The d- and f-

block elements
Done by group - 2
Aysha, Divyashree, Emil, Fathima Aazmeen,
Fathima Farha, Jalisha
Physical properties :

● Metallic properties
● The high melting points of these metals are
attributed to the involvement of greater
number of electrons from (n-1)d in addition to
the ns electrons in the interatomic metallic
bonding.
● In general, greater the number of valence
electrons, stronger is the resultant bonding.
● Also, the metals of the second and third series
have greater enthalpies of atomisation than
the elements belonging to the first series.
 Variation in atomic and ionic sizes of
transition metals

● The atomic/ionic radii first DECREASES till the middle, becomes almost
constant and then INCREASES towards the end of the period.
● New electron enters a d orbital each time the nuclear charge increases by
unity, but the shielding effect of a d electron is not that effective,
hence the net electrostatic attraction between the nuclear charge and the
outermost electron increases and the ionic radius decreases.
● However the increased nuclear charge is
partly cancelled by the increased screening
effect of electrons in the d-orbitals of the
penultimate shell.
● When the increased nuclear charge and
increased screening effect balance each
other, the atomic radii becomes almost
constant.
● Increase in atomic radii toward the end may
be attributed to the electron-electron
repulsion. In fact the pairing of electrons in
d-orbitals occur after d5 configuration
● The repulsive interaction between the
paired electron causes increase in
atomic/ionic radii
● There is an increase from the first 3d to the second 4d series of the
elements.

● But the radii of the third 5d series are virtually the same as 4d.

● This is due to the intervention of the 4f orbitals which must be filled

before the 5d series elements begin.

● There is a steady decrease in atomic radii from La due to the poor

shielding effect of the inner core eletring (4f). This is known as
Lanthanoid contraction.
Ionisation Enthalpies
➢ The ionization enthalpy of an element can be defined as the amount of energy required
to remove an electron from an isolated gaseous atom in its gaseous state.

➢ The ionisation enthalpy of transition elements generally increases from left to

right. This is due to increase in the nuclear charge from left to right which
reduces the size of the atom making the removal of outer electrons different.

➢ The irregular trend in the first ionisation enthalpy of the 3d metals is explained
by considering the removal of one electron, the relative energies of 4s and 3d
orbitals get changed. Hence the remaining electron in the 4s level is transferred
to 3d level. So the unipositive ions have dn configuration with no 4s electrons.
During this re-organisation of electrons, some energy is released and it is known
as exchange energy.
Ionisation Enthalpies
➢ So the net energy required to remove the 1st electrons is equal to the sum of
ionisation enthalpy and exchange energy.

➢ The first ionisation enthalpies of Cr and Cu are low. This is because the removal
of one electron does not change their d configuration.

➢ The 2nd I.E of Cr and Cu are very high. This is because the removal of one more
from these metals disrupted their stable configuration (d5 or d10).

➢ Similarly first ionisation enthalpy of Zn is high because after the removal of one
electron there is no change in the d configuration.
Ionisation Enthalpies
➢ The 2nd ionisation enthalpies of Mn and Zn are low, this is because after the
removal of one more electron, they attain the stable half filled or completely
filled electronic configuration.

➢ Because the increase in third ionisation enthalpy does not involve 4s orbitals,
the removal of an electron from Mn²⁺ (d5) and Zn²⁺(d10) ions is more difficult
than it would be otherwise. As a result, there is a significant discrepancy
between the third ionisation enthalpies of iron (26) and manganese (25).

➢ The first I.E of 5d elements is higher than 3d and 4d because of the weak
shielding effect of 4f electrons as a result of which the nuclear charge increases
attractive forces increases and thus ionisation enthalpy increases.
Oxidation States-
➔ The net numerical charge assigned to an atom of an element in its combined state is known as
its oxidation state or oxidation number.

❖ With the exception of a few elements, most of the d-block elements show more than one
oxidation state i.e, they show variable oxidation states. D-Block elements show variable
oxidation states due to tendency of (n–1)d as well as ns electrons to take part in bond formation
(except 3rd and 12th group elements). Atoms of d-block elements have the same energies and
therefore electrons can be removed from “(n-1)d” orbitals as easily as “s” orbitals. After removing
“s” electrons, the remaining is called Kernel of the metal cations.

❖ All transition elements show variable oxidations state except last element in each series.

❖ Minimum oxidation state= Total no. of electrons in 4s lost.

❖ Maximum oxidation state= Total no. of electrons in 4s + number of unpaired electrons in 3d
lost.
Oxidation States-
❖ In “3d” series all element contains 2 electrons in “4s” and hence they all give a common
minimum oxidation state of +2, except Cr and Cu where minimum oxidation state is +1.

❖ The elements which give the greatest number of oxidation states occur in or near the middle of
the series. The maximum oxidation state is given by Mn(+2 to +7) in which two electrons are
removed from 4s and five unpaired electrons are removed from 3d orbitals. Highest oxidation
state of d-block element is found in mid of the series [Stability of highest oxidation state is
increases upto mid of the series and then start decreasing].

❖ The lesser number of oxidation states at the extreme ends stems from either too few electrons
to lose or share (Sc, Ti) or too many d electrons (hence fewer orbitals available in which to share
electrons with others) for higher valence (Cu, Zn). Thus, early in the series scandium(II) is
virtually unknown and titanium (IV) is more stable than Ti(III) or Ti(II).

❖ The only oxidation state of zinc is +2 (no d electrons are involved).

Oxidation States-
❖ The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals in such a way that their oxidation states differ from each other by
unity. This is in contrast with the variability of oxidation states of non transition elements where
oxidation states normally differ by a unit of two.

❖ Although in the p–block the lower oxidation states are favoured by the heavier members (due to
inert pair effect), the opposite is true in the groups of d-block.

❖ D-block metals can also show zero oxidation state (low oxidation state) when a complex
compound has ligands capable of p-acceptor character in addition to the s-bonding. For
example : [Ni(CO)4], [Fe(CO)5].

❖ Highest oxidation state of d-block metals is found in their compounds with oxygen and fluorine,
since oxygen and fluorine have smaller atomic size and higher electronegativity. Therefore, they
can oxidize metals to their oxidation state.So highest oxidation states one shown in the oxides
and fluorides of transition metals.
Periodic table
1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 13 14 15 16 17 18
Na Mg Al Si P S Ci Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
87 88 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fi Mc Lv Ts Og
57 58 59 60 61 62 63 64 65 66 67 68 69 70
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
89 90 91 92 93 94 95 96 97 98 99 100 101 102
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
 02
Electronic
configuration of the
d-block elements
● In general, the electronic configuration of outer orbitals of these
elements is (n-1)d^1– 10 ns^1–2 except for Pd with electronic
configuration 4d^10 5s^0 .
● The (n–1) stands for the inner d orbitals which may have one to ten
electrons and the outermost ns orbital may have one or two electrons.
This has many exceptions due to very little energy difference between
(n-1)d and ns orbitals.
● Half and completely filled sets of orbitals are relatively more stable.
● A consequence of this factor is reflected in the electronic configurations
of Cr and Cu in the 3d series. Consider the case of Cr, which has 3d^5 4s^1
configuration instead of 3d^4 4s^2 ; the energy gap between the two sets
(3d and 4s) of orbitals is small enough to prevent electron entering the 3d
orbitals. Similarly in case of Cu, the configuration is 3d^10 4s^1 and not
3d^9 4s^2 .
The ground state electronic configurations of the
outer orbitals of transition elements
● The electronic configurations of outer orbitals of Zn, Cd, Hg and Cn are
represented by the general formula (n-1)d^10 ns^2 .
● The orbitals in these elements are completely filled in the ground state as well as
in their common oxidation states. Therefore, they are not regarded as transition
elements.
● The d orbitals of the transition elements protrude to the periphery of an atom
more than the other orbitals (i.e., s and p), hence, they are more influenced by the
surroundings as well as affect the atoms or molecules surrounding them.
● ions of a given d^n configuration (n = 1 – 9) have similar magnetic and electronic
properties.
● With partly filled d orbitals these elements exhibit certain characteristic properties
such as display of a variety of oxidation states, formation of coloured ions and
entering into complex formation with a variety of ligands. transition metals and
their compounds also exhibit catalytic property and paramagnetic behaviour.
● There are greater similarities in the properties of the transition elements of a
horizontal row in contrast to the non-transition elements. However, some group
similarities also exist.
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