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E- Content Development
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Chapter No.
8

Transition and inner transition

elements
Marks without option
-
6
Marks with option - 8

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Transition
1. Introduction :- Elements
 Elements which have incomplete d - subshell or elements which gives
cations with
incomplete d-subshell are known as transition elements.
 They exhibit properties between those of s and p- block elements.
 (n-1) d -orbital successively filled in each element. They are d- block
elements.
 It consists of four series. i) 3d series – from Scandium (Z=21) to
Zinc( z= 30)
ii)4d series – from Yttrium (Z= 39) to Cadmium (Z= 48)
iii)5d series – from Lanthanum (Z= 57) to Mercury(Z= 80) [Without
those from
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Cerium to Lutetium]
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.2 Position in periodic
table elements are placed at the centre of periodic table in
 Transition
between s and
p - block.
 They are placed in four long periods 4 to 7.
 They are placed in groups 3 to 12.
 They constitute 3d, 4d, 5d and 6d series of 10 elements each.
 They belongs to d- block of periodic table.

Four Transition series

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
elements
 8.3 Electronic
configuration
 General electronic configuration of d-block element is (n-1) d 1-10 ns 1-2

 General electronic configuration of four series of d -block elements.

1) 3 d series => [Ar] 3d 1-10 4s 1-2

2) 4 d series => [Kr] 4d 1-10 5s 0-2

3) 5 d series => [Xe] 5d 1-10 6s 2

4) 6 d series => [Rn] 6d 1-10 7s 2

• Zn has completely filled (n-1)d- orbital in ground state ([Ar] 3d104s2)

and in it’s common oxidation state (+2) is ([Ar] 3d10). Therefore it is
not regarded as transition metal.
* Similarly Cd, Hg and Cn are not considered as transition metal
as the have completely filled d- orbital.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Electronic configuration of 3d-
series

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.3.1 Electronic configuration of Chromium and Copper
Expected electronic configuration of Cr is [Ar] 3d4 4s2 and that of
Cu is
[Ar] 3d9 4s2
 Half filled subshells and completely filled subshells are
more stable than partially filled subshells.
4s and 3d- orbitals have close energies.

To attain extra stability ,last electron occupies 3d- orbital

instead of 4s
orbital.
 Therefore observed electronic configuration of Cr is [Ar]
3d54s1 and that of Cu isShri[Ar] 3d Shikshan
Swami Vivekanand10
4sSanstha
1. , Kolhapur
 8.4 Oxidation states of first transition
1) Transition
series elements show variety of oxidation states in their
compounds.
2) Variable Oxidation states are due to loss of electrons from 4s and 3d-
orbital.
3) As number of unpaired electrons in 3d- orbital increases the
number of oxidation states of element increases.
4) Common oxidation state is +2 .
5) In 3d series Mn has highest oxidation state is +7. * Mn
show O.S. from +2 to +7.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.5 Physical properties of first transition
series:
 They show characteristic metallic properties.

 They are hard , lustrous, malleable, ductile and form

alloy .

 They are good conductors of heat and electricity.

 They have metallic structure (except Zn, Cd, Hg and

Cn).

 They are hard and have low volatility (except Zn, Cd

and Hg).

 They have high melting point and boiling point.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Trends in Melting point of transition
metals
• In transition metals atoms are held strongly by metallic bond due to low
ionization
enthalpy and vacant d- orbitals in outermost shell. The metallic bond
has strong covalent character due to presence of unpaired electrons in (n-
1) d – orbital.
• Transition metals have high melting point and boiling point.
• In all the transition series melting point steadily
increases up to nd5 configuration.
• Cr, Mo, W show highest melting point in their
respective series.
• After nd5 configuration, with increase in atomic
number melting point decreases regularly.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6 Trend in atomic properties of first transition
8.6.1series:
Atomic & ionic
radii
i. Atomic radii decreases gradually from left to right .
ii. This is due to increase in nuclear charge from left to right, last filled
electron enters in same penultimate i.e. (n-1) d - orbital and poor
iii screening effect of d - electrons. With increase in nuclear charge ionic
.
radii gradually decreases for same oxidation state. Example - (Cr2+
82pm , Cu2+ 72 pm).
iv. With variable oxidation states of same metal , ionic radii decreases with
higher
oxidation state due to increase in effective nuclear charge.
v. Ionic radii decreases from M2(+) to M3(+)
elements of same Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

vi. Ionic radii of transition metals are smaller than ionic radii of
period.
Note:-Values are not expected from students , only trends are
expected.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6.2 Ionization enthalpy:

1. Ionization enthalpy :- The energy required to remove an

electron from the isolated gaseous atom in its ground state is
called ionization enthalpy.
2. Ionisation enthalpies of transition metals are intermediate
between s -block and
p- block elements.
3. Ionization enthalpy increases from left to right .
4. Transition elements are less electropositive than elements of group
1 and 2.
5.Generally in lower oxidation state they form ionic compound and in
higher oxidation state they form covalent compound.
6. Ionization enthalpy increases from first Ionization Enthalpy to third I.E.
(IE1 to IE3)
7.Ionization enthalpies of elements of third transition series has
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Note:-Values are not expected from students , only trends are
expected. Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6.3 Metallic
character:
 Transition elements have low ionization enthalpies and vacant d -
orbitals in
outermost shell.
 They form metallic bonds with covalent character due to
presence of unpaired electron in (n-1) d- orbital.
 They show typical metallic properties .

 They are hard and have high melting point.

 They have simple hexagonal close packed (hcp), cubic close

packed (ccp) or body centred cubic lattice (bcc).
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6.4 Magnetic properties:
1) Compounds of transition metals exhibit magnetic property due to
presence of unpaired electrons.
2) Compound which are attracted towards magnetic field are
Paramagnetic.
Example – Compounds containing Cu2+, Mn2+,Fe3+
3) When all electrons are paired then compounds are repelled by
magnetic field.
These are called as diamagnetic substances. Example – Zn2+ ,
Cu1+ , Sc3+
4) Substances which are attracted very strongly towards magnetic field
are known as ferromagnetic. Example - Fe, Co, Ni
5) These metals can be magnetized i.e. they acquire permanent
magnetic moment.
* Each unpaired electron gives smallShikshan
Shri Swami Vivekanand magnetic
Sanstha , Kolhapur moment due to spin
The spin only formula for magnetic moment is

μ= 𝑛 𝑛+
2
BM where n = no. of unpaired
electrons.
μ = magnetic moment expressed in Bohr
Magneton
Problem :- Calculate the spin only magnetic moment of divalent
cation of transition metal with atomic number (Z)
=25.
Solution:- Electronic configuration of element with atomic
no(Z)=25 is [Ar] 3d5 4s2.

Electronic configuration of divalent cation with atomic no(Z)=25

is

[Ar] 3d5
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6.5 Colour :

1)The ionic and covalent compounds formed by the transition elements

are coloured.
2)Colour depends upon the wavelength of absorption in the visible region
of
electromagnetic radiations.
3)Transition metal contain unpaired electrons in their d-orbitals.
4)In presence of ion or ligands d- orbitals split into two sets: t2g and
eg of slight different energies.
5) Small amount of energy is required for transition of electron from one
d-orbital to other d- orbital (d-d transition).
6) Small energy required for this transition is available by absorption
of radiations having certain wavelength from visible region.
7) Remaining light is transmitted andShikshan
Shri Swami Vivekanand observed colour of compound
Sanstha , Kolhapur
7)If red coloured light is absorbed then colour of compound is blue.

8) The ions having no-unpaired electrons are colourless. Example-

Cu+,Ti+4,Zn2+.

9) Colour depends upon ligand and geometry of complex formed by

metal ion.
Example- [Co(H2O)6]2(+) - octahedral geometry -
pink colour [CoCl4]2(-) – tetrahedral geometry -
deep blue colour
Colour of transition metal ion relates to
10)Presence of unpaired d- electron
11)d-d transition
12)Nature of ligands attached to the metal ion
13)Geometry of complex
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 • Example
8.6.6 Catalytic properties : Sr. Catalyst
s Uses
1) Transition metals and their No

compounds exhibit good 1 MnO2 Decomposition of KClO3

catalytic properties because 2 Mo/Fe Manufacture of NH3 by Haber’s
they have ability to process.

participate in different 3 Co-Th Synthesis of gasoline in Fischer

alloy Tropsch Process.
oxidation – reduction steps
4 Ni Hydrogenation of ethene to
of catalytic properties.
ethane.
2) They acts as homogeneous Hydrogenation of oils into
and heterogeneous fats (margarine
production)
catalysts. 5 Fe-Cr Formation of CO2 and H2
3) In homogeneous catalysis from carbon monoxide and
reaction , metal ions form steam.
6 Platinise Production of H2SO4 by
unstable intermediates. d contact process.
asbestos
 8.6.7 Formation of interstitial
compounds
Definition: :
- Compounds formed by trapping small atoms like
hydrogen, carbon, boron, nitrogen etc. in the interstitial
spaces within the crystal lattice of metal are called
interstitial compounds.
• Example- steel, cast iron are interstitial compound of C and Fe.
• Properties
1)They are good:- conductors of heat and Uses:
electricity. -)
1 Tungsten
carbide --
2)They are hard. Cutting tool
3) Their chemical properties are similar to 1) Iron carbide --
parent metal. Manufacture of
steel
4) Their melting point is higher than pure
6) metal
Metal .carbides are chemically inert and extremely hard as
diamond.
5) Densities are less than parent metal.
7)Hydrides of transition metals are used as powerful
 • Uses of
8.6.8 Formation of
alloys:-
alloys:
1)Transition metal forms alloy. Alloy Uses
2) In alloy atoms of one metal Bronze Making statues, medals and
distributed randomly in the An alloy trophies.
of
lattice of another metal. (Cu+Sn)
3) Metals with similar radii Cupra nickel Making machinery parts of
and similar properties An alloy marine ships boats like
readily form alloys. of (Cu marine condenser tubes.
+Ni)
4) There are two types of
Stainless steel Construction of outer fuselage of
alloys - An alloy ultra high speed air craft.
i) Ferrous alloy- Atoms of of (Fe +
their elements distributed C)
Nichrom Making gas turbine engines.
randomly in iron. e An alloy
Example - steel, chromium of (Ni
steel, +Cr)
stainless steel Titanium alloy In ultra high speed flight fire
An alloy of proof bulkheads (barrier
ii)Non ferrous alloy - Alloy (Ti + V + between two compartments)
formed by mixing atoms of Al) & exhaust shrouds
 8.7 Compounds of Manganese (Mn) &
Chromium(Cr)
[KMnO4 and K2Cr2O7]
• 8.7.1 Preparation of potassium permanganate
• Chemical oxidation :-
Finely divided manganese dioxide (pyrolusite ore - MnO2) heated
strongly with fused mass of caustic potash (KOH ) and oxidizing
agent potassium chlorate(KClO3) then potassium manganate
(K2MnO4) is formed. It is dark green coloured.

In neutral or acidic medium K2MnO4 disproportionates to KMnO4

and MnO2.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

• Liquid is filtered and evaporated until crystallisation.
• Black purple crystals of KMnO4 are formed.
Electrolytic oxidation
• Alkaline solution of magnate ion is electrolysed between iron
electrodes separated by diaphragm.
*Overall reaction is

The Oxygen evolved at anode convert magnate to permanganate .

• Solution is filtered and evaporated get deep purple black crystals
of KMnO4 .

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.7.2 Chemical properties of
KMnO4 :
*Oxidizing reactions in acidic
medium

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 b) In neutral or weakly alkaline
medium: of I Θ to iodate IO3
i) Oxidation
Θ :-

ii)
)to Oxidation of thiosulphate( S2O3) :-
sulphate(SO 4
2Θ
2Θ

iii) Oxidation of Manganous salt to

MnO2:-

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.7.3 Uses of KMnO4:
1)It is used as an antiseptic.

2) It is used for unsaturation test in laboratory.(Bayer’s

reagent-alkaline KMnO4 is used for this test.)

3) It is used in volumetric analysis of reducing agents.( like

oxalic acid , ferrous

salts , hydrogen peroxides)

4) It is used for detecting halides in qualitative analysis.

5) It is used as powerful oxidising agent in laboratory and

industry. Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.7.4 K2Cr2O7 : Preparation of Potassium
dichromate
*
 It is prepared from chromite ore (FeO.Cr2O3).
A) Chromite ore is heated with anhydrous sodium carbonate and flux of
lime in air
in a reverberatory furnace.
B) Sodium chromate(Na2CrO4) formed is extracted with water and
treated with
conc. H2SO4. Then sodium dichromate is obtained.
Na2Cr2O7 + Na2SO4+ H2O
C) Sodium dichromate when treated with potassium chloride gives
orange red
coloured potassium dichromate.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.7.5 Chemical properties of K2Cr2O7
i) Oxidation of I (-) from aq. solution of KI
Acidified K2Cr2O7 oxidises KI and gives iodine. Liberated iodine turns
the solution
brown. Potassium dichromate is reduced to chromic sulphate.

ii) Oxidation of H2S

When H2S is oxidized by acidified K2Cr2O7 gives yellow
precipitate of sulphur. As potassium dichromate is reduced to
chromic sulphate , colour of solution
changes from orange to green.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.8 Common properties of d- block elements
 Physical properties:-
1)All d -block elements are lustrous and shining.
2) They are hard and have high density.
3) They have high melting and boiling point.
4) They are good electrical and thermal conductors.
5) They have high tensile strength and malleability.
6) They form alloy with other transition and non transition
elements.
7)Most of metals are efficient catalysts.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Chemical properties of d-block elements :
1)They are electropositive metals.
2) They exhibit variable valencies and form colored salts and
complexes.
3) They are good reducing agents.
4) They form insoluble oxides and hydroxides.
5) They catalyse biological reactions.
6) Iron , cobalt ,copper , molybdenum and zinc are biologically
important metals.
Differences:- Most of the properties of d- block elements are same.
Elements of first row differ from second and third row in stabilization
of higher oxidation states in their compound. Example Mo (V) and W
(VI) compounds are more stable than Cr (VI) and Mn (VII).
• Highest oxidation state Shri
for elements
Swami of first
Vivekanand Shikshan Sanstha , Kolhapur row is +7 and in
 8.9 Extraction of
Metals
•Mineral : A naturally occurring substance found in the earths crust
containing inorganic salts, solids, siliceous matter etc. is called
a mineral.
•Ore : The mineral which contains high percentage of the metal and
from which the
metal can be extracted is called as ore.
List of minerals and ores of some transition
metals.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Metallurgy

Pyrometallurgy Hydrometallurgy
Electrometallurgy

1. Metallurgy : The commercial extraction of metals from their

ores is called metallurgy.
Different methods are used for their extraction depending
on the
nature of a metal and its ore.
a. Pyrometallurgy: The process in which ore is reduced to metal at
high temperature
using reducing agents like carbon, hydrogen, aluminium, etc. is
called pyrometallurgy.
b.Hydrometallurgy : The process of extracting metals from the
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
aqueous solution of their salts using suitable reducing agent is called
Steps Involved in Process of
Extraction:
Concentration :
Gangue : The sand, mud and other unwanted impurities which remain
mixed with the ore deposit are called gangue.
During the process of concentration, the ore is separated from
the gangue material using different methods such as washing, hydraulic
classification, magnetic separation, froth floatation, etc.
8.9.2 Extraction of Iron from Haematite ore using Blast
furnace:
Composition of Haematite ore :
Fe₂O₃ + SiO₂ + Al₂O₃ + phosphates

Gangue
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Flow Chart of Extraction of
Iron Reduction by
Iron Ore Crushing
and coke Reduction
Grinding by CO
Concentrati Reductio Reduction by
on n
heat Reduction
Magnetic Gravity Leachin Froth by Al Reduction
Separati Separati g flotatio
on on Refinin by electrolysis
Pure
n
g Iron

Liquificatio Distillatio Oxidatio Electro-

n n n refining
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Iron is extracted from haematite by its reduction using coke and
limestone.
Carbon in the limestone is reduced to carbon monoxide. Carbon
and carbon monoxide together reduce Fe2O3 to metallic iron .
The extraction of iron from haematite ore involves the
following steps.
i. Concentration :
The powdered ore is washed in a powerful current of water
introduced into the hydraulic classifier. The lighter gangue
particles are separated and the concentrated ore is collected at
the bottom. Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
ii. Roasting :
The concentrated ore is heated in a current of air. The sulfur
and arsenic impurities present in the ore get converted into their
oxides and escape as vapour. Ferrous oxide in the ore is converted to
Fe₂O₃.

The roasted ore is converted into lumps by sintering.

iii. Reduction (Smelting) :
• This step is carried out in a blast furnace.
• Blast furnace is a tall cylindrical steel tower which is lined with
refractory bricks.
• The height of a typical blast furnace is 25 m and its diameter varies
between 5 and
10 m.
• The furnace works on counter current
Shri Swami Vivekanand principle
Shikshan Sanstha , Kolhapur where the charge
 Blast Furnace

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

Reactions in the blast furnace :
There are 3 temperature zones in the
1. furnace.
Zone of combustion : [Combustion of coke with O₂ in the air.]
The hot air blown through the tuyers reacts with coke from the charge
to form CO.

Some of the CO formed dissociates to form finely divided carbon.

2. Zone of Reduction (22-25 m near the top):

Here, the temperature is around 900 K. Fe₂O₃ is reduced to spongy
iron by CO

some amount of Fe2O3 is reduced to iron by carbon

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

Summary of reactions taking place in blast furnace at
different temperature zones:

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

3. Zone of slag formation (20 m unit) :
The gangue present in the ore is converted to slag. Limestone
decomposes to give CaO(quick lime).

CaO combines with gangue to form molten slag of calcium silicate

and calcium aluminate.

4. Zone of fusion (15 m ht) :

The slag which is lighter floats on the surface of molten iron. Molten slag
and iron are collected through separate outlets. The molten iron is removed
and cooled in moulds. It is called pig iron or cast iron.
5.Refining:
Pure iron can be obtained by electrolytic refining of impure iron or other
methods
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
given in flow chart.
Commercial forms of on: Iron
Ir

Cast Wrought Steel

Differences between st iron, wrought d steel:
ca iron an
Cast iron Wrought iron Steel
1. Hard and brittle 1. Very soft 1. Neither too hard no
too
soft.
2. Contains 4% carbon. 2.Contains less than 2. Contains 0.2 to
0.2% carbon 2% carbon
3. Used for making 3. Used for making 3. Used in buildings
pipes, manufacturing pipes, bars for stay infrastructure, tools,
automotive parts, pots, bolts, engine bolts
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
ships, automobiles,
 8.10 Inner Transition (f-block)
Elements Lanthanoids And
Actinoids
 Introduction
:
 Elements whose f-orbitals get filled up by electrons are called f-block
elements.
 These elements are placed separately at the bottom of the periodic
table.
 They are a subset of 6th and 7th periods.
 Since f-orbital lies much inside the d-orbital, in a relation to transition
metals the f-
block elements are called inner transition elements.
 These elements have 1 to 14 electrons in there f-orbital, 0 (Zero) or 1
in the penultimate energy level and 2 electrons in the outermost
orbital. The lanthanoids are characterized
Shri Swami by gradual filling of 4f and
Vivekanand Shikshan Sanstha , Kolhapur
 8.11 Properties of f-block
elementsof: f-block elements are similar to d-block elements.
1)Properties
2) Electrons are added to f-subshells of (n-2) level.
3) They are placed between (n-1) d and ns block elements.
4) Lanthanoids begin with atomic number 57 and end at 71.
5) Lanthanoids are termed as rare earth elements, they are fairly
abundant in earth crust.
6) These metals are soft with moderate densities of about 7 g/cm3.
7) They have high melting (near about 1000 o c) and boiling points
(near about 3000 o c).
8) Lanthanoids in the metallic state are very reactive like alkali and
alkaline earth metals.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 9)The common oxidation state of lanthanoids is +3 . Some
elements ,Europium (Eu) and Ytterbium (Yb) show +2 oxidation state.
Higher oxidation states are unusual for lanthanoids only exception of
Cerium which show stable +4 oxidation state.
10) Lanthanoids have lower heat of atomization than transition metals.
11)Europium and Ytterbium resemble with alkaline earth metals, they
dissolve in liquid ammonia to give blue conducting solutions
12) Their ionic radii decreases from 117 pm of La to 100 pm for Lu.
13) Lanthanoid ions have higher coordination number varies from 6 to
12.
14) All the lanthanoids form hydroxides of the general formula Ln(OH)3.
These are ionic and basic. Since the ionic size decrease from La3+ to
Lu3+,the basicity of hydroxide decreases.
15)Lanthanoids react with nitrogen and halogens to give nitrides and
halides of the
formulae LnN and LnX3 respectively.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.12 Properties of
Lanthanoids
 They are soft metals with silvery white color and moderate densities of
nearly 7
g/cm3.
 They are good conductor of heat and electricity.
 Except Promethium (Pm),all are non-radioactive in nature.
 The atomic and ionic radii decrease gradually from Lanthanum (La) to
Lutetium
(Lu) this is known as lanthanoid contraction.
 Binding to water is common (i.e.) such that H2O is often found in
products when
isolated from aqueous solutions.
 Coordination numbers usually are greater than 6, typically 8, 9,…(up
to 12 found).
 spectra in
The lanthanoids are strongly paramagnetic.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Table 8.11 Electronic Configuration, atomic & ionic radii of
lanthanoids
Observ
Expecte (+2 (+3 Ionic
Atomi ed
d oxidatio oxidatio Atomic radii
Element Symbo c (groun
(ground n state) n state) radii, (Ln+3,
l numb d state)
state) pm 6-coordinate),
er
pm

Lanthanum La 57 [Xe]4f 05d16s2 [Xe]4f 05d16s2 4f 0

4f 0
187 103
Cerium Ce 58 [Xe]4f 26s2 [Xe]4f 15d16s2 4f 1
183 102
Praseodymiu Pr 59 [Xe]4f 36s2 [Xe]4f 36s2 4f 2
4f 2
182 99
m
Neodymium Nd 60 [Xe]4f 46s2 [Xe]4f 46s2 181 98.3
Promethium Pm 61 [Xe]4f 56s2 [Xe]4f 56s2 4f 4
181 97
Samarium Sm 61 [Xe]4f 66s2 [Xe]4f 66s2 4f 5
4f 5
180 95.8
Europium Eu 63 [Xe]4f 76s2 [Xe]4f 76s2 4f 6
199 94.7
Gadolinium Gd 64 [Xe]4f 86s2 [Xe]4f 75d16s2 4f 7
178 93.8
Terbium Tb 65 [Xe]4f 96s2 [Xe]4f 96s2 4f 8
177 92.3
Dysprosium Dy 66 [Xe]4f 6s2
10
[Xe]4f 10
6s2 4f 9
176 91.2
4f 10
Holmium Ho 67 [Xe]4f 6s2
11
[Xe]4f 11
6s2 4f 10 175 90.1

Erbium Er 68 [Xe]4f 6s2

12
[Xe]4f 12
6s2 174 89
Thulium Tm 69 [Xe]4f 6s2 Shri[Xe]4f
13 13
6s2 Shikshan
Swami Vivekanand 4f 12
4f 12Sanstha , Kolhapur 173 88
 8.12.1 Electronic
Configuration:
 The general valence shell electronic configuration of lanthanoids is

[Xe] 4f 0−145d0−2 6s2

 Elements La, Gd and Lu possess single electron in 5d subshell. In
case of other lanthanoids 5d orbital is empty.
 f 0 , f 7 , f 14 electronic configuration achieve extra stability due to
empty, half filled and completely filled f-orbitals.
 Examples - La ( 4f 0), Gd ( 4f 7 ) and Lu ( 4f 14 )

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Ionization enthalpies :
 The ionization enthalpies of inner transition metals are quiet
high and lie
between those of s-block and p-block elements.
 The first ionisation enthalpy increases with increase in
atomic Lanthanoid
number across IE a given
1 IE innerIEtransition series.
2 3

La 538.1 1067 1850.3

Ce 528.0 1047 1949
Pr 523.0 1018 2086
Nd 530.0 1034 2130
Pm 536.0 1052 2150
Sm 543.0 1068 2260
Values are not expected
Eu 547.0 1085 2400
Gd 592.0 1170 1990
from students . Only
Tb 564.0 1112 2110
Dy 572.0 1126 2200
trends
Ho 581.0 1139 2200
are expected.
Er 589.0 1151 2190
Tm 596.7 1163 2284
Yb 603.4 1175 2415
Lu 523.5 1340 2022
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
8.12.2 Oxidation
state :
 These elements have common +3 oxidation state to all
elements. Two

electrons from s-subshell and one from d or f-subshell are

removed.

 As 4f electrons are strongly screened by inner electrons of 5s

and 5p-

elecrons ,4f-electrons are not involved in bonding.

 Besides these, some lanthanoids show oxidation states +2 and

+4.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
8.12.3 Color and Spectra:
 Some trivalent ions (M3) are colored in solid state as well as
in solution.
 The color of lanthanoid ion is due to f-f transitions.
 (14
The –color
n) f- of ions having n f-electrons is about the same as
those having Number of No. of
electrons .Ln
electrons in colo f-
io
f - orbital r electrons
n
(14 -n)
Pr3 4f 2 gree f-
n electrons
4f 12
=14-2
n f-
Tm3 gree
=12
electrons
n
=12
(14 -n)
4f 3 Pin f-
Nd3
k electrons
=14-3
nf-
4f 11 Pin
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Er3 =11
electrons
k
 8.12.4 Atomic and ionic radii (Lanthanoid
Contraction):
 As we move along the lanthanoid series, there is a decrease in
atomic and ionic radii.
 This steady decrease in the atomic and ionic radii is called
Lanthanoid
contraction.
 As we move from one element to another the nuclear charge
increases by one unit and one electron is added.
 The new electrons are added to the same inner 4f-subshell.
 Thus the 4f-electrons shield each other poorly due to diffused
shape.
 Hence, with increase in atomic number, the effective nuclear
charge
experienced by each 4f-electrons increases.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Lanthanoid contraction – The atomic and ionic radii of
lanthanoids shows gradual decrease with increase in
atomic number. It is known as lanthanoid contraction.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.13 Applications :
 The inside surface of a television tube or computer monitor is coated
with tiny patches of three different lanthanoid compositions to give
three colors that make the color image.
Example- mixed oxide of Europium and Yttrium
(Eu,Y)2O3 releases an intense red color.
 The optoelectronics application uses of lanthanoid
ions are active ions in
luminescent materials.
Example- Nd: YAG laser (Nd: YAG = Neodymium
doped Yttrium
aluminium garnet).
 Erbium-doped fibre amplifiers are significant devices in the
optical fibre communication systems.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.14
Actinoids :
 The last row of elements in the periodic table is the actinoid series.

 It begins with Thorium (Z =72) and ends with Lawrencium (Z=103).

 Most of these elements are not found in nature.

 They are all radioactive and man-made ( synthetic/artificial) .

 These elements have high densities (nearly 15-20 g cm-3).

 High melting points (nearly 1000 o c) and high boiling points (nearly
3000 o c).

 Actinoids are less reactive than lanthanoids.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Example - they react with hot, but not cold water
to give the hydroxide and hydrogen gas.

 Unlike lanthanoids, they exhibit a range of

oxidation numbers in
their compounds which varies from +2 to +8.

The series of elements from Thorium (Z=90)

to
Lawrencium (Z=103) on which 5f-orbitals
are progressively filled are called
Actinoids.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Table 8.14 Electronic
configuration
 The general valence :
shell electronic configuration of

[Rn] 5f 0−14 6d0−2 7s2 Electronic configuration

Actinoids is
Atomic *Atomic *Ionic radii
Element Symbol number ground radii, pm
+3 oxidation state (Ac3 ), pm
state
Actinium Ac 89 [Rn]5f 5f 0 203 126
0
6d 7s
1 2

Thorium Th 90 [Rn]5f 5f 1 180 -

0
6d 7s
2 2

Protactinium Pa 91 [Rn]5f 5f 2 162 118

2
6d 7s
1 2

Uranium U 92 [Rn]5f 5f 3 153 118

3
6d 7s
1 2

Neptunium Np 93 [Rn]5f 5f 4 150 116

4
6d 7s
1 2

Plutonium Pu 94 [Rn]5f 5f 5 162 115

6
6d 7s
0 2

Americium Am 95 [Rn]5f 5f 6 173 114

7
6d07s2
Curium Cm 96 [Rn]5f 5f 7 174 112
7
6d 7s
1 2

Berkelium Bk 97 [Rn]5f 5f 8 170 110

9
6d 7s
0 2

Californium Cf 98 [Rn]5f 5f 9 186 109

10
6d 7s Shikshan Sanstha , Kolhapur
0 2
Shri Swami Vivekanand
8.15 Properties of
actinoids : silvery white in color.
 They appear
 These are highly reactive radioactive elements.
 They experience decrease in the atomic and ionic radii from
Actinium (Ac) to Lawrencium (Lw) known as Actinoid
contraction.
 They usually exhibit +3 oxidation state. Elements of first half of the
series usually exhibit higher oxidation states.
Actinoid contraction – The
6 atomic and ionic radii of
5
4 Actinoids shows gradual
Oxidation
numbers

3
2
1
decrease with increase in
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
atomic number. It is known as
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.16 Applications of
actinoids :

Th(IV) oxide, ThO2 with 1% CeO2 was used as a major

source of

indoor lighting before incandescent lamps came into

existence only because these oxides convert heat energy

from burning natural gas to an intense light.

 Even today, there is a great demand for these lights

for outdoor camping.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Similarities and differences between lanthanides and
actinoids :
Similarities Differences
Both the series show a +3 oxidation state Lanthanoids show a maximum oxidation
state of
+4 while actinoids show oxidation states
of +3,
+4, +5, +6 and +7
In both the series, the f-orbitals are Lanthanoids do not form complexes
filled easily. Actinoids have a greater
gradually tendency to form complexes with
ligands such as thio-ethers
Ionic radius of the elements in both All lanthanoids are non-radioactive
series decreases with an increase in except promethium but actinides are
atomic number radioactive in nature.
The electronegativity of all the Lanthanoids do not form oxocations,
elements in both the series is low and but actinides form oxocations su2ch as
are said to be highly reactive UO+, PuO+, NpO+
The nitrates, perchlorates and Shri
sulphates Most
Swami Vivekanand Shikshan of, Kolhapur
Sanstha the lanthanoids are colorless in
 Table 8.15 Some comparison between Pre-Transition, Lanthanoids & Transition
Metals :
Pre-Transition Metals Lanthanoids Transition Metals
Essentially in (+3)
Essentially monovalent - oxidation state (+2/+4 Show variable oxidation
show group (n+) for certain states
oxidation state configurations)
Periodic trends dominated
by effective nuclear charge Lanthanoid contraction of Ln3 Size changes of Mn,
at noble gas configuration less marked
Similar properties for a Substantial changes in
Similar properties
given properties
group
Always 'hard' (O, X, N heavier metals (increasingly
Always 'hard' (O, X, N
donors, preferably from Fe-Cu) may show a
donors, preferably
negatively charged) 'soft' character
negatively charged)
No ligand field effects Insignificant ligand field effects Substantial ligand field effects
Coordination
Poor coordination High coordination numbers (C.N.
properties(C.N. determined by size) number 6 is typical
determined by size) maximum (many
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
exceptions)
 8.17 Postactinoid
elements :
 The elements with atomic number greater than 92 (after Uranium) are
called
‘Transuranium elements. Example – Np ( Z=93), Pu (Z=94)

 Elements from atomic number 93 to 103 now are included in actinoid

series and those from 104 to 118 are called as postactinoid elements.

 Example – Rf(Z= 104) , Bh( Z =107)

The postactinoid elements are transition elements.

They are included as post actinoids because similar to actinoid elements,
they can be synthesized in the nuclear reactions.
 is difficult to study their chemistry owing their short half life.
 Previously asked Questions in HSC Board
Examination
• Feb.2020
Marks
Q.1) During oxidation of ferrous sulphate using mixture of dil.H2SO4and
potassium dichromate; oxidation state of chromium changes from (1
)
a) +6 to +2 b) +6 to +3 c) +6 to +1 d)
+6 to +4
(1
2) What is electrometallurgy ? )
3) Write name and chemical formula of one ore of zinc. (1
)
4) What is action of acidified potassium dichromate on
a) KI b) H2S (2)
following:
3) Write general electronic configuration of lanthanides. Why are (3
)
most of the compounds of transition metals are colored?
•
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
• July 2019 Mark
1) Distinguish between lanthanides and actinides. s
2) Write note on lanthanoid contraction. Write two uses of (2)
KMnO4. (3)
Feb.2019
Q.1) Oxidation states of scandium are---- (1)
a) +1, +2 b) +1, +3 c) +2, +3 d) +3, +4
2) How is potassium dichromate prepared from chrome iron ore? (4
)
3) Explain the position of actinoid in periodic table . Calculate
the magnetic
moment of divalent ion in aqueous solution if its atomic number
(Z)= 24. (3)

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

Deleted and non-evaluative portion due to COVID 19 for HSC
examination
Feb./Mar. 2020-21
Sr. Pag Deleted non-evaluative portion
No. e
No
1 165 8.1.1 General introduction
2 169 Table 8.5 Atomic properties of first Transition series
3 170 Table 8.6 Ionization enthalpy of first Transition
series, Remember
4 175 8.7 Compound of Mn and Cr
5 177 1. Metallurgy
2. Extraction of iron from hematite ore using blast
furnace
6 184 Table 8.12 Ionization Enthalpy of Lanthanoids,
Problem
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
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ोल्हा .
ा ा र अभ्
ा
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