4.

Chemical bonding and Molecular Structure

1. Lewis dot structures are shorthand to represent the valence electrons of an atom. The
structures are written as the element symbol surrounded by dots that represent the valence electrons.
Method to write Lewis structure
a) Calculate the number of electrons available in the valence shell (A)
b) Calculate the total number of electrons needed by al the atoms to achieve noble gas
configuration(N)
c) Number of shared electrons (S) =N-A
d) Remaining electrons as nonbonding electrons
CO32-
A =4+6x3+2 =24 e-
N= 1x8+ 3x8 =32e-
Number of shared electrons S= 32-24 =8e-. (4 pairs).
No.of non-bonding electrons =24-8 =16
Then draw the structure.

2. Covalent Bonds- The bond formed between two atoms by mutual sharing of electrons
between them so as to complete their octets or duplets. When two atoms share one electron pair they are
said to be joined by a single covalent bond.e.g H2 If two atoms share two electron pairs of electrons, the
covalent bond between them is called a double bond. e.g O2 If two atoms share three electron pairs of
electrons, the covalent bond between them is called a triple bond. e.g N2

3. Octet Rule- Kossel and Lewis in 1916 developed an important theory of chemical
combination between atoms known as electronic theory of chemical bonding. According to this, atoms
can combine either by transfer of valence electrons from one atom to another or by sharing of valence
electrons in order to attain their octet. This is known as octet rule.

4. Limitations of octet rule-

a) Incomplete octet of the central atom: In some compounds the number of electrons surrounding
the central atom is less than eight. This is especially the case with elements having less than four
valence electrons. (refer diagram from text book)Examples-LiCl ,BeCl2 , BCl3

b) Odd-electron molecules: In molecules with an odd number of electrons like nitric oxide, NO
and nitrogen dioxide, the octet rule is not satisfied for all the atoms. (refer diagram from text book)
c) The expanded octet : Elements in and beyond the third period of the periodic table have, apart
from 3s and 3p orbitals, 3d orbitals also available for bonding. In a number of compounds of
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 these elements there are more than eight valence electrons around the central atom. This is termed as the
expanded octet. Some of examples of such compounds are: PF5, SF6.(refer structure from text book)
d) This theory does not account for the shape of molecules.
e) This theory doesn’t explain the relative stability of the molecule.

5. Electrovalent bond or Ionic Bond: The chemical bond as result of transfer of electron from
one atom(electropositive) to another atom (electronegative).Ionic bonds will be formed more easily
between elements with comparatively low ionization enthalpies and elements with comparatively high
negative value of electron gain enthalpy. Most ionic compounds have cations derived from metallic
elements and anions from non-metallic elements.
M(g) M++ e- (Ionisation enthalpy)
X(g)+ e- X-(g) (electron gain enthalpy)
M+(g) + X-(g) MX(s) (lattice energy)

Lattice Enthalpy
Energy required to completely separate one mole of a solid ionic compound into gaseous constituents
ions. Eg: NaCl =+ 788KJ/Mol
Conditions which favor ionic bond formation:
a) Low ionization enthalpy favors cation formation.
b) High electron gain enthalpy favors anion formation
c) High lattice enthalpy favors the formation of ionic bond.

6. Bond parameters

a) Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a
molecule
b) Bond angle: Angle between the orbitals containing bonding pairs of electrons around the central
atom in a molecule/complex ion and hence it helps us in determining its shape
c) Bond enthalpy: It is defined as the amount of energy required to break one mole of bonds of a
particular type between two atoms in a gaseous state. The unit of bond enthalpy is kJ mol–1
d) Bond Order : The Bond Order is given by the number of bonds between the two atoms in a
molecule. E.g.: Bond Order of O2= 2. With increase in bond order, bond enthalpy increases and bond
length decreases and stability increases.
7. Resonance: It is the phenomenon as a result of which a molecule can be expressed in different
forms of similar energy, position of nuclei, bonding and non-bonding electrons each of which can
explain most of the properties of molecule but none of which can explain all the properties of the
molecule. The actual structure of the molecule is intermediate of all these structures called as resonance
hybrid.
Different forms of the same molecule of similar energy, position of nuclei, bonding and non-bonding
electrons are called as canonical structure.

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  More the number of resonance structures, more stable is the molecule.
 Energy of the resonance hybrid is lower than the canonical structure.

8. Polarity of bonds: In case of heteronuclear molecules like HCl, the shared pair of electron between
the two atoms gets displaced more towards chlorine since the electronegativity of chlorine is far greater
than that of hydrogen. The resultant covalent bond is called a polar covalent bond.

9. Dipole moment: As a result of polarization, the molecule possesses the dipole moment which
can be defined as the product of charge and the distance between the centers of positive and negative
charge.
Dipole moment (µ ) = charge (Q) x Distance of separation (r)

Dipole moment of BeF2 =0. Reason: Two equal bond dipoles point in opposite direction and cancel the
effect of each other.
Dipole moment of BF3 =0. Reason: Each B-F bonds are oriented at an angle of 1200 to one another. The
three bond moments give a net sum of zero as the resultant of any two is equal and opposite to the third.
Dipole moment of NH3 > NF3. Reason: In case of NH3 the orbital dipole due to lone pair of electrons is
in the same direction as the resultant dipole moment of the N-H bonds. Whereas in NF3 the orbital dipole
because of lone pair of electron is of the opposite direction as a resultant dipole moment of the N-F
bonds. (structure refer text book page107 &108)

Fajans rule
Partial covalent character of the ionic bonds
The cation polarizes the anion by pulling the electronic charge towards itself and thereby
increasing the electronic charge between 2.

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Therefore partial covalent character in ionic bond depends on
1. Polarizing power of cation. Smaller the size more the power
2. Polarisability of anion, Larger size more polarisability
3. Extent of distortion
4. Greater the charge on cation more the polarizing power.
5. For cations of the same size, the one with the electronic configuration (n-1)d ns (transition
elements) have more polarizing power than others.
Therefore LiI has more covalent character than LiF.

10. VSEPR Theory

Lewis concept doesn’t explain the shape of molecule. Sidwick & Powell proposed a theory based on the
repulsive interactions of the electrons pairs in the valence shell of the atoms.
 Shape of molecule depends upon the number of valence shell electron pairs (bonded or non-
bonded) around the central atom.
 Pairs of electrons in the valence shell repel one another since their electron clouds are negatively
charged.
 These pairs of electrons tend to occupy such positions in space that minimize repulsion and thus
maximize distance between them
 The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone pair (lp) >
Lone pair (lp) – Bond pair (bp) > Bond pair (bp) –Bond pair (bp)

Geometry of Molecules on the basis of VSEPR Theory

Bond pair Lone pair Shape Examples
2 0 Linear BeCl2
3 0 Trigonal Planar BCl3
2 1 Bent SO2
4 0 Tetrahedral CH4
3 1 Pyramidal NH3, ,PH3,
2 2 V-shape H2O
5 0 Trigonal bipyramidal PCl5
4 1 See saw SF4
3 2 T-shaped CIF3,
2 3 Linear XeF2
5 1 Square pyramidal CIF5, IF5
4 2 Square planar XeF4,
6 1 Distorted Octahedral XeF6

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 Lewis theory fails to explain the formation of chemical bond and the geometry of different
molecules.
 It doesn’t explain the difference in bond length and bond dissociation enthalpy of similar
molecules. Ex: Bond length and bond dissociation enthalpy of H2 &F2 are different even though both
are linked by single covalent bond.
 VSEPR gives geometry of simple molecules theoretically but fails to explain the formation.
To overcome these limitations two important theories are introduced, they are Valence Bond Theory
& Molecular Orbital Theory.

11. Valence bond theory

By Heitler and London

Principle:
1. Overlap of atomic orbitals
2. Hybridisation of atomic orbitals
Formation of H2
H (g) + H (g) H2 (g) - 435.8KJ/mol
Energy of H2 < H when atoms approach each other
1) Nucleus of one atom is attracted towards the electron of its own and the electron of the
other. E is released here.
2) Nuclei of the atoms repel each other and electrons of two atoms also repel each other.
Energy is needed to overcome the force of repulsion.
Magnitude of attractive f > repulsive f. Therefore a bond or a molecule is formed.
When 2 hydrogen atoms approach each other energy is decreased and a point is reached where
minimum energy is attained and attractive, repulsive f balance each other. There the stable H2 is
formed where 2 hydrogen atoms are bonded. Bond length 74pm

74pm

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 Therefore in the formation of H2; 1s orbital of hydrogen atom overlap with 1s orbital of
another hydrogen atom.

+
435.8 KJ/mol energy is released when a bond is formed between two hydrogen atoms.
12. Types of overlapping and nature of covalent bond
Sigma bond(σ ) Pi bond(π)
Bond is formed by the axial overlap Bond is formed by the side wise overlap.
Ex: s-s overlap, px-px overlap Ex: py-py,pz-pz overlap
Extent of overlap is more Less
Strong bond Weak bond
Only one lobe of p- orbital is involved in
Both lobes of p-orbitals are involved
the overlap
Electron cloud is symmetrical about 2 electron clouds, one above and below the
inter-nuclear axis inter nuclear axis
Free rotation about the bond is possible Free rotation about the bond is not possible

A multiple bond consists of both sigma bond and pi bond ( double bond consists of one
sigma and one pi bond triple bond consists one sigma and two pi bonds

13. Hybridization: It can be defined as the process of intermixing of the orbitals of slightly
different energies so as to redistribute their energies, resulting in the formations of new set of
orbitals of equivalent energies and shape.

Salient Features of hybridization:

• The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
• The hybridised orbitals are always equivalent in energy and shape.
• The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
• These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement.

Conditions of hybridization
• Valence orbital is involved
• Orbitals undergoing hybridization should have almost equal energy
• Promotion of electron is not an essential condition prior to hybridization
• Even filled orbital can take part in hybridization.

14. Types of Hybridisation

 sp hybridisation- This type of hybridisation involves the mixing of one s and one p
orbital resulting in the formation of two equivalent sp hybrid orbitals Shape: linear.
Bond angle:1800.e.g.BeCl2.
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 BeCl2 : Be has the ground state configuration as 1s22s2. In the excited state one of the 2s
electron is promoted to 2p orbitals. One 2s and 2p orbital of excited Be atom undergo
hybridization to form two sp-hybridise orbitals. The two sp- hybridized orbitals are linear and
oriented in opposite directions at an angle of 1800. Each of the sp- hybridized orbital overlaps
with p orbital of Cl atom to form two Be-Cl sigma bonds. Due to sp hybridization it has
linear shape. ( refer diagram in the text book)
Acetylene(C2H2) : C(g.s): 1s22s22p2 C(e.s) : 1s2 2s1 2p3
Both carbon atoms in acetylene (ethyne) assume sp-hybrid state. In acquiring sp-hybrid state,
one 2s orbital and one 2p orbital excited C atom(1s22s12px12py12pz1) get hybridized to form two
sp-hybridised orbitals. The two sp- hybridized orbitals are linear and oriented in opposite
directions at an angle of 1800. C atom uses its one of the sp-hybrid orbital for overlapping with
similar orbital of the other C atom to form C-C sigma bond. The other sp- hybrid orbital of each
C atom overlaps axially with 1s orbital of H atom to form C-H sigma bond. Each of the two
unhybridised orbitals of both the C atoms overlap side ways to from two π bonds. ( refer diagram
in the text book)

 sp2 hybridisation- C(g.s): 1s22s22p2 C(e.s) : 1s2 2s1 2p3
In this hybridisation there is the involvement of one s and two p-orbitals in order to form
three equivalent sp2 hybridised orbitals. Shape: Trigonal planar. Bond angle: 1200
e.g.BCl3
BCl3: B has ground state configuration 1s22s2 2p1x . B (excited state)- 1s22s1 2p1x2p1y. 
One 2s and two 2p orbitals of B hybridise to form 3 sp2 hybrid orbitals which form a
trigonal planar structure of 1200. Each sp2 orbital overlap with p orbital of F to form 3 B-F
sigma bonds.
Ethylene(C2H4): C(g.s): 1s22s22p2 C(e.s) : 1s2 2s1 2p3
Both C atoms in ethylene assume sp2 hybrid state. In acquiring sp2hybrid state, one 2s
and two 2p orbitals of excited C atom get hybridized to form three sp2 hybridised orbitals.
However one 2p orbital does not take part in hybridisation. One of the sp2 hybrid orbital
of C atom overlaps axially with similar orbital of the other C atom to form C-C σ bond.
The other two sp2 hybrid orbitals of each C atom overlap with 1s orbital of H atom
forming sp2 –s σ bond with two H atoms.. The unhybridised 2p-orbital of the two C
atoms overlap sideways to form a π bond.
The Bond angle: H-C-C:1210. H-C-H :117.50
 sp3 hybridisation- C(g.s): 1s22s22p2 C(e.s) : 1s2 2s1 2p3
When there is mixing of one s and three p-orbitals of the valence shell to form four sp3
hybrid orbitals of equivalent energies and shape. Shape: tetrahedral. Bond angle: 109.50
e.g.CH4
CH4:Here one 2s and three 2p orbital of excited C atom undergo hybridization to form 4sp3
hybrid orbitals directed towards the corners of a regular tetrahedron making angle of
109.50. Each sp3hybrid orbital overlap with 1s orbital of H atom forming 4 sp3-s σ bonds.
 In NH3. Hybridisation :sp3 but bond angle: 1070. Reason: reduce the repulsion between
lone pair and bond pair molecule get distorted and bond angle reduced to 1070
 In H2O: Hybridisation: sp3 but bond angle: 104.50. Reason: It contains 2 lone pairs of
electrons. Lone pair lone pair repulsion is more than lone bond pair. To reduce the
repulsion between lone pair and lone pair and lone pair and bond pair molecule get
distorted and bond angle get reduced to 104.50.
Explain the hybridization in ethane?

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  sp3d hybridization- When there is mixing of one s, three p-orbitals and one d of the
valence shell to form five sp3d hybrid orbitals of equivalent energies and shape. Shape:
trigonal bipyramidal. Bond angle: 1200 & 900 e.g.PCl5
PCl5 : P(g.s) :1s22s22p63s23p3.
P(e.s) : 1s22s22p63s13p33d1.
Now 5 orbitals one 3s ,three 3p and one 3d undergo hybridization to form five sp 3d hybrid
orbitals which point towards the five corners of a trigonal bipyramid.
Each of the five sp3dhybrid orbital overlap with p orbital of 5 Cl atoms to form 5 P-Cl σ
bonds. Three of the five P-Cl bonds lie in one plane at an angle 1200. These are called as
equatorial bonds. The other two P-Cl bonds are at right angles to equatorial bonds ( one
above and the other below the plane) called axial bonds making an angle 900 . As axial
bonds suffer more repulsive interaction, therefore axial P-Cl bonds are slightly longer.
 sp3d2 hybridization- When there is mixing of one s, three p-orbitals and two d of the
valence shell to form six sp3d2 hybrid orbitals of equivalent energies and shape. Shape:
octahedral. Bond angle: 900 e.g.SF6
SF6 : S(g.s) : 1s22s22p63s23p4
S(e.s) : 1s22s22p63s13p33d2.
Now 6 orbitals one 3s ,three 3p and two 3d undergo hybridization to form six sp3d2 hybrid
orbitals which form octahedral geometry.
Each of the six sp3d2hybrid orbital overlap with p orbital of 6 F atoms to form 6 S-F σ
bonds. (Refer notes on hybridization)
Explain the formation of square pyramidal BrF5 molecule.

15. Molecular orbital.In an atom electrons are present in different energy level. They represent the
probability of finding electrons around an atom. This observation led to the development of molecular
orbital theory by F Fund & R S Mulliken. They postulated that electrons in a molecule exist in
different energy which represent the probability of finding electrons around the molecule. It gives
electron probability distribution around a group of nuclei in a molecule. They are filled in the same
way as atomic orbitals. Molecular orbitals are formed by linear combination of atomic orbitals.
Atoms are monocentric: Electrons in an atom are influenced by only one nuclei.
Molecule is polycentric: Electrons in a molecule are influenced by more than one nuclei.
For atomic orbital to combine to form molecular orbital, they must have similar energy and
symmetry. ie. If 2px of one atom has energy equal to 2py of another atom, they can’t combine because
they don’t have same symmetry.
No.of atomic orbitals combine = No.of molecular orbitals formed.
Electrons in molecular orbitals are filled in accordance with Aufbau principle, Pauli’s Exclusion
Principle &Hund’s Rule.

16. Bonding molecular orbital. A molecular orbital that is formed by addition overlap (i.e., when the
lobes of atomic orbitals overlap with the same sign) or constructive interference of two atomic orbitals
is known as bonding molecular orbital. It is represented as
MO A B Its energy is lower than the atomic orbitals from which it is formed. It
stabilizes the bond and favours bonding.It increases the electron density in the space between the
nuclei of atomic orbitals. It is represented by σ & π.
17.Anti-bonding molecular orbital. A molecular orbital that is obtained by the subtraction overlap (i.e.,
when the lobes of atomic orbitals overlap with the opposite sign) or destructive interference of two
atomic orbitals is known as anti-bonding molecular orbital. It is represented as

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 * MO A B Its energy is higher than the atomic orbitals from which it is formed. It
destabilizes the molecule and does nt not favour bonding. The electron density is less (nodal
plane) between the nuclei of the combined atomic orbitals. It is represented by σ* & π*.
18.Bond order. It is defined as half of the difference between number of electrons in bonding and
anti-bonding orbitals, i.e., B.O. = ½ (Nb – Na) ‗where Nb are number of electrons in bonding
orbitals‘ and Na are number of electrons in anti-bonding orbitals. Bond order helps in estimating
stability of atom.

19.Relationship between electronic configuration and molecular behaviour :

(a) If Nb is greater than Na, the molecule is stable.
(b) The molecule is unstable if Na is greater than Nb.
(c) The molecule is also unstable if Na is equal to Nb because anti-bonding effect is stronger than
bonding effect.

20. Conditions for the Combination of Atomic Orbitals. The linear combination of atomic
orbitals takes place only if the following conditions are satisfied :
(i) The combining atomic orbitals must have same or nearly same energy.
(ii) The combining atomic orbitals must have the same symmetry about the molecular axis. By
convention, x-axis is taken as the molecular axis.
(iii) The combining atomic orbitals must overlap to the maximum extent. Greater the extent of
overlapping, the greater will be electron density between the nuclei of a molecular orbital.

21. Energy level Diagrams for Molecular Orbitals. The increasing order of energies of various
molecular orbitals for O2 and F2 is given below.

However, this sequence of energy levels of molecular orbitals is not correct for remaining
molecules Li2, Be2, B2, C2, N2. For instance, it has been observed experimentally that for
molecules such as B2, C2, N2 etc., the increasing order of energies of various molecular
orbitals is

1s   *1s   2s   *2s   2pz   2 py   2 px   *2 Py=π*2pz<σ*2px

22. Hydrogen bonding: The attractive force which binds hydrogen of one molecule with
electronegative atom (F, O, N) of another. It’s weaker than covalent bond and stronger
than Vander Waal’s force. It is maximum in solid and minimum in the gaseous state.

Give reason: ice has lower density than water.

In case of solid ice, the H-bonding give rise to an open cage like structure and each
molecule is linked tetrahedrally. Therefore molecules are not so closely packed as they
are in the liquid state. When ice melts, this cage like structure collapses and the
molecules come close to each other. Thus the same mass of water, volume decreases and
density increases.

Give reason water has maximum density at 277K.

On heating ice, the H-bonds collapse resulting in decrease of volume and increase of
density. This goes up to 277K. After 277K, the increase in volume due to expansion of
liquid water becomes more than the decrease in volume due to breaking of H- bonds.
Thus after 277K, there is a net increase in volume and decrease in density.
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