d- and f-Block Elements

Important Compounds of Transition Elements

What you already know

● Magnetic properties​ of Transition

Elements
● Colour of Transition Elements​
● Formation of Complex Compounds​
● Catalytic Property of Transition Metals​
● Formation of Interstitial Compounds​
● Alloy Formation​
● Important Oxides of Transition Metals
● Preparation​ of Potassium Dichromate
Important Compounds of Transition Elements

What you will learn

● Properties​, Structure​ and Uses​ of Potassium

Dichromate​
● Preparation​, Properties​, Structure​ and Uses​
of Potassium Permanganate
● Electronic Configurations​, Atomic and Ionic
Size​, Oxidation States​, Properties​ and Uses
of Lanthanoids and Actinoids
 Oxides

Compounds
of transition
elements

Oxoanions

K2Cr2O7 KMnO4
 Potassium Dichromate

Preparation

Properties

K2Cr2O7

Structure

Uses
Potassium Dichromate: Preparation

Generally, dichromate is
prepared from chromate,

The chemical reaction

carries out in 3 steps
 Preparation of K2Cr2O7
i
Fusion of chromite
ore with Na2CO3

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

Filtered Yellow solution

 Preparation of K2Cr2O7
ii
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

4FeCr2O3 + 2Na2CO3 +7O2 8Na2CrO4 + 2Fe2O3 + 8CO2

Yellow solution

2Na2CrO4 + 2H+ Na2Cr2O7 + 2Na+ + H2O

Orange solution

Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl

Orange solution
Properties of K2Cr2O7

2–
+H+ 2–
CrO4 −
Cr2O7
+OH

Chromate Dichromate

Weak acid

Alkaline
solution
 Properties of K2Cr2O7

Oxidising Strong oxidising agent

nature

Na2Cr2O7 K2Cr2O7

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

K2Cr2O7
 Properties of K2Cr2O7

In acidic
medium Oxidising action

+6 2–
Cr2O7 + 14H+ + 6e– 2Cr3+ + 7H2O

Standard electrode potential

E0 = 1.33 V
 Do you know!
Potassium dichromate
is used to catch drink
and drive cases!

Well, thanks to its

application in
breath
analyser!
Breathe
analyser
Cr6+ ion
(Orange)
Breathe
analyser
Cr3+ ion
(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–

 Oxide of Chromium

Chromium (VI) peroxide (CrO5)

Preparation
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
d3 s
hybridised

Tetrahedral
 Dichromate: Structure

Dichromate ion

Tetrahedral Tetrahedral
 The sum of the total number of bonds between
chromium and oxygen atoms in chromate and
dichromate ions is:

Total Cr−O bonds in chromate 4σ and 2π while in dichromate ion 8σ and

4π bonds. Hence, the total Cr−O bonds will be 6+12=18.
 Uses

Used in leather To prepare

industry azo compounds
 Oxides

Compounds
of transition
elements

Oxoanions

K2Cr2O7 KMnO4
 Preparation

Physical properties

KMnO4 Structure

Chemical properties

Uses
Potassium Permanganate: Preparation

Methods of
preparation

Method-2 Method-3
Method-1
(commercial) (laboratory)
Potassium Permanganate: Preparation

Methods of
preparation

Method-2 Method-3
Method-1
(commercial) (laboratory)
 Potassium Permanganate: Preparation
i
Fusion of pyrolusite
(MnO2)

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

Black solid Dark green

 Potassium Permanganate: Preparation
ii
Disproportionation of
2−
manganate (MnO4 )
Disproportionation
reaction

2− −
3MnO4 + 4H+ 2MnO4 + MnO2 + 2H2O

Dark purple
Potassium Permanganate: Preparation

Methods of
preparation

Method-2 Method-3
Method-1
(commercial) (laboratory)
 Potassium Permanganate: Preparation

Commercial
method Step-1
Fused with KOH, 2−
MnO2 MnO4
oxidised with air or KNO3

Step-2
2− Electrolytic oxidation
MnO4 MnO−4
in alkaline solution
Potassium Permanganate: Preparation

Methods of
preparation

Method-2 Method-3
Method-1
(commercial) (laboratory)
 Potassium Permanganate: Preparation

Laboratory
Oxidation of manganese(II) ion
method
2− 2− +
2Mn2+ + 5S2O8 + 8H2O 2MnO4− + 10SO4 + 16H
 When MnO2 is fused with KOH, a coloured
compound is formed. Find the compound
and its colour, respectively?

A K2MnO4, purple-green

B KMnO4, purple

C Mn2O3, brown

Hence, option A is the correct D Mn3O4, black

answer.
 2_ _
Colour of MnO4 and MnO4 Ions

Manganate ion Permanganate ion

Green Purple
Diamagnetism

Temperature-dependent,
weak paramagnetism
 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

 Select the incorrect statement:

A Manganate and permanganate

ions are paramagnetic.

Manganate and permanganate

B ions are tetrahedral.

Manganate ion is green in

C colour and permanganate
ion is purple in colour.

D In manganate and permanganate

ions, П-bonding takes place by
Hence, option A is the correct overlap of p-orbitals of oxygen
answer. and d-orbital of manganese.
 Potassium Permanganate: Chemical Properties

Oxidising
nature Oxidising properties
of KMnO4 in

Neutral or
Acidic Alkaline
faintly alkaline
medium medium
medium
 Potassium Permanganate: Chemical Properties

+7
In acidic –
MnO4 + 8H+ + 5e– Mn2+ + 4H2O
medium

E0 = 1.52 V
Potassium Permanganate: Chemical Properties

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
Permanganate titration is not
carried out in the presence
of hydrochloric acid. Why?
2KMnO4(aq) + 16HCl(aq) 2KCl(aq) + 2MnCl2(aq) + 8H2O(l) + 5Cl2(g)

Endpoint ❌
 Potassium Permanganate: Chemical Properties

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

E0 = 1.69 V
Potassium Permanganate: Chemical Properties

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
 Consider the following reaction, the value of x, y,
and z in the reaction are respectively:
xMnO4– + yC2O42– + zH+ xMn2+ + 2yCO2 + z/2 H2O

A 5, 2, and 16

B 2, 5, and 8
2MnO4– + 5C2O42– + 16H+ -> 2Mn2+ +
10 CO2 + 8H2O
C 2, 5, and 16

Hence, option C is the correct

answer. D 5, 2, and 8
 4KOH, O2
A 2B (Green)+ 2H2O
HCl
3B 2C (Purple) + MnO2 + 2H2O
H2O, Kl
2C 2A + 2KOH + D
In the above sequence of reactions, A and D,
respectively, are

A KI and KMnO4
MnO2(A) + 4KOH + O2 → K2MnO4(B) +
2H2O
3K2MnO4 + 4HCl → 2KMnO4 + MnO2 + 2H2O B MnO2 and KIO3
+ 4KCl
2KMnO4 + KI + H2O → 2MnO2 + 2KOH +
KIO3 C KI and K2MnO4
Hence, option B is the correct
answer. D KIO3 and MnO2
 Thermal decomposition of a Mn compound (X) at 513 K results
in compound (Y), MnO2 and a gaseous product. MnO2 reacts
with NaCl and concentrated H2SO4 to give a pungent gas Z. X,
Y and Z, respectively, are

A K3MnO4, K2MnO4 and Cl2

B K2MnO4, KMnO4 and SO2

C KMnO4, K2MnO4 and Cl2

Hence, option C is the correct

answer. D K2MnO4, KMnO4 and Cl2
Uses

For bleaching of
wool and textiles

Decolourising
of oils
 Periodic Table

d-Block f-Block
elements elements
 Lanthanoids
(Ln)

f-Block

Actinoids
(An)
 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
The 71st electron of an element X with an
atomic number of 71 enters into the orbital:

A 4f

B 6p

C 5d

D 6s
In the lanthanoid series, the atomic number of fourteen 4 f –block elements
ranges from 58 (Ce) to 71 (Lu).
Ytterbium, Yb(Z = 70) has electronic configuration : [Xe] 4 f 146s2. So, the 71st
electron of lutetium, Lu(Z = 71) should enter into 5d orbital and its (here, Lu is ‘X
’) electronic configuration will be : [Xe]4 f 145d16s2

Hence, option c is the correct answer.

 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
200
in atomic size
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: 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+
Dy3+
90 Pr4+
Ho3+
Er3+ 3+
Tm
Yb3+
Tb4+ Lu3+

57 59 61 63 65 67 69 71
Atomic number
Recall

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
The correct order of atomic radii is:

A Ho > Nd > Eu > Ce

B Nd > Ce > Eu > Ho

C Eu > Ce > Nd > Ho

D Ce > Eu > Ho > Nd

(i) Rest of all the 3 members are lanthanides with Eu having stable half-filled
configuration thus with bigger size than rest two.
(ii) Among Ce, Nd and Ho, Ce has larger size and Ho has smaller size which can
be explained on the basis of “Lanthanoid contraction”.

Hence, option c is the correct answer.

 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
Samarium(Sm) Metal Samarium (Steel Hard)

High melting points

Gadolinium(Gd) Metal
High electrical conductivity High thermal conductivity
Colour of Lanthanoid Ions

La3+ Lu3+

[Xe] 4f0 [Xe] 4f14

No unpaired
electron

Colourless
 Lanthanoids: Physical Properties

Magnetic
properties f0 type f14 type

La3+ & Ce4+ Yb2+ & Lu3+

Other than these,

all other ions are
paramagnetic.
 The correct electronic configuration and spin-
only magnetic moment (BM) of Gd3+ (Z = 64),
respectively, are:

A [Xe] 5f7 and 7.9

[Xe] 4f7 5d1 6s2

B [Xe] 4f7 and 7.9

C [Xe] 5f7 and 8.9

Hence, option B is the correct

answer.
D [Xe] 4f7 and 8.9
Point to Remember

Ionisation enthalpies are

fairly low and comparable to
alkaline earth metals.

Hence, they are good

reducing agents.
Extra stability of f0, f7
and f14 orbitals

La2+ La3+
[Xe] 4f0 5d1 [Xe] 4f0

Gd2+ Gd3+ Low values of

[Xe] 4f7 5d1 [Xe] 4f7 ionization
enthalpy (III)

2+ 3+
Lu Lu
14
[Xe] 4f14 5d1 [Xe] 4f
 Lanthanoids : Reducing Agents

Eo values
Ln3+ (aq) + 3e– Ln (s)

Eo ≈ -2.2 to -2.4 v

Except
Eu = -2.0 V
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

Basic

With C, 2773 K
LnN
Ln(OH)3 + H2

LnC2, Ln3C and Ln2C3

 Uses

Alloy steels
Phosphors in
television screen

Catalysts in
petroleum cracking
 Mischmetall

A well known alloy,

mischmetal, which consists of
a lanthanoid metal (~ 95%),
iron (~ 5%) and traces of S, C,
Ca and Al.
 Lanthanoids
(Ln)

f-Block

Actinoids
(An)

Or Actinides
Actinoids
 Actinoids are
radioactive elements

Earlier Latter
members members
Lr
(lawrencium)
Relatively, Half-life: A
day to 3
long half-lives
minutes

Prepared only in
nanogram quantities
 Electronic configurations

Actinoids Atomic and ionic size

(An)
Oxidation states

General characteristics
 Actinoids: Electronic Configuration

General
configuration
Variable occupancy

5f0-14 6d0-2 6s2

d2 d1 d0

Ac, Pa, U, All other

Th
Np, Cm, Lr elements
 Actinoids: Electronic Configuration

Electronic configurations of Electronic

actinium and actinoids Atomic 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 actinoids Atomic 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 Electronic

actinium and actinoids Atomic 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
The difference between the
energy levels of 5d and 6f
orbitals are small

Thus in Ac, Th, Pa, U and

Np electrons may occupy
either 5d or 6f orbitals.
 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
 5f orbital extend in
space, comparatively
more than 4f orbital,
hence 5f electrons
participate in bonding
to a greater extent
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

+3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7
 The maximum number of possible oxidation states
of actinoides are shown by:

Nobelium (No) and

A
Lawrencium (Lr)

B Neptunium (Np) and

Plutonium (Pu)

Actinium (Ac) and

C Thorium (Th)
Hence, option B is the
D Berkelium (Bk) and
correct answer.
Californium (Cf)
 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 : General Characteristics
Chemical Actinoids are highly
properties reactive metals

1 H2O (Boil) ✔
2 Most non-metals ✔
3 HCl ✔ But why?

4 HNO33
HNO
 Actinoids : General Characteristics
Chemical Hydrochloric acid attacks all
properties metals but most metals are
less affected by nitric acid.

Due to formation of
protective oxide layer.
 Actinoids : General Characteristics

Magnetic
properties

Ions are paramagnetic or

diamagnetic depending upon the
number of unpaired 5f electrons.
Applications of
d- and f-block
elements
Construction material- Dry cell
Iron and steel battery

Construction material- Coinage metal

Iron and steel

TiO2 as white
pigment
 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