Contact Details

Name: Dr WT Mhlongo

Office No.: Arcadia Campus: 3-614A

Telephone No.: 012-382 6405

E-mail address: [email protected]

Faculty of Science)
Department of Chemistry
Live your life. Create your destiny.

Transition metals:
d-Block Elements

Faculty of Science)
Department of Chemistry
 Outcomes

• Describe the transition (d-block) element

• Uses
• D-block elements configurations
• Properties

Faculty of Science)
Department of Chemistry
 Faculty of Science)
Department of Chemistry
Periodic Table

d-block transition elements

f-block transition elements

Faculty of Science)
Department of Chemistry
Why Study Descriptive Chemistry of
Transition Metals

Transition metals and their compounds have many

useful applications
• Fe is used to make steel
• Ti is used to make lightweight alloys
• Transition metal compounds are used as pigments
• TiO2 = white
• PbCrO4 = yellow
• Fe4[Fe(CN)6]3, iron(III) hexacyanoferrate(II), (prussian blue)= blue
• Transition metal compounds are used in industrial
processes

Faculty of Science)
Department of Chemistry
Transition Metals
• Transition metals are found in nature
• Between S and P- block
• Rocks and minerals contain transition metals
• The color of many gemstones is due to the presence of
transition metal ions
• Rubies are red due to Cr
• Sapphires are blue due to presence of Fe and Ti
• biomolecules contain transition metals
• Hemoglobin, myoglobin, and cytochrome C contain Fe
• Vitamin B12 contains Co

Faculty of Science)
Department of Chemistry
Characteristics
They have very similar physical and chemical characteristics.
Metals with high melting and boiling point. NB. Zn, Cd, Hg
High densities.
Have good mechanical properties
 High tensile strength (resistance to break when under tension)
 Malleable (hammered or pressed into shape without braking)
 Ductile (able to be deformed without losing toughness; pliable, not
brittle)
They exhibit interesting magnetic properties.

Faculty of Science)
Department of Chemistry
Have variable oxidation numbers.
Form coloured ions.
Form a large number of complexes and complex ions.
Small highly charged ions, vacant low energy orbitals to accept
lone pairs of electrons
 Can use orbitals from 2 different shells for bonding (e.g. 4s & 3d).
Have catalytic activity.

Faculty of Science)
Department of Chemistry
 What are transition
elements?
• A transition element is defined as the one which
has incompletely filled d orbitals in its ground
state or in any one of its oxidation states. i.e.

• A transition element should have partially filled

(n-1) d orbital.

Faculty of Science)
Department of Chemistry
 How are d - Block Elements
&Transition elements different?
All transition elements are d-block
elements but not all d-block elements
are transition elements

NB: Zinc have full d10 configuration in their ground state as well as in their
common oxidation state, which is not according to definition of transition
elements .

Faculty of Science)
Department of Chemistry
Electronic Configuration

• Across the 1st row of the d block (Sc to Zn) each element
• has 1 more electron and 1 more proton
• Each “additional” electron enters the 3d sub-shell
• The core configuration for all the period 4 transition elements
is that of Ar
• 1s22s22p63s23p6

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Department of Chemistry
 Electronic
Arrangement
Elemen Z 3d 4s
t
Sc 21 [Ar]  
Ti 22 [Ar]   
V 23 [Ar]    
Cr 24 [Ar]      
Mn 25 [Ar]      
Fe 26 [Ar]      
Co 27 [Ar]      
Ni 28 [Ar]      
Cu 29 [Ar]      
Zn 30 [Ar]      

Faculty of Science)
Department of Chemistry
Chromium and Copper
• Cr and Cu don’t fit the pattern of building up the
3d sub-shell, why?
• In the ground state electrons are always arranged to give
lowest total energy
• Electrons are negatively charged and repel each other
• Lower total energy is obtained with e- singly in orbitals rather
than if they are paired in an orbital
• Energies of 3d and 4s orbitals are very close together in
Period 4
• To achieve a more stable arrangement of lower energy, one
of the 4s electrons is promoted into the 3d.

Faculty of Science)
Department of Chemistry
 Energy 4p

3
4 d
s
3p

3
s 2
2 p
s Ar
1s 1s2 2s2 2p6 3s2 3p6

Faculty of Science)
Department of Chemistry
 Energy 4p

3
4s d
3p

3
s 2
2 p
Sc
s
1s 1s2 2s2 2p6 3s2 3p6 3d1 4s2

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Department of Chemistry
 Energy 4
p
3d
4
s
3
p
3s
2p
2s

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

Faculty of Science)
Department of Chemistry
 Energy 4
p
3
4 d
s
3
p
3
s
2
p
2
s
1s
Cu 1s2 2s2 2p6 3s2 3p6 3d10
4s1
Faculty of Science)
Department of Chemistry
 A transition element is defined as the
one which has incompletely filled d
orbitals in its ground state or in any
one of its oxidation states. i.e.
A transition element should have partially
filled (n-1) d orbital.
Scandium and zinc don't have transitional metal properties .
Sc3+ :  Sc3+ ion has no d electrons
Zn2+ :  Zn has full 3d subshell

Faculty of Science)
Department of Chemistry
• Transition element forms at least one ion with an incomplete
subshell.
• They can use orbitals from 2 different shells for bonding. E.g
Fe3+.

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 Physical Properties
• Transition elements have very similar physical properties
• due to relatively small difference in effective nuclear
charge.
• the atomic (metallic) radius, ionic radius & first ionisation
energy are relatively constant.

Faculty of Science)
Department of Chemistry
 Atomic Radii
The atomic and ionic radii of elements V to Cu remains almost
constant compared to the elements in the third Period (Na to
Cl).
From Na to Cl, electrons are added to the outer shell (3s and
3p subshells)  nuclear charge increase  electrons are
pulled closer towards the nucleus  atomic radii decrease
across the period.

Faculty of Science)
Department of Chemistry
 Atomic Radii
The atomic and ionic radii of elements V to Cu remains almost
constant compared to the elements in the third Period (Na to
Cl).
But from Sc to Zn, electrons are added to inner shell (3d
subshell).
The inner electrons are able to shield the outer electrons
from the nucleus.
Hence cancelling the increasing nuclear charge across the
period.
The atomic radii remain almost constant from V to Cu.

Faculty of Science)
Department of Chemistry
 Faculty of Science)
Department of Chemistry
 First ionisation energy
• There is little change in the first ionisation energy of transition
elements from Ti to Cu. This is because :
a) the atomic radii remain almost constant.
b) the attractive forces on the outer electrons remain almost
constant.

Faculty of Science)
Department of Chemistry
 Melting and BoilingPoints
• Transition elements have higher melting and boiling points
compared to non-transition metals.
• Due to strong metallic bonds.
• Transition elements have a lot of electrons (from 3d and 4s
subshells)
• which can be used for metallic bonding.
• Exceptions are Zn (420 °C), Cd (321 ° C) and Hg, which is liquid
at room temperature and melts at
-38 ° C.
• These three behave in this manner because d shell is
complete, and d electrons do not participate in metallic
bonding.

Faculty of Science)
Department of Chemistry
 Characteristic properties
Color: The complexes of the d-block metal ions are usually colored, except,
very often, those of d0 and d10 metal ions. The colors are due to:

• electronic transitions of d-electrons within the d sub-shell, these are known as

d→d transitions. d0 and d10 metal ions do not show these transitions.

• electronic transitions from the metal ion to the ligand (M→L transitions) or
L→M transitions, which are known as charge-transfer transitions, and these
can occur for d0 to d10 metal ions.

• The ligands themselves may be colored, and this color may contribute to the
color of the complex.

Faculty of Science)
Department of Chemistry
 Zinc sulfate
Hepta-
Nickel(II)
Titanium sodium hydrate
Potassium nitrate
oxide chromate (ZnSO4.7H2O)
ferricyanide hexa-
(TiO2) hydrate

Vanadyl Manganese(II)
Scandium Copper(II)
Sulphate chloride Cobalt(II)
(III) sulfate
dihydrate Tetrahydrate chloride
Oxide penta-
(Sc2O3) hydrate

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Department of Chemistry
 Catalytic activity
• Transition elements have catalytic ability as compared to other elements.

• Due to variable oxidation state.

• Thus, for example, Mn displays oxidation states from Mn(III) in [Mn(CO)

(NO2)3] through Mn(0) (in [Mn2(CO)10]) to Mn(VII) (in [MnO4]-).

• Transition elements are able to change their oxidation states in a catalytic

cycle

Faculty of Science)
Department of Chemistry
 Variable oxidation states
• Transition elements have variable oxidation states in their
compounds. E.g Fe(II) and Fe(III) compounds.

• The variable oxidation states are due to the small energy

difference between the 4s and 3d subshells.

• Fe has oxidation states +1, +2, +3, +4, +5 and +6. Only +2 and
+3 are common.

• When compounds are formed, energy is needed to remove

electrons from the atoms.

• The energy for this ionisation is supplied by energy given out

when the new bonds are formed. Faculty of Science)
Department of Chemistry
 Oxidation states of first-row d-block
ions:
The most stable oxidation states are in red, rarer oxidation states pale blue:
3 4 5 6 7 8 9 10 11 12
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1 1 1 1 1 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 4 4 4
5 5 5 5
6 6 6
7 The higher oxidation
states become
progressively less
stable as the divalent
These achieve state becomes
the group dominant
oxidation state Maximum at Mn(VII)
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• Variable oxidations states arises from similar energies
required for removal of 4s and 3d electrons.
• The maximum oxidation number of an element
corresponds to the maximum number of electrons
available for bonding.
• E.g : Max. oxidation state for Cr is VI – all 3d5 and 4s1
electrons used in bonding.
• all (except scandium) have an M2+ ion.
• stability of the +2 oxidation state increases across the
row - marked increase in 3rd I.E.

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• maximum oxidation state increases from Sc to Mn and
decreases from Mn to Zn due to decrease in num. of
single electrons in the 3d subshell and the 4s
electrons.

• From Mn to Zn, some electrons in the 3d subshell are

paired – unreactive and not used in bonding.

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Comparison with s-block
elements.

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 OS-Summary
• Transition elements have variable oxidation states
• due to very small energy difference between (n-1)d & ns sub-
shell electrons from both the sub-shell take part in bonding
• maximum OS decrease as the energy required to remove more
electrons becomes very high

Faculty of Science)
Department of Chemistry