8.

TRANSITION AND INNER TRANSITION ELEMENTS

8.2 Position in the periodic table

Do you know ?
In which block of the modern The transition elements are placed in
perodic table are the transition and the periods 4 to 7 and groups 3 to 12 those
inner transition elements placed ? constitute 3d, 4d, 5d and 6d series (Fig.8.1).
8.1 Introduction They are placed at the centre with
The transition elements belong to s block on one side and p on the other. The
d block of the periodic table. As per IUPAC electropositivity, reactivity and other properties
convention the transition metal atom has an show a gradual change from s block to p block
incomplete d-subshell or it give cations with through those of the d block elements.
incomplete d subshell. They exhibit properties 8.3 Electronic configuration
between those of s and p block elements. The
The 3d series begins with Sc (Z = 21) and
transition elements of the modern periodic
ends with Zn (Z=30). Argon, Ar is the noble
table appear as groups 3 to 12 or as four long
gas preceding the 3d series and its electronic
periods. The (n-1) d-orbital is comprised of
configuration is 1s2 2s2 2p6 3s2 3p6. Calcium
successively filled in each element, where ‘n’
(Z = 20) belonging to ‘s’ block of 4th period
is the ultimate or valence shell. The 3d series is
has electronic configuration 1s2 2s2 2p6 3s2 3p6
comprised of elements from scandium (Z=21)
4s2. Hence 21st electron in scandium (Z = 21)
to zinc (Z=30), 4d series has elements from
enters in the available 3d orbital. Electronic
yttrium (Z=39) to cadmium (Z=48), 5d series
configuration of Sc is written as 1s2 2s2 2p6 3s2
from lanthanum (Z=57) to mercury (Z=80)
3p6 3d1 4s2 or also can be represented as [Ar]
without those from cerium to lutecium, and
3d1 4s2.
6d series has actinium to copernicium without
those from thorium to lawrentium. The general
electronic configuration of transition elements
is (n-1)d1-10 ns1-2.
Table 8.1 Shows the four transition series elements
Group
3 4 5 6 7 8 9 10 11 12
d series

3d Sc(21) Ti(22) V(23) Cr(24) Mn(25) Fe(26) Co(27) Ni(28) Cu(29) Zn(30)

4d Y(39) Zr(40) Nb(41) Mo(42) Tc(43) Ru(44) Rh(45) Pd(46) Ag(47) Cd(48)

5d La(57) Hf(72) Ta(73) W(74) Re(75) Os(76) Ir(77) Pt(78) Au(79) Hg(80)

6d Ac(89) Rf(104) Db(105) Sg(106) Bh(107) Hs(108) Mt(109) Ds(110) Rg(111) Cn(112)

165
 s - block p - block
1 18
1
2 13 14 15 16 17
2
d - block
3 3 4 5 6 7 8 9 10 11 12
4
5

Series
and
f - block

Fig. 8.1 Position of d-block elements in the modern periodic table

The electronic configuration of the 8.3.1 Electronic configuration of chromium

elements of 3d series is given in Table 8.2. and copper

Since zinc has completely filled Table 8.2 indicates that the expected
(n - 1)d orbital in the ground state (3d10,4s2) electronic configuration of chromium (Z = 24)
and (3d10) in its common oxidation state +2, differs from the observed configuration.
it is not regarded as transition element. On the This can be explained on the basis of
same ground, cadmium and mercury from 4d the concept of additional stability associated
and 5d series are not considered as transition with the completely filled and half filled
elements. Copper in the elementary state (3d10 subshells.
4s1) contains filled 3d orbitals but in the +2 Remember...
oxidation state it has partly filled 3d orbital
Any subshell having a half filled
(3d9), hence copper is a transition element.
or completely filled electronic
General electronic configuration of configuration has extra stability.
four series of d-block elements of periodic
table can be represented as given below: The general electronic configuration
of the elements of the 3d series is 3d1-10 4s2
i. 3d series : [Ar] 3d1-10 4s2
with the exceptions of Cr and Cu. The 3d and
ii. 4d series : [Kr] 4d1-10 5s0-2 4s orbitals are close in energy and in order to
iii. 5d series : [Xe] 4f14(except La) 5d1-10 6s2 gain extra stability the last electron instead of
occupying 4s orbital occupies the 3d orbital
iv. 6d series : [Rn] 5f14(except Ac) 6d1-10 7s2 that assigns Cr the 3d5, 4s1 and Cu 3d10, 4s1
configuration.

166
 Table 8.2 Electronic configuration of 3d series of d-block elements

Elements Symbol At. No. Expected electronic Observed electronic

configuration configuration
Scandium Sc 21 [Ar] 3d1 4s2 [Ar] 3d1 4s2
Titanium Ti 22 [Ar] 3d2 4s2 [Ar] 3d2 4s2
Vanadium V 23 [Ar] 3d3 4s2 [Ar] 3d3 4s2
Chromium Cr 24 [Ar] 3d4 4s2 [Ar] 3d5 4s1
Manganese Mn 25 [Ar] 3d5 4s2 [Ar] 3d5 4s2
Iron Fe 26 [Ar] 3d6 4s2 [Ar] 3d6 4s2
Cobalt Co 27 [Ar] 3d7 4s2 [Ar] 3d7 4s2
Nickel Ni 28 [Ar] 3d8 4s2 [Ar] 3d8 4s2
Copper Cu 29 [Ar] 3d9 4s2 [Ar] 3d10 4s1
Zinc Zn 30 [Ar] 3d10 4s2 [Ar] 3d10 4s2

Use your brain power

Fill in the blanks with correct outer electronic configurations.

2nd series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
valence 4d15s2 4d25s2 4d45s1 4d65s1 4d85s1 4d105s0 4d105s2
shell
electronic
configuration
3rd series
La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
valence shell 5d 6s2
1
5d 6s2
3
5d 6s2
4
5d66s2 5d 6s2
7
5d 6s1
9
5d106s2
electronic
configuration
4th series
Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
Z 89 104 105 106 107 108 109 110 111 112
valence shell 6d 7s2
1
6d27s2 6d47s2 6d57s2 6d67s2 6d77s2 6d87s2 6d107s2
electronic
configuration

Table 8.3: Oxidation states of first transition series elements

Elements Outer Oxidation states Elements Outer Oxidation states

electronic electronic
configuration configuration
Sc 3d1 4s2 +1, +2, +3 Fe 3d6 4s2 +2, +3, +4, +5, +6
Ti 3d2 4s2 +2, +3, +4 Co 3d7 4s2 +2, +3, +4, +5
V 3d3 4s2 +2, +3, +4, +5 Ni 3d10 4s2 +2, +3, +4
Cr 3d5 4s1 +2, +3, +4, +5, +6 Cu 3d10 4s1 +1, +2
Mn 3d5 4s2 +2, +3, +4, +5, +6, +7 Zn 3d10 4s2 +2

167
Remember... From Table 8.3 it is clear that as the number
of unpaired electrons in 3d orbitals increases,
Electronic configuration of Cr
the number of oxidation states shown by the
is [Ar] 3d5 4s1 and
element also increases. Scandium has only
Cu is : [Ar]3d10, 4s1. one unpaird electron. It shows three oxidation
8.4 Oxidation states of first transition states while manganese with 5 unpaired d
series electrons shows six different oxidation states.
The elements which give the greatest
One of the notable features of transition number of oxidation states occur in or near the
elements is the great variety of oxidation states middle of the series. Manganese, for example,
they show in their compounds. Table 8.3 lists shows oxidation states from +2 to +7.
the common oxidation states of the first row 8.5 Physical properties of first transition
transition elements. series : All transition elements are metals
and show properties that are characteristic of
Can you tell ?
metals. They are hard, lustrous, malleable,
Which of the first transition series ductile and form alloys with other metals. They
elements shows the maximum are good conductors of heat and electricity.
number of oxidation states and why? Except Zn, Cd, Hg and Mn, all the other
Which elements in the 4d and 5d series will transition elements have one or more typical
show maximum number of oxidation states? metallic structures at ambient temperature.
These transition metals (with the exception
Loss of 4s and 3d electrons progressively of Zn, Cd and Hg) are very hard and have
leads to formation of ions. The transition low volatility. They possess high melting and
elements display a variety of oxidation states boiling points.
in their compounds. Loss of one 4s electron
leads to the formation of M⊕ ion, loss of two
4s electrons gives a M2⊕ ion while loss of
unpaired 3d and 4s electrons gives M3⊕, M4⊕
ions and so on. Some examples are as shown
in Table 8.4

Try this...
Write the electronic configuration
of Mn6⊕, Mn4⊕, Fe4⊕, Co5⊕, Ni2⊕
Fig. 8.2 : Trends in melting points of transition
elements

Table 8.4: Electronic configuration of various ions of 3d elements

Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic no : 21 22 23 24 25 26 27 28 29 30
Valence shell Electronic Configuration
Species
M 3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s2 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2
M⊕ 3d1 4s1 3d2 4s1 3d3 4s1 3d5 3d5 4s1 3d6 4s1 3d7 4s1 3d8 4s1 3d10 4s0 3d10 4s1
M2⊕ 3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9 3d10
M3⊕ [Ar] 3d1 3d2 3d3 3d4 3d5 3d6 3d7 - -

168
8.6 Trends in atomic properties of the first

atomic radii in nm
transition series
8.6.1 Atomic and ionic radii
Atomic radii of the elements of the
transition series decrease gradually from left
to right (Fig. 8.3 and Table 8.5). As we move
across a transition series from left to right the
nuclear charge increases by one unit at a time.
The last filled electron enters a penultimate
Fig. 8.3 : Trends in atomic radii of d block
(n-1)d subshell. However, d orbitals in an elements
atom are less penetrating or more diffused and,
therefore d electrons offer smaller screening Ionic radii of transition elements show
effect. The result is that effective nuclear the same trend as of the atomic radii (Table
charge also increases as the atomic number 8.5)
increases along a transition series. Hence The elements of first transition series
the atomic radii decrease gradually across a show variable oxidation states. The trends
transition series from left to right. in ionic radii, thus, can be studied with (i)
The explanation for the minor variation elements having same oxidation state or (ii)
in atomic radii within a particular transition considering various oxidation states of the
series is out of the scope of this textbook. same element.
(i) For the same oxidation state, with an
increase in nuclear charge a gradual decrease
in ionic radii was observed. The trend is
pronounced for the divalent ions of the first
transition series (Cr2⊕ - 82 pm, Cu2⊕ - 73 pm).

Table 8.5 Atomic properties of first transition series elements

Element Atomic Density Atomic/ionic radius (pm) Ionisation
(M) number (g/cm3) M M2⊕ M3⊕ enthalpy (kJ/mol)
(Z)
Sc 21 3.43 164 - 73 631
Ti 22 4.1 147 - 67 656
V 23 6.07 135 79 64 650
Cr 24 7.19 129 82 62 653
Mn 25 7.21 127 82 65 717
Fe 26 7.8 126 77 65 762
Co 27 8.7 125 74 61 758
Ni 28 8.9 125 70 60 736
Cu 29 8.9 128 73 - 745
Zn 30 7.1 137 75 - 906

169
(ii) The oxidation states of the same element The atoms of elements of third
shows difference of one unit such as M⊕, M2⊕, transition series possess filled 4f- orbitals. 4f
M3⊕, M4⊕ and so on. With higher oxidation state orbitals show poor shielding effect on account
the effective nuclear charge also increases and of their peculiar diffused shape. As a result,
hence, decrease ionic radii can be observed the valence electrons experience greater
from M2⊕ to M3⊕ (Table 8.5). Ionic radii of nuclear attraction. A greater amount of energy
transition elements are smaller than ionic radii is required to ionize elements of the third
of representative elements of the same period. transition series. The ionization enthalpies of
8.6.2 Ionization Enthalpy : The ionization the elements of the third transition series are,
enthalpies of transition elements are therefore much higher than the first and second
intermediate between those of s-block and series (Fig.8.4).
p-block elements. This suggests that transition 8.6.3 Metallic character : Low ionisation
elements are less electropositive than elements enthalpies and vacant d orbitals in the
of group 1 and 2. Depending on the conditions, outermost shell are responsible for the metallic
they form ionic or covalent bonds. Generally in character of the transition elements. These
the lower oxidation states these elements form favour the formation of metallic bonds and
ionic compounds while in the higher oxidation thus these elements show typical metallic
states they form covalent compounds. properties. The hard nature of these elements
Ionization enthalpies shown in suggests the formation of covalent bonds in
Table 8.6 reveal that for a given element there them. This is possible due to the presence of
is substantial increase from the first ionization unpaired (n-1)d electrons in these elements.
enthalpy IE1 to the third ionization enthalpy
Nearly all transition metals have simple
IE3.
hexagonal closed packed (hcp), cubic closed
As we move across the transition series, packed (ccp) or body centered cubic (bcc)
slight variation is observed in the successive lattices which are characteristic of true
enthalpies IE1, IE2, IE3 of these elements (Table metals (You have learnt more about this in
8.6). Chapter 1).

Remember...
Hardness, high melting points
and metallic properties of the
transition elements indicate that the
metal atoms are held strongly by metallic
bonds with covalent character.

Fig. 8. 4: Trends in first ionisation enthalpies of

d block elements
Table 8.6 Ionisation enthalpies of first transition series elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
IE
IE1 632 659 650 652 717 762 756 736 744 906
IE2 1245 1320 1376 1635 1513 1563 1647 1756 1961 1736
IE3 2450 2721 2873 2994 3258 2963 3237 3400 3560 3838
(IE = Ionisation Enthalpy in kJ/mol)
170
 In all the transition series the melting Each unpaired electron gives rise to a
points steadily increase upto d5 configuration. small magnetic field (magnetic moment) due
Cr, Mo and W show highest melting points to its spin angular momentum and orbital
in their respective series. Mn and Tc display angular momentum. In case of the first row
anomalous values of melting points. After this transition elements, the contribution from
with increasing atomic number the melting the orbital angular momentum is quenched
point decreases regularly. and hence, can be neglected. The spin-only
8.6.4 Magnetic Properties : formula for magnetic moment is :
Can you recall ? m = n(n + 2) BM
1. What happens when magnetic where n is the number of unpaired
field is applied to substances ? electrons and m is the magnetic moment
2. What is meant by the terms expressed in Bohr Magneton (BM). A single
paramagnetism and diamagnetism ? unpaired electron has magnetic moment
m = 1.73 BM.
The compounds of transition metals
exhibit magnetic properties due to the unpaired From the magnetic moment (m)
electrons present in their atoms or ions. When measurements of the metal complexes of the
a magnetic field is applied, substances which first row transition elements, the number of
are attracted towards the applied magnetic unpaired electrons can be calculated, with the
field are called paramagnetic, while the ones use of spin-only formula. As magnetic moment
which are repelled are called diamagnetic. is directly related to number of unpaired
electrons, value of m will vary directly with
Some substances are attracted very the number of unpaired electrons.
strongly and these are called ferromagnetic
substances. Try this...
What will be the magnetic
Remember... moment of transition metal having
Paramagnetism and 3 unpaired electrons ?
ferromagnetism arises due to a. equal to 1.73 BM,
presence of unpaired electrons in a species. b. less than 1.73 BM
When all electron spins are paired, the c. more than 1.73 BM
compound becomes diamagnetic.
Magnetic moments are determined
Among transition metals Fe, Co, Ni experimentally in solution or in solid state
are ferromagnetic. When magnetic field is where the central metal is hydrated or bound
applied externally all the unpaired electrons in to ligands. A slight difference in the calculated
these metals and their compounds align in the and observed values of magnetic moments
direction of the applied magnetic field. Due to thus can be noticed.
this the magnetic susceptibility is enhanced.
These metals can be magnetized, that is, they Use your brain power
acquire permanent magnetic moment. A metal ion from the first transition
series has two unpaired electrons.
Try this... Calculate the magnetic moment.
Pick up the paramagnetic species Table 8.7 gives the calculated and
Cu1⊕, Fe3⊕, Ni2⊕, Zn2⊕, Cd2⊕, Pd2⊕. observed magnetic moments of cations of 3d
series.

171
 Table 8.7 Magnetic moments of ions of first transition series elements (values in BM)
Ion Outer electronic Number of Calculated value Experimental
configuration unpaired of magnetic value
electrons moment
Sc3⊕ 3d0 0 0 0
Ti3⊕ 3d1 1 1.73 1.75
V3⊕ 3d2 2 2.84 2.76
Cr3⊕ 3d3 3 3.87 3.86
Cr2⊕ 3d4 4 4.90 4.80
Mn2⊕ 3d5 5 5.92 5.96
Fe2⊕ 3d6 4 4.90 5.3-5.5
Co2⊕ 3d7 3 3.87 4.4-5.2
Ni2⊕ 3d8 2 2.84 2.9-3.0, 4.0
Cu2⊕ 3d9 1 1.73 1.8-2.2
Zn2⊕ 3d10 0 0 0

Problem : Calculate the spin only magnetic Can you tell ?

moment of divalent cation of a transition Compounds of s and p block
metal with atomic number 25. elements are almost white. What
Solution : For element with atomic number could be the absorbed radiation : uv or
25, electronic configuration for its divalent visible ?
cation will be The ionic and covalent compounds
3d 4s formed by the transition elements are coloured.
[Ar] Transition elements contain unpaired electrons
in their d orbitals. When the atoms are free or
There are 5 unpaired electrons, so n = 5.
isolated, the five d orbitals are degenerate;
∴ m = 5(5 + 2) = 5.92 BM or have the same energy. In complexes, the
metal ion is surrounded by solvent molecules
Try this... or ligands. The surrounding molecules affect
the energy of d orbitals and their energies are
Calculate the spin only
no longer the same [You will learn more about
magnetic moment of divalent cation
this in Chapter 9]. As the principal quantum
of element having atomic number 27.
number of ‘d’ orbitals is the same, the amount
In second and third transition series, of energy required for transition of electron
orbital angular moment is significant. from one d orbital to another is quite small.
Therefore, the simple spin only formula is not The small energy required for this transition
useful and more complicated equations have to is available by absorption of radiation
be employed to determine magnetic moments. having certain wavelength from the visible
The magnetic moments further are found to be region. Remaining light is transmitted and the
temperature dependent. observed colour of the compound corresponds
to the complimentary colour of light absorbed.
8.6.5 Colour : A substance appears coloured if
That means, if red light is absorbed then the
it absorbs a portion of visible light. The colour
transmitted light contains excess of other
depends upon the wavelength of absorption in
colours in the spectrum, in particular blue, so
the visible region of electromagnetic radiation.

172
the compound appears blue. The ions having Thus the colour of a transition metal ion
no unpaired electrons are colorless for example relates to the
Cu⊕(3d10); Ti4⊕(3d0). Table 8.8 enlists colours 1. presence of unpaired d electrons
of 3d transition metal ions. 2. d - d transitions
620 nm
3. nature of ligands attached to the metal ion
800 nm 4. geometry of the complex formed by the
580 nm
400 nm red orange metal ion

Do you know ?
violet yellow
Colour of transition metal ions
may arise due to charge transfer. For
blue green
560 nm
example, MnO4 ion has an intense purple
colour in solution. In MnO4 , an electron is
430 nm momentarily transferred from oxygen (O) to
490 nm metal, thus momentarily changing O2 to O
Let us see how colour of the transition and reducing the oxidation state of manganese
metal ion depends upon ligand and geometry from +7 to +6. For charge transfer transition
to take place, the energy levels of the two
of the complex formed by metal ion.
different atoms involved should be fairly close.
When cobalt chloride (Co2⊕) is dissolved Colours of Cr2O72 , CrO4 , Cu2O and Ni-DMG
in water, it forms a pink solution of the (where DMG = dimethyl glyoxime) complex
complex [Co(H2O)6]2⊕ which has octahedral thus can be explained through charge transfer
transitions.
geometry. But when this solution is treated
with concentrated hydrochloric acid, it turns 8.6.6 Catalytic Properties : Transition metals
deep blue. This change is due to the formationand their compounds exhibit good catalytic
of another complex [CoCl4]2 which has a properties. They have proven to be good
tetrahedral structure. homogeneous and heterogeneous catalysts.
partly because of their ability to participate in
[Co(H2O)6]2⊕ + 4Cl [CoCl4]2 + 6H2O different oxidation-reduction steps of catalytic
reactions.
Table 8.8 Colour of 3d transition metal ions
Ion Outer electronic configuration Number of unpaired electrons Colour
Sc 3⊕
3d 0
0 Colourless
Ti3⊕
3d 1
1 Purple
Ti4⊕
3d 0
0 Colourless
V 3⊕
3d 2
2 Green
Cr 3⊕
3d 3
3 violet
Mn2⊕ 3d5 5 Light pink
Mn 3⊕
3d 4
4 Violet
Fe 2⊕
3d 6
4 Pale green
Fe 3⊕
3d 5
5 Yellow
Co 2⊕
3d 7
3 Pink
Ni 2⊕
3d 8
2 Green
Cu 2⊕
3d 9
1 Blue
⊕
Cu 3d 10
0 Colourless
Zn 2⊕
3d 10
0 Colourless

173
 These steps involve changes in the formed are called interstitial compounds.
oxidation states of these metal ions. Sometimes sulphides and oxides are also
Compounds of Fe, Co, Ni, Pd, Pt, Cr, etc. are trapped in the crystal lattice of transition
used as catalysts in a number of reactions. elements. Steel and cast iron are examples of
Their compounds enhance the rate of the interstitial compounds of carbon and iron. Due
chemical reactions. to presence of carbon, the malleability and
ductility of iron is reduced while its tenacity
In homogeneous catalysis reactions, the
increases.
metal ions participate by forming unstable
intermediates. In heterogeneous catalysis Some properties of interstitial compounds
reactions on the other hand, the metal provides i. They are hard and good conductors of heat
a surface for the reactants to react. and electricity.
Examples : ii. Their chemical properties are similar to the
1. MnO2 acts as a catalyst for decomposition parent metal.
of KClO3. iii. Their melting points are higher than the
2. In manufacture of ammonia by Haber’s pure metals.
process Mo/Fe is used as a catalyst. iv. Their densities are less than the parent
3. Co-Th alloy is used in Fischer Tropsch metal.
process in the synthesis of gasoline. v. The metallic carbides are chemically inert
4. Finely divided Ni, formed by reduction of and extremely hard as diamond.
the heated oxide in hydrogen is an extremely vi. Hydrides of transition metals are used as
efficient catalyst in hydrogenation of ethene powerful reducing agents.
to ethane at 140 0C.
H2C = CH2 + H - H
∆
H3C - CH3 Remember...
Ni, 140 0C
• Tungsten carbide is used for
Commercially, hydrogenation with nickel as
cutting tools.
catalyst is used to convert inedible oils into
solid fat for the production of margarine. • Iron carbide is used in manufacture
of steel.
5. In the contact process of industrial
production of sulfuric acid; sulphur dioxide 8.6.8 Formation of Alloys
and oxygen from the air react reversibly
over a solid catalyst of platinised asbestos. Can you recall ?
platinised • What is an alloy ?
2SO2 + O2 2SO3
asbestos
• Do atomic radii of 3d transition
6. Carbon dioxide and hydrogen are
elements differ largely ?
formed by reaction of the carbon monoxide
and steam at about 500 0C with an Fe-Cr Transition metals form alloys where
catalyst. atoms of one metal are distributed randomly
Fe-Cr
CO + H2O CO2 + H2 in the lattice of another metal. The metals with
catalyst
(steam)
similar radii and similar properties readily
form alloys.
8.6.7 Formation of interstitial compounds
Alloys are classified into ferrous and non-
When small atoms like hydrogen, carbon ferrous.
or nitrogen are trapped in the interstitial spaces
within the crystal lattice, the compounds
174
Ferrous alloys have atoms of other elements 3MnO2 + 6KOH + KClO3 ∆
3K2MnO4 +
distributed randomly in atoms of iron in the KCl + 3H2O
mixture. As percentage of iron is more, they
In neutral or acidic medium the green potassium
are termed ferrous alloys eg. nickel steel,
manganate disproportionates to KMnO4 and
chromium steel, stainless steel etc. All steels
MnO2.
have 2% carbon.
3K2MnO4 + 4CO2+ 2H2O 2KMnO4 +
Non-ferrous alloys are formed by mixing
MnO2 + 4KHCO3
atoms of transition metal other than iron with
a non transition element. eg. brass, which is 3MnO42 + 4H⊕ 2MnO4 +
an alloy of copper and zinc. Ferrous and non- MnO2 + 2H2O
ferrous alloys are of industrial importance. The liquid is filtered through glass
Uses of alloys wool or sintered glass and evaporated
until crystallisation occurs. Potassium
• Bronze, an alloy of copper and tin is tough,
permanganate forms small crystals which are
strong and corrosion resistant. It is used for
almost black in appearance.
making statues, medals and trophies.
ii. Electrolytic oxidation
• Cupra-nickel, an alloy of copper and nickel
is used for making machinary parts of In electrolytic oxidation, alkaline solution
marine ships, boats. For example, marine of manganate ion is electrolysed between iron
condenser tubes. electrodes separated by a diaphragm. Overall
reaction is as follows :
• Stainless steels are used in the construction
of the outer fuselage of ultra-high speed air 2K2MnO4 + H2O + [O] 2KMnO4 + 2KOH
craft. The oxygen evolved at the anode converts
• Nichrome an alloy of nickel and chromium manganate to permanganate.
in the ratio 80 : 20 has been developed The solution is filtered and evaporated to
specifically for gas turbine engines. get deep purple black coloured crystals of
• Titanium alloys withstand stress up to KMnO4.
high temperatures and are used for ultra- 8.7.2 Chemical properties of KMnO4 :
high speed flight, fire proof bulkheads and
a. In acidic medium :
exhaust shrouds.
The oxidizing reactions of KMnO4 in acidic
8.7 Compounds of Mn and Cr (KMnO4 and
medium
K2Cr2O7)
i. Oxidation of iodide to iodine :
Remember...
Both KMnO4 and K2Cr2O7 are 2MnO4 + 10 I + 16H⊕ 2Mn2⊕ +
strong oxidising agents. 8H2O + I2
ii. Oxidation of Fe2⊕ to Fe3⊕
8.7.1 Preparation of potassium permaganate
MnO4 + 5Fe2⊕ + 8H⊕ 5Fe3⊕ + Mn2⊕
i. Chemical oxidation
+4H2O
When a finely divided manganese dioxide
iii. Oxidation of H2S
(MnO2) is heated strongly with fused mass
of caustic potash (KOH) and an oxidising H2S 2H⊕ + S2
agent, potassium chlorate (KClO3), dark green 5S2 + 2MnO4 + 16H⊕ 2Mn2⊕ + 5S + 8H2O
potassium manganate, K2MnO4 is formed.

175
iv. Oxidation of oxalic acid : Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
⊕
2MnO4 + 5H2C2O4 + 6H 2Mn + 2⊕
8.7.5 Chemical properties of K2Cr2O7 :
10CO2+ 8H2O
i. Oxidation of I- from aq. solution of KI
b. In neutral or weakly alkaline medium : by acidified K2Cr2O7 gives I2. Potassium
i. Oxidation of iodide I to iodate IO3 . dichromate is reduced to chromic sulphate.
Liberated I2 turns the solution brown.
2MnO4 + H2O + I 2MnO2 + 2OH + IO3
K2Cr2O7 + 6KI + 7H2SO4 4K2SO4 +
ii. Thiosulphate (S2O32 ) is oxidised to sulphate
Cr2(SO4)3 + 7H2O + 3I2
(SO42 )
ii. When H2S gas is passed through acidified
8MnO4 + 3S2O32 + H2O 8MnO2 +
K2Cr2O7 solution, H2S is oxidised to pale
6SO4 + 2OH
2
yellow precipitate of sulphur. Simultaneously
iii. Manganous salt is oxidised to MnO2. potassium dichromate is reduced to chromic
2MnO4 + 3Mn2⊕ + 2H2O 5MnO2 + 4H⊕ sulphate, which is reflected as colour change
of solution from orange to green.
8.7.3 Uses of KMnO4 :
K2Cr2O7 + 4H2SO4 + 3H2S K2SO4 +
• An antiseptic. Cr2(SO4)3 + 7H2O + 3S
• For unsaturation test in laboratory. 8.8 Common properties of d block elements
• In volumetric analysis of reducing agents. Physical properties
• For detecting halides in qualitative i. All d block elements are lustrous and
analysis. shining.
• Powerful oxidising agent in laboratory and ii. They are hard and have high density.
industry.
iii. Have high melting and boiling points.
8.7.4 K2Cr2O7 : Preparation of potassium
iv. Are good electrical and thermal conductors.
dichromate
v. Have high tensile strength and malleability.
In the industrial production, finely powdered
chromite ore (FeOCr2O3) is heated with vi. Can form alloys with transition and non
anhydrous sodium carbonate (Na2CO3) and a transition elements.
flux of lime in air in a reverbatory furnace. vii. Many metals and their compounds are
4(FeO.Cr2O3) + 8Na2CO3 + 7O2 8Na2CrO4 ∆ paramagnetic.
+ 2Fe2O3 + 8CO2. viii. Most of the metals are efficient catalysts.
Sodium chromate (Na2CrO4) formed in this Chemical properties
reaction is then extracted with water and
i. All d block elements are electropositive
treated with concentrated sulphuric acid to
metals.
get sodium dichromate and hydrated sodium
sulphate : ii. They exhibit variable valencies and form
colored salts and complexes.
2Na2CrO4 + H2SO4 Na2Cr2O7 + 2NaCl +
iii. They are good reducing agents.
Na2Cr2O7.H2O
iv. They form insoluble oxides and hydroxides.
Addition of potassium chloride to concentrated
v. Iron, cobalt, copper, molybdenum and
solution of sodium dichromate precipitates
zinc are biologically important metals
less soluble orange-red coloured potassium
dichromate, K2Cr2O7. vi. catalyse biological reactions.

176
Differences : Although most properties Table 8.9 : List of minerals and ores of some
exhibited by d block elements are similar, the transition metals.
elements of first row differ from second and Metals Mineral Ore
third rows in stabilization of higher oxidation Iron Haematite Fe2O3 Haematite
states in their compounds. Magnetite Fe3O4
For example, Mo(V) and W (VI) compounds Limonite 2Fe2O3, 3H2O
Iron pyrites FeS2
are more stable than Cr(VI) and Mn (VIII).
Siderite FeCO3
Highest oxidation state for elements of first row Copper Chalcopyrite CuFeS2 Chalcopyrite
is +7, and in the case of 3rd row +8 oxidation Chalcocite Chalcocite
state as in (RuO4) and (OsO4). Cuprite Cu2O
Zinc Zinc blende ZnS Zinc blende
Can you recall ?
Zinccite ZnO
Calamine ZnCO3
• How are metals found in nature?
• Name two the salts of metals that Metallurgy
are found in nature.
Pyrometallurgy Hydrometallurgy Electro-
Internet my friend metallurgy
8.9.1 Metallurgy : Commercial extraction of
1. Collect the information on metals from their ores is called metallurgy.
different steps involved in the Different methods are used for their extraction
extraction of metals from their ores. depending on the nature of a metal and its ore.
2. Collect information about place where a. Pyrometallurgy: A process in which the
deposits of iron ores are found. ore is reduced to metal at high temperature
using reducing agents like carbon, hydrogen,
8.9 Extraction of metals aluminium, etc. is called pyrometallurgy.
Most metals are found in the earth’s b. Hydrometallurgy : The process of
crust in the form of their salts, such as extracting metals from the aqueous solution
carbonates, sulphates, sulphides and oxides. of their salts using suitable reducing agent is
called hydrometallurgy.
A few metals are nonreactive and occur in
the free state in the earth’s crust, for example, c. Electrometallurgy : A process in which
silver, gold, and platinum. metal is extracted by electrolytic reduction of
molten (fused) metallic compound is called
Mineral : A naturally occuring substance electrometallurgy.
found in the earth’s crust containing inorganic
Steps Involved in Process of Extraction
salts, solids, siliceous matter etc, is called a
mineral. Do you know ?
The mineral which contains high 1. Extraction of iron has been
percentage of the metal and from which the known to Indians since 700 BC.
metal can be extracted economically is called Indian blacksmiths also knew the
an ore. thermo-mechnical process for forging.
During Archaeological studies in Harappa,
Madhya Pradesh different iron objects
belonging to middle iron age were found.
2. Famous iron pillar in Delhi is 1300 years
old and is free of rust till to date.

177
Concentration : After mining the ore from the Iron is extracted from haematite by its
earth’s crust it is subjected to concentration. reduction using coke and limestone. Carbon in
In this step, impurities termed as gangue the limestone is reduced to carbon monoxide.
are removed from the ore and the ore gets Carbon and carbon monoxide together reduce
concentrated. Fe2O3 to metallic iron.
The sand, mud and other unwanted Limestone acts as flux, it combines with
impurities which remain mixed with the ore the gangue material to form molten slag.
deposit are called gangue. Extraction of iron from haematite ore involves
During the process of concentration, the following steps.
the ore is separated from the gangue material i. Concentration : The powdered ore is washed
using different methods such as washing, in a powerful current of water introduced into
hydraulic classification, magnetic separation, the hydraulic classifier.
froth floatation, etc. The lighter gangue particles are
The method chosen for concentration separated and the concentrated ore is collected
depends upon the nature of the ore. at the bottom.
8.9.2 Extraction of Iron from Haematite ore ii. Roasting : The concentrated ore is heated
using Blast furnace in a current of air. The sulfur and arsenic
impurties present in the ore get converted into
Do you know ? their oxides and escape as vapour. Ferrous
Iron is the fourth most oxide in the ore is converted to Fe2O3.
abundant element in the earth’s
4FeO + O2 2Fe2O3
crust
The roasted ore is converted into lumps
Composition of Haematite ore : by sintering.
Fe2O3 + SiO2 + Al2O3 + phosphates iii. Reduction (Smelting) : This step is carried
out in a blast furnace. Blast furnace is a tall
{

cylindrical steel tower which is lined with

Gangue refractory bricks.
The height of a typical blast furnace is
Internet my friend 25 m and its diameter varies between 5 and
Find percentage of oxygen, silicon, 10 m. The furnace works on counter current
aluminium and iron in earth’s crust. principle where the charge comes down and

Reduction by coke
Iron ore Crushing and grinding
Reduction by CO
Reduction by heat
Concentration Reduction
Reduction by Al
Reduction by electrolysis

Magnetic Gravity Leaching Froth Flotation Refining Pure iron

separation separation

Liquification Distillation Oxidation Electro-refining

178
 Burden charging

3Fe2O3 + CO 2Fe3O4 + CO2 2500C Charge distribution

Fe3O4 + CO 3FeO + CO2 Low temperature
distribution
FeO + C Fe + CO CO + N2 Indirect reduction
MnO + C Mn + CO Stack
Swelling and
softening
P2O5 + 5C P2 + 5CO
12000C Coke solution
SiO2 + 2C Si + 2CO
Bosh direct reduction
primary slag
formation
17000C Food phenomena
Hot blast air
C + O2 CO2 CO2 + C 2CO Tuyeres
15000C Effect of raceway
Slag tap hole
conditions
1/2 SiO2, 1/3CaO, 1/3Al2O3 13500C
MgO, MnO Hearth Pig iron tap hole Fe, C, Si, S, P,
Mn - 93% Iron

Fig. 8.5 : Blast furnace

hot gases move up the tower. The furnace is Chemical reactions taking place in different
comprised of 3 parts - 1. Hearth, 2. Bosh and zones of the blast furnace
3. Stack 1. Zone of combustion : This is 5 - 10 m from
The charge containing ore and lime the bottom. The hot air blown through the
stone is introduced into the furnace through a tuyers reacts with coke from the charge to form
cup and cone arrangement. In this arrangement CO.
the cone enables uniform distribution of charge 1
and the cup prevents the loss of gases. A blast C+ O2 CO, ∆H = -220 kJ
2
of preheated air is introduced into the furnance The reaction is highly exothermic; thus
below the bosh. The charge and hot air come in the temperature of this zone is around 2000 K.
contact with each other and various reactions Some of the CO formed dissociates to form
take place. finely divided carbon.
Reactions in the blast furnace : There are 2 CO 2 C + O2
different temperature zones in the blast furnace.
The hot gas rich in CO rises upwards
The temperature goes on increasing from
in the blast furnace. The charge coming down
top to bottom in the furnace. At the top, the
gets heated and reacts with CO. Thus CO acts
temperature is 500 K. Maximum temperature
as a fuel and also a reducing agent.
of the furnace is 2000 K above the tuyers.
There are 3 temperature zones in the furnace. 2. Zone of Reduction (22-25 m near the top)
1. Zone of combustion - Combustion of coke Here, the temperature is around 900 K.
with O2 in the air. Fe2O3 is reduced to spongy iron by CO
2. Zone of reduction - Reduction of Fe2O3 to Fe2O3+ 3 CO 2Fe + 3 CO2
metallic iron some amount of Fe2O3 is reduced to iron by
3. Zone of slag formation - Formation of slag carbon
by reaction of gangue with limestone Fe2O3 + 3C 2 Fe + 3 CO

179
 Table 8.10 : Summary of reactions taking place in blast furnace at different temperature zones
Temp K Changes taking place Reaction
500 loss of moisture from ore
900 Reduction of ore by CO Fe2O3 + 3CO 2 Fe + 3CO2
1200 Decomposition of lime CaCO3 ∆ CaO + CO2
1500 Reduction of ore by C Fe2O3 + 3C 2Fe + 3CO
CaO + SiO2 CaSiO3
2000 Slag formation
12CaO + 2Al2O3 4Ca3AlO3 + 3 O2

3. Zone of slag formation (20 m unit) : 5. Refining : Pure iron can be obtained
The gangue present in the ore is converted to by electrolytic refining of impure iron or
slag. This slag can be used for making road other methods given in the flow chart. The
foundation. Temperature of this zone is 1200 choice of extraction technique is governed
K. The gangue contains silica, alumina and by the following factors. 1. Nature of ore
phosphates. Removal of this gangue is effected 2. Availability and cost of reducing agent,
by adding lime-stone in the charge, which acts generally cheap coke is used. 3. Availability of
as flux. Limestone decomposes to give CaO hydraulic power. 4. Purity of product (metal)
(quick lime) required. 5. Value of byproducts for example,
CaCO ∆ CaO + CO
3 2
SO2 obtained during roasting of sulphide ores
is vital for manufacture of H2SO4. Knowledge
CaO combines with gangue to form of electrochemical series provides solutions to
molten slag of calcium silicate and calcium many problems.
aluminate.
Commercial forms of Iron
CaO + SiO2 CaSiO3
Iron
12 CaO + 2Al2O3 4Ca3 AlO3 + 3 O2
4. Zone of fusion (15 m ht) : MnO2 and Cast Wrought Steel
Ca3(PO4)2 present in the iron ore are reduced
to Mn and P. Some of the silica is also reduced Remember...
to Si.
1. Iron melts at a very high
The spongy iron coming down in the temperature (1800 K). On
furnace melt absorbs impurities like C, Si, Mn, addition of carbon its melting
P and S. This molten iron collects at the bottom point decreases depending upon
in the furnace. The slag which is lighter floats percentage of carbon.
on the surface of molten iron. Molten slag and
2. Mechanical properties of steel can
iron are collected through separate outlets. be modified by addition of small
Molten iron is poured into moulds. amounts of suitable elements such
These solid blocks are called pigs. This iron as manganese, chromium, sulfur,
contains about 4% of carbon. When pig iron nickel etc. These elements are
is remelted, run into moulds and cooled, it called alloying elements and steels
becomes cast iron. The waste gases containing are alloy steels.
N2, CO and CO2 escape through the outlet at
the top. These hot gases are used for preheating
the blast of air.
180
Differences between cast iron, wrought iron and (n-1)f orbitals are very similar and are
and steel sensitive to electronic configurations.
Cast iron Wrought Steel
iron Do you know ?
1. Hard and 1. Very soft 1. Neither too Glenn Seaborg first proposed a
brittle hard nor too
revised design of periodic table with
soft.
2. Contains 2.Contains 2. Contains a whole new series of elements. When
4% carbon. less than 0.2 to 2% he showed his design to two prominent
0.2% carbon inorganic chemists of the time, they warned
carbon
him against publishing it. They told him
3. Used for 3. Used for 3. Used in
making pipes, making buildings that tampering with the established periodic
manufacturing pipes, infrastructure, table will affect his career. Seaborg went
automotive bars for tools, ships, ahead and published it. He later remarked
parts, pots, stay bolts, automobiles,
“I did not have any scientific reputation, so
pans, utensils engine bolts weapons etc.
and rivetts. I published it anyway”. Now we see that
elements 89 -102 (filling of 5f orbitals) fit
Do you know ? in Seaborg’s proposed order.
Iron possesses a high degree
of magnetism below 1042 K. This is
known as ferromagnetism.
8.11 Properties of f-block elements
8.10 Inner Transition (f-block) Elements:
i. Properties are similar to d block elements
Lanthanoids and Actinoids : Elements whose
f orbitals get filled up by electrons, are called ii. Electrons are added to f subshells of (n-2)
f block elements. These elements are placed level
separately at the bottom of the periodic table. iii. Placed between (n-1)d and ns block
They are a subset of 6th and 7th periods. elements
Can you tell ? Lanthanoids begin with atomic number 57 and
• Why f-block elements are end at 71. Although, historically, lanthanoids
called inner transition metals? are termed as rare earth elements, they are
• Are there any similarities between fairly abundant in earth’s crust. For example,
transition and inner transition metals? thulium is found more in abundance than silver
(4.5 x 10-5 vs 0.79 x 10-5 percent by mass). The
Since f orbital lies much inside the d orbital, name rare earth elements was coined because
in relation to the transition metals the f block of difficulty in extracting them economically
elements are called inner transition elements. in pure form from other lanthanoids having
These elements have 1 to 14 electrons in their similar chemical properties. Now, due to newer
f orbital, 0 or 1 in the penultimate energy level separation methods like ion exchange resins,
and 2 electrons in the outermost orbital. The the separation of these elements has become
lanthanoids are characterized by gradual easier and more economical.
filling up of 4f and actinides by the 5 f orbitals.
There are 14 elements filling the f orbital in
each series. The relative energies of the nd

181
 These metals are soft with moderate decreases. La(OH)3 is the strongest base
densities of about 7 g cm-3. They have high while Lu(OH)3 is the weakest base.
melting (~1000 0C) and boiling points (~3000 Lanthanoids react with nitrogen and
0
C). Similar to groups 1 and 2, lanthanoids halogens to give nitrides and halides of the
in the metallic state are very reactive and formulae LnN and LnX3 repectively. While
resemble alkali and alkaline earth metals in doing so, lanthanoids lose their outermost
their reactivities than transition metals. For 3 electrons to form stable compound in +3
example, they react with water to give the oxidation state. When lanthanoids are heated
metal hydroxide and hydrogen gas at elevated temperatures (~ 2800 K) with
2M(s) + 6 H2O (l) 2M(OH)3(s) + 3H2(g) carbon, the carbides with general formula
LnC2 are obtained.
Although, the common oxidation state
for lanthanoids is +3, the +2 oxidation state In +3 oxidation state, many of the
is also important. They all form stable oxides lanthanoids are coloured, mostly green, pink
and yellow. This is attributed to the electronic
of the type M2O3 where M is metal ion. Eu2+
transitions among the f orbitals. Like transition
and Yb2+ are the most stable dipositive metal
metals the electronic spectra of lanthanoids
ions. Higher oxidation states are unusual for
however, do not get affected with different
lanthanoids with the only exception of cerium
ligands.
which forms a stable +4 species. The energy
required to break up the metal lattice is heat 8.12 Properties of Lanthanoids
of atomization. Lanthanoids have lower heat i. Soft metals with silvery white colour and
of atomization than transition metals. This moderate densities of ~ 7 g cm-3. Colour and
is because with d electrons, transition metals brightness reduces on exposure to air
are much harder and require high heat of ii. Good conductors of heat and electricity.
atomization. Europium and ytterbium have the
iii. Except promethium (Pm), all are non-
lowest enthalpies of vaporization and largest
radioactive in nature.
atomic radii of lanthanoids, resemble barium.
These two elements resemble alkaline earth iv. The atomic and ionic radii decrease from
elements; they dissolve in liquid ammonia to lanthanum (La) to lutetium (Lu). This is known
give blue conducting solutions. as lanthanoid contraction.
Their ionic radii decrease from 117 pm of v. Binding to water is common (i.e.) such that
La to 100 pm for Lu. This is because 5f orbitals H2O is often found in products when isolated
do not shield the outer 5s and 5p electrons from aqueous solutions.
effectively, leading to increase in effective vi. Coordination numbers usually are greater
nuclear charge and decrease in the ionic size. than 6, typically 8, 9,... (up to 12 found).
Such large ions have higher coordination vii. The lanthanoides are strongly
number that varies from 6 (most common) to paramagnetic. Gadolinium becomes
9, 10 and upto12 in some cases. For example, ferromagnetic below 16 C (Curie point). The
0

hydrated lanthanum ion is a nonahydrate, other heavier lathanoids terbium, dysprosium,

[La(H2O)9]3+. holmium, erbium, thulium, and ytterbium
All the lanthanoids form hydroxides of – become ferromagnetic at much lower
the general formula Ln(OH)3(Ln represents temperatures.
any elements of lanthanoid series). These are viii. Magnetic and optical properties are
ionic and basic. Since the ionic size decreases largely independent of environment (similar
from La3+ to Lu3+, the basicity of hydroxides spectra in gas/solution/solid).

182
 Table 8.11 : Electronic configuration and atomic ionic radii of lanthanoids

Electronic configuration Ionic radii

Atomic (Ln+3,
Element Symbol Atomic number Observed
Expected radii, pm 6-coordinate),
(ground (+2 oxidation state) (+3 oxidation state)
(ground state) pm
state)

Lanthanum La 57 [Xe]4f 05d16s2 [Xe]4f 05d16s2 4f 0, 5d1 4f 0 187 103

Cerium Ce 58 [Xe]4f 26s2 [Xe]4f 15d16s2 4f 2 4f 1 183 102

Praseodymium Pr 59 [Xe]4f 36s2 [Xe]4f 36s2 4f3 4f 2 182 99

Neodymium Nd 60 [Xe]4f 46s2 [Xe]4f 46s2 4f 4 ............ 181 98.3

Promethium Pm 61 [Xe]4f 56s2 [Xe]4f 56s2 4f 5 ............ 181 97

Samarium Sm 61 [Xe]4f 66s2 [Xe]4f 66s2 4f 6 4f 5 180 95.8

183
Europium Eu 63 [Xe]4f 76s2 [Xe]4f 76s2 4f7 4f 6 199 94.7

Gadolinium Gd 64 [Xe]4f 86s2 [Xe]4f 75d16s2 4f 7, 5d1 ............ 178 93.8

Terbium Tb 65 [Xe]4f 96s2 [Xe]4f 96s2 4f 9 4f 8 177 92.3

Dysprosium Dy 66 [Xe]4f 106s2 [Xe]4f 106s2 4f 10 4f 9 176 91.2

Holmium Ho 67 [Xe]4f 116s2 [Xe]4f 116s2 4f 11 4f 10 175 90.1

Erbium Er 68 [Xe]4f 126s2 [Xe]4f 126s2 4f 12 ............ 174 89

Thulium Tm 69 [Xe]4f 136s2 [Xe]4f 136s2 4f 13 4f 12 173 88

Ytterbium Yb 70 [Xe]4f 146s2 [Xe]4f 146s2 4f 14 ............ - 86.8

Lutetium Lu 71 [Xe]4f 145d16s2 [Xe]4f 145d16s2 4f 14, 5d 1 4f 14 - 86.1

8.12.1 Electronic configuration : The Table 8.12: First, second, third and fourth
electronic configuration of lanthanoids ionization enthalpies of lanthanoids in kJ/mol
is [Xe] 4f0-14 5d 0-2 6s2. This is because
Lanthanoid IE1 IE2 IE3
1s22s22p63s23p64s23d104p65s24d105p6 is the
electronic configuration of xenon and we La 538.1 1067 1850.3
can simplify the electronic configuration of Ce 528.0 1047 1949
lanthanoids by writting [Xe] 4f0-145d0-26s2.
Pr 523.0 1018 2086
The lanthanoids involve gradual filling of
f-orbitals. The energies of 5d and 4f orbitals Nd 530.0 1034 2130
are very close. For lanthanum 4f is slightly Pm 536.0 1052 2150
higher in energy than 5d. The lanthanum has Sm 543.0 1068 2260
electronic configuration [Xe]6s25d1 and not
Eu 547.0 1085 2400
[Xe]6s24f1. Gadolinium (Gd) and lutetium
(Lu) have 5d1 electron to make f-orbital Gd 592.0 1170 1990
half-filled and full-filled which render them Tb 564.0 1112 2110
extra stability. The electronic configuration Dy 572.0 1126 2200
of lanthanoids have variable occupancy in 4f
(0 to 14) orbitals. This can be noticed from Ho 581.0 1139 2200
Table 8.11. Number of electrons in 6s orbitals Er 589.0 1151 2190
remains constant in the ground state. The Tm 596.7 1163 2284
valence shell electronic configuration of these
Yb 603.4 1175 2415
elements, thus can be represented as: (n-2)f 0,2-
14
(n-1)d0,1,2 ns2 Lu 523.5 1340 2022

The electronic distribution in different

orbitals of elements in their ground and excited
states are shown in Table 8.11. Problem : Which of the following will
have highest fourth ionization enthalpy
Try this... IE4? La4⊕, Gd4⊕, Lu4⊕.

Fill in the blanks in Table 8.11. Solution : First write electronic

configuration of that element/ion. Check
Ionization Enthalpies for any unpaired electrons present. The
energy required for removal of that electron
Can you recall ? will be less as compared to the energy
• What is ionization enthalpy? required to remove an electron from an
• Some elements have variable electron pair.Also compare the energies of
oxidation states and some have only the orbitals occupying those electrons. It
two. Can this be justified based on will be easier to remove an electron from
their ionization enthalpies? an orbital that is lower in energy than the
one with higher in energy. First ionization
The ionization enthalpies of lanthanoids are enthalpy generally decrease across the
given in Table 8.12 period.

184
8.12.2 Oxidation state : +3 oxidation state is nuclear charge poorly owing to their diffused
common to all elements in which 2 electrons nature. With increasing atomic number and
of s- subshell and one from d or f- subshell are nuclear charge, the effective nuclear charge
removed. The 4f electrons are strongly screened experienced by each 4f electrons increases. As
by inner 5s and 5p electrons. Thus, 4f electrons a result, the whole of 4f electron shell contracts
are not involved in the bonding. Besides these, at each successive element.
some lanthanoids show oxidation states +2
and +4. They are formed in case of f0, f7 and f14
configurations or resulting ions.
For example : Ce4⊕ (f 0) ; Eu2⊕ and Tb4⊕ (f 7) ;
Yb2⊕ (f 14) Refer Table 8.11.
8.12.3 Colour and Spectra :
Some trivalent ions (M3⊕) are coloured in
solid state as well as in solution. The colour of
lanthanoid ion is due to f-f transitions which
correspond to energy in the visible region of
Fig. 8.6 : Ionic radii of lanthanoids in +3
the electromagnetic spectrum. The colour of
ions having nf electrons is about the same as oxidation state
those having (14 – n)f electrons. (where n is an In section 8.6.4 we have learnt about
integer 1-13). the magnetic behaviour of transition metal
Ln No. of Colour complexes.
ion f-electrons
Pr3⊕ 4f 2 green (14 -n) Use your brain power
f-electrons • Do you think that lanthanoid
=14-2 =12 complexes would show
Tm3⊕ 4f 12 green n f-electrons magnetism?
=12
• Can you calculate the spin only
Nd3⊕ 4f 3 pink (14 -n) magnetic moment of lanthanoid
f-electrons complexes using the same formula
=14-3 =11 that you used for transition metal
Er3⊕ 4f 11 pink nf-electrons complexes?
=11 • Calculate the spin only magnetic
8.12.4 Atomic and ionic radii (Lanthanoid moment of La3+. Compare the value
Contraction) : As we move along the with that given in Table 8.13 Is it same
lanthanoid series, there is a decrease in atomic or different?
and ionic radii (Fig.8.6). 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 from the

185
Table 8.13: Effective magnetic moments of For example, mixed oxide of europium and
lanthanoids in +3 oxidation state yttrium (Eu,Y)2O3 releases an intense red
colour when bombarded with the high energy
Ln Ln3+ No. of Observed electrons.The optoelectronics applications use
oxidation unpaired magnetic lanthanoid ions as active ions in luminescent
state electrons moment, materials. The most notable application is the
μeff B.M Nd: YAG laser (Nd: YAG = neodymium doped
La 4f0 0 0 yttrium aluminium garnet). Erbium-doped fibre
Ce 4f1 1 2.3-2.5 amplifiers are significant devices in the optical-
fibre communication systems. Lanthanoids
Pr 4f2 2 3.4-3.6 are used in hybrid cars, superconductors and
Nd 4f 3
3 3.5-3.6 permanent magnets.
Pm 4f4 4 -- 8.14 Actinoids : The last row of elements in the
Sm 4f 5
5 1.4-1.7 periodic table is the actinoid series. It begins
Eu 4f6 6 3.3-3.5 at thorium (Z =72) and ends at lawrencium
(Z=103). Most of these elements are not
Gd 4f7 7 7.9-8.0 found in nature. They are all radioactive and
Tb 4f 8
6 9.5-9.8 man-made. The half-lives of the isotopes
Dy 4f9 5 10.4-10.6 of thorium (Th-232=1.4 x 1010 years) and
uranium (U-238=4.5 x 109 years) are so long
Ho 4f10 4 10.4-10.7
that these elements exist in rocks on earth.
Er 4f11 3 9.4-9.6 The long lived isotopes such as thorium,
Tm 4f 12
2 7.1-7.6 protactinium, uranium, neptunium, plutonium
Yb 4f13 1 4.3-4.9 and americium, are studied in more details.
These elements have high densities (~ 15-20
Lu 4f14 0 0
g cm-3), high melting points (~1000 oC) and
8.13 Applications high boiling points (~3000 oC). Actinoids are
less reactive than lanthanoids. For example,
The lanthanoid compounds are present
they react with hot, but not cold water to
in every household. It is inside the colour
give the hydroxide and hydrogen gas. Unlike
television tubes. When electrons are bombarded
lanthanoids, they exhibit a range of oxidation
on certain mixed lanthanoid compounds, they
numbers in their compounds which varies
emit visible light over a small wavelength
from +2 to +8. The most common oxidation
range. Therefore, the inside surface of a
numbers of the actinoids are shown in Fig. 8.7.
television tube or computer monitor is coated
with tiny patches of three different lanthanoid As can be seen from Fig.8.7, the most
compositions to give three colours that make common oxidation state of early actinoids
the colour image. reflects the loss of all outer electrons which
is similar to transition metals than the
lanthanoids. A ready loss of 5f electrons by
early actinoids indicates that these electrons
are much closer in energy to 7s and 6d electrons
Promethium Europium Actinium Berkelium
than the 4f electrons to 6s and 5d electrons as
in lanthanoids. All three sets of orbitals that
is 6d, 5f and 7s have similar energies. For Th,
Pa and Np difference in energy levels is small
Bohrium Nobelium Mendelenium Seaborgium

186
 Internet my friend
With the help of internet find out the applications of the elements listed in
table below. Share this information with your friends
Element Applications
Lanthanum
Ytterbium
Erbium
Praseodymium
Samarium
Promethium

so electrons occupy either 6d or 5f orbitals. In attraction by 7s electrons. As a result all three

actinoids series the 5f orbitals are appreciably sets of orbitals i.e. 6d, 5f and 7s have very
lower in energy, thus from Pu onwards 5f shell similar energies. The ionic radius decreases as
gets filled in a regular way. we move across the series which is known as
The electronic configuration of actinoids is ‘Actinoid contraction’. This is attributed to
[Rn] 5f0-14 6d0-2 7s2, where Rn is the electronic poor shielding offered by f electrons.
configuration of radon. As seen from Fig. 8.7,
the most stable oxidation state in actinoids
is +3. The highest common oxidation states
of early actinoids reflect the loss of all outer
electrons which is similar to transition metals
than lanthanoids. For example, uranium has
electronic configuration of [Rn]7s25f 36d1. The
formation of +6 oxidation state corresponds
to an electronic configuration of [Rn]. Similar
Fig. 8. 8 Figure depicting contraction of ionic
to lanthanoids, loss of s and d electrons occur
radii of lanthanoids and actinoids
before f electrons, in formation of 3+ ions. A
ready loss of 5f electrons by early actinoids 8.15 Properties of Actinoids
indicates that these electrons are much closer i. Similar to lanthanoids, they appear silvery
in energy to 7s and 6d electrons than the 4f white in colour.
electrons are to 6s and 5d electrons in the
ii. These are highly reactive radioactive
lanthanoids. In turn, 5f and 6d orbitals expand
elements
as they are partially shielded from the nuclear
Oxidation numbers

6
5
4
3
2
1
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Fig. 8. 7 The most common oxidation numbers of actinoids

187
iii. They experience decrease in the atomic and
ionic radii from actinium (Ac) to lawrencium Do you know ?
(Lr), known as actinoid contraction Uranium is another actinoid which
iv. They usually exhibit +3 oxidation state. is in great demand as it is used in
Elements of first half of the series usually the nuclear reactors. One of the extraction
exhibit higher oxidation states.
methods for uranium has a very interesting
8.16 Applications of actinoids : We have chemistry. The ore containing U(IV) oxide,
seen that the half-lives of natural thorium
UO2, is first treated with Fe(III) ion to give
and uranium isotopes are so long that we get
very negligible radiation from these elements. U(VI) oxide, UO3
We find them in everyday use. For example, UO2 (s) + H2O(l)  UO3 (s) + 2H⊕ (aq)
Th(IV) oxide, ThO2 with 1% CeO2 was used + 2e
as a major source of indoor lighting before Fe (aq) + e  Fe (aq)
3⊕ 2⊕

incandescent lamps came into existence only

Addition of H2SO4 to this solution produces
because these oxides convert heat energy from
burning natural gas to an intense light. Even uranyl sulphate containing UO22⊕ cation:
today, there is a great demand for these lights UO3 (s) + H2SO4 (aq)  UO2SO4 (aq) +
for outdoor camping. H2O (l)
After purification, ammonia is added to the
solution giving bright yellow precipitate of
ammonium diuranate, (NH4)2U7O7:
2 UO2SO4 (aq) + 6 NH3 (aq) + 3 H2O (l)
 (NH4)2U7O7 (s) + 2 (NH4)2SO4 (aq)
This yellow cake is the marketable form of
uranium!

Similarities and differences between lanthanoids 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. Actinoids
gradually have a greater tendency to form complexes with
ligands such as thioethers
Ionic radii of the elements in both series All lanthanoids are non-radioactive except
decreases with an increase in atomic number promethium but actinoids are radioactive in nature

The electronegativity of all the elements in Lanthanoids do not form oxocations, but actinoids
both the series is low and are said to be highly form oxocations such as UO+, PuO+, NpO2+
reactive
The nitrates, perchlorates and sulphates of all Most of the lanthanoids are colourless in nature
the elements are soluble while the hydroxides, whereas the actinoids are coloured ions
fluorides and carbonates are insoluble

188
 Table 8.14 Electronic configuration of actinoids and their ionic radii in +3 oxidation state
Element Symbol Atomic *Atomic *Ionic radii
Electronic configuration
number radii, pm (Ac3⊕), pm
ground state +3
oxidation
state
Actinium Ac 89 [Rn]5f 06d17s2 5f 0 203 126
Thorium Th 90 [Rn]5f 06d27s2 5f 1 180 -
Protactinium Pa 91 [Rn]5f 6d 7s
2 1 2
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 6d 7s
6 0 2
5f 5
162 115
Americium Am 95 [Rn]5f 76d07s2 5f 6 173 114
Curium Cm 96 [Rn]5f 6d 7s
7 1 2
5f 7
174 112
Berkelium Bk 97 [Rn]5f 96d07s2 5f 8 170 110
Californium Cf 98 [Rn]5f 6d 7s
10 0 2
5f 9
186 109
Einsteinium Es 99 [Rn]5f 116d07s2 5f 10 186 98
Fermium Fm 100 [Rn]5f 126d07s2 5f 11 198 91
Mendelevium Md 101 [Rn]5f 6d 7s
13 0 2
5f 12
194 90
Nobelium No 102 [Rn]5f146d07s2 5f 13 197 95
Lawrencium Lr 103 [Rn]5f 6d 7s
14 1 2
5f 14
171 88

Table 8.15 : Some comparison between s - block, Lanthanoids and Transition Metals
s - block Metals Lanthanoids Transition Metals
Essentially in (+3)
Essentially monovalent - Show variable oxidation
oxidation state
show group (n+) oxidation states
(+2/+4 for certain
state
configurations)
Periodic trends dominated Lanthanoid contraction of
Size changes of Mn⊕, less
by effective nuclear charge Ln3⊕ marked
at noble gas configuration
Similar properties for a Similar properties Substantial changes in
given group properties
Always 'hard' (O, X, Always 'hard' (O, X, heavier metals
N donors, preferably N donors, preferably (increasingly from Fe-Cu)
negatively charged) negatively charged) may show a 'soft' character
Insignificant ligand field Substantial ligand field
No ligand field effects
effects effects
Poor coordination High coordination Coordination number 6
properties(C.N. determined numbers (C.N. determined is typical maximum (many
by size) by size) exceptions)
Fixed geometries (ligand
Flexibility in geometry Flexibility in geometry
field effects)
No magnetism Show magnetism Show magnetism

189
8.17 Postactinoid elements : You have seen With half-lives of miliseconds only a little is
that elements with atomic number greater than known about the chemistry of these elements.
92 are called ‘Transuranium’. Elements from Rutherfordium forms a chloride, RfCl4, similar
atomic number 93 to 103 now are included to zirconium and hafnium in the +4 oxidation
in actinoid series and those from 104 to 118 state. Dubnium resembles to both, group 5
are called as postactinoid elements. The transition metal, niobium(V) and actinoid,
postactinoid elements that are known so far protactinium(V).
are transition metals. They are included as
postactinoids because similar to actinoid Do you know ?
elements, they can be synthesized in the Traditionally, no element was
nuclear reactions. So far, nine postactinoid
named after a still-living scientist.
elements have been synthesized. It is difficult
to study their chemistry owing their short half- This principle was put to an end with
lives. For example, element 112 has a half-life naming the element 106 as ‘Seaborgium’.
of only 2.8 x 10-4 seconds.

Exercises

1. Choose the most correct option.

i. Which one of the following is c. 3d10, 4s1; 3d10, 4s0
diamagnetic d. 3d8, 4s1; 3d10, 4s0
a. Cr2⊕ b. Fe3⊕ vii. Which of the following have d0s0
c. Cu2⊕ d. Sc3⊕ configuration
ii. Most stable oxidation state of a. Sc3⊕ b. Ti4⊕
Titanium is c. V5⊕ d. all of the above
a. +2 b. +3 viii. Magnetic moment of a metal
c. +4
d. +5 complex is 5.9 B.M. Number of
iii. Components of Nichrome alloy are unpaired electrons in the complex is
are a. 2 b. 3
a. Ni, Cr, Fe b. Ni, Cr, Fe, C c. 4 d. 5
c. Ni, Cr d. Cu, Fe ix. In which of the following series
iv. Most stable oxidation state of all the elements are radioactive in
Ruthenium is nature
a. +2 b. +4 a. Lanthanoids
c. +8 d. +6 b. Actinoids
v. Stable oxidation states for chromium c. d-block elements
are d. s-block elements
a. +2, +3 b. +3, +4 x. Which of the following sets of ions
c. +4, +5 d. +3, +6 contain only paramagnetic ions
vi. Electronic configuration of Cu and a. Sm3⊕, Ho3⊕, Lu3⊕
Cu+1 b. La3⊕, Ce3⊕, Sm3⊕
a. 3d10, 4s0; 3d9, 4s0 c. La3⊕, Eu3⊕, Gd3⊕
d. Ce3⊕, Eu3⊕, Yb3⊕
b. 3d9, 4s1; 3d94s0
190
 xi. Which actinoid, other than uranium, ii. Name different zones in the Blast
occur in significant amount furnace. Write the reactions taking
naturally? place in them.
a. Thorium b. Actinium iii. What are the differences between cast
c. Protactinium d. Plutonium iron, wrought iron and steel ?
xii. The flux added during extraction of iv. Iron exhibits +2 and +3 oxidation states.
Iron from hematite are its? Write their electronic configuration.
a. Silica Which will be more stable ? Why ?
b. Calcium carbonate v. Give the similarities and differences in
elements of 3d, 4d and 5d series.
c. Sodium carbonate
vi. Explain trends in ionisation enthalpies
d. Alumina
of d block elements.
2. Answer the following
vii. What is meant by diamagnetic and
i What is the oxidation state of paramagnetic metal ? Give one example
Manganese in (i) MnO42- (ii) MnO4- ? of diamagnetic and paramagnetic
ii. Give uses of KMnO4 transition metal and lanthanoid metal.
iii. Why salts of Sc3⊕, Ti4⊕, V5⊕ are viii.Why the ground-state electronic
colourless ? configurations of gadolinium and
iv. Which steps are involved in lawrentium are different than expected?
manufacture of potassium dichromate ix. Write steps involved in metallurgical
from chromite ore ? process
v. Balance the following equation x. Cerium and Terbium behaves as good
(i)KMnO4+H2C2O4+H2SO4 MnSO4 + oxidising agents in +4 oxidation state.
K2SO4 + H2O + O2 Explain.
(ii) K2Cr2O7 + KI + H2SO4 K2SO4 + xi. Europium and Ytterbium behave as
Cr2(SO4)3 + 7H2O + 3I2 good reducing agents in +2 oxidation
vi. What are the stable oxidation states state explain.
of plutonium, cerium, manganese,
Europium ?
vii. Write electronic configuration of Activity :
chromium and copper.
Make groups and each group
viii. Why nobelium is the only actinoid
with +2 oxidation state? prepares a powerpoint presentation
on properties and applications of one
ix. Explain with the help of balanced
element. You can use your imagination
chemical equation, why the solution of
to create some innovative ways of
Ce(IV) is prepared in acidic medium.
presenting data.
x. What is meant by ‘shielding of
You can use pictures, images, flow
electrons’ in an atom?
charts, etc. to make the presentation
xi. The atomic number of an element is easier to understand. Don’t forget to
90. Is this element diamagnetic or cite the reference(s) from where data
paramagnetic? for presentation is collected (including
3. Answer the following figures and charts). Have fun!
i. Explain the trends in atomic radii of d
block elements

191