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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 Elements
8.1 Introduction :-
❖ 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
Cerium to Lutetium]
iv) 6d series – from Actinium (Z= 89) to Curium (Z = 112) [ Without those from
Thorium to Lawrentium]
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.2 Position in periodic table
❖ Transition elements are placed at the centre of periodic table in 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 elements

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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 is [Ar] 3d104s1.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.4 Oxidation states of first transition series
1) Transition 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.
• Mn and Tc show anomalous value of melting point.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6 Trend in atomic properties of first transition series:
8.6.1 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 screening effect of d - electrons.
iii. 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(+)
vi. Ionic radii of transition metals are smaller than ionic radii of representative
elements of same period. Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Note:-Values are not expected from students , only trends are expected.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.6.2 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 higher ionization
enthalpy than the second and first transition series.
8. This is due to poor shielding effect of 4f-orbital.Therefore valence electron
experience more nuclear attraction.
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 small magnetic moment due to spin angular moment
and orbital angular moment.
*In case. of first transition series elements contribution from angular moment is
neglected.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
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

No. of unpaired electron (n) = 5

μ= 5 5+2 = 5.92 𝐵𝑀
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 and observed colour of compound corresponds to
complementary colour of absorbed light.
Shri Swami Vivekanand Shikshan 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
1) Presence of unpaired d- electron
2) d-d transition
3) Nature of ligands attached to the metal ion
4) Geometry of complex
*Colour also arise due to charge transfer.
Example- MnO4(-) has intense purple colour.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 • Examples
8.6.6 Catalytic properties : Catalyst
Sr. Uses
1) Transition metals and their No
compounds exhibit good catalytic 1 MnO2 Decomposition of KClO3
properties because they have 2 Mo/Fe Manufacture of NH3 by Haber’s
ability to participate in different process.
oxidation – reduction steps of 3 Co-Th Synthesis of gasoline in Fischer
alloy Tropsch Process.
catalytic properties.
2) They acts as homogeneous and 4 Ni Hydrogenation of ethene to ethane.
Hydrogenation of oils into fats
heterogeneous catalysts. (margarine production)
3) In homogeneous catalysis 5 Fe-Cr Formation of CO2 and H2 from
reaction , metal ions form unstable carbon monoxide and steam.
intermediates.
6 Platinised Production of H2SO4 by contact
4) In heterogeneous catalysis reactions asbestos process.
metal provides surface for reactants to
react.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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 electricity. Uses:-
1) Tungsten carbide --
2) They are hard. Cutting tool
3) Their chemical properties are similar to parent metal. 1) Iron carbide --
Manufacture of steel
4) Their melting point is higher than pure metal .
5) Densities are less than parent metal.
6) Metal carbides are chemically inert and extremely hard as diamond.
7) Hydrides of transition metals are used as powerful reducing agents.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.6.8 Formation of alloys: • Uses of alloys:-

1) Transition metal forms alloy. Alloy Uses

2) In alloy atoms of one metal Bronze Making statues, medals and trophies.
distributed randomly in the lattice An alloy of
(Cu+Sn)
of another metal.
3) Metals with similar radii and Cupra nickel Making machinery parts of marine
similar properties readily form An alloy of ships boats like marine condenser
(Cu +Ni) tubes.
alloys.
4) There are two types of alloys - Stainless steel Construction of outer fuselage of ultra
i) Ferrous alloy- Atoms of their An alloy of high speed air craft.
(Fe + C)
elements distributed randomly in
iron. Nichrome Making gas turbine engines.
Example - steel, chromium steel, An alloy of
(Ni +Cr)
stainless steel
ii) Non ferrous alloy - Alloy Titanium alloy In ultra high speed flight fire proof
An alloy of bulkheads (barrier between two
formed by mixing atoms of transition (Ti + V + Al) compartments) & exhaust shrouds
metals other than iron. ( protective covering).
Example – Brass ( Cu+ Zn)
 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:
i) Oxidation of I Θ to iodate IO3 Θ :-

ii) Oxidation of thiosulphate( S2O32Θ )to sulphate(SO42Θ) :-

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 for elements of first row is +7 and in second and third
row is +8 as in OsO4 and RuO4.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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

8.9.1 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 aqueous solution of
their salts using suitable reducing agent is called hydrometallurgy.
c. Electrometallurgy : A process in which metal is extracted by electrolytic reduction of
molten (fused) metallic compound is called electrometallurgy.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
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 coke
Iron Ore Crushing and
Grinding Reduction by CO
Reduction by heat
Concentration Reduction Reduction by Al
Reduction by
Magnetic Gravity Leaching Froth electrolysis
Separation Separation flotation Refining Pure Iron

Liquification Distillation Oxidation Electro-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 principle where the charge comes down.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 Blast Furnace

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

Reactions in the blast furnace :
There are 3 temperature zones in the furnace.
1. 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
given in flow chart.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
Commercial forms of Iron:
Iron

Cast Wrought Steel

Differences between cast iron, wrought iron and steel:
Cast iron Wrought iron Steel
1. Hard and brittle 1. Very soft 1. Neither too hard nor too
soft.
2. Contains 4% carbon. 2.Contains less than 0.2% 2. Contains 0.2 to 2%
carbon carbon
3. Used for making pipes, 3. Used for making pipes, 3. Used in buildings
manufacturing automotive bars for stay bolts, engine infrastructure, tools, ships,
parts, pots, pans and bolts and rivets. automobiles, weapons etc.
utensils.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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 by gradual filling of 4f and actinides by 5f-orbitals.
❖There are 14 elements filling the f-orbital in each series.

Shri Swami Vivekanand Shikshan Sanstha , Kolhapur

 8.11 Properties of f-block elements :
1) Properties of f-block elements are similar to d-block elements.
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).
1) 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.
16) In +3 oxidation state many of the lanthanoids are colored.
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).
❖ The lanthanoids are strongly paramagnetic.
❖ They becomes ferromagnetic at much lower temperatures.
❖ Magnetic and optical properties are largely independent of environment (similar
spectra in gas/solution/solid). Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 ❖Table 8.11 Electronic Configuration, atomic & ionic radii of lanthanoids
Observe
Expected (+2 (+3 Ionic radii
Atomic d
(ground oxidation oxidation Atomic radii, (Ln+3,
Element Symbol numbe (ground
state) state) state) pm 6-coordinate), pm
r state)
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
2
Praseodymium Pr 59 [Xe]4f 36s2 [Xe]4f 36s2 4f 4f 2 182 99
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
7 2 7 2 6
Europium Eu 63 [Xe]4f 6s [Xe]4f 6s 4f 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 106s2 [Xe]4f 106s2 4f 9 176 91.2
10
Holmium Ho 67 [Xe]4f 116s2 [Xe]4f 116s2 4f 10 4f 175 90.1
12 2 12 2
Erbium Er 68 [Xe]4f 6s [Xe]4f 6s 174 89
Thulium Tm 69 [Xe]4f 136s2 [Xe]4f 136s2 4f 12 4f 12 173 88
Ytterbium Yb 70 [Xe]4f 146s2 [Xe]4f 146s2 4f 13 86.8
Lutetium Lu 71 [Xe]4f 145d16s2 [Xe]4f 145d16s2 4f 14 86.1
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.12.1 Electronic Configuration:

❖ The general valence shell electronic configuration of lanthanoids is

[Xe] 4f 0−14 5d0−2 6s 2
❖ 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 number
across a given inner transition series.
Lanthanoid IE1 IE2 IE3
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 Values are not expected
Sm 543.0 1068 2260
Eu 547.0 1085 2400 from students . Only trends
Gd 592.0 1170 1990
Tb 564.0 1112 2110 are expected.
Dy 572.0 1126 2200
Ho 581.0 1139 2200
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.

❖ They are formed in case of f 0, f 7, f 14 configurations of resulting ions.

Example : Ce 4(f 0) , Eu2 and Tb4 (f 7) ; Yb 2 (f 14)

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.
❖ The color of ions having n f-electrons is about the same as those having
(14 – n) f-electrons .
Number of No. of
Ln
electrons in f - color f-electrons
ion
orbital
(14 -n)
Pr3 4f 2 green f-electrons
=14-2 =12
4f 12 n f-electrons
Tm3 green
=12
(14 -n)
Nd3 4f 3 Pink f-electrons
=14-3 =11
4f 11 nf-electrons
Er3 Pink
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur =11
 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.
❖As a result, the whole of 4f-electron shell contracts at each successive
element.
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.
❖Lanthanoids are used in hybrid cars, superconductors and permanent magnets.
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 Actinoids is
[Rn] 5f 0−14 6d0−2 7s2
Atomic Electronic configuration *Atomic *Ionic radii
Element Symbol number ground state +3 oxidation state radii, pm (Ac3 ), pm
Actinium Ac 89 [Rn]5f 06d17s2 5f 0 203 126
Thorium Th 90 [Rn]5f 06d27s2 5f 1 180 -
Protactinium Pa 91 [Rn]5f 26d17s2 5f 2 162 118
Uranium U 92 [Rn]5f 36d17s2 5f 3 153 118
Neptunium Np 93 [Rn]5f 46d17s2 5f 4 150 116
Plutonium Pu 94 [Rn]5f 66d07s2 5f 5 162 115
Americium Am 95 [Rn]5f 76d07s2 5f 6 173 114
Curium Cm 96 [Rn]5f 76d17s2 5f 7 174 112
9 0 2
Berkelium Bk 97 [Rn]5f 6d 7s 5f 8 170 110
Californium Cf 98 [Rn]5f 106d07s2 5f 9 186 109
Einsteinium Es 99 [Rn]5f 116d07s2 186 98
5f 10
Fermium Fm 100 [Rn]5f 126d07s2 198 91
5f 11

Mendelevium Md 101 [Rn]5f 136d07s2 194 90

5f 12
Nobelium No 102 [Rn]5f146d07s2 197 95
5f 13
Lawrencium Lr 103 [Rn]5f 146d17s2 171 88
5f 14
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 8.15 Properties of actinoids :
❖They appear silvery white in color.
❖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 atomic

Oxidation numbers

6 and ionic radii of Actinoids shows

5
4 gradual decrease with increase in
3
2
1
atomic number. It is known as
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Actinoid contraction.
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 filled Lanthanoids do not form complexes easily.
gradually Actinoids have a greater tendency to form
complexes with ligands such as thio-ethers
Ionic radius of the elements in both series All lanthanoids are non-radioactive except
decreases with an increase in atomic number promethium but actinides are radioactive in
nature.
The electronegativity of all the elements in Lanthanoids do not form oxocations, but
both the series is low and are said to be highly actinides form oxocations such
2
as UO+, PuO+,
reactive NpO+
The nitrates, perchlorates and sulphates of all Most of the lanthanoids are colorless in nature
the elements are soluble while the hydroxides, whereas the actinoids are colored ions
fluorides and carbonates are insoluble
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 Table 8.15 Some comparison between Pre-Transition, Lanthanoids & Transition Metals :
Pre-Transition Metals Lanthanoids Transition Metals
Essentially in (+3) oxidation
Essentially monovalent - show state (+2/+4 for certain Show variable oxidation states
group (n+) oxidation state configurations)
Periodic trends dominated by
effective nuclear charge at noble Lanthanoid contraction of Ln3 Size changes of Mn, less
gas configuration marked
Similar properties for a given Substantial changes in
Similar properties
group properties
Always 'hard' (O, X, N donors, heavier metals (increasingly from
Always 'hard' (O, X, N donors,
preferably negatively Fe-Cu) may show a 'soft'
preferably negatively charged)
charged) character
No ligand field effects Insignificant ligand field effects Substantial ligand field effects
Coordination number 6
Poor coordination properties(C.N. High coordination numbers (C.N.
is typical maximum (many
determined by size) determined by size)
exceptions)
Fixed geometries (ligand field
Flexibility in geometry Flexibility in geometry effects)
No magnetism Show magnetism Show magnetism
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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.
Example- element (Z=112) has a half-life of only 2.8 x 10-4 seconds.
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
 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
2) What is electrometallurgy ? (1)
3) Write name and chemical formula of one ore of zinc. (1)
4) What is action of acidified potassium dichromate on following:
a) KI b) H2S (2)
3) Write general electronic configuration of lanthanides. Why are most of the (3)
compounds of transition metals are colored?
•
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
• July 2019 Marks
Q.1) Distinguish between lanthanides and actinides. (2)
Q.2) Write note on lanthanoid contraction. Write two uses of KMnO4. (3)

Feb.2019
Q.1) Oxidation states of scandium are---- (1)
a) +1, +2 b) +1, +3 c) +2, +3 d) +3, +4
Q.2) How is potassium dichromate prepared from chrome iron ore? (4)
Q.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. Page Deleted non-evaluative portion

No. 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 8.9.1 Metallurgy
8.9.2 Extraction of iron from hematite ore using blast furnace

6 184 Table 8.12 Ionization Enthalpy of Lanthanoids, Problem

7 186 Table 8.13 Effective magnetic moments of Lanthanoids
Shri Swami Vivekanand Shikshan Sanstha , Kolhapur
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