4102609923604691

Maha Marathon : INORGANIC
INORGANIC CHEMISTRY
Shilpi Kaushik
NIT Jalandhar
INORGANIC CHEMISTRY
CBSE -2023
INORGANIC CHEMISTRY
Complete Theory
+
NCERT Intext Q
+
PYQs
+
Case Based Q
INORGANIC CHEMISTRY
CBSE
Chapter Wise Weightage of chemistry CBSE Class 12
Chapter Name d and f block
Weightage 7 Marks
Chapter Name Coordination Compounds
Weightage 7 Marks
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
d-block Elements
Last electron enters into the ‘d-orbital’ of the
penultimate shell i.e. (n-1)d orbital, where ‘n’ is the last
shell.
The d-block consisting of Groups 3-12 occupies the

large middle section of the periodic table.
general electronic
(n-1 ) d1-10ns1-2
configuration
inner d orbitals Outermost shell

INORGANIC CHEMISTRY
Transition elements
Transition elements are those elements whose atom
in ground state or ion in common oxidation state
contains incomplete d - subshell
1st series Zn 3d10 4s2
2nd series Cd 4d10 5s2
3rd series Hg 5d10 6s2
d block metals
Transition metals
INORGANIC CHEMISTRY
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Exceptional configuration
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Properties of d-block Elements

Physical Properties
High tensile strength Ductility Malleability
Very hard and low

High thermal and volatility (exception Zn,
Metallic lustre
electrical conductivity Cd, Hg)
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Melting Point
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Melting Point
High Melting Point
❖ Cr, Mo, W → d5 configuration
❖ ∴ Highest melting points
Exceptions
❖ Mn & Tc → d5 configuration
❖ But Low melting points
“Due to weak
metallic bond”
INORGANIC CHEMISTRY

Formation of coloured ions: Due to d-d transitions and
charge transfer transitions
Observed colour is always complementary colour of the

colour which is absorbed by the substance
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Catalytic Property:
Variable Large surface Ability to form

Oxidation states area complexes
Note: Catalyst provides alternate path with lower Ea

but does not change the equilibrium constant.
Example:
(1) Haber process: N2 + 3H2 → 2NH3 Catalyst: Finely
divided Fe; Promoter: Mo, 200 bar, 723-773 K
INORGANIC CHEMISTRY

(2) Ostwald’s process:
NH3 + O2 → NO + H2O
NO + O2 → NO2
NO2 + H2O + O2 → HNO3
Catalyst: Pt, 573K
INORGANIC CHEMISTRY
Example
V 2 O5
Step 1: 2SO2(g) + O2(g) 2SO3(g)↑
Sulphur dioxide Sulphur trioxide
Vanadium
Step 2: SO3(g) + H2SO4(l) H2S2O7(g) Pentoxide
Oleum catalyst
Step 3: H2S2O7(g) + H2O(l) H2SO4(l)

Sulphuric acid
INORGANIC CHEMISTRY

Interstitial compounds:
→ Small atoms like H, N, C or B trapped inside the crystal
lattice of metals.
→ Non stoichiometric and neither ionic nor covalent.
Example: Mn4N, Fe3H etc. FeO0.98O etc.
→ They have high MP than these of pure metals.
→ Very hard, some borides approach diamond in hardness.
→ Retain metallic conductivity.
INORGANIC CHEMISTRY

Formation of complex compounds:
● Comparatively smaller size of metal ions.
● High charge on ions
● Increase e/m ratio
● Availability of vacant d-orbitals for bond
formation.
Example - [Fe(CN)6 ]3-, [ Fe(CN)6 ]4-
Ligand
Metal
Ni(CO)4
INORGANIC CHEMISTRY

Alloy formation
→ Homogeneous solid solutions
→ Radius within 15% of each other
→ Because of similar radii and similar properties
alloys are readily formed by transition metals
→ Hard and often high MP
Example: Steel and Bronze, brass etc.
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Enthalpy of Atomisation
The order of enthalpy of atomisation
3d<4d<5d due to more metal-metal bonding
in compounds of heavy transition metals
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Solution
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Magnetic Properties
Due to unpaired electrons they exhibit paramagnetic behaviour
Paramagnetism ∝ number of unpaired electrons
Movement of electron
⟶ About own axis
⟶ About nucleus
Magnetic Moment (Spin only)
n = No. of Unpaired electron

Unit - Bohr Magneton (BM)
Magnetic Properties
μ= n (n + 2)
n = the number of unpaired electrons

µ = the magnetic moment in units of Bohr magneton (BM)
No. of unpaired Calculated magnetic

Ion Configuration
electrons moment (BM)
Sc3+ 3d0
Ti3+ 3d1
Ni2+ 3d8
V2+ 3d3
Cr2+ 3d4
Mn2+ 3d5
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Magnetic Properties
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Formation of Coloured ions
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Atomic radius
nuclear charge Effective
Atomic radii
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Atomic radius
Less number
of electrons
in the d -
orbitals
Nuclear charge Number of d

predominates electron
increases
The atomic radii of transition series decreases e-- e- repulsion

from Sc to Cr remains almost constant till Cu and predominates
then increases towards the end.
INORGANIC CHEMISTRY
The atomic radii of transition series decreases

from Sc to Cr remains almost constant till Cu and
then increases towards the end.
Reason - Increase in atomic radii towards the end may

be attributed to the electron-electron repulsions In
fact, the pairing of electrons in d-orbitals occurs after
d5 configuration. The repulsive interactions between
the paired electrons in d-orbitals become very
dominant towards the end of the period and cause
the expansion of electron cloud and thus, resulting in
increased atomic size. The ionic radii also follow the
similar trend.
INORGANIC CHEMISTRY
Atomic radius
Variation in atomic size is 3d < 4d ≈ 5d Lanthanoid contraction
due to the lanthanoid contraction example
atomic radii of Zr (160pm) &
Hf (159pm)
Atomic radii of 4 d series ≅ 5 d series
Due to filling of 4f before 5d orbital

INORGANIC CHEMISTRY
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Lanthanoid Contraction
Lanthanide contraction is the steady decrease in

atomic and ionic size of lanthanides as their atomic
number increases
Causes of Lanthanide contraction:
1. In f-block elements, the positive charge on the nucleus
rises by one unit, and one additional electron enters the
same 4f subshell, as the atomic number increases.
2. Electrons in the 4f subshell poorly shield each other.
Shielding is less in a 4f subshell than in a d subshell.
3. As the nuclear charge increases, the valence shell is
drawn closer to the nucleus. Hence, as a result
contraction takes place.
INORGANIC CHEMISTRY
Ionization enthalpy
Effective nuclear charge
Ionisation
enthalpy
Ionisation enthalpy
INORGANIC CHEMISTRY
Ionization enthalpy
IE of 3rd transition series are higher as compared to

1st and 2nd transition series
Due to poor shielding of 4f electrons and increase in

effective nuclear charge acting on outer valence electron
INORGANIC CHEMISTRY
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Variable Oxidation States
❖ Due to similar energies of ns and (n – 1)d orbitals e-s both can

participate to show variable oxidation state.
Maha Marathon : INORGANIC CHEMISTRY
Oxidation state
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
Too many d electrons

Fewer electrons to lose ( fewer orbitals
or share available) in which to share
electrons with others
Oxidation state
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
Oxidation state
INORGANIC CHEMISTRY
Noteworthy features of oxidation states of the transition
elements are.
1. For the elements of first transition series +2 oxidation
state is the most common oxidation state.
2. The highest oxidation state shown by any transition
metal is + 8.
3. Some transition metals also show oxidation state of zero
in their compounds. [Ni(CO)4] [Fe(CO)5].
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Trends in the M2+/M standard electrode potentials:
The general trends towards less (-) E0 values along the
series is due to the general increase in the sum of 1st and 2nd
ionisation enthalpies. (IE1 + IE2)
INORGANIC CHEMISTRY
The value of E0 for Mn, Ni and Zn are more negative than
expected from the general trend due to greater stability of
half-filled d-subshell (d5) in Mn2+, an completely filled
d-subshell (d10) in Zn2+.
Mn+2 + 2e- 🠆 Mn
Ni+2 + 2e- 🠆 Ni
Zn+2 + 2e- 🠆 Zn
INORGANIC CHEMISTRY
Cu shows a unique behaviour in the series as it is the only
metal having positive value for E°, which is due to the reason
that the sum of enthalpies of sublimation and ionization is not
balanced by hydration E. Thus it does not liberate H2 gas
from cids.
Cu2+ + 2e 🠆 Cu Eo = +ve.
INORGANIC CHEMISTRY
Trends in the M3+/M2+ standard electrode potentials:
The highest value for Zn is on account of very high stability of
Zn2+ ion (d10) conf.
i.e. it is difference remove an electron from it to change it into
+3 state.
INORGANIC CHEMISTRY
The comparatively high value of E0 (Mn3+/Mn2+) shows that
Mn2+ is very stable which is an account of stable d5 conf. of
Mn2+.
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The low value of E0 (Fe3+/Fe2+) is an account of extra stability
of Fe3+ (d5) i.e. Low I3 of Fe
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The low value of V is an account of the stability of V2+ ion due
to its half-filled t32g configuration.
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Solution
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Solution
Potassium permanganate (KMnO4)
Potassium permanganate Prepared from

KMnO4 Pyrolusite (MnO2)
Colour and melting point Solubility

Dark violet crystalline solid Fairly soluble in water giving a
Melting point → 523 K purple solution 6.4g/100g
It is isostructural with KClO4

INORGANIC CHEMISTRY
Potassium Permanganate
Preparation From mineral
Pyrolusite (MnO2)
Step 1:
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O

Potassium
Manganate
Step 2: (Green)
Disproportionation
3MnO42- + 4H+ 2MnO4- + MnO2 + 2H2O

Manganate ion Permanganate ion
INORGANIC CHEMISTRY
Commercial Preparation
Step 1:
Fused with KOH,
oxidised with air
MnO2 MnO42-
Manganate ion
Step 2:
Electrolytic oxidation in
alkaline sol.
MnO42- MnO4-
Permanganate ion
INORGANIC CHEMISTRY
Magnetic Properties
Laboratory Preparation
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Chemical Reactions
Action of Heat
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INORGANIC CHEMISTRY
Potassium permanganate (KMnO4)
Potassium dichromate(K2Cr2O7)
Potassium Prepared from

dichromate Chromite ore
FeCr2O4
Colour and
Solubility
melting point
Orange red crystalline Moderately soluble in
solid Melting point → cold water but readily
670 K soluble in hot water
INORGANIC CHEMISTRY
Potassium Dichromate
Preparation
Step 1: 4FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
Chromite Sod. Sodium Ferric
ore carbonate chromate oxide
Step 2: Conc. H2SO4
2KCl
Na2Cr2O7 + Na2SO4 + H2O
2NaCl + K2Cr2O7
Step 3: Sodium Sodium
Potassium
dichromate dichromate sulphate
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Magnetic Properties
Chemical Reactions
1 Oxidising Action in Acidic Medium
Cr2O72- + 14H+ + 6Fe2+ 2Cr3+ + 6Fe3+ + 7H2O
Ferrous Ferric
Cr2O72- + 14H+ + 6I- 2Cr3+ + 3I2 + 7H2O

Iodide Iodine
INORGANIC CHEMISTRY
Potassium Dichromate
Chemical Reactions
2 Reaction with H2O2
Cr2O72- + 2H+ + 4H2O2 2CrO5 + 5H2O
Chromium oxide
peroxide
Butterfly structure Deep blue

colour
Oxidation No. of Cr = +6
Potassium dichromate(K2Cr2O7)
INORGANIC CHEMISTRY
f-block Elements
The f-block consists of the two series -
Lanthanoids (4f series, 14 elements after La)
Actinoids (5f series, 14 elements after Ac)

INORGANIC CHEMISTRY
Lanthanide
General Electronic
Configuration
[Xe] 4f1-14 5d0-1 6s2
Exception
[Xe]4f7 5d1 6s2
[Xe]4f8 5d0 6s2

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Electronic configuration
Exception
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The Lanthanoids
Chemical Properties
● They combine with hydrogen when gently heated in the gas.
● The carbides, Ln3C, Ln2C3 and LnC2 are formed when the
metals are heated with carbon
● Their oxides and hydroxides are basic like alkaline earth
metal oxides and hydroxides.
INORGANIC CHEMISTRY
Atomic and ionic size of lanthanides series
The regular decrease in

the size of lanthanide ions
from La3+ to Lu3+ is called
lanthanide contraction
Greater effect of the

increased nuclear charge
than screening effect
INORGANIC CHEMISTRY
Oxidation state
Common stable oxidation state : +3
Ce and Tb exhibit +4 oxidation state
But it is a strong oxidant changing to common +3 oxidation state

INORGANIC CHEMISTRY
Oxidation state
Eu and Yb exhibit +2 oxidation state
Strong reducing agent changing to +3 state
Strong reducing agent

INORGANIC CHEMISTRY
Lanthanide
Oxidation state
+3 is most common Oxidation state”

Elements Oxidation state
La, Ho, Er, Lu, Gd +3

Ce, Pr, Tb, Dy +3, +4
Sm, Eu, Tm, Yb, Pm +2, +3
Nd +2, +3, +4
INORGANIC CHEMISTRY
Actinoids
General electronic configuration : [Rn]5f1-146d0-1 7s2
Atomic Number Name Symbol Electronic [M]
89 Actinium Ac 6d17s2
90 Thorium Th 6d27s2
91 Protactinium Pa 5f26d17s2
92 Uranium U 5f36d17s2
93 Neptunium Np 5f46d17s2
94 Plutonium Pu 5f67s2
95 Americium Am 5f77s2
96 Curium Cm 5f76d17s2
97 Berkelium Bk 5f97s2
98 Californium Cf 5f107s2
99 Einsteinium Es 5f117s2
100 Fermium Fm 5f127s2
101 Mendelevium Md 5f137s2
102 Nobelium No 5f147s2
103 Lawrencium Lr 5f146d17s2
INORGANIC CHEMISTRY
Actinoids
General Electronic
Configuration
[Rn] 5f1-14 6d0-1
7s2
Exception
[Rn]5f7 6d1 7s2
[Rn]5f8 6d0 7s2

INORGANIC CHEMISTRY
Ionic sizes and oxidation states

Decrease in size of atoms / M3+ ion
Actinoid contraction Due to poor shielding of 5f electrons

Oxidation state:
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
INORGANIC CHEMISTRY
Physical and Chemical Properties
● Silvery in appearance
● Highly reactive specially in finely divided
● Paramagnetic
● Tarnish in air due to oxide coating
INORGANIC CHEMISTRY
Actinoids
Atomic size
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Lanthanoids
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Difference Lanthanides and Actinides

INORGANIC CHEMISTRY
PYQs-d- AND f- BLOCK

ELEMENTS
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Solution:
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Solution:
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Solution:
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Solution:
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Solution:
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Solution:
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Solution:
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COORDINATION COMPOUNDS
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Coordinate Bond
INORGANIC CHEMISTRY
Ex: [Co(NH3)3Cl3]
Cl
Cl H3N Cl
H
H Co
H3N Cl
N Cl
NH3
H H Co
N H Coordination
Cl complex/ entity
H N H
H
H
INORGANIC CHEMISTRY
Coordination Compound
In the formula
Counter
Ion K4[Fe(CN)6 Coordinati
on sphere
Central
metal atom
] Ligand
L
INORGANIC CHEMISTRY
Classification of complexes
INORGANIC CHEMISTRY
Ligands
Types of ligands
● Monodentate : They have one donor atom, i.e they
provide only one e- pair to central metal atom or ion.
Example : F-, Cl-, Br-, H2O, NH3, CN-, NO2-
● Bidentate : They have two donor atom and have the
ability to link with central metal ion at two
positions. Example :
Ethylenediamine(en) Oxalate(ox)
Types of ligands
● Tridentate : ligands having three donor atoms
Example :
Diethylene triamine (Dien)

● Tetradentate: Posses four donor atoms.
Example :
Triethylenetetramine (Trien)
Types of ligands
● Pentadentate : Posses five donor atoms
Example :
Ethylenediamine triacetate ion (EDTA)-3

● Hexadentate : Posses six donor atoms.
Example :
Ethylenediaminetetraacetate ion (EDTA)4-

Types of ligands
● Ambidentate Ligands: They can ligate through
two different sites present in it.
Example : CN-, NO2- and SCN¯ ions
Nitrito - N Nitrito - O
Types of ligands
● Chelating ligand : When a polydentate ligand is
bonded with MA from one or more donor atoms,
then the resulting structure is a 5- or 6-
membered ring structure, then the ligand is
known as chelating ligand
INORGANIC CHEMISTRY
IUPAC Nomenclature Rules
Rule 1
Cationic name anionic name
Rule 2
For Naming of Ligand
Follow Use Use Use

Use
Alphabetical Di, Tri, Bis, Tris, “ium”
“O” suffix
Order Tetra Tetrakis suffix
For no. For -ve For +ve
If ligand
of Ligands Ligands
name has
Ligands
number
INORGANIC CHEMISTRY
IUPAC Nomenclature Rules
Rule 3
Write Central Metal Atom Name
For Anionic complex For Cationic/Neutral

Use complex
No Suffix
Suffix “ate”
Rule 4
Write O.No. of CMA in Roman
within (brackets)
INORGANIC CHEMISTRY
IUPAC Nomenclature Examples
[Ag(NH3)2]Cl Diamminesilver(I) chloride
[Cr(en)3]Cl3 Tris(ethane-1,2-diammine)chromium(III) chloride
K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)

INORGANIC CHEMISTRY
Werner’s Theory
Experimental Work
CoCl3 + NH3
CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3 CoCl3.4NH3

INORGANIC CHEMISTRY
Werner’s Theory
Experimental Work Rxn. with excess AgNO3 sol.
AgNO3
1 mol CoCl3.6NH3 3 mol AgCl
(Yellow)
AgNO3
1 mol CoCl3.5NH3 2 mol AgCl
(Purple)
AgNO3
1 mol CoCl3.4NH3 (Green) 1 mol AgCl
AgNO3
1 mol CoCl3.4NH3 (Violet) 1 mol AgCl
INORGANIC CHEMISTRY
Werner’s Theory
Formulation of Cobalt (III) Chloride- Ammonia Complexes

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Postulates of Werner’s Theory
In Coordination Compounds
[Pt(NH3)6]Cl4
Also called as Also called as

Oxidation State Coordination Number
INORGANIC CHEMISTRY
Ionisable
Satisfied by negative ions

Example
aq
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl-
Primary Valency of Co = 3
INORGANIC CHEMISTRY
Non ionisable & fixed for a metal
Satisfied by neutral molecule/ negative ions
Example
aq
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl-
Secondary Valency of Co3+ = 6
INORGANIC CHEMISTRY
“Secondary valency Gives definite geometry to the
complex”
Example
[Co(NH3)6]3+ [PtCl4]2-
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Solution
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Postulates of Valence Bond Theory
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Postulates of Valence Bond Theory
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Coordination Complexes
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Valence Bond Theory
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Valence Bond Theory
Different Geometries
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Valence Bond Theory
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Magnetic Properties
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Magnetic Properties
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Solution
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Solution
Hybridisation
Coordination number = 6
Octahedral
sp3d2 d2sp3
nd orbital used (n-1)d orbital used
Outer orbital complex Inner orbital complex

Hybridisation
Example - [CoF6] 3– ( Paramagnetic)
4d
4d
Hybridisation

Orbitals of Co+3 ion
3d 4s 4p 4d
sp3d2 hybridised orbitals
3d 4d
3d 4d
Six pairs of electrons from six F-
Hybridisation

sp3d2 hybridised orbitals
3d Six pairs of electrons from six F- 4d
● Unpaired electrons ⇒ (Paramagnetic)
● The outer d orbital (4d) is used in hybridisation, the complex is

called an outer orbital or high spin or spin free complex.
Hybridisation
Example - [Co(NH3)6] 3+ (Diamagnetic)
Oxidation state of Co = +3
Orbitals of Co
3d 4s 4p
Orbitals of Co+3
3d 4s 4p
Orbitals of Co+3
3d 4s 4p
Hybridisation
3d 4s 4p
d2sp3 hybrid orbitals
3d
3d Six pairs of electrons

from six NH3 molecules
Hybridisation

d2sp3 hybrid orbitals
3d Six pairs of electrons

from six NH3 molecules
● No unpaired electron ⇒ Diamagnetic
● The inner d orbital (3d) is used in hybridisation, the complex is called an

inner orbital or low spin or spin paired complex.
Hybridisation
In octahedral complex with configuration of CMA/CMI as d1, d2

and d3, always inner orbital complex is formed with d2sp3
hybridization regardless of the nature of ligand. i.e.,
[Ti(H2O)6]+2, [Ti(CO)6]+2, [Ti(ox)3]-4
[Sc(H2O)6]+2, [Sc(CO)6]+3, [Sc(NH3)6]+2 d2sp3
[V(CO)6]+2, [V(CN)6]-2, [V(H2O)6]+3
In octahedral complex with configuration of CMA/CMI as d8,

d9 and d10, always outer orbital complex is formed with sp3d2
hybridization regardless of the nature of ligand. i.e.,
[Ni(H2O)6]+2, [Ni(CN)6]-4, [Ni(CO)6]+2
sp3d2 outer
orbital complexes [Cu(NH3)6]+2, [Cu(H2O)6]+2, [Zn(NH3)6]+2
[Zn(H2O)6]+2, [Zn(CN)6]-4
Hybridisation
Coordination number = 4 C.N. =4
sp3 (tetrahedral) dsp2 (square planar)
M M
ns and np orbital used (n-1)d , ns and np orbital used

Outer orbital complex Inner orbital complex
Hybridisation
Example - [NiCl4] 2– ( Paramagnetic)
Orbitals of Ni+2
3d 4s 4p
sp3 hybridised orbitals
3d
3d Four pairs of electrons

from four Cl-
Hybridisation
Example - [NiCl4]2– ( Paramagnetic)

sp3 hybridised orbitals
3d Four pairs of electrons

from four Cl-
● Unpaired electron ⇒ (Paramagnetic)
● Geometry - tetrahedral M
● The outer ns and np orbital are used in

hybridisation, the complex is called an outer
orbital complex.
Hybridisation
Example - [Ni(CN)4] ( Diamagnetic)
2–
Orbital of Ni2+
3d 4s 4p
dsp2 hybridised orbitals
3d 4p
3d Four pairs of electrons 4p

from four CN-
Hybridisation
Special Note: With 4d and 5d series elements, all of the ligands acts as strong.
Example - [PdCl4]2–
Pd2+ = [Kr] 4d8
→ Normally Cl– acts as weak ligand and thus the complex should have been a
tetrahedral, paramagnetic, sp3 hybridised complex.
→ But in reality it is found to be square planar, diamagnetic, dsp2 hybridised
complex.
Pd2+ =
4d 5s 5p
dsp2 hybridised orbitals
4d 5p
Limitations of VBT
● It does not explain the colour exhibited by coordination compounds
● It does not give a quantitative interpretation of the thermodynamic or kinetic

stabilities of coordination compounds.
Example: Why [Cu(NH3)6]2+ is a stable compound whereas it forms an outer
orbital complex?
● It does not make exact predictions regarding the tetrahedral and

square-planar structures of 4-coordinate complexes.
● It does not distinguish between strong and weak ligands.
Example: Why [Mn(CN)6]3- form inner orbital complex whereas [MnCl6]3-

form outer orbital complex?
Crystal Field Theory (CFT)
Postulates of CFT
● The five d orbitals in an isolated gaseous metal atom/ion have same energy.
(they are degenerate)
● This degeneracy is maintained if a spherically symmetrical field of negative
charges surrounds the metal.
M L L
M or +
M
+
Free metal atom/ion
L L
Symmetrical field of ligands

Degenerate
Energy of all the d orbitals is raised

All d orbitals are of same energy
Crystal Field Theory (CFT)
Postulates of CFT
Because of unsymmetrical field of ligands the degeneracy of the d orbitals is

lost and cause splitting of the d orbitals.
The pattern of splitting depends upon the nature of the crystal field.
L
M
M or + L L
M
+
Free metal atom/ion
L L
L
Degenerate unsymmetrical field of ligands
All d orbitals are of same energy Splitting of d- orbital

CFT: Octahedral complexes

Shape of d orbitals
Non-axial d-orbitals

Shape of d orbitals
Axial d-orbitals
dz2 dx2 -y2

● In an octahedral coordination entity electrostatic repulsion is due to e–
present in metals d-orbitals and electrons of ligand.
● In octahedral complexes ligand approaches the metal through the 3 axes.
z
y
x
● Axial orbitals (dx2-y2, dz2) which point towards the axis along the
direction of the ligand will experience more repulsion and will be
raised in energy relative to the average energy in the spherical
crystal field.
● Non axial orbitals (dxy, dyz and dzx) orbitals which are directed
between the axes will be lowered in energy relative to the average
energy in the spherical crystal field.
L
Energy
L
L
M M M L
L
L eg
dz2dx2- y 2
Barycenter
3/5Δo Δo t 2g
dxy dyzdzx dz2dx2- y 2 2/5Δo
dxy dyzdzx
dxy dyzdzx d2z dx2- y 2 Metal atom
surrounded
Splitting of d-orbital in
Free metal atom by
Octahedral crystal field
Spherical
crystal field
Δo is energy separation due to Crystal Field Splitting


● Octahedral complex yield-
three orbitals of lower energy, t2g set
two orbitals of higher energy, eg set.
● This splitting of the degenerate levels due to the presence of
ligands in a definite geometry is termed as crystal field splitting.
● Energy separation is denoted by Δo (the subscript o is for octahedral).
It is also called crystal field splitting energy (CFSE).
● The energy of the two eg orbitals will increase by (3/5)Δo and that of
the three t2g will decrease by (2/5)Δo.
NOTE: CFSE also has the meaning crystal field stabilization energy, which is
defined differently. Unless it is mentioned, we will consider CFSE to be
crystal field splitting energy.
INORGANIC CHEMISTRY
Factors a ecting ∆
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY

Spectrochemical series
● Ligands can be arranged in a series in the orders of increasing field strength.

I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < EDTA4–
< NH3 < en < CN– < CO
● Such a series of ligands is termed as spectrochemical series.
● It is an experimentally determined series based on the absorption of light
by complexes with different ligands.
E.C. in octahedral complexes
d1 complexes eg
e_ goes to t2g orbital 3/5 ∆0 ∆0

2/5 ∆0
t2g
d2 complexes
eg
e_ go to t2g orbitals
3/5 ∆0 ∆0
2/5 ∆0
t2g

d3 complexes
e_ go to t2g orbitals
eg
3/5 ∆0 ∆0
2/5 ∆0
t2g
● Crystal Field Splitting energy (Δo) – Energy separation between t2g and eg.
● Pairing Energy (P) – Energy required for electron pairing in single orbital.
Two possibilities for d4 configuration
Weak Field Ligands Strong Field Ligands

Creates less crystal field splitting Creates more crystal field splitting
Δo < P, 4th e_ will enter in eg Δo > P, 4th e_ will enter in t2g
orbital orbital
High Spin Low Spin
Complex Complex
d4 configuration d4 configuration
● Similar analysis has to be done in case of other configurations.

CFT: Tetrahedral Complexes
● In tetrahedral coordination entity formation, the d orbital splitting is inverted.
L
M M
M
L L L
Energy
dxy dyz dzx
t2
2/5 ∆t ∆t
dxy dyz dzx dz 2 dx 2 - y 2 3/5 ∆t
dxy dyz dzx dz 2 dx 2 -y 2 e

Metal atom surrounded by
dZ2 dx 2 - y2
Spherical crystal field
Free metal atom
Splitting of d - orbital in
tetrahedral crystal field
CFT: Tetrahedral Complexes
● For tetrahedral orbital complexes splitting axial orbitals are named as “t2” and
nonaxial orbitals are named as “e” .
● “g” subscript is not used because there is no center of symmetry.
Tetrahedral complex Octahedral complex

Centre of symmetry absent Centre of symmetry present
CFSE In Octahedral Versus
Tetrahedral
Octahedral Tetrahedral
Limitations of Crystal Field Theory
● This theory take assumptions that the ligands are

point charges.
● This theory follows that anionic ligands should

exert the greatest splitting effect but anionic
ligands actually are found at the low end of the
spectrochemical series.
● It does not take into account the covalent

character of bonding between the ligand and the
central atom.
INORGANIC CHEMISTRY
Crystal Field Splitting Energy

“The difference of energy between two
sets of d-orbitals”
INORGANIC CHEMISTRY
Crystal Field Splitting Energy

INORGANIC CHEMISTRY
Isomerism
Isomers are two or more compounds that have the same
chemical formula but a different arrangement of atoms.
they differ in one or more physical or chemical properties.
Structural isomerism
● Ionisation isomerism : when the counter ion in a
complex salt is itself a potential ligand and can
displace a ligand which can then become the counter
ion. Example: [Co(NH3)5SO4]NO3 and
[Co(NH3)5NO3]SO4
● Hydration isomerism : Due to presence of different
number of water molecule inside a coordination
sphere.Example :[Co(NH3)4Cl2]Cl.H2O and
[Co(NH3)4(H2O)Cl]Cl2
Structural isomerism
● Coordination isomerism : Arises from the
interchange of ligands between cationic and anionic
entities of different metal ions present in a
complex.Example: [Cu(NH3)4][PtCl4] and
[Pt(NH3)4][CuCl4]
● Linkage isomerism : isomerism arises in a
coordination compound containing ambidentate
ligands like NO2-, CN- , SCN- Example:
[Co(NH3)4(NO2)Cl]+ and [Co(NH3)4(ONO)Cl]+
INORGANIC CHEMISTRY
Structural Isomerism
Ionisation Isomerism
+ AgNO3
[Co(NH3)5SO4]+ + AgBr
+BaCl2
[Co(NH3)5Br]2+ + BaSO4
INORGANIC CHEMISTRY
Hydrate/Solvate Isomerism
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Coordination Isomerism
INORGANIC CHEMISTRY
Stereoisomerism
INORGANIC CHEMISTRY
Geometrical/ Cis-trans Isomerism
“Isomerism due to Different geometrical arrangement of
Ligands around Central Metal Atom”
cis trans
INORGANIC CHEMISTRY
Geometrical/ Cis-trans Isomerism
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Geometrical Isomerism
INORGANIC CHEMISTRY
(i) MA2B2 type
Example Pt(NH3)2Cl2
H H H
Cl N Cl
H N
H H
H H H H
Cl N Cl N
H H
INORGANIC CHEMISTRY
Geometrical
GeometricalIsomerism
Isomerism
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Optical Isomers
INORGANIC CHEMISTRY
Optical Isomerism
INORGANIC CHEMISTRY
Why Square planar complex doesn’t show Optical Isomerism?

INORGANIC CHEMISTRY
Optical Isomerism
INORGANIC CHEMISTRY
Optical Isomerism
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Solution
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Solution
INORGANIC CHEMISTRY
INORGANIC CHEMISTRY
Solution
INORGANIC CHEMISTRY
Bonding in Metal Carbonyls
INORGANIC CHEMISTRY
Synergic Bonding
INORGANIC CHEMISTRY
Metal Carbonyls Compounds
INORGANIC CHEMISTRY
PYQs-COORDINATION
COMPOUNDS
INORGANIC CHEMISTRY
CBSE 2023
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CBSE 2023
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INORGANIC CHEMISTRY
CBSE 2023
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CBSE 2023
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Solution:
INORGANIC CHEMISTRY
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CBSE 2023
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Solution:
INORGANIC CHEMISTRY
CBSE 2023
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Solution:
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CBSE 2023
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Solution:
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CBSE 2023
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Solution:
INORGANIC CHEMISTRY
CBSE 2023
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CBSE 2023
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CBSE 2023
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Solution:
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CBSE 2023
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Solution:
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CBSE 2023
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Maha Marathon : INORGANIC

Chapter Wise Weightage of chemistry CBSE Class 12

Chapter Name d and f block

Chapter Name Coordination Compounds

The d-block consisting of Groups 3-12 occupies the

inner d orbitals Outermost shell

1st series Zn 3d10 4s2

2nd series Cd 4d10 5s2

3rd series Hg 5d10 6s2

Properties of d-block Elements

High tensile strength Ductility Malleability

Very hard and low

Properties of d-block Elements

Observed colour is always complementary colour of the

Properties of d-block Elements

Variable Large surface Ability to form

Note: Catalyst provides alternate path with lower Ea

Properties of d-block Elements

Step 3: H2S2O7(g) + H2O(l) H2SO4(l)

Properties of d-block Elements

Properties of d-block Elements

Properties of d-block Elements

Paramagnetism ∝ number of unpaired electrons

Magnetic Moment (Spin only)

n = No. of Unpaired electron

n = the number of unpaired electrons

No. of unpaired Calculated magnetic

nuclear charge Eﬀective

Nuclear charge Number of d

The atomic radii of transition series decreases e-- e- repulsion

The atomic radii of transition series decreases

Reason - Increase in atomic radii towards the end may

Atomic radii of 4 d series ≅ 5 d series

Due to filling of 4f before 5d orbital

Lanthanide contraction is the steady decrease in

Eﬀective nuclear charge

IE of 3rd transition series are higher as compared to

Due to poor shielding of 4f electrons and increase in

❖ Due to similar energies of ns and (n – 1)d orbitals e-s both can

Too many d electrons

Potassium permanganate Prepared from

Colour and melting point Solubility

It is isostructural with KClO4

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

3MnO42- + 4H+ 2MnO4- + MnO2 + 2H2O

Potassium Prepared from

Step 2: Conc. H2SO4

Cr2O72- + 14H+ + 6I- 2Cr3+ + 3I2 + 7H2O

Butterfly structure Deep blue

Lanthanoids (4f series, 14 elements after La)

Actinoids (5f series, 14 elements after Ac)

[Xe]4f7 5d1 6s2

[Xe]4f8 5d0 6s2

Atomic and ionic size of lanthanides series

The regular decrease in

Greater effect of the

Common stable oxidation state : +3

Ce and Tb exhibit +4 oxidation state

But it is a strong oxidant changing to common +3 oxidation state

Strong reducing agent changing to +3 state

Strong reducing agent

+3 is most common Oxidation state”

La, Ho, Er, Lu, Gd +3