Chapter 2: Structure and Properties of Organic Molecules: Bonding Theories

Any theory of bonding needs to explain why & how bonds form, and the resulting observed
molecular geometries.
There are two basic theories Valence Bond and Molecular Orbital (MO) theory. Both use the idea
of orbital overlap to create bonds. The main difference is when orbitals are allowed to merge.

Valence Bond Theory: Bonds are created by orbital overlap to produce s or p bonds.
To explain many observed molecular geometries, pure “s” and “p” atomic orbitals are
combined to produce a set of “hybrid” orbitals on atoms. These hybrid orbitals then
form bonds between atoms producing the correct geometry.

Orbitals are combined in various portions to make equivalent hybrid orbitals, i.e.

AOs(#(s, p)) hybrid orientation

1, 1 2 sp linear
1, 2 3 sp2 trigonal planar
1, 3 4 sp3 tetrahedral

Note: for a given atom, all hybrid orbitals have the same energy.
The total number hybrid orbitals equals the total number of AOs used to make them
Unhybridized “p” orbitals can be used to form p bonds (or remain empty).

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Atomic Orbitals Combine
to Form Molecular Orbitals

Orbitals are Conserved

# of Molecular Orbitals = # of Atomic
Orbitals Combined

Side-to-Side Overlap of In-Phase

p Orbitals Forms a π Bond

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Methane (CH4)
Geometry: tetrahedral
The 4 C-H bonds have the same length.
All the bond angles are the same (109.5°)

In Order to Form Four Bonds,

Carbon Must Promote an Electron

Four Orbitals are Mixed to

Form Four Hybrid Orbitals

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An sp3 orbital has a large lobe and a small lobe

The Carbon in Methane is sp3

Carbon is tetrahedral. The tetrahedral

bond angle is 109.5°

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 The Bonding in Ethane ethane

End-on Overlap of Orbitals

Forms a σ Bond

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 Ethene

Carbon bonds to 3 atoms, so

it needs to hybridize 3 atomic orbitals

An sp2 Carbon Has Three sp2

Orbitals and One p Orbital

Gemetry: trigonal planar

The Bonding in Ethene

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Ethyne (Acetylene)
Carbon bonds to 2 atoms, so it needs
to hybridize 2 atomic orbitals

The Two sp Orbitals Point in Opposite Geometry: linear

Directions; The Two p Orbitals are
Perpendicular

The Bonding in Ethyne

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The Carbon in the Methyl Cation
and in the Methyl Radical are sp2

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In Ammonia (NH3) If N used p orbitals to form bonds, the bond angles would be 90°.

The observed bond angles are 107.3°,

so nitrogen must used hybridized orbitals.
Molecular geometry: trigonal pyramidal
Electronic Geometry: Tetrahedral

Molecular geometry is the three-dimensional arrangement of the atoms that

constitute a molecule.
Electronic Geometry: The geometric arrangement of orbitals containing the
shared and unshared electron pairs surrounding the central atom of a molecule
or polyatomic ion. 9
In water (H2O) the observed bond Molecular geometry: Bent
angles are 104.5°, so oxygen Electronic Geometry: Tetrahedral
must used hybridized orbitals.

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 Hybridization and
Molecular Geometry

The orbitals used in bond formation determine the bond angle.

Hybridization of C, N, and O

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Bond Strength and Bond Length

The more bonds holding 2 atoms

together, the stronger and shorter
it is.

The greater the electron density in

the region of overlap, the stronger
and shorter the bond.

The more s character in the orbital,

the stronger and shorter is the bond.

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• The shorter the bond, the stronger it is.
• The greater the electron density in the region of
• orbital overlap, the stronger the bond.
• The more s character, the shorter and stronger the bond.
• The more s character, the larger the bond angle.

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 Rotation Around Double Bonds

• Double bonds cannot rotate.

• Compounds that differ in how their substituents are arranged around the double bond
can be isolated and separated.

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 Isomerism
• Molecules that have the same molecular formula but differ in the arrangement of their
atoms are called isomers.
• Constitutional (or structural) isomers differ in their bonding sequence.
• Stereoisomers differ only in the arrangement of the atoms in space.

Constitutional Isomers (structural)

• Constitutional isomers have the same chemical formula, but the atoms are connected in a
different order.
• Constitutional isomers have different properties.
• The number of isomers increases rapidly as the number of carbon atoms increases.

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 Geometric Isomers: Cis and
Trans

• Stereoisomers are compounds with the atoms bonded in the same order, but their
atoms have different orientations in space.
• Cis and trans are examples of geometric stereoisomers; they occur when there is a
double bond in the compound.
• Since there is no free rotation along the carbon–carbon double bond, the groups on
these carbons can point to different places in space.

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 Bond Dipole Moments

Dipole Moments of Molecules

•Dipole moments are due to differences in electronegativity.
•They depend on the amount of charge and distance of separation.
•They are measured in debyes (D).

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 Molecular Dipole Moment

• The molecular dipole moment is the vector sum of the bond dipole moments.
• Depends on bond polarity and bond angles.
• Lone pairs of electrons contribute to the dipole moment.

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Intermolecular Forces
• Strength of attractions between molecules influences the melting point (m. p.),
boiling point (b. p.), and solubility of compounds.
• Classification of attractive forces:
– Hydrogen bonding in molecules with —OH or —NH groups.
– Dipole–dipole forces.
– London dispersions forces.

Hydrogen Bonding
• Strong dipole–dipole attraction.
• Organic molecules must have N—H or O—H to be able to form a hydrogen bond.
• The hydrogen from one molecule is strongly attracted to a lone pair of electrons on the
oxygen of another molecule.
• O—H is more polar than N—H, so alcohols have stronger hydrogen bonding.

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Dipole–Dipole Forces
• Dipole–dipole interactions result from the approach of two polar molecules.
• If their positive and negative ends approach, the interaction is an attractive one.
• If two negative ends or two positive ends approach, the interaction is repulsive.
• In a liquid or a solid, the molecules are mostly oriented with the positive and negative ends
together, and the net force is attractive.

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London Dispersion Forces
• One of the Van der Waal forces.
• A temporary dipole moment in a molecule can induce a temporary dipole
moment in a nearby molecule.
• An attractive dipole–dipole interaction results for a fraction of a second.
• Main force in nonpolar molecules.
• Larger atoms are more polarizable.

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 Effect of Branching on Boiling Point

• The long-chain isomer (n-pentane) has the greatest surface area and the
highest boiling point.
• As the amount of chain branching increases, the molecule becomes more
spherical and its surface area decreases.
• The most highly branched isomer (neopentane) has the smallest surface area
and the lowest boiling point.

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Boiling Points and Intermolecular Forces

C H C H O H CH O CH
3 2 3 3

ethanol, b. p. = 78 °C dimethyl ether, b. p. = -25 °C

Hydrogen bonding increases the b. p. of the molecule.

C H C H OH C H C H N H
3 2 3 2 2
ethanol, b. p. = 78 °C
ethyl amine, b. p. 17 °C

O—H is more polar than N—H, so alcohols have stronger hydrogen

bonding and, therefore, higher boiling points.

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Polarity Effects on Solubility
• Like dissolves like.
• Polar solutes dissolve in polar solvents.
• Nonpolar solutes dissolve in nonpolar solvents.
• Molecules with similar intermolecular forces will mix freely.

Rank the following compounds in order of increasing boiling points.

Explain the reasons for your chosen order.

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