Chapter 8 Molecular

structure and covalent

bonding
theories
Describe the basic ideas of the valence
shell electron pair repulsion (VSEPR) theory
Decribe the relationships between
molecular shapes and polarities
Predict whether a molecule is polar or
nonpolar
Describe the basic ideas of valence bond
(VB) theory
Basic understanding about hybrid orbitals

Valence shell electron pair

repulsion (VSEPR) theory

Each set of valence shell

electrons on a central atom is
significant. The sets of valence shell
electrons on the central atom repel
one another. They are arranged
about the central atom so that
repulsions among them are as small
as possible.

We define a set" of electrons as

any number of electrons that
occupy a localized region around an
atom. Thus, an electron set may
consist of a single bond, a double
bond, a triple bond, a lone pair, or
even a lone electron.

Central atom is any atom that is

bonded to more than one other atom
Regions of high electron density
around the central atom

Each bonded atom is counted as one

region of high electron density (whether
the bonding is single, double, or triple)
Each unshared pair of valence electrons
on the central atom is counted as one
region of high electron density

According to VSEPR theory, the molecule or

ion is most stable when the regions of high
electron density on the central atom are as
far apart as possible. The arrangement of
these regions of high electron density
around the central atom is referred to as
electronic geometry of the central atom
The arrangement of atoms around the
central atom is called the molecular
geometry.

Example

CO2, NH3, CH4, SO42-

Central atom?
Number of regions of high e
density

Formula

CO2

NH3

CH4

SO42-

Lewis dot formula:

Central atom:
Number of atoms
bonded to central atom:
Number of unshared
pairs on central atom:
Total number of regions
of high electron density
on central atom:

Exercise
Identify the central atom (or
atoms) in each of the following
compounds or ions:
HCO3-; SiO2; SO2; Al(OH)4-; BeBr2;
(CH3)4Pb

Number of Regions of High Electron Density About a Central A

No. Regions

Electronic Geometry

of High Electron

Description

Density

Angles
2

Line Drawing

linear
180o

trigonal planar
120o

tetrahedral
109.5o

trigonal bipyramidal
90, 120, 180o

octahedral;
90o; 180o

Effect of Lone Pairs

The relative magnitudes of the repulsive

forces between pairs of electrons on an
atom are
lp/lp>>lp/bp>bp/bp
Where lp refer to lone (unshared) pairs and
bp refer to bonding pairs of valence shell
electrons.

Because a lone pair is held by

only one nucleus, it is less
confined and exerts stronger
repulsions than a bonding pair.

Effect of Double Bonds

HCHO

Effect of Double Bonds

the double bond, with its greater

electron density, repels the two
single bonds more strongly than
they repel each other

MOLECULAR SHAPE AND

MOLECULAR POLARITY

One of the most important and farreaching effects of molecular shape

is molecular polarity, which can
influence melting and boiling
points, solubility, chemical
reactivity, and even biological
function.

In molecules with more than two

atoms, both shape and bond polarity
determine molecular polarity.

Polar molecules: the

influence of molecular
geometry

For a molecule to be polar, two

conditions must both be met:

1. There must be at least one polar bond or

lone (unshared) pair on the central atom,
and
2. (a) The polar bonds, if there are more
than one must not be arranged so that
their polarities (bond dipoles) cancel, or
(b) If there are two or more lone (unshared)
pairs on the central atom, they must not be
arranged so that their polarities cancel

Example

HF
CO2

H 2O

Each bond dipole is viewed as an

electronic vector with magnitude
and direction

Exercise

From electronegativity (EN) values

predict whether each of the following
molecules is polar and show the
direction of bond dipoles and the
overall molecular dipole when
applicable:

Exercise
Which of the following molecules
are polar? Why?
CH4; CH3Br; CH2Br2; CHI3;CI4

Molecular Shapes with

More Than One Central
Atom

The shapes of these molecules are

combinations of the molecular
shapes for each central atom
CH3-CH3 and CH3-CH2-OH

Valence bond (VB) theory

Describe how bonding occurs

VSEPR theory describes the
orientations of the regions of high
electron density
VB theory describes the atomic
orbitals that overlap to produce the
bonding with the geometry mentioned
in VSEPR theory

When other atoms are nearby (in a

molecule or ion), an atom can combine
its valance shell orbitals to form a new
set of orbitals
The process is called hybridization,
and the new orbitals that are formed
as called hybrid orbitals
These hybrid orbitals can overlap with
orbitals on other atoms to share
electrons and form bonds.

The number of hybrid orbitals

obtained equals the number of
atomic orbitals mixed.
The type of hybrid orbitals obtained
varies with the types of atomic
orbitals mixed

Relation Between Electronic Geometrie

and Hybridization
Regions of

Atomic Orbitals Mixed

High Electron

Electronic

from Valence Shell

Density

Geometry

of Central Atom

Linear

Trigonal planar

Tetrahedral

Trigonal bipyramidal

Octahedral

Hybridization

one s, one p

sp

one s, two p's

sp2

one s, three p's

sp3

one s, three p's, one d

sp3d

one s, three p's, two d's

sp3d2

sp hybridization

sp2 hybridization

sp3 hybridization

Compounds containing
double bonds

A sigma bond is a bond resulting from

head-on overlap of atomic orbitals. The
region of electron sharing is along and
cylindrically around an imaginary line
connecting the bonded atoms (bond axis)
A pi bond is a bond resulting from sideon overlap of atomic orbitals. The regions
of electrons sharing are on opposite sides
of an imaginary line connecting the
bonded atoms and parallel to this line.

Sigma bond

Pi bond

STRUCTURE OF C2H4:
sp2 HYBRIDZATION

One 2p orbital is
left unhybridized

A process for obtaining

sp2-hybridized carbon
atoms

The three sp2 orbitals that result

from hybridization are directed
toward the corners of a regular
triangle

A model for the bonding molecular orbitals of ethane formed from two
sp2-hybridized carbon atoms and four hydrogen atoms

Picture of double bonds

Compounds containing
triple bonds

A triple bond consists of one sigma

bond and two pi bonds
Example of some molecules
containing triply bonded atoms are
N2, HCN, C2H2

STRUCTURE OF ETHYNE
sp HYBRIDZATION

The carbon-carbon triple bond consists of two

bonds and one bond

Picture of triple bonds

Exercise

Write the Lewis formula for each

of the following. Indicate which
bonds are polar. Indicate which
molecules are polar. (a) CS2; (b)
AlF3; (c) H2S; (d) SnF2.

Write Lewis formulas and three

dimensional structures for the
following (a) BrF3; (b) BrF; (c) BrF5.

Exercise

What is the hybridization of the

central atom in each of the
following? (a) NCl3; (b) molecular
AlCl3; (c) CF4; (d) SF6; (e) IO4-