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MES 604: Chemistry of Materials

Part III: Chemistry of Organic Materials

Reference Book: “Introduction to Organic Chemistry, 3rd Edition”, William
Brown and Thomas Poon, John Wiley & Sons, Inc., 2005.
Lecture 1:
Introduction
Bond Angles and the Shapes of Molecules

In Section 1.3, we used a shared pair of electrons as the
fundamental unit of a covalent bond and drew Lewis
structures for several small molecules containing various
combinations of single, double and triple bonds. We can
predict bond angles in these and other molecules in a very
straightforward way by using the Valence Shell Electron
Repulsion (VSEPR) model.

According to this model, the valence electrons of an atom may
be involved in the formation of single, double or triple bonds,
or they may be unshared. Each combination creates a
negatively charged region of space. Because like charges
repel each other, the various regions of electron density
around an atom spread so that each is far away from the
others as possible.
Examples
Orbital Overlap Model of Covalent Bonding

As much as the Lewis and VSEPR models help us to
understand covalent bonding and the geometry of
molecules, they leave many questions unanswered. The
most important of these questions is the relation between
molecular structure and chemical reactivity. For
example, carbon-carbon single bonds are quite
unreactive, but carbon-carbon double bonds react with a
wide variety of reagents. The Lewis model gives us no
way to account for these differences. Therefore, let us
turn to a newer model of covalent bonding, namely, the
formation of covalent bonds by the overlap of atomic
orbitals.
Shapes of Atomic Orbitals

All s orbitals have the shape of a
sphere, with its center at the
nucleus
•of the s orbitals, a 1s orbital
is the smallest, a 2s orbital is
larger, and a 3s orbital is
larger still

A p orbital consists
of two lobes
arranged in a
straight line with the
center at the
nucleus

Note: We do NOT study d and f orbitals in this class.
Orbital Overlap Model

Covalent bonds (both σ and π
bonds) form when a portion of an Overlap of s orbitals
atomic orbital of one atom overlaps a forms a σ bond
portion of an atomic orbital of another
atom

•in forming the σ covalent bond
in H-H, for example, there is head-
to-head overlap of the 1s orbitals
of each hydrogen

•In forming the π covalent bond
in C=C, for example, there is
shoulder to shoulder overlap of the
2p orbitals of each carbon
Hybrid Orbitals
The Problem:
overlap of 2s and 2p atomic orbitals would give bond angles of
approximately 90°. instead we observe bond angles of
approximately 109.5°, 120°, and 180°

A Solution:
hybridization of atomic orbitals. 2nd row elements use sp3, sp2, and
sp hybrid orbitals for bonding

We study three types of hybrid atomic orbitals
sp3 (one s orbital + three p orbitals give four sp3 orbitals)
sp2 (one s orbital + two p orbitals give three sp2 orbitals)
sp (one s orbital + one p orbital give two sp orbitals)

Overlap of hybrid orbitals can form two types of bonds (i.e. σ and π
bonds), depending on the geometry of the overlap
One type of bond are formed by “direct” overlap (σ bond)
One type of bond are formed by “parallel” overlap (π bond)
sp3 Hybrid Orbitals

• Each sp3 hybrid orbital has two
lobes of unequal size
• The four sp3 hybrid orbitals are
directed toward the corners of a
regular tetrahedron at angles of
109.5°

orbital overlap bonding in water, ammonia, and methane
sp2 Hybrid Orbitals

An sp2 hybrid orbital has two lobes of unequal size
•the three sp2 hybrid orbitals are directed toward the corners
of an equilateral triangle at angles of 120°
•the unhybridized 2p orbital is perpendicular to the plane of
the three sp2 hybrid orbitals
a carbon-carbon double bond consists of one sigma (σ ) bond and one
pi (π ) bond

a carbon-oxygen double bond also consists of one sigma (σ ) bond
and one pi (π ) bond
sp Hybrid Orbitals

Each sp hybrid orbital has two lobes of unequal size
•the two sp hybrid orbitals lie in a line at an angle of 180°
•the two unhybridized 2p orbitals are perpendicular to each
other and to the line through the two sp hybrid orbitals
a carbon-carbon triple bond consists of one sigma (σ ) bond
and two pi (π ) bonds
Summary of orbitals and bond types
Structural formula
Structural formula: the order of bond for the carbon atoms in the chain.
In the “(expanded) structural formula”: all the individual atoms and
their covalent bonds are drawn.
In the “condensed structural formula”: each carbon atom is grouped
with its bonded hydrogen atoms.
H H
H C becomes CH3— or CH3 & C becomes —CH2— or CH2
H H

An abbreviated structure called the line-angle (line-bond) formula
shows only the bonds from carbon to carbon. The ends of the lines
and the corners where the lines meet are understood to be carbon
atoms attached to the proper number of hydrogen atoms to give four
bonds. For instance hexane:
CH3CH2CH 2CH 2CH 2CH 3
Functional Groups
Functional group:
group an atom or group of atoms within a molecule that
shows a characteristic set of physical and chemical properties
Functional groups are important for three reasons, they are
•the units by which we divide organic compounds into classes
•the sites of characteristic chemical reactions
•the basis for naming organic compounds
Functional Groups -- Hydroxyl group

HH H H H
H-C-C-O-H C C
HH H H O H
An alcohol
wedges and
 (Ethanol) ball-and-stick model space-filling model dashes model

Alcohols are classified as primary (1°), secondary (2°) and tertiary (3°),
depending on the number of carbon atoms bonded to the carbon
bearing the –OH groups:
H H CH3
CH3 C OH CH3 C OH CH3 C OH
H CH3 CH3

a 1° alcohol a 2° alcohol a 3° alcohol
Functional Groups – Amino group

Amines are classified as primary (1°), secondary (2°) and tertiary (3°),
depending on the number of carbon atoms bonded to the nitrogen
atom:

CH3 N H CH3 N H CH3 N CH3
H CH3 CH3
(a 1° amine) (a 2° amine) (a 3° amine)
Functional Groups – Carbonyl group

Carbonyl group of aldehydes and ketones

O O
CH3-C-H CH3 -C-CH3
An aldehyde A ketone
Functional Groups – Carboxyl group

Carboxyl group of carboxylic acids

O
CH3-C-O-H or CH3COOH or CH3CO2H
Acetic acid
Organic Compounds in Household Products