The Inner Transition Elements
(f – Block Elements)
The Inner Transition Elements
(f – Block Elements)
The f-block consists of the two series comprising of lanthanoids
and actinoids.
The Lanthanoids
Lanthanoids are the fourteen elements following lanthanum.
These elements are called 4f-block elements because while
writing electronic configuration, the last electron enters into the
4f-subshell.
Electronic Configurations
In the electronic configuration of all lanthanoids 6𝑠 2 is common
but 4f orbitals have variable occupancy. However, the electronic
configuration of all the tripositive ions are of the form 4𝑓 𝑛 .
Atomic and Ionic Sizes
On moving across lanthanoids, there is regular decrease in the
atomic and ionic radii, which is known as lanthanoid
contraction.
Atomic and Ionic Sizes
The nuclear charge increases with increasing atomic number.
However, the new electron is added into the 4f – subshells
which has poor/imperfect shielding effect.
Due to this imperfect shielding, increased nuclear charge is not
counter balanced and as a result contraction in the size is
observed.
The decrease in atomic and ionic radii among the lanthanoids is
very small.
Consequences of Lanthanoid
Contraction
(a) Basicity of hydroxides :
It is due to lanthanide contraction that there is variation in the basic
strength of lanthanide hydroxides. Basic strength decreases from
𝐿𝑎(𝑂𝐻)3 to 𝐿𝑢(𝑂𝐻)3 due to increase in covalent character of
hydroxide. Hence, 𝐿𝑎(𝑂𝐻)3 is most basic whereas 𝐿𝑢(𝑂𝐻)3 is
least basic.
Consequences of Lanthanoid
Contraction
(b) Difficulty in separation of lanthanoids :
Since, the decrease in atomic/ionic radii along the lanthanoids is
very small, their chemical properties are similar. Due to this, the
separation of lanthanoids in pure state is difficult.
Consequences of Lanthanoid
Contraction
(c) Similarity in size of elements belonging to same group of
second and third transition series :
The elements belonging to same group of second and third
transition series like Zr and Hf have similar size because of
lanthanoids contraction. Similarly, Nb and Ta also have similar
sizes. Due to similar sizes, these elements are also similar in their
properties.
Oxidation States
The most common oxidation state of lanthanoids is +3.
However, in few cases, some of the elements also show +2 and
+ 4 oxidation states in their compounds.
+2 Oxidation State +4 Oxidation State
Nd (60) Ce (58)
Sm (62) Pr (59)
Eu (63) Nd (60)
Tm (69) Tb (65)
Yb (70) Dy (66)
Oxidation States
The +2 and +4 oxidation states are shown by the elements,
which by losing 2 or 4 electrons acquire stable configuration of
𝑓 0 , 𝑓 7 or 𝑓 14 . For example,
Oxidation States
In some of the other cases, like 𝑃𝑟 4+ 4𝑓 1 , 𝑁𝑑 2+ 4𝑓 4 ,
𝑁𝑑4+ 4𝑓 2 , 𝑆𝑚2+ 4𝑓 6 etc. do not have 𝑓 0 , 𝑓 7 or 𝑓 14
configuration.
Therefore, this type of behaviour cannot be correlated with the
electronic configurations of these elements.
General Characteristics
All the lanthanoids are silvery white soft metals and tarnish
rapidly in air.
The hardness increases with increasing atomic number.
These are metallic and are good conductors of heat and
electricity.
Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be
attributed to the presence of f electrons.
Except promethium they are non-radioactive.
General Characteristics
Lanthanoids are used for the production of alloy steels for
plates and pipes. For example, mischmetal that consists of a
lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C,
Ca and Al. It is used in Mg-based alloy to produce bullets,
shell and lighter flint.
The Actinoids
Actinoids are the fourteen elements following actinium.
These elements are called 5f-block elements because while
writing electronic configuration, the last electron enters into the
5f-subshell.
Electronic Configurations
In the electronic configuration of all actinoids, 7𝑠 2 is common but
5f and 6d orbitals have variable occupancy.
Atomic and Ionic Sizes
On moving across actinoids, there is regular decrease in the
atomic and ionic radii of 𝑀3+ , which is known as actinoid
contraction.
Oxidation States
Beside +3 oxidation state, they show higher oxidation states of + 4
(inTh) + 5(in Pa), +6(in U) and +7 (in Np) due to small energy gap
between 5f, 6d and 7s orbitals.
Thus, there is a greater range of oxidation states in actinoids as
compared to lanthanoids.
General Characteristics
The actinoid metals are all silvery in appearance but display a
variety of structures.
The actinoids are highly reactive metals.
The action of boiling water on them gives a mixture of oxide
and hydride.
Hydrochloric acid attacks all metals but most are slightly
affected by nitric acid owing to the formation of protective
oxide layers; alkalies have no action.
All the actinoids are radioactive.
General Characteristics
The magnetic properties of the actinoids are more complex
than those of the lanthanoids.
The ionization enthalpies of the early actinoids are expected
to be lower than for the early lanthanoids.
The chemistry of lanthanoids is more important because the
chemistry of elements succeeding the actinoids are much less
known at the present time.
Some Applications of d- & f- Block
Elements
Iron and steels are the most important construction materials.
Many compounds are industrially important. For example,
TiO is used in pigment industry, MnO2 is use in dry cell
batteries. The battery industry also requires Zn and Ni/Cd.
The elements of Group 11 (Cu, Ag and Au) are the coinage
metals. Although Ag and Au are restricted to collection items,
the contemporary UK 'copper' coins are copper-coated steel
and the 'silver' UK coins are a Cu/Ni alloy.
Some Applications of d- & f- Block
Elements
Many of the metals and/or their compounds are used as
catalysts in the chemical industry.
For example, V2O5 catalyzes the oxidation of SO2 in the
manufacture of sulphuric acid. TiCl4 with Al(CH3)3 forms the
basis of the Ziegler catalysts used in the manufacture of
polythene. Nickel is used as catalyst in hydrogenation of fats.
Nickel complexes are useful in the polymerization of alkynes
and other organic compounds such as benzene.
Online Chemistry Classes
Dr. Sourabh Monga
(9897057948)
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