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Periodic table
Chemical Bonding
Coordination comp.
Metallurgy
Hydrogen
S-Block
P-block
d & f block
Periodic Table
A table which classifies all known elements in accordance with

their properties in such a way that elements with similar
properties are grouped together in the same vertical column &
dissimilar elements are separated from
each other.
Lavoisier’s classification
He classified elements into
Metals Non-Metals
Hard Soft/Brittle
Malleable Non-Malleable
Lustrous Non-Lustrous
Lavoisier’s classification
Limitations
❖ Properties chosen to classify metals were not applicable to all of

them.
Example: Mercury is lustrous but neither hard nor malleable
❖ Some elements show properties of both metals & non metals

Example: Antimony
Dobereiner’s Classification
❖ In 1829, Dobereiner arranged elements with similar

physical and chemical properties into a group of three
called 'Triads'.
❖ In each case,the atomic mass of middle element is average of

atomic mass of the other two elements
❖ This is called as “ Law of Triads”

Dobereiner’s Triad
+
2
Dobereiner’s Classification
Limitations
❖ All the known elements could not be arranged as triads.
❖ Some elements with similar properties could not form a triad.
Example: Nitrogen, Phosphorus & Arsenic
Newlands’ Classification
❖ In 1865, he arranged elements in increasing order of their

atomic mass and noted that every eighth element had
properties similar to the first element.
❖ Just like eighth note of a musical scale
❖ This is known as “Newlands’ Law of Octaves”

Newlands’ Octaves
Newlands’ Classification
Limitations
❖ This concept was only applicable for lighter elements

(upto Calcium).
❖ With the discovery of noble gases, the properties of 8th element
were no longer similar to those of the first one.
Hence this also failed.
Lothar Meyer Classification (1869)
❖ Lothar Meyer plotted a curve between atomic weight

and atomic volume of different elements.
❖ He observed that the elements with similar properties

occupied similar positions on the curve.
❖ The graph is known as “ Lothar Meyer’s curve”

Lothar Meyer’s curve
➔ Alkali metals (Li, Na, K, Rb, Cs)
occupy the peak positions on the
curve.
➔ Alkaline earth metal (Be, Mg, Ca, Sr,
Ba) occupy the descending position
on the curve.
➔ Metalloids (Si, Ge, As, Sb, Te, Po, At)

and transition metals occupy
bottom part of the curve.
➔ Halogens (F, Cl, Br, I) occupy the

ascending position on the curve.
Lothar Meyer’s curve
Conclusion
“On the basis of this curve Lother Meyer proposed that the
physical properties of the elements
are periodic function of their atomic weight”.
Limitation
“Lacked practical utility as it was not easy to keep in mind the
various positions of the curve”
Mendeleev's Periodic Table (1869)
❖ The first real breakthrough in classification of elements was

given by Mendeleev.
❖ He gave “Periodic law” which states that:
“The physical and chemical properties of elements

are the periodic function of their atomic weight”.
❖ He arranged 63 known elements in 7 periods (horizontal rows)

and 8 groups (vertical columns) in the increasing order of
atomic weights.
Mendeleev's Periodic Table
Merits of Mendeleev Periodic Table
❖ Systematic Study of Elements
❖ Left gaps in his periodic table, for elements yet

to be discovered.
Eka Boron Scandium
Eka Silicon Germanium
Eka Aluminium Gallium
Eka Manganese Technetium

Merits of Mendeleev Periodic Table
❏ Correction of doubtful Atomic weights

Atomic
Beryllium Valency
Weight
Earlier 13.5 3
Corrected 9.01 2
❏ Corrections were also done in atomic weight of elements like –

U, Be, In, Au, Pt.
Demerits of Mendeleev Periodic Table
❖ Position of Hydrogen element was not justified.

❖ Position of isotopes : As atomic wt. of isotopes differs, they should
have placed in different position in Mendeleev's periodic table. But
there were no such places for isotopes in Mendeleev's table.
❖ Anomalous pairs of elements : There were some pair of elements

which did not follow the increasing order of atomic weights.
Ex: Ar and Co were placed before K and Ni respectively in the
periodic table, but having higher atomic weights.
Demerits of Mendeleev Periodic Table
❖ Like elements were placed in different groups :
❖ Unlike elements were placed in same group : Eg: Placement of Alkali

metal (K) with coinage metal (Cu) in the same group.
Modern Periodic Table (Modified Mendeleev Periodic Table)
❖ A plot of √ν (where √ν is frequency of X-rays

emitted) against atomic number (Z ) gave a
straight line and not the plot of √ν vs atomic
mass.
∴
❖ It showed that Atomic number is a more

fundamental property of an element than its
atomic mass.
Modern Periodic Law
The physical & chemical properties of elements are the

periodic function of their atomic number.
It means that when the elements are arranged in the
increasing order of their atomic number, elements having
similar properties are repeated after regular interval.
Long Form/ Present form of Modern Periodic Table
❖ It is based on the Bohr-Bury electronic configuration concept and

atomic number.
❖ This model is proposed by Rang & Werner.
❖ It has 7 periods (horizontal rows) and 18 groups (Vertical columns)
❖ The periodic table is divided into 4 blocks:
S P D F
General Electronic Configuration
1-2
ns
H
Li Be
Na Mg
K Ca
Rb Sr
Cs Ba
Fr Ra
2 1-6
ns np
He
B C N O F Ne
Al Si P S Cl Ar
Ga Ge As Se Br Kr
In Sn Sb Te I Xe
Tl Pb Bi Po At Rn
1–10 0–2
(n-1)d ns
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
La Hf Ta W Re Os Ir Pt Au Hg
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1–14 0–1
(n-2)f (n-1)d
ns2
Identification of Block
Case1 When Electronic Configuration is given
❏ If np electron present then p - block (ns2 np1-6)
(i) S = 1s2 2s2 2p6 3s2 3p4 P Block
(ii) Ar = 1s2 2s2 2p6 3s2 3p6 P Block

❏ If (n–2)f0 (n–1)d0 ns1–2 = s block
(i) Mg = 1s2 2s2 2p6 3s2 S Block
(ii) Ca = 1s2 2s2 2p6 3s2 3p6 4s2 S Block

❏ If (n–2)f1–14 (n–1)d0–1 ns2 = f block
(i) Sm = [Xe] 4f⁶ 6s² F Block
(ii) Gd = [Xe] 4f7 5d1 6s2 F Block

❏ If any other configuration or

(n–1)d1–10 ns0–2 (d-block)
(i) Ti = 1s2 2s2 2p6 3s2 3p6 4s2 3d2 D Block
(ii) Fe = 1s2 2s2 2p6 3s2 3p6 4s2 3d6 D Block

Identification of Period
“The highest Principal Quantum no. available in Electronic

Configuration is the period no. of that element”
13
Al = [Ne] 3s² 3p¹ Period No. = 3
24
Cr = [Ar] 4s¹ 3d⁵ Period No. = 4
0
46
Pd = [Kr] 4d¹⁰ 5s
Period No. should be 4
But Period No. is 5

Case2 When Atomic No. is given
❏ Check if given no. x is between 58-71

❏ Then 6th Period (Lanthanoid)
(i) X= 65 Period No. = 6

(ii) X= 70 Period No. = 6
❏ Check if given no. x is between 90-103

❏ Then 7th Period (Actinoid)
(i) X= 93 Period No. = 7

(ii) X= 97 Period No. = 7
Inert Gas Atomic No. Period No.

Period No. of X = Period No.
He 2 1
of next Inert Gas
Ne 10 2
Ar 18 3
Kr 36 4
Xe 54 5
Rn 86 6
Og 118 7
(i) X= 44
Next Inert Gas (NIG) = 54 (Xe) Period No. = 5
(ii) X= 32
Next Inert Gas (NIG) =36 (Kr) Period No. = 4
Identification of Group

For S-Block
Group no. = Total no. of Valence
Shell e- in it
(i) E.C. = 1s2 2s2

Total Valence shell e- = 2 Group No. = 2
(ii) E.C. = 1s2 2s2 2p6 3s1

Total Valence shell e- = 1 Group No. = 1
For P-Block
Group no. = Total no. of Valence Shell e- + 10
[ns + np + 10]
(i) E.C. = 1s2 2s2 2p6 3s2 3p1

Total Valence shell e- + 10 = 3+ 10 = 13 Group No. = 13
(ii) E.C. = 1s2 2s2 2p6 3s2 3p5

Total Valence shell e- + 10 = 7+ 10 = 17 Group No. = 17
For D-Block
Group no. = (n–1)d electron + ns electron

(i) E.C. = 1s2 2s2 2p6 3s2 3p6 4s2 3d1

(n–1)d electron + ns electron = 1+ 2 = 3 Group No. = 3
(ii) E.C. = 1s2 2s2 2p6 3s2 3p6 4s2 3d5

(n–1)d electron + ns electron = 5+ 2 = 7 Group No. = 7
For F-Block
All Elements are placed in Group 3 or

Group IIIB
(i) E.C. = [Xe] 4f5 6s2

Group No. = 3 or IIIB
(ii) E.C. = [Rn] 5f9 7s2

Group No. = 3 or IIIB
Case2 When Atomic No. is given
❏ Check if given no. x is between 58-71 or 90-103

❏ Then Group 3 or IIIB
(i) X= 63 Group 3 or IIIB

(ii) X= 96 Group 3 or IIIB
❏ Check if given no. x is between 104 -118

Group number = last two digits in atomic number of element
(i) X= 104 Group No. = 4

(ii) X= 110 Group No. = 10
Group No. = 18 - (N.I.G. - X)

“If the value of this formula is negative then
use 32 instead of 18 in formula”
Group No. = 32 - (N.I.G. - X)

(i) X= 44 Next Inert Gas (NIG) = 54 (Xe)

Gp. No. = 18 -(54 - 44) Group No. = 8
(ii) X= 32 Next Inert Gas (NIG) =36 (Kr)

Gp. No. = 18 -(36 - 32) Group No. = 14
Shielding/Screening E ect
The decrease in force of attraction on valence e– due to inner

shell e– is called screening effect or shielding effect.
(i.e. total repulsive force is called shielding effect.)
E ective Nuclear Charge
❏ If nuclear charge = Z,
❏ Effective nuclear charge = Zeff ,
❏ 𝛔(Sigma)= Screening constant or shielding constant.
Zeff = (Z - 𝞼)
Order of Shielding E ect
❖ For same shell shielding effect has the order as
s p d f
“Due to penetration effect”
(i) Zeff for different ions of an element
(ii) Zeff of isoelectronic species
Atomic Radius
“Half the internuclear distance(d) between two atoms in a

homodiatomic molecule is known as atomic radius.”
Atomic Radius
A Covalent Radius
B Metallic Radius
C Van der Waal’s radius
D Ionic Radius
Covalent Radius
For Homoatomic Molecule
A dAA A
rAA
Covalent Radius
For Heteroatomic Molecule
Shomaker & Stevenson Formula:

δ+ δ–
A dAB B dA–B = rA + rB – 0.09 (Δx) in Ao
dA–B = rA + rB – 9 (Δx) in pm
rA rB Δx = Electronegativity difference
If rH= 0.74Ao, dCl-Cl= 198 pm , E.N. (H) = 2.1 & E.N. (Cl) = 3
then dH-Cl= ?
dCl-Cl 198
rCl = = = 99 pm = 0.99Ao
2 2
dH–Cl = rH + rCl – 0.09 (Δx)
dH–Cl = 0.74 + 0.99 – 0.09 (3 - 2.1)
dH–Cl = 1.649 Ao
Metallic Radius
❖ Half of the internuclear distance between two rm

adjacent metallic atoms in crystalline lattice
structure.
dAA
r m + rm
rm
❖ There is no overlapping of atomic orbitals, so

Metallic radius > Covalent radius
Van der Waal’s Radius
❖ It is defined for noble gases &

gaseous molecules in solid state
❖ It also depends upon the type

of Van der waal force like
Dipole-dipole, dipole induced rvw
ion etc.
❖ It is maximum as there is no
bonded region.
Van der Waal’s Radius
❖ In molecules of nonmetals solid both covalent and van der Waal's

radius exists.
Comparison of di erent Atomic Radii
Van der Waal's radius > Metallic radius > Covalent radius
Ionic Radius
“ Ionic radius can be calculated by measuring the distance

between cations & anions in an ionic crystal.”
Cationic Radius
❏ Cationic radius is always smaller than atomic radius because after

loosing e– number of e– reduces, but number of protons remains same,
due to this Zeff increases, hence electrons are pulled towards nucleus
and atomic radius decreases.
A > A+ > A+2 > A+3

e 10 9 8 7
p 10 10 10 10
+ve charge ↑, size↓

Cationic Radius
(i) Na >>> Na+ > Na+2 “ Due to change in shell

2s2 2p6 3s1 2s2 2p6 2s2 2p5 no.”
(ii) Mg > Mg+ >>> “ Due to change in shell

+2
Mg 2s2 2p6 3s2 2s2 2p6 3s1 2s2 2p6 no.”
Anionic Radius
❏ Anionic radius is always greater than atomic radius because in an anion

e– are more than protons and interelectronic repulsion increases, which
also increases screening effect. So Zeff reduces, so distance between e–
and nucleus increases and size of anion also increases.
X < X- < X-2

e 10 11 12
p 10 10 10
-ve charge ↑, size↑

Anionic Radius
(i) O < O- < O-2
(i) N < N- < N-2 < N-3

Size of Isoelectronic Species
“Those species having same number of e– but different
nuclear charge forms isoelectronic series.”
Atomic Radii ∝ 1 ∝ -ve charge

Zeff +ve charge
(i) N-3 > O2- > F- > Na+ > Mg2+ > Al3+
Factors a ecting Atomic radius
(i) Zeff ↑ then Radius↓
(ii) no. of shells ↑ then Radius ↑
(iii) Bond order ↑ then Radius↓
(iv) 𝞼↑ then Radius ↑

General Trend for Atomic Radius
Atomic Radius decreases ↓
Atomic
Radius
Increases ↑
Factors a ecting Atomic Radius
In a Period
Li > Be > B > C > N > O > F

Factors a ecting Atomic Radius
In a Group
Li < Na < K < Rb < Cs

Periodic variation of atomic size
Across a period
“On moving Left to Right in periodic table, size of element
decreases due to increase in effective nuclear charge (Zeff)”
Li > Be > B > C > N > O > F

In a Group
[He] 2s1
“On moving down the group in
periodic table, size of element [Ne] 3s1
increases due to increase in extra
shell in each step.” [Ar] 4s1
[Kr] 5s1
Li < Na < K < Rb < Cs
[Xe] 6s1
Decreases
Increases
First Exception
For Noble Gases
❖ It is observed that size of inert gas is very large as

compared to Halogen.
❖ This is due to Van der Waal size measurement in case of
inert gases.
Ne >> F
Second Exception
For Transition series
Second Exception
For Transition series
❖ There is no regular variation of Sc

size in 3d series because
interelectronic repulsion Zn
increases after d5 configuration Atomic
Cu
size
Fe ≈ Co ≈ Ni
Atomic No.
Third Exception
Lanthanoid Contraction
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
≈ ≈ ≈ ≈ ≈ ≈ ≈ ≈ ≈
La Hf Ta W Re Os Ir Pt Au Hg
Third Exception
3d < 4d ≈ 5d
Third Exception
Ti (22) 3d2 4s2

18
Zr (40) 4d2 5s2 Shell↑, Size ↑
≈ 32
Hf (72) 4f14 5d2 6s2 Poor 𝞼, Z more than 𝞼

∴ Zeff ↑ dominantly
Third Exception
❖ Due to Lanthanoid contraction,
there occurs an overall decrease La3+
Atomic Radius
in atomic & ionic radii from La3+
to Lu3+
Lu3+
Atomic No.
Third Exception
Actinoid Contraction
❖ Due to Actinoid contraction,
Ac
there occurs an overall decrease
Atomic Radius
in atomic & ionic radii from
Actinium to Lawrencium.
Lr
Atomic No.
Fourth Exception
Transition/ Scandide contraction
Exception Ga has smaller atomic radii than Al
“ Due to poor shielding effect

of d electrons &
∴ increased nuclear charge
in Gallium”
Overall Order
Actinoid Lanthanoid Scandide

Contraction Contraction Contraction
Ionization Energy (I.E.)
❏ Minimum energy required to remove most loosely

bonded outer most shell e– in ground state from an I.E.
isolated gaseous atom is known as ionization
energy.
M(g) + I.E. → M+(g) + e-

Successive Ionization Energy
❏ For an atom M(g) successive ionization energies are as follows -
M(g) + IE1 → M+(g) + e- IE1 = 1st Ionization Energy
M+(g) + IE2 → M+2(g) + e- IE2 = 2nd Ionization Energy
M+2(g) + IE3 → M+3(g) + e- IE3 = 3rd Ionization Energy
IE1 < IE2 < (Always for an element)

IE3….
Factors A ecting Ionization Energy
In a Period
(i) Effective nuclear charge (Zeff)
Ion with high positive oxidation state will have high

ionisation energy.
Fe3+ > Fe2+ > Fe

(ii) Stability of half filled and fully filled orbitals :

Half filled p3,d5, f7 or fully filled p6 , d10, f14 are more stable than others so
it requires more energy.
IE1 N O
1s2 2s2 2p3 1s2 2s2 2p4
(ii) Stability of half filled and fully filled orbitals :

After losing 1e–, O attains electronic configuration of N, so IInd
ionisation energy of O is more than N.
IE2 N O
1s2 2s2 2p2 1s2 2s2 2p3
(iii) Penetration power of sub shells :

❏ Order of attraction of subshells towards nucleus (Penetration power)
is
s p d f
❏ 's' subshell is more closer to nucleus so more energy will be required
to remove e– from s-subshell as comparison to p,d & f subshells.
IE1 Be B
1s2 2s2 1s2 2s2 2p1
(iii) Penetration power of sub shells :

After losing 1e–, B attains electronic configuration of Be, so IInd
ionisation energy of B is more than Be.
IE2 Be B
1s2 2s1 1s2 2s2
In a Group
(i) Atomic Size:
Comparison of Ionization Energy
Across the Period

❏ On moving left to right in a period ,Zeff increases so removal of
electron becomes difficult and ionisation energy increases.
Order of IE of 2nd period elements
Li < B < Be < C < O < N < F < Ne

Comparison of Ionization Energy
In a Group
❖ On moving top to bottom in a

group ,size increases so ionisation
energy decreases.
Exceptions
In Group 13
Expected: B > Al > Ga > In > Tl
Observed: B > Tl > Ga > Al > In

Exceptions
In 4d & 5d period
Ionisation Energy of 5d > 4d “Due to Lanthanide

contraction”
Hf > Zr
Applications of Ionization Energy
Metallic and non metallic character :
❖ Generally for Metals → Ionisation Energy is low.

❖ For Non-metals → Ionisation Energy is high.
Reactivity of metals :
❏ Reactivity of metals increases down the group as ionisation

energy decreases.
Stability of oxidation states of an element :

❖ If the difference between two successive ionisation energy of an
element ≥ 16eV, then its lower oxidation state is stable.
ΔIE =
42.7eV
“Difference between ionisation energy > 16 eV.

So Na+ is more stable.”
❖ If the difference between two successive ionisation energy of an

element ≤ 11 eV, then its higher oxidation state is stable.
ΔIE = 7.4eV
“Difference of ionisation energy < 11 eV

So Mg2+ is more stable.”
To determine the number of valence electron of

an element :
❏ See the jump between successive Ionization energy

❏ If jump of (IEn2 - IEn1 ) is maximum then valence e- is n1
IE1 IE2 IE3

❏ Example- 5, 100, 120…. ⇒ Valence e- = 1
Electron A nity (EA)
❖ The amount of energy released when an electron is added to the

valence shell of an isolated gaseous atom known as Electron affinity.
X(g) + e- → X-(g) + Electron Affinity
Electron A nity (EA)
O(g) + e- → O-(g) ΔHegI = –141 KJ/mol
O-(g) + e- → O2-(g) ΔHegII = +744 KJ/mol
O(g) + 2e- → O2-(g) ΔHeg = +603 KJ/mol

Factors a ecting Electron A nity
Atomic size
Electron Affinity ∝ 1
Atomic size
Effective nuclear charge (Zeff)

Stability of completely filled or half
filled orbitals
❖ Electron affinity of elements having full-filled or half filled
configuration is very less or zero so for these elements electron
gain enthalpy (ΔHeg) will be positive.
(i) EA ⇒ ns1 > ns2
(ii) EA ⇒ np2 > np3

General Trend
Electron Affinity Generally Increases

Generally Decreases
Variation of Electron A nity
In 2nd Period
Li Be B C N O F Ne
Ne < Be < N < B < Li < C < O < F
Endothermic
In Group
❖ Electron affinity of 3rd period element is greater than electron

affinity of 2nd period elements of the respective group.
F Cl
[He] 2s2 2p5 [Ne] 3s2 3p5
In Group
“N & P have low electron affinity due to stable half filled configuration.”
Chemical Bond
➔ Attraction between two or more than
two atoms in a molecule is known as
Chemical Bond.
➔ Atoms for chemical bond to attain

stability, by releasing energy.
Octet Rule
➔ Reason for the formation of chemical bond was initially given as the
“Octet Rule”
➔ It means that atoms form chemical bonds to attain 8e- in their outermost
shell (or two e- in duplet rule) to attain inert gas configuration.
➔ But in 1962, Neil Bartlett discovered the first compound of
Noble Gas
➔ First, he prepared a red compound
O2 + [PtF6] → O2+[PtF6]-
➔ Then he noted that I.E. of O2 ≈ I.E. of Xe

Neil Bartlett
➔ He made efforts to prepare same type of compound
with Xe
First prepared
comp. of Noble Gas
➔ After this discovery, a number of xenon compounds

have been synthesised.
➔ Bartlett discovery led to the scraping of the Octet Rule

& led to the proposal of the
“Potential Energy Rule”
Potential Energy Rule
When two atoms approach each other, the following forces act on them.
eB
NA NB
eA
● eA eB → Repulsion
● NA NB → Repulsion
● NA eB → Attraction
● NB eA → Attraction
As two atoms approach each other, potential energy change in the
formation of a covalent compound H2 is shown
➔ Zero energy when two H-atoms are separated by a great

distance.
➔ A drop in Potential Energy (net attraction) as two H-atoms

approach each other.
➔ When stable H2 molecule is formed, internuclear distance is

about (74pm) at a minimum P.E. (-435.8 kJ/mol)
➔ An increase in P.E. as atoms approach more closely.

Valence Bond Theory
Postulates
For a covalent bond to form, two atoms must come closer to
each other so that orbitals of one overlap with the other.
Valence Bond Theory
Overlapping
➔ When two atoms approach each other, there will be
force of attraction as well as force of repulsion.
➔ If Force of attraction > Force of repulsion, then

they form a common area which is known as
overlapping area.
➔ When overlapping area increases, the covalent bond

strength increases.
Valence Bond Theory
Postulates
Overlapping orbitals must have:
➔ Half filled nature i.e. must have unpaired e-
➔ Anti spin electrons
Valence Bond Theory
Postulates
As a result of overlapping, a new localized bond orbital is
formed, in which probability of finding e- pair is maximum.
Covalent bond energy arises due to:

➔ Electrostatic attraction between nuclei & accumulated e- cloud
➔ Cancellation or attraction between spins of Anti spin
electron.
Valence Bond Theory
Postulates
Greater is the overlapping:
➔ Lesser will be the bond length
➔ More will be attraction
➔ More will be Bond Energy
➔ Bond strength will also be high.
Types of Overlapping
1) Axial/ Head-on/ Coaxial Overlapping

“ Forms sigma (σ) bond”
2) Sideways/ Collateral Overlapping

“ Forms pi (π) bond”
Axial Overlapping
+
1. s-s overlap Ex: H2
1s 1s σ
2. s-p overlap Ex: HCl

1s 2p σ
3. p-p overlap Ex: F2

2p 2p σ
Sideways Overlapping
(i) p𝛑-p𝛑 overlap

(ii) p𝛑-d𝛑 overlap

(iii) d𝛑-d𝛑 overlap (Two lobe interaction)

Di erence between σ & π bond
σ Bond π Bond
Formed by axial overlap of orbitals Formed by sideways overlap
Overlapping of s-s, s-p & p-p orbitals Overlapping of p-p, p-d & d-d orbital
Stronger bond Weaker bond
Can exist with or without π Always exist with σ
It is a directional bond so it decides Non-directional bond ,
geometry so no role in geometry
Free Rotation possible Restricted Rotation
Delta (𝛅) Bond
“In d orbitals , when four lobe interaction takes place then
𝛅 bond is formed”
dxy dyz dxz dz2 dx2-y2

Delta (𝛅) Bond
dxy - dxy overlap
➔ Along x & y axis: π bond is formed
➔ Along z axis: δ bond is formed

Delta (𝛅) Bond
dyz - dyz overlap
➔ Along y & z axis: π bond is formed
➔ Along x axis: δ bond is formed

Delta (𝛅) Bond
dxz - dxz overlap
➔ Along x & z axis: π bond is formed
➔ Along y axis: δ bond is formed

Delta (𝛅) Bond
dx2-y2 - dx2-y2 overlap
➔ Along x & y axis: 𝞂 bond is formed
➔ Along z axis: δ bond is formed

Delta (𝛅) Bond
dz2 - dz2 overlap
➔ Always σ bond is formed

In bonding only e-s participate, not vacant orbital
O2
E.C. 1s2 2s2 2p4
Px Px
(1 σ & 1π Bond)
N2
E.C. 1s2 2s2 2p3
(1 σ & 2π Bond)
Bond Strength
Bond ∝ 1
Strength Size
Bond Strength of F2 > I2
∵ High e- density in ∵ Low e- density in

Overlapping area Overlapping area
Bond Strength
When size is constant
Bond ∝ Directional character
Strength (p-character for atomic orbital)
➔ Axial-Non directional Orbital
+
1s 1s ⅓+⅓
⅓ e- probability on each axis

Bond Strength
➔ Axial- Directional Orbital
Px Px ½+½
½ e- probability in each lobe on axis
∴ More the directional character (more % of

p-character), more is the bond strength
Order of Bond Strength
2p𝝿- 2p𝝿 > 2p𝝿- 3d𝝿 > 2p𝝿- 3p𝝿 > 3p𝝿- 3p𝝿
3p𝝿- 3p𝝿 < 3p𝝿- 3d𝝿 < 3d𝝿- 3d𝝿

3p𝝿- 3p𝝿 < 3p𝝿- 3d𝝿 < 3d𝝿- 3d𝝿
● ∵ P-orbitals are perfectly perpendicular to internuclear axis

so they will have to bend towards each other to form 𝝿 bond,
resulting in less overlapping area.
● ∵ d-orbitals are already a little bit bend towards internuclear

axis, so they will give more overlapping area in 𝝿 bond
➔ Tendency of polymerization decreases with increasing 𝝿
bond strength.
➔ Weak 𝝿 bond tend to break them & convert to some more

stable structure (polymer)
O = Si = O O = Si - O -
(SiO2)n Giant Molecule

# All Giant molecules are covalent solids
Write correct order of Bond Strength
1s-1s , 1s-2p, 1s-2s, 2p-2p, 2s-2p, 2s-2s, 2s-3p, 2s-3s,
3p-3p, 3s-3p, 3s-3s
1s-1s > 1s-2p > 1s-2s > 2p-2p > 2s-2p > 2s-2s >
2s-3p > 2s-3s > 3p-3p > 3s-3p > 3s-3s
Arrange in increasing order of Bond Strength
2p𝝿- 2p𝝿 , 2s - 2s, 2s - 2p, 2p - 2p
2p𝝿- 2p𝝿 < 2s - 2s < 2s - 2p < 2p - 2p

Arrange in decreasing order of Bond Strength
1s - 3p; 1s - 2p; 1s - 4p; 1s - 5p
1s - 2p > 1s - 3p > 1s - 4p > 1s - 5p
Size of Orbital increases, bond strength decreases

Bond Energy
Bond energy is a measure of the bond strength of a chemical bond.

It is the amount of energy required to break one mole of bonds of a
particular type so as to separate them into gaseous atoms.
Ex: H2 has bond enthalpy/energy of 435.8 kJ mol–1

Bond Energy
Bond ∝ 1
Energy Size
C-C Si-Si Ge-Ge Sn-Sn Pb-Pb
Increasing Size
Bond Energy
Bond ∝ 1
Energy L.P.-L.P. repulsion
Only for 2nd Period due to small size

Hybridization
6
C E.C. 1s2 2s2 2p2
G.S. Unpaired e- = 2
E.S. Unpaired e- = 4
Covalency = 4
Hybridization
➔ Acc. to VBT covalency of C seems to be two 2 as it has only 2 unpaired e-s.
➔ But we know that C has covalency of 4
➔ In order to explain it extension to VBT was proposed.
Electrons which are paired in valence shell can enter into overlapping
to show bond formation if they can be unpaired by exciting them to
higher energy subshell.
Hybridization
CH4 G.S.
E.C. 1s2 2s2 2p2
E.S.
s
Acc. to VBT str. is s p s
s p
p
s
∵ p-s overlapping > s-s overlapping (Bond strength)
∴ 1 bond in CH4 should have Bond Energy different from (less than) other three.
Hybridization
“All four bonds in CH4 have equal Bond Energies &

it could not be explained by VBT”
Hence; in 1931 Pauling proposed that a

phenomenon called Hybridization takes place
during the formation of CH4”
Linus Pauling
Hybridization
Hypothetical Concept
Intermixing of atomic orbitals of an atom of nearly same energy,

but different shape to form entirely new orbitals, equal in no. of
mixed atomic orbitals, having identical shape & energy
These newly formed orbitals are called as hybridized/ hybrid orbitals
Ex: s + p + p + p = 4sp3 Hybrid orbitals

Hybridization
➔ No. of hybrid orbitals = No. of Atomic orbitals which participate

in hybridization.
➔ Half filled, full filled & vacant orbitals can participate in

hybridization because it is mixing of orbitals not electrons.
Characteristics of Hybridization
Orbitals of nearly same energy hybridize.
Hybridized orbitals have identical shape & energy
2s 2p 2 hybrid sp orbitals
Hybridized orbitals are dumbell type; one loop larger & one smaller &
can therefore be directed towards the other atom more effectively
than atomic orbitals.
Hence they can overlap more strongly with orbitals of other atom than
atomic orbitals & hence stronger bond.
Hybridised orbitals have different orientation in space.
sp hybridization sp2 hybridization sp3 hybridization

2 hybrid orbitals 3 hybrid orbitals 4 hybrid orbitals at
at 180o at 120o 109.5oor 109o28’
o
Hybridised orbitals show only head on overlapping & thus forms only
𝞼 bond.
% s character increases
➔ Electronegativity increases
➔ Size of Hybridized orbitals decreases
➔ Overlapping increases
➔ Bond length decreases
➔ Bond strength increases
➔ Bond energy increases
Types of Hybridization
s+p s+p+d
sp sp2 sp3 sp d3
sp d 3 2
sp3d3
sp Hybridization
sp sp
s p
sp Hybridization
BeCl2
Be → 1s2 2s2 G.S.
E.S.
sp sp
sp Hybridization
BeCl2
sp2 Hybridization
sp2 Hybridization
BCl3
Be → 1s2 2s2 2p1 G.S.
E.S.
sp2 sp2 sp2

120o
Trigonal planar
BCl3
sp3 Hybridization
sp3 Hybridization
CH4 G.S.
C → 1s2 2s2 2p2
E.S.
109.5o
Tetrahedral
CH4
sp3d Hybridization
sp3 d Hybridization
PCl5 G.S.
P → 1s2 2s2 2p6 3s2 3p3
E.S.
sp3 d Hybridization
PCl5
sp3d2 Hybridization
sp3 d2 Hybridization
SF6 G.S.
S → 1s2 2s2 2p6 3s2 3p4
E.S.
sp3d3 Hybridization
7 sp3d3
(5 coplanar & 2
Perpendicular)
dxy dz2 dx2-y2

sp3d3 Hybridization
IF7
sp3d3 Hybridization
IF7
How to find Hybridization State?
ep = electron pair
ep = bp + lp bp = bond pair
lp = lone pair
lp = 1
2 [ No. of Valence e-
on Central atom
- Valency
SA
of
- Charge
]
How to find Hybridization State?
Electron pair (ep) Hybridization

2 sp
3 sp2
4 sp3
5 sp3d
6 sp3d2
7 sp3d3
Q. Calculate the hybridization state of the following
BF3
ep = bp + lp
= 3 + 1 [3-3-0]
2
= 3 → sp2
BF4-
ep = bp + lp
= 4 + 1 [ 3 - 4 - (-1 )]
2
= 4 → sp3
ICl3 sp3d
SO3 sp2
VSEPR (Valence Shell Electron Pair Repulsion) Theory
To predict the shapes of

covalent molecules
H N
H
H
Trigonal Pyramidal
Bent
VSEPR Theory
Postulates
Shape of molecule depends on total valence electrons around
central atom.
N
H
H
H
V.E. around ‘C’ = 4e- V.E. around ‘N’ = 5e-
Tetrahedral Trigonal Pyramidal
VSEPR Theory
Postulates
Valence electrons repel one another due to same charge
NH3 : lp-bp & bp-bp

VSEPR Theory
Postulates
Electrons occupy such positions in space that minimize repulsions
& maximise distance between them.
Ex:
VSEPR Theory
Repulsion order: Lp-Lp > Lp-Bp > Bp-Bp

Let’s discuss
all cases
with
Example
VSEPR Theory
AB2
B.P. L.P. Geometry Shape Example
2 0 Linear Linear CO2
VSEPR Theory
AB3
3 0 Trigonal Trigonal BF3
Planar Planar
VSEPR Theory
AB2L
2 1 Trigonal Bent SO2, O3
Planar
VSEPR Theory
AB4
4 0 Tetrahedral Tetrahedral CH4, CCl4
VSEPR Theory
AB3L
3 1 Tetrahedral Trigonal NH3
Pyramidal
VSEPR Theory
AB2L2
2 2 Tetrahedral Bent H 2O
VSEPR Theory
AB5
5 0 Trigonal Trigonal PCl5
Bipyramidal Bipyramidal
Cl
Cl
Cl P
Cl
Cl
VSEPR Theory
AB4L
4 1 Trigonal See Saw SF4
Bipyramidal
VSEPR Theory
AB3L2
3 2 Trigonal T-shape ClF3
Bipyramidal
VSEPR Theory
AB2L3
2 3 Trigonal Linear XeF2
Bipyramidal
VSEPR Theory
AB6
6 0 Octahedral Octahedral SF6
VSEPR Theory
AB5L
5 1 Octahedral Square BrF5
pyramidal
VSEPR Theory
AB4L2
4 2 Octahedral Square XeF4
planar
Dipole Moment
Polarity of any polar covalent bond or molecule is

measured in terms of dipole moment.
Dipole Moment
❖ The product of positive or negative charge (q) and the distance (d)
between two poles is called dipole moment.
Unit = D (Debye)
μ= q x d 1D = 3.33 × 10–30 C m
1D = 1 × 10–18 esu cm
Dipole Moment
❖ Dipole moment is a vector quantity ,i.e., it has both magnitude as well

as direction.
❖ Direction of dipole moment is represented by an arrow pointing from

electro +ve to electro -ve element and from central atom to lone pair of
electrons.
Dipole Moment
Direction of Dipole Moment
Electro +ve to Electro -ve element Central atom to lone pair

Dipole Moment
❖ In the diatomic molecule, 𝛍 depends upon difference of Electronegativity

𝛍 ∝ Δ EN
Order of 𝛍:
H-F H-Cl H-Br H-I

Dipole Moment
❖ 𝛍= 0 for following molecules:
Non-polar Molecules
Dipole Moment
❖ For polyatomic molecules, 𝛍 depends on the vector sum of dipole

moments of all the covalent bonds.
(i) CCl4
μnet = 0 D
Dipole Moment
(ii) CHCl3
μnet ≠ 0 D
Dipole Moment
❖ For molecules with symmetrical geometry, 𝛍net = 0
(i) PCl5
μnet = 0 D
Dipole Moment
(ii) SF6
μnet = 0 D
Dipole Moment
(iii) BF3
μnet = 0 D
Dipole Moment
❖ Benzene, naphthalene, diphenyl have 𝛍 = 0 due to planar structure.
μnet = 0 D
Dipole Moment
❖ Dipole moment: μ(NH3) > μ(NF3)
Resultant dipole
Resultant dipole N moment = 0.24D
N
moment = 1.47 D F F
H H
H F
NF3
NH3
Direction of 3 dipoles add to Direction of 3 dipoles oppose

the effect of lone pair of the effect of lone pair of
electrons of N atom electrons of N atom
Write the order of the dipole moment of following compounds ?
CH3Cl, CH2Cl2, CHCl3, CCl4
𝛍 =0 < 1.02 < 1.55 < 1.93

Applications of Dipole Moment
1 To determine polarity and geometry of molecule
➔ If 𝛍 = 0 compound is non-polar and symmetrical
CO2, BF3, CCl4, CH4, BeF2etc.
➔ If 𝛍 ≠ 0 compound is polar and unsymmetrical.
H2O, SO2, NH3, Cl2O, CH3Cl, CHCl3 etc.

Applications of Dipole Moment
2 To calculate % ionic character

Calculate the 𝛍 of HCl ? If bond distance is 1.34 A°,
charge = 4.8 × 10–10 esu and calculate % ionic character if
experimental value of 𝛍 = 1.08 D ?
Q. Find dipole moment & identify if compound is polar or non-polar
1 CO2
μnet = 0 D Non polar

2 BeF2
μnet = 0 D Non polar

3 H 2O
μnet ≠ 0 D Polar
4 1,4-Dicyanobenzene
μnet = 0 D
Non-Polar
5 SF4
μnet ≠ 0 D
Polar
6 SO3
μnet = 0 D
Non-Polar
Hydrogen Bonding
It is an electrostatic attractive force between covalently bonded

hydrogen atom of one molecule and an electronegative atom.
Hydrogen Bonding
❖ Apart from F, Hydrogen bonds can be formed with other highly

electronegative atoms such as N & O
Hydrogen Bonding
➔ It is not formed in ionic compounds.
➔ H–bond forms in polar covalent compounds, (not in non-polar).
➔ It is very weak bond but stronger than vanderwaal's force.

Hydrogen Bonding
Main condition for H–bonding
H should be covalently bonded with high electro –ve element

like F, O, N.
Atomic size of electro –ve element should be small.

Order of atomic size is : N > O > F
Order of electronegativity is : F > O > N
(4.0) (3.5) (3.0)
Hydrogen Bonding
Main condition for H–bonding
Types of Hydrogen Bonding
Intermolecular Intramolecular
H–bonding H–bonding
Homointermolecular
Heterointermolecular
Intermolecular H-Bonding
H–bond formation between two or more molecules of either the

same or different compounds known as intermolecular H-bonding
(i) Homo intermolecular:
H–bond between molecules of same compound.

Homointermolecular H-Bonding
H2O & HF
Intermolecular H-Bonding
(ii) Hetero intermolecular:
H–bond between molecules of different compounds
H-bond between alcohol and water

Intramolecular H-Bonding
Intramolecular hydrogen bonds are those which occur within

one single molecule.
➔ This type of H–bond is mostly occurred in organic

compounds (Aromatic)
➔ It results in ring formation (chelation).

Intramolecular H-Bonding
o–nitrophenol Salicylaldehyde
E ect of H-Bond on Physical Properties
1 Solubility
(a) Intermolecular H–bonding
➔ Few organic compounds (Non-polar) are soluble in

water (Polar solvent) due to H–bonding.
Alcohol in water
(b) Intramolecular H–bonding
➔ It decreases solubility as it form chelate by H–bonding,

so H is not free for other molecule.
➔ It can not form H–bond with water molecule so it can

not dissolve.
2 Viscosity
➔ H–bond associates molecules together so viscosity increases.
(i)
(ii)
3 Molecular weight
➔ Molecular wt. of CH3COOH is double of its molecular formula,

due to dimer formation occur by H–bonding.
4 Melting point and boiling point
➔ Due to intermolecular H–bond M.P. & B.P. of compounds increases.
➔ In case of Intramolecular H-bonding, melting and boiling points

are low.
4 Melting point and boiling point
➔ Boiling points of VA, VIA, VIIA hydrides are as shown below :
(Group 15 Hydrides)→ SbH3> NH3> AsH3> PH3

(Group 16 hydrides) → H2O > TeH2> SeH2> H2S
(Group 17 hydrides) → HF > HI > HBr > HCl
❖ Increase in boiling point of NH3, H2O and HF is due to H–bonding.

Molecular Orbital Theory
Developed in 1932 by
Friedrich Hund Robert S. Mulliken

To explain the properties, which the old VBT
(Valence bond theory) was unable to explain.
Example:
As per VBT Experimentally
Diamagnetic Paramagnetic
oxygen proves to be PARAMAGNETIC
(unpaired electrons - weakly attracted to Mag. field)
Liquid Oxygen - Paramagnetic behaviour

Atomic orbital lose their identity during molecule formation
(overlapping) and form new orbitals termed as molecular orbitals.
Postulates
Electrons in a molecule are present in the various molecular orbitals as
the electrons of atoms are present in the various atomic orbitals.
Only atomic orbitals of comparable energies and proper symmetry

combine to form molecular orbitals
An atomic orbital is monocentric while a molecular orbital is polycentric.
Example:
H H
H
Influenced by one nucleus Influenced by both nuclei

Total AOs combining = Total MOs formed

MOs formed are “Bonding Molecular Orbitals (BMO)” &
“Anti-Bonding MO (ABMO)”
High Energy
Less Stability
Low Energy
More Stability
Electronic configuration in various molecular orbital are governed

by same three rules.
(i) Aufbau Rule
(ii) Hund's Rule
(iii) Pauli's exclusion principle

Formation of Molecular Orbitals
The formation of molecular orbitals can be explained on the basis of
Linear combination of atomic orbitals (LCAO)
Constructive interference
Wave function for bonding molecular orbital is

Formation of Molecular Orbitals
Destructive interference
Wave function for antibonding molecular orbital is

Di erence b/w Bonding & Antibonding Molecular Orbital
Bonding MO Antibonding MO
Formed by LCAO when their wave Formed by LCAO when their wave
functions are added functions are subtracted
Generally it does not have nodal It always have a nodal plane between
plane. two nuclei of bonded atom.
Electron density increases between Electron density decreases in between
two nuclei resulting attraction two nuclei, leads to repulsion between
between two atoms. two atoms.
Di erence b/w Bonding & Antibonding Molecular Orbital
Bonding MO Antibonding MO
Energy of BMO is less, hence stable. Energy of ABMO is high.
Electron placed in a BMO stabilizes a Electron placed in the ABMO

molecule. destabilizes the molecule.
Notation of Molecular Orbitals
For bonding molecular orbital 𝞂, 𝛑 etc.
For antibonding molecular orbital 𝞂*, 𝛑* etc.

Shapes of Molecular Orbitals
𝜎 Molecular Orbital {By combination of s orbitals}

𝜎 Molecular Orbital {By combination of p orbitals}
ABMO
𝞂*2pz
BMO
𝞂2pz
𝜋 Molecular Orbital
ABMO
BMO
σ*2pz
Eg: B2, C2 and N2
π*2p π*2p
2p x y 2p
σ
Energy
Electronic Configuration π π 2py 2pz
2px
σ1s < σ* 1s < σ2s< σ* 2s < (π2px= π2py ) σ*2s
< σ2pz < (π*2px=π* 2py ) < σ* 2pz 2s 2s
σ 2s
σ*1s
1s 1s
σ 1s
σ*2pz
Eg: O2, F2, Ne2
π*2p π*2p
2p x y 2p
Electronic Configuration π π 2py
Energy
2px σ
σ1s < σ* 1s < σ2s< σ* 2s< σ2pz
2pz
< (π2px= π2py ) < (π*2px=π* 2py ) σ*2s
< σ* 2pz 2s 2s
σ 2s
σ*1s
1s 1s
σ 1s
Applications of MOT
Bond Order
Bond Length
Stability
Magnetic Nature
Applications of MOT
Bond Order
e- in BMO e- in ABMO
Nb - N a
Bond Order =
2
Applications of MOT
Bond Length
C-C B.O = 1 B.O = 2 B.O = 3

Applications of MOT
Stability
Nb > N a Stable (Molecule exists)
Nb < N a
Unstable
(Molecule doesn’t exists)
Na = N b
Applications of MOT
Stability
Stable Unstable
↿⇂
Energy
↿⇂ ↿⇂
↿⇂
H2 molecule He2 molecule
B.O = (2-0)/2 B.O = (2-2)/2

=1 =0
Applications of MOT
Magnetic Nature
Paramagnetic Diamagnetic
Molecular orbitals have Molecular orbitals have
unpaired e-s all electrons paired up
↿ ⇅
Attracts Repels
(i) H2
σ*1s
Energy
H H
1s 1s
σ 1s
❖ E.C. = (σ 1s)2
N b – Na 2–0
❖ Bond Order = = = 1
2 2
❖ Magnetic Property = Diamagnetic
❖ Stability = Quite stable (having single bond)

(ii) H2+
σ*1s
Energy
H H
1s 1s
σ 1s
❖ E.C. = (σ 1s)1
N b – Na 1–0
❖ Bond Order = = = ½
2 2
❖ Magnetic Property = Paramagnetic
❖ Stability = Less stable (In comparison to H2)

(iii) H2- σ*1s
H
Energy
H
1s 1s
σ 1s
❖ E.C. = (σ 1s)2 (σ* 1s)1
N b – Na 2–1
❖ Bond Order = = = ½
2 2
❖ Magnetic Property = Paramagnetic
❖ Stability = Less stable than H2+ & as it has e- in ABMO

(iv) He σ*1s
Energy
He He
1s 1s
σ 1s
❖ E.C. = (σ 1s)2 (σ* 1s)2

N b – Na 2–2
2 2
“Does not exist”

(v) N2
❖ E.C. = KK* (σ 2s)2 (σ* 2s)2

(π 2px) 2 (π2py) 2 (σ 2pz)2
N b – Na 10 – 4
2 2
❖ Magnetic Property = Diamagnetic

σ*2pz
(vi) O2
2 2 2
❖ E.C. = KK* (σ 2s) (σ* 2s) (σ 2pz) π*2px π*2p
(π 2px)2 (π2py)2 (π* 2px)1 π 2px yπ 2py
(π* 2py)1 2p 2p
Energy
σ 2pz
N b – Na 10 – 6
2 2 σ*2s
2s 2s
❖ Magnetic Property = Paramagnetic σ 2s
K K*
Ionic Bond
Bond formed between two or more atoms as a result of the complete

transfer of one or more electrons from one atom to another.
Ex: NaCl,LiCl, KCl, CaCl2, etc

Ionic Bond
E.g. IA and VIIA group elements form maximum ionic compound.
❖ More the distance between two elements in periodic table more will
be ionic character of bond.
Electrovalency
“Total no. of electron lose or gained is called electrovalency”
2e-
Electrovalency
2
1e-
2e-
Ionic Bond
● Many Ionic solids formed exhibit 3D crystalline structure called Lattice structure
● Ionic compound do not have molecular formula. It has only empirical formula.
● E.g. NaCl is empirical formula of sodium chloride

Conditions for Forming Ionic Bonds
Formation of Ionic bond depends upon these three factors:
a Ionisation energy
Amount of energy required to remove an electron from the outermost orbit of
an isolated gaseous atom to form the +ve ion or cation.
en
er
gy
A e A + e
Lesser Ionisation energy → Greater tendency to form cation
Cation formation
Tendency
b Electron affinity
Amount of energy released when an electron is added to an isolated gaseous
atom to form –ve ion (anion).
y
n erg
e
e
+ B B e
Higher electron affinity → Greater tendency to form anion
Anion formation
Tendency
c Lattice energy
Amount of energy released when one mole of crystal lattice is formed
Na+
Cl-
Higher lattice energy → Greater will be the stability or strength of ionic

compound.
Factors a ecting lattice energy
1 Magnitude of charge
● Lattice energy increases
● Charge of cation increases

Factors a ecting lattice energy
2 Size of Cation
LiCl NaCl KCl RbCl CsCl
● Size of cation increasing
● Size of anion is constant
● Lattice energy decreases

Properties of Ionic Compound
a Physical State
Ionic compounds are hard, crystalline and brittle due to strong
electrostatic force of attraction.
b Boiling Point & Melting Point

High boiling point and melting point due to strong electrostatic force
of attraction among oppositely charged ions.
c Conductivity
Solid state → No free ions - Bad conductor of electricity.
Fused/aqueous solution→ Due to free ions - Good conductor of electricity.
Conductivity order:
Solid state < fused state < Aqueous solution
d Solubility
➔ Highly soluble in Polar solvents like water.
➔ Less soluble in non polar solvents like benzene.
Polarisation (Fajan's Rule)
(Covalent Nature in Ionic Bond)
“Polarisation of anion by cation”

➔ When a cation approaches an anion closely the positive charge of a

cation attract the electron cloud of the anion towards itself, due to the
electrostatic force of attraction between them.
➔ At the same time cation also repel the positively charge nucleus of anion.
➔ Due to this combined effect, cloud of anion is bulged or elongated

towards the cation. This is called distortion, deformation or Polarisation
of the anion by the cation and anion is called Polarised.
Polarisation power:
Ability of cation to polarise a nearby anion is called

Polarisation power of cation.
Na e
Cl
Polarisation power
Polarizability:
Ability of anion to get polarized by the cation
Polarizability
𝝳𝝳𝝳-
Distortion of Na e
Cl
electron
Magnitude of polarisation depends upon a no. of factors,

suggested by Fajan and are known as Fajan's rule.
Factors A ecting Polarisation
a Size of cation
BeCl2
MgCl2 ● Size of cation increases
CaCl2 ● Covalent character decreases

● Ionic character increases
SrCl2
BaCl2
Greatest polarising power of Be2+, shows its maximum covalent character

Na+ , Mg+2 , Al+3 , Si+4
● Cation size decreases

● Covalent character increases
b Size of anion
CaF2
● Size of anion increases
CaCl2
CaBr2 ● Ionic character decreases
CaI2
c Charge on cation and anion
(i) Polarisation (covalent character) ∝ Charge on cation
● Charge on cation increases

● Ionic character decreases (M.P. decreases)
(ii) Polarisation ∝ Charge of anion
F- , O2- , N3-
● Charge increases
d Electronic configuration of cation

Cu+ and Na+ both the cation (Pseudo inert & inert respectively) have same
charge and size but polarising power of Cu+ is more than Na+ because:
So CuCl has more covalent character than NaCl

Q. Arrange the following in increasing order of covalent character
LiF, LiCl , LiBr , LiI
LiF < LiCl < LiBr < LiI
CaCl2, FeCl3, FeCl2
CaCl2 < FeCl2 < FeCl3

Thermal Stability
(i) Thermal stability of compound having polyatomic anion:
Thermal Stability
(ii) For fluoride, hydride & normal oxide:
Thermal Stability order
BeSO4 MgSO4 CaSO4 SrSO4 BaSO4
LiNO3 NaNO3 KNO3 RbNO3
LiHCO3 NaHCO3 KHCO3 RbHCO3 CsHCO3

Solubility of Ionic Compounds
Soluble in polar solvents like water which have high

dielectric constant
Factors a ecting Solubility of Ionic Compounds
(i) Dielectric constant of the solvent increases, the solubility of

compound increases
(ii) If heat of hydration of ions exceeds the lattice energy (L.E.) of ionic
compounds, the ionic compounds will be soluble in water.
➔ Lattice energy as well as hydration energy depend on the size of

ions.
➔ Both lattice energy and hydration energy decrease with increase
in ionic size.
Two general rule, regarding the solubility is that :

1 ➔ If the anion and the cation are of comparable size, the cationic
radius will influence the lattice energy.
➔ Since lattice energy decreases much more than the hydration

energy with increasing ionic size, solubility will increase as we go
down the group.
Solubility increases
2 ➔ If the anion is large compared to the cation, (i.e. compound

contain ions with widely different radii) the lattice energy will
remain almost constant i.e. change is very small within a
particular group.
➔ Since the hydration energies decrease down a group, solubility

will decrease.
Solubility decreases
Some Important Solubility Orders
BeSO4 MgSO4 CaSO4 SrSO4 BaSO4 {SO4–2 larger}
CsF CsCl CsBr CsI {Cs+ larger}

Some Important Solubility Orders
BeS MgS CaS SrS BaS {S–2 larger}

IUPAC Nomenclature Rules
Rule 1
Cationicname anionicname
Rule 2
For Naming of Ligand
Follow Use
Use Use Use
Alphabetical Bis, Tris,
Di, Tri, Tetra “O” suffix “ium” suffix
Order Tetrakis
For no. of If ligand For -ve For +ve
Ligands name has Ligands Ligands
number
IUPAC Nomenclature Rules
Rule 3
Write Central Metal Atom Name
For Anionic complex For Cationic/Neutral complex

Use
No Suffix
Suffix “ate”
Rule 4
Write O.No. of CMA in Roman
within (brackets)
IUPAC Nomenclature Examples
[Ag(NH3)2]C Diamminesilver(I) chloride
l
[Cr(en)3]Cl3 Tris(ethane-1,2-diammine)chromium(III) chloride
Potassium trioxalatoaluminate(III)
K3[Al(C2O4)3]
VBT
postulates
Valence Bond Theory
Postulates
Ligand with Metal with Ligand-Metal

Lone Pair Vacant orbital Coordinate Bond
Valence Bond Theory
Postulates
“Vacant orbitals of metal

should have
equal energy”.
Valence Bond Theory
Postulates
Metal can use
(n-1)d, ns, np ns, np, nd

orbitals orbitals
“To form equivalent orbitals

of definite geometry”
Inner &
Outer Orbital
Complex
Coordination
Valence BondComplex
Theory
Inner Orbital Outer Orbital

Complex Complex
Inner (n-1)d orbital Outer nd orbital

used for used for
hybridisation hybridisation
Valence Bond Theory
Table “ Types of Hybridisation & Geometry”
Coordination No. Types of Hybridisation Geometry

4 sp3 Tetrahedral
4 dsp2 Square planar
5 sp3d Trigonal bipyramidal

6 sp3d2 Octahedral
6 d2sp3 Octahedral
Valence Bond Theory
Different Geometries
Valence Bond Theory
Postulates
“Hybrid orbitals of metal overlap with Ligand orbitals”
Valence Bond Theory
Magnetic
Properties of
Coordination
Compounds
Valence
MagneticBond
Properties
Theory
Coordination Compound
Unpaired electron No unpaired

present electron
Spin Magnetic
μ = √n(n + 2) BM
moment :
Valence
MagneticBond
Properties
Theory
No. of unpaired electrons Magnetic Moment

1 1.73 BM
2 2.82 BM
3 3.87 BM
4 4.89 BM
5 5.91 BM
Let’s understand
With
Examples
Valence Bond Theory
1 Example [Fe(CN)6]4-
Valence Bond Theory
d2sp3 hybridisation
Valence Bond Theory
Magnetic moment (μs) = √n(n+2) BM

= 0 BM
Valence Bond Theory
2 Example [Fe(H2O)6]3+
Valence Bond Theory
sp3d2 hybridisation
Valence Bond Theory

= √5(5+2) BM
= 5.91 BM
Valence Bond Theory
3 Example [Ni(CO)4]
Valence Bond Theory
3 Example [Ni(CO)4]
sp3 hybridisation
Valence Bond Theory
3 Example [Ni(CO)4]

= 0 BM
Valence Bond Theory
4 Example [Ni(CN)4]2-
Valence Bond Theory
dsp2 hybridisation
Valence Bond Theory

= 0 BM
Crystal
Field
Theory
Crystal Field Theory
Postulates
“Metal -Ligand bond

is ionic”.
Postulates
Ligand
Anionic Neutral
Treated as Treated as
point charge dipole
- δ δ
Postulates
“d orbitals in isolated gaseous metal atom are
degenerate”.
Postulates
“d orbitals split in the presence of Ligands”
Postulates
“Splitting pattern depends upon
nature of crystal field”
Splitting
in
Octahedral
Field
Octahedral Field
L
L
L
L L
L
Octahedral Field
d orbitals
dx2-y2 dz2
Octahedral Field
d orbitals
dxy dyz dxz

Octahedral Field
d orbitals
dx2-y2, dz2 dxy, dyz, dxz

More repulsion from Less repulsion from
Ligand e- Ligand e-
Splitting in Octahedral Field
Barycentre
Crystal Field
Splitting
Energy
(Octahedral)
Crystal Field Splitting Energy
“The difference of energy between
two sets of d-orbitals”
C.F.S.E. = -0.4n t2g + 0.6n eg

Δo
CFSE (Δo)
Nature of Ligand
Strong field Ligand Weak field Ligand

More splitting Less splitting
Δo > P Δo < P
Pair up electrons Can’t pair up

electrons
Spectrochemical Series
I- < Br- SCN- < Cl- < F- < OH- < H2O < NCS- < NH3 < en < CN- < CO
Increasing Ligand Strength

Example
Splitting
in
Tetrahedral
Field
Tetrahedral Field
L
L
L
L
Tetrahedral Field
dxy dxz dyz

Tetrahedral Field
dx2-y2 dz2
Splitting in Tetrahedral Field
t2
Bary center
e
Crystal Field
Splitting
Energy
(Tetrahedral)
Crystal Field Splitting Energy
C.F.S.E. = -0.6n e + 0.4n t2 Δt
4
ΔT = Δ0
9
“Because Tetrahedral field has less no.

of Ligands”
Let’s see
One
Example
C.F.S.E. for high spin d4 octahedral complex is
Solution
C.F.S.E. = -0.4n t2g + 0.6n eg Δo

= -0.4 x 3 + 0.6 x 1 Δo
= -1.2 + 0.6 Δo
= -0.6 Δo
Colour of
Coordination
Compounds
Colour of Coordination Compounds
Colour of Coordination Compounds
Structural Isomerism
“ Same chemical formula but
different bonds”
Ionisation Isomerism
Hydrate/Solvate
Isomerism
Linkage Isomerism
Coordination Isomerism
Ionisation Isomerism
+ AgNO3
[Co(NH3)5SO4]+ + AgBr
+BaCl2
[Co(NH3)5Br]2+ + BaSO4
Hydrate/Solvate
Isomerism
Linkage Isomerism
[Co(NH3)5(NO2)]Cl2 & [Co(NH3)5(ONO)]Cl2

Coordination Isomerism
Stereoisomerism
“ Same chemical formula & bonds but
different spatial arrangement”
Shown by
Geometrical /cis-trans
Isomerism
Square planar, Octahedral
Shown by
Optical Isomerism Tetrahedral, Octahedral
Stereoisomerism
Geometrical /cis-trans
Isomerism
Shown by
Square planar Octahedral
complexes complexes
MA2B2 MA4B2
MA2BC MA2(BB)2
MABCD MA3B3
Examples for Square Planar
MA2B2 MA2BC
Pt Pt
Examples for Square Planar
MABCD
cis trans cis

Examples for Octahedral
MA4B2 MA2(BB)2
Cr Cr
MA3B3
fac-isomer mer-isomer
Stereoisomerism
Optical Isomerism
Tetrahedral Shown by Octahedral
complexes complexes
MA2B2C2 M(AA)2B2
MABCD
MABCDEF M(AA)B2C2
M(AA)3
“Only cis forms”
Example for Tetrahedral
MABCD
MA2B2C2 MABCDEF
M(AA)3 M(AA)2B2
M(AA)B2C2
Metallurgy
“The branch of chemistry which deals with the method of
extraction of metals from their ores by profitable means.”
Ore: The mineral from which a metal can be extracted

profitably and easily is called an ore.
Gangue: The undesirable impurities present in an ore are

called gangue.
Types of Metallurgy
STEPS INVOLVED IN THE EXTRACTION OF METALS
The extraction of a metal from its ore is completed in the
following four steps.
(A) Concentration of the ore

(B) Conversion of concentrated ore into oxide form.
(C) Reduction of the metal
(D) Refining of the metal.
Concentration of ores
Gangue removal
Process
Hydraulic Washing
Froth Floatation
Electromagnetic
Separation
Leaching
Hydraulic
Washing
Heavy metals
Sn, Pb, Fe
Froth
Floatation
Sulphide ores Cu, Zn, Fe
& Pb
Procedure
➢ Finely powdered ore is mixed with water and pine oil
➢ Mixture is agitated with compressed air
➢ Ore particles rise to the surface along with froth
➢ Gangue being wetted by water remain

in water below the foam
Froth
Floatation
Froth
CH3 stabilizers
: NH2 OH
Aniline Cresol
Substances that separate two sulphide ores by

Depressants selective prevention of froth formation by one ore
and allowing the other to come into froth
Used when mixture of sulphide ore is present
Ex: NaCN, Na2CO3
PbS + NaCN No reaction

ZnS + NaCN Na2[Zn(CN)4]
Electromagnetic
separation
separation of magnetic and
non-magnetic
Leaching - silver
is a Process, where ore is treated with chemicals to convert the
valuable metals within into soluble salts while impurity remain
insoluble
4Ag2S + 8NaCN + O2 4Na[Ag(CN)2] + 4Na2S

Sodium
argentocyanide
complex
Reduction
Zn
2Na[Ag(CN)2] 2Ag + Na2[Zn(CN)4 ]
Reduction of ores
Roasting Smelting
Sulphide ores Metal oxides
with O2 with O2
Calcination
CO32- & HCO3- ores
without O2
Reduction of ores
Roasting Heating below its melting point
ZnS + O2 ZnO + SO2

white
Self-Reduction
Cu2S + O2 Cu2O + SO2 Cu + SO2

Cu2S
Blister copper
Reduction of ores
Calcination Absence of O2
(1) CaCO3 CaO + CO2

(Calcite)
(2) ZnCO3 ZnO + CO2
(Calamine)
(3) FeCO3 Fe2O3 / FeO + CO2

( Siderite )
Reduction of ores
Smelting Reducing agents used are C, CO , Al
(1) ZnO + C Zn + CO
(Zincite)
O2
(2) SnO2 + C Sn + CO CO2
trace
(Tin stone)
THERMODYNAMICS OF REDUCTION PROCESSES (ELLINGHAM DIAGRAM)
➔ It is explanation of the feasibility of pyrometallurgical process by using gibbs

equation
❖ If ∆G = – ve Process is stable or Spontaneous

❖ ∆G = + ve or Less – ve then process is Unstable or non-Spontaneous
➔ When pyrometallurgical process contains more than one type of reaction

then stability of reaction can be explained by Ellingham diagram. Ellingham
diagram contains plot
➔ According to Ellingham diagram, the metal below can reduce the oxide of
metal above it in the curve, as affinity of metal below for oxygen is more.
Example:
● Al Metal can reduce Cr2O3 but can not reduce MgO & CaO .
● At very high T after 'A' Point Al' metal can reduce MgO because
Formation of MgO contains less – ve ∆G.
● According to diagram at high T (710° OR above 710°C) Oxidation of C

contains more – ve ∆G so at high T 'C' is good Reducing agent.
● At Low T (below 710°C) Oxidation of CO contains more –ve ∆G so at Low

T, CO is good Reducing agent.
Applications
Electrochemical principles
Cathode:
Hall-Heroult process - Aluminium Al3+ (melt) + 3e– → Al (l)
Anode:
C(s) + O2– (melt) → CO(g) + 2e–
C(s) + 2O2– (melt) → CO2 (g) + 4e–
Refining
Liquation
Distillation
Electrolytic refining
Zone refining
Vapour phase refining
Chromatography
Refining
Liquation
Ex:Tin (Sn) , Lead (Pb), Bismuth(Bi)

Refining
Distillation Low boiling metals
Condenser with water

in and out
Mixture
of Desired metal
metals Ex: Zn, Hg
Refining
Electrolytic refining
Ex: Cu, Zn, Sn

Refining
❖ Highly pure semiconductors are

Zone refining
obtained like Ge, Si, Be, Ga, In.
Refining
Vapour phase refining 1. Mond process
350 Κ
Ni + 4CO Ni (CO)4
Volatile
unstable
complex
Ni + 4CO
Highly Along with O 470Κ
2
pure & N2
Refining
Vapour phase refining 2. Van arkel
870 Κ 2075 Κ
Zr + 2I2 ZrI4 Zr + 2I2
Volatile Along with
unstable O2 & N2
complex
500 Κ 1700 Κ
Ti + 2I2 TiI4 Ti + 2I2
Volatile Along with
unstable O2 & N2
complex
LIST OF ORES AND THEIR NAMES
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A table which classifies all known elements in accordance with

He classified elements into

❖ Properties chosen to classify metals were not applicable to all of

❖ Some elements show properties of both metals & non metals

❖ In 1829, Dobereiner arranged elements with similar

❖ In each case,the atomic mass of middle element is average of

❖ This is called as “ Law of Triads”

❖ In 1865, he arranged elements in increasing order of their

❖ Just like eighth note of a musical scale

❖ This is known as “Newlands’ Law of Octaves”

❖ This concept was only applicable for lighter elements

❖ Lothar Meyer plotted a curve between atomic weight

❖ He observed that the elements with similar properties

❖ The graph is known as “ Lothar Meyer’s curve”

➔ Metalloids (Si, Ge, As, Sb, Te, Po, At)

➔ Halogens (F, Cl, Br, I) occupy the

❖ The first real breakthrough in classification of elements was

❖ He gave “Periodic law” which states that:

“The physical and chemical properties of elements

❖ He arranged 63 known elements in 7 periods (horizontal rows)

❖ Systematic Study of Elements

❖ Left gaps in his periodic table, for elements yet

Eka Boron Scandium

Eka Silicon Germanium

Eka Aluminium Gallium

Eka Manganese Technetium

❏ Correction of doubtful Atomic weights

❏ Corrections were also done in atomic weight of elements like –

❖ Position of Hydrogen element was not justified.

❖ Anomalous pairs of elements : There were some pair of elements

❖ Like elements were placed in different groups :

❖ Unlike elements were placed in same group : Eg: Placement of Alkali

❖ A plot of √ν (where √ν is frequency of X-rays

❖ It showed that Atomic number is a more

The physical & chemical properties of elements are the

❖ It is based on the Bohr-Bury electronic configuration concept and

❖ This model is proposed by Rang & Werner.

❖ It has 7 periods (horizontal rows) and 18 groups (Vertical columns)

❖ The periodic table is divided into 4 blocks:

Case1 When Electronic Configuration is given

❏ If np electron present then p - block (ns2 np1-6)

(i) S = 1s2 2s2 2p6 3s2 3p4 P Block

(ii) Ar = 1s2 2s2 2p6 3s2 3p6 P Block

❏ If (n–2)f0 (n–1)d0 ns1–2 = s block

(i) Mg = 1s2 2s2 2p6 3s2 S Block

(ii) Ca = 1s2 2s2 2p6 3s2 3p6 4s2 S Block

❏ If (n–2)f1–14 (n–1)d0–1 ns2 = f block

(i) Sm = [Xe] 4f⁶ 6s² F Block

(ii) Gd = [Xe] 4f7 5d1 6s2 F Block

❏ If any other configuration or

(i) Ti = 1s2 2s2 2p6 3s2 3p6 4s2 3d2 D Block

(ii) Fe = 1s2 2s2 2p6 3s2 3p6 4s2 3d6 D Block

Case1 When Electronic Configuration is given

“The highest Principal Quantum no. available in Electronic

But Period No. is 5

Case2 When Atomic No. is given

❏ Check if given no. x is between 58-71

(i) X= 65 Period No. = 6

❏ Check if given no. x is between 90-103