Melting and Boiling Points : These metals have very high melting and boiling points due

to stronger metallic bonding. The melting points of the transition elements first rise to a maximum
and then fall as the atomic number increases Manganese and technetium have abnormally low
melting points.
In a particular series, the metallic bond strength increases upto the middle with increasing
number of unpaired electrons. Thus Cr, Mo and W have maximum number of unpaired d-electrons
and have highest melting points in their respective series. Tungsten has the highest melting point
(3683 K) among the d-block elements.
As there are no unpaired electrons in Zn, Cd and Hg, they have low melting points. Hg is
liquid at ordinary temperature with lowest melting point (234 K) among the transition metals.
Ionization Enthalpies : The first ionization enthalpies of d-block elements are higher than
those of s-block elements and are lesser than those of p-block elements. The ionization enthalpies
of 3d and 4 d-series are irregular but increase across the series while those 5d-series are much
higher than 3d and 4 d-elements. This is because of the weak shielding of nucleus by 4 f electrons
in 5d-transition series which result in greater effective nuclear charge acting on the outer valence
electrons.
Electrode Potentials and Reducing Character : Quantitatively the stability of transition
metal ions in different oxidation states in solution can be determined on the basis of electrode
potential data. The lower the electrode potential (i.e., more negative the standard reduction potential)
of the electrode, more stable is the oxidation state of the transition metal ion in aqueous solution.
Electrode potential values depend upon energy of sublimation of the metal, the ionization enthalpy
and the hydration enthalpy.
Oxidation States : All transition elements except the first and the last member in each
series show variable oxidation states. This is because difference of energy in the (n1) d and ns
orbitals is very little. Hence electrons from both the energy levels can be used for bond formation.
(i) The highest oxidation states of transition metals are found in fluorides and oxides since
fluorine and oxygen are the most electronegative elements. The highest oxidation state shown by
any transition elements is + 8. Osmium shows highest oxidation state of + 8 in OsO4. Oxygen is
superior to fluorine in showing higher oxidation state because it has the ability to form multiple
bonds with metals.
(iv) Lower oxidation states (zero or + 1) are stabilized by ligands which can accept electrons
from the metal through -bonding (Such as CO), i.e., with -acceptor ligands.
(v) In going down a group, the stability of higher oxidation states increases while that of lower
oxidation states decreases.
(vii) The relative stability of different oxidation states of transition metal atoms can be
determined with the help of standard electrode potential data. For example, E Values for the
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Chemistry

couples Cr3+/Cr2+ = 0.41 V, Mn3+/Mn2+ = + 1.57V suggests that Cr2+ is unstable and is oxidised to
Cr3+ (which is more stable) and acts as a reducing agent whereas Mn3+ is unstable and is reduced
to Mn2+ (which is more stable) and acts as an oxidising agent. It may be noted that both Cr2+ and
Mn3+ are d4 species.
Catalytic Properties : Many transition metals (like Co, Ni, Pt Fe, Mo etc.) and their compounds
are used as catalysts because of the following reasons.
(i)

Transition metal ions change their oxidation states e.g.

Fe3+ Catalyses the reaction between 1 and S2O24 ions
2Fe3+ + 2I 2Fe2+ + I2
2Fe2+ + S2O82 2Fe3+ + 2SO42

(ii)

Because of variable oxidation states, they easily combine with one of the reactants to form
intermediate which reacts with the second reactant to form the final products.

(iii)

They have tendency to adsorb reactants on the surface. This has the effect of increasing the
concentration of reactants and weakening of bonds in reactants.

Coloured Ions: Most of the transition metal compounds are coloured both in the solid state
and in aqueous solution. This is because of the presence of incompletely filled d-orbitals.
When white light falls on these compounds, some wavelength is absorbed for promotion of
electrons from one set of lower energy orbitals to another set of slightly higher energy within the
same d-subshell. This is called d-d transition. The remainder light is reflected which has a particular
colour.
Colours of Cr2O72, CrO42, MnO4, MnO42, Cu2O, AgBr, AgI are due to charge transfer
transitions.
Compounds of s and p-block elements are generally white as high energy is required for
promotion of s and p-electrons of incomplete subshells.
Magnetic Properties : Due to the presence of unpaired electrons in the (n-1) d-orbitals, the
most of the transition metal ions and their compounds are paramagnetic i.e., they are attracted by
the magnetic field. As the number of unpaired electrons increases from 1 to 5, the magnetic
moment and hence paramagnetic character also increases. Those transition elements which have
paired electrons are diamagnetic i.e., they are repelled by the magnetic field.
The magnetic moment of species depends upon the sum of orbital and spin contributions for
each unpaired electron present. In transition metal ions, the orbital magnetic moment is largely
suppressed or quenched by the electrostatic field of other atoms, ions or molecules surrounding the
metal ion. Thus the effective magnetic moment arises mainly from the spin of electrons.
A paramagnetic substance is characterised by its effective magnetic moment () which is
calculated by using spin-only formula

n n 2 B. M .

where n is the number of unpaired electrons and B.M. stands for Bohr magneton.
Complex Formation : Transition metal ions form a large number of complexes in which the
central metal ion is linked to a number of ligands. This is because of the following characteristic
properties of transition metal ions :
(i)
(ii)

They have high nuclear charge and small size i.e., charge/size ratio (charge density is large.
Thus in complexes, metal ions behave as Lewis acids and the ligands as Lewis bases.

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Chemistry

Formation of Interstitial Compounds : Transition metals form a number of interstitial

compounds in which small non-metal atoms such as H, C, B, N and He occupy the empty spaces
(interstitial sites) in their lattices and also form bonds with them.
Alloy Formation : Due to similarity in atomic sizes, atoms of one transition metal can easily
take up positions in the crystal lattice of the other in the molten state and are miscible with each
other forming solid solutions and smooth alloys on cooling. Alloys are generally harder, have higher
melting points and more resistant to corrosion than the individual metals.
Some Important Compounds of Transition Elements
(1) Potassium Dichromate (K2Cr2O7)
Preparation : It is prepared from chromite ore (Fe2Cr2O4 or FeO.Cr2O3) through the following
reactions :
4FeCr2O4 + 16NaOH + 7O2 8Na2CrO4 + 2Fe2O3 + 8H2O
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
2Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
(ii)

In the solution, dichromate ions (Cr 2O 72) exist in equilibrium with chromate ions
(CrO42) as follows :

OH
2

Cr2O72 H2O
2CrO4 2H
H+
Yellow

Orange

In alkaline solution, equilibrium shifts in the forward direction and the solution is yellow. In
the acidic medium, equilibrium shifts in the backward direction and the solution is orange. This
conversion takes place with change in pH of the solution
2. Potassium Permanganate (KMnO4)
Preparation : It is prepared from pyrolusite ore (MnO 2) through the following reactions :
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
(green)

MnO42 undergoes disproportionation in a neutral or acid medium to give KMnO 4.

3MnO42 + 4H+ 2MnO4 + MnO2 + 2H2O.
(green)

(purple)

(b) Electrolytic oxidation : This is the most preferred method. The manganate solution is
electrolysed. The electrode reactions are as follows :
At anode : MnO24 MnO4 e
Green

At cathode : 2H+ + 2e H2.

Purple

The solution is filtered and evaporated to get deep purple black crystals of KMnO 4.

OXIDISING ACTION OF K2Cr2O7 AND KMnO4

Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O (acidic medium),
MnO4 + e MnO42 (highly alkaline medium),
79

E = 1.33 V
E = 0.56 V
Chemistry

MnO4 + 2H2O + 3e MnO2 + 4OH (alkaline medium),

MnO4 + 8H+ + 5e Mn2+ + 4H2O (acidic medium),

E = 1.69 V
E = 1.52 V

Acidified K2Cr2O7 Oxidises

(i)
(ii)

Iodides to iodine : 2l I2 + 2e
Surphides to sulphur : H2S S + 2H+ + 2e.

(iii)

tin (II) to tin (IV) : Sn2+ Sn4+ + 2e

(iv)

Iron (II) to iron (III) : Fe2+ Fe3+ + e

Acidified KMnO4 Oxidises

(i)
(ii)

Iodides to iodine : 2I I2 + 2e
Iron (II) to iron (III) : Fe2+ Fe3+ + e

(iii)

Hydrogen sulphides to sulphur : H2S 2H+ + S + 2e

(iv)

Oxalate iron or oxalic acid to CO2 : C2O42 2CO2 + 2e

(v)

Sulphites to sulphate : SO32 + H2O SO42 + 2H+ + 2e

(vi)
(vii)

Nitrite to nitrate : NO2 + H2O NO3 + 2H+ + 2e

hydrogen peroxide to O 2 : H2O2 2H+ + O2 + 2e

Neutral or Faintly Alkaline KMnO4 Oxidises

(i)
(ii)

Iodide to iodate : I + 6OH IO3 + 3H2O + 6e

Thiosulphate to sulphate : S2O32 + 10.OH 2SO42 + 5H2O + 8e

Lanthanoids and Actinoids

(a)

Lanthanoids : The elements with atomic numbers 58 to 71 i.e., cerium to letetium (which
come immediately after lanthanum Z = 57) are called lanthanoids. These elements involve
the filling of 4f-orbitals. Their general electronic configuration is [Xe]4f114 5d016s2
Promethium (Pm), At. No. 61 is the only synthetic radioactive lanthanide.
Lanthanoid contraction is due to imperfect shielding of 4f electrons. This causes the radii
of the members of third transition series to be very similar to those of the corresponding
members of second transition series.
Oxides and hydroxides of lanthanoids are basic in nature. Trivalent lanthanoid ions are
coloured (except La 3+ and Lr3+) due f f transition which occurs by the absorption of visible
light.

(b)

Actionoids : The elements with atomic numbers 90 to 103 i.e., thorium to lawrencium
(which come immediately after actinium, Z = 89) are called actinoids or actinides.
These elements involve the filling of 5 f-orbitals. Their general electronic configuration is
[Rn] 5f114 6d01 7s2.
5f orbitals in actinoids penetrate less into the inner core of electrons than 4f orbitals in
lanthanoids, i.e., 5f electrons have poorer shielding effect than 4f electrons. Hence actioid
contraction from element to element is more than lanthanoid contraction.
5f orbitals are not as buried as 4f orbitals. Hence 5f electrons participate in bonding to a
far greater extent in actinoids compared with lanthanoids resulting in the participation of
5f electrons of actinoids in bond formation.
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Chemistry