Atoms of different elements excepting noble gases donot have complete octet so they combine with other

atoms to form chemical bond. The force which holds the atoms or ions together within the molecule is called a

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chemical bond and the process of their combination is called Chemical Bonding.
Chemical bonding depends on the valency of atoms. Valency was termed as the number of chemical bonds
formed by an atom in a molecule or number of electrons present in outermost shell i.e., valence electrons. Valence
electrons actually involved in bond formation are called bonding electrons. The remaining valence electrons still
available for bond formation are referred to as non-bonding electrons.


      +  –
LA
        
 p+n    p+ n    p +n 
 p+ n  
        
  
         
 
 
Na (2, 8, 1) Cl (2, 8, 7) Bond formation takes place

3.1 Cause and Modes of chemical combination.

Chemical combination takes place due to following reasons.
(1) Chemical bonding takes place to acquire a state of minimum energy and maximum stability.
A

(2) By formation of chemical bond, atoms convert into molecule to acquire stable configuration of the nearest
noble gas.
Modes : Chemical bonding can occur in the following manner.
Transfer of electrons from one
atom to another Ionic bond
B

Mutual sharing of electrons between

Covalent bond
the atoms

Mutual sharing of electrons provided Co-ordination bond

entirely by one of the atoms
3.2 Electrovalent bond.
When a bond is formed by complete transfer of electrons from one atom to another so as to complete their
outermost orbits by acquiring 8 electrons (i.e., octet) or 2 electrons (i.e., duplet) in case of hydrogen, helium etc.
and hence acquire the stable nearest noble gas configuration, the bond formed is called ionic bond,
electrovalent bond or polar bond. Compounds containing ionic bond are called ionic, electrovalent or polar
compounds.

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  
   
    

Example : Na   Cl   Na    Cl   or
 Na  Cl 
       
Some other examples are: MgCl2, CaCl2, MgO, Na2S, CaH2, AlF3, NaH, KH, K 2 O , KI, RbCl, NaBr, CaH2 etc.
(1) Conditions for formation of electrovalent bond
(i) Number of valency electrons : The atom which changes into cation (+ ive ion) should possess 1, 2 or
3 valency electrons. The other atom which changes into anion (– ive ion) should possess 5, 6 or 7
electrons in the valency shell.
(ii) Electronegativity difference : A high difference of electronegativity (about 2) of the two atoms is
necessary for the formation of an electrovalent bond. Electrovalent bond is not possible between

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similar atoms.
(iii) Small decrease in energy : There must be overall decrease in energy i.e., energy must be released.
For this an atom should have low value of Ionisation potential and the other atom should have high
value of electron affinity.
(iv) Lattice energy : Higher the lattice energy, greater will be the ease of forming an ionic compound. The
amount of energy released when free ions combine together to form one mole of a crystal is called lattice
energy (U).
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Charge of ion
Magnitude of lattice energy 
size of ion
A  (g)  B  (g)  AB(s)  U
Determination of lattice energy (Born Haber cycle)
When a chemical bond is formed between two atoms (or ions), the potential energy of the system constituting
the two atoms or ions decreases. If there is no fall in potential energy of the system, no bonding is possible, the
energy changes involved in the formation of ionic compounds from their constituent elements can be studied with
the help of a thermochemical cycle called Born Haber cycle.
Example : The formation of 1 mole of NaCl from sodium and chlorine involves following steps :
A

Step I : Conversion of metallic sodium into gaseous sodium atoms: Na(s) S  Na(g) , where S= sublimation
1 mole

energy i.e., the energy required for the conversion of one mole of metallic sodium into gaseous sodium atoms.
Step II : Dissociation of chlorine molecules into chlorine atoms : Cl 2 (g)  D  2Cl(g) , where D = Dissociation
energy of Cl 2 so the energy required for the formation of one mole of gaseous chlorine atoms  D / 2 .
B

Step III: Conversion of gaseous sodium atoms into sodium ions : Na(g) IE  Na  (g)  e  , where
1 mole

IE = Ionisation energy of sodium.

1
Na(s) + Cl 2 (g)
Step IV: Conversion of gaseous chlorine atoms into chloride +S
2 H f
  1/2D
ions : Cl (g) e  Cl (g)  EA , where EA = Electron affinity of
1 mole Na(g) Cl (g) NaCl (Crystal)
+IE – e– – EA +e–
chlorine. –U
Na (g) + Cl  (g)
Step V : Combination of gaseous sodium and chloride ions
(Born Haber Cycle)
to form solid sodium chloride crystal.
Na  (g)  Cl  (g)  NaCl (s) U , where U  lattice energy of NaCl
1 mole

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 1
The overall change may be represented as : Na(s)  Cl 2 (g)  NaCl (s), H f , where H f is the heat of
2
formation for 1 mole of NaCl (s) .
According to Hess's law of constant heat summation, heat of formation of one mole of NaCl should be same
whether it takes place directly in one step or through a number of steps. Thus,
1
H f  S  D  IE  EA  U
2
(2) Types of ions
The following types of ions are encountered :

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(i) Ions with inert gas configuration : The atoms of the representative elements of group I, II and III by
complete loss of their valency electrons and the elements of group V, VI, and VII by gaining 3,2 and 1
electrons respectively form ions either with ns 2 configuration or ns 2 p 6 configuration.
(a) Ions with 1s 2 (He) configuration : H  , Li  , Be 2 etc. The formation of Li  and Be 2 is difficult due to
their small size and high ionisation potential.
(b) Ions with ns 2 p 6 configuration : More than three electrons are hardly lost or gained in the ion formation
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Cations : Na  , Ca 2 , Al 3 etc.
Anions : Cl  , O 2 , N 3 , etc.
(ii) Ions with pseudo inert gas configuration : The Zn 2 ; ion is formed when zinc atom loses its outer 4s
electrons. The outer shell configuration of Zn2 ions is 3s 2 3 p 6 3d 10 . The ns 2 np 6 nd 10 outer shell
configuration is often called pseudo noble gas configuration which is considered as stable one.
Examples: Zn 2 , Cd 2 , Hg 2 , Cu  Ag  , Au  , Ga 3  etc
(iii) Exceptional configurations : Many d- and f block elements produce ions with configurations different
than the above two. Ions like Fe 3 , Mn2 , etc., attain a stable configuration half filled d- orbitals
Fe 3  3 s 2 3 p 6 3d 5 ; Mn 2 3 s 2 3 p 6 3d 5
A

Examples of other configurations are many.

Ti 2 (3 s 2 3 p 6 3d 2 ) ; V 2 (3 s 2 3 p 6 3d 3 )
Cr 2 (3s 2 3 p 6 3d 4 ) ; Fe 2 (3 s 2 3 p 6 3d 6 )
However, such ions are comparatively less stable
B

(iv) Ions with ns 2 configuration : Heavier members of groups III, IV and V lose p-electrons only to form ions
with ns 2 configuration. Tl  , Sn2 , Pb 2 , Bi 3 are the examples of this type. These are stable ions.
(v) Polyatomic ions : The ions which are composed of more than one atom are called polyatomic ions.
These ions move as such in chemical reactions. Some common polyatomic ions are
NH 4 (Ammonium); NO 3 (Nitrate)

PO 43  (phosphate); SO 42 (Sulphate)

CO 32  (Carbonate) ; SO 32 (Sulphite), etc.
(vi) Polyhalide ions : Halogens or interhalogens combine with halide ions to form polyhalide ions.
I 3 , ICl 4 , ICl 2 etc. Fluorine due to highest electronegativity and absence of d-oribitals does not form
polyhalide ions.

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 The atoms within the polyatomic ions are held to each other by covalent bonds.
The electro valencies of an ion (any type) is equal to the number of charges present on it.
(3) Method of writing formula of an ionic compound
In order to write the formula of an ionic compound which is made up of two ions (simple or polyatomic)
having electrovalencies x and y respectively, the following points are followed :
(i) Write the symbols of the ions side by side in such a way that positive ion is at the left and negative ion at
the right as AB.
(ii) Write their electrovalencies in figures on the top of each symbol as A x B y

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(iii) Divide their valencies by H.C.F
x y
(iv) Now apply criss cross rule as , i.e., formula Ay Bx
A B

Examples :
Name of Exchange of Formula Name of Exchange of Formula
compound valencies compound valencies
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Calcium chloride 2 1 CaCl 2 Aluminium oxide 3 2 Al 2 O3
Ca Cl Al O

Potassium 1 3 K3 PO4 Magnesium nitride 2 3 Mg3 N2

K PO4 Mg N
phosphate
Calcium oxide 2 2
1 1 CaO Ammonium sulphate 1 2 (NH 4 ) 2 SO4
CaO or
Ca O NH 4 SO4

(4) Difference between atoms and ions

The following are the points of difference between atoms and ions.
A

Atoms Ions
1. Atoms are perfectly neutral in nature, i.e., number of protons Ions are charged particles, cations are positively charged, i.e.,
equal to number of electrons. Na (protons 11, electrons 11), Cl number of protons more than the number of electrons. Anions are
(Protons – 17, electrons –17) negatively charged, i.e., number of protons less than the number of
electrons.
Na+ (protons 11, electrons 10), Cl– (protons 17, electrons 18)
B

2. Except noble gases, atoms have less than 8 electrons in the Ions have generally 8 electrons in the outermost orbit, i.e., ns2np6
outermost orbit configuration.
Na 2,8,1; Ca 2,8,8,2 Na+ 2,8; Cl– 2,8,8
Cl 2,8,7; S 2,8,6 Ca2+ 2,8,8
3. Chemical activity is due to loss or gain or sharing of electrons The chemical activity is due to the charge on the ion. Oppositely
as to acquire noble gas configuration charged ions are held together by electrostatic forces

(5) Characteristics of ionic compounds

(i) Physical state : Electrovalent compounds are generally crystalline is nature. The constituent ions are
arranged in a regular way in their lattice. These are hard due to strong forces of attraction between
oppositely charged ions which keep them in their fixed positions.

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 (ii) Melting and boiling points : Ionic compounds possess high melting and boiling points. This is because
ions are tightly held together by strong electrostatic forces of attraction and hence a huge amount of
energy is required to break the crystal lattice. For example order of melting and boiling points in
halides of sodium and oxides of IInd group elements is as,
NaF  NaCl  NaBr  NaI , MgO  CaO  BaO
(iii) Hard and brittle : Electrovalent compounds are har in nature. The hardness is due to strong forces of
attraction between oppositely charged ion which keep them in their alloted positions. The brittleness
of the crystals is due to movement of a layer of a crystal on the other layer by application of external
force when like ions come infront of each other. The forces of repulsion come into play. The breaking
of crystal occurs on account of these forces or repulsion.

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(iv) Electrical conductivity : Electrovalent solids donot conduct electricity. This is because the ions remain
intact occupying fixed positions in the crystal lattice. When ionic compounds are melted or dissolved
in a polar solvent, the ions become free to move. They are attracted towards the respective electrode
and act as current carriers. Thus, electrovalent compounds in the molten state or in solution conduct
electricity.
(v) Solubility : Electrovalent compounds are fairly soluble in polar solvents and insoluble in non-polar
solvents. The polar solvents have high values of dielectric constants. Water is one of the best polar
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solvents as it has a high value of dielectric constant. The dielectric constant of a solvent is
defined as its capacity to weaken the force of attraction between the electrical charges immersed in that
solvent. In solvent like water, the electrostate force of attraction between the ions decreases. As a result
there ions get separated and finally solvated.
The values of dielectric constants of some of the compounds are given as :

Compound Water Methyl AIc Ethyl AIc. Acetone Ether

Dielectric constant 81 35 27 21 4.1
Capacity to dissolve electrovalent compounds decreases
A

Lattice energy and solvation energy also explains the solubility of electrovalent compounds. These
compounds dissolve in such a solvent of which the value of solvation energy is higher than the lattice
energy of the compound. The value of solvation energy depends on the relative size of the ions. Smaller the ion
more of solvation, hence higher the solvation energy.
Note :  Some ionic compounds e.g., BaSO 4 , PbSO 4 , AgCl , AgBr , AgI , Ag 2 CrO 4 etc. are sparingly soluble in
B

water because in all such cases higher values of lattice energy predominates over solvation energy.
(vi) Space isomerism :The electrovalent bonds are non-rigid and non-directional. Thus these compound
do not show space isomerism e.g. geometrical or optical isomerism.
(vii) Ionic reactions : Electrovalent compounds furnish ions in solution. The chemical reaction of these
compounds are ionic reactions, which are fast. Ionic bonds are more common in inorganic
compounds.
     
K  Cl   Ag NO3  Ag Cl   K NO3
(Precipitate)

(viii) Isomorphism : Electrovalent compounds show isomorphism. Compound having same electronic
structures are isomorphous to each other.

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 (ix) Cooling curve : Cooling curve of an ionic compound is not smooth, it has two break points
corresponding to time of solidification.

A  liquid

M.Pt-
Temp B C

Time

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Solidification time

(x) Electrovalency and Variable electrovalency : The capacity of an element to form electro-valent or ionic
bond is called its electro-valency or the number of electrons lost or gained by the atom to form ionic
compound is known as its electro-valency.
Certain metallic element lose different number of electrons under different conditions, thereby
showing variable electrovalency. The following are the reasons:
LA
(a) Unstability of core : The residue configuration left after the loss of valency electrons is called kernel or
core. In the case of the atoms of transition elements, ions formed after the loss of valency electrons do
not possess a stable core as the configuration of outermost shell is not ns 2 np 6 but ns 2 np 6 d 1 to 10 . The
outer shell lose one or more electrons giving rise to metal ions of higher valencies.
Example : Fe 2  3 s 2 3 p 6 3d 6 ,4 s 0 (not stable)

Fe 3   3 s 2 3 p 6 3d 5 ,4 s 0 (stable)
(b) Inert pair effect : Some of heavier representative elements of third, fourth and fifth groups having
configuration of outermost shell ns 2 np 1 , ns 2 np 2 and ns 2 np 3 show valencies with a difference of
A

2, i.e., (1 : 3) (2 : 4) (3 : 5) respectively. In the case of lower valencies, only the electrons present in p–
subshell are lost and ns2 electrons remain intact. The reluctance of s-electron pair to take part in bond
formation is known as the inert pair effect.
3.3 Covalent bond.
B

Covalent bond was first proposed by Lewis in 1916. The bond formed between the two atoms by mutual
sharing of electrons so as to complete their octets or duplets (in case of elements having only one shell) is called
covalent bond or covalent linkage. A covalent bond between two similar atoms is non-polar covalent bond
while it is polar between two different atom having different electronegativities. Covalent bond may be single,
double or a triple bond.
Example : Formation of chlorine molecule : chlorine atom has seven electrons in the valency shell. In the
formation of chlorine molecule, each chlorine atom contributes one electron and the pair of electrons is shared
between two atoms. both the atoms acquire stable configuration of argon.
 **  
 *   
 Cl   Cl *   Cl * Cl  or Cl  Cl
 ** 

( 2, 8, 7) ( 2, 8, 7)
( 2, 8, 8 ) ( 2, 8,8 )

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 Formation of HCl molecule : Both hydrogen and chlorine contribute one electron each and then the pair of
electrons is equally shared. Hydrogen acquires the configuration of helium and chlorine acquires the configuration
of argon.
* *  
H  Cl *
*
 H 
* Cl 
 or H  Cl
* *  
(1) ( 2, 8 , 7 ) ( 2) ( 2, 8 , 8 )

Formation of water molecule : Oxygen atom has 6 valency electrons. It can achieve configuration of neon by
sharing two electrons, one with each hydrogen atom.
** 
H O   H  H 
* O 
 H or H  O  H

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** 
(1) ( 2, 8 , 7 ) (1)
( 2) ( 2, 8 , 8 ) ( 2)

Formation of O2 molecule : Each oxygen atom contributes two electrons and two pairs of electrons are the
shared equally. Both the atoms acquire configuration of neon.
**   
O **  O  O  
  O or O  O
**   
( 2, 6 ) ( 2, 6 ) ( 2, 8 ) ( 2, 8 )

Formation of N2 molecule : Nitrogen atom has five valency electrons. Both nitrogen atoms achieve
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configuration of neon by sharing 3 pairs of electrons, i.e., each atom contributes 3 electrons.
*
* N * 
* 
*  N 
  *
* N ** 
 N  or N  N
( 2, 5) ( 2, 5) ( 2, 8 ) ( 2, 8 )

Some other examples are : H2S, NH3, HCN, PCl3, PH3, C 2 H 2 , H2, C2H4, SnCl 4 , FeCl 3 , BH 3 , graphite,
BeCl 2 etc.
(1) Conditions for formation of covalent bonds
(i) Number of valency electrons : The combining atoms should be short by 1, 2 or 3 electrons in the
A

valency shell in comparison to stable noble gas configuration.

(ii) Electronegativity difference : Electronegativity difference between the two atoms should be zero or
very small.
(iii) Small decrease in energy : The approach of the atoms towards one another should be accompanied
by decrease of energy.
B

(2) Characteristics of covalent compounds

(i) Physical state : These exist as gases or liquids under the normal conditions of temperature and
pressure. This is because very weak forces of attraction exist between discrete molecules. Some
covalent compounds exist as soft solids.
(ii) Melting and boiling points : Diamond, Carborandum (SiC), Silica (SiO2), AlN etc. have giant three
dimensional network structures; therefore have exceptionally high melting points otherwise these
compounds have relatively low melting and boiling points. This is due to weak forces of attraction
between the molecules.
(iii) Electrical conductivity : In general covalent substances are bad conductor of electricity. Polar covalent
compounds like HCl in solution conduct electricity. Graphite can conduct electricity in solid state since
electrons can pass from one layer to the other.

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 (iv) Solubility : These compounds are generally insoluble in polar solvent like water but soluble in non-
polar solvents like benzene etc. some covalent compounds like alcohol, dissolve in water due to
hydrogen bonding.
(v) Isomerism : The covalent bond is rigid and directional. These compounds, thus show isomerism
(structural and space).
(vi) Molecular reactions : Covalent substances show molecular reactions. The reaction rates are usually
low because it involves two steps (i) breaking of covalent bonds of the reactants and (ii) establishing of
new bonds while the ionic reactions involved only regrouping of ions.
(vii) Covalency and Variable covalency : The number of electrons contributed by an atom of the element
for sharing with other atoms is called covalency of the element. The variable covalency of an element

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is equal to the total number of unpaired electrons in s, p and d-orbitals of its valency shell.
Covalency = 8 – [Number of the group to which element belongs]
Examples : Nitrogen 7 N = Covalency of N = 3
2s 2p
The element such as P, S, Cl, Br, I have vacant d-orbitals in their valency shell. These elements show variable
covalency by increasing the number of unpaired electrons under excited conditions. The electrons from paired
orbitals get excited to vacant d-orbitals of the same shell.
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Promotion energy : The energy required for excitation of electrons.
Promotion rule : Excitation of electrons in the same shell
Phosphorus : Ground state
Covalency 3
3s 3p
Phosphorus : Excited state
Covalency-5
3s 3p 3d
PCl3 is more stable due to inert pair effect.
A

Sulphur : Ground state

3s 3p Covalency-2 (as in SF2)

3d
Sulphur : Excited state
1st excited state Covalency-4 (as in SF4)
3s 3p 3d
B

2nd excited state Covalency-6 (as in SF6)

3s 3p 3d
So variable valency of S is 2, 4 and 6.
Iodine can have maximum 7 unpaired electrons in its orbitals. It's variable valencies are 1, 3, 5 and 7.
Four elements, H, N, O and F do not possess d-orbitals in their valency shell. Thus, such an excitation is not
possible and variable valency is not shown by these elements. This is reason that NCl3 exists while NCl5 does not.
(3) The Lewis theory : The Lewis theory gave the first explanation of a covalent bond in terms of electrons
that was generally accepted. The tendency of atoms to achieve eight electrons in their outermost shell is
known as lewis octet rule. Octet rule is the basis of electronic theory of valency. It is suggested that valency
electrons themselves are responsible for chemical combination. The valency electrons in atoms are shown in
terms of Lewis dot formulae. To write Lewis formulae for an element, we write down its symbol surrounded by a

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 ALL IN ONE PCMB #2.0

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ALL IN ONE PCMB #1.0
A

ISC AND ICSE 1.0#

B

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number of dots or crosses equal to the number of valency electrons. Lewis dot formulae are also used to represent
atoms covalently bonded in a molecule. Paired and unpaired valency electrons are also indicated.
Lewis symbols for the representative elements are given in the following table :

1 2 13 14 15 16 17
Group IA IIA IIIA IVA VA VIA VIIA
    
Lewis symbol X X   X X  X  X X
   


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 
CO is not an exception to octet rule : C  O : or : C  O
..
:

(4) Failure of octet rule :

There are several stable molecules known in which the octet rule is violated i.e., atoms in these molecules have
number of electrons in the valency shell either short of octet or more than octet.
In BF3 molecules, boron atom forms three single covalent bonds with three fluorine atoms, i.e., it attains six
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electrons in the outer shell.




F
 F 
*    
|
* B* + 3  F  
F  


 * B * F   BF
|
F
PCl5 molecule : Phosphorus atom have five electrons in valency shell. It forms five single covalent bonds with
five chlorine atoms utilising all the valency electrons and thereby attains 10 electrons in the outer shell.
A

  


 Cl   Cl
 Cl Cl 
F

*    P F
P*   
Cl   Cl 
*
*
+
5  Cl    P 
*   
Cl Cl
  



Cl

 
Cl Cl
 

B


F
(i) Sugden’s concept of singlet linkage explains the stability of such molecules. In PCl 5 , three chlorine atoms
are linked by normal covalent bonds and two chlorine atoms are linked by singlet linkages, thus,
phosphorus achieves 8 electrons in the outermost shell.
 

 Cl  Cl

Cl
  

 Cl 
P Cl  Cl P F
  
 
 

Cl
 
Cl 

 Cl Cl
 
F

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 This structure indicates that the nature of two chlorine atoms is different than the other three as singlet
linkage is weaker than normal covalent bond. The above observation is confirmed by the fact that on
heating, PCl 5 dissociates into PCl 3 and Cl 2 .

PCl 5 ⇌ PCl 3  Cl 2

Similarly, in SF6 four singlet linkages are present while in IF7 , six singlet linkages are present.


 

  F
 F 

 F 
 F F
 


   S
F 
S  F


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
   

F F


 F

 
  F F
 

(ii) Sidgwick’s concept of maximum covalency

 This rule states that the covalency of an element may exceed four and octet can be exceeded.
 The maximum covalency of an element actually depends on the period of periodic table to which it
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belongs.
 This rule explains the formation of PCl5 and SF6.
 This also explains why nitrogen does not form NF5 or NCl 5 because nitrogen belongs to second
period and the maximum covalency of nitrogen is three.
(iii) Odd electron bond : In 1916 Luder postulated that there are number of stable molecules in which double
bonds are formed by sharing of an odd number of electrons, i.e., one, three, five, etc., between the two
bonded atoms. the bonds of this type are called odd electron bonds.
 **
The normal valence bond structure of oxygen molecule,  O  O ** , fails to account for the paramagnetic
A

nature of oxygen. Thus, structure involving three electrons bond has been suggested by Pauling. The
following structure :  O   O . Explains the paramagnetic nature and high dissociation energy of
  
  

oxygen molecule.
–
N  
B

 O 
Some other examples are :  N O 

   

O
 

Nitric oxide O O 
(NO)   
Nitrogen dioxide ( NO2 ) Superoxide ion (O 2 )

The number of singlet bonds = Total number of bonds – Number of electrons required to complete the octet.
Properties of Odd Electron bond
(i) The odd electron bonds are generally established either between two like atoms or between different
atoms which have not more than 0.5 difference in their electronegativities.
(ii) Odd electron bonds are approximately half as strong as a normal covalent bond.
(iii) Molecules containing odd electrons are extremely reactive and have the tendency to dimerise.

CLASSES BY ANKUR SIR @7983744732

 (iv) Bond length of one electron bond is greater than that of a normal covalent bond. Whereas the bond
length of a three electron bond is intermediate between those of a double and a triple bond.
(v) One electron bond is a resonance hybrid of the two structures i.e., A  B  A  B

Similarly, a three electron bond is a resonance hybrid of the two structures i.e., A  
 B  A   B

(5) Construction of structures for molecules and poly atomic ions : The following method is
applicable to species in which the octet rule is not violated.
(i) Determine the total number of valence electrons in all the atoms present, including the net charge on
the species (n1).

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(ii) Determine n2 = [2 × (number of H atoms) + 8 × (number of other atoms)].
(iii) Determine the number of bonding electrons, n3, which equals n2 – n1. No. of bonds equals n3/2.
(iv) Determine the number of non-bonding electrons, n4, which equals n1 – n3. No. of lone pairs equals
n4/2.
(v) Knowing the central atom (you‟ll need to know some chemistry here, math will not help!), arrange and
distribute other atoms and n3/2 bonds. Then complete octets using n4/2 lone pairs.
LA
(vi) Determine the „formal charge‟ on each atom.
(vii) Formal Charge = [valence electrons in atom) – (no. of bonds) – (no. of unshared electrons)]
(viii) Other aspects like resonance etc. can now be incorporated.
Illustrative examples :
(i) CO32 ; n1  4  (6  3)  2  24 [2 added for net charge]
n 2 = (2 × 0) + (8 × 4) = 32 (no. H atom, 4 other atoms (1‟C‟ and 3 „O‟)
n 3 = 32 – 24 = 8, hence 8/2 = 4 bonds
n 4 = 24 – 8 = 16, hence 8 lone pairs.
A

Since carbon is the central atom, 3 oxygen atoms are to be arranged around it, thus,
O
|
O  C  O , but total bonds are equal to 4.
..
O .O :
| . | ..
B

Hence, we get O  C  O . Now, arrange lone pairs to complete octet : O  C  O :

..

(ii) CO2 ; n1 = 4 + (6 × 2 ) = 16
n2 = (2 × 0) + (8 × 3) = 24
n3 = 24 – 16 = 8, hence 4 bonds
n4 = 16 – 8 = 8, hence 4 lone-pairs
Since C is the central atom, the two oxygen atoms are around to be arranged it thus the structure would
be; O – C – O, but total no. of bonds = 4
.. ..
Thus, O = C = O. After arrangement of lone pairs to complete octets, we get, : O  C  O : and thus
.. ..
final structure is : O  C  O :

CLASSES BY ANKUR SIR @7983744732

3.4 Co-ordinate covalent or Dative bond.
This is a special type of covalent bond where the shared pair of electrons are contributed by one species only
but shared by both. The atom which contributes the electrons is called the donor while the other which only shares
the electron pair is known as acceptor. This bond is usually represented by an arrow (  ) pointing from donor to
the acceptor atom.
For example, in BF3 molecule, boron is short of two electrons. So to complete its octet, it shares the lone pair
of nitrogen in ammonia forming a dative bond as shown in figure

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 

H

 F 
 H  F  H F
      | |
H* N  B*
*

 F 
  H 
* N 
 B 
 F 
  H  N B  F
     | |

H  
H H F
F 
 
 F 
  

Formation of a co - ordinate
bond between NH 3 and BF3
LA
Examples : CO, N2O, H2O2, N2O3, N2O4, N2O5, HNO3, NO 3 , SO2, SO3, H2SO4, SO42 , SO22 ,
H 3 PO4 , H 4 P2 O7 , H 3 PO3 , Al 2 Cl 6 (Anhydrous), O3 , SO2 Cl 2 , SOCl 2 , HIO3 , HClO4 , HClO3 , CH 3 NC, N 2 H 5 ,

CH 3 NO 2 , NH 4 , [Cu( NH 3 )4 ] 2 etc.

(1) Characteristics of co-ordinate covalent bond

(i) Melting and boiling points : Their melting and boiling points are higher than purely covalent
compounds and lower than purely ionic compounds.
A

(ii) Solubility : These are sparingly soluble in polar solvent like water but readily soluble in non-polar
solvents.
(iii) Conductivity : Like covalent compounds, these are also bad conductors of electricity. Their solutions
or fused masses do not allow the passage to electricity.
(iv) Directional character of bond : The bond is rigid and directional. Thus, coordinate compounds show
B

isomerism.

Table: Electron dot formulae and Bond formulae or Dash formulae of some compounds
No. Molecular formula Electron dot formula Dash formula or Bond formula
 –
1. Sodium chloride NaCl Na+  Cl 
 Na  Cl 

Cl N
  N
– ++     –
2. Magnesium chloride MgCl2  Cl Mg  Cl   Cl  Mg   Cl 
   
N Cl N
3.  – N ++
  –
Cl Ca  Cl 
Calcium chloride CaCl2 
 


Cl Ca   Cl 
N Cl NN
  ––
4. Magnesium oxide MgO Mg++  O

Mg   O 
Cl N
N

CLASSES BY ANKUR SIR @7983744732

 
5. Sodium sulphide Na2S Na+  S  – – Na+ Na  S  Na 

Cl N Cl
6. Calcium hydride CaH 2 NH – Ca++NH– H Ca   H 
+
Cl N Cl
 
N – 3+  N –
 F  Al  F F  Al 3 F 
7. Aluminium flouride AlF3
F
   
N ClF  – N

NN

8. Hydrogen chloride HCl H Cl 
 H  Cl

Cl N
HN O
 
9. Water H 2O H
 H OH
 
Cl N Cl

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
H2S NH  S N
10. Hydrogen sulphide H HSH
 
Cl N Cl
N HN H
 |
11. Ammonia NH 3 H  Cl
N  HN

Cl H N |
H
N Cl
H  CN  N 

12. Hydrogen cyanide HCN H C  N
LA
H H
 |
13. Methane CH 4 H  C Cl H H  C H

Cl N N Cl
H |

N Cl N H
H NH H H
Ethane   | |
  
14. C2 H 6 H C Cl C Cl H H  C C H
 
Cl H N H
N N Cl | |

N Cl Cl N H H
NH NH H
|
H
|
CCl C Cl
15. Ethene C2 H 4   CC
NN
H H N N | |
Cl Cl H H
A

16. Ethyne C2 H 2 H  CN C N H H C  CH

Cl N N Cl
N    N
17. Phosphene PH3 H  P H H  P H
 |
Cl H N Cl
N Cl N H

 N
    
B

Phosphorous  Cl  P Cl 
 
Cl  P  Cl
18. PCl 3    
trichloride ClCl
 N Cl
 |

N Cl N Cl
+  N Na  O  H 
 –
19. Sodium hydroxide NaOH Na * O  H

Cl N Cl –
20. Potassium cyanide KCN K+ * C  N
N N K  C  N 
Cl
2
N  
   2–
Ca++ * O 
C O    
21. Calcium carbonate CaCO 3     * Ca O  C  O
Cl N  
N N
 O 
||

N  O 
N 
   
22. Carbon mono oxide CO  C  O  CO
N  N  
23. Nitrous oxide N 2O  
 N   N  O  N  N O

N Cl Cl
N N

CLASSES BY ANKUR SIR @7983744732

      H  O  O  H or H  O  O
 O  H or H  O  O 
  
24. Hydrogen peroxide H 2 O2 H  O 
   

   |
Cl N N Cl Cl Cl N H N H
N      N N N 
 Cl
O  N N  O
O   N N  O 
25. Dinitrogen trioxide N 2 O3  N 
N  O N  N N
 O
N
 
H  O  H+ H  O  H
26. Hydronium ion H3O   |
Cl H N Cl H
  N Cl N  
O  
  N  N  O
 O N N O
27. Nitrogen dioxide N 2 O4   N  
 N  
  
N O  NO N
  O O
N N

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     

O   N    O  N O  N  O
O  N   O 

28. Nitrogen pentaoxide N 2 O5 
       
N O N  N N
 
O  N

O O
   
N N
 
H * O  N 
 O
H O N  O
29. Nitric acid HNO3  
N  N

N N O O
 
N

– * O  N   
 
ON O
  O 
30. Nitrate ion NO3 
     
LA
N  O Cl  N O
 
N
   
31. Nitrous acid HNO2 H O

  
N   O  H O N  O
N N Cl N
– *   N   
32. Nitrite ion NO 2  

 O N  O 

O N  O
N Cl N
   
 N   

33. Sulphur dioxide SO2 
O S
 
O  OSO
N Cl N
  
  N    OS O
O S  O
     
34. Sulphur trioxide SO3 Cl N
N O  

 
 O
N
N
A

O O

 
  
   
Peroxysulphuric acid O
  O 
35. H 2 S2 O8         H O S OO S OH
(Marshal acid) H *  O  N
 S   O   O  N
 S O
  *H

Cl Cl  O
 
Cl Cl Cl  O
 
Cl Cl Cl  
   
N N NN N N N N N N O O
B

   
36. H* O   Cl 
Hypochlorous acid HOCl     H  O  Cl
Cl N N
HClO2 N      
37. Chlorous acid H*  O
Cl O 
   
H  O  Cl  O
Cl N N N
N   
 
O 
  O O
O 
        
 N
38. Perchloric anhydride Cl 2 O7  O  Cl   O   Cl

N  O 
 O Cl  O  Cl O
    
    
N  Cl

O

 Cl  Cl O N O O

N N N N

CLASSES BY ANKUR SIR @7983744732

 O


O 

 
   
H 2 SO4 N O H
H O S    
H O S OH
39. Sulphuric acid *   *

N N N
N N O 



 
N
O


O 

O
–          – 
40. Sulphate ion SO42 O S  N O 
*     *

O  S  O
N N O 
N N N




O
 N   
H * O 
S  O H H  O  S O  H
41. Sulphurus acid H 2 SO3       * 
N N  O N  N N

JI
 O

N
–        – 
O  S  O
O
*   S  O
42. Sulphite ion SO32 N N  O

* 
N  N N O

N
 
 O
O  
    
H*O   
NPO
     *H
H O  PO  H
43. Phosphoric acid H 3 PO4 N NO N N N
|
* O
N
H |
LA
N H
O O
   
 
 
  O O
  H O  PO  PO  H
        | |
44. Pyrophosphoric acid H 4 P2 O7 *     *
H O N
P O PN O H
          O O
N N 
 
N N O
O
  N N N

 | |
* * 
N
H N
H H H
N N
 
O
 
O  
       

Persulphuric acid H O N
S O O H
* 
  *
 
45. H 2 SO5   
     H O S OOH
(caro‟s acid) N N N
O N N N




A

 
N
O


  S
S        
46. Thiosulphurous acid H 2 S2 O3 H O NS O H
*



  

 
*
H  O  S O  H
N N NO N N 


 
 O
N
B

H H
|
  
47. Phosphorous acid H 3 PO3 H O PN O H
*   * H O PO H
    
N N O
N N N 


 O

N
     

 Cl   Cl  Cl 
Al 2 Cl 6 NAl N Al N Cl Cl Cl
48. Aluminium chloride Al Al
(Anhydrous)  Cl Cl  Cl Cl Cl
 Cl Cl Cl
 


   
N N N N N

CLASSES BY ANKUR SIR @7983744732

 
O O
49. Ozone O3 
 O O 



 
N NN O O

**
Cl
* * Cl
  *  * *  |
50. Sulphuryl chloride SO2 Cl 2 
 S O
 
O N  
  *  

O S O
*
*Cl N
N *
*
|

N N
** Cl

*    
* *
O S Cl
* 
* * 
   O  S  Cl
51. Sulphonyl chloride SOCl 2 NNCl N




|
 
N Cl

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    
  
H * O  I  O H O I O
    
52. Iodic acid HIO3 N NN 
O N
 

N O

 

 O 

O
      
53. Perchloric acid HClO4 *
H O Cl



N O



 H  O  Cl  O
      
N N N 
 O N
 O
LA
 
 N
 
S
  S
     
Hyposulphurous H O S 
 N O O H  * 
54. H 2 S2 O4 *
     
  H  O  S O  O  H
acid N NN 
 O NN N

 
 O
N

 
 S S
        
55. Pyrosulphurus acid H 2 S2 O5 H * OO  SN O O * H
    H  O  O  S O  O  H
N N NN 
O  N N N 
 O
N
   
H * O 
 Cl  O 
  H  O  Cl  O
     
56. Chloric acid HClO3 N N N 
O N 
 O
A

3.5 Polarity of covalent bond.

A covalent bond in which electrons are shared equally between bonded atoms, is called non polar covalent
bond while a covalent bond, in which electrons are shared unequally and the bonded atoms acquire a partial
positive and negative charge, is called a polar covalent bond. The atom having higher electronegativity draws the
B

bonded electron pair more towards itself resulting in partial charge separation. This is the reason that HCl molecule
in vapour state contains polar covalent bond
 
Polar covalent bond is indicated by notation : H – Cl
(1) Bond polarity in terms of ionic character : The polar covalent bond, has partial ionic character.
Which usually increases with increasing difference in the electronegativity (EN) between bonded atom
H – F H – Cl H – Br H – I
EN 2.1 4.0 2.1 3.0 2.1 2.8 2.1 2.5
Difference in EN 1.9 0.9 0.7 0.4
Ionic character decreases as the difference in electronegativity decreases

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 (2) Percentage ionic character : Hennay and Smith gave the following equation for calculating the
percentage of ionic character in A–B bond on the basis of the values of electronegativity of the atoms A and B.
Percentage of ionic character = [16 ( A   B )  3.5 ( A   B )2 ] .
Whereas (x A  x B ) is the electronegativity difference. This equation gives approximate calculation of
percentage of ionic character, e.g., 50% ionic character corresponds to (xA  xB) equals to 1.7.
3.6 Dipole moment.
“The product of magnitude of negative or positive charge (q) and the distance (d) between the centres of
positive and negative charges is called dipole moment”.
It is usually denoted by . Mathematically, it can be expressed as follows :

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 = Electric charge  bond length
As q is in the order of 10 esu and d is in the order of 10–8 cm,  is in the order of 10–18 esu cm. Dipole
–10

moment is measured in “Debye” (D) unit. 1D  1018 esu cm = 3.33  1030 coulomb metre.
Generally, as electronegativity difference increases in diatomic molecules, the value of dipole moment
increases. Greater the value of dipole moment of a molecule, greater the polarity of the bond between the atoms.
Dipole moment is indicated by an arrow having a symbol ( ) pointing towards the negative end. Dipole
moment has both magnitude and direction and therefore it is a vector quantity.
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Symmetrical polyatomic molecules are not polar so they do not have any value of dipole moment.
H
F

O C O C
B H H
F F
H
 = 0 due to symmetry
Some other examples are – CCl4,CS2 , PbCl 4 , SF6 , SO3 , C6 H 6 , naphthalene and all homonuclear molecules (H2,
O2, Cl2 etc)
Note :
A

 Benzene, Naphthalene have zero dipole moment due to planar structure.

 Amongst isomeric dihalobenzenes, the dipole moment decreases in the order : o > m > p.
 A molecule of the type MX4, MX3 has zero dipole moment, because the -bonding orbitals used by
M(Z < 21) must be sp3, sp2 hybridization respectively (e.g. CH4, CCl4, SiF4 , SnCl4, BF3 , AlCl3 etc.)

sp 3 sp 2
B

Unsymmetrical polyatomic molecules always have net value of dipole moment, thus such molecules are
polar in nature. H2O, CH3Cl, NH3, etc are polar molecules as they have some positive values of dipole moments.

Cl

S N
O C
O O H H
H H H H
H
Water  = 1.84D Sulphur dioxide H Ammonia
 = 1.60D Methyl chloride  = 1.46D
 = 1.86D
  0 due to unsymmetry
Some other examples are – CH3Cl, CH2Cl2, CHCl3, SnCl2, ICl, C6H5CH3 , H2O2, O3, Freon etc.

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 Applications of dipole moment
(i) In determining the symmetry (or shape) of the molecules : Dipole moment is an important factor in
determining the shape of molecules containing three or more atoms. For instance, if any molecule
possesses two or more polar bonds, it will not be symmetrical if it possesses some molecular dipole
moment as in case of water (  1.84 D) and ammonia (  1.49 D). But if a molecule contains a
number of similar atoms linked to the central atom and the overall dipole moment of the molecule is
found to be zero, this will imply that the molecule is symmetrical, e.g., in case of BF3 , CH 4 , CCl 4 etc.,
(ii) In determining percentage ionic character : Every ionic compound having some percentage of
covalent character according to Fajan‟s rule. The percentage of ionic character in a compound having

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some covalent character can be calculated by the following equation.
Observed dipole moment
The percent ionic character   100
Calculated dipole moment assuming 100% ionic bond
(iii) In determining the polarity of bonds as bond moment : As   q  d , obviously, greater is the
magnitude of dipole moment, higher will be the polarity of the bond. The contribution of individual
bond in the dipole moment of a polyatomic molecule is termed as bond moment. The measured
LA
dipole moment of water molecule is 1.84 D. This dipole moment is the vectorial sum of the individual
bond moments of two O-H bonds having bond angle 104.5o.
Thus,  obs  2 O H cos 52.25 or 1.84 = 2O – H × 0.6129 ; O – H = 1. 50 D

Note :   EN  dipole moment, so HF > HCl > HBr > HI ,

Where, EN = Electronegativity difference
  EN  bond polarity, so HF > H2O > NH3 > H2S.
 If the electronegativity of surrounding atom decreases, then dipole moment increases. NCl 3  NBr3  NI 3
(iv) To distinguish cis and trans forms : The trans isomer usually possesses either zero dipole moment or
very low value in comparision to cis–form
A

H  C  Cl H  C  Cl
|| ||
H  C  Cl Cl  C  H
Cis – 1, 2 – dichloro ethene   1.9 D Trans – 1, 2 –dichloro ethene,   0
Example: Calculate the % of ionic character of a bond having length = 0.92 Å and 1.91 D as its observed dipole moment.
B

(a) 43.25 (b) 86.5 (c) 8.65 (d) 43.5

Solution: (a) Calculated  considering 100% ionic bond [When we consider a compound ionic, then each ionic sphere
should have one electron charge on it of 4.80  10 10 esu (in CGS unit) or 1.60  10 19 C (in SI unit)]
= 4.8 × 10–10 × 0.92 × 10–8 esu cm = 4.416 D
1.91
% Ionic character   100  43.25.
4.416
Important Tips

 The dipole moment of CO molecule is greater than expected. This is due to the presence of a dative (co-ordinate) bond.
 Critical temperature of water is higher than that of O2 because H2O molecule has dipole moment.
 Liquid is not deflected by a non uniform electrostatic field in hexane because of  = 0

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3.7 Change of ionic character to covalent character and Fajan’s rule.
Although in an ionic compound like M+X– the bond is considered to be 100% ionic, but it has some covalent
character. The partial covalent character of an ionic bond has been explained on the basis of polarization.
Polarization : When a cation of small size approaches an anion, the electron cloud of the bigger anion is
attracted towards the cation and hence gets distorted. This distortion effect is called polarization of the anion. The
power of the cation to polarize nearby anion is called its polarizing power. The tendency of an anion to get distorted
or polarized by the cation is called polarizability. Due to polarization, some sort of sharing electrons occurs between
two ions and the bond shows some covalent character.
Fajan’s rule : The magnitude of polarization or increased covalent character depends upon a number of

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factors. These factors were suggested by Fajan and are known as Fajan‟s rules.
Factors favouring the covalent character
(i) Small size of cation : Smaller size of cation greater is its polarizing power i.e. greater will be the
covalent nature of the bond. On moving down a group, the polarizing power of the cation goes on
decreasing. While it increases on moving left to right in a period. Thus polarizing power of cation
follows the order Li   Na   K   Rb   Cs  . This explains why LiCl is more covalent than KCl .
LA
(ii) Large size of anion : Larger the size of anion greater is its polarizing power i.e. greater will be the
covalent nature of the bond. The polarizability of the anions by a given cation decreases in moving left
to right in a period. While it increases on moving down a group. Thus polarzibility of the anion follows
the order I   Br   Cl   F  . This explains why iodides are most covalent in nature.
(iii) Large charge on either of the two ions : As the charge on the ion increases, the electrostatic attraction
of the cation for the outer electrons of the anion also increases with the result its ability for forming the
covalent bond increases. FeCl3 has a greater covalent character than FeCl2. This is because Fe3+ ion
has greater charge and smaller size than Fe2+ ion. As a result Fe3+ ion has greater polarizing power.
Covalent character of lithium halides is in the order LiF < LiCl < LiBr < LiI.
A

(iv) Electronic configuration of the cation : For the two ions of the same size and charge, one with a
pseudo noble gas configuration (i.e. 18 electrons in the outermost shell) will be more polarizing than a
cation with noble gas configuration (i.e., 8 electron in outer most shell). CuCl is more covalent than
NaCl, because Cu+ contains 18 electrons in outermost shell which brings greater polarization of the
anion.
B

Important tips
Ionic character
 en (Electronegativity difference) 
Covalent character
 Increase of polarization brings more of covalent character in an ionic compound. The increased covalent character is indicated by
the decrease in melting point of the ionic compound
 Decreasing trends of melting points with increased covalent character
NaF < NaCl < NaBr < NaI (size of anion increases)
M.Pt (oC) 988 801 755 651
BaCl2 < SrCl2 < CaCl2 < MgCl2 < BeCl2 (size of cation decreases)
M.Pt (oC) 960 872 772 712 405
 Lithium salts are soluble in organic solvents because of their covalent character
 Sulphides are less soluble in water than oxides of the same metal due to the covalent nature of sulphur.

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 3.8 Quantum theory (Modern theory) of covalent bond and overlapping.
(1) A modern Approach for covalent bond (Valence bond theory or VBT)
(i) Heitler and London concept.
(a) To form a covalent bond, two atoms must come close to each other so that orbitals of one overlaps
with the other.
(b) Orbitals having unpaired electrons of anti spin overlaps with each other.
(c) After overlapping a new localized bond orbital is formed which has maximum probability of finding
electrons.

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(d) Covalent bond is formed due to electrostatic attraction between radii and the accumulated electrons
cloud and by attraction between spins of anti spin electrons.
(e) Greater is the overlapping, lesser will be the bond length, more will be attraction and more will be
bond energy and the stability of bond will also be high.
(ii) Pauling and slater extension
(a) The extent of overlapping depends upon: Nature of orbitals involved in overlapping, and nature of
overlapping.
LA
(b) More closer the valence shells are to the nucleus, more will be the overlapping and the bond energy
will also be high.
(c) Between two sub shells of same energy level, the sub shell more directionally concentrated shows more
overlapping. Bond energy : 2s  2s < 2s  2 p < 2 p  2 p
(d) s -orbitals are spherically symmetrical and thus show only head on overlapping. On the other hand,
p -orbitals are directionally concentrated and thus show either head on overlapping or lateral
overlapping.
(iii) Energy concept
(a) Atoms combine with each other to minimize their energy.
A

(b) Let us take the example of hydrogen molecule in which the bond between two hydrogen atoms is
quite strong.
(c) During the formation of hydrogen molecule, when two hydrogen atoms approach each other, two
types of interaction become operative as shown in figure. 
The force of attraction between the molecules of one atom Attraction
+ Repulsion +
and electrons of the other atom. The force of repulsion
B

Attraction
between the nuclei of reacting atoms and electrons of the 

reacting atoms
(d) As the two hydrogen atoms approach each other from the infinite distance, they start interacting with
each other when the magnitude of attractive forces is more
+ve
than that of repulsive forces a bond is developed between
two atoms.
O

(e) The decrease in potential energy taking place during formation P.E. decreases as
E
of hydrogen molecule may be shown graphically ()
–ve
)

d0
(f) The inter nuclear distance at the point O have minimum
energy or maximum stability is called bond length.

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 (g) The amount of energy released (i.e., decrease in potential energy) is known as enthalpy of formation.
(h) From the curve it is apparent that greater the decrease in potential energy, stronger will be the bond
formed and vice versa.
(i) It is to be noted that for dissociation of hydrogen molecule into atoms, equivalent amount of energy is
to be supplied.
(j) Obviously in general, a stronger bond will require greater amount of energy for the separation of
atoms. The energy required to cleave one mole of bonds of the same kind is known as the bond
energy or bond dissociation energy. This is also called as orbital overlap concept of covalent bond.
(2) Overlapping

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(i) According to this concept a covalent bond is formed by the partial overlapping of two half filled atomic
orbitals containing one electron each with opposite spins then they merge to form a new orbital known
as molecular orbital.
(ii) These two electrons have greater probability of their presence in the region of overlap and thus get
stabilised i.e., during overlapping energy is released.
Examples of overlapping are given below :
LA
Formation of hydrogen molecule : Two hydrogen atoms having electrons with opposite spins come close to
each other, their s-orbitals overlap with each other resulting in the union of two atoms to form a molecule.

+ – + – + + +

H-atom H-atom H2-molecule

Formation of fluorine molecule : In the formation of F2 molecule p-orbitals of each flourine atom having
electrons with opposite spins come close to each other, overlapping take place resulting is the union of two atoms.
2px 2px
A

2py 2py

2pz + 2pz
B

F-atom F-atom F2-molecule

Formation of fluorine molecule

Types of overlapping and nature of covalent bonds ( - and  - bonds) : overlapping of different type
gives sigma () and pi () bond. Various modes of overlapping given below :
s – s overlapping : In this type two half filled s-orbitals overlap along the internuclear axis to
form -bond.
+
s-orbital s-orbital s-s overlap
-bond
s-s overlapping

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 s-p overlapping : It involves the overlapping of half filled s-orbital of one atom with the half filled p-orbital of
other atom This overlapping again gives -bond e.g., formation of H – F molecule involves the overlapping of 1s
orbital of H with the half filled 2pz – orbital of Fluorine.

+
s-orbital p-orbital s–p overlap
s – p overlapping -bond

p-p overlapping : p-p overlapping can take place in the following two ways.
(i) When there is the coaxial overlapping between p-orbitals of one atom with the p-orbitals of the

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other then -bond formation take place e.g., formation of F2 molecule in which 2pz orbital of one F
atom overlap coaxially with the 2pz orbitals of second atom. -bond formation take place as shown
below :

+
pz-orbital pz -orbital pz – pz overlap
LA
-bond
p – p overlapping

(ii) When p–orbitals involved in overlapping are parallel and perpendicular to the internuclear axis. This
types of overlapping results in formation of pi bond. It is always accompanied by a  bond and consists
of two charge clouds i.e., above and below the plane of sigma bond. Since overlapping takes place on
both sides of the internuclear axis, free rotation of atoms around a pi bond is not possible.

+ +


+  Internuclear axis
A


– –  -bond
p-orbital p-orbital
p-p overlapping

Table : Difference in  and  bonds

B

Sigma () bond Pi () bond

It results from the end to end overlapping of two s-orbitals or two It result from the sidewise (lateral) overlapping of two p-orbitals.
p-orbitals or one s and one p-orbital.
Stronger Less strong
Bond energy 80 kcals Bond energy 65 kcals
More stable Less stable
Less reactive More reactive
Can exist independently Always exist along with a -bond
The electron cloud is symmetrical about the internuclear axis. The electron cloud is above and below the plane of internuclear
axis.

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 Important Tips

 To count the  and  bonds in molecule having single, double and triple bond first we write its expanded structure.
H
|
C
CN
H
| H C CH
  H\ |
ex. H  H , OO , N  N, C  C C  N , N  C CC  N , | ||
  2 / H C CH
H |
(3 , 6 )
CN C
(8 , 8 ) |
H

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(3 , 12 )

All the single bonds are -bond. In a double bond, one will be  and the other  type while in a triple bond, one will be  and other two .
OH
|
 The enolic form of acetone has 9, 1 and two lone pairs CH 2  C  CH 3 (enol form of acetone)

H H H H
|  |
\  /
 It is the  bond that actually takes part in reaction, CC  H 2  H  C  C  H , but the shape of molecule is decided
/  \ | |
H H H H
LA
by -bond.
 The number of sp2-s sigma bonds in benzene are 6.
 When two atoms of the element having same spin of electron approach for bonding, the orbital overlapping and bonding both does
not occur.
 Head on overlapping is more stronger than lateral, or sidewise overlapping.
p-p > s-p > s-s > p-p
Head on overlapping Sidewise
overlapping

3.9 Hybridization.
The concept of hybridization was introduced by Pauling and Slater. It is defined as the intermixing of
dissimilar orbitals of the same atom but having slightly different energies to form same number of new orbitals of
A

equal energies and identical shapes. The new orbitals so formed are known as hybrid orbitals.
Characteristics of hybridization
(1) Only orbitals of almost similar energies and belonging to the same atom or ion undergoes hybridization.
(2) Hybridization takes place only in orbitals, electrons are not involved in it.
(3) The number of hybrid orbitals produced is equal to the number of pure orbitals, mixed during
B

hybridization.
(4) In the excited state, the number of unpaired electrons must correspond to the oxidation state of the central
atom in the molecule.
(5) Both half filled orbitals or fully filled orbitals of equivalent energy can involve in hybridization.
(6) Hybrid orbitals form only sigma bonds.
(7) Orbitals involved in  bond formation do not participate in hybridization.
(8) Hybridization never takes place in an isolated atom but it occurs only at the time of bond formation.
(9) The hybrid orbitals are distributed in space as apart as possible resulting in a definite geometry of molecule.
(10) Hybridized orbitals provide efficient overlapping than overlapping by pure s, p and d-orbitals.
(11) Hybridized orbitals possess lower energy.

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 Depending upon the type and number of orbitals involved in intermixing, the hybridization can be of various
types namely sp, sp2, sp3, sp3d, dsp2, sp3d2, sp3d3. The nature and number of orbitals involved in the above
mentioned types of hybridization and their acquired shapes are discussed in following table

Type of hy- No. of No. of Actual

Geometry of molecules as
Character bonded lone shape of Example
brisation per VSPER theory
atoms pairs molecules

180o CO2, HgCl2, BeF2, ZnCl2 ,

s-character=50%, A A MgCl 2 , C2 H 2 , HCN, BeH 2
sp 2 0 Linear
p -character= 50% Linear C2 H 2 , CS2 , N 2 O, Hg 2 Cl 2 ,
[ Ag{NH 3 ) 2 ]

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BF3 , AlCl 3 , SO3 , C2 H 4 ,

120o NO3 , CO32  , HCHO

s-character= 33.33%, A Trigonal
sp 2 3 0 C6 H 6 , CH 3 graphite,
p-character=66.67% Planar
C2 Cl 4 , C2H2Cl2, [HgI3 ] ,
Trigonal Planar, 120o
[Cu(PMe 3 )3 ]
V-shape
<120o 2 1 NO2 , SO2 , SnCl 2
(bent)
LA
CH 4 , SiH 4 , SO42 , SnCl 4 ,
ClO4 , BF4 , NH4 , CCl4 ,
109o28 SiF4 , H 2  NH 2 ,
s-character = 25%, A
[BeF4 ]  , XeO 4 ,
sp 3 p-character = 75% 4 0 Tetrahedral
[ AlCl 4 ] , SnCl4 , PH 4 ,
Tetrahedral , 109.5o
Diamond, silica,
Ni(CO)4 , Si(CH 3 )4 , SiC,
SF2 , [ NiCl 4 ]2 , [MnO4 ] [VO4 ]3 

NH 3 , PCl 3 , PH3 , AsH 3

Trigonal
< 109.5o 3 1
pyramidal ClO3 , POCl 3 H 3 O  , XeO 3
A

V-shape H2O, H2S, PbCl 2, OF2, NH2

104.5o 2 2
(bent) ClO 2

90o
s-character = 25%
Square [Cu( NH 3 ) 4 ] 2 , [ Ni(CN) 4 ] 2
dsp 2 p – character = 50% 4 0
planar [Pt ( NH3 )4 ]2
B

d – character = 25%
Square planar

90o
s-character = 20%, PCl 5 , SbCl5 , XeO3 F2 , PF5
3 120 o A Trigonal AsF5 , PCl 4 , PCl 6 , [Cu(Cl)5 ]3
sp d p-character = 60%, 5 0
bipyramidal
d-character = 20% [ Ni(CN)5 ] 3 , [Fe(CO)5 ]

Trigonal bipyramidal
Irregular TeCl4 , SF4
4 1
tetrahedral
3 2 T-shaped ClF3 , IF3

2 3 Linear I 3 , XeF2

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 s-character = 25% SF6 , PF6 , SnCl6 , MoF6 ,
sp 3 d 2 p – character = 50% 6 0 Octahedral (BaCl6 ) , (PF6 ) ,
d – character = 25% [Fe(CN)6 ] 4  , [Fe(H 2 O)6 ] 3

Octohedral
Square ICl 5 , BrF5 , IF5 XeOF4
5 1
pyramidal
Square
4 2 XeF4 , ICl 4
planar

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90o

72o
s-character= 14.28%, A
Pentagonal IF7 , [ ZrF7 ]3 [UF7 ]3
sp 3 d 3 p-character= 42.86%, 7 0
bipyramidal [UO 2 F5 ] 3
d-character= 42.86%
LA
Pentagonal bipyramidal
Distorted XeF6
6 1
octahedral
Short trick to find out hybridization : The structure of any molecule can be predicted on the basis of
1
hybridization which in turn can be known by the following general formulation. H  (V  M  C  A)
2
Where H = Number of orbitals involved in hybridization viz. 2, 3, 4, 5, 6 and 7, hence nature of hybridization
will be sp, sp2, sp3, sp3d, sp3d2, sp3d3 respectively.
V = Number electrons in valence shell of the central atom, M = Number of monovalent atom
A

C = Charge on cation, A = Charge on anion

Few examples are given below to illustrate this:
Type : (A) When the central atom is surrounded by monovalent atoms only, e.g. BeF2, BCl3, CCl4, NCl3,
PCl5, NH3, H2O, OF2, TeCl4, SCl2, IF7, ClF3, SF4, SF6, XeF2, XeF4, etc. Let us take the case of PCl5.
1
B

H (5  5  0  0)  5 . Thus, the type of hybridization is sp3d.

2

Type : (B) When the central atom is surrounded by divalent atoms only; e.g. CO2, CS2, SO2, SO3, XeO3 etc.
1
Let us take the case of SO3. H  (6  0  0  0)  3 . Thus, the type of hybridization in SO3 is sp2.
2
Type : (C) When the central atom is surrounded by monovalent as well as divalent atoms, e.g. COCl2, POCl3,
1
XeO2F2 etc. Let us take the case of POCl3. H  (5  3  0  0)  4 . Thus, the nature of hybridization in POCl3 is sp3.
2
Type : (D) When the species is a cation, e.g. NH4+, CH3+, H3O+ etc. Let us take the case of CH3+.
1
H  (4  3  1  0)  3 . Thus, the hybridization in CH3+ is sp2.
2

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 Type : (E) When the species is an anion, e.g. SO42–, CO32–, PO43–, NO2–, NO3–, etc. Let us take the case of
1
SO42–. H  (6  0  0  2)  4 . Thus, hybridization in SO42  is sp3 .
2

Type : (F) When the species is a complex ion of the type ICl4–, I3–, ClF2–, etc. Let us take the case of ClF2–.
1
H  (7  2  0  1)  5 . Thus, in ClF2–, Cl is sp3d hybridized.
2
Type : (G) When the species is a complex ion of the type [PtF6]2 –, [Co(NH3)6]2+, [Ni(NH3)4Cl2] etc. In such
cases nature of hybridization is given by counting the co-ordination number.
Important Tips

JI
 The sequence of relative energy and size of s – p type hybrid orbitals is sp < sp2 < sp3.
 The relative value of the overlapping power of sp, sp2 and sp3 hybrid orbitals are 1.93, 1.99 and 2.00 respectively.
 An increase in s-character of hybrid orbitals, increases the bond angle. Increasing order of s-characters and bond angle is sp3 < sp2 < sp.
 Normally hybrid orbitals (sp, sp2, sp3, dsp2, dsp3 etc.) form -bonds but in benzyne lateral overlap of sp2-orbitals forms a -bond.
 Some iso-structural pairs are [ NF3 , H3O ], [ NO3 , BF3 ], [SO42 , BF4 ] . There structures are similar due to same hybridization.
 In BF3 all atoms are co-planar.
In PCl5 the state of hybridization of P atom is sp3d. In its trigonal bipyramidal shape all the P-Cl bonds are not equal.
LA
 The  bond formed between S and O atoms in SO2 molecule is due to overlap between their p-orbitals ( P  P bonding) or
between p orbital of O-atom with d-orbital of S-atom (called p – d bonding)

16 S  1s 2 2s 2 2 p 6 3s 2 3 p x2 3 p1y 3 p1z (Ground state configuration)

 1s 2 2s 2 2 p 6 3s 2 3 p1x 3 p1y 3 p1z 3d 1 (Excited state configuration)

p- d p- p
8O  1s 2 2s 2 2 p x2 2 p1y 2 p1z bonding 3p bonding
2p d
2p

S
S
A

d
S-atom undergoes sp2 hybridization leaving one half-filled 3pz orbital and one d-orbital unhybridized. Out of two half filled
orbitals of O-atom, one is involved in formation of -bond with S-atom and the other in forming -bond.

3.10 Resonance.
B

The phenomenon of resonance was put forward by Heisenberg to explain the properties of certain
molecules.
In case of certain molecules, a single Lewis structure cannot explain all the properties of the molecule. The
molecule is then supposed to have many structures, each of which can explain most of the properties of the
molecule but none can explain all the properties of the molecule. The actual structure is in between of all these
contributing structures and is called resonance hybrid and the different individual structures are called
resonating structures or canonical forms. This phenomenon is called resonance.
To illustrate this, consider a molecule of ozone O3 . Its structure can be written as
O O O

O O O O O O
(a) (b) (c )

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 It may be noted that the resonating structures have no real existence. Such structures are only theoretical. In
fact, the actual molecule has no pictorial representation. The resonating structures are only a convenient way of
picturing molecule to account for its properties.
As a resonance hybrid of above two structures (a) and (b. For simplicity, ozone may be represented by
structure (c), which shows the resonance hybrid having equal bonds between single and double.
Resonance is shown by benzene, toluene, O3, allenes (>C = C = C<), CO, CO2, CO 3 , SO3, NO, NO2 while
it is not shown by H2O2, H2O, NH3, CH4, SiO2.
(1) Conditions for writing resonance structures
The resonance contributing structures :

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(i) Should have same atomic positions.
(ii) Should have same number of bond pairs and lone pairs.
(iii) Should have nearly same energy.
(iv) Should be so written such that negative charge is present on an electronegative atom and positive
charge is present on an electropositive atom.
(v) The like charges should not reside on adjacent atoms. But unlike charges should not greatly separated.
LA
(2) Characteristics of resonance
(i) The contributing structures (canonical forms) do not have any real existence. They are only imaginary.
Only the resonance hybrid has the real existence. E1

(ii) As a result of resonance, the bond lengths of single and double E2

bond in a molecule become equal e.g. O–O bond lengths in E3
ozone or C–O bond lengths in CO32 – ion.
Resonance energy
Energy

(iii) The resonance hybrid has lower energy and hence greater
E0
stability than any of the contributing structures.
(iv) Greater is the resonance energy, greater is the stability of the Resonating structures
A

Concept of resonance energy. Energies E1, E2

molecule. and E3 for three structures and E0 is the
experimentally determined bond energy
(v) Greater is the number of canonical forms especially with nearly
same energy, greater is the stability of the molecule.
(3) Resonance energy
B

It is the difference between the energy of resonance hybrid and that of the most stable of the resonating
structures (having least energy). Thus,
Resonance energy = Energy of resonance hybrid – Energy of the most stable of resonating structure.
(4) Bond order calculation
In the case of molecules or ions having resonance, the bond order changes and is calculated as follows:
Total no. of bonds between two atoms in all the structures
Bond order 
Total no. of resonating structures

e.g., (i) In benzene 



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 double bond  single bond 2  1
Bond order    1.5
2 2
O O O
| || |
(ii) In carbonate ion C  C  C
// \ / \ / \\

O O O O 
O O
211
Bond order   1.33
3
Important Tips

JI
 Resonance structure (canonical form) must be planar.
 O 
 
 In case of formic acid H  C , the two CO bond lengths are different but in formate ion
 O  H 

 O O  

H  C  H  C  the two C  O bond lengths are equal due to resonance.
 
 O O 
LA
 In resonance hybrid, the bond lengths are different from those in the contributing structure.
 Resonance arises due to delocalisation of  electrons. Resonating structures have different electronic arrangements.
 The resonating structures do not have real existence.
 Resonance energy = [Experimental heat of formation]–[Calculated heat of formation of most stable canonical form].
   
 Three contributing structure of CO 2 molecule are – O  C  O  O  C  O  O C  O
 
 
 Resonance structure of carbon monoxide is C O  C  O


 Resonance energy of benzene is 152.0 kJ / mol .

A

3.11 Bond characteristics.

(1) Bond length
“The average distance between the centre of the nuclei of the two bonded atoms is called bond length”.
It is expressed in terms of Angstrom (1 Å = 10–10 m) or picometer (1pm = 10–12 m). It is determined
experimentally by X-ray diffraction methods or spectroscopic methods. In an ionic compound, the bond length is
B

the sum of their ionic radii (d = r++ r–) and in a covalent compound, it is the sum of their covalent radii (e.g., for HCl, d
= rH + rCl).
Factors affecting bond length
(i) Size of the atoms : The bond length increases with increase in the size of the atoms. For example, bond
length of H  X are in the order , HI  HBr  HCl  HF
1
(ii) Electronegativity difference : Bond length  .
EN
(iii) Multiplicity of bond : The bond length decreases with the multiplicity of the bond. Thus, bond length
of carbon–carbon bonds are in the order , C  C  C  C  C – C
(iv) Type of hybridisation : As an s-orbital is smaller in size, greater the s-character shorter is the hybrid
orbital and hence shorter is the bond length. For example, sp 3 C – H  sp 2 C – H  sp C – H

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 (v) Resonance : Bond length is also affected by resonance as in benzene and CO2 . In benzene bond
length is 1.39 Å which is in between C  C bond length 1.54 Å and C = C bond length 1.34 Å


In CO2 the C-O bond length is 1.15 Å .
(In between C  O and C  O )
 
O  C  O O C  O  O  CO
(vi) Polarity of bond : Polar bond length is usually smaller than the theoretical non-polar bond length.

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(2) Bond energy
“The amount of energy required to break one mole of bonds of a particular type so as to separate them into
gaseous atoms is called bond dissociation energy or simply bond energy”. Greater is the bond energy, stronger
is the bond.
Bond energy is usually expressed in kJ mol –1 .

Factors affecting bond energy

LA
1
(i) Size of the atoms : Bond energy  Greater the size of the atom, greater is the bond length and
atomic size
less is the bond dissociation energy i.e. less is the bond strength.
(ii) Multiplicity of bonds : For the bond between the two similar atoms, greater is the multiplicity of the
bond, greater is the bond dissociation energy. This is firstly because atoms come closer and secondly,
the number of bonds to be broken is more, C  C  C  C  C  C , C  C  C  N  N  N
(iii) Number of lone pairs of electrons present : Greater the number of lone pairs of electrons present on
the bonded atoms, greater is the repulsion between the atoms and hence less is the bond dissociation
A

energy. For example for a few single bonds, we have

Bond C–C N–N O–O F–F

Lone pair of electrons 0 1 2 3
Bond energy (kJ mol–1) 348 163 146 139
B

(iv) Percentage s–character : The bond energy increases as the hybrid orbitals have greater amount of s
orbital contribution. Thus, bond energy decreases in the following order, sp  sp 2  sp 3

(v) Bond polarity : Greater the electronegativity difference, greater is the bond polarity and hence greater
will be the bond strength i.e., bond energy, H  F  H  Cl  H  Br  H  I ,
(vi) Among halogens Cl – Cl > F – F > Br – Br > I – I, (Decreasing order of bond energy)
(vii) Resonance : Resonance increases bond energy.
(3) Bond angle
In case of molecules made up of three or more atoms, the average angle between the bonded orbitals (i.e.,
between the two covalent bonds) is known as bond angle .

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 Factors affecting bond angle
(i) Repulsion between atoms or groups attached to the central atom : The positive charge, developed due
to high electronegativity of oxygen, on the two hydrogen atoms in water causes repulsion among
themselves which increases the bond angle, H–O–H from 90º to 105º.
(ii) Hybridisation of bonding orbitals : In hybridisation as the s character of the s hybrid bond increases,
the bond angle increases.
Bond type sp3 sp2 sp
Bond angle 109º28 120 o
180o

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1
(iii) Repulsion due to non-bonded electrons : Bond angle  . By increasing
No. of lone pair of electrons
lone pair of electron, bond angle decreases approximately by 2.5%.
CH4 NH3 H2O
Bond angle 109º 107 o
105o

(iv) Electronegativity of the atoms : If the electronegativity of the central atom decreases, bond angle
LA
decreases.
H 2O  H 2S  H 2 Se  H 2 Te
o o o
Bond angle 104.5 92.2 91.2 89.5 o
In case the central atom remains the same, bond angle increases with the decrease in electronegativity
of the surrounding atom, e.g.
PCl 3 PBr3 PI 3 , AsCl 3 AsBr3 AsI 3
o o o o o
Bond angle 100 101.5 102 98.4 100.5 101 o
Example: Energy required to dissociate 4 grams of gaseous hydrogen into free gaseous atoms is 208 kcal at 25oC the bond
A

energy of H–H bond will be [CPMT 1989]

(a) 104 Kcal (b) 10.4 Kcal (c) 20 .8 Kcal (d) 41.6 Kcal
Answer: (a) 4 gram gaseous hydrogen has bond energy 208 kcal
208
So, 2 gram gaseous hydrogen has bond energy  kcal = 104 kcal.
2
B

Important Tips
 More directional the bond, greater is the bond strength and vice versa. For example :
sp 3  sp 3  sp 2  sp 2  sp  sp  p  p  s  p  s  s

 The hybrid orbitals with more p-character are more directional in character and hence of above order.
 The terms ‘bond energy’ and ‘bond dissociation’ energy are same only for di-atomic molecules.
 The order of O–O bond length in O2, H2O2 and O3 is H2O2 > O2 > O3
 Because of higher electron density and small size of F atom repulsion between electron of it two F atoms, weakens the F-F bond.
 The bond length increases as the bond order decreases.
 Carbon monoxide (CO) has the highest bond energy(1070 kJmol 1 ) of all the diatomic molecules. Bond energy of N 2(946kJmol 1)
and that of H2(436 kJmol-1) are other diatomic molecules with very high bond energies.

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3.12 VSEPR (Valence shell electron pair repulsion) theory.
The basic concept of the theory was suggested by Sidgwick and Powell (1940). It provides useful idea for
predicting shapes and geometries of molecules. The concept tells that, the arrangement of bonds around the central
atom depends upon the repulsion‟s operating between electron pairs(bonded or non bonded) around the central
atom. Gillespie and Nyholm developed this concept as VSEPR theory.
The main postulates of VSEPR theory are
(i) For polyatomic molecules containing 3 or more atoms, one of the atoms is called the central atom to
which other atoms are linked.
(ii) The geometry of a molecule depends upon the total number of valence shell electron pairs (bonded or

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not bonded) present around the central atom and their repulsion due to relative sizes and shapes.
(iii) If the central atom is surrounded by bond pairs only. It gives the symmetrical shape to the molecule.
(iv) If the central atom is surrounded by lone pairs (lp) as well as bond pairs (bp) of e  then the molecule
has a distorted geometry.
(v) The relative order of repulsion between electron pairs is as follows : Lone pair-lone pair>lone pair-
bond pair>bond pair-bond pair
LA
A lone pair is concentrated around the central atom while a bond pair is pulled out between two bonded
atoms. As such repulsion becomes greater when a lone pair is involved.
Steps to be followed to find the shape of molecules :
(i) Identify the central atom and count the number of valence electrons.
(ii) Add to this, number of other atoms.
(iii) If it is an ion, add negative charges and subtract positive charges. Call the total N.
(iv) Divide N by 2 and compare the result with the following table and obtain the shape.
A

Total N/2 Shape of molecule or ion Example

2 Linear HgCl2 / BeCl2

3 Triangular planar BF3

3 Angular SnCl2 , NO2

4 Tetrahedral CH4 , BF4

B

4 Trigonal Pyramidal NH 3 , PCl 3

4 Angular H 2O
5 Trigonal bipyramidal PCl5 , PF5

5 Irregular tetrahedral SF4 , IF4

5 T-shaped CIF3 , BrF3

5 Linear XeF2 , I 3

6 Octahedral SF6 , PF6

6 Square Pyramidal IF5

6 Square planar XeF4 , ICI 4

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 Geometry of Molecules/Ions having bond pair as well as lone pair of electrons
No. of
Type of No. of lone
bond Hybridi- Expected Actual
mole- pairs of Bond angle Examples
pairs of zation geometry geometry
cule electrons
electron
V-shape,
Trigonal
AX 3 2 1 sp 2 < 120o Bent, SO2, SnCl2, NO2–
planar
Angular
V-shape, H2O, H2S, SCl2, OF2, NH2–,
AX 4 2 2 sp 3 < 109o 28 Tetrahedral
Angular ClO2–
NH3, NF3 , PCl3, PH3, AsH3, ClO3–
AX 4 3 1 sp 3 < 109o 28 Tetrahedral Pyramidal
, H3O+

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Trigonal Irregular
AX 5 4 1 sp 3 d < 109o 28 SF4, SCl4, TeCl4
bipyramidal tetrahedron
Trigonal
AX 5 3 2 sp 3 d 90o T-shaped ICl3, IF3, ClF3
bipyramidal
Trigonal
AX 5 2 3 sp 3 d 180o Linear XeF2, I3–, ICl2–
bipyramidal
Square
AX 6 5 1 sp 3 d 2 < 90o Octahedral ICl5, BrF5, IF5
pyramidal
Square
AX 6 sp 3 d 2
LA
4 2 – Octahedral XeF4, ICl4–
planar
Pentagonal Distorted
AX7 6 1 sp 3 d 3 – XeF6
pyramidal octahedral

3.13 Molecular orbital theory.

Molecular orbital theory was given by Hund and Mulliken in 1932. When two or more constituent atomic
orbital merge together, they form a bigger orbital called molecular orbital (MO). In atomic orbital, the electron is
influenced by only one nucleus whereas in case of molecular orbital, the electron is influenced by two or more
constituent nuclei. Thus, atomic orbital is monocentric and molecular orbital is polycentric. Molecular orbitals follow
Pauli's exclusion principle, Hund‟s rule, Aufbau's principle strictly.
A

      

Atomic orbital According to VBT Molecular orbital According to MOT

(AO) (MO)

The main ideas of this theory are : (i) When two atomic orbitals combine or overlap, they lose their identity
B

and form new orbitals. The new orbitals thus formed are called molecular orbitals. (ii) Molecular orbitals are the
energy states of a molecule in which the electrons of the molecule are filled just as atomic orbitals are the energy
states of an atom in which the electrons of the atom are filled. (iii) In terms of probability distribution, a molecular
orbital gives the electron probability distribution around a group of nuclei just as an atomic orbital gives the electron
probability distribution around the single nucleus. (iv) Only those atomic orbitals can combine to form molecular
orbitals which have comparable energies and proper orientation. (v) The number of molecular orbitals formed is
equal to the number of combining atomic orbitals. (vi) When two atomic orbitals combine, they form two new
orbitals called bonding molecular orbital and antibonding molecular orbital. (vii) The bonding molecular orbital has
lower energy and hence greater stability than the corresponding antibonding molecular orbital. (viii) The bonding
molecular orbitals are represented by  ,  etc, whereas the corresponding antibonding molecular orbitals are
represented by  * ,  * etc. (ix) The shapes of the molecular orbitals formed depend upon the type of combining
atomic orbitals.

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 Formation of bonding and antibonding molecular orbitals
(Linear combination of atomic orbitals – LCAO)
When two atomic orbitals overlap they can be in phase (added) or out of phase (subtracted). If they overlap in
phase, constructive interaction occurs in the region
between two nuclei and a bonding orbital is Antibonding M.O.
Subtraction
produced. The energy of the bonding orbitals is Repulsive
always lower (more stable) then the energies of

Energy
the combining atomic orbitals. When they overlap
Atomic Atomic
out of phase, destructive interference reduces the orbital orbital

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probability of finding an electron in the region
Addition
between the nuclei and antibonding orbital is Bonding M.O.
Attractive
produced. The energy of an antibonding orbital is Formation of bonding and antibonding molecular orbitals
higher (less stable) than the energies of the
combining atomic orbitals. Thus, the number of molecular orbitals formed from atomic orbitals is equal to the
number of atomic orbitals responsible for their formation.
According to LCAO method, the following combination is not allowed. [consider the z-axis as the molecular
LA
axis). np x  npy , np x  npz or npy  npz .

Table : Difference in Bonding molecular orbitals and Antibonding molecular orbitals.

Bonding molecular orbitals Antibonding molecular orbitals
It is formed by linear combination of two atomic orbitals It is formed by linear combination of two atomic orbitals when their
when their wave functions are added. wave functions are subtracted.
i.e., b   A  B i.e., a   A  B

Its energy is less than the combining atomic orbitals. Its energy is more than the combining atomic orbitals.
It increases the electron density between the nuclei. It It decreases the electron density between the nuclei. It therefore
therefore stabilises the molecule. destabilises the molecule.
A

It has no nodal plane (plane where electron density is zero). It has nodal plane.
It is symmetrical about internuclear axis. It is symmetrical about internuclear axis and about a line
perpendicular to it.

 and  – Molecular orbitals

A sigma () M.O. is one that has cylinderical symmetry around the internuclear axis. It does not show any
B

change of sign or rotation through 180 o about the axis. Sigma M.O. has no nodal plane (in which electron density
is zero) along the internuclear axis. The bonding M.O. is designated by  and antibonding by  * .
+
+ + +
+ + +
     
(1s)
1s 1s
Bonding M.O.

+ – + –
    +  –
*(1s)
1s 1s
Antibonding M.O.
Formation of  (1s) and  * (1s) M.O. from 1s atomic orbital
Sigma () M.O. is also formed when two p-atomic orbitals overlap in head on (along their axes) position.

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 –  + +  – –  + –  +
2pz 2pz 2pz

–  + +  – –  + –  +

–  +  – –  + –  +
(2pz) *(2pz)

Formation of  (2pz and  * (2 p z ) molecular orbitals.

-molecular orbital is formed by the sideways overlapping of the p-atomic orbitals. It consists of two electrons
clouds, one lying above and the other lying below a plane passing through the nuclei. It has nodal planes. Since the

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energy of a M.O. is directly related to the nuclei of nodal planes. The -MO is more energetic than the -MO. This
explains why a -bond is a weaker bond than a -bond.
+ + ++
+

   
 
–

– – – – Nodal Plane
2px  (2px)
LA
2px
(or 2py) (or 2py) or  (2py)

+ – + – + –

     

– +
– + – +
2px 2px Nodal Plane * (2px)
(or 2py) (or 2py) or * (2py)

Formation of  (2 p x ) or  (2 p y ) and  * (2 p x ) or  * (2 p y ) molecular orbitals.

A

Relative energies of Molecular orbitals : Initial energy of the atomic orbitals and the extent of their
overlap is the criteria which determines the energy of the M.O.
(1) 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.
(2) As the overlap is much more effective than -overlap,  p-molecular orbital is of lowest energy, even
B

though originally all the three p-orbitals are of equal energy.

(3) The relative energies of the M.O. are obtained experimentally from spectroscopic data.
(4) The sequence in the order of increasing energy for O 2 , F2 and Ne 2
 1s   * 1s   2s   * 2s   2 p z   2 p x   2 p y   * 2 p x   * 2 p y   * 2 p z
(5) It may be noted that  2 p y an  2 p x bonding molecular orbitals are degenerate (i.e. have same energy).
Similarly  * 2 p y and  * 2 p x antibonding molecular orbitals are also degenerate (have the same energy).

(6) The main difference between the two types of sequences in energy level is that for molecules O 2 , F2 and
Ne 2 (Hypothetical) the  2 p z M.O. is lower in energy than  2 p x and  2 p y .

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 (7) It has been found experimentally that in some of the diatomic molecules such as Li 2 , B2 , C 2 and N 2
 2 p z M.O. is higher in energy than  2 p y and  2 p x M.O.’s. Therefore, the order of increasing energy of these
M.O.s changes to  1s   * 1s   2s   * 2s   2 p x   2 p y   2 p z   * 2 p x   * 2 p y   * 2 p z .
Cause of exceptional behaviour of MO’s in B2 , C 2 and N 2
In atoms with Z upto 7, energy of 2s and 2p atomic orbitals lie fairly close. As a result the interaction between
2s and 2p orbitals is quite large. Thus  2s and  * 2s MO’s become more stable with less energy at the cost of
 2 p x and  * 2 p x which gets unstabilised (higher energy).
Stability of the molecules : Stabitity of the molecules can be explain in following ways.

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(1) Stability of molecules in terms of bonding and antibonding electrons
Since electrons in bonding orbitals ( N b ) increase the stability of the molecule, on the whole, depends on their
relative numbers. Thus
(i) If N b  N a , the molecule is stable. (ii) If N b  N a , the molecule is unstable.
(iii) Even if N b  N a , the molecule is unstable. This is due to the fact the anti bonding effect is some what
stronger than the bonding effect.
LA
(2) Stability of molecules in terms of bond order
(i) The relative stability of a molecule is further evaluated by a parameter known as bond order.
(ii) It can be defined as number of covalent bonds present between two atoms in a molecule.
(iii) It is given by one half of the differences between the number of electrons in bonding molecular
orbitals and those in antibonding molecular orbitals.
1
(iv) Bond order  [No. of electrons in bonding molecular orbitals – No. of electrons in antibonding
2
molecular orbitals].
(v) The bond order of 1, 2 and 3 corresponds to single, double and triple bonds respectively. It may be
mentioned that according to M.O theory, even a fractional bond order is possible, but cannot be
A

negative.
1
(vi) bond order  Stability of molecule  Dissociation energy 
Bond length

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

MO energy level diagrams of some molecules : Energy level diagrams of some molecules are given below.
H2 Molecule : H 2 molecule is formed from 1s1 atomic orbitals of two H- atoms. The atomic orbitals (1s 1 ) will
combine to form two molecular orbitals  (1s) and  * (1s) . Two electrons are accommodated in  (1s) and  * (1s)
1
remains vacant. Thus bond order for H 2  (2  0)  1 . It is stable and diamagnetic in nature.
2
*1s
Increasing energy

1s 1s
H H

1s
H2

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 He2 molecule : If two atoms of He (1s 2 ) combine to form He 2 , the probability of the formation of molecular
orbitals is as shown in the figure.

Increasing energy
*(1s2)
Filling of electrons is as follows
He 2   (1s) 2 ,  * (1s) 2 1s2 1s2
He He
1
Thus bond order  (2  2)  0
2 (1s)2
Hence there is no possibility for the existence of He 2 molecule.
N2 molecule : Total number of electrons in N 2 are 14, of which 4 are in K shell and the 10 electrons are
arranged as, KK( 2s)2 ( * 2s)2 ( 2 px )2 ( 2 py )2 ( 2 pz )2

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 * (2 p z )
1
Bond order  (10  4)  3 2p
2 2p
*(2px) *(2py)
Increasing energy

 (2pz)
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 (2px)= (2py)

* (2s)

2s 2s
N (AO) N (AO)

 (2s)
N2 (MO)
M.O. energy level diagram for N2 molecule.
O2 molecule : Total number of electrons in O2  16
Electronic arrangement in M.O.’s , [KK( 2s) 2 ( * 2s) 2 ( 2 p z ) 2 ( 2 p x ) 2 ( z 2 p y ) 2 ( * 2 p x )1 ( * 2 p y )1 ]
A

1
Bond order  (8  4)  2
2  * (2 p z )

* 2px * 2py
B Increasing energy

 2px= 2py

 2pz

* 2s

O (AO) O (AO)

 2s
O2 (MO)
M.O. Energy level diagram for O2 molecule

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 Table : Bond order and magnetic nature of some molecules & ions
Valence Magnetic
Molecule Molecular Orbital Configuration Nb Na B.O.
electrons Nature

H2 σ1s2 2 2 0 Diamagnetic 1

H 2 σ1s1 1 1 0 Paramagnetic 0.5

H 2 σ1s 2 σ* 1s 1 3 2 1 Paramagnetic 0.5

2 Molecule does
He 2 σ1s2  σ 1s  4 2 2 0

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  not exist

He 2 σ1s2 σ* 1s1 3 2 1 Paramagnetic 0.5

He 2 KK ' σ 2s
1
1 1 0 Paramagnetic 0.5

KK ' σ 2s σ* 2s

2 2
Be2 4 2 2 Diamagnetic 0

B2 KK ' ( 2s)2 ( * 2s)2 ( 2 px )1 ( 2 py )1 6 4 2 Paramagnetic 1

LA
C2 
KK '  2s 2 * 2s 2 π 2 px 2 π 2 py 2 8 6 2 Diamagnetic 2

N2 
KK '  2s 2 *2s 2 π 2 px 2 π 2 py 2  2pz 2 10 8 2 Diamagnetic 3

N 2 
KK '  2s 2 * 2s 2 π 2 px 2 π 2 py 2  2pz 1 9 7 2 Paramagnetic 2.5

N 2 
KK '  2s 2 * 2s 2 π 2 px 2 π 2 py 2  2pz 2  * 2px 1 11 8 3 Paramagnetic 2.5

O2 
KK '  2s 2 * 2s 2  2 pz 2 π 2 px 2 π 2 py 2  * 2px 1  * 2py 1 12 8 4 Paramagnetic 2
A

O2 KK  2s 2 * 2s 2  2 pz 2 π 2 px 2 π 2 py 2 π* 2 px 1 π* 2 py 0 11 8 3 Paramagnetic 2.5

O 22 KK ' ( 2s)2 ( * 2s)2 ( 2 pz )2 ( 2 px )2 ( 2 py )2 10 8 2 Diamagnetic 3

O2 KK σ2s 2 σ* 2s 2  2 pz 2 π 2 px 2 π 2 py 2  * 2 px 2  * 2 py 1 13 8 5 Paramagnetic 1.5

KK  2s 2 *2s 2  2 pz 2 π 2 px 2 π 2 py 2  * 2 px 2  * 2 py 2
B

O 22 14 8 6 Diamagnetic 1

F2 KK  2s 2 * 2s 2  2 pz 2 π 2 px 2 π 2 py 2 π* 2 px 2 π* 2 py 2 14 8 6 Diamagnetic 1

Ne 2 KK '
 2s 2 *2s 2  2 pz 2 π 2px 2 π 2py 2 π* 2px 2 π* 2 py 2 Molecule does
16 8 8 0
π* 2pz 2 not exist

CO 
KK '  2s 2 * 2s 2  2 pz 2 π 2 px 2 π 2 py 2 10 8 2 Diamagnetic 3

NO KK '  2s 2 *2s 2  2pz 2 π 2px 2 π 2py  2 π 2px 1 11 8 3 Paramagnetic 2.5

NO  
KK '  2s 2 * 2s 2  2 pz 2 π 2 px 2 π 2 py 2 10 8 2 Diamagnetic 3

CLASSES BY ANKUR SIR @7983744732

3.14 Hydrogen bonding.
In 1920, Latimer and Rodebush introduced the idea of ―hydrogen bond‖ to explain the nature of
association of substances in liquid state like water, hydrogen fluoride, ammonia, formic acid, etc.
(1) Conditions for the formation of hydrogen bonding
(i) High electronegativity of atom bonded to hydrogen : The molecule should contain an atom of high
electronegativity such as F, O or N bonded to hydrogen atom. The common examples are H 2 O ,
NH 3 and HF .
     
H— X   H— X   H— X
(ii) Small size of the electronegative atom : The size of the electronegative atom should be quite small.

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This is due to the fact that the smaller the size of electronegative atom, the greater will be its attraction
for the bonded electron pair. This will cause greater polarity in the bond between H and
electronegative atom, which results in stronger hydrogen bond.
(2) Types of hydrogen bonding
(i) Intermolecular hydrogen bond : Intermolecular hydrogen bond is formed between two different
molecules of the same or different substances. For example:
(a) Hydrogen bond between the molecules of hydrogen fluoride.
LA
(b) Hydrogen bond in alcohol and water molecules
(ii) Intramolecular hydrogen bond (Chelation) : Intramolecular hydrogen bond is formed between the
hydrogen atom and the highly electronegative atom (F, O or N) present in the same molecule.
Intramolecular hydrogen bond results in the cyclisation of the molecules and prevents their
association. Consequently, the effect of intramolecular hydrogen bond on the physical properties is
negligible. For example : Intramolecular hydrogen bonds are present in molecules such as o-
nitrophenol, o-nitrobenzoic acid, etc.
O H
|| |
O C C
H O O
A

H
O O H
N N O
|| || Salicyldehyde
(o-hydroxy benzaldehyde)
O O
Ortho nitrophenol Ortho nitrobenzoic acid

The extent of both intramolecular and intermolecular hydrogen bonding depends on temperature.
B

(3) Effects of hydrogen bonding

Hydrogen bond helps in explaining the abnormal physical properties in several cases. Some of the properties
affected by H-bond are given below:

(i) Dissociation : In aqueous solution, hydrogen fluoride dissociates and gives the difluoride ion (HF2 )
instead of fluoride ion (F  ) . This is due to H-bonding in HF. This explains the existence of KHF 2 . On
the other hand, the molecules of HCl , HBr , HI do not have H-bonding (because Cl, Br, I are not
so highly electronegative). This explains the non-existence of compounds like KHCl 2 , KHBr2 or
KHI 2 . H-bond formed is usually longer than the covalent bond present in the molecule (e.g. in H2O,
O–H bond = 0.99 Å but H-bond = 1.77 Å).

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(ii) Association : The molecules of carboxylic acids exist as dimers because of the hydrogen bonding.
The molecular masses of such compounds are found to be double than those calculated from their
simple formulae. For example, molecular mass of acetic acid is found to be 120.
(iii) High melting and boiling point : The compounds having hydrogen bonding show abnormally
high melting and boiling points.
The high melting points and boiling points of the compounds (H 2 O, HF and NH 3 ) containing
hydrogen bonds is due to the fact that some extra energy is needed to break these bonds. A few
examples are given below:
(a) H 2 O is a liquid whereas H 2 S, H 2 Se and H 2 Te are all gases at ordinary temperature. The reason
for this is that in case of water, hydrogen bonding causes association of the H 2 O molecules with the

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result that the boiling point of water is more than that of the other compounds. On the other hand,
there is no such hydrogen bonding in H 2 S, H 2 Se and H2Te.
(b) NH 3 has higher boiling point than PH3. This is again because there is hydrogen bonding in NH 3 but
not in PH3.
(c) Ethanol has higher boiling point than diethyl ether because there is hydrogen bonding in the former
but there is no hydrogen bonding in the later.
Intramolecular hydrogen bonding is not possible in case of m - and p -isomers because of the size of
LA
the ring which would be formed. Thus, here the intermolecular hydrogen bonding takes place which
causes some degree of association with the result the m -and p -isomers melt and boil at higher
temperatures.
(iv) Solubility : The compound which can form hydrogen bonds with the covalent molecules are soluble
in such solvents. For example, lower alcohols are soluble in water because of the hydrogen bonding
which can take place between water and alcohol molecules as shown below :
     
H  O ................ H  O ............... H  O

C2 H5 H C2 H5
Similarly, ammonia ( NH 3 ) is soluble in water because of hydrogen bonding as represented below:
A

 
H H
           
H N ....... H — O ............... H N ....... H — O
  
H H H H
The intermolecular hydrogen bonding increases solubility of the compound in water while, the
B

intramolecular hydrogen bonding decreases. This is due to the fact that the formation of internal
hydrogen bond prevents hydrogen bonding between the compound and water which thus reduced
solubility of the compound in water.

O H O H OH
H

O
N ON O
||
O p  Nitropheno l
o- Nitrophenol

Due to chelation, – OH group is not available to form hydrogen – OH group available to form hydrogen bond with
bond with water hence it is sparingly soluble in water. water, hence it is completely soluble in water.

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 (v) Volatility : As the compounds involving hydrogen bonding between different molecules
(intermolecular hydrogen bonding) have higher boiling points, so they are less volatile.
(vi) Viscosity and surface tension : The substances which contain hydrogen bonding exist as
associated molecules. So their flow becomes comparatively difficult. In other words, they have higher
viscosity and high surface tension.
(vii) Explanation of lower density of ice than water and maximum density of water at 277K :
In case of solid ice, the hydrogen bonding gives rise to a cage like structure of water molecules as
shown in following figure. As a matter of fact, each water molecule is linked tetrahedrally to four other
water molecules. Due to this structure ice has lower density than water at 273 K. That is why ice floats

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on water. On heating, the hydrogen bonds start collapsing, obviously the molecules are not so closely
packed as they are in the liquid state and thus the molecules start coming together resulting in the
decrease of volume and hence increase of density. This goes on upto 277K. After 277 K, the increase
in volume due to expansion of the liquid water becomes much more than the decrease in volume due
to breaking of H-bonds. Thus, after 277 K , there is net increase of volume on heating which means
decrease in density. Hence density of water is maximum 277 K .
LA
H
0.90 Å
1.77 Å
(99 pm) O
(177 pm)
H H H
Vacant
O O Spaces

H H H H

O O

H H H H
A

O O
H H H H
O O
H H

Cage like structure of H2O in the ice

B

Important Tips
 Hydrogen bonding is strongest when the bonded structure is stabilised by resonance.
 The bond length of hydrogen bond is the order of 250 to 275 pm.
 The bond that determines the secondary structure of protein is hydrogen bond.
 Pairs of DNA are held together by hydrogen bonds.
 Chlorine has the same electronegativity as nitrogen but does not form strong hydrogen bonds. This is because of the larger size than
that of nitrogen.

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3.15 Types of bonding and forces in solids.
(1) Ionic bonding : Solid containing ionic bonds consists of any array or a net work of positive and negative
ions arranged systematically in a characteristic pattern. The binding forces are strong electrostatic bonds between
positive and negative ions. e.g., Compounds of elements of group 1 and 2 with elements of group 16 and 17 e.g.,
NaCl, CaS etc.
(2) Covalent bonding : The solid containing covalent bonding consists of an array of atoms that share
electrons with their neighbouring atoms. The atoms are linked together by strong covalent bonds extending into
three dimensional structure. e.g., Diamond, Silicon carbide, Silicon dioxide etc.
(3) Molecular bonding : The solid containing molecular bonding consists of symmetrical aggregates of

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discrete molecules. However, these molecules are further bound to other molecules by relatively weak force such as
dipole-dipole forces (Vander Waal forces), dispersion forces or H-bonds depending upon the nature of molecules.
The existence of weak attractive forces among the non polar molecules was first proposed by S.D. Vander waal.
Vander waal's forces are non-directional, non valence force of attraction. Vander Waal force  molecular mass
 Boiling point  Size of atom or molecule. The forces present in the crystals of naphthalene, Iodine and dry ices
solid CH 4 , solid hydrogen are Vander Waals forces. SiO2 Possesses giant covalent molecular structure due to
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tetravalency and catenation nature of Si .

(4) Metallic Bond

The constituent particles in metallic solids are metal atoms which are held together by metallic bond. Lorentz
proposed a simple theory of metallic bond. This theory is known as electron gas model or electron sea model.
A metal atom consists of two parts, valence electrons and the remaining part (the nucleus and the inner shell
electrons) called kernel. The kernels of metal atoms occupy the lattice sites while the space in-between is occupied
by valence electrons. These electrons are not localized but are mobile. The attraction between the kernels and the
mobile electrons, which hold the kernel together, is known as metallic bond. Low ionisation energy and sufficient
A

number of vacant orbital in the valency shell are essential conditions for metallic bonding. Metallic bond is
electrostatic in nature. The strength of the metallic bond depends on the number of valency electron and the charge
on the nucleus. As the number of valency electron and the charge increase, the metallic bond becomes strong. Due
to this fact alkali metals are soft and have low melting and boiling points while transition metals and hard and have
high melting and boiling points. Strong metallic bonding is also favoured by smaller size of kernel. Ge, Cu, Zn has
B

metallic bonding while brass etc does not have metallic bonding.
Metals have properties like metallic lustre, thermal and electrical conductivity due to delocalized mobile
electrons. Thermal conductivity of metal decreases with increase in temperature because the kernels start vibrating.
Since the metallic bond is non-directional; metals can be twisted, drawn into wires or beaten into sheets. This
is because the kernels can slip over each other when a deforming force is applied.
The relative strength of various bonds is Ionic >Covalent>Metallic>H-bond>vander waal forces.

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