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12C08

The d- and f- Block Element

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12C08.1

Position & General Properties of Transition element

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Learning objectives :

Position & Electronic Configuration

General Properties Part -1 ( Physical Properties , Ionic size , Ionization energy, Oxidation State )

General Properties Part -2 ( Standard electrode Potential , Stability and Mangnetic Prop )

General Properties Part -3 ( Color ions ,complex compounds , Catalyst , interstitial , Alloy Formation )

Position & General Properties of Transition Element :

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12C08.1

CV 1

Position & Electronic Configuration

�

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Definition of transition Element

According to IUPAC, transition metals are defined as metals which have incomplete d subshell either in neutral atom or in their ions.

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Position of different blocks in periodic table

d Block

S Block

P Block

F Block

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Series in d block

4d series (Y to Cd)

5d series (La and Hf to Hg)

6d series (Ac and Rf to Cn)

3d series

(Sc to Zn)

d Block

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Electronic Configuration

3d series	Sc	Ti	V	Cr	Mn	Fe	Co	Ni	Cu	Zn
Z	21	22	23	24	25	26	27	28	29	30
4s	2	2	2	1	2	2	2	2	1	2
3d	1	2	3	5	5	6	7	8	10	10

Half filled Configuration

Full filled Configuration

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12C08.1

CV 2

General Properties Part - 1

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Good Conductor of Heat and Electricity

Transition Metal

Metallic Properties :

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Lustre and Hard

Lustre

Hard

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Exception :

Mn , Zn , Cd , Hg

Ductility and Malleability

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Mettalic Structure

Body Center Cubic (bcc)

Hexagonal close packed (hcp)

Cubic close packed (ccp)

Sc , V , Ti , Cr , Fe

Mn, Ti , Cr , Fe , Zn

Cr , Co , Ni , Cu

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Melting Point and Boiling Point

Mo(42)

5s¹

4d⁵

W(74)

6s¹

5d⁵

Unpaired electron ↑ Metallic Bond ↑

Cr(24)

4s¹

3d⁵

Atomic Number

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Enthalpy of Atomization

Cr(24)

4s¹

3d⁵

Mo(42)

5s¹

4d⁵

W(74)

6s¹

Unpaired electron ↑ Metallic Bond ↑ Enthalpy ↑

Atomic Number

KJ/Mol

4d⁵

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16

Atomic Radii :

3d

4d

5d

Effective Nuclear Charge

Atomic Radii

Lanthanide Contraction

Radius/nm

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3d

4d

5d

Radius/nm

4d-series

5d-series

Effective

Nuclear

Charge

Atomic

Size

s > p > d > f

Shielding Order

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Concept Test

Ready for a challenge

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Q :In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest, i.e., 126 kJ

mol^–1. Why?

Sol :

Pause the video

Time Duration - 2 minutes

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Zn(30)

4s²

3d¹⁰

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12C08.1

CV 3

General Properties Part - 2

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Ionization Enthalpy :

Effective Nuclear Charge

Ionization Enthalpy

First Ionization Enthalpy < Second Ionization Enthalpy < Third Ionization Enthalpy

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Factors affecting Ionization Enthalpy

Attraction of electron towards Nucleus

Repulsion between electron

Exchange of Energy

Cr⁺

4s²

Cr⁺

Mn⁺

>

Fe⁺²

Mn⁺²

<

3d⁵

Mn⁺

4s²

3d⁵

Mn⁺²

4s²

3d⁵

Fe⁺²

4s²

3d⁵

Stable Configuration

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24

Compounds	Oxidation State
MnO	+2
Mn₂O₃	+3
MnO₂	+4
Mn₃O₄	+8/3
Mn₂O₇	+7

Mn(25)

4s²

3d⁵

Oxidation State :

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+3

+2

+3

+4

+2

+3

+4

+5

+2

+3

+4

+5

+6

+2

+3

+4

+5

+6

+7

+2

+3

+4

+6

+2

+3

+4

+2

+3

+4

+1

+2

Sc(21)

4s²

3d⁵

Zn(30)

4s²

3d¹⁰

3d-series

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Fe(26)

4s²

3d⁶

8

+3

+2

+3

+4

+2

+3

+4

+5

+2

+3

+4

+5

+6

+2

+3

+4

+5

+6

+7

+2

+3

+4

+6

+2

+3

+4

+2

+3

+4

+1

+2

3d-series :

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d⁵ Configuration

d⁰Configuration

d¹⁰ Configuration

d¹⁰ > d⁵ > d⁰ > any other configuration

Stability order of d Configuration :

3d⁰

3d¹

3d⁵

3d³

Oxidation State depends :

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28

+1 , +2 , +3

+1 , +2

+3,+4,+5,+6,+7

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d block Element	Oxidation State
Mn	+7 (KMnO₄)
Ru	+8 ( RuO₄)
Os	+8 ( OsO₄)

More stable

Zero Oxidation State

Ni (CO)₄

Fe (CO)₅

Ni

Fe

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Oxidation State

Ionic Character

Compound	Character	Oxidation State	Acidic Nature
MnO	Ionic	+2	Basic
MnO₂	Ionic & Covalent	+4	Amphoteric
Mn₂O₇	Covalent	+7	Acidic

Acidic Character

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31

+6

Most stable state Mo , W MoO₃ , WO₃

Most stable state Cr +3

Oxidizing Agent

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Standard Electrode Potential ( M²⁺/ M ) :

Observed Value

Calculated Value

Standard Electrode Potential/V

+ V

Strong Reducing Agent

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Mn⁺²

4s⁰

3d⁵

Zn⁺²

4s⁰

3d¹⁰

Ni related with high negative Hydration Energy

Observed Value

Calculated Value

6

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Standard Electrode Potential ( M³⁺/ M²⁺ ) :

Sc⁺²

4s⁰

3d¹

Zn⁺²

4s⁰

3d¹⁰

Mn⁺²

4s⁰

3d⁵

Sc⁺³

Mn⁺³

Zn⁺³

Fe⁺²

4s¹

3d⁵

Fe⁺³

Standard Electrode Potential depends :

Enthalpy of atomization + Ionization energy – Hydration Energy

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12C08.1

CV 4

General Properties Part - 3

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Stability of Higher Oxidation State :

MnO₃F +7 oxidation state

Compounds

Higher Oxidation State

High Bond Enthalpy

Higher Oxidation State in Halides :

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Compounds

Lower Oxidation State

Does’nt form Floride

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Compounds

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Higher Oxidation State in Oxides :

+3 Oxidation State

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Stability of Higher Oxidation State in 3d-series

Oxides > Floride

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Mangnetic Properties :

Mangnetic Behaviour

Dimangnetic

Paramagnetic

Ferromagnetic

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Cr(24)

4s¹

3d⁵

Mn(25)

4s²

3d⁵

Zn(26)

4s²

Unpaired electron ↑ Paramagnetic ↑

6 unpaired electron

5 unpaired electron

0 unpaired electron

Paramagnetic

Dimagnetic

3d⁵

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Mangnetic Moment ( Spin only )

Movement of electron

About own axis

About nucleus

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Formation of Colored ions :

Coloured ions d – d transition Unpaired electron

+3

+2

+4

+5

+3

+2

+6

+7

+2

+3

+2

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Low energy d orbitals

High energy d orbitals

Some Exceptions

Charge Transfer

Visible Range

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Formation of Complex Compounds :

Smaller size

High ionic Charge

Availability of d-electron

Ligand

Metal

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Catalyst Properties :

Reactants Products

Catalyst

Multiple Oxidation State

Form Complexes

Contact Process

Haber’s Process

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Formation of Interstitial Compounds :

Ionic

Covalent

Stoichiometric

Properties :

Higher Melting Point

Very Hard

Retain Conductivity

Chemically Inert

Small size Atom (H , C , N )

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Alloy Formation :

Alloy Blend of Metal with Metal /Metalloid / Non-Metal

Advantage :

More Stiffness

Lighter in Weight

Easy to shape

More resistance to Corrosion

High strength to weight ratio

Brass

Bronze

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Similar Radii of transition element

Easy replacement of Atoms

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Alloy

Ferrous Alloy

Non Ferrous Alloy

Less than 0.1%

Iron Alloy

Higher than 0.1%

Steel Alloy

Don’t contain Fe

Like Brass , Bronze

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Vanadium Steel

Chromium Steel

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Concept Test

Ready for a challenge

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Q :Calculate the ‘spin only’ magnetic moment of M²⁺(aq) ion (Z = 27).

Sol :

Pause the video

Time Duration - 2 minutes

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M(27)

4s²

3d⁷

M²⁺

4s⁰

3d⁷

3 unpaired electron

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12C08.2

Compounds of Transition element

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Learning objectives :

Chromium Compound – K₂Cr₂O₇

Manganes Compound – KMnO₄

Compounds of Transition Element :

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12C08.2

CV 1

Chromium Compound – K₂Cr₂O₇

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Introduction of Potassium Dichromate – K₂Cr₂O₇ :

Chromite Ore/ Iron Chromite

FeO.Cr₂O₃ or FeCr₂O₄

Potassium Dichromate

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Preparation of Potassium Dichromate ( K₂Cr₂O₇) :

Step - 1

Preparation of Sodium Chromate ( Na₂CrO₄ )

Step - 2

Conversion of Sodium Chromate ( Na₂CrO₄ ) to Sodium Dichromate ( Na₂Cr₂O₇)

Step - 3

Conversion of Na₂Cr₂O₇ to K₂Cr₂O₇

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Step - 1

Preparation of Sodium Chromate ( Na₂CrO₄ )

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Filteration

Na₂CrO₄ (impure)

Na₂CrO₄

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Step - 2

Conversion of Sodium Chromate ( Na₂CrO₄ ) to Sodium Dichromate ( Na₂Cr₂O₇)

+

Na₂CrO₄

H₂SO₄

Na₂Cr₂O₇

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Step - 3

Conversion of Na₂Cr₂O₇ to K₂Cr₂O₇

Na₂Cr₂O₇

KCl

+

K₂Cr₂O₇

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Properties of Potassium Dichromate ( K₂Cr₂O₇) :

Crystalline Ionic Solid with bright Red Orange colour

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CrO₄^2- and Cr₂O₇^2- are interconvertible in aqueous solution depend upon PH value

CrO₄^2- Cr₂O₇^2-

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CrO₄^2- and Cr₂O₇^2- are interconvertible in aqueous solution depend upon PH value

Weak Acid

Alkaline / Carbonate Solution

Cr₂O₇²^-

CrO₄²^-

Low PH

High PH

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Structure of CrO₄^2- and Cr₂O₇^2-

Cr₂O₇²^-

CrO₄²^-

126⁰

Tetrahedral

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Soluble in water

water

K₂Cr₂O₇ in water

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In Acidic Solution , K₂Cr₂O₇ furnishes Nascent Oxygen [O]

+6

+3

Oxidizing Agent

Alcohol ( CH₃CH₂OH )Ascetic Acid ( CH₃COOH )

K₂Cr₂O₇/H⁺

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In Acidic Solution , K₂Cr₂O₇ furnishes Nascent Oxygen [O]

Ferrous Sulphate

Ferric Sulphate

Hydrogen Sulphide

Sulphur

Hydrogen Cloride

Cromium Cloride

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In Acidic Solution , K₂Cr₂O₇ furnishes Nascent Oxygen [O]

Potassium Iodide

Iodine

Stennous Cloride

Stennic Cloride

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K₂Cr₂O₇ is preferred over Na₂Cr₂O₇ in Volumetric Titration

Na₂Cr₂O₇

K₂Cr₂O₇

Non - Hygroscopic

Hygroscopic

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Uses of Potassium Dichromate ( K₂Cr₂O₇) :

It is used in Tanning the Leather

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Uses of Potassium Dichromate ( K₂Cr₂O₇) :

It is used in Tanning the Leather

Used as Mordant in Dyes

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Uses of Potassium Dichromate ( K₂Cr₂O₇) :

It is used in Tanning the Leather

Used as Mordant in Dyes

Used in Volumetric estimation of Ferrous salt , Iodides and Sulphides

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12C08.3

CV 2

Manganese Compound – KMnO₄

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Potassium Permanganate – KMnO₄ :

HMnO₄ + KOH KMnO₄ + H₂O

Salt

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79

5

Preparation of KMnO₄ :

Manganese dioxide

or Pyrolusite

Caustic

Potash

Potassium

Manganate

Manganese dioxide

or Pyrolusite

Potassium

Carbonate

Potassium

Nitrate

Potassium

Manganate

Oxygen

Potassium

Permanganate

Potassium

Manganate

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laboratory Preparation of KMnO₄

Peroxodisulphate

Permanganate

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Industrial Preparation of KMnO₄

Manganate

Permanganate

Electrolyte

Oxidation

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Properties of Potassium Permanganate ( KMnO₄) :

Dark purple , Anhydrous , Needle like Crystal

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Properties of Potassium Permanganate ( KMnO₄) :

Dark purple , Anhydrous , Needle like Crystal

Isostructural with KClO₄

Mn

O

_

K

+

Cl

O

_

K

+

Tetrahedral

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Properties of Potassium Permanganate ( KMnO₄) :

Dark purple , Anhydrous , Needle like Crystal

Isostructural with KClO₄

Moderately soluble in water

water

KMnO₄in water

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Properties of Potassium Permanganate ( KMnO₄) :

Dark purple , Anhydrous , Needle like Crystal

Isostructural with KClO₄

Moderately soluble in water

On strong heating , It decomposes into K₂MnO₄

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Ions are Tetrahedral

Mn

O

_

K

+

O

Mn

O

_

K

+

O

_

MnO₄^-1

MnO₄^-2

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Ions are Tetrahedral

Manganate is Paramangnetic

Permanganate is Dimangnetic

Mn²⁵

4s²

3d⁵

K₂MnO_4,Mn⁺⁶

KMnO_4,Mn⁺⁷

4s⁰

3d¹

4s⁰

3d⁰

1 unpaired electron

0 unpaired electron

Paramangnetic

Dimangnetic

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Chemical properties of Potassium Permanganate ( KMnO₄) :

Powerful Oxidising Agent

Acidic Medium

Basic Medium

Neutral Medium

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Powerful Oxidising Agent

Acidic Medium

Hydrogen Sulphide

Sulphur

Sulphur Dioxide

Sulphuric Acid

-2

0

+4

+6

Arsenite

Arsenate

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Powerful Oxidising Agent

Acidic Medium

Sulphite

Sulphate

Nitrite

Nitrate

+4

+6

+3

+5

Ferrous Sulphate

Ferric Sulphate

+2

+3

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Powerful Oxidising Agent

Acidic Medium

Potassium Iodide

Iodine

-1

0

Hydrogen Peroxide

Oxygen

-1

0

+3

+4

Oxalic

Acid

Carbon Dioxide

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Powerful Oxidising Agent

Basic Medium & Neutral Medium

Potassium Iodide

-1

+5

Sodium Thiosulphate

+2

+4

+2

+6

Potassium Iodate

Manganese Dioxide

Sodium sulphate

Manganese Sulphate

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Uses of Potassium Permanganate ( KMnO₄) :

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Uses of Potassium Permanganate ( KMnO₄) :

Bleaching of wool , cotton , silk and other textile fibre

Bleached

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Uses of Potassium Permanganate ( KMnO₄) :

Bleaching of wool , cotton , silk and other textile fibre

Decolorisation of Oils

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Uses of Potassium Permanganate ( KMnO₄) :

Bleaching of wool , cotton , silk and other textile fibre

Decolorisation of Oils

Alkaline KMnO₄ ( Bayer Reagent ) Oxidizing Agent

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12C08.3

F block Elements

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Learning objectives :

Lanthanoides

Actinoides

F block element :

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12C08.3

CV 1

Lanthanoids

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Introduction of Lanthanoids:

F block

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Lanthanoids

Actinoids

4f- series

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Electronic Configuration of Lanthanoids:

⁵⁹Pr

1s²

2s²

2p⁶

3s²

3p⁶

4s²

3d¹⁰

4p⁶

5s²

4d¹⁰

5p⁶

6s²

4f³

4f^1-145d^0-16s²

Ln

Exception of electronic configuration

La

Ce

Gd

Lu

Lanthanoids

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+

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Atomic and Ionic Size :

Crystle structure

+

m

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Oxidation State :

+3 Oxidation State

More stable

+3

Less stable

+2 , +4

Lanthanoids

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+3 Oxidation State

Ce⁵⁸

6s²

5d¹

4f¹

Ce⁵⁸

+4 Oxidation State

Ce⁺⁴

Ce⁺³

+ e^-

Strong Oxidant

Element	Pr	Nd	Tb	Dy
Oxides

Lanthanoids

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Lanthanoids

Eu⁶³

6s²

4f⁷

Eu⁶³

+2 Oxidation State

Eu²⁺

Eu⁺³

- e^-

Strong reducing Agent

Yb⁷⁰

6s²

4f¹⁴

Eu⁷⁰

+2 Oxidation State

Strong reducing Agent

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Lanthanoids

Tb⁶⁵

+4 Oxidation State

Tb⁺⁴

Tb⁺³

+ e^-

Strong Oxidant

Sm⁶³

+2 Oxidation State

Sm²⁺

Sm⁺³

- e^-

Strong reducing Agent

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Physical Charaterstics :

Silvery White Soft Metal

Cerium

Dysprosium

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Physical Charaterstics :

Silvery White Soft Metal

Tarnish rapidly in Air

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Physical Charaterstics :

Silvery White Soft Metal

Tarnish rapidly in Air

Hardness increases with Atomic Number

Hardness

Lanthanoids

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Physical Charaterstics :

Silvery White Soft Metal

Tarnish rapidly in Air

Hardness increases with Atomic Number

Good conductor of Heat & electricity

Lanthanoids

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Physical Charaterstics :

Silvery White Soft Metal

Tarnish rapidly in Air

Hardness increases with Atomic Number

Lanthanoids Ions show color in both Soild state and Aqueous solution

Good conductor of Heat & electricity

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Physical Charaterstics :

Silvery White Soft Metal

Tarnish rapidly in Air

Hardness increases with Atomic Number

Lanthanoids Ions show color in both Soild state and Aqueous solution

Lanthanoids are Paramagnetic except La³⁺, Ce⁴⁺, Yb²⁺and Lu³⁺

Good conductor of Heat & electricity

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Melting Point & Density increases with Atomic Number

Melting Point

Lanthanoids

Density

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Chemical Charaterstics :

Ln

Lanthanoids

with Acid

with Halogens

heated with

C at 2773 K

heated with S

heated with N

Burn in O₂

with H₂O

H₂

LnX₃

Ln(OH)₃ + H₂

LnC₂

LnN

Ln₂S₃

Ln₂O₃

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12C08.3

CV 2

Actinoids

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Introduction of Actinoids:

Lanthanoids

Actinoids

5f- series

NATURE

Artificial Process

F block

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Electronic Configuration of Actinoids:

⁹⁴Pu

1s²

2s²

2p⁶

3s²

3p⁶

4s²

3d¹⁰

4p⁶

5s²

4d¹⁰

5p⁶

6s²

4f¹⁴

5f^1-146d^0-17s²

Actinoids

Exception of electronic configuration

Actinoids

5d¹⁰

6p⁶

7s²

5f⁶

Ac , Th , Pa , U , Np , Cm , Lr

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Atomic and Ionic Size :

Actinoids

Radii of Actinoids

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Oxidation State :

Actinoids

3

4

5

6

7

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Physical Charaterstics :

Silvery in Appearance

Neptunium

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Physical Charaterstics :

Silvery in Appearance

Highly Reactive especially in Finely divided

Thorium

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Physical Charaterstics :

Silvery in Appearance

Highly Reactive especially in Finely divided

Paramagnetic

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Physical Charaterstics :

Silvery in Appearance

Highly Reactive especially in Finely divided

Paramagnetic

Tarnish in Air due to Oxide Coating

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Chemical Charaterstics :

An

with HCL

with Nitric Acid

NaOH

with Halogens

heated with H2

with O₂

With hot H₂O

AnCl₃ +H₂

No Reaction

AnH₃ + AnO₂

AnH₃

AnX₄

An₃O₈

Actinoids

No Reaction

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Difference between Lanthanoids & Actinoids :

+7

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12C08.3

CV 3

Applications of D and F block

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Applications of D and F block :

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