CLASS – XII CHEMISTRY.

UNIT 8 d- BLOCK ELEMENTS.

GENERAL PROPERTIES OF TRANSITION ELEMENTS

1. METALLIC CHARACTER :-
Nearly all the transition elements display typical metallic properties
such as tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre. Most of them exist in typical
metallic structures like hcp, ccp and bcc.
2. MELTING AND BOILING POINTS :-
a) The transition metals (except Zn, Cd and Hg) have high melting and
boiling points. This is due to the involvement of (n-1)d electrons in
addition to the ns electrons in interatomic metallic bonding.
b) In any row, the m.p increases to a maximum at d5 configuration
(middle) except for Mn and Tc and then decreases regularly thereafter.
c) The maxima at the middle of each period indicate that one unpaired
electron per d orbital is favourable for strong interatomic bonding.
d) Metals of the 2nd and 3rd series have greater m.p and enthalpy of
atomization than the corresponding elements of the first series which
shows that the metal-metal bonding in these elements is stronger
than that of 1st series. [REF: pages 212 & 213 graphs ]
3. VARIATION IN ATOMIC AND IONIC SIZES :-
a) In a given series, the ions show progressive decrease in radius with
increasing atomic number. This is because, as the new electron enters
a d-orbital each time, the nuclear charge increases by unity. As the
shielding effect of a d- electron is not that effective, the net
electrostatic attraction between the nuclear charge and the outermost
electron increases and the ionic radius decreases.
b) The radii of 5d series are virtually the same as those of the
corresponding members of 4d series. This is because of the
intervention of 4f orbitals (lanthanoids) which must be filled before
the 5d series of elements begin. The filling of 4f before 5d orbital
results in a regular decrease in atomic radii called lanthanoid
contraction, which compensates for the expected increase in atomic
 size down the group. Due to this, Zirconium and Hafnium have
similar physical and chemical properties.
c) The decrease in metallic radius coupled with increase in atomic mass
results in a general increase in the density of these elements.
[ REF : GRAPH – Page.214]
4. IONIZATION ENTHALPIES :-
a) Due to an increase in nuclear charge which accompanies the filling of
the inner d-orbitals, there is an increase in ionization enthalpy along
each series of the transition elements from left to right.
b) The irregular trend in the first I.E of 3d metals is due to the fact that
removal of one electron from the 4s level alters the relative energies of
4s and 3d orbitals. Cr+ and Cu+ have no electrons in the 4s level. This
decreases the exchange energy. Hence the increase in I.E1 value is
less, compared to V and Ni.
c) In Mn and Zn , there are two 4s electrons. They have higher value for
first I.E because of their completely filled 4s level.
d) Second ionization enthalpy is higher than the first ionization enthalpy
because, the effective nuclear charge is greater in M+.
e) Second ionization enthalpy is greater for Cu and Cr than expected
because of stable electronic configurations in Cu+ and Cr+.
f) The second ionization enthalpy of Zn is less because Zn2+ ion has
half-filled stability.
g) The third ionization enthalpies are high as electrons are removed from
smaller M2+ ions having high effective nuclear charge.
h) Manganese has high value for third ionization enthalpy because Mn2+
has half filled stability.
i) Iron has comparatively low value for third ionization enthalpy because
by achieving Fe3+ configuration, it attains half-filled stability.
5. OXIDATION STATES :-
a) Transition metals show a variety of oxidation states because both ns
and (n-1)d electrons can take part in bonding as they are of
comparable energy.
b) The elements which give the greatest number of oxidation states occur
in or near the middle of the series. Thus Mn exhibits all oxidation
states from +2 to +7.
c) The lesser no. of oxidation states are shown by those elements at the
extreme ends because there are too few electrons to lose or share or
too many d electrons so that only fewer orbitals are available to share
with other orbitals.
6. TRENDS IN STANDARD ELECTRODE POTENTIALS:-
a) The EMF value depends on the total energy involved in the process of
converting the solid metal into the corresponding metal ion in the
aq.solution.[ie, ∆totalH =∆atH + IE + ∆hydH ]
b) The low E0M2+/M value for Mn and Zn is related to their half-filled
and completely filled configurations in their 3d orbitals respectively.
c) The E0M2+/M value for Ni shows the stability of the +2 state due to its
high negative ∆hydH.
d) The low value of E0M3+/M2+ of E0M3+/M2+ of scandium shows the extra
stability of +3 ion state. This is because in the +3 state, Sc has
achieved inert gas configuration.
e) The high E0M3+/M2+ values for Zn and Mn explains the extra stability
of their +2 state due to full filled and half filled 3d levels.
f) The low E0M3+/M2+ value for V is due to the stability of V2+(half filled
t2g ).
7. TRENDS IN THE STABILITY OF HIGHER OXIDATION STATE:-
a) The higher oxidation states are achieved in oxides and fluorides due
to their high electronegativities.
b) The highest oxidation states are shown by oxides than fluorides
because, in addition to its high electronegativity, oxygen has the
ability to form multiple bonds. Thus the highest fluoride of Mn is
MnF4 whereas the highest oxide is Mn2O7.
c) Many Cu(1) compounds are unstable in aq.solutions and undergo
disproportionation. This is because, Cu2+ ions are stable in aq.
Solutions because of high negative ∆hydH which can compensate the
high 2nd I.E.
8. MAGNETIC PROPERTIES:-
a) Mainly two types of magnetism are observed; diamagnetism and
paramagnetism.
Diamagnetic substances are repelled by a magnet. They have only
paired electrons.
Paramagnetic substances are attracted by a magnetic field. They
have unpaired electrons.
If the substance is strongly attracted by a magnetic field, then it is
called ferromagnetic. Ferromagnetism is an extreme case of
paramagnetism.
b) For compounds of the first transition series, the contribution of
orbital angular momentum (due to the circulation motion in the
orbit) is very less and hence the magnetic moment is determined
by the no. of unpaired electrons. Thus the magnetic moment due
 to the spin –only formula is μ = {n(n+2)}1/2 where n is the no. of
unpaired electrons. Its unit is BOHR MAGNETON.
9. FORMATION OF COLOURED IONS:-
a) Most of the transition metal compounds are coloured both in the
solid state and in aqueous solutions. Colour is due to the presence of
incomplete d-subshell. When anions or ligands approach the
transition metal ions, their d-orbitals split into two groups, one with
lower energy and the other with higher energy. By absorbing energy
from light, the electrons can jump from a lower to a higher d-level of
the same subshell. The remaining light will be emitted. Thus the
colour of the compound will be the colour of the emitted light.
( complementary colour)
b) If the d-orbitals are completely filled or completely empty, then the
compound will be colourless.
10. FORMATION OF COMPLEX COMPOUNDS:-
Transition metals form a large number of complex or co-ordination
compounds because of
a) Smaller sizes of the metal ions
b) Their high ionic charges
c) Availability of vacant d-orbitals for bond formation.
11. CATALYTIC PROPERTIES:-
The transition metals and their compounds act as good catalysts.
This is because, they
a) Provide a good surface for adsorption
b) Exhibit variable oxidation states.
c) Form complexes.
12. FORMATION OF INTERSTICIAL COMPOUNDS:-
a) Intersticial compounds are those which are formed when small
atoms like H,C or N are trapped inside the crystal lattices of metals.
b) They are usually non-stoichiometric and are neither typically ionic
nor covalent.
c) They have high m.p,higher than those of pure metals.
d) They are very hard.
e) They retain metallic conductivity.
f) They are chemically inert.
13. ALLOY FORMATION:-
a) Alloys are homogeneous mixtures of two or more metals in which
atoms of one metal are distributed randomly among the atoms of
the other. Transition metals form alloys because of their similar
radii. (Their metallic radii are within about 15% of each other.)
b) They are hard and have often high melting points.
c) Examples- brass(Cu-Zn) bronze(Cu-Sn).

GENERAL CHARECTERISTCS OF LANTHANOIDS AND

LANTHANOIDS ACTINOIDS
1) Besides +3 o.s (stable) , 1) Besides +3 o.s ,they show
they show +2 and +4 higher oxidation states of
oxidation states only in few +4,+5,+6,+7 also.
cases.
2) Smaller tendency for 2) Strong tendency for
complex formation. complex formation.
3) Do not form oxo ions. 3) Do form oxo ions like UO2+
, PuO2+ etc.
4) Except promethium, they 4)All actinoids are radioactive.
are non-radioactive.
5) Compounds are less 5)Compounds are more basic.
basic.
6) Many ions are coloured in 6)The actinoid ions in general
the solid state as well as are coloured.
in solutions. The colour is
attributed to f-f transition
since they have partially
filled f-orbitals.
7) The M3+ ions generally 7)These elements also show
show paramagnetism due paramagnetism, but are
to unpaired electrons in f- more complex than those of
orbitals. lanthanoids.