The Nature of Chemical Bonds and Theories of
Chemical Bonding
The Nature of Chemical Bonds and Theories of Chemical
Bonding
- Introduction
to Matter and Elements:
- Matter
consists of distinct elements.
- Under
normal conditions, elements exist as independent atoms except for noble
gases.
- Formation
of Molecules:
- Atoms
group together to form molecules.
- Molecules
are collections of atoms with characteristic properties.
- A
molecule is held together by a force known as a chemical bond.
- The
Concept of Chemical Bonds:
- Chemical
bonds are attractive forces between atoms, ions, etc.
- Chemical
bonds are responsible for holding together the constituents of different
chemical species.
- Questions
about Chemical Bonding:
- The
process of forming chemical compounds from combinations of atoms raises
questions.
- Why
do atoms combine? Why are specific combinations possible?
- What
determines why certain atoms combine while others do not?
- Why
do molecules have definite shapes?
- Theories
and Concepts of Chemical Bonding:
- Kössel-Lewis
Approach:
- A
theory explaining the transfer of electrons between atoms to achieve
stable electron configurations.
- Focuses
on achieving noble gas electron configurations through electron
transfer.
- Valence
Shell Electron Pair Repulsion (VSEPR) Theory:
- Describes
molecular shapes based on the repulsion between valence electron pairs.
- Explains
the three-dimensional arrangement of atoms in molecules.
- Valence
Bond (VB) Theory:
- Explains
chemical bonding in terms of overlapping atomic orbitals.
- Emphasizes
the role of unpaired electrons in the formation of bonds.
- Molecular
Orbital (MO) Theory:
- Describes
chemical bonding using molecular orbitals formed by the combination of
atomic orbitals.
- Electrons
are treated as wave-like entities, leading to a more comprehensive
understanding of bonding.
- Relation
to Atomic Structure and Periodic Table:
- Development
of bonding theories closely linked to advancements in atomic structure
understanding.
- Electronic
configurations of elements and their placement in the periodic table
influence bonding behavior.
- Stability
and Bonding:
- Systems
tend to achieve stability.
- Bonding
is a natural process that reduces the energy of a system, leading to
increased stability.
The nature of chemical bonds and the theories of chemical
bonding have evolved over time to address fundamental questions about atomic
combinations, molecule formation, shapes, and stability. The theories,
including Kössel-Lewis, VSEPR, Valence Bond, and Molecular Orbital theories,
provide different perspectives on the forces that hold atoms together in
molecules, considering electron configurations, atomic orbitals, and molecular
shapes. These theories have been influenced by our understanding of atomic
structure and the periodic table, ultimately explaining why atoms combine, the
possible combinations, and the shapes of molecules. Bonding serves as nature's
mechanism to achieve stability within systems.
KOSSEL-LEWIS APPROACH TO CHEMICAL BONDING
Kössel-Lewis Approach to Chemical Bonding
- Introduction:
- In
1916, independent efforts by Kössel and Lewis brought about a
satisfactory explanation for chemical bonding based on electron
interactions.
- Their
approach was grounded in understanding valence and drew inspiration from
the inert properties of noble gases.
- Lewis's
Model of the Atom:
- Lewis
conceptualized atoms as having a "Kernel" comprising the
nucleus and inner electrons, surrounded by an outer shell.
- The
outer shell could accommodate up to eight electrons, distributed at the
corners of a cube that enveloped the "Kernel."
- This
arrangement formed a stable octet of electrons, promoting stability in
the atom.
- Stable
Octet and Chemical Bonds:
- Lewis
proposed that atoms attain stability by achieving the octet electron
configuration.
- For
atoms to achieve this stable state, they form chemical bonds.
- In
the example of sodium (Na) and
chlorine (Cl), sodium donates
an electron to chlorine, resulting in the formation of Na+ and Cl– ions.
- The
transfer of an electron from one atom to another leads to the formation
of ionic bonds.
- Covalent
Bonds and Octet Rule:
- In
molecules like Cl2, H2,
F2, etc., atoms form bonds by sharing pairs of electrons.
- This
sharing of electrons enables each atom to complete its outer shell and
attain the stable octet configuration.
- The
concept of the octet rule underlines the tendency of atoms to seek eight
electrons in their outer shell, mirroring noble gas electron
configurations.
- Lewis
Symbols:
- In
molecular formation, only the outer shell electrons (valence electrons)
partake in chemical bonding.
- Inner
shell electrons are shielded and usually remain uninvolved in bonding.
- G.N.
Lewis, an American chemist, introduced a simplified notation to represent
valence electrons in atoms, known as Lewis symbols.
Advantages and Insights of Kössel-Lewis Approach:
- Explanation
of Valence: Kössel and Lewis provided a logical explanation for
valence based on the stable octet configuration.
- Inertness
of Noble Gases: The concept of achieving noble gas-like electron
configurations explained why noble gases are chemically inert.
- Ionic
and Covalent Bonds: The approach distinguished between ionic and
covalent bonds, elucidating how electron transfer and sharing contribute
to bond formation.
- Octet
Rule: The octet rule became a guiding principle for understanding
chemical behavior and predicting molecular stability.
The Kössel-Lewis approach to chemical bonding, developed by
Kössel and Lewis, introduced a model of atoms based on the outer shell's
electron arrangement. This approach elucidated the significance of achieving a
stable octet configuration for atoms through chemical bonding. The concept of
Lewis symbols simplified the representation of valence electrons. The
approach's insights into ionic and covalent bonding, the octet rule, and the
inertness of noble gases contributed significantly to the understanding of
chemical interactions and molecular stability.
SIGNIFICANCE OF LEWIS SYMBOLS
Significance of Lewis Symbols and Kössel's Contributions
to Chemical Bonding
- Lewis
Symbols and Valence Electrons:
- Lewis
symbols represent an element's valence electrons as dots around its
chemical symbol.
- The
number of dots in a Lewis symbol corresponds to the number of valence
electrons.
- This
representation aids in calculating the common or group valence of the
element.
- Group
Valence Calculation:
- Group
valence of an element is often either equal to the number of dots in its
Lewis symbol or 8 minus the number of dots (valence electrons).
- Kössel's
Observations in Chemical Bonding:
- Kössel's
contributions to chemical bonding shed light on critical observations:
- The
periodic table separates highly electronegative halogens and highly
electropositive alkali metals with noble gases in between.
- Formation
of negative ions from halogen atoms and positive ions from alkali metal
atoms involves electron loss and gain, respectively.
- Negative
and positive ions formed acquire stable noble gas electronic
configurations, especially the octet (eight electrons) in the outer
shell (ns²np⁶).
- The
stability of noble gas configurations implies that ions aim to achieve
similar electron arrangements.
- Stabilization
through Electrostatic Attraction:
- The
interaction between positive and negative ions formed due to electron
transfer results in electrostatic attraction.
- This
type of bond was termed the "electrovalent bond."
- Electrovalence
corresponds to the number of unit charges on the ion. For instance,
calcium carries a positive electrovalence of two, while chlorine bears a
negative electrovalence of one.
- Implications
and Applications of Kössel's Postulations:
- Kössel's
ideas laid the groundwork for modern concepts related to ion formation
through electron transfer and the creation of ionic crystalline
compounds.
- These
insights contributed significantly to understanding and systematizing
ionic compounds.
- While
Kössel's concepts were valuable, they also recognized that certain
compounds deviated from these ideas.
Key Contributions and Insights:
- Electronegativity
and Electropositivity: Kössel highlighted the contrasting
properties of halogens and alkali metals, separated by noble gases in the
periodic table.
- Ionic
Formation: Kössel's observations explained the electron gain and
loss during ion formation, leading to stable noble gas-like
configurations.
- Stable
Outer Shell: Kössel emphasized that negative and positive ions
achieve stability by acquiring noble gas outer shell electron
configurations.
- Electrovalent
Bonds: The electrostatic attraction between oppositely charged
ions was termed as electrovalent bonding, with electrovalence representing
ion charge.
- Ionic
Compounds Understanding: Kössel's ideas significantly enhanced
the comprehension and organization of ionic compounds.
Kössel's contributions revolutionized the understanding of
chemical bonding, emphasizing the connection between electron transfer and ion
formation. His insights into electronegativity, electron gain and loss, stable
electron configurations, and electrovalent bonding laid the foundation for
modern concepts. While his ideas provided a profound understanding of ionic
compounds, they also acknowledged that certain compounds didn't conform to these
concepts, reflecting the evolving nature of chemical understanding.
THE OCTET RULE IN CHEMICAL BONDING
The Octet Rule in Chemical Bonding
- Introduction:
- In
1916, Kössel and Lewis introduced the electronic theory of chemical
bonding.
- This
theory explains how atoms combine through the transfer or sharing of
valence electrons.
- Fundamental
Idea - Octet Rule:
- Atoms
can attain stability by having a complete outer electron shell.
- The
octet rule states that atoms tend to combine in a way that allows them to
achieve a stable configuration of eight electrons in their valence shell,
resembling the noble gases' electronic configuration.
- Two
Modes of Combination:
- Electron
Transfer (Ionic Bonding):
- Involves
the transfer of valence electrons from one atom to another.
- One
atom gains electrons to fill its valence shell, becoming negatively
charged (anion), while the other loses electrons and becomes positively
charged (cation).
- The
electrostatic attraction between oppositely charged ions leads to the
formation of ionic compounds.
- Electron
Sharing (Covalent Bonding):
- Atoms
share pairs of electrons to complete their valence shells.
- By
sharing electrons, each atom achieves a stable configuration similar to
noble gases.
- Covalent
bonding is common in molecular compounds and forms when atoms have
similar electronegativities.
- Significance
of the Octet Rule:
- The
octet rule guides the formation of various chemical compounds by
dictating how atoms will interact to achieve stability.
- It
explains why atoms either gain, lose, or share electrons during bonding.
- Stability
and Noble Gas Configuration:
- Noble
gases possess a stable electron configuration with eight electrons in
their valence shell (except helium, which has two).
- Other
elements aim to emulate this stable state by following the octet rule
during chemical bonding.
- Predictive
Power:
- The
octet rule aids in predicting the types of bonds that will form between
different elements.
- It
also provides insights into the properties of resulting compounds.
- Limitations
and Exceptions:
- While
the octet rule is a useful guideline, it doesn't explain every type of
chemical bonding.
- Some
molecules and compounds don't strictly adhere to the octet rule,
especially for elements with d or f orbitals that can accommodate more
than eight electrons.
Implications of the Octet Rule:
- Ionic
and Covalent Bond Types: The octet rule underlies the fundamental
distinction between ionic and covalent bonds based on electron transfer
and sharing, respectively.
- Stability
and Noble Gas Mimicry: The pursuit of the octet configuration
drives atoms towards enhanced stability by resembling the noble gas
electron arrangements.
- Predictive
Tool: The octet rule is an invaluable predictive tool, aiding in
explaining the behavior of various elements during bonding.
- Beyond
Octet Rule: While essential, the octet rule has limitations,
especially for elements with more complex electron configurations.
The octet rule, developed by Kössel and Lewis, forms the
cornerstone of chemical bonding theories. It elucidates how atoms combine by either
transferring or sharing valence electrons to achieve a stable configuration
with eight electrons in their valence shell. While it provides a strong basis
for understanding most bonding scenarios, exceptions exist due to the intricate
electron arrangements of certain elements.
COVALENT BONDING AND LEWIS-LANGMUIR THEORY
Covalent Bonding and Lewis-Langmuir Theory
- Introduction:
- Langmuir
(1919) built upon Lewis's ideas, refining the concept of chemical
bonding.
- Langmuir
introduced the term "covalent bond" and expanded on Lewis's
octet rule.
- Evolution
from Lewis to Lewis-Langmuir Theory:
- Lewis's
idea of atoms bonding through electron sharing was enhanced by Langmuir.
- Langmuir
abandoned the concept of a fixed cubic arrangement of the octet and
introduced the term "covalent bond."
- Chlorine
Molecule Example - Cl2:
- The
Cl atom has the electronic
configuration [Ne]3s²3p⁵,
lacking one electron for the argon configuration.
- Cl2 formation involves
the sharing of a pair of electrons between two chlorine atoms.
- Each
chlorine atom contributes one electron to the shared pair.
- The
result is that both chlorine atoms achieve the outer shell octet of
argon, leading to a stable configuration.
- Representation
of Covalent Bonds - Lewis Dot Structures:
- Lewis
dot structures use dots to represent electrons in atoms and molecules.
- These
structures provide visual insights into the arrangement of shared
electrons.
- Lewis
dot structures are applicable to different molecules with identical or
different combining atoms.
- Key
Conditions of Covalent Bonding:
- Electron
Pair Sharing: Covalent bonds form by sharing an electron pair
between atoms.
- Contribution
of Electrons: Each atom involved contributes at least one
electron to the shared pair.
- Achievement
of Stable Configuration: Combining atoms achieve noble gas
configurations due to shared electrons.
- Examples
of Covalent Bonds:
- Water
(H2O) and Carbon Tetrachloride (CCl4): In
these molecules, atoms share electron pairs to form covalent bonds,
fulfilling the conditions of electron sharing and noble gas
configurations.
- Multiple
Bonds:
- Single
Covalent Bond: Formed when two atoms share one electron pair.
- Double
Bond: Two pairs of electrons are shared between atoms. Example:
Carbon dioxide (CO2).
- Triple
Bond: Three pairs of electrons are shared between atoms.
Examples: Nitrogen gas (N2),
ethyne (C2H2).
Implications of the Lewis-Langmuir Theory:
- Advancement
of Covalent Bond Concept: Langmuir's covalent bond concept
refined Lewis's ideas, focusing on electron sharing and arrangement.
- Visualization
through Lewis Dot Structures: Lewis dot structures provide a visual
representation of electron distribution in molecules.
- Universal
Application: The Lewis-Langmuir theory's principles apply to
various compounds, guiding our understanding of covalent bonding.
- Explanation
of Multiple Bonds: The theory explains the formation of single,
double, and triple bonds through shared electron pairs.
Langmuir's extension of Lewis's ideas gave rise to the
Lewis-Langmuir theory of covalent bonding. This theory emphasizes electron
sharing between atoms to achieve stable electron configurations, visualized
through Lewis dot structures. Examples like the chlorine molecule showcase how
covalent bonds lead to noble gas-like outer shell configurations. Additionally,
the theory accounts for multiple bonds, elucidating the formation of double and
triple bonds through shared electron pairs.
The Nature of Chemical Bonds and Theories of
Chemical Bonding
Lewis Representation of Simple Molecules (Lewis
Structures)
- Introduction
to Lewis Dot Structures:
- Lewis
dot structures visually depict molecular and ionic bonding through shared
electron pairs and adherence to the octet rule.
- While
not exhaustive, they greatly aid in understanding molecule formation and
properties.
-
- Importance
and Utility:
- Lewis
dot structures contribute to understanding bonding patterns and
properties of molecules, albeit not providing a complete explanation.
- They
are valuable tools in explaining and predicting molecular behavior.
- Steps
to Write Lewis Dot Structures:
- Determine
Total Electrons: Calculate the total electrons required for the
structure by summing the valence electrons of combining atoms.
- Account
for Charges: For anions, add electrons equal to the negative
charge, while for cations, subtract electrons equal to the positive
charge.
- Distribute
Electrons: Using chemical symbols of the atoms and knowledge of
the compound's skeletal structure, distribute electrons as shared pairs
proportionally among atoms.
- Central
Atom Placement: Typically, the least electronegative atom
occupies the central position within the molecule or ion.
- Terminal
Atom Placement: More electronegative atoms usually occupy the
terminal positions.
- Multiple
Bonds and Octet Rule: Distribute remaining electron pairs after
accounting for single bonds. These pairs may contribute to multiple bonds
or remain as lone pairs, ensuring each bonded atom achieves an octet of
electrons.
- Illustrative
Examples:
- CH4
Molecule: In methane (CH4),
eight valence electrons are available (4 from carbon, 4 from hydrogen)
for bonding.
- Anions
and Cations: Anions gain electrons according to their negative
charge, while cations lose electrons based on their positive charge.
- Central
Atom Position: Generally, the least electronegative atom becomes
the central atom. In compounds like
NF3 and CO3²⁻,
nitrogen and carbon serve as central atoms, while fluorine and oxygen
occupy terminal positions.
- Octet
Rule and Electron Distribution: The distribution of electrons in
Lewis structures ensures that each atom achieves an octet of electrons,
promoting stability.
Significance and Implications:
- Visual
Bonding Representation: Lewis dot structures visually convey the
bonding arrangement in molecules and ions.
- Octet
Rule Reinforcement: Lewis structures emphasize adherence to the
octet rule, reflecting the tendency of atoms to attain noble gas configurations.
- Predictive
Tool: These structures help predict molecular behavior and
properties based on electron distribution.
- Central
Atom Positioning: The choice of the central atom and terminal
atoms is influenced by electronegativity differences.
- Balancing
Charges: Lewis structures effectively accommodate anions and
cations, adjusting the number of electrons as per charge.
Lewis dot structures serve as valuable tools to visualize
bonding in molecules and ions, showcasing shared electron pairs and the octet
rule's importance. While not exhaustive, these structures provide insights into
molecular properties and behavior, offering a foundational understanding of
chemical bonding.
FORMAL CHARGE IN LEWIS DOT STRUCTURES:
Formal Charge in Lewis Dot Structures
- Limitations
of Lewis Dot Structures:
- Lewis
dot structures are valuable tools for understanding molecular bonding but
do not directly depict actual molecular shapes.
- Especially
in polyatomic ions, the net charge is distributed across the ion as a
whole, rather than being concentrated on a specific atom.
- Assignment
of Formal Charge:
- To
address the distribution of charge in polyatomic ions, the concept of
formal charge is introduced.
- Formal
charge is assigned to individual atoms within a molecule or ion to
evaluate their electron distribution.
- Defining
Formal Charge:
- Calculation
Basis: Formal charge quantifies the difference between an atom's
valence electrons in its isolated (free) state and the electrons
allocated to it in the Lewis structure.
- Formula: Formal
Charge = Valence Electrons (Free Atom) - Assigned Electrons (Lewis
Structure)
- Purpose
of Formal Charge:
- Formal
charge helps in assessing the electron distribution among atoms in a
molecule or ion, considering their Lewis structure.
- It
aids in understanding the extent to which an atom has gained or lost
electrons, relative to its neutral state.
- Application
to Polyatomic Molecules and Ions:
- Polyatomic
Ions: In polyatomic ions, the net charge is distributed among
multiple atoms, making it necessary to consider individual atoms'
charges.
- Formal
Charge Allocation: By assigning formal charges to each atom in
the ion's Lewis structure, a clearer picture of electron distribution and
charge is obtained.
Significance and Implications of Formal Charge:
- Addressing
Charge Distribution: Formal charge rectifies the limitation of
Lewis structures by considering how charge is distributed across atoms in
polyatomic ions.
- Determining
Electron Distribution: Formal charges assist in understanding
which atoms carry a surplus or deficit of electrons within a molecule or
ion.
- Comparing
Alternative Lewis Structures: Formal charge evaluation guides the
selection of the most appropriate Lewis structure when there are multiple
possibilities.
Formal charge, a concept used alongside Lewis dot
structures, offers a solution to the challenges of representing charge
distribution in polyatomic ions. It calculates the difference between valence
electrons of an atom in its free state and the electrons assigned to it within
the Lewis structure. While Lewis structures are limited in illustrating
molecular shapes, the addition of formal charges enables a more comprehensive
understanding of charge distribution and electron allocation within complex
molecules and ions.
LIMITATIONS OF THE OCTET RULE:
Limitations of the Octet Rule:
- Limited Applicability:
- The
octet rule is not universally applicable.
- Primarily
applies to second-period elements in the periodic table.
- Most
useful for understanding the structures of organic compounds.
- Incomplete Octet:
- Some
compounds do not follow the octet rule, especially when the central atom
has fewer than four valence electrons.
- Examples
include LiCl, BeH2,
and BCl3, as Li, Be, and B have 1, 2, and 3 valence electrons, respectively.
- Additional
examples include AlCl3 and
BF3.
- Odd-Electron Molecules:
- Molecules
with an odd number of electrons, such as nitric oxide (NO) and nitrogen dioxide (NO2), do not satisfy
the octet rule for all atoms.
- Expanded Octet:
- Elements
in and beyond the third period of the periodic table have 3d orbitals in
addition to 3s and 3p orbitals available for bonding.
- Some
compounds of these elements exceed the octet rule, termed as an
"expanded octet."
- Examples
include PF5, SF6,
H2SO4, and various coordination compounds.
- Notably,
sulfur forms compounds where it both follows and deviates from the octet
rule, as seen in sulfur dichloride (SCl2).
Other Drawbacks of
the Octet Theory:
- Based
on the chemical inertness of noble gases, but some noble gases like xenon
and krypton form compounds like XeF2,
KrF2, XeOF2, etc.
- Does
not provide insights into molecular shapes.
- Fails
to explain the relative stability of molecules and does not address
molecular energy considerations.
FORMATION OF IONIC OR ELECTROVALENT BOND:
Formation of Ionic or
Electrovalent Bonds:
- Ion Formation:
- Ionic
bond formation depends on the ease of forming positive and negative ions
from neutral atoms.
- Positive
ions (cations) are formed by ionization, which involves removing
electrons from neutral atoms.
- Negative
ions (anions) are formed by adding electrons to neutral atoms.
- Enthalpy Changes:
- Ionization
enthalpy refers to the energy required to remove an electron from a
neutral atom, which is always endothermic.
- Electron
gain enthalpy represents the energy change when a gas-phase atom gains an
electron, and it can be either exothermic or endothermic.
- Electron
affinity is the negative of the energy change during electron gain.
- Factors in Ionic Bond Formation:
- Ionic
bonds are more likely to form between elements with:
- Low
ionization enthalpies (easy electron removal).
- High
negative values of electron gain enthalpy (favorable electron addition).
- Composition of Ionic Compounds:
- Most
ionic compounds consist of cations from metallic elements and anions from
non-metallic elements.
- Exception:
The ammonium ion (NH4+)
forms the cation in some ionic compounds.
- Crystal Structure:
- Ionic
compounds in the crystalline state have three-dimensional arrangements of
cations and anions held together by coulombic interaction energies.
- The
crystal structure varies based on ion sizes, packing arrangements, and
other factors.
- Energy Considerations:
- The
sum of electron gain enthalpy and ionization enthalpy may be positive,
but ionic compounds stabilize due to energy released during crystal
lattice formation.
- Example:
NaCl formation, where ionization enthalpy for Na+(g) and
electron gain enthalpy for Cl– (g) are compensated by the
enthalpy of lattice formation for NaCl(s).
- Qualitative Measure of Stability:
- The
stability of an ionic compound is assessed by its enthalpy of lattice formation,
not solely by achieving an octet of electrons around the ionic species in
the gaseous state.
- Role of Lattice Enthalpy:
- Lattice
enthalpy is crucial in the formation of ionic compounds and determines
their stability.
- Understanding
lattice enthalpy is important for studying the energetics of ionic bond
formation.
Lattice Enthalpy:
- Definition:
- Lattice
enthalpy refers to the energy required to completely separate one mole of
a solid ionic compound into its constituent ions in the gaseous state.
- For
example, the lattice enthalpy of NaCl is 788 kJ mol–1, indicating that
788 kJ of energy is needed to separate one mole of solid NaCl into one
mole of Na+ (g) and one mole of Cl– (g), moving
them to an infinite distance apart.
- Energy Components:
- Lattice
enthalpy considers both attractive forces between ions of opposite
charges and repulsive forces between ions of like charges within the
solid crystal structure.
- Three-Dimensional Structure:
- Ionic
solids have a three-dimensional crystal structure, making it impossible
to calculate lattice enthalpy solely from ion-ion interactions.
- Factors
related to the crystal's geometry and arrangement must be taken into
account.
- Calculation Complexity:
- Calculating
lattice enthalpy involves a combination of ion-ion interactions, crystal
geometry, and intermolecular forces.
- These
complex interactions require advanced computational methods and
experimental data.
Lattice enthalpy represents the energy needed to separate
ionic compounds into their constituent ions in the gaseous state, accounting
for both attractive and repulsive forces, along with the geometric factors
within the crystal lattice. Calculating lattice enthalpy requires a
comprehensive understanding of these interactions and often involves
sophisticated techniques.
BOND PARAMETERS:
BOND LENGTH
Bond Parameters: Bond Length
- Definition:
- Bond
length is the equilibrium distance between the nuclei of two atoms that
are bonded together in a molecule.
- Techniques
such as spectroscopy, X-ray diffraction, and electron diffraction are
used to measure bond lengths, typically in more advanced chemistry
studies.
- Contribution of Atoms:
- In
a molecule, each atom contributes to the overall bond length.
- For
covalent bonds, the contribution of each atom is referred to as the
covalent radius of that atom.
- Covalent Radius:
- The
covalent radius is approximately determined as the radius of an atom's
core that comes into contact with the core of an adjacent atom in a
bonded state.
- It
is calculated as half of the distance between two similar atoms joined by
a covalent bond within the same molecule.
- Van der Waals Radius:
- The
van der Waals radius represents the overall size of an atom, including
its valence shell, in a nonbonded situation.
- It
is calculated as half of the distance between two similar atoms in
separate molecules in a solid.
- Illustration of Covalent and Van der
Waals Radii:
- Covalent
and van der Waals radii are illustrated for chlorine in Figure
- Typical Bond Lengths:
Some average
bond lengths for single, double, and triple bonds are provided in Table
- Table
presents bond lengths for common molecules.
- Covalent Radii of Common Elements:
- Table
lists the covalent radii of some common elements.
Bond length is the distance between the nuclei of bonded
atoms in a molecule. It is a fundamental parameter in understanding molecular
structure and is determined through various measurement techniques. The
covalent radius represents an atom's contribution to the bond length in a
molecule, while the van der Waals radius accounts for the overall size of an
atom in nonbonded situations. Specific bond lengths for different types of
bonds and common molecules are available in reference tables.
BOND PARAMETERS:
BOND ANGLE
Bond Angle:
- Definition:
- Bond
angle is the angle measured in degrees between the orbitals containing
bonding electron pairs around the central atom in a molecule or complex
ion.
- Measurement:
- Bond
angles can be experimentally determined using spectroscopic methods.
- Importance:
- Bond
angles provide insights into the distribution of orbitals around the
central atom within a molecule or complex ion.
- Bond
angles are crucial in determining the overall shape of a molecule.
- Example:
- For
instance, the H–O–H bond angle in water (H2O) can be
represented as an example:
Bond angle is the angle between the orbitals containing
bonding electron pairs around a central atom within a molecule or complex ion.
It helps determine the molecular or ion's shape and is measured in degrees
using spectroscopic techniques.
BOND PARAMETERS:
BOND ENTHALPY
Bond Enthalpy:
- Definition:
- Bond
enthalpy is defined as the amount of energy required to break one mole of
bonds of a specific type between two atoms in a gaseous state.
- The
unit of bond enthalpy is kJ mol–1.
- Example:
- For
instance, the H–H bond enthalpy in a hydrogen molecule is 435.8 kJ mol–1,
represented as: H2(g) →
H(g) + H(g); ∆aH = 435.8 kJ mol–1
- Strength
of Bonds:
- Bond
enthalpy is a measure of bond strength; the larger the bond dissociation
enthalpy, the stronger the bond in the molecule.
- For
molecules with multiple bonds, such as O2 and N2,
the bond enthalpies are as follows:
- O2 (O = O) (g) → O(g) +
O(g); ∆aH = 498 kJ mol–1
- N2 (N ≡ N) (g) → N(g) +
N(g); ∆aH = 946.0 kJ mol–1
- Heteronuclear
Diatomic Molecules:
- In
the case of heteronuclear diatomic molecules like HCl, the bond enthalpy
is determined as follows:
- HCl
(g) → H(g) + Cl(g); ∆aH = 431.0 kJ mol–1
- Polyatomic
Molecules:
- Measuring
bond strength in polyatomic molecules is more complex.
- For
example, in H2O, breaking the two O–H bonds doesn't require
the same amount of energy:
- H2O(g) → H(g) + OH(g); ∆aH1
= 502 kJ mol–1
- OH(g) → H(g) + O(g); ∆aH2
= 427 kJ mol–1
- Average
Bond Enthalpy:
- To
account for variations in bond strengths within polyatomic molecules, the
concept of average bond enthalpy is used.
- It
is calculated by dividing the total bond dissociation enthalpy by the
number of bonds broken.
- For
example, in water (H2O): Average bond enthalpy = (502 + 427) /
2 = 464.5 kJ mol–1
Bond enthalpy quantifies the energy required to break a
specific type of bond in a gaseous state. It is an indicator of bond strength,
with larger bond dissociation enthalpies corresponding to stronger bonds. In
polyatomic molecules, variations in bond strength are addressed by calculating
the average bond enthalpy.
BOND PARAMETERS: BOND ORDER
Bond Order:
- Definition:
- In
the Lewis description of a covalent bond, bond order refers to the number
of bonds between two atoms within a molecule.
- It
quantifies the sharing of electron pairs between the bonded atoms.
- Examples
of Bond Orders:
- Bond
order is often represented as an integer:
- In
H2, with one shared electron pair, the bond order is 1.
- In
O2, with two shared electron pairs, the bond order is 2.
- In
N2, with three shared electron pairs, the bond order is 3.
- In
CO, with three shared electron pairs between C and O, the bond order is
3.
- Isoelectronic
Molecules and Ions:
- Isoelectronic
molecules and ions have identical bond orders.
- For
example, F2 and O22– both
have a bond order of 1.
- N2, CO, and NO+ all have a bond
order of 3.
- Relationship
with Bond Enthalpy and Bond Length:
- There
is a general correlation between bond order, bond enthalpy, and bond
length in molecules.
- As
bond order increases, bond enthalpy (the energy required to break the
bond) typically increases, while bond length (the distance between bonded
atoms) decreases.
- Example
of High Bond Order:
- N2 has a bond order of
3 and a high bond enthalpy (946 kJ mol–1), making it one of
the highest for a diatomic molecule.
Bond order quantifies the number of bonds between two atoms
in a molecule and is a fundamental concept in understanding the nature of
covalent bonds. It can provide insights into bond strength and molecular
stability, with higher bond orders generally corresponding to stronger bonds
and shorter bond lengths.
BOND PARAMETERS:
RESONANCE STRUCTURES
Resonance Structures:
- Need
for Multiple Structures:
- In
many cases, a single Lewis structure is insufficient to accurately
represent a molecule based on its experimentally determined properties.
- For
instance, consider the ozone (O3)
molecule, which can be represented by two Lewis structures, I and II.
- Ozone
Example:
- Both
structures I and II depict an O–O
single bond and an O=O double
bond.
- Normal
O–O and O=O bond lengths are 148 pm and 121 pm, respectively.
- Experimentally
determined oxygen-oxygen bond lengths in O3 are identical (128 pm), indicating the bonds
are intermediate between double and single bonds.
- Neither
of the two Lewis structures accurately represents this situation.
- Introduction
of Resonance:
- The
concept of resonance is introduced to address such cases where a single
Lewis structure falls short.
- Resonance
suggests that when a single Lewis structure is inadequate, multiple
structures with similar energy, nuclear positions, and electron pairs are
considered as canonical structures to describe the molecule accurately.
- Resonance
Hybrid:
- In
the case of O3,
structures I and II constitute the canonical structures or resonance
structures.
- The
hybrid of these structures, represented as III, provides a more accurate
depiction of O3 and
is termed the resonance hybrid.
- Resonance
is denoted by a double-headed arrow (⇌).
- Examples:
- Other
examples of molecules with resonance structures include the carbonate ion
and carbon dioxide.
- Stabilization
and Averaging:
- Resonance
serves two key purposes:
- It
stabilizes the molecule as the energy of the resonance hybrid is lower
than that of any single canonical structure.
- It
averages the characteristics of bonds throughout the molecule.
- Energy
Consideration:
- The
energy of the O3 resonance hybrid is lower than either of the
two individual canonical forms I and II.
Resonance structures are used when a single Lewis structure
cannot accurately describe a molecule's properties. Resonance involves multiple
canonical structures with similar characteristics, and their hybrid provides a
more precise representation. Resonance stabilizes molecules and helps average
bond characteristics, leading to a more accurate depiction of the molecule's
behavior.
BOND PARAMETERS:
MISCONCEPTIONS ABOUT RESONANCE
Dispelling Misconceptions about Resonance:
- Non-Existence
of Canonical Forms:
- Canonical
forms (resonance structures) do not have a real, independent existence as
separate entities.
- No
Fractional Existence:
- The
molecule does not exist for a fraction of time in one canonical form and
then switch to another canonical form. It doesn't physically shift
between these forms.
- Absence
of Equilibrium:
- There
is no equilibrium between canonical forms, as is seen in tautomeric forms
(such as keto and enol) in tautomerism. Resonance does not involve
dynamic interconversion between forms.
- Single
Molecular Structure:
- The
molecule has a single, well-defined structure, which is the resonance
hybrid of the canonical forms.
- This
resonance hybrid cannot be accurately represented by a single Lewis
structure.
It's crucial to understand that resonance involves a single
molecule with a resonance hybrid structure derived from multiple canonical
forms. There is no physical transition or equilibrium between these forms, and
the canonical forms themselves are not separate, independently existing
entities. Resonance is a tool for more accurately describing the distribution
of electrons within a molecule.
BOND PARAMETERS:
POLARITY OF BONDS
Polarity of Bonds:
- Idealized
Bond Types:
- In
reality, no bond or compound is purely ionic or purely covalent; they
represent idealized situations.
- Nonpolar
Covalent Bonds:
- When
covalent bonds form between identical atoms, like H2, O2,
Cl2, N2, or F2, the shared electron pair
is equally attracted by both atoms.
- Electron
pair is situated exactly between the two identical nuclei.
- Such
bonds are termed nonpolar covalent bonds.
- Polar
Covalent Bonds:
- In
heteronuclear molecules, like HF, the shared electron pair is displaced
more towards the more electronegative atom, like fluorine.
- This
results in a polar covalent bond, where one end is more electron-rich
(negative) and the other end is more electron-deficient (positive).
- Dipole
Moment:
- Polarization
leads to the molecule having a dipole moment (µ), expressed as µ = charge
(Q) × distance of separation (r).
- Dipole
moments are usually measured in Debye units (D), with 1 D = 3.33564 × 10–30
C m.
- Dipole
moment is a vector quantity, depicted as a crossed arrow ( ⇀ ) with the cross at the positive end and
the arrowhead at the negative end.
- Contribution
in Polyatomic Molecules:
- In
polyatomic molecules, the dipole moment depends not only on individual
bond dipoles but also on their spatial arrangement.
- For
example, in H2O, the net dipole moment results from the
orientation of the two O–H bond dipoles.
- Canceling
Dipole Moments:
- In
some cases, like BeF2, bond dipoles point in opposite
directions and cancel each other, resulting in a zero net dipole moment.
- NH3 vs. NF3:
Let us study an interesting case of NH3 and NF3
molecule. Both the molecules have pyramidal shape with a lone pair of electrons
on nitrogen atom. Although fluorine is more electronegative than nitrogen, the
resultant, dipole moment of NH3 (4.90 × 10–30 C m) is
greater than that of NF3 (0.8 × 10–30 C m). This is
because, in case of NH3 the orbital dipole due to lone pair is in
the same direction as the resultant dipole moment of the N – H bonds, whereas
in NF3 the orbital dipole is in the direction opposite to the
resultant dipole moment of the three N–F bonds. The orbital dipole because of
lone pair decreases the effect of the resultant N – F bond moments, which
results in the low dipole moment of NF3 as represented below:
- Interesting
cases like NH3 and NF3 demonstrate the influence of
lone pairs on dipole moments.
- Despite
fluorine being more electronegative, NH3 has a higher dipole
moment due to the direction of the lone pair's orbital dipole.
- Partial
Covalent Character in Ionic Bonds:
- Both
covalent and ionic bonds have some partial characteristics of the other
type.
- Fajans'
rules explain the partial covalent character of ionic bonds:
- Smaller
cations and larger anions increase covalent character.
- Greater
charge on cations increases covalent character.
- Transition
metal cations with (n-1)dnnso
electronic configuration are more polarizing than noble gas
configuration (ns²np⁶).
- Factors
Influencing Covalent Character:
- Polarizing
power of the cation, polarisability of the anion, and the extent of
distortion (polarisation) of the anion determine the percentage of
covalent character in an ionic bond.
No bond is entirely ionic or covalent, and the polarity of a
bond depends on the electronegativity of the atoms involved. Dipole moments
reflect bond polarity, and they can be influenced by lone pairs and molecular
geometry in polyatomic molecules. Ionic bonds also have some degree of covalent
character, which can be explained by Fajans' rules, considering factors like
cation size, charge, and electronic configuration.
BOND PARAMETERS:
VSEPR THEORY
- Origin
and Development:
- Proposed
by Sidgwick and Powell in 1940 and later refined by Nyholm and
Gillespie in 1957.
- Developed
to address the limitations of the Lewis concept, which couldn't explain
molecular shapes.
- Basic
Premise:
- VSEPR
theory is based on the repulsive interactions of electron pairs in the
valence shell of atoms.
- It
assumes that electron pairs (both bonding and non-bonding) around a
central atom arrange themselves in a way that minimizes electrostatic
repulsion to achieve the most stable geometry.
- Electron
Pair Types:
- VSEPR
considers two main types of electron pairs: bonding pairs and
non-bonding pairs (lone pairs).
- Geometric
Arrangement:
- The
theory predicts the three-dimensional arrangement of atoms around a
central atom.
- It
provides a simple procedure to predict the shape of covalent molecules.
- Steric
Number:
- The
steric number of an atom is the sum of the number of bonded atoms and
the number of lone pairs around it.
- The
steric number is used to determine the molecular geometry.
- Molecular
Geometries:
- VSEPR
theory predicts various molecular geometries based on the steric
number.
- Common
geometries include linear, trigonal planar, tetrahedral, trigonal
bipyramidal, and octahedral, among others.
- Electron
Pair Repulsion:
- The
theory postulates that electron pairs (both bonding and lone pairs)
repel each other.
- Lone
pairs exert stronger repulsion than bonding pairs, leading to specific
bond angles and shapes.
- Bond
Angles:
- VSEPR
theory provides specific bond angles for different molecular
geometries.
- For
example, in a tetrahedral molecule like methane (CH4), the bond angle is approximately 109.5
degrees.
- Application:
- VSEPR
theory is widely used in chemistry to predict the shapes of molecules
and polyatomic ions.
- It
helps in understanding and explaining the physical and chemical
properties of compounds.
- Limitations:
- VSEPR
theory provides a qualitative understanding of molecular shapes but
doesn't consider the influence of other factors like bond polarity.
- It
may not accurately predict the shapes of molecules with complex or
unusual bonding patterns.
- Advancements:
- While
VSEPR theory laid the foundation for understanding molecular shapes,
more advanced theories like molecular orbital theory and hybridization
have been developed to provide a deeper insight into molecular
structure and bonding.
|
Valence Shell Electron Pair Repulsion (VSEPR) Theory:
- Introduction:
- The
Lewis concept is insufficient for explaining the shapes of molecules.
- Sidgwick
and Powell (1940) introduced the VSEPR theory based on repulsive
interactions of electron pairs in the valence shell.
- Nyholm
and Gillespie (1957) further refined the theory.
- Main
Postulates:
- The
shape of a molecule is determined by the number of valence shell electron
pairs (bonded or nonbonded) around the central atom.
- Electron
pairs in the valence shell repel each other due to their negative charge.
- Electron
pairs position themselves to minimize repulsion and maximize distance.
- The
valence shell is treated as a sphere, with electron pairs localizing on
its surface.
- Multiple
bonds are treated as single electron pairs, and multiple bond electron
pairs are treated as a single super pair.
- VSEPR
is applicable to any resonance structure when multiple structures exist.
- Dependence
on Valence Shell Electron Pairs:
- The
shape of a molecule is determined by the number of valence shell
electron pairs (both bonded and nonbonded) surrounding the central
atom.
- Electron
Pair Repulsion:
- Electron
pairs in the valence shell exert mutual repulsion because their
electron clouds carry a negative charge.
- Minimization
of Repulsion:
- Electron
pairs arrange themselves in three-dimensional space to minimize
repulsive interactions, thus maximizing the distance between them.
- Spherical
Valence Shell:
- The
valence shell of the central atom is treated as a spherical surface,
with electron pairs localizing on this spherical surface at the maximum
possible distance from each other.
- Treatment
of Multiple Bonds:
- Multiple
bonds (e.g., double and triple bonds) are treated as if they were
single electron pairs, with the two or three electron pairs of a
multiple bond considered as a single "super pair" for the
purpose of geometry prediction.
- Applicability
to Resonance Structures:
- When
multiple resonance structures can represent a molecule, the VSEPR model
is applicable to any such structure.
|
- Repulsion
Strength:
- Electron
pair repulsion decreases in the order: Lone pair (lp) – Lone pair (lp)
> Lone pair (lp) – Bond pair (bp) > Bond pair (bp) – Bond pair
(bp).
- Lone
pairs occupy more space than bonding pairs, leading to increased
repulsion.
- Influence
on Molecular Shapes:
- Repulsion
effects lead to deviations from idealized shapes and alterations in bond
angles.
- Categories
for Prediction:
- To
predict molecular shapes using VSEPR, molecules are categorized into two
types: (i) Central atom with no lone pairs (ii) Central atom with one or
more lone pairs.
- Arrangement
of Electron Pairs:
- The table below depicts the arrangement of electron pairs around a central atom A
(without lone pairs) and the resulting geometries of molecules/ions of
the type AB.
- Shapes
with Lone Pairs:
- Table
4.7 shows shapes of molecules/ions where the central atom has one or more
lone pairs.
- Reasons
for Distortions:
- Table
4.8 explains the reasons for deviations from ideal geometries in
molecules.
- Examples:
- The
VSEPR theory successfully predicts the geometries of molecules,
especially those of p-block elements.
- It
works well even when energy differences between possible structures are
small.
- Theoretical
Basis:
- The
VSEPR theory's theoretical foundation regarding the impact of electron
pair repulsions on molecular shapes is not entirely clear and remains a
topic of discussion.
The VSEPR theory is a powerful tool for predicting the
shapes of molecules based on the repulsion between electron pairs in the
valence shell. It successfully describes a wide range of molecular geometries,
especially for p-block elements, although its theoretical basis is still a
subject of debate.