L.

04 - Chemical bonding and molecular structure

● Aggregate of atoms having distinct properties from those of the constituent atoms
are called molecules.
● Molecules are formed from atoms because molecules are more stable than atom.
● The attractive force which holds various constituents (atoms, ions, etc) together
in different chemical species is called a chemical bond.

Lewis electron dot formula

● Only outer electrons are involved in chemical bonding and they are called
valence electrons.
● G.N. Lewis represented these valence electrons as dots around the symbol of
the elements.These are called electron dot symbol or Lewis symbols.

Octet rule
● Octet rule states that atoms combine to form molecules in such a way that each
atom attains an octet ie, eight electrons in their valence shell.
● Atoms combine together to acquire stable configuration as in noble gases (ns​2
np​6 ​except for He).
● Completion of octet or duplet may take place in three possible ways giving rise to
three different types of valencies, namely, electrovalency, covalency and
coordinate covalency.
● The bonds thus formed are called electrovalent, covalent and coordinate bonds.

Ionic bond​ (Electrovalent bond)

● Bond formed by the transfer of electrons from an electropositive element to an
electronegative element is called ionic bond.
● Electropositive element becomes a positive ion or cation and electronegative
element becomes a negative ion or anion.
● These oppositely charged ions are held together by electrostatic force of
attraction and this force of attraction is called ionic bond.
Factors favoring the formation of ionic compounds
● Low ionisation energy of metal atom
● High electron affinity of the non-metal atom.
● High lattice energy of the compound formed.

(Lattice energy is defined as the energy released when one mole of an ionic compound
is formed from its gaseous ions.)

General characteristics of ionic compounds

● Physical nature - Solids, somewhat hard because of strong electrostatic force of
attraction. They are generally brittle.
● MP and BP - High MP and BP because considerable amount of energy is required to
break the strong inter - ionic attraction.
● Solubility - Soluble in water but insoluble in solvents such as kerosene, petrol etc.
● Conduction of electricity - Conduct electricity in aqueous state due to the movement of
ions towards opposite electrodes. They also conduct electricity in molten state because
electrostatic force of attraction is overcome by the heat supplied. In solid state they do
not conduct electricity.
● Ionic reaction - Ionic compounds produce ions in the solution which gives very fast
reaction with oppositely charged ions.

Covalent bond - Lewis -Langmuir concept

● The bond formed by the mutual sharing of electrons between two atoms are
called covalent bonds.
● In most cases sharing takes place in such a way to satisfy the octet
configuration.
● The shared electron pair becomes common to both the atoms and this shared
pair is called bond pair of electrons.
● The valence electron pair which is not involved in bond formation are called lone
pairs of electrons.
● When two atoms share one electron pair they are said to be joined by single
covalent bond, if by two electron pairs, the covalent bond between them is called
double bond and if by three it is called triple bond
Covalent radius :​It is the radius of an atom core which is in contact with the core of an
adjacent atom.

Van der waals radius ​: It represents the overall size of the atom which includes its
valence shell

Limitations of the Octet rule:

1. The incomplete octet of the central atom: In some covalent compounds the
central atom has less than eight electrons. i.e, it has an incomplete octet

Li : Cl H: Be: H

2. Odd-electron molecule: There are certain molecules in which they have odd number
of electrons. The octet rule is not applied for all atoms.

3. Expanded octet : In many compounds there are more than eight valence electrons
around the central atom. It is termed as expanded octet.

Eg. PCl​5​ (10 electrons) , SF​6​ (12 electrons)

Other drawbacks of octet theory

1. Some noble gases, also combine with oxygen and fluorine to form a number of
compounds like XeF​2​ , KrF​2​ , XeOF​2​ etc.
2. This theory does not account for the shape of molecules
3. It does not give any idea about the energy of the molecule and relative stability.

Bond Parameters

● Bond length​ - It is defined as the equilibrium distance

between the centres of the nuclei of the two bonded atoms. It
is expressed in A​o​. Experimentally it can be determined by
X-ray diffraction or electron diffraction method,

● B​ond angle: It is defined as the angle between the orbitals containing bonding
electron pairs around the central atom in a molecule/complex ion.

● Bond enthalpy​/energy: It is the amount of energy required to break one mole of

particular bond into gaseous atoms.
● It is usually taken as the average value for polyatomic molecules.
Resonance

● If a molecule can have more than one structure, each structure explains most of
the properties, but not all the properties and if the actual structure lies in between
various resonating structure, the phenomenon is called resonance.

Eg: Benzene

Resonance hybrid

Rules for writing resonating structure

1. The contributing structures should have the same position of atoms.

2. The contributing structures should have the same number of unpaired electrons
3. The contributing structures should have nearly same energy.
4. Negative charge should be on the electronegative atom and positive charge on
the electropositive atom.
1. Resonance in carbon dioxide molecule (CO​2​)

2. . Carbonate ion ( CO​3​2-​)

Partial ionic character of covalent bond

If two atoms linked together have different electronegativities, then bond formed is
polar. The bond is said to possess partial ionic character.

❖ If the electronegativity difference between two atoms is 1.7 the bond is 50% ionic
and 50% covalent.
❖ If the electronegativity difference between two atoms is more than 1.7 the bond
is more ionic.
❖ If the electronegativity difference between two atoms is less than 1.7 the bond is
predominantly more covalent.

Dipole moment ​(𝛍)

● It is the product of magnitude of negative or positive charge (​q​) and the distance
(​d​) between the charge of positive and negative charges is called dipole moment.
​𝛍 = q x d
● SI unit is Debye (D)
● 1D = 3.33564 x 10​-30​ C m where C is coulomb and m is meter.

Dipole moment and molecular structure

Dipole moment is a vector quantity and is used for determining the geometry of
molecules.
● For AB​2 type
​ molecule if 𝛍 = 0 , geometry - linear

eg: CO​2​, BeF​2

 ● For AB​3​ type of molecules, if 𝛍 = 0 , geometry - planar triangular

Eg: BF​3

● For AB​4​ type of molecule, if 𝛍 = 0 , geometry -tetrahedral

Eg: CCl​4

Dipole moment of NH​3​ is higher than NF​3

𝛍 = 0.23D 𝛍 = 1.47D
 ● In NH​3​ the resultant dipole moment of N-H bond and dipole moment due to lone
pairs are in the same direction hence it will add up.
● In NF​3​ , the resultant dipole moment of N-F bond and dipole moment due to lone
pairs are in the opposite direction hence it will subtract.

Partial covalent character of ionic bond (Fajan’s rule)

❖ Covalent character of ionic bond is increased by
● Small positive ion (cation) and large negative ion (anion)
● Greater charge on cations
● Electronic configuration - For cations of the same size and charge, the one with
electronic configuration (n-1)d​n​ns​0​, is more polarized than the one with a noble
gas configuration, ns​2​ np​6
❖ For a fixed cation covalent character follows the order NaI > NaBr > NaCl > NaF
❖ For a fixed anion covalent character follows the order BeCl​2​ > MgCl​2​>
CaCl​2​>SrCl​2

VSEPR Theory​ ( Valence shell electron pair repulsion theory) ( Sidgwick and
Powell - Later developed by Nyholm and Gillespie)
This theory was proposed to explain geometry of molecules. The important postulates
are
1. The shape of the molecule depends upon the number of bond pair and lone pair
around the central atom.
2. The electron pairs are arranged in space around central atom to minimize the
repulsion.
3. The following types of repulsion are possible
Lone pair - lone pair > lone pair - bond pair > bond pair - bond pair
No: of electron Formula Geometry Example
pair

2 AB​2 Linear BeF​2​, BeCl​2

3 AB​3 Triangular planar BF​3​, SO​3

AB​2​L V- shape NO​2​, SnCl​2​, SO​2

4 AB​4 Tetrahedral CH​4​, NH​4​+

AB​3​L Trigonal pyramidal NH​3​ , PH​3
AB​2​L​2 V-shape H​2​O, H​2​S

5 AB​5 Trigonal bipyramidal PCl​5​, AsF​5

SeeSaw
AB​4​L T - Shape SF​4
AB​3​L​2 Linear ClF​3
AB​2​L​3 XeF​2​, ICl​2​-

6 AB​6 Octahedral SF​6

AB​5​L Square pyramidal ClF​5​, IF​5
AB​4​L​2 Square planar XeF​4
Valence bond theory​ (VBT) - Heitler and London
According to this theory
a. Covalent bond is formed by the overlapping of two half filled atomic orbitals
having electrons with opposite spin.
b. Strength of the covalent bond depends on the extent of overlapping.

Depending on these factors covalent bonds are classified into two types -
(i) Sigma bond ( 𝛔 )
(ii) Pi-bond ( 𝜋 )

Sigma (​𝛔 )​ bond

● When two half filled atomic orbitals involved in the formation of molecular orbital
overlap end to end along the internuclear axis, then the bond formed is a sigma
bond. It can be formed by s-s, s-p and p-p overlapping.
a. s-s overlapping
b. s-p overlapping

c. p-p overlapping

Pi (𝜋 ​ )​ bond
● When half filled p - orbital involved in bond formation are oriented in a direction
perpendicular to the internuclear axis, then the bond formed is a pi bond. (lateral
or sidewise overlapping of p orbitals)
Difference between 𝛔 and 𝜋 bonds

𝛔 bond 𝜋 bond

1. Formed by the axial overlapping of atomic 1. Formed by sidewise overlapping of p-orbitals

orbitals only

2. The extent of overlapping is large and bond 2. The extent of overlapping is small and bond
formed is stronger. formed is weaker.

3. Free rotation about ​𝛔 ​bond is possible 3. Free rotation about pi bond is not possible

4. The ​𝛔 ​bond is found alone or along with pi 4. Always found along with a ​𝛔 ​bond
bond

Hybridisation
● The process of intermixing of atomic orbitals of different energies to form new
orbitals of equivalent energy and identical shape is called hybridisation.
Important characteristics of hybridisation are:
➢ The orbitals taking part in hybridisation should have almost same energy.
➢ The number of hybrid orbitals formed is equal to the number of atomic orbitals
taking part in hybridisation.
➢ The hybrid orbitals have same energy and shape.
➢ Both half filled and fully filled orbitals can undergo hybridisation.
➢ The hybrid orbitals are more efficient in forming stable bond than atomic orbitals.
➢ Hybrid orbitals have specific orientation in space, hence decides the geometry of
the molecule.
sp​3​ hybridisation
● It involves the intermixing of one s and three p orbitals to form four sp​3​ hybrid
orbitals of same energy and shape. sp​3​ hybrid orbitals are directed towards the
corners of regular tetrahedron with a bond angle 109.5​0
Formation of Methane

● The 2s and three 2p orbitals hybridise to form four sp​3​ hybrid orbitals.
● These hybrid orbitals are directed towards the four corners of a regular
tetrahedron.
● All sp​3​ hybrid orbitals overlap with 1s orbitals of four hydrogen atoms to form four
C - H sigma bonds.
● Thus methane molecule has tetrahedral shape with H-C-H bond angle 109​0​28’.
● The C - H bond length in methane is 109 A​0

sp​2​ hybridisation
● It involves the intermixing of one s and two p orbitals to form three sp​2​ hybrid
orbitals of same energy and shape. sp​2​ hybrid orbitals are directed towards the
 corners of planar triangle with a bond angle 120​0
Formation of Boron trifluoride

● One of the 2s electron is promoted to vacant 2p orbital.

● The 2s and two 2p orbitals hybridise to form three sp​2​ hybrid orbitals.
● These hybrid orbitals are arranged in a trigonal planar manner.
● All sp​2​ hybrid orbitals overlap with 1s orbitals of three 2pz orbital of three fluorine
atoms to form three B - F sigma bonds.
● Thus BF​3​ molecule has trigonal planar geometry with F-B-F bond angle 120​0​.

●
Formation of Ethene​ ( C​2​H​4​ )
 ● One of the sp​2​ hybrid orbitals of one carbon atom overlaps with one of the sp2
hybrid orbital of other carbon atom to form C - C sigma bond.
● The other sp​2 ​hybrid orbitals on each carbon atom overlap with the 1s orbital of H
atoms to C-H sigma bonds.
● The unhybridized 2p orbital of one carbon atom overlaps sidewise with the
similar orbital of other carbon atom to form C - C pi bond.
● Thus ethene molecule contains one C - C sigma bond and one C - C pi bond.
● The bond angles are 120​0​.

sp hybridisation​ (diagonal hybridisation)

● It involves the intermixing of one s and one p orbitals to form two sp hybrid
orbitals of same energy and shape. sp hybrid orbitals are arranged linearly with a
bond angle 180​0
Formation of Beryllium difluoride ​(BeF​2​)

● One of the 2s electron is promoted to vacant 2p orbital.

● The 2s and one 2p orbitals hybridise to form two sp hybrid orbitals.
● These hybrid orbitals are oriented in a linear arrangement.
 ● All sp hybrid orbitals overlap with 1s orbitals of three 2pz orbital of two fluorine
atoms to form two Be - F sigma bonds.
● Thus BeF​2​ molecule has linear geometry with F-Be-F bond angle 180​0​.

Formation of acetylene (Ethyne)​ ( C​2​H​2​ )

● In the formation of ethene, both C

atoms undergo sp hybridisation.
● One of the sp hybrid orbitals of one carbon atom overlaps with one of the sp
hybrid orbitals of the other carbon atom to form C - C sigma bond.
● The other sp hybrid orbital on each carbon atom overlaps with the 1s orbital of
two H-atom to form two C-H sigma bonds.
● The unhybridized 2p orbitals of one C atom overlaps sidewise with the similar
orbital of the other C to form two C - C pi bond.
● Thus , acetylene molecule contains one C - C sigma bond and two C-C pi bond.
● The bond angles are 180​0​ and shape of the molecule is linear.
sp​3​d hybridisation
● It involves the intermixing of one s , three p orbitals and one d orbital to form five
sp​3​d hybrid orbitals of same energy and shape. These orbitals are directed
towards the corners of a trigonal bipyramid with bond angle 90​0​ and 120​0​.
● Ex: PCl​5
●

sp​3​d​2 ​hybridisation
● It involves the intermixing of one s , three p orbitals and two d orbitals to form six
sp​3​d​2​ hybrid orbitals of same energy and shape. These orbitals are directed
towards the corners of an octahedron with bond angle 90​0​.
● Ex: SF​6
●

●
sp​3​d​3 ​hybridisation
● It involves the intermixing of one s , three p orbitals and three d orbitals to form
seven sp​3​d​3​ hybrid orbitals of same energy and shape. These orbitals are
directed towards the corners of an pentagonal bipyramid with bond angle 90​0 ​and
72​0
● Ex: IF​7

Limitation of VBT
● It could not explain paramagnetic behaviour of oxygen molecule.
● It could not explain the bonding in electron deficient compounds.
Molecular orbital theory​ (MOT) - Hund and Mulliken
● In molecules, electrons are present in a special type of orbitals called molecular
 orbitals.
● Like atomic orbitals, the molecular orbitals are characterised by a set of quantum
numbers.
● Molecular orbitals are formed by the combination of atomic orbitals of nearly
same energy.
● The number of molecular orbitals formed is equal to the number of atomic
orbitals combined.
● The molecular orbitals are filled in accordance with Aufbau principle, Pauli’s
exclusion principle and Hund’s rule.
Linear combination of atomic orbital (LCAO)
● Formation of molecular orbital can be explained by LCAO method.
● According to this molecular orbitals are formed by the combination of atomic
orbitals.
● The atomic orbitals can combine by (i) addition and (ii) subtraction of their wave
function. This is called linear combination of atomic orbitals (LCAO) method
Ψ​MO​ = Ψ​A​ ∓ Ψ​B
Ψ​BMO = Ψ​
​ A +
​ Ψ​B ​ and Ψ​AMO = ​Ψ​A -​ Ψ​B
● Ψ​BMO formed
​ by the addition overlap of atomic orbitals is called bonding molecular
orbital and Ψ​AMO ​ formed by the subtraction overlap of atomic orbitals is called
antibonding molecular orbital.
● In BMO the electrons are mainly localised in between the nuclei and so greater
force of attraction in the orbital. Hence BMO has lower energy than the
corresponding atomic orbitals.
● In AMO, the electrons are mainly localised away from the nuclei, so lower force
of attraction in the orbital. Hence AMO has higher energy than the corresponding
atomic orbitals.
Comparison of bonding and antibonding molecular orbitals

BMO AMO

1. Formed by the addition of atomic orbitals 1. It is formed by the subtraction of atomic

orbitals

2. Electron density is increased between the 2. Electron density is decreased between the
nuclei nuclei

3. May or maynot have a node 3. Always have a node

4. Lower energy than atomic orbitals 4. Higher energy than atomic orbitals

5. Represented by 𝛔 and 𝝅 5. Represented by ​ 𝛔

​ * and 𝝅*

Bond Order
● It is defined as one half the difference between the number of electrons present
in the bonding and antibonding orbitals.
● It is the number of chemical bonds between a pair of atoms.
● Eg : Diatomic nitrogen bond order is 3,
● In acetylene, the bond order between two carbon atoms is

3, and the C-H bond order is one.

● Bond order gives an indication of the stability of a bond.

Bond order =

Significance of bond Order

● Positive value of bond order indicates a stable molecule.
 ● The greater the bond order, the greater the bond energy and hence high
dissociation energy.
● Integral value of bond order is equal to number of bonds. The bond order of 1,2
or 3 in a diatomic molecule corresponds to single, double or triple bond.
● Bond length decreases as bond order increases.
Bond Order of molecules with resonance
Bond order = ​Total number of bonds between two atoms in all the structure
Total number of resonating structures
In Benzene,

B.O. = ​2+1​ = 1.5

2

In CO​3​2-​,

B.O. = ​2+1+1​ = 1.33

3

Increasing order of energies for lighter molecules like Li​2​ , Be​2​ , B​2​ , C​2​ and N​2
Molecular orbital configuration is 𝜎1s < 𝜎*1s < 𝜎2s < 𝜎*2s < (𝝅2p​x​ = 𝝅2p​y​)< 𝜎2p​z​ <
(𝝅*2p​x​ = 𝝅*2p​y​), < 𝜎*2p​z
Increasing order of energies for heavier molecules like O​2​ , F​2
Molecular orbital configuration is 𝜎1s < 𝜎*1s < 𝜎2s < 𝜎*2s < 𝜎2p​z​< (𝝅2p​x​ = 𝝅2p​y​) <
(𝝅*2p​x​ = 𝝅*2p​y​), < 𝜎*2p​z
​Magnetic nature
● If all the molecular orbitals in a molecule are doubly occupied, the substance is
diamagnetic ( repelled by magnetic field).
● If one or more molecular orbitals are singly occupied it is paramagnetic (attracted
by magnetic field).
● Magnetic moment, where n is the number of unpaired
electrons.

Hydrogen bonding
● It is the force of attraction between covalently bonded hydrogen atom of one
molecule and an electronegative atom of same or another molecule.

● Condition for hydrogen bonding - Hydrogen should be connected to

electronegative elements like F, N, O etc

Types of hydrogen bonding

● Intermolecular hydrogen bonding: ​This occurs when the hydrogen atom and
the electronegative atom belong to different molecules.
 ● Intramolecular hydrogen bonding: ​This occurs when the hydrogen atom and
the electronegative atom exist in same molecules.

Consequences of hydrogen bonding

● It leads to the association and hence boiling point of those compounds having
hydrogen bonds increases
● Solubility - Compounds which can form H-bond with water molecules becomes
more soluble in water.
● Surface tension and viscosity increases due to H-bonding.
● Influence on the physical state - Water is a liquid while H​2​S is a gas at ordinary
temperature. In H​2​O hydrogen bonding is present while in H​2​S hydrogen bond is
absent.
Hydrogen bonding in Water
● Each water molecule forms four H-bonds, two through O-atom and two through
H-atoms. Thus each H​2​O molecule is linked to four H​2​O molecules tetrahedrally.
● The high specific heat of water relative to other liquids or solids suggest that
large amount of energy is required to break H-bonds in H​2​O.
● Intermolecular hydrogen bonding in ice gives it an open cage like structure. As a
result , ice has lower density than liquid water.