10+2 Chemistry

d and f-Block Elements

(NCERT, Competitive
Based)
Classification of d – block elements : There are ten groups in this block (group 3 to group 12).
These elements have general electronic configuration (n–1) d1 – 10 ns1 – 2 [exception: Pd 4d10 5so].
Transition elements have partially filled d-subshell in their elementary form (ground state) or in their
commonly occurring oxidation state.
i.e., (n – 1)d1 – 9 and belong to groups 3 to 11.
According to above definition, elements of 12th group, Zn, Cd & Hg are not transition elements because
they do not have partly filled d-subshells in their elementary or in any of their commonly occurring state
but still they are classified as d-block elements because of their quite similar properties with d-block
elements. These are called as non-transition or pseudo–transition elements.
There are four different transition series
Ist Sc (Z = 21) to Zn (Z = 30) (3d)
IInd Y (Z = 39) to Cd (Z = 48) (4d)
IIIrd La (Z = 57) & Hf (Z = 72) to Hg (Z = 80) (5d)
IVth Ac (Z = 89) & Rf (Z = 104) to Uub (Z=112) (6d)
For K (Z = 19) & Ca (Z=20), 4s < 3d, because of greater penetration tendency of 4s towards the nucleus
than 3d. But, after Ca (Z =20), there is sharp decrease in energy of 3d subshell on
gaining electron and its energy becomes lower than 4s. (i.e. 3d< 4s) also as the nuclear charge increases
from Sc to Zn, 3d electrons shield the 4s electron from the nucleus. Therefore when electrons are to be
removed from these atoms, the electrons will go from 4s rather than 3d orbital, although 4s were filled
earlier than 3d.
Changes to
In short 4s < 3d 3d< 4s
Similarly 5s < 4d 4d < 5s
6s < 5d 5d < 6s
Similarly lanthanum and actinium are classified as transition element as energies of 4f, 5d, 6s lie very
closely and one electron goes to 5d rather than 4f orbital.
For La (Z = 57), expected configuration is [Xe]54 4f1 6s2 while actually it is [Xe]54 5d1 6s2. In all other
lanthanides, 4f is stabilized relative to 5d and electron goes to 4f orbital and hence are called f-block
elements.
Similarly, for Ac (Z = 89), expected configuration is [Rn]86 5f1 7s2 while actually it is [Rn]86 6d1 7s2.
Hence La, Ac are classified as d-block elements rather than f-block elements.
GENERAL PROPERTIES
1. Position of d – block:
d – Block elements are the elements which lie between electropositive ‘s’ – and most electronegative p
– blocks in the long form of the periodic table.
They are so called because last electron in them enters in the d – orbitals of the (n – 1) or
penultimate shell.
They are also called transition elements because their properties lie in between those of s – block and
p – block elements and represent a transition (change) from them.
2. Electronic configuration: General electronic configuration of the transition elements is (n –1) d1–10 ns1–2
where n is the outermost shell.
(i) The definition excludes Zn, Cd and Hg from transition elements because they do not have incomplete
d– subshell in the atomic state or their common oxidation state (viz, Zn2+, Cd2+, Hg2+) having 3d10,
4d10 and 5d10 respectively. So they do not show properties of transition elements to any appreciable
extent except for their ability to form complexes. Thus are called non – typical transition elements.
(ii) Some exceptional electronic configurations of transition elements are as follows:
(a) Cr = 3d5 4 s1; Cu = 3 d10 4 s1,
(b) Nb = 4d4 5 s1; Mo = 4 d5 5 s1; Ru = 4 d7 5 s1; Rh = 4 d8 5 s1; Pd = 4 d10 5 s0; Ag = 4 d10 5 s1.
(c) Pt = 5d9 6 s1; Au = 5 d10 6 s1
The irregularities in the observed configurations of Cr, Cu, Mo, Pd, Ag and Au are explained on the basis
of the concept that half filled and completely filled orbitals are relatively more stable than other d – orbital
configurations. The observed irregularities can be explained by other factors such as
(a) Nuclear – electronic attraction,
(b) Shielding of one electron by several other electrons,
(c) Inter electronic repulsion,
 (d) Exchange energy forces.
3. Atomic and ionic radii: The atomic radii of transition elements show the following trends:
They lie in between those of s – and p – block elements i.e., they are smaller than s – block elements
and are larger than p – block elements in the periodic table.
In a series, the atomic radii first decrease with increase in atomic number upto the middle of the
series, then become constant and at the end of the series show a slight increase. The atomic radius
decreases as the nuclear charge increases. While with the increase in the d – electrons, screening
effect increases which counter balances the increased nuclear charge due to increase in atomic
number.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
16 147 135 129 127 126 125 125 128 137 (pm)
4

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
18 160 14 139 136 134 134 137 144 154 (pm)
0

La Hf Ta W Re Os Ir Pt Au Hg
18 158 146 139 137 135 136 138 144 157 (pm)
7
The atomic radii increase down the group from first transition series to the second transition series
but the atomic radii of the second and third transition series are almost the same because of
lanthanide contraction.
4. Ionization energy: The ionization enthalpies of 3d and 4d – series are irregular but increase across the
series while those of 5d – series are much higher than 3d and 4d – elements. This is because of weak
shielding of nucleus by 4 f electrons in 5d transition series.
5. Standard reduction potential: Lower the value of electrode potential (i.e., more negative the standard
reduction potential) of the electrode, more stable is the oxidation state of the transition metal ion in
aqueous solution. Electrode potential values depend upon energy of sublimation of the metal, the
ionization enthalpy and the hydration enthalpy.
Cu+ having E o Cu 2 / Cu = +0.34 volts is more stable in aqueous solution than Cu+ having E o Cu / Cu = + 0.52V.
The emf. E o M 2 / M have no regular trend as the sum (IE1 + IE2) & H sublimation do not show regular trends.
E.M.F: V = –1.18V, Cr = –0.91V, Mn = –1.18V, Fe = –0.44V, etc.
6. Metallic character:
All the transition elements are metals having hcp, ccp or bcc lattices. Metallic bonding is due to the
presence of ns1–2 electrons in the outermost energy level.
As the number of unpaired d – electrons increases metallic bonding increases and metals will be
hard e.g., Cr, Mo and W. Absence of unpaired electrons results in a weak metallic bonding and the
metals will be soft e.g., Zn, Cd and Hg.
7. Density:
They have high densities.
Osmium has the highest density (22.6 g cm3) whereas Scandium has the lowest (3.1 g cm–3) and is
the lightest transition element.
8. Oxidation state: All transition elements show variable oxidation states, because of difference of energy in
the (n – 1) d and ns orbitals is very less. Hence electrons from both the energy levels can be used for bond
formation.
The highest oxidation states of transition metals are found in fluorides and oxides since fluorine and
oxygen are the most electronegative elements. eg. Both Os and Ru show + 8 oxidation states.
The most common oxidation state of 3 d – transition metals is +2 (except Sc with + 3)
Mostly ionic bonds are formed in + 2 and + 3 oxidation states. But higher oxidation states give
covalent bond.
Higher oxidation states are stabilized by atoms of high electronegativity like O or F whereas lower
oxidation states (zero or + 1) are stabilized by ligands which can accept electrons from the metal
through – bonding (such as CO).
In going down a group, the stability of higher oxidation states increases while that of lower oxidation
states decreases.
 The relative stability of different oxidation states of transition metal atoms with respect to oxidation
can be determined with the help of standard electrode potential data.
9. Magnetic property:
Due to the presence of unpaired electrons in the (n – 1) d – orbitals, the most of the transition metal
ions and their compounds are paramagnetic i.e., they are attracted by the magnetic field. Those
transition elements, which have paired electrons, are diamagnetic i.e., they are repelled by the
magnetic field.
The magnetic moment is expressed in Bohr magnetoms (B.M.)
eh
1 B.M. =
4 mc
Where h is the Planck’s constant, e is the electronic charge, c is the velocity of light and m is the
mass of electron.
The magnetic moment of any species depends upon the sum of orbital and spin contributions for
each unpaired electron present. In case of d – block, orbital motion is quenched, only spin
contributes.
A paramagnetic substance is characterized by its effective magnetic moment ( eff) which is given by
the expression, this expression is based on spin only formula.
eff = n n 2 B.M.
10. Coloured ions:
Most of the transition metal compounds are coloured both in the solid state and in aqueous solution.
This is because of the presence of incompletely filled d – orbitals. When a transition metal compound
is formed the degenerate d – orbitals of the metal split into two sets, one (having three orbitals dxy,
dyz and dxz called t2g orbitals) with lower energy and the other (having two orbitals dx2 – y2 and dz2
called eg orbitals) with slightly higher energy in an octahedral field. This is called crystal field
splitting.
When white light falls on these compounds, some wavelength is absorbed for promotion of electrons
from one set of lower energy orbitals to another set of slightly higher energy within the same d –
subshell. This is called d – d transition.
11. Catalytic properties: Many transition metals (like Co, Ni, Pt, Fe, Mo etc) and their compounds are used
as catalysts, the following reasons:
(a) Because of variable oxidation states, they easily absorb and re – emit wide range of energies to
provide the necessary activation energy.
(b) Because of variable oxidation states, they easily combine with one of the reactants to form an
intermediate, which reacts with the second reactant to form the final products. For example, iron (III)
catalysed reaction between iodide and persulphate ions
2I– + S2 O28 I2 + 2 S O 24
The involved mechanism is
2Fe3+ + 2I– 2 Fe2+ + I2
2Fe2+ + S2 O82
2 Fe3+ + 2S O 24
(c) Because of presence of various valencies on the surface, they can absorb the reacting molecules,
thereby increasing the concentration of the reactants on the surface and hence the rate of reaction.
e.g.,
V2O5 is used in the manufacture H2SO4 by contact process.
Co – Th alloy is used in the Fischer – Tropsch process in the synthesis of gasoline (petrol),
inely divided Ni is used in the hydrogenation of oils into fats,
spongy platinum is used in the manufacture of H2SO4 by contact process and in the oxidation of
ammonia of nitric acid by Ostwald’s process.
Iron is used in the synthesis of ammonia by Haber’s process and molybdenum is used as a
promoter.
12. Interstitial compounds:
Transition metals form a number of interstitial compounds in which small non – metal atoms such
as H, C, B, N and He occupy the empty spaces (interstitial sites) in their lattices and also form bonds.
e.g. hydrides, carbides, borides, nitrides and halides.
 They have higher melting points than those of pure metals, retain metallic conductivity, are
chemically inert, hard and rigid e.g., steel and cast iron which are interstitial compounds of Fe and C
are hard where malleability and ductility of the metal decreases but tenacity increases.
13. Alloy formation:
Due to similarity in atomic sizes, atoms of one transition metal can easily take up positions in the
crystal lattice of the other in the molten state and are miscible with each other forming solid
solutions and smooth alloys on cooling.
Alloys are generally harder, have higher melting points and more resistant to corrosion than the
individual metals.
Metals such as Cr, V, Mo, W and Mn are used in the production of alloy steels and stainless steels.
Alloys containing mercury as one of the constituent elements are called amalgams.
Fe and Pt do not form amalgams.
14. Non – stoichiometric compounds:
Non – stoichiometric compounds are those in which the chemical composition does not correspond to
their ideal chemical formulae.
The compounds of transition metals with O, S, Se and Te are generally non – stoichiometric and have
indefinite composition. The non – stoichiometry is due to
(a) variable valency of transition metals
(b) presence of defects in their solid state (structure)
1. Potassium Dichromate (K2Cr2O7):
Preparation: It is prepared from chromite ore (FeCr2O4 or FeO.Cr2O3) through the following steps:
(i) Fusion of the ore with molten alkali in presence of air
4 FeCr2O4 + 16 NaOH + 7 O2 8 Na2 CrO4 (sodium chromate) + 2 Fe 2O3 + 8 H2O
The fused mass is extracted with water and filtered.
(ii) Conversion of sodium chromate into sodium dichromate by treating the filtrate with dil H2SO4
2 Na2 CrO4 + H2SO4 Na2Cr2O7 (sodium dichromate) + Na2SO4 + H2O
Na2SO4 being less soluble is separated as Na2SO4.10 H2O by fractional crystallisation.
(iii) Conversion of sodium dichromate into potassium dichromate by heating with KCl
Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl
Potassium dichromate being less soluble is obtained by fractional crystallization.
Properties:
(i) K2Cr2O7 is orange red coloured crystalline compound soluble in water.
(ii) In the solution, dichromate ions Cr2 O 27 exist in equilibrium with chromate ions CrO 24 as follows:
OH–, pH= 8
Cr2 O72 (Orange) + H2O 2 CrO 24 (Yellow) + 2H+
+
H , pH = 4
In alkaline solution, equilibrium shifts in the forward direction and the solution is yellow. In the
acidic medium, equilibrium shifts in the backward direction and the solution is orange. This
conversion takes place with change in pH of the solution.
2 K2Cr2O7 + 2 KOH 2 K2 CrO4 + H2O
2 K2CrO4 + H2SO4 K2Cr2O7 + K2SO4 + H2O
(iii) It is a strong oxidising agent in the acidic medium
K2Cr2O7 + 4 H2SO4 K2SO4 + Cr2 (SO4)3 + 4 H2O + 3 (O)
In order words Cr2 O 72 ion takes up electrons and hence acts as an oxidising agent
Cr2 O 72 + 14 H+ + 6 e– 2 Cr3+ + 7 H2O (Eo = + 1.31 V)
In this reaction Cr (+ 6) is reduced to Cr (+ 3)
Therefore, equivalent weight of K2Cr2O7 is one sixth the molecular mass of K2Cr2O7 i.e., 294/6 = 49.
Some of the oxidation reactions are given below:
2 KI + H2SO4 + (O) K2SO4 + H2O + I2
H2S + (O) H2O + S
2FeSO4 + H2SO4 + (O) Fe2(SO4)3 + H2O
Na2SO3 + (O) Na2SO4
2 HCl + (O) H2O + Cl2
SO2 + (O) + H2O H2SO4 (Industrial Method for the manufacture of Chrome Alum)
SnSO4 + H2SO4 + (O) Sn (SO4)2 + H2O
 K2Cr2O7 /H2SO4
O
CH3CH2OH (Ethanol) + (O) CH3CHO (Acetaldehyde) CH3COOH (Acetic acid)
H2O
(iv) Chromyl chloride test: A metal chloride on heating with solid K2Cr2O7 and conc. H2SO4 gives red
vapours of chromyl chloride (CrO2Cl2)
K2Cr2O7 + 4 KCl + 6 H2SO4 2 CrO2 Cl2 + 6 KHSO4 + 3 H2O
These are passed through dilute NaOH solution to give yellow solution of Na2CrO4. Yellow solution is
acidified with CH3COOH and lead acetate solution is added to give yellow precipitate of PbCrO4
CrO2Cl2 + 4 NaOH Na2CrO4 + 2 NaCl + 2 H2O
Na2CrO4 + Pb (CH3COO)2 PbCrO4 (yellow ppt) + 2 CH3COONa
This reaction is used in the detection of chloride ions in quantitative analysis
(v) Action of heat: When heated to a white heat, it decomposes with the evolution of oxygen
Heat
4 K2Cr2O7 4 K2 CrO4 + 2 Cr2O3 + 3 O2
(vi) Action of concentrated sulphuric acid:
(a) In cold, red crystals of chromic anhydride (CrO3) are formed. CrO3 is highly acidic and is called
“chromic acid”. [H2CrO4 is hypothetical]
K2Cr2O7 + 2 H2SO4 2 CrO3 + 2 KHSO4 + H2O
(b) On heating with dilute H2SO4, oxygen is evolved
2 K2Cr2O7 + 8 H2SO4 2 K2SO4 + 2 Cr2 (SO4)3 + 8 H2O + 3 O2
(vii) Reaction with H2O2: Acidified ice cold solution of dichromate ion forms a deep blue colour with H2O2
due to the formation of peroxo compound [CrO (O2)2] or CrO5. The blue colour fades away to green
due to the decomposition of CrO5 to Cr3+ and oxygen
Cr2 O 27 + 4 H2O2 + 2 H+ 2 CrO5 + 5 H2O
O\ /O
The structure of CrO5 is Cr | in which Cr is in + 6 oxidation state.
|
O / || \ O
O
7
2CrO5 + 3H2SO4 Cr2(SO4)3 + 3 H2O + O 2.
2
Uses: In volumetric analysis, in chrome tanning in leather industry, in the preparation of chrome alum,
in calico printing and in organic chemistry as an oxidizing agent

Structure:
2– 2–
O O
O 179 pm O
126o
Cr O Cr Cr O

O O O 163 pm O
O Dichromate ion
Chromate ion
Structure of chromate ion CrO 24 is tetrahedral (Cr is sp3 – hybridized) in which all Cr – O bonds are
equivalent. The dichromate ion (Cr2O7)2– consists of two tetrahedra sharing one oxygen atom at the common
corner. Here all Cr – O bonds are not equivalent. The two Cr – O bonds which share an oxygen atom at the
common vertex of the two tetrahedral units are longer (bond length 179 pm) than the other equivalent six Cr –
O bonds (bond length 163 pm). The Cr – O – Cr bond angle at the common vertex is 126o. Here Cr (VI) in
CrO 24 and Cr2 O 72 has do configuration, so the yellow and orange colours respectively arise from charge
transfer and not form d – d transition.
2. Potassium Permagnate (KMnO4):
Preparation: It is prepared from pyrolusite ore (MnO 2) through the following steps:
(i) Conversion of pyrolusite into potassium manganate: The finely powdered pyrolusite ore is fused
with KOH or K2CO3 in the presence of air or oxidising agent such as KNO3 or KClO3 (potassium
chlorate) to give green coloured potassium manganate (K2MnO4)
2 MnO2 + 4 KOH + O2 2 K2MnO4 + 2 H2O
2 MnO2 + 2 K2CO3 + O2 2 K2MnO4 + 2 CO2
 MnO2 + 2 KOH + KNO3 K2MnO4 + KNO2 + H2O
3 MnO2 + 6 KOH + KClO3 3 K2MnO4 + KCl + 2 H2O
(ii) Oxidation of potassium manganate to potassium permanganate:
(a) Chemical oxidation: The fused mass is extracted with water and the solution after filtration is
converted into KMnO4 by bubbling CO2, Cl2 or ozonised oxygen through the green solution.
3 K2MnO4 + 2 CO2 2 KMnO4 + MnO2 + 2 K2CO3
2 K2MnO4 + Cl2 2 KMnO4 + 2 KCl
2 K2MnO4 + H2O + O3 2 KMnO4 + 2 KOH + O2
K2MnO4 undergoes disproportionation in acid medium to give KMnO4.
3K2MnO4 + 2H2O 2 KMnO4 + MnO2 + 4 KOH
(b) Electrolytic oxidation: This is the most preferred method. The manganate solution is
electrolysed between iron electrodes separated by diaphragm. The electrode reactions are as
follows:
At anode: MnO 24 (Green) MnO 4 (Purple) + e–
At cathode: 2 H+ + 2e– H2
The oxygen evolved at the anode converts manganate to permanganate
2 K2MnO4 + H2O + O 2 KMnO4 + 2 KOH
The solution is filtered and evaporated to get deep purple black crystals of KMnO4.
Properties:
(i) It is a deep purple crystalline solid, moderately soluble in water at room temperature.
(ii) Action of heat: When heated to 746 K, it readily decomposes to give oxygen
Heat
2 KMnO4 K2MnO4 (Pot. manganate) + MnO2 + O2
746 K
At red heat, K2MnO4 further decomposes to potassium manganite (K2MnO3) and oxygen
Re d heat
2 K2MnO4 2 K2MnO3 + O2
(iii) Action of H2SO4: With well cooled conc. H2SO4, KMnO4 gives Mn2O7 (an explosive oil) which on
warming ( even at 25oC) decomposes to MnO2
2 KMnO4 + 2 H2SO4 Mn2O7 + 2 KHSO4 + H2O
2 Mn2O7 4 MnO2 + 3 O2
On heating with dilute H2SO4, O2 gas is evolved
4 KMnO4 + 6 H2SO4 2 K2SO4 + 4 MnSO4 + 6 H2O + 5 O2
(iv) With H2: When heated in a current of H2, solid KMnO4 gives KOH, MnO and water vapours
2 KMnO4 + 5 H2 2 KOH + 2 MnO + 4 H2O
(v) Oxidising properties: KMnO4 is a powerful oxidising agent.
(a) In neutral solution: It acts as a moderate oxidising agent because of the reaction
2 KMnO4 + H2O 2 KOH + 2 MnO2 + 3 O
or MnO 4 + 2 H2O + 3e– MnO2 + 4 OH–
During the reaction, the alkali generated renders the medium alkaline even when we start with
neutral medium. The equivalent weight of KMnO4 in alkaline and neutral media is the same i.e., one
third of its molecular mass i.e., 158/3 = 52.6.
A few examples of substances oxidised are:
2 KMnO4 + 3 MnSO4 + 2 H2O K2SO4 + 2 H2SO4 + 5 MnO2
8 KMnO4 + 3 Na2S2O3 + H2O 3 K2SO4 + 8 MnO2 + 3 Na2SO4 + 2 KOH
2 KMnO4 + 4 H2S 2 MnS + S + K2SO4 + 4 H2O
(b) In alkaline solution: It acts as a strong oxidising agent because of the reaction
2 KMnO4 + 2 KOH 2 K2MnO4 + H2O + O
2
or MnO 4 + e – MnO 4
K2MnO4 is further reduced to MnO2 when a reducing agent is present
K2MnO4 + H2O MnO2 + 2 KOH + O
or MnO 24 + 2 H2O + 2 e – MnO2 + 4 OH–
So the complete reaction is
2 KMnO4 + H2O 2 MnO2 + 2 KOH + 3 O
or MnO 4 + 2 H2O + 3 e – MnO2 + 4 OH– (Eo = + 1.23 V)
 which is the same as that for neutral medium.
A few examples of the substances oxidized are:
2 KMnO4 + H2O + KI 2 MnO2 + 2 KOH + KIO3 (Pot. iodate)
CH 2 CH 2 OH
|| (Ethylene) + H2O + O | (Ethylene glycol)
CH 2 CH 2 OH
Alkaline KMnO4 when used for olefinic compounds, as a test for unsaturation & called Baeyer’s
reagent.
C6H5CH3 (Toluene) + 3 O C6H5COOH (Benzoic acid) + H2O
(c) In acidic medium: The presence of dil. H2SO4, it acts as a strong oxidising agent because of the
reaction
2 KMnO4 + 3 H2SO4 K2SO4 + 2 MnSO4 + 3 H2O + 5 O
or MnO 4 + 8 H + 5e
+ – Mn + 4 H2O
2+ (Eo = + 1.51 V)
Thus, the equivalent weight of KMnO4 is one fifth of its molecular mass i.e. 158/5 = 31.6
A few examples of substances oxidised are:
6KMnO4 + 10 FeC2O4 + 24 H2SO4 3 K2SO4 + 6 MnSO4 + 5 Fe2(SO4)3 + 20CO2 +
24 H2O
2 FeSO4 + H2SO4 + (O) Fe2 (SO4)3 + H2O
H2O2 + O H2O + O2
C2H2O4 (Oxalic acid) + (O) 2 CO2 + H2O
H2S + (O) H2O + S
SO2 + (O) + H2O H2SO4
KNO2 + (O) KNO3
Na2SO3 + (O) Na2SO4
2 KI + H2SO4 + (O) K2SO4 + H2O + I2
2 HX + (O) H2O + X2
CH3CH2OH (Ethyl alcohol) + (O) CH3CHO (Acetaldeyde) + H2O
Uses: In volumetric analysis, as a strong oxidizing agent in the laboratory as well as in industry, as
Baeyer’s reagent for testing unsaturation, as disinfectant and germicide.
Structure of permanganate ion: Mn in MnO 4 is sp3 – hybridized and hence four oxygen atoms are
arranged tetrahedrally around manganese. Here, Mn (VII) has d0 configuration, so the deep purple colour
arises from charge transfer and not from d – d transition
O
||
Mn
O | O
| –

O
LATHANOIDS:
1. Electronic configuration : The elements with atomic numbers 58 to 71 i.e. cerium to lutetium (which
come immediately after lanthanum Z = 57) are called lanthanoids or lanthanides or lanthanones or rare
earths. These elements involve the filling of 4 f –orbitals. Their general electronic configuration is [Xe] 4 f
1–14 5 d 0–1 6 s2.

Promethium (Pm), At. No. 61 is the only synthetic (man made) radioactive lanthanide. Because La closely
resembles the lanthanoids, it is also included among the lanthanoids for which the general symbol Ln is
often used.
2. Oxidation State : Most stable oxidation state of lanthanides is + 3. Oxidation states + 2 and + 4 also
exist but they revert to + 3 e.g. Sm2+, Eu2+, Yb2+ lose electron to become + 3 and hence are good
reducing agents, whereas Ce4+, Pr4+, Tb4+ in aqueous solution gain electron to become + 3 and hence are
good oxidizing agents. There is a large gap in energy of 4f and 5d subshells and thus the number of
oxidation states is limited.
3. Chemical Reactivity : Lanthanoids are highly electropositive in nature and they have almost similar
chemical reactivity. This is probably due to the reason that the electrons and filled in 4f sub–shells. These
are effectively shielded from interaction with other elements by the overlying 5s, 5p and 6s electrons. e.g.,
Lanthanoids are, in general, more reactive than d – block elements.
(i) They tarnish readily on exposure to air.
 (ii) In finely divided state, all burn in air to form sesquioxide of formula Ln2O3 (where Ln stands for
lanthanoids element) except Ce which gives CeO2.
(iii) They are stronger bases than Al(OH) 3 but weaker than Ca(OH)2.
(iv) Lanthanoids react with hydrogen at 575–675 K giving LnH3. Thus they can act as strong reducing
agents and can be used to reduce oxides of other metals.
4. Lanthanoid Contraction:
Cause : The regular decrease in the size of lanthanoid atoms and ions from La3+ to Lu3+ is known as
lanthanoid contraction. It is due to greater effect of the increased nuclear charge than that of the
screening effect, or we can say that f– orbital are not in a position to exert as much shielding effects
because of their diffused shapes as is expected from them, thus atomic and ionic radii decreases from left
to right.
Consequence :
(a) It results in slight variation in their chemical properties, which helps in their separation by ion
exchange methods.
(b) Each element beyond lanthanoids has very close atomic radius as that of the element lying above it
in the same group e.g., Zr 145 pm and Hf 144 pm; Nb 134 pm and Ta 134 pm; Mo 129 pm and W
130 pm etc.
(c) The covalent character of hydroxides of lanthanoids increases as the size decreases from La3+ to Lu3+.
Hence the basis strength decreases. Thus La (OH)3 is most basic whereas Lu (OH)3 is least basic.
Similarly, the basicity of oxides also decreases in the order from La3+ to Lu3+.
(d) Tendency to form stable complexes from La3+ to Lu3+ increases as the size decreases in that order.
(e) There is a slight increase in electronegativity of the trivalent ions from La to Lu.
(f) Since the radius of Yb3+ ion (86 pm) is comparable to the heavier lanthanoids Tb, Dy, Ho and Er,
therefore, they occur together in natural minerals.
Electronic configurations and radii of lanthanum and lanthanoids
Electronic configuration Radii /pm
Atomic Name Symbol Ln Ln2+ Ln3+ Ln4+ Ln Ln3+
Number
57 Lanthanum La 5d 16s2 5d 1 4f 0 187 106
58 Cerium Ce 4f 5d 6s
1 1 2 4f 2 4f 1 4f 0 183 103
59 Praseodymium Pr 4f 36s2 4f 3 4f 2 4f 1 182 101
60 Neodymium Nd 4f 4 6s2 4f 4 4f 3 4f 2 181 99
61 Promethium Pm 4f 56s2 4f 5 4f 4 181 98
62 Samarium Sm 4f 66s2 4f 6 4f 5 180 96
63 Europium Eu 4f 76s2 4f 7 4f 6 199 95
64 Gadolinium Gd 4f 75d16s2 4f 75d1 4f 7 180 94
65 Terbium Tb 4f 96s2 4f 9 4f 8 4f 7 178 92
66 Dysprosium Dy 4f 6s
10 2 4f 10 4f 9 4f 8 177 91
67 Holmium Ho 4f 116s2 4f 11 4f 10 176 89
68 Erbium Er 4f 126s2 4f 12 4f 11 175 88
69 Thulium Tm 4f 136s2 4f 13 4f 12 174 87
70 Ytterbium Yb 4f 146s2 4f 14 4f 13 173 86
71 Lutetium Lu 4f 145d16s2 4f 4f 14 – – –
145d1

7. Uses of Lanthnoids:
(i) Misch metal: Misch metal [Lanthanoids (94 – 95%), Iron 5% and traces of element Ca, C,S and Al] is
used for making jet engine parts. Pyrophoric alloy [Ce 40.5%, La + Nd 44%, Fe 4.5%, Al 0.5% and
traces of elements Ca, C, Si] is used for producing sparks.
(ii) In alloys lanthanoids are extensivelye used. E.g. Ln in steel.
(iii) Various compounds of lanthanoids are used as catalysts for hydrogenation, dehydrogenation,
oxidation and petroleum cracking.
(iv) Glass containing cerium absorbs both heat and U.V. radiations and therefore it is much used in
glare reducing spectacles.
(v) Oxides of rare earth metals are used for polishing glass.
(vi) Neodymium and Praseodymium oxides are used for making coloured glasses for goggles.
ACTINIDES :
Electronic configuration Radii /pm
Atomic Name Symbol M M3+ M4+ M3+ M4+
Number
89 Actinium Ac 6d 17s2 5f 0 111
90 Thorium Th 6d 27s2 5f 1 5f 0 99
91 Protactinium Pa 5f 26d1 7s2 5f 2 5f 1 96
92 Uranium U 5f 36d 17s2 5f 3 5f 2 103 93
93 Neptunium Np 5f 6d 7s
4 1 2 5f 4 5f 3 101 92
94 Plutonium Pu 5f 67s2 5f 5 5f 4 10 90
95 Americium Am 5f 77s2 5f 6 5f 5 99 89
96 Curium Cm 5f 76d 17s2 5f 7 5f 6 99 88
97 Berkelium Bk 5f 97s2 5f 8 5f 7 98 87
98 Californium Cf 5f 107s2 5f 9 5f 8 98 86
99 Einstenium Es 5f 117s2 5f 10 5f 9 – –
100 Fermium Fm 5f 127s2 5f 11 5f 10 – –
101 Mendelevium Md 5f 7s
13 2 5f 12 5f 11 – –
102 Nobelium No 5f 147s2 5f 13 5f 12 – –
103 Lawrencium Lr 5f 146d 17s2 5f 14 5f 13 – –
1. Electronic Configuration: Actinoids are with atomic numbers 90 to 103 i.e. thorium to lawrencium
(which come immediately after actinium, Z = 89). They are also called actinoids or actinides or actinones.
These elements involve the filling of 5 f–orbitals. Their general electronic configuration is [Rn] 5 f 1–14 6 d 0–
1 7 s2. Exception is Th 6d2 7s2.

2. Oxidation state: The dominant oxidation state of actinoids is + 3 which shows increasing stability for the
heavier elements. Np shows + 7 oxidation state but this is oxidising and is reduced to the most stable
state + 5. Pu also shows states upto + 7 and Am upto + 6 but the most stable drops to Pu (+ 4) and Am
(+ 3). Bk in + 4 state is strongly oxidising but is more stable than Cm and Am in + 4 state due to f7
configuration. Similarly, No is markedly stable in + 2 state due to its f14 configuration.
When the oxidation number increases to + 6, the actinoid ions are no longer simple. The high charge
density causes the formation of oxygenated ions e.g., UO 22 , NpO 22 etc. The exhibition of large number
of oxidation states of actinoids is due to the fact that there is a very small energy gap between 5f, 6d and
7s subshells and thus all their electrons can take part in bond formation.
3. Radioactivity: They include three naturally occurring elements Thorium, Protactinium and Uranium and
eleven transuranium elements or transuranics which are produced artificially by nuclear reactions. They
are mostly synthetic or man made elements. Thus all actinoids are radioactive.
4. Actinoid contraction: There is a regular decrease in ionic radii with increase in atomic number from Th
to Lr. This is called actinoid contraction analogous to the lanthanoid contraction. It is caused due to
imperfect shielding of one 5f electron by another in the same shell. This results in increase in the effective
nuclear charge which causes contraction in size of the electron cloud.
5. Uses :
(i) Thorium used as a nuclear fuel in the atomic reactors. Thorium oxide is used in the preparation of
incandescent gas mantles.
(ii) Uranium is used as a nuclear fuel in atomic reactors. Salts of uranium impart a green colur to the
glass. Uranyl nitrate is used for the volumetric estimation of phosphates and in medicines.
(iii) Plutonium is used as nuclear fuel in atomic reactors and in atomic weapons.
Comparison of Lanthanoids and Actinoids
Resemblance
(i) Both lanthanoids and actinoids show a dominant oxidation state of + 3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanoids and actinoids are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanoids show
lanthanoid contraction and actinoids show actinoid contraction.
Difference
Lanthanoids Actinoids
1. Besides the most common oxidation Besides the most common oxidation state of + 3,
state of + 3, lanthanoids show +2 and actinoids show + 4, + 5 and + 6 oxidation states in
+ 4 oxidation states in case of certain case of certain elements.
elements.
2. Lanthanoids, have less tendency Actinoids have a stronger tendency towards
towards complex formation. complex formation.
3. Except promethium, they are non All the actinoids are radioactive
radioactive.
4. Their magnetic properties can be Their magnetic properties are not easy to explain.
explained but not so easily as for
d – block elements.
5. Lanthanoids do not form oxocations. Actinoids form oxocations like UO 22 , PuO 32 , etc
6. Oxides and hydroxide of lanthanoids Oxides and hydroxoids of actinoids are more basic
are less basic.
NCERT & EXEMPLAR
SOLVED