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D and F – Block elements :[U-8] SRL – 1 By Nitul Sir Marks - 5

GENERAL POINTS TO BE REMEMBERED: ---

1. The elements of periodic table belonging to group 3 to 12 are known as d-Block
elements.
2. The general electronic configuration of these elements is (n -1)d1-10 ns 0-2
3. d- Block elements are collectively known as Transition Elements because properties of
these elements vary in between s-Block and p-Block elements.
4. A transition element should have partially filled (n-1) d orbital.
5. Group 12 elements i.e. Zn, Cd, Hg have completely filled (n-1) d-orbital in atomic & ionic
state & thus these elements are considered as Typical Transition Elements.
6. All these elements are metals. They are less electropositive than s-block elements &
more electropositive than p-block elements.
7. The atomic radii decreases from group 3 to 6 (i.e. Sc to Cr) because of increase in
effective nuclear charge gradually.
8. The atomic radii of group 7,8 9 &10 elements (i.e. Fe,Co,Ni) is almost same because
pairing of electrons take place in (n-1)d orbital causing repulsion i.e. shielding of (n-1)d
orbital.
9. Group 11 &12 elements i.e. Cu & Zn have bigger size due to strong shielding of
completly filled (n-1)d orbital.
10. The transition elements show variable oxidation state due to small energy difference
between (n-1)d &ns orbital as a result both (n-1)d &ns electrons take part in bond
formation.
11. The highest oxidation state of an element is equal to number of unpaired electrons
present in (n-1)d &ns orbital.
12. Transition elements have high enthalpy of atomization/ sublimation Because of large
number of unpaired electrons in their atoms, they have stronger inter atomic interaction
and hence strong metallic bonding is present between atoms.
13. Most of transition elements are paramagnetic due to presence of unpaired electrons in
(n-1) d orbital.
14. Most of transition elements are used as catalyst. It is due to (i) partially filled (n-1) d
orbital (ii) Variable oxidation state (iii) Ability to change oxidation state frequently.
15. Most of transition elements form coloured compounds due to presence of unpaired
electrons in (n-1) d orbital & thus they can undergo d-d transition.
16. Most of transition elements form complex compounds due to (i) small size (ii) high
charge (iii) presence of vacant d-orbital of suitable energy.
17. Transition elements have lower value of Reduction Potential due to high ionization
potential, high heat of sublimation & low enthalpy of hydration.
18. Transition elements form interstitial compounds because size of interstitial voids is
similar to size of non- metals C, N, O, H.
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19. Transition elements form alloys due to similar ionic radii.

20. The oxides of transition metals in lower oxidation state are BASIC, intermediate
oxidation state are AMPHOTERIC, highest oxidation state are ACIDIC.
21. The elements in which the last electron enters into (n−2) f-orbital of the atoms are
called f-block elements. In these elements, the last electron enters in to the
prepenultimate (n−2) shell (called antepenultimate). The general valence electronic
configuration is: (n–2)f 1−14(n–1)d0−1 ns2.

GENERAL POPERIES OF TRANSITION ELEMENTS

ELECTRONIC CONFIGURATION OF d-BLOCK ELEMENTS The general outer electronic

configuration of d-block elements is (n─1)d1─10ns0─2 . The (n─1) stands for the inner d
orbitals which may have one to ten electrons. The outermost ns orbitals may have zero
or two electrons. The d block elements consist of four rows of elements. These rows are
called first, second, third and fourth transition series. They involve the filling of 3d, 4d, 5d
and 6d orbitals respectively. 3d series Sc (21) to Zn (30) 4d series Y (39) to Cd (48) 5d
series La (57) and Hf (72) to Hg (80) 6d series Ac (89) and elements 104 to 112

FIRST TRANSITION SERIES (3d series) Scandium, Titanium, Vanadium, Chromium,

Manganese, Iron, Cobalt, Nickel, Copper and Zinc.
SECOND TRANSITION SERIES (4d series) Yttrium, Zirconium, Niobium, Molybdenum,
Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium
THIRD TRANSITION SERIES (5d series) Lanthanum, Hafnium, Tantalum, Tungsten,
Rhenium, Osmium, Iridium, Platinum, Gold, Mercury
FOURTH TRANSITION SERIES (6d series) Actinium, Rutherfordium, Dubnium,
Seaborgium, Bohrium, Hassium, Meitnerium, Darmstadtium, Roentgenium, Copernicium

1. Atomic radii: Atomic and ionic radii of elements of all transition series

 Decreases rapidly, from column 3 to 6

 Remains steady, from column 7 to 10 and

 Starts increasing from column 11 to 12.

For example, in the first transition series, atomic radii, the decrease is more from Sc
to Cr (group 3 to 6 ), is almost the same for Mn, Fe, Co, Ni (group 7,8 9 &10) and
increase in cu and Zn.

 The larger decrease in atomic radii, in column 3 to 6 elements is due to the

increase in effective nuclear charge but poor shielding because of the smaller
number of d-electrons.
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 In elements of column 7 to 10 increasing effective nuclear charge is balanced

by the repulsion between the shared d electrons so that radii remain the
same.
 In the case of 11 and 12 columns elements, the d orbital is full with ten
electrons and shield the electrons present in the higher s-orbital. So, groups
11 and 12 elements like Cu and Zn have bigger sizes than their earlier
elements in the block.

2. Melting and boiling points

The transition metals have high m.p. & b.p. The m.p. and b.p. of metals rise to a maximum
value and then decrease with increase in atomic number. However, Mn and Tc have
abnormally low m.p. & b.p.
Reason – The high m.p. & b.p. is due to strong metallic bonds between the atoms of these
elements. The metallic bond is formed due to interaction of electrons in the outermost
orbital. The strength of bonding depends on the number of outer most electrons. Greater
is the number of valance electrons, stronger is the metallic bonding and consequently, m.p.
is high. Therefore metallic strength increase up to the middle till d5 configuration and then
decreases with the decrease in availability of unpaired d- electrons (from Fe onwards) .
Therefore, m.p. decrease after the middle because of increase an pairing of electrons. The
dip in the curve in Mn is due to the fact that Mn has stable electronic configuration (3d 5
4s2). As a result 3d electrons are more tightly held by Mn atomic nucleus and this reduces
delocalization of electrons resulting in weaker metallic bonding.

3. Ionization Enthalpies- Ionization Energy of the d block elements is larger than s-block
and smaller than the p-block elements, between which, they are placed.
Reason - The increase in ionization enthalpy is due to the effect of increasing nuclear
charge which would tend to attract outer electron with greater force. Consequently,
ionization enthalpy is expected to increase. But the addition of electrons take place in last
but one d-sub shell and this increases the screening effect. With the increase in electrons
in d-sub shell the outer electrons are shielded more & more. Thus, effect of increased
nuclear charge is opposed by additional screening effect of the nucleus and ionization
enthalpy increases but slowly. The irregular trend in first I.E. of first transition series
elements is due to the fact that removal of one electron alters the relatives energies of 4s
and 3d orbitals. Therefore, there is reorganization energy which gains in exchange energy
due to increase in no. of electrons in dn configuration and from transference of s-electrons
in d- orbital.
Some exceptions observed in ionization enthalpies are:-
a) Cr and Cu have high I.E. This is attributed to their half filled (d 5) and completely
(d10) electronic configuration .
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b) The value of second I.E. for zinc is low because ionization involves removal of an
electron resulting in stable 3d10 configuration.
c) The trend in third I.E. shows high value for Mn +2 and Zn+2 because of stable 3d5
and 3d10 electronic configuration.
Similarly, I.E3 for Fe <I.E3 for Mn because of stable 3d5 in Mn. In general, third I.E.
values are very high because of filled 4f-orbitals which have poor shielding effect.

4. Oxidation States:
Transition metals exhibit a larger number of oxidation states in their compound.
Reason – a) This is because of participation of inner (n -1)d electrons in addition to outer
ns electrons because the energies of ns and ( n -1)d electrons are almost equal.
The elements which gave the greatest number of oxidations states occur in or near the
middle of the series. Eg. Mn ; oxidation states from + 2 & +7
The lesser number of oxidation states at the extreme ends is either due to too few
electrons to lose or share or too many d electrons, hence fewer orbital are available in to
available to share electrons with others, thus higher valence cannot be attained. eg. Cu can
have oxidation state of +1& +2 , Zn can have oxidation state of +2 only
b) Except Sc, the most common oxidation state of first rose correlation elements is +2
which arises due to loss of 4s- electrons. This means Sc, 3d–orbitals are more stable and
lower in energy than 4s- orbital. As a result electrons are first removed from 4s- orbital.
c) Zinc is +2 in which no d-electrons are involved.
d) Within a group, maximum oxidation state increases with atomic number. For e.g. in
group 8 , Fe shows +2 and +3 but Rutheniun and Osmium form compounds in +4 , +6 and
+ 8 oxidation state .
e) In + 2 and + 3 oxidation state, bonds formed are ionic and in the compounds of higher
oxidation state bonds are covalent.
Transition elements show low oxidation states in some compounds or complexes having
ligands such as CO, for e.g. in Ni (CO)4 , Ni has zero oxidation state.

5. Catalytic Properties:
a) Transition metals show catalytic property because of their ability to adopt multiple
oxidation states. Catalysts at a solid surface involve the formation of bond between
reactant molecules and atoms of the surface of the catalyst. This has the effect of
increasing the concentration of the reactants at the catalyst surface and also weakening of
the bonds in the reacting molecules & the activation energy is lowered, moreover
transition metals can change their oxidation states. Eg- Fe3+ catalyses the reaction
between I2 & persulphate ions.
b) The catalytic property of transition metals is due to their tendency to form reaction
intermediates with suitable reactants. These intermediates give reaction paths of low
activation energy and therefore increase the rate of reaction. The reaction intermediates
decompose yielding products and regenerating the original substance. The transition
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metals form reaction intermediates due to the presence of vacant orbitals & tendency to
form variable oxidation state.

6. Formation of interstitial compounds :-

Many of the transition metals form interstitial compounds which are formed when small
atoms like B,H, N or C are trapped inside the crystal lattices of metals. They are usually
non stoichiomatric and are neither typically ionic nor covalent.
Physical & Chemical characteristics of these compounds
(i) High m.pt, higher than pure metals.
(ii) Very hard , some borides approach diamond in hardness
(iii) Retain metallic conducting
(iv) Chemically inert

7. Alloy Formation:- Atomic radii of the transition elements in any series are not much
different from each other. As a result, they can very easily replace each other in the lattice
and form solid solutions over an appreciable composition range. Atoms within 15% of the
difference in radii can form alloys. The alloys formed have high m.pt & are hard.
Eg. Alloys of Cr, V, W, Mo, Mn etc, stainless steel is or alloys of Fe, Ni, Cr
Some of the common examples of alloys are stainless steel, brass, bronze, etc.

8. Formations of complex compounds :-

The transition metals form a large no. of complex compounds due to
(i) The comparatively smaller sizes of the metal ions,
(ii) Their high ionic charges and
(iii) The availability of vacant d-orbital for bond formation

9. Paramagnetic character
The transition metal ions are generally containing one or more unpaired electrons in
Them & hence their compounds are generally paramagnetic. Paramagnetic character
increases with the increase in the number of unpaired electrons For these, the magnetic
moment is determined by the number of unpaired electrons and can be calculated by ‘spin
only’
μ = √ n(n+2) BM , n= no. of unpaired e-
μ = Magnetic moment in Bohr magnetron (μb ) units

10. Formation of coloured ions-

Most of the compounds of transition metals are coloured in solid or solution form.
Reason- The colour is due to the presence of incomplete (n-1)d sub shell. Under the
influence of approaching ions towards central metal ion, the d-ordinals of central metal
split into different energy levels. This phenomenon is called crystal field splitting. For e.g.
When six ions or molecules approach the metal ion (octahedral field) , the d-orbitals split
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into two sets:- One set consisting of two d-orbital of higher energy (dx2-y2, dz2) end other
set consisting of d-orbitals (dxy, dyz & dxz ) of lower energy. The electrons are easily
promoted from one to another energy level in the same d-sub shell. There are called d-d
transition. The amount of energyrequired to excite some of the electrons to higher energy
states within the same d-sub shellcorresponds to energy of certain colours of visible light.
Therefore, when white light falls on thecompounds, some part of its energy corresponding
to certain colour is absorbed and theelectron gets raised from lower energy to higher
energy & the excess colour is transmited. Theobserved colour is complementary of colour
absorbed. Eg-Ti+3 (d1) is purple

Answer the following questions. Each question carries one mark

1. Define transition elements.

Ans. 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.
2. What is the position of the d block elements in the periodic table?
Ans. The d block elements are in the middle of s and p blocks, comprising the groups 3 to
12. They are the four rows of elements in the periods 4th (3d series), 5th (4d series), 6th (
5d series) and 7th ( 6d series).
3. Zinc, cadmium and mercury of group 12 are not regarded as transition metals, Why ?
Ans. Zinc, cadmium and mercury of group 12 have full d 10 configuration ( d orbitals are
completely filled ) in their ground state as well as in their common oxidation states and
hence, are not regarded as transition metals
4. Why d- block elements are named as ‘transition elements ‘ ?
Ans. The d–block elements occupies the middle of the periodic table and their properties
are transitional between s– and p– block elements.
5.Why do transition metals have higher enthalpies of atomization?
Ans. Involvement of a large number of unpaired electrons of d orbitals favour stronger
inter atomic interactions resulting in stronger bonds between the atoms of a metal and
higher enthalpies of atomization.
6..Name one 3d series elements, that do not show variable oxidation states.
Ans. Sc (+3)
7.Transition metals exhibit variable oxidation states in its compounds, why?
Ans. Transition metals exhibit variable oxidation states in its compounds due to the
availability of both ns & (n – 1 ) d electrons for bond formation.
8. Name 3d series metal which shows highest oxidation state.
Ans. The highest oxidation state shown by 3d series transiNa tion metals is +7 by Mn