D block
The d-block contains the elements of the groups 3-12 in which the
d- orbitals are progressively filled in each of the four long periods.
They are also known as transition metals.
The f- block contains elements of group 3 where the 4 f and 5 f
orbitals are progressively filled. They have been taken out to form
a separate f-block of the periodic table. They are also known as
inner-transition metals.
There are three main series for transition metals. They are,
●3d series- Scto Zn
●4d series- Yto Cd
●5d series- La to Hg
●6d series- Ac to unknown (incomplete series)
A transition element is defined as the one having incompletely
filled d orbitals in its ground state or in any one of its oxidation
states. In this regard, Zn,Cd and Hg have fully filled d10
configuration in their ground state and their oxidation states and
are not regarded as transition metals. They are the end members
of the transition series.
Precious metals such as silver, gold and platinum and industrially
important metals like iron, copper and titanium are transition
metals.
Their general electronic configuration is (n-1) d-10 ns1-2. Here (n-
1) stands for inner d- orbitals and ns stands for outermost s-
orbital. The energy difference between (n-1) d and ns orbitals are
very less.
Fully filled or half- filled orbitals have extra stability.
E.g., Cr (3d5 4s1) and Cu (3d10 4s1). Since the energy gap
between the orbitals are less, electrons can easily move to 3d
orbitals.
On the basis of incompletely filled 3d orbitals in case of scandium
atom in its ground state (3d
1
),it is regarded as a transition element. On the other hand, zinc
atom has completely filled d orbitals (3d
10
) in its ground state as well as in its oxidised state, hence it is not
regarded as a transition element.
Having partly filled d-orbitals they exhibit certain characteristic
properties such as various oxidation states, formation of coloured
ions and complex formation with a variety of ligands.
They are used as catalysts and are paramagnetic.
All transition elements exhibit metallic properties such as high
tensile strength, ductility, malleability, high thermal and electrical
conductivity and metallic lustre. But Zn,Cd,Hg and Mn have more
than one metallic structure at room temperature.
They have very high melting and boiling points. The high melting
points of these metals are due to the participation of greater
number of electrons from (n-1) d orbitals in addition to the ns
electrons in the interatomic metallic [Link] melting point of
the metals in any row increases to a maximum for d5 species
(except Mn and Tc) and then decreases with increase in atomic
number.
curves of 4d series shows an increase from 3d series but the radii
of the 5d series are almost the same as the elements of the 4d
series. This phenomenon is due to the intervention of the 4f
orbitals 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. The net
result of the lanthanoid contraction is that the second (4d) and
the third (5d) series exhibit similar radii (e.g., Zr 160 pm and Hf
159 pm) and have very similar physical and chemical
[Link] factor responsible for Lanthanoid contraction is the
imperfect shielding of one electron by another in the same set of
orbitals. The shielding of one 4f- electron by another is less than
that of one d- electron by another. So, as the nuclear charge
increases along the series, there is a decrease in the size of the
entire 4fn [Link] first three ionisation enthalpies of elements
of 3d series do not increase as steeply as in the main group
elements. But the second and third ionization enthalpy values of
them are much higher. This is because the removal of an electron
alters the relative energies of 4s- and 3d- orbitals, giving a dn
configuration with no 4s- [Link] factors responsible for the
value of ionization enthalpy are,
Attraction of each electron towards nucleus
Repulsion between the electrons
Exchange [Link] +
has 3d5 4s1 configuration and for Cr +
it is [Link], ionisation enthalpy of Mn + is lower than Cr +
Also, Fe 2+ has d6 configuration and Mn 2+ has 3d5
configuration. So, ionisation enthalpy of Fe 2+ is lower than the
Mn 2+
or we can say that the third ionisation enthalpy of Fe is lower than
that of [Link] third ionization enthalpy of Mn 2+
(d5) and Zn 2+
(d10) is very high due to the difficulty in removing an electron
from stable [Link] Properties of the Transition
Elements (d-Block)
Physical Properties
All transition elements exhibit metallic properties such as high
tensile strength, ductility, malleability, high thermal and electrical
conductivity and metallic lustre. But Zn,Cd,Hg and Mn have more
than one metallic structure at room temperature.
Lattice Structures of Transition Metals
They are very hard and less volatile (except Zn,Cd and Hg).
They have very high melting and boiling points. The high melting
points of these metals are due to the participation of greater
number of electrons from (n-1) d orbitals in addition to the ns
electrons in the interatomic metallic bonding.
Trends in melting points of transition elements
Here, the melting point of the metals in any row increases to a
maximum for d5 species (except Mn and Tc) and then decreases
with increase in atomic number.
They have high enthalpy of atomization (very high boiling point).
Trends in enthalpies of atomisation of transition elements
The maxima at the middle of each series indicates that one
unpaired electron per d- orbital is favorable for strong interatomic
interaction. The greater the number of valence electrons, stronger
is the resultant bonding.
The metals of the 2nd and 3rd series have greater enthalpies of
atomisation than the elements of the first series. This results in
greater metal-metal bonding in heavier transition metals.
Variation in Atomic and Ionic Sizes of Transition Metals
Ions of the same charge in each series show progressive decrease
in radius with increasing atomic number. This is because the new
electron is added to the d orbital, and the nuclear charge
increases by unity. Since the shielding effect of a d electron is not
that effective, the net electrostatic attraction between the
nucleus and the outermost electron increases and the ionic radius
decreases.
Trends in atomic radii of transition elements
From the graph, the curves of 4d series shows an increase from
3d series but the radii of the 5d series are almost the same as the
elements of the 4d series. This phenomenon is due to the
intervention of the 4f orbitals 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. The net result of the lanthanoid contraction is that
the second (4d) and the third (5d) series exhibit similar radii (e.g.,
Zr 160 pm and Hf 159 pm) and have very similar physical and
chemical properties.
The factor responsible for Lanthanoid contraction is the imperfect
shielding of one electron by another in the same set of orbitals.
The shielding of one 4f- electron by another is less than that of
one d- electron by another. So, as the nuclear charge increases
along the series, there is a decrease in the size of the entire 4fn
orbitals.
With increase in atomic mass, the metallic radius increases and
density of the metal increases.
Ionization Enthalpies
Within a series from left to right ionization enthalpy increases due
to an increase in nuclear charge with the filling of the inner d
orbitals.
The first three ionisation enthalpies of elements of 3d series do
not increase as steeply as in the main group elements. But the
second and third ionization enthalpy values of them are much
higher. This is because the removal of an electron alters the
relative energies of 4s- and 3d- orbitals, giving a dn configuration
with no 4s- electrons. A reorganization energy accompanies the
ionisation as the number of electrons increases and from the
transfer of s- electrons into d- orbitals, there is an increasing trend
in the values as the effective nuclear charge increases.
In the case of increasing trend of second ionisation enthalpy, the
effective nuclear charge increases because one d electron does
not shield another electron from the influence of nuclear charge
because d-orbitals are directed differently.
The factors responsible for the value of ionization enthalpy are,
Attraction of each electron towards nucleus
Repulsion between the electrons
Exchange energy
When several electrons occupy a set of degenerate orbitals, the
lowest energy state is where a maximum extent of single
occupation of orbital and parallel spins is possible ((Hunds rule),
minimum exchange energy). The loss of exchange energy
increases the stability causing ionization difficult.
But for Mn 2+ and Fe 3+
this trend breaks. There is no loss of exchange energy at d6
configuration. Mn + has 3d5 4s1 configuration and for Cr +
it is [Link], ionisation enthalpy of Mn +
is lower than Cr +
Also, Fe 2+
has d6 configuration and Mn 2+
has 3d5 configuration. So, ionisation enthalpy of Fe 2+
is lower than the Mn 2+
or we can say that the third ionisation enthalpy of Fe is lower than
that of Mn.
The lowest common oxidation state of these metals is +2.
The second ionisation enthalpy for Cr and Cu are unusually high,
because the M +
ions have the d5 and d10 configurations respectively. But for Zn
it is comparatively low because ionisation causes the removal of
one 4s electron which results in the formation of stable d10
configuration.
The third ionization enthalpy of Mn
2+ (d5) and Zn 2+ (d10) is very high due to the difficulty in
removing an electron from stable configuration. From this, it is
clear why it is difficult to obtain an oxidation state greater than
two for Cu,Ni and Zn.
Oxidation States
The common oxidation states of first row transition elements are
given below.
Oxidation States of the first row Transition Metals (the most
common ones are in bold types)
The elements exhibiting greater oxidation states are found at the
middle of the series.
For e.g., Mn
The elements with lesser oxidation states are at the extreme ends
of the series.
For e.g., Sc,Ti (few electrons to share or accept) and Cu,Zn (many
d- electrons thus, few available orbitals to share electrons).
Ti(IV) is more stable than Ti(III) and Ti(II).
The maximum stable oxidation states corresponding to the sum of
the s and d- electrons exists upto Mn.
After Mn there is an abrupt decrease in stability of higher
oxidation states. E.g., FeII,III
CoII,III
Ni(II)
Cu (I,II)
Zn (II.)
The formation of variable oxidation state by a transition element
is due to incomplete filling of d- orbitals in such a way that their
oxidation states differ from each other by [Link]:- 2,3,4,5etc
The oxidation states of non- transition elements usually vary by
two units.
For p–block elements, the lower oxidation states are exhibited by
the heavier members (due to inert pair effect), but for d-block
elements it is just the opposite.
For e.g., in Group 6, Mo(VI) and W(VI) are more stable than Cr(VI).
Thus, Cr(VI) in the form of dichromate in acidic medium is a
strong oxidising agent, while MoO and WO are not.
In a complex compound having ligands capable of π-acceptor
character in addition to the σ-bonding, the oxidation state of the
central metal atom is zero.
E.g., In Ni(CO) , and Fe(CO)
5. the oxidation state of Ni and Fe is zero.