- Limitations
of Lewis Approach:
- Lewis
structures help in representing molecular structures but do not explain
the formation of chemical bonds.
- Lewis
structures cannot account for variations in bond dissociation enthalpies
and bond lengths in different molecules.
- Introduction
of Valence Bond (VB) Theory:
- Valence
Bond theory was developed by Heitler and London in 1927 and further
advanced by Linus Pauling and others.
- It
is based on quantum mechanical principles and aims to provide a deeper
understanding of chemical bonding.
- Atomic
Orbitals and Electronic Configurations:
- VB
theory relies on knowledge of atomic orbitals and the electronic
configurations of elements.
- Overlap
Criteria of Atomic Orbitals:
- In
VB theory, the formation of chemical bonds is explained by the overlap of
atomic orbitals of two atoms.
- Overlap
occurs when two atomic orbitals occupy the same region in space.
- Hybridization
of Atomic Orbitals:
- VB
theory incorporates the concept of hybridization, where atomic orbitals
mix to form new hybrid orbitals.
- Hybrid
orbitals have specific shapes and are used to explain molecular
geometries.
- Principles
of Variation and Superposition:
- VB
theory utilizes principles of variation and superposition to describe the
wave functions of electrons in molecules.
- Formation
of Hydrogen Molecule (H2):
- Consider
two hydrogen atoms, A and B, each with a nucleus (NA and NB) and an electron (eA and eB).
- Initially,
when the atoms are far apart, there is no interaction between them.
- Forces
at Play During Approach:
- As
the two atoms approach each other, attractive and repulsive forces come
into play.
- Attractive
forces include the attraction between a nucleus and its own electron and
the attraction between the nuclei of one atom and the electrons of the
other.
- Repulsive
forces arise from the electron-electron and nucleus-nucleus interactions.
- Net
Attractive Forces:
- Experimentally,
it's observed that the attractive forces become dominant as the atoms
approach each other.
- The
net force of attraction between the two atoms exceeds the repulsive
forces.
- Bond
Formation:
- At
a certain point, the net attractive force balances the repulsive force,
leading to a minimum potential energy.
- At
this stage, the two hydrogen atoms are bonded together to form a stable H2
molecule.
- The
distance at which this occurs is the bond length, which is about 74
picometers (pm) for H2.
- Bond
Enthalpy:
- Energy
is released when the H2 bond is formed, making the H2
molecule more stable than isolated hydrogen atoms.
- The
energy released during bond formation is known as bond enthalpy.
- For
H2, the bond enthalpy is 435.8 kJ/mol, which means 435.8 kJ of
energy is released when one mole of H2 molecules is formed.
- Conversely,
435.8 kJ of energy is required to dissociate one mole of H2 molecules
into individual hydrogen atoms.
Valence Bond theory provides a quantum mechanical
explanation for the formation of chemical bonds, using concepts like atomic
orbitals, hybridization, and attractive and repulsive forces to describe the
process of bond formation in molecules like H2.
Attractive Forces:
(i) Nucleus-Electron Attraction (NA - eA and
NB - eB):
- Attractive
forces arise due to the electrostatic attraction between the positively
charged nucleus of one atom (NA) and the negatively charged electron in
its own atomic orbital (eA).
- Similarly,
the nucleus of the other atom (NB) attracts its own electron
(eB).
- These
attractive forces originate from the fundamental electrostatic
interaction between opposite charges, where opposite charges attract
each other.
- These
forces tend to pull the electrons closer to the nuclei, promoting the
formation of a chemical bond.
(ii) Nucleus-Electron Attraction Across Atoms (NA - eB
and NB - eA):
- Attractive
forces also occur between the nucleus of one atom (NA) and
the electron of the other atom (eB), and vice versa (NB
- eA).
- Again,
this attraction arises from the electrostatic interaction between the
positively charged nucleus and the negatively charged electron, which
tend to be in close proximity.
- These
forces further encourage the two atoms to come closer together.
Repulsive Forces:
(i) Electron-Electron Repulsion (eA - eB):
- Repulsive
forces emerge from the electron-electron interaction, specifically
between the two electrons (eA and eB) from the two
approaching atoms.
- Electrons
are negatively charged particles, and like charges repel each other
according to Coulomb's law.
- When
electrons from different atoms come too close, they experience a strong
repulsion, preventing them from occupying the same space.
(ii) Nucleus-Nucleus Repulsion (NA - NB):
- Another
source of repulsion is the nucleus-nucleus interaction between the two
positively charged atomic nuclei (NA and NB).
- Similar
to electron-electron repulsion, like charges (positively charged nuclei)
also repel each other due to Coulomb's law.
- As the
two atoms approach each other closely, the repulsive force between their
nuclei becomes significant.
Net Effect:
- As
two atoms move closer to each other, both attractive and repulsive
forces come into play.
- Initially,
at large distances, the attractive forces dominate because they increase
with decreasing distance.
- However,
as the atoms get closer, the repulsive forces become stronger due to
electron-electron and nucleus-nucleus repulsions.
- At a
certain distance, a balance is reached where the net force of attraction
from the attractive forces equals the net force of repulsion from the
repulsive forces.
- At
this point of equilibrium, the potential energy of the system is
minimized, indicating the formation of a stable chemical bond between
the two atoms.
- This
bond length corresponds to the distance at which the atoms are held
together in a stable molecule.
The interplay between attractive forces (arising from
nucleus-electron and nucleus-nucleus attractions) and repulsive forces (due
to electron-electron and nucleus-nucleus repulsions) determines the distance
at which two atoms will form a chemical bond. The establishment of this
equilibrium distance leads to the formation of stable molecules with specific
bond lengths and geometries.
Top of Form
|
- Historical
Development:
- Valence
Bond theory was initially formulated by Walter Heitler and Fritz London
in 1927. It was further advanced by Linus Pauling and other scientists.
- This
theory emerged as a response to the limitations of Lewis structures in
explaining the nature of chemical bonds.
- Quantum
Mechanical Foundation:
- The
Valence Bond theory is firmly rooted in the principles of quantum
mechanics, which is the fundamental theory governing the behavior of
particles at the atomic and subatomic levels.
- Quantum
mechanics provides a rigorous framework for understanding the electronic
structure of atoms and molecules.
- Focus
on Electron Pairing:
- At
its core, VB theory is concerned with the behavior of electrons in the
formation of chemical bonds.
- It
emphasizes the concept of electron pairing, where two electrons with
opposite spins occupy the same region of space.
- Atomic
Orbitals and Electron Configuration:
- VB
theory utilizes the concept of atomic orbitals, which are regions of
space around the nucleus where electrons are likely to be found.
- It
relies on knowledge of the electronic configurations of atoms, which
describe how electrons are distributed in various atomic orbitals.
- Overlap
of Atomic Orbitals:
- A
key principle of VB theory is the overlap of atomic orbitals from
different atoms.
- When
two atoms approach each other in a molecule, their atomic orbitals can
overlap, leading to the sharing of electrons between the atoms.
- Bond
Formation by Electron Pairing:
- In
VB theory, chemical bonds are formed when two electrons, each from a
different atom, are paired together in a shared orbital.
- This
electron pairing represents the formation of a covalent bond, where electrons
are shared between atoms.
- Hybridization:
- VB
theory also introduces the concept of hybridization, where atomic
orbitals from the same atom mix to form new hybrid orbitals.
- These
hybrid orbitals have specific shapes and orientations that allow for effective
overlap with orbitals from other atoms, facilitating bond formation.
- Explanation
of Molecular Geometry:
- VB
theory helps explain the shapes and geometries of molecules based on the
arrangement of hybridized orbitals and the distribution of electron
pairs.
- It
provides insights into why molecules have specific bond angles and
shapes.
- Quantitative
Predictions:
- While
the introduction of VB theory here focuses on qualitative explanations,
it can be used for quantitative calculations, such as predicting bond
lengths and bond strengths.
- VB
theory calculations often involve complex mathematical equations based on
wave functions and quantum mechanical principles.
- Complementing
Molecular Orbital (MO) Theory:
- VB
theory is one of two major theories used to describe chemical bonding,
with the other being Molecular Orbital (MO) theory.
- These
two theories offer complementary perspectives on bonding, with VB theory
emphasizing the role of localized electron pairs and MO theory focusing
on the delocalization of electrons in molecular orbitals.
The Valence Bond theory is a foundational concept in
chemistry that provides a detailed understanding of chemical bonding at the
quantum mechanical level. It explains how electrons interact, overlap, and pair
to form chemical bonds, and it helps elucidate the structure and properties of
molecules. This theory, along with the Molecular Orbital theory, is essential
for comprehending the nature of chemical compounds and their behavior in
various chemical reactions.
Attractive Forces:
(i) Nucleus-Electron Attraction (NA - eA
and NB - eB):
- Attractive
forces arise due to the electrostatic attraction between the positively
charged nucleus of one atom (NA) and the negatively charged
electron in its own atomic orbital (eA).
- Similarly,
the nucleus of the other atom (NB) attracts its own electron (eB).
- These
attractive forces originate from the fundamental electrostatic interaction
between opposite charges, where opposite charges attract each other.
- These
forces tend to pull the electrons closer to the nuclei, promoting the
formation of a chemical bond.
(ii) Nucleus-Electron Attraction Across Atoms (NA
- eB and NB - eA):
- Attractive
forces also occur between the nucleus of one atom (NA) and the
electron of the other atom (eB), and vice versa (NB
- eA).
- Again,
this attraction arises from the electrostatic interaction between the
positively charged nucleus and the negatively charged electron, which tend
to be in close proximity.
- These
forces further encourage the two atoms to come closer together.
Repulsive Forces:
(i) Electron-Electron Repulsion (eA - eB):
- Repulsive
forces emerge from the electron-electron interaction, specifically between
the two electrons (eA and eB) from the two
approaching atoms.
- Electrons
are negatively charged particles, and like charges repel each other
according to Coulomb's law.
- When
electrons from different atoms come too close, they experience a strong
repulsion, preventing them from occupying the same space.
(ii) Nucleus-Nucleus Repulsion (NA - NB):
- Another
source of repulsion is the nucleus-nucleus interaction between the two positively
charged atomic nuclei (NA and NB).
- Similar
to electron-electron repulsion, like charges (positively charged nuclei)
also repel each other due to Coulomb's law.
- As
the two atoms approach each other closely, the repulsive force between
their nuclei becomes significant.
Net Effect:
- As
two atoms move closer to each other, both attractive and repulsive forces
come into play.
- Initially,
at large distances, the attractive forces dominate because they increase
with decreasing distance.
- However,
as the atoms get closer, the repulsive forces become stronger due to
electron-electron and nucleus-nucleus repulsions.
- At
a certain distance, a balance is reached where the net force of attraction
from the attractive forces equals the net force of repulsion from the
repulsive forces.
- At
this point of equilibrium, the potential energy of the system is
minimized, indicating the formation of a stable chemical bond between the
two atoms.
- This
bond length corresponds to the distance at which the atoms are held
together in a stable molecule.
The interplay between attractive forces (arising from
nucleus-electron and nucleus-nucleus attractions) and repulsive forces (due to
electron-electron and nucleus-nucleus repulsions) determines the distance at
which two atoms will form a chemical bond. The establishment of this
equilibrium distance leads to the formation of stable molecules with specific
bond lengths and geometries.
1. Attraction and Repulsion during Bond Formation:
- When
two hydrogen atoms approach each other, attractive forces between the
positively charged nuclei (NA and NB) and the
negatively charged electrons (eA and eB) start to
operate.
- These
attractive forces tend to pull the two atoms closer together, leading to a
decrease in potential energy.
- Simultaneously,
there are repulsive forces between the electrons (eA - eB)
due to the negatively charged electrons.
- There
are also repulsive forces between the positively charged nuclei (NA
- NB) due to their like charges.
2. Balance of Forces:
- Initially,
at a very large separation distance, the attractive forces dominate
because they decrease as the atoms come closer together.
- However,
as the atoms approach each other, the repulsive forces between the
electrons and nuclei become stronger.
- At
a certain distance, the net force of attraction starts to balance the net
force of repulsion.
- When
the attractive forces equal the repulsive forces, the system reaches a
state of minimum potential energy. This is a stable configuration.
3. Formation of a Stable Hydrogen Molecule:
- At
the point where the net force of attraction balances the force of
repulsion, the two hydrogen atoms are said to be bonded together to form a
stable molecule.
- This
stable configuration corresponds to a specific distance between the two
hydrogen nuclei, which is approximately 74 picometers (pm).
4. Release of Energy:
- The
process of two hydrogen atoms coming together and forming a stable H2
molecule involves a decrease in potential energy.
- According
to the law of conservation of energy, this decrease in potential energy
results in the release of energy.
- The
energy released during the formation of a chemical bond is referred to as
bond enthalpy or bond energy.
5. Bond Enthalpy (Energy):
- Bond
enthalpy (ΔH) is the amount of energy released when one mole of a chemical
bond is formed or the energy required to break one mole of that bond.
- For
H2, the bond enthalpy is 435.8 kJ/mol, which means that when
one mole of H2 molecules is formed from isolated hydrogen atoms, 435.8 kJ
of energy is released.
6. Reverse Process:
- Conversely,
if we want to break the H2 molecule and dissociate it into individual
hydrogen atoms, we need to supply energy.
- The
energy required to dissociate one mole of H2 molecules into individual H
atoms is 435.8 kJ/mol.
7. Chemical Reaction:
- This
process can be represented as a chemical reaction:
H2(g) + 435.8 kJ/mol → H(g) + H(g)
The formation of a hydrogen molecule (H2)
involves a balance between attractive and repulsive forces between atoms. When
these forces reach equilibrium, a stable molecule is formed, and energy is
released in the process, leading to a decrease in potential energy. This
released energy is known as bond enthalpy. Conversely, to break the H2
molecule apart and return to individual hydrogen atoms, energy must be
supplied, which is equal to the bond enthalpy.
1. Formation of a Hydrogen Molecule (H2):
- To
understand orbital overlap, let's consider two hydrogen atoms, each with
one electron, denoted as H-A and H-B.
- Initially,
these atoms are separate, and their electrons are in their respective 1s
atomic orbitals.
2. Atomic Orbitals:
- Each
hydrogen atom has one electron in its 1s atomic orbital.
- The
1s atomic orbital is a region in space around the nucleus where there is a
high probability of finding the electron.
3. Concept of Overlapping:
- In
the process of forming a hydrogen molecule (H2), the two
hydrogen atoms approach each other.
- As
they come closer, their 1s atomic orbitals can partially overlap.
4. Partial Interpenetration:
- The
partial merging or interpenetration of atomic orbitals from the two
hydrogen atoms occurs when they are very close together.
- This
partial interpenetration results in the sharing of electron density
between the two atoms.
5. Overlapping of Atomic Orbitals:
- The
merging or overlapping of the 1s atomic orbitals is what we refer to as
"overlapping of atomic orbitals."
- This
overlap allows the electrons from both hydrogen atoms to exist in the same
region of space.
6. Pairing of Electrons:
- In
the overlapping region, the two electrons, one from each hydrogen atom,
pair up.
- These
paired electrons have opposite spins (according to the Pauli Exclusion
Principle), meaning one has a "spin-up" orientation while the
other has a "spin-down" orientation.
7. Formation of Covalent Bond:
- The
pairing of electrons in the overlapping region signifies the formation of
a covalent bond between the two hydrogen atoms.
- This
covalent bond is characterized by the sharing of the electron pair between
the two atoms.
8. Strength of the Covalent Bond:
- The
extent of orbital overlap between the atomic orbitals of the two atoms
influences the strength of the covalent bond.
- Greater
overlap results in a stronger bond.
- The
strength of the bond is related to the proximity and extent of electron
sharing.
9. Importance of Orbital Overlap Concept:
- The
orbital overlap concept is fundamental to understanding covalent bonding
in molecules.
- It
explains how atoms share electrons and form stable molecules.
- This
concept extends to more complex molecules where multiple atomic orbitals
overlap to create molecular orbitals.
10. Hydrogen Molecule (H2) and Orbital
Overlap: - In the case of the hydrogen molecule (H2), two hydrogen atoms
come together, and their 1s atomic orbitals overlap. - The overlap allows the
two electrons to pair up in a region of space that is shared between the two
atoms, forming a covalent bond. - This bond is characterized by the presence of
a molecular orbital that spans both hydrogen nuclei, binding them together.
The concept of orbital overlap is crucial in covalent bond
formation. It explains how electrons from different atoms can occupy the same
region of space, leading to the formation of stable molecules. The extent of
overlap directly affects the strength of the covalent bond, with greater
overlap resulting in a stronger bond. Orbital overlap is a fundamental concept
in understanding the chemistry of covalent compounds.
VALENCE BOND THEORY: DIRECTIONAL PROPERTIES OF BONDS
1. Formation of Covalent Bonds:
- Covalent
bonds in polyatomic molecules are formed through the sharing of electrons
between atoms, just like in diatomic molecules such as H2.
- However,
in polyatomic molecules, the geometry of the molecule is crucial in
addition to bond formation.
2. Tetrahedral Geometry in CH4:
- Let's
take the example of methane (CH4).
- Methane
consists of one carbon (C) atom and four hydrogen (H) atoms.
- The
Valence Bond Theory explains the formation of methane in the following
way:
- Carbon
(C) has an electronic configuration of 1s² 2s² 2p².
- To
form four bonds in CH4, carbon needs to promote one of its 2s
electrons to the 2p orbital. This results in four half-filled orbitals.
- These
four half-filled orbitals are available for overlap with the 1s orbitals
of the four hydrogen atoms.
- The
overlap occurs between each of the four carbon orbitals and one of the
four hydrogen 1s orbitals.
- This
results in the formation of four sigma (σ) bonds, which are covalent
bonds with cylindrical symmetry.
- The
tetrahedral shape of CH4 arises because the four sigma bonds
are arranged tetrahedrally around the carbon atom.
3. Bond Angles in CH4:
- In
a tetrahedral geometry, all bond angles are 109.5 degrees.
- This
angle results from the arrangement of four sigma bonds around the central
carbon atom, pushing them apart as far as possible while maintaining a
uniform distribution in 3D space.
4. Pyramidal Shape in NH3:
- Now,
let's consider ammonia (NH3).
- Ammonia
has a pyramidal shape, and the Valence Bond Theory explains it as follows:
- Nitrogen
(N) has an electronic configuration of 1s² 2s² 2p³.
- Nitrogen's
three unpaired electrons are used to form bonds with three hydrogen
atoms.
- Nitrogen
promotes one of its 2s electrons to an empty 2p orbital to form four
half-filled orbitals (three 2p and one 2s).
- The
three half-filled 2p orbitals overlap with the 1s orbitals of three
hydrogen atoms to form three sigma (σ) bonds.
- The
unshared electron pair in the fourth orbital gives ammonia its pyramidal
shape, as it repels the three sigma bonds, pushing them closer to the
nitrogen atom.
- This
results in a bond angle of approximately 107 degrees between the three
hydrogen atoms in NH3.
5. Angular Shape in H2O:
- Finally,
let's consider water (H2O).
- Water
has an angular shape, and the Valence Bond Theory explains it as follows:
- Oxygen
(O) has an electronic configuration of 1s² 2s² 2p⁴.
- Oxygen
needs to form two sigma (σ) bonds with two hydrogen atoms and also
accommodate two unshared electron pairs.
- To
achieve this, oxygen promotes one of its 2s electrons to an empty 2p
orbital to form four half-filled orbitals.
- Two
of these half-filled orbitals overlap with the 1s orbitals of two
hydrogen atoms to form two sigma bonds.
- The
two unshared electron pairs are in the remaining two half-filled
orbitals, creating repulsion between the electron pairs.
- This
results in an angular shape with a bond angle of approximately 104.5
degrees between the two hydrogen atoms in H2O.
The Valence Bond Theory explains the directional properties
of bonds in polyatomic molecules based on orbital overlap and hybridization of
atomic orbitals. The specific geometry of these molecules (tetrahedral,
pyramidal, angular) is a result of the arrangement of sigma bonds and unshared
electron pairs around the central atom. This theory provides a fundamental
understanding of the shapes, bond angles, and formation of covalent bonds in
polyatomic molecules.
OVERLAPPING OF ATOMIC ORBITALS:
The directional characteristics of bonds in molecules like
CH4, NH3, and H2O cannot be fully explained by
simple atomic orbital overlap. This limitation of atomic orbitals led to the
development of hybridization theory, which provides a more accurate description
of the geometry and directional properties of these molecules. Let's discuss
each molecule individually:
1. CH4 (Methane):
- Methane
(CH4) consists of one carbon (C) atom and four hydrogen (H)
atoms.
- The
Valence Bond (VB) theory alone using pure atomic orbitals suggests that
carbon's three p orbitals and one s orbital overlap with the 1s orbitals
of the four hydrogen atoms to form four sigma (σ) bonds.
- This
would imply that all four C-H bonds should be oriented at 90 degrees to
each other, resulting in a square planar arrangement.
- However,
in reality, the bond angles in CH4 are approximately 109.5
degrees, forming a tetrahedral shape.
- This
discrepancy cannot be explained by considering only pure atomic orbitals.
2. NH3 (Ammonia):
- Ammonia
(NH3) consists of one nitrogen (N) atom and three hydrogen (H)
atoms.
- Similar
to methane, if we consider pure atomic orbitals, nitrogen's three p
orbitals and one s orbital would overlap with the 1s orbitals of the three
hydrogen atoms.
- This
would suggest that the H-N-H bond angles should be 90 degrees, resulting
in a trigonal planar arrangement.
- However,
in reality, the bond angles in NH3 are approximately 107
degrees, forming a pyramidal shape.
3. H2O (Water):
- Water
(H2O) consists of one oxygen (O) atom and two hydrogen (H)
atoms.
- Again,
if we only consider pure atomic orbitals, oxygen's three p orbitals and
one s orbital would overlap with the 1s orbitals of the two hydrogen
atoms.
- This
would imply that the H-O-H bond angles should be 90 degrees, resulting in
a linear arrangement.
- However,
in reality, the bond angles in H2O are approximately 104.5
degrees, forming a bent or angular shape.
Explanation Using Hybridization:
- To
explain these bond angles and geometries, we need to consider
hybridization of atomic orbitals.
- Hybridization
involves the mixing of atomic orbitals to form new hybrid orbitals with
specific shapes and orientations.
- In CH4, carbon undergoes sp3 hybridization, resulting in four
equivalent sp3 hybrid orbitals that are tetrahedrally arranged,
allowing for bond angles of approximately 109.5 degrees.
- In NH3, nitrogen undergoes sp3 hybridization, leading to three
equivalent sp3 hybrid orbitals and one unhybridized p orbital.
The bond angles are approximately 107 degrees.
- In
H2O, oxygen undergoes sp3 hybridization, producing
two equivalent sp3 hybrid orbitals and two unhybridized p
orbitals. The bond angles are approximately 104.5 degrees.
The simple Valence Bond theory based solely on pure atomic
orbitals cannot account for the observed bond angles and geometries in
molecules like CH4, NH3, and H2O.
Hybridization theory, which involves the mixing of atomic orbitals to form
hybrid orbitals, provides a more accurate description of the directional
properties of these molecules and explains their tetrahedral, pyramidal, and
bent shapes, respectively. Hybridization theory is a critical concept in
understanding the geometry and properties of covalent compounds.
VALENCE BOND THEORY: TYPES OF OVERLAPPING AND NATURE OF COVALENT BONDS
A sigma bond is a type of covalent bond formed by the
end-to-end (head-on) overlap of atomic orbitals along the internuclear axis.
There are three main types of sigma bond formation:
1. s-s Overlapping:
- Sigma
bonds can be formed by the overlap of two half-filled s-orbitals along the
internuclear axis.
- When
two atoms approach each other, and their s-orbitals overlap, the electrons
from each orbital are shared between the two nuclei.
- The
resulting sigma bond is characterized by a cylindrical symmetry around the
internuclear axis.
- Examples
include the formation of H2 molecules, where the two hydrogen
atoms each have a single electron in their 1s orbital, and these electrons
overlap to create a sigma bond.
2. s-p Overlapping:
- In
this type of overlap, a half-filled s-orbital of one atom overlaps with a
half-filled p-orbital of another atom along the internuclear axis.
- When
this overlap occurs, the electrons from both orbitals are shared between
the two nuclei.
- The
sigma bond formed in s-p overlapping also exhibits cylindrical symmetry
around the internuclear axis.
- For
instance, in the formation of HCl molecules, the hydrogen atom's 1s
orbital overlaps with the chlorine atom's 3p orbital to create a sigma
bond.
3. p-p Overlapping:
- Sigma
bonds can also be formed when two half-filled p-orbitals from different
atoms overlap along the internuclear axis.
- In
p-p overlapping, the electrons from each p-orbital are shared between the
nuclei.
- Similar
to the other sigma bonds, p-p overlapping results in a bond with
cylindrical symmetry around the internuclear axis.
- An
example is the formation of Cl2 molecules, where two chlorine
atoms each contribute one unpaired electron from their 3p orbitals to
create a sigma bond.
Nature of Sigma Bonds:
- Sigma
bonds are characterized by strong overlap and a high degree of electron
density between the two nuclei.
- They
are the most stable and strongest type of covalent bond.
- Sigma
bonds are highly directional, with electron density concentrated along the
axis connecting the two nuclei.
- They
allow free rotation around the internuclear axis because the cylindrical
symmetry permits relative movement of the bonded atoms.
- Sigma
bonds are typically denoted as σ bonds and are often found in single bonds
in molecules.
Sigma (σ) bonds are a type of covalent bond formed by the
head-on overlap of atomic orbitals along the internuclear axis. They can be
formed through s-s, s-p, or p-p overlapping. Sigma bonds are characterized by
their strong overlap, high electron density between nuclei, and directional
nature along the internuclear axis. They are often the strongest and most
stable type of covalent bond, making them a fundamental component in the
formation of molecules.
Formation of Pi (π) Bond:
- Pi
bonds are a type of covalent bond that forms when two atoms share
electrons through the sidewise or lateral overlap of atomic orbitals.
- Unlike
sigma (σ) bonds, where the overlap occurs head-on along the internuclear
axis, in pi bonds, the overlap takes place in a side-to-side manner with
the orbital axes parallel to each other and perpendicular to the
internuclear axis.
- Pi
bonds are typically formed by the overlap of p orbitals, although they can
also involve d orbitals or hybridized orbitals in more complex molecules.
Nature of Pi Bonding Orbitals:
- When
two p orbitals overlap laterally, they create a pi bonding orbital.
- The
result is the formation of two electron-rich regions, often depicted as
"saucer" or "dumbbell" shapes, located above and below
the plane defined by the participating atoms.
- These
electron-rich regions are the locations where the shared electrons are
most likely to be found.
- The
pi bonding orbitals have a cylindrical symmetry around the internuclear
axis and do not allow free rotation.
Comparison with Sigma Bond:
- Unlike
sigma bonds, which are characterized by a strong head-on overlap and high
electron density along the internuclear axis, pi bonds have electron
density localized above and below the plane of the bonded atoms.
- Pi
bonds are generally weaker than sigma bonds because the electron density
in pi bonds is not as concentrated between the nuclei as in sigma bonds.
- The
directional properties of pi bonds are different from sigma bonds. While
sigma bonds allow for free rotation around the internuclear axis, pi bonds
restrict rotation due to the presence of electron density above and below
the bond plane.
Example:
- One
common example of a pi bond is found in the carbon-carbon double bond
(C=C) in molecules like ethene (ethylene).
- In
ethene, each carbon atom forms a sigma bond with one hydrogen atom and a
pi bond with the other carbon atom.
- The
pi bond is formed by the side-to-side overlap of the two carbon atoms' p
orbitals.
pi (π) bonds are covalent bonds formed by the lateral
overlap of atomic orbitals, typically p orbitals, with their axes parallel to
each other and perpendicular to the internuclear axis. They create
electron-rich regions above and below the bond plane. Pi bonds are weaker than
sigma bonds and play a significant role in the structure and properties of
molecules with double or triple bonds.
The strength of a covalent bond indeed depends on the extent
of orbital overlap between the participating atoms. Sigma (σ) bonds are
typically stronger than pi (π) bonds because of the differences in the nature
of their overlapping and electron density distribution.
1. Sigma (σ) Bonds:
- Sigma
bonds are formed by head-on, direct overlap of atomic orbitals along the
internuclear axis.
- The
extent of overlapping in sigma bonds is greater than that in pi bonds. In
sigma bonds, the electron density is concentrated along the internuclear
axis, forming a strong and stable bond.
- The
electron cloud in a sigma bond is more directly between the nuclei of the
bonded atoms, leading to a strong attraction.
- Sigma
bonds allow for free rotation around the internuclear axis because the
cylindrical symmetry of the sigma bond permits relative movement of the
bonded atoms.
- Sigma
bonds are typically denoted as σ bonds and are found in single bonds in
molecules.
2. Pi (π) Bonds:
- Pi
bonds are formed by the lateral, sidewise overlap of atomic orbitals with
their axes parallel to each other and perpendicular to the internuclear
axis.
- The
extent of overlapping in pi bonds is smaller than that in sigma bonds. In
pi bonds, the electron density is localized above and below the bond
plane.
- The
electron cloud in a pi bond is not directly between the nuclei but above
and below them, resulting in weaker bonding.
- Pi
bonds do not allow for free rotation around the internuclear axis because
the electron density restricts rotation.
- Pi
bonds are typically weaker than sigma bonds and are often found in
multiple bonds in molecules, such as double (C=C) and triple (N≡N) bonds.
Formation of Multiple Bonds:
- In
the formation of multiple bonds (double or triple bonds) between two atoms
in a molecule, both sigma and pi bonds are involved.
- For
example, in a carbon-carbon double bond (C=C), there is one sigma bond and
one pi bond.
- In
a nitrogen-nitrogen triple bond (N≡N), there is one sigma bond and two pi
bonds.
- Multiple
bonds arise because two atoms can share more than one pair of electrons,
leading to the formation of both sigma and pi bonds.
- The
presence of multiple bonds typically results in a higher bond strength
overall compared to a single bond.
Sigma bonds are stronger than pi bonds due to the extent of
overlapping and electron density distribution. Sigma bonds are formed by
head-on overlap and allow for free rotation. Pi bonds are formed by lateral
overlap and restrict rotation. Multiple bonds, such as double and triple bonds,
involve the formation of both sigma and pi bonds, resulting in overall higher
bond strength. The relative strengths of sigma and pi bonds play a crucial role
in determining the properties and reactivity of molecules.
VALENCE BOND THEORY: HYBRIDIZATION OF ATOMIC ORBITALS
Hybridization is a concept in chemistry that was introduced
to explain the characteristic geometric shapes and molecular structures of
polyatomic molecules. Linus Pauling, a renowned chemist, developed the theory
of hybridization to better understand and predict molecular shapes and bond
angles. The key idea behind hybridization is the mixing or intermingling of
atomic orbitals to form new sets of equivalent orbitals called hybrid orbitals.
These hybrid orbitals are then used in the formation of covalent bonds within a
molecule.
Here are the salient features and important conditions of
hybridization:
Salient Features of Hybridization:
- Equal
Number of Hybrid Orbitals: The number of hybrid orbitals formed is
equal to the number of atomic orbitals that undergo hybridization. For
example, when one 2s orbital and three 2p orbitals of carbon combine, four
equivalent sp3 hybrid orbitals are formed.
- Equivalent
in Energy and Shape: Hybrid orbitals resulting from hybridization are
always equivalent in both energy and shape. This uniformity simplifies the
prediction of molecular geometry.
- Increased
Bonding Effectiveness: Hybridized orbitals are more effective in
forming stable covalent bonds compared to the pure atomic orbitals they
originate from. This results from the fact that hybridized orbitals have a
directional character that minimizes repulsion between electron pairs.
- Directionality:
Hybrid orbitals have a specific spatial orientation that minimizes
electron pair repulsion. This orientation is essential for understanding
the geometry of molecules and predicting bond angles.
Important Conditions for Hybridization:
(i) Valence Shell Orbitals: The orbitals involved in
hybridization are typically those present in the valence shell of the atom.
These are the outermost electron orbitals involved in bonding.
(ii) Similar Energy Levels: The atomic orbitals
undergoing hybridization should have approximately similar energies. This ensures
that the hybrid orbitals formed are of similar energy levels. For example, the
2s and 2p orbitals of carbon are relatively close in energy, making them
suitable for hybridization.
(iii) Promotion of Electrons Not Always Necessary:
Hybridization does not always require the promotion of electrons from lower
energy levels to higher energy levels before hybridization. While this is
necessary for some elements, like carbon, in other cases, even filled orbitals
of the valence shell can take part in hybridization.
(iv) Half-Filled Orbitals Not a Requirement: Contrary
to a common misconception, hybridization does not require that only half-filled
orbitals participate. In some cases, even completely filled orbitals can
undergo hybridization.
Examples of Hybridization:
- sp3
Hybridization: In methane (CH4), carbon undergoes sp3
hybridization, resulting in the formation of four equivalent sp3 hybrid
orbitals that form sigma bonds with four hydrogen atoms, leading to a
tetrahedral molecular shape.
- sp2
Hybridization: In ethene (C2H4), each carbon
atom undergoes sp2 hybridization, resulting in the formation of three
equivalent sp2 hybrid orbitals. The remaining p orbital on each carbon
forms a pi bond between the carbon atoms. This results in a planar,
trigonal geometry.
- sp
Hybridization: In acetylene (C2H2), each carbon
atom undergoes sp hybridization, forming two equivalent sp hybrid orbitals
and two unhybridized p orbitals. Two sigma bonds are formed between the
carbon atoms, and two pi bonds are formed using the unhybridized p
orbitals. The molecule has a linear geometry.
Hybridization is a fundamental concept in chemistry used to
explain molecular shapes, bond angles, and the nature of chemical bonding in
molecules. It involves the mixing of atomic orbitals to form new sets of
equivalent orbitals called hybrid orbitals. The resulting hybrid orbitals are
then used to construct molecular structures, providing a valuable tool for
understanding the behavior of molecules and predicting their properties.