They were earlier called as rare earth metals as it was believed that they exist in earth's crust to a veryless

extent for e.g.: Pm, does not exist in the earth's crust. But this terminology is now not applicable asthey exist
in earth's crust to a sufficient extent.

(A) INNER TRANSITION ELEMENTS

The elements in which the additional electron enters in (n - 2) forbitals are called inner transitionelements. or
f-block elements.

(a) Position in the periodic table

The lanthanides resemble yttrium in most of their properties. So it became necessary to accomodate all the
fifteen elements together at one place. This has been done by placing the first element, lanthanum below
yttrium and placing the remaining fourteen elements separately in the lower part of the periodic table.

Lanthanide series (Z = 58 - 71) (Ce - Lu)

(b) Lanthanides (4f-block elements)

Lanthanides are reactive elements so do not found in free state in nature. Most important minerals for lighter
Lanthanides are - Monazite, cerites and orthite and for heavier lanthanides - Gadolinite and Xenotime

(c) Electronic configuration

The general configuration of lanthanides may be given as 4f ^ (2 - 14) * 5s ^ 2 * 5p ^ 6 * 5d ^ (0/1) * 6s ^ 2

i. It is to be noted here that filling of 4f orbitals in the atoms is not regular. A 5d electron appears in
gadolinium (z=64) with an outer electronic configuration of 4f 7 5d 1 6s2 and not 4f 6 6s 2 . This is
because the 4f and 5d electrons are at about the same potential energy and that the atoms have a
tendency to retain stable half filled configuration.
ii. On the other hand, the filling of f orbitals is regular in tripositive ions.

iii. After losing outer electrons, the f-orbitals shrink in size and became more stable. Pm is the only
synthetic radioactive lanthanide.

i. Oxidation states in brackets are unstable states

ii. The lanthanides contains twos electrons in the outermost shell, they are therefore expected to exhibit a
characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.

iii. This corresponds to the use of two outermost electrons (6s2) along with one inner electron. The inner
electron used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.

iv. All the lanthanides attains +3 oxidation state and only cerium, Praseodymium, and terbium exhibit
higher oxidation state (+4).
Oxidation states +2 and +4 occur particularly wen they lead to

i. A half filled 'f' orbital eg. Ea2+ , Tb4+ ,( f 7 )

ii. A noble gas configuration e.g. .Ce4+ (f 0)

iii. A completely filled 'f' orbital eg Yb2+ (f14 )

(e) Magnetic properties:

Therefore, in higher oxidation state, they act as oxidising while in lower state as reducing agents.

In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to
Gadolinium (0 to 7) and then continuously decreases upto lutecium (7 to 0). So lanthanum and luteciumions
which are diamagnetic, all other tripositive lanthanide ions are Paramagnetic.

Colour-The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible
region of light and undergo f-f transition and hence exhibit colour. The colour exhibited depends on the
number of unpaired electrons in the 4f orbitals. The ions often with 4f configuration have similar colour to
those ions having 4f14-n configuration.Lanthanide ions having 4f 0, 4f7 ,4f14 colourless. Lanthanide ions 4f1
and 4d13 are also colourless.

(f) Other Properties:

i. Highly dense metals with high m.pts. (do not show any regular trend).

ii. lonisation Energies-Lanthanides have fairly low ionisation energies comparable to alkaline earth metals.

iii. Electropositive Character - High due to low I.P.

iv. Complex formation-Do not have much tendency to form complexes due to low charge density
because of their large size.
Lu+3 smallest in size can only form complex.

(e) Reducing Agent - They readily lose electrones so are good reducing agent.

i. In+3 oxidation states, nitrates, perchlorates and sulphates of lanthanides and actinides are water soluble,
while their hydroxides, fluorides and carbonates are water insoluble.

ii. Alloys of lanthanides with Fe are called misch metals

iii. La(OH)3 is most basic in nature while Lu(OH)3 least basic.

iv. Lanthanides form MC2 type carbide with carbon, which on hydrolysis gives C2H2

(B) LANTHANIDE CONTRACTION:

i. In the lanthanide series with increasing atomic number, there is a progressive decrease in the size from
lanthanum to lutecium or from La+3 to Lu+3. This contraction in size is known as lanthanide contraction.

ii. The general electronic configuration of these elements is 4f0-14 5s2 p6 d0-16s2. In these elements the added
electron enters the deep seated f-orbitals and therefore experiences considerable pull by the nucleus.

iii. Such an electron cannot add to the size of the element and also because the intervening 5s²p6d1
electronic shells, it is very little screening effect on the outermost 6s2 electrons. Hence with increasing
atomic number, the enhanced nuclear charge leads to contraction in the size of atoms and ions.

iv. The atomic volumes of europium and ytterbium are unexceptedly large. The large atomic size of Eu and
Yb suggest weaker bonding in the solid elements. Both these elements have only two electrons extra
than the stable configurations (half filled, f7 and completely filled, f14), hence they utilise two electrons
in metallic bonding as in the case with barium.

(C) EFFECTS OF LANTHANIDE CONTRACTION

i. Close resembalace of Lanthanides:- The general decrease in the sizes of the lanthanides with an increase
in their nuclear charges result in a small increase in their ionisation energies. Hence their basic and ionic
nature gradually decreases from La to Lu. This also explains the variations in properties such as increased
tendency for hydrolysis and formation of complex salts and decreased thermal stability, solubility of their
salts.

ii. Similarity of yttrium with lanthanides: The properties of yttrium are so similar to the lanthanides that it is
considered more a member of the lanthanide series than a congener of scandium.

iii. Anomalous behaviour of post-lanthanides:- The following anomalies may be observed in the behaviour
of post-lanthanide elements.

a) Atomic size - The ionic radii of Zr+4 is about 9% more than Ti+4. Similar trend is not maintained on
passing from the second to third transition series. The ionic radius of Hf +4 instead of increasing
(because of inclusion of one more electronic shell), decreases (or is virtually equal to Zr+4) as a
consequence of the lanthanide contraction. This explains the close similarities between the members of
the second and third transition series than between the elements of the first and second series.

b) lonisation potential and electronegativity: The effect of lanthanide contraction is also seen in the
increase in the ionisation potential values and electronegativities of the elements of the third transition
series, contrary to the general trend.
Because of the lanthanide contraction, the post-lanthanide elements have stronger positive field and thus the
electrons are held more tightly.

The greater effective nuclear charge of the former make them more electronegative than the latter.

(c) High density:- Because of lanthanide contraction the atomic sizes of the post lanthanide elements
become very small. consequently, the packing of atoms in their metallic crystals become so much compact
that their densities are very high.

The densities of the third transition series elements are almost double to those of the second series elements.

(D) APPLICATION OF LANTHANIDES

Cerium is most useful element in the lanthanides

i. Ceramic application-CeO2, La₂O3, Nd₂O₃ and Pr₂P3 are used as decolourizing agents for glasses.

ii. CeS (m.p.-2000°C) is used in the manufacture of a special type of crucibles and refractories.

iii. Lanthanide compounds like cerium molybdate, cerium tungstate are used as paints and dyes.

iv. In textile and leather industries (Ce salts).

(E) ACTINIDES (5f - BLOCK ELEMENTS)

1. The elements in which the extra electron enters 5f-orbitals of (n-2)th main shell are known as actinides,

2. The man made eleven elements Np93-Lr103 are placed beyond uranium in the periodic table and are
collectively called trans-uranic elements.

3. Th. Pa and U first three actinides are natural elements.

 Electronic configuration - The general configuration of actinides may be given as 5f 1-14 6d 0/1,7s2.