In the periodic classification of elements, the elements have been divided into four

blocks. This division is based on the type of atomic orbital which receives the last
electron in the atom. The d-block elements are called transition elements. This
block consists of elements lying between s and p-blocks i.e., between Groups 2 and
13 , starting from fourth period on wards. In these elements, the outermost shell
contains one or two electrons in their s-orbital (ns) but the last electron enters the
last but one d-subshell i.e., (n - 1) d. The elements of this block have general
characteristic properties intermediate between the elements of s-block and

p-

block. In other words d-block elements represent change (or transition) in

properties from most electropositive s-block elements to least electropositive pblock elements. Therefore, these are called Transition Elements.
Definition and Electronic Configurations
The transition elements are those elements which have partially filled dsubshells in their elementary form or in their commonly occurring oxidation states.
The definition covers coinage metals, Cu, Ag and Au as transition metals
because in their commonly occurring oxidation states , they have partially filled dsubshells. For example, Cu2+ has 3d9 configuration, Au3+ has 5d8 configuration,
although all these atoms have completely filled d-subshell in their elementary
states(Cu ; 3d10 : Ag ; 4d10 : Au ; 5d10 ). However, it may be noted that, the
above definition does not include elements of Group-12 i.e., Zn, Cd and Hg. These
elements do not have partially filled d-subshells in their elementary state or in their
commonly occurring oxidation states. However, these may be treated along with
transition elements because they are quite similar to other transition elements in
some of their chemical properties.

Electronic configurations
In the transition elements , the d-orbitals are successively filled. The general
electronic configuration for atoms of d-block is : (n-1) d1-10 ns1-2
Transition Series
The transition elements consist of three complete rows of the elements and
one incomplete row. These rows are called first, second and third transition series
which involve the filling of 3d, 4d and 5d-orbitals respectively. These series are
also called Transition series.
First transition Series
Scandium (Z = 21) to Zinc ( Z = 30). 3d-orbitals are gradually filled.
Second transition Series
Yttrium(Z=39) to cadmium ( Z = 48). 4d-orbitals are gradually filled.
Third transition Series
Lanthanum (Z = 57) , Hafnium( Z = 72) to mercury

(Z = 80) . 5d-orbitals

are gradually filled.

Fourth transition Series
This series starts from Actinium(Z=89) and is incomplete. It will include
elements from atomic number 104 onwards (only some of these are isolated).
Electronic configurations
The first transition series consists of elements from Scandium (Z=21) to
Zinc (Z=30). In Scandium, the 3d-orbital starts filling up and its electronic
configuration is [Ar]4s23d1. As we move from scandium onwards, 3d-orbitals get
filled up more and more till the last element, zinc, in which the 3d-orbitals are
completely filled, i.e., [Ar]4s23d10.

Element

Symb Atom

Outer

ol

ic

Electronic

numb

configurat

Sc

er
21

ion
3d14s2

m
Titanium Ti
Vanadiu V

22
23

3d24s2
3d34s2

m
Chromiu Cr

24

3d54s1

m
Mangane Mn

25

3d54s2

Scandiu

se
Iron
Fe
26
3d64s2
Cobalt
Co
27
3d74s2
Nickel
Ni
28
3d84s2
Copper
Cu
29
3d104s1
Zinc
Zn
30
3d104s2
It may be noted that the configuration of chromium and copper are
anomalous. The half-filled and completely filled electronic configurations (i.e., d 5
and d10) have extra stability, one of the 4s-electron goes to nearby 3d-orbital , so
that 3d-orbitals become half-filled in case of chromium and completely filled in the
case of copper respectively. Therefore the electronic configuration of chromium is
[Ar]3d54s1 rather than [Ar]3d44s2 while that of Cu is [Ar]3d 104s1 instead of
[Ar]3d94s2.
Second transition Series
The second transition series consist of elements from Yttrium Y (Z= 39) to
cadmium(Z=48)

i.e.,

Yttrium(Z=39),

zirconium

(Z=40),

niobium(Z=41),

molybdenum (Z=42), technetium (Tc = 43), ruthenium (Z = 44), Rhodium

(Z=45) , Palladium (Z = 46), silver (Z = 47) and cadmium (Z= 48) . This series
involves the filling of 4d-orbitals (TABLE)

Electronic configuration of Second Transition Series

Element

Symb Atom Outer

ol

ic

Electronic

numb configurat
Yttrium
Zirconium
Niobium
Molybden

Y
Zr
Nb
Mo

er
39
40
41
42

um
Technetiu

Tc

43

4d55s2

m
Rutheniu

Ru

44

4d75s1

m
Rhodium Rh
45
Palladium Pd
46
Silver
Ag
47
Cadmium Cd
48
Third transition Series

ion
4d15s2
4d25s2
4d45s1
4d55s1

4d85s1
4d105s0
4d105s1
4d105s2

The series consists of elements Lanthanum( Z = 57) and from Hafnium

(Z=72) to mercury (Z=80) i.e., Lanthanum (La), Hafnium(Hf), Tantalam(Ta),
Tungsten (W), Rhenium(Re), Osmium(Os), Iridium(Ir), Platinum(Pt), Gold(Au)
and Mercury(Hg). In between Lanthanum and Hafnium, there are fourteen
elements called Lanthanides which involve the filling of 4f-orbitals and do not
belong to this series. The elements of this series involve the gradual filling of 5dorbitals.

Element

Symb Atomic

Outer

ol

Electronic

number

configurati
Lanthan

La

um
Hafnium Hf

57

on
[Xe]

72

5d16s2
[Xe]
4f145d26s

Tantalu

Ta

73

2
[Xe]

4f145d36s

Tungsten W

2
[Xe]

74

4f145d46s
Rhenium Tc

75

2
[Xe]
4f145d56s

Osmium

Os

76

2
[Xe]
4f145d66s

Irridium

Ir

77

2
[Xe]
4f145d76s

Platinum Pt

78

2
[Xe]
4f145d96s

Gold

Au

79

1
[Xe]
4f145d106

Mercury

Hg

80

s1
[Xe]
4f145d106

s2
It may be noted in the second and third transition series, there are many
anomalous configurations in comparison to those of the first transition series.
These are attributed to factors like nuclear-electron and electron-electron forces.
Fourth transition series
It involves the filling of 6d-subshell starting from actinium (Z=89) ; which
has the configuration 6d17s2. This series is incomplete.
Element

Actinium
Rutherfordiu
m
Dubinium
Seaborgium
Bohrium
Hassnium
Meitnerium
Dasmstarium

Symbol Atomic

Ac
Rf
Db
Sg
Bh
Hs
Mt
Ds

Outer

number

Electronic

89
104

configuration
[Rn] 6d17s2
[Rn]

105

5f146d27s2
[Rn]

106

5f146d37s2
[Rn]

107

5f146d47s2
[Rn]

108

5f145d57s2
[Rn]

109

5f145d67s2
[Rn]

110

5f146d77s2
[Rn]
5f146d87s2

Uuu

111

Uub

112

It would be of interest to consider the change in the relative energies of various

sub-shells with change in atomic number. The relative energies of subshells of
third , fourth and fifth energy shells are given in Fig. As is clear from the figure ,
upto

Z = 20, 4s-sub-shell has lower energy than 3d-subshell. Therefore

calcium(Z=20) has the electronic configuration 1s22s22p63s23p64s2. Beyond this

there is a sharp decrease in energy of 3d-subshell and its energy becomes less than
the 4s-subshell.
Starting with scandium(Z=21) upto zinc(Z = 30) , the 3d orbitals are filled and the
d-electrons become more effective in shielding the 4s-electrons from attractive
force of the nucleus. Therefore, 3d-subshells get pulled lower than 4s.
The transition elements with partly filled d-orbitals exhibit certain
characteristic properties. For example, they display a variety of oxidation states,
form coloured ions and enter into complex formation with different anions and
neutral molecules. These metals and their compounds also exhibit catalytic
property and many of them show paramagnetic behaviour. There are greater
horizontal similarities in the properties of transition elements in contrast to the
main group elements.
Ionisation of atoms
It is observed that after calcium, the energy of 4s-subshell is more than 3dsubshell (Fig above) . Therefore , when electrons are to be removed from these
atoms, the electrons will go from 4s-orbital rather than 3d-orbital , though the
former was filled earlier. For example.
Fe ( Z = 26) : [Ar ] 3d6 4s2
Fe3+

: [Ar] 3d5

Ni (Z = 28) : [Ar] 3d84s2

Ni2+ : [Ar] 3d8

The same trend is repeated for 5s, 4d and 6s, 5d orbitals in second and
third transition series. In lanthanum, the energies of 4f, 5d and 6s-orbitals lie very
close to one another and one electron goes to 5d-orbital before 4f-orbitals. Its
configuration is 5d16s2. In other elements 4f-orbitals are stabilised relative to 5d
and electron go into

4f-orbitals.

PROPERTIES OF TRANSITION ELEMENTS

Physical Properties
Nearly all the transition elements display typical metallic properties such as
high tensile strength, ductility, malleability , high thermal and electrical
conductivity and metallic lustre. Except mercury which is a liquid at room
temperature , other elements have typical metallic structures.
Their melting and boiling points are high. The Fig 2 shows the melting
points of 3d. 4d and 5d transition metals.
The high melting points are attributed to strong interatomic bonding , which
involves the participation of both ns and (n-1)d electrons. In any row the melting
points of these metals rise to maximum at d6 except for anomalous values of Mn
and Tc and fall regularly as the atomic number increases.
With the exception of zinc, cadmium and mercury , the transition elements
are much harder and less volatile. They exhibit high enthalpies of atomisation (Fig
3 Page 4) ; the maxima at about the middle of each series indicates that one
unpaired electron per d-orbital is particularly favourable for strong interatomic
interaction. In general, , greater the number of valence electrons , stronger is the
resultant bonding. Since the enthalpy of atomisation is an important factor in

determining the standard electrode potential of a metal, those with highest enthalpy
of atomisation (highest boiling point) tend to be noble metals.
The metals of the second (4d) and third (5d) series have greater enthalpies
of atomisation than the corresponding elements of the first series ; this is an
important factor for their having much more frequent metal-metal bonding in their
compounds.
The decrease in metallic radius coupled with increase in atomic mass
results in a general increase in density of these elements. Thus , from titanium to
copper the increase in the density may be noted (TABLE).

Electronic configuration and some properties of first series of transition

elements
Element
Atomic

Sc
21

Ti
22

V
23

Cr
24

Mn
25

Fe
26

Co
27

Ni
28

Cu
29

Zn
30

3d24

3d34

3d54

3d54

3d64

3d74

3d84

3d104

3d104

number
Ele.
configurati 3d14
on

s2

s2

s2

s1

s2

s2

s2

s2

s1

s2

3d14

3d24

3d34

3d5

3d54

3d64

3d74

3d84

3d10

3d104

M+

s1

s1

s1

3d4

s1

s1

s1

s1

3d9

s1

M2+

3d1

3d2

3d3

3d3

3d5

3d6

3d7

3d8

3d8

3d10

M3+
Enthalpy

[Ar]
326

3d1
473

3d2
575

397

3d4
281

3d5
416

3d6
425

3d7
430

339

3d9
126

of
atomisatio
n kJ/mol
Ionisation

enthalpy

631

656

650

653

717

762

758

736

745

906

1235 1309 1414 1592 1509 1561 1644 1752 1958

1734

II

2393 2657 2833 2990 3260 2962 3243 3402 3556

3829

164

147

135

129

137

126

125

125

128

137

M2+

79

82

82

77

74

70

73

75

M3+
E (V)

73

67

64

62

62

65

61

60

M2+/M

-1.18 -

- 0.76

M3+/M2+

1.18

0.90

+1.5

0.44

0.28

0.25

0.34

- -0.41 7

+0.7

+1.9

7.18

7
7.8

7
8.7

8.9

8.9

III
r pm

Density
(g/cm3)

3.43

4.1

0.26
6.07

7.21

7.1

Variation in Atomic and Ionic sizes

In general , ions of the same charge in a given series show progressive
decrease in radius with increasing atomic number. This is because the extra
electron enters a d-orbital each time the nuclear charge increases by unity. The
shielding effect of a d-electron is small, the net electrostatic attraction between the
the nuclear charge and outermost electron increases and the ionic radius decreases.
The atomic radius also decreases in the same way. The variation within a series is
quite small. An interesting point emerges when sizes of elements in one series are
compared with the sizes of the corresponding elements in other series. The data in
Fig 4 shows that an increase from the first (3d) to second (4d) series of the
elements but the radii of the third (5d) series are virtually the same as those of the
corresponding members of the second series. This phenomenon is associated with
the intervention of the 4f-orbitals, which must be filled before the 5d-series of
elements begin. The filling of 4f before 5d orbital results in a regular decrease in
atomic radii called lanthanoid contraction which essentially compensate for the
expected increase in atomic size with increasing atomic number. The net result of
lanthanoid contraction is that the second and third d-series exhibit similar radii
(e.g., Zr 160 pm , Hf 159 pm) and have very similar physical and chemical
properties.
Ionisation Enthalpies
With increasing nuclear charge, which accompanies the filling of the inner
d-orbitals , there is an increase in ionization enthalpy along each series of the
transition elements from left to right , but many small variations occur. TABLE 1
gives the ionisation enthalpies of the first row elements. These values show that
although the first ionisation enthalpy in general, increases , the increase in the
second and third ionization enthalpies for the successive elements are not of the
same magnitude. However, the trend is similar for the second ionization

enthalpies , which for the most part increase smoothly as the atomic number
increases, the exceptions are chromium and copper for which these values are
notably larger than those of their neighbours. These exceptions are attributed to the
extra stability of half-filled or completely filled set of d-orbitals in chromium and
copper. The third ionization enthalpies are quite high and there is a marked break
between the values for Mn2+ and Fe2+. Also , the high values for copper, nickel and
zinc indicate why it is difficult to obtain oxidation state greater than two for these
elements.
Problem
02.

Why do transition elements exhibit higher enthalpies of atomization ?

Oxidation states
The transition elements exhibit a large number of oxidation states. With the
exception of few elements, most of these show variable oxidation states. These
different oxidation states are related to the electronic configuration of their atoms.
For example, the oxidation states exhibited by the transition elements of the first
series are listed in TABLE.
Different oxidation states of First transition series
Elem Outer
ent

Oxidation states

electroni
c
configura

Sc
Ti
V
Cr
Mn

tion
3d14s2
3d24s2
3d34s2
3d54s1

+2,+3
+2,+3,+4
+2,+3,+4,+5
(+1),+2,+3,(+4),

3d54s2

(+5),+6
+2,+3,+4,(+5),

Fe
Co
Ni
Cu
Zn

3d64s2

+6,+7
+2,+3,(+4),(+5),

3d74s2
3d84s2
3d104s1
3d104s2

(+6)
+2,+3,(+4)
+2,+3,+4
+1,+2
+2

*Oxidation states with in the brackets are unstable.

Explanation
The existence of the transition elements in different oxidation states means
that their atoms can lose different number of electrons. This is due to the
participation of inner

(n-1) d-electrons in addition to outer ns-electron

because, the energies of the ns and (n-1) d-subshells are almost equal. For example,
scandium has the electronic configuration of 3d14s2. It exhibits an oxidation state
of +2 when it uses both of its two

4s-electrons for bonding. It can also show

oxidation state of +3 when it uses its two s-electrons and one d-electron.
Variable oxidation states of second and third transition series
The elements of the second and third transition series also exhibit variable
oxidation states as given in the following TABLE.
Different oxidation states of elements of second and third transition series.
Second Transition series
Y Z

M T

+3 +

+4 4

+5 +

+6 5

+
6
+
7
+
8
Third Transition series
L H T
a

W R
e

O Ir
s

Pt A

-1 +

5
+
6
+
7
*The oxidation states in italics are uncommon.
Important conclusion regarding oxidation states of transition elements
The examination of common oxidation states shown by different transition
metals reveals the following facts :
(i)

The variable oxidation states of transition metals are due to participation of

inner (n -1) d and outer n s-electrons. The lowest oxidation state corresponds to
the number of

ns-electrons. For example, in the first transition series , the

lowest oxidation states of Cr (3d54s1) and Cu(3d104s1) are +1 while for others , it
is +2 (3d104s2)
(ii)

Except scandium, the most common oxidation state of the first row transition
elements is +2 which arises due to loss of two 4s-electrons. This means that after

scandium 3d-orbitals become more stable and therefore , are lower in energy than
the 4s-orbitals. As a result, electrons first removed from 4s-orbitals.
(iii)

For the first five elements, the minimum oxidation state is equal to the number
of electrons in the s-orbitals and the other oxidation states are given by the sum of
outer s - and some or all d-electrons. The highest oxidation state is equal to the
sum of the outer s (ns ) and (n -1) d-electrons. For the remaining five elements , the
minimum oxidation state is given by the electrons in s-orbital while the maximum
oxidation state is not related to their electronic configurations. The highest
oxidation state shown by any transition metal is +8.

(iv)

In the +2 and +3 oxidation states, the bonds formed are mostly ionic. In the
compounds of higher oxidation states (generally formed wth oxygen and fluorine),
the bonds are essentially covalent. Thus the bonds in +2 and +3 oxidation states are
generally formed by the loss of two or three electrons respectively, while the bonds
in higher oxidation states are formed by sharing of d-electrons. For example MnO4(Mn in +7 ) state all the bonds are covalent.

(v)

Within a group, the maximum oxidation state increases with atomic number.
For example, iron (Group 8) shows common oxidation states of +2 and +3 but
ruthenium and osmium in the same group form compounds in the +4 , +6 and +8
oxidation states.

(vi)

Transition metals also form compounds in low oxidation states such as +1 and
0 or negative. The common examples are [Ni(CO)4], [Fe(CO)5] in which nickel and
iron are in zero oxidation state.
Formation of coloured ions
Most of the compounds of the transition metals are coloured in the solid
form or solution form. This is in contrast to the compounds of s- and p-block
elements which are usually white.

The colour of the compounds of transition metals may be attributed to the

presence of (n-1) d-subshell. In the case of compounds of transition metals,
energies of five

d-orbitals in the same sub-shell do not remain equal. Under the

influence of approaching ions towards the central metal ion, the d-orbitals of the
central metal split into different energy levels. This phenomenon is called crystal
field splitting. For example, when six ions or molecules approach the metal
ion(called octahedral field) , the five d-orbitals split into two sets : one set
consisting of two

d-orbitals(dx2- y2, dz2) of higher energy and the other

set consisting of three d-orbitals (dxy, dyz, dxz) of lower energy.

In the case of transition metal ions, the electrons can be easily promoted
from one energy level to another in the same

d-subshell. These are called d-d

transitions. The amount of energy required to excite some of the electrons to

higher energy states with in the same d-subshell corresponds to energy of certain
colours of visible light. Therefore , when white light falls on transition metal
compound, some of its energy corresponding to a certain colour is absorbed and
the electron gets raised from lower energy set of orbitals to higher energy set of
orbitals as shown below:
The other colours constituting white light are transmitted and the compound
appears coloured. The observed colour of the substance is always complimentary
colour of the colour which is absorbed by the substance. For example, Ti3+
compounds contain one electron in d-subshell (d1). It absorbs green and yellow
portions from the visible light and blue and red portions are emitted. Therefore
Ti3+ ions appear purple. Similarly, hydrated cupric compounds absorb radiations
corresponding to red light and the transmitted colour is greenish blue(which is
complimentary colour to red colour). Thus cupric compounds have greenish-blue
colour.

The frequency of the light absorbed is determined by the nature of the

ligand. In aqueous solutions where water molecules are the ligands, the colour of
the ions obseved are listed in TABLE.
The colours of some of the first row transition metal ions (aquated)
Configuratio Example

Colour

n
3d0
3d0

Sc3+
Ti4+

Colouless
Colourles

Ti3+
V4+
V3+
V2+
Cr3+
Mn3+
Cr2+
Mn2+
Fe3+
Fe2+
Co2+
Ni2+
Cu2+
Zn2+

s
Purple
Blue
Green
Violet
Violet
Violet
Blue
Pink
Yellow
Green
Pink
Green
Blue
Colourles

3d1
3d1
3d2
3d3
3d3
3d4
3d4
3d5
3d5
3d6
3d7
3d8
3d9
3d10

s
It may be noted that the transition metal ions containing completely filled dorbitals (d10) such as Zn2+, Cd2+, Hg2+, Cu+ etc. are generally white. For
example ZnCl2 is white. Similarly Sc3+ and Ti4+ are white because they have
completely empty d-orbitals.
Chemical Reactivity and E values
Transition metals vary widely in their chemical reactivity. Many of them
are suffiently electropositive to dissolve in mineral acids, although a few are
noble , that is they are unaffected by simple acids.

The metals of the first series with the exception of copper are relatively
more reactive and are oxidised by 1 M H+ , though the actual rate at which these
metals react with oxidising agents like hydrogen ion (H+) is some times slow. For
example, titanium and vanadium , in practice , are passive to dilute

non-

oxidising acids at room temperature. The E values for M2+/M (Table 1) indicate a
decreasing tendency to form divalent cations across the series. The general trend
towards less negative E values is related to the general increase in sum of first and
second ionisation enthalpies. The E values of for Mn, Ni and Zn are more
negative than expected from the general trend. Whereas the stabilities of half-filled
d-subshell (d5 )in Mn2+ and completely filled d-subshell (d10) in zinc are related
to their E values ; for nickel, Evalue is related to the highest negative enthalpy of
hydration.
An examination of the E values for the redox couple M3+/ M2+ (Table 1)
shows that Mn3+and Co3+ ions are the strongest oxidising agents in aqueous
solutions. The ions Ti2+, V2+ and Cr2+ are strong reducing agents and will
liberate hydrogen from a dilute acid, e.g.
2 Cr2+(aq) + 2 H+(aq) 2 Cr3+(aq) + H2(g)
Magnetic Properties
The magnetic properties of a compound is a measure of the number of unpaired
electrons in it. There are two main types of substances :
i) Paramagnetic substances : The substances which are attracted by magnetic field
are called paramagnetic substances and this character arises due to the presence of
unpaired electrons in the atomic orbitals.
ii) Diamagnetic substances : The substances which are repelled by magnetic field
are called diamagnetic substances and this character arises due to the presence of
paired electrons in the atomic orbitals.

Most of the compounds of transition elements are paramagnetic in nature

and are attracted by the magnetic field.
The transition elements involve the partial filling of

d-subshells. Most

of the transition metal ions or their compounds have unpaired electrons in dsubshell (configuration from d1 to d9) and therefore, they give rise to paramagnetic
character. The magnetic character is expressed in Bohr magnetons abbreviated as
B.M. The magnetic moments of some ions of the first transition series are given in
the following TABLE.
Magnetic moments of ions of first transition series.
Ion

Outer

Number

Magneti

configurati

of

on

unpaire

moment

(mB)

electron
Sc3+ 3d0
Ti
3d1

s
0
1

0
1.75

3+
V3+
Cr3+
Cr2+
Mn2

3d2
3d3
3d4
3d5

2
3
4
5

2.76
3.86
4.8
5.96

+
Fe2+ 3d6
Co2 3d7

4
3

5.10
4.4-5.2

+
Ni2+ 3d8
Cu2 3d9

2
1

2.9 - 3.4
1.8 - 2.2

+
Zn2

3d10

+
The magnetic moments arise only from the spin of electrons. This can be
calculated from the relation :

where n is the number of unpaired electrons and B.M represents Bohr magneton. It
is clear from the Table that as the number of unpaired electron increases from 1 to
5, the magnetic moment and hence the paramagnetic character also increases. After
d5 configuration, there is decrease in magnetic moment due to decrease in number
of unpaired electrons. For example, d6 configuration has 4 unpaired electrons, d7
configuration has

3 unpaired electrons and so on.

In addition to paramagnetic and diamagnetic substances, there are a few

substances such as iron metal, iron oxide which are highly magnetic (about 1000
times more than ordinary metals). These are called Ferromagnetic substances.