Chemical Bonding and Molecular

Structure Class 11 Notes Chemistry

Chapter 4
January 19, 2024 by Bhagya

Next
Stay

Chemical Bonding and Molecular Structure Class

11 Notes Chemistry Chapter 4
• Chemical Bond
The force that holds different atoms in a molecule is called chemical bond.
• Octet Rule
Atoms of different elements take part in chemical combination in order to complete their octet or
to attain the noble gas configuration.
• Valence Electrons
It is the outermost shell electron which takes part in chemical combination.
• Facts Stated by Kossel in Relation to Chemical Bonding
— In the periodic table, the highly electronegative halogens and the highly electro-positive alkali
metals are separated by noble gases.
— Formation of an anion and cation by the halogens and alkali metals are formed by gain of
electron and loss of electron respectively.
— Both the negative and positive ions acquire the noble gas configuration.
— The negative and positive ions are stabilized by electrostatic attraction Example,

• Modes of Chemical Combination

— By the transfer of electrons: The chemical bond which formed by the complete transfer of
one or more electrons from one atom to another is termed as electrovalent bond or ionic bond.
— By sharing of electrons: The bond which is formed by the equal sharing of electrons between
one or two atoms is called covalent bond. In these bonds electrons are contributed by both.
— Co-ordinate bond: When the electrons are contributed by one atom and shared by both, the
bond is formed and it is known as dative bond or co-ordinate bond.
• Ionic or Electrovalent Bond
Ionic or Electrovalent bond is formed by the complete transfer of electrons from one atom to
another. Generally, it is formed between metals and non-metals. We can say that it is the
electrostatic force of attraction which holds the oppositely charged ions together.
The compounds which is formed by ionic or electrovalent bond is known as electrovalent
compounds. For Example, ,
(i) NaCl is an electrovalent compound. Formation of NaCl is given below:

Na+ ion has the configuration of Ne while Cl– ion represents the configuration of Ar.
(ii) Formation of magnesium oxide from magnesium and oxygen.

Electrovalency: Electrovalency is the number of electrons lost or gained during the formation of
an ionic bond or electrovalent bond.
• Factors Affecting the Formation of Ionic Bond
(i) Ionization enthalpy: As we know that ionization enthalpy of any element is the amount of
energy required to remove an electron from outermost shell of an isolated gaseous atom to
convert it into cation.
Hence, lesser the ionization enthalpy, easier will be the formation of a cation and have greater
chance to form an ionic bond. Due to this reason alkali metals have more tendency to form an
ionic bond.
For example, in formation of Na+ ion I.E = 496 kJ/mole
While in case of magnesium, it is 743 kJ/mole. That’s why the formation of positive ion for
sodium is easier than that of magnesium.
Therefore, we can conclude that lower the ionization enthalpy, greater the chances of ionic
bond formation.
(ii) Electron gain enthalpy (Electron affinities): It is defined as the energy released when an
isolated gaseous atom takes up an electron to form anion. Greater the negative electron gain
enthalpy, easier will be the formation of anion. Consequently, the probability of formation of
ionic bond increases.
For example. Halogens possess high electron affinity. So, the formation of anion is very
common in halogens.

(iii) Lattice energy or enthalpy: It is defined as the amount of energy required to separate 1 mole
of ionic compound into separate oppositely charged ions.
Lattice energy of an ionic compound depends upon following factors:
(i) Size of the ions: Smaller the size, greater will be the lattice energy.
(ii) Charge on the ions: Greater the magnitude of charge, greater the interionic attraction and
hence higher the lattice energy.
• General Characteristics of ionic Compounds
(i) Physical’State: They generally exist as crystalline solids, known as crystal lattice. Ionic
compounds do not exist as single molecules like other gaseous molecules e.g., H2 , N2 , 02 ,
Cl2 etc.
(ii) Melting and boiling points: Since ionic compounds contain high interionic force between
them, they generally have high melting and boiling points.
(iii) Solubility: They are soluble in polar solvents such as water but do not dissolve in organic
solvents like benzene, CCl4etc.
(iv) Electrical conductivity: In solid state they are poor conductors of electricity but in molten
state or when dissolved in water, they conduct electricity.
(v) Ionic reactions: Ionic compounds produce ions in the solution which gives very fast reaction
with oppositely charged ions.
For example,

• Covalent Bond—Lewis-Langmuir Concept

When the bond is formed between two or more atoms by mutual contribution and sharing of
electrons, it is known as covalent bond.
If the combining atoms are same the covalent molecule is known as homoatomic. If they are
different, they are known as heteroatomic molecule.
For Example,
• Lewis Representation of Simple Molecules (the Lewis Structures)
The Lewis dot Structure can be written through the following steps:
(i) Calculate the total number of valence electrons of the combining atoms.
(ii) Each anion means addition of one electron and each cation means removal of one electron.
This gives the total number of electrons to be distributed.
(iii) By knowing the chemical symbols of the combining atoms.
(iv) After placing shared pairs of electrons for single bond, the remaining electrons may account
for either multiple bonds or as lone pairs. It is to be noted that octet of each atom should be
completed.

• Formal Charge
In polyatomic ions, the net charge is the charge on the ion as a whole and not by particular
atom. However, charges can be assigned to individual atoms or ions. These are called formal
charges.
It can be expressed as
• Limitations of the Octet Rule
(i) The incomplete octet of the central atoms: In some covalent compounds central atom has
less than eight electrons, i.e., it has an incomplete octet. For example,

Li, Be and B have 1, 2, and 3 valence electrons only.

(ii) Odd-electron molecules: There are certain molecules which have odd number of electrons
the octet rule is not applied for all the atoms.

(iii) The expanded Octet: In many compounds there are more than eight valence electrons
around the central atom. It is termed as expanded octet. For Example,

• Other Drawbacks of Octet Theory

(i) Some noble gases, also combine with oxygen and fluorine to form a number of compounds
like XeF2 , XeOF2 etc.
(ii) This theory does not account for the shape of the molecule.
(iii) It does not give any idea about the energy of The molecule and relative stability.
• Bond Length
It is defined as the equilibrium distance between the centres of the nuclei of the two bonded
atoms. It is expressed in terms of A. Experimentally, it can be defined by X-ray diffraction or
electron diffraction method.

• Bond Angle
It is defined as -the angle between the lines representing the orbitals containing the bonding –
electrons.
It helps us in determining the shape. It can be expressed in degree. Bond angle can be
experimentally determined by spectroscopic methods.
• Bond Enthalpy
It is defined as the amount of energy required to break one mole of bonds of a particular type to
separate them into gaseous atoms.
Bond Enthalpy is also known as bond dissociation enthalpy or simple bond enthalpy. Unit of
bond enthalpy = kJ mol-1
Greater the bond enthalpy, stronger is the bond. For e.g., the H—H bond enthalpy in hydrogen
is 435.8 kJ mol-1.
The magnitude of bond enthalpy is also related to bond multiplicity. Greater the bond
multiplicity, more will be the bond enthalpy. For e.g., bond enthalpy of C —C bond is 347 kJ
mol-1 while that of C = C bond is 610 kJ mol-1.
In polyatomic molecules, the term mean or average bond enthalpy is used.
• Bond Order
According to Lewis, in a covalent bond, the bond order is given by the number of bonds
between two atoms in a molecule. For example,
Bond order of H2 (H —H) =1
Bond order of 02 (O = O) =2
Bond order of N2 (N = N) =3
Isoelectronic molecules and ions have identical bond orders. For example, F2 and O22- have
bond order = 1. N2, CO and NO+ have bond order = 3. With the increase in bond order, bond
enthalpy increases and bond length decreases. For example,

• Resonance Structures
There are many molecules whose behaviour cannot be explained by a single-Lew is structure,
Tor example, Lewis structure of Ozone represented as follows:
Thus, according to the concept of resonance, whenever a single Lewis structure cannot explain
all the properties of the molecule, the molecule is then supposed to have many structures with
similar energy. Positions of nuclei, bonding and nonbonding pairs of electrons are taken as the
canonical structure of the hybrid which describes the molecule accurately. For 03, the two
structures shown above are canonical structures and the III structure represents the structure of
03 more accurately. This is also called resonance hybrid.
Some resonating structures of some more molecules and ions are shown as follows:

• Polarity of Bonds
Polar and Non-Polar Covalent bonds
Non-Polar Covalent bonds: When the atoms joined by covalent bond are the same like; H2, 02,
Cl2, the shared pair of electrons is equally attracted by two atoms and thus the shared electron
pair is equidistant to both of them.
Alternatively, we can say that it lies exactly in the centre of the bonding atoms. As a result, no
poles are developed and the bond is called as non-polar covalent bond. The corresponding
molecules are known as non-polar molecules.
For Example,
Polar bond: When covalent bonds formed between different atoms of different electronegativity,
shared electron pair between two atoms gets displaced towards highly electronegative atoms.
For Example, in HCl molecule, since electronegativity of chlorine is high as compared to
hydrogen thus, electron pair is displaced more towards chlorine atom, thus chlorine will acquire
a partial negative charge (δ–) and hydrogen atom have a partial positive charge (δ+) with the
magnitude of charge same as on chlorination. Such covalent bond is called polar covalent
bond.

• Dipole Moment
Due to polarity, polar molecules are also known as dipole molecules and they possess dipole
moment. Dipole moment is defined as the product of magnitude of the positive or negative
charge and the distance between the charges.

• Applications of Dipole Moment

(i) For determining the polarity of the molecules.
(ii) In finding the shapes of the molecules.
For example, the molecules with zero dipole moment will be linear or symmetrical. Those
molecules which have unsymmetrical shapes will be either bent or angular.
(e.g., NH3with μ = 1.47 D).
(iii) In calculating the percentage ionic character of polar bonds.
• The Valence Shell Electron Pair Repulsion (VSEPR) Theory
Sidgwick and Powell in 1940, proposed a simple theory based on repulsive character of
electron pairs in the valence shell of the atoms. It was further developed by Nyholm and
Gillespie (1957).
Main Postulates are the following:
(i) The exact shape of molecule depends upon the number of electron pairs (bonded or non
bonded) around the central atoms.
(ii) The electron pairs have a tendency to repel each other since they exist around the central
atom and the electron clouds are negatively charged.
(iii) Electron pairs try to take such position which can minimize the rupulsion between them.
(iv) The valence shell is taken as a sphere with the electron pairs placed at maximum distance.
(v) A multiple bond is treated as if it is a single electron pair and the electron pairs which
constitute the bond as single pairs.
• Valence Bond Theory
Valence bond theory was introduced by Heitler and London (1927) and developed by Pauling
and others. It is based on the concept of atomic orbitals and the electronic configuration of the
atoms.
Let us consider the formation of hydrogen molecule based on valence-bond theory.
Let two hydrogen atoms A and B having their nuclei NA and NB and electrons present in them
are eA and eB .
As these two atoms come closer new attractive and repulsive forces begin to operate.
(i) The nucleus of one atom is attracted towards its own electron and the electron of the other
and vice versa.
(ii) Repulsive forces arise between the electrons of two atoms and nuclei of two atoms.
Attractive forces tend to bring the two atoms closer whereas repulsive forces tend to push them
apart.
• Orbital Overlap Concept
According to orbital overlap concept, covalent bond formed between atoms results in the
overlap of orbitals belonging to the atoms having opposite spins of electrons. Formation of
hydrogen molecule as a result of overlap of the two atomic orbitals of hydrogen atoms is shown
in the figures that follows:

Stability of a Molecular orbital depends upon the extent of the overlap of the atomic orbitals.
• Types of Orbital Overlap
Depending upon the type of overlapping, the covalent bonds are of two types, known as sigma
(σ ) and pi (π) bonds.
(i) Sigma (σ bond): Sigma bond is formed by the end to end (head-on) overlap of bonding
orbitals along the internuclear axis.
The axial overlap involving these orbitals is of three types:
• s-s overlapping: In this case, there is overlap of two half-filled s-orbitals along the
internuclear axis as shown below:

• s-p overlapping: This type of overlapping occurs between half-filled s-orbitals of one atom
and half filled p-orbitals of another atoms.
• p-p overlapping: This type of overlapping takes place between half filled p-orbitals of the two
approaching atoms.

(ii) pi (π bond): π bond is formed by the atomic orbitals when they overlap in such a way that
their axes remain parallel to each other and perpendicular to the internuclear axis.The orbital
formed is due to lateral overlapping or side wise overlapping.

• Strength of Sigma and pf Bonds

Sigma bond (σ bond) is formed by the axial overlapping of the atomic orbitals while the π-bond
is formed by side wise overlapping. Since axial overlapping is greater as compared to side wise.
Thus, the sigma bond is said to be stronger bond in comparison to a π-bond.
Distinction between sigma and n bonds
• Hybridisation
Hybridisation is the process of intermixing of the orbitals of slightly different energies so as to
redistribute their energies resulting in the formation of new set of orbitals of equivalent energies
and shape.
Salient Features of Hybridisation:
(i) Orbitals with almost equal energy take part in the hybridisation.
(ii) Number of hybrid orbitals produced is equal to the number of atomic orbitals mixed,
(iii) Geometry of a covalent molecule can be indicated by the type of hybridisation.
(iv) The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
Conditions necessary for hybridisation:
(i) Orbitals of valence shell take part in the hybridisation.
(ii) Orbitals involved in hybridisation should have almost equal energy.
(iii) Promotion of electron is not necessary condition prior to hybridisation.
(iv) In some cases filled orbitals of valence shell also take part in hybridisation.
Types of Hybridisation:
(i) sp hybridisation: When one s and one p-orbital hybridise to form two equivalent orbitals, the
orbital is known as sp hybrid orbital, and the type of hybridisation is called sp hybridisation.
Each of the hybrid orbitals formed has 50% s-characer and 50%, p-character. This type of
hybridisation is also known as diagonal hybridisation.

(ii) sp2 hybridisation: In this type, one s and two p-orbitals hybridise to form three equivalent
sp2 hybridised orbitals.
All the three hybrid orbitals remain in the same plane making an angle of 120°. Example. A few
compounds in which sp2 hybridisation takes place are BF3, BH3, BCl3 carbon compounds
containing double bond etc.
(iii) sp3 hybridisation: In this type, one s and three p-orbitals in the valence shell of an atom get
hybridised to form four equivalent hybrid orbitals. There is 25% s-character and 75% p-
character in each sp3 hybrid orbital. The four sp3 orbitals are directed towards four corners of the
tetrahedron.

The angle between sp3 hybrid orbitals is 109.5°.

A compound in which sp3 hybridisation occurs is, (CH4). The structures of NH2 and H20
molecules can also be explained with the help of sp3 hybridisation.
• Formation of Molecular Orbitals: Linear Combination of Atomic Orbitals (LCAO)
The formation of molecular orbitals can be explained by the linear combination of atomic
orbitals. Combination takes place either by addition or by subtraction of wave function as shown
below.
The molecular orbital formed by addition of atomic orbitals is called bonding molecular orbital
while molecular orbital formed by subtraction of atomic orbitals is called antibonding molecular
orbital.
Conditions for the combination of atomic orbitals:
(1) The combining atomic orbitals must have almost equal energy.
(2) The combining atomic orbitals must have same symmetry about the molecular axis.
(3) The combining atomic orbitals must overlap to the maximum extent.
• Types of Molecular Orbitals
Sigma (σ) Molecular Orbitals: They are symmetrical around the bond-axis.
pi (π) Molecular Orbitals: They are not symmetrical, because of the presence of positive lobes
above and negative lobes below the molecular plane.
• Electronic configuration and Molecular Behaviour
The distribution of electrons among various molecular orbitals is called electronic configuration
of the molecule.
• Stability of Molecules

• Bond Order
Bond order is defined as half of the difference between the number of electrons present in
bonding and antibonding molecular orbitals.
Bond order (B.O.) = 1/2 [Nb-Na]
The bond order may be a whole number, a fraction or even zero.
It may also be positive or negative.
Nature of the bond: Integral bond order value for single double and triple bond will be 1, 2 and
3 respectively.
Bond-Length: Bond order is inversely proportional to bond-length. Thus, greater the bond
order, smaller will be the bond-length.
Magnetic Nature: If all the molecular orbitals have paired electrons, the substance is
diamagnetic. If one or more molecular orbitals have unpaired electrons, it is paramagnetic e.g.,
02 molecule.
• Bonding in Some Homonuclear (Diatomic) Molecules
(1) Hydrogen molecule (H2): It is formed by the combination of two hydrogen atoms. Each
hydrogen atom has one electron in Is orbital, so, the electronic configuration of hydrogen
molecule is

This indicates that two hydrogen atoms are bonded by a single covalent bond. Bond
dissociation energy of hydrogen has been found = 438 kJ/mole. Bond-Length = 74 pm
No unpaired electron is present therefore,, it is diamagnetic.
(2) Helium molecule (He2): Each helium atom contains 2 electrons, thus in He2 molecule there
would be 4 electrons.
The electrons will be accommodated in σ1s and σ*1s molecular orbitals:
• Hydrogen Bonding
When highly electronegative elements like nitrogen, oxygen, flourine are attached to hydrogen
to form covalent bond, the electrons of the covalent bond are shifted towards the more
electronegative atom. Thus, partial positive charge develops on hydrogen atom which forms a
bond with the other electronegative atom. This bond is known as hydrogen bond and it is
weaker than the covalent bond. For example, in HF molecule, hydrogen bond exists between
hydrogen atom of one molecule and fluorine atom of another molecule.
It can be depicted as

• Types of H-Bonds
(i) Intermolecular hydrogen bond (ii) Intramolecular hydrogen bond.
(i) Intermolecular hydrogen bond: It is formed between two different molecules of the same
or different compounds. For Example, in HF molecules, water molecules etc.
(ii) Intramolecular hydrogen bond: In this type, hydrogen atom is in between the two highly
electronegative F, N, O atoms present within the same molecule. For example, in o-nitrophenol,
the hydrogen is in between the two oxygen atoms.