The d – and f – block elements

d – block elements: The elements in which last electron enters d – subshell of penultimate shell.

They are located in 4th, 5th,6th and 7th periods flanked between s and p block elements. They belong to
3rd group to 12th group.

The transition elements are those which possess incompletely filled d – subshell either in their atomic
state or in any one of their most common oxidation state.

Except the elements of 12th group d – block elements are called transition elements. The elements of
12th group zinc, Cd, Hg have full d10 configuration in the ground state as well as in their common
oxidation states. Hence they are not transition metals.

The general electronic configuration of d – block elements is [noble gas](n – 1)d1 – 10ns1 – 2 .

There are four series of d – block elements.

First transition series or 3d series: It corresponds to the filling of 3d sub shell. It includes 10
elements of the 4th period from Sc to Zn.

General electronic configuration of 3d series is [Ar] 3d 1- 10 4s1 – 2.

Elements Atomic no Symbol Electronic configuration

Scandium 21 Sc [Ar] 3d 1 4s 2
Titanium 22 Ti [Ar] 3d 2 4s 2
Vanadium 23 V [Ar] 3d 3 4s 2
Chromium 24 Cr [Ar] 3d 5 4s 1
Manganese 25 Mn [Ar] 3d 5 4s 2
Iron 26 Fe [Ar] 3d 6 4s 2
Cobalt 27 Co [Ar] 3d 7 4s 2
Nickel 28 Ni [Ar] 3d 8 4s 2
Copper 29 Cu [Ar] 3d 10 4s 1
Zinc 30 Zn [Ar] 3d 10 4s 2

The configuration of Cr is [Ar]3d54s1 instead of [Ar]3d44s2 :This is due to extra stability of half
filled 3d subshell which is due to symmetry and exchange energy.

The configuration of Cu is [Ar]3d104s1 instead of [Ar]3d94s2 : This is due to extra stability of

completely filled 3d – subshell.

Second transition series or 4d –series:

This series corresponds to the filling of 4d – subshell. It include 10 elements of 5th period from Y to Cd.
The general electronic configuration of 4d series is [Kr]4d1 – 105s1 – 2

Elements Atomic no Symbol Electronic configuration

Yttrium 39 Y [Kr] 4d 1 5s 2
Zirconium 40 Zr [Kr] 4d 2 5s 2
Niobium 41 Nb [Kr] 4d 3 5s 2
Molybdenum 42 Mo [Kr] 4d 5 5s 1
Technetium 43 Tc [Kr] 4d 6 5s 1
 Ruthenium 44 Ru [Kr] 4d 7 5s 1
Rhodium 45 Rh [Kr] 4d 8 5s 1
Palladium 46 Pd [Kr] 4d 10 5s 0
Silver 47 Ag [Kr] 4d 10 5s 1
Cadmium 48 Cd [Kr] 4d 10 5s 2

Third transition series or 5d series: It includes elements of 6th period La and from Halfnium to
Mercury. General electronic configuration [Xe] 5d1- 10 6s1 – 2

Elements Atomic Symbol Electronic

no configuration
Lanthanum 57 La [Xe] 5d 1 6s 2
Halfnium 72 Hf [Xe] 4f 14 5d 2 6s 2
Tantalum 73 Ta [Xe] 4f 14 5d 3 6s 2
Tungsten 74 W [Xe] 4f 14 5d 4 6s 2
Rhenium 75 Re [Xe] 4f 14 5d 5 6s 2
Osmium 76 Os [Xe] 4f 14 5d 6 6s 2
Iridium 77 Ir [Xe] 4f 14 5d 7 6s 2
Platinum 78 Pt [Xe] 4f 14 5d 9 6s 1
Gold 79 Au [Xe] 4f 14 5d 10 6s 1
Mercury 80 Hg [Xe] 4f 14 5d 106s 2
Fourth transition series or 6d series:

Elements Atomic no Symbol Electronic

configuration
Actinium 89 Ac [Rn]6d17s2
Rutherfordium 104 Rf [Rn] 5f14 6d27s2
Dubnium 105 Db [Rn] 5f14 6d37s2
Seaborgium 106 Sg [Rn] 5f14 6d47s2
Bohrium 107 Bh [Rn] 5f14 6d57s2
Hassium 108 Hs [Rn] 5f14 6d67s2
Meitherium 109 Mt [Rn] 5f14 6d77s2
Darmstadium 110 Ds [Rn] 5f14 6d87s2
Rontgenium 111 Rg [Rn] 5f14 6d107s1
Copernicium 112 Cn [Rn] 5f14 6d107s2

Physical properties:

1. Transition elements exhibit metallic properties such as high tensile strength, ductility,
malleability, high thermal and electrical conductivity and metallic lustre.
2. Melting and boiling points: T.he melting and boiling points of the transition metals maximum
at the middle of each series due to the presence of more number of unpaired electrons. In the
middle of each series, metallic bonding between the atoms is very strong due to the electrons
from both (n – 1)d and ns electrons . Melting points of transition metals increases upto d5
configuration and then decreases. This is because upto d5 configuration, number of unpaired
electrons increases. So metallic bond becomes stronger and hence melting point becomes
higher. After d5 configuration pairing of electrons takes place and number of unpaired
electrons decreases. Metallic bond becomes weaker and hence melting point decreases.
 Even though more number of unpaired electrons are present in Mn, Tc and Re their
melting point are less Why? Mn, Tc and Re have stable half filled d5 electronic configuration.
Therefore electrons are held tightly by the nucleus. So delocalisation of electrons is less and
hence metallic bond is weak. Therefore they have low melting point.
3. Enthalpy of atomisation: is heat required to break the strong inter atomic bond to get free
atoms. Transition metals have high enthalpies of atomisation due to strong inter atomic
bonding is due to the presence of large number o unpaired electrons.
4. Atomic radii: Along a transition series, with the increases in atomic number, the atomic radii
first decreases up to the middle of the series, remains constant up to almost the end and at the
end slightly increases.
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Decreases constant increase

Due to increase in Since the number of d In Zn, the electrons get
effective nuclear – electrons increases, paired and electron –
charge and electrons shielding effect also electron repulsion will
are added to the same increases be maximum. So Zn
shell i.e., improper has slightly larger size
shielding effect than Cu

Melting point of 3d series less than 4d and 5d due to high enthalpy of atomisation of 4d and 5d series.

5. Ionisation enthalpies:The ionisation enthalpy gradually increases along a transition series

due to increase in nuclear charge. But this trend is not regular and there are some irregular
variations.

Second ionisation enthalpy of Cr is higher than Mn due to stable d5 electronic

configuration and Cu is higher than Zn due to stable d10 electronic configuration.

6. Variable oxidation states: The transition metals exhibit variable oxidation states due to very
little energy difference between (n – 1)d and ns orbitals. Therefore the electrons from ns and
(n – 1)d orbitals can take part in bond formation.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
• In 3d series Mn shows a maximum oxidation state of +7
• The oxidation states of Ni and Fe in the complexes [Ni(CO)4] and [Fe(CO)5] is zero
because the ligands CO are capable of π – acceptor character in addition to the σ –
bonding.
• Fe3+ is more stable than Fe2+. Hence Fe2+ acts as reducing agent.
• Cr3+ is more stable than Cr2+ hence Cr2+ acts as reducing agent.
 • In 4d series Ruthenium (Ru) shows a maximum oxidation state of +8
• In 5d series Osmium (Os) shows a maximum oxidation state of +8
• Mn2+ is more stable than Mn3+ . Hence Mn3+ acts as oxidising agent.

7. Magnetic properties: When a substance is placed in an external magnetic field,

a. Paramagnetic substances are attracted by the magnetic field. The paramagnetic
behaviour is due to the presence of unpaired electrons.
b. Diamagnetic substances repelled by the external magnetic field. These substances do
not have unpaired electrons.
c. Ferromagnetic substances which are attracted very strongly to the magnetic field.

Extent of paramagnetsim is calculated by magnetic moment (μ). The magnetic moment is

determined by the number of unpaired electrons and is calculated by using spin
only formula μ = √𝒏(𝒏 + 𝟐)𝑩. 𝑴 (Bohr Magneton) where n – number of unpaired
electrons.

Calculate the magnetic moment of

1. V3+ = μ = √𝑛(𝑛 + 2) = √2(2 + 2) = √8 = 2.828𝐵. 𝑀

2. Ti3+ = μ = √𝑛(𝑛 + 2) = √1(1 + 2) = √3 = 1.73𝐵. 𝑀
3. Fe3+ = μ = √𝑛(𝑛 + 2) = √5(5 + 2) = √35 = 5.92𝐵. 𝑀
4. Mn3+ = μ = √𝑛(𝑛 + 2) = √5(5 + 2) = √35 = 5.92𝐵. 𝑀
8. Formation of coloured ions: In the compounds of transition metals, when anions or ligands
approach the transition metal ions, their d-orbitals do not remain degenerate. They split into
two sets, one consisting of dxy, dyz, dzx, (t2g), and other consisting of dx2 – y2 , dz2 (eg). Energy gap
between two energy levels in the same d – sub shell being small, only small amount of energy
is required to excite electrons from one energy level to the other .Transition metal compounds
having unpaired electrons, absorb colour from the visible region and undergo d-d transition.
The colour of a transition metal ions is due to
1. The presence of unpaired electrons in d – orbitals
2. Incompletely filled d – orbitals.
3. The unpaired d – electrons absorb colour from the visible region and undergo d – d
transition and transmit complimentary colour.

Example electronic configuration colour

Sc3+ 3d0 colourless

Fe2+ 3d6 green

Mn2+ 3d5 pink

Cu2+ 3d9 blue

Zn2+ 3d10 colourless

Zn compounds are colourless due to the absence of unpaired d – electrons or completely filled
d – orbitals.

9. Catalytic property: d – block elements can act as catalyst in various chemical reactions. This
is due to partially filled d – orbitals , exhibit variable oxidation states, large surface area
 for adsorption of reactant molecules, By adsorbing reactant molecules, the concentration of
the reactants on the surface of the catalyst increases, hence energy of activation decreases and
rate increases.
10. Formation of complex compounds: The transition metals have tendency to form complex
salts. Example [Cu(NH3)4]2+, [Fe(CN)6]4 – . This is due to a)smaller size of transition metal
ions.
b) vacant d- orbitals c) high polarising power - it is the capacity of polarising electron
cloud towards its, high +ve charge density enables transition metal ions to receive electrons
donated by ligands.
11. Formation of interstitial compounds: These are the compounds which are formed when
small atoms like H, B, C, N etc gets trapped into the interstitial site of the crystal lattices of
metals.
Properties of interstitial compounds:
1. They are non Stoichiometric
2. They have high melting point higher than those of pure metals
3. They are very hard,
4. They are chemically inert
5. They retain metallic conductivity.

Note:The empty space present in the crystal lattice is called as interstitial site or void.

12. Formation of alloys: Alloys are homogeneous solid solutions of two or more metals obtained
by melting the components and then cooling the melt. Transition elements have strong
tendency to form alloys because they have almost similar atomic size and therefore atoms of
one metal can easily take up position in the crystal lattice of other. Alloys are hard and have
high melting point. Alloys formed will have different but improvised properties than the metal
w.r.t hardness, appearance, elasticity etc. Example stainless steel is an alloy of Fe,, C, Cr, and
Ni. Brass (Copper + zinc) Bronze (copper + tin)
13. Trends in the M2+/M standard electrode potential):
Standard electrode potential (E0): the potential difference between an element and its own
ions in solution at equilibrium when the concentration of the ions 1M at standard conditions of
temperature and pressure (298K and 1 bar) is known as standard electrode potential.
The electrode potential is a measure of the total enthalpy change when solid metal (M)
is brought into equilibrium medium in the form of Mn+(aq).
The total enthalpy change depends on sublimation energy, ionisation energy and
hydration energy of the metal. ∆HT = ∆HS + I. E + ∆Hhyd
Reduction potential: The tendency of metal ions to get reduced to metal M2+ + 2e – → M. E0
for this reaction is known as standard reduction potential (SRP).
if standard reduction potential of a metal is low then the tendency of the metal ion to
undergo reduction is less and the tendency of the metal to undergo oxidation is high.
Oxidation potential: the tendency of metal to convert into its ions. Lower the value of SRP
more is the reducing power. Along 3d series SRP increases.
Element Ion electrode reaction E0 /volt
Sc Sc3+ Sc3+ + 3e – → Sc - 2.10
Ti Ti 2+ Ti + 2e → Ti
2+ – - 1.63
V V2+ V2+ + 2e – → V - 1.18
Cr Cr 3+ Cr + 3e → Cr
3+ – - 0.90
Mn Mn 2+ Mn + 2e → Mn
2+ – - 1.18
Fe Fe2+ Fe2+ + 2e – → Fe - 0.44
Co Co2+ Co2+ + 2e – → Co - 0.28
 Ni Ni2+ Ni2+ + 2e – → Ni - 0.25
Cu Cu2+ Cu2+ + 2e – → Cu +0.34
Zn Zn2+ Zn2+ + 2e – → Zn - 0.76

Along 3d series the tendency of the metal to undergo oxidation decreases. It is due to
increase in sum of first and second ionisation enthalpies.

Cu has +ve SRP is lesser tendency to undergo oxidation to Cu2+ ions, is due to high
energy required to transform Cu to Cu2+ is not balanced by hydration enthalpy of Cu2+.

Zn has negative SRP. It has more tendencies to undergo oxidation to Zn2+ than Cu due
to completely filled d – sub shell in Zn2+.

The stability of the oxidation state of metal depends on the electrode potential. When
the electrode potential is less the stability is more.

14. Trends in the M3+/M2+ standard electrode potential:

The low value for Sc reflects the stability of Sc3+ which has noble gas configuration.
Mn shows comparatively high value due to the stability of Mn2+ (d5 configuration)
Comparatively low value for Fe shows the extra stability of Fe3+(d5 configuration)
15. Chemical reactivity and E0 values: Standard reduction potential associated with chemical
reactivity.
Lesser the value of SRP more is the reducing power or greater tendency to undergo oxidation.
So metal with lower SRP is more reactive or electro potential.
Most of the transition metals except copper have negative SRP. They displace hydrogen form
mineral acids.
16. Oxides and oxoanions of metals:
Oxides:Transition metals form metal oxides. The metal oxides in which metals are in lower
oxidation state are ionic and they form basic oxides. Example MnO, FeO, CrO etc
The metal oxides in which the metals are in the highest oxidation state are covalent
and they are acidic oxides. Example Mn2O7, CrO3.
The metal oxides in which the metals are in their intermediate oxidation state form
amphoteric oxides. Example:Cr2O3, Mn2O3.
They also form oxo anions. Example: permaganate ion MnO4 – , dichromate ion Cr2O7 2 – .
CrO3 dissolves in water to give chromic acid (H2CrO4) and dichromic acid (H2Cr2O7).

Some important compounds of transition metals:

Potassium dichromate: (K2Cr2O7)

It is orange coloured solid used in leather industry and as an oxidant for preparation of many azo
compounds.

Manufacture of K2Cr2O7 from chromite ore

Finely powdered chromite ore is fused with Na2CO3 in excess of air, yellow mass due to the
formation of sodium chromate is obtained.

4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2

The yellow mass is extracted with water and filtered. The filtrate contains sodium chromate
and is acidified with sulphuric acid to get an orange coloured sodium dichromate solution.
 2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

Concentrated solution of sodium dichromate is treated with KCl, to get potassium dichromate
which is less soluble than sodium chloride. Crystallises out on cooling as orange crystals.

Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl

Structures of chromate and dichromate ions:

The chromates and dichromates are inter convertible in aqueous solutions depending upon pH of the
solution.

In acidic medium pH <7, 2 CrO42– + 2H+ → Cr2O7+ + H2O

In basic medium pH > 7, Cr2O72– + 2 OH – → 2 CrO42– + H2O

Sodium and potassium dichromates are strong oxidising agents. The sodium salt has a greater
solubility in water and is used as an oxidising agent in organic chemistry.

Potassium dichromate is used as a primary standard in volumetric analysis.

In acidic solution oxidising action of dichromate ion can be represented as follows.

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O (E0 = 1.33V)

Example:

1. Acidified potassium oxidises iodides to iodine:

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

[2I – → I2 + 2e – ] x 3

------------------------------------------------------------------

Cr2O72– + 14H+ + 6I – → 2Cr3+ + 3I2 + 7H2O

-----------------------------------------------------------------

2. Acidified potassium oxidises H2S to S:

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

[H2S → S + 2H+ + 2e – ] x 3

------------------------------------------------------------------
 Cr2O72– + 8H+ + 3H2S → 2Cr3+ + 3S + 7H2O

-----------------------------------------------------------------

3. Acidified potassium ferrous salts to ferric salts

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

[Fe2+ → Fe3+ + e – ] x 6

------------------------------------------------------------------

Cr2O72– + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O

-----------------------------------------------------------------

4. Acidified potassium oxidises stannous salts to stannic salts:

Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

[Sn2+ → Sn4+ + 2e – ] x 3

------------------------------------------------------------------

Cr2O72– + 14H+ + 3Sn2+ → 2Cr3+ + 3Sn4+ + 7H2O

-----------------------------------------------------------------

Potassium permanganate [KMnO4]

Preparation of KMnO4 using pyrolusite ore (MnO2)

KMnO4 is prepared by fusion of MnO2 with KOH in the presence of air

2MnO2 + 4KOH + O2 + heat → 2K2MnO4 + 2H2O
When potassium manganate is acidified, which disproportionate to give permanganate.
3MnO4 2 – + 4H+ → 2MnO4 – + MnO2 + 2H2O

Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by electrolytic oxidation
of manganate ion.

In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate

2Mn2+ + 5S2O82– + 8H2O → 2MnO4– + 10SO42– + 16H+

The manganate and permanganate ions are tetrahedral shape.

Properties of KMnO4:

1. Effect of heat: on heating KMnO4 decomposes to give potassium manganate and oxygen gas.
2KMnO4 → K2MnO4 + MnO2 + O2
2. Oxidising property: KMnO4 is a powerful oxidising agent in acidic, basic and neutral medium

In acidic medium MnO4– + 8H+ + 5e– → Mn2+ + 4H2O( EV = + 1.52 V)

1. MnO4 – oxidises iodide to iodine:

[MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] x 2

[2I – → I2 + 2e – ] x 5

-----------------------------------------------------------------------------

2MnO4 – 1 + 16H+ + 10I – → 2Mn2+ + 8H2O + 5I2

2. MnO4 – oxidises Fe2+ to Fe3+:

MnO4– + 8H+ + 5e– → Mn2+ + 4H2O

[Fe2+ → Fe3+ + e – ] x 6

-----------------------------------------------------------------------------

MnO4 – 1 + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+

3. MnO4 – oxidises oxalic acid carbon dioxide at 333K:

[MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] x 2

[C2O42 – → 2CO2 + 2e – ] x 5

-----------------------------------------------------------------------------

2MnO4 – 1 + 16H+ + 5C2O4 2 – → 2Mn2+ + 8H2O + 10CO2

4. MnO4 – oxidises H2S to S:

[MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] x 2

[S 2 – → S + 2e – ] x 5

-----------------------------------------------------------------------------

2MnO4 – 1 + 16H+ + 5S2 – → 2Mn2+ + 8H2O + 5S

 5. MnO4 – oxidises sulphite to sulphate: 2MnO4 – 1 + 6H+ + 5SO3 2 – → 2Mn2+ + 3H2O + 5SO4 2 –
6. MnO4 – oxidises nitrite to nitrate: 2MnO4 – 1 + 6H+ + 5NO2 – → 2Mn2+ + 3H2O + 5NO3 –

In neutral or faintly alkaline solutions:

MnO4 – + 2H2O + 3e – → MnO2 + 4 OH –

(a) A notable reaction is the oxidation of iodide to iodate:

2MnO4– + H2O + I– —> 2MnO2 + 2OH– + IO3–
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8MnO4– + 3S2O32– + H2O ——> 8MnO2 + 6SO42– + 2OH–
(c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide catalyses the
oxidation:
2MnO4– + 3Mn2+ + 2H2O ——> 5MnO2 + 4H+

Uses of KMnO4:

1. KMnO4 used as an oxidising agent in the laboratory

2. It is used in volumetric analysis for the estimation of ferrous salts, oxalates
3. Used as disinfectant and germicide
4. Used for bleaching wool, cotton and silk.

The inner transition elements [f – block elements]

The elements in which the last electron enters the f – sub shell of anti penultimate shell are called f –
block elements. These elements are also knows as rare earths.

They are divided into two series.

1. Lanthanoids or 4f series.
2. Actinoids or 5f series.

General electronic configuration of f – block elements is [noble gas] (n – 2 )f1 – 14(n – 1 )d0 – 1 ns2

Lanthanoids:The 14 elements which follow lanthanum are called lanthanoids. (At. No 58 – 71)

In these elements 4f – subshell is progressively filled. So they are the elements of 4f – series.

General symbol of lanthanoids is ‘Ln’

Electronic configuration of lanthanoids: [noble gas] 4f1 – 145d0 – 1 6s2

Electronic
At. No Name Symbol
configuration
57 Lanthanum La [Xe]4f05d16s2
58 Cerium Ce [Xe]4f15d16s2
59 Praseodymium Pr [Xe]4f35d06s2
60 Neodymium Nd [Xe]4f45d06s2
61 Promethium Pm [Xe]4f55d06s2
62 Samarium Sm [Xe]4f65d06s2
63 Europium Eu [Xe]4f75d06s2
64 Gadolinium Gd [Xe]4f75d16s2
65 Terbium Tb [Xe]4f96s2
66 Dysprosium Dy [Xe]4f105d06s2
 67 Holmium Ho [Xe]4f115d06s2
68 Erbium Fr [Xe]4f125d06s2
69 Thulium Tm [Xe]4f135d06s2
70 Ytterbium Yb [Xe]4f145d06s2
71 Lutetium Lu [Xe]4f145d16s2
Properties:

1. Oxidation state: The most common oxidation state exhibited by Lanthanoids is +3.
However some exceptions due to extra stability of empty, half filled or completely filled f – sub
shell.
Ce4+ : [Xe]6s05d04f0 – empty f – sub shell.
Eu2+ : [Xe]6s05d04f7 – half – filled f - sub shell
Yb2+ : [Xe]6s05d04f14 – completely filled f – sub shell.

Ce 4+ formation favoured by noble gas configuration but it is a strong oxidant reverting to the
+3 state.
The E0 value for Ce4+/Ce3+ is +1.74V which can suggest that it can oxidise water. Hence it is a
Ce4+ good analytical reagent.
Eu2+ is formed by losing two electrons form 6s – sub shell and forms half – filled 4f7
configuration. However Eu2+ is a strong reducing agent changing to the common +3 state.
Similarly Yb2+ which has f14 configuration is a reductant.
2. Atomic radii: The gradual decrease in the atomic radii/ ionic radii with increase in
atomic number of lanthanoids is called Lanthanoid contraction.
Cause for Lanthanoid contraction: along Lanthanoid series, with the increase in atomic
number, the newly added electron enters the inner 4f – sub shell. Due to imperfect shielding
effect by 4f – electrons, the nuclear charge experienced by the outer electrons increases. This
result in gradual decrease in size of Lanthanoids.
Consequences of lanthanoid contraction:
1. Due to Lanthanoid contraction the elements of 4d and 5d series have almost same atomic
and ionic radii. As a result they show similarity in their properties.
2. Due to Lanthanoid contraction, change in atomic and ionic radii is very small and the
chemical properties of Lanthanoids become similar. As a result the separation of elements
in the pure state becomes difficult.

General characteristics:

1. Lanthanoids are silvery white soft metals and tarnish rapidly in air.
2. They have high M.P and B. P [1000 – 1200K]
3. They are good conductors of heat and electricity.

Ionisation enthalpies: the first and second ionisation enthalpies of lanthanoids are
comparable to those of alkaline earth metals.

Colour: most of the trivalent Lanthanoids ions are coloured due to the presence of unpaired
electrons.

Magnetic behaviour: Except La3+, Lu3+ all other trivalent Lanthanoids are paramagnetic.

Chemical reactions: Lanthanoids have low SRP values comparable with alkaline earth metals.
So they are reactive as alkaline earths metals.
 The earlier members of the series are quite reactive similar to calcium but with increasing
atomic number. They behave more like aluminium.

4Ln + 3O2 + heat → 2Ln2O3 2Ln + 3S + heat → Ln2S3

Ln + C + heat → Ln2C, LnsC3, LnC2 (different carbides)

2Ln + 6H2O + heat → 2Ln(OH)3 + 3H2 2Ln + N2 + heat → 2LnN

2Ln + 3X2 → 2Ln X3 2Ln + 6 HCl + heat → 2LnCl3 + 3H2

Uses of Lanthanoids:

1. Used for the production of alloy steels for plates and pipes.
2. Misch metal (Lanthanoid metal 95% and iron 5% and traces of S, C , Ca and Al) used in Mg
based alloy to produce bullets, shell and lighter flint.
3. Mixed oxides of Lanthanoids are used as catalyst in petroleum cracking
4. Some Ln oxides are used as phosphors in television screens.

Actinoids

They contains fourteen elements from Th to Lr.

All the elements of this series are radioactive in nature, where earlier members are have long half
lives where as latter ones have less half lives.

The general electronic configuration of actinides is [Rn]5f1-146d0-17s2

Atomic No. Name Symbol Electron configuration

89 Actinium Ac [Rn] 6d1 7s2
90 Thorium Th [Rn] 6d2 7s2
91 Protactinium Pa [Rn] 5f2 6d1 7s2
92 Uranium U [Rn] 5f3 6d1 7s2
93 Neptunium Np [Rn] 5f4 6d1 7s2
94 Plutonium Pu [Rn] 5f6 7s2
95 Americium Am [Rn] 5f7 7s2
96 Curium Cm [Rn] 5f7 6d1 7s2
97 Berkelium Bk [Rn] 5f9 7s2
98 Californium Cf [Rn] 5f1 7s2
99 Einsteinium Es [Rn] 5f11 7s2
100 Fermium Fm [Rn] 5f12 7s2
101 Mendelevium Md [Rn] 5f13 7s2
102 Nobelium No [Rn] 5f14 7s2
103 Lawrencium Lr [Rn] 5f14 6d1 7s2

Electronic configuration: All the actinoids are believed to have the electronic configuration of 7s2
and variable occupancy of the 5f and 6d subshell. The irregularities in the electronic configurations
of the actinoids, like those in the lanthanoids are related to the stabilities of the f 0, f 7 and f 14
occupancies of the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f 77s2 and [Rn] 5f
76d17s2. Although the 5f orbitals resemble the 4f orbitals in their angular part of the wave-function,

they are not as buried as 4f orbitals and hence 5f electrons can participate in bonding to a far greater
extent.

Ionic size: The general trend in lanthanoids is observable in the actinoids as well. There is a gradual
decrease in the size of atoms or M3+ ions across the series.

Actinoid contraction:The gradual decrease in the size of atoms of actinoids across the
actinoide series is called actinoid contraction

The contraction is, however, greater from element to element in this series resulting from

poor shielding by 5f electrons.

Oxidation states: The actinoids show in general +3 oxidation state. The elements, in the first half of

The series frequently exhibit higher oxidation states. For example, the maximum oxidation state

increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and Np but decreases in succeeding

elements. The actinoids resemble the lanthanoids in having more compounds in +3 state than in the

+4 state. However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states

among the actinoids is so uneven and so different for the earlier and latter elements, it is

unsatisfactory to review their chemistry in terms of oxidation states.

General characteristics:

1. They all are metals with silvery white in appearance.

2. They show variety in their structure due to irregularities in metallic radii.

3. They are highly reactive in their finely divided form.

4. When they react with water they form a mixture of oxide and hydride.

5. They combine with non metal at moderate temperatures.

6. They reacts with Hcl.

7. They are becomes passive when treated with nitric acid due to formation of protective oxide layer.

8. They magnetic property is highly complicated, which vary with the number of unpaired 5f.

Applications of d – block elements:

1. Iron and steel used as construction materials.

2. TiO is used as industrial pigments.

3. Zn, Ni or Cd and MnO2 is used in dry battery cells.

4. V2O5 is used as catalyst during manufacturing of sulphuric acid by contact process.

5. TiCl4 along with Al(CH3)3 known as Ziegler catalyst used in the manufacture of polythene.

6. Iron is used as catalyst during the manufacturing of ammonia by Haber’s process.

7. Ni is used as catalyst during hydrogenation of oils.

8. PdCl2 used as catalyst during oxidation of ethyne to ethanal by Wacker process.

9. Nickel complexes are used in polymerisation of akynes and other organic compounds such as
benzene.

10. AgBr is used as photographic industry due to its light sensitive property.