Unit- 8

The d & f block elements

 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 21Sc to 30Zn

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

• 3rd Transition series or 5d series 57La, 72Hf to

80Hg

• 4th Transition series or 6d series 89Ac, 104Rf 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
• Formation of complexes
• Oxidation state

• Standard electrode • Catalytic properties

potential.
• Formation of interstitial
• Reactivity compounds.
 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

• 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.

• IE1 of 5d series is much higher than those of 4d and 3d

due to weak shielding by 4f electrons.
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 α 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 Δ aH 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 compounds
of 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 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

• 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 Na 2Cr2O7

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 H2SO4
• Nitrite(NO2-) is oxidised to Nitrate(NO3-)
• Oxallic acid is oxidised to CO2
• 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 KMnO4
• Used as an oxidising agent in laboratory and industry.

• 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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