INNER TRANSITION ELEMENTS (F-BLOCK ELEMENTS) -Lanthanides

The first series are called the lantanides or lathanones (rare earth elements). They lie between
57
La and 72Hf and they show close similarities. The second seriesmade up of 14 elements are
called the actinides or actinodes which lie between 89Ac and 103Lr. In the lanthanides and
actinides the last electron enters the f-shell belonging to the antepenultimate shell making the
elements to be referred to as f-block elements. Since lanthanides occurs in period 6, the first
electron enter (n-2) f= 4sub shell (n=6). Similarly since the actinides are present in then=7
period, the first electron enter (n-2) f= 5f block elements.

Lanthanides
Though lanthanum is included in the lanthanide, it has no electrons in the f orbital and it should
be included in the d block elements, but it properties resemble those of the lanthanides and hence
the inclusion.

Oxidation states
The most stable oxidation state is +3 with a few showing the oxidation state of +2 and +4
oxidation state. But most of the +2 and +4 oxidation state is converted to +3 oxidation state. E.g.
Sm2+ +H2O → SM3+ +2OH- + H2
Sm2+ is a good reducing agent.
Ce4+ +Fe2+ → Ce3+ + Fe3+
Ce4+ is a good oxidizing agent. Only Eu (3+, 2+) and Ce (4+, 3+) show redox chemistry.
In some cases where M2+, M3+ and M4+ are observed, it is due to the formation of fo, f7 and f14
which are stable electronic configurations since they are either half or fully filled. E.g.
La3+ = [Xe]4f0
4+
Ce = [Xe]4f0
Eu2+ = [Xe]4f7
3+
Gd = [Xe]4f7
Tb4+ = [Xe]4f7
Atomic /ionic radii and lanthanide contraction
There is a steady decrease of the atomic/ionic radii of the lanthanides as the atomic number
increases as the period is moved from the left to the right. The steady decrease in the
atomic/ionic radii (M3+) of the lanthanides with increasing atomic number is called the lanthanide
contraction. The lanthanide contraction is caused by the shielding by the f orbitals, the increase
in the atomic number and the effective nuclear charge.
As a period is transversed from the left to the right, the nuclear charge (atomic number) increase
by+1 from one element to next. Thus movement from Ce to Lu, due to increase of the nuclear
charge, the attraction between the nucleus and the outermost shell electron increases gradually at
each step. The added electron goes to 4f orbital.
The 4f orbitals have diffused shape and hence the electrons in these orbitals do not shield
effectively the outer electrons from the nucleus attraction. Due to the gradual increase in the
nuclear charge the outermost electrons are attracted by the nucleus and as a result there is a
gradual decrease of the size of the lanthanide elements.

Consequences of lanthanide contraction

The lanthanide contraction determines the chemistry of lanthanides and heavier transition
elements. These include:
a) Basic character
Due to the lanthanide contraction, the size of M 3+ ions decreases with increase in atomic number,
the covalent character between M3+ and OH- increases from La(OH)3 to Lu(OH)3. As a result the
basic character decreases from La3+ to Lu3+.
b) Their chemical properties are similar due to small change in the radii. This similarity in
chemical behavior makes the isolation of the lanthanides very difficult.

Colour
Like transition elements, most of M3+ compounds are colored in the solid as well as in the
aqueous solution and only a few are colorless. E.g. Gd3+ [Xe]4f7 is colorless. Compare Gd3+ and
Mn2+ [Ar]3d5 (slightly pale pink) and Lu3+ [Xe]4f14 with Zn2+ [Ar]3d10 which is colorless. The
half/fully filled states are very stable and therefore they will resist any electronic transitions and
hence most of their solutions are colorless or slightly colored due to orbit spin coupling. d 0, d5,
d10, empty, half and filled d orbitals are very stable and will have no electronic transitions and if
they occur, they are forbidden transitions according to the selection rules. This also applies to f 0,
f7 and f14 where compounds with these configurations are colorless.

Magnetic properties
Most M3+ ions contain unpaired electrons except La 3+ and Lu3+ and therefore their compounds are
paramagnetic. In M3+ ions, the 4f orbitals are deeply buried in the atom and hence shielded by the
5S and 5P orbitals from the incoming ligands. Therefore the 4f orbitals are not able to interact
with the incoming ligands. Thus the orbital motion of the electron s in 4f orbitals is not quenched
as is the case of the d block elements. Hence the observed paramagnetism in 4f block elements is
due to both factors, namely the orbital motion of the electron and its spinning round the axis.
Spin orbit coupling> ligand field splitting, the magnetic moments range from 0µB (La 3+) to 10.55
µB (Dy3+).

Complex formation
Its noticed that the charge to size ratio is very small in the lanthanides and hence they have very
little tendency to form complexes. However they do form complexes with the following ligands;
i) Chelating oxygen containing ligands like EDTA, 2-hydroxy-EDTA, Citric, oxalic acid and
acetylacetone.
ii) Nitrogen containing ligands like ethylenediamine(en) and NCS.

Formation of anhydrous chlorides, MX3

These are readily formed by heating a mixture of the metal oxides and ammonium chloride at
3000C.
M2O3(s) +6NH4CL(s) →2MCl3(s) +H2O(l) +6NH3(g)

Formation of stable carbonates

M3+ ions insolution reacts readily with soluble carbonates to form stable metal carbonates,
M2(CO3)3. This is unusual because small cations especially ones with high charge polarize CO3 2-
e.g Ferric carbonate and aluminium carbonate do not exist
Formation of insoluble fluorides and oxalates
Lanthanide ions react readily with fluorides to form their insoluble salts

M3+ + 3F- →MF3(s)

The ions also react with oxalate to form insoluble oxalates which is a very useful property as it is
used for the separation of lanthanides from other transition elements.

Task
Suppose you are employed as a county chemist in your home county and an ore has been
discovered containing Al3+, Fe3+ and Ce3+. Explain to the county executive how you can separate
the three elements in the ore to convince them of its viability. Use chemical illustrations in your
explanation.

The lanthanide contraction is also observed among transition elements and elements in other
blocks of the periodic table though not as conspicuous as in the lanthanides.
For example for given oxidations state the ionic sizes decreases from the left to the right as can
be seen from the following:
Ion Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+
Ionic 0.94 0.88 0.84 0.80 0.78 0.73 0.70 0.68
radius(Ao)
Ion Zr4+ Nb4+ Mo4+ Te4+ Ru4+ Rh4+ Pd4+ Ag4+
Ionic 0.79 0.74 0.70 - 0.67 0.63 0.62 -
o
radius(A )
Ion Hf4+ Ta4+ W4+ Re4+ Os4+ Ir4+ Pt4+ Au4+
Ionic 0.78 0.68 0,70 0.67 - - - -
radius(Ao)
The decrease of ionic size from the left to right is observed in all the series and it’s called the
lanthanide contraction as it’s conspicuously observed among the lanthanides.
When a solution of potassium iodide is added to acidified copper sulphate solution a white
precipitate is formed and the solution left is deep brown. Explain this observation.
Explanation
Cu2+(aq) + 2I-(aq) → CuI(s) + 1/2I2(s)
2I-(aq) + 1/2I2(s) → I3-(aq) =[ I-I-I]- (linear structure which is deep brown in colour)

Explain the following trend of trichlorides formed by the 1st d series elements;

TiCl3, VCl3, CrCl3, MnCl3, FeCl3, CoCl3, NiCl3, CuCl3 (x-they don’t form).
3+
This is because the size of M decreases from the left to the right of the period. The atomic
number increases in the same trend. This increases the charge density or the polarizing power of
the cations as a period is moved from the left to the right making them to withdraw electrons
from anions. This increases from Ti to Fe whereby it is not strong enough enabling the cations
to coexist with the cation. In Co 3+ and the subsequent cations the polarizing power is high
enough to polarize chloride ions not enabling them to coexist together. Thus the solution of
cobalt trichloride takes an electron from one chloride anion oxidizing it to chlorine gas and the
solution is converted into cobalt (II) chloride which is stable.
CoCl3(aq) → CoCl2(aq) + ½ Cl2(g)
 Explain why Co2O3 when dissolved in sulphuric acid oxygen gas is liberated?
Co3+ in acidic medium has high polarizing power and it oxidizes oxide into oxygen gas which is
liberated.
Co3+ + O2- → [Co(H2O)6]2+(aq) + 1/2O2(g)

Permanganate is a strong oxidizing agent the rhenate. Explain this observation?

Explanation
As the group is descended the size of the ions of the elements increases. This means that Mn 7+
ion in MnO4- has a smaller size than Re7+ in ReO4-. Due to the small size of Mn7+ ion is has a high
polarizing power which makes it to withdraw electrons from the oxide ion to extent to release
oxygen which enables to be a strong oxidizing agent. Re 7+ has a large size and hence a lower
polarizing power than Mn7+ which make it to have lower electron withdrawing ability from the
oxide and hence lower oxygen releasing ability. This makes ReO 4- to be a weaker oxidizing
agent.

Heavy d elements have high tendency to form cluster complexes e.g. chromium chloride in
water undergoes fully ionization to form chromium (II) and chloride ions while MoCl 2 is only an
empirical formula it should be formulated as Mo 6Cl12 which undergoes partial dissociation in
water to form chloride and [Mo6Cl8]4+ cluster ion. It is found that only one third of the chloride in
the molybdenum chloride is ionized.
CrCl2 + ∞H20→ [Cr(H2O)6]2+ + 2Cl-(aq)
Mo6Cl12 + ∞H2O → [Mo6Cl8]4+ + 4Cl-(aq)
Similarly, WBr3 = W6Br18 and ionizes to form [W6Br12]6+ + 6Br-
CrCl2 is paramagnetic while WCl2 is diamagnetic as a consequence of the lanthanide contraction.
CrCl2 has unpaired electrons in Cr2+ which accounts for the magnetic character while the cation
in WCl2 exist as a cluster ion in which all the electrons are paired as they are used to form bonds
within the structure making it to be diamagnetic. The other compounds which are diamagnetic
include NbCl2, NbCl3, MoCL3, TeCl2, TeCl3, WCl3, HfCl2, HfCl3, ZrCl2, and ZrCl3.
ZrX2, HfX2, MoX2, MoX3, TeX2, TeX3, TaX2, TaX3, NbX2 and NbX3(x= Cl, Br, I)

ZrX2, HfX2, TaX2 have the structure

 M

M M

M M

It has six vertices and twelve edges on each vertice of a regular octahedron there is Zr or Hf or
Ta atom and on each edge there is X.
The general formula of the complex is M6X12 and this unit is present in Zr2+, Zr3+, Hf3+, Hf2+,
Nb2+, Nb3+, Ta2+, Ta3+ and W3+ species. If chlorine, bromine or iodine is added to this unit (M6X12)
the incoming halogens form bridges and are added in stages e.g.
Zr6Cl12 +1/2Cl2 → Zr6Cl13
Zr6Cl12 + Cl2 → Zr6Cl14
Zr6Cl12 + 3/2Cl2 → Zr6Cl15
Zr6Cl12 + 2 Cl2 → Zr6Cl16
Zr6Cl12 + 5/2Cl2→ Zr6Cl17
Zr6Cl12+ 3Cl2 → Zr6Cl18
Zr6Cl12 + 7/2Cl2→ Zr6Cl19
Zr6Cl12 + 4Cl2 → Zr6Cl20
Zr6Cl12 + 9/2Cl2→ Zr6Cl21
Zr6Cl12 + 5Cl2 → Zr6Cl22
Zr6Cl12 +11/2Cl2→ Zr6Cl23
Zr6Cl12+6Cl2 → Zr6Cl24
ReX3(X=Cl, Br, I) are best formulated as (ReX3)3 and has the structure

X X
X

Re Re

X
X
X X

Re

X X

The physical and chemical properties of 2 nd and 3rd d series elements in a given period are very
similar as a consequence of the lanthanide contraction. Thus all the minerals which contain
zirconium contains hafnium, all minerals containing niobium also contains tantalum. Hence in
the metallurgy of zirconium the first problem to solve is to separate hafnium. Similarly in the
metallurgy of niobium the first problem to be solved is the separation of tantalum. Many
minerals of molybdenum also contain tungsten. The condensed oxo species of molybdenum and
tungsten are very similar in chemical and physical reactions.