d & f Block

Elements
Introduction to f-block
Elements
 Introduction to Inner
Transition Elements

 The elements in which the last electron enters

in f subshell of anti penultimate shell are called
inner transition or f-block elements.

 The f-block consists of the two series,

lanthanoids (the fourteen elements following
lanthanum) and actinoids (the fourteen
elements following actinium).
 Introduction to Inner
Transition Elements

Lanthanoid series
 The elements with atomic numbers 58 to 71 i.e.
Cerium to Lutetium are called lanthanoids or
rare earth metals.

 These elements involve the filling of 4f-orbitals.

 Their general electronic configuration is,

[Xe]4f1–14 5d0–1 6s2.
 Introduction to Inner
Transition Elements

Actinoid series
 The elements with atomic numbers 90 to 103
i.e. Thorium to Lawrencium are called actinoids
or actinons.

 These elements involve the filling of 5f-orbitals.

 Their general electronic configuration is,

[Rn]5f1–14 6d0–1 7s2
 Electronic Configuration
 Lanthanoids

Atomic Element Symbol Outer Configuration

numbe electronic +3 ion
r atomic
58 Cerium Ce 4f1 5d16s2 4f1

59 Praseodymi Pr 4f3 6s2 4f2

um
60 Neodymium Nd 4f4 6s2 4f3

61 Promethium Pm 4f5 6s2 4f4

62 Samarium Sm 4f6 6s2 4f5

63 Europium Eu 4f7 6s2 4f6

64 Gadolinium Gd 4f7 5d1 6s2 4f7

 Electronic Configuration

 Lanthanoids

Atomic Element Symbol Outer Configuration +3

numbe electronic ion
r atomic
65 Terbium Tb 4f9 6s2 4f8

66 Dysprosiu Dy 4f10 6s2 4f9

m
67 Holmium Ho 4f11 6s2 4f10

68 Erbium Er 4f12 6s2 4f11

69 Thulium Tm 4f13 6s2 4f12

70 Ytterbium Yb 4f146s2 4f13

71 Lutetium Lu 4f14 5d1 6s2 4f14

 Electronic Configuration

 Filling of 4f orbitals in the atoms is not regular.

 A 5d electron appears in Gd (z = 64) with an outer

electronic configuration of 4f7 5d1 6s2 (and not 4f8
6s2).

 Filling of orbitals is regular in tri-positive ions.

 Pm is the only synthetic radioactive lanthanide.

Trends in Properties
of Lanthanoids
 Oxidation States

 Lanthanoids

Elements Oxidation states

Ce58 +3, +4
Pr59 +3, (+4)
Nd60 +3
Pm61 +3
Sm62 (+2); +3
Eu63 +2, +3
Gd64 +3
 Oxidation States

 Lanthanoids

Elements Oxidation states

Tb65 +3, +4
Dy66 +3; (+4)
Ho67 +3
Er68 (+2), +3
Tm69 (+2), +3
Yb70 +2, +3
Lu71 +3
 Oxidation States

 Most stable oxidation state of lanthanides is +3.

 +2 and +4 oxidation states also exist but they

revert to +3.

 Sm2+, Eu2+, Yb2+ lose electron to become +3 and

hence are good reducing agents.

 Ce4+, Pr4+, Tb4+ in aqueous solution gain electron

to become + 3 and hence are good oxidizing
agents.
 Oxidation States

 Oxidation states +2 and +4 occur particularly

when they lead to

(i) A noble gas configuration e.g. Ce4+ (f0)

(ii) A half filled ‘f’ orbital e.g. Eu2+, Tb4+, (f7)

(iii) A completely filled ‘f’ orbital e.g. Yb2+ (f14)

 Atomic and Ionic Sizes

 In the lanthanoid series with increasing atomic

number, there is a progressive decrease in the
size from lanthanum to lutetium or from La +3 to
Lu+3. This contraction in size is known as
lanthanoid contraction.
 Atomic and Ionic Sizes

Effects of Lanthanoid contraction

 Close resemblance of Lanthanides:

• Small increases in their ionization energies.

• Gradual decrease in their basic and ionic
nature from La to Lu.
 Atomic and Ionic Sizes

Effects of Lanthanoid contraction

 Anomalous behaviour of post-lanthanides:

• Identical radii of Zr (160 pm) and Hf (159

pm).

• Increase in the ionization potential values

and electronegativities of the elements of
5d transition series.

• The densities of the third transition series

elements are almost double to those of the
second series elements.
Chemical Reactions of Lanthanoids
Actinoids
 Electronic Configuration

 Actinoids

Atomic Element Symbo Outer Configuration

numbe l electronic +3 ion
r atomic
90 Thorium Th 6d2 7s2 5f1

91 Protactinium Pa 5f26d17s2 5f2

92 Uranium U 5f36d17s2 5f3

93 Neptunium Np 5f46d17s2 5f4

94 Plutonium Pu 5f67s2 5f5

95 Americium Am 5f77s2 5f6

96 Curium Cm 5f76d17s2 5f7

 Electronic Configuration

 Actinoids

Atomic Element Symbo Outer Configuration

numbe l electronic +3 ion
r atomic
97 Berkelium Bk 5f97s2 5f8

98 Californium Cf 5f107s2 5f9

99 Einsteinium Es 5f117s2 5f10

100 Fermium Fm 5f127s2 5f11

101 Mendelevium Md 5f137s2 5f12

102 Nobelium No 5f147s2 5f13

103 Lawrencium Lr 5f146d17s2 5f14

 Electronic Configuration

 All the actinoids are believed to have the electronic

configuration of 7s2 and variable occupancy of the
5f and 6d subshells.

 The irregularities in the electronic configurations of

the actinoids, are related to the stabilities of
the f0, f7 and f14 occupancies of the 5f orbitals.
 Th, Pa and U first three actinoids are natural
elements.

 The man-made eleven elements Np – Lr are placed

beyond uranium in the periodic table and are
collectively called trans-uranium elements.
 Oxidation States

 Actinoids

Actinoids Oxidation state

Th90 +4
Pa91 (+4), +5
U92 (+3), (+4), (+5), +6
Np93 (+3), (+4), +5, (+6),
(+7)
Pu94 (+3), +4, (+5), (+6),
(+7)
Am95 +2, (+3), (+4), (+5),
(+6)
Cm96 +3, (+4)
 Oxidation States

 Actinoids

Actinoids Oxidation state

Bk97 +3, (+4)
Cf98 +3
Es99 +3
Fm100 +3
Md101 +3
No102 +3
Lw103 +3
 Oxidation States

 In actinoids, +3 oxidation state is the most

common for elements.

 Actinoids show more variable oxidation number

than lanthanoids due to participation of 5f
electrons as well.

 This oxidation state becomes increasingly more

stable as the atomic number increases in the
actinoid series.
 Atomic and Ionic Sizes

Actinoid contraction
 There is a regular decrease in ionic radii with
increase in atomic number from Th to Lr.

 This is called actinoid contraction analogous to

the lanthanoid contraction.

 It is caused due to imperfect shielding of one 5f

electron by another in the same shell.
 General Characteristics

 Actinoids are all silvery in appearance but

display a variety of structures.

 The structural variability is obtained due to

irregularities in metallic radii which are far
greater than in lanthanoids.
 General Characteristics

Color of the ions

 Ions of actinoids are generally colored which is
due to f-f transitions.

 It depends upon the number of electrons in 5f

orbitals.
 General Characteristics

Magnetic properties
 Actinoids are strongly paramagnetic in nature.
 General Characteristics

Complex formation
 Actinoids have a greater tendency to form
complexes because of higher nuclear charge
and smaller size of their atoms.

 They from complexes even with π-bonding

ligands such as alkyl phosphines,
thioethers etc, besides EDTA, β-diketones, etc.
 General Characteristics

 The actinoids are highly reactive metals,

especially when finely divided.

 The action of boiling water on them gives a

mixture of oxide and hydride.
Comparison with Lanthanoids

Lanthanoids Actinoids
Differentiating Differentiating
electron enters in 4f electron enters in 5f
orbital orbital
Lanthanoid Actinoid Contraction
Contraction
Besides +3 Besides +3, they
oxidation state, they show +4, +5,+6 and
show +4 and +2 in +7 in some cases
some cases
Less tendency to More tendency to
form complexes form complexes
 Uses of d and f
block elements

 Iron and steels are the most important

construction materials.

 Some compounds are manufactured for special

purposes such as TiO for the pigment industry and
MnO2 for use in dry battery cells.

 The battery industry also requires Zn and Ni/Cd.

 The elements of Group 11 are still worthy of being

called the coinage metals.

 UK ‘copper’ coins are copper-coated steel, ‘silver’

UK coins are a Cu/Ni alloy.
 Uses of d and f
block elements

 V2O5 catalyzes the oxidation of SO2 in the

manufacture of sulphuric acid.

 TiCl4 with Al(CH3)3 forms the basis of the Ziegler

catalyst used to manufacture polythene.

 Iron catalysts are used in the Haber process to

produce ammonia.

 In the Wacker process the oxidation of ethyne to

ethanal is catalyzed by PdCl2.