Periodic table

The transition elements

(d-block)
d-block elements:
•Elements belonging to group 3 to12 (10grps) of
the periodic table are known as d-block elements.
•In these elements last electron enter in to
penultimate (n-1)d-orbital.
•d-block elements lie between s and p-block
elements.
•Definition: The elements which contains
incompletely filled d orbitals in their GS or most
common oxidation state.
•Transition from highly electro+ metals to electro-
non metals
• 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.

They have d10 configuration.
They have always +2 oxd state
They are pseudo transition elements.
Explain with EC
General Electronic Configuration

(n-1)d1-10 ns1-2
 Outline
•Transition series
•General electronic configuration
•General characteristics
∙ Metallic properties
∙ M.p & B.p
∙ Atomic and ionic size
∙ Ionisation enthalpy
∙ Oxidation state
∙ Magnetic properties
. Coloured ions.
. Formation of complexes
. Catalytic properties
.Formation of interstitial compounds
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, to 80Hg

• 4th Transition series or 6d series 89Ac, to

112
Cn
METALLIC PROPERTIES

. Full metals ( electron donation)

. More valence electrons or more electron donation means
good electro positive metal
. They are hard metals
. High density
 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. From L to R, it increases then
it decreases.
Specific cases:
• Exceptionally Zn ,Cd and Hg have low melting and
boiling point.
• Group 6 elements have highest m.p in corresponding
period (Cr, Mo, W).
• Tungsten has highest m.p among metals. So used in
bulb filaments.
 Melting points
•Trends of melting points of transition elements
 Variation in atomic and ionic radii
• Atomic size decreases left to right.
• Should increase from top to
bottom.
3d
4d
5d
6d
• 4d & 5d series have almost same
size.(due to lanthanoid contraction
and poor shielding effect of f
orbitals)
•Eg: Zr and Hf have same properties
due to same size
Ionisation Enthalpy
.Generally increases due to increases in nuclear charge
from left to right in series and decreases from top to
bottom.

.3d, 4d, 5d, 6d: It should decrease but 5d>4d and 3d due to
lanthanoid contraction and weak shielding by 4f electrons.

. IE1<IE2< IE3

eg. Cu and Cr : half filled and fully filled requires more

energy
Oxidation State (n-1)d1-10 ns1-2

• 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

Common oxd state is +2 except Sc.

Zn is +2
Highest oxidation state is +7 for Mn
 Magnetic Moment
• Transition metals and compounds are paramagnetic due to the
presence of unpaired electrons in their d-subshell.

• Weakly attracted-----Paramagnetic

• The spin only magnetic moment can be calculated by the formula

µ=√ n(n+2) BM where n is the no .of unpaired electrons.
 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
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 )
 Interstitial Compounds
•Due to void space of suitable size in their lattices, small
atoms can be easily accommodated.
 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 .
• Ability to form complexes.
 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.
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.

 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.

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

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

(chromate)
(chromite ore)

• 2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

• Na2Cr2O7 + 2 KCI → K2Cr2O7 + 2 NaCl

• Orange crystals of K2Cr2O7 are obtained on crystallisation.
Structure of ions
 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.
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.

Reduction takes place.
POTASSIUM
PERMANGANATE (KMnO4)
• POTASSIUM PERMANGANATE (KMnO4)

Preparation:
From pyrolusite ore (MnO2)

•2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

potassium manganate dark green
on disproprtionation

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

MnO4- OH-
MnO42-
H+
Structure of ions
 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
 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
• H 2S is oxidised to Sulphur
• SO2 is oxidised to H 2SO4
• Nitrite(NO2-) is oxidised to Nitrate(NO3-)
• Oxalic 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 .
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

Periodic table
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.
After La, Cerium(at. No. 58) to Lutetium(at. No.71)
• Actinoids: last electron enters one of the 5f orbital.
After Ac,Thorium (at.no.90)to Lawrentium(at. No.103)
•They are also known as ‘inner transition elements’.
 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 after La, 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
Trend in ionic 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. They have comparable sizes.
•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)
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.
Chemical reactions of
Lanthanoids
Properties 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

Ac, Th(at.no.90) to Lr(at.no.103)

•The actinoids are radioactive elements.

 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
THANK YOU