THE INNER TRANSITION ELEMENTS ( f-BLOCK)

The f-block consists of the two series:-

lanthanoids (the fourteen elements following lanthanum) and
Actinoids (the fourteen elements following actinium).
lanthanum closely resembles the lanthanoids, it is included in the
discussion of the lanthanoids with the symbol Ln.
Similarly, a discussion of the actinides includes actinium besides
the fourteen elements constituting the series.
The lanthanoids resemble one another more closely than the
members of ordinary transition elements in any series.

LANTHANOIDS ACTINOIDS
The chemistry of the actinoids is, on the
other hand, much more complicated. The
complication arises partly due to the
occurrence of a wide range of oxidation
states in these elements and partly
They have only one stable oxidation state because their radioactivity creates special
and their chemistry provides an excellent problems in their study.
opportunity to examine the effect of small The actinoids are radioactive elements and
changes in size and nuclear charge along earlier members have relatively long
a series of similar elements. half-lives, the latter ones have half-life
values ranging from a day to 3 minutes for
lawrencium (Z =103). The latter members
could be prepared only in nanogram
quantities. These facts render their study
more difficult.
Have electronic configuration with 6s2 Electronic configuration
common.The electronic configurations of Have the electronic configuration of
all the tripositive ions (the most stable [Rn] 5f 1-14 6d0-1 7s2
(+3)oxidation state of all the lanthanoids) and variable occupancy of the 5f and 6d
are of the form 4fn subshells. The fourteen electrons
(n = 1 to 14 with increasing atomic are formally added to 5f, no electron in f
number). orbital of thorium (Z = 90) but from Pa
[Xe] 4f3 5d0 6s2 ----> Pr onwards the 5f orbitals are complete upto
Pr 3+ ----->[Xe] 4f2 element 103. The irregularities in the
electronic configurations of the actinoids,
are related to the stabilities of the f0, f7
and f14 of the 5f orbitals. Thus, the
configurations of Am and Cm are
[Rn] 5f7 7s2 and [Rn] 5f7 6d1 7s2. 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.( difference 1)

The overall decrease in atomic and ionic

radii from lanthanum to lutetium due to
lanthanoid contraction which is a unique
feature in the chemistry of the Ionic Sizes
lanthanoids. The decrease in atomic radii gradual decrease in the size of atoms or
(derived from the structures of metals) is M3+ ions across the series due to the
not quite regular as it is regular in M 3+ actinoid contraction (like lanthanoid
ions. This contraction is similar to that in contraction). The contraction is greater
an ordinary transition series due to the from element to element in this series
imperfect shielding of one electron by resulting from poor shielding by 5f
another in the same subshell. However, electrons.
the shielding of one 4 f electron by
another is less than one d electron by
another with the increase in nuclear
charge along the series. There is a fairly
regular decrease in the sizes with
increasing atomic numbers.
The contraction of the lanthanoid series is
known as lanthanoid contraction, causing
the radii of the members of the third
transition series to be very similar to those
of the corresponding members of the
second series.
The almost identical radii of Zr(160 pm)
and Hf (159 pm) is a consequence of the
lanthanoid contraction and also account
for the occurrence of elements together in
nature and face difficulty in their
separation.
Oxidation States
Oxidation States

La(II) and Ln(III) compounds are predominant Greater range of oxidation states, which is
species. Occasionally +2 and +4 ions in solution due to the comparable energies of 5f, 6d
or in solid compounds are also obtained.This
and 7s levels.
irregularity (as in ionisation enthalpies) arises
due to the extra stability of empty, half-filled or
The actinoids show in general +3 oxidation
filled with subshells . state. The elements in the first half of the
The formation of Ce(IV) is favoured by its noble series frequently exhibit higher oxidation
gas configuration, but it is a strong oxidising states. For example, the maximum
agent back to the common +3 state. oxidation state increases from +4 in Th to
The Eo value for Ce4+/ Ce3+ is + 1.74 V which
+5 in Pa, +6 in U and +7 in Np , but
suggests that it can oxidise water.
The reaction rate is very slow and hence Ce(IV)
decreases in succeeding elements.
is a good analytical reagent. The actinoids resemble the lanthanoids in
Pr, Nd, Tb and Dy also exhibit +4 states only in having more compounds in +3 state than in
oxides - MO2 . the +4 state. However +3 and +4 ions tend
Eu2+ is formed by losing the two s electrons and to hydrolyse.
its f 7 configuration accounts for the formation of
Because the distribution of oxidation states
this ion.
Eu2+ is a strong reducing agent changing to the
among the actinoids is so uneven and so
common +3 state. different for the former and later elements,
Yb2+ which has f 14 configuration is a reductant. it is unsatisfactory to review their chemistry
Tb(IV) has half-filled f-orbitals and is an oxidant. in terms of oxidation states.
The behaviour of samarium is very much like
europium, exhibiting both +2 and +3 oxidation
states.

General Characteristics And Comparison

General Characteristics With Lanthanides
● silvery in appearance
● Display a variety of structures. The
structural variability is obtained due
to irregularities in metallic radii which
● silvery white soft metals and tarnish are far greater than in
rapidly in air. lanthanoids.(difference 2)
● The hardness increases with increasing
● The actinoids are highly reactive
atomic number, samarium being steel
hard. metals, especially when finely
● Their melting points range between 1000 divided.(difference 3)
to 1200 K but samarium melts at 1623 K. ● The action of boiling water on
● They have a typical metallic structure and actinoids, gives a mixture of oxide
are good conductors of heat and and hydride.
electricity.
● combination with most non metals
● Density and other properties change
smoothly except for Eu and Yb and takes place at moderate
occasionally for Sm and Tm. temperatures.
● Hydrochloric acid attacks all metals
but most are slightly affected by nitric
acid (oxidising agent) owing to the
formation of protective oxide
layers;
● alkalies have no action.

● Trivalent lanthanide ions are coloured

both in the solid state and in aqueous ● The magnetic properties of the
solutions.
actinoids are more complex than
● Colour of these ions may be due to the
presence of f electrons. those of the lanthanoids (difference
● Neither La3+ nor Lu3+ ion shows no 3). Although the variation in the
colour due empty f orbital and completely magnetic susceptibility of the
filled d orbital but the rest do so. actinoids with the number of unpaired
Absorption bands are narrow 5 f electrons is parallel to the
because of the excitation within f level.
corresponding results for the
The lanthanoid ions other than the f0 type
(La3+ and Ce4+) and the f 14 type (Yb2+ and lanthanoids, but the lanthanoids have
Lu3+) are all paramagnetic. higher values.

Ionisation enthalpy IONISATION ENTHALPY

The ionisation enthalpies of the early
actinoids, though not accurately known, but
are lower than for the early
lanthanoids(difference 4). This is quite
ionisation enthalpies of the lanthanoids are reasonable since it is to be expected that
around 600 kJ mol–1, the second about 1200 kJ
when 5f orbitals are occupied in the
mol–1 comparable with those of calcium.
The variation of the third ionisation enthalpies
begining , they will penetrate less into the
indicates that the exchange enthalpy inner core of electrons.
considerations (as in 3d orbitals of the first The 5f electrons will be more effectively
transition series), appear to impart a certain shielded from the nuclear charge than the
degree of stability due to empty, half-filled and 4f electrons of the corresponding
completely filled orbitals f level.
lanthanoids.
This is indicated from the abnormally low value
of the third ionisation enthalpy of lanthanum,
Because the outer electrons are less firmly
gadolinium and lutetium. held, they are available for bonding in the
actinoids.
A comparison of the actinoids with the
lanthanoids, with respect to
different characteristics, reveals that
behaviour is similar to that of the
lanthanoids is not evident until the second
half of the actinoid series.
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.
chemical behaviour

The earlier members of the series

are quite reactive similar to calcium but,
with increasing atomic number, they
behave more like aluminium.
The earlier members of the series are
quite reactive similar to calcium but, EV of
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. a very small variation.

When the metal heated with

(i) hydrogen - forms hydrides
(ii) carbon - carbides (Ln3C, Ln2C3 and
LnC2)
(iii) with acids - hydrogen liberated
(iv) burns with halogen - halides
(v) with oxygen - oxides ( M2O3)
(vi) with water - hydroxide (M(OH)3) -
basic
like alkaline earth metal oxides and
hydroxides.
USES
● 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.

QUESTIONS:
1. Name a member of the lanthanoid series which is well known
to exhibit +4 oxidation
2.Actinoid contraction is greater from element to element than
lanthanoid contraction. Why?
Some Application of d- and f-Block Elements
● Iron and steel are the most important construction materials.
● Their production is based on the reduction of iron oxides,
the removal of impurities and the addition of carbon and
alloying metals such as Cr, Mn and Ni.
● 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, although Ag and Au are restricted to
collection items and the contemporary UK ‘copper’ coins are
copper-coated steel.
● The ‘silver’ UK coins are a Cu/Ni alloy.
● Many of the metals and/or their compounds are essential
catalysts in the chemical industry.
● V2O5 catalyses the oxidation of SO2 in the manufacture of
sulphuric acid.
● TiCl4 with Al(CH 3)3 forms the basis of the Ziegler catalysts
used to manufacture polyethylene (polythene).
● Iron catalysts are used in the Haber process for the
production of ammonia from N2/H2 mixtures.
● Nickel catalysts enable the hydrogenation of fats to proceed.
● In the Wacker process the oxidation of ethyne to ethanal is
catalysed by PdCl2.
● Nickel complexes are useful in the polymerisation of alkynes
and other organic compounds such as benzene.
● The photographic industry relies on the special
light-sensitive properties of AgBr.
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