The d & f Block Elements
Inner transition elements (f block elements)
The elements in which the last electron enters in the anti-penultimate f-subshell are called f-block elements.
They are also called inner transition elements.
Since lanthanum (57La) closely resembles lanthanides, it is also included along
with them. Similarly, actinium (89Ac) is included along with actinoids because of its close resemblance
with them.
Lanthanoids : Last electron enters one of the 4f-orbitals. Cerium (at. no. 58) to lutetium (at. no. 71).
Actinoids : Last electron enters one of the 5f-orbitals. Thorium (at. no. 90) to lawrencium (at. no. 103).
General electronic configuration: (n – 2)f 1 – 14 (n – 1)d 0 – 1 ns2
LANTHANOIDS
1. The 14 elements after Lanthanum (57La) having atomic number 58 (Cerium) to 71
(Lutetium ) are collectively known as Lanthanoids.
2. General electronic configuration: 4f 1 – 14 5d 0 – 1 6s2
3. Atomic and Ionic Sizes (lanthanoid contraction):
In lanthanides, the atomic and ionic radii decrease regularly from lanthanum to
lutetium.
This regular decrease in the atomic and ionic radii along lanthanide series (though
very slightly) is called lanthanide contraction.
Reason: In lanthanides, as the atomic number increases, the nuclear charge increases one
by one and the electrons are added to the anti-penultimate f subshell. Due to poor shielding
effect of f orbitals, the nucleus attract the outer most electrons strongly and as a result the
radii decreases.
Consequence of the lanthanoid contraction
1) Due to Lanthanide Contraction the 2nd and 3rd row transition series elements
have similar radii. E.g. Zr – 160 pm and Hf -159 pm.
2) Lanthanides have similar physical properties and they occur together in nature.
So their isolation is difficult.
3) The basic character of their hydroxides decreases from lanthanum to lutetium.
i.e, La(OH)3 is more basic than Lu(OH)3.
Oxidation States:
Most common oxidation state of these elements is +3, However,
occasionally
+2 and +4 ions in solution or in solid compounds are also obtained. This
irregularity arises mainly from the extra stability of empty, half-filled (f 7)or
filled (f 14) subshell.
The formation of Ce(IV) is favoured by its noble gas configuration, but it is a
strong oxidant reverting to the common +3 state.
Eu2+ ( 4f7 ) is a strong reducing agent changing to the common +3 state.
Yb2+ which has f 14 configuration is a reductant.
Tb(IV) has half-filled ( 4f 7 ) f-orbitals and is an oxidant.
Eu2+ Eu3+
Most common
oxidation state
Eu2+
oxi Eu3+ + e
Most common
oxidation state
Therefore, Eu2+ is a good reducing agent.
Similarly Yb2+ also a good reducing agent.
Reduction
Ce (+4) Ce (+3)
Most common
oxidation state
Therefore, Ce (+4) is a good oxidising agent.
Similarly Tb(IV), is a good oxidising agent.
Colour Formation
Many trivalent lanthanoid ions ( f1 to f13 only) are coloured.
Colour of these ions may be attributed to the presence of unpaired
electrons in f subshell.
Neither La3+(f 0) nor Lu3+(f 14) ion shows any colour due to
absence of unpaired electrons in f subshell.
Magnetic Behaviour
The lanthanoid ions other than the
f 0 type (La3+ and Ce4+) and the
f 14 type (Yb2+ and Lu3+) are
All ions ( f 1 to f 13 ) are paramagnetic.
The paramagnetism rises to maximum in neodymium.
Paramagnetic
( f 1 to f 13 )
Coloured
Diamagnetic
( f 0 & f 14 )
Colourless
Ionisation Enthalpies
The first ionisation enthalpies of the lanthanoids are around 600 kJ mol–1.
The second about 1200 kJ mol–1 comparable with those of Ca.
Chemical behaviour
In their, in general, the earlier members of the series are quite reactive
similar to calcium.
but, with increasing atomic number, they behave more like aluminium.
Chemical reactions
of the lanthanoids.
Uses of Lanthanoids:
1. Production of alloy steels for plates and pipes.
2. A well known alloy is mischmetall which consists of a
lanthanoid metal(~ 95%) and
iron (~ 5%) and
traces of S, C, Ca and Al.
3. A good deal of mischmetal is used in Mg-based alloy to produce bullets,
shell and lighter flint.
4. Mixed oxides of lanthanoids are employed as catalysts in petroleum
cracking.
5. Some individual Ln oxides are used as phosphorsin television screens and
similar fluorescing surfaces.
Rare Earth Elements | Application | Strategic Importance
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Trends in the M2+/ M Standard Electrode Potentials
Q.26
The E0(M2+/M) value for copper is positive (+0.34V). What is possibly
the reason for this?
Copper is the only metal in the first series of Transition elements
showing this behavior ?
Ans—
The reduction potential value depends on relative value of three
enthalpies viz ΔaH0 , ΔiH0 and - ΔhydH0 .
The copper has high ΔaH0 and ΔiH0 .
Therefore high enthalpy required to transform Cu(s) to Cu2+(aq) is
not balanced by its low ΔhydH0 .
Q.14 Explain why Cu+ ion is Ans--Cu+ in aqueous solution underoes
not stable in aqueous disproportionation,
solutions? i.e.,
2Cu+(aq) → Cu2+(aq) + Cu(s) . Cu ++ is
more stable .
The E0 value for this is favourable.
Cu++ has higher hydration enthalpy than Cu+
