Class: 12th Subject: Chemistry

Unit: d and f – block elements

(d – Block Elements)
INTRODUCTION:
Those elements in which the last electron enters (n-1)d orbital i.e.
penultimate shell are called d-block elements. These elements are also
called transition metals as they represent change in behaviour from
highly electropositive s-block elements to highly electronegative p-
block elements. The d-block contains elements from G-3 to G-12. It is
divided into 4 transition series i.e. 3d-series (Sc = 21 to Zn = 30), 4d-
series (Y = 39 to Cd = 48), 5d-series (La = 57, Hf = 72 to Hg = 80) and 6d-
series (Ac = 89, Rf = 104 to Uub = 112).

Electronic Configuration:
The general outer-shell electronic configuration of d-block elements is
(n-1) d¹⁻¹⁰ ns¹⁻² i.e. there is progressive filling up of (n-1) d – orbital.
However, there are several exceptions due to very little energy
difference between (n-1) d and ns orbitals. Furthermore, the half and
completely filled orbitals are more stable as compared to other orbitals
and therefore some elements (like Cr and Cu in 3d series) have
exceptional electronic configuration. The general electronic
configuration of first transition series (3d-series) is given below:-
 Element Atomic No. (Z) Electronic configuration
Scandium (Sc) 21 [Ar] 3d¹ 4s²
Titanium (Ti) 22 [Ar] 3d² 4s²
Vanadium (V) 23 [Ar] 3d³ 4s²
Chromium (Cr) 24 [Ar] 3d⁵ 4s¹
Manganese (Mn) 25 [Ar] 3d⁵ 4s²
Iron (Fe) 26 [Ar] 3d⁶ 4s²
Cobalt (Co) 27 [Ar] 3d⁷ 4s²
Nickel (Ni) 28 [Ar] 3d⁸ 4s²
Copper (Cu) 29 [Ar] 3d¹⁰ 4s¹
Zinc (Zn) 30 [Ar] 3d¹⁰ 4s²

Supplementary:
● The most of transition elements have 2 electrons in outermost ns –
orbital.

● Palladium (Pd) has no electron in ns – orbital. Its electronic

configuration is (Z=46) [Kr] 4d¹⁰ 5s⁰.

● Technetium (Tc) is the only man-made transition metal.

● Mercury (Hg) is the only transition metal in liquid state.

● Osmium (Os) has highest density in the periodic table.

● G-3 and G-12 are non-typical transition elements. G-3 elements do

not show properties of transition elements and in G-12 there is not
progressive filling up of d-orbital.
General characteristic of d-block elements (Trends in Properties):

Physical Properties:
The transition metals display typical metallic properties like
malleability, ductility, high tensile strength, high thermal and electrical
conductivity, metallic luster etc. The transition metals (with the
exception of Zn, Cd and Hg) are very hard and have low volatility. The
melting and boiling points of transition metals are generally high. The
melting points of 3d, 4d and 5d series are shown in figure.

Fig: Melting point of transition metals Fig: Enthalpy of atomization

Of transition metals
The high melting point of transition metals is attributed to the
involvement of greater no. of electrons from (n-1) d in addition to ns
electrons. The melting points of these metals rise to a maximum at d 5
(except Mn and Tc) and then decreases regularly with the increase in
atomic no.

The transition metals have high enthalpies of atomization as shown in

figure. The enthalpy of atomization is maximum at d5 which indicates
that each unpaired electron is favorable for strong inter-atomic
interaction. Therefore, greater the no. of valence electrons, stronger is
the resultant bonding. The metals of the second and third series have
greater enthalpies of atomization than the corresponding elements of
the first series.

Atomic and ionic Radii:-

The atomic radii decrease across a period due to increase in atomic
number. The atomic radii for transition metals are smaller than their
corresponding s – block elements. The atomic radii of transition metals
decreases with increase in atomic number but this decrease becomes
small after midway.

e.g. In 3d-series, order of atomic radii is

Sc > Ti > V > Cr ≈ Mn ≈ Fe ≈ Co ≈ Ni < Cu < Zn

The decrease in atomic radii is due to increase in nuclear charge but the
addition of extra electrons to (n – 1) d – orbitals increases screening
effect, so after midway there is no change in atomic radii.
The values of atomic radii at the end of series are bit higher due to
electron – electron repulsions.

The variation of atomic radii of transition elements in a series is shown

below:-

Fig: Trends in atomic radii of transition elements

The ionic radii follow the same trend as atomic radii i.e. it decreases
across a transition series. In case of ions of same atom, the ionic radii
decrease with increase in charge of ions.

e.g. Fe³+ < Fe2+, Ni3+ < Ni2+, Mn3+ < Mn2+ etc.
Ionization Energy:
The ionization energy increases across a series due to increase in
nuclear charge but the increase is not regular.

e.g. in case of 3d – series, ionization energy values of Sc, Ti, V and Cr are
nearly close to one another. Similarly, Ionization energy values of Fe,
Co, Ni and Cu are almost similar. This is due to increase in screening
effect which neutralizes the increasing nuclear charge, so ionization
energy quite slowly increases.

The 2nd and 3rd ionization energies are greater than 1st ionization
energy.

In each series, the elements of G-12 (Zn, Cd, Hg etc.) have highest value
of ionization energy due to extra stability of associated with their filled
(n-1) d and ns – orbitals.

The 2nd ionization energy of Cu and Cr are sufficiently higher because

electron is to be removed from completely filled sub-shell i.e. 3d¹⁰ in
case of Cu and half filled sub-shell i.e. 3d⁵ in case of Cr. Similarly, the 3rd
ionization energy of Mn is very high because 3rd electron is to be
removed from a stable half filled 3d - sub-shell i.e. 3d⁵.

Oxidation State:
The transition metals show a large no. of oxidation states due to
involvement of (n-1) d and ns electrons. The common oxidation state of
3d series is +2 (except Sc in which it is +3). The oxidation states of 3d
series are shown below:-
 Element Electronic Oxidation State
Configuration
Scandium (Sc) [Ar] 3d1 4s2 +2, +3
Titanium (Ti) [Ar] 3d2 4s2 +2, +3, +4
Vanadium (V) [Ar] 3d3 4s2 +2, +3, +4, +5
Chromium (Cr) [Ar] 3d5 4s1 +1, +2, +3, +4, +5, +6
Manganese (Mn) [Ar] 3d5 4s2 +2, +3, +4, +5, +6, +7
Iron (Fe) [Ar] 3d6 4s2 +2, +3, +4, +6
Cobalt (Co) [Ar] 3d7 4s2 +2, +3, +4
Nickel (Ni) [Ar] 3d8 4s2 +2, +3, +4
Copper (Cu) [Ar] 3d10 4s1 +1, +2
Zinc (Zn) [Ar] 3d10 4s2 +2

In 3d series, the highest oxidation state is shown by Mn (+7) and the

highest oxidation state shown by any transition metal is +8 shown by
Ru and Os. The elements which give the greatest no. of oxidation states
occur in or near the middle of the series. The elements at the extreme
show lesser no. of oxidation states either due to lesser no. of electrons
available for bonding.

The stability of transition metals also depends on oxidation states.

e.g. Mn2+ (3d5) is more stable than Mn3+ (3d4). In d – block, the higher
oxidation states are more stable for heavier elements.

Some transition elements form compounds in zero oxidation state.

e.g. Ni in [Ni (CO)4] and Fe in [Fe (CO)5].
Standard Electrode Potential (E°):-

The standard electrode potential of all transition metals is lower than

that of hydrogen (except Cu and Hg). Lower the electrode potential,
more stable is oxidation state. The metals which have negative value of
electrode potential are better reducing agents. All the transition metals
except Cu, Pt, Ag, Hg, Au etc. have negative values of electrode
potential. The negative value of electrode potential decreases across a
series due to increase in ionization energy. The E° values of Mn and Zn
in 3d series are more negative than expected due to extra stability of
3d⁵ and 3d¹⁰ configurations.

Magnetic Properties:-

The d – block elements are either paramagnetic (attracted by magnetic

field) or diamagnetic (repelled by magnetic field). The paramagnetic
behaviour arises due to presence of one or more unpaired electrons.

The magnetic character is expressed in terms of magnetic moment (μ)

which is given by

μ= √n (n+2) BM (where BM is Bohr Magneton

which is equal to eh/4πmc)

Where n = no. of unpaired electrons

Greater the no. of unpaired electrons more will be the value of

magnetic moment and hence greater will be paramagnetic character.
The transition metals and ions having d⁵ configuration possess
maximum magnetic moment.

The transition metals which are strongly attracted by magnetic field are
called ferromagnetic. e.g. Fe, Co, Ni etc.

Formation of Interstitial compounds:-

The small non-metallic atoms such as H, B, C, N etc. are able to occupy
interstitial spaces of transition metals to form interstitial compounds.
These compounds are non-stoichiometric in nature e.g. FeO0.95, TiH1.7,
VH0.56 etc.

These compounds do not follow common rules of valency. The bonds

are neither completely ionic nor covalent. Their formula does not
correspond to any normal oxidation state of metal.

Interstitial compounds have similar chemical properties as parent metal

but differ in physical properties like density, hardness, m.p and b.p etc.
The important characteristics of these compounds are:-

1. They have high melting points, higher than those of pure metals.

2. They are very hard, some metal borides are as hard as diamond.

3. They retain metallic conductivity.

4. They are chemically inert.

e.g. steel is an interstitial compound of Fe and C.

Complex Formation:-
The d-block elements have remarkable ability to form complex
compounds due to following reasons:-

(1) Small Size

(2) High nuclear charge

(3) Presence of vacant d-orbitals

These complexes are commonly called as co-ordination compounds.

e.g. [Cu (NH3)4] SO4 , Na3 [Fe (CN)6] , [Cr (NH3)6] Cl3 etc.

The transition metals form a large no. of complex compounds due to

small size, high ionic charge and availability of d-orbitals for bond
formation.

Alloy Formation:-
Alloys are homogeneous mixtures of 2 or more elements in which at
least one of the elements is a metal. The transition elements form a
large no. of alloys because they have nearly same atomic size and
therefore atoms one metal can substitute atoms of another metal.

Alloy Composition Use

Brass Cu + Zn In making utensils
Bronze Cu (90%) + Sn (10%) In making statues
 Gun metal Cu + Sn + Zn In automobiles for
making gears and
bearings
Stainless Steel Steel + Cr + Ni In making house hold
utensils
Cupro Nickel Ni + Cu In making silver coins
Alnico Steel + Al + Ni + Co In making permanent
magnets
Dental Alloy Ag + Sn + Hg In filling of tooth
cavities
Monel metal Ni + Cu + Fe (traces) Resistant to corrosion
Bell metal Cu (80%) + Sn (20%) In making bells
Coinage Silver Ag + Cu + Ni In making Coins
Invar Steel + Ni Heat resistant

Colour Formation:-

The most of compounds of transition metals and their ions are

coloured. This colour arises due to excitation of electrons from d-
orbitals of lower energy to d-orbitals of higher energy (i.e. d – d
transition). The energy required for d – d excitation is available in
visible region. The transition metals absorb radiations from visible
region and exhibit complementary colour.

The transition metal ions which have completely filled d – orbitals (3d10,
4d10 or 5d10) such as Zn2+, Cd2+, Hg2+, Cu+, Ag+, Au+ etc are colourless.

e.g. Fe2+ (3d6) is green, Fe3+ (3d5) is yellow, Co2+ (3d7) is pink, Cu2+ (3d9)
is blue, Ti3+ (3d10) is purple, Cr3+ (3d3) is violet, Mn2+ (3d5) is light pink.
Catalytic Property:-

The transition metals and their compounds act as catalysts in various

reactions. The catalytic property is due to utilization of (n – 1 )d –
orbitals or formation of interstitial compounds.

e.g. Pt is used in the manufacture of H2SO4, Fe/Mo is used in the

manufacture of NH3 in Haber’s process, Ni is used in the hydrogenation
of oils, V2O5 in oxidation of SO2 into SO3, MnO2 in decomposition of
KClO3 to prepare oxygen etc.

Important compounds of d – block

Potassium dichromate (K2Cr2O7):-
It is the most important compound of Cr. It is prepared from chromite
ore or ferrochrome or chrome iron (FeCr2O4) as

4FeCrO4 + 8Na2 CO3 + 7O2 ────> 8Na2CrO4 + 2Fe2O3 + 8CO2

(sodium chromate)

2Na2CrO4 + H2SO4 ────> Na2Cr2O7 + Na2SO4 + H2O

(sodium dichromate)

Na2Cr2O7 + 2KCl ────> K2Cr2O7 + 2NaCl

(potassium dichromate)
Properties of K2Cr2O7

1. It is orange red coloured crystalline compound.

2. It is moderately soluble in cold water but freely soluble in hot water.

3. On heating strongly, it decomposes to give oxygen.

2K2Cr2O7 ─────> 2K2CrO4 + Cr2O3 + 3/2 O2

4. When an alkali is added to an orange-red solution of K 2Cr2O7, a

yellow solution of K2CrO4 is obtained.

K2Cr2O7 + 2KOH ─────> 2K2CrO4 + H2O

(Cr2O72-) (CrO42-)

Orange Yellow

5. On acidifying, yellow coloured solution of K2CrO4 changes back to

orange-red K2Cr2O7.

2K2CrO4 + H2SO4 ─────> K2Cr2O7 + K2SO4 + H2O

(Conc.)

6. It acts as a powerful oxidizing agent in presence of dilute H2SO4 as

K2Cr2O7 + 4H2SO4 ─────> K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

─> It liberates I2 from KI as

K2Cr2O7 + 4H2SO4 ─────> K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

[2KI + H2SO4 + [O] ─────> K2SO4 + H2O + I2] × 3

=> K2Cr2O7 + 7H2SO4 + 6KI ─────> 4K2SO4 + Cr2(SO4)3 + 7H2O + 3I2

─> It oxidizes H2S to Sulphur

K2Cr2O7 + 4H2SO4 ─────> K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

[H2S + [O] ─────> H2O + S] × 3

=> K2Cr2O7 + 4H2SO4 + 3H2S ─────> K2 SO4 + Cr2(SO4)3 + 7H2O + 3S

─> It oxidizes SO2 to H2SO4

K2Cr2O7 + 4H2SO4 ─────> K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

[SO2 + [O] + H2O ─────> H2SO4 ] × 3

=> K2Cr2O7 + 4H2SO4 + 3SO2 + 3H2O ───> K2SO4 + Cr2(SO4)3 + 3H2SO4 + 4H2O

Structure K2Cr2O7
Uses of K2Cr2O7

1. It is used in the volumetric analysis for estimation of Fe and I2 in

redox titrations.

2. It is used in leather tanning, calico printing and dyeing.

3. It acts as an oxidizing agent.

4. Its acidified solution provides a test to find out whether a person is

drunk or not. The orange red K2Cr2O7 changes into green colour due to
formation of Cr2(SO4)3 as

5. In photography in the hardening of gelatin films.

Potassium Permanganate (KMnO4):-
It is the most important compound of Manganese. It is prepared from
pyrolusite ore (MnO2).

The pyrolusite (MnO2) is fused with KOH (or K2CO3) in presence of

atmospheric O2 to form K2MnO4 (Potassium manganate) as

2MnO2 + 4KOH + O2 ─────> 2K2MnO4 + 2H2O

The potassium manganate formed is treated with a current of Cl 2 (or O3

or CO2) to convert it into potassium permanganate as

2K2MnO4 + Cl2 ─────> 2KMnO4 + 2KCl

The potassium manganate can also be electrolyzed to give potassium

permanganate as

K2MnO4 <──────> 2K+ + MnO42-

At Anode:

MnO42- ─────> MnO4- + e-

At cathode:

2H+ + 2e- ──────> H2

Properties of KMnO4
1. It is purple coloured crystalline compound.

2. It is fairly soluble in hot water but sparingly soluble in cold water.

3. When heated alone or treated with alkali, it decomposes to give
oxygen.

2KMnO4 ───∆───> K2MnO4 + MnO2 + O2

4KMnO4 + KOH ─────> 4K2MnO4 + 2H2O + O2

4. On treatment with cold conc. H2SO4, it forms Mn2O7 (manganese

heptaoxide).

2KMnO4 + 2H2SO4 ─────> Mn2O7 + 2KHSO4 + H2O

5. It acts as a powerful oxidizing agent.

(a) In acidic medium:-

=> Fe2+ ion (green) is converted to Fe3+ ion (yellow) as

5Fe2+ + MnO4- + 8H+ ─────> Mn2+ + 4H2O + 5Fe3+

=> Iodine is liberated from potassium iodide

10 I- + 2MnO4- + 16H+ ─────> 2Mn2+ + 8H2O + 5I2

(b) In neutral or faintly alkaline medium:-

=> Oxidation of iodide to iodate

2MnO4- + H2O + I- ─────> 2MnO2 + 2OH- + IO3-

=> Thiosulphate is oxidized to sulphate

8MnO4- + 3S2O32- + H2O ─────> 8MnO2 + 6SO42- + 2OH-

Structure of MnO4- and MnO42-

Uses of KMnO4:-
1. In volumetric estimation of H2O2, ferrous salts, oxalates etc.

2. As disinfectant.

3. As germicide.

4. As Baeyer’s reagent for detecting unsaturation in a compound.

5. As a strong oxidizing agent.

6. In purifying water.
 Whatever the mind of man can
conceive & believe, it can achieve.

(Thanks)