Chemical Bonding IPE

Prepared by V.
Aditya vardhan
Chemical Bonding 1 adichemadi @ gmail.com
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CHEMICAL BONDING
Chemical Bond : The attraction between two atoms or ions is called a chemical bond. Chemical bond
is formed either due to sharing or transfer of electrons between atoms.
A chemical bond is formed by an atom inorder to get stability by lowering its potential energy.
Atoms (noble gases) with octet configuration in outer shell are stable. Hence every atom tries to get
octet configuration either by losing or gaining or sharing electrons.
Types of chemical bond :

1) Ionic bond
2) Covalent bond
3) Metallic bond
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1) Ionic bond :The electrostatic force of attraction between two oppositely charged ions is called ionic
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bond.
* An ionic bond is formed due to transfer of electrons from one atom to another.
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* The atom which loses electrons will form a cation and the atom which gains electrons will form an
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anion. These oppositely charged ions come closer to each other due to electrostatic force of attraction
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and thus form an ionic bond.

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* An ionic bond is formed between two atoms when their electronegativity difference is greater
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than 1.7.
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* Usually an ionic bond is formed between a metal and a nonmetal.

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E.g., NaCl, LiF, MgCl2 etc.,

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2) Covalent Bond : The attraction between two atoms formed due to the sharing of electron pair(s) is
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called covalent bond.

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* It is formed when electronegativity difference between two atoms is less than 1.7.
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* Usually two nonmetals form a covalent bond.

E.g., H2, F2, HCl, H2O etc.,
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3) Metallic bond: It is the attraction between metal atoms in a metallic crystal. It is formed between
electropositive metal atoms.
KOSSELL AND LEWI'S ELECTRONIC THEORY OF CHEMICAL BONDING

* The atoms of inert gases are stable due to octet configuration (ns2np6) in the outer shell. Hence atoms
must posses eight electrons in their outer shell to get stability. This is referred to as octet rule.
* Helium is also highly stable due to 1s2 configuration.
* Hence every atom tries to get nearest inert gas configuration either by losing or gaining or sharing
electrons.
* Only the electrons in outer shell participate in bond formation. These electrons are called valence
electrons.
The electrons in the inner shell are called core electrons and do not participate in bond formation.
* An ionic bond is formed due to transfer of electrons between atoms whereas a covalent bond is
formed due to sharing of valence electrons.
Electrovalency: The number of valence electrons either lost or gained by an atom during the ionic
Prepared by V. Aditya vardhan
bond formation is called electrovalency.
IONIC BOND FORMATION
1) LiF (Lithium fluoride)

In the formation of Lithium fluoride, Li loses one electron to get nearest inert gas - Helium's con-
figuration. Fluorine atom gains one electron to get nearest inert gas - Neon's configuration. Thus formed
Li+ and F- ions form the ionic compound LiF.
1) Li 
 Li + + 1e-
 
z=3
 He 2s1  He
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2) F + 1e - 
 F-
HA
 z=9
 He 2s 2 2p5  He 2s2 2p6
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3) Li  F 
 LiF
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* The electrovalencies of Li and F are equal to one.

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2) MgCl2 (Magnesium chloride)

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Magnesium loses two electrons to get Neon's configuration. Chlorine atom gains one electron to
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get Argon's configuration. Thus formed Mg2+ and Cl- ions combine together by forming MgCl2.
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1)
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Mg   Mg 2+ + 2e-
 z=12 
 Ne 3s 2  Ne
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2) 2 x ( Cl + 1e - 
 Cl- )
 z=17 
 Ne 3s 2 3p5  Ne 3s2 3p6
3) Mg 2+  2Cl  
 MgCl2
* The electrovalency of Mg is 2 and that of Cl is 1

3) AlF3 (Aluminium Fluoride)
Aluminium loses 3 electrons and Fluorine atom gains 1 electron to get Neon's configuration. The
formed Al3+ and F- ions are combined to form AlF3.
Al 
 Al3+ + 3e-
 z=13
  3s2 3p1
Ne  Ne
2) 3 x( F + 1e - 
 F- )
 z=9 
  2s 2 2p5
He  He 2s2 2p6
3) Al3+ + 3F - 
 AlF3
* The electrovalency of Al is 3 and that of F is 1.

4) Na2O (Sodium monoxide)
Sodium loses 1 electron and oxygen gains 2 electrons to get nearest inert gas Neon's configuration.
Thus formed Na+ and O2- ions combine to give Na2O.
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1)
2x  Na   Na + + 1e  
HA
 z=11
1s 2 2s2 2p 6 3s1 1s2 2s 2 2p 6
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2)
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O + 2e  
 O 2
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 z  8
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1s 2 2s 2 2p 4 1s2 2s 2 2p 6
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CH
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3) 2Na + + O 2-
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
 Na 2O
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* The electrovalency of 'Na' is 1 and that of 'O' is 2.

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FACTORS FAVOURING THE FORMATION OF IONIC BOND

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Ionic bond is electrostatic force of attraction between cation and anion. Hence factors
favouring their formation also favour the formation of ionic bond.
Factors favouring the formation of cation :

Big atomic size : In bigger atoms, the nuclear attraction over the outer electrons is less. Hence they
lose the electrons easily to form cations.
E.g. The ease of formation of cation increases from Li+ to Cs+ in IA group with increase in size.
2) Low ionization energy : The removal of electrons is easy from atoms with low ionization energy
values. Hence these atoms form cation easily.
E.g. IA and IIA group elements readily form cations due to low ionization energies.
3) Low charge on cation : As the successive ionization energies are increased, the formation of
cations becomes difficult with increase in charge on them.
E.g. Among Na+, Mg+2 and Al+3 , the order of ease of formation is as follows
Na+ > Mg+2 > Al+3
i.e., Na is formed more readily than Mg+2 and Al+3
+
4) Octet electronic configuration : The cations with 8 electrons in the outer shell (octet configura-
tion) are highly stable and hence formed readily. Whereas cations with 18 electrons in outer shell
(Pseudo inert gas configuration) are comparatively less stable and hence are not formed easily.
E.g. Ca2+ 1s 2 2s 2 2p 6 3s 2 3p 6 with octet configuration is formed easily.

8
Zn2+ 1s 2 2s 2 2p 6 3s 2 3p6 3d10 with pseudo inert gas configuration cannot be formed
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easily.
Factors favouring the formation of anion

1) Small atomic size : Atoms with small atomic size have stronger attraction towards electron and
hence can form anions readily.
2) High electron affinity and electronegativity : The atoms, with high electron affinity and elec-
tronegativity, gain electrons easily and hence form anions readily.
E.g., Halogens can form anions readily due to small size, high electron affinity and high electronega-
tivity.
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3) Low charge on anion : The formation of highly charged anions is difficult as the addition of succes-
sive electrons to the atoms becomes difficult due to repulsion from electrons in the atom. Hence anion
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with low charge is formed readily.
E.g., Among C4-, N3-, O2- and F- ions, the anion with low charge (F-) is formed readily whereas the
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formation of anion with higher charge (C4-) is difficult.
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i.e., The order of ease of formation is C4- < N3- < O2- < F-
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FAJAN'S RULES
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These rules are used to predict the nature of the bond formed by atoms based on their polarizing
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power and polarizability.

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1) Greater the size of cation, greater is the ionic nature.

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E.g. In IA group elements ionic nature increases with increase in the size of cation from Li+ - Cs+.
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i.e, Increasing order of ionic nature : Li+ < Na+ < K+ < Rb+ < Cs+
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less more
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ionic ionic
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2) Greater the size of anion, greater is the covalent nature.

E.g. Among the halides of the calcium the covalent nature increases from CaF2 to CaI2 with in-
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crease in the size of anion.

Increasing order of covalent nature : CaF2 < CaCl2 < CaI2
3) Greater the charge on cation, greater is the covalent nature.
E.g. In case of Na+, Mg+2 and Al+3 , the covalent nature of cations increases with increase in the
charge as follows.
Na+ < Mg+2 < Al+3
i.e., The compounds of Al3+ are more covalent.
4) The cations with octet configuration in the valence shell exhibit more ionic nature whereas cation with
pseudo inert gas configuration exhibit more covalent nature in their compounds.
E.g. CaCl2 is more ionic [  Ca2+ has octet configuration]
Whereas CuCl, AgCl, ZnCl2 are more covalent. [ Cu+, Ag+, Zn2+ have Psuedo inert gas configu-
ration].
CRYSTAL LATTICE ENERGY (U)

The amount of energy liberated when one mole of the crystalline substance is formed from
the gaseous ions is called lattice energy (U) of the crystal.
ENERGY CHANGES IN IONIC BOND FORMATION

The crystal lattice energy of an ionic crystal can be calculated by using Born-Haber cycle. For
example the lattice energy of NaCl can be calculated as follows:
BORN-HABER CYCLE : The principle involved in Born-Haber cylcle is Hess's law of constant
heat summation which can be stated as follows.
Hess's Law : The total energy change in a reaction remains same whether the reaction takes
place in one step or in several steps.
Calculation of lattice energy of NaCl

NaCl can be obtained from sodium metal and chlorine gas either in one step or in several steps as
shown below.
Direct step : NaCl crystals are formed by combining Na metal with chlorine gas in one step. The
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energy evolved during this reaction is called heat of formation  ΔH f  .
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1
Na  s   Cl2 g  
 NaCls  ; ΔH f = -410.5 kJ/mol
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Indirect method : The formation of NaCl crystals may occur in several steps as follows.
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i) Sublimation of sodium : Solid sodium is first converted gaseous sodium by absorbing 108.7 kJ/
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mole of energy. This is called sublimation energy  ΔH s or + S  .

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Pr
Na  s  
 Na  g  ; ΔHs = + S = +108.7 kJ/mol
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ii) Ionization of sodium : Gaseous sodium atoms are ionized by absorbing 492.82 kJ / mole of
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energy. It is called ionization energy  ΔH i or + I  .

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 Na +g  + 1e-
Na  g   ; ΔH i = + I = + 492.82 kJ/mol
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iii) Dissociation of chlorine molecule : One mole of gaseous chlorine molecules are dissociated into
two moles of chlorine atoms by absorbing energy equal to 239.1 kJ/mole. This is called dissociation
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energy  ΔH d or  D  .
Cl 2g  
 2Cl g  ; ΔH d = +D = 239.1 kJ/mol
But the energy required to get one mole of chlorine atoms is equal to
+D 139.2
= = +119.55 kJ/mol
2 2
1 1 +D
Cl 2 g  
 Cl g  ; ΔH d = = +119.55 kJ/mol
2 2 2
Chloride ion formation : The gaseous chlorine atoms are added with electrons to get gaseous chlo-
ride ions. The energy liberated in this process is called electron affinity (ΔH e or  E) .
Cl 2 g  + e- 
 Cl- g  ; ΔH e = - E = -361.6 kJ/mol
Formation of NaCl Crystals : The gaseous Na+ and Cl- ions unite to form one mole of NaCl crys-
tals. The energy liberated during this process is called lattice energy  ΔH u or -U  . This value can be
calculated by using Hess's law as follows.
Na +g  + Cl- g  
 NaCl s  ; ΔH u = -U
According to Hess's law the energy change in the steps involved in indirect method.
1
i.e. H f  H s  H f  H d  H e  H u
2
(or)
D
H f   S  I   E U
2
H d
i.e., U  H f  H S  H i   H e
2
U  410.5  108.7  492.82  119.55  (361.6)  769.97 kJ .mol 1
1 Hf
Na(s) + /2Cl2(g) NaCl(s)
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H d
Hs= +S
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2
Na(g) Cl(g)
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Hi= +I He= +E
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+ -
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Na (g) + Cl (g)
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Born-Haber cycle
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BORN LANDE EQUATION

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The lattice energy of an ionic crystal is equal to the sum of attractive and repulsive forces in the crystal.
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It can be calculated by using Born Lande equation as follows:

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 AZ  .Z  Be 2 
U   N o  No n 
 r r 
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attractive repulsive
force force
Where A = Madelung constant (which depends on geometry of the crystal)
 AZ  .Z  e 2 r n 1 
B  = Repulsion coefficient
 n 
(This depends on the structure and approximately proportional to the number of nearest
neighbours)
No = Avogadro's number
Z+ & Z- = Charges on the positive and negative ions respectively.
e = Charge of an electron.
r = Distance between the oppositely charged ions
n = Born exponent (a constant which is usually taken as 9)
Born Lande equation can be written as follows

AZ  .Z  e 2 N o  1
U 1  n 
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CRYSTAL STRUCTURES
Unit cell : The smallest part of the crystal which produces entire crystal upon repeating three dimen-
sionally is called unit cell.
Coordination number : Maximum number of nearest oppositely charged ions surrounding any par-
ticular ion in ionic crystal is called the coordination number of that ion.
r
Limiting radius ratio ( ): The ratio of radius of positive ion to that of negative ion is called limiting
r
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radius ratio.
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The coordination number and crystal structure of an ionic crystal can be predicted from the limiting
radius ratio value. RD
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r Coordination
Limiting radius ratio ( ) Structure
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r number
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less than 0.155 2 linear

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0.155 - 0.225 3 Planar triangle

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0.225 - 0.414 4 Tetrahedral

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0.4142 - 0.732 4 Squared planer

0.4142 - 0.732 6 Octahedral
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0.732 - 0.999 8 Body centered cubic

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1) Crystal structure of Cesium chloride

rCs 
V.
* Limiting radius ratio ( )= 0.93.

rCl 
* The coordination number is equal to 8.
* Crystal structure is body centered cubic (bcc).
* Each unit cell contains 1 Cs+ and 1 Cl- ions.
Cl- Cl-
There are eight Cl- ions at the corners

Cl- Cl -
each of which contributes only 1/8th
part and one Cs+ at the centre. Hence
Cs+ 1
Number of Cl- ions = 8 x =1
8
Cl- Cl- Number of Cs+ ions = 1
Cl- Cl-
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2) Crystal structure of sodium chloride
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rNa
* Limiting radius ratio ( )= 0.52
rCl  RD
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* The coordination number is equal to 6.
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* The crystal structure is face centered cubic (fcc).

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* Each unit cell contains 4 Na+ and 4 Cl- ions.
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Pr
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Cl- Na+ Cl-

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1
Na+ Cl- Na+ Number of Cl- ions at corners = 8 x =1
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8
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Cl- Na+ Cl- 1

Number of Cl- ions at the centre of faces = 6 x =3
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2
Na+ Cl- Na+
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Total number of Cl- ions = 1+3 = 4

Cl- Na+ Cl-
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Na+ Cl- Na+ 1

Number of Na + ions on the edges = 12 x =3
4
Cl- Na+ Cl- Number of Na + ions at the centre = 1
Na+ Cl- Na+ Total number of Na + ions = 3+1 = 4
Cl- Na+ Cl-
Properties of ionic compounds

1) Ionic compounds contain oppositely charged ions which are strongly attracted to each other.
Hence these are hard substances with high melting and boiling points.
2) Ionic bond is direction less and the electrostatic forces of attraction are present in all directions
around an ion. Hence there is no isolated discrete molecule in the ionic crystal. Entire crystal is consid-
ered as the giant molecule.
3) In the solid state, ions cannot move freely and hence they do not conduct electricity . But in
fused state or in aqueous solutions, they exhibit electrical conductivity as the ions are free to move.
4) Ionic compounds are polar in nature and hence they are soluble in polar solvents like water.
These compounds do not dissolve in non polar solvent like benzene, carbon tetrachloride etc.,
5) The reactions between ionic compounds occur very fast due to presence of separate ions.
e.g. A white precipitate of AgCl is formed instantly when aqueous solution of NaCl and AgNO3 are
mixed.
NaCl(aq) + AgNO3(aq)  NaNO3(aq) + AgCl 
6) Ionic compounds do not exhibit isomerism due to non directional nature of ionic bond.
Formula weight: Ionic compounds contain only ions and there are no molecules in it. Hence their
molar mass is expressed as formula weight instead of molecular weight.
COVALENT BOND FORMATION & LEWI'S DOT STRUCTURES

A covalent bond is formed by sharing of pair of electrons between two atoms.
It is formed between two atoms when their electronegativity difference is less than 1.7 . Usually a
covalent bond is formed between two nonmetals.
The formation of covalent bonds can be explained based on Lewi's dot structures. Atoms contrib-
ute their valence electrons for the bond formation and get octet or nearest inert gas configuration.
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Covalency : The number of electrons contributed by the atom of an element in the formation of
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covalent compound is known as covalency of that element.
Examples
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1) H2 molecule
* Electronic configuration of hydrogen is 1s1.
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* Each hydrogen atom contribute one electron to form a pair of electrons, which is shared in between
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the two atoms. Thus a covalent bond is formed.

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* Thus in H2 molecule, each hydrogen atom gets its nearest inert gas - Helium's configuration.
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Pr
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* Covalency of hydrogen is 1.
CH
.
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H. + .H H.H
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or
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H H
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2) Cl2 molecule
V.
2 2 6 2 5
* The electronic configuration of Cl is 1s 2s sp 3s 3p .
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* In order to get the nearest inert gas- Argon's configuration, each chlorine contributes one electron for
the bond formation.
* Covalency of chlorine is 1.
.. .. .. ..
. + . Cl .
..
..
. . . Cl
..
..
Cl
.. .. Cl ..
or
.. ..
..
. . Cl
..
Cl ..
3) Hydrogen chloride (HCl)

2 2 6 2 5
* Electronic configuration of chlorine is 1s 2s sp 3s 3p .
7
* In the formation of HCl molecule, the hydrogen and chlorine atoms contribute one electron each for
the bond formation. Thus both of them get their nearest inert gas configurations.
.. ..
H X . Cl
..
..
.. or H Cl
..
4) Methane (CH4)
2 2 2
* The electronic configuration of carbon is 1s 2s 2p .
4
1
* The electronic configuration of hydrogen is 1s .
* The carbon atom forms four covalent bonds by contributing four of its valence electrons for the bond
formation. It forms 4 bonds with four hydrogen atoms. Thus it gets octet configuration.
* Covalency of carbon is 4.
H H
.x
.
H x C. . x H or H C H
N
x
H
HA
H
5) Ammonia (NH3) : RD
* The electronic configuration of nitrogen is 1s2 2s 2 2p3 .
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1
* The electronic configuration of hydrogen is 1s ,
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* In the formation of Ammonia molecule, nitrogen atom contributes 3 of its electrons to form three
EM
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bond pairs which are shared with hydrogen atoms. Thus nitrogen forms 3 single bonds with three
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hydrogen atoms and gets the configuration of Neon.

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* Covalency of nitrogen is 3.
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.. ..
W
.N.
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H x x H or H N H
.
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H H
V.
5) H2O molecule
* Electronic configuration of oxygen is 1s2 2s 2 2p 4 .
6
1
* Electronic configuration of Hydrogen is 1s .
* In the formation of water molecule, oxygen atom contributes two electrons to form two bond pairs
which are shared with hydrogen atoms. Thus two bonds are formed by oxygen atom to get the configu-
ration of neon. There are also two lone pairs on oxygen atom.
* Covalency of oxygen is 2.
.. ..
H .O.
x x H or H O H
.. ..
6) Oxygen molecule (O2)
2 2 4
* The electronic configuration of oxygen is 1s 2s 2p .
6
* In the formation of oxygen molecule, each oxygen atom contributes 2 electrons to form 2 bond pairs.
Thus a double bond is formed between oxygen atoms. Thus each oxygen atom gets Neon's configura-
tion.
.. . . .. .. ..
.. .
O .O.. or O
.. O
..
7) Nitrogen molecule (N2)
* The Electronic configuration of nitrogen is 1s2 2s 2 2p3 .
5
* In the formation of Nitrogen molecule, each nitrogen atom contributes 3 electrons to form 3 bond
pairs. Thus a triple bond between nitrogen atoms is formed. Each nitrogen atom gets Neon's configura-
tion.
or
...
...
.. N N N N
..
..
..
8) Carbon dioxide (CO2)
N
2 2 2
* Electronic configuration of carbon is 1s 2s 2p .
HA
4
2 2 4
* Electronic configuration of oxygen is 1s 2s 2p .
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6
ed
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* In carbon dioxide, carbon atom forms double bond with each oxygen. Thus both oxygen and carbon
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atoms get the octet configuration in their valence shell.

EM
Pr
.. .. ..
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..
or C O
CH
O
..
O
..
O C
..
..
..
..
..
..
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9) Ethylene molecule (C2H4)

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2 2 2
* Electronic configuration of carbon is 1s 2s 2p
4
V.
* Electronic configuration of hydrogen is 1s1

H H H H
*. . . .*
.C . . C. or C C
* *
H H H H
Molecules violating octet rule:
BeCl2 (Beryllium chloride)

* Electronic configuration of Beryllium is 1s 2 2s 2
2
2 2 6 2 5
* Electronic configuration of Chlorine is 1s 2s sp 3s 3p .
7
* In the formation of Beryllium chloride, the beryllium atom contributes its two valence electrons and
forms two bond pairs. These are shared with chlorine atoms.
* BeCl2 is a stable molecule, even though beryllium gets only four electrons in its valence shell. This is
the violation of octet rule.
* Covalency of beryllium is 2.
.. .. .. ..
Cl . . Cl or Cl Be Cl
..
..
Be
..
..
x x
.. .. .. ..
BCl3 (Boron trichloride)
2 2 1
* Electronic configuration of Boron is 1s 2s 2p .
3
2 2 6 2 5
7
* In BCl3 molecule, boron contributes 3 of its valence electrons and forms three bond pairs with
chlorine atoms. There are only six electrons in the valence shell of boron atom in BCl3. But still it is
N
stable. It is an electron deficient compound. It is also the violation of octet rule.
* Covalency of boron is 3.
HA
..
RD ..
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Cl
..
..
Cl
..
..
.
ed
.. .. .. ..
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x
. . Cl or Cl
..
B Cl B
a..r
..
Cl
..
x x
.. .. .. ..
AD
ep
EM
Pr
PCl5 (Phosphorous pentachloride)

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CH
2 2 6 2 3
* Electronic configuration of phosphorus is 1s 2s 2p 3s 3p .
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5
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2 2 6 2 5
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7
In the formation of PCl5 molecule, phosphorus contributes five electrons in it's valence shell and
V.
forms five bonds with chlorine atoms. There are 10 electrons in the valence shell of phosphorus in this
molecule. It is a stable molecule and violates octet rule.
* Covalency of phosphorus in this molecule is 5.
.. ..
Cl
..
..
.. Cl
..
..
..
. .. ..
Cl . Cl
..
x
.
..
Cl
..
.. x Cl
..
x .. or ..
P .. P
x x
. .. .. ..
.. .
Cl Cl
..
..
Cl Cl
..
..
.. .. .. ..
SF6 (Sulphur hexafluoride) :

* Electronic configuration of Sulphur is 1s 2 2s2 2p 6 3s 2 3p 4 .
6
* Electronic configuration of Fluorine is 1s2 2s 2 2p5
7
* Sulphur contributes six of its valence electrons to form 6 bonds with six fluorine atoms. Thus there
are 12 electrons in the valence shell in sulphur atom.
In violates octet rule and is still stable.
* Covalency of sulphur in this molecule is 6.
F F
F * F F F
* * or
S
* *
S
F * F F F
F F
N
Conclusion: Lewi's electronic theory could not explain the shapes and bond angles of molecules. It
HA
also could not explain why some molecules are stable eventhough they violate octet rule.
Some more examples:

RD
VA by
1) H2S 2) CO32-
OM
ed
I.C
_ _
ar
x
AD
x
ep
O O
EM
Pr
.. .. x
C xx O C O
YA
H .S. x or
CH
x x H or H S H
.. .. Ox O
x _
DI
W IT
Hydrogen sulphide _
.A
Carbonate ion
W
AD
W
3) SiCl4 4) HCOOH
V.
.. ..
Cl O O
..
..
Cl ..
..
..
.. .x .. ..
x.
Si . x Cl Cl Si Cl H C OR H C
..
Cl
..
or
..
..
.. .x .. .. ..
Cl O H O H
..
..
Cl
..
..
..
..
Silicon tetrachloride Formic acid
5) NF3 6) HNO3
.. xx .. xx + +
. N . F F N F O N O H O N O H
..
F x
..
x
.. . .. or
x
` O O
F F - -
Nitrogen trifluoride Nitric acid
7) CO 8) O3
:
:
::: : : O :O
: :
O:
: :
C O or C O or :
: :
:
:
:
O O
: O
:
:
Carbon monoxide molecule Ozone molecule
-1 +
8) NO2 9) NH4
+ +
- H
- H
O N O or O N O ..
H x .N. x H or H N H
.
x
Nitrite ion
H H
Formal charge (Qf)

It is the charge on an atom in a molecule assigned by assuming all the atoms have same electrone-
N
gativity and the electron pairs are shared equally. It is calculated as follows:
HA
1
Qf = N A - N LP - N BP
2 RD
Where NA = Number of electrons in the valence shell of free atom.
VA by
OM
NLP = Number of electrons in the lone pairs (unshared pairs).
ed
NBP = Number of electrons in the bond pairs.

I.C
ar
AD
ep
Examples:
EM
Pr
1) PH3 molecule
YA
Lewi's dot structure:

CH
DI
W IT
.. ..
.A
H x .P. x H H P H
.
W
AD
x or
W
H H
V.
1 6
Formal charge on 'P' = N A - N LP - N BP  5  2   0
2 2
1 2
N BP  1  0   0
Formal charge on 'H' = N A - N LP -
2 2
2) N2O molecule: It exists in following two resonance forms.
For the following first resonance form:
- + - +
:
:
:
:N N O
: or : N : :N : :O :
(1 ) (2 ) (1 ) (2 )
1 4
Formal charge on first nitrogen 'N(1)' = N A - N LP - N BP  5  4   1
2 2
1 8
Formal charge on second nitrogen 'N(2)' = N A - N LP - N BP  5  0   1
2 2
1 4
Formal charge on 'O' = N A - N LP - N BP  6  4   0
2 2
For the following second resonance form:

+ - + -
:
:N N O
:
or :N : ::
N
:
O
:
(1 ) (2)
:
(1 ) (2 )
1 6
Formal charge on first nitrogen 'N (1)' = N A - N LP - N BP  5  2   0
2 2
1 8
Formal charge on second nitrogen 'N (2) ' = N A - N LP - N BP  5  0   1
2 2
1 2
Formal charge on 'O' = N A - N LP - N BP  6  6   1
2 2
N
HA
Hence the formal charges vary with structural environment.
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY

RD
VA by
* Following are the important postulates of VSEPR's theory proposed by Nyholm, Gillespie.
OM
1) The shape of a molecule can be determined from the arrangement and repulsions between the
ed
I.C
electron pairs present in the valence shell of central atom of that molecule.
ar
AD
2) There are two types of valence shell electron pairs viz.,

ep
i) Bond pair and ii) Lone pair

EM
Pr
YA
3) The electron pairs in the valence shell the repel each other and determines the shape of the molecule.
CH
The magnitude of the repulsion depends upon the type of electron pair.
DI
4) The bond pair is attracted by nuclei the occupies less space and hence it causes less repulsion.
W IT
.A
Whereas, the lone pairs are only attracted by one nucleus and hence occupy more space. As a result,
W
AD
the repulsion caused by them is greater.

W
The order of repulsion between different types of electron pairs is as follows :

Lone pair - Lone pair > Lone Pair -Bond pair > Bond pair- Bond pair
5) When the valence shell of central atom contains only bond pairs, the molecule gets symmetrical
V.
structure, whereas the symmetry is distorted when there are lone pairs along with bond pairs.
6) The bond angle decreases due to the presence of lone pairs.
7) The repulsion increases with increase in the number of bonds between two atoms.
E.g. Triple bond causes more repulsion then double bond which in turn causes more repulsion than
single bonds.
8) The repulsion between electron pairs increases with increase electronegativity of central atom and
hence the bond angle increases.
9) Shapes of molecules can be predicted from the number of electron pairs in the valence shell of central
atom as follows:
THE GEOMETRY OF MOLECULES CONTAINING ONLY BOND PAIRS IN THE CENTRAL ATOM
Number of
Formula Molecular geometry Examples
bond pairs
2 AB2 Linear B A B BeCl2, BeF2
B
Trigonal
3 AB3 BF3, BCl3
planar A
B B
4 AB4 Tetrahedral A
B
CH4, CCl4
B
B
N
B
HA
B
Trigonal
5 AB5 B A PCl5, PF5
bipyramidalRD B
VA by
OM
B
ed
I.C
B
ar
AD
ep
B B
EM
Pr
6 AB6 Octahedral A SF6

YA
CH
B B
DI
B
W IT
.A
W
AD
W
V.
GEOMETRY OF MOLECULES CONTAINING CONTAINING ONE OR MORE

LONE PAIRS IN CENTRAL ATOM
Total
number Number Number
Shape of
of of bond of lone Formula Bond angle Examples
molecule
electron pairs pairs
pairs
o
3 2 1 AB2E Angular 120 SO2
o
Trigonal 107 48’ NH3
3 1 AB3E
Pyramidal 102o30’ NF3
4
Angular 104o28’ H2O
2 2 AB2E2 o
(V- shaped) 103 F2O
4 1 AB4E See-Saw SCl4 , SF4
90o
N
5 3 2 AB3E2 T-Shape ClF3
o -
2 3 AB2E3 Linear 180 XeF2, I3
HA
Square o
5 1 AB5E 90 BrF5
pyramidal
6 RD
Square o
VA by
4 2 AB4E2 90 XeF4
OM
planar
ed
Where A = central atom

I.C
B = atom linked to the central atom
ar
AD
ep
E = Lone electron pair

EM
Pr
YA
CH
Explanatory examples:
DI
1) BeCl2: The valence shell of central atom, beryllium contains only two bond pairs. Hence it is linear
W IT
.A
in shape with 180o bond angle.

W
AD
W
180o
Cl Be Cl
V.
Linear molecule
2) BF3: The valence shell of the central atom - boron contains only three bond pairs. Hence it's shape
is trigonal planar with 120o bond angle.
Cl
Cl
120o Cl
Trigonal planar shape
3) CH4: The valence shell of the central atom - carbon contains only four bond pairs. Hence it is
tetrahadral in shape with 109o28' bond angle.
The bond pairs are arranged tetrahedral symmetry so as to minimize repulsions. If the bond pairs
are arranged in square plane, the angles between them will be only 90o and the repulsions will be more
than in case of tetrahedral arrangement. Hence tetrahedral structure is more favorable than square
planar structure.
109o28'
C
H
H
H
Tetrahedral structure of methane
4) NH3: There are three bond pairs and one lone pair in the central atom, nitrogen. The bond angle is
N
decreased from 109o28' to 107o48' due to repulsion caused by lone pair.
HA
RD
VA by
N
OM
H H
ed
I.C
107o48'
ar
H
AD
ep
Trigonal pyramidal structure of ammonia molecule

EM
Pr
YA
CH
5) H2O: There are two bond pairs and two lone pairs in the central atom, oxygen. The bond angle is
decreased from 109o28' to 104o28' due to repulsion caused by two lone pairs.
DI
W IT
.A
W
AD
W
O
V.
H
o
104 28'
H
Angular shape of water molecule
VALENCE BOND THEORY (VBT)

This theory was proposed by Heitler and London to explain the formation of covalent bond. The
main postulates are as follows:
* A covalent bond is formed by the overlapping of two half filled atomic orbitals containing electrons
with opposite spins.
* Thus formed electron pair is shared between two atoms.
* The electron density along the internuclear axis between two bonded atoms increases due to over-
lapping. This confers stability to the molecule.
* Greater the extent of overlapping, stronger is the bond formed. The direction of the covalent bond is
decided by the direction of overlapping.
* There are two types of covalent bonds based on the pattern of overlapping as follows:
(i)  bond:- The covalent bond formed due to overlapping of atomic orbital along the inter nucleus
axis is called  bond.
It is a stronger bond with cylindrical symmetry.
(ii) π bond :- The covalent bond formed by sidewise overlapping of atomic orbitals is called π -
bond.
In this bond, the electron clouds are present above and below the internuclear axis. It is a weaker
bond.
Note: The 's' orbitals can only form  bonds, whereas the p, d & f orbitals can form both  and π
bonds.
Examples
1) H2 molecule
* In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the
internuclear axis and thus form a  s-s bond.
H + H H H
N
1s orbital 1s orbital  s  s bond
HA
2) Cl 2 molecule
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1
RD
* The two half filled 3pz atomic orbitals of two chlorine atoms overlap along the internuclear axis and
VA by
OM
thus by forming a  p-p bond.
ed
I.C
Cl + Cl Cl Cl
ar
AD
ep
3pz orbital 3pz orbital  p p bond

EM
Pr
YA
CH
3) HCl molecule
DI
W IT
* Electronic configuration of Cl is 1s2 2s2 2p6 3s2 3px2 3py2 3pz1

.A
* The half filled 1s orbital of hydrogen overlap with the half filled 3pz atomic orbital of chlorine atom
W
AD
W
along the internuclear axis to form a  s  p bond.

V.
H + Cl H Cl
1s orbital 3pz orbital  s  p bond
4) O2 molecule
* Electronic configuration of O is 1s2 2s2 2px2 2py1 2pz1
* The half filled 2px orbitals of two oxygen atoms overlap along the internuclear axis and form
 p-p bond. The remaining half filled 2pz orbitals overlap laterally to form a π p-p bond. Thus a double
bond (one  and one  ) is formed between two oxygen atoms.
 p  p bond
 p  p bond
O + O O O
5) N2 molecule
* Electronic configuration of N is1s2 2s2 2px1 2py1 2pz1
*  p-pbond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic
orbitals axially. The remaining half filled 2py and 2pz orbitals form two π p-p bonds due to lateral
overlapping. Thus a triple bond (one  and two  )is formed between two nitrogen atoms.
 p p
 p p
 p p
N N
Valence bond theory could not explain the structures and bond angles of molecules with more than
three atoms. E.g. It could not explain the structures and bond angles of H2O, NH3 etc.,
Inorder to explain the structures and bond angles of molecules, Linus Pauling modified the valence
bond theory by proposing hybridization concept.
N
HA
HYBRIDIZATION
The intermixing of atomic orbitals of almost equal energies of an atom to give an equal
number of identical and degenerate hybrid orbitals is called hybridization.
RD
VA by
OM
Characteristics of hybridization :
ed
I.C
1) Pure atomic orbitals of same atom should participate in the hybridization.
ar
2) The energies of atomic orbitals participating in hybridization must be nearly same.

AD
ep
3) The number of hybrid orbitals formed is equal to the number of atomic orbitals participating in the
EM
Pr
hybridization.
YA
CH
4) The hybrid orbitals formed are identical in shape and degenerate.

5) These hybrid orbitals are symmetrically arranged around the nucleus so as to minimize the repulsion
DI
W IT
between them and thus get maximum stability.

.A
6) The filling of electrons into hybrid orbitals follows Pauli's exclusion principle and Hund's rule of
W
AD
maximum multiplicity.
W
7) A hybrid orbital may be empty or half-filled or full filled.

8) Usually hybrid orbitals form sigma bonds only.
V.
TYPES OF HYBRIDIZATION
1) 'sp' hybridization
* Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degen-
erate hybrid orbitals is called 'sp' hybridization.
* These sp-hybrid orbitals are arranged linearly at 180o of angle.
* They possess 50% 's' and 50% 'p' character.
s orbital p orbital sp hybrid orbitals
Examples:
1) BeCl2
* Electronic configuration of 'Be' in ground state is 1s2 2s2
* Electronic configuration of 'Be' in excited state is 1s 2 2s1 2p1x
2s 2px 2py 2pz
sp
hybridization
(2σ bonds)
* In the excited state, beryllium undergoes 'sp' hybridization by using a 2s and a 2p orbitals. Thus two
half filled 'sp' hybrid orbitals are formed. These are arranged linearly.
* These half filled sp-orbitals form two  sp  p bonds with two 'Cl' atoms.
* Thus BeCl2 is linear in shape with the bond angle of 180o.
 sp  p  sp  p
N
HA
Cl Be Cl
BeCl2
Hybridization - sp
RD
VA by
180o
OM
Shape - linear
ed
Cl Be Cl
I.C
Bond angle - 180o
ar
AD
ep
Linear molecule
EM
Pr
YA
2) Acetylene (C2H2)
CH
* Electronic configuration of 'C' in ground state is 1s2 2s2 2p2

DI
1s2 2s1 2p3

W IT
* Electronic configuration at 'C' in excited state is

.A
W
AD
W
2s 2px 2py 2pz

V.
sp
hybridization
(2σ bonds) pure
orbitals
form
2 bonds
* Each carbon atom undergoes 'sp' hybridization by using one 2s and one 2p orbitals in the excited
state. Thus two half filled 'sp' orbitals are formed. These are arranged linearly.
The two carbon atoms form one  sp sp bond with each other by using sp-orbitals. They also form
two  p  p bonds by overlapping half filled pure p-orbitals ( 2py and 2pz). Thus a triple bond (1 & 2 )
is formed between carbon atoms.
Each carbon also forms a  sp s bond with the hydrogen atom.
Thus acetylene molecule is linear with 180o bond angle.
 p p
 p p
 sp s  sp  sp
H C C H
C2 H 2 - Acetylene
Hybridization - sp
Shape - linear
180o
Bond angle - 180o
H C C H
Linear structure of acetylene molecule
N
HA
sp2 hybridization :
* Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degener-
RD
ate hybrid orbitals is known as sp2 hybridization.
VA by
OM
* The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 1200 to each other.
ed
* sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.
I.C
ar
AD
ep
EM
Pr
YA
+ +
CH
DI
W IT
.A
W
AD
sp2 hybrid orbitals

W
s orbital px orbital py orbital
Examples:
V.
1) BCl3
* Electronic configuration of 'B' in ground state is 1s2 2s2 2p1
* Electronic configuration of 'B' in excited state is 1s2 2s12px12py1
2s 2px 2py 2pz
sp2
hybridization
(3σ bonds)
In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p orbitals. Thus
three half filled sp2 hybrid orbitals which are oriented in trigonal planar symmetry are obtained.
Boron forms three σ sp2 -p bonds by using sp2 hybrid orbitals with three chlorine atoms. Each
chlorine atom uses it's half filled p-orbital for the bond formation.
Thus the shape of BCl3 is trigonal planar with Cl-B-Cl bond angles equal to 120o.
Cl
Cl
B
B
Cl
120o Cl
Cl Cl
Trigonal planar structure of BCl3
N
HA
BCl3 - Boron trichlorine
RD
VA by
hybridization - sp 2
OM
ed
shape - Trigonal planar

I.C
ar
Bond angle - 120o

AD
ep
EM
Pr
2) Ethylene (C2H4).
YA

CH
* Electronic configuration at 'C' in excited state is 1s2 2s1 2p3

DI
W IT
.A
W
AD
2s 2px 2py 2pz

W
sp2
V.
hybridization
(3σ bonds)
pure
orbital
forms
one  bond
* In the excited state, each carbon in ethylene undergoes sp2 hybridization by mixing 2s and two 2p
orbitals. Thus three half filled sp2 hybrid orbitals are formed in trigonal planar symmetry. There is also a
half filled 2pz orbital on each carbon.
* The carbon atoms form a  sp2 -sp 2 bond with each other by using hybrid orbitals.
The remaining pure atomic orbitals overlap laterally and form a  p-p bond.
* There is a double bond (1 & 1 ) between two carbon atoms.
* Each carbon atom also forms two  sp 2 -s bonds with two hydrogen atoms.
* Thus ethylene molecule is planar with H-C-H & C-C-H bond angles equal to 120o.
* All the atoms are present in one plane.
 p p
H H
 sp 2  sp 2 H H C2 H 2 - Ethylene
o
C C 120
C C  sp 2  s Hybridization - sp 2
H H
Shape - planar
H H
Bond angle - 120o
Planar structure of ethylene molecule
sp3 hybridization:-
* Intermixing of one 's' and three 'p' orbitals of almost equal energy to give four identical and degener-
ate hybrid orbitals is called sp3 hybridization.
* Thus formed four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109028' angle with
N
each other.
HA
* In these orbital the ‘s’ character is 25% and ‘p’ character is 75%.
RD
VA by
+ + + OM
ed
I.C
ar
AD
ep
EM
Pr
YA
s orbital px orbital py orbital pz orbital sp3 hybrid orbitals

CH
DI
Examples:
W IT
.A
Methane (CH4)
W
AD

W

V.
2s 2px 2py 2pz
sp3
hybridization
(4σ bonds)
* In the excited state, the carbon atom undergoes sp3 hybridization by mixing one ‘2s’ and three 2p
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry.
* Each of these form σsp3 - s bond with hydrogen atom. Thus carbon forms four  bonds with four
hydrogen atoms.
* Methane molecule is tetrahedral in shape with 109028' bond angle.
H H
 sp3  s
109o28'
CH 4 - Methane
C C
H H Hybridization - sp3
H H Shape - Tetrahedral
H H Bond angle - 109o 28 '
Tetrahedral structure of methane
2) Ethane (C2H6)
N
2s 2px 2py 2pz
HA
sp3
hybridization
RD
VA by
(4σ bonds)
OM
ed
I.C
* In the excited state, each carbon atom undergoes sp3 hybridization by using one 2s and three 2p
ar
orbitals. Thus four half filled sp3 hybrid orbitals are formed in tetrahedral symmetry around each car-
AD
ep
bon.
EM
Pr
YA
* The two carbon atoms form a σsp3 - sp3 bond with each other by overlapping sp3 hybrid orbitals
CH
axially.
DI
W IT
Each carbon atom also forms three σsp3 -s bonds with hydrogen atoms.
.A
W
AD
* Thus there is tetrahedral symmetry around each carbon with HCH and HCC bond angles equal
W
to 1090 28' .
V.
H H
 sp3  sp 3 H 109o28' H
 sp3  s 109o28'
C C C
C H H H
H
H H
H H
Structure of Ethane molecule
C 2 H 6 - Ethane
Hybridization - sp3
Bond angle - 109o 28 '
3) Ammonia (NH3)
* Electronic configuration of nitrogen is 1s2 2s2 2px1 2py1 2pz1
2s 2px 2py 2pz
sp3
hybridization
(3σ bonds)
* Nitrogen undergoes sp3 hybridization by using one 2s and three 2p orbitals. Thus formed four sp3
orbitals are arranged in tetrahedral symmetry. Among them three are half filled and one is full filled.
* Nitrogen forms 3 σsp3 -s bonds with three hydrogen atoms by using three half filled hybrid orbitals.
The bond angle is decreased from 1090 28'to 1070 48' due to the repulsion caused by lone pair.
Thus ammonia acquires trigonal pyramidal shape.
N
HA
N  sp3  s N NH 3 - Ammonia
H H H Hybridization - sp3
H 107o48'
RD Shape - Trigonal pyramidal
H
VA by
OM
H Bond angle - 107o 48'
ed
I.C
Trigonal pyramidal structure of ammonia molecule
ar
AD
ep
4) H2O (Water molecule)

EM
Pr
* Electronic configuration of oxygen is 1s2 2s2 2px2 2py1 2pz1

YA
CH
DI
W IT
2s 2px 2py 2pz

.A
W
AD
sp3
W
hybridization
(2σ bonds)
V.
* Oxygen atom undergoes sp3 hybridization by mixing a 2s and three 2p orbitals and forms four sp3
hybrid orbitals arranged in tetrahedra symmetry. Among thenm two are half filled and the remaining two
are completely filled.
Oxygen forms two σsp3 -s bonds with hydrogen atoms by using half filled hybrid orbitals.
The bond angle is decreased from 1099 28' to 1040 28' due to repulsions caused by two lone
pairs. Thus water molecule gets angular shape (V shape).
 sp 3  s O water - H 2 O
O
H Hybridization - sp3
H o
104 28' shape - Angular
H
H Bond angle - 104o 28'
Angular shape of water molecule
sp3d Hybridization
* The intermixing of one 's', three 'p' and one 'd' orbitals to give five identical and degenerate hybrid
orbitals is called sp3d hybridization.
* Thus formed sp3d orbitals are arranged in trigonal bipyramidal symmetry. Among them, three are
arranged in trigonal plane and the remaining two orbitals are present perpendicularly above and below
the trigonal plane.
sp3d hybrid orbitals
Examples:
1) PCl5 (phosphorus pentachloride)
N
* E.configuration of 'P' in ground state is 1s2 2s2 2p6 3s2 3p3
HA
* E.configuration of 'P' in excited state is 1s2 2s2 2p6 3s1 3p3 3d1
RD 3s 3p 3d
VA by
OM
ed
sp3d
I.C
ar
hybridization
AD
(5σ bonds)
ep
EM
Pr
YA
* In the excited state, phosphorus undergoes sp3d hybridization by using a 3s, three 3p and one 3d
CH
orbitals which are arranged in trigonal bipyramidal symmetry.

DI
* By using these half filled sp3d orbitals, phosphorous forms five σsp3d - p bonds with chlorine atoms.
W IT
.A
Each chlorine atom makes use of half filled 3pz orbital for the bond formation.
W
AD
W
* The shape of PCl5 molecule is trigonal bipyramidal with 1200 and 900 of  Cl - P - Cl bond angles.
Cl
V.
Cl PCl5 (Phosphorous pentachloride)

90o
Cl P 120o Hybridization - sp3d
Shape - Trigonal bipyramidal
Cl Bond angles - 120o & 90o
Cl
sp3d2 hybridization
* Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and
degenerate hybrid orbitals is called sp3d2 hybridization.
* These six sp3d2 orbitals are arranged in octahedral symmetry by making 900 angles to each other.
sp3d2 hybrid orbitals
Examples:
1) Sulfur hexa flouride (SF6)
* E.configuration of 'S' in ground state is 1s2 2s2 2p6 3s2 3p4
* E.configuration of 'S' in 2nd excited state is 1s2 2s2 2p6 3s1 3p3 3d2
N
3s 3p 3d
HA
sp3d2
hybridization
RD (6σ bonds)
VA by
OM
* In the second excited state, sulfur under goes sp3d2 hyrbidization by mixing a 3s, three 3p and two 3d
ed
I.C
orbitals. Thus formed six half filled sp3d2 hybrid orbitals are arranged in octahedral symmetry.
ar
AD
ep
Sulfur atom forms six σsp3d 2 - p bonds with 6 fluorine atoms by using these sp3d2 orbitals. Each
EM
Pr
flourine uses is half-filled 2pz orbitals for the bond formation.

YA
CH
SF6 is octahedral in shape with F -S- F bond angles equal to 90o.

DI
W IT
F
.A
F F SF6 - Sulfur hexafluoride

W
AD
sp3d 2
W
Hybridization -
S
shape - Octahedral
F F Bond angle - 90o
V.
Properties of covalent compounds

1) In covalent compounds, weak vander Wall's forces of attraction are present between the
molecules. Hence they have low melting and boiling points.
2) Covalent compounds do not conduct electricity because of absence of either free electrons or
ions in them.
3) Covalent compounds are mostly non polar and hence are more soluble in non polar solvents like
benzene, carbon tetrachloride etc.
But some covalent compounds are polar in nature like glucose, fructose etc., and hence are soluble
in polar solvents like water and alcohol.
4) The reactions between covalent compounds involve bond breaking and bond making. As the
bond breaking requires energy, the reactions between them occur slowly.
5) Covalent bond has specific direction. Hence these compounds exhibit isomerism.
Isomerism is the phenomenon exhibited by different compounds possessing the same
molecular formula.
e.g. Following are the isomers with the molecular formula C2H6O.
C2H5OH - Ethyl alcohol
CH3-O-CH3 - Diethyl ether
COORDINATE COVALENT BOND

The covalent bond formed due to the donation of a pair of electrons by one atom to the
other is called coordinate covalent bond.
* The atom which donates the electron pair is called as donor, whereas the atom which accepts that
pair is called as acceptor.
* Both donor and acceptor will share the electron pair.
* Coordinate bond is also known as dative bond.
* It is represented by an arrow pointing towards the acceptor.
Examples:
1) Formation of Ammonium ion (NH4+)
* Ammonium ion is formed when ammonia reacts with hydrogen ion. In the formation of ammonium
N
ion, the sp3 orbital with a lone pair on nitrogen overlaps with the empty 1s orbital of hydrogen ion to
form a coordinate covalent bond.
HA
H3N: + H+ [H3N H]+ (or) [NH4]+
RD
VA by
OM
Donor Acceptor Ammonium ion
ed
I.C
* Ammonium ion contains 4 bond pairs in the valence shell of nitrogen atom and hence it is tetrahedral
ar
AD
in shape with 109o28' bond angles. The hybridization of nitrogen will remain sp3 only.
ep
EM
Pr
YA
+
CH
H
DI
W IT
109o28'
.A
N
W
AD
H
H
W
Tetrahedral shape of NH4+

V.
Note: In NH4Cl, there are three covalent bonds, one coordinate covalent bond and an ionic bond.
Ionic bond is present between NH4+ and Cl- ions.
2) Formation of Ammonia-boron trifluoride

* The ammonia molecule donates a lone pair of electrons on nitrogen atom to the empty 'p' orbital of
boron in BF3. Thus a coordinate bond is formed. During the bond formation, the sp3 orbital containing
the lone pair on nitrogen overlaps the empty 'p' orbital of boron.
H3N: + BF3 [H3N BF3]

Donor Acceptor
* The hybridization in boron is changed from sp2 to sp3 during the formation of coordinate covalent
bond. Hence the geometry around boron in the complex formed will be tetrahedral.
H H
H H
N B
H H
3) Formation of Hydronium ion
* The sp3 orbital containing lone pair on oxygen in water molecule overlaps with the empty 1s orbital on
hydrogen ion to form a coordinate covalent bond.
:
:
H2O: + H+ [H2O H]+ or H3O+
Donor Acceptor Hydronium ion
2) Formation of [AlCl4]-
* The chloride ion (Cl-) donates a lone pair of electrons to the empty 'p' orbital of aluminium in AlCl3.
N
Thus a coordinate bond is formed. During the bond formation, the 'p' orbital containing the lone pair on
chloride ion overlaps the empty 'p' orbital of aluminium.
HA
RD _
Cl
VA by
OM
Cl _ :
Cl
Pr : :
ed
Cl Al + : Cl : Al Cl :
I.C :
ar
Cl Cl
AD
ep
AlCl4-
EM
Acceptor donor
YA
Planar Tetrahedral
CH
DI
W IT
* The hybridization in aluminium is changed from sp2 to sp3 during the formation of coordinate covalent
.A
bond. Hence the geometry around aluminium in AlCl4- will be tetrahedral.

W
AD
W
More examples:
SO2 and SO3 also considered to have coordinate covalent bonds according to octet rule as shown
V.
below.
O
:
S S
O O O O
Properties of compounds containing coordinate covalent bond

Properties of compounds having coordinate covalent bond are similar to covalent compounds.
They do not conduct electricity because of absence of either free electrons or ions in them. They are
soluble mostly in non polar solvents like benzene, carbon tetrachloride etc., . But less soluble in polar
solvents like water and alcohol.
But their boiling and melting points are niether very high as in case of ionic compounds nor very
low like in case of covalent compounds.
MOLECULAR ORBITAL THEORY (MOT)

* Molecular orbital theory was proposed by Hund and Mulliken.
* The important postulates of this theory are given below.
1) According to this theory, the orbitals in a molecule are different from those of atoms. The
electrons of all the bonded atoms in a molecule revolve under the influence of all the nuclei in molecular
orbitals.
2) The atomic orbitals (AO's) of the bonded atoms combine linearly to form molecular orbitals
(MO's) which are occupied by the electrons of bonded atoms.
Molecular orbital is a region around the nuclei of all the bonded atoms in a molecule where
the probability of finding electrons is maximum.
3) Only those atomic orbitals with almost same energy and symmetry with respect to internuclear
axis can combine to form molecular orbitals.
4) The number of molecular orbitals formed is numerically equal to the number of atomic orbitals
combining.
5) The shapes of molecular orbitals depend on the shapes of atomic orbitals.
6) Each molecular orbital can accommodate a maximum of only two electrons.
7) Each molecular orbital is associated with certain amount of energy and are arranged in their
N
increasing order of energy.
8) The degenerate molecular orbitals posses same energy and are filled with electrons according to
HA
Hund's rule. But they may be arranged in different directions.
9) The MO's which have lower energy than AO's are called bonding orbitals, whereas those with
RD
higher energy are known as anti bonding orbitals. The number of bonding orbitals formed is equal to
VA by
OM
the number of anti bonding orbitals.
ed
The orbitals which are not involved in the combination are called non bonding orbitals.
I.C
ar
The order of energies of different types of MO's is:

AD
ep
Bonding orbitals < Non bonding orbitals < Anti bonding orbitals
EM
Pr
YA
Schematic diagram of MO's

CH
DI
W IT
.A
Anti bonding orbitals

W
AD
W
Energy AO's AO's

V.
Non bonding orbitals
Bonding orbitals
10) The bond order of the molecule can be calculated by using the following formula.
number of bonding electrons - number of antibonding electrons
Bond order (B.O) =
2
Differences between Atomic and Molecular orbitals

S.No Atomic orbitals Molecular orbitals
1. They belong to one specific atom only. They belong to all the atoms in a
molecule.
2. Characteristic of atoms. Formed when atomic orbitals of almost
same energy combine.
3. Simple shapes. Complex shapes.
4. Named as s, p, d, f… Named as  ,  ,  ....
5. Less stable than bonding and more Either more or less stable than atomic
stable than anti bonding orbitals. orbitals.
Bonding and Anti bonding orbitals

Bonding molecular orbitals are formed when the orbitals with same signs of wavefunction are
N
combined, whereas anti bonding molecular orbitals are formed when the orbitals with different signs of
HA
wavefunctions are combined.
Depending on the pattern of overlapping, number of nodes and symmetry, the molecular orbitals
are again divided into two types viz.,  &  . RD
VA by
σ -Molecular orbitals
OM
 -Molecular orbitals are formed due to linear combination of atomic orbitals along the inter-
ed
I.C
nuclear axis of bonded atoms. They have cylindrical symmetry about the axis. Bonding orbital is
ar
AD
designated as  , whereas antibonding orbital is designated as  * .

ep
Illustrations:
EM
Pr
YA
Combination of two 's' orbitals along the internuclear axis

CH
+ + + + +
DI
+
W IT
.A
+
W
AD
s
W
s s
bonding orbital
V.
+ - + - + -
+
s s
s *
anti bonding
orbital
Combination of 's' and 'p' orbitals along the internuclear axis
+ + +
+ + - + -
+
-
p  s p
s
bonding orbital
- -
+ - -
N
+ + - + -
HA
p  s p *
s
bonding orbital
Combination of two 'p' orbitals along the internuclear axis

RD
VA by
OM
ed
+
+ -
I.C
- + + - - ++ - -
+
ar
AD
ep
p p p
EM
Pr
bonding orbital
YA
CH
DI
W IT
+
.A
- + - + - +- + - + - +
W
AD
p*
W
p p
anti bonding
orbital
V.
π -Molecular orbitals
 -Molecular orbitals are formed due to sidewise overlapping of atomic orbitals on either sides of
the internuclear axis of bonded atoms. The electron density is concentrated on either side of the axis.
Bonding orbital is designated as  , whereas antibonding orbital is designated as  * .
Illustrations:
Combination of two 'p' orbitals above and below the internuclear axis
+
+
+
+
+
- -
- - - -
p
bonding orbital
- -
+
+
-
+
+
N
-
+
- -
+
HA
p*
anti bonding
orbital
RD
VA by
OM
ed
I.C
DIFFERENCES BETWEEN σ AND π MOLECULAR ORBITALS
ar
AD
S.No σ -Molecular orbital π -Molecular orbital

ep
1. Formed by end on overlapping along Formed by sidewise overlapping

EM
Pr
YA
the internuclear axis. perpendicular to the internuclear axis.

CH
2. Large overlapped region. Small overlapped region.

DI
3. Rotation about the internuclear axis is Rotation about the internuclear axis is
W IT
.A
symmetrical. unsymmetrical.
W
4. Strong bonds are formed. Weak bonds are formed.

AD
W
V.
ELECTRONIC CONFIGURATIONS OF MOLECULES

1) The MO's are arranged in their increasing order of energy and filled with electrons.
2) The lowest available MO is filled first (Aufbau principle).
3) Each MO can accomodate a pair of electrons with opposite spins (Pauli's exclusion principle).
4) Pairing occurs only after all the degenerate MO's are filled with one electron each (Hund's rule).
5)The order of energy of homonuclear diatomic MO's upto nitrogen molecule is:
  2 py    *2 p y 
 1s   *1s   2 s   *2 s      2 px      *2 px
2p    *2 p 
 z  z 
But for elements heavier than nitrogen i.e., from oxygen onwards, the order will be as follows:
  2 py    *2 p y 
 1s   *1s   2 s   *2 s   2 px       *2 px
2p    *2 p 
 z   z 
MOLECULAR ORBITAL ENERGY LEVEL DIAGRAMS (MOED)
1) MOED of H2
 *1s
Energy H H
1s 1s
N
HA
 1s
RD H2
VA by
OM
* Electronic configuration of H2 molecule is  1s 2  *1s 2
ed
I.C
ar
number of bonding electrons - number of antibonding electrons

AD
ep
Bond order (B.O) =

2
EM
Pr
2-0
YA
= 1
CH
2
DI
* Hence there is a single bond between two atoms in H2 molecule.

W IT
.A
W
AD
2) MOED of N2
W
V.
 *2 p x
 *2 p y  *2 pz
2pz 2py 2px 2px 2py 2pz
 2 px
 2 p y  2 pz
N
 *2 s
HA
Energy
2s RD 2s
VA by
OM
 2s
ed
I.C
ar
AD
ep
EM
Pr
YA
CH
 *1s
DI
W IT
.A
1s 1s
W
AD
W
 1s
V.
N atom N2 molecule N atom
* Electronic configuration of N2 molecule is  1s 2  *1s 2  2 s 2  *2 s 2  2 p y 2  2 p z 2  2 p x2
10 - 4
* Bond order (B.O) = 3
2
* Hence there is a triple bond in N2 molecule.
2) MOED of O2
 *2 p x
 *2 p y  *2 pz
2pz 2py 2px 2px 2py 2pz
 2 p y  2 pz
 2 px
N
 *2 s
HA
Energy
2s RD 2s
VA by
OM
 2s
ed
I.C
ar
AD
ep
EM
Pr
YA
CH
 *1s
DI
W IT
.A
1s 1s
W
AD
W
 1s
V.
O atom O2 molecule O atom
* Electronic configuration of O2 molecule is  1s 2  *1s 2  2 s 2  *2 s 2  2 px 2  2 p y 2  2 pz 2  *2 p y1  *2 pz1
10 - 6
* Bond order (B.O) = 2
2
* Hence there is a double bond in O2 molecule.
* It is paramagnetic due to presence of two unpaired electrons.
HYDROGEN BONDING
The electrostatic force of attraction between partially positively charged hydrogen in a polar
molecule and an electronegative atom is called hydrogen bond.
It is represented by dotted line.
Characteristics of Hydrogen bond

1) The hydrogen must be bonded to highly electronegative atom and should posses sufficient positive
charge to make hydrogen bond.
2) The electronegative atom should be smaller in size and possess high charge density to attract hydro-
gen.

Chemical Bonding IPE

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Types of chemical bond :

and thus form an ionic bond.

* Usually an ionic bond is formed between a metal and a nonmetal.

E.g., NaCl, LiF, MgCl2 etc.,

called covalent bond.

* Usually two nonmetals form a covalent bond.

KOSSELL AND LEWI'S ELECTRONIC THEORY OF CHEMICAL BONDING

IONIC BOND FORMATION

1) LiF (Lithium fluoride)

* The electrovalencies of Li and F are equal to one.

2) MgCl2 (Magnesium chloride)

* The electrovalency of Mg is 2 and that of Cl is 1

* The electrovalency of Al is 3 and that of F is 1.

* The electrovalency of 'Na' is 1 and that of 'O' is 2.

FACTORS FAVOURING THE FORMATION OF IONIC BOND

Factors favouring the formation of cation :

E.g. Ca2+ 1s 2 2s 2 2p 6 3s 2 3p 6 with octet configuration is formed easily.

Factors favouring the formation of anion

power and polarizability.

1) Greater the size of cation, greater is the ionic nature.

2) Greater the size of anion, greater is the covalent nature.

crease in the size of anion.

CRYSTAL LATTICE ENERGY (U)

ENERGY CHANGES IN IONIC BOND FORMATION

Calculation of lattice energy of NaCl

mole of energy. This is called sublimation energy  ΔH s or + S  .

energy. It is called ionization energy  ΔH i or + I  .

BORN LANDE EQUATION

It can be calculated by using Born Lande equation as follows:

Born Lande equation can be written as follows

less than 0.155 2 linear

0.155 - 0.225 3 Planar triangle

0.225 - 0.414 4 Tetrahedral

0.4142 - 0.732 4 Squared planer

0.732 - 0.999 8 Body centered cubic

1) Crystal structure of Cesium chloride

* Limiting radius ratio ( )= 0.93.

There are eight Cl- ions at the corners

* The crystal structure is face centered cubic (fcc).

Cl- Na+ Cl-

Cl- Na+ Cl- 1

Total number of Cl- ions = 1+3 = 4

Na+ Cl- Na+ 1

Cl- Na+ Cl-

Properties of ionic compounds

COVALENT BOND FORMATION & LEWI'S DOT STRUCTURES

the two atoms. Thus a covalent bond is formed.

3) Hydrogen chloride (HCl)

hydrogen atoms and gets the configuration of Neon.

atoms get the octet configuration in their valence shell.

9) Ethylene molecule (C2H4)

* Electronic configuration of hydrogen is 1s1

Molecules violating octet rule:

BeCl2 (Beryllium chloride)

PCl5 (Phosphorous pentachloride)

* Electronic configuration of chlorine is 1s 2s sp 3s 3p .

SF6 (Sulphur hexafluoride) :

Some more examples:

Formal charge (Qf)

NBP = Number of electrons in the bond pairs.

Lewi's dot structure:

For the following second resonance form:

VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY