William L.

Masterton
Cecile N. Hurley
http://academic.cengage.com/chemistry/masterton

Chemical Bonding

Edward J. Neth University of Connecticut

William L. Masterton
Cecile N. Hurley
http://academic.cengage.com/chemistry/masterton

Covalent Bonding

Edward J. Neth University of Connecticut

Outline
1.
2.
3.
4.

Lewis Structures; the Octet Rule

Molecular Geometry
Molecular Polarity
Atomic Orbitals; Hybridization

Covalent Bonding Introduction, 1

Recall that electrons in atoms are placed into atomic orbitals
according to the Aufbau principle and Hunds Rule
In this section of the course, we will look at the location of
electrons in molecules containing covalent bonds

Covalent Bonding Introduction, 2

Electron density
Electrons are located between nuclei
Electrostatic energy of the system is lowered
When two hydrogen atoms come together, electron
density is spread over the entire molecule

Study of the covalent bond as it exists in

molecules and polyatomic ions

Figure 7.1 The Hydrogen Molecule

Figure 7.2

Lewis Structures
Recall that atoms may form ions that are
isoelectronic with the nearest noble gas
Na forms Na+ 1s22s22p63s1 1s22s22p6
F forms F1s22s22p5 1s22s22p6
Some atoms share electrons rather than ionize
Sharing results in atoms becoming isoelectronic
with the nearest noble gas, as they do in forming
ions

Valence
Outermost electrons are called valence electrons
Consider F
1s22s22p5
1s are core electrons
2s and 2p are valence electrons

Consider HF
Hydrogen contributes a 1s electron to form a covalent
bond
F contributes seven electrons and shares one more
Total of eight valence electrons
F in HF now has a total of eight valence electrons; H
has two

Tools
Lewis structures
Distribute electron pairs in a molecule such that
each atom achieves an octed (hydrogen a duet)
Molecular geometry
Location of both shared and unshared electron
pairs leads to VSEPR geometry

Table 1.1

Electron Ownership
An atom owns
All lone electrons
Shown as lone pairs

Half the number of bonding electrons

A bond pair is shown as a line
Multiple bonds are possible
Double bonds are two pairs
Triple bonds are three pairs

Examples of Lewis Structures

OH-, H2O, NH3, NH4+, C2H4, C2H2

The Octet Rule

Main group elements seek to attain an octet of
electrons
Recall that an s2p6 configuration is isoelectronic
with a noble gas
Closed electron shells
Exception: H
The duet rule

Writing Lewis Structures*

1. Count the number of valence electrons
2. Draw a skeleton structure for the species, joining
the atoms by single bonds
3. Determine the number of valence electrons still
available for distribution
4. Determine the number of valence electrons
required to fill out an octet for each atom (except H)
in the structure

*see p. 169 of the text

1. Counting the Valence Electrons

Total the valence electrons for each atom present in
the molecule or ion.
For an anion, add one electron for each unit of
negative charge
For a cation, subtract one electron for each unit of
positive charge

2. Drawing the Skeleton Structure

One atom must be central
This is usually the first one written in the formula
Less electronegative elements are usually central
Atoms that are usually terminal, not central
Hydrogen (must be terminal)
Halogens
Oxygen

3. Determining the Number of Valence Electrons

Left
Each bond represents a pair of electrons

4. Completing the Octets

Distribute the remaining electrons to complete the
octet for each element
In some cases, multiple bonds are required
Some elements never participate in multiple bonds:
hydrogen and halogens

Example 7.1

Example 7.1 (contd)

Resonance Forms
In certain cases, Lewis structures do not represent
chemical or physical reality
Consider SO2
Both S-O bonds are equal in length, yet the Lewis
structure indicates one double and one single
bond

Nitrate Ion

Benzene

Notes on Resonance Structures

1. Resonance forms are not different molecules, nor
are they representations of electron shifting
2. Resonance structures arise when two Lewis
structures are equally plausible
3. Only electrons can be shifted in resonance
structures. Atoms cannot be moved.

Example 7.3

Formal Charges
Formal charges are analogous to oxidations
numbers:
They are not actual charges
They keep track of electron ownership

Formal Charges
Formal charges are determined by totaling the number of
valence electrons (X), and then subtracting the total of the
number of lone electrons (Y) plus half the number of
bonding electrons (Z/2)

Z
Cf X Y
2

Table 7.2 BeF2 and BF3

Rules Governing Formal Charge

The quality of a Lewis structure can be determined
by the distribution of formal charge
Minimize charges
Best to have no Cf or small Cf

Watch electronegativity
The most electronegative atoms should have the most
negative formal charge

Minimize separation of charge

Example

Exceptions to the Octet Rule, 1

Electron deficient molecules
Odd electron species (free radicals)
Paramagnetic
Examples: NO, NO2

Exceptions to the Octet Rule, 2

Molecular oxygen, O2
Molecular oxygen is paramagnetic
Although it has an even number of electrons, it exists
as a diradical (two unpaired electrons)
Lewis structure for O2 is difficult to draw

Expanded Octets, 1
Some elements are capable of surrounding
themselves with more than four pairs of electrons
Expanded octets
PCl5, SF6

Period

Grp 15

Grp 16

Grp 17

Grp 18

Cl

As

Se

Br

Kr

Sb

Te

Xe

Example 7.4 Expanded Octets

Molecular Geometry
Diatomic molecules are the easiest to visualize in
three dimensions
HCl
Cl2
Diatomic molecules are linear

Figure 7.4 Ideal Geometries

There is a fundamental geometry that corresponds
to the total number of electron pairs around the
central atom: 2, 3, 4, 5 and 6

linear

trigonal
planar

tetrahedral

trigonal
bipyramidal

octahedral

Valence Shell Electron Pair Repulsion Theory

The ideal geometry of a molecule is determined by
the way the electron pairs orient themselves in
space
The orientation of electron pairs arises from
electron repulsions
The electron pairs spread out so as to minimize
repulsion

Two electron pairs

Linear
Bond angles
The bond angle in a linear molecule is always
180

Three electron pairs

Trigonal planar
The electron pairs form an equilateral triangle
around the central atom
Bond angles are 120

Four Electron Pairs

Tetrahedral
Bond angles are 109.5

Five Electron Pairs

Trigonal bipyramid
Bond angles vary
In the trigonal plane, 120
Between the plane and apexes, 90
Between the central atom and both apexes, 180

Six Electron Pairs

Octahedron
The octahedron is a square bipyramid
Bond angles vary
90 in and out of plane
180 between diametrically opposite atoms and
the central atom

Figure 7.5 - Molecular Geometry Summarized - 1

Figure 7.5 - Molecular Geometry Summarized, 2

Unshared Pairs and Geometry

Electron pair geometry
Consider the terminal atoms and the lone pairs
around the central atom
Molecular geometry
Consider only the terminal atoms around the
central atom

Figure 7.6-7.7 - Ammonia and Water

Bond Angles and Lone Pairs

Ammonia and water show smaller bond angles than
predicted from the ideal geometry
The lone pair is larger in volume than a bond pair
There is a nucleus at only one end of the bond so
the electrons are free to spread out over a larger
area of space

The A-X-E Notation

A denotes a central atom

X denotes a terminal atom
E denotes a lone pair
Example
Water
H2O
O is central
Two lone pairs
Two hydrogens

AX2E2

Table 7.3 - Molecular Geometry Summary with

Lone Pairs Included

Example 7.5

Multiple Bonds
For molecular geometry purposes, multiple bonds
behave the same as single bonds
All of the electron pairs are located in the same
place (between the nuclei)
The geometry of the molecule is determined by
the number of terminal atoms, which is not
affected by the presence of a double or triple bond

Example 7.6

Example 7.6 (contd)

Figure 7.8 - Molecular Geometry Summary 1

Figure 7.8 - Molecular Geometry Summary 2

Polarity - Bonds
Recall that a polar bond has an asymmetric
distribution of electrons
X-X is nonpolar
X-Y is polar
Polarity of a bond increases with increasing
difference in electronegativity between the two
atoms
Bond is a dipole
One end is (+), while the other is (-)

Polarity - Molecules
Molecules may also possess polarity
Positive and negative poles
Molecule is called a dipole
Consider HF
H is + while F is
Consider BeF2
Be-F bond is polar
BeF2 is nonpolar

Figure 7.11 - Polarity of Molecules

Example 7.7

Example 7.7 (contd)

Atomic Orbitals and Hybridization

Valence Bond Model
Linus Pauling
Nobel Prize, 1954

Orbital diagrams
Isolated F atom () () ()()( )
1s
2s
2p
F atom in HF
() () ()()()
1s
2s
2p

Valence Bond Theory

Unpaired electrons from one atom pair with unpaired
electrons from another atom and give rise to
chemical bonds
Simple extension of orbital diagrams

Figure 7.12 - Atomic Orbital Mathematics

Two atomic orbitals produce two hybrid orbitals
One s + one p two sp

Table 7.4 - Hybrid Orbitals and Geometry

Hybrid Orbitals and Electron Occupancy

Same rules we have seen before
In an atom, an orbital holds two electrons
In a molecule, an orbital also holds two electrons
What electrons go into hybrid orbitals?
Lone pairs
One pair per bond
Even for a double bond, only one pair goes into the
hybrid orbital

Example 7.9

Multiple bonds
Sigma () bonds
Electron density is located between the nuclei
One pair of each bond is called a sigma pair
Pi bonds ()
Electron density is located above and below or in
front of and in back of the nuclei
One pair of a double bond is called pi ()
Two pairs of a triple bond are called pi ()

Figure 7.13 - Ethylene and Acetylene

Example 7.11

Key Concepts
1. Draw Lewis structures for molecules and
polyatomic ions.
2. Write resonance forms.
3. Use VSEPR theory to predict molecular geometry.
4. From the geometry of a species, predict whether it
will be polar or not.
5. State the hybridization of a species.
6. State the number of sigma and pi bonds in a
species.