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Valence Bond Theory (VBT) with Detailed Explanations

Valence Bond Theory (VBT) is a quantum mechanical model that explains the formation of covalent bonds between atoms. It
proposes that a covalent bond forms when atomic orbitals of two atoms overlap, allowing their electrons to pair up.

Key Postulates of VBT:

1. Orbital Overlap: When two atomic orbitals from different atoms overlap, a covalent bond is formed. The greater the
overlap, the stronger the bond.
2. Pairing of Electrons: Each overlapping orbital contributes one electron to the bond. These electrons pair up, forming a
shared electron pair.
3. Hybridization: In many cases, atomic orbitals combine to form hybrid orbitals, which have different shapes and
energies than the original atomic orbitals. This hybridization allows for more effective overlap and stronger bonding.

Types of Overlap and Bond Formation:

 Sigma (σ) Bond: Formed by head-to-head overlap of atomic orbitals along the internuclear axis. This type of bond is
stronger and more stable.
 Pi (π) Bond: Formed by side-to-side overlap of atomic orbitals. This type of bond is weaker than a sigma bond.

Hybridization:

 sp Hybridization: One s orbital and one p orbital combine to form two sp hybrid orbitals. This is common in
molecules with linear geometry, such as BeCl2.
 sp2 Hybridization: One s orbital and two p orbitals combine to form three sp2 hybrid orbitals. This is common in
molecules with trigonal planar geometry, such as BF3.
 sp3 Hybridization: One s orbital and three p orbitals combine to form four sp3 hybrid orbitals. This is common in
molecules with tetrahedral geometry, such as CH4.

Examples of VBT:

 H2 molecule: Two 1s orbitals of hydrogen atoms overlap to form a sigma bond.

 CH4 molecule: The carbon atom undergoes sp3 hybridization, forming four sp3 hybrid orbitals. Each hybrid orbital
overlaps with a 1s orbital of a hydrogen atom to form four sigma bonds.
 O2 molecule: Oxygen atoms form two sigma bonds and one pi bond through the overlap of 2p orbitals.

Limitations of VBT:

 Cannot explain delocalized bonding: In molecules with resonance structures, the electrons are delocalized over
multiple bonds, which VBT cannot adequately describe.
 Does not account for molecular geometry: While VBT can explain bond formation, it does not provide a direct
explanation for molecular shapes.

In conclusion, Valence Bond Theory provides a useful model for understanding the formation of covalent bonds. By considering
orbital overlap, electron pairing, and hybridization, VBT can explain the structure and bonding of many molecules. However, it
has limitations in describing delocalized bonding and molecular geometry.

Limitations of Valence Bond Theory (VBT)

Valence Bond Theory (VBT) is a valuable tool for understanding covalent bonding, but it has certain limitations:

1. Inability to Explain Delocalized Bonding: VBT assumes that electrons are localized between two specific atoms in a
covalent bond. However, in molecules with resonance structures, electrons are delocalized over multiple bonds. This
means that they are not confined to a single pair of atoms. VBT struggles to accurately represent this phenomenon.

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2. Difficulty with Molecular Geometry: While VBT can explain bond formation, it does not provide a direct
explanation for molecular shapes. To predict molecular geometry, additional theories like VSEPR (Valence Shell
Electron Pair Repulsion) theory are often used in conjunction with VBT.
3. Oversimplification of Bonding: VBT assumes that bonds are formed by the overlap of atomic orbitals. However, in
reality, the formation of bonds is more complex and involves the interaction of multiple electrons and nuclei. VBT does
not fully capture the intricacies of chemical bonding.
4. Limited Accuracy for Complex Molecules: VBT becomes less accurate as molecules become more complex. For
large or highly conjugated molecules, the calculations required to determine orbital overlap and hybridization can
become cumbersome and less reliable.

In summary, while VBT provides a useful framework for understanding covalent bonding, its limitations highlight the need for
more sophisticated theories, such as molecular orbital theory, to accurately describe the electronic structure and properties of
molecules.

VSEPR Theory: Importance and Limitations

Valence Shell Electron Pair Repulsion (VSEPR) Theory is a simple yet powerful model used to predict the molecular
geometry of molecules based on the repulsion between electron pairs (bonding and lone pairs) around a central atom.

Importance of VSEPR Theory:

 Predicting Molecular Geometry: VSEPR theory allows us to accurately predict the three-dimensional arrangement of
atoms in a molecule.
 Understanding Molecular Properties: The molecular geometry of a molecule directly influences its physical and
chemical properties, such as polarity, reactivity, and intermolecular forces.
 Relating Structure to Properties: VSEPR theory helps us to understand the relationship between a molecule's
structure and its observed properties.

Limitations of VSEPR Theory:

 Exceptions: There are a few exceptions to VSEPR theory, such as molecules with lone pairs on the central atom that
deviate from the predicted geometry.
 Oversimplification: VSEPR theory assumes that electron pairs are point charges that repel each other equally. In
reality, the repulsion between electron pairs is more complex and can be influenced by factors such as bond polarity
and atomic size.
 Inability to Explain Bond Angles: While VSEPR theory can predict the overall molecular geometry, it does not
provide precise information about bond angles.
 Limited Applicability to Transition Metal Complexes: VSEPR theory is less effective in predicting the geometry of
transition metal complexes due to the involvement of d orbitals and the complexity of their electronic structures.

In conclusion, VSEPR theory is a valuable tool for understanding molecular geometry and predicting the properties of
molecules. However, it has limitations and may not be able to accurately explain the geometry of all molecules, especially
complex ones.

VSEPR vs. VBT:

Feature VSEPR Theory VBT

Focus Molecular geometry Bond formation
Assumptions Electron pair repulsion Orbital overlap
Approach Based on electron pair arrangement Based on atomic orbital overlap
Predictions Molecular shape, bond angles Bond types (sigma and pi)
Basis Electron-electron repulsion Orbital overlap

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Exceptions to predicted geometry, inability to Difficulty with delocalized bonding, limited accuracy
Limitations
explain bond angles for complex molecules
Complementary
Often used together Often used together
Nature
Hybridization Not directly involved Involves hybridization of atomic orbitals
Bonding Types Does not explicitly discuss bond types Focuses on sigma and pi bonds
Predicting molecular shapes, understanding Explaining bond formation, understanding molecular
Applications
polarity properties

Explain the directional properties of bonds in molecules like CH4, NH3, and H2O using valence bond theory.

Response:

Valence Bond Theory (VBT) provides a framework for understanding the formation and directional properties of covalent
bonds in molecules. It posits that bonds form when atomic orbitals overlap, and the strength and direction of the bond depend on
the extent and type of overlap.

Overlapping of Atomic Orbitals:

When orbitals of two atoms come close, their overlap can be positive, negative, or zero based on the phase and orientation of
their wave functions. For bond formation, positive overlap is essential, meaning the orbitals must have the same sign (phase) and
orientation. Directional Properties of Bonds:

The directional properties of bonds in polyatomic molecules like CH4, NH3, and H2O are explained by considering the
hybridization of atomic orbitals.

1. CH4 (Methane):

 Hybridization: Carbon undergoes sp3 hybridization, mixing its 2s and three 2p orbitals to form four equivalent
hybrid orbitals.
 Overlap: Each sp3 hybrid orbital of carbon overlaps with the 1s orbital of a hydrogen atom to form a sigma (σ) bond.
 Geometry: The four C-H bonds are arranged in a tetrahedral geometry around the central carbon atom, with bond
angles of 109.5°.

2. NH3 (Ammonia):

 Hybridization: Nitrogen also undergoes sp3 hybridization.

 Overlap: Three sp3 hybrid orbitals of nitrogen overlap with the 1s orbitals of three hydrogen atoms to form three N-H
sigma bonds.
 Geometry: The remaining sp3 hybrid orbital on nitrogen contains a lone pair of electrons. The repulsion between the
lone pair and the three bonded pairs causes the N-H bonds to be slightly compressed, resulting in a trigonal pyramidal
geometry with bond angles of approximately 107°.

3. H2O (Water):

 Hybridization: Oxygen also undergoes sp3 hybridization.

 Overlap: Two sp3 hybrid orbitals of oxygen overlap with the 1s orbitals of two hydrogen atoms to form two O-H
sigma bonds.
 Geometry: The remaining two sp3 hybrid orbitals on oxygen contain lone pairs of electrons. The repulsion between
the lone pairs and the bonded pairs causes the O-H bonds to be further compressed compared to NH3, resulting in a
bent or angular geometry with bond angles of approximately 104.5°.

Conclusion:

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The directional properties of bonds in CH4, NH3, and H2O are primarily determined by the hybridization of the central atom and
the arrangement of bonded atoms and lone pairs around it. The VBT effectively explains the observed molecular geometries and
bond angles based on the overlap and hybridization of atomic orbitals.

VBT and VSEPR Quiz: Questions

VBT (Valence Bond Theory)

1. What is the basic principle of VBT?

2. Explain the concept of orbital overlap in VBT.
3. What are sigma and pi bonds? How do they differ?
4. What is hybridization? Explain the different types of hybridization.
5. How does VBT explain the formation of a covalent bond in the H2 molecule?
6. Explain the concept of resonance in VBT.
7. What are the limitations of VBT?
8. How does VBT differ from Molecular Orbital Theory (MOT)?
9. Can VBT explain the delocalized bonding in benzene?
10. How does VBT account for the molecular geometry of a molecule?

VSEPR (Valence Shell Electron Pair Repulsion) Theory

11. What is the basic principle of VSEPR theory?

12. How does VSEPR theory predict molecular geometry?
13. What are lone pairs and bonding pairs? How do they affect molecular geometry?
14. Explain the VSEPR model for molecules with no lone pairs on the central atom.
15. Explain the VSEPR model for molecules with one, two, or three lone pairs on the central atom.
16. What is the difference between a molecular shape and an electron-pair geometry?
17. How does VSEPR theory explain the bond angles in molecules like CH4 and NH3?
18. What is the relationship between VSEPR and hybridization?
19. Can VSEPR theory explain the molecular geometry of molecules with multiple central atoms?
20. What are the limitations of VSEPR theory?

Combined VBT and VSEPR

21. How can VBT and VSEPR be used together to explain the structure and bonding of a molecule?
22. Explain the relationship between hybridization and molecular geometry.
23. How can VSEPR theory be used to predict the molecular geometry of a molecule with a double bond or a triple bond?
24. What is the difference between a polar covalent bond and a nonpolar covalent bond? How do VBT and VSEPR help
explain these concepts?
25. How can VBT and VSEPR be used to explain the properties of a molecule, such as its polarity and solubility?
26. What is the role of lone pairs in determining the molecular geometry and polarity of a molecule?
27. How can VBT and VSEPR be used to explain the reactivity of a molecule?
28. What is the difference between a sigma bond and a pi bond in terms of their strength and orientation?
29. How can VBT and VSEPR be used to explain the concept of resonance structures?
30. What are the limitations of using VBT and VSEPR together?

NEET/JEE Level Multiple Choice Questions on VBT and

VSEPR
Valence Bond Theory (VBT)

1. Hybridization:

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o What is the hybridization of the central atom in NH3?

 (a) sp
 (b) sp2
 (c) sp3
 (d) dsp2
o How many hybrid orbitals are formed in sp3 hybridization?
 (a) 2
 (b) 3
 (c) 4
 (d) 5
2. Bond Formation:
o Which of the following is a sigma bond?
 (a) C‐H in CH4
 (b) C=C in ethene
 (c) C≡C in acetylene
 (d) All of the above
o What is the difference between a single bond, a double bond, and a triple bond?
 (a) Single bond has one sigma bond, double bond has two sigma bonds, and
triple bond has three sigma bonds.
 (b) Single bond has one sigma bond, double bond has one sigma and one pi
bond, and triple bond has one sigma and two pi bonds.
 (c) Single bond has one sigma and one pi bond, double bond has two sigma and
one pi bond, and triple bond has three sigma and two pi bonds.
 (d) Single bond has one sigma and one pi bond, double bond has two sigma and
two pi bonds, and triple bond has three sigma and three pi bonds.
3. Molecular Geometry:
o What is the molecular geometry of a molecule with sp3 hybridization and no lone pairs?
 (a) Linear
 (b) Trigonal planar
 (c) Tetrahedral
 (d) Trigonal bipyramidal
o How does the presence of lone pairs affect molecular geometry?
 (a) Lone pairs repel bond pairs.
 (b) Lone pairs attract bond pairs.
 (c) Lone pairs do not affect molecular geometry.
 (d) Lone pairs repel each other.

VSEPR (Valence Shell Electron Pair Repulsion) Theory

1. Basic Principles:
o According to VSEPR theory, the arrangement of electron pairs around a central atom is
determined by (a) the number of valence electrons (b) the electronegativity of the
atoms (c) the size of the atoms (d) the repulsion between electron pairs.
o VSEPR theory predicts the (a) molecular geometry (b) bond angles **(c) both (a) and (b)
**(d) none of the above.
2. Molecular Shapes:
o What is the molecular shape of a molecule with two bonding pairs and two lone pairs?

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 (a) Linear
 (b) Bent
 (c) Trigonal planar
 (d) Tetrahedral
o Predict the molecular shape of SF6.
 (a) Octahedral
 (b) Square planar
 (c) Trigonal bipyramidal
 (d) Tetrahedral
3. Bond Angles:
o How does the presence of lone pairs affect bond angles?
 (a) Lone pairs increase bond angles.
 (b) Lone pairs decrease bond angles.
 (c) Lone pairs have no effect on bond angles.
 (d) Lone pairs increase bond angles in some cases and decrease them in others.
o Predict the bond angle in a molecule with sp2 hybridization.
 (a) 109.5°
 (b) 120°
 (c) 180°
 (d) It depends on the specific molecule.

Combined VBT and VSEPR

1. Hybridization and Molecular Geometry:

o Explain how hybridization and VSEPR theory work together to predict molecular
geometry.
 (a) Hybridization determines the number of electron pairs around the central
atom, and VSEPR theory determines the arrangement of these pairs.
 (b) VSEPR theory determines the number of electron pairs around the central
atom, and hybridization determines the arrangement of these pairs.
 (c) Hybridization and VSEPR theory are not related.
 (d) Both hybridization and VSEPR theory are used to determine the molecular
geometry, but they are not related.
2. Resonance and VSEPR:
o How does resonance affect the molecular geometry of a molecule?
 (a) Resonance has no effect on molecular geometry.
 (b) Resonance can change the molecular geometry.
 (c) Resonance can change the bond angles but not the molecular shape.
 (d) Resonance can change the molecular shape but not the bond angles.
3. Exceptions to VSEPR:
o Which of the following is an exception to the VSEPR theory?
 (a) XeF2
 (b) SF6
 (c) CH4
 (d) NH3

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