CHEMICAL BONDING

“The force which holds the atoms / ions together within the molecule is called a chemical bond.”

Types of Chemical Bonds

1. Electrovalent Bond:- The chemical bond formed between two or more atoms as a result of the
transfer of one or more electrons from an electropositive to electronegative atom is called
electrovalent / Ionic / Polar bond.

Conditions for forming electrovalent bond

1. Conditions for forming electrovalent or ionic Bond :
(i) No. of valency electrons: One atom should posses (electropositive / metallic)1, 2, 3 valency electrons while the
other atom should have (electronegative non metallic) 6, 7 valency electrons.

(ii) Difference is electronegativity : The formation of electrovalent bond will be easier if the difference in the
electronegativities of the two atoms is high ΔEN minimum should be 2.1. (On Pauling Scale).
(iii) Overall decrease in energy : In the formation of an electrovalent bond, there must be overall decrease in energy, i.e.

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energy must be released.

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Energy changes are involved in the following steps:

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(a) Energy equivalent to ionization energy is required to convert a neutral isolated gaseous atom into a Cation.

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A (g) + I.E.  A+(g) + e

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Lower the value of I.E. greater will be the ease of formation of the cation from it. Thus for better ionic character an

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atom should have low I.E.

(b) Energy Equivalent to electron affinity is released when an e is added to a neutral isolated Gaseous atom to make it
univalent anion. B(g) + e  Bg + E.A.
So higher the value of E.A. of the atom, greater the ease of formation of the anion from it.
i.e. for better ionic character an atom should have high value of E.A.

(c) Lattice Energy  When A+ & B react to form A+B electrostatic attraction energy is released. Higher
will be the energy released, more favorable will be the reaction.

So high Lattice energy is favorable for ionic bond formation.

Kq1q 2
Now |U|  U is high when q1 & q2 are larger and r is smaller..
r
For eg. NaCl is more stable than CsCl as ( rNa   rCl  ) is lesser than ( rCs   rCl  ).

 Ionic bonds are non rigid and non- directional .

General Characteristics of Electrovalent Compounds:

(1) Crystalline Nature: Due to non-directional force of attraction between ions electrovalent compounds form solid
crystals.Each ion is surrounded by a number of oppositely charged ions and this number is called Coordination
number.
(2) M.P.&B.P.: Due to strong electrostatic force of attraction, usually M.P. & B.P. of ionic compounds are high.

(3) Hard & Brittle : Electrovalent compounds are hard due to strong forces of attraction between oppositely charged
ion which keep them in allotted position.

(4) Electrical Conductivity :

Ionic compounds in solid form do not conduct electricity. Ions remain intact on account of electrostatic forces of
attraction. The ions donot move when electric current is applied. But when ionic compounds are melted or dissolved

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 in a polar solvent, the ions become mobile & move towards the respective electrode & act as a carrier of electric
current.

(5) Space Isomerism : Due to non-directional forces ionic compounds do not show space or stereo isomerism

(6) Isomorphism : Compounds having same electronic structure are isomorphous to each other.
For eg. Na+F & Mg2+O2
(2, 8) (2, 8) (2, 8) (2, 8)
(7) Electrovalent compounds furnish ions in solution. Ionic reactions are fast due to fast Recombination of ion.

2. Covalent Bond :- The bond formed between two atoms by mutual sharing of electrons so as to complete their
octets is called Covalent bond. In this bond the atoms do not acquire any charge as the electrons are not lost or
gained completely. The electrons which are shared occupy such a position in between the nuclei of the two atoms
where there is maximum force of attraction from the two nuclei due to their different effective nuclear charge.This
bond is termed as non-polor bond.
Covalent bond may be single, double or triple bond. Double & triple bonds are called multiple covalent bond.

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Single covalent bond  Sharing of one electron pair ()

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Double covalent bond  Sharing of two electron pairs (=)

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Triple covalent bond  Sharning of Three electron pairs (  )

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Covalency :

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It is defined as the number of electrons contributed by an atom of the element for sharing with other atoms as to

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achieve noble gas configuration.

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Normally maximum covalency of an element (except hydrogen) is equal to (8  group number)
C(IV) 84=4 Si (IV) 84=4
N(V) 85=3 P(V) 85=3
O(VI) 86=2 S(VI) 86=2
F(VII) 87=1 Cl (VII) 8  7 = 1

The elements having vacant d-orbitals in their valence shell like P,S,Cl,Br, I show variable covalency by increasing
the no. of unpaired electrons under excited conditions. This type of shifting is not possible in case of H,
N,O & F due to unavailability of vacant d-orbitals.

Conditions for the formation of Covalent bonds:

(1) Electronegativity : For forming a covalent bond the electronegativity difference between the bonding atoms must
be either zero or very small.
(2) Electronic configuration:- When both the atoms are short in electrons to achieve 8 electrons in their valence shell
then such atoms complete their octet by sharing of electrons.
All the organic compound and few compounds formed by the combination of two different non-metals are covalent
in nature. eg.  H2, X2, O2, N2, S8, P4

Strength of covalent bond

Covalant bond strength is determined by bond energy only.
B.E.  B.S 
As B.L. B.E.  & B.S. 
As no. of bond   B.E.  & B.L. 
As bond polarity  force of altraction  & B.L. 
Characteristics of Covalent Compounds:

(1) Physical state :Under the normal conditions of temperature & pressure these exist as gases or liquids of low boiling
points. This is due to very weak forces of attraction ( vander waal’s forces). Some exist as soft solids if their
molecular masses are high. eg. sulphur, phosphorus, iodine are soft solids.

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(2) Melting and Boiling Points :With the exception of few which have giant 3-D structures such as diamond,
carborundum (SiC), silica (SiO2) others have realtively low melting and boiling points.
M.P. & B.P. of these compounds increase with increase in molecular weights.
Low M.P. & B.P. since molecules are held by vandenwaals forces (S, P, I2etc.)
Moderate M.P. & B.P. Flat layer structure (Graphite)
High M.P. & B.P. Giant molecular structures (eg.  SiC, AlN, Diamond etc.)

(3) Bond Fission :

Homolytic bond fission  C2H5Br  C2H5 + Br ;  H= 67.2 KCal/Mol (Normally in pure covalent molecules)
Heterolytic bond fission  C2H5Br  C2H5+ + Br ;  H= 183 KCal/Mol

Homolytic bond fission energy < Hetrolytic bond fission energy

(4) Electrical conductivity :

(a) In general covalent substances are bad conductors of electricity.

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(b) Substances which have polar character like HCl in solution, can conduct electricity.

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(c) Covalent solids having giant molecules, are bad conductors since they do not contain charged particles or free

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elelctrons.

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(d) The graphite can conduct electricity since electrons can pass through one layer.

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(e) Some of the compounds shows conductivity due to self ionisation e.g. Liq NH3

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NH3 + NH3  NH4+ + NH2; H2O + H2O  H3O+ + OH

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(5) Solubility :

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In general covalent substances are insoluble in polar solvent like water but soluble in non polar solvents like
benzene, CCl4, ether etc.. This is based on the principle “ like dissolves like.”
Some of the covalent compounds like alcohols, amines dissolve in water due to hydrogen-bonding.
Covalent solids having giant molecules are practically insouble in all solvents.

(6) Molecular Reactions :

Covalent substances show molecular reactions. Reaction rates are usually slow as it involves first breaking of
covalent bonds and then establishing of new bonds.

(7) Isomerism:
The covalent bond is rigid & directional. On account of this, there is a possibility of different arrangements of
atoms in space. Covalent compounds can thus show isomerism.

3.Coordinate bond:-
This is a special type of covalent bond where the shared pair of electrons are contributed by one specie only but is
shared by both.It is also known as dative bond
The atom which contributes electron pair is called the ‘donor’ while the atom which accepts is called ‘
acceptor’.This bond is represented by an arrow(  ) pointing from donor to the acceptor..

Note: Co-ordinate bond after formation is indistinguishable from a covalent bond.

Examples: CO, N2O, H2O2, N2O3, N2O5, HNO3,SO2, SO3, H2SO4, O3 etc.
Charectristics of Co-ordinate Covalent Compounds
(1). Their m.p. and b.p. are higher than purely covalent compounds and lower than purely ionic compounds.
(2). These are sparingly soluble in polar solvents like water but readily soluble in non-polar solvents.
(3). These bonds are rigid and directional and thus these compounds show isomerism.

KOSSEL-LEWIS APPROACH TO CHEMICAL BONDING

Lewis Octet Rule:- “The tendency of atom to achieve eight electrons in their outermost shell is known as Lewis
octet rule.”
Lewis dot structures :- Lewis structures (also known as Lewis dot diagrams, electron dot diagrams, and electron
dot structures) are diagrams that show the bonding between atoms of a molecule and the lone pairs of electrons

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that may exist in the molecule.

Exceptions to Octet rule:-

1. Molecules with incomplete octet:- Molecules having less than 8 electrons are placed in this category. These are
electron deficient molecules and can act as Lewis acids(electron pair acceptors) .For e.g. BCl3, BeCl2, AlCl3 etc.

2. Molecules with expanded octet :- In these type of compounds the central atom have more than 8 electrons. For

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e.g. In PCl5, SF6, IF7, the central atom contains 10, 12 & 14 e-s respectively.

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3. Cations with pseudo inert gas configuration :- Cations of transition metals which contain 18

c e
e-s in their outermost shell. for e.g. Ga3+, Cu+, Ag+, Zn2+, Sn4+, Pb4+ etc.

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4. Odd electron molecules : Molecules having odd electrons in their valence shell.

P
NO, NO2, ClO2

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Formal Charge :- It can be defined as the difference between the number of valence electrons of an atom in free
state and the number of electrons assigned to that atom in lewis structure.

F.C. = V -2  L.P. -

Where, V = No. of valence elctrons

B.P

L.P. = No. of lone pairs

B.P. = No. of bond pairs

1
O

3
2O O
Formal charge on Oxygen marked No. 1 = 6- 2  1 - 3 = 1
Formal charge on Oxygen marked No. 2 = 6- 2  2 - 2 = 0

Formal charge on Oxygen marked No. 3 = 6- 2  3 - 1 = -1

1
O

Thus the structure with formal charges can be written as

3
2O O

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Note :- The lewis structure with lowest formal charge will be having the least energy.

COVALENT CHARACTERS IN IONIC COMPOUNDS(FAJAN’S RULE)

When a positively charged ion (cation) comes closer to a negatively charged ion (anion) the electron cloud
of the anion is attracted towards the cation, as a result of this attraction the electron cloud of the anion get distorted,
this effect is called polarisation of the anion.

Polarising power :- The ability of cation to distort the electron cloud of anion i.e. to polarise the cation is called its
polarising power. More is the polarising power of cation more will be the covalent characters in the ionic bond.
Polarisibility :- The tendency of anion to get polarised is called its polarisibility.

 Due to polarisation sharing of electrons occur between two ions to some extent and the bond shows
some covalent character.So higher will be the polarisation, higher will be the covalent character.The magnitude of
polarisation depends upon a number of factors which are known as FAJAN’S RULE 

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(1)Charge on cation: (Assuming other factors to be same ) higher the positive charge, more will be the polarisation,

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more is the covalent character.

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AlCl  MgCl  NaCl across the period size remaning same

c e
3 
   2  

i n
covalant charc. increases B.Pt. decreases

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2+ 3+
Fe < Fe (less covalent)FeCl2 < FeCl3(more covalent) PbCl4 > PbCl2

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(2)Size of the cation: Smaller the size of cation, more is the polarisation of anion & hence more is the covalant
BeCl  MgCl  CaCl  SrCl  BaCl
  2  2   2    2  2
character.
covalant charc. increases B.Pt. decreases

Polarising power: Li+ > Na+ > K+ > Rb+ > Cs+ & F < Cl < Br < I

Covalant character: LiCl > NaCl > KCl > RbCl > CsCl & LiF < LiCl < LiBr < LiI

The overall polarizing power of cation depends on its charge by radius ratio i.e.
chrageon cation
polarisation power α also known as ionic potential().
size of cation
Thermal stability of carbonates increases as the value of ionic potential decreases

(3) Charge on anion:- Greater the charge on anion, more it will be polarisable. (N3 > O2– > F–)

(4) Size of anion :

Larger will be the size of anion, larger it will be polarised so greater will be the covalent character.
AlF3  AlCl 3  AlBr 3  AlI 3
covalent charac. increases
(5) Configuration of cation : The cations with 18 es in outer most shell bring greater polarisation of the anion than
those with inert gas config.(8 electrons in outermost shell) even if both the cations have same size & same charge.
Cu+ Na+
Configuration 2,8,8 2,8
size 0.96 Å 0.95 Å
M.Pt. CuCl (442oC) NaCl (800oC)
So CuCl is more covalent than NaCl.
Due to poor shielding of d-orbitals.
(ns2np6nd10) > (ns2np6)

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 Application Of Fajan’s Rule
Charge on cation
Ionic potential 
Size of cation
1. Covalent Character:- Covalent characters increases with increasing value of  .
2. Nature of Oxides:-
  Acidic nature

If  < 2.2 , than oxide will be basic.

If  = 2.2 to 3.2 , oxide will be amphoteric.

if  > 3.2 , than oxide will be acidic.

e.g. Li2O < Na2O < K2O < Rb2O < Cs2O

     
Basic character increases


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3. Thermal stability of metal carbonates :-

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1
Theramal stability 

e


i n c
e.g. BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3

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           

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Thermal stability increases

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4. Colour of compounds :- Colour intensity 
thus more are the covalent charaters more will be the colour intensity.
e.g. AgF AgCl AgBr AgI
(Colourless) (white) (Light yellow) (Dark yellow)

5. Solubility :- As covalent character increases the solubility of compound in polar solvents decreases but in non
polar solvents increases.

VALENCE BOND THEOREY

It was proposed by Heitler and London and extended by Pauling and Slater.
The main points of the theory are 
(1) A covalent bond is formed by overlapping of atomic orbitals of valence shell of the two atoms.

(2) Only the orbitals which have singly occupied electrons can enter into overlapping process. The
resulting bond acquires a pair of electrons with opposite spins.

(3) The atoms with singly filled orbitals must come closer to one another with their axes in proper
directions for overlapping.
(4) Overlapping of orbitals result in decrease of energy.
(5) As a result of overlapping, there is maximum electron density somewhere between the two atoms.
(6) Greater is the extent of overlapping higher is the strength of covalent bond.

(7) The amount of energy released per mole during overlapping is termed as bond energy.

(8) Electrons which are already paired in valency shell can enter into bond formation if they can be unpaired
first and shifted to vacant orbitals of slightly higher energy of same main energy shell. This point explains the
pentavalency of phosphorus, hexavalency of sulphur and hepta valency of halogens.

Two types of the bonds are formed between two atoms on account of overlapping 

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 (a) sigma bond () (b) Pi bond ()

(a)sigma bond: A bond formed between two atoms by the axial overlapping(along their axis)
of singly occupied orbitals(containing one elctron) is called sigma () bond.

 bond formed by s-s overlapping of orbitals

Electron cloud in this bond is symmetrical about the line joining the two nuclei of the two atoms. Sigma bond can,
thus be defined as “Bond orbital which is symmetrical about the line joining the two nuclei is known as sigma
bond.”

It is formed by headon or axial overlap.

(1) SS overlapping

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s-orbital s-orbital

S
molecular orbital after overlapping

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(2) S  P overlapping

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+
s-orbital p-orbital
axial overlapping

molecular orbital after overlapping

(3) PP Overlapping

p-orbital p-orbital Molecular orbital after overlapping

 Strength of bond formed by overlapping

Between the two orbitals of the same stability (i.e. having same energy) one more directionally concentrated would
form a stronger bond. If both are present in the same main energy shell dumbbell shaped porbitals will form
stronger bond as compared to spherically symmetrical sorbital. When both are taking part in same type of
overlapping.

(b) π -bond:
π bonds are are formed as a result of sidewise or lateral overlapping of p  orbitals.

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The Overlapping takes place at the side of two lobes and hence, the extent of overlapping is smaller. Thus π bond
is weaker than bond.

i r
Px Py

i n c e S
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More is the overlapping, more is the decrease is energy and higher the energy released, stronger will be the

P
Covalent Bond.

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A single bond consist of one  bond .
 A double bond consist of one  and one π bond.
 A triple bond consist of one  and two π bond.

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 S.No. Sigma () bond Pi () bond
1. It result from the end to end It result from the sidewise (lateral)
overlapping of two s orbitals or two overlapping of two p orbitals.
porbitals or one s and one porbital.

2. Its bonded orbitals consist of a single Its bonded orbitals consist of two electron
electron cloud which is symmetrical clouds one is above and the other is below
about internuclear axis. the plane of participating atom.
3. More stronger Less stronger.

4. Bond energy ~ 80 kcals. ~ 65 kcals.

5. Less reactive. More reactive.
6.  bond can have independent  bond always exists along with a bond.
existence.

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7. Hybridization depends upon bonds. Doesn’t depend.

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8. The groups or atoms can undergo Due to resistance to rotation around the

c e
rotation about single sigma () bond. bond the groups attached to it are not free

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to rotate.

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9. The electrons are referred as In bond the electrons are held less firmly

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localised bond. Thus can be easily dissociated or

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polarised by an external charge and hence
the electron are
referred as mobile electrons.
10. The shape of the molecule is  bonding does not affect the shape of the
determined by the  bond present in molecule in which it occurs.
the molecule.
1. Bond energy increases from a single bond to a triple bond.
Bond energy: Single bond < Double bond < Triple bond.

2. Bond strength increases from a single bond to triple bond.

Bond strength : Single bond < Double bond < Triple bond.

3. Bond length of a multiple bond ( double or triple) is always shorter than the corresponding single bond.
Bond Length: Single bond > Double bond > Triple bond

4. Reactivity of a multiple bond is always more than the single bond. This is due to the fact that π  electrons are
mobile in nature.
Reactivity : Single bond < Double bond < Triple bond

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 HYBRIDISATION
The intermixing of atomic orbitals having slight difference in their energies to form new orbitals
having identical size and energy is called hybridisation. The orbitals formed are called hybrid
orbitals.

Characteristics of Hybridisation

1. Orbitals of the same atom and having slight difference in their energies can participate in
hybridisation. Orbitals of two different atoms can not undergo hybridisation.

2. Only orbitals participate in hybridisation not electrons.

3. The number of hybrid orbitals poduced after hybridisation are equal to the number of
orbitals participating in hybridisation.

4. Both half filled and fulfilled orbitals of equivalent energy can participate in Hybridisation.

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5. The hybrid orbitals are identical in shape, size and energy.

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6. orbitals involved in  bond formation do not participate in hybridisation.

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7. Hybridization never takes place in an isolated atom but it occurs only at the time of bond

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formation.

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8. The hybrid orbitals are distributed in space in such a way that the repulsion between the
hybridised orbitals is minimum.

9. Hybridized orbitals provide efficient overlapping than overlapping by pure s, p and d

orbitals due to the same energy.

10. Hybridised orbitals possess lower energy.

Types of Hybridisation

1. sp hybridisation:- One s and one p orbital hybridise together to form two new sp hybridised orbitals having same
energy. These orbitals arrange themselves at an angle of 1800 to have minimum repulsion.Thus the geometry of
molecule is linear.

+ +
sp sp
s p

examples : C2H2, BeCl2, CO2, CS2, HgCl2, NO2 etc.

2. sp2hybridisation:- One s and two p orbitals hybridise together to form three new sp2 hybridised orbitals
having same energy. These orbitals arrange themselves at an angle of 1200 to minimize repulsion.Thus the geometry
of molecule is trigonal planner.

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 + +
s p p

3- sp2 hybridised orbitals

120o

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Trigonal planner geometry

example

c e S i
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Determination of Hybridisation state

P
1

By
Method-1 Steric no.(X) = [S +V ± Q]
2
S = Total no. of monovalent surrounding atoms
V = Valence shell electrons of central atoms
Q = Charge on the species (if any)
(+) for anionic species
(–) for cationic species
Limitations :
(i) Not applicable for compounds having more than one central atom and odd electronic species
(ii) Not applicable for all hydroxy acid (e.g. H2SO3)

Method -2 To determine the hybrisiation state we need to calculate the total number of  bonds.
1. Calculate number of single bonds. Each single bond corresponds to a  bond.
2. Each lone pair is considered as a  bond.
3. One co-ordinate bond is considered as a  bond.
4. Each multiple bond contains a  bond .

Value of X Hybridisation state Geom etry

Or
No. of  bonds
2 Sp Linear
3 sp 2 Triagonal Planner
4 sp 3 Te trahe dra l
5 sp 3d Trigona l bipyra midal
6 sp 3d 2 Octa he dral( squa re bipy ram ida l)
7 sp 3d 3 P enta gona l bipyram idal

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VALENCE SHELL ELECTRON PAIR REPULSION THEOREY(VSEPR THEOREY)
This theorey was extensively developed by Gillespie and it can be summarised as -
(1) The shape of a molecule is determined by repulsions between the electron pairs present in the valence shell of
the central atom.

(2) the order of repulsion between different kinds of electron pairs is :

L.P.- L.P. > L.P. - B.P. > B.P. - B.P.

(3) As no of bonds increases repulsion increases i.e. double bond causes more repulsion than single bond and triple
bond causes more repulsion than a double bond.

(4) Effect of Electronegativity

(i) if electronegativity of surrounding atoms increases than bond angle will decrease.
1


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Bond angle

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Electronegativityof surrounding atoms

e S
for e.g. NH3 and NF3 both have same tetrahedral structure with one lone pair on N atom. As F has high

c
electronegativity the shared pair of electron is pulled towards fluorine. As a result of this the repulsion between the

i n
lone pair and bond pair increases and bond angle decreases. Thus NF3 has a smaller F-N-F bond angle (102030’) than

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H-N-H bond angle (107048’) in NH3.

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H
P N

H
H Due to B.P.- L.P. repulsion the H-N-H bond angle decreases(107048’) in NH .
3

Due to high electronegativity of fluorine

N N lone pairs are shifted towards F and as
F F F F
 a result of that B.P. - L.P. repulsion
F F increases.

Similarly the bond angle in H2O is (104027’) and in F2O it is (1020).

(ii) If electronegativity of central atom increases than bond angle increases.

Bond angle  Electronegativity of central atom

For e.g.
In NH3, PH3 and AsH3 the bond angle order is

NH3>PH3>AsH3

the more elctronegative atom i.e. N will hold the lone pair more closely and thus the lone pair will be nearer to the
central atom and the repulsion between the L.P. and B.P. will be less resulting in increased bond angle.

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 SHAPES OF MOLECULES BASED ON VSEPR THEORY
Total no. No. of b.p. No. of General Geometry Stereo Shape Exam.
of hybrid (bond pairs) unshared formula chemical
orbitals pair i.e. lp formula

2 2 0 AB2 SP B–A–B linear BeCl2

3 3 0 AB3 SP2 Trigonal BCl3,

planar GaF3

3 2 1 AB2 Bent or GeF2,

SP2 angular O3

4 4 0 AB4 Tetrahedral CH4

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SP3

4 3

c e S
1

i AB3 SP3 Trigonal

pyramid
NH3
PCl3

P
2

r i n 2 AB2 sp3 Bent or H2 O

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angular

4 1 3 AB sp3 linear HF

5 5 0 AB5 SP3d Trigonal PF5,

bipyramidal SbBr5

5 4 1 AB4 sp3d Seesaw SF4

5 3 2 AB3 sp3d T-shaped ClF3,

BrF3

5 2 3 AB2
sp3d Linear ICI2–
XeF2

6 6 0 AB6 sp3d2 Octahedral SF6

6 5 1 AB5 sp3d2 Square IF5

pyramidal
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 Types of covalent Bonds
1. Non- polar covalent bond :- The covalent bond between two similar type of atoms is termed as
a non - polar covalent bond as both the bonding atoms have same electronegativity. These type of
bonds are true covalent bonds. Molecules containing non-polar covalent bonds are called non-polar
molecules.
e.g. H2, Cl2 etc.

2. Poar covalent bonds :- The covalent bond formed between two dissimilar atoms is termed as a
polar covalent bond. Higher is the elctronegativity difference between the two bonding atoms more
polar will be the covalent bond. Molecules containing poar covalent bonds are called polar
molecules .

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e.g. HCl, HF, H2O etc.

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Note  It is not necessary that a molecule containing polar bond will always be polar in

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nature the polar nature of a molecule depends on the overall geometry of the molecule.

i n c e
Percentage Ionic Character In a Polar Covalent Bond

r
% ionic character in a covalent bond depends on the electronegativity difference of the two

P
atoms.

By
(i) When E.N. > 1.7, Then the % ionic character in the covalent bond are greater than 50% and the
bond is predominantly ionic.
(ii) When E.N. = 1.7, the bond has 50% ionic and 50% covalent character.
(iii) When E.N. < 1.7, the bond is predominantly covalent.
The % ionic character in a covalent bond can be calculated by Hanny and smith equation
% ionic character in AB bond = 16 (A - B) + 3.5 (A - B)2

Polar nature of a molecule can be explained completely on the basis of Dipole moment .
Dipole Moment ()
It is defined as the product of the magnitude of charge on any of the atoms and the distance between
them. It is a vector quantity and is denoted by . It is represented by an arrow pointing from positive
charged atom towards the negative charged atom.
 = q r
Unit  The SI unit is coloumb - m. Generally used unit is Debye(D) .
1 D = 1  10-18 e.s.u.-cm
Application of dipole moment
1.In determining the Polar nature :- Greater is the magnitude of dipole moment greater will be the
polarity of bond.
O

H H
 = 1.03 D  = 1.29 D

Note :- It is not necessary that a molecule possesing some dipole moment will always be
polar in nature. The overall polarity of the molecule depends on the overall geonetry of the
molecule.
14
2. Calculation of % ionic character :-
Experimental value of dipole moment
% ionic character   100
Theoretical value of dipole moment

3. Shape or Symmetry of molecule :- If the dipole moment is zero than the molecule will have a
symmetrical geometry. for example, CO2, CCl4 etc.

Some Noteworthy Points

PCl5 is covalent in liquid and gaseous states but ionic in solid state because in solid state it
exist as [PCl4]+(tetrahedral) and [PCl6]-(Octahedral).
PBr5 exists as [PBr4]+Br- and PI5 exist as [PI4]+I- in solution.

i r
XeF6 in solid state exist as [XeF5+] F

i n c e SMISCELLANEOUS TYPES OF BONDS

r
1. Banana Bond(3 center 2 electron bond):- This type of bonding is present in B2H6. There are

P
two types of H atoms Terminal and bridging.

By
One of the hybridised orbital of boron overlap with 1s orbital of H atom to form a delocalised orbital
containing two electrons and covering the nuclei of all the three atoms i.e B-H-B, as shown in second
diagram.On account of repulsion between the two hydrogen nuclie, the delocalised orbitals of bridges
are drifted away from each other giving the shape of banana, so this is also called banana bond.

15
 Molecular Orbital Theory
(a) There is another approach to chemical bonding known as molecular orbital theory (MOT) developed by Muliken
(1932) and Hund. Which explains the bonding characteristics in a better way.

(b) The molecular orbital theory considers the entire molecule as a unit with all the electrons moving under the influence
of all the nuclei present in the molecular.
(c) This approach recognizes that each electron belongs to the molecule as a whole and may move within the entire
molecule.

Important Features of M.O.T.

(i) Like an A.O. (atomic orbital) which is around the nucleus of an atom there are M.O. (Molecular orbital) which are
around the nuclei of a molecule.

(ii) The molecular orbitals are entirely different from the atomic orbitals from which they are formed.

i r
(iii) The molecular orbitals possess different energy levels like atomic orbitals in an isolated atom.

S
(iv) The shape of molecular orbitals are dependent upon the shapes of atomic orbitals from which they are formed.

n c e
(v) Molecular orbitals are arranged in order of increasing energy just like atomic orbitals.

r i
(vi) The number of molecular orbitals formed is equal to the number of atomic orbitals combining in bond formation.

By P
(vii) Like atomic orbitals, the filling of electron in molecular orbitals is governed by the three principles such as Aufbau
principle, Hund’s rule and Pauli’s exclusion principle.

Conditions for atomic orbitals to form M.O.

(i) The combining A.O. should be a comparable energy

(ii) The combining atomic orbitals must overlap to a large extent greater the overlap, stable is the molecule formed.

Different between A.O. and M.O.

A.O. (Atomic orbital) M.O. (Molecular Orbital)
– –
1. An e in an A.O. is under the influence An e in a M.O. is under the influence
of only one nucleus. of nuclei of two or more atoms of a molecule.

2. Their existence is because of inherent These are formed by the combination of atomic
property of the atoms orbitals of comparable energies

3. They are less stable than bonding M.O. They are less or more stable than A.O.
Which are more stable than antibonding M.O.

4. They have simple shapes They have complex shapes

5. They are represented by s, p, d, f They are represented by ,*, , * etc.

Formation of Bonding and Antibonding Molecular orbitals (LCAO method)

(i) An electron in an atom is described by a wave function,  called an atomic orbitals. Similarly, the behavior of an
electron in a molecule is described by a molecular wave function called molecular orbitals.

(ii) Quantum mechanics shows that linear combination of two functions gives, not one but two combination and hence
two molecule orbitals; a bonding orbital and an antibonding orbital.

(iii) Such an orbital. Obviously cannot lead to the formation of a chemical bond and is therefore, termed as an antibonding
M.O. combination of atomic orbitals-sigma () and Pi () molecular orbitals.

(iv) In the M.O. theory, orbitals are identified as  or  depending upon the type of the symmetry of the molecular orbital.
16
(v) A sigma () M.O. is one that has cylindrical symmetry around the internuclear axis, i.e. it does not show any change
of sigma on rotation through 180º about the axis.

(vi) It can be said that a sigma M.O. has no nodal plane (in which the electron density is zero) along the inter nuclear axis.

   
+ +
+ 
1s 1s 1s

—  —   —
 
+ +

1s 1s s*

Formation of  1s and * is bonding anti bonding M.O.

S i r
(vii) The bonding orbital is designated simply as  orbital and antibonding as *.

c e
(viii) Such a sigma () orbital is also formed when any two p-atomic orbitals overlap in end -on (along their axes) position.

P r i n
(ix) By
Since the energy of a molecular orbital is directly related to the number of nodal planes, the -orbital is more
energetic then the -orbital. The explains why a -bond is weaker bond then a -bond.

Relative energies of M.O. and filling of e–

(i) Two general criteria, which determine the energy of the molecular orbitals are
(i) Initial energy of the atomic orbitals
(ii) The extent of the overlap of the atomic orbitals
(ii) It is obvious that molecular orbitals formed from lower energy atomic orbitals have lower energy than the molecular
orbitals formed from higher energy atomic orbitals.
(iii) As the  overlap is much more effective than -overlap,  p-molecular orbital is of lowest energy, even through
originally all the three -orbitals are of equal energy.
(iv) The relative energies of the M.O. are obtained experimentally from spectroscopic data.
(v) The sequence in the order of increasing energy is given below i.e., for more than N .
1s 2
 < *1s < 2s < *2s < 2p < 2p = 2p < * 2px = *2p < *2
z x y y z
17
(vi) Using preceding figures for respective molecules as a guide, we can build up the electronic structure of simple
diatomic molecules.

i r
(vii) The filling of electrons in various M.O. follows similar rules to those for filling A.O. similar M.O. belongs to entire

S
molecule, the total number of electrons are taken into consideration and accommodated in molecular orbitals

e
according to the following rules.

n c
(i) Aufbau principle : The M.O. of lower energy is filled up first.

r i
(ii) Pauli exclusion principles. Each M.O. can accommodate a maximum of two electrons having opposite spins.
(iii) Hund’s rule. Whenever two equal energy M.O. are available electrons prefer to remain unpaired. This is

P
particularly significant for -orbitals because -bonding and -antiboding M.O. have equal energies.

By
Stability of Molecules

(A) Stability of molecules in terms of bonding and antibonding electrons :

(i) If N > N , the molecule is stable.
b a
(ii) If N < N , the molecule is unstable.
b a
(iii) Even if N = N , the molecule is unstable. This is due to the fact that antibonding effect is some what stronger
b a
than the bonding effect.

(B) Stability of molecules in terms of bond order :

(a) The relative stability of a molecule is further evaluated by a parameter known as bond order.
(b) It can be defined as number of covalent bonds formed in molecule.
(c) It is given by one half of the difference between the number of electrons in bonding orbitals and those in antibonding
orbitals.
1
(d) Bond order = [No. of electrons in bonding orbitals – No. of electrons in antibonding orbitals]
2
1
= [Nb – Na ]
2
(e) The bond order of 1, 2 and 3 corresponds to single, double and triple bonds respectively. It may be mentioned that
according to MO theory, even a frictional bond order is possible.

(f) Stability of molecule  bond order

(g) Dissociation energy  bond order
1
(h) bond length  bond order

(i) If all the electrons in a molecule are paired the substance is diamagnetic on the other hand it there are unpaired
electron in the molecules, the substance is paramagnetic. More the number of unpaired electron in the molecule
greater is the paramagnetism of the substance.

18
 JEE-MAINS
Q.1. What is the difference between bond angles in cationic species of PCl 5 and
PBr5 in solid state.
(A) 60° (B) 109°28¢ (C*) 0° (D) 90°

Q.2 All possible bond angles in anionic part of PCl5 in solid state are-

(A) 109° 28° only (B*) 90°, 180°

(C) 90°, 120° , 180° (D) 72°, 90°, 180°

Q.3 The hybridisation and shape of XeO3F2 molecule is

r
(A) sp3 and tetrahedral (B) sp3d and see-saw

i
(C*) sp3d and TBP (D) sp3d2 and octahedral

Q.4

c e S
TeF5¯, XeF2 , I3+ , XeF4 , PCl3

i n
Which of the following shape does not describe to any of the above species ?

P r
(A) Square pyramidal (B) Square planar

By
(C*) Trigonal planar (D) Linear

Q.5 Which of the following species does not exist?

(A*) XeF3 (B) XeF4 (C) XeF5 (D) XeF6

Q.6 The orbital is not participated in sp d hybridisation.
3 2

(A) px (B*) dxy (C) d x 2  y 2 (D) pz

Q.7 The orbital is not participated in sp 3d3 hybridisation.

(A) px (B) dxy (C*) d x 2  y 2 (D) pz

Q.8 Which of the following set of overlap can not provide p-bond formation.

(A) 3d and 2p (B) 2p and 3p (C) 2p and 2p (D*) 3p and 1s

Q.9 The ratio of number of s-bond to p-bond in N2 and CO molecules are

1 1 1 1
(A) 2.0 , 2.0 (B) 2, (C*) , (D) ,2
2 2 2 2

Q.10. Assuming pure 2s and 2p orbitals of carbon are used in forming CH 4

molecule, which of the following statement is false?

19
 (A) Three C–H bonds will be at right angle
(B) One C–H bond will be weaker than other three C–H bonds
(C*) The shape of molecule will be tetrahedral
(D) The angle of C–H bond formed by s–s overlapping will be uncertain with
respect to other three bonds.

Q.11 Covalency of carbon in CO molecule is three because:

(A) An unexcited C atom has two unpaired elctrons
(B*) the carbon atom can be acceptor of an electron pair
(C) The C atom has 4 valence elctrons
(D) maximum covalency of C is three
Q.12. What will be the correct bond order of following
(A) NH3 > NH2- > NH4+ (B) NH4+ > NH2- > NH3
(C) NH3 > NH4 > NH2
+ - (D*) NH2- > NH3 >NH4+

(A) PCl3F2

e S i r
Q.13 Which of the following compounds is polar in nature
(B) PCl2Br3 (C) PCl5 (D*) PCl3Br2

P
(A) sp

r i n c
Q.14. The hybridisation of central atom in AlF4- is :
(B) sp2 (C) sp3 (D) dsp2

By
Q.15. Of the species given below, which two have the same shape. Also, mention
their shape and the shape of the rest of the species.
NI3, I3 , SO32 , NO3
(A) NI3, NO3- (B) I3-, NI3 (C*) SO32-, NO3- (D) I3-, SO32-

Q.16. The number of water molecules attached with the oxygen atom in the
structure of ice is
(A) 2 (B) 3 (C) 4 (D) 0

Q.17. The species which does not show paramagnetism is

(A) O2 (B)O2+ (C*) O22– (D) H2+

Q.18. The shape of a molecule which has three bond pairs and one lone pairs
is
(A) Octahedral (B)Triangular planar
(C)* Pyramidal (D)Tetrahedral

Q.19. Which molecule is T-shaped.

(A) BeF2 (B)BCl3 (C) NH3 (D*) ClF3

Q.20. The pair having similar geometry is

(A) BF3, NH3 (B*) BF3, AlF3

(C) BeF2, H2O (D) BCl3, PCl3
20
Q.21 How many unpaired electrons are present in N 2+
(A*) 1 (B) 2
(C) 3 (D) 4

Q.22 PCl5 exist, but NCl5 does not exist because

(A*) Nitrogen has no vacant 2-d orbital
(B) NCl5 is unstable
(C) N-atom is much smaller than P

i r
(D)Nitrogen is highly inert

Q.23

i n c e S
The following compounds have been arranged in order of their

r
increasing thermal stabilities identify the correct order

By P K2CO3(I)
CaCO3(III)
(A) I < II < III < IV
(C) IV < II < I < III
MgCO3(II)
BeCO3 (IV)
(B*) IV < II < III < I
(D) II < IV < III < I

Q.24 Among the following compounds the one that is polar and
has the central atoms with sp2 hybridisation is
(A*) H2CO3 (B) SiF4
(C) BF3 (D) HClO2

Q.25. In the formation of N2+ from N2 the electron is removed from

(A*) A  orbital (B) A -orbital
(C) A * M orbital (D) A -M orbital

Q.26 CO2 has the same geometry as

(A) HgCl2 (B) NO2
(C) C2H­2 (D*) Both (A) and (C)

21
Q.27. Among the following species identify the isostructural pairs
NF3, NO3–, BF3 H3O+, HN3
(A) [NF3, NO3– and [BF3H3O+] (B)[NF3, HN3] and [NO3–, BF3]
(C*) [NF3, H3O+] and [NO3–, BF3] (D)[NF3, H3O+] and [HN3, BF3]

Q.28. Among KO2, AlO2–, BaO2 and NO­2+ one unpaired electron is
present in
(A) O2+ and BaO2 (B) KO2 and AlO2–
(C*) KO2 only (D) BaO2 only
Q.29. Which ion has the higher polarising power
(A) Mg2+

e S i r (B)* Al3+

c
(C) Ca2+ (D) Na+

P r i n
By
Q.30. The correct order of decreasing polarisability of ion is
(A) Cl– > Br– > I– > F– (B) F– > I– > Br– > Cl
(C*) I– > Br– > Cl– > F– (D) F– > Cl– > Br– > I–

Q.31. Amongst LiCl, RbCl, BeCl2 and MgCl2 the compounds with
greatest and least ionic character respectively are
(A*) LiCl and RbCl (B) RbCl and BeCl2
(C) RbCl and MgCl­2 (D) MgCl2 and BeCl2

Q32. The ion which is isoelectronic with CO is

(A) CN– (B) O2

(C) O2 (D) N2

Q.33. Which of the following structures are isoelectronc

(I) CH3 (II) H3O+ (III) NH3 (IV) CH3

(A) I and II (B) III and IV

(C) I and III (D) II,III and IV

22
Q.34. CO2 is isostructural with

(A) NO2+ (B) SnCl2

(C) C2H4 (D) NO2

Q.35. Which of the following has tetrahedral disposition?

(A) SO2 (B) SO2

(C) SO 24  (D) SO32 

Q.36 Which is incorrect statement?

r
(A)CO2 is a monomer while SiO2 is a three dimensional giant molecule.

S i
(B) Graphite is anisotropic with respect to electricity

c e
n
(C) (CH3)3N has C – N – C bond angle of 107.9° whereas in (SiH 3)3N has

r i
Si – N – Si a bond angle of 120°.

By P
(D)Bond lengths of four apical P – O bonds are greater than calculated in
PO 4 3- .

Q.37 Which of the following cannot exist on the basis of MO theory

(A) H2 (B) He2

(C) He2 (D) O2

Q.38. Which of the following has a bond order of 2.5?

(A) CO (B) NO

(C) He2+ (D) O2

Q.39. Which of the following have identical bond order

(I) CN– (II)NO (III) NO+ (IV) CN+

(A) I & II (B) I & III

(C) II & III (D) III & IV

Q.40 Which of the following species is paramagnetic

(A) N2 (B) O22–

(C) O2 (D)F2
23
Q.41 Which has got highest bond angle among NO2, NO2+ and NO2–

(A)NO 2– (B) NO 2+

(C) NO2 (D)All are equal

Q.42. Highest covalent character is found in

(A) CaF2 (B) CaCl2

(C) CaBr2 (D) CaI2

Q.43 (CH3)3SiOH is stronger acid than (CH3)3COH because

i r
(A)Conjugate base anion in (CH 3)3SiO– is stabilized by p – d bond

S
formation

c e
(B) Bulkiness of (CH3)3SiO– anion inhibits its stabilization

P r i n
(C) Electronegativity of Si is greater than C

By
(D)All of the above

Q.44. Two elements X and Y have 2, and 7 electrons respectively in their

valence shell. The expected compound formed by combination of X and Y

(A) XY2 (B) X5Y2

(C) X2Y5 (D) XY5

Q45. When NH3 is treated with HCl H – N – H bond angle

(A)Increases (B) Decreases

(C) Remains same (D)Depends upon temperature

Q.46. o-Nitrophenol is more volatile than p-nitro phenol because of

(A) Resonance

(B) Presence of intramolecular hydrogen bonding in the o-isomer

(C) Absence of intermolecular hydrogen bonding in the o-isomer

(D) none of these

Q.47. The correct bond order among halogens is

(A)F2 > Cl2 > Br2 > I2 (B) Cl2 > F2 > Br2 > I2

24
 (C) Br2 > Cl2 > F2 > I2 (D)I2 > Cl2 > Br2 > F2

Q.48. Among the following compounds the one that is non-polar and has
central atom sp2 hybridised is

(A) H2CO3 (B) SiF4

(C) BF3 (D) HClO2

Q.49. Among the following compounds which has the largest dipole
moment

(A) CH3OH (B) CH4

(C) CF4 (D) CH3F

Q.50.

S i r
Resonance is not shown by

e
c
(A) C6H 6 (B) NO2 (C) CO32- (D) SiO2

Q.51.

P r i n
Of the following species, the one having planar structure is

By
(A) NH4+ (B) BF4- (C) XeF4 (D) CCl4

Q.52. Which of the following Lewis dot diagrams is(are) incorrect ?


Cl  H  H H
   |  | |
(A*) Na  O  C l  (B) Cl (C)  H  N  H  [ S] (D) H  N  N  H
2-
C Cl
   |   
Cl  H 
2

Q.53. How many s- and p- bonds are there in salicylic acid?

(A) 10s, 4p (B*) 16s, 4p (C) 18s, 2p (D) 16s, 2p

Q.54 Which of the following has been arranged in increasing order of size of the
hybrid orbitals ?

(A*) sp  sp 2  sp 3 (B) sp 3  sp 2  sp (C) sp 2  sp 3  sp (D) sp 2  sp  sp 3

Q.55 In the context of carbon, which of the following is arranged in the correct
order of electronegativity :

(A*) sp  sp 2  sp 3 (B) sp 3  sp 2  sp (C) sp 2  sp  sp 3 (D) sp 3  sp  sp 2

Q.56 When 2s  2s, 2 p  2 p and 2 p  2s orbitals overlap, the bond strength decreases
in the order :
(A) p  p  s  s  p  s (B*) p  p  p  s  s  s
25
 (C) s  s  p  p  p  s (D) s  s  p  s  p  p

Q.57 The shapes of IF5 and IF7 are respectively :

(A*) distorted square pyramidal and pentagonal bipyramidal
(B) octahedral and pyramidal
(C) trigonal bipyramidal and pentagonal bipyramidal
(D) distorted square planar and distorted octahedral

Q.58 Carbon atoms in C 2 (CN ) 4 are :

(A) sp-hybridized (B) sp 2 -hybridized
(C*) sp- and sp 2 hybridized (D) sp, sp 2 and sp 3 - hybridized

Q.59. The formal charges on the three O-atoms in O3 molecule are

(A) 0, 0, 0 (B) 0, 0, –1 (C) 0, 0, +1 (D*) 0, +1, –1

Q.60

S i r
The types of bonds present in CuSO4·5H2O are

e
(A) electrovalent and covalent

n c
(B) electrovalent , coordinate covalent & H-bond

r i
(C) covalent, coordinate covalent & H-bonds

P
(D*) electrovalent, covalent, coordinate covalent & H-bond

By
Q.61 Which of the following has been arranged in order of decreasing dipole
moment ?
(A*) CH 3Cl  CH 3 F  CH 3 Br  CH 3 I (B) CH 3 F  CH 3Cl  CH 3 Br  CH 3 I
(C) CH 3Cl  CH 3 Br  CH 3 I  CH 3 F (D) CH 3 F  CH 3Cl  CH 3 I  CH 3 Br

Q.62. The bond angle in PH 3 is :

(A*) Much lesser than NH 3 (B) Equal to that in NH 3
(C) Much greater than in NH 3 (D) Slightly more than in NH 3

Q.63 H  B  H bond angle in BH 4 is :



(A) 180º (B) 120º (C*) 109º (D) 90º

Q.64. The strongest P-O bond is found in the molecule :

(A) F3PO (B) Cl3PO (C) Br3PO (D)(CH3)3PO

Q.65. The correct order of boiling point is :

(A) HF > NH3>H2S (B) HF > H2S >NH3
(C) HF <H2S <NH3 (D) HF < NH3 < H2S

Q.66. The number of 3C-2e bonds in diborane is

(A) 0 (B) 2 (C) 4 (D) 6

Q.67. The correct solubility order is -

(I) CaCO3 > SrCO3 > BaCO3 (II) Li2CO3 < Na2CO3 < K2CO3
(III) K2CO3 <Rb2CO3 <Cs2CO3

(A) I (B) I,II (C) I,II,III (D) II,III

26
Q.68. The geometry with respect to central atome of the following molecules
are : N(SiH3)3 ; (CH3)3N ; (SiH3)3P
(A) Planar , Pyramidal, pyramidal (B)Planar , Planar, pyramidal
(C) Planar , Pyramidal, planar (D) Pyramidal, pyramidal, Planar
Q.69. In which of the following C-C bond length is highest
(A) CH3- CF3 (B) FCH2-CH2F
(C) F2CH-CHF2 (D) CF3-CF3

Q.70. Which of the following does not show H- bonding

(A) HF (B) HCl (C) liq. NH3 (D) Water

ANSWER KEY
1.C 2.B 3.C 4.C 5.A 6.B 7.C 8.D 9.C 10.C 11.B 12.D 13.D

i r
14.C 15.C 16.A 17.C 18.C 19.D 20.B 21.A 22.A 23.B 24.A 25.A 26.D

S
27.C 28.C 29.B 30.C 31.A 32.A 33.D 34.B 35.C 36.D 37.C 38.B 39.B

e
40.C 41.B 42.D 43.A 44.A 45.A 46.B 47.D 48.C 49.A 50.D 51.C 52.A

n c
53.B 54.A 55.A 56.B 57.A 58.C 59.D 60.D 61.A 62.A 63.C 64.A 65.A

r i
66.B 67.C 68.A 69.B 70.B

By P

27