hemistry: Chemical Bonding

ALLEN
Pre-Medical
.0 INTRODUCTIOON CHEMICAL BONDING
s well known fact
that except inert
ordinary condition. gases, no other element exists as independent atoms under
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
a Strength of the bond.
Therefore molecules are more stable than atoms.

Classification of Bonds
CHEMICAL BONDS

STRONG BOND WEAK BOND

(Inter atomic) (Inter molecular)
(Energy 200 KJ/mole) (Energy 2-42 KJ/moe)

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

lonic Covalent Co-ordinate Metallic Hydrogen Vander waal's
bond bond bond bond bond bond

Cause of Chemical Combination

(A) Tendency to acquire minimum energy
a) When two atoms approaches towards each other, Nucleus of one atom attracts the electron of
another atom.
(6) Two nuclei and electron of both the atoms repel each other.
(c) lf net result is attraction, the totai energy of the system (molecule) decreases and a chemical bond
forms.

(d) So Attraction -oc Stability.

Potential energy
(e) Bond formation is an exothermic process (AH =
-ve)

Distance of separation

XBond
Energy
Internuclear distance

47
 Chemistry:ChemicalBone

ALLEN Pre Medical configuration

:

to acquire noble gas

(B) Tendency conliguralio.
nearest noble gas in bond lorrnalion,
Atom
combines to acquire participate
and (n-1)d electrons have stable
(b) oulermost
electron i.e, ns, np formation,
as they eec
y participate in bond or ns'np)
gas elements
do not configuration 1s
(C) ert (Stable
minimum enerqy.
and hence
rallon
(d) Octet rule can be accomplished by
electrons
(6Hi) Transfer of electrons
0 equal sharing of electrons (i) Unequal
sharing of
2.1 VALENCY

tis defined as the combining capacity of the elements.

New concept : This concept is based on the electronic configuration. According

to this concept val valency
s
from VA to zero group, l
t o iVA
group elements is equal to number of valence shell e and
18-(number of valence e)
Valency = No. of valence e Valency (8- no. of valence e)
IA IIA IIA IVA VA VIA VII 0
ns
ns ns'np' ns'np? ns'np ns'np ns'np ns'np
Valence 1 2 3 4 8
5 6 7
shell e

Valency 1 2 3 4 3 2
(8-5) (8-6) (8-7) (8-8)
= 3 -2 = 1 =
0
Note: Al the elements of a
group have same valencies because they have same number of valence shell
electrons.
2.2 KOSSEL LEWIS APPROACH
TOWARDS CHEMICAL BONDING
Every atom has a tendency to
complete its octet in outermostshell
H, Li has the tendency to
complete its duplet. i.e. why they never follow octet rule.
To acquire inert
gas configuration atoms loose or
The tendency of atoms to achieve gain electron or share electron.
eight electrons in their outer most shell is known as Lewis octet r'
H9o0H)
Obeys octet rule
Doesn't obey octet rule
Exception of Octet Rule (Failure)
(a) Incomplete octet molecules or electron deficient
molecules or
Compound in which central atom has less than 8 e in outermost shell. hypovalent.
Example- Halides of IlIA groups, BF,, AlCI, BCl, hydride of IlI
A/13" group etc.
In BCl, Boron has only 6 electrons]

Other examples BeCI, (4e), HgCI, (4e), GalCHJ, (6e)

-

(b) Expansion of octet or electron efficient molecules or

hypervalent :C)PCI
Compound in which central atom has more than 8e in outermost shell.
Example - In PCI, SF, IF,, the central atom P, S and I contain 10, 12

and 14 electrons respectively.

48
 ALLEN

Chemistry: Chemical Bonding

P r e - M e d i c a l

(c) Pseudo inert gas o u t e r m o s t

shell but

Cations which
contains
configuration having
fully
filled

the 18 electrons in cation

Ex.
configuration is not ns'np". oue
Shell or

Ga, Cu',
Ag', Zn", Cd", Sn", Pb" etc.
Electronic
configuration of Ga -1s 2s'2p",3s 3p 30 ,4s4p
Electronic configuration of
Ga" -1s,2s ,2p.
L-

(d) Odd electron 18e

In which molecules
central atom outer most
in their
e.g. NO, NO,, contain od
Oud no (7e, 1le etc) of electrons
CIO, etc.
2.3 COVALENT BOND
negative
electro
A of
O
covalernt bond is two
ns
atoms

eenents formed by mufual

the mutual sharing of
ol electrons between
to
complete their octet. (Except H which C
compietc

.
H molecule
The shared
H-H
O2 molecule
0-0 No molecule

localised
between
wo
atoms

pair of electrons should have spins, and are

concerned. v opposite sp
Opposite

Sharing ot electrons may occurs in

three ways
No. of
electrons shared Bond
between two atoms Electron pair
2 Single bond
Double bond
6 3 Triple bond

Examples H-N-H Three single bonds (not triple bond)

N=N Triple bond

O-0 Double bond
H-O-H (Two single bonds.)
Orbital Concept of Covalent Bond
According to this concept:
O n e orbital can accommodate maximum 2 electrons with opposite spins 1
i1ts
Halt filled orbital or unpaired electron orbital accepts one electron from another atom, to complete
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.

2.4 VARIABLE VALENCY IN COVALENT BONDS

Variable valencies are shown by those elements which have vacant 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
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, C) can show variable valencies.

49
Pre-Medical Chemistry: Chemical Bond
a element shows odd or even valency in ground state then it will show odd or even in exciteds
also with the difference of 2.
The required for excitation of electrons is called promotion energy/excitation energy.
T gy
Promotion rule Excitation of electrons takes place in different subshell of the same shell.

Example
(a) Nitrogen > Ground state
Covalency 3 (NCI)
2s 2p

Nitrogen No excited state

not exist
Not possible due to absence of vacant orbital
thats why (NCI,) does

(b) Phosphorus Ground state

1111 Covalency 3 (PCI)

3s 3p

Phosphorus > Excited state

1
3s
1 1
3p
1 | | Covalency - 5 (PCI)
3d

Note

NCl, exists

Nitrogen.) While PCI, and PCI, both

exist-
(due to absence of d-orbitals in
NCI doesn't exists
because 3d orbitals are present in phosphorus
SF, and SF
due to absence of d-orbitals While
OF2 exists, but OF, and OF, doesn't exists
exists due to presence of d-orbital, present
in its valence shell.

It can explain existence of molecules.

Ground state.
(c) Sulphur >

Covalency 2 (SF)

3s 3p 3d

Sulphur > Excited state

Covalency - 4 (SF,)

1"excited state
3d
s 3p
Covalency - 6 (SF)

2d excited state
3p 3d
3s

of S is 2, 4 & 6.
So variable covalency their compound in excited state
but 2
elements forms
that only 3, 4, 5,
6 period
Note :It is not neccessary excited state.
also forms compound in
period elements
of their compound
in excited state
most
Example
-

Be, B, C forms

(1) Be 1s, 2s
Covalency = 0
Ground state 1 U
Covalency = 2
Excited state 1 1
50
Chemistry: Chemical Bonding ALLEN Pre-Medical
(2) C 1s', 2s', 2p?
Ground state 1 111 Covalency 2
Excited state 1 1111 Covalency - 4
2.5 VBT (VALENCE BOND THEORY)
(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 -
of tWo
(a o form a covalent bond overlapping occurs between half filled orbitals of valence shell
atoms.
Orbitals come closer to each other from that direction in which extent of overlapping is maximun.
(b)
(c) So covalent bond has directional character.
d) Strength of covalent bond x extent of overlapping.
(e) Extent of overlapping depends on two factors.
) Nature of orbitals -

a) p. d and fare directional orbitals more overlapping

S-orbital - non directional - less overlapping
bond
of directional orbital is more stronger than the
Ihe bond is formed by the overlaping
formed by overlapping of non-directional orbital.

P-P>S-p>s-s

S-S
p
- p p-S

(b) If nis same 2p-2p> 2s -2p > 2s-2s

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

ls -2p> 2s -2p > 3s 3p

Co-axial overlapping of overlapping more.
extent
(i)Nature of overlapping less
Collateral overlapping extent ofoverlapping

Order of strength of Co axial overlapping- P p>s-p>ss

formed on account of overlapping.

Two types of bonds are

(2) Pi (7) bond

(1) Sigma (o) bond
Bond
(1) Sigma (o) along their axis (end to
by the overlapping of half filled orbitals
(a) Bond formed between two atoms
bond.
end overlap) is called sigma

(b) o bond is directional.

between electron clouds and hence it is strong bond.
c) Maximum overlapping is possible
There be only one o bond between two atoms.
(d) can

three types of overlapping

Sigma bonds are formed by
half filled s-orbital overlap along any axis because it is non-
s overlapping (H,) - Two
i) s
axis is not fixed..
directional in nature so internuclear

1s 1s o bond ls 1s
(Formation of H, molecule)

51
ALLENT Chemistry: Chemical R
Pre-Medical
(i) When half filled s-orbital ot one atom overlap .
fillo
filled pping (Formation of HF) -

p-orbital of other atom.

ls of Hydrogen H-F
2p of Fluorine

iii) P - It involves the coaxial overlapping between hal

p overlapping -

(Coaxial) half f
p-orbitals of two different atoms.

p-p overlapping
Ex. Formation of Cl, F. Br
(2) T-Bond
(a) The bond
formed by sidewise (lateral) overlapping are knowm as t bonds.
(b) Lateral overlapping is
more as
only partial, so bonds formed are weaker (Repulsion between nucleus i
orbitals have to come much close to each other)
Example - Formation of O, molecule

O, molecule
Note : Only p, and p, of oxygen atom have unpaired e in each orbital for bonding.
Electronic configuration of oxygen is 1s' 2s 2p. 2p, 2p,
(c) r bond is weaker than o bond (Bond energy difference is 63.5 KJ 15 K
or cal/mole)
d) T bonds are less directional, so do not determine the shape of a molecule.
Illustrations
Illustration 1. Predict the nature of bond

S.N.Orbitals Internuclear axis | Bond

(i) s+ s any axiss

ii) S+px x-axis

s + py y-axis
(ii)
s+px Z-axis no overlapping
(iv) X-axis
(v) px +px
Py y-axis
(vi) pz + pZ Z-axis
(vii) px +px y or z-axis
(ix) py+pyy x or z axis
x or y axis
(x) pz +pz

BEGINNER'S BOX.1
According the valence bond theory,
to
when a covalent bond is formed between two roacti
becomes-
potential energy of the system (3) minimum
(1) negative (2) positive (4) maxinmum
chlorine molecuBle is-
The total number of lone pairs in
a
2 (2) thre2e (3) four (4) seven
(1) six

52