CHAPTER 4

TRANSITION METAL
 Contents
I. Introduction to Transition Metals

II. First Row Transition Metals

III. Electron Configuration of Atoms and Ions

IV. General Properties: Atomic Size, Ionization

Energy and Electronegativity

V. Special Characteristics

VI. Metallurgy of Iron

 LEARNING OUTCOMES
Upon completion of this chapter,
students will be able to:

 Apply the knowledge of

electron configuration of
transition metals.
 Explain the general properties
and special characteristics of
transition metals.
 Describe the process of
metallurgy of iron.
 Conduct, observe and report
scientific investigation in selected
areas of inorganic and
coordination chemistry
 INTRODUCTION

 Transition elements are the element with the partially-filled d

orbitals.

 (Zn, Cd & Hg are not considered as transition element because

do not have this characteristic)

 Also known as the d-block elements.

 Found in the fourth row of the periodic table.

 Located in groups 3 through 11.

 They are called transition metals because they transition

between the highly reactive s block metals and the much
less reactive metals of group 12 and the p block
 FIRST ROW TRANSITION METAL

For element which the 3d electron shell contains between

one and nine electrons.

Zinc is not normally considered a transition element since in

both the element and its compounds the 3d electron shell
remains filled.
 ELECTRON CONFIGURATION OF ATOMS & IONS

 3d orbital are filled after the 4s orbital is fully occupied

by electrons.
 The filling of electrons in d-orbitals follows the same
rules discussed earlier.

1s
2s 2p

3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
 ELECTRON CONFIGURATION OF ATOMS & IONS

Ti = 22
Orbital
Diagram

Electron
configuration

Fe = 26

Orbital
Diagram

Electron
configuration
Why is the energy of 4s orbital less than that
of 3d orbital?
● 3d orbital electrons feel a lot of repulsion between the
other 3rd level electrons (those in 3s and 3p).
● The 4s orbital, while farther away, requires less energy
for the electron to occupy because it is not repelled as
much by the coexisting electrons.
 ELECTRON CONFIGURATION OF ATOMS & IONS

 4s orbital which will fill first, followed by all the 3d orbitals.

 the 4s orbital behaves as the outermost, highest energy orbital.

 ELECTRON CONFIGURATION OF ATOMS & IONS

 When transition metals form simple ions, the electrons from

4s orbital are removed first before the electrons in 3d
orbitals.

• Fe26 : 1s2 2s2 2p6 3s2 3p6 4s2 3d6

• Fe2+ : 1s2 2s2 2p6 3s2 3p6 3d6

• Fe3+ : 1s2 2s2 2p6 3s2 3p6 3d5

 ELECTRON CONFIGURATION OF ATOMS & IONS

 Chromium & Copper are the two transition element that

show irregularities in electronic configuration.

 To achieve stability, the electronic configuration is

preferred to have filled or half-filled orbital.
 ELECTRON CONFIGURATION OF ATOMS & IONS

 Expected electronic configuration:

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑
Cr24
1s 2s 2p 3s 3p 4s 3d

Cr24 : 1s2 2s2 2p6 3s2 3p6 4s2 3d4

 one electrons from 4s orbital occupies 3d orbital to have half-filled orbital arrangement.

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑

1s 2s 2p 3s 3p 4s 3d

 Cr24 : 1s2 2s2 2p6 3s2 3p6 4s1 3d5

 ELECTRON CONFIGURATION OF ATOMS & IONS

 Expected electronic configuration:

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑
Cu29 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
1s 2s 2p 3s 3p 4s 3d

Cu29 : 1s2 2s2 2p6 3s2 3p6 4s2 3d9

 one electrons from 4s orbital occupies 3d orbital to have half-filled orbital arrangement.

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
1s 2s 2p 3s 3p 4s 3d

 Cu29 : 1s2 2s2 2p6 3s2 3p6 4s1 3d10

 ELECTRON CONFIGURATION OF ATOMS & IONS
Ar Inner core configuration : [Ar]18 = 1s22s22p63s23p6

ELEMENT ELECTRONIC CONFIGURATION ABBREVIATED EC

Sc 1s22s22p63s23p64s23d1 [Ar] 4s23d1
Ti 1s22s22p63s23p64s23d2 [Ar] 4s23d2
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
 TRY THIS
● Write the subshell electron configurations for:

a) Cu

b) Cr3+

c) Mn4+

d) Ni

e) Zn

f) Fe

g) Fe2+

h) Fe3+

i) Co2+
 GENERAL PROPERTIES & TREND: ATOMIC
SIZE
ACROSS THE PERIOD

 Decrease at first, then remains relatively constant.

 additional electrons are added to the inner 3d subshell resulting

in stronger attraction to the nucleus.
 3d electrons shield the outer 4s electrons from the increasing of
nuclear charge.
 GENERAL PROPERTIES & TREND: ATOMIC
SIZE
GOING DOWN THE GROUP

Atomic size increases from Period 4 to 5

Total number of shells increase and orbitals get larger leading to greater size.

Atomic size for Period 5 to 6 almost the same size .

 The third row of transition metals contains many more protons in their nuclei.

 The third row "contracts" because of these additional protons. This effect is
called the “lanthanide contraction”.
 GENERAL PROPERTIES & TREND: IONIZATION ENERGY

ACROSS THE PERIOD

 Amount of energy required to remove an electron from its ground
state.

 Increase relatively little across the transition metals of a particular period.

 Across the period, atomic size decreasing so electrons are more

closely attracted to the nucleus, thus the electron is more difficult to be
removed.
 GENERAL PROPERTIES & TREND: IONIZATION ENERGY

GOING DOWN THE GROUP

Generally increases moving down a group.

Because of two factors:

1) Relatively small increase in size

2) Relatively large increase in nuclear charge.

As the element going down the group, there are just small increasing in
size and the nuclear charge increase. Atom with higher nuclear charge
held electrons closely to the nucleus. Therefore, ionization energy
increase.
Counter to the pattern in the main groups.
 GENERAL PROPERTIES & TREND: ELECTRONEGATIVITY

ACROSS THE PERIOD

 ability of an atom to attract the bonding electrons to
itself.

 Increase relatively little across the transition metals of a particular period.

 Crossing the period, atomic size decrease. The smaller the atomic
size, the higher the ability to attract bonding to itself.
GENERAL PROPERTIES & TREND: ELECTRONEGATIVITY

GOING DOWN THE GROUP

Increase within a group from Period 4 to 5, then

generally remains unchanged from Period 5 to 6.

o Down the group, atomic mass increase. The heavier

elements often have high EN values.
SPECIAL CHARACTERISTIC OF TRANSITION
ELEMENT

Variable Oxidation States Complex Ion

UNIQUENESS

Coloured Compounds Catalytic Properties

 PHYSICAL PROPERTIES
● Hard, tough and strong
-because of the strong metallic atom–atom bonding.

● Good conductors of heat and electricity

-there have many free electrons per atom to carry
thermal or electrical energy

● High Melting Points and Boiling Points

-The bonding between the atoms in transition metals
is very strong

● High density
-strong bonding between the atoms in transition
metals making they are tightly held together.
 PHYSICAL PROPERTIES

● Malleable : Transition metals are easily hammered

and bent into shape

● Ductile : Transition metals can be drawn out

into strong wire.

● Transition metals are typically lustrous/shiny

solids.
 Variable Oxidation States

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1 +1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4
+5 +5 +5
+6 +6
+7
 Variable Oxidation States

 oxidation state arises from the loss of the 4s and 3d electrons.

 All transition metals exhibit a +2 oxidation state (electrons are first

removed from the 4s sub-shell).
 This is because the electrons in the d shell are closer to the nucleus than
the atoms in the s shell. As a result, the electrons in the highest s shell
tend to be lost first, rather than the electrons in the d shell.
 since transition metals have 5 d-orbitals which d-orbital has a variety of
oxidation states. The d electrons are fairly easy to remove, but there are
certain states that are more stable than others.
 The half-full set of 'd' orbitals is spherically symmetrical and has an extra
degree of stability.
 Variable Oxidation States

 Increase in the number of oxidation states from Sc to Mn because of the

unpaired electrons increases. This is because, unpaired valence electrons
are unstable and eager to bond with other chemical species.

 Decrease in the number of oxidation states from Mn to Zn, due to the

pairing of d electrons occurs after Mn.
DETERMINATION OF OXIDATION NUMBER

1. Determine the oxidation state of cobalt (Co) inCoBr2.

Br= -1 Br2 = 2 x (-1) = -2

CoBr2 has an overall neutral charge
-2 + Co = 0
Co = +2

2. Determine the oxidation state of Mn in MnO4-

O= -2 O4 = 4 x (-2) = -8
Overall charge for MnO4- = -1
-8 + Mn =-1
Mn = +7
 COLOURED COMPOUND

 Colors can vary depending on the charge, number & groups of atom
attach to the metal ion (ligands).

 When ligands are present, some d orbitals become higher / lower

energy than before.

 When the d-level is not completely filled, it is possible to promote

electron from a lower energy d-orbital to a higher energy d orbital by
absorption of a photon of electromagnetic radiation (d-d transitions).

 The wavelength of the light absorbed is affected by the size of the

energy gap between the d orbitals.
FARHA
 COMPLEX ION

 A complex ion has a transition metal ion at its centre with a

number of ligands surrounding it.

 Ligands have active lone pairs of electrons which used

to
form co-ordinate bonds with the metal ion.

 Other metals also form complex ions - it isn't something

that only transition metals do. However, transition metal
form a very wide range of complex ions.
 CATALYTIC PROPERTIES

 Transition metals and their compounds are often good

catalysts.

 Transition metals and their compounds function as catalysts

either because of their ability to change oxidation state or, in
the case of the metals, to adsorb other substances on to
their surface and activate them in the process.
 CHEMICAL PROPERTIES

● Good catalytic properties

● - either as the metal itself or as a compound.

● - Homogeneous catalysts are those in the same

physical phase as the other reactants e.g. all in
solution together in the same solvent, or all are
gases.

● - Heterogeneous catalysts are those in a different

physical phase to the rest of the reactants. e.g. two
different liquids in contact with catalysis occurring
at the interface between them, or more commonly a
solid catalyst and a solution, or a solid and gases.
 CATALYTIC PROPERTIES

Hydrogenation (Reduction)

Ni
→ CH3-CH3(g)
CH2=CH2(g) + H2(g)

The Haber Process

Formation of ammonia from nitrogen and hydrogen using iron as

the catalyst.
Fe
→
N2(g) + 3H2(g) 2NH3(g)
 CHEMICAL PROPERTIES

● They tend to be much less reactive than the

Alkali Metals.

- Transition metals do not react as quickly with water

or oxygen so do not corrode as quickly.
- Many transition metals will react slowly with acids.

● Many form compounds which are paramagnetic

(have unpaired electrons)
 METALLURGY OF IRON

Iron is found in nature in form of its oxides, carbonates and

sulphates.

The main ores are:

 Haematite (Fe2O3)

 Magnetite (Fe3O4)

 Iron Pyrites (FeS2)

Iron ore contain impurities.

Iron ore is reduced to iron metal by heating with carbon

 METALLURGY OF IRON

STEP 1 : CONCENTRATION
 The ore is crushed in crushers and is broken to small pieces.

 It is concentrated with gravity separation process in which it is

washed with water to remove clay, sand, etc.

STEP 2 : CALCINATION
 The ore is then heated in absence of air (calcined).
 METALLURGY OF IRON

STEP 3 : SMELTING
 The concentrated ore is mixed with calculated quantity of coke, limestone
and the mixture is put in the blast furnace from top.
Blast Furnace
 METALLURGY OF IRON

REACTION IN BLAST FURNACE

1) Formation of carbon monoxide:

 Coke burns in air to form carbon dioxide & a lot of heat is produced
(about 1875 K).

C + O2 → CO2 + Heat

 This CO2 further racts with more coke and is reduced to CO.

C + CO2 → 2CO
 METALLURGY OF IRON

REACTION IN BLAST FURNACE

2) Reduction of ores to iron:

 Iron ores is reduced to Iron by CO.

 This molten Iron is collected at the bottom of the

furnace.

Fe2O3 + 3CO → 2Fe + 3CO2 Heamatite

Fe3O4 + 4CO → 3Fe + 4CO2 Magnetite

 METALLURGY OF IRON

FUNCTION OF LIMESTONE
 Acts as flux to remove sand from haematite in form of liquid slag.

 Limestone decomposes to produce calcium oxide (CaO) and CO2.

CaCO3 + heat → CaO + CO2

 This CaO reacts with silica (sand) present in the ore to form slag (CaSiO3)

CaO + SiO2→ CaSiO3

 COMMERCIAL FORM OF IRON

 3 major forms of iron.

1) Cast Iron

Contain 2-5% carbon along with traces of other impurities.

2) Wrought iron

The purest form of iron and contain carbon to the extent of 0.25%.

3) Steel

Contains 0.5 to 1.5% carbon along with variying amount of other

elements.
 TRY THIS

1) Name three ores of Iron.

2) Write the chemical reaction taking place in a blast furnace

during extraction of Iron.

3) What 3 major types of iron. How do they differ from each other?

4) Draw a neat labeled diagram of Blast Furnace.

 REVISION

1) What distinguishes a transition metal from a representative metal?

2) Why zinc is not considered as transition metal?

3) Explain why atomic radii decrease very gradually from Sc to Cu.

THANK YOU