CHEMICAL BONDING

KEY CONCEPTS
(b) So the remaining elements also try to
1. Chemical Bond
acquire the same by loosing, gaining or
sharing of electrons.
The force of attraction which hold various
constuents (atom, ions etc) together in different (c) Lewis octet rule : The tendency of atoms
chemical species is called a chemical bond. to achieve eight electrons in their
outermost shell is known as Lewis octet
2. Valency rule.

Valency of an element is defined as the number of (d) Exception of Octet Law : PCl5, SF6, IF5,
chemical bonds formed by an element. IF7, ClO2, BF3, AlCl3, GaCl3, BeCl2.

(ii) Tendency to acquire minimum energy.

3. Causes of Chemical bond
4. Types of chemical bond
(i) Tendency to acquire noble gas configuration :
(a) Noble gases do not react with other On the basis of electronic valency theory and
elements due to most stable configuration structure, chemical bonds can be classified as
(8 electrons in outer most shell). follows.

Chemical Bond

Formed by transfer Other type of Typical bonds

or sharing of electrons bonds or forces
Odd electron bond
Metallic bond
Ionic bond Covalent Co-ordinate
bond bond H-bond
(i) intramolecular Banana bond
(ii) intermolecular
Back bond
Vander waals
(i) London forces
(ii) Dipole-dipole forces
(iii) dipole-induced dipole
forces

Ion-dipole forces

Ion-induced dipole forces

5. Electrovalent bond The energy changes involved in the

formation of ionic compounds from their
(a) Condition necessary for formation of constituent elements can be studied with
ionic crystal : the help of a thermochemical cycle called
[EA + Lattice Energy] > [Sublimation Energy as Born-Haber cycle.
e.g.: Formation of 1 mole of NaCl from sodium
+ IP + (Bond dissociation E/2)] and chlorine
(b) Born Haber cycle :
 Na (s) + 1/2 Cl2(g) 8. Valence bond theory (A modern
H1
S.E. 1/2 D.E. Approach for Covalent bond)
Na(g) Cl(g) NaCl (crystal) (i) Main points of this theory are :
I.E. – e –
–I.E. + e –
U (a) For a covalent bond to form, two atoms must
come closer to each other so that orbitals of one
Na+(g) + Cl– (g) overlaps with the other.
Hf = S.E + 1/2 D.E + I.E – E.A – U (b) Overlapping orbitals must have
If Hf value is more negative, more stable is (i) half filled nature i.e. must have unpaired
the formed product. electron
(c) Condition necessary for solubility : (ii) electrons with opposite spin.
Solvation Energy > Lattice Energy
(ii) Types of overlapping :
(d) Variable electrovalency :
Depending upon the type of overlapping, the
(i) Unstability of core
covalent bonds may be divided into two types.
e.g. : Iron exists as Fe2+, Fe3+ ; copper exists as
Cu+, Cu2+. (A) Sigma () bond -
(ii) Inert pair effect : (a) This type of covalent bond is formed by the end
Some of the heavier representative to end overlapping of bonding orbitals along
elements of third, fourth, fifth and sixth the internuclear axis.
groups having configuration of outermost (b) The overlap is known as head on overlap or
shell ns2 np1, ns2 np2 , ns2 np3 and ns2 np4 axial overlap.
show valencies with a difference of 2, i.e.,
(1, 3), (2, 4), (3, 5) and (4, 6) respectively. Examples :
(I) s-s overlapping :
6. Covalent bond
A covalent bond is defined as the bond formed by + 
mutual sharing of electrons between the combining s-orbital s-orbital
atoms (which are short of electrons) of comparable
(II) s-p overlapping :
electronegativity.
e.g.: + 
•• •• •• ••
••F •
••
+ •F••
••
 •• F • • F••
•• ••
1s-orbital 2-p orbital s-p overlapping
(III) p-p overlapping :
F– F F2 – – 
+ + + +
7. Coordinate covalent bond (dative bond) 2pz orbitals 2pz orbitals p-pcoaxial
(i) The bond in which both electrons for sharing are of F atom of F atom overlapping in F2
is contributed by only one atom but shared by molecule or
both atoms is called coordinate covalent bond. (c) If two atoms are bonded with a single bond, it
(ii) To form this bond, one of the atom should have is always  bond only.
a pair of electrons extra while the other atom
(B) Pi () bond -
consists of a vacant orbital to receive these
electrons. (a) This type of covalent bond is formed by the
(iii) The atom which donates the electrons is called side wise (or lateral) overlapping of half filled
as donor while the other which accepts the atomic orbitals of bonding atoms.
electron pair is know as acceptor. (b) The orbitals involved in overlap must be
(iv) This bond is usually represented by an arrow parallel to each other and are perpendicular to
() pointing from donor to the acceptor atom. the internuclear axis.
e.g.: NH3  H+ ; H2O  H+ Example :

41
 + + ++  Inter (iii) Hybridization :
+   nuclear Hybridization is defined as the intermixing of
– – ––  axis
dissimilar orbitals of the same atom which are
having slightly different energies to form same
p-orbital p-orbital p-p overlapping for 
bonding. number of new orbitals of equal energies and
identical shapes.

(iv) Hybridisation and shape (geometry) of molecule :

No. of bond No. of lone Total
Types of Hybridiz
pair of pair of number of Geometry Examples
molecule ation
electrons electrons electron pair
AB2 2 0 2 sp Linear BeF2 Ag[(NH3)2]+
AB3 3 0 3 sp2 Trigonal planar BCl3, BH3
AB4 4 0 4 dsp2 Square pyramidal Ni[(CN)4]2–
AB4 4 0 4 sp3 Tetrahedral CH4, NH4+
AB5 5 0 5 sp3d Trigonal bipyramidal PF5
AB6 6 0 6 sp3d2 Octahedral SF6[SbF6]–
AB7 7 0 7 sp3d3 Pentagonal bipyramidal IF7
AB2L 3 1 3 sp2 V-shaped SnCl2, PbCl2
AB3L 3 1 4 sp3 Pyramidal NH3, PX3
AB2L2 2 2 4 sp3 V-shaped H2O, NH2–, SeCl2
AB4L 4 1 5 sp3d See-Saw SF4, TeBr4
AB3L2 3 2 5 sp3d T-shape ClF3
AB2L3 2 3 5 sp3d Linear IF5, CIF3
AB5L 5 1 6 sp3d2 Square pyramidal BrF5, IF5
AB4L2 4 2 6 sp3d2 Square planar XeF4, ICl4–
(v) Geometry or shapes of Molecules : H2O  104.5° because (LP-LP) repulsion >
(LP-BP) > (BP-BP)
(a) The direction of overlap gives the direction of
the bond. Thus in case of molecules containing 10. Molecular orbital Theory
three or more atoms, one of them is the central
atom and the other atoms are linked to it in (i) The relative energies of the M.O. are obtained
definite directions. experimentally from spectroscopic data.

(b) A particular arrangement obtained by bonding

a number of atoms in definite directions to the (ii) The sequence in the order of increasing energy
central atom of a molecule is called the is given below.
geometry or shape of the molecule.
1s < *1s < 2s < *2s <  2 pz  2 p x

9. VSPER Theory
= 2 p y   *2 p x   *2 p y   *2 pz
(i) (LP-LP) repulsion > (LP-BP) > (BP-BP)
Energy diagram is shown below
(ii) NH3  Bond Angle 107.5° because (LP-BP)
repulsion > (BP-BP)

42
 (I) If Nb > Na, the molecule is stable
* 2pz
(II) If Nb < Na, the molecule is unstable.
* 2px = * 2py (III)Even if Nb = Na, the molecule is
2p 2p
unstable. This is due to the fact that
 2px =  2py anti bonding effect is some what
stronger than the bonding effect.
2pz
(b) Stability of molecules in terms of bond
order :
* 2s
(I) Bond order can be defined as number
2s 2s of covalent bonds formed in molecule.
1
(II) Bond order = [No. of electrons in
 2s 2
Figure - 1 bonding orbitals – No. of electrons in
1
antibonding orbitals] = [Nb – Na].
2
(iii) It has been found experimentally that in some
of the diatomic molecules (which have 14 or (III)The bond order of 1, 2 and 3 corresponds to
less than 14 electrons)  2 p z M.O. has higher in single, double and triple bonds respectively. It
may be mentioned that according to MO
energy than  2 p x and  2 p y M.O.’s. Therefore, theory, even a fractional bond order is possible.
the order of increasing energy of these M.O.s Thus
changes to
(i) Bond order  Stability of molecule 
  1s < *1s < 2s < *2s <  2 p x
(ii) Bond order  Dissociation energy 
=  2 p y <  2 p z <  *2 p x =  *2 p y <  *2 pz
(iii) Bond order  Bond length 

* 2pz 11. Fajan’s Factors

* 2px = * 2py Following factors are helpful in bringing covalent

2p 2p character in Ionic compounds :
 2pz (i) Small cation
2pz = 2py (ii) Big anion

(iii) High charge on cation

* 2s
(iv) High charge on anion
2s 2s
(v) Cation having pseudo inert gas configuration
(ns2p6d10) eg. Cu+, Ag+, Zn+2, Cd+2
 2s
Figure - 2
(vi) Coming of colour or darkness of colour in
(iv) Stability of Molecules : compounds formed with colourless ions.

(a) Stability of molecules in terms of Ionic potential () = Charge on cation/radius of cation
bonding and antibonding electrons
12. Dipole Moment ()
 (i) % ionic character = p/t ×100 where t = ed 15. Hydrogen bonding

(ii) R =  2A   2B  2 A  B cos  (i) (a) When a hydrogen atom is linked to a highly

electronegative atom (like F,O or N) comes
under the influence of another strongly
(iii) for o, m, p compounds  is 60°, 120° & 180°
electronegative atom, then a weak bond is
respectively.
developed between them, which is called as
hydrogen bond.
(iv) examples of
(b) It is represented by dotted line as follows
 = 0 [H2, Cl2, F2, CO2, CCl4, BeF2, BF3, PH3,
CH4,CS2]
+ – + – + –
H—X----H—X----H—X
(v)  NH3 (1.7D) >  NF3 (0.12D)
(where X is F,O or N)

(ii) Types of hydrogen bonding :

13. Resonance
(a) Intermolecular hydrogen bonding : When
It has been found that the observed properties of hydrogen bonding takes place between
certain compounds cannot be satisfactorily different molecules of the same or different
explained by writing a single lewis structure. The compounds, it is called intermolecular
molecule is then supposed to have many structures, hydrogen bonding e.g. HF, H2O, ROH (same
each of which can explain most of the properties of compound) water-alcohol, water ammonia
the molecule but no one can alone explain all the (different compound) etc.
properties of the molecule. The actual structure is in
between of all these contributing structures and is (b) Intramolecular hydrogen bonding :
called resonance hybrid and the different individual
structures are called resonating structures or The hydrogen bonding which takes place
within a molecule itself, is known as
canonical forms. This phenomenon is called
intramolecular H–Bonding. This is also known
resonance.
as chelation.
Example : Examples :
O O O O OH

O O O OO O N C
resonance hybrid
O O
14. Metallic Bonding H H

(i) In order to explain the nature of metallic bond O O

Lorentz proposed a simple theory known as o-Nitrophenol Salicylic acid
electron gas model or electron sea model.
16. Vander Waal’s forces (V.W.F.)
(ii) A metal atom is supposed to consists of two
parts, valence electrons and the remaining part (A) This type of intermolecular attractive forces
(the nucleus and the inner shells) called kernel. occurs in case of non polar molecules such as
H2, O2, Cl2, CH4, CO2 etc. and also in polar
(iii) The kernels of metal atoms occupy the lattice
molecules.
sites while the space between the kernels is
occupied by valence electrons. (B) molecular weight  V.W.F. 
 Atomic weight  V.W.F.  (b) The example of one electron bond is H2+.

Boiling point  V.W.F.  (c) The one electron bond also exist in
ferromagnetic metals.
 (C) Types of Vander Waal’s forces (d) This bond is only half as strong as a shared
electron pair bond.
(a) Dipole-Dipole attraction : It is again in
between two polar molecules such as HF (e) NO and NO2 are the examples of odd
and HCl. molecule having three electron bonds

+ – + – e.g. :
HF HCl(g) O
N==O N
(b) Dipole-Induced dipole attraction : In this O
case a neutral molecule is induced as a
dipole by another dipole as shown in fig. (B) Back bonding :
(a) In BF3 molecule, the 2p orbitals of each F
– + + – + +
atom are fully filled, while one of 2p
HCl Cl2 orbital of the B atom is vacant. The two
2p-orbitals of B are involved in the
(c) Induced dipole-induced dipole attraction formation of B–F bond and third 2p orbital
or London dispersion force : Between is vacant, therefore overlap laterally
two non polar molecules as in Cl2, He etc. resulting in the transference of electron of
the fluorine atom into vacant orbitals of
17. Ion-dipole attraction B-atom.

This force is between an ion such as Na+ and a

polar molecule such as HCl F
F––––B
F
+ – +

Na+ HCl (b) The bonding is effective since energy level

of both orbitals is same.
18. Ion-induced dipole attraction
(c) An additional p-p bond is formed
In this case a neutral molecule is induced by an between Boron and Fluorine atom. This is
ion as a dipole as shown in figure. known as back bond.

(C) Banana bonding :

+ + + +
(a) This type of bonding is present in B2H6.

The relative strength of various bonds is as follows (b) A bridge structure for diborane was
Ionic bond > Covalent bond > Metallic bond > proposed by Dilthey in 1921.
H-bond > Vander waal bond.
H 1.23Å H H

19. Typical bonds 122º B 97º B

H H H
(A) Odd electron bond :
(a) These include one electron bond and three
electron bond. 1.77Å
(c) The formation of diborane molecule is H H H
depicted below.
B B

H H H

H H H

B B
H H H