Unit- 8The d & f block

elements

RAJESH KUMAR G
PGT CHEMISTRY
JNV KOLLAM,KERALA
HYDERABAD REGION
 The transition elements
(d-block)Introduction

d-block elements:
Elements belonging to group 3 to12 of
the periodic table are known as d-block
elements.

In these elements last electron enter in

to penultimate d-orbital.

d-block elements lie between s and p-

block elements.
 Outline
Transition series

General electronic configuration

General characteristics

• M.p & B.p • Atomic and ionic size

• Ionisation enthalpy • Oxidation state
• Reactivity • Magnetic properties

• Standard electrode
potential.
Periodic table
Transition series
Transition series
d-block consists of four transition series

1st Transition series or 3d series Sc to

21
30Zn

2nd Transition series or 4d series 39 Y to 48 Cd

3rd Transition series or 5d series 57 La, Hf

72
to 80Hg

4th Transition series or 6d series 89 Ac, 104 Rf

to 112Cn
Transition Elements
Transition elements:
Element which has partially filled penultimate d-
subshell in ground state or most common oxidation
state are known as transition elements.

All d-block elements are not transition elements but

all transition elements are d- block elements.

Transition elements have partially filled d- subshell

in ground state or most common oxidation
state .But all d-block elements not follow this.

Zn, Cd & Hg are not considered as transition

metals.
General Electronic
Configuration
(n-1)d1-10 ns1-2
General properties of transition
elements

M.p & B.p Magnetic properties.

Atomic and ionic
size Coloured ions.
Ionisation enthalpy
Oxidation state Formation of complexes
Standard electrode
potential.
Reactivity
Catalytic properties

Formation of interstitial
compounds.
Oxide formation.
 Melting and Boiling Point
Melting and Boiling Point: Generally High
d block elements have large no. of unpaired
electrons hence they form strong metallic bond.
Their melting and boiling points are high.

Specific cases:
Exceptionally Zn ,Cd and Hg have low melting and
boiling point.
Mn and Tc have abnormally low m.p.
Group 6 elements have highest m.p in corresponding
period (Cr, Mo, W).
Tungsten has highest m.p among metals.
Melting points
Trends of melting points of transition elements
Variation in atomic and ionic
radii
Atomic size decreases left to
right.

Increases at the end of series.

4d & 5d series have almost

same size.(due to lanthanoid
contraction)
Ionisation Enthalpy
Its endothermic

Down the group IE should decrease but anonymously IE of

5d is more as compared to 3d and 4d because poor
shielding of 4f orbital

Generally increases due to increases in nuclear charge

from left to right in series .

IE1<IE2< IE3 in each group due to positive charge on

them.
Oxidation State

Transition elements have variable oxidation

state , due to very small energy difference
between(n-1)d and ns subshell . Electrons from
both the subshell take part in bonding.

No. of Oxidation states is directly proportion to

the no. of unpaired electrons.

Mn shows all oxidation states from +2 to +7 .

Variation in oxidation state

Low oxidation state are found when a

complex compound has ligands capable of
π-acceptor character in addition to the
sigma bonding, e.g. Ni(CO)4, Fe(CO)5.
Standard electrode
potential
Value of electrode potential depends on enthalpy of atomisation ,
sum of ionisation enthalpies and hydration enthalpy.

Reduction potential α ΔaH α I.E α 1/ΔhydH

Due to positive electrode potential, Cu does not
liberate hydrogen from acids .
It must be noted that the value of E0 for Mn , Ni and
Zn are more negative than expected from the trend.
Standard electrode
potential
Reactivity

Though the transition elements are moderately

electropositive, yet they are
not very reactive

because of their

(i) High heat of sublimation

(ii) High ionisation enthalpy

Reactivity
Magnetic Moment
Transition metals and compounds are paramagnetic due
to the presence of unpaired electrons in their d-subshell.

Substances which do not contain unpaired electrons and

repel by magnetic field are dia-magnetic.

Weakly attracted-----Paramagnetic

Strongly attracted-----Ferromagnetic

The spin only magnetic moment can be calculated by the

formula µ=√ n(n+2) BM where n is the no .of
unpaired electrons.
Magnetic Moment
General Properties of d-
Block elements
Outline
General characteristics of d-Block elements:

Formation of coloured ions.

Formation of complex compound.

Catalytic property.

Formation of interstitial compounds.

Alloy formation.
Formation of Coloured
compounds
Most of the transition metal compound are
coloured both in solid state and in aqueous
solution.

Generally atoms or ions have unpaired

electrons.

Due to d- d transition produce coloured

compound.
Coloured ions
Complimentary colour
chart
Standard reduction potential
of higher oxidation states
Complex Formation
The tendency to form complex compounds is due to-
Small size of the ion
High charge on the transition metal ion.
The availability of d orbitals for accommodating
electrons donated by the ligands.

Cu2+ (aq) + 4 NH3 (aq) → [Cu(NH3)4]2+ (aq)

(blue) (deep blue)

AgCl (s) + 2 NH3 (aq) → [Ag (NH3)2]Cl (aq)

(white ppt) (Colourless )
Catalytic Properties
Their catalytic properties are due to-
• Presence of unpaired electron in their incomplete
d-subshell.
• Variable oxidation state of transition metal and ability to
form complexes .

In most cases provide large surface area with free

valency .
Interstitial Compounds
Due to void space of suitable size in their
lattices, small atoms can be easily
accommodated.
 Alloy formation
Most of transition metals form alloys because of
their
• similar radii due to which transition metals can
mutually substitute their position in their crystal
lattice.
Formation of Oxides
Transition metals form oxides of general
composition MO, M2O3, MO2 and MO6, etc.
Lower oxidation state: Basic
Higher oxidation state: Amphoteric or
Acidic

MnO Mn2O3,Mn3O4,MnO2 Mn2O7

Basic Amphoteric
Acidic
 Some important
compoundsof transition
elements
Outline
Potassium dichromate:

Methods of preparation , Properties and Uses.

Potassium permanganate:

Methods of preparation , Properties and Uses.

Structure of Permanganate and Dichromate

ions.
Potassium dichromate (K2Cr2O7)
Preparation: From Chromite ore (FeCr2O4)

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

(chromite ore)

2 Na CrO + H SO → Na Cr O + Na SO + H O
2 4 2 4 2 2 7 2 4 2

Na2Cr2O7 + 2 KCI → K2Cr2O7 + 2 NaCl

Orange crystals of K2Cr2O7 are obtained on crystallisation.
Properties of potassium
dichromate
Physical Properties:
Orange-red coloured crystalline compound.

Moderately soluble in cold water but freely soluble in

hot water.
It melts at 398°C.

K2Cr2O7 is preferred over Na2Cr2O7 as a primary

standard in volumetric estimation because Na2Cr2O7
is hygroscopic in nature but K2Cr2O7 is not.
Effect of pH on Potassium
dichromate
Cr2O72- + 2 OH- → 2 CrO42- + H2O
(Orange) (Yellow)

2 CrO42- + 2 H+ → Cr2O72- + H2O

(Yellow) (orange)
Oxidising nature of Potassium
dichromate
Powerful oxidising agent in acidic medium (dil. H2SO4)

Cr2O7 2-
+ 14H+ + 6e- → 2Cr3+ + 7H2O (E° = 1.33 V)

6Fe2+ + Cr2O7 2-
+ 14 H+ → 6Fe3+ + 2Cr3+ + 7H2O

6I- + Cr2O7 2-
+ 14 H+ → 3I2 + 2Cr3+ + 7H2O

3Sn2+ + Cr2O7 2-
+ 14 H+ → 3Sn4+ + 2Cr3+ + 7H2O

3H2S + Cr2O7 2-
+ 14 H+ → 3S + 2Cr3+ + 7H2O

Note: Oxidation state of Cr changes from +6 to +3

Uses Of Potassium
Dichromate
Used as a primary standard in volumetric
analysis for the estimation of reducing agents
such as oxalic acid, ferrous ions, iodide ions,
etc.

For tanning of leather, calico printing,

photography etc.

As a cleansing agent for glass ware in the form

of chromic acid.
POTASSIUM
PERMANGANATE (KMnO4)
POTASSIUM PERMANGANATE (KMnO4)

Preparation:
From pyrolusite ore(MnO 2)

2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

(K2MnO4 → 2K+ + MnO42-)

3MnO42- + 4H+ → 2MnO4- + 2H2O +

MnO2
Properties
Physical Properties :
It is purple coloured crystalline
compound.
Sparingly soluble in water at room
temperature.
Chemical Properties:
Effect of heating

2KMnO4 751K
K2MnO4 + MnO2 +
O2
Effect of pH

MnO4- OH-
MnO42-
H+
Oxidising nature of KMnO4
KMnO4 shows strong oxidising nature.
It shows different oxidising nature in different
medium.

Acidic medium:
MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O

Neutral or faintly alkaline medium:

MnO4- + 2H2O + 3e- → MnO2 + 4OH-

Strongly alkaline medium:

MnO4- + e-→ MnO42-
 Oxidising nature of KMnO4
In acidic medium (presence of dil. H2SO4) :
MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O

5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ +

7H2O
Iodide is oxidised to Iodine
H2S is oxidised to Sulphur
SO2 is oxidised to H 2SO4
Nitrite(NO2-) is oxidised to Nitrate(NO3-)
Oxallic acid is oxidised to CO 2
This reaction is slow at room temperature, but is rapid
at 60°C.
Mn(II) ions produced catalyse the reaction; thus the
reaction is autocatalytic.
 Oxidising nature of KMnO4
In slightly alkaline & neutral medium :
In slightly alkaline medium KMn04 is reduced to MnO2
(MnO4- to MnO2)
2 MnO4- + I- + H2O → 2 MnO2 + IO3- + 2 OH-

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

Point to be noted:
Permanganometric titrations in the presence of HCl are

unsatisfactory as HCl is oxidised to chlorine by KMn04 .

 Uses of KMnO 4
Used as an oxidising agent in laboratory and
industry.
(i)

Alkaline potassium permanganate is called Bayer's

reagent. This reagent is used in organic chemistry for
testing unsaturation.

KMnO4 is used in the manufacture of saccharin,

benzoic acid, acetaldehyde,etc.

KMnO4 is used as a reagent in qualitative analysis and

as primary standard in quantitative analysis.
KMnO4 is used as an antiseptic
Structure of ions
 The Inner
transition
elements(f-block)
OUTLINE
General electronic configuration.

General properties of inner transition elements.

Lanthanide and Actinide contraction.

Properties of lanthanides and Actinides

Uses of Lanthanides and Actinides

Difference between lanthanides and actinides

Introduction of f-block
elements
Inner transition elements(f -Block elements):

They are present in separate block in the periodic

table.

Last electron enters in pre-penultimate f-subshell,

so they are known as f-block elements.
Lanthanoids: last electron enters one of the 4f
orbital. Cerium(at. No. 58) to Lutetium(at. No.71)
Actinoids: last electron enters one of the 5f
orbital. Thorium (at.no.90)to lutetium(at.
No.103)

They are also known as ‘inner transition

elements’.
Lanthanoids
Lanthanoids
General electronic configuration:
4f1-145d0-16s2
last electron enters one of the 4f-orbitals, so
they are known as f-block elements.
Lanthanoids are Ce(at. No. 58) to Lu(at.
No.71)
They are coming just after Lanthanum so
they are known as Lanthanoids.
Electronic Configuration and
Radii of Lanthanoids
Lanthanoid Contraction
Lanthanoid contraction :
In Lanthanoid series, with increasing atomic number,
there is progressive decrease in atomic/ionic radii due to
poor shielding effect of 4f-orbitals.
Reason :
Due to addition of new electrons into (n-2) f-subshell
which shows more poor shielding effect.
Consequences :
Their separation is difficult as they have small
difference in size.
Basic strength of hydroxide decreases from left to
right.
( La(OH)3 is more basic than Lu(OH)3 )
4d and 5d transition series have almost same atomic
radii.
(Zr and Hf have similar properties due to similar size)
Trend in ionic radii of
lanthanoids
Physical properties of
Lanthanoids
The lanthanoids are highly dense metals.
They have high melting points.
They form alloys easily with other metals.
They are soft, malleable and ductile with
low tensile strength.
Properties of lanthanoids
Chemical reactions of
Lanthanoids
Uses of lanthanoids
Used in mischmetal an alloy of a
lanthanoid
( 95%) with iron ( 5%) and traces of S, C, Ca
& Al.

It is used to make tracer bells, shells and

lighter flints.
Actinoids

The actinoids include the fourteen

elements from Th(at.no.90) to
Lr(at.no.103)

The actinoids are radioactive elements.

The earlier members have relatively long

half-lives, latter ones have half life values
ranging from a day to 3 minutes for
lawrencium (Z =103).
Variation in Electronic
configuration and radii
General electronic configuration 5f1-146d0-17s2
Ionic radii and Oxidation
state
Variation in Oxidation
states
Properties of actinoids
Differences between
Lanthanoids and Actinoids
Uses
Uses of actinoids :
Th is used in atomic reactor and
treatment of cancer.
U and Pu are used as fuel in nuclear
reactor.
Summary

Transition (d- block ) elements.

Transition series.

General electronic configuration.

Trends of properties in series.

General characteristics
General characteristics of d-Block elements:

Formation of coloured ions.

Formation of complex compound.

Catalytic property.

Formation of interstitial compounds.

Alloy formation.
Potassium dichromate:

Methods of preparation , Properties and Uses.

Potassium permanganate:

Methods of preparation , Properties and Uses.

Structure of Permanganate and Dichromate ions.

General properties of inner transition elements.
General electronic configuration.
Lanthanoid and Actinoids contraction.
Properties of lanthanoids and Actinoids
Uses of Lanthanoids and Actinoids
Differences between lanthanoids and Actinoids
Home Assignment
Account for the following:

Transition elements exhibit higher enthalpies of atomization.

Transition metals show paramagnetic behaviour.

Transition metal ions form complexs .

Transition metals form interstitial compounds.

Most of the transition metals form alloys.

Transition element form generally coloured compounds

Transition elements show variable oxidation state.

How Potassium dichromate is prepare from
Chromite ore.

Write the chemical reactions involved in the

preparation of potassium permanganate.

The chromates and dichromates are

interconvertible in aqueous solution depending
upon pH of solution. Give reactions.

What is meant by ‘disproportionation of an

oxidation state ? Give two example.
Give reasons for the following questions:

Chemistry of all the lanthanoids are quite similar.

Size of trivalent lanthanoid cations decreases with

increase in the atomic number.

It is difficult to separate lanthanoid elements in pure

state.

Ce4+ in aqueous solution is a good oxidizing agent.

Ce3+ can be easily oxidized to Ce4+.

d-block elements exhibit more oxidation states than

f - block elements
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