d and f block elements

General Characteristics of transition elements:

a) Metallic character: All transition elements are metallic in nature, i.e. they have strong
metallic bonds due to the presence of unpaired electrons. This gives rise to properties like
high density, high enthalpies of atomization, and high melting and boiling points.
b) Atomic radii: The atomic radii decrease from Sc to Cr because the effective nuclear charge
increases. The atomic size of Fe, Co, Ni is almost same because the increase in nuclear
charge is cancelled by the increase in shielding effect of d electrons added with the increase
in atomic number. Cu and Zn have bigger size because the electron-electron repulsions
increases. (Atomic and ionic radii increase from 3d-series to 4d-series but the radii of the
third (5d) series elements are virtually the same as those of the corresponding member of the
second series. It can be explained on the basis of lanthanoid contraction [poor shielding of 4f
electrons].
c) Lanthanoid Contraction: The steady decrease in the atomic and ionic radii of the transition
metals with the increases in atomic number, due to the ineffective shielding of 4f orbitals
which is being filled before the 5d orbitals is called lanthanoid contraction. It is because of
lanthanoid contraction that the atomic radii of the second row of transition elements are
almost similar to those of the third row of transition elements.
d) Ionisation enthalpy: In a series as we move from left to right, ionization enthalpy increases
due to increase in nuclear charge but not in regular trend. The slight and irregular variation in
ionization energies of transition metals due to irregular variation of atomic size. The I.E. of
5d transition series is higher than 3d and 4d transition series because of Lanthanoid
Contraction.
e) Oxidation state: Transition metals show variable oxidation states due to tendency of (n-1)d
as well as ns electrons to take part in bond formation.
*The transition elements in their lower oxidation states (+2 and +3) usually forms ionic
compounds. In higher oxidation state, compounds are normally covalent.
*High oxidation states are more stable for higher elements. For example in group 6, Mn (VI)
and W(VI) are found to be more stable than Cr(VI).
*The higher oxidation state of an element is exhibited in its compounds with fluorine and
oxygen because these are highly electronegative and strong oxidising agents. The ability of
fluorine to stabilise the highest oxidation state is due to either higher lattice enthalpy or
higher bond enthalpy Ability of oxygen to stabilise these higher oxidation state exceeds that
of fluorine due to its ability to form double bonds.
f) Magnetic properties: Most of transition metals are paramagnetic in nature due to presence
of unpaired electrons. It increases from Sc to Cr and then decreases because number of
unpaired electrons increases from Sc to Cr and then decreases.
Magnetic moment of a paramagnetic species is given by μ= n(n+2) B.M. where n is the
number of unpaired electrons.
g) Catalytic properties: Most of transition metals are used as catalyst because of (i) variable
oxidation state (ii) large surface area, (iii) presence of incomplete or empty d – orbitals, (iv)
ability to form complexes, e.g., Fe, Ni, V2O3, Pt, Mo, Co and used as catalyst.
h) Formation of coloured compounds: They form coloured ions due to presence of
incompletely filled d – orbitals and unpaired electrons, they can undergo d – d
transition by absorbing colour from visible region and radiating complementary colour.
* Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured. Give reason.
Ans. Transition metal ions are coloured due to d−d transition. Unpaired electrons in d orbitals
are excited from lower energy level to higher energy level. For this, energy from visible
region is absorbed.
Sc3+ has outer electronic configuration of 3d04s0 with zero unpaired electrons. Hence, it is
colourless. Ti3+ has outer electronic configuration of 3d14s0 with one unpaired electron.
Hence, it is purple coloured.
(i) Formation of complexes: Transition metals form complexes due to (i) presence of vacant
d – orbitals of suitable energy (ii) smaller size (iii) higher charge on cations.
e.g.,K4[Fe(CN)6]
(j) Interstitial compounds: Transition metals have voids or interstitials in which C, H, N,
B etc. can fit into, resulting in formation of interstitial compounds. They are non –
stoichiometric, i.e., their composition is not fixed, e.g., steel. They are harder and less
malleable and ductile.
(k) Alloys formation: They form alloys due to similar ionic size. Metals can replace each
other in crystal lattice, e.g., brass, bronze, steel etc.
(l) Enthalpy of atomisation: Transition elements exhibit higher enthalpies of atomization.
Because of the presence of a large number of unpaired electrons in their atoms, they have
stronger interatomic interactions and hence, stronger bond.
(m) Trends in the M2+ / M standard electrode potentials Eo M2+ / M
is governed by three factors., Enthalpy of atomisation, enthalpy of ionisation and enthalpy of
hydration. The irregular trend in 3d series is due to irregular variation in ionisation enthalpy
and enthalpy of atomisation. Except copper, 3d – elements are good reducing agents. [If sum
of the first and second ionisation enthalpies is greater than hydration enthalpy, standard
electrode potential will be positive, and reactivity will be lower and vice-versa.]
Negative electrode potential value means oxidised species is more stable than reduced
species. Mn and Zn have half-filled and completely filled d orbitals. It gives them stability
and not get reduced. Ni has high negative hydration enthalpy. Therefore, the value of standard
electrode potential of Mn, Zn, Ni is more negative.
Note: [ Cr3+:t2g3, Mn2+: d5 , Fe3+ :d5]
*Give reason: The E∘ value for the Mn3+/Mn2+ couple is much more positive than that
for Cr3+ /Cr2+ couple or Fe3+ /Fe2+ couple.
Ans. Because Mn3+ ion receiving an electron gets d-subshell half-filled(d5) which is highly
stable, while in case of Fe3+, d−subshell is already half-filled, so it does not receive electron
easily.
* Account for: E0 value for the Mn3+/Mn2+ couple is highly positive (+1.57V) as compared
to Cr3+ /Cr2+
Ans. Much large third ionisation energy of Mn (where the required change is stable half-
filled d5 to d4) is mainly responsible for E0 value for the Mn3+/Mn2+ couple being highly
positive (+1.57V) as compared to Cr3+/Cr2+
* Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Ans. Cr2+ has a d4 configuration while after reduction it gets converted to Cr3+
:d3 configuration which has half-filled t2g3 orbital which is very stable. Fe2+ is also oxidised
to Fe3+ because the stable d5 configuration of Fe3+. Since both Cr2+ and Fe2+ get oxidised to
their +3 oxidation state, both the species can act as reducing agent. But t2g3 configuration is
of Cr3+ is more stable than d5 configuration of Fe3+ . Hence, Cr3+ is a strong reducing agent.
(n) Melting and boiling point: As the no. of unpaired electrons increases the interatomic
interactions increases, increasing the strength of the metallic bond which inturn increases the
m.p. and b.p. The m.p. of these elements becomes maximum and then decreases with the
increase in atomic number.
Manganese and technetium show abnormal values in the trend. Tungsten has the highest m.p.
(3410oC). Mercury is liquid at room temperature (m.p. – 38.9°C) due to absence of unpaired
electrons, and weak metallic bonding.