AN INTRODUCTION TO

TRANSITION METAL
CHEMISTRY

KNOCKHARDY PUBLISHING
2008
SPECIFICATIONS
 KNOCKHARDY PUBLISHING

TRANSITION METALS
INTRODUCTION
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TRANSITION METALS

CONTENTS
• Definition
• Metallic properties
• Electronic configurations
• Variable oxidation state
• Coloured ions
• Complex ion formation
• Shapes of complexes
• Isomerism in complexes
• Catalytic properties
 TRANSITION METALS

Before you start it would be helpful to…

• Recall the definition of a co-ordinate (dative covalent) bond

• Recall how to predict the shapes of simple molecules and ions
 THE FIRST ROW TRANSITION ELEMENTS

Definition D-block elements forming one or more stable ions with

partially filled (incomplete) d-sub shells.

The first row runs from scandium to zinc filling the 3d orbitals.

Properties arise from an incomplete d sub-shell in atoms or ions

 THE FIRST ROW TRANSITION ELEMENTS

Definition D-block elements forming one or more stable ions with

partially filled (incomplete) d-sub shells.

The first row runs from scandium to zinc filling the 3d orbitals.

Properties arise from an incomplete d sub-shell in atoms or ions

Metallic
properties all the transition elements are metals
strong metallic bonds due to small ionic size and close packing
higher melting, boiling points and densities than s-block metals

K Ca Sc Ti V Cr Mn Fe Co

m. pt / °C 63 850 1400 1677 1917 1903 1244 1539 1495

density /
g cm-3 0.86 1.55 3 4.5 6.1 7.2 7.4 7.9 8.9
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

POTASSIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

‘Aufbau’
1s2 2s2 2p6 3s2 3p6 4s1 Principle

In numerical terms one would expect the 3d orbitals to be filled next.

However, because the principal energy levels get closer together as you go further
from the nucleus coupled with the splitting into sub energy levels, the 4s orbital is of
a LOWER ENERGY than the 3d orbitals so gets filled first.
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

CALCIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2

As expected, the next electron in pairs up to complete a filled 4s orbital.

This explanation, using sub levels fits in with the position of potassium and
calcium in the Periodic Table. All elements with an -s 1 electronic configuration are
in Group I and all with an -s2 configuration are in Group II.
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

SCANDIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d1

With the lower energy 4s orbital filled, the next electrons can now fill p the 3d
orbitals. There are five d orbitals. They are filled according to Hund’s Rule.
BUT WATCH OUT FOR TWO SPECIAL CASES.
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

TITANIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d2

The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair
up but goes into an empty orbital in the same sub level.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

VANADIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d3

The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair
up but goes into an empty orbital in the same sub level.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

CHROMIUM

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s1 3d5

One would expect the configuration of chromium atoms to end in 4s 2 3d4.

To achieve a more stable arrangement of lower energy, one of the 4s electrons is
promoted into the 3d to give six unpaired electrons with lower repulsion.
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

MANGANESE

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d5

The new electron goes into the 4s to restore its filled state.
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

IRON

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d6

Orbitals are filled according to Hund’s Rule. They continue to pair up.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

COBALT

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d7

Orbitals are filled according to Hund’s Rule. They continue to pair up.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

NICKEL

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d8

Orbitals are filled according to Hund’s Rule. They continue to pair up.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

COPPER

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s1 3d10

One would expect the configuration of copper atoms to end in 4s 2 3d9.

To achieve a more stable arrangement of lower energy, one of the 4s electrons is
promoted into the 3d.
HUND’S RULE OF
MAXIMUM MULTIPLICITY
 ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS

ZINC

4f
INCREASING ENERGY /

4d
4
DISTANCE FROM

4p
NUCLEUS

3d
4s
3 3p

1s2 2s2 2p6 3s2 3p6 4s2 3d10

The electron goes into the 4s to restore its filled state and complete the 3d and 4s
orbital filling.
 ELECTRONIC CONFIGURATIONS

K 1s2 2s2 2p6 3s2 3p6 4s1

Ca 1s2 2s2 2p6 3s2 3p6 4s2
Sc 1s2 2s2 2p6 3s2 3p6 4s2 3d1
Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2
V 1s2 2s2 2p6 3s2 3p6 4s2 3d3
Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Mn 1s2 2s2 2p6 3s2 3p6 4s2 3d5
Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Co 1s2 2s2 2p6 3s2 3p6 4s2 3d7
Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8
Cu 1s2 2s2 2p6 3s2 3p6 4s1 3d10
Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d10
 VARIABLE OXIDATION STATES
Arises from the similar energies required for removal of 4s and 3d electrons

maximum rises across row to manganese Sc Ti V Cr Mn Fe Co Ni Cu Zn

+7
maximum falls as the energy required to
remove more electrons becomes very high +6 +6 +6
+5 +5 +5 +5 +5
all (except scandium) have an M ion
2+
+4 +4 +4 +4 +4 +4 +4

stability of +2 state increases across the row +3 +3 +3 +3 +3 +3 +3 +3

due to increase in the 3rd Ionisation Energy +2 +2 +2 +2 +2 +2 +2 +2 +2
+1
THE MOST IMPORTANT STATES ARE IN RED

When electrons are removed they come from the 4s orbitals first

Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2
Cu+ 1s2 2s2 2p6 3s2 3p6 3d10 Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9 Ti3+ 1s2 2s 2p6 3s2 3p6 3d1
Ti4+ 1s2 2s2 2p6 3s2 3p6
 COLOURED IONS
A characteristic of transition metals is their ability to form coloured compounds

Theory ions with a d10 (full) or d0 (empty) configuration are colourless

ions with partially filled d-orbitals tend to be coloured
it is caused by the ease of transition of electrons between energy levels
energy is absorbed when an electron is promoted to a higher level
the frequency of light is proportional to the energy difference

ions with d10 (full) Cu+,Ag+ Zn2+

or d0 (empty) Sc3+ configuration are colourless
e.g. titanium(IV) oxide TiO2 is white

colour depends on ... transition element

oxidation state
ligand
coordination number
 3d ORBITALS
There are 5 different orbitals of the d variety

xy xz yz

x2-y2 z2
 SPLITTING OF 3d ORBITALS

Placing ligands around a central ion causes the energies of the d orbitals to change
Some of the d orbitals gain energy and some lose energy
In an octahedral complex, two (z2 and x2-y2) go higher and three go lower
In a tetrahedral complex, three (xy, xz and yz) go higher and two go lower

OCTAHEDRAL TETRAHEDRAL

3d 3d

Degree of splitting depends on the CENTRAL ION and the LIGAND

The energy difference between the levels affects how much energy is absorbed when
an electron is promoted. The amount of energy governs the colour of light absorbed.
 COLOURED IONS
The observed colour of a solution depends on the wavelengths absorbed
Copper sulphate solution appears blue because the energy absorbed corresponds to
red and yellow wavelengths. Wavelengths corresponding to blue light aren’t absorbed.

WHITE LIGHT SOLUTION

GOES IN APPEARS BLUE

ENERGY CORRESPONDING TO
THESE COLOURS IS ABSORBED

Absorbed colour nm Observed colour nm

VIOLET 400 GREEN-YELLOW 560
BLUE 450 YELLOW 600
BLUE-GREEN 490 RED 620
YELLOW-GREEN 570 VIOLET 410
YELLOW 580 DARK BLUE 430
ORANGE 600 BLUE 450
RED 650 GREEN 520
 COLOURED IONS
a solution of copper(II)sulphate is blue because
red and yellow wavelengths are absorbed

blue and green

white light not absorbed
 COLOURED IONS
a solution of copper(II)sulphate is blue because
red and yellow wavelengths are absorbed
 COLOURED IONS
a solution of copper(II)sulphate is blue because
red and yellow wavelengths are absorbed
 COLOURED IONS
a solution of nickel(II)sulphate is green because
violet, blue and red wavelengths are absorbed
FINDING COMPLEX ION FORMULAE USING COLORIMETRY
• a change of ligand can change the colour of a complex
• this property can be used to find the formula of a complex ion
• ight of a certain wavelength is passed through a solution
• the greater the colour intensity, the greater the absorbance
• the concentration of each species in the complex is altered
• the mixture with the greatest absorbance identifies ratio of ligands and ions

RED
WHITE LIGHT
LIGHT

BLUE COLORIMETER
FILTER SOLUTION
FINDING COMPLEX ION FORMULAE USING COLORIMETRY
• a change of ligand can change the colour of a complex
• this property can be used to find the formula of a complex ion
• ight of a certain wavelength is passed through a solution
• the greater the colour intensity, the greater the absorbance
• the concentration of each species in the complex is altered
• the mixture with the greatest absorbance identifies ratio of ligands and ions

Finding the formula of an iron(III) complex

White light is passed through
a blue filter. The resulting
red light is passed through
mixtures of an aqueous
iron(III) and potassium
thiocyanate solution.
Maximum absorbance occurs
first when the ratio of Fe3+
and SCN¯ is 1:1.

This shows the complex has

the formula [Fe(H2O)5SCN]2+
FINDING COMPLEX ION FORMULAE USING COLORIMETRY
• a change of ligand can change the colour of a complex
• this property can be used to find the formula of a complex ion
• ight of a certain wavelength is passed through a solution
• the greater the colour intensity, the greater the absorbance
• the concentration of each species in the complex is altered
• the mixture with the greatest absorbance identifies ratio of ligands and ions

Finding the formula of an nickel(II) edta complex

Filtered light is passed
through various mixtures of
an aqueous solution of
nickel(II) sulphate and edta
solution.

The maximum absorbance

occurs when the ratio of Ni2+
and edta is 1:1.
 COMPLEX IONS - LIGANDS

Formation ligands form co-ordinate bonds to a central transition metal ion

Ligands atoms, or ions, which possess lone pairs of electrons

form co-ordinate bonds to the central ion
donate a lone pair into vacant orbitals on the central species

Ligand Formula Name of ligand

chloride Cl¯ chloro
cyanide NC¯ cyano
hydroxide HO¯ hydroxo
oxide O2- oxo
water H2O aqua
ammonia NH3 ammine

some ligands attach themselves using two or more lone pairs

classified by the number of lone pairs they use
multidentate and bidentate ligands lead to more stable complexes
 COMPLEX IONS - LIGANDS

some ligands attach themselves using two or more lone pairs

classified by the number of lone pairs they use
multidentate and bidentate ligands lead to more stable complexes

Unidentate form one co-ordinate bond Cl¯, OH¯, CN¯, NH3, and H2O

Bidentate form two co-ordinate bonds H2NCH2CH2NH2 , C2O42-

 COMPLEX IONS - LIGANDS

some ligands attach themselves using two or more lone pairs

classified by the number of lone pairs they use
multidentate and bidentate ligands lead to more stable complexes

Multidentate form several co-ordinate bonds

EDTA

An important complexing agent

 COMPLEX IONS - LIGANDS

some ligands attach themselves using two or more lone pairs

classified by the number of lone pairs they use
multidentate and bidentate ligands lead to more stable complexes

Multidentate form several co-ordinate bonds

HAEM

A complex containing iron(II) which

is responsible for the red colour in
blood and for the transport of
oxygen by red blood cells.

Co-ordination of CO molecules
interferes with the process
 COMPLEX IONS - LIGANDS

some ligands attach themselves using two or more lone pairs

classified by the number of lone pairs they use
multidentate and bidentate ligands lead to more stable complexes

Multidentate form several co-ordinate bonds

 CO-ORDINATION NUMBER & SHAPE
the shape of a complex is governed by the number of ligands around the central ion
the co-ordination number gives the number of ligands around the central ion
a change of ligand can affect the co-ordination number

Co-ordination No. Shape Example(s)

6 Octahedral [Cu(H2O)6]2+

4 Tetrahedral [CuCl4]2-

Square planar Pt(NH3)2Cl2

 ISOMERISATION IN COMPLEXES
Some octahedral complexes can exist in more than one form

[MA4B2]n+

TRANS CIS

[MA3B3]n+
 ISOMERISATION IN COMPLEXES

GEOMETRICAL (CIS-TRANS) ISOMERISM

Square planar complexes of the form [MA2B2]n+ exist in two forms

trans platin cis platin

An important anti-cancer drug. It

is a square planar, 4 co-ordinate
complex of platinum.
 ISOMERISATION IN COMPLEXES

OPTICAL ISOMERISM

Some octahedral complexes exist in two forms

Octahedral complexes with bidentate ligands can

exist as a pair of enantiomers (optical isomers)
 ISOMERISATION IN COMPLEXES

OPTICAL ISOMERISM AND GEOMETRICAL ISOMERSIM

The complex ion [Co(en)2Cl2]+ exhibits both types of isomerism

OPTICAL
ISOMERISM
 ISOMERISATION IN COMPLEXES

OPTICAL ISOMERISM AND GEOMETRICAL ISOMERSIM

The complex ion [Co(en)2Cl2]+ exhibits both types of isomerism

OPTICAL
ISOMERISM

GEOMETRICAL
ISOMERISM

CIS TRANS
 CATALYTIC PROPERTIES
Transition metals and their compounds show great catalytic activity

It is due to partly filled d-orbitals which can be used to form bonds with adsorbed
reactants which helps reactions take place more easily

Examples of catalysts
IRON Manufacture of ammonia - Haber Process

NICKEL Hydrogenation reactions - margarine manufacture

RHODIUM Catalytic converters

VANADIUM(V) OXIDE Manufacture of sulphuric acid - Contact Process

 AN INTRODUCTION TO

TRANSITION METAL
CHEMISTRY
THE END

© 2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING