The d and f-Block Elements Class 12 Notes Chemistry Chapter

Introduction

In this chapter, we are going to study the usual and unusual

properties of d-block element. Classification of elements in blocks is
based on their characteristic properties. During filling of electrons,
the last electron decides the block of the element. d-block contains
3 to 12 group. A number of compounds of this block elements are
important catalyst in industry.

Position in the Periodic Table

The d-block of the periodic table contains the elements of group 3-

12 in which the d orbitals are progressively filled in each of the four
long periods. The name “transition” given to the element of d-block
is only because of their position between s and p-block elements.
There are four series of the transition metals 3d series (Sc to Zn), 4d
series (Y to Cd) and 5d (La, Hf to Hg) and 6d series (AC, unq to Uub).

Definition of Transition Element

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
state. Zn, Cd and Hg are not typical transition elements because
they have full d10 configuration in their ground state as well as in
their common oxidation state.
However, being the last members of three transition series, their
chemistry is studied along with the chemistry of transition metals.

Electronic Configurations of the d-Block Elements

General E.C. of the d-block element is as

For 3d series 3d1–10 4s1–2

For 4d series 4d1–10 5s1–2
For 5d series 5d1–10 6s1–2
For 6d series 6d1–10 7s1–2
Overall (n–1) d1–10 ns1–2

The d orbitals of the transition element project to the periphery of

an atom more than the other orbitals (s and p). Hence, they are
more influenced by the surrounding as well as affecting the atoms
or molecules surrounding them.

General Properties of the Transition Elements

1. Physical Properties

Nearly all the transition elements display metallic properties such as

high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.

The transition metals (with the exception of Zn, Cd, Hg) are very
much harder and have low volatility. Their melting points and boiling
points are high.
In any row the melting points of these metals rise to maximum at d5
except for anamolous behaviour of Mn and Tc and fall regularly as
the atomic number increases. They have high enthalpies of
atomisation.

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,
metals with very high enthalpy of atomisation i.e., very high boiling
point tend to be noble in their reactions.

2. Atomic and Ionic size

In general, ions of the same charge in given series show progressive

decrease in radius with increasing atomic number. This is because
the new electron enters a d orbital each time the nuclear charge
increases by unity and shielding effect of d electron is not effective
hence net electrostatic attraction between the nuclear charge and
outer most electron increases and the ionic radius decreases.

The filling of 4f before 5d orbitals results in regular decrease in

atomic radii called Lanthanoid contraction which essentially
compensates for the expected increase in atomic size with
increasing atomic number.

3. Density

The decrease in metallic radius coupled with increase in mass

results in a general increase in the density of these elements. Thus
from Ti to Cu the significant increase in density may be noted.
4. Ionisation Enthalpy

Due to increase in nuclear charge which accompanies the filling of

the inner d orbitals there is an increase in ionisation enthalpy along
each series of the transition elements from left to right. However
many small variations occur.

5. Oxidation State

One of the notable feature of a transition element is the great

variety of oxidation states. The elements which give the greatest
number of oxidation states occur in or near the middle of series. Mn
exhibits all oxidation states from +2 to +7.

6. Chemical Reactivity

Transition metals vary widely in their chemical reactivity. Many of

them are sufficiently electropositive to dissolve in mineral acid
although a few are noble, it means these do not react with single
acid. The metal of 3d series except Cu are relatively more reactive
and are oxidised by 1M H+ though the actual rate at which these
metals react with oxidising agents like hydrogen ion (H +) is some
time slow.

7. Magnetic Properties

When magnetic field is applied to substance. Mainly two types of

magnetic behaviour are observed: diamagnetism and
paramagnetism. Diamagnetic substance contain no unpaired
electron and repelled by magnet while paramagnetic substances are
attracted and contain one or more unpaired electron. The substance
which are strongly attracted by magnet are said to be
ferromagnetic. Paramagnetism arises due to presence of unpaired
electrons, each such electron having a magnetic moment associated
with its spin angular momentum and orbital angular momentum.

μ=√ n(n+2) μ=�(�+2) BM

where n is number of unpaired electron and BM–Bohr magneton.

8. Formation of Coloured Ions

When an electron from a lower energy d orbital is excited to higher

energy d orbital, the energy of excitation corresponds to the
frequency of light absorbed. This frequency absorbed generally lies
in the visible region. The colour observed corresponds to the
complementary colour of light absorbed. The frequency of light that
is absorbed is determined by (i) Nature of ligand, (ii) Size of metal
ion and (iii) Oxidation state of metal.

9. Formation of Complex Compound

Due to smaller size of the metal ions high ionic charges and the
availability of d orbitals for bond formation, transition elements form
a number of complex compounds. Example of some complex
compounds/ions are:

[Fe(CN)6]3–, [Cu(NH3)4]2+, [Mn(H2O)4]2+, [CuCl4]2-

10. Catalytic Properties

The transition metals and their compounds are known for their
catalytic activity. This activity is ascribed to them due to their ability

1. To adopt multiple oxidation states

2. To form complexes

Catalyst at a solid surface involve the formation of bonds between

reactant molecules and atoms of the surface of 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. Also because transition metal ions can change their
oxidation states, they become more effective as catalyst.

11. Formation of Interstitial Compounds

Interstitial compounds are those which are formed when small

atoms like H, C or N are trapped inside the crystal lattice of metals.
These are usually non stochiometeric and are neither typically ionic
nor covalent. For example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7 etc.

The principle physical and chemical characteristics of these

compounds are :

1. They have high melting point, higher than those of pure metal.
2. These are very hard.
3. They retain metallic conductivity.
4. They are chemically inert.
12. Alloy Formation

Alloy may be homogeneous solid solution in which the atoms of one

metal are distributed randomly among the atoms of the other. Such
alloys are formed by atoms with metallic radii that are within about
15 percent of each other. Because of similar radii and other
characterstics of transition metals alloys are readily formed by these
metals. The alloys so formed are hard and have often high melting
point. The best known are ferrous alloys. Cr, V, W, Mo and Mn are
used for the production of a veriety of steels and stainless steel.

Preparation and Properties of the Compounds of d-Block Elements

(1) Potassium permanganate (KMnO4)

Potassium permanganate is prepared from pyrolusite (MnO 2)

involving the following steps:

(i) Conversion of pyrolusite (MnO2) into potassium

manganate: Powdered pyrolusite is fused with KOH in the presence
of air or an oxidising agent like KNO 3, or KClO3 to give green
coloured potassium manganate.

2MnO2 + 4KOH + O2 ⟶ 2K2MnO4 + 2H2O

(ii) Oxidation by chlorine

2K2MnO4 + Cl2 ⟶ 2KMnO4 + 2KCl

Properties of Potassium Permanganate

1. Potassium permanganate forms dark purple needle like
crystals with a metallic lusture. Its m.p. is 523 K. It is
moderately soluble in water giving a purple solution.
2. On heating, potassium permanganate changes into manganate
and oxygen gas is evolved.

2KMnO4 ⟶ K2MnO4 + MnO2 + O2

3. On heating with alkalies, potassium permanganate changes

into manganate and oxygen gas is evolved.

4KMnO4 + 4KOH ⟶ 4K2MnO4 + 2H2O + O2

4. Oxidising agent: KMnO4 is a powerful oxidising agent in acidic,

neutral and alkaline medium. In acidic medium:

2KMnO4 + 3H2SO4 ⟶ K2SO4 + 2MnSO4 + 3H2O + 5[O]

Structure of manganate and permanganate ion

(a) MnO42– ion-tetrahedral structure.

(a) MnO4– ion-tetrahedral structure.

(2) Potassium dichromate, K2Cr2O7

It is the most important compound of chromium. K 2Cr2O7 is prepared

from chromite ore (FeO.Cr2O3). The various steps involved are:

(i) Preparation of sodium chromate: The powdered ore is

heated with sodium hydroxide in the presence of air, sodium
chromate is formed and CO2 is given out.

4FeCr2O4 + 16NaOH + 7O2 ⟶ 8Na2CrO4 + 2Fe2O3 + 8H2O.

(ii) Conversion of sodium chromate into sodium

dichromate: The solution of sodium chromate is treated with dil.
H2SO4 to get sodium dichromate, Na2Cr2O7.

2Na2CrO4 + H2SO4 ⟶ Na2Cr2O7 + Na2SO4 + H2O

(iii) Conversion of sodium dichromate into potassium

dichromate: Sodium dichromate is filtered and then treated with
dil. H2SO4. Being less soluble, sodium sulphate separates out. Then
hot concentrated solution is cooled when red crystals of sodium
dichromate separates out on standing and then a hot concentrated
solution of sodium dichromate is treated with potassium chloride to
get potassium dichromate.

Na2Cr2O7 + 2KCl ⟶ K2Cr2O7 + 2NaCl

Properties

1. It is an orange crystalline solid with melting point 670 K.

2. It is appreciably soluble in hot water but moderately soluble in
cold water.
3. On heating K2Cr2O7 decomposes to give potassium chromate
and chromic oxide.

4K2Cr2O7 ⟶ 4K2CrO4 + 2Cr2O3 + 3O2

(d) Chromyl chloride test: When a mixture of metal chloride is

heated with K2Cr2O7 and conc. H2SO4 acid, orange red fumes of
chromyl chloride are formed.

K2Cr2O7 + 4NaCl + 6H2SO4 ⟶ 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 +

3H2O

(e) Reaction with H2O2: Acidified solution of dichromate ions form

a deep blue colour with H2O2 due to the formation of [CrO(O2)2].

Cr2O72– + 4H2O2 + 2H+ ⟶ 2CrO5 +5H2O

Uses of K2Cr2O7
1. For the volumetric estimation of ferrous salts, iodides and
sulphides.
2. For the preparation of other chromium compounds such as
chrome alum, chrome yellow etc.
3. Used in chrome tanning in leather industry.
4. Used as an oxidising agent.

Structure of chromate and dichromate ion

(a) CrO42– ion-tetrahedral structure.

(b) Cr2O72– ion-two tetrahedra sharing one oxygen atom at one

corner.
The Inner Transition Elements

The f block consists of two series lanthanoids and actinoids.

Lanthanum closely resembles the lanthanoids, it is usually included
in any discussion of the lanthanoids for which the general symbol Ln
is often used. Similarly a discussion of the actinoids includes
actinium besides the fourteen elements constituting the series.

Lanthanoids resemble one another more closely than do the

members of ordinary transition elements in any series. They have
only one stable oxidation state and their chemistry provides an
excellent opportunity to examine the effect of small size and nuclear
charge along a series of otherwise similar elements.

The Lanthanoids

1. Electronic Configuration

It may be noted that the atoms of these elements have electronic

configuration as 6s2 5d0 or 1 4f1–14.
2. Atomic Size and Ionic Size

Decrease in size from La to Lu is a unique feature in chemistry of

lanthanoids. This is due to lanthanoid contraction. The decrease in
atomic radii is not quite regular as it is regular in M 3+ ion. This
contraction is similar to that observed in an ordinary transition
series and is attributed to same cause, the imperfect shielding of
one electron by another in the same sub-shell.
3. Oxidation state

In the lanthanoids, La(II) and Ln(III) compounds are predominant.

However some element may show oxidation state of III and IV. Pr,
Nd, Tb and Dy can exhibit +4 O.S. only in MO 2 oxide.

4. General Characterstics

1. All the lanthanoids are silvery white soft metals and tarnish
rapidly.
2. Hardness increases with increasing atomic number, samarium
(Sm) being steel hard.
3. These are good conductor of electricity.
4. Density and other properties change smoothly except for Eu
and Yb and occasionally for Sm and Tm.
5. Many trivalent lanthanoid ions are coloured both in solid state
and in aq. solution. Colour of these ions may be attributed to
the presence of f electrons.

5. Reaction
6. Uses

1. Best use of the lanthanoids is for the production of alloy steels

for plate and pipe.
2. A well known Mischmetal consists of a lanthanoid metal
(~95%) and iron (~5%) and traces of S, C, Ca and Al. It is used
in Mg-based alloy to form bullets.
3. Mixed oxide of lanthanoids are employed as catalysts in
petroleum cracking.
4. Some individual lanthanoid oxide are used in television screen
and similar florescing surfaces.

The Actinoids

Actionid include the fourteen elements from Th to Lr. The name

symbol and some properties of these element are shown as
The actinoids are radioactive elements and the earlier members
have relatively long half life, the latter ones have half life values
ranging from a day to 3 minute for Lawrencium (Z-103).

1. Electronic Configuration

General electronic configuration of all elements can be consulted

from table. The fourteen electrons are formally added to 5f though
not in thorium (Z-90) but from Pa onward the 5f orbitals are
complete at element 103. The irregularities in the electronic
configurations of the actinoids like those in the Lanthanoids are
related to the stabilities of the f 0, f7, f14 occupancies of the 5f
orbitals.

2. Atomic Size and Ionic Size

There is gradual decrease in the size of atoms or M3+ ions across

the series. This is referred to as actinoid contraction which is greater
than lanthanoid contraction.

3. Oxidation state

There is greater range of oxidation states which is in part attributed

to the fact that the 5f, 6d and 7s level are of comparable energies.
The elements, in first half of actinoids frequently exhibit higher
oxidation states. However, +3 and +4 ions tend to hydrolyse.

4. General Characterstics

1. All are silvery in appearance but display a variety of structure.

This is due to irregularity in metallic radii.
2. These are highly reactive metal.
3. HCl react with all actinoids.
4. Most of them are slightly affected by HNO 3 owing to the
formation of protective oxide layer. However, alkalies have no
action.
5. Magnetic properties of the actinoids are more complex than
those of lanthanoid.
6. IE1 of early actinoids are lesser than early Lanthanoid because
5f orbitals are deeply burried.
7. Actinoids compound or their ions are coloured most probably
due to charge transfer or f-f transition.

Some Applications of d & f-Block Elements

1. Iron and steels are the most important construction material.

Their production is based on reduction of iron oxides, the
removal of impurities and the addition of carbon and alloying
metals like Cr, Mn and Ni.
2. Some compounds are manufactured for special purpose such
as TiO for the pigment industry and MnO 2 for use in dry cell
along with use of Zn.
3. Many of the elements or compounds of this block elements are
important catalyst.
4. AgBr is an important chemical used in photography. Along with
AgBr, Ag and AgI can also be used.
5. Some compounds like MnO4–, CrO42– are good oxidising agents.

Summary

1. Transition element: It is defined as one which has

incompletely filled d orbitals in its ground state or in any one of
its oxidation states.
2. General E.C. of d-block : (n – 1)d1–10 ns0–2
3. Melting point increases up to middle and then decreases.
4. Hg exists in liquid state at room temperature.
5. Ionisation energy increases from left to right but trend is not
regular. Successive ionisation enthalpies do not increase as
steeply as the main group elements with increasing atomic
number.
6. These elements show variable oxidation states.
7. Generally these elements and their compounds are coloured.
8. Due to the presence of unpaired electrons, these are generally
paramagnetic.
9. KMnO4 and K2Cr2O7 are good oxidising agents.
10. KMnO4 is prepared from MnO2.
11. In f-block two series are present

(i) Lanthanoid

(ii) Actinoid

12. All actinoids are radioactive while in lanthanoid only Pm is

radioactive.
13. For Lanthanoid +3 is most common oxidation state.
14. Decrease in size due to poor screening of 4f orbitals is known
as lanthanoid contraction.
15. Generally lanthanoids and actinoids or their compounds are
coloured.
16. Lanthanoids have little tendency to form complex.
17. Actinoids have more tendency to form complex.