MODULE 3: CHEMISTRY OF THE ELEMENTS

1st ROW TRANSITION ELEMENTS

SPECIFIC OBJECTIVES
SPECIFIC OBJECTIVES
SPECIFIC OBJECTIVES
 THE FIRST ROW TRANSITION ELEMENTS

Definition:
• A transition element is a d block element which forms one or more stable ions
with an incomplete d electron sub-shell.
The first row runs from scandium to zinc filling the 3d orbitals.

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

ELECTRONIC CONFIGURATION

NOTE: Though scandium and zinc are d-block elements they are NOT
transition elements as they CANNOT form ions with incomplete d-subshell.
THE FIRST ROW TRANSITION ELEMENTS
 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 4s2 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 4s2 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

Element Electronic Configuration

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
▪ maximum falls as the energy required to +7
▪ remove more electrons becomes very high +6 +6 +6
▪ all (except scandium) have an M2+ ion +5 +5 +5 +5 +5
▪ stability of +2 state increases across the row +4 +4 +4 +4 +4 +4 +4
▪ due to increase in the 3rd Ionisation Energy +3 +3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
▪ THE MOST IMPORTANT STATES ARE IN RED +1
 Characteristics of Transition Metals

Transition elements have typical metallic properties but have some properties which
set them apart from other metals:
▪ They form compounds with different oxidation states.
▪ Transition element ions form coloured compounds.
▪ Transition element ions form complex ions.
▪ Transition elements and their compounds are often good catalysts [this is often
related to the differences in oxidation states].
▪ Transition elements have very high density.
▪ Transition elements have very high melting points and boiling points.
▪ They have typical magnetic properties:

• Most compounds and ions of the transition elements are paramagnetic:

• when placed in a magnetic field, they align themselves with the field.
• But they do not retain their magnetism when the magnetic field is removed.
• Fe, Co and Ni are ferromagnetic.
• They retain permanent magnetism after the magnetic field has been withdrawn.
 lonisation energy, atomic and ionic radii
• In Periods 2 and 3 of the Periodic Table there is a considerable variation in the
values of the first ionisation energy and the atomic and ionic radii.
• The transition elements, however, show only small changes in these values
from titanium to copper.
 COLOURED IONS
A characteristic of transition metals is their ability to form coloured compounds
 3d ORBITALS
There are 5 different orbitals of the d variety

xy xz yz

x2-y2 z2
SPLITTING OF ORBITALS
SPLITTING OF ORBITALS
SPLITTING OF ORBITALS
 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
 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 nickel(II)sulphate is green because
violet, blue and red wavelengths are absorbed
[4 marks]
COMPLEX IONS
 COMPLEX IONS - LIGANDS

Ligands:
 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, H2O

Bidentate form two co-ordinate bonds H2NCH2CH2NH2 , C2O42-

 COMPLEX IONS - LIGANDS

Multidentate form several co-ordinate bonds

EDTA

An important complexing agent

 COMPLEX IONS - LIGANDS

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

Multidentate form several co-ordinate bonds

 CO-ORDINATION NUMBER & SHAPE
Shape:

Coordination
Number:
CO-ORDINATION NUMBER & SHAPE
ISOMERISATION IN COMPLEXES
ISOMERISATION IN COMPLEXES
 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

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

REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
REACTIONS OF SOME TRANSITION METAL IONS
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