following observations.
(i) The melting points of calcium and iron are 850℃ and 1535℃
respetively.
(ii) The melting points of the transition metals are generally high.
(iii) Both manganese and zinc melt at un expectedly low temperatures.

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 (iv) Melting points of the d-block elements decrease with increase in
the number of electrons in the 3d orbitals.

3. They form ions/compounds in variable oxidation states.

Definition:
Oxidation state is the net charge that would remain on an atom in a
compound when all the other atoms bonded to it were removed.
Or:
It is a net charge on an atom in a compound assuming the compound is
ionic.
The elements form ions/compounds in variable oxidation states since
there is a very small energy difference between the 4s and 3d sub
energy levels. Therefore, electrons are lost from the 3d sub energy level
as easily as they are lost from the 4s sub energy level. Transition
elements therefore, utilize both the 4s and 3d sub shell electrons for
bonding during chemical reactions and this results into variable oxidation
states.
For example;
Mn …3d5 4s 2 forms Ca 1s2 2s2 2p6 3s2 3p6 4s2 forms
𝑀𝑛2+ …3d5 𝐶𝑎2+ …3p6 (very stable EC)
𝑀𝑛3+ …3d4
𝑀𝑛4+ …3d3
𝑀𝑛5+ …3d2
𝑀𝑛6+ …3d1
𝑀𝑛7+ …3p6

The oxidation states of transition elements exhibit in ions/compounds

are:
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation +7
states +6 +6 +6
+5 +5 +5 +5
+4 +4 +4 +4 +4 +4 +4
+3 +3 +3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
+1 +1

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 Note:
 Some oxidation states are uncommon and unstable.
 +2 and +3 are found in most elements.
The relative stability of the two oxidation states is governed by the
value for electrode potential for the half-reaction;
𝑀3+ (𝑎𝑞) + 𝑒 − ⟶ 𝑀2+ (𝑎𝑞); i.e. the conversion of 𝑀3+ to 𝑀2+ .
The relative stability of +2 and +3 oxidation states in Mn and Fe can
be interpreted using their ECs as follows:
𝐹𝑒 2+ ; 1s 2 2s2 2p6 3s2 3p6 3d6 𝑀𝑛2+ ; 1s2 2s2 2p6 3s2 3p6 3d5
𝐹𝑒 3+ ; 1s 2 2s2 2p6 3s2 3p6 3d5 𝑀𝑛3+ ; 1s2 2s2 2p6 3s2 3p6 3d4
In both 𝑀𝑛2+ and 𝐹𝑒 3+ ions, the 3d sub energy levels are half filled
and this makes the ions stable whereas in both 𝑀𝑛3+ and 𝐹𝑒 2+ ions,
the 3d sub energy levels have both 4 and 6 electrons. These make the
3d sub energy levels neither half-filled nor fully filled and thus, the
ions are unstable.
 The elements show highest oxidation states in compounds with oxygen,
fluorine and some extent with chlorine. This is because oxygen and
fluorine are the most electronegative elements. Thus, both oxide and
fluoride ions are less polarized by the highly charged cations.
 In lower oxidation sates, compounds are mainly ionic and oxides are
mainly basic; whereas in higher oxidation states, compounds are mainly
covalent and oxides are acidic. In intermediate oxidation states;
bonding in compounds is partly ionic and partly covalent, and the
oxides are amphoteric.
 Acidity in the oxides of the transition metals increase with increase in
the oxidation states. For example;

Oxide Oxidation state of Nature of

metal oxide
MnO +2 Basic
Mn2O3 +3 Basic
MnO2 +4 Amphoteric
Mn2O7 +7 Acidic

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  Vanadium, chromium, manganese and iron never form simple ions in
their highest oxidation states. This is due to the very high charge
density associated with the cations.
 The zero (0) oxidation state in compounds is encountered in carbonyls.
For example; Ni(CO)4, Fe(CO)5, Co(CO)8 and so on.

Activity 4:
Calculate the oxidation state of the transition metal atom in the
following ions and compounds.
(i) [CuCl4 ]2− (iv) [Cu(NH3 )4 ]2+ (v) [Fe(CN)6 ]3− (vi) [Fe(CN)6 ]4−
(ii) [Cr(H2 O)4 (OH)2 ]+ (vii) MnO− 4 (viii) K 2 Cr2 O7 (ix) [Co(NH3 )5 Cl]Cl
(iii) CrO2−4 (x) Ni(CO) 4

4. The elements form coloured ions/compounds.

Colours of some aqueous transition metal ions are shown in the table
below:
Ion Sc 3+ (aq) Ti3+ (aq) V 3+ (aq) Cr 3+ (aq) Ni2+ (aq) Mn2+ (aq)
Colour Colourless Purple/ Green Green/ Green Pale pink
violet Violet
No. of
0
3𝑑 3𝑑1 3𝑑 2 3𝑑 3 3𝑑 8 3𝑑5
electrons
in 3d
orbitals

Ion Fe2+ (aq) Fe3+ (aq) Co2+ (aq) Cu+ (aq) Cu2+ (aq) Zn2+ (aq)
Colour Green Yellow/ Pink Colourles Blue Colourles
Brown s s
Reddish
-brown
No. of 3𝑑 6 3𝑑 5 3𝑑 7 3𝑑10 3𝑑 9 3𝑑10
electron
s in 3d
orbitals

Coloured ion/compound formation in transition metals is associated with

incompletely filled 3d sub energy level, the nature of the ligand and the
charge on the cation.

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 The main cause of colour in transition metal ions/compounds is due to
d−d electron transitions when white light falls on the ion/compound. The
observed colour is due to the colour of the light transmitted not
absorbed. For example; hydrated copper(II) ion is blue because it
absorbs red light (i.e. white light minus red light gives blue).

Sc3+ ions have no electrons in the 3d sub energy level; hence no d-d
electron transitions are possible when white light falls on the
ion/compound containing the ions. This makes the ion/compounds
colourless in aqueous solution and its solid compounds white.

Both Cu+ and Zn2+ ions have fully filled 3d sub energy level; hence no d-d
electron transitions are possible when white light falls on the
ions/compound containing the ions. This makes the ions/compounds in
aqueous solution colourless and their compounds in solid state are white.

Different ligands affect electrons in the 3d sub energy level differently.

Thus, the colours will vary if the same metal cation is bonded to
different ligands. For example;

[Cu(H2 O)6 ]2+ ; pale blue [Cu(NH3 )4 ]2+ ; deep blue

Cationic charge and radius also affect the colour of the ions/compounds
differently. For example;
Fe2+ ; green Fe3+ ; brown/reddish-brown/yellow

Supplement:
Theory (origin) of colour of transition metal ions/compounds
When a transition metal ion is in an isolated gaseous state (i.e. in
absence of external disturbance), all its five 3d orbitals are
degenerate (i.e. have exactly the same energy).
However, under external influence (e.g. in presence of ligands), the 3d
orbitals split into two sets of orbitals having different energies, the
higher energy set with two orbitals having the same energy while the
lower energy set with three equal energy orbitals. This can be shown as
in the diagram below:

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 ∆E = Energy difference and is given by the Planck equation,
∆E = h𝑣 where h = Planck ′ s constant
𝑣 = frequency of radiation
 A substance appears black if it absorbs all radiations of visible light
and reflects none.
 A substance appears white if it does not absorb visible light
radiations (i.e. if all the incident light is reflected/transmitted).

Activity 5:
Explain each of the following observations:
(a) Aqueous solutions of scandium(III) and zinc salts are colourless.
(b) Copper(II) chloride is green whereas copper(I) chloride is white.

5. Most transition elements and their compounds are catalysts/show

catalytic activity.
Examples of some transition metals and their compounds that are used as
catalysts are:
Vanadium(V) oxide in contact Finely divided iron in Haber
process process
Nickel in the catalytic Copper in oxidation of ethanol to
hydrogenation of alkenes and ethanal
alkynes
Manganese(IV) oxide in
decomposition of hydrogen
peroxide

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 Their catalytic activity is either homogeneous (both the reactants and
catalysts are in the same phase) or heterogeneous (reactants and the
catalysts are in different phases).
Transition metals and their compounds are able to alter the rate of a
chemical reaction because:
(a) They form ions with variable oxidation states. This enables them to
take part in a sequence of reaction stages and emerge unchanged at
the end. As a result, the elements/their ions provide alternative
reaction paths/routes of a much lower activation energy compared to
the uncatalyzed reaction.
(b) The metals or their ions have partially filled 3d orbitals. This allows
the reactant particles to get adsorbed on their surfaces and thus,
form temporary/weak bonds with them. This weakens the bonds in the
reactant particles and also increases the concentration of the
reactant particles (brings reactant particles closer to each other) on
the surface of the catalyst. As a result, the frequency of collision
between the reacting particles increases, an activated complex forms
more easily and hence, faster rate of reaction.
Energy diagram for a catalyzed and uncatalyzed reaction takes the
following form:

Activity 6:

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 (a) Using the same axes, draw a labelled diagram for energy-reaction
coordinate for a catalysed and un-catalysed reaction.
(b) State:
(i) the difference in your diagrams in (a).
(ii) how a catalyst increases the rate of a reaction.

6. Transition metals and their compounds are paramagnetic.

When transition metal cations or compounds are placed in a magnetic
field, they exhibit different behaviors which include:
(i) Paramagnetism

A paramagnetic substance is one that is weakly attracted by a magnetic

field. Some transition metal ion/compounds are paramagnetic. This is due
to the presence of unpaired electrons in the 3d orbitals which spin to
generate a magnetic moment (field) that can be attracted by an external
magnetic field. The greater the number of unpaired electrons in the 3d
orbitals; the more paramagnetic the ion/compound is.

(ii) Diamagnetism:

Diamagnetic substances are those that are repelled by a magnetic field.

They repelled due to lack of unpaired electrons in their 3d orbitals.
Scandium(III) and zinc ions, and their compounds are diamagnetic. This is
because both Sc 3+ and Zn2+ ions do not have unpaired electrons in their
3d orbitals and this makes their net magnetic moment zero.

(iii) Ferromagnetism:

Substances are said to be ferromagnetic if they are strongly attracted

to a magnetic field. This arises due to the high number of unpaired
electrons in their 3d orbitals. Examples of some transition metals that
are ferromagnetic include: iron, cobalt and nickel. Such metals can be
magnetized.

7. They form interstitial ‘compounds’.

Transition metals can allow atoms of some non-metal to occupy the
interstices (spaces between their atoms) in their crystal lattices and
thus, form interstitial ‘compounds’. The number of atoms that can be

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 accommodated by a given metal is not fixed and thus, interstitial
‘compounds’ are non-stoichiometric.
Interstitial ‘compounds’ have many useful properties. For example, they
are very hard, have high melting points and are good electrical
conductors.

8. Transition elements form complex ions/complexes

A complex is an ion or a neutral compound consisting a central metal atom
or cation linked/bonded a number of neutral molecules with lone pair of
electrons or negatively charged ions through dative (or coordinate)
bonds.
A complex ion is either a negatively charged ion or positively charged ion
that contains a central metal cation linked to atoms or group of atoms
with a negative charge or lone pair of electrons through dative (or
coordinate) bonds.

Transition metals have much greater tendency to form complexes

because they:
(a) possess vacant 3d orbitals of suitable/appropriate energy which can
accept and accommodate lone pairs of electrons from the surrounding
ligands.
(b) form cations with small ionic radii and high charge; and hence, high
charge density. This enables the cations to strongly attract the lone
pairs of electrons from the ligands and as a result form strong dative
bonds with the ligands.

Coordination number is the total number of ligands which are directly

bonded to the central metal atom or cation.
Or:
It is the total number of dative bonds formed between the ligands and
the central metal atom or ion.

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 The common coordination numbers are; 2, 4 and 6 and they depend on the
size of the:
(a) central metal atom/cation.
(b) ligands.

For example;

Complex Coordination Oxidation state

ion/compound number
[Cu(NH3 )4 ]2+ 4 +2
[CuCl4 ]2− 4 +2
[Fe(CN)6 ]4− 6 +2
6 +3
+
[Cr(H2 O)4 (OH)2 ]
6 +3
3+
[Fe(H2 O)6 ]
6 +3
3+
[Co(NH3 )6 ]
6 +2
2+
[Ni(NH3 )6 ]
6 +2
+
[CrCl(H2 O)5 ]
6 +3
2+
[Cr(H2 O)5 OH]
K 4 [Fe(CN)6 ] 6 +2
[Cr(H2 O)6 ]Br3 6 +3
[Ni(H2 O)4 ](OH)2 4 +2
[Co(NH3 )5 Cl]Cl 6 +2

A ligand refers to a molecule with lone pair of electrons or a negatively

charged ion that bonds to the central metal atom/cation via a dative (or
coordinate) bond.
Structurally a complex is represented as [𝑴𝑳𝒏 ]𝒚 :
M is the central metal atom/cation; y is the charge on the complex; n is
the coordination number and L represents the ligands directly bonded
to M.
Note:
(a) The coordination number of M is the same regardless of the type
of ligand. For example:
[Cu(NH3 )4 ]2+ [CuCl4 ]2− [Cu(H2 O)4 ]2+
[Cr(NH3 )6 ]3+ [Cr(OH)6 ]3− [Cr(H2 O)6 ]3+

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 (b) Common coordination numbers for metal atoms/ions are:
Ion/ 𝐹𝑒 2+ 𝐹𝑒, 𝐶𝑟 3+ 𝐶𝑢2+ 𝑀𝑛2+ 𝑁𝑖 2+ 𝑁𝑖 𝐶𝑜2+ 𝑍𝑛2+ 𝐴𝑔+
atom 𝐹𝑒
3+ 𝐶𝑢+
C.N 6 5 6 4/6 6 4/6 4 4/6 4 2

(c) In aqueous solution, transition metal ions exist as hydrated

complexes with water molecules as ligands. For example;
[Fe(H2 O)6 ]3+ , [Cu(H2 O)4 ]2+ , [Ni(H2 O)6 ]3+ e.t.c.

NOMENCLATURE OF COMPLEXES

 The names of complexes identify the following features about the complexes:
(i) Whether the complex is ionic, an ion or neutral.
(ii) Oxidation number/state of the central metal atom/cation.
(iii) Number of ligands directly bonded to the central metal atom/cation.
 The IUPAC rules followed are:
(i) The names of the complexes consist of two parts written as one word.
(ii) If the complex is ionic, the cation is always named first before the anion;
regardless of whether it is a complex or not.

(iii) Names of the ligands precede the name of the central metal atom/ion.
Prefixes; di, tri, tetra, penta, hexa etc. are used to denote the number of
ligands in the complex.
(iv)When two or more ligands are directly bonded to the central metal
atom/cation, their names are written in alphabetical order disregarding the
Greek prefixes denoting their number.
(v) The oxidation state of the central metal atom/cation is indicated in Roman
numerals immediately after its name.
(vi)If the complex is negatively charged, the name of the central metal cation
ends with ‘ate’.
(vii) The names of anionic ligands end with ‘o’. For example:

Cl− ; chloro C̅N; cyano OH − ; hydroxo 𝐶2 𝑂42− ; oxalato

Neutral ligands usually possess their normal names except:

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 H2 O; aqua NH3 ; ammine CO; carbonyl

 Examples of complexes and their names:

Complex Name
[Cu(NH3 )4 ]2+ Tetraamminecopper(II) ion
Hexaaquacopper(II) ion
2+
[Cu(H2 O)6 ]
Tetraaquadihydroxochromium(III) ion
+
[Cr(H2 O)4 (OH)2 ]
Hexaaquairon(III) ion
3+
[Fe(H2 O)6 ]
Hexaamminecobalt(III) ion
3+
[Co(NH3 )6 ]
Hexaamminenickel(II) ion
2+
[Ni(NH3 )6 ]
Hexaaquacobalt(II) ion
2+
[Co(H2 O)6 ]
Hexaaquanickel(II) ion
2+
[Ni(H2 O)6 ]
Pentaaquachlorochromium(II) ion
+
[CrCl(H2 O)5 ]
Pentaaquahydroxochromium(III) ion
2+
[Cr(H2 O)5 OH]
Pentaamminesulphatocobalt(III) ion
+
[Co(NH3 )5 SO4 ]
Tetraamminediaquachromium(II) ion
2+
[Cr(NH3 )4 (H2 O)2 ]
Pentaamminebromocobalt(III) ion
2+
[Co(NH3 )5 Br]
Tetrachlorocuprate(II) ion
2−
[CuCl4 ]
Ni(CO)4 Tetracarbonylnickel(0)
Hexacyanoferrate(II) ion
4−
[Fe(CN)6 ]
Tetracyanonickelate(II) ion
2−
[Ni(CN)4 ]
Tetrahydroxozincate(II) ion
2−
[Zn(OH)4 ]
Hexanitrocobaltate(IV) ion
2−
[Co(NO2 )6 ]
Hexacyanoferrate(II) ion
4−
[Fe(CN)6 ]
Tetracyanonickelate(II) ion
2−
[Ni(CN)4 ]
Tetrachlorocobaltate(II) ion
2−
[CoCl4 ]
Tetrahydroxozincate(II) ion
2−
[Zn(OH)4 ]
Hexanitrocobaltate(IV) ion
2−
[Co(NO2 )6 ]
Pentacyanonitrosylferrate(III) ion
2−
[Fe(CN)5 NO]
Amminepentahydroxochromate(II) ion
3−
[CrNH3 (OH)5 ]
[CrCl(NH3 )5 ]Cl2 pentaamminechlorochromium(III) chloride
[Cr(NH3 )4 (H2 O)2 ]SO4 Tetraamminediaquachromium(II) sulphate
Na2 [Zn(OH)4] Sodium tetrahydroxozincate(II)
K 4 [Fe(CN)6] Potassium hexacyanoferrate(II)

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 Activity 7:
(a) Define the term complex ion.
(b) Explain why transition metals form many complexes.
(c) [Fe(CN)6 ]3− and [CuCl4 ]2− are complex ions formed by iron and copper
respectively.
(i) State the oxidation of iron and copper in the complex ions,
(ii) State the coordination number of iron and copper in the complex
ions.
(iii) Name each of the complex ions.

DISPLACEMENT REACTIONS IN COMPLEXES

 These reactions involve displacement of a ligand by another. The reactions
usually bring about change in colour or solubility or both and can be used to
identify the metal cations.
 The reactions depend on:
(a) Nature of the ligand
(b) Concentration of the ligand
 Examples of some displacement reactions are:
(i) Copper(II) ions in aqueous solution are hydrated and exist as Cu(H2 O)2+
6 (aq)
or Cu(H2 O)4 (aq); which make the solution appear pale blue.
2+

When little aqueous ammonia solution is added, a pale blue precipitate forms.

Cu(H2 O)2+ ̅
4 (aq) + 2OH(aq) ⟶ Cu(H2 𝑂)2 (OH)2 (s) + 2H2 O(l)

Or Cu(H2 O)2+ ̅
6 (aq) + 2OH(aq) ⟶ Cu(H2 𝑂)4 (OH)2 (s) + 2H2 O(l)

The above two equations can simply be written as follows:

̅ H(aq) ⟶ Cu(OH)2 (s)
Cu2+ (aq) + 2O

When excess ammonia solution is added, the ammonia molecules displaces

the water molecules and hydroxide ions as ligands completely to form a
soluble complex ion called tetraamminecopper(II) ions.
Cu(H2 𝑂)2 (OH)2 (s) + 4NH3 (aq) ⟶ Cu(NH3 )2+ ̅
4 (aq) + 2H2 O(l) + 2OH(aq)
Or Cu(H2 𝑂)4 (OH)2 (s) + 4NH3 (aq) ⟶ Cu(NH3 )2+ ̅
4 (aq) + 4H2 O(l) + 2OH(aq)
The above two equations can be simply written as follows:
Cu(OH)2 (s) + 4NH3 (aq) ⟶ Cu(NH3 )2+ ̅
4 (aq) + 2OH(aq)
On dilution, the deep blue solution turns pale blue again.

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 (ii) Cobalt(II) ions in aqueous solution are pink due to Co(H2 O)2+
6 (aq) ions.
On addition of concentrated hydrochloric acid or any other soluble chloride,
the pink solution turns blue due to the formation of [CoCl4 ]2− ions.
Co(H2 O)2+ − 2−
6 (aq) + 4Cl (aq) ⇌ [CoCl4 ] (𝑎𝑞) + 6H2 O(l)
On dilution, the blue solution turns pink again.
(iii) Aqueous solutions of copper(II) ions are pale blue due to Cu(H2 O)2+ 4 (aq) or
Cu(H2 O)6 (aq) ions.
2+

If sufficient concentrated hydrochloric acid or a concentrated solution of

any soluble chloride is added to the pale blue solution, it turns green and
then yellow.
The yellow solution is due to the [CuCl4 ]2− ions formed by complete
replacement of water molecules as ligands by chloride ions.
Cu(H2 O)2+ − 2−
6 (aq) + 4Cl (aq) ⇌ [CuCl4 ] (𝑎𝑞) + 6H2 O(l)
Or
Cu(H2 O)2+ − 2−
4 (aq) + 4Cl (aq) ⇌ [CoCl4 ] (𝑎𝑞) + 4H2 O(l)
On dilution, the yellow solution turns green and then, finally pale blue.

Activity 8:
1. Compound R contains cobalt 24.8%, chlorine 29.8% and water 45.4%.
(a) (i) Calculate the empirical formula of R.
(ii) Determine the molecular formula of R. (RFM of R =237.9)
(b) To a solution of R in water was added concentrated hydrochloric
acid dropwise until in excess.
(i) State what was observed.
(ii) Write equation for the reaction that took place.
(c) The resultant solution in (b) was diluted.
(i) State what was observed.
(ii) Write equation for the reaction that took place.
(d) State what would be observed when aqueous ammonia is added
dropwise to an aqueous solution of R.
2. When to an aqueous solution of copper(II) sulphate was added
concentrated hydrochloric acid dropwise until in excess, the pale blue
solution turns yellow. On dilution, the solution turns to pale blue again.
Explain this observation.

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 3. Compound T contains 25.6% copper, 12.8% sulphur, 25.6% oxygen and
the rest being water.
(a) (i) Calculate the empirical formula of T.
(ii) Determine the molecular formula of T. (T =260)
(b) To a solution of T in water was added concentrated hydrochloric
acid dropwise until in excess.
(i) State what was observed.
(ii) Write equation for the reaction that took place.
(c) The resultant solution in (b) was diluted.
(i) State what was observed.
(ii) Write equation for the reaction that took place.
(d) State what would be observed when aqueous sodium hydroxide is
added dropwise to an aqueous solution of T and the mixture heated
strongly.
(e) To an aqueous solution of T was added dilute nitric acid followed by
barium nitrate solution.
(i) State what was observed.
(ii) Write equation for the reaction that took place.

Supplement!!!
Structure and shape of complex ions
The shape of a complex ion depends on its coordination number.
Complexes with a coordination number of two are linear. Those with the
coordination number of four are usually tetrahedral. However, some complex ions
with coordination number of four are square planar.
Complex ions with a coordination number of six often have octahedral structures.

ISOMERISM IN TRANSITION METAL COMPLEXES

 Some isomerism of interest in complexes are:

(a) Ionisation isomerism
This occurs when due to interchange of ions inside and outside the
coordination sphere. Example are:
[Co(NH3 )5 SO4 ]Br [Co(H2 O)5 Br]Cl and [Co(H2 O)5 Cl]Br
and Co(NH3 )5 Br] SO4
The isomers have chemical properties that differ. For example;

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 In [Co(NH3 )5 SO4 ]Br; the bromide ions are free and thus, an aqueous solution
of the isomer gives a positive test with acidified silver nitrate
solution/lead(II) nitrate (ethanoate) solution.
Ag + (aq) + 𝐵𝑟 − (aq) → AgBr(s); Pb2+ (aq) + 2𝐵𝑟 − (aq)) → PbBr2 (s)

While in Co(NH3 )5 Br] SO4 ; the sulphate ions are free and thus, an aqoueus
solution of the isomer gives a positive test with acidified solution of barium
nitrate /lead(II) nitrate (ethanoate).
Ba2+ (aq) + SO2− 2+ 2−
4 (aq) → BaSO4 (s); Pb (aq) + SO4 (aq) → PbSO4 (s)

(b) Hydrate isomerism

Arises due to the difference in the number of water molecules which are
coordinated to the central metal ion.
For example; hydrated chromium(III) chloride, CrCl3 . 6H2 O has four isomers
below:
Isomer No. of moles of Colour of No. of
free chloride the isomer conducting
ions per ions per
molecule of molecule of
isomer isomer
3 Violet/grey- 4
3+ −
[Cr(H2 O)6 ] (Cl )3
Or blue
[Cr(H2 O)6 ]Cl3
[Cr(H2 O)5 𝐶𝑙]2+ (Cl− )2 . H2 O 2 Light green 3
Or
[Cr(H2 O)5 Cl]Cl2 . H2 O
[Cr(H2 O)4 𝐶𝑙2 ]+ (𝐶𝑙 − ). 2H2 O 1 Dark green 2
Or
[Cr(H2 O)4 Cl2 ]Cl. 2H2 O
[Cr(H2 O)3 Cl3 ].3H2O 0 0

The isomers can be distinguished by:

(a) Conductivity measurements
(b) Depression of freezing point
(c) Addition of excess (of standard) silver nitrate solution

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 Activity 9:
1. (a) State why chromium is considered a transition element.
(b) Write the formulae of all the possible isomers of chromium(III)
chloride-6-water, CrCl3 . 6H2O.
(c) To an aqueous solution of chromium(III) chloride was added
ammonia solution dropwise until in excess. State what was observed
and write equation(s) for the reaction(s) that would take place.

2. The molecular formula of a complex of cobalt is [Co(NH3 )3 (H2 𝑂)]Cl3 .

(a) (i) Write the name of the complex.
(ii) State the coordination number of cobalt in the complex.
(b) Excess ammonia solution was added to the complex. State what was
observed and write equation for the reaction that took place.
(c) To 10.0 cm3 of a 0.5 M solution of the complex was added excess
silver nitrate solution.
(i) State what observed.
(ii) Write the equation for the reaction that took place.
(d) The mixture from (c) above was filtered and the residue dried.
Calculate the mass of the dried residue.

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