THE INNER

TRANSITION

ELEMENTS

(F-BLOCK)
Group 5
CONTENT

8.5 The Lanthanoids

8.5.1 Electronic Configurations

8.5.2 Atomic and Ionic Sizes

8.5.3 Oxidation States

8.5.4 General Characteristics

8.6 The Actinoids

8.6.1 Electronic Configurations

8.6.2 Ionic Sizes

8.6.3 Oxidation States

8.6.4 General Characteristics and Comparison with Lanthanoids

8.7 Some Applications of d- and of d- and of-Block Elements

What are Inner

Transition Elements?
The elements constituting the f-block are those in which 4f and 5f orbitals are
progressively filled. These elements are formal members of group 3 but are shown
separately as f-block of the periodic table. The elements of f-block are also called inner
transition elements.

The f-block consists of the two series,

lanthanoids (the fourteen elements
following lanthanum) and actinoids
(the fourteen elements following
actinium).
LANTHANOIDS
ELECTRONIC

CONFIGURATIONS

All of these elements have electronic

configuration 6s² common and all these elements
have variable occupancy of 4f level.
These elements exist in tripositive ions
They are in the form of 4f ⁿ
{n=1 to 14 with increasing atomic number}
Atomic and ionic sizes

The overall decrease in atomic and ionic radii from Lanthanum [La] to Lutetium [Lu] is called
Lanthanoid contraction.
It is because of poor shielding effect of f-electron.
Outermost electrons are shielded or screened from the nucleus by the inner electrons. This is
known as shielding effect or screening effect. Poor shielding therefore means poor screening
of nuclear charge. In other words, the nuclear charge is not effectively screened by electrons.
In series 1 and series 2 , series 2 will have bigger sizes. Similarly in series 2 and series 3 ,both will
have same sizes.
Series 2 and series 3 both will have same sizes. It is due to lanthanide contraction as series 3
has lanthanum{La}.So series 3 will show Lanthanoid contraction.
In Zirconium {Zr} and Hafnium {Hf} both have same radii it is because of lanthanoid contraction
Both of these elements occur together in nature’
It is very difficult to separate them.
Oxidation states

In the lanthanoids, La(II) and Ln(III) compounds are predominant species.

However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained.
This irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty, half-
filled or filled f subshell.
Thus, the formation of CeIV is favoured by its noble gas configuration, but it is a strong oxidant
reverting to the common +3 state.
The Eo value for Ce4+/ Ce3+ is + 1.74 V which suggests that it can oxidise water.
However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2.
Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts for the formation
of this ion.
However, Eu2+ is a strong reducing agent changing to the common +3 state.
TbIV has half-filled f-orbitals and is an oxidant.
The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation
states.
General characteristics

All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
The hardness increases with increasing atomic number, samarium being steel hard.
Their melting points range between 1000 to 1200 K but samarium melts at 1623 K. They have
typical metallic structure and are good conductors of heat and electricity.
Density and other properties change smoothly except for Eu and Yb and occasionally for Sm
and Tm.
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.
Neither La3+ nor Lu3+ ion shows any colour but the rest do so.
However, absorption bands are narrow, probably because of the excitation within f level.
The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and
Lu3+) are all paramagnetic.
In their chemical behaviour, in general, the earlier members of the series are quite
reactive similar to calcium but, with increasing atomic number, they behave more like
aluminium.
→
Values for EV for the half-reaction: Ln3+(aq) + 3e– Ln(s)
are in the range of –2.2 to –2.4 V except for Eu for which the value is –2.0 V. This is, of
course, a small variation.
The metals combine with hydrogen when gently heated in the gas.
The carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated
heated with carbon.
They liberate hydrogen from dilute acids and burn in halogens to form halides.
They form oxides M2O3 and hydroxides M(OH)3.
The hydroxides are definite compounds, not just hydrated oxides.
They are basic like alkaline earth metal oxides and hydroxides.
The best single use of the lanthanoids is for the production of alloy steels for plates and pipes.
A well known alloy is mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and
traces of S, C, Ca and Al.
A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
Some individual Ln oxides are used as phosphors in television screens and similar fluorescing
surfaces.
ACTINOIDS
Actinoids include the 14 elements from Th to Lr
They are radioactive elements
Earlier members have relatively long half lives
Latter ones have half life values ranging from a day to 3 minutes for Lawrencium
Latter members can only be prepared in nanogram quantities
ELECTRONIC

CONFIGURATIONS

Electronic configuration of 7s2

Variable occupancy of the 5f and 6d subshells
The 14 electrons is formally added to 5f
Exception case - Thorium
From Pa onwards the 5f orbitals are complete at Lr
Irregularities - stabilities of the f^0, f^7 and f^14
occupancies of the 5f orbitals
Configurations of Am and Cm are {Rn} 5f^7 7s^2
and {Rn} 5f^76d^17s^2
5f orbitals resemble the 4f orbitals in their angular
part of the wave function , they are not as buried
as 4f orbitals
Hence 5f electrons can participate in bonding to
far greater extent
Ionic sizes

General trend in lanthanoids is observable in the actinoids

A gradual decrease in the size of atoms or M3+ ions across the
series - Actinoid contraction
Contraction is however greater from element to element
resulting from poor shielding by 5f electrons
Oxidation states of Actinoids

There is a greater range of oxidation states, which is in part attributed to the fact that the 5f, 6d
and 7s levels are of comparable energies.
The actinoids show in general +3 oxidation state. The elements, in the first half of the series
frequently exhibit higher oxidation states.
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 former and later elements, it is unsatisfactory
to review their chemistry in terms of oxidation states.
General Characteristics and

Comparison with Lanthanoids

The actinoid metals 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.
The actinoids are highly reactive metals, especially when finely divided. The action of boiling
water on them, for example, gives a mixture of oxide and hydride and combination with most
non metals takes place at moderate temperatures.
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.
The magnetic properties of the actinoids are more complex than those of the lanthanoids.
Although the variation in the magnetic susceptibility of the actinoids with the number of
unpaired 5 f electrons is roughly parallel to the corresponding results for the lanthanoids, the
latter have higher values.
Actinoids that the ionisation enthalpies of the early actinoids, though not accurately known, but
are lower than for the early lanthanoids.
This is quite reasonable since it is to be expected that when 5f orbitals are beginning to be
occupied, they will penetrate less into the inner core of electrons. The 5f electrons, will therefore,
be more effectively shielded from the nuclear charge than the 4f electrons of the corresponding
lanthanoids.
Because the outer electrons are less firmly held, they are available for bonding in the actinoids.
Behaviour similar to that of the lanthanoids is not evident until the second half of the actinoid
series.
However, even the early actinoids resemble the lanthanoids in showing close similarities with
each other and in gradual variation in properties which do not entail change in oxidation state.
The lanthanoid and actinoid contractions, have extended effects on the sizes, and therefore, the
properties of the elements succeeding them in their respective periods.
The lanthanoid contraction is more important because the chemistry of elements succeeding the
actinoids are much less known at the present time.
Some Applications of d-

and f-block Elements

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you!