THE TRANSITION ELEMENTS

Definition:
These are elements which have partially filled d or f shells.

Broad defn:
- Includes elements which have partially filled d or f shells in any of
their commonly occurring oxidation states. This includes:
1. CuII = [Ar]3d9
2. AgII = [Kr]4d9
3. AuIII = [Xe] 5d8

Three groups of Transition elements are recognized:

(i) The main Transition elements or d-block elements.
(ii) The Lanthanoid elements
(iii) The Actinoid elements.

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(i) The Main Transition  d-block elements.
(a) The First Transition series
Sc=4s23d1 = Lightest member
Sc Ti V Cr Mn Fe Co Ni and Cu
Cu = 3d104s1
 Have partially filled 3d shells either in the ground state of the free
atom [All EXCEPT Cu] or in one or more of their chemically
important ions [ALL EXCEPT Sc].
Note: from Zn = 3d104s2 until next 9 elements = NON-TRANSITION
(Sr).

(b) The Second Transition series

From Yttrium = 5s24d1
Y Zr Nb Mo Tc Ru Rh Pd Ag
All have partially filled 4d shells either in the free element [ALL
EXCEPT Ag] or in one or more of the chemically important ions
[ALL EXCEPT Y].
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(ii) The Lanthanoids: Elements 57-71
  Starts with Lanthanum = 6s25d1.
 4f shell becomes slightly more stable than 5d shell.
 Next 14 elements electrons enter the 4f shell until Lu (Lutetium).
4f25s25p66s2 4f7
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu = 4f145d16s2.
The elements La – Lu have very similar chemical and physical
properties.

(c) The Third Transition series.

The Third Transition series starts with Hf = 6s25d2.
4f146s15d10
Hf Ta W Re Os Ir Pt and Au
 All have partially filled 5d shells in one or more of their chemically
important oxidation states as well as in the neutral atom [EXCEPT
Au].
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(iii) The Actinoids: Elements 89-103.
Starts with Ac = 7s26d1 = Actinium
 Initially Not so great difference between 5f and 6d orbitals.

 For Elements immediately following Ac and their ions there

may be electrons in 5f or 6d or both.

 After FOUR or FIVE more electrons have been added to the

Ac configuration, the 5f orbitals become the more stable.
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr.

(iv) The Transactinoid elements = Element 104 (Rutherfordium,

Rf) to 118 (Ununoctium, Uuo).

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Differences between the Three classes of Transition
elements.
1. d-block elements Partially filled 3d, 4d or 5d orbitals.
 Electrons occupying them are strongly influenced by
the surroundings and vice versa. ORBITALS PROJECT
TO THE PERIPHERY OF ATOMS/IONS.

2. The Lanthanoids  Partially filled 4f orbitals.

 Electrons occupying them are largely screened from
the surroundings by the overlying shells [5s, 5p] of
electrons.
 4f orbitals deeply buried in atoms/ions

• Therefore Reciprocal interactions of 4f electrons and

surroundings are of little chemical significance.

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 RESULT:

(i) Chemistry of Lanthanoids  Homologous.

(ii) Chemistry of d-block elements.

Erratic and Irregular variations in chemical properties through a
series of d-block elements.

3. The Actinoids elements.

- Behaviour lies between d-block and the Lanthanoids.
- 5f orbitals  not so exposed as the d-orbitals and not so well
shielded as 4f-orbitals.

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Factors affecting the stability of Electronic
configurations:
1. Effective nuclear charge.
• In hydrogen (one electron atom) all the subshells of
each principal shell are equienergetic.

• In multi-electron atoms  Energies of subshell

depend on the populations of all the other levels.
The s, p, d, f etc. sub-shells split apart and drop to
lower energies.

REASON: Steady increase in the Effective Nuclear

charge.
• Each electron is IMPERFECTLY SHIELDED from
the nuclear charge by other electrons.
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2. Direct interactions between electrons (Inter-electronic
forces).
eg. Special stability of half filled shells.
eg. Cr = [Ar] 4s13d5 1st Transition series.
Cu = [Ar] 4s13d10
Gadolinium  Gd = [Xe] 4f76s25d1 Lanthanoid.

Therefore:
Inter-electronic forces and variations in total nuclear charge play a
large part in determining the configurations of ions.
e.g. 4s orbital  Occupied before 3d but are not always the
more stable.

Example: Elements of the First Transition series ionize by the loss

of the 4s first instead of the 3d.
e.g. Cu = [Ar] 4s13d10
Cu2+ = [Ar] 3d9.
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THEREFORE: Stability of an electronic configuration is
determined by:
(i) Nuclear-electronic attraction.
(ii) Shielding of one electron by others.
(iii) Inter-electronic repulsions.
(iv) Exchange energy of half filled shells.

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 General Properties:
1. They are all metals.
2. They are almost all hard, strong, high-melting, high-boiling metals
that conduct heat and electricity well.
3. They form alloys with one another and with other metallic elements.
4. Many of them are sufficiently electropositive to dissolve in mineral
acids although a few are “noble”
5. With very few exceptions, they exhibit variable valence.
6. Their ions and compounds are coloured in one if not all oxidation
states (with very few exceptions).
7. Due to partially filled shells, they form some paramagnetic
compounds.

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Some general observations.
1. The most common oxidation states are +2 and +3.

2. Species that exhibit low oxidation states can exist as discretely

charged ions either in solution or in a crystalline lattice e.g. Cr2+,
Fe2+ are well known ionic species e.g. FeSO4

3. Elements in higher oxidation states are very polarizing and can

exist only in an environment of highly electronegative atoms
(oxyanions or binary compds of oxygen and fluorine).
eg. +6 for Cr is found in CrO42-
+6 for Mo is found in MoO42-
+6 for W is found in WO42-

4. Oxidation states less than II, except Cu are found only with -
acid type ligands or in organometallic compounds.

5. Lower oxidation states of metals = BASIC

Higher oxidation state of metals = ACIDIC
+4 Oxidation state of metals = AMPHOTERIC
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 ELEMENTS OF THE FIRST TRANSITION SERIES
• Comprised of the elements Ti to Cu, EC: 3dn4s2.

• Energies of 3d and 4s orbitals in the neutral atoms are very

similar.

• Configurations: 3dn4s2 except Cr = 3d54s2, Cu = 3d104s1

• General Observations
1. From Ti to Mn, the highest valence corresponds to total
number of d and s electrons. Stability of highest state
decreases from Ti(IV) to Mn(VII).

2. The oxides of a given element become more acidic with

increasing oxidation state

3. In the II and III oxidation states complexes in aqueous

solutions or in crystals are usually in either FOUR or SIX
coordination

4.The oxidation states less than II except for Cu, are found only
with -acid type ligands or in organometallic compounds 12
OXIDATION STATES

The II state:
• All the elements TiCu form well defined binary
compds (e.g.oxides and halides) in the DIVALENT
STATE. These are essentially ionic eg. MO, MX2.
• Aqua ions are well defined:
• [M(H2O)6]2+ except Ti.
The III state:
• All the elements form at least some compds in this
state. (Highest for Cu).
• eg. Ti2O3, CrF3.
• Fluorides and oxides are generally ionic. Chlorides
may have considerable covalent character eg. FeCl3.
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• The IV state:
• This is an important oxidation state for Ti and V.
• For Cr-Ni, the IV state is found mainly in Fluorides, Fluoro
complex anions, cationic complexes and salts of the oxo
ions.
(iv) The V, VI and VII states:
These occur only as Vv, CrV,VI; MnV,VI,VII and FeV,VI
• All the compounds in these oxidation states are powerful
oxidizing agents eg. CrF5, CrF6, MnO3F.

(v) The lower oxidation states: I,O,-I.

• All the elements form some compds in these states BUT
ONLY WITH -ACID TYPE LIGANDS.

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Ligands

• There are two main types of ligands

1. Classical or simple donor ligands.

These act as electron pair donors to acceptor ions or
molecules and form complexes with all types of lewis
acids, metal ions or molecules.

2. Non-classical, -acid or -bonding ligands.

These form compounds largely with transition metal

atoms.

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-acid ligands
(eg. Substituted phosphines ie. PR3, CN-, PF3, PCl3 etc).

 These are ligands which have lone pairs and vacant -

orbitals. The vacant orbitals accept electron density
from filled metal orbitals to form a type of bonding that
supplements the –bonding.

 The ability of the ligands to accept electron density into

their LOW-LYING -orbitals is called -acidity. The
word acidity being used in the LEWIS SENSE.

e.g. NR3 and amines – NOT -acid. d-orbitals are of too

high energy
PR3 = -acid due to d-orbitals of low energy.

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 THE LANTHANOIDS
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu.

LARGEST NATURAL OCCURING GROUP

The Lanthanoids are strictly the 14 elements that follow Lanthanum in the
Periodic Table, in which fourteen 4f electrons are successively added to
the Lanthanum configuration.
• Prime Oxidation state = +3.
 La = [Xe]5d16s2 Lu = [Xe]4f145d16s2.

The Lanthanoid contraction.

This is the significant and steady decrease in the size of atoms and ions of
the Lanthanoids with increasing atomic number (Z).
 Due to imperfect shielding of one electron by another in the same
SUBSHELL.

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 The largest decrease occurs with the first f electrons added
and also after f7. i.e. between Gd and Tb.

• Elements  highly electropositive.

Prime Oxidation State = +3 This is due to the stabilizing effect

on the 4f orbitals i.e. being deeply deeply buried in the ions.

 Sum of first THREE ionization energies is relatively Low.

 They form [M(H2O)n]3+ n = 6-9.

 Ce can form Ce4+

 Ce = [Xe]6s24f15d1 Ce4+ = [Xe].
 Europium (Eu) and Yttebium (Yb) can form M2+.

Eu2+ = [Xe]4f7 Yb2+ = [Xe]4f14

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Some properties of the Lanthanoids.
1. The metals are very reactive.

2. They all react directly with water, slowly in the cold,

rapidly on heating liberating H2:
2M(s) + 6H2O(l)  2M(OH)3(s) + 3H2(g)

3. React exothermically with hydrogen though heating to

300-350oC is often required to initiate the reaction.
NOTE:
The products are formulated as MH2 but are composed
of MIII, 2H- and e-, the electron being delocalized in a
metallic conduction band.

4. Eu and Yb dissolve in liquid ammonia at –78oC giving

blue solutions. These solutions are those expected for
M2+ ions and solvated electrons.
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 THE TRIVALENT STATE
This is the characteristic oxidation state for all the lanthanoids.
They form:
(i) Oxides and hydroxides [M2O3 and M(OH)3] resembling the
Ca Ba group.
 Basicity decreases with increasing atomic number.

(ii) MX3 ionic halides. The MF3 compounds are insoluble in

water.
(iii) M2S3 and MX (X = N, P, As, Sb or Bi).

THE TETRAVALENT STATE

1. Ce(IV) is the only +4 Lanthanoid ion that exist in aqueous solution as

well as in the solid state.
Compounds: CeO2 (Ceric Oxide), CeO2.nH3O, (Hydrous Ceric Oxide),
CeF4.
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2. Pr (Praseodymium), Tb (Terbium), Nd (Neodymium) and Dy
(Dysprosium) solid compounds of oxidation state IV are
known.
eg. NaPrF5, PrF4, TbO2, TbF4, Cs3 NdF7.

THE DIVALENT STATE

Aqueous solutions and solid compounds of Eu2+ and Yb2+ are

known whereas solid compounds of M2+ of Nd, Sm, Dy and
Tm are known but are unstable in water.

e.g. NdO and SmO (both golden yellow) and EuO (dark red) have
successfully been prepared..

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SOME USES OF THE LANTHANOIDS

1. Additives in special purpose steels. E.g. making

pipes.
2. Catalysis (mixed metal oxides are used).
3. The phosphors inside colour television tubes and
computer monitors.

The impact of electrons on certain mixed lanthanoid

compounds results in the emission of visible light
over a small wavelength range.

E.g.
A mixed oxide of Europium and Yttrium, (EuY)2O3
releases an intense red colour when bombarded by
high energy electrons.

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