5.

d & f BLOCK ELEMENTS

1.2 Electronic configuration

1. INTRODUCTION
(1) In d-block elements with increase in atomic number, the d-
1.1 Definition orbitals of penultimate shell i.e. (n-1) d are gradually filled
by electrons. The general electronic configuration of d-
“The elements in which the last differentiating electron enters
block element is,
into the d-orbitals of the penultimate shell i.e.
(n-11) d1-10, ns0-2.
(n–1) d where n is the last shell are called d-block elements”.
(2) Depending upon the d-orbitals of which penultimate shell
A transition element may also be defined as the element
i.e. n = 4, 5, 6, 7 are filled, four rows (called series) os ten
which partially filled d-orbital in their ground state or most
elements each obtained. They correspond to 3d, 4d, 5d and
stable oxidation state.
6d subshells.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(3) Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9
subshell, hence orbital is filled first then (n – 1) d orbitals.
(Cupric ion)
(4) The general electronic configuration of d-block/d-series
The properties of these elements are intermediate between elements be shown as follows :
the properties of s-block and p-block elements.
1. First (3d) Transition Series (Sc–Zn)
These elements represent a change or transition in
properties from more electropositive elements (s-block) to
less electropositive elements (p-block). Therefore these
elements are called transition elements.
2. Second (4d) Transition Series (Y-Cd)
Position in the periodic table
The position of d-block element has been shown in periodic
table as follows :

3. Third (5d) Transition Series (La–Hg)

4. Fourth (6d) Transition Series

Exceptional configuration of Cr and Cu. The exceptions

observed in the first series are in case of electronic
(1) d-block elements lie in between ‘s’ and ‘p’ block elements, configurations of chromium (Z = 24) and copper (Z = 29). It
i.e. these elements are located in the middle of the periodic may be noted that unlike other elements, chromium and
table. copper have a single electron in the 4s-orbital. This is due
(2) d-block elements are present in, to the gain of additonal stability by the atom by either having
4th period (21Sc to 30Zn, 10 elements) o1st Transition series. half-filled configuration (i.e., containing 5 electrons in the
5th period (39Y to 48Cd, 10 elements) o2nd Transition series. d-sublevel) or completely filled configuration, (i.e.,
6th period (51La, 72Hf to 80Hg, 10 elements) o3rd Transition containing 10 electrons in the d-sublevel). The 3d-level in
series. case of chromium gets excatly half-filled with configuration
7th period (89Ac, 104Rf to 112Uub, 10 elements) o4th Transition 3d5 4s1 and that in case of copper, it gets completely filled
series. with configuration 3d10 4s1. This can be explained on the
basis of exchange energy
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 140 d AND f BLOCK ELEMENTS
Thus, the electronic configuration of chromium (Z = 24)
and copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 1.5 Metallic character
2p6 3s6 3p6 3d10 4s1 respectively.
Except for mercury which is a liquid, all the transition
elements have typical metallic structure. They exhibit all
1.3 Properties the characteristics of metals. ductile, have high melting and
boiling points, high thermal and electrical conductivity and
1. Atomic Raddii
high tensile strength.
(i) The atomic radii of the transition metals lie in-between those Transition elements have relatively low ionization energies
of s- and p-block elements. and have one or two electrons in their outermost energy level
(ns1 or ns2). As a result, metallic bonds are formed. Hence, they
(ii) Generally the atomic radii of d-block elements in a series behave as metals. Greater the number of unpaired d electrons,
decreas with increase in atomic number but the decrease in stronger is the bonding due to the overlapping of unpaired
atomic size is small after midway. electrons between different metal atoms.
Explanation 1.6 Melting Point
The atomic radius decreases with the increase in atomic
Transition metals have high melting points which is due to
number as the nuclear charge increases whereas the their strong metallic bond. The metallic bond. The metalic
shielding effect of d-electron is small. After midway, as the bonding depends upon the number of unpaired e–. The
electrons enter the last but one (penultimate) shell, the added melting point first increases (Sc-Cr), reaches a maximum value
d-electron shields (screens) the outermost electron. Hence, (Cr) and then decreases (Fe-Zn)
with the increase in the d-electrons, screening effect * Tungsten (W) has the highest melting point.
increases. This counterbalances the increased nuclear * Mercury (Hg) has the lowest melting point.
charge due to increase in atomic number. As a result, the * Mn has the lowest melting point in 3d series typicl
atomic radii remain practically same after chromium. For transition elements.
example in Fe, the two opposing tendencies almost
1.7 Ionisation energies or Ionisation enthalpies
counterbalance and there is no change in the size from Mn
to Fe. (i) The first ionisation enthalpies of d-block elements lie between
s-block and p-block elements. They are higher than those of s-
(iii) At the end of the period, there is a slight increase in the
block elements and are lesser than those of p-block elements.
atomic radii.
The ionisation enthalpy gradually increases with increase in
Explanation atomic number along a given transition series though some
irregularities are observed
Near the end of series, the increased electron-electron
Explanation
repulsions between added electrons in the same orbitals
(i) The increasing ionization enthalpies are due to increased
are greater than the attractive forces due to the increased
nuclear charge with increase in atomic number which reduces
nuclear charge. This results in the expansion of the electron
the size of the atom making the removal of outer electron
cloud and thus the atomic radius increases. difficult.
(iv) The atomic radii increase down the group. This means that (ii) In a given series, the difference in the ionisation enthalpies
the atomic radii of second series are larger than those of between any two successive d-block elements is very much
first transition series. But the atomic radii of the second less than the difference in case of successive s-block or p-
and third transition series are almost the same. block elements.
Explanation
The atomic radii of the elements of the second and third The addition of d electrons in last but one [(n — 1) or
transition metals are nearly same due to lanthanide penultimate] shell with increase in atomic number provides
contraction (or also called lanthanoid contraction) a screening effect and thus shields the outer s electrons
discussed later. from inward nuclear pull. Thus, the effects of increased
nuclear charge and addition of d electrons tend to oppose
1.4 Ionic radii each other.
(i) The trend followed by the ionic radii is the same as that
(iii) The first ionization enthalpy of Zn, Cd and Hg are, however,
followed by atomic radii. very high because of the fully filled (n-1) d 10 ns 2
(ii) Ionic radii of transition metals are different in different configuration.
oxidation states. (iv) Although second and third ionization enthalpies also, in
(iii) The ionic radii of the transition metals are smaller than those general, increase along a period, but the magnitude of
of the representative elements belonging to the same period. increase for the successive elements is much higher.
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 d AND f BLOCK ELEMENTS 141

(v) The high values of 3rd ionization enthalpies for Cu, Ni and In ‘3d’ series all element contain 2 electrons in ‘4s’ and hence
Zn explain why they show a maximum oxidation state of +2. they all give a common minimum oxidation state of +2.
(vi) The first ionisation enthalpies of 5d elements are higher as (Except ‘Cr’ and ‘Cu’ where minimum oxidation state is +1.]
compared to those of 3d and 4d elements. This is because The maximum oxidation state is given by Mn i.e. Mn+7 in
the weak shielding of nucleus by 4f electrons in 5d elements which two electrons are removed from 4s and five unpaired
results in greater effective nuclear charge acting on the electrons are removed from 3d orbitals.
outer valence electrons. (4) The highest oxidation state is shown by Ruthenium (Ru)
and Osmium (Os) i.e. +8.
1.8. Oxidation state
(5) Across the period oxidation state increases and it is maximum
at the centre and than decreases even if atomic number
“The net numerical charge assigned to an atom of an element
increases. The element which shows highest oxidation state
in its combined state is known as its Oxidation state or
occur in the middle or near the middle of the series and than
Oxidation number”.
decreases.
(1) With the exception of few elements, most of the d-block
(6) Transition metals also show zero oxidation states in metal
elements show more than one oxidation state i.e. they show
carbonyl complex. (Nickel tetracarbonyl).
variable oxidation states. The elements show variable
Example : Ni in Ni (CO)4 has zero oxidation state.
oxidation state because of following reasons:
(7) The bonding in the compounds of lower oxidation state
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block elements
(+2, +3) is mostly ionic and the bonding in the compounds
have almost same energies and therefore electron can be
of higher oxidation state is mostly covalent.
removed from ‘(n-1)d’ orbitals as easily as ‘s’ orbitals
(8) The relative stabilities of some oxidation states can be
electrons.
explained on the basis of rule extra stability, according to
(ii) After removing ‘s’ electrons, the remainder is called Kernel which d0, d5 and d10 are stable configurations.
of the metal cations. In d-block elements, the kernel is
For example, the stability order of some ions is as follows:
unstable and therefore it loses one or more electrons from
Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
(n – 1)d electrons. This results in formation of cations with
different oxidation states. Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)
(2) All transition elements show variable oxidation state except
last element in each series. (9) Cu+2 is more stable than Cu+1 even when Cu+1 is 3d10 while
Cu+2 is 3d due to high heat of hydration.
(3) Minimum oxidation state = Total number of electrons in 4s
lost. Maximum oxidation state = (Total number of electrons Variable oxidation states shown by 3d-series of d-block elements.
in 4s + number of unpaired electrons in 3d lost).
Oxidation States

ELECTRONIC Sc Ti V Cr Mn Fe Co Ni Cu Zn

CONFIGURATION d 1s 2 d 2s 2 d 3s2 d 4s 2 d5s 2 d6s2 d 7s2 d8s2 d 9s 2 d 10 s 2

d 5s 1 d 10 s 1

+1 +1

+2 +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

+5 +5 +5 +5 +5

+6 +6 +6

+7
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