CHEMICAL BONDING

Total number of Questions in Chemical Bonding are :

In Chapter Examples ....................................... 36

Solved Examples ............................................ 23

Total no. of questions ................................... 59

STRUCTURES / FORMULAE OF IMPORTANT COMPOUNDS

Compound Structure Electron dot/Cross formula

× –
1. Sodium Sulphide (Na2S) (Na+)2S– – Na+ S
×
Na+

– –
2. Calcium Hydride (CaH2) Ca++(H–)2 H× Ca++ H ×

3. Hydrogen Peroxide (H2O2) H–O–O–H H× O O ×

H

H
| H
×
4. Phosphene (PH3) H–P–H H ×
P ×
H
××

5. Carbon mono-oxide(CO) C O ×
× C ×
× O

6. Carbon di-oxide (CO2) O C O O ×

× C ×
× O

× ×
7. Hydrogen Cyanide (HCN) H C N H C ×
×
N

–
+– ××
8. Potassium Isocyanide (KNC) K N C K+ × N ×
× C

–
–
9. Sodium Hydroxide (NaOH) Na+ O H Na+ × O × H

××
10. Nitrous oxide (N2O) N N O ×
× N ××
×× N ×
× O

×× ××
11. Nitric oxide (NO or N2O2) O N N O O ×
× N ×
× N ×
× O

O
O ×
12. Dinitrogen tri oxide (N2O3) O N N O ×
×× ×
O × N ×× N ×× O

O O
O O×
13. Dinitrogen tetraoxide (N2O4) O N N O ×
×× ×
O × N ×× N ×× O

O O
O O
×× ××
14. Nitrogen Penta oxide (N2O5) O N O N O O ×
× N × O × N ×× O

××
15. Nitrous acid (HNO2) H O N O H O × N ×× O

O
O
16. Nitric acid (HNO3) H O N O ××
H O × N ×× O
 Compound Structure Electron dot/Cross formula
–
O
O
–
17. Nitrate Ion (NO3–) O N O
O ×
××
O
× N ×

+
H H
×
– × –
H N H Cl H × N H Cl×
18. Ammonium Chloride (NH4Cl) ×

H H

––
O O
19. Carbonate Ion (CO3– – ) –
O C O
–
O ×
××
C × O

××
20. Sulphur di-oxide (SO2) O S O O ×
× S ×
× O

O O
××
21. Sulphur Tri-oxide (SO3) O S O O ×
× S ×× O

––
O O
22. Sulphite Ion (SO3– – ) –
O S O
–
O ×
××
× O
S
××

––

O
O ××
×
– –
O S × O
23. Sulphate Ion (SO4– – ) O S O ××

O
O

––
××
××
××

S S
××
×
–
O S O
– O S × O
24. Thio-sulphate Ion (S2O3– – ) ××

O O
 Compound Structure Electron dot/Cross formula

H
H
O O
×
25. Phosphoric Acid (H3PO4) H O P O H H O× P × O H
××

O O

H H
×

26. Phosphorous acid (H3PO3) H O P O H H O× P × O H

××
O O

– O
O ×
×
– – O P × O
27. Phosphate Ion (PO4– – –) O P O ××

O O

O
O ××

O ×
Mn ×× O
28. Potassium Permagnate (KMnO4) K+ O Mn O ××

O
O

Compound Structure

29. Carbon di-sulphide (CS2 ) S C S

+
30. Nitronium Ion (NO2+) O N O

31. Nitrite Ion (NO2–) O N O

–

+
32. Hydronium Ion (H3O+) H O H

Cl
33. Sulphuryl chloride (SO2Cl2)
O S O
Cl
 Compound Structure
–
O
34. Potassium chlorate (KClO3) K+ O Cl O

–
O

35. Potassium per-chlorate (KClO4)

K+ O Cl O

–2
O O

36. Potassium dichromate (K2Cr2O7) (K+)2 O Cr O Cr O

O O

–3
– –
N C C N
– –
37. Ferry-cyanide Ion [Fe(CN)6]–3 N C Fe+++ C N
– –
N C C N

–4
– –
N C C N
– –
38. Fero-cyanide Ion [Fe(CN)6]–4 N C Fe++ C N
– –
N C C N

Cl Cl Cl
39. Aluminium chloride (Al2Cl6) Al Al
Cl Cl Cl

O O

40. Pyro phosphoric acid (H4P2O7) H O P O P O H

O O
H H

O
41. Hypophosphate acid (HPO3)
H O P O

O O

42. Per-di-sulphuric acid (H2S2O8) H O S O O S O H

O O
 Compound Formula Structure

O
43. Sulphurous acid H2SO3
H O S O H

O
44. Persulphuric acid H2SO5 H O S O O H

Peroxo monosulphuric acid O

(caro’s acid)

45. Thiosulphuric acid H2S2O 3 H O S O H

××
46. Chlorous acid HClO2 H O Cl O
××

×× O
47. Chloric acid HClO3 H O Cl
O

O
48. Perchloric acid HClO4 H O Cl O
O

O O

O Cl O Cl O
49. Perchloric anhydride Cl2O7
O O

50. Hypophosphorous acid H3PO2 H O P O

H

O
O O
51. Perchromate CrO5 Cr
O O

O
Cl Cr Cl
52. Chromyl Chloride CrO2Cl2
O
 Compound Formula Structure

53. Carbon suboxide C3O2 O C C C O

O Cl
54. Bleaching Powder CaOCl2 Ca
Cl

–2
C C
55. Calcium carbide CaC2 Ca or Ca+2
C C

O
56. Ozone O3

O
O

57. Ground state of phosphorous P4 P P

P

S S S
58. Ground state of sulphur S8 S
S S
S S

59. Nitrosyl chloride (Tilden reagent) NOCl Cl N O

S
60. Sodium thiosulphate Na2S2O 3 2Na+ O
–
S
–
O

O
 CHEMICAL BONDING
1. INTRODUCTION
(I) It is well known fact that except for inert gases , no other element exists as independent atoms under
ordinary condition.
(II) Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form
molecules and why do atoms form bonds ? Such doubts will be discussed in this chapter.
(III) A molecule will only be formed if it is more stable and has a lower energy, than the individual atoms.

2. CHEMICAL BOND
(I) A force that acts between two or more atoms to hold them together as a stable molecule.
(II) It is union of two or more atoms involving redistribution of e– among them.
(III) This process accompanied by decrease in energy.
(IV) Decrease in energy  Strength of the bond.
(V) Therefore molecules are more stable than atoms.

3. CAUSE OF CHEMICAL COMBINATION

1. Tendency to acquire minimum energy :
(I) When two atoms approaches to each other. Nucleus of one atom attracts the electron of another atom.
(II) Two nuclei and electron of both the atoms repells each other.
(III) If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond forms.
(IV) So Attraction  1/energy  Stability.
(V) Bond formation is an exothermic process
2. Tendency to acquire noble gas configuration :
(I) Atom combines to acquire noble gas configuration.
(II) Only outermost electron i.e. ns, np and (n-1)d electrons participate in bond formation.
(III) Inert gas elements do not participate, as they have stable electronic configuration and hence minimum
energy. (Stable configuration 1s2 or ns2np6)

Examples
based on Causes of Chemical Bond
Ex.1 When two atoms combine to form a molecule -
(A) Energy is released (B) Energy is absorbed
(C) Energy is neither released nor absorbed (D) Energy may either released or absorbed
Sol. (A) To attain stability energy is released.

4. LEWIS OCTET RULE

(I) Every atom has a tendency to complete its octet outermost.
(II) H has the tendency to complete its duplet.
(III) To acquire inert gas configuration atoms loose or gain electron or share electron.
(IV) The tendency of atoms to achieve eight electrons in their outer most shell is known as Lewis octet
rule.

H × O × H Cl × Be × Cl

Obeys octet rule Doesn't obeys octet rule

Exception of Octet Rule :
(a) Incomplete octet molecules : - or (electron defficient molecules)
Compound in which octet is not complete in outer most orbit of central atom.
Examples - Halides of IIIA groups, BF3, AlCl 3, BCl 3, hydride of III A/13th group etc.

Cl ×
B× Cl In BCl3 
 
×

Boron has only 6 electrons

Cl
Other examples - BeCl2 (4e–), ZnCl2(4e–), Ga(CH3)3 (6e–)

(b) Expansion of octet or (electron efficient molecules) Cl

Cl ×
×
Compound in which central atom has more than 8e– in outermost orbits. P
× Cl
×
Example - In PCl5, SF 6, IF7, the central atom P, S and I contain 10, 12,

×
Cl
and 14 electrons respectively. Cl

Electron dot formula of PCl5

(c) I-Pseudo inert gas configuration : -
(I) Cations of transition metals, which contains 18 electrons in outermost orbit
Examples : Ga+3, Cu+, Ag+, Zn+2, Cd+2, Sn+4, Pb+4 etc.
Electronic configuration of Ga - 1s2, 2s22p6, 3s23p63d10, 4s24p1
3s2 3p6 3d10
Electronic configuration of Ga+3 - 1s2, 2s2 2p6,
18e–
(d) Odd electron molecules : -
××
Central atom have an unpaired electron or odd no (7e–, 11e– etc) of electrons ×N × O
×
in their outer most shell.
Examples : NO, NO2 ClO2 etc. 7e– 8e–

Examples
based on Octet Rule
Ex.2 Which follows octet rule -
(A) FeCl 2 (B) AgCl (C) CaCl2 (D) CuCl
Sol. (C) Because in other compounds there is more than 8 e– in outermost shell of central atom.

Ex.3 The octet rule is not obeyed in -

(A) CO 2 (B) BCl3 (C) PCl5 (D) SiF4
Sol. (B) & (C) As B is electron dificient, P undergoes octet expansion.

Classification of bonds : -

CHEMICAL BONDS

STRONG BOND WEAK BOND

(Inter atomic) (Inter Molecular)
(Energy 200 KJ/mole) (Energy 2 - 40 KJ/mole)

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

Ionic Covalent Co-ordinate Metalic Hydrogen Vander waal's
bond bond bond bond bond bond
(10 - 40 KJ) (2 - 10 KJ)
5. ELECTROVALENT OR IONIC BOND

(I) The chemical bond formed between two or more atoms as a result of the complete transfer of one or
more electrons from one atom to another is called Ionic or electrovalent bond.
(II) Electro +ve atom loses electron (group IA to IIIA)
(III) Electro –ve atom gains electron (group VA to VIIA)
(IV) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
Electronegativity difference  nature of ionic bond.
Example IA and VIIA group elements form maximum ionic compound.
Na + Cl  Na+ + Cl –
2, 8, 1 2, 8, 7 2, 8 2, 8, 8
1e– (Ne configuration) (Ar configuration)

(V) More the distance between two elements in periodic table more will be ionic character of bond.
(VI) Total number of electron lose or gained is called electrovalency.
Example –

(a) Mg O
2, 8, 2 2, 6 electrovalency of Mg = 2
electrovalency of O = 2
2e–

Ca Cl
(b) 2,8,8,2 2,8,7 electrovalency of Ca = 2
electrovalency of Cl = 1
One e–
Cl
One e – 2,8,7

Ca + O  CaO
(c)
Ca O
2, 8, 8, 2 2, 6 electrovalency of Ca = 2
electrovalency of O = 2
2e–

(VII) The force of attraction is equal in all direction so ionic bond is non-directional.
(VIII) Ionic compound do not have molecular formula. It has only empirical formula. eg. NaCl is empirical
formula of sodium chloride.

Conditions for Forming Ionic Bonds :

Formation of Ionic bond depends upon these three factors –
(a) Ionisation energy :
Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous
atom to form the +ve ion or cation. (energy absorbed)
Lesser Ionisation energy  Greater tendency to form cation.

e.g Na   Mg2  Al3 

 Cation formation tendency
Cs  Rb   K   Na   Li 
 (b) Electron affinity
Amount of energy released when an electron is added to an isolated gaseous to form –ve ion
(anion) energy released.
Higher electron affinity  Greater tendency to form anion
e.g. Cl– > F– > Br– > I –
F– > O –2 > N–3
(c) Lattice energy - (Energy released) Amount of energy released when one mole of crystal lattice
is formed Higher lattice energy  Greater will be the stability or strength of ionic compound.
Factors affecting lattice energy :
(i) Magnitude of charge  U  z+ z– (Ionic charge)
Lattice energy  Magnitude of charge
NaCl MgCl2 AlCl 3
Na+ Mg+2 Al+

– Lattice energy increases

– Size of cation decreases.
1
(ii) Size of Cation : – Lattice energy  
r  r–
LiCl NaCl KCl RbCl CsCl

– Size of cation increasing

– Size of anion is constant
– Lattice energy decreases

(d) Overall lowering of energy :

Energy must be released during bond formation.
Energy changes are involved in the following steps –
A + IE = A+ + e–
and B + e– = B– + EA
This concludes that for lower value of IE and higher value of EA there is more ease of formation of the
cation & anion respectively and consequently more chances of electrovalent bond formation.

Representation of formula of compounds :

(a) Write the symbols of the ions side by side in such a way that positive ion is at the left and negative
ion is at the right as A+B–
(b) Write their electrovalencies in figure at the top of each symbol as AxBy
x y
(c) Now apply criss cross rule as , i.e formula AyBx.
A B
2 1
Examples : Calcium chloride = CaCl 2
Ca Cl

Properties of ionic compounds :

(a) Physical state –
Ionic compounds are hard, crystalline and brittle due to strong electrostatic force of attraction.
 Brittleness 

+ – + – + + – + – +
– + – + – – + – + –
+ – + – +
+ – + – +
– + – + –
– + – + –

Attraction Repulsion

(Same charged ions comes nearer. So they repell each other)

(b) Isomorphism –
(I) Two compounds are said to be isomorphous if they have similar no. of electrons i.e.similar
configuration of their cation and anion.
(II) They have similar crystal structure.
Example –
Na+ F– Mg+2 O –2
Valency + 1, –1 + 2, –2
electronic configuration 2, 8, 2, 8 2, 8 2, 8
similarly Ca +2 2Cl –1 2K +1 S –2
2, 8, 8, 2, 8, 8 2, 8, 8 
  2, 8, 8
2, 8, 8  2, 8, 8

(c) Boiling point and melting point –

Ionic compounds have high boiling point and melting point due to strong electrostatics force of
attraction among oppositely charged ions.
(d) Conductivity –
It depends on ionic mobility. In solid state - No free ions - Bad conductor of electricity.
In fused state or aqueous solution Due to free ions - Good conductor of eletricity.
conductivity order : Solid state > Fused state < Aqueous solution
(e) Solubility –
Highly soluble in water (Polar solvents)
Example : NaCl in water
(I) The Na+ ions get associates with– vely charged ‘O’ of water
(II) And Cl– ions associates with +vely charged ‘H’ of water.
H2O–

H2O–

+ – + –
H O H O
O–
+

O–
+

2 + H 2 2 + H 2

+ –
Na +
H2O– Cl +
– – H2O–
+
H 2O +
H 2O
+

+
HO–

HO–
H 2O

H 2O
2

2
–

–
+

–
Oxygen atom of H2O give its electron to Na+ H atom of H2O gain electron from Cl
 (III) Thus charge on Na+ and Cl– decreases and electrostatics force of attraction also decreases which
leads to free ion.
(IV) The energy released due to interaction between solvent and solute is called solvation energy.If water
is used as solvent it is called hydration energy.
(V) For an ionic compound to be soluble in water – Hydration energy > Lattice energy

1
Lattice energy  Solubility

Hydration energy  Solubility.

1 1
Hydration energy (H)  
 {r+ & r– are radius of cation and anion}
r r–
1
(VI) Hydration energy mainly depends on the cation radius because the value is negligible in
r–
1
comparison to .
r
(VII) Down the group both the lattice energy & hydration energy decreases, if decreases in lattice is
greater than hydration energy, solubility increases down the group and vice versa.

Examples
based on Ionic Bond

Ex.4 Out of following which has maximum value of lattice energy -

(A) NaF (B) NaCl (C) NaBr (D) NaI
Sol. (A) Due to small size of anion.

Ex.5 The crystal lattice of electrovalent compound is composed of -

(A) Atoms (B) Molecules
(C) Oppositely charged ions (D) Both molecules and ions
Sol. (C) It is the fact that electovalent compounds are made of ions.

Ex.6 Ions are formed from neutral atoms by -

(A) Loss of electron (B) Gain of electrons
(C) Sharing of electrons (D) Loss and gain of electrons
Sol. (D) Cation and anion are formed by losing and sharing of electrons respectively.

Factor affecting solubility :

(I) Dielectric constant –
The capacity of solvent to neutralise the charge of ionic compounds is called Dielectric
constant. It is represented by “”
(a) Water has maximum dielectric constant ( = 80)
(CH3OH  = 35) , (Acetone  = 21)
(C2H5OH  = 27) , (Ether = 4.1)
(Benzene  = 2.3)
H2O > CH3OH > CH3CH2OH > CH3COCH3 > CH3OCH3 > C6H6
(b) Ionic compounds are more soluble in the solvents, having high dielectric constant.
(c) H2SO 4 and H2O2 have high dieletric constant but these are not a good solvent due to
oxidising nature
 (II) Size of ion :
(a) Keeping size of cation constant, the lattice energy decreases with the increases of anionic
radius.
Hence order of solubility of LiX in water is LiF < LiCl < LiBr < LiI

1
As solubility 
lattice energy
(b) in LiI covalent nature is more according to Fajan’s rule but HE > LE therefore Li is more soluble
in water.
(c) Keeping size of anion constant, the hydration energy decreases with the increase of cationic
radius. hence order of solubility of MSO4 will be –
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO 4 (Exception of Fajan’s rule)
(d) If size of cation and anion is very large, solubility decreases from top to bottom.
(e) Solubility decreases in a period (as ionic nature decreases and covalent nature increases)
NaCl > MgCl2 > AlCl3
(III) Polarisation of anion :
Polarisation capacity is maximum in pseudo inert gas configuration.

1
solubility 
polarisation
AgF > AgCl > AgBr > AgI

– Polarisation increases.
– Covalent character increases.
– Solubility decreases.
(IV) Ionic reaction –
(a) Ionic compounds shows ionic reaction and covalent compounds shows-molecular reaction.
(b) Ionic reactions are faster than molecular reaction because of free ions.
e.g. When NaCl is added in AgNO3 solution, white ppt of AgCl is formed at once.
 Na+ NO – + AgCl 
Ag+NO 3– + Na+NO –  3

white ppt.

6. POLARISATION

(Fajan’s Rule) (Covalent nature in ionic bond)

(I) When a cation approaches an anion closely the positive charge of a cation attract the electron
cloud of the anion towards itself, due to the electrostatic force of attraction between them.
(II) At the same time cation also repel the positively charge nucleus of anion.
(III) Due to this combined effect, cloud of anion is bulged or elongated towards the cation. This is
called distortion, deformation or Polarisation of the anion by the cation and anion is called Polarised.
Polarisation Power :
The ability of cation to polarise a nearby anion is called Polarisation power of cation.
– –
C+ A C+ A
 Polarizability :
(I) ability of anion to get polarised by the cation.
(II) Polarisation of anion causes some sharing of electron between the ions so ionic bond acquires
certain covalent character.
(III) Polarisation  Covalent character
(IV) Magnitude of polarisation depends upon a no. of factors, suggested by Fajan and are known as
Fajan’s rule.
Fajan’s rule : (Factors Affecting Polarisation)
(a) Size of cation : - Polarisation of the anion increases as the size of cation decreases.
1
Polarisation  size of cation
In a group –
BeCl2
MgCl2 - Size of cation increases
CaCl2 - Covalent character decreases
SrCl2 - Ionic character increases
BaCl2

 Greatest polarising power of Be2+, shows its maximum covalent character

In a period –
Na+, Mg+2, Al+3, Si+4

- Size of cation decreases

- Covalent charater increases
(b) Size of anion : - If the size of the anion increases for a given cation, the covalent character
increases/Nature Polarisation  size of anion.

CaF2
CaCl2 - Size of anion increases
CaBr2 - Covalent character increases
Cal2 - Ionic character decreases
(c) Charge on cation and anion : -
 Polarisation  charge on cation anion
(I) Charge on cation  Polarisation (covalent character)
eg. NaCl MgCl2 AlCl 3 SiCl 4
Na + Mg ++ Al +++ Si ++++

- Charge on cation increases

- Covalent character increases
- Ionic character decreases (M.P. decreases)
1
Charge on anion  polarisation  covalent nature 
M.P.
(d) Electronic configuration of cation : -
Polarisation capacity of cation having pseudo inert gas configuration is high. If the size of cations
is same than that of cation having inert gas configuration.
 CuCl (M.P. 442°C) – Cu+ 2, 8, 18 (Covalent)
NaCl (M.P. 800°C) – Na+ 2, 8 (Ionic)
+ +
Cu and Na both the cation (Pseudo & inert) have same charge and size but polarising power
of Cu+ is more than Na+ because –
zeff of ns2p6 (inert) < zeff. of ns2p6d10 (pseudo)
Na+ < Cu+
(Ionic) (Covalent)
So CuCl has more covalent character than NaCl.

Examples
based on Fajan's Rule
Ex.7 Compound with maximum ionic character is formed from -
(A) Na and Cl (B) Cs and F (C) Cs and  (D) Na and F
Sol. (B) Using fajan’s rule, larger cation and smaller anion will have max. Ionic character.

Ex.8 Out of the following which one has the highest values of covalent character -
(A) ZnCl2 (B) CaCl2 (C) CdCl2 (D) CuCl
Sol. (A) Because Zn+2 has smallest size among the all.

Ex.9 Compound having highest M.Pt. –

(A) BeCl 2 (B) MgCl 2 (C) CaCl2 (D) SrCl2
Sol. (D) As the size of cation increases polarisizing power decreases hence ionic character increases

7. COVALENT BOND

(I) A covalent bond is formed by the mutual sharing of electrons between two atoms of electro negative
elements to complete their octet. (Except H which completes its duplet).

H H H H O O O O N N N N
H2 molecule O2 molecule N2 molecule
(II) The shared pair of electrons should have opposite spins, and are localised between two atoms
concerned.
(III) Shairing of electrons may occurs in three ways –

No. of electrons shared Electron pair Bond

between two atoms

2 1 Single bond ( )
4 2 Double bond ( )
6 3 Triple bond ( )

Examples – H N H Three single bonds (not triplet bond)

H
N N Triple bond. (not three bond) O O Double bond (Not two single bond) H O H (Two single
bonds.)
Lewis structure and covalent bond :
(I) Electron dot structures, also known as Lewis structures of covalent molecules, are written in accordance
with octet rule.
(II) All atoms in a formula will have a total of eight electrons by sharing in the valence shell except the
H-atom which forms the largest number of bonds with other atoms placed in the centre of skeleton
structure. Other atoms surrounds it to complete the octet.
(III) Structure in which valence electrons are represented by dots are called lewis structures.
(IV) Structure represented by line (–) or dashes are known as couper structrue.
(V) Lewis dot formulae show only the number of valency electron, the number and kinds of bonds, but do
not depict the three dimensional shapes molecules and polyatomic ions.
Orbital concept of covalent bond :

(I) One orbital can accomodate at the most 2 electrons with opposite spins
(II) Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its
orbitals.
(III) Tendency to complete orbital or to pair the electron is an essential condition of covalent bond. Completion
of octet is not the essential condition of covalent bond.
(IV) Covalency : It is defined as the number of electrons contributed by an atom of the element for shairing
with other atoms to achieve noble gas configuration.
(V) If the outermost orbit has empty orbitals then covalent bonds are formed in exicted state.
Variable valency in covalent bonds :
(I) Variable valencies are shown by those elements which have empty orbitals in outermost shell.
(II) Lone pair electrons gets excited in the subshell of the same to form the maximum number of unpaired
electrons. Maximum covalency is shown in excited state.
(III) The energy required for excitation of electrons is called promotion energy.
(IV) Promotion rule – Excitation of electrons in the same orbit.
Example –
(a) Phosphorus  Ground state

Covalency 3 (PCl3)
3s 3p
Phosphorus  Excited state

Covalency – 5 (PCl5)
3s 3p 3d
(b) Sulphur  Ground state.

Covalency – 2 (SF2)
3s 3p 3d
Sulphur  Excited state

1st excited state Covalency – 4 (SF4)

3s 3p 3d

2st excited state Covalency – 6 (SF6)

3s 3p 3d
So variable covalency of S is 2, 4 & 6.
 (c) Iodine has three lone pair of electrons

(Ground state)
5s 5p 5d
So it shows three excited states – Maximum number unpaired electrons = 7
Variable Valencies are 1, 3, 5, 7

Applications of Variable Valency :

(I) To explain existence of molecules –
NCl3 – exists
NCl5 – doesn’t exists (due to absence of d-orbitals in Nitrogen.) While PCl 3 and PCl 5 both exist
because 3d orbitals are present in phosphorus.
OF2 –– exists, but OF4 and OF6 doesn’t exists due to absence of d-orbitals While SF4 and SF6 exists
due to presence of d-orbital, present in its valence shell.
(II) Hydrolysis of compounds –
CCl4 + H2O  No reaction occurs
SiCl4 + H2O  Reaction occurs
In C-atom there are no empty d-orbitals to accept the lone pair of electrons from water. While SiCl 4 has
empty 3d-orbitals.
SiCl4 + 4H2O   Si(OH)4 – SiO 2
– 4 HCl

Unstable

Examples
based on Covalent Bond
Ex.10 A covalent bond is possible between -
(A) Similar atom (B) Dissimilar atoms
(C) Similar and dissimilar atoms (D) Similar molecules
Sol. (C) It is related to electronegativity.

Ex.11 Which of the following is most covalent -

(A) AlF3 (B) AlCl 3 (C) AlBr3 (D) Al3
Sol. (D) As the size of anion increases covalent character increases.

Ex.12 Among LiCl, BeCl2, BCl 3 and CCl 4, the covalent bond character follows the order -
(A) LiCl < BeCl2 > BCl3 > CCl 4 (B) LiCl > BeCl2 < BCl3 < CCl 4
(C) LiCl < BeCl2 < BCl3 < CCl 4 (D) LiCl > BeCl2 > BCl3 > CCl 4
Sol (C) The covalent character increases according to charge on cation.

Wave mechanical concept of chemical bonding – (Overlapping)

To explain the nature of covalent bond two theories based on quantum mechanics have been proposed.
(1) Valence bond theory (VBT) (2) Molecular orbital theory (MOT)

8. VALENCE BOND THEORY

(I) It was presented by Heitler & London to explain how a covalent bond is formed.
It was extended by Pauling & Slater.
(II) The main points of theory are –
(a) To form a covalent bond overlapping occurs between half filled valence shell orbitals of the two
atoms.
(b) Resulting bond acquires a pair of electrons with opposite spins to get stability.
(c) Orbitals come closer to each other from the direction in which there is maximum overlapping
(d) So covalent bond has directional character.
(e) Extent of overlapping  strength of chemical bond.
(f) Extent of overlapping depends on two factors.
(i) Nature of orbitals – p, d and f are directional orbitals  more overlapping
s-orbitals  non directional – less overlapping
(ii) Nature of overlapping – Co-axial overlapping - extent o overlapping more.
Collateral overlapping - extent of overlapping less
Order of strength of Co - axial overlapping – p - p > s - p > s - s

p-p p-s s-s

(g) As the value of n increases, bond strength decreases.
1 - 1 > 1 - 2 > 2- 2 > 2 - 3 > 3 - 3
(h) If n is same 2p - 2p > 2s - 2p > 2s - 2s
1s - 2p > 2s - 2p > 3s - 3p
(i) Electron which is already paired in valency shell can enter into bond formation, it they can be
unpaired first and shifted to vacant orbitrals of slightly higher energy of the same energy shell.
(j) This point can explain the trivalency of boron, tetravalency of carbon, penta valency of phosphorus
etc.
(k) Two types of bonds are formed on acount of overlapping.
(A) Sigma () bond (B) Pi () bond

(A) Sigma () bond :

(I) Bond formed between two atoms by the overlapping of half filled orbitals along their axis (end to end
overlap) is called sigma bond.
(II)  bond is directional.
(III)  bond do not take part in resonance.
(IV) Free rotation is possible about a single  bond.
(V) Maximum overlapping is possible between electron clouds and hence it is strong bond.
(VI) There can be only  bond between two atoms.
Sigma bond are formed by four types of overlapping
(a) s - s overlapping (H2) - Two half filled S-orbitals overlap along the internuclear axis.

1s  bond 1s 1s
1s
(Formation of H2 molecule)
 (b) s - p overlapping (Formation of HF) – When half fill s-orbital of one atom overlap with half filled
p-orbital of other atom.

1s of Hydrogen 2p of Fluorine H–F

(c) Bond between two hybrid orbitals –

sp3 - sp3, sp2 - sp2, sp3 - sp2, sp3 - sp etc.

overlapping of orbitals form  bond.
sp sp sp sp

formation of C2H2

sp-sp hybrid orbital

(d) p - p overlapping – (Coaxial) – It involves the coaxial overlapping between half filled p-orbitals of
two different atoms.
eg. Formation of Cl2, F2, Br2

p p
– + + + – –

(B) Pi () bond

(I) The bond formed by sidewise (lateral) overlapping are known as  bonds.
(II) Lateral overlapping is only partial, so bonds formed are weaker and hence more reactive than  bonds
(Repulsion between nucleus is more as orbitals have to come much close to each other for  bonds
formation)
Example – Formation of O2 molecule –


Py Py

Pz + Pz 


O2 molecule


Only py and pz of oxygen atom have unpaired e– in each orbital for bonding.
Electron configuration of oxygen is – 1s22s22px2 2py12pz1
(III) Free rotation about a  bond is not possible.
(IV)  bond is weaker than  bond (Bond energy difference is 63.5 KJ or 15 K cal/mole)
(V)  bonds are non-directional, so do not determine the shape of a molecule.
(VI)  bond takes part in resonance.
(VII)  bond formed by pure or unhybrid orbitals.
9. HYBRIDISATION
Consider an example of Be compound :-
If it is formed without hybridisation then -
s–p p–p
Cl Be Cl
both the Be–Cl bonds should have different parameters and p-p bond strength >s-p bond strength.
Practically bond strength and distance of both the Be-Cl bonds are same.
This problem may overcome if hybridisation of s and p-orbital occurs.

Hybridisation :
(I) It is introduced by pauling, to explain equivalent nature of covalent bonds in a molecule.
(II) Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution
of energy to form new orbitals, of same shape & same energy. These new orbitals are called hybrid
orbitals. and the phenomenon is called hybridisation.
Now after considering s-p hybridisation in BeCl 2
sp – sp sp – p
Cl Be Cl
bond strength of both the bonds will be equal.

Characteristic of Hybridisation :

(I) Hybridisation is a mixing of orbitals and not electrons. Therefore in hybridisation

full filled, half filled and empty orbitals may take part.
(II) Number of the hybrid orbitals formed is always be equivalent to number of atomic
Structure of
orbital which have taken part in the process of hybridisation.
hybrid orbital

(III) Each hybrid orbital having two lobes, one is larger and other is smaller. Bond will be formed from large
lobe.
(IV) The number of hybrid orbitals on central atom of a molecule or ion = number of  bonds
+ lone pair of electron.
(i) The 1st bond between two atoms will be sigma.
(ii) The other bond between same two atoms will be pi bond.
(iii) Maximum two pi bonds may be present on a single atom.
(iv) The electron pair of an atom which do not take part in bond formation called as lone pair of electron.
(V) One element can represent many hybridisation state depending on experimental conditions for example,
C showing sp, sp2 and sp3 hybridisation in its compounds.
(VI) Hybrid orbitals are differentiated as sp, sp 2, sp 3 etc.
(VII)The order of repulsion between Ip & bp is : Ip - Ip > Ip - bp > bp - bp
(VIII)The directional properties in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form
stronger sigma bond. The directional property of different hybrid orbitals will be in following order.
sp < sp2 < sp 3 < sp3d < sp2d 2 < sp3d 3
Difference between hybridisation & overlapping

Overlapping Hybridisation

 It occurs between orbitals of two atoms  It occurs among orbitals of the same atom

 Only half filled orbitals takes part in

overlapping
 Any type of orbital can participates

 It occurs during bond formation bond

formed after hybridisation
 Process, just before overlapping.

 Orbital of different energies may participates

in excited states.
 It may takes place in ground or in excited
state
Inground state– NH3, NCl3, PH3, PCl3,

 Molecular orbitals are formed  Hybridised orbitals are formed

Determination of hybridisation state –

Method (I) :
Count the following pair of e– arround the central atom :
(a) Count all pure  bonded electron pairs (or  bonds) (b) Count all lone pair of electron
(c) Count Co ordinate bond (d) Count negative charge
Method (II) :

To predict hybridisation following formula may be used :

1
No. of hybrid orbital = [Total number of valence e– in the central atom + total number of
2
monovalent atoms – charge on cation + charge on anion]
1
eg. NH4 [5 + 4 – 1] = 4 sp 3 hybridisation.
2

1
SF 4 [ 6 + 4 ] = 5 sp3d hybridisation.
2

1
SO 24– [ 6 + 2 ] = 4 sp3 hybridisation.
2
(‘O’ is divalent so add only charge on anion)
1
NO 3– [5 + 1] = 3 sp2 hybridisation.
2
If such type of e– pairs are –
two – sp hybridisation
three – sp 2 hybridisation
four – sp 3 hybridisation
five – sp3d hybridisation
six – sp3d2 hybridisation

seven – sp3d3 hybridisation

Types of Hybridisation :
sp hybridisation :
(I) In this hybridisation one s– & one P–orbital of an atom are mixed to give two new hybrid orbitals which
are equivalent in shape & energy known as sp hybrid orbitals.
(II) These two sp hybrid orbitals are arrange in straight line & at bond angle 180°.
(III) s-character 50%
2s 2p
Be (ground state)

2s 2p
Be (excited state)

2s 2p
Be atom accepts two electrons from F in BeF2,
sp sp
sp hybridisation sp hybridisation
CO2 Molecule (O = C = O ) :
In CO2 molecule, C has two sp hybrid orbitals & two unhybridised p orbitals.

 bond

 bond
Molecular orbital picture of CO2

 Thus, CO2 molecule is a linear in shape & having 180° bond angle.

 The bond length between C–O bond is reduced due to the presence of  bond.
CH CH [H CA CB H]

In CH CH molecules, each C atom contains two sp hybrid orbitals & two unhybridised p orbitals
2s 2p
C(ground state)

C(excited state)

C atom accepts four electrons

from H & C, In C2H2 sp hybridisation
  sp hybrid orbital of each C overlaps to give sigma bond between C – C.

 The remaining one sp hybrid orbital of each C atom overlaps with s orbital of H, forming sigma bond
between C – H.

 The two unhybridised p orbitals of each C atom (py and px) overlap laterally to form two pi() bonds.

 Therefore in H–XCA  CB–H

sigma bond between CA – CB is formed sp – sp overlapping
sigma bond between CA – H is formed sp – s overlapping
sigma bond between CB – H is formed sp – s overlapping
pi bond between CA – CB is formed : py – py, px – px overlapping

 Each C atom forms two sigma bonds but in C2H2, total sigma bonds are 3

 Each C atom forms two  bonds. Total  bonds in C2H2 are two

 Total number of bonds in acetylene are :

3 + 2 bond = 5 bonds

Examples on sp hybridisation

Example  bond I.p.e. Hybridisation Bond angle Shape

BeH2 2 - sp 180° Linear

BeF2 2 - sp 180° Linear

BeCl2 2 - sp 180° Linear

BeBr2 2 - sp 180° Linear

BeI2 2 - sp 180° Linear

CO 2 2 - sp 180° Linear

CO 1 1 sp 180° Linear

NO2 2 - sp 180° Linear

C2H2 2 - sp 180° Linear

HCN 2 - sp 180° Linear

ZnCl2 2 - sp 180° Linear

HgCl2 2 - sp 180° Linear

CdCl2 2 - sp 180° Linear

N2O 2 - sp 180° Linear

N3– 2 - sp 180° Linear
sp2 Hybridisation :
(I) In this hybridisation one & two p orbitals are mixed to give three new sp2 hybrid orbitals which all
are in the same shape & equivalent energies.
(II) These three sp2 hybrid orbitals are at angle of 120° & giving trigonal planar shape.
2s 2p
B (ground state)

B (excited state)

B atom accepts 3 electrons

From 3 F atom  in BF 3
(III) s - character 33.3% sp2 hybrid orbitals
Graphite :

 The hybridisation on each carbon atom of graphite is sp2

 Three sp2 hybrid orbital are present on each carbon atom at 120° & they overlap to sp2 hybrid orbitals
of adjacent C atoms forming layers of hexagons.
 On each carbon atom, one unhybridised. p orbital is also present, which is perpendicular to the plane
of sp2 hybrid orbitals.
 The distance between two layer in graphite is 3.35 Å.

3.35 Å
3.35 Å

1.42 Å
SnX2 (X = F, Cl, Br, I)
5s 5p
Sn (ground state)

Sn (excited state)

Sn after hybridisation

sp2
shares 2e– with 2 atom.
 SnX2 having two  bonds & one LP electron therefore hybridisation is sp2 N

 The bond angle is SnX2 will be less than 120° (due to presence of one LPe.) H

 The shape of SnX2 molecule is bent.

H

MolecuarpymidbtfNH3
 Examples on sp 2 hybridisation
Example  bond I.p.e. Hybridisation Bond angle Shape

BH3 3 - sp2 120° Trigonal planar

BF3 3 - sp2 120° Trigonal planar

BCl3 3 - sp2 120° Trigonal planar

CH3 3 - sp2 120° Trigonal planar

CH2= CH2 3, 3 - sp2 120° Trigonal planar

Graphite 3 - sp2 120° Trigonal planar

HNO3 3 - sp2 120° Trigonal planar

NO3– 3 - sp2 120° Trigonal planar

HNO2 2 - sp2 < 120° Angular (V)

SO2 2 - sp2 < 120° Angular (V)

SO3 3 - sp2 120° Trigonal planar

HCO3– 3 - sp2 120° Trigonal planar

CO 3–2 3 - sp2 120° Trigonal planar

SnCl2 2 1 sp2 < 120° Angular (V)

SnBr2 2 1 sp2 < 120° Angular (V)

SnI2 2 1 sp2 < 120° Trigonal planar

AlCl3 3 - sp2 120° Trigonal planar

GaCl3 3 - sp2 120° Trigonal planar

PbCl2 2 1 sp2 < 120° Angular (V)

sp3 Hybridisation :
(I) In this hybridisation one s orbital & three p orbitals of an atom of a molecule or ion, are mixed to give
four new hybrid orbitals called as sp3 hybrid orbitals.
(II) The angle between these four hybrid orbitals will be 109°28’
2s 2p
C (ground state)

C (excited state)

C atom share

four electrons with sp3 hybridisation

4 hydrogen atoms
(III) The shape obtained from these hybrid orbitals would be tetrahedron.
Three following examples represent this condition.

(a) Four sigma bonds with zero lone pair electron :

The following examples represent this condition.
CH4, CF4, CCl4, CBr4, Cl4, NH4+, BF 4–, AlF4–, BeF4–2,
In above compounds, bond angle is 109°28’ & tetrahedron shape.

(b) Three sigma bonds & one lone pair of electron :

(I) This condition is shown by following compounds & ions. N
NH3,PH3,AsH3,SbH3,BiH3,NF3,PF3,NCl3,PCl3 : CH3,H3O+ ClO3–
H H
(II) sp3 hybridisation, pyramidal shape & bond angle will be less
than due to the presence of the lone pair electron on nirtogen
repels bond pair electron more therefore bond angle is reduced
H
from 109°28’ to 107°.
The repulsion between IP – b.p > bp – bp. Molecular pyramidal orbital
of NH3

(c) Two sigma bonds & two lone pair lone pair electrons :
(I) This condition is shown by following compounds and ions.
O
H2O, H2S, H2Se, H2Te, OCl2, OBr2, OF 2, OI 2 etc.
(II) In all above examples, the central atom showing sp3 hybridisation, H
angular shape and bond angle will be either less then 109°28’ or
more than 109°28’.
H

Molecular angular orbital of H2O

In H2O the hybridisation on O atom is sp3, but due to presence of two lone pair electrons they
repell each other and then repell their adjacent bond pair electron. These repulsion will be in
following order.
I.p. – I.p. > I.p. – b.p. > b.p. – b.p.
l.p. = lone pair electron
b.p. = bond pair electron

Examples on sp3 Hybridisation

Example  bond I.p.e. Hybridisation Shape

CH4 4 - sp 3 Tetrahedron
3
CCl4 4 - sp Tetrahedron
CBr4 4 - sp 3 Tetrahedron
PCl4+ 4 - sp 3 Tetrahedron
NH4+ 4 - sp 3 Tetrahedron
BF4– 4 - sp 3 Tetrahedron
AlF4– 4 - sp 3 Tetrahedron
BeF4–2 4 - sp 3 Tetrahedron
MgF4–2 4 - sp 3 Tetrahedron
Example  bond I.p.e. Hybridisation Shape
Ni(CO)4 4 - sp 3 Tetrahedron
NF3 3 - sp 3 Pyramidal
NCl3 3 1 sp 3 Pyramidal
N(CH3)3 3 1 sp 3 Pyramidal
PF3 3 1 sp 3 Pyramidal
PCl3 3 1 sp 3 Pyramidal
AsCl3 3 1 sp 3 Pyramidal
SbCl3 3 1 sp 3 Pyramidal
BiCl3 3 1 sp 3 Pyramidal
NH3 3 1 sp 3 Pyramidal
: –CH3 3 1 sp 3 Pyramidal
H3O+ 3 1 sp 3 Pyramidal
SO32– 3 1 sp 3 Pyramidal
ClO3 3 1 sp 3 Pyramidal
XeO3 3 1 sp 3 Pyramidal
H2O 2 2 sp 3 Angular (V)
H2S 2 2 sp 3 Angular (V)
NH2– 2 2 sp 3 Angular (V)
OF2 2 2 sp 3 Angular (V)
Cl2O 2 2 sp 3 Angular (V)
SCl2 2 2 sp 3 Angular (V)
Diamond 4 - sp 3 Tetrahedron
SiO2 4 - sp 3 Tetrahedron
SiC 4 - sp 3 Tetrahedron

sp3d Hybridisation :
(I) In this hybridisation one s orbitals and one d orbital are mixed to give five new hybrid orbitals which
are equivalent in shape and energy called as sp3d hybrid orbitals.
(II) Out of these five orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are perpendicular
to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is trigonal
bipyrmaidal.
For example, PF5 showing sp3d hybridisation

3s 3p 3d
P (ground state)

3s 3p 3d
P* (excited state)
3s 3p 3d
P atom share with five e of F

3
sp hybridisation
(III) In this hybridisation dz2 orbital is hybridised with s and p orbitals.
In this way five sp3d hybrid orbitals form five sigma bond with five F atoms and give a molecule of
PF5, shape of this molecule is trigonal bipyramidal.
Axial two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion between 3 equatorial
bp of e– and 2 axial b.p. of e–
In above hybridisation there are four conditions
Cl
(a) Five sigma bonds and zero lone pair electron :
The following examples represent this conditions.
PF5, PCl5, PBr5, Pl5, AsF5, AsCl5, SbCl 5, SbF5 etc. Cl P
Cl
The shape of all above molecules is trigonal bipyramidal.

Cl
(b) Four sigma bonds and one lone pair of electron :
The following examples represent this condition.
SF4, SeF4, TeF4, PoF4, PF 4–, SbF4–, SCl4, SeCl4, TeCl 4 etc. Cl
The shape of all above examples will be irregular tetrahedron. Structure of PCl5
Examples SF4

3s 3p 3d
S ground state
F
3p 3d
F
3s
S excited state S ••

3s 3p 3d F
F
S atom share with four e– of F Structure of SF4
3
five-sp d hybrid orbitals

(c) Three sigma bonds & two lone pair of electrons : F

••

The following examples represent this condition.

CIF3, BrF3, IF 3, BrCl3, ICI3 etc. Cl F
The shape of all above compounds is ‘T’ shape.
••

F
(d) Two sigma bonds & three lone pair of electrons :
Structure of CIF3
The following examples represent this condition.
ICl2–, IBr2–, ClF2–, IF2–, BrF2–, XeF2–, I3–, Br3–
The geometry of above examples will be linear

sp3d 2 Hybridisation :
(I) In this hybridisation, one s-orbitals, three p-orbitals & two d-orbitals are mixed to give six new hybrid
orbitals known as sp3d2 hybrid orbitals.
(II) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral.
(III) The angle between all hybrid orbitals will be 90°.
Example : SF6, AlF6–2, PF 6–, ICl5, XeF4, XeOF 4, ICl4–,
 (IV) Two ‘d’ orbital participates in the hybridisation are dx2–y2 and dz2.
SF6 :
3s 3p 3d
S (ground state)

3s 3p 3d
S (excited state)

3s 3p 3d
S (after hybridisation)

3 2
sp d hybridisation

sp3d3 Hybridisation :
(I) In this hybridisation, one s-orbitals & three d-orbitals are mixed to give seven new hybrid orbitals known
as sp3d3 hybrid orbitals.
(II) In this hybridisation d-orbitals used are dxy dxz & dyz orbitals.
(III) These seven sp3d3 orbitals are configurated in pentagonal bipyramidal shape.
(IV) Five bond angles are of 72° & two bond angles of 90°.
(V) The following examples showing sp3d3 hybridisation –IF7 & XeF6.
F
F

F F
I

F F
F
Structure of IF7

Shape of covalent molecules :

• It was given by Sidgwick & Powel.

• According to this concept the shape of covalent compound depends on total pairs of electron
(bonded or non bonded) present on the central atom. Which is given as below –

S.No. Total pair of e– Shape Hybridisation

1. Two Linear sp
2. Three Coplaner trigonal (Triangular) sp 2
3. Four Tetrahedral sp 3
4. Five Trigonal bipyramidal sp3d
5. Six Octahedral (Square bipyramidal) sp3d 2
6. Seven Pentagonal bipyramidal sp3d 3
Examples
based on Hybridization
Ex.13 The hybridization of carbon atoms ion C – C single bond of H – C  C – CH = CH2 is -
(A) sp3-sp3 (B) sp2-sp (C) sp-sp2 (D) sp3-sp
Sol. (C) As the first carbon has triple bond and second one has double bond with other two carbon atom.

Ex.14 C – C bond in C2H6 undergoes heterolytic fission, the hybridisation of carbon is/are -
(A) sp2 (B) sp3 (C) sp2, sp3 (D) sp, sp2
Sol. (C) During heterolytic fission there will be formation of CH3+ and CH3¯ which has sp2 and sp3 hybridization
respectively.

Ex.15 The enolic form of actone contain  bond (a),  bond (b) lone pair (c) -
(A) 9a, 1b, 2c (B) 8a, 2b, 2c (C) 10a, 1b, 1c (D) 9a, 2b, 1c
Sol. (A) This is clear from its structure as shown below.
H – H
| |
H — C — C =C — H
| |
H H

Ex.16 The hybridization and geometry of BrF3 molecule are -

(A) sp3d and distorted trigonal bipyramidal (B) sp3d2 and Tetragonal
(C) sp3d and bent (D) None
Sol. (A) There is one s, three p and one d orbital while hybridization

Glesspie and Nyhom theory or VSEPR theory :

(Valence shell electron pair repulsion theory)
(I) If the cenral atom possess only bonded pairs of electrons along with identical atoms then shape of
the compound is symmetrical and according to Sidgwick & Powl.
eg. BF3 – 120° – triangular
CH4 – 109°28’ – tetrahedral
CO2 – 180° – linear
(II) If the central atom possess bonded pair of electrons as well as lone pair of electron, then shape
of the molecule will be unsymmetrical ie. the original bond angle will disturbed due to repulsion
between lone pair of electrons.
similarly on having different type of side atoms, molecule becomes unsymmetrical due to unequal
force of repulsion between e–. Order of repulsion is –
1
.p, – .p > .p – b.p. > b.p. – b.p. Bond angle  No. of lone pair of electron

(III) By increasing one lone pair of electron, bond angle is decreased approx by 2.5°.
e.g. CH4 NH3 H2O – sp 3
109° 107° 105° hybridisation
(IV) In the different molecules if central atom have same number of lone pair of electron then bond
angle will depend on electronegativities of A & B.
 In ABx type of molecules if side atoms are same EN of central atom increases the bond angle
increases

O•• S ••

••

••
>
105° 92°
H H H H
more repulsion less repulsion bp-bp

Electronegativity of 'O' > Electronegativity of 'S'

Bond angle of – NH3 > PH3 > AsH3
In ABx type molecules, if central atoms are same and the EN of side atoms increases then
bond angle decreases.
O•• O••
••

••
110° 103°
Cl Cl H H

Electronegativity of Fluorine is greater than chlorine

PF3 < PCl3 < PBr3 < Pl3 (EN of side atom decrease)
OF2 < Cl2O < Br2O
SF2 < SCl2 < SBr2
Bond angle depends on size of side atom, On increasing size of atom bond angle increases.
Cl2O > H2O

•
•O •• •
•O
••

105° 110°
H H Cl Cl

Examples
based on VSEPR Theory

Ex.17 In following which central atom has different hybridisation than other –
(A) Cl2O (B) OF 2 (C) H2O (D) SO 2
Sol. 2 3
(D) Because it has sp hybridisation other three have sp hybridisation.

Ex.18 In following hydrocarbon which one has 75% p character and 25% s charater -
(A) C2H4 (B) C2H2 (C) CH4 (D) :CH2
Sol. 3
(C) CH4 because it has sp hybridisation.

Ex.19 Which of the following statement in incorrect -

(A) Non-bonding pairs occupy more space than bonding pairs
(B) The bonding orbitals in a trigonal bipyramidal molecule are described as sp3d hybrid
(C) SnCl2 has linear shape
(D) PCl4+ and AlCl4– are isoelectronic
Sol. (C) SnCl2 is a bent shape molecule due to presence of lonepair of electron other choices are correct.
Ex.20 Shape of NH3 is very similar to -
(A) CH4 (B) CH3¯ (C) BH3 (D) CH3+
Sol. (B) Both have the same state of hybridization with one lone pair of e¯ each.

Ex.21 Which of the following has pyramidal shape-

(A) XeO3 (B) XeF4 (C) XeF2 (D) XeF6
Sol. (A) Due to presence of lone pair of electron.

Ex.22 Ether and water have same hybridization at oxygen. What angle would you
expect for them -
Sol. In H2O bond angle is less than 109º28’ due to lone pair and bond pair repulsion. But in ether, due to
strong mutual repulsion between two alkyl groups bond angle becomes greater then 109º28’

Characteristic of Covalent Compound :

(I) Physical state :- Covalent compounds are found in all the three states - Gas, Solid & Liquid.
Separate molecules – In gaseous state
Associate molecules – In liquid & solid state
(Due to strong vander waal’s force and hydrogen bonding among the molecules.)
As the molecule weight increases physical state changes -
eg. F2 and Cl 2 Br2 l2, At 2
gas liquid solid

Top to bottom in a group. Vander waal’s force increases between the molecules.
(II) Covalent solid : - Those solids in which atoms are linked together by covalent bonds, forms
inifinite three dimensional giant structure.
e.g. Diamond, Graphite, AIN, SiC, SiO2 etc.
Molecular solid : - Discrete (separate) molecules are formed by covalent bonds and then the
molecules associated due to intermolecular force of attraction. (Vanderwaal force)
eg. Solid I2, dry ice (Solid CO2) etc.
(III) Conductivity : - Mostly covalent compounds are bad conductor of electricity. But few polar
covalent compounds due to self ionisation can conduct electricity.e.g. H2O, liq. NH3 etc.
H2O + H2O H3O+ + OH–
2NH3 NH4+ + NH2–
Free ions are formed which can conduct electricity.
Exceptions : - Graphite, HCl in water.
(IV) Solubility : - Non polar compound are soluble in non polar solvents. Non polar compounds forms
Vander waal bond with non polar solvent molecules.
(V) Isomerism : - Covalent bond is rigid and directional, so it shows isomerism.
eg. Organic compounds.
(VI) Reaction : - Reaction between covalent compounds are slow. Because it involves breaking of odl
bonds and formation of new bonds.
10. DIPOLE MOMENT

(Ionic Nature in Covalent Bond)

(I) Polarity of any polar covalent bond or moleucule is measured in terms of dipole moment.
(II) For measurement of extent of polarity, Pauling introduced the concept of dipole moment ().
The product of positive or negative charge (q) and the distance (d) between two poles is called dipole
moment.
Here -  = q × d (magnitude of charge × distance)
(III) Dipole moment is a vector quantity i.e. it has both magnitude as well as direction.
(IV) Direction of dipole moment is represented by an arrow pointing from electro +ve to electro -ve element
and from central atom to lone pair of electrons.
 

or central atom lone pair of electron

(V) Unit of dipole moment is Debye

1 Debye = 1 × 10–18 esu cm.
= 1.6 × 10–29 coulomb metre
(VI) In the diatomic molecule  depends upon difference of EN i.e.   EN
order of  : H–F > H–Cl > H–Br > H–I
 = 0 for H–H, F–F, Cl–Cl, Br–Br, O–O
(VII) For polyatomic molecules  depends on the vector sum of dipole moments of all the covalent bonds.
(VIII) For PCl5 and SF 6, etc.  = 0 due to their regular geometry.
(IX) Benzene, naphthalene, diphenyl have  = 0 due to planar structure.
(X) If the vector sum is zero, than compound is non-polar compound or symmetrical compound (and it is
not essential that individual  of every bond should be zero).
Example : (A) BX3, CCl4, SiCl 4, CH4, CO 2CS2, PCl5, SiH4 etc.
In these examples the bond B–F, C–Cl, C–H, C–O, P–Cl etc. are polar even though compounds are
non-polar.

•• •• ••
(B) NH3 PH3 NF3
3 H H F
P H
••

N 2H
••

4 N F
••

4 4
1 H H F
 =1.47D EN of P H
 =0.24D

Total  = 1 + 2 + 3 + 4 = 1.47D

(XI) Dipole moment of H2O is 1.85 D which is resultant  of two O–H bonds.

O

  
H H
of H2O of H2S because electronegativity of oxygen is higher than sulphur.
(XII) Angular structure of molecule have greater dipole moment.
Application of dipole moment :
(I) To determine polarity and geometry of molecule -
If  = 0 compound is non polar and symmetrical
eg. CO2, BF3, CCl4, CH4. BeF2 etc.
If 0 compound will be polar and unsymmetrical.
H2O, SO2, NH3, Cl 2O, CH3Cl, CHCl 3 etc.

(II) To calculate % ionic character :-

Experimental value of 
% Ionic character   100
Theoritical value of 

(III) To distinguish cis form or trans form:-

(a) Dipole moment of cis isomers is normally higher than trans isomers.
eg. –

Cl—C—H Cl—C—H

Cl—C—H H—C—Cl

 
cis-form Trans-form
Polar (  ) Non Polar (  )
(b) If two groups have opposite inductive effect than trans-isomer will have greater dipole moment \-
eg.
H Cl H Cl

C C
C C

CH3 H H CH3

1
(IV) To locate position of substituents in aromatic compounds.   Bond angle
(a) If same substituents are preset in the symmetrical position of benzene ring compounds will be
zero
Cl
Cl Cl
Cl

Cl Cl
         

Angle 180° Angle 120° Angle 60°
p-dichloro benzene m-dichloro benzene o-dichloro benzene

(b) As angle between subtituents decrease value of increase

Some important orders of diple moments-
HF > H2O > NH3 > NF 3 H2O > H2S
CH3Cl > CH3F > CH3Br > CH3I BF3 < NF3 < NH3
HF > H2O > SO 2 > NH3 PH3 < PCI 3
NO2– > NO2 > NO 2 H2O < H2O 2
Examples
based on Dipole Moment

Ex.23 Which of the following bonds is most polar -

(A) O – H (B) P – H (C) C – F (D) S – Cl
Sol. (C) Due to maximum electronegativity difference.

Ex.24 Bond length of HCl is 1.275 Å (Charge = 4.8 × 10–10 e.s.u.) if  = 1.02 D, then HCl is -
(A) 100% ionic (B) 83% covalent (C) 50% covalent (D) 40% ionic
Sol. (B) % ionic character
observed  102
.
= × 100 = × 100 = 17% ionic = 83% covalent
theoritical  1275
. x 4.8

Ex.25 The dipole moment of the ammonia molecule is 1.48D. The length of the dipole is -
(A) 3.08 × 10–11 m (B) 5 × 102 m (C) 308 m (D) None
Sol. (A) M = 1.48 × 3.33 × 10 –30 cm
= 4.93 × 10–30 cm.
q = 1.6 × 10–19C

 4.93  10 30
l = = = 3.08 × 10–111 m = 0.0308 nm
q 1.6  10 19
The NH3 molecule can not have the shape of an equilateral triangle because in the case its dipole
moment would equal zero. It is actually constructed in the form of a triangular pyramid with the
nitrogen atom at its vertex and the hydrogen atoms at the corners of its base.

11. COORDINATE BOND

(I) It is a covalent bond in which the shared e– pair come from one atom is called coordinate bond.
(II) Necessary conditions for the formation of co-ordinate bond are-
(a) Octet of donor atom should be complete and should have atleast one lone pair of electron.
(b) Acceptor atom should have a defficiency of at least one pair of electron.
××
•• ×
••
••

eg. X  Y × or X  Y

•• ××

(III) Atom which provide electron pair for shairing is called donor.
(IV) Other atom which accepts electron pair is called acceptor. That is why it is called donor-acceptor or
dative bond

H F

H N•• + B F NH3NH3

H F
BF3 is electron defficient compound.
Example:
H

 H3 N + H+  H N H

H
(Lowry - Bronsted acid)
(e– acceptor)
 H H
 + •• +
O+ H
H3O O H

••
   ••
H H
••
•• •• O
O O

••
O

••

••
O3 •• •
•O

••
O•
•• •

••
•••• ••
O

••

••
N2O N N
••
Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows-
NH4Cl, CuSO4, K4[Fe(CN)6], KNC, Na3PO 4, KNO3, etc

Examples
based on Coordinate Covalent Bond
Ex.26 The compound which contains both covalent and co-ordinate bond is -
(A) C2H5NC (B) C2H5CN (C) HCN (D) None
Sol. (A) Though all compounds have covalent bond but there is coordination bond also between N and C
in C2H5 NC

Ex.27 The type of bond present in N2O5 are -

(A) Only covalent (B) Only ionic (C) Ionic and covalent (D) Covalent and coordinate
Sol. (D) The structure of N2O5 clears about it
O  N — O — N  O
|| ||
O O

Ex.28 No. of covalent and co-ordinate bond in pyrosulphuric acid are -

(A) 6, 4 (B) 6, 6 (C) 4, 4 (D) 4, 6
Sol. (A) Structure of H2S2O7 is as follows

O O
 
H—O— S —O— S —OH
 
O O

Ex.29 Which is not true according to VBT -

(A) A covalent bond is formed by the overlapping of orbitals with unpaired electrons of opposite spins
(B) A covalent bond is formed by the over lapping of orbitals with unpaired electrons of same spin
(C) The greater the extent of overlapping the stronger is the bond
(D) Overlapping takes place only in the direction of maximum electron density of the orbital
Sol. (B) Electrons of same spin never combine to form a bond. Other facts are true for VBT.

Ex.30 Why covalent bonds are always directional -

Sol. As the covalent bonds are formed due to overlapping of orbitals which are directional

Ex.31 Allyl cyanide has -

(A) 9 sigma bonds and 4 Pi bonds (B) 9 sigma bonds, 3 pi bonds and 1 lonepairs
(C) 8 sigma bonds and 5 pi bonds (D) 8 sigma bonds, 3 pi bonds an 4 non-bonding electrons
Sol. (B) This is clear from structure of allylcyanide

H H H
| | |
H— C = C — C —CN:
|
H

12. HYDROGEN BOND

Definintion :
(I) It is an electrostatic attractive force between covalently bonded hydrogen atom of one molecule and
an electonegative atom (F, O, N)
(II) It is not formed in ionic compounds
(III) H–bond forms in polar covalent compouds, (not in non-polar)
(IV) It is also known as dipole-dipole attraction
H — F– .... H+ — F –...... H+ — F–

Main condition for H-bonding : -

(I) H— should be covalently bonded with high electro–ve element like F, O, N
(II) Atomic size of electro–ve element should be small.
Decreasing order of atomic size is–
N > O > F
Decreasing order of atomic size is–
F > O > N
(4.0) (3.5) (3.0)
1
(III) Strength of H–bond  Electronegativity of Z (element)  atomic size of Z
(IV) Hydrogen bonding occurs in HCN, due to (–C N) triple bond (sp hybridisation), electronegativities of
carbon and nitrogen increases.
H — C  N .........H — C  N ..........H — C  N
Types of Hydrogen Bonding

Inter Molecular Intra Molecular

Homo Inter Molecular Hetero Inter Molecular

(A) Intermolecular H–bond

H–bond formation berween two or more molecules of eithe the same or different compounds known as
Inter molecular H–bonding
These are two types.
(i) Homointermolecular :- H–bond between molecules of same compounds.
eg.
H H H H F

O O O H H H H

H H H H F F
 (ii) Hentro intermolecular :- H–bond between molecules of different compounds.
eg. alcohol, water
O — H O — H O — H O — H 

R H R H

alcohol Water alcohol alcohol

(B) Intra molecula H–bond :- It takes place within the molecule.

(i) H–bonded with electronegative elements of a functional group, form H–bond with another
electronegative element present on nearest position on the same molecule.
(ii) This type of H–bond is mostly occured in organic compounds.
(iii) It result in ring formation (Chelation).
eg.
H
O H O O
H
C O C
O O O
H
N H
H
O O F O
O–nitrophenol Salicylaldehyde O–fluorophenol 2-6 dihydroxyl benzoate

Effect of H–bond on physical properties :

(I) Solubility
(A) Inter molecular H–bonding
(a) Few organic compounds (Non-polar) are soluble in water (Polar solvent) due to H–bonding
O — H O — H 

R H
Other examples–Glucose, Fructose etc, dissolve in water.
(b) Ketone, ether, alkane etc. are insoluble (no H–bond). Dimethyl ether is soluble in water while
diethyl ether is partially soluble, due to bulky ethyl groups H–bonding interupts
(c) Solubility order– CH3OCH3 < CH3OH
Primary amine > secondary amine > tertiary amine

(B) Intra molecular H–bonding: H O

C H
(a) It decreases solubility as it form chelate by H–bonding, so H–is
O
not free for other molecule.
(b) It can not form H–bond with water molecule so can not dissolves.
 (C) Inter molecular H–bond
O — HO C—H O — H 

C C
H O O — H O H
p–hydroxy benzaldehyde
It can form H–bond with water molecule so it can dissolvel

(II) Viscosity:
H – bond associates molecules together so viscosity increases

CH2 — OH
CH2 — OH
CH3OH < < CH — OH
CH3 — OH
CH2 — OH

H2O > CH3 — OH > CH3 — O — CH3

water alcohol ether

(III) Melting point and boilling point

(a) Due to intermolecular H–bond M.P. & B.P. of compounds increases.
H2O > CH3OH > CH3 — O—CH3
(b) Trihydric alcohol > dihydric alcohol > monohydic alcohol
Monocarboxylic acid form stronger H–bond than alcohol of comparable molecular weight. Therefore
B.P. of carboxylich acid is higher than alcohol.
(c) Decreasing order of M.P. & B.P. isomer amines-
1°–amine > 2°–amine > 3°–amine

R
|
R — NH2 > R — NH — R > R — N — R (no hydrogen with nitrogen atom)
(d) Boiling points of VA, VIA, VIIA hydrides decreases on decreasing molecular weights.
VA VIA VIIA
NH3 H2O HF b.p. HF > HI > HBr > HCl
PH3 H2S HCl H2O > TeH2 > SeH2 > H2S
AsH3 SeH2 HBr NH3 > SbH3 > AsH3 > PH3
SbH3 TeH2 HI
(e) But sudden increase in boiling point of NH3, H2O and HF is due to H–bonding
H2O > HF > NH3 PH3 < H2S < HCl
Intramolecular H–bonding gives rise to ring formation, so the force of attraction among these molecules
are vander waal force. So M.P. and B.P are low.
 (IV) Molecular weight :
Molecular wt. CH3COOH is double of its molecular formula, due to dimer formation occur by H–bonding
O  H — O
R—C C—R
O — H  O
(V) Physical state:
H2O is liquid while H2S is gas.
Water and Ice:- Both have H–bonding even then density of ice is less than water.
Volume of ice is more because of open cage like crystal structure, from by association of water
molecules with the help of H–bond.
H2O becomes solid due to four hydrogen bond among water molecule are formed in tetrahedral manner.
H H H H
3
1
O 2 O O O
4
H H H H
(VI) Base strength
CH3NH2, (CH3)2 NH, (CH3)3 N form H–bond with water. So less hydrolysis i.e. it gives OH– ions.
–
While (CH3)4 N+ OH (ammonium compound) will give OH– ion in large amount due to no H–bonding.
H H
+ –
CH3 — N H — O CH3 — N —H + OH

H H H

+
CH3
(Ammonium compound.)
CH3 N CH3 NO H–atom bonded directly with N–atom
so no hydrogen bonding occurs.
CH3

Effect of intramolecular H–bonding

(I) Strength of acid
(a) The formation of intramolecular H–bonding in the conjugate base of an acid gives extra stability to
conjugate base and hence acid strength increases eg. Salicylic acid is stronger than benzoic acid
and 2, 6 – dihydroxy benzoic acid > salicylic acid.
H –
O O O O
C H C H
+
O O+H

Conjugate base

–1/2
O O –1/2
H C H
O O
+ H+

2, 6 dihydroxy benzoate ion

 (b) C2H2SH is more acidic than C2H5OH. In C2H5OH, H–bond forms so H+ is not free
(c) HF is weaker acid than HI, due to H–bond in H – F, H+ is not free

(II) Stability of chloral hydrate:-

If two or more OH group on the same atom are present it will be unstable, but chloral hydrate is stable
(due to H–bonding).

Cl  H
O
Cl C C H Chloral hydrate
O
Cl  H
(III) Maleic acid (cis) is stronger acid than fumaric acid (trans).
O O

H C H C
–
C OH C O +
H + H
C OH C OH
Stable conjugate base of maleic acid
H C H C

O O
H COOH
C

C
HOOC H
Fumaric acid (No-intramolecular H-bonding)

Examples
based on Hydrogen Bond

Ex.32 Which one of the following does not have intermolecular H-bonding -
(A) H2O (B) o-Nitrophenol (C) HF (D) CH3
Sol. Nitrophenol has intermolecular H bonding as shown below

Hence (2)

Ex.33 Arrange in incresing order of their boiling point-

HF, HCl, HBr, H
Which order is correct –
(A)HCl < HBr < H < HF (B)HCl > HBr > H > HF
(C)HCl < HBr > H < HF (D) None
Sol. (A) HCl < HBr < H < HF
due to strong hydrogen bonding in HF
13. VANDER WAAL’S FORCES

(a) This type of attractive forces occurs in case of non polar molecules such as H2, O2, Cl 2, CH4, CO 2
etc.
(b) The existence of weak attractive forces among the nonpolar molecule was first proposed by dutch
scientist J.D. Vander Waal
(c) Vander waal force  molecular weight
 Atomic weight
 Boiling point

Types of Vander Waal’s force : -

(i) Ion dipole attraction - This force is between an ion such as Na+ and a polar molecule such as HCl

+ – +
+
Na HCl

(ii) Dipole Dipole attraction - It is again in between two polar molecules such as HF and HCl

HF HCl(g)
(iii) Ion induced dipole attraction - In this case a neutral molecule is induced by an ion as a dipole as
shown in fig

+  + +

Na+ Cl 2
Before induction after induction
(iv) Dipole - Induced dipole attraction : In this case a neutral molecule is induced as a dipole by
another dipole as shown in fig.

 + +

e.g. HCl Cl 2

(v) Induced dipole - induced dipole attraction or London dispersion force between two non polar molecules
as in Cl2, He etc.

+
+

Cl2 Cl 2
Note: The relative strength of various bonds is as follows
Ionic bond > Covalent bond > Metallic bond > H-bond > Vander waal bond
POINTS TO REMEMBER
(a) Bond energy of a diatomic molecule is enthalpy change to dissociate one mole of the diatomic
gaseous molecule to form the respective gaseous atoms.
(b) Strong metallic bonding is favoured by smaller size of kernel.
(c) Band theory is related with metallic nature
(d) The resonance structure do not have independent existence.
(e) The hydration of ionic compounds involves evolution of heat, weakening of attractive forces and
dissociation into ions
(f) The maximum covalency is equal to the actual number of s-and p-electrons in the outermost shell
(g) Many ionic crystals dissolve in water because water decreases the interionic attraction in the crystal
lattice due to solvation.
(h) Hydrogen bond stabilizes the secondary structure of proteins.
(i) Isoelectronic molecular species have similar molecular orbitals and similar structure according to iso
electric principle
(j) The amount of energy required to break one mole of the bond and separate the bonded atoms in the
gaseous state is known as bond dissociation energy
(k) The average angle between the bonded orbitals is known as bond angle .
(l) Bond length may be defined as the average distance between the centres of nuclei of two bond atoms.
(m) Polymorphism (Allotropy) is a term used when one and the same substance can crystallise in more
than one forms.
(n) In SO2 there is p - p bonding as well as p - d bonding due to overlap of filled p orbitals of oxygen
with the vacant 3d orbitals of sulphur.
(o) H2SO 3 exists in two forms which are always in equilibrium with one another

(Symmetrical sulphurous acid)

(Unsymmetrical sulphurous acid)

The unsymmetrical form containing S – H bond explains the reducing character of H2SO 3.
(p) The anion of H2SO 3 i.e. SO 32– has a pyramidal structure with S atom in sp3 hybridization and all the
S – O bonds are of equal bond length (134 pm)
(q) In the gas phase, SO3 is a planar triangular molecule with sulphur atom in sp2 hybridization state
 In order to account for the equivalency of all the S – O bonds and short S – O distance of 143 pm,
SO3 may be considered as a resonanchybrid involving p-p S – O bonding along with additional p-
p bonding.
(r) In the solid phase, SO3 polymerizes to puckered rings or the more stable layer structure as shown.

O O O O

S S S S
O O
O O O
O O
O O O
S

O O O O O O

Ring Structure Layer Structure

Molecular Orbital theory (MOT):

MOT put forward by Hund & Mulliken, which can be applied to explain the properties, which the old
VBT (Valence bond theory) was unable to explain eg. Paramagniic nature Of O2 molecule, as per VBT
(:O: :O :) it should be diamagnetic.
Definition:
The atomic orbital lose their identity during molecule formation (overlapping) and form new orbitals
termed as molecular orbitals.

Characteristic of molecular orbitals:

(I) Molecular orbital formed by overlapping of atomic orbital of same energy
(II) Number of melecular orbital formed = number of atomic orbital involved in overlapping
(III) Half of the molecular orbital have lower energy are called Bonding molecular orbital.
(IV) Half are of higher energy - termed as Antibonding molecular orbital
(V) Electronic configuration in various molecular orbital are governed by same three rules.
(a) Aufbau’s rule (b) Hund’s rule (c) Pauli’s exclusion principle

Comparision of Bonding molecular orbital & Antibonding molecular orbital :

Bonding molecular orbital (BMO) Antibonding Molecular orbital (ABMO)

Bonding MOis the result fo the linear ABMO is result of linear combination of AO
combination of AO when their wave when their wave function are substracted
function are added b = A + B b = A + B
It does not have node. It always have a node between two nuclei of
bonded atom.
Charge density increase between two Charge density decrease in between two nuclei,
nuclei resulting attraction between two leads to repulsion between two atoms.
atoms
Energy of BMO is less, hense stable Energy of ABMO is high, hence unstable
 Notation of molecular orbitals:
As atomic orbitals are known by letters s, p, d and f depending on their shapes. Similarly for molecular
orbital.

For bonding molecular orbital-  etc.

For antibonding molecular orbital- etc.
are used for different shapes of electron cloud.

Energy Level Diagram of molecular orbital :

On the basis of Aufbau’s rule - increasing order of energies of various molecular orbitals is-
 1s <  1s <  2s <  2s <  2pz <  2px  2py <  2px   2py <  2pz
Energy level diagram for homonuclear diatomic molecules like, O 2, F2, Ne2

For O2 molecule-

'2pz

1
Bond order =2 (8 – 4) = 2
’ ’
2px 2py Bond order O2 = 1/2 [8 – 4] = 2
2p 2p O2+ = 1/2 [8 – 4] = 2.5
 
Having two unpaired
'2px '2py O–2 = 1/2 [8 – 5] = 1.5
electrons so paramagnetic
 O2–
2 = 1/2 [8 – 5] = 1.5

2pz O+2
2 = 3
Increasing energy

 Stability order –
+2 +
'2s O2 >O2 > O2> O2– > O22–
Bond length –
2– –
O2 >O2 > O2> O+2 > O+2
2

2s 2s

2s


'1s

1s 1s

s

Energy level diagram for B2, C2 and N2 molecules –

 1s <  1s <  2s <  2s < 2px  2py <  2pz <  2px    2py <  2pz
For N2 molecule
 '2pz

’ ’
2px 2py
2p 2p

'2pz

Increasing energy in N2 molecule

 
'2px 2py

'2s

2s 2s

2s


'1s


1s 1s

s

Cause of exceptional behavior of molecular orbital in B2, C2 and N2:

 Energy of 2s and 2p atomic orbitals lie fairly close
 Due to small energy difference between 2s and 2pz orbitals, the interaction between them is quite large.
 This results in loss of energy by  2s and 2s and thus  2s and  2s becomes more stable at
the cost of  2px and 2px which gets unstablised (Higher energy).

Electronic configuration of molecules and their related properties :-

for writing electronic configuration of diatomic molecules following two rules to be followed-
 Count the number of electrons present in two atoms and then fill in the appropiate energy level diagram
according to Aufbau rule.
 The pairing in 2px and 2py or 2px and  2py will take place only when each molecular orbital
of indenticle energy has one electron.
 After writing the molecular orbital diagram following parameter about molecules/ion may be predicted.
(i) Bond order :-
Bond order = ½ [No. of electron in bonding molecular orbital ie. Nb
– No. of electron in antibonding molecular orbital ie. Na] = ½[Nb–Na]
B.O. = ½ [Nb–Na]

1
(ii) Bond length :- (distance between two nuclei) Bond length 
Bond order
If Nb  Na Molecule exists

Nb  Na 
 Molecule do not exists
Nb  Na 
 (iii) Stability of molecules - stability  Bond order of molecule
(iv) Dissociation energy - Bond disssociation energy Bond order
(v) Magnetic property -
(a) When electron in MO are paired – diamagnetic
(b) When electron in MO are unpaired – paramagnetic

Bonding in molecules :-
(I) Hydrogen molecule-
Having two H atoms with one electron each (1s’)



 2s

1s' 1s'
(Atomic orbital)  H2 (Atomic orbital)
1s
Molecular orbital

M.O. configuration of H2 = (1s)2 ( 1s)0

Bond order = ½ [Nb – Na]
= ½ [2 – 0] = 1 i.e. single bond
Having paired electron so diamagnetic.
Stability quite stable (having single bond)
(II) H2+ ion –
Configuration of H2+ = (is) 1 (is)0 

One electron in bonding molecular orbital.  1s
So paramagnetic 1s 1s
Bond order = ½ [1– 0] = ½  
+
1s H2
Less stable

(III) H2– anion -

M.O. configuration - (1s)2 (1s)1

Paramagnetic 
 1s
Bond order = ½ [2 – 1] = ½
Stability is less than [H2+] because H2– 1s 1s
 
Contain ab ABMO electron 1s H2
–

(IV) Helium molecule (He2) :

 M.O. configuration (1s)2 (1s)2

 Diamagnetic 
 Bond order = ½ [2 – 2] = 0 (zero)

 1s
 Bond order zero indicates no linkage
1s 1s
between He atoms. Hence He2 molecule does not exist  
 Stability (He2) Highly unstable molecule He2 1s
Examples
based on M.O.T.
Ex.34 The bond order of N2¯ anion is -
(A) 1 (B) 2 (C) 2.5 (D) 3
Sol. (C) Out of 15 e¯ in N2¯, 10 are in bonding MO’s and 5e¯ are in the anti bonding MO’s Hence bond order
1
= (10 - 5) = 2.5
2

Ex.35 Which of the following has maximum bond strength –

(A) O2 (B) O2+ (C) O2¯ (D) O22–
Sol. (B) Bond order of O2+ is 2.5 which is maximum among all the species hence its bond strength will
also be the maximum.

Ex.36 Which of the molecules B2 and C2 has a higher energy of dissociation into atoms? compare the
magnetic properties of these molecules.
Sol. We draw energy level diagrams showing the formation of B2 and C2 molecules
AO’s MO’s AO’s
B B2 B
AO’s MO’s AO’s
C C2 C

Energy level diagrams showing the formation of B2 and C2 molecules.

The difference between the number of bonding and the number of antibonding electrons in the B2
molecule can be seen to be two, and in the C2 molecule, four. This corresponds to a bond multiplicity
of 1 and 2, respectively. Consequently, the C2 molecule having a higher multiplicity of the bond between
the atoms must be more stable. This conchosion corresponds to the experimentally established values
of the energy of dissociation into atoms of the molecules B2 (276 KJ/mol) and C2(605 KJ/mol)
In the B2 molecule, two electrons are arranged, according to Hund’s rule, in two px 2py orbitals. The
presence of two unpaired electrons imparts paramagnetic properties to this molecule. In the C2 molecule,
all the electrons are paired, consequently, this molecule is diamagnatic

14. BOND PARAMETERS

(I) Bond Lengthe (Bond distance) (II) Bond Angle (III) Bond Energy
(I) Bond Lenght :- The average distance between the nucleus of two atoms is known as bond lenght,
normally it is represented in Å. eg. A  B

 It depends mainly on electronegativilties of constituent atoms

Case - I Electronegativity difference is zero then-
Bond length = rA + rB
Or dA –B = rA + rB
 whereA is covalent radius of A
rB is covalent radius of A
XA is electronegativity of A
XB is electronegativity of B
If rA = rB then Bond length = 2rA or 2rB
Case II Electronegative difference is not equal to zero then-
Bond length is given by shomaker & Stevenson formula is Bond length = rA + rB – 0.09 (XA – XB )
Difference in electronegativities

Factors affecting Bond Length :-

1
(a)  electronegativity :- Bond lengh   ( While B.E. EN)
EN
H–F < H–Cl < H–Br < H–I
1
(b) bond order or number of bonds :- Bond length 
Number of bond or bond order
Bond energy Number of bond
e.g. C–C, C = C, C  C
Bond length 1.54 Å 1.34 Å 1.20 Å increa sin g
  
Bond energy 80 140 180–200K.Cal. increa sin g
  
C—0 C O C O
1.43 Å 120 Å 1.13Å

C N C N C N
1.47 Å 1.28 Å 1.15 Å

(c) Resonace :- (due to resonance bond length affected)

eg.1. Benzene
C—C bond length 1.54Å but bond length is between
C—C bond length 1.34 Å single & double bond is = 1.39 Å

eg. 2.Bond length of C—O in CO2 is 1.15 Å Resonance occurs in CO2 a follows-
O C O  O– — C O+ O+ C — O–
Bond length = 1.15 Å (Between double & triple bond)
1
(d) Hybridisation : - Bond length  s character

Ethane sp3 sp3 1.54 Å

S-character increases

sp3 2
sp 1.51 Å

sp3 sp 1.47 Å
2 2
sp sp 1.46 Å
2
sp sp 1.42 Å
sp sp 1.37 Å
(II) Bond Angle :- The angle between any two adjacent bond is known as bond angle. It is represented
in degree (°), min (‘) and second (‘’)
Factors affecting the bond angle-
(a) Number of bond : Bond angle  Number of bonds (Bond order)
109° 120° 180°

C C C C C C

(b) Hybridisation :-
Case 1
When hybridisation is same, bonded atoms are same, central atom and lone pair are different.
1
Then bond angle 
No. of lone pair
•• ••
Example :- CH4 N H3 H 2O
••

Hybridisation sp 3 sp 3 sp 3
Bond angle 109 > 107 > 105
No 1.p. one 1.p. two 1.p.
Case-II
When hybridisation is same, bonded atoms are same lone pair is same but central atom is different.
Then bond angle  electrongativity of central atom
•• •• ••
Example:- NH3 P H3 As H3
Bond angle 107° 93° 91°

– Eletronegativity decreasing
– Bond angle will decrease
Case-III
When hybridisation is same, lone pair are same, Central atom is same, bonded atoms are different.
sp 3 OF2 103 – 105° Electronegativity
sp 3 Cl2O 109 – 111° of bonded atom is
sp 3 Br2O 116 – 118° decreasing
1
Here bond angle   size of side atom
electrongativity of bonded atom
(III) Bond Energy (BE) :- Bond energy may be difined as-
(a) Bond formation energy:- Energy released when any bond is formed is known as bond formation
energy or bond energy.
(b) Bond dissociation energy :- Energy required to dissociate any bond is known as bond dissociation
energy.
Calculation of released energy is more diffcult than the dissociation energy therefore dissociation
energy of bond is calculated and is assumed as bond energy or bond formation energy.
Case-I In diatomic molecule :
Bond energy = bond dissociation energy
eg :- N2 > O 2 > H2 > F 2
Case-II For polyatomic molecule :-
Bond energy  Bond dissociation energy (D)
H
|
eg;- H  C  H Bond energy = per CH bond is 99.5 K. Cal/mole
|
H
 Theoritical values of bond dissociation energy (D) of individual CH bonds CH4 are given below-
D (CH3H) = 102 K Cal/mole
D (CH2H) = 105 K Cal/mole
D (CHH) = 108 K Cal/mole
D (CH) = 83 K Cal/mole
398
Hence bond energy E per CH bond in methane  = 99.5 K Cal/mole.
4

 Bond dissociation energy (D) is related to the state of hybirdisation.

Factors affecting the bond energy : -
(a)  Electronegativity (b) Bond order (c) Atomic size (d) Bond polarity
(e) Resonance (f) Hybridisation (g) Lone pair electron
(a)  Electronegativity :- Bond energy EN
eg. HF > HCl > HBr > HI

(b) Bond order :- Bond energy  Bond order

eg. CC < C = C < C  C
79 K. Cal, 143.3 K. Cal., 199.0 K. Cal.
1
(c) Atomic size :- Bond energy  Atomic size
eg. CC < CN < NN
Exception :- In case of halogen group, order of bond energy is-
Cl  Cl > Br  Br > F  F > I  I
Because of higher electron densityb and small size of F atoms, repulsion between of two F atom,
weakens the bond energy.
Other ex. S – S > O – O C – C > Si – Si > Ge – Ge
(d) Bond Polarity :- Bond energy  polarity
eg. HF > HCl > HBr > HI

(e) Resonance :- Bond energy increases due to resonance

eg. In benzene bond energy of CC increases due to  electrons of C = C.

(f) Hybridisation :- Bond energy  s-character in hybrid orbitals.

eg. spsp > sp2sp2 > sp3sp3
s. character- 50% 33.3% 25%
1
(g) Lone pair of electrons :- Bond energy  lone pair of electrons

×× ×× ×× ×× ×× ××
×
C C > N N > O O > ×F ×F×××
×× ×× ××

Size of F and O atoms small so their bond energy should be high (small atomic radius) but it is actually
less due to lone pair of electrons present on F and O atoms, which repells each other in FF and
OO type of bonds.

15. RESONANCE

(I) The concept of resonance was introduced by heisen berg (1920) , and later developed by pauling and
ingold, to explain the properties of certain molecules,
 (II) It has been found that the observed properties of certain compounds cannot be satisfactorily explained
by writing a single lewis structure. 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
molecules. The actual structure is in between of all these contributing structures and is called resonane
hybrid and the different individual structures are called resonating structures or canonical forms. This
phenomeni is called resonance.

(III) Let us discuss resonance in ozone, according to its resonance structure it should have one single bond
(OO = 1.48Å) but experiments show that both the bonds are same which can be proved by its
resonance hybrid as shown below.
O O O
O O O O O O
Resonance hybrid
To calculate bond order in the polyatomic molecule or ion use following formula :

Bond order = Total number of bonds in a molecule

Re sonating Structures
eg.
O¯ 4
O C CO Bond order   1.33
O¯ 3

O¯
O P O¯ 5
PO Bond order   1.25
4
O¯

O
O P O¯ 7
ClO Bond order   1.75
4
O¯

16. METALLIC BOND

(a) The constituent particles of metallic solids are metal atoms which are held together by metallic
bond.
(b) In order to explain the nature of metallic bond Lorentz proposed a simple theory known as electron
gas model or electron sea model.
(c) A metal atom is supposed to consist of two parts, valence electrons and the remaining part (the
nucleus and the inner shells) called kernel.
(d) The kernels of metal atoms occupy the lattice sites while the space between the kernel is occupied
by valence electrons.
(e) Due to small ionisation energy the valence electrons of metal atoms are not held by the nucleus
firmly. Therefore, the electrons leave the field of influence of one kernel and come under the
influence of another kernel. Thus the electrons are not localised but are mobile.
(f) The simultaneous attraction between the kernels and the mobile electrons which hold the kernel
together is known as metallic bond.
11.1 Properties of metals and their explanation by electron sea model :
1. Metallic lusture :
(a) It is due to presence of delocalised mobile electrons
(b) These loosely bond electrons vibrate due to energy photon of incident light and radiates energy
immediately
2. Electrical conductivity :
(a) It is due to mobile electrons.
(b) These electrons flow equaly in all direction.
(c) While applying a potential difference across a metal, there will be a directed flow of electrons
towards the positive electrode.
(d) The directed flow of electrons carries the electric current from one point to another and therefore,
the metals are known to be good conductors.

3. Thermal conductivity :
(a) It can also be explained on the basis of electron gas model.
(b) While heating a metal kinetic energy of electron increases and propagates through collisons.

4. Malleability and ductility :

(a) This property is due to non directional nature of metallic bond.
(b) Basically the kernels can slip over each other when a deforming force is applied.

5. High tensile strength :

It is due to positively charged kernels and the mobile valence electrons.
 SOLVED EXEMPLES
Q.1 (SiH3)3N is a weaker base than (CH3)3N. Q.5 Using VSEPR theory, draw the shape of PCl5
Sol. Lone pair of electrons on nitrogen in (SiH3)3N and BrF5.
are used up in p-d back bonding while in
(CH3)3N such a p-dbonding is not possible
due to absence of vacant d-orbitals in carbon.
therefore (CH 3 ) 3N is more basic than
(SiH3)3N . Sol.

Q.2 The dipole moment of NH3 is more than that

of NF3
Q.6 Indicate the type of hybridization of each
Sol. The dipole moment of NH3 acts in the
carbon atom in the following compounds
directions H  N and thus moment due to
(A) CH3CN (B) CH3CH = CH2
unshared pair of electron will naturally
increase the moment of the NH3 molecule (C) H3C–CC–CH3 (D) HCC–CH=CH2
while in the case of NF3,the dipole moment Sol. (A) sp3 and sp (B) sp3, sp2, sp2
acts in the direction N  F and thus (C) sp3, sp, sp, sp3 (D) sp, sp, sp2, sp2
unshared electron pair will partially
neutralizwe the dipole moment, causin ga Q.7 Among the following compounds/species
write the order O–O bond length in O 2,
lower moment of NF3 relative of NH3
O2[AsF 4], K[O 2]
Sol. O2
2 Total 2 Total O2 [AsF4] or O 2 [AsF 4]¯
•• ••
I N I I N I K[O2] or K+ O 2
I I
H H F F The bond length decreases with increasing
H F bond order
 
Species O2
Q.3 o-Hydroxy benzaldehyde is a liquid at room O2 O2
Bond order 2.0 2.5 1.5
temperature while p-hydroxy benzalehye is a
 
high melting solid Bond length < O2 <
O2 O2
Sol. o-Hydroxy benzaldehyde show intramolecular Q.8 Two elements X and Y have following
H-bonding or chelation, which are weaker electronic configuration-
than intermolecular H-bonding in p-hydroxy X 1s2, 2s2, 2p6 ; 3s2, 3p6 ; 4s2
benzaldehyde. Y 1s2, 2s2, 2p6 ; 3s2, 3p5
The expected compound f ormed by
O–H combination of X and Y will be expressed as-
O–H O– CHO (A) XY2 (B) X5Y2 (C) X2Y5 (D) XY5
C=O |
| Sol.(A) Valency of element X is 2(2 electrons in the
H OHC H outermost shell) while that of element Y is
1(1 electron required in the outermost shell
Q.4 The central carbon-carbon bond in 1,3- to complete octet) So the formula of the
compound between X and Y is XY2-
butadiene is shorter than of n-butane
2 1
Sol. Buta 1-3-diene, i.e., CH2 = CH–CH=CH2 has X Y
sp 2–sp 2 (C–C) bond length more is s-
character in hybridisation lesser is bond
X Y2
length.
Q.9 An atom of element A has three electrons in Sol.(A) NaCl is an ionic compound solubility of an
its outer shell and B has six electrons in its ionic compound depends on the value of
outermost shell. The formula of the compound dielectruic constant of the solvent. Higher the
formed between these will be- value of dielectric constant of the solvent more
(A) A6B6 (B) A2B3 (C) A3B2 (D) A2B is the solubitlity of the lonic compound.
Sol.(B) In this case the valence electron in the atom
Solvent H2O C2H5OH CH3COCH3 C2H5OC2H5
A is three and hence its valency is generally
3. In the atom B the number of valence Dielectric
electron is six. Hence its valency is usually constant 80 27 21 4.1
2. Hence the formula of the molecule formed
from A and B could be A2B3. An example of Q.14 Which has maximum covalent character ?
two such elements are Al and O and the (A) NaCl (B) SiCl 4
formula of Aluminium oxide is Al 2O3.
(C) AlCl3 (D) MgCl2
Q.10 The electronegativity of H and Cl are 2.1 and Sol.(B) Polarisation in the molecule increases with
3.0 respectively. The correct statement (s) increase of charge and decreases in size of
about the nature of HCl is/are the cation when the anion is same.
(A) HCl is 17% ionic (B) 83% ionic
(C) 50% ionic (D) 100% ionic Q.15 The dipole moment of HBr is 2.6 × 10–30 cm
Sol.(A) % ionic character = 16(XA–XB)+ 3.5 (XA– XB)2 and the interatomic spacing is 1.41 Å. The
=16(3.0–2.1)+3.5(3.0–2.1)2 percentage of ionic character in HBr is-
= 14.4 + 2.83 (A) 10.5 (B) 11.5
= 17.235  17% (C) 12.5 (D) 13.5
Q.11 The electronegativity of O.F.N. Cl and H are Sol.(B) % ionic character =
3.5, 4.0, 3.0 and 2.1 respectively. The
Observed dipole moment
strongest bond will be :  100 Theoretical
Theoretical dipole moment
(A) F – O (B) O – Cl
(C) N – H (D) O – H dipole moment of a 100% ioinic character
Sol.(D) Bond strength  difference in = e×d = (1.6×10–19C)×(1.41×10–10m)
electronegativity of atoms = 2.256 × 10–29 cm
Q.12 The ratio of  to  bonds in mesitylene is
Q.16 Which of the following hydrocarbons has the
(A) 3 (B) 7 (C) 5 (D) 6
lowest dipole moment

H (A) CH3 C=C

H (B) CH C  CH
3 3
| H CH3
H–C–H
H (C) CH3CH2C  C (C) CH2 = CH–C  CH
H
| | Sol.(B) Symmetrical with linear structure will have
Sol.(B) C
C zero dipole moment
H | | H
H H
Q.17 CO2 is isostructural with
Total number of -bonds = 21 (A) HgCl2 (B) SnCl 2
Total number of -bonds = 3 (C) C2H2 (D) NO 2
Sol.(A,C) The structure of CO2 is linear O=C=O,
Q.13 In which solvent NaCl has maximum solubility
similarly the structures of HgCl2 (Cl–Hg–Cl)
(A) H2O (B) C2H5OH
and C2H2 (HCC–H) are linear. SnCl2 and
(C) CH3COCH3 (D) C2H5OC2H5
NO2 have angular structures.
Q.18 Identify the correct sequence of increasing Q.21 Where dative bond is not involved :
number of -bonds in the structures of the (A) Protonationof ether
following molecules : (B) dissolution of HCl in water
(I) H2S2O 6 (II) H2SO 3 (III) H2S2O 5 (C) Dimerisation of benzoic acid
(A) I, II, III (B) II, III, I (D) Formation of Be2Cl 4
(C) II, I, III (D) I, III, II Sol.(C) Dimerasation of benzoic acid involves
intermolecular H-bonding.
OO
|| || O H O
Sol.(B) H2S2O 6 HO–S–S–OH 4-bonds C–C6H5
|| || C6H5–C
O O O H O

O Q.22 The atomic number of Sn is 50. The shape

|| of gaseous SnCl2 molecule is :
H2SO 3 HO–S 1-bonds
| ••
OH ••
Sn
(A) Cl–Sn–Cl (B)
OO Cl Cl
|| ||
H2S2O 5 HO–S–S–OH 3-bonds
|| Cl ••
O ••
Sn Sn

••
(C) (D)
• • Cl
Q.19 Enol form of acetone contains the following: Cl Cl
(A) 9–bond, I -bond and two lone pair of
5s 5p
electrons
Sol.(D) Sn[Z = 50], [Kr]
(B) 8–bond, 2 -bond and two lone pair of
electrons
(C) 10–bond, I -bond and one lone pair of sp2 – hybridisation :
electrons
(D) 9–bond, 2 -bond and one lone pair of Q.23 In which case hydrogen bond will not be
electrons observed
Sol.(A) Enol form of acetone is
(A) H3O2 (B) H2O
CH2=C–CH3 [9  and 1  bond and 2p]
| (C) H5O2 (D) H3O +
••

OH
••
Sol.(D) H 3O 2 species H bonding in H2O
Q.20 The decreasing order of solubility of silver
halide is 
H H
(A) Agl > AgBr > AgCl > AgF
(A) O H O H (B) O H O H
(B) AgF > AgCl > AgBr > Agl
H
(C) AgCl > AgF > AgBr > Agl
(D) AgBr > AgF > Agl > AgCl
H5 O2 (H-bonding) H3O +(no H-bonding)
Sol.(B) Agl has maximum covalent character [  I¯
is a large anion], while AgF has minimum + +
H H H
covalent character, Therefore, it has more (C) O H O (D) O H
H H H
solubility