Contents of lecture No.
II
Electronic structure of the f elements
Ionization energy of f elements
Metallic and ionic radii
f-Orbitals
Electronic structure of the f elements
The 4-f electrons in the antepenultimate shell
are very effectively shielded from their chemical
environment outside the atom by the 5s and 5p
electrons.
Consequently the 4f-electrons don’t take part in
bonding .
It might be expected that the 14 elements from
cerium to lutetium would be formed by adding,
1,2,3 …electrons into the 4f level.
However, it is energetically favoured to remove
the single 5d electron into the 4f level in most of
the elements. (but not in Gd and Lu…give
reason?)
The elecectronic Configuration of Lanthanum is:.
[Xe] 5d1 6S2
Cerium is [Xe] 4f1 5d1 6S2 not [Xe] 4f2 6S2
This is because at the beginning of the series,
4f and 5d orbitals have comparable energy.
Then after,:
As the atomic number increases the 4f will have
lower energy than 5d, so 5d orbital will be
unoccupied , but not in Gd and Lu……..give
reasons……….?
Gd has the electronic configuration:
[Xe] 4f7 5d1 6s2
Lu has the electronic configuration:
[Xe] 4f14 5d1 6s2
The reason why Gd has a 5d1 arrangement is
that, this leaves a half filled 4f level ,which
gives increased stability
Lu has a 5d1 arrangement because the f shell
is already full.
Ionization energies of f-elements
I.E. is defined as the amount of energy required to
remove an electron from a neutral atom in its
gaseous state
The sum of the first three ionization energies are
lower than the fourth ionization energy.
The (+III) oxidation state is the dominant state for Ln
The extra energy required to remove the fourth
electron is so much and not compensated through
bond formation, so that the fourth electron will not
participate into bond formation and consequently ,
the (+IV) state will be unstable and not common
The following diagram shows the values of the
different I. E. of lanthanides. From which it is
clear that the fourth I.E. is considerably higher
than the first three , which makes the (+IV) state
unstable and not common
values of the different I. E. of lanthanides
The following figure shows the sum of the different
ionization energies of Ln. Curve a, represents the sum
of the firsr two I. E, curve b, represents the sum of the
first three I.E. curve c, shows the sum of the four I.E.
The +II Oxidation state
The only (+II) lanthanides which exist in solution
are , Eu2+ (4f7), Yb2+ (4f14) and Sm2+ (4f6).
The most stable divalent lanthanide is Eu 2+.
This is stable in water but the solution is strongly
reducing.
Aqueous solutions of Eu2+, which are colourless
are obtained by treating Eu(III) solutions with
various reducing agents such as magnesium,
aluminium, iron or zinc, and the reduction may be
carried out electrolytically at a mercury cathode.
The (+III) Oxidation state
The lanthanides are characterized by the uniform
(+III) oxidation state shown by all the metals .
The (+III) state is also common in Gd(III) and
Lu(III). They are easily ionized to the (+III) state
because this renders them having half and
completely filled 4f orbital respectively.
The additional electron in 5d is less stable than 4f
, so it will be easier to ionize to (+III)
A detailed study of the third I. E. showed the
stability of a half-filled and completely filled
shell.
Variation of the third ionization
energy I3 of the lanthanides.
The (+IV) Oxidation state
The only (+IV) lanthanide which exist in solution
and has aqueous chemistry is Ce4+. It is rare to
find (+IV) ions in solution. The high charge on
the ions leads to make it heavily hydrated.
Ce4+ solutions are widely used as an oxidizing
agent in volumetric analysis instead of KMnO4
The elements, Pr ,Dy, Tb and Nd also form (+IV)
state.
These are generally unstable, occur only as solids,
and are found as fluorides or oxides which may
be nonstoichiometric
Metallic and ionic radii
Covalent and ionic radii normally increase on descending a
group in the periodic table due to the presence of extra
filled shells of electron.
On moving from left to right across a period, the covalent
and ionic radii decreases because the extra orbital
electrons incompletely shield the extra nuclear charge
Lanthanide contraction
The contraction in size due to the additive
effect over the 14 lanthanide elements from Ce
to Lu is known as the lanthanide contraction .
Since the properties of an ion depend on
its size and charge, the Ln3+ ions change
by only a small amount from one element
to the other , and their charge is the
same, consequently their chemical
properties are almost the same .
Eu and Yb are best regarded as Ln 2+ which are
larger in size than Ln3+ with only two electrons
per atom involved in metallic bonding which
causes increase in metallic radii with respect to
other Ln.