Welcome to

The d and f-Block

Elements
Coinage Metals Some ancient
(Cu, Ag, Au) metal artifacts

Copper,
iron used
to make
weapons.

“Dancing Girl”

Made up of
bronze metal These f-block
used in Harappan elements are
civilization. used in nuclear
power plants.
 d-Block
elements

3d series
4d series
5d series
6d series
 Pneumonic for d-Series
Sachin Yes Larry
Tendulkar Zebras Have fun
Very Never but Travelling
Crazy Most World and
Man Technicians Reach
Free Run Out
Coaching to Rhymes Ireland and
Nitin’s Purely sweet Please
Cou And Ask
Zin Cute Her
 f-Block
elements

Lanthanoids
Actinoids
 d-Block Elements

d-Block & f-block elements are Known as

known as transition and inner transition metals
transition elements, respectively

Metals that have

Generally, d-block elements are incomplete d subshell
called transition elements either in neutral atom
or in their ions.

Because their chemical properties

are transitional between
those of s- & p-block elements
Transition Elements
Incomplete d
subshell

Fe : [Ar]

Neutral 3d6 4s2

Fe3+ : [Ar]

Ion 3d5 4s0

Incomplete d
subshell
Inner Transition Elements

f-Block elements are called

inner transition elements

Because their valence shell

electrons lie in anti-penultimate
energy level

Example: Cerium (58)

[Xe] 4f1 5d1 6s2
 Non-transition d-Block Elements

Zn (30) : [Ar] 3d10 4s2

Zn, Cd, Hg of group 12
Zn2+ : [Ar] 3d10 4s0 have full d10 configuration in
their ground state as well as
: [Kr] 4d10 5s2 in their common oxidation
Cd (48)
states.

Cd2+ : [Kr] 4d10 5s0

Known as
Hg (80) : [Xe] 4f14 5d10 6s2 non-transition
metals

Hg2+ : [Xe] 4f14 5d10 6s0

 Transition d-Block Elements

Ag : [Kr]
(41)
Neutral 4d10 5s1
Silver is a transition
element as it has
incomplete d-orbital in Ag+ : [Kr]
its +2 oxidation state.
Ion 4d10 5s0

Ag2+ : [Kr]

Ion 4d9 5s0

Incomplete in
ionic state
 Position in the
periodic table

Transition Electronic
elements configuration

General
properties
 Position
of d-Block
elements
Electronic Configuration of d-Block Elements

General configuration Last electron enters in the d-orbital

Example
(n-1)d1-10 ns1-2

Sc(21) 1s2 2s2 2p6 3s2 3p6 3d1 4s2

Inner d-orbital
Co(27) 1s2 2s2 2p6 3s2 3p6 3d7 4s2
 Electrons filling in 3d elements

For 3d-series elements, electrons

enters in 3d orbitals which is
occupied generally after 4s
orbital.
 Examples
The electronic configuration has several exceptions because of very little
difference in energy of (n-1)d and ns electrons. This can be reflected in
electronic configuration of Cr (half filled) and Cu (fully filled) in 3d series.

Cr(24) [Ar] 3d4 4s2 ❌ Ag(47)

Cr(24) [Kr] 3d94 5s
[Ar] 4d 4s2 ❌

Cr(24) [Ar] 3d5 4s1 ✔ Ag(47)

Cr(24) [Kr] 3d10
[Ar] 4d 5s11
5 4s
✔

Mo(42) [Kr] 4d4 5s2 ❌ Cu(29) [Ar] 3d9 4s2 ❌

Mo(42)
Cr(24) [Ar] 4d5 4s
[Kr] 3d 5s1 ✔ Cu(29)
Cr(24) [Ar] 3d10
[Ar] 3d 4s11
5 4s
✔
 Examples

Au(79)
Cr(24) [Xe] 14 5d
4f3d
[Ar] 9 6s
4 4s 2 2 ❌

Au(79)
Cr(24) [Xe] 4f14
[Ar] 3d5d 10 16s1
5 4s
✔

Pd(46) [Kr] 4d8 5s2 ❌

Pd(46)
Cr(24) [Kr] 3d10
[Ar] 4d 5s10
5 4s
✔

Pt(78) [Xe] 4f14 5d8 6s2 ❌

Pt(78)
Cr(24) [Xe] 14 5d
[Ar]4f3d 9 6s
5 4s 1 1
✔
 Transition elements exhibit certain
characteristic properties due to
partially filled d-orbitals.

Physical properties

General Atomic properties

properties
Chemical properties
 Physical Properties

High tensile strength

All the transition
elements display typical
metallic properties High thermal and electrical conductivity

Malleability

Ductility

Metallic lustre

Hard and less volatile

High melting and boiling points

High tensile strength

High electrical conductivity High thermal conductivity

 Ductility: They are ductile
Malleability: Metals
and can be drawn into
are highly malleable
very thin wire

Metallic lustre: Metals Volatility: Metals are

are lusturous in nature non-volatile in nature
High boiling point High melting point

Metals generally
have high melting
and boiling points
Melting Point of Transition Elements

Melting point of transition metal

is high because of the
involvement of greater number
of electrons from (n-1)d in
addition to the ns electrons in
the interatomic metallic
bonding.
 Melting Point of Transition Elements

General rule In any row, Except for

anomalous
3d metals rise to a values of
Greater the number of maximum at d5 Mn and Tc
unpaired electrons

Then, fall regularly

as the atomic
Higher will be the number increases
melting point
Boiling Point of Transition Elements

Transition elements
have high boiling point
due to high enthalpy
of atomisation
 Enthalpy of Atomisation

Transition elements exhibit higher

enthalpies of atomization due to
It is the enthalpy high effective nuclear charge and
change on breaking large number of valence electrons.
one mole of bonds
completely to obtain
atoms in the gaseous
phase. Form very strong metallic bonds.

Arise due to unpaired electrons

in the (n−1)d subshell.
A2(g) 2A(g)
 Boiling Point of Transition Elements

Greater the number of

General rule
valence electrons

Stronger is the
resultant bonding

Higher will be the

boiling point.
 Boiling Point of Transition Elements

900 5d Series The maxima at about the

800
4d Series middle of each series
700
3d Series indicate that one unpaired electron
600
∆aH°/kJ mol-1

per d orbital is particularly

500
favourable for
400
strong interatomic interaction.
300
200
100

Atomic number
 Boiling Point of Transition Elements

900 5d Series
800
4d Series
700
3d Series
600 Boiling point of transition
∆aH°/kJ mol-1

500 elements increases down

400 the group.
300
200
100

Atomic number
 Boiling Point of Transition Elements

Zero unpaired
Zn, Cd and Hg have
low boiling point electrons

Zn

Cd Weak metallic bonding

Hg
Lowest boiling and
melting point
 Atomic radii and
ionic radii
Atomic
properties Ionisation enthalpy
 Atomic Radii – 3d Series
Decreases gradually Due to poor shielding by d electrons,
attraction increases more than repulsion

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

Nearly constant Increases

Repulsion almost Repulsion dominates

balances out attraction attraction

No. of (n-1)d electrons are

very high
 Atomic Radii of Transition Elements

New Attractive Left to right

electron force

Nuclear Attraction
e–
charge on
e– increases outermost
Repulsive
force e- increases

++ e–

Increased electron Repulsion

nuclear in (n-1)d between
charge subshell electrons
increases
 Atomic Radii of 3d, 4d and 5d Series
Due to lanthanoid Radius of 4d series is
contraction similar to radius of
5d series

19
18
The filling of 4f before 5d
17

Radius/mm
16
orbital results in a regular
15
decrease in atomic radii.
14
13
12
Sc Ti V Cr Mn Fe Co Ni Cu Zn
The imperfect shielding
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd of one electron by another
La Hf Ta W Re Os Ir Pt Au Hg
in the same set of orbitals.
Lanthanoid Contraction(Effect on Radii)
Down
the
group
Titanium (Ti) 4s2 3d2 147 pm

Zirconium (Zr) 5s2 4d2 160 pm

Hafnium (Hf) 4f14 6s2 5d2 159 pm

Ti < Zr ≈ Hf
 Lanthanoid Contraction

Reason 1
Shielding power
s>p>d>f
of orbitals

Size Nuclear attraction on

decreases outermost e− increases
 Lanthanoid Contraction

Reason 2
Drastic increment
in charge
Titanium (Ti, 22)

+18 increase in
positive charge
Increase in attraction
Zirconium (Zr, 40)

+32 increase in
positive charge
Decrease in radii
Hafnium (Hf, 72)
 Lanthanoid Contraction

Lanthanoid contraction essentially Due to decrease in radii and

compensates for the expected increase in atomic mass,
increase in atomic size with density of transition
increasing atomic number. elements is generally high.

Due to lanthanoid contraction, Density

4d and 5d elements have very increases
similar physical and chemical down the
properties. group
 Density increases
from Sc to Cu along
the period
 Trends in Ionisation Enthalpy

Reason

Due to an increase
In general, from in nuclear charge
left to right ionization
enthalpy increases
Gradually. Accompanied by the filling
of the inner d-orbitals

Ionisation enthalpy increases

Ionisation Enthalpy Values For 3d Series
3d series I.E1 (kJmol-1) I.E2 (kJmol-1) I.E3 (kJmol-1)
Sc 631 1235 2393
Ti 656 1309 2657
V 650 1414 2833
Cr 653 1592 2990
Mn 717 1509 3260
Fe 762 1561 2962
Co 758 1644 3243
Ni 736 1752 3402
Cu 745 1958 3556
Zn 906 1734 3837
 Ionisation Enthalpy

Zinc have significantly rZn > rCu

higher ionisation First
enthalpy than copper ionisation
I.E.Zn > I.E.Cu enthalpy

Due to completely filled d and s 3d10 4s2 3d10 4s1

electrons in Zn, its first ionisation
energy is more than Cu.

Fully filled More stable High I.E.

 Chemical Properties

Formation of complex
Oxidation state
compounds

Standard electrode
Catalytic properties
potential and reactivity

Formation of interstitial
Magnetic properties
compounds

Colour Alloy formation

 Oxidation State of Transition Elements

Due to incomplete Mn2+ Mn6+ Mn7+

filling of d-orbitals

Transition elements
show a great variety
of oxidation states

Manganese in different
oxidation states
 Oxidation States of 3d Series Elements

Oxidation states form

regular pyramid Sc Ti V Cr Mn Fe Co Ni Cu Zn

+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
 Oxidation State of 3d Transition Elements

Sc3+ Common Ti(IV) is more Ti2+ [Ar]3d2 4s0

oxidation states stable than
Ti(III) or Ti(II)
Ti4+ Ti3+ [Ar]3d1 4s0

d0 configuration Ti4+ [Ar]3d0 4s0

V5+

Noble gas Inert gas

Cr6+
configuration
configuration

Mn7+
Stable More stable
Oxidation State of 3d Transition Elements

Common oxidation states

Mn2+(25)
Zn2+ 3d10 4s0
3d5 4s0

Fully filled
Fe3+(26)
Half-filled orbital

Stable More stable

Oxidation State of 3d Transition Elements

Requires high energy

for removing electron

Sc : [Ar]
3d1 4s2

Sc+ : [Ar]
3d1 4s1

Sc2+ : [Ar]
3d1 4s0
Oxidation State Stability - Down the Group

Inert pair effect

p-block
Lower oxidation states are
favoured by heavier elements

Higher oxidation states are favoured

by the heavier elements
d-block
Easier to remove
valence electrons
 Oxidation State Stability - Down the Group

Example
Stability order

Mo (VI) & W (VI) > Cr (VI)

MoO3 and WO3 Dichromate ion

2–
are not oxidising (Cr2O7 ) in acidic
agents medium is a
strong oxidising
agent
 Inert pair effect

p-block
Oxidation state normally
differ by unit of 2.

Oxidation state normally

differ by unity
d-block
Successive removal of
electrons from d-orbital
Oxidation State in d-block Elements

Fe and Ni in Fe(CO)5 and Ni(CO)4

have zero oxidation states despite
the d block elements favouring
higher oxidation states

Low oxidation state is favoured

by metals when a complex
compound has ligands

Which are not just strong σ-donors

but also π-acceptors like in Ni(CO)4
and Fe(CO)5, etc.
 Halides of 3d metals

Oxidation
X :F→I Number
Group 3 4 5 6 7 8 9 10 11 12
XI : F → Br
+6 CrF6
XII : F, Cl
XIII: Cl → I +5 VF5 CrF5

+4 TiX4 VX4I CrX4 MnF4

+3 TiX3 VX3 CrX3 MnF3 FeX3I CoF3

+2 TiX2III VX2 CrX2 MnX2 FeX2 CoX2 NiX2 CuX2II ZnX2

+1 CuXIII
 Stability of Higher Oxidation States
Stability
Fluorine stabilizes Example: CoF3
through
the highest
oxidation state

Higher lattice energy

Higher bond enthalpy

(higher covalent
compound)
Example:
VF5, CrF6
Instability of CuII Iodides

Cu2+ oxidises I – to I2

2Cu2+ + 4I – Cu2I2 (s) + I2

 Oxides of 3d Metals
Oxidation
Group 3 4 5 6 7 8 9 10 11 12
* : Mixed oxides number

+7 Mn2O7

+6 CrO3

+5 V2O5

+4 TiO2 V2O4 CrO2 MnO2

+3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3

Mn3O4* Fe3O*4 Co3O*4

+2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO

+1 Cu2O
 Oxides of 3d Metals

The ability of oxygen

to stabilise these high
oxidation states exceeds Oxides are more
that of fluorine. stable than halides
due to ability of oxygen
to form multiple bonds
with metals.
MnF4 Mn2O7

Highest Mn Highest Mn
fluoride oxide
Reactivity of Transition Metals

Transition metals vary

widely in their chemical
reactivity.

The study of standard

electrode potential is
important to understand the

Reactivity of Stability of various

transition elements oxidation states
Standard electrode potentials Trends in standard
are measurements of the electrode potentials
equilibrium potentials.

Mn+ + ne– M, EM0n+/M M2+ M M3+ M2+

0
(EM2+/M) (EM0 3+/M2+ )

Standard
reduction
potential
 Cu shows positive standard electrode potential Sublimation
enthalpy(+ve)
Enthalpy of
atomisation & Cu (s) Cu (g); △sH
ionisation energies
+ High

The high energy required to Cu (g) Cu2+ (g); △iH

transform Cu (s) to Cu2+ (g)
Ionisation enthalpy
(I.E.1 + I.E.2), +ve
Not balanced by its
hydration energy Cu2+ (g) Cu2+ (aq); △HydH Low

Hydration enthalpy(-ve)
 Result
Inability to liberate
H2 from acid

Only oxidising acids (HNO3,

Cu (s) + 2HCl (aq) ❌ CuCl2 (aq) + H2 (g)
hot conc. H2SO4) react with
Cu to liberate NO2 and SO2
and oxidise Cu to Cu2+
Whereas,

Zn (s) + 2HCl (aq) ZnCl2 (aq) + H2 (g)

Reaction of metals
with HCl

Iron Nails
Reaction of metals
with HCl

Nickel Balls
Copper Spring
Reaction of Cu with
Cu + 2H2SO4 CuSO4 + SO2↑ + 2H2O
hot and conc. H2SO4

1 2

4
3
Trends in the E0M2+/M Standard Electrode Potential

In +2 state, Mn shows d5, Ni with d8 has

completely filled t2g and Zn has
completely filled d10). So, they show
more negative E0 values than expected
 Hydration Energy
Due to high
charge
19
18
density

Radius/nm
17
16
Ni2+ ion has the highest negative
15
enthalpy of hydration among the
14
elements of 3d series.
13
12
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
La Hf Ta W Re Os Ir Pt Au Hg
 Chemical Reactivity

Transition metals vary

widely in their chemical
reactivity.

Many are electropositive

and dissolve in mineral
acids.

A few metals are noble or

remain unreactive towards
single acids.
Standard electrode potential (V)
Chemical Reactivity
0.5
Less negative
0 E0 values
-0.5

-1 The E0M2+/M values indicate

Across the series decreasing tendency to form
-1.5
divalent cation
-2
Ti V Cr Mn Fe Co Ni Cu Zn
Observed Calculated
values values

Due to increase in the sum of first

two ionisation enthalpies
 Magnetic Properties

Each electron has an

Transition elements are
associated magnetic
paramagnetic in nature. moment, due to

Spin angular Orbital angular

momentum momentum

Electron Electron

Direction of spin
Nucleus
 Spin-only
Magnetic
moment magnetic
moment (in BM)

μ = √ n(n + 2)

Where,
No. of unpaired
n = electron(s)
Magnetic Moments of Mn2+ Ion

Mn2+ [Ar] 3d54s0

5 unpaired
electrons

μ = √ 5(5 + 2)
= 5.92 BM
 Calculated and Observed Magnetic Moments(BM)
Unpaired Magnetic moment
Ion Configuration
electron(s) Calculated Observed
Magnetic moment Sc3+ 3d0 0 0 0
increases with number
Ti3+ 3d1 1 1.73 1.75
of unpaired electrons.
Tl2+ 3d2 2 2.84 2.76
V2+ 3d3 3 3.87 3.86
Cr2+ 3d4 4 4.90 4.80
Mn2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3-5.5
Co2+ 3d7 3 3.87 4.4-5.2
Ni2+ 3d8 2 2.84 2.9-3.4
Cu2+ 3d9 1 1.73 1.8-2.2
Zn2+ 3d10 0 0
Formation of Coloured Ions:3d Metal Ions

Ti3+ Cr3+ Mn2+ Fe3+

Ti3+ : Purple
Cr3+ : Green
Mn2+ : Light pink
Fe3+ : yellow
Co2+ : pink
Ni2+ : green Co2+ Ni2+ Cu2+
Cu2+ : blue
Formation of Coloured Ions

When an electron
from a lower energy Due to this excitation,
d orbital is excited to the compounds shows
a higher energy a color.
d-orbital
 Complex Compounds

Compounds in which the metal

atoms/ions bind to a number of
anions/neutral molecules, by sharing
of electrons and forming complex
species with characteristic properties.

Example: [Fe(CN)6]3–, [PtCl4]2–, etc.

Haemoglobin
Brown Ring Test

In nitrate solution, add FeSO4,

slowly add H2SO4 solution such A brown ring will be formed at
that acid forms a layer below the junction of the two layers.
aqueous solution.
Formation of Complex Compounds

Comparatively
smaller sizes
Reasons for
complex High ionic charges
formation
Availability of d-orbitals
for bond formation
Catalytic Property of Transition Metals

Transition metals show

catalytic property due to
the ability to

Adopt multiple
Form complexes
oxidation states
Catalytic Property of Transition Metals

Iron(III) catalyses the reaction

between iodide and persulphate ions.

– 2– 2–
2I + S2O8 I2 + 2SO4

Catalytic action,

2Fe3+ + 2I– 2Fe2+ + I2

2– 2–
2Fe2+ + S2O8 2SO4 + 2Fe3+
Formation of Interstitial Compounds
 Formation of Interstitial Compounds

TiC

Interstitial compounds Mn4N Usually,

are formed when small
atoms like H, C, or N Fe3H
are trapped inside the
crystal lattices of
VH0.56
metals.
non-stoichiometric
compounds are
neither typically
ionic nor covalent.

TiH1.7
Characteristics of Interstitial Compounds

Higher than
those of pure
metals i High melting points.

Some borides
approach diamond ii Very hard.
in hardness.
Retain metallic
iii
conductivity.

iv Chemically inert.
 Alloy

An alloy is a
blend of metals
prepared by
mixing the
components.

Alloys may be homogeneous solid

solutions in which the atoms of one
metal are distributed randomly among
the atoms of the other.
Alloy Formation
 Alloy Formation

Properties
a
of alloys:
Are hard

Transition metals form alloys

b
due to similar radii along with
Often have high
the other characteristics
melting points

c
Within about 15% of Show better
each other conductivity
 Alloy Formation

Ferrous alloys

Steel Stainless Steel

Cr, V, W, Mo, and Mn are used

to produce various varieties.
 Alloy Formation

Steel Stainless steel

Main metal Other element Main metal Other metals

Chromium,
Iron Carbon Iron
Nickel
 Alloy Formation

Brass Bronze

Main metal Other metal Main metal Other metal

Copper Zinc Copper Tin

 Oxides

Compounds of
transition
elements

Oxoanions

K2Cr2O7 KMnO4
 Metal Oxides
Oxidation
Group 3 4 5 6 7 8 9 10 11 12
Number

+7 Mn2O7
Metal oxides are formed
by reaction of metals with +6 CrO3
oxygen at high
+5 V2O5
temperature.
+4 TiO2 V2O4 CrO2 MnO2

+3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3

Mn3O4 Fe3O4 Co3O4

+2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO

+1 Cu2O
Properties of Transition Metal Oxides

Ionic character
Properties
of metal Melting point
oxides
Acidic or basic nature
 Ionic Character of Transition Metal Oxides

Mn2O7 Covalent green oil

Ionic
character
of the oxide
Oxidation decreases.
number
of a metal
in metal
oxide
increases
 Transition Metal Oxides: Melting Points

1
Oxidation number ∝
Ionic character

Oxidation
Ionic character ∝ Melting point number Acidic
of a metal character of
in metal the oxide
oxide increases.
Hence, CrO3 and V2O5 have low increases
melting points
Important Oxides of Transition Metals

Strong acid

Mn2O7 + H2O 2HMnO4

3CrO3 + 2H2O H2CrO4+ H2Cr2O7

Strong acid
 Important Oxides of Transition Metals

+3 +4 +5
Oxides of Vanadium
V2O3 V2O4 V2O5

More basic Less basic Amphoteric

Oxides of Chromium +2 +3 +6
CrO Cr2O3 CrO3

Basic Amphoteric Acidic

Potassium Dichromate

Preparation

Properties

K2Cr2O7

Structure

Uses
 Preparation of K2Cr2O7
i
Fusion of chromite
ore with Na2CO3

4FeCr2O4 + 2Na2CO3 +7O2 8Na2CrO4 + 2Fe2O3 + 8CO2

ii Filtered Yellow solution

Reaction with
H2SO4
2Na2CrO4 + 2H+ Na2Cr2O7 + 2Na+ + H2O

Orange solution
 Preparation of K2Cr2O7
ii
More soluble
Reaction with KCl Crystallised
than K2Cr2O7

Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl

Orange
solution
Preparation of K2Cr2O7
+
2– +H 2–
CrO4 Cr2O7
+OH−

Chromate Dichromate

Weak acid

Alkaline
solution
 Properties of K2Cr2O7

Oxidising Strong oxidising agent

nature

Na2Cr2O7 K2Cr2O7 K2Cr2O7

In organic As a primary
chemistry standard in
volumetric
analysis
Also greater solubility
in the polar solvent like
CH3COOH
 Properties of K2Cr2O7

In acidic
medium Oxidising action

+6 2–
Cr2O7 + 14H+ + 6e– 2Cr3+ + 7H2O

Standard electrode potential

E0 = 1.33 V
Breathe When orange K2Cr2O7 reacts with
alcohol, it converts into green solution
analyser containing chromium sulfate.

Cr6+ ion Cr3+ ion

(Orange) (Green)
 Properties of K2Cr2O7

Oxidation by
Half reactions
acidified K2Cr2O7

Iodides to Iodine 6I– → 3I2 + 6e–

Sulphides to Sulphur 3H2S → 6H+ + 3S + 6e–

Tin (II) to Tin (IV) 3Sn2+ → 3Sn4+ + 6e–

Fe (II) to Fe (III) 6Fe2+ → 6Fe3+ + 6e–

When orange
K2Cr2O7 reacts
with alcohol, it
converts into
green solution
containing
chromium
sulfate.
 Oxide of Chromium

Chromium (VI) peroxide (CrO5)

Bright blue
Preparation compound

2–
Cr2O7 + 2H+ + 4H2O2 2CrO5 + 5H2O
 Chromium (VI) Peroxide (CrO5)

Structure

_1 _1
Peroxy +6
Peroxy
bond bond
_1 _1

_2

Butterfly
structure
 Chromate: Structure

Chromate ion Dichromate ion

d3s
hybridised

Tetrahedral Tetrahedral

Tetrahedral
Used in leather
industry

To prepare
azo compounds
 Preparation

Physical properties

KMnO4 Structure

Chemical properties

Uses
 Potassium Permanganate: Preparation
i
Fusion of pyrolusite 2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
(MnO2)

Black solid Dark green

Disproportionation reaction
ii in presence of an oxidising
Disproportionation of agent(KNO3 or KClO3)
2−
manganate (MnO4 )
2− −
3MnO4 + 4H+ 2MnO4 + MnO2 + 2H2O

Dark purple
 Potassium Permanganate: Preparation
Step-1
Commercial
method Fused with KOH, 2−
MnO2 MnO4
oxidised with air or KNO3

Step-2
2− Electrolytic oxidation
MnO4 MnO4−
in alkaline solution

Laboratory Oxidation of manganese(II) ion

method
2− 2−
2Mn2+ + 5S2O8 + 8H2O 2MnO4− + 10SO4 + 16H+
 2_ _
Colour of MnO4 and MnO4 Ions

Intense color Manganate ion Permanganate ion

(dark purple)

Green Purple
 Magnetic Property of KMnO4

Heating
effect Diamagnetic Paramagnetic
(no unpaired (one unpaired
electron) electron)

∆
2KMnO4 K2MnO4 + MnO2 + O2
513 K

Dark Green Black

purple
Potassium Permanganate: Structure

Tetrahedral

Manganate ion Permanganate ion

 Potassium Permanganate: Chemical Properties

Oxidising Oxidising properties

nature of KMnO4 in

Neutral or
Acidic Alkaline
faintly alkaline
medium medium
medium

+7 –
In acidic MnO4 + 8H+ + 5e– Mn2+ + 4H2O E0 = 1.52 V
medium
 Oxidising nature of
KMnO4 in acidic medium

6HCl + 2KMnO4 + 5NaHSO3 -> 3H2O + 2KCl + 2MnCl2 + 5NaHSO4

Potassium Permanganate: Chemical Properties

Oxidising nature of
KMnO4 in acidic medium

Liberation of I2 from I– solution:

–
10I– + 2MnO4 + 16H+ 2Mn2+ + 8H2O + 5I2

Conversion of Fe(II) to Fe(III):

–
5Fe2+ + MnO4 + 8H+ Mn2+ + 4H2O + 5Fe3+

Green Yellow
Potassium Permanganate: Chemical Properties

Oxidation of oxalate ion:

2– –
5C2O4 + 2MnO4 + 16H+ 2Mn2+ + 8H2O + 10CO2

Oxidation of Nitrite ion:

– – + –
5NO2 + 2MnO4 + 6H 2Mn2+ + 5NO3 + 3H2O
2KMnO4(aq) + 16HCl(aq) 2KCl(aq) + 2MnCl2(aq) + 8H2O(l) + 5Cl2(g)

Endpoint ❌

Permanganate titration is
not carried out in the presence of
hydrochloric acid because some of the
hydrochloric acid gets oxidised to chlorine
gas. Hence, we do not get the correct
endpoint for the given titration.
 Potassium Permanganate: Chemical Properties

In neutral
+7 +4
medium – + –
MnO4 + 4H + 3e MnO2 + 2H2O

E0 = 1.69 V
Potassium Permanganate: Chemical Properties
Oxidising nature of
KMnO4 in neutral
medium

Thiosulphate is oxidised to sulphate:

– 2–
8MnO4 + 3S2O3 + H2O 8MnO2 + 6SO42– + 2OH –

Oxidation of iodide to iodate:

2MnO4– + I– + H2O 2MnO2 + 2OH – + IO3–

Potassium Permanganate: Chemical Properties

The oxidation of
manganous salt to MnO2

–
2MnO4 + 3Mn2+ + 2H2O 5MnO2 + 4H+

ZnSO4 or ZnO
catalyst
 Potassium Permanganate: Chemical Properties

In alkaline +7 – –
+6 2–
medium MnO4 + e MnO4

E0 = 0.56 V
 Uses of KMnO4

For bleaching of
wool and textiles

Decolourising Decolourising
of oils of oils
Silver Nitrate Copper Oxide
(AgNO3) (CuO)

Zinc Chloride Iron (II) oxide

(ZnCl2) Some (FeO)
Important
d-Block
White Vitriol Compounds Green Vitriol
(ZnSO4) (FeSO4)

Blue Vitriol Ferric Chloride

(CuSO4.5H2O) (FeCl3)
 Silver Nitrate (AgNO3)

It is called as lunar caustic because on contact

with skin it produces a burning sensation like that
with caustic soda along with the formation of finely
divided silver (black coloured).

Preparation When metallic Ag is dissolved in

conc. HNO3 it produces AgNO3.

Ag + 2HNO3 AgNO3 + NO2 + H2O

 Properties of AgNO3

Black metallic
residue

Δ
1 2AgNO3 (Thermal 2Ag + 2NO2 + O2
Decomposition)

2 2AgNO3 + 2NaOH H2O + 2NaNO3 + Ag2O

Silver Oxide
Silver mirror
test
Ag2O + C6H12O6 2Ag + C6H12O7

Glucose Gluconic acid

 Properties of AgNO3

3 AgNO3 + NaCl/NaBr/NaI NaNO3 + AgCl/AgBr/AgI

White/pale yellow/Yellow ppt.

4 2AgNO3 + Na2S2O3 2NaNO3 + Ag2S2O3

White ppt.

Ag2S2O3 + 3Na2S2O3 2Na3[Ag(S2O3)2]

Soluble
 Properties of AgNO3

5 3AgNO3 + Na3PO4 3NaNO3 + Ag3PO4

Yellow ppt.

6 2AgNO3 + K2CrO4 2KNO3 + Ag2CrO4

Brick red
ppt.

7 2AgNO3 + K2Cr2O7 2KNO3 + Ag2Cr2O7

Reddish
brown ppt.
 Uses of AgNO3

1 4
For identifying presence of In the preparation of inks
Cl‒, Br‒ and I‒ ions and hair dyes.

2 5
Tollen's reagent In preparation of
silver mirror

3
For making AgBr, used in
photography.
 Zinc Chloride (ZnCl2)

It is a deliquescent white solid

when anhydrous.

Preparation

ZnCO3 ＋ 2HCl ZnCl2 ＋ H2O ＋ CO2

ZnO ＋ 2HCl ZnCl2 ＋ H2O

 Zinc Chloride (ZnCl2)

Uses For impregnating timber to

01 prevent destruction by insects.

As dehydrating agent 02
when anhydrous.

ZnO.ZnCl2 is used in
03 dental fillings.
 Zinc Sulphate (ZnSO4)

Colourless, crystalline solid,

soluble in water which is used in
dietary supplements. It was
historically called as white vitriol.

Preparation

Zn ＋ dil. H2SO4 ZnSO4 ＋H2

ZnO ＋ dil. H2SO4 ZnSO4 ＋H2O

 Zinc Sulphate (ZnSO4)

Uses
01 In eye lotions.

Lithopone(ZnS + BaSO4) is 02
used as white pigment.

Used in the prevention and

03 treatment of zinc deficiency.
 Blue Vitriol (CaSO4)

Preparation CuO ＋ dil. H2SO4 CuSO4 ＋ H2O

Cu(OH)2 ＋ dil. H2SO4 CuSO4 ＋ 2H2O

Properties

It is crystallised It is used as a herbicide and a

as CuSO4.5H2O fungicide, as battery electrolytes
and it is called and as mordant during a
as blue vitriol. vegetable dyeing process.
 Copper Oxide (CuO)

Preparation Δ
CuCO3.Cu(OH)2 2CuO ＋H2O ＋CO2

Malachite Green
Δ
Cu(OH)2 CuO ＋ H2O

It decomposes when
Properties 1 It is insoluble in water. 2
heated above 1100°C

> 1100°C
4CuO 2Cu2O ＋O2

Black Red
 FeO

Δ
Preparation FeC2O4 FeO ＋CO ＋ CO2
In absence of air

Properties It is stable at high

temperatures and on cooling
slowly disproportionates
into Fe3O4 and Fe.

4FeO Fe3O4 ＋Fe

 Green Vitriol (FeSO4)

Preparation
Fe(scarp)＋ H2SO4 FeSO4 ＋ H2

FeS ＋ dil. H2SO4 FeSO4 ＋ H2S

Properties It undergoes oxidation forming

1
basic ferric sulphate

It is crystallised as green
2 It act as a reducing agent 3
vitriol(FeSO4.7H2O)
 Ferric Chloride (FeCl3)

Dark red
Preparation deliquescent solid
Δ
2Fe ＋ 3Cl2 (dry) 2FeCl3
Iron wire
Anhydrous

2Fe(OH)3 + 3HCl FeCl3 + 3H2O

The solution on evaporation and cooling

deposits yellow crystals of hydrated ferric
chloride, FeCl3.6H2O.
 Ferric Chloride (FeCl3)

Properties
It dissolves in water. The solution is
acidic in nature due to its hydrolysis. The
solution is stabilised by the addition of
HCl to prevent hydrolysis.

FeCl3 + 3H2O Fe(OH)3 + 3HCl

FeCl3 + 3NH4OH Fe(OH)3 + 3NH4Cl

Reddish
brown ppt.
 Ferric Chloride (FeCl3)

Properties

FeCl3 + 3NH4CNS Fe(SCN)3 + 3NH4Cl

Deep red color

complex

4FeCl3 + 3K4[Fe(CN)6] Fe4[Fe(CN)6]3 + 12KCl

Potassium Prussian blue

ferrocyanide (Ferri ferrocyanide)
Periodic Table

d-Block f-Block
elements elements
Point to Remember

La and Ac closely resemble the

lanthanoids and actinoids,
respectively.

Included in discussion of the

respective series besides the 14
elements.
Lanthanoids
 Electronic configurations

Atomic and ionic size

Lanthanoids
(Ln) Oxidation states

Physical properties

Chemical properties

Uses
 Lanthanoids: Electronic Configuration

General
configuration Variable occupancy

4f1-14 5d0-1 6s2

d1 d0

All other
Ce, Gd, Lu
elements
 Lanthanoids: Electronic Configuration

Electronic configurations of Electronic

lanthanum and lanthanoids Atomic configuration
Name Symbol
number
Ln
57 Lanthanum La 5d1 6s2
58 Cerium Ce 4f1 5d1 6s2
59 Praseodymium Pr 4f3 6s2
60 Neodymium Nd 4f4 6s2
61 Promethium Pm 4f5 6s2
62 Samarium Sm 4f6 6s2
63 Europium Eu 4f7 6s2
64 Gadolinium Gd 4f7 5d1 6s2
 Lanthanoids: Electronic Configuration

Electronic configurations of Electronic

lanthanum and lanthanoids Atomic configuration
Name Symbol
number
Ln
65 Terbium Tb 4f9 6s2
66 Dysprosium Dy 4f10 6s2
67 Holmium Ho 4f11 6s2
68 Erbium Er 4f12 6s2
69 Thulium Tm 4f13 6s2
70 Ytterbium Yb 4f14 6s2
71 Lutetium Lu 4f14 5d1 6s2
 Lanthanoids: Atomic and Ionic Size

Lanthanoids
(left to right)

Due to lanthanoid
La → Lu contraction

Overall decrease in
atomic and ionic radii
 Lanthanoids: Atomic Sizes

Overall decrease Eu Half filled

200
in atomic size f-orbital
195

190

Atomic radii/pm
La
185
Pr Pm
Ce
180 Nd Tb
Sm Gd Ho
175 Dy Tm
Er
Yb
170
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Atomic number
 Lanthanoids: Ionic Sizes
Sm2+
Overall decrease 110
Eu2+
in ionic size
La3+
Ce3+
Pr3+
100 Nd3+
Pm3+

Ionic radii/pm
Sm3+
Eu3+ Tm2+
Gd3+
Ce4+ Tb3+ Yb2+
4+
Dy3+
90 Pr Ho3+
Er3+ 3+
Tm
Yb3+
Tb4+ Lu3+

57 59 61 63 65 67 69 71
Atomic number
 Lanthanoid
Contraction

Decrease in sizes
fairly regular for Ln
as compared to
transition elements

Three regions
where electron
Two regions density falls to
where electron zero
One region density falls to
where electron zero
Electron density falls to
density is zero
equally
distributed
 Lanthanoids: Oxidation States

Common
oxidation state Common oxidation
state is Ln(lll) Easy removal of
two 6s and one 5d
(or 4f) electrons
except Eu and Yb
Occasionally +2 and +4
oxidation states are also
obtained Extra stability of
empty, half-filled
and fully filled f
subshell
 Lanthanoids: Oxidation States

Ce4+ Ce3+ Eo = + 1.74 V Eu2+ Eu3+

1 6
[Xe] 4f0 [Xe] 4f [Xe] 4f7 [Xe] 4f

All these ions shift

back to +3 state
hence they act as
Tb4+ Tb3+ Yb2+ Yb3+
reducing or
oxidising agents.

[Xe] 4f
7
[Xe] 4f8 [Xe] 4f
14
[Xe] 4f13
Samarium(Sm) Metal

Lanthanoids are silvery

white soft metals and
tarnish rapidly in air.

Gadolinium(Gd) Metal
Samarium (Steel Hard) The hardness increases with
increasing atomic number,
samarium being steel hard.
High melting points

Their melting points range

between 1000 to 1200 K
but samarium melts at
1623 K.
 Density

Density and other

properties change
smoothly except for Eu
and Yb and occasionally
for Sm and Tm.
High electrical conductivity High thermal conductivity

They are good conductors

of heat and electricity.
 Trivalent
lanthanoid ions

Many trivalent lanthanoid

ions are coloured both in the
solid state and in aqueous
solutions due to incomplete
filling of f-orbitals except
La3+ and Lu3+

Pr+3 Sm+3
(aq. solution) (aq. solution)
Colour of Lanthanoid Ions

La3+ Lu3+

[Xe] 4f0 [Xe] 4f14

No unpaired
electron

Colourless
Magnetic Properties

f0 type f14 type

La3+ & Ce4+ Yb2+ & Lu3+

Other than these,

all other ions are
paramagnetic.
 Point to Remember

Ionisation enthalpies are fairly

low and comparable to La3+, Gd3+ and Lu3+
alkaline earth metals. have abnormally low third
ionisation enthalpy values.

Hence, they are good Extra stability of f0, f7

reducing agents. and f14 orbitals
 Lanthanoids: Ionisation Enthalpy

o
E values
La2+ La3+
[Xe] 4f0 5d1 [Xe] 4f0

Ln3+ (aq) + 3e– Ln (s)

Gd 2+
Gd 3+ Low values of
[Xe] 4f7 5d1 [Xe] 4f7 ionization
enthalpy (III)
Eo ≈ -2.2 to -2.4 v

Lu2+ Lu3+
[Xe] 4f14 5d1 [Xe] 4f14
Good reducing Except
agents due to Eu = -2.0 V
low IE values
Lanthanoids : Chemical Properties

The earlier members of the

series are quite reactive

Like calcium
However, with increasing
atomic number, they behave
more like aluminium.

Typically form compounds which

are ionic and trivalent(Ln3+)
Chemical Reaction of Lanthanoids
Ln2O3 H2
Basic

Ln2S3 Heated with S Ln With halogens LnX3

With C, 2773 K
Basic

LnN
Ln(OH)3 + H2

LnC2, Ln3C and Ln2C3

 Uses of Inner Transition Metals

Alloy steels Catalysts in

petroleum cracking

Phosphors Phosphors in
television
screen
 It consists of a
lanthanoid metal
Mischmetall (~ 95%), iron (~ 5%)
and traces of
S, C, Ca and Al.

Mischmetal
Mischmetal in
bullets and
lighter flint
shells
Radioactive and used Hiroshima and
in nuclear reactors Nagasaki bomb attack

Chernobyl
disaster Radiotherapy
Actinoids
 Uranium is the
heaviest naturally Actinoids are radioactive
occurring element. elements

After uranium, 12 more

elements has been artificial
synthesized (atomic number Earlier Latter
more than 92) and are called members members
the transuranium elements Lr
(lawrencium)
Relatively, Half-life: A
day to 3
long half-lives minutes

Prepared only in
nanogram quantities
 Electronic configurations

Actinoids (An) Atomic and ionic size

Oxidation states

General characteristics
 Actinoids: Electronic Configuration

Electronic configurations of
actinium and actinoids Atomic Electronic configuration
Name Symbol
number
An An3+
89 Actinium Ac 6d1 7s2 5f0
90 Thorium Th 6d2 7s2 5f1
91 Protactinium Pa 5f2 6d17s2 5f2
92 Uranium U 5f3 6d17s2 5f3
93 Neptunium Np 5f4 6d17s2 5f4
94 Plutonium Pu 5f6 7s2 5f5
95 Americium Am 5f7 7s2 5f6
 Actinoids: Electronic Configuration

Electronic configurations of
actinium and actinoids Atomic Electronic configuration
Name Symbol
number
An An3+
96 Curium Cm 5f7 6d1 7s2 5f7
97 Berkelium Bk 5f9 7s2 5f8
98 Californium Cf 5f10 7s2 5f9
99 Einstenium Es 5f11 7s2 5f10
100 Fermium Fm 5f127s2 5f11
101 Mendelevium Md 5f13 7s2 5f12
102 Nobelium No 5f14 7s2 5f13
103 Lawrencium Lr 5f146d1 7s2 5f14
 Actinoids: Electronic Configuration

Electronic configurations of
actinium and actinoids Atomic Electronic configuration
Name Symbol
number
An An3+
89 Actinium Ac 6d1 7s2 5f0
90 Thorium Th 6d2 7s2 5f1
91 Protactinium Pa 5f2 6d17s2 5f2
92 Uranium U 5f3 6d17s2 5f3
93 Neptunium Np 5f4 6d17s2 5f4
94 Plutonium Pu 5f6 7s2 5f5
95 Americium Am 5f7 7s2 5f6
 Actinoids: Electronic Configuration
Electronic
configurations of
Electronic
actinium and Atomic configuration
Name Symbol
actinoids number
An An3+ Half
96 Curium Cm 5f7 6d1 7s2 5f7 filled
97 Berkelium Bk 5f9 7s2 5f8 f7
98 Californium Cf 5f10 7s2 5f9
99 Einstenium Es 5f11 7s2 5f10
100 Fermium Fm 5f127s2 5f11
101 Mendelevium Md 5f13 7s2 5f12
Fully
102 Nobelium No 5f14 7s2 5f13 filled
103 Lawrencium Lr 5f146d1 7s2 5f14 f14
The difference between the
energy levels of 5f and 6d
orbitals are small 5f orbital extend in
space, comparatively
more than 4f orbital,
hence 5f electrons
participate in bonding
Thus in Ac, Th, Pa, U and Np
to a greater extent
electrons may occupy either
5d or 6f orbitals.
Actinoids: Atomic and Ionic sizes

Due to actinoid
contraction

Gradual decrease in the

size of atoms or An3+
ions across the series
 Oxidation States of Actinium and Actinoids
Oxidation states form
regular pyramid
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

The actinoids resemble

the lanthanoids in
having more +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3
compounds in +3 state
+4 +4 +4 +4 +4 +4 +4 +4
than in the +4 state.
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7
 Actinoids : General Characteristics

Physical
properties

Actinoid metals are all silvery

in appearance but display a
variety of structures.

Due to irregularities in
metallic radii which are
far greater than in
lanthanoids
 Actinoids : Chemical Properties

Actinoids are highly Hydrochloric acid attacks all

reactive metals metals but most metals are
less affected by nitric acid.

1 H2O (Boil) ✔
Due to formation of

✔
protective oxide layer.
2 Most non-metals

3 HCl ✔
4 HNO3
 Uses of d & f Block Elements

Alloying metals like Cr, Mn,

Ni are used in production of
Iron and steels which
are most important
construction materials.

TiO2 as white Dry cell

pigment battery
 Application as Catalysts

Important Catalyst Process

V2O5 Contact process

Ziegler catalyst Polythene

[TiCl4 with Al(CH3)3] manufacturing

Iron Haber process

Nickel Hydrogenation of fats

PdCl2 Wacker process

Polymerisation of
Nickel complex
alkynes and benzene