BASIC CONCEPTS OF BONDING

CHEMICAL BONDING:
DEFINITION: The attractive force that holds various constituents(atoms, ions)
together and stabilize them is called chemical bonding.
Therefore, Chemical compounds are reliant on strength of chemical bonds
between their constituents, Stronger the bonding between the constituents, the
more stable the resulting compound will be.
TYPES OF CHEMICAL BONDING:
Chemical bonding may be:
1.Intramolecular bonding
2.Intermolecular bonding

Intramolecular bonding refers to the bonds that hold atoms together within a
molecule.
The main types of intramolecular bonding are:

1. Covalent Bonds: Covalent bonds involve the sharing of electrons between

atoms to achieve a stable electron configuration. These bonds are typically found
in molecules composed of nonmetal atoms.
EXAMPLE: In a hydrogen molecule, two hydrogen atoms share a pair of electrons
to form a covalent bond. Each hydrogen atom contributes one electron to the
shared pair, resulting in a stable molecule.

2. Ionic Bonds: Ionic bonds are formed when one or more electrons are
transferred from one atom to another, resulting in the formation of positively and
negatively charged ions that are held together by electrostatic forces.
EXAMPLE: Sodium chloride, commonly known as table salt, is a classic example of
an ionic compound. In this compound, sodium (Na) forms a cation with a +1
charge, and chlorine (Cl) forms an anion with a -1 charge. The electrostatic
attraction between the positively charged sodium ions and the negatively charged
chloride ions holds the compound together.

3. Metallic Bonds: Metallic bonds occur in metals, where metal atoms share a sea
of delocalized electrons. This bonding results in the formation of a lattice structure
held together by the electrostatic attraction between the positive metal ions and
the delocalized electrons.
EXAMPLE: In copper, metallic bonding occurs between the positively charged
copper ions (Cu^2+) and the delocalized electrons that are free to move
throughout the metal lattice.

Intermolecular bonding refers to the attractive forces that exist between

molecules, holding them together in a substance. The main types of
intermolecular forces are:
1. Hydrogen bonding: Hydrogen bonding is a special type of interaction that
occurs when a hydrogen atom bonded to an electronegative atom (such as
oxygen, nitrogen, or fluorine) is attracted to a lone pair of electrons on
another electronegative atom.
2. London dispersion forces: These are the weakest type of van der Waals
forces, resulting from temporary fluctuations in electron distribution within
molecules, leading to temporary dipoles.
3. Dipole dipole interactions: Dipole-dipole interactions occur between polar
molecules, where the positive end of one polar molecule is attracted to the
negative end of another polar molecule.

LOCALIZED AND DELOCALIZED BONDING:

Localized bonding: Localized chemical bonds are normal sigma and pi

bonds or lone electron pairs that exist on a single atom. These bonds are
concentrated on a limited region of a molecule. These regions have a
concentrated electron distribution. In other words, the electron density of this
region is very high.
Examples: Examples of localized bonding include:
1. Covalent Bonds: Covalent bonds are formed by the sharing of electrons
between atoms. Each atom contributes one or more electrons to the
shared pair, resulting in the formation of localized bonds.
For example, in methane (CH4), each hydrogen atom shares a pair of
electrons with the carbon atom, forming four localized covalent bonds.

2. Ionic Bonds: Ionic bonds are formed by the transfer of electrons from one
atom to another, resulting in the formation of positively and negatively
charged ions that are held together by electrostatic attraction. While the
overall structure of the compound may involve ions interacting with each
other, the bonding within each ion is localized.
3. Hydrogen Bonds: Hydrogen bonds are a type of non-covalent interaction
between a hydrogen atom bonded to an electronegative atom (e.g.,
nitrogen, oxygen, or fluorine) and a nearby electronegative atom. These
bonds are localized between specific pairs of atoms and contribute to the
stability of molecules, such as in water (H2O) and DNA base pairs.

In these types of localized bonding, the resulting molecules or compounds are

held together by strong forces of attraction between the atoms involved in the
bond. These bonds contribute to the overall stability and properties of the
molecules or compounds and determine their chemical behavior and
reactivity. Additionally, localized bonding plays a crucial role in determining
the physical properties of substances, such as melting and boiling points,
solubility, and conductivity.

Delocalized bonding:
Delocalised chemical bonds are the chemical bonds that do not associate with
only a single atom but with several atoms or other chemical bonds. We call the
electrons in these bonds as ‘delocalised electrons’. Delocalization occurs in the
conjugated pi system. A conjugated pi system has double bonds and single
bonds in an alternating pattern.
One of the most common examples of delocalized bonding is found in
molecules or materials with pi (π) bonds, such as conjugated organic
compounds and aromatic hydrocarbons. In these molecules, pi electrons are
delocalized over multiple atoms in a conjugated system, leading to enhanced
stability and unique electronic properties.
EXAMPLES:
Conjugated Systems: In conjugated systems, such as polyenes or conjugated
dienes, alternating single and multiple bonds create a series of overlapping p-
orbitals along the chain of atoms. This allows the pi electrons to be delocalized
over the entire conjugated system, resulting in increased stability compared to
isolated double bonds. The delocalization of electrons in conjugated systems
also leads to unique optical and electronic properties, making them important
in organic chemistry and materials science.
The structure of 1,2butadiene is shown below:

Aromatic Compounds: Aromatic compounds, such as benzene and its

derivatives, exhibit a special type of delocalized bonding known as aromaticity.
In these molecules, the pi electrons are delocalized over a ring of carbon
atoms, forming a stable aromatic system. Aromatic compounds are
characterized by enhanced stability, high reactivity, and unique chemical
properties due to the delocalization of pi electrons.
The structure of benzene is shown below:
Metallic Bonding: Metallic bonding in metals is another example of
delocalized bonding. In metallic bonding, metal atoms contribute their valence
electrons to form a "sea" of delocalized electrons that are free to move
throughout the metal lattice. These delocalized electrons are responsible for
the high electrical and thermal conductivity, malleability, and ductility of
metals.

Overall, delocalized bonding plays a crucial role in determining the properties

and behavior of various molecular and solid-state systems. It contributes to
the stability, reactivity, and electronic properties of molecules and materials,
making it a fundamental concept in chemistry and materials science.

Following is the difference between localized and delocalized bonding:

ASPECT LOCALIZED BONDING DELOCALIZED BONDING

Bonding between Bonding where

specific atoms within a electrons are spread out
Definition molecule, where over a larger region
electrons are localized within a molecule or
between those atoms. material.

Covalent and Ionic Pi (π) Bonds and

Type of Bonds Bonds Metallic Bonds

Electrons are confined Electrons are not

to the space between confined to the space
Nature of electrons specific atoms involved between specific atoms
in the bond. Such but are spread out over
electrons are called multiple atoms or ions.
localized electrons. Such electrons are
called delocalized
electrons.
 Examples
H2O (Water), NaCl Benzene, Conjugated
(Sodium Chloride) Dienes, Metals

Generally low electrical Can exhibit high

Electrical conductivity conductivity electrical conductivity,
(ionic compounds especially in metals, due
conduct in molten and to the presence of
aqueous form) delocalized electrons.

Influences the reactivity Can significantly affect

Chemical reactivity of individual molecules the reactivity and
or compounds. chemical behavior of
molecules or materials
due to the presence of
delocalized electrons. |

Hybridization:
Definition: The phenomenon of mixing up of atomic orbitals of similar energies
and formation of equivalent number of entirely new orbitals of identical shape
and energy is known as "hybridization" and the new orbitals so formed is called as
"hybrid orbitals”

Principles of Hybridization:
- Hybridization involves the mixing of atomic orbitals to form new hybrid
orbitals.
- The number of hybrid orbitals formed is equal to the number of atomic
orbitals participating in the hybridization.
- Hybrid orbitals have shapes and energies that are intermediate between those
of the atomic orbitals from which they are formed.
- The type of hybridization is determined by the number of electron pairs and/or
bonds around the central atom in a molecule.
 Types of Hybridization:

(1) sp Hybridization: In sp hybridization, one s orbital and one p orbital

from the valence shell of an atom combine to form two sp hybrid
orbitals. Each sp hybrid orbital contains 50% s character and 50% p
character. Bond angle between sp hybrid orbitals is 180° and geometry is
linear.
This type of hybridization occurs in molecules where atoms have linear
geometry, such as in acetylene (C2H2).

2. sp2 Hybridization: In sp2 hybridization, one s orbital and two p

orbitals from the valence shell of an atom combine to form three sp2
hybrid orbitals. Each sp2 hybrid orbital contains 33.3% s character and
66.7% p character. Bond angle between sp2 hybrid orbitals is 120° and
geometry is Triangular Planar.

This type of hybridization occurs in molecules where atoms have

trigonal planar geometry, such as in ethene (C2H4).

3.sp3 Hybridization: In sp3 hybridization, one s orbital and three p

orbitals from the valence shell of an atom combine to form four sp3
hybrid orbitals. ach sp3 hybrid orbital contains 25% s character and 75%
p character. Bond angle between sp3 hybrid orbitals is usually 109.5 but
it may decreases to 107.5 or 104.5, depending upon presence of lone
pairs.
Geometry is Tetrahederal, but Pyramidal and Bent geometry also exists
in some molecules(due to presence of lone pair of electrons)
This type of hybridization occurs in molecules where atoms have
tetrahedral geometry, such as in methane (CH4).

(4) sp3d Hybridization: In sp3d hybridization, one s orbital, three p

orbitals, and one d orbital from the valence shell of an atom combine to
form five sp3d hybrid orbitals. This type of hybridization occurs in
molecules where atoms have trigonal bipyramidal geometry, such as in
phosphorus pentachloride (PCl5)

(5) sp3d2 Hybridization: In sp3d2 hybridization, one s orbital, three p

orbitals, and two d orbitals from the valence shell of an atom combine to
form six sp3d2 hybrid orbitals. This type of hybridization occurs in
molecules where atoms have octahedral geometry, such as in sulfur
hexafluoride (SF6).
(6) SP3D3 hybridization: This type of hybridization occurs when one s
orbital, three p orbitals (px, py, pz), and three d orbitals (dxy, dyz, dz2)
combine to form seven sp3d3 hybrid orbitals. This type of hybridization
is commonly observed in molecules with pentagonal bipyramidal or
distorted octahedral geometry, Such as iodine heptafluoride (IF7).

Importance of HYBRIDIZATION:

1. Predicting Molecular Geometry: Hybridization helps determine the

three-dimensional shapes of molecules.

2. Explaining Bonding Properties: It elucidates how atomic orbitals

combine to form hybrid orbitals, influencing bond angles and strengths.

3. Understanding Reactivity: Hybridization affects a molecule's reactivity

by influencing electron distribution.
4. Designing Molecules: Chemists use hybridization to engineer
molecules with desired properties for various applications.

5. Interpreting Spectroscopic Data: Hybridization influences molecular

spectroscopic properties, aiding in structural analysis.

6. Biological Systems: Understanding hybridization is crucial for

deciphering the structures and functions of biological molecules.