Chemical Bonding

Introduction
• It is well known fact that except inert gases, no other element exists as independent atoms under ordinary condition.
• Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form molecules and
why do atoms form bonds? Such doubts will be discussed in this chapter.
• A molecule will only be formed if it is more stable and has a lower energy, than the individual atoms.

Chemical Bond
• A force that acts between two or more atoms to hold them together as a stable molecule.
• It is union of two or more atoms involving redistribution of e– among them.
• This process accompanied by decrease in energy.
• Decrease in energy  Strength of the bond.
• Therefore, molecules are more stable than atoms.

Cause of Chemical Combination

Tendency to acquire minimum energy
(a) When two atoms approach towards each other, Nucleus of one atom attracts the electron of another atom.
(b) Two nuclei and electron of both the atoms repel each other.
(c) If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond is formed.
(d) So, Attraction  1/energy  Stability.
(e) Bond formation is an exothermic process (H = negative)

Classification of Bonds
CHEMICAL BONDS

STRONG BOND WEAK BOND

(Inter atomic) (Inter molecular)
(Energy ≃ 200 KJ/mole) (Energy ≃ 2.42 KJ/mole)

(A) (B) (C) (D) (E) (F)

Ionic Covalent Co-ordinate Metallic Hydrogen Vander Waal's
bond bond bond bond bond bond

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Chemical Bonding

Ionic or Electrovalent bond

(a) The chemical bond formed between two or more atoms as a result of the complete transfer of one or more
electrons from one atom to another is called Ionic or electrovalent bond.
(b) Electropositive (metal) atom loses electron
(c) Electronegative (non-metal) atom gains electron
(d) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.

Electronegativity difference  nature of ionic bond.

e.g. IA and VIIA group elements form maximum ionic compound.

Total number of electrons lose or gained is called electro valency.

Example –
(1) (2)

Electro valency of Mg = 2 electro valency of Ca = 2

Electro valency of O = 2 electro valency of Cl = 1

(3)

Electro valency of Ca = 2
Electro valency of O = 2
During formation of ionic bond octet will be completed.

Representation of formula of compounds :

(1) Write the symbols of the ions side by side in such a way that positive ion is at the left and negative ion is at the
right as A+B–
(2) Write their electro valency in figure at the top of each symbol as Ax By
x y
(3) Now apply Criss cross rule as , i.e. formula AyBx.
A B

Example: Calcium chloride = CaCl2

(c) Lattice energy (L.E.) ;

Amount of energy released when one mole of crystal lattice is formed from its constituents ions or amount of
energy required to break one mole of crystal lattice into its constituents ion is known as lattice energy.
Higher lattice energy → Greater will be the stability or strength of ionic compound.

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Chemical Bonding

Factors affecting lattice energy

(a) Magnitude of charge → U  z+ z– (Ionic charge)
Lattice energy  Magnitude of charge
NaCl MgCl2 AlCl3
Na +
Mg +2
Al+3
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
– Lattice energy increases
– Charge of cation increases
1
(b) Size of Cation :- Lattice energy µ + −
(r +r )
LiCl NaCl
KCl RbCl CsCl
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
– Size of cation increasing
– Size of anion is constant
– Lattice energy decreases.

Various energy terms

(a) Heat of sublimation (Hsub.)
It is heat required to change one mole of a substance from solid state to gaseous state.
A(s) ⎯→ A(g) ; Hsub. = positive

(b) Heat of vaporisation (Hvap.)

It is heat required to change one mole of liquid substance into gas.
A() ⎯→ A(g) ; Hvap. = positive

(c) Heat of fusion (Hfus)

It is heat required to change one mole of solid substance into liquid.
A(s) ⎯→ A() ; Hfus = positive

(d) Heat of atomization (Hatm)

It is change in enthalpy when one mole of a substance is converted into its constituent gaseous atoms.

(e) Heat of solution (Hsol.)

It is the change in enthlapy when one mole of a solute is dissolved in excess amount of solvent.
NaCl(s) + aq. ⎯→ Na(aq.)
+ –
+ Cl(aq.) , Hsol. of NaCl(s)

(f) Bond dissociation energy (B.D.E.) and Bond Energy (B.E.)

It is the amount of heat require to break one mole of bond between two atoms of a gaseous molecule into
gaseous atoms.

(g) Heat of formation (Hf)

It is the change in enthalpy when one mole of substance is formed from it's element in standard state.

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Chemical Bonding

Hess's Law :
The standard enthalpy of an overall reaction is the sum of the standard enthalpies of individual reactions into
which a reaction may be divided.

Example :
In the reaction A → B, total enthalpy change is H and in A → C, C → D, D → A is H, H2 and H3 respectively
as shown then
H = H1 + H2 + H3
H
A B

H1 H3

C D
H2
BORN-HABER CYCLE
The Born-Haber cycle is an approach to analyse reaction energies.

Born Haber cycle of NaCl(s)

1 ∆Hf
Na(s) + Cl2(g)
2 NaCl(s)
∆Hsub 1
∆H
2 diss

Na(g) Cl(g)
Lattice
Energy
I.E. ∆H
EGE

Na+(g) + Cl–(g)

1
∆H = ∆H + I.E. + ∆H + ∆H + LE
f sub 2 diss EGE

Hf = HS + I + ½Hd + E + U

Example : MgO, AF3

Conditions for Forming Ionic Bonds

Formation of Ionic bond depends upon these three factors –

(a) Ionisation energy (I.E.) :

Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous atom to
form the +ve ion or cation. (energy absorbed)

Lesser Ionisation energy → Greater tendency to form cation.

Na+ >Mg+2 > Al+3 


e.g.
+
Cationformationtendency
Cs >Rb >K >Na >Li 
+ + + +


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Chemical Bonding

(b) Electron affinity (E.A.) :

Amount of energy released when an electron is added to an isolated gaseous atom to form –ve ion (anion)
energy released.
Higher electron affinity → Greater tendency to form anion
Cl– > F– > Br– > I–
F– > O–2 > N–3

Covalent Bond
• A covalent bond is formed by the mutual sharing of electrons between two atoms of electro negative elements to
complete their octet. (Except H which completes its duplet)

H : H :O :: O: .N N.

H2 molecule O2 molecule N2 molecule

H—H O == O NN

• The shared pair of electrons should have opposite spins, and are localised between two atoms concerned.
• Sharing of electrons may occurs in three ways –

No. of electrons shared Electron pair Bond.

between two atoms
2 1 Single bond (—)
4 2 Double bond ( )
6 3 Triple bond ( )
..
Examples – H—N—H Three single bonds (not triple bond)
|
H
N  N Triple bond. (not three single bond)
O==O Double bond (Not two single bond)
H — O — H (Two single bonds.)

Orbital Concept of Covalent Bond

According to this concept :
• One orbital can accommodate maximum 2 electrons with opposite spins .
• Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its orbital.
• Tendency to complete orbital or to pair the electron is an essential condition of covalent bond.
• Completion of octet is not the essential condition of covalent bond.
• Covalency : It is the number of covalent bonds which an atom makes in a molecule, either in ground state or in
excited state.

Variable Valency in Covalent Bonds

• Variable valencies are shown by those elements which have empty orbitals in outermost shell.
• Lone pair electrons get excited in the subshell of the same shell to form the maximum number of unpaired electrons.
Maximum covalency is shown in excited state.

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Chemical Bonding

• 3, 4, 5, 6 period elements due to the presence of vacant d-orbital in the presence of highly electro negative elements
such as (F, O, Cl) can show variable valencies.
• If an element shows odd or even valency in ground state then it will show odd or even in excited state also with the
difference of 2.
• The energy required for excitation of electrons is called promotion energy.
• Promotion rule – Excitation of electrons takes place in the same orbit.
Example –
(a) Nitrogen → Ground state

2s 2p
Covalency 3 (NCl3)
Nitrogen → No excited state
Not possible due to absence of vacant orbital that’s why (NCl5) does not exist

(b) Phosphorus → Ground state

3s 3p
Covalency 3 (PCl3)
Phosphorus → Excited state

Covalency – 5 (PCl5)
Note :
NCl3 — exists
NCl5 — doesn't exists
(due to absence of d-orbitals in Nitrogen.) While PCl3 and PCl5 both exists because 3d orbitals are present in
phosphorus.
OF2 — exists, but OF4 and OF6 doesn't exists due to absence of d-orbitals While SF4 and SF6 exists
due to presence of d-orbital, present in its valence shell.
• It can explain existence of molecules.

(c) Sulphur → Ground state.

3s 3p 3d
Covalency - 2(SF2)
Sulphur → Excited state
1st excited state Covalency - 4 (SF4)
3s 3p 3d

2nd excited state Covalency - 6 (SF6)

So variable covalency of S is 2, 4, & 6.

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Chemical Bonding

Note :
It is not necessary that only 3, 4, 5, 6 period elements forms their compound in excited state but 2 period
elements also forms compound in excited state.

Example - Be, B, C forms most of their compound in excited state.

(1) Be – 1s2, 2s2

Ground state Covalency = 0

Excited state Covalency = 2

(2) C = 1s2, 2s2, 2p2

Ground state Covalency = 2

Excited state Covalency = 4

Co-ordinate bond (Dative bond)

(a) It is a covalent bond in which the shared e– pair come from one atom is called coordinate bond.
(b) Atom which provide electron pair for sharing is called donor (Lewis base).
(c) Other atom which accepts electron pair is called acceptor (Lewis acid). That is why it is called donor-acceptor or
dative bond.

Lewisbase Lewis acid

⎯⎯
→ NH3 ⎯⎯
→ BF3

BF3 is electron deficient compound.

(d) Necessary conditions for the formation of coordinate bond are -
(a) Octet of donor atom should be complete and should have atleast one lone pair of electron.
(b) Acceptor atom should have vacant orbital to accommodate L.P.

eg. :- ⎯⎯→ or X ⎯⎯→ Y

Protonation (Addition of H+ ion)

Example : NH4+ (Ammonium ion)
NH3 + H+ → NH4+

Example : H3O+ (Hydronium ion)

+

H
H ..
O.. + H + ⎯→ O
.. H
H H

Other examples of co-ordinate bond

••
•• •• •• O
O3 ; O == O O ••
••
••

••

•• O
••

O ••

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•• ••
N2O ; NN O

••
••
••

O O H—O O
N2O5 ; N— O — N H2SO4 ; S
O O H—O O
Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows -
NH4Cl, Na3PO4, KNO3, etc.

Lewis Dot Structures or Lewis Symbols

According to Lewis in the formation of a molecule, only the outer most shell electrons take part in chemical
combination & they are called valence electrons. The inner shell electrons are well protected and are generally not
involved in the combination process. Lewis introduced simple notations to represent valence electrons in an atom.
These notations are called Lewis symbols or Lewis dot structure.

Lewis symbols for atoms and monoatomic ions :

Lewis symbol for second period elements are : ••
• •

•••
•

•••

•Li •Be• •B• •C•

••• •

N O F Ne
••

••
••
••

••

•• ••
Number of dots around the symbol represents the number of valence electrons.
Lewis symbol for some anions are
2–
F O

How to draw the Lewis electron dot/Bond line structure of inorganic covalent compounds :
1. (i) First of all, identify the central atom in the given species. Central atom in a given molecule/ion is usually that
atom which is least electronegative.
(ii) Hydrogen can't be central atom as its covalency is one.
(iii) Sometimes the central atom is that atom which is less in number.
(iv) Sometimes the central atom in the given molecule/ion can't be decided on the basis of electronegativity or
number of atoms (less). In such cases, that atom is central atom which appears in central position of given
formula of molecule/ion.
To make it more clear, central atoms in the following species are starred (*).
 CH4, NH3, H2O, CH2Cl2, CHF3
(Note-that electronegativity of H is less than that of central atom).
CO2, SO2, SO3, SOCl2, PSCl3

OCl2, OBr2

(Note that oxygen is more electronegative, but it is less in number)
* - , (order of appearance)
 (SCN )
2. Surrounding atoms are the atoms which are directly bonded to central atom.
3. Arrange the surrounding atoms around the central atom and first form single bond between all surrounding
atom with central atom.
4. Always make sure that octet of all the surrounding atoms is complete. If it is not achieved by forming single
bond, then try to make the double bond or triple bond between central atom and surrounding atom, as required
to complete the octet of surrounding atoms.

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Chemical Bonding

e.g., CO2
O C O O–C–O O=C=O

SNF3

N N
F S F F—S—F
F F

5. After the bond formation, represent the lone pair of electrons on central atom as well as on surrounding atoms.
6. Make sure that, in the structure you have made, the octet of the all surrounding atoms must be completed.
7. If the central atom belongs to second period, it can have ≤ 8 (max.) electrons i.e. ≤ 4 bonds, but never greater
than 8 electrons (i.e. > 4 bonds).
8. However, if the central atom belongs to third or lower period it can have  8 electrons.
9. At last verify the covalency of central atom.
10. Lewis Structure of ions :
Distribute the negative charge on surrounding atom in such a way that octet of none of the surrounding atom
is complete before the bond formation with central atom. If however, the octet of surrounding atom is complete
by making it non negatively charged (particularly in case of halogen which contain seven valence electron), then
such surrounding atom will attach itself with central atom through a co-ordinate covalent bond.
O

N N
O O O O

But the above structures of NO3– is incorrect as the central nitrogen belongs to second period, it can never form
five covalent bond i.e., it can't have more than 8 electrons, so its actual structure is :
O O
N or
N
O 
O O O
NO3–

F
O F
or ⊖
F B F
C F B F
O O F
F
CO2−
3
BF4–

O O Cl
Cl
O P O S Cl P
Cl
O O
O Cl Cl

PO3– PCl6
–
4 SO 32–

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⊖  ⊖ ⊖  2–
N N N or N N N or N N N
N 3–

⊖ ⊖
S C N or S C N

SCN –

Formal Charge

Lewis dot structures, in general, do not represent the actual shapes of the molecules. In case of polyatomic ions,

the net charge is possessed by the ion as a whole and not by a particular atom. It is, however, feasible to assign

a formal charge on each atom.

𝟏
Formal Charge : QF = NA – NL.P. – NB.P.
𝟐

Where :

NA = Total number of valence electron in the free atom

NL.P. = Total number of non bonding (lone pair) electrons

NB.P. = Total number of bonding(shared) electrons

Molecule Structure Formal Charge

1
O
2 3 1
O3 O(1) = 6 –2 – (6) = + 1
O O 2

1
O(2) = 6 – 4 – (4) = 0
2
1
O(3) = 6 – 6 – (2) = – 1
2
C O 1
CO C = 4 – 2 – (6) = –1
2
1
O = 6 – 2 – (6) = +1
2
+
H1

N 1
NH4+ N=5–0– (8) = +1
4 2
H
2
H
H3

1
On each H = 1 – 0 –
(2) = 0
2
• Formal charges help in the selection of the lowest energy structure from a number of possible Lewis
structures for a given species.

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Chemical Bonding

Exception of Octet Rule (Failure)

(a) Incomplete octet molecules or electron deficient molecules or hypovalent.
Compound in which octet is not complete in outer most orbit of central atom.
Example - Halides of IIIA groups, BF3, AlCl3, BCl3, hydride of III A/13th group etc.
•• ••
Cl Cl [In BCl3 Boron has only 6 electrons]
••
••

•• B ••
••
Cl
••
••

••
Other examples – BeCl2 (4e–), HgCl2 (4e–), Ga(CH3)3 (6e–)

(b) Expansion of octet or electron efficient molecules or hypervalent

Compound in which central atom has more than 8e– in outermost orbit.
Example - In PCl5, SF6, IF7, the central atom P, S and I contain 10, 12, and 14 electrons respectively.
•• PCl5
Cl
••
••
•• •• ••
Cl Cl
••
••

•• P ••
•• ••
Cl Cl
••
••

•• ••
(c) Pseudo inert gas configuration :-
Cations which contains 18 electrons in outermost orbit
Ex. Ga+3, Cu+, Ag+, Zn+2, Cd+2, Sn+4, Pb+4 etc.
Electronic configuration of Ga - 1s2,2s22p6,3s23p63d10,4s24p1
Electronic configuration of Ga+3 - 1s2,2s2,2p6, 3s2 3p6 3d10
18e-

(d) Odd electron molecules :-

In Which central atom have an unpaired electron or odd no (7e–, 11e– etc) of electrons in their outer most shell.
e.g. NO, NO2, ClO2 etc.

Resonance
When a molecule cannot be completely represented by a single Lewis structure but it's characteristic properties can
be described by two or more different structures, with similar energy position of nuclei, bonding and non-bonding
pairs of electrons, then the true structure is said to be resonance hybrid of these structures. The phenomenon is
called resonance and different contributing structures are called resonating structures or canonical structures.
• Resonance stabilizes the molecule as the energy of the resonance hybrid is less than the energy of any single
canonical structure.
• Resonance averages the bond characteristics as a whole.
• The canonical forms have no real existence.

Resonance Energy :
Energy difference between most stable resonating structure and resonance hybrid structure is called resonance
energy.

Rules For Writing Resonating Structures :

To explain the characteristics of a molecule, a number of resonating structures may be written.
(1) The contributing structure having similar energy contribute equally to the resonance hybrid. The canonical form
having higher energies contribute to a lesser extent to the resonance hybrid.

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Chemical Bonding

(2) The contributing structures should have the same atomic positions. They should differ only in the position of
electrons. For Example, the following two structures of phosphorus acid (H3PO3) are not resonating structures
because they have different positions of atoms in the two structures.
H
H O P O H
H O P O H
& O are not resonating structures.
O H
I II
(3) The contributing structures should have the same number of unpaired electrons.
(4) The contributing structures should not differ much in energy.
(5) Contributing structures should be so written that the negative charge resides on more electronegative element
and positive charge resides on less electronegative element.
(6) In contributing structures, like charges, should not reside on adjacent atoms. This means that contributing
structures should be so written that unlike charges reside on neighbouring atoms while like charges are
separated as far apart possible. For example, resonating structures of N 2O may be written as follows :
2–

NN—O N == N== O N—NO

I II III

In this case structure (III) is not feasible because it place a positive charge on the electronegative oxygen atom
and also has same positive charges on the adjacent nitrogen atom.
(7) A resonating structure that violate octet Rule will be least stable
– + + –
Example : CH2 == CH — Cl CH2 — CH == Cl CH2 — CH == Cl
I II III
Order of stability
1 > II > III
Bond order : Number of bonds between two atoms is called bond order.

Resonance Structure of Some Molecules/Ions :

(i) Azide ion, N3– :
The azide ion may be represented as –
2– 2–
– + – + +
N == N — N N—NN NN—N
I II III
The structures II and III contribute equally and the molecule has almost double bond character in each N–N
bond.

(ii) Carbonate, CO32-

O– O–
2–
O O

C C C C
–O O– O O– –O O O
O

B.O. = 1.33

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(iii) Benzene, C6H6

BO = 1.5

(iv) Carboxylate ion, RCOO–

– –
O O O
R—C R—C R—C
O O O
–

2+1 3
Bond order = = =1.5
2 2

Valence bond theory (VBT)

(A) It was presented by Heitler & London to explain how a covalent bond is formed.
It was extended by Pauling & Slater.

(B) The main points of theory are –

(a) To form a covalent bond overlapping occurs between half-filled valence shell orbitals of the two atoms.
(b) Orbitals come closer to each other from the direction in which there is maximum overlapping
(c) So covalent bond has directional character.
(d) Strength of covalent bond  extent of overlapping.
(e) Extent of overlapping depends on two factors.

(i) Nature of orbitals –

(a) As the value of n increases, bond strength decreases.
1-1>1-2>2-2>2-3>3-3
1s - 2p > 2s - 2p > 3s - 3p

(b) p, d and f are directional orbitals → more overlapping

s-orbital → non-directional – less overlapping
The bond is formed by the overlapping of directional orbital is more stronger than the bond
formed by overlapping of non-directional orbital.
p–p > s–p > s–s

p-p p–s s–s

(c) If n is same 2p - 2p > 2s - 2p > 2s - 2s

(ii) Nature of overlapping – Co-axial overlapping - extent of overlapping more.

Collateral overlapping - extent of overlapping less
Order of strength of Co - axial overlapping – p - p > s - p > s – s

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Types of Overlapping and Nature of Covalent Bonds

The covalent bond may be classified into following types depending upon the types of overlapping :-
(i) sigma () bond (ii) pi () bond (iii) delta () bond

(i) Sigma () bond :

This type of covalent bond is formed by the end to end (head on or axial) overlap of bonding orbitals along the
internuclear axis. This can be formed by any one of the following types of combinations of atomic orbitals.

• s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the internuclear axis as shown
below

s - orbital s - orbital s-s overlapping

• s-p overlapping: This type of overlap occurs between half filled s-orbital of one atom and half filled p-orbital of
another atom.

s - orbital p – orbital s – p orbital

• p-p overlapping : This type of overlap takes place between half filled similar p-orbitals of the two approaching
atoms.

p - orbital p - orbital p – p overlapping

(ii) pi () bond :

In the formation of  bond the atomic orbitals overlap in such a way that their axis remains parallel to each other
and perpendicular to the internuclear axis. The orbitals formed due to sidewise overlapping consists of two
saucer type charged clouds above and below the plane of the participating atoms.
(a) p–p

p-orbital p-orbital p-p overlapping

(b) p–d

+ →

p-orbital d-orbital p-d orbital overlapping

(ii) delta () bond :
Delta () bond are the covalent bonds where four lobes of d-orbital of one atom overlap with four lobes of the
similar d-orbital of other atom. Except dz2 all d orbitals form  bond.

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Atomic orbitals Internuclear axis Type of covalent bond

x axis 
s + px y axis ×
z axis ×
x axis ×
s + py y axis 
z axis ×
x axis ×
s + pz y axis ×
z axis 
x axis 
px + px y axis 
z axis 
x axis 
py + py y axis 
z axis 
x axis 
pz + pz y axis 
z axis 
x axis ×
px + py y axis ×
z axis ×
x axis ×
py + pz y axis ×
z axis ×
x aixs ×
px + pz y axis ×
z axis ×
x axis ×
px + dxy y axis 
z axis ×
x axis ×
px + dyz y axis ×
z axis ×
x axis ×
px + dzx y axis ×

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z axis 
x axis 
py + dxy y axis ×
z axis ×
x axis ×
py + dyz y axis ×
z axis 
x axis ×
py + dzx y axis ×
z axis ×
x axis ×
pz + dxy y axis ×
z axis ×
x axis ×
pz + dyz y axis 
z axis ×
x axis 
pz + dzx y axis ×
z axis ×
x axis 
dxy + dxy y axis 
z axis 
x axis 
dyz + dyz y axis 
z axis 
x axis 
dxz + dxz y axis 
z axis 

Strength of sigma and -Bonds

Basically the strength of a bond depends upon the extent of overlapping- In case of sigma bond, the overlapping
of orbitals takes place to a larger extent. Hence, it is stronger as compared to the -bond where the extent of
overlapping occurs to a smaller extent. Further, it is important to note that pi bond between two atoms is formed
in addition to a sigma bond. It is always present in the molecules containing multiple bond (double or triple
bonds)

Advantages of VBT :
• It explain various bond characteristics e.g., bond length, bond strength.

• It explains the quantitative relationship between the extent of overlapping and bond dissociation energy.

• This theory accounts for shape and nature of bonding of the molecule whose covalency is not according to the
number of half-filled orbitals present in the ground state.
• This theory redefined the stability of molecules e.g. BF 3, AlCl3, PCl5, SF6 etc which are exception to octet rule.

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Disadvantages of VBT :
• According to this theory three bond angle in CH4 should be 90°, as these are formed by p–p overlapping, but
actually it has four 109°28 angles. In NH3 & H2O, angle should be 90°. This is in disagreement with the actual
bond angles of 107° & 104.5° in NH3 & H2O molecules respectively.
• In order to explain the characteristic geometrical shapes of polyatomic molecules like CH 4, NH3, H2O etc. Pauling
introduced the concept of hybridisation.

Hybridisation
(a) It was introduced by Pauling, to explain equivalent nature of covalent bonds in a molecule.
(b) Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution of
energy to form new orbitals, of same shape & same energy. These new orbitals are called hybrid orbitals and
the phenomenon is called hybridisation.
(c) Central atom undergoes hybridisation
(d) This process takes place before bond formation
(e) In hybridisation fulfilled, half-filled and empty orbitals can participate

Structure of
hybrid orbital

(f) Number of the hybrid orbitals formed is equal to number of atomic orbitals participate in hybridisation.
(g) Each hybrid orbital having two lobes, one is major and other is minor. Bond will be formed from major lobe.
(h) The directional properties in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form stronger
sigma bond.
(i) Hybrid orbital should be arranged in such a way that repulsion between hybrid orbital should be minimum.
CH4
C → (He) 2s2 2p2

atomic
orbitals

2s 2p y 2p x 2pz

Hybrid
orbitals

sp 3 sp 3 sp 3 sp3

CH4 molecule

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Determination of hybridisation state

To predict hybridisation following formula may be used :

Method-1 :
1
No. of hybrid orbital = [Total number of valence e– in the central atom + total number of monovalent atoms –
2
charge on cation/ + charge on anion]

Method-2 :
Steric Number (S.N.) = Number of -bond around that atom + Number of lone pair on that atom.
Molecule Method-1 Method-2 Hybridisation
1
NH4+ [5 + 4 – 1] = 4 S.N. = 4 + 0 = 4 sp3 hybridisation.
2
1
SF4 [6 + 4] = 5 S.N. = 4 + 1 = 5 sp3d hybridisation.
2
1
SO2–
4 [6 + 2] = 4 S.N. = 4 + 0 = 4 sp3 hybridisation.
2
1
NO–3 [5 + 1] = 3 S.N. = 3 + 0 = 3 sp2 hybridisation.
2

Number of hybrid orbitals Hybridisation

Two sp
Three sp2
Four sp3
Five sp3d
Six sp3d2
Seven sp3d3

Types of Hybridisation :
(I) sp hybridisation :
In this type of hybridisation one s-orbital & one p-orbital belong to the same shell of an atom mix together and
form two new hybrid orbitals. Which are arrange in straight line at 180° angle.

Example : Formation of BeF2 molecule :

2s
Ground
State of Be
2s 2p + or (or)
Excited
State of Be
2s 2px 2p
2p z
y
sp
sp hybridisation

180°
Two sp hybrid orbitals
Two sp hybrid orbitals

180°
'P' s s 'P'
F Be F
F sp Be sp F Linear

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Examples of sp hybridisation
BeH2, BeF2, BeCl2, BeBr2, BeI2, CO2, CO, NO2+, C2H2, HCN, ZnCl2, HgCl2, CdCl2, N2O, N3–

(II) sp2 hybridisation :

This type of hybridisation is formed when one s & two p-orbitals belonging to the same shell of an atom mix
together and form three new hybrid orbitals. These three sp2 hybrid orbitals are at angle of 120° & giving trigonal
planar shape.
Example : Formation of BF3 molecule :

2s 2p
Ground
State of B
+ + or
Excited
State of B
2s 2p x
2p y 2p z
2
sp

sp hybridisation
2

Three sp2 hybrid orbitals

F
F

120° 120°
B
B

F F F F

Examples of sp2 hybridisation

BF3, BCl3, CH2= CH2, Graphite, HNO3, NO3–, SO3, HCO3–, CO3–2, AlCl3, GaCl3, SnCl2, SnBr2, SnI2, PbCl2, HNO2, SO2

(III) sp3 Hybridisation :

This type of hybridisation is formed when one s & three p-orbital belong to the same shell of an atom mix
together & form four new hybrid orbitals. The angle between these four hybrid orbitals will be 109°28’
Example : Formation of Methane molecule :
2s 2p
Ground
State of C
Excited
State

sp3 hybridisation

Four sp3 hybrid orbitals

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H-atom
H H
1s

sp3
109°28' 109°28'
C C
sp3 H
sp3 H
H H
1s
1s
H
H-atom H-atom H
sp3
1s
H-atom

Formation of Ethane molecule :

H-atom H-atom
1s 1s
sp
3
sp 3
H H
1s 1s
sp 3
sp 3

sp3 sp3
H 109°28' H
C C

sp3 sp3
C-atom H H
1s 1s
H-atom H-atom

Examples of sp3 Hybridisation

CH4, CCl4, CBr4, PCl4+, NH4+, BF4–, AlF4–, BeF4–2, NF3, NCl3, N(CH3)3, PF3, PCl3, AsCl3, SbCl3, BiCl3, NH3, –CH3, H3O+,
SO32–, ClO3, XeO3, H2O, H2S, NH2–, OF2, Cl2O, SCl2, Diamond, SiO2, SiC

(IV) sp3 d Hybridisation :

In this hybridisation one s orbital, three p-orbital and one d orbital( d z2 ) are mixed to give five new hybrid

orbitals which are equivalent in shape and energy called as sp3d hybrid orbitals.
Out of these five orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are perpendicular to
the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes trigonal bipyramidal.
In this way five sp3d hybrid orbitals form five sigma bond with five Cl atoms and give a molecule of PCl 5, shape
of this molecule is trigonal bipyramidal.
Axial(a) two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion between 3 equatorial(e) bp
of e– and 2 axial b.p. of e–
In this type of hybridisation one s, three p-orbital and one d-orbital (dz2) belong to the same shell of an atom
mix together & form five hybrid orbitals.
Example : Formation of PCl5 molecule

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3s 3p
Ground
State of P
Cl(a)
3s 3p 3d Cl(e)
Excited
State of P P Cl(e)

sp3 d Cl(e)
Cl(a)

Five sp3 d hybrid orbitals e = equitorial

a = areial

Examples of sp3d Hybridisation

PF5, PCl5, PBr5, AsF5, AsCl5, SbCl5, SbF5, SF4, SeF4, TeF4, PF4–, SbF4–, SCl4, SeCl4, TeCl4, ClF3, BrF3, IF3, BrCl3, ICl3, ICl2–
, IBr2–, ClF2–, IF2–, BrF2–, XeF2, I3–, Br3–,

(V) sp3d2 Hybridisation :

(
In this type of hybridisation one s orbital, three p-orbitals and two d-orbitals d z 2 & d x 2 − y2 ) belong to the same
shell of an atom mix together and form six hybrid orbitals. The angle between all hybrid orbitals will be 90°.
Formation of SF6 molecule :
3s 3p
F
Ground
State of S F F

3s 3p 3d
Excited S
State of S
F F
sp3 d 2
F

3 2
Six sp d hybrid orbitals

Examples of sp3d2 Hybridisation

SF6, AlF63–, PF6–, ICl5, XeOF4, ClF5, SF5–, XeF4, ICl4–

(VI) sp3d3 Hybridisation :

(
This type of hybridisation is formed when one s orbital, three p-orbitals and three d-orbitals d xy ,d z2 ,d x 2 − y2 )
belonging to the same shell of an atom mix together & form seven hybrid orbitals. These seven sp 3d3 orbitals
are arranged in pentagonal bipyramidal shape. Five bond angles are of 72° & two bond angles of 90°.
Example : Formation of IF7 molecule :

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5s 5p
Ground
State of I

F
5s 5p 5d F
Excited
State of I F

I F
sp d
3 3

F F
Seven sp 3d3 hybrid orbitals

Examples of sp3d3 Hybridisation

IF7, XeF6, XeF5–

Illustration 1
Explain the bonding in C2H2 and C2H4 molecules.
Solution:
Formation of C2H2 molecule :

2s 2p -Bond 2p y
Excited
State of C 2p y 2p z
2p z
H H
sp sp sp sp sp
1s  Bond 1s

Two sp hybrid Two Unhybridzed

orbitals p-orbital for  bond
formation
H H

H C  C H

Formation of C2H4 molecule :

H sp 2 sp 2 H H–C–H bond angle = 117.6°

 H–C–C bond angle = 121°
C C
 Bond length (C=C) = 134 pm
H H Bond length (C–H) = 108 pm

2s 2p
Excited 1s 1s
State of C

sp
2

Unhybridised p orbital 1s 1s
for  bond H-atom H-atom
formation

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2pz 2pz


H H H H
C C C C

H H H H

 
Formation of sigma and pi bonds in ethene
Illustration 2
Explain the bonding in SO2 molecules.
Solution:
Formation of SO2 molecule :

S
O O
3s 3p 3d
S
G. State
3s 3p 3d
In excited
state

2
sp hybridised Two unhybridised orbitals
3p 3d

Two  bonds in sulphur are formed by p -p & p− d overlapping with p-orbital of oxygen
Atomic orbitals involved in hybridisation.
s + px + py + pz + dxy + dyz + dzx + dx2 −y2 + dz2

sp : s + any p orbital
sp2 : s + any two p orbital
sp3 : s + all p orbital
sp3d : s + px + py + pz + dz2
sp3d2 : s + p x + p y + pz + d z 2 + d x 2 − y 2
sp3d3 : s + px + py + pz + dz2 + dx2 − y2 + dxy
Illustration 3
IF7
Solution:
sp3d3

s + p x + p y + dx2 − y2 + dxy + p z + dz2

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Illustration 4
IF5
Solution:
sp3d2

s + p x + p y + dx 2 − y 2 + p z + d z 2

Illustration 5
ClF3
Solution:
sp3d : s + px + py + pz + dz2

Illustration 6
CCl4
Solution:
sp3 : s + px + py + pz

Illustration 7
SO2 (in yz plane)
Solution:
sp2 : s + py + pz

Illustration 8
CO2 (in z - axis)
Solution:
sp : s + pz

Valence Shell Electron Pair Repulsion (VSEPR) theory :

(a) Molecules having covalent bond have definite geometry as covalent bonding has directional characteristics. A
simple theory was given for the molecular shape of the covalent molecules by Gillespie and Nyholm in 1957.
(b) This theory predicts the shape of the molecule by considering the most stable configuration of the bond angles
in the molecule. This theory states
(i) Electron pairs in the valence shell of the central atom of a molecule, whether bonding or lone pairs are
regarded as occupying localised orbitals. These orbitals arrange themselves in so as to minimize the mutual
electronic repulsions.
(ii) The magnitude of the different types of electronic repulsions follows the order given below:
lone pair-lone pair > lone pair - bond pair > bond pair - bond pair
(iii) The electronic repulsion between two pairs of electrons will be minimum if they are as far apart as possible.
(iii) The actual shape of the molecules containing lone pairs is a little distorted from the basic shape as in the NH3
and H2O molecules, the bond angles are not 109º28' but 107º and 104.5º respectively due to presence of
one lone pair in NH3 and two lone pairs in H2O.

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Shapes of molecules based on VSEPR theory

Total No. of No. of
Stereo
no. of b.p. unshared General Type of
chemical Shape Exam.
hybrid (bond pair i.e. formula hybridisation
formula/str.
orbitals pairs) lp
180°
2 2 0 AB2 sp B—A—B linear BeCl2

B 120° B
A BCl3, NO3–,
3 3 0 AB3 sp2 Trigonal planar
GaF3, CO3– –
B

A V or Bent
3 2 1 AB2 sp 2
or angular SnCl2, O3, SO2
B <120° B

B
A 109°28’ CH4, SiF4,
4 4 0 AB4 sp3 Tetrahedron +
B B N H4
B

A
4 3 1 AB3 sp3 Trigonal pyramidal NH3, CH 3−
B B
B <109°

A V or Bent or
4 2 2 AB2 sp3 H2O, SF2
angular
B <109° B
B bond
angle
4 1 3 AB sp 3 A N.A. Linear ClO–

B
90° B
A Trigonal PF5, SF5+,
5 5 0 AB5 sp d
3 B 120°
bipyramidal SbBr5, XeO3F2
B B
B
B
SF4
5 4 1 AB4 sp3d A <120° Seesaw
••

B B

B
<90°
ClF3, BrF3
5 3 2 AB3 sp3d B A T-shaped
B
B

5 2 3 AB2 sp3d A 180° Linear ICl2–, XeF2, I3–

B
B
B B Octahedral or
A 90°
6 6 0 AB6 sp d
3 2
Square SF6, IF6+
B B B
bipyramidal
All bond = 90°

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B B
B
A <90°
6 5 1 AB5 sp d
3 2
Square pyramidal IF5, XeOF4, BrF5
B B
All less than 90°

B B
6 4 2 AB4 sp d
3 2 A 90°
Square planar IF4–, XeF4, ICl4–
B B
B B
B 90° 72°
B Pentagonal
7 7 0 AB7 sp3d3 A IF7
bipyramidal
B B B

B B
7 5 2 AB5 sp d
3 3 72° A B Pentagonal Planar XeF5¯
B B

To identify planarity of molecule, first we predict hybridisation of molecule and draw its shape.
In planar structure all atoms are present in same plane and number of such planer are one.
While in non polar structure first visualise structure in 3d then carefully we check maximum atoms in plane and
number of such planes.

Example.
sf6 , CO32− , XeO3f2
Number of planer 3 (1) ( 4)

Bond Parameters
(A) Bond Angle
(B) Bond Length (Bond distance)
(C) Bond Energy

(A) Bond Angle

The angle between any two adjacent bonds is known as bond angle.
It is represented in degree (°), min (') and second (")

Factors affecting the bond angle -

Step I : Hybridisation or % 's' character : Bondangle  % scharacter

BeCl2 > BCl3 > CCl4

180° 120° 109°28'

Step II : Lone pair

When hybridisation is same, lone pair are different.
1
Bondangle 
No.of Ionepair

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•• ••
Example :- CH4 NH3 H2 O :
Hybridisation sp3 sp3 sp3
Bond angle 109°.28' > 107° > 104.5°
(No l.p.) (one l.p.) (two l.p.)
• In the different molecules if central atom have same number of lone pair of electron then bond angle will depend
on electronegativities of A & B.

Step III : Electronegativity

Bondangle  Electronegativity of centralatom

If side atoms are same and EN of central atom increases the bond angle increases.

..O.. .. ..
S

>
105°
92°
H H H H
more repulsion
less repulsion bp–bp
• Electronegativity of 'O' > Electronegativity of 'S'
• Bond angle of – NH3 > PH3 > AsH3
•• •• ••
Example :- NH P H3 A sH3
3
Bond angle 107° 93° 91°
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
- Electronegativity decreasing.
- Bond angle will decrease
Step IV : Side atom
1
Bondangle   sizeof sideatom
Electronegativity of bondedatom

In ABx type molecules, if central atoms are same and the EN of side atoms increases then bond angle
decreases.
..O..
..O.. .. ..
O

110° 110°
103°
Cl Cl Cl Cl F F

Electronegativity of Fluorine is greater than chlorine

PF3 < PCl3 < PBr3 < PI3 (EN of side atom decrease)

OF2 < Cl2O < Br2O

SF2 < SCl2 < SBr2

Bond angle depends on size of side atom, On increasing size of side atom bond angle increases.

Cl2O > H2O

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.. . . .. . . .. ..
O O O

110° 105° 110°

Cl Cl H H Cl Cl
When hybridisation is same, lone pair are same, Central atom is same, bonded atoms are different.
sp3 OF2 103 - 105° Electronegativity
sp3 Cl2O 109 - 111° of bonded atom is
sp3 Br2O 116 - 118° decreasing

(B) Bond Length

The average distance between the nucleus of two atoms is known as bond length, normally it is represented in
Å. eg. A ——— B
It depends mainly on electronegativities of constituent atoms.
Case -I. Electronegativity difference is zero then -
Bond length = rA + rB or dA–B = rA + rB
Where rA is covalent radius of A
rB is covalent radius of B
xA is electronegativity of A
xB is electronegativity of B
If rA = rB then Bond length = 2rA or 2rB

Example : - Cl – Cl
Case - II Electronegativity difference is not equal to zero then –
Bond length is given by Schomaker and Stevenson formula is - Bond length = rA + rB – 0.09 (xA – xB)
xA – xB = Difference in electronegativities
Factors Affecting Bond Length
(a)  electronegativity :-
1
Bond length α {While B.E.  EN)
ΔEN
H—F < H—Cl < H—Br < H—I

(b) Bond order or number of bonds :-

1
Bond length α
Number of bonds or bond order
ex. C—C, C = C, C  C
Bond length 1.54 Å 1.34 Å 1.20 Å ⎯⎯⎯
increa sin g
⎯
Bond energy 80 140 180-200 K.Cal. ⎯⎯⎯⎯
increa sin g
→
C—O C OC O
1.43 Å 1.20 Å 1.13 Å

—C—N C N— C N
1.47 Å 1.28 Å 1.15 Å
1
Bond length α
%scharacter

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(C) Bond Energy (BE)

Bond energy may be defined as –
(i) Bond formation energy :- Energy released when any bond is formed is known as bond formation energy
or bond energy.

(ii) Bond dissociation energy :- Energy required to dissociate any bond is known as Bond dissociation energy.
Calculation of released energy is more difficult than the dissociation energy therefore dissociation energy
of bond is calculated and is assumed as bond energy or bond formation energy.

• In diatomic molecule :
Bond energy = bond dissociation energy
Example : - N2 > O2 > H2 > F2
(N ≡ N) (O = O) (H − H) (F − F)

Factors Affecting The Bond Energy

(a)  Electronegativity (b) Bond order (c) Atomic size (d) Bond polarity
(e) Resonance (f) Hybridisation (g) Lone pair electron

(a)  Electronegativity :- Bond energy  EN

eg. HF > HCl > HBr > HI

(b) Bond order :- Bond energy  Bond order.

eg. C— C < C === C < CC
79 K. Cal, 143.3 K. Cal., 199.0 K. Cal.

1
(c) Atomic size :- Bond energy 
Atomic size
Example : CC < CN < NN

Exception :- In case of halogen group, order of bond energy is –

Cl — Cl > Br — Br > F — F > I — I

Because of higher electron density and small size of F atoms, repulsion between electrons of two F atoms,
weakens the bond energy.

Other example S – S > O – O

C – C > Si – Si > Ge – Ge

(d) Bond Polarity :- Bond energy  Bond polarity

Example : H — F > H — Cl > H — Br > H — I

(e) Resonance :- Bond energy increases due to resonance.

Example : In benzene bond energy of C — C increases due to  electrons of C = C.

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(f) Hybridisation :- Bond energy  s-character in hybrid orbitals.

Example : sp — sp > sp2— sp2 > sp3— sp3
% s character - 50 % 33.3 % 25 %

1
(g) Lone pair of electrons :- Bond energy 
lone pair of electrons
×× ×× ×× ×× ×× ××
N—N > —O—O— > × ×
—C— C— >
×× ×× ××F×—××F×

Size of F and O atoms are small so their bond energy should be high (small atomic radius) but it is actually less,
due to lone pair of electrons present on F and O atoms, which repells each other in F—F and —O—O–type of
bonds.

Important Note :
(i) Bond strength  overlapping (if orbitals are given)
1
(ii) Bond strength ∝
size of orbitals
e.g. 1s – 2p > 1s – 3p > 1s – 4p
(iii) If orbitals are of same shell
Bond strength  extent of overlapping  directional properties
2p – 2p (axial) > 2s – 2p (axial) > 2s – 2s (axial) > 2p – 2p (co-lateral)
(iv) -bond strength
2p – 2p > 2p – 3d > 2p – 3p > 3p – 3p
(v) O = O exist but S = S does not exist at room temperature.
(vi) N  N exist but P  P does not exist at room temperature.
(vii) O = C = O exist but O = Si = O does not exist.

Hybridisation of following species in specified state :

Species Cationic part Anionic part

PCl5 PCl4+ (sp3) PCl6– (sp3d2)

PBr5 PBr4+ (sp3) Br–
XeF6 XeF5+ (sp3d2) F–
N2O5 NO2+ (sp) NO3– (sp2)
I2Cl6 (liquid) ICl2+ (sp3) ICl4– (sp3d2)
Cl2O6 ClO2+ (sp )
2
ClO4– (sp3)

Bent's Rule
(i) A lone pair of electron prefers to occupy that hybrid orbitals which has greater percentage of s-character.
(ii) A more electronegative atom/group prefers to occupy that hybrid orbital which has smaller percentage of s-
character.
As s-orbital is more close to nucleus, the electron pair present in s-orbital will experience more attraction of the
nucleus, i.e. stability of the system increases, therefore, a lone pair prefers to occupy that hybrid orbital which
has greater percentage of s-character.
A more electronegative atom has tendency to attract the shared pair of electron towards itself, thus it will prefer
to overlap with that hybrid orbital which has less percentage of s-character (i.e. relatively more distant from
nucleus of central atom) because by doing so, it increases the stability of the system.

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Illustration 9
Compare C–C bond length in C2H6 and C2Cl6
Solution:
In C2H6 and C2Cl6 both carbon atom are sp3 hybrid and there is no lone pair of electron on central atom, but all the four
sp3 hybrid orbital around any of the carbon are non-equivalent.
In C2H6 molecule, to one of the C-atom three hydrogen atom (less electronegative) and one carbon atom (more
electronegative than H) is attached. According to Bent rule, more electronegative carbon will overlap with that hybrid
orbital has less character of s-character.
H Cl
s p  sp
sp C H sp C Cl
H Cl
sp C H sp C Cl
H Cl
H Cl
whereas in C2Cl6 molecule three Cl-atom (attached to any one of the carbon) will overlap with that hybrid orbital which
has less s-character and the other (fourth atom attached with one carbon) being less electronegative will overlap with
hybrid orbital which has more s-character. Due to more p-character in C–C bond, bond length in C2H6 is more than that
in C2Cl6. Hence.
C – C(C2H6) > C – C(C2Cl6)

Illustration 10
Draw the geometry of PCl3F2
Solution:
F Cl
Cl F
Cl P Cl P
Cl Cl
F F
Correct Wrong
Structure Structure
Because highly electronegative atom occupy axial position (axial position has smaller percentage of s-character).

Drago Generalisation
On the basis of experimental bond angles of certain molecules fulfilling the following three conditions,
(i) Belongs to third or lower period in periodic table
(ii) Contain atleast one lone pair of electron, and
(iii) Electronegativity of surrounding atom is  2.5
Drago generalised that in such molecules justification of experimental bond angle can be made satisfactory if one
considers no hybridisation, i.e., overlapping of almost pure atomic orbitals.
In such molecules bond angle is approximately 90°.

Group 15 Bond angle Group 16 Bond angle

NH3 107°48' H2O 104°28'
PH3 93°36' H2S 92°
AsH3 91°48' H2Se 91°
SbH3 91°18' H2Te 90.5°
• Right order of bond angle.
(a) H2O > H2S > H2Se > H2Te (b) NH3 > PH3 > AsH3 > SbH3

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Odd Electronic Species

(1) NO2
It is observed that the N–O bond length is in between single bond length and double bond length.
Structure of NO2 :
Free electron occupies the one sp2 hybrid orbital.

N N
+ +
O O O O

O O O O
when cooled to
N N –11°C N N

O O O O
Paramagnetic Diamagnetic
(unpaired electron) (no unpaired electron)
Brown colour gas white coloured solid
(2) ClO3
Bond angle = 119°
Hybridisation = sp3
Shape = pyramidal
Structure :
O O
sp3
readily
Cl 2ClO3 Cl2O6 Cl Cl
dimerises
O O O O
O O O

•
(3) C H3
Bond angle = 120°
Hybridisation = sp2
Shape = planer
Structure :

Free e– reside in p-orbital

H 2CH3 → C2H6

C H
H

•
(4) C F3
Bond angle = 109°28'
Hybridisation = sp3
Shape = pyramidal
Structure :

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free electron present in one sp3 hybrid orbital

C

F F
F
Since the fluorine is more electronegative element which increases the p character in its attached orbital and
finally accesses the sp3 hybridisation hence it is pyramidal in shape.

Molecules that do not exist :

(1) SF4, SF6, PF5 exist while. OF4, OF6, NF5 do not exist
Reason :- Due to the non availability of vacant 2d-orbital, N and O atom can’t expand their octet.
(2) (a) PI5(vap) & SCl6 do not exist
Reason :- Due to the steric crowding of the surrounding atoms.
(b) SCl6 does not exist while TeCl6 exist
Reason :- Size of Te > Size of S.
(c) PI5 (Solid) exist
Reason :-Steric crowding is avoided by the formation of ion pair like [PI4]+ [I–] (Steric crowding is avoided).
(3) SF6, PF5, XeF6, XeF4, XeF2 exist while SH6, PH5, XeH6, XeH4, XeH2 do not exist
Reason :- F is more electronegative and causes d-orbital contration by which the required hybridisation is
possible and H is less electronegative, can’t do so and the required hybridisation is not possible, hence above
compounds do not exist.

DIPOLE MOMENT : (Ionic Nature in Covalent Bond)

Due to difference in electronegativity a covalent bond acquires a partial polar character. The two charged ends of
the polar bond behave as electric dipoles and degree of polarity is expressed in term of dipole moment.
Dipole moment is defined as the product of the magnitude of charge on any one of the atoms and the distance
between them
µ=q×d
q = charge on any one of the atom which is in the order of 10 –10 esu or 10–19 coloumb and
d = distance between charged atoms is in the order of 10–8 cm.
10–18 esu cm = 1 debye (unit of dipole moment)
In S.I. system
1.6×10−19
1 esu = =3.33 × 10−10 C
4.8×10−10
1 cm = 10–2 m
1 D = 10–18 × 3.33 × 10–10 × 10–2 cm
1 D = 3.33 × 10–30 cm

Note :
1. Symmetrical molecule without lone pair of electrons has µ = 0. e.g. CO 2, BeF2, BF3, CCl4, etc.
2. Dipole moment is a vector quantity. Therefore individual dipole moments should be added vectorially to get
net dipole moment.
3. In a bond H–X, the hydrogen atom is the positive end of dipole where X is an atom more electronegative than H.
4. In a bond C–X, the carbon atom is the positive end of the dipole where X is an atom other than carbon. However,
in the C–H bonds of hydrocarbons, the value and directions of the dipole are not constant and depends upon
the state of hybridization of the carbon.

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Diatomic molecules will always have dipole moment if it is made of two different atom. Dipole moment further
increases with electronegativity differences.
5. The direction of dipole is towards negative centre. It is represented by an arrow pointing from positive centre
towards the negative centre
6. The resultant dipole moment depends upon magnitude of bond moments and the angles between the bonds
and given by parallelogram law as : ( )
7. Polyatomic molecules : A poly atomic molecules is made up of more than two atoms joined by polar covalent
bonds and their dipole moment will be the vector sum of dipole moment of different bond & lone pair which
depends on spatial orientation of bond.

µresultant = √µ12 + µ22 + 2µ1 µ2 cos θ

For example :
••
•• •• NF 3
NH3 PH3
F
3 H µ1
H
4 N F
N H P H µ2
4 4
2
µ3
F
1 H H
 =1.47D µ = 0.58D  =0.24D
(XI) Dipole moment of H2O is 1.85 D which is resultant  of two O–H bonds.
−
O

+ +
H H
Application of dipole moment :
(I) To determine polarity and geometry of molecule -
If  = 0 compound is non-polar and symmetrical
eg. CO2, BF3, CCl4, CH4. BeF2 etc.
If   0 compound will be polar and unsymmetrical.
H2O, SO2, NH3, Cl2O, CH3Cl, CHCl3 etc.

(II) To calculate % ionic character :-

Experimental value of µ
% Ionic character = ×100
Theoritical value of µ

Some important orders of diple moments-

1. (i) HF > H2O > NH3 > NF3
(ii) CH3Cl > CH3F > CH3Br > CH3I
(iii) HF > H2O > SO2 > NH3 > PH3 < PCI3
(iv) NO2– > NO2 > 𝑁𝑂2+
(v) CH3Cl > CH2 Cl2 > CHCl3 > CCl4
(vi) H2O > H2S
(vii) BF3 < NF3 < NH3
(viii) H2O < H2O2

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2. Inorganic substances:
(a) Monoatomic molecules such as He, Ne, etc., have zero dipole moment becaue they are symmetrical.
(b) Diatomic molecules such as H2, Cl2 and N2 have no dipole moment; so these molecules are symmetrical.
(c) Triatomic molecules some of these molecules possess zero dipole moment so they have a symmetrical linear
structure, Ex. CO2, CS2, HgCl2. Others like water and sulphur dioxide have definite dipole moments. They are
said to have angular or bent structures. (V-shaped)
O S

H H O O O=C=O S=C=S Cl – Hg – Cl
1.84 D 1.63 D 0D 0D 0D
(d) Tetratomic molecules some molecules like BCl3 have zero dipole moment. They are said to possess a flat
NO 3−
and symmetrical (triangular) structure; other example are BF3, BBr3, 𝐶𝑂32− , and
Cl

B µ=0

Cl Cl
(e) PCl3, AsCl3, NH3, PH3, AsH3, H3O have appreciable dipole moment. They possess trigonal pyramidal
+

structure.
••
P

Cl Cl Cl

3. Organic substances :
(a) Mathane and CCl4 have zero dipole moment. So thay posess symmetrical tetrahedral structures with C atom
at the centre of the tetrahedron.
H

C
H H
H
Methane
(b) Benzene has zero dipole moment. All the 6C and 6H atoms are assumed to be in the same plane
(symmetrical hexagonal structure).
H

H H

H H
H
(c) Measurement of dipole moments will enable us to detect cis-and trans isomers of organic compounds (you
will learn about cis-trans or geometrical isomerism later in the organic chemistry).
The trans-isomer, which is symmetrical, has zero dipole moment while the cis-isomer has a definite dipole
moment.

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H Br
H H
C C
C C
Br H
Br Br
cis-dibromoethylene (µ = 1.4D) trans-dibromoethylene (µ = 0)
(d) The dipole moments of the aromatic compounds present a very good illustration of dipole moment. We
know that when substituted benzene is treated with reagent different products (namely ortho, meta and
para products) are formed. The dipole moments of these products are different since the orientation of the
groups is different. Let us take an example to clarify it. Let us take three isomers. o-nitrophenol, m-
nitrophenol and p-nitrophenol. We also have three other isomers, o-aminophenol, m-aminophenol and p-
aminophenol. We want to arrange these isomers in the order of their dipole moments.
X X X
Y

Y
Ortho Meta Para
In those cases where X = Y, the para isomer becomes symmetrical and have zero dipole moment. In order
to find their dipole moment, we need to know about the nature of the groups linked to the benzene ring.
In nitro phenols, one group (OH) is electron pushing and the other (NO2) is electron withdrawing while in
aminophenols, both the groups (OH and NH2) attached are electron pushing. So, depending on the nature
of the groups attached, the isomers have different dipole moment.

Hydrogen Bonding
Definition
(a) It is an electrostatic attractive force between covalently bonded hydrogen atom of one molecule and an
electronegative atom (F, O, N & sp hybrid carbon)
(b) It is not formed in ionic compounds.
(c) H–bond forms in polar covalent compounds, (not in non-polar).
(d) It is very weak bond but stronger than vander waal's force.
(e) It is also known as dipole-dipole attraction.
H+ — F− H+ — F− ............ H+ — F−

Main condition for H–bonding

(a) H should be covalently bonded with high electro –ve element like F, O, N.
(b) Atomic size of electro –ve element should be small.
Decreasing order of atomic size is -
N > O > F
Decreasing order of electronegativity is -
F > O > N
(4.0) (3.5) (3.0)
1
(c) Strength of H–bond  Electronegativity of Z (element) α
atomic size of Z
(d) Hydrogen bonding occurs in HCN, due to (–C  N) triple bond (sp hybridisation), electronegativities of carbon
and nitrogen increases.

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H — C  N ............. H — C  N .......... H — C  N
TYPES OF HYDROGEN BONDING

Inter molecular Intra molecular

Homo inter molecular Hetro inter molecular

Intermolecular H–Bond
H–bond formation between two or more molecules of either the same or different compounds known as Inter
molecular H-bonding.

More association takes place in intermolecular H-bonding that’s why having more strength.
These are of two types :-
(i) Homo intermolecular :- H–bond between molecules of same compounds

O
H H
O O
eg. H H H H
O F
H H H H H H
F F
Extent of H-bonding is more because Strength of H-bonding is more in HF molecule
one molecule of H2O attached due the high electron negativity of flourine as
with 4 H2O molecule compare to oxygen

(ii) Hetro intermolecular :- H–bond between molecules of different compounds

O—H O—H O—H O—H

R H R H
Eg. between alcohol and water alcohol Water alcohol alcohol
Intramolecular H–bond
It takes place within the molecule.
(a) H–bonded with electronegative element of a functional group, form H–bond with another electronegative
element present on nearest position on the same molecule.
(b) This type of H–bond is mostly occurred in organic compounds.
(c) It results in ring formation (Chelation).
(d) Less association in comparison to inter molecular H-bond, so it will have less strength.
O H Cl H
H O
C O
eg. O Cl C C H
O H
N O
H Cl
O O F H
O–nitrophenol Salicylaldehyde O–fluorophenol Chloral hydrate

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Effect of H–bond on Physical Properties

(A) Solubility
• Inter molecular H–bonding
(i) Few organic compounds (Non-polar) are soluble in water (Polar solvent) due to H–bonding.
O—H O—H

R H
Other examples - Glucose, Fructose etc. dissolve in water.
(ii) Ketone, ether, alkane etc. are insoluble (no H–bond). Dimethyl ether is soluble in water while diethyl ether
is partially soluble, due to bulky ethyl groups H–bonding interrupts.
(iii) Solubility order-CH3OCH3 < CH3OH
O—H O C —H O— H

C
C
O— H O H
H O
p–hydroxy benzaldehyde.
It can form H–bond with water molecule so it can dissolve.

• Intra molecular H–bonding

H O
C H
O

(i) It decreases solubility as it form chelate by H–bonding, so H– is not free for other molecule.
(ii) It can not form H–bond with water molecule so it can not dissolve.

(B) Viscosity
Viscosity  extent of H-bonding  – OH groups
H–bond associates molecules together so viscosity increases.
C H — OH
C H2OH
C H — OH
eg. CH3OH < C H2OH < C H — OH
(Glycol) (Glycerol)

eg. H2O > CH3OH > CH3—O—CH3

water alcohol ether
eg. H3PO4 > H2SO4 > HNO3

(B) Surface Tension

Surface tension of a liquid  extent of H-bonding.

(C) Melting point and boiling point

(i) Due to intermolecular H–bond M.P. & B.P. of compounds increases.
H2O > CH3OH > CH3 — O — CH3

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(ii) Boiling points of VIA, VIIA hydrides are as shown below :

(Group 16 hydrides) H2O > TeH2 > SeH2 > H2S
(Group 17 hydrides) HF > HI > HBr > HCl
(iii) Sudden increase in boiling point of NH3, H2O and HF is due to H–bonding.
(iii) Intramolecular H–bonding gives rise to ring formation, so the force of attraction among these molecules
are vander waal force. So M.P. and B.P. are low.
so, o-derivative < p-derivative

1
(E) Volatility : Volatility 
H−bonding strength
Intramolecular H-bonding > Intermolecular H-bonding

(F) Molecular weight

Molecular wt. of CH3COOH is double of its molecular formula, due to dimer formation occur by
H–bonding.
O H— O
R —C C—R
O—H O

(G) Physical states

H2O is liquid while H2S is gas.
Water and Ice :- Both have H–bonding even then density of ice is less than water.

O
H H
O O
H H H H
O
H H

Volume of ice is more because of open cage like crystal structure, form by association of water molecules with
the help of H-bond.
H2O becomes solid due to four hydrogen bond among water molecule are formed in tetrahedral manner.

VANDER WAAL’S FORCES

(a) These are the weakest type of inter molecular forces that exist among the molecules which being significant
change in physical properties.
(b) These are non-directional, non-valence cohesive forces. These attractive forces being played between the two
molecules are independent of the presence of other molecules.
(c) Solid, liquid or gaseous states of many molecules are explained on the basis of inter molecular forces other than
covalent, ionic or metallic bonds. Although inert gases do not form any type of bond but may exist in liquid and
solid states. This shows that the atoms of inert gases are attracted by each other through some type of inter
molecular forces. These intermolecular forces are called Vander Walls forces and may be of the following
types:

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(1) Dipole-dipole attraction :

The force of attraction between the oppositely charged poles of two polar molecules (for example : H 2O, H–F,
NH3 etc.) is called dipole-dipole attraction. This type of attraction is weaker than the ion-dipole attraction.
–
O
+ – + +
H–Cl H H

O – O

+ +
H H H H

(2) Dipole-induced dipole attraction :

This type of cohesive forces occurs in a mixture of polar and non polar molecules. The former induce polarity in
non polar molecules by disturbing their electron system. for example force of attraction between Cl 2 and H2O.
+
O
–
H
–
O
 +
 +

H H +
+ Cl – Cl → H
+ −
........ Cl– Cl induced dipole

(3) Instantaneous dipole-Induced dipole :

The weak intermolecular forces operating in similar non polar gaseous molecules are called London forces.
These forces are very weak in nature and exists only at low temperature. For example weak intermolecular forces
in F2, Cl2, N2, molecules and in nobal gasses.

+ +

– –
+ +

Note : Other weak interactions

(1) Ion-dipole attraction :
Polar molecules are atracted by ions. The negative pole is attracted by cation and positive pole attracted by the
anion. This type of attraction is called ion dipole attraction, ion-dipole attraction is observed generally in the
process of solvation when sodium chloride (Na+ Cl–) is dissolved in water because negative poles of water
aggregate around Na+ ions and positive poles around Cl– ions.
+
 – H
Na+ ····· O
+
H
(2) Ion-induced dipole attraction :
When non polar molecules come in contact with ions, its electron cloud gets polarised and the oppositely
charged end of it is attracted by the ion. For example attraction between Na + and Cl2 molecule.
 – +
Na+ + Cl – Cl → Na+ ........ Cl – Cl

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Factory affecting London dispersion force.

1. Size of Molecule
2. Polarisable Electrons
3. Molecular Mass

Energy distance relationship for the different types of interaction

1
• Ionic Interaction E 
r
1
• Ion dipole interaction E 
r2
1
• Dipole – Dipole interaction E  (for stationary polar molecule)
r3
1
• Ion – induced dipole interaction E 
r4
1
• Dipole – induced dipole interaction E 
r6
1
• Instantaneous dipole – induced dipole interaction E 
r6
MOLECULAR ORBITAL THEORY (MOT)
The molecular orbital theory was developed by F. Hund and R.S. Mulliken in 1932. The salient features are:
(i) Just as electrons of any atom are present in various atomic orbitals, electrons of the molecule are present in
various molecular orbitals.
(ii) Molecular orbitals are formed by the combination of atomic orbitals of comparable energies and proper
symmetry.
(iii) An electron in an atomic orbital is influenced by one nucleus, while in a molecular orbital it is influenced by two
or more nuclei depending upon the number of the atoms in the molecule. Thus an atomic orbital is
monocentric while a molecular orbital is polycentric.
(iv) The number of molecular orbitals formed is equal to the number of combining atomic orbitals. When two atomic
orbitals combine, two molecular orbitals called bonding molecular orbital and anti-bonding molecular
orbital are formed.
(v) The bonding molecular orbital has lower energy and hence greater stability than the corresponding antibonding
molecular orbital.
(vi) Just as the electron probability distribution around a nucleus in an atom is given by an atomic orbital , the
electron probability distribution around a group of nuclei in a molecule is given by molecular orbital.
(vii) The molecular orbitals like the atomic orbitals are filled in accordance with the Aufbau principle obeying the
Pauli Exclusion principle and the Hund’s Rule of Maximum Multiplicity.

Formation of Molecular Orbitals : Linear Combination of Atomic Orbitals(LCAO)

According to wave mechanics, the atomic orbitals can be expressed by wave function (), which represent the
amplitude of the electron waves. These are obtained from the solution of Shrodinger wave equation.
According to LCAO, the wave function () of individual atomic orbital linearly combined and form molecular
orbitals i.e. during the formation of AB molecule  of A and B will linearly combine as MO = A ± B
Case I : When two waves are in same phase (constructive interference) the wave adds up and amplitude of new
wave is the sum of wave functions of individual atomic orbitals.
MO = A + B (Bonding M.O.)
Case II : When two waves are out of phase, the waves are substracted from each other so that the amplitude of
new wave is :
*MO = A – B (Antibonding M.O.)

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Conditions for the combination of atomic orbitals

The linear combination of atomic orbitals to form molecular orbitals takes place only if the following conditions
are satisfied :
1. The combining atomic orbitals must have the same or nearly the same energy.
It may be noted that in the homonuclear diatomic molecules of the type A 2 (e.g. H2, O2, N2, F2 ect.), the
participating atomic orbitals must have comparable energies. This means that 1s atomic orbital of one atom can
combine with 1s atomic orbital of the other atom and not with its 2s orbital. However, in heteronuclear molecules
AB(e.g. HF, HCl etc.) such a combination is permissible

2. The combining atomic orbitals must have the same symmetry about the molecular axis. By convention z-
axis is taken as the molecular axis. It is important to note that atomic orbitals having same or nearly the same
energy will not combine if they do not have the same symmetry. For example, 2pz orbital of one atom can
combine with 2pz orbital of the other atom but not with the 2px or 2py orbitals because of their different
symmetries.

2s 2pz
2s
2py

Possible Net overlap = 0

3. The combining atomic orbitals must overlap to the maximum extent. Greater the extent of overlap, the
greater will be the electron probability density between the nuclei of a molecular orbital.

TYPES OF MOLECULAR ORBITALS

Molecular orbitals of diatomic molecules are designated as (sigma), (pie), (delta) etc.
In this nomenclature, the sigma () molecular orbitals are symmetrical around the inter molecular axis
(assume to be z-axis) while pi () molecular orbitals are not symmetrical.

(1) s-s combination of orbitals

Molecular Nodal plane
orbitals
Atomic Atomic
orbital orbital
* 1s 1s 1s*
1s
Energy

Antibonding sigma
molecular orbital
1s 1s

1s 1s 1s
1s
Bonding sigma
molecular orbital
p-p combination of orbitals(end to end overlap)

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Molecular
orbitals Nodal plane

Atomic Atomic – + – + – – + – +
orbital orbital
2p* 2pz 2pz 2p
*z
Energy

z
Antibonding sigma
molecular orbital
2p z 2p z
– + + + – +
2p z 2p z
2pz
2pz Bonding sigma
molecular orbital
(3) p-p combination of orbitals (side by side overlap)
Molecular Nodal plane
orbitals
Atomic
Atomic
orbital
orbital
2p
* 2p
x 2p x 2p x *x
Energy

Antibonding pi
molecular orbital
2p x 2p x
Nodal
plane
2p 2px
x 2p x 2p x
Bonding pi
molecular orbital
(4) s-p combination of orbitals
Molecular Nodal plane
orbitals
Atomic Atomic
+ – + – + – +
orbital orbital
2sp
*
*z
2sp z
Antibonding sigma
Energy

molecular orbital
2pz
2s
+ + + – + –

2spz
2spz Bonding sigma
molecular orbital
Note-1 :

The molecular orbital wave functions are designated as (g) & (u) ; ‘g’ stands for gerade (even) and ‘u’ for

ungerade (odd). ‘g’ & ‘u’ refers to symmetry of the orbital about its centre. For determining symmetry of the

MO is to rotate the orbital about the line joining the two nuclei and then about a line perpendicular to this. If

the sign of the lobes remains the same, the orbital is gerade & if the sign changes, the orbital is ungerade.

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 s bonding *s bonding  p bonding  * p bonding

 (g)  (u)  (g)  (u)

Nodal plane

 (u)
 (u)

Note-2 : -type of molecular orbitals are obtained by involvement of d-orbitals into bonding.

Energy level diagram from MOs

Molecular orbital energy diagram for up to N 2 (molecule having  14 electrons)
1s < *1s < 2s < *2s < 2px = 2py < 2pz < *2px = *2py < *2pz

Molecular orbital energy diagram for O2 and F2 (molecule having > 14 electrons)
1s < *1s < 2s < *2s < 2pz < 2px = 2py < *2px = *2py < *2pz
    = antibonding molecular orbital
  = bonding molecular orbital
Note : 1s and 1s* molecular orbitals are collectively represented as KK. KK refers to closed K-shell structure.

B B2 B B B2 B
atom molecule atom atom molecule atom

*2p *2p

*2p *2p
2p 2p *2p *2p
2p 2p
2p 2p 2p

2p 2p 2p

E E
*2s
*2s
2s 2s
2s 2s

2s
2s The correct MO energy-level diagram for the B2 molecule.
The expected MO energy-level diagram When p-s mixing is allowed, the energies of the 2p and
for the B2 molecule. According to which 2p orbitals are reversed. Therefore, this diagram
B2 is diamagnetic explains the observed paramagnetism of B2

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sp-mixing :
Rules of Filling up of Molecular Orbital with Electrons :
(1) The molecular orbital with lower energy will be filled first. (Aufbau Principle)
(2) The molecular orbital can accommodate maximum only two electrons. (Pauli's exclusion principle)
(3) If the two MOs have same energy then molecular orbital will first get singly filled and after that pairing will start.
(Hunds Rule)

ELECTRONIC CONFIGURATION AND MOLECULAR BEHAVIOUR

The distribution of electrons among various molecular orbitals is called the electronic configuration of the
molecule. From the electronic configuration of the molecule, it is possible to get important information about
the molecule as discussed below.
(i) The molecule is stable if Nb is greater than Na, and
(ii) The molecule is unstable if Nb is less than Na
In (i) more bonding orbitals are occupied and so the bonding influence is stronger and a stable molecule results.
In (ii) the antibonding influence is stronger and therefore the molecule is unstable.
Where :- Nb is number of electrons in bonding molecular orbitals and Na is number of electrons in antibonding
molecular orbitals.

Bond order

Bond order (B.O.) is defined as follows Bond order (B.O.) = (Nb – Na)
2
A positive bond order (i.e., Nb > Na) means a stable molecule while a negative value (i.e., Nb < Na) (i.e., Nb = Na)
bond order means an unstable molecule. If bond order zero then molecular does not exist.

NATURE OF THE BOND

Integral bond order values of 1, 2 or 3 correspond to single, double or triple bonds respectively.

BOND-LENGTH
The bond order between two atoms in a molecule may be taken as an approximate measure of the bond length.
The bond length decreases as bond order increases.

MAGNETIC NATURE
If one or more molecular orbitals are singly occupied it is paramagnetic (attracted by magnetic field), e.g., O 2
molecule. Otherwise diamagnetic (eg : N 2)

MOLECULAR ORBITAL DIAGRAM IN SOME HOMONUCLEAR DIATOMIC SPECIES

Species MO Configuration Nb Na B.O Magnetic

behaviour
H2 (1s)2
2 0 1 Diamagnetic
He2 (1s)2
(1s)
2
2 2 0 _________
Li2 (1s)2
(1s) (2s)
2 2
4 2 1 Diamagnetic
Be2 (1s)2
(1s) (2s) (2s)
2 2 2
4 4 0 _________
B2 (1s)2 (1s)2 (2s)2(2s)2 (2px = 2py) 6 4 1 Paramagnetic
C2 (1s)2
(1s) (2s) (2s) (
2 2 2 
2px = 
2py) 8 4 2 Diamagnetic

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N2 (1s)2 (1s)2 (2s)2(2s)2 (2px = 2py) 22pz 10 4 3 Diamagnetic

N2+ (1s)2
(1s) (2s) (2s)
2 2 2
(2px = 
2py)  1
2pz 9 4 2.5 Paramagnetic
N2– (1s)2
(1s) (2s) (2s) (
2 2 2 
2px = 
2py)  2pz  2px
2 *1
10 5 2.5 Paramagnetic
O2 (1s)2
(1s) (2s) (2s)
2 2 2
22pz (2px = 
2py) 10 6 2 Paramagnetic
(*12px = *12py)
O2+ (1s)2 (1s)2 (2s)2(2s)2 22pz (2px = 2py) *12px 10 5 2.5 Paramagnetic
O22+ (1s)2
(1s) (2s) (2s)
2 2 2
22pz (2px = 
2py) 10 4 3 Diamagnetic
O2– (1s)2
(1s) (2s) (2s)
2 2 2
22pz (2px = 
2py) 10 7 1.5 Paramagnetic
(*22px = *12py)
O22– (1s)2 (1s)2 (2s)2(2s)2 22pz (2px = 2py) 10 8 1 Diamagnetic
(*22px = *22py)
F2 (1s)2 (1s)2 (2s)2(2s)2 22pz (2px = 2py) 10 8 1 Diamagnetic
(*22px = *22py)
Ne2 (1s)2 (1s)2 (2s)2(2s)2 22pz (2px = 2py) 10 10 0 _________
(*22px = *22py) *22pz

Halogens (f2, Cl2, Br2 and I2) are coloured Reason behind their Colour is HOMO – LUMO transition on moving
down the group energy gap between homo-LUMO decreases that's why different halogens shown different
colour.
F2 – yellow
Cl2 – Greenish yellow
Br2 – Reddish brown
I2 – Violet
Ionisation energy of molecule and atom can also be compared by their M.O. diagrams.
To compare ionisation energy, we compare energy level of HOMO and Atomic orbital of atom. If HOMO
having high energy as compere to Atomic orbital then remolsl of electron is easy.

Hydration Energy
It is the energy released when 1 mol of gaseous ions are hydrated in water. It is directly proportional to nuclear
charge and inversely proportional to size. It always decreases down the group.
(a) As the charge density of ion increases hydrated size (or aqueous radius) increases.
Size : Li+(aq) > Na+(aq) > K+(aq) > Rb+(aq) > Cs+(aq)

(b) As the hydrated size of ion increases ionic mobility decreases, which thus, decreases conductivity of ions.
Mobility : Li+(aq) < Na+(aq) < K+(aq) < Rb+(aq) < Cs+(aq)

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Conductivity : Li+(aq) < Na+(aq) < K+(aq) < Rb+(aq) < Cs+(aq)
(c) Hydration energy also affects the solubility of ionic compounds. If hydration energy is greater than lattice
energy then ionic compound will be soluble in water. More is the hydration energy, greater is the solubility,
whereas, if lattice energy decreases, solubility of ionic compound increases.

Fajan rule
Just as all the covalent bonds have some partial ionic character, the ionic bonds also have partial covalent
character. The partial covalent character of ionic bonds was discussed by Fajan in terms of the following
rules :
• The smaller the size of the cation and the larger the size of the anion, the greater the covalent character of an
ionic bond.
• The greater the charge on the cation, the greater the covalent character of the ionic bond.
• For cations of the same size and charge, the one, with electronic configuration (n-1)dxns0, typical of transition
metals, is more polarising than the one with a noble gas configuration, ns 2 np6, typical of alkali and alkaline earth
metal cations.
• The cation polarises the anion, pulling the electronic charge toward itself and thereby increasing the electronic
charge between the two. This is precisely what happens in a covalent bond, i.e., buildup of electron charge
density between the nuclei. The polarising power of the cation, the polarisability of the anion and the extent of
distortion (polarisation) of anion are the factors, which determine the per cent covalent character of the ionic
bond.
 Polarisation power of a cation is usually called ionic potential or charge density.
Chargeon cation
Ionic potential  (phi) =
Size of cation
• Polarisation Power :
The ability of cation to polarise a nearby anion is called polarisation power of cation.
• Polarizability :
(I) It is the ability of anion to get polarised by the cation.
(II) Polarisation of anion causes some sharing of electron between the ions so ionic bond acquires certain covalent
character.
(III) Increase in polarisation increases covalent character.
(IV) Magnitude of polarisation depends upon a number of factors, suggested by Fajan and are known as Fajan’s rule.

Fajan’s rule : (Factors Affecting Polarisation) :

(a) Size of cation :
Polarisation of the anion increases as the size of cation decreases.
In a group –
BeCl2
MgCl2 - Size of cation increases
CaCl2 - Covalent character decreases
SrCl2 - Ionic character increases
BaCl2
Greatest polarising power of Be2+, shows its maximum covalent character.
In a period –
Na+, Mg+2, Al+3, Si+4

- Size of cation decreases

- Covalent charater increases

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(b) Size of anion :

If the size of the anion increases for a given cation, then covalent character increases.
CaF2
CaCl2 - Size of anion increases
CaBr2 - Covalent character increases
CaI2 - Ionic character decreases

(c) Charge on cation and anion :

Polarisation increases with increase in charge on cation and anion.
(I) Charge on cation and anion  Polarisation (covalent character)
eg. NaCl MgCl2 AlCl3 SiCl4
Na +
Mg 2+
Al3+
Si4+

- Charge on cation increases

- Covalent character increases
- Ionic character decreases

(c) Electronic configuration of cation :

Polarisation capacity of cation having pseudo inert gas configuration is high.
CuCl (M.P. 442°C) –→ Cu+ 2, 8, 18 (Covalent)
NaCl (M.P. 800°C) –→ Na +
2, 8 (Ionic)
Cu and Na both the cation (Pseudo-inert & inert) have same charge but polarising power of Cu+ is more than
+ +

Na+ because –
Zeff of ns2p6 (inert) < Zeff. of ns2p6d10 (pseudo-inert)
Na+ < Cu+
(Ionic) (Covalent)
So, CuCl has more covalent character than NaCl.

Increased polarisation
Increased polarisation is responsible for the following changes in the properties of the compounds :
(I) Melting point : The increase of the covalent character is reflected in decreasing melting point of the compounds
as illustrated in the following tables. However, other factors may also contribute to the melting point

(II) Solubility in polar solvents : As the covalent character increases, solubility in polar solvents decreases. Thus
AgI is much less soluble in water than AgF (or AgCl, or AgBr). Lattice energy consideration alone cannot explain
this. Here the solubility decreases from fluoride to iodide due to increasing polarisation of the anion and hence
increasing covalent character. The same explanation fits the series HgF 2 > HgCl2 > HgBr2 > HgI2 (Solublity in
polar solvent).

(III) Electrical conductance in fused state and tendency to ionise in solution : As covalent character increases
conductivity in fused state decreases.
Compound Electrical conductance in Compound Electrical conductance in
fused state (ohm cm ) fused state (ohm cm )
–1 2 –1 2

LiCl 166 NaCl 133

BeCl2 0.086 MgCl2 29

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(IV) Intensification of colour : Polarised anions seem to be responsible for colour in some compounds. As
polarisation increases from chloride to iodide, the colour of many metal halides are intensified, as for example :
Colourless HgCl2 AgCl SnCl 4 PbCl2
Coloured HgI2 AgI SnI4 PbI 2
red yellow red Dark yellow

Note : Important thermal stability trends

It is the strength of a compound at high temperatures i.e. a molecule with more thermal stability has more
resistance to decomposition at high temperatures.
(1) For compounds having monoatomic anions, thermal stability is decided by the inter-ionic distance. As the inter
ionic distance increases lattice energy decreases so thermal stability decreases and its vice versa.
Ex. (a) Li3N > Na3N > K3N
(b) Li2O > Na2O > K2O > Rb2O > Cs2O
(c) LiX > NaX > KX > RbX > CsX (where X = F, Cl, Br, I)
(d) BeX2 > MgX2 > CaX2 > SrX2 > BaX2 (where X = F, Cl, Br, I)
(e) Be3N2 > Mg3N2 > Ca3N2 > Sr3N2 > Ba3N2
(f) BeO > MgO > CaO > SrO > BaO

(2) For the ionic compounds having polyatomic anions, Thermal stability depends on packing of the cations and
anions. Larger anions are more stable with larger cations. hence for these anions, thermal stability increases
down the group. For example
Ex. (a) LiClO3 < NaClO3 < KClO3 < RbClO3 < CsClO3
(b) LiNO3 < NaNO3 < KNO3 < RbNO3 < CsNO3
(c) LiOH < NaOH < KOH < RbOH < CsOH
(d) Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
(e) Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2
(f) Super oxides, peroxides and ozonides of alkali & alkaline earth metals also have the same order.

(e) Solubility :
Ionic compounds are more soluble in polar solvents and less soluble in non polar solvents.
M X(s) M+(aq) + X–(aq)  G° < O

+U
+–
M (g), X(g) – H hydration  G° =  H° – TS°
For the solubility of ionic compounds in water, it is necessary that G° must be negative.
Favourable conditions for solubility of ionic compound in water is
Hhydration > HLattice-energy
1 1 1
LE ∝ + - , HE ∝ + + -
r +r r r
If lattice energy decreases, solubility increases
If hydration energy decreases, solubility decreases

Note : Solubuility of ionic compounds in water mainly depends upon hydration energy & lattice energy.
Note : Some important solubility trends of ionic compounds.

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(1) In Sulphates of alkaline earth metals solubility decreases down the group

BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4

(2) In Chlorides of alkaline earth metals solubility decreases down the group

BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2

(3) In Hydroxides of alkali metals solubility increases down the group

LiOH < NaOH < KOH < RbOH < CsOH

(4) In Hydroxides of alkaline earth metals solubility increases down the group

Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2

(5) In carbonates of alkali metals solubility increases down the group

Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3

(6) In HCO3– of alkaline earth metals solubility increases down the group

Be(HCO3)2 < Mg(HCO3)2 < Ca(HCO3)2 < Sr(HCO3)2 < Ba(HCO3)2

(7) In F– of alkali metals solubility increases down the group

LiF < NaF < KF < RbF < CsF

(8) In Oxides of alkaline earth metals solubility increases down the group.

BeO < MgO < CaO < SrO < BaO

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