Cambridge Court World School,Jaipur

Class-XI, Chapter: 4 -Synopsis

Chemical Bonding & Molecular Structure

Chemical Bond -The force of attraction between two elements which holds them together is chemical Bond.
Causes of Chemical Bond-To attain stability by completing octet of an element.

Types of Bonds-i) Ionic Bond ii) Covalent Bond iii) Coordinate Bond iv) Metallic Bond v) Hydrogen Bond

i)Ionic Bond-The force of attraction between two oppositely charged ions, is Ionic Bond or Electrovalent
Formation of Ionic Bond-It is a five step process. 1.Sublimation of metal 2. Formation of Cation 3.
Dissociation of gas 4. Formation of Anion 5. Formation of bond.

Examples:-A. NaCl 1.Sublimation of metal Na(s) → Na(g)

le
2. Formation of cation Na  Na+
2, 8, 1 2, 8

3. Dissociation of gas ½ Cl2(g) → Cl(g)

le
4 4.Formation of Anion Cl  Cl-
2, 8, 7 2, 8, 8
5. Formation of Ionic Bond Na + Cl- → NaCl
+

 2  
1. Mg 

2e le
B.MgCl2 Mg 2. 2Cl   2Cl
2, 8, 2 2, 8 2, 8, 7 2, 8, 8

3. Mg2+ +2Cl- → MgCl2

2e 2e
C. MgO 1. Mg  Mg2+ 2. O  O2-

2,8,2 2,8 2,6 2,8

2-
3. Mg+ O → MgO

Energy Changes during Formation of Ionic Bond

1 Enthalpy of sublimation-Energy required to convert solid metal to gas.

2.Ionization Enthalpy- Energy required to take out an electron.Endothermic process (+).

3.Enthalpy of dissociation-Energy required to dissociate one mole gas into free atoms

4.Electron Gain Enthalpy- Energy released on addition of an electron. Exothermic process (-).

5.Lattice Energy - Energy released in the formation of one mole of Ionic bond. Exothermic process (-).

Total energy change- Total energy change must be negative (-)

Note: Stability of Ionic Bond depends on negative value of Δ E .

Δ E = ΔHsub+ IE + ΔHDiss+ EGE + LE= (-)
Favouring Factors for stability of Ionic Bond a) Low Ionization energy b) High electron gain enthalpy
c) High lattice energy.

To make a stable ionic bond 1. Size of ions should be smaller. 2.More charge on ions .

Ex: MgO has high lattice energy than CaO and it is also more stable than CaO because of small size of
cation.NaCl has high lattice energy than KCl. MgO has high lattice energy than NaCl due to small size of ions.

Properties of Ionic compounds

1.Nature of Ionic Compound- Ionic compounds are polar in nature in which they have different charges.Ex.
Na+— Cl- .

2.Solubility- According to` like dissolves like’ Ionic Compounds are soluble in polar
solvent like H2O and HCl etc.
3.Physical State-Solid States. In Crystalline Solids.
4.Conductivity- Ionic Compounds are Bad Conductors in solid State but good conductors in aqueous state,
molten form or fused state. Due to formation of free ions in aqueous state, molten form or fused state they
show conductivity. 5.Ionic
Reactions-These reactions are always faster than molecular reactions. 6.High
Boiling and Melting Point-These compounds have High Boiling and Melting Point due to strong electroststic
forces.

Covalent Bond- The Force of attraction between two atoms which is formed by mutual/equal sharing of
electrons is known as Covalent Bond.

Cl Cl

Cl - Cl
Co-ordinate-Covalent Bond (Dative Bond)-The force of attraction between two elements which is formed by
unequal sharing of electrons in which shares pair of electrons contributed only by one of the atoms .Ex-O3

1 2 3
O O O

(DA) Doner Acceptor (AD)

Alom Alom

Properties of Covalent compounds

1.Nature -Covalent compounds are non-polar in nature.

2.Solubility- According to` like dissolves like’ covalent compounds are soluble in non-polar solvent like
benzene,toluene ,ethanoletc. 3.Physical
State-Most of covalent compounds exist in liquid or gaseous state.Few covalent compounds exist in solid state
also like sugar,diamond,quartz etc. 4.Conductivity- Covalents
compounds are Bad Conductors due to absence of free ions except gr 5.Molecular Reactions-These
reactions are slower than ionic reactions. 6.Low Boiling and Melting Point-These
compounds have Low Boiling and Melting Point due to weak intermolecular forces.

Formal Charge- Charge remained on an atom if all other atoms are separated in form of ions called formal
charge.It is difference between the number of valence electrons in an isolated atom and the number of
electrons assigned to that atom in a Lewis structure.
1
FC  VE  SE  USE VE – Valence electrons, SE – Shared electrons
2
USE – Un -shared electron
Ex-1.Formal charge on` O’ atoms of Ozone[O3]

1 1
O1 =6 44= 6 – 2 – 4 = 0 , O2 = 6  6  2 = 6 – 1 – 6 = -1
2 2
1
O3 = 6 26 = 6 – 1 – 6 = - 1
2

Limitations of Octet Rule

1.Formation of lower octet molecules-In some compounds central atom has less than 8 electrons even after
bonding means its octet is not complete. Ex: BF3(6e-) ,BCl3 (6e-),BeF2(4e-), BeCl2 (4e-).
2.Formation of super octet or expended octet molecules-In these compounds central atom has more than 8
electrons after bonding. Ex- PCl5 (10e-), SF6 (12-), IF7 (14e-)
3.Formation of odd electron molecule-In few compounds central atom has odd number of electrons.
Ex-NO, NO2.
O N O , O=N→O

4.Formation of compounds of noble gases. Like XeF2, XeF4, XeF6, XeO3 .

Bond Parameters
1.Bond length- Internuclear distance between two bonded atoms is Bond length.Bond length increases with
the size of atoms and decreases with the multiplicity of bonds.
NOTE- Stability of Bond is inversely proportional to bond length.
2.Bond Energy or Bond Enthalpy- Amount of energy released when one mole of bond is formed. Bond
enthalpy decreases with the size of atoms and increases with the multiplicity of bonds.
NOTE-Stability of Bond  Bond energy.
3.Bond Dissociation Enthalpy- Amount of energy required to break one mole of bond. It is directly
proportional to stability of bond. Note:-
Bond energy and Bond Dissociation Enthalpy both are numerically equal for a bond. 4.Bond Order- It
is half of difference between bonding and antibonding electrons in a molecule. NOTE-Stability of Bond is
directly proportional to Bond Order. 5.Bond Angle- It is average angle
between two consecutive bonds or lines representing the orbitals having bonding electrons.

Theories of Covalent Bond I) VBT (Valence Bond Theory) II) MOT (Molecular Orbital Theory)
VBT (Valence Bond Theory):This was given by Hitler and London.It is based on orbital overlap concept.

Postulates of VBT

1. Covalent Bond is formed by overlapping of valence orbitals of atoms. 2.

Only half-filled valence orbitals take part in overlapping. 3.
Half filled orbitals having electron with opposite spin only overlap to form covalent bond. 4.
Stability of covalent bond depends on extent of overlapping.The greater the overlapping ,more is the
energy released and stronger will be covalent bond. 5.
Hybrid orbitals of central atom overlap to form covalent Bond. 6.
Geometry of molecule depends on type of hybridization.
Types of Covalent Bond-Based upon type of overlapping 1.
Sigma Bond ( – Bond) – Single Bond. 2.
Pi Bond (π – Bond) – Multiple Bond.

1.Sigma Bond[ – Bond]–It is formed by axial overlapping or head on overlapping of half filled atomic
orbitals.There are three types of overlapping to form sigma bond. A) S-S
overlap (B) S – P overlap

C) P – P (Axial) overlap
S p
P P

Strength of sigma bonds as per extent of overlapping

P-P > P-S > S-S

2.Pi-Bond[π Bond]-It is formed by lateral overlapping or sidewise overlapping of half filled atomic orbitals.

P – P (Side wise)

(Cobateral Overlapping)

Note-1. Sigma Bond is much stronger than π – Bond due to more extent of overlapping. 2.Pi
–bond is formed only in addition to a sigma bond.It is found in multiple bonds only. 3.The
shape of molecule depends on sigma framework only. 4.Stability of
Bond-Triple bond is highly stable, then double bond and then single bond according to their bond
dissociation enthalpy.

Cl – Cl > O = O > N  N

Q. How many sigma and Pi Bonds are present in following molecule?

H Sigma Bond – 10, π Bond - 3

I
H ─ C ─ C =CH─C  C ─ H
| |
H H
Hybridization-Intermixing of two or more orbitals having almost similar energy to form identical orbitals
known as hybridization and these orbitals are called as Hybrid orbitals.

Features of Hybridization

i) Orbitals having less energy difference take part in hybridization.

ii) All three types of orbitals[empty, half filled and full filled ]can take part in hybridization.
iii) Hybrid orbital are identical in shape, size and energy.
iv) The number of hybrid orbital equals to number of hybrid orbitals taking part in hybridization.
V) The hybrid orbitals can form stronger bonds as they can effectively overlap.
v) Geometry of molecule depends on type of hybridization.

Note-1. Hybridization occurs among orbitals of central atom only.

2. Hybrid orbitals of central atom overlap with valence orbitals of surrounding atoms to form
bonds.

Types of Hybridization and their Geometry

S.No. X[No. of hybrid orbitals] Hybridization Geometry Example

1. 2 sp Linear BeCl2 [Cl – Be – Cl]

F

2. 3 sp2 Triangular BF3 B F

3. 4 sp3 Tetrahedral CH4

4. 5 sp3d Trigonal Bipyramidal PCl 5

5. 6 sp3d2 Octahedral SF6

6. 7 sp3d3 Pentagonal Bipyramidal IF7

Calculation of `X’ (No. Hybrid Orbitals)-Different formulas are used to calculate`X’.

1. X= No.of bP[Bond Pairs]+ No. of lp[Lone Pairs]
Ex.

a) BCl3 X=3+0=3 , sp2

b) NH3 X=3 + = 4,sp3 ,Pyramidal

C) PF5 X = 5+0 =5 ,sp3d, Trigonal Bipyramidal(T.B.P)

2.X=1/2[VE+Monovalent atoms +Charge]

Ex.1. CH4
H
X= 4 
1
4  4  0 =4,sp3 ,Tetrahedral
|
2
C
H | H
H

2.BF3

X= 3 
1
3  3  0=3, sp2 , Triangular
2

3.NH3 ,X= 3 
1
5  3  0=3 +1= 4 , Sp3,Pyramidal
2

N
H | H
H
4.SO4-2
X=4+1/2[6-0+2]=4, sp3,Tetrahedral

5.NH4+
X=4+1/2[5-4+1]=4, sp3,Tetrahedral

Hybridization of carbon in Hydrocarbons as per bonds

1. Alkanes-Carbon having four sigma bonds is sp 3 hybridised.
|
─ C ─ Sp3
|

2.Alkenes-Carbon having three sigma and one pi bonds is sp 2 hybridised.

─C=C─ Sp2

3.Alkynes-Carbon having two sigma and two pi bonds is sp hybridised.

 ─ C C ─ Sp

Q.Give hybridization of each carbon atom in following compound.

Sp3 Sp2 Sp2 Sp3 Sp3

C7 ─ C6 = C5 ─ C4 ─ C3 Sp3
| |
Sp C8
3 C2  C1
Sp Sp

Orbital Structure and Bond formation in Molecules

1.Methane ,CH4

Hybridisation X= 4 
1
4  4  0 =4,sp3 ,Tetrahedral
2
In methane, 4 sp3 hybrid orbitals of carbon overlap with`S’ orbital of hydrogen by sp3-s overlapping to
form 4 sigma bonds in tetrahedral shape.

H
|
C C
H | H
H
H
H
H

2.Boron Triflouride,BF3

X= 3 
1
3  3  0=3,sp2, Triangular.
2
In BF3 ,3 sp2 hybrid orbitals of boron overlap with`p’ orbital of flourine by sp2-p overlapping to form 3 sigma
bonds in triangular shape.

F 2
Sp - p

B F
Sp2 - p
F
3.Ammonia,NH3 ,X= 3 
1
5  3  0= 4,sp3 , Pyramidal . In ammonia, 3 sp3 hybrid orbitals of
2
nitrogen overlap with`S’ orbital of hydrogen by sp3-s overlapping to form 3 sigma bonds in
Pyramidal shape.Fourth sp3 hybrid orbital has one lone pair.

N
H | H
H

4.Ethane,C2H6

In ethane each carbon is sp3 hybridised having four sp3 hybrid orbitals.Each carbon atom form four sigma
bonds.There are 3 C–H bonds for every carbon atom formed by overlapping of sp3 and s orbital of hydrogen
and one C-C bond is formed by overlapping of sp3 and sp3 orbitals of carbon atoms.

4 sp3 Orbitals[3 sp3 – s of H ,1 sp3-sp3 of C]

H H
| |
C ─ C
H H H H

C C H
H
Sp3 Sp3

H H
5.Ethene,C2H4

In ethene each carbon is sp2 hybridised having three sp2 hybrid orbitals and one unhybridised P orbital.Each
carbon atom form three sigma bonds and one pi bond.There are 2 C–H sigma bonds for every carbon atom
formed by overlapping of sp2 orbital of carbon and s orbital of hydrogen and one C-C sigma bond is formed by
overlapping of sp2 and sp2 orbitals of carbon atoms.One pi bond between carbon and carbon is formed by
sidewise overlapping of `p’ orbitals of carbon atoms.

H H
C ═ C
Sp2 Sp2
H H

6.Ethyne[Acetylene],C2H2
In ethyne each carbon is sp hybridised having two sp hybrid orbitals and two unhybridised P orbital.Each
carbon atom form two sigma bonds and two pi bond.There are 1 C–H sigma bond for every carbon atom
formed by overlapping of sp orbital of carbon and s orbital of hydrogen and one C-C sigma bond is formed by
overlapping of sp and sp orbitals of carbon atoms.Two pi bonds between carbon and carbon are formed by
sidewise overlapping of `p’ orbitals of carbon atoms.

Limitations of VBT (Valence Bond Theory)

1.Few molecules do not have geometry according to their hybridization like NH 3, H2O, etc.
2.It does not explain paramagnetic nature of O2.
3.Bond angles of few molecules are not explained based on VBT.

VSEPR'S THEORY(Valence Shell Electron Pair Repulsion Theory)

Concepts

1.Geometry of molecule depends on repulsion amongs electron pairs present on central atom.
2. To minimize repulsion between electron pairs bonds around central atom arrange themselves at a particular
distance to make a stable molecule. 3. Maximum
Repulsion is between two lone pairs. Repulsion amongs electron pairs as per following order.
lp  lp lp  bp bp  bp
4.When all the electron pairs are in form of bond pairs then molecule has regular geometry but when lone
pairs are also present around central atom then geometry of molecule becomes ir-regular or distorted.
5.Due to distortion bond angle decreases with increase of repulsion between electron pairs.

EX-
CH4 H 2O
 sp3 sp3

H O
| H H
C
|
H H H

109.28’ 104.5º
bp – bp lp – lp

Highest lp  lp repulsion is found in H2O because of 2 lone pairs hence its bond angle is lowest.

MOT (Molecular Orbital Theory)-Feature

1.Atomic orbitals having nearly same energy of two atoms combine to form molecular orbitals.
2.All types of atomic orbitals of an atom (half, full and empty) can combine to form molecularorbitals.
3.No. of molecular orbitals formed is equal to no. of combining atomic orbitals.
4.Two types of molecular orbitals are formed according/ based on energy difference.
i) Bonding Molcular Orbitals having low energy.
Ii Antibonding Molecular Orbitals having higher energy.
5.Half molecular orbitals are of bonding type and half of molecular orbitals are of antibonding type.
6.S-orbitals form sigma Molecular Orbitals and p-orbitals form pi- Molecular Orbitals.
7.Electron filling in molecular orbitals takes place according to all rules[Aufbau rule,Pauli’s principle,Hunds
rule].

LCAO-Linear Combination Of Atomic Orbitals-Formation of molecular orbitals takes place according to LCAO
method.In this method electron wave functions of atomic orbitals are redistributed during formation of
molecular orbitals.On the addition overlap of atomic orbitals bonding molecular orbitals are formed and on
the substraction overlap of atomic orbitals antibonding molecular orbitals are formed.Electron density
becomes high onthe addition overlap of atomic orbitals hence bonding molecular orbitals increase stability
but electron density becomes low on the substraction overlap of atomic orbitals hence antibonding molecular
orbitals decrease stability.
1.Addition Overlap

2.Substraction overlap

Molecular Orbital Diagram

LS
1. H2 molecule
H – lS1
A.MO Configuration-σ1s2

B.Magnetic property- Diamagnetic

lS lS
 Nb  Na
C.Bond order [BO] =
2
Nb -No. of Bonding electrons
Na -No. of Anti Bonding electrons.
2  0 2
for H2 Holecules   = =1
 2  2

NOTE- Magnetic properties of Molecules-There are two types of magnetic properties.

a)Paramagnetic:The substances having at least one unpaired electron and these substances are
attracted towards magnetic field.
b)Diamagnetic:The substances having all electrons paired and these substances are repelled by
magnetic field.
Significances of Bond Order
i) Stability of Molecule  Bond order
ii) Bond Energy/Bond Dissociation Energy.
Bond energy  Bond order.
iii) No. of Bonds between atoms.
No. of Bonds = Bond order.
iv) If Bond order is zero then molecules does not exist.
v) Bond order can be in fraction also.
LS2
2.He2 molecule
He – ls2

A.MO Configuration- σ1s2 σ1s2 lS lS

B.Magnetic property- Diamagnetic

22 0 He He
C.Bond order [BO]=  =0
2 2 lS

He2 molecule does not exist because it has bond order Zero.
3.Li2 molecule
A.MO Configuration- σ1s2 σ1s2σ2s2
B.Magnetic property- Paramagnetic
4−2 2
C.Bond order [BO]= =2=1
2

4. Be2 Molecule
A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2
B.Magnetic property- Diamagnetic
4−4
C.Bond order [BO]= =0
2

Be2 molecule does not exist because it has bond order Zero

4.B2 Molecule[2121]-(10 electrons)-

A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2π2Px1π2Py1
B.Magnetic property- Paramagnetic
 2−0 2
C.Bond order [BO]= =2=1
2

6.C2 Molecule[2121]-(12electrons)-
A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2π2Px2π2Py2
B.Magnetic property- Diamagnetic
4−0 4
C.Bond order [BO]= =2=2
2

7.N2 Molecule[2121]- (14 electrons)-

A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2π2Px2 π2PY2 σ2PZ2
B.Magnetic property- Diamagnetic
10−4
C.Bond order [BO]= 2 = 3
8.O2 Molecule[1221]- (16 electrons)-
A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2σ2PZ2π2Px2 π2PY2 π2Px1π2Py1
B.Magnetic property- Paramagnetic
10−6
C.Bond order [BO]= = 2
2

9.F2 Molecule[1221]- (18 electrons)-

A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2σ2PZ2π2Px2 π2PY2 π2Px2π2Py2
B.Magnetic property- Diamagnetic
10−8
C.Bond order [BO]= 2 = 1
10.Ne2 Molecule[1221]- (20 electrons)-
A.MO Configuration- σ1s2 σ1s2σ2s2 σ2s2σ2PZ2π2Px2 π2PY2 π2Px2π2Py2σ2PZ2
B.Magnetic property- Diamagnetic
10−10
C.Bond order [BO]= 2 = 0
Ne2 molecule does not exist because it has bond order Zero.
Dipole Moment-It is product of the magnitude of charge on any one bonded atom and the distance
between them.
µ=qxd

Applications of Dipole Moment

1.Nature of molecule.
a)Polar Molecules-The compound in which charge separation takes place at bonded atoms. That molecule is
called polar molecule .These molecules have dipole moment   0 NaCl=Na+─ Cl-
b)Non Polar Moleules-The compound in which separation of charge doesn’t take place.These
molecules do not have dipole moment.   0
2.Extent of Polarity.
Extent of Polarity   [ Dipole Moment]
3.Geometry of molecules sometimes decides dipole moment of molecule.
Example.i)H2O is polar molecule.It has high dipole moment[1.85 Debye] due to its bent shape.

ii)BeCl2 and CO2 are non-polar-BeCl2 is non polar because of equal and opposite dipoles.Its dipole
moment is cancelled out. CO2 and BeF2 are also non polar in nature due to same reason.

iii) BF3- BF3 is non polar is nature becauase Net Dipole of two B-F bonds is equal and opposite of third
B-F bond therefore Its dipole moment is cancelled out.

Q.Out of NF3 and NH3,Which has more dipole moment and why?
Ans.NH3 is more polar than NF3 because of more electro-negativity of nitrogen than hydrogen,
electron density increases at nitrogen. But in NF3,flourine is more electronegative than nitrogen
therefore, electron density decreases at nitrogen.

Note- 1.Ionic compounds are always polar in nature and they have dipole moment.
2.Pure covalent compounds (Covalent Bond Between two identical atoms Cl 2, Br2, F2) are
non-polar in nature and have zero dipole moment.
Polarity in Covalent Bond-If a covalent bond is found between two elements having difference in
their electro-negativity, then partial negative and partial positive charges are developed at both
bonded atom, then a covalent bond becomes polar covalent bond.
Covalent nature in Ionic Bond-Sometimes ionic compounds show covalent character.According to
FAZAN’s rule covalent character is doveloped due to high polarizing power of small cation and high
polarizability of large anion.Ex-LiCI is covalent in nature due to small cation.NaI is more covalent than
NaF due to large anion.

RESONANCE
De-localization of pi[ ]electrons gives different structures of molecule known as resonating structures
or canonical forms of this phenomena is called as Resonance.Resonance is found in molecules having
pi bonds (Double triple or unsaturated compounds).Pi electrons are loosely bonded hence these can
change their position within a molecule.

Ex-Ozone,O3

O
O O
Resonance Hybrid

SO2

S S
O O

(Resonance Hybrid)

SO3

O O O

S S S
O O O O O O
(Resonance Hybrid)

HYDROGEN BOND
Force of attraction between hydrogen and highly electronegative atom (FON only) is hydrogen bond.
Types of hydrogen bonds
1.Inter Molecular
2.Intra Molecular
Inter Moleculecular Hydrogen bond -Hydrogen bond between hydrogen and electronegative atom
two different molecules.Ex-H2O,HF, NH3 etc.
Effects of inter molecular hydrogen bonding
i) Association of molecules occurs.
ii) High molecular mass due to association.
iii)Boiling point and Melting point increases due to hydrogen bonding.
iv) Solubility in water increase if a molecular forms hydrogen bond with water.

Intra Moleculecular Hydrogen bond-Hydrogen bond between hydrogen and electronegative atom
within a molecule.Ex: O-Hydroxy Benzoic acid,O-nitro phenol.

Q. HF is a liquid but HCl is a gas. Why?

Ans.Due to Hydrogen bonding in HF.

Q. O-Nitro phenol has low boiling point or it is more volatile than p-nitro phenol.Why?
Ans. Due to intra molecular Hydrogen bonding in o-nitro phenol.