D BLOCK ELEMENTS

d Block Elements
The elements that can be found from the third group to the twelfth group of the modern periodic
table are called d-block elements. The valence electrons of these elements fall under the d
orbital. d-block elements are also called transition elements or transition metals because they
exhibit transitional behaviour between s block and p block elements. In d-block elements, the
valence shell has a constant number of electrons, whereas the number of electrons in the
penultimate shell goes on increasing. Elements that have at least one unpaired electron in their
d orbital in atomic or any oxidation state are called transition elements. All transition elements
are d-block elements, but all d-block elements are not transition elements.

The series of transition elements is given below.

First series: These are called the 3d series of elements. They are classified in the 4th period.
Atomic numbers are from 21 to 30. (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn)

Second series: These are called the 4d series of elements. They are classified in the 5th
period. Atomic numbers are from 39 to 48. (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd).

Third series: These are called the 5d series of elements. They are classified in the 6th period.
Atomic numbers are 57 and 72 to 80. (La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg).

Fourth series: These are called the 6d series of elements. They are classified in the 7th period.
Atomic numbers are 89 and 104 to 112. (Ac, Ku to Uub). This is an incomplete series.

General electronic configuration

The general configuration for d block elements is (n-1)d1-10 ns1-2.

Here, (n-1) denotes the penultimate shell; the d orbital may have 1 to 10 electrons, and the s
orbital of the ultimate shell (n) may have 1 to 2 electrons.
General Properties of d-block elements
 Except copper, all the elements of the 3d series are good reducing agents.
 Due to the shielding effect, the ionisation potential of transition elements increases by negligible
amounts.
 The reactivity of transition elements is less. The reactivity decreases with increasing atomic number.
 The atomic radii of transition elements decrease by negligible amounts due to the shielding of valence
shell electrons, provided by the electrons of d orbitals of the penultimate shell.

Metallic character

All the transition elements are metallic in nature. All of them have simple ccp, hcp or bcc
lattices. A metallic bond is quite strong due to its greater effective nuclear charge and a large
number of valence electrons. These are hard and possess high densities and high enthalpies of
atomisation. Due to the presence of free electrons, these are good conductors of heat and
electricity. The order of conductivity is Ag > Cu > Au > Al.

Density

The atomic volume of the transition elements is low compared to the s block. Their density is
comparatively high. Os and Ir have the highest density. All the d-block elements, except Sc Y
and Ti, have densities greater than 5 gm cm-3.

In all the groups, there is a normal increase in density from 3d to 4d series and from 4d to 5d; it
increases just double due to the lanthanide contraction. That means, due to a double increase
in atomic mass, the density of 5d elements is nearly twice that of 4d elements. Ti<Zr<<Hf.

In 3d series,
Sc→ Cr density increases.

Mn, Fe, Co Ni → almost constant

Cu → Zn decreases

In the 3d series, Cu has the highest density, and Sc has the lowest density.

Melting point and boiling point

Due to a stronger metallic bond and the presence of a covalent bond formed by unpaired d
electrons, the melting point and boiling point of d-block are greater than s block elements. There
is no unpaired electron present in the d orbital of Zn, Cd and Hg. So, due to the absence of a
covalent bond, their melting point and boiling point are very low.

In 3d series

Sc → Cr melting point and boiling point increase

Mn → Zn melting point and boiling point decrease

Atomic size

Atomic radii depend on effective nuclear charge Zeff and screening effect.

Ionic radii and atomic radii of d-block elements are smaller than s-block elements.

In 3d series,

Sc → Cr radius decreases

Mn → Ni radius remains constant

Cu → Zn radius increases

Characteristic properties of transition metals

 Formation of alloys
 Variable oxidation state
 Coloured properties
 Paramagnetic properties
 Formation of interstitial compounds
 Catalytic properties
 Formation of complexes

Formation of alloy
The reactivity of transition elements is very less and their sizes are almost similar. Because of
this, a transition metal atom in the lattice can be easily replaced by other transition metal atoms,
and hence they have a maximum tendency to form alloys. These metals are hard and have a
high melting point.

Variable oxidation states

(a) They exhibit variable valency due to the involvement of (ns) and (n-1)d electrons in bonding.
This is because of the less energy difference between these electrons.

(b) For transition elements, the highest oxidation state can be calculated using the formula n+2,
where n is the number of unpaired electrons. (this is not used for Cr and Cu).

(c) The transition metals, having stable configurations, are stable.

(d) Most common oxidation state among the transition elements is +2.

(e) In an aqueous medium, Cr+3 is stable.

(f) Co+2 and Ni+2 are stable.

(g) The common oxidation state shown by elements Sc, Y, La and Ac is +3 since their divalent
compounds are highly unstable.

(h) Highest oxidation state shown by transition elements of the 4d and 5d series is +8.
Ruthenium and Osmium are the elements showing this oxidation state.

(i) In the lower oxidation state, transition elements form ionic compounds, and in the higher
oxidation state, their compounds are covalent.

(j) Usually, higher oxidation states are shown in the compounds that are formed with highly
electronegative elements like O and F.

(k) They also show zero oxidation state in their carbonyl compounds like Ni(CO)4.

(l) Transition metal ions in their lower oxidation state act as reducing agents. Ti+2, V+2, Fe+2 etc.,
are reducing agents.

(m) Transition metal ions in their higher oxidation state act as oxidising agents. Cr+6, Mn+7,
Mn+4 etc., are oxidising agents.

Colour Property

Due to the presence of unpaired electrons in their d orbitals, most of the transition metal ions
show colour properties. They need only a less amount of energy to excite electrons. Hence,
they absorb visible regions of light exhibiting colour. Ti+2[Ar]d2, V+2[Ar]3d3 etc., have unpaired
electrons in their d orbitals. Therefore, they are coloured.

Transition metals which do not have any unpaired electrons in their d orbitals (3d0 and
3d10 configuration) do not show any colour property. For example, Sc+3[Ar]3d0, Cu+1[Ar]3d10 are
colourless ions.

Potassium permanganate KMnO4 (dark pink) and K2Cr2O7 (orange) have a d0 configuration
because of the charge transfer spectrum. The below table shows coloured metal ions.

Ni+2 Green

Cu+2 Blue

Co+2 Blue

Fe+2 Pale green

Ti+3 Purple

Magnetic properties

A diamagnetic substance is one that is slightly repelled by a magnetic field. Paramagnetism is

The magnetic moment due to the spinning of unpaired electrons can be found by using the
equation μ = √(n(n+2)).

Here, n denotes the number of unpaired electrons in the metal ion. μ is the magnetic moment in
Bohr magnetons. For diamagnetic substances, the magnetic moment will be zero. When the
number of unpaired electrons increases, the magnetic moment also increases, and thus the
paramagnetic nature increases. Transition metal ions with d5 configuration have a maximum
number of unpaired electrons, and hence they have maximum paramagnetic nature.

Catalytic property

Transition elements show catalytic properties because of their variable valency and free
valencies on their surfaces. The catalytic properties exhibited will be greater when the transition
elements are in a powdered state. This is because of the greater surface area in the powdered
state. Transition metals and their compounds exhibiting catalytic properties in various processes
are given below.
(a) V2O5 is used in the contact process for the manufacture of H2SO4.

(b) Fe is used in Haber’s process for the manufacture of NH3.

(c) Ni is used in the hydrogenation of oils.

(d) FeSO4 is used in the oxidation of Benzene with H2O2.

(e) Cu is used in the dehydrogenation of alcohols.

(f) TiCl4 is used as a catalyst in Vinyl polymerisation.

(g) Pt is used in Ostwald’s process of nitric acid.

Important Alloys
Bronze Cu (75-90%) + Sn(10 – 25%)

Gunmetal (Cu + Zn + Sn) 87:3:10

Bell metal Cu (80%) + Sn (20%)

Alnico Al, Ni, Co

Type metal Pb +Sn +Sb

Brass Cu (60-80%) + Zn(20 – 40%)

Nichrome Ni + Cr + Fe

1. Alloys of steel

(a) Vanadium steel – V (0.2-1%)

(b) Chromium steel – Cr (2-4%)

(c) Nickel steel – Ni (3-5%)

(d) Manganese steel – Mn (10-18%)

(e) Stainless steel Cr (12-14%) and Ni (2-4%)

(f) Tungsten steel – W (10-20%)

(g) Invar – Ni (36%)

2. Magnalium – Mg (10%) + Al (90%)

4. Artificial Gold – Cu (90%) + Al (10%)

5. Constantan – Cu (60%) + Ni (40%)

6. 14 carat gold – 54% Au +Ag(14 to 30%) + Cu ( 12-28%)

7. 24 Carat Gold – 100% Au

8. Solder – Pb + Sn

Percentage of carbon in different types of iron

Name Percentage of Carbon

Wrought iron 0.1 to 0.25

Steel 0.25 to 2.0

Cast iron 2.6 to 4.3

Pig iron 3.5 to 4.6

Formation of Interstitial Compounds

Transition elements react with elements like nitrogen, hydrogen, boron, etc., to form interstitial
compounds. The smaller-sized atoms get trapped in between the interstitial spaces of the metal
lattices. These interstitial compounds are non-stoichiometric in nature. So, they cannot be given
any definite formula. Weak Vander Waals forces of attraction are responsible for holding
smaller-sized elements in interstitial spaces of transition elements. The interstitial compounds
have the same chemical properties as the parent metals. But they differ in physical properties,
such as hardness and density.

Physical and chemical properties

The physical and chemical properties of the interstitial compounds are as follows:

 These compounds are chemically inert in nature.

Non-stoichiometry
Non-stoichiometry is shown by transition metal compounds of group 16 elements. The transition
elements form non-stoichiometric compounds because of variable valency. These compounds
are of indefinite proportion and structure. Non-stoichiometry is caused by a defect in the solid
structure.

f Block Elements
f block elements are also called inner transition elements. The elements in which the electrons
enter (n-2)f orbitals are called the f block elements. The electronic configuration of f block
elements is (n-2)f(0−14)(n-1)d(0−1)ns2.

Position of f block elements

f block elements are placed separately at the bottom of the periodic table. They are a subset of
the 6th and 7th periods.

Properties of f block elements

(a) Properties f-block elements are similar to d-block elements.

(b) f block elements have electrons added to the f sub-orbitals of the (n-2) level.

(c) These elements are placed between (n-1)d and ns block elements in the periodic table.

Lanthanides

They are called lanthanides because the elements in the series are chemically similar to
lanthanum. These are reactive elements. So, they are not found in nature in the free state.

Lanthanides are non-radioactive (except for promethium, which is radioactive).

Properties of Lanthanides

(a) Lanthanides are good conductors of electricity and heat.

(b) They have melting points ranging from 1000 K to 1200 K (Samarium is an exception, 1623
K).

(c) These are soft metals with a silvery-white colour.

(d) When exposed to air, their brightness reduces rapidly, and their colour dulls.

(e) A decrease in atomic and ionic radii from lanthanum to lutetium is observed. This is called
the lanthanoid contraction.
(f) They are non-radioactive in nature except for promethium.

Actinides

The second series of elements are called actinides. These are elements with atomic numbers
starting from 89 and ending at 103. These elements are radioactive in nature.

Properties of Actinides

(a) Actinides have a radioactive nature.

(b) These elements appear to be silvery.

(c) A decrease in atomic and ionic radii from actinium to lawrencium is seen. This is known as
actinoid contraction.

(d) These metals usually exhibit an oxidation state of +3. Elements belonging to the first half of
the series are known to exhibit higher oxidation states.

(e) These metals are highly reactive. The reactivity increases when they are finely divided.

The following table shows the difference between lanthanides and actinides.

Lanthanides Actinides

Lanthanides are non-radioactive in nature except promethium. All actinides are radioactive.

The paramagnetic properties of lanthanides can be easily This is difficult in the case of actinides.
explained.

Lanthanides are involved in the filling of 4f- orbitals. Actinides are involved in the filling of 5f-
orbitals.

The compounds formed by lanthanides are less basic. The compounds of actinides are highly
basic.

Lanthanides do not have a tendency to form oxo-cations. Oxo-cations of actinide series exist.

Less reactive than actinides. More reactive than lanthanides.

Similarities between Lanthanides and Actinides

The lanthanides and actinides are characterised by filling of (n-2) f subshell. They have almost
similar outermost electronic configurations. Thus, they exhibit similar properties.

The following are some similarities:

(b) Lanthanides and actinides have a prominent oxidation state of +3.

(c) Lanthanides and actinides are highly electropositive and very reactive in nature.

(d) They show magnetic properties.

(e) As the atomic number increases, there is a decrease in atomic and ionic size.

Lanthanide Contraction
The gradual decrease in the atomic and ionic size of lanthanoids with an increase in atomic
number is called lanthanide contraction.

The gradual decrease in the size of the ions and atoms of the lanthanoids with increasing
atomic numbers from lanthanum (atomic number 57) to lutetium (atomic number 71) is termed
as lanthanide contraction. For every consecutive atom, the nuclear charge can be more positive
by a single unit, followed by the corresponding increase in the electron count present in the 4f
orbitals surrounding the nucleus. The 4f electrons imperfectly protect each other from the
increased positive charge of the nucleus. This results in a steady rise in the effective nuclear
charge attracting every electron as the lanthanide elements progress, resulting in a decrease in
ionic and atomic radii.

Consequences of lanthanide contraction

(a) Difficulty in the separation of Lanthanides:

Since there is only a small change in the ionic radii of the lanthanides, their chemical properties
are the same. Thus, it becomes difficult to separate the elements in the pure state.

(b) Atomic size:

The size of the atom of the third transition series is almost similar to that of the atom of the
second transition series. For example, the radius of Nb = radius of Ta.

(c) Electronegativity:

It increases from the elements La to Lu.

(d) Effect on the basic strength of hydroxides

The size of the lanthanides decreases from the elements La to Lu. Then, the covalent character
of the hydroxides increases. Hence, their basic strength decreases. So, Lu(OH)3 is said to be
the least basic, and La (OH)3 is more basic.
(e) Ionization energy

The ionization energy of the 5d elements is much larger compared to 4d and 3d. In the 5d
series, the total elements, except Pt and Au, contain a filled s-shell. Elements from hafnium to
rhenium have similar ionization energy, and after that, the ionization energy increases with the
number of shared d-electrons such that gold and iridium have the maximum ionization energy.