Lesson 4

LEWIS STRUCTURE AND CHEMICAL BONDS

Objectives:

At the end of the lesson, the student should be able to do the following:

1. Explain why compounds are formed;

2. Identify and distinguish interatomic and intermolecular bond; and
3. Differentiate the different types of interatomic and intermolecular bonds.

LEWIS STRUCTURE: ELECTRON DOT FORMULA

In drawing these, the symbol for each element is used to represent the nucleus and
all inner electrons. The valence electrons are then shown as dots around the symbol.
All the valence electrons in the molecule are arranged in such a way that each atom
has eight electrons around it, except hydrogen, which only have two atoms. In some
cases this may require double or triple bonds between some atoms.

Consider the following examples:

1. H2O

The most probable arrangement is HOH. Putting in two electrons between

each two atoms gives

H : O : H

Placing the remaining four valence electrons (from the total 6 + 1 + 1 = 8)

around the oxygen gives

:
H : O : H
:

This gives the oxygen atom eight electrons around it; each H, two; and all eight
valence electrons are accounted for. Thus, it must be the correct Lewis
Structure.

2. NH3

The most probable arrangement is

 H N H
H

Putting one pair of electrons between each two atoms gives

H : N : H
••
H

There are two more valence electrons (from a total of 5 + 1 + 1 + 1 = 8), and N
needs two more. Therefore, the correct structure is

••
H : N : H
••
H

We usually represent BF3 solely by the leftmost resonance structure in which there
are only six electrons around boron. The chemical behavior of BF3 is consistent with
this representation. Thus, BF3 reacts energetically with molecules having an
unshared pair of electrons that can be used to form a bond with boron. For example,
it reacts with ammonia, NH3, to form the compound NH3BF3:

H F H F
H N: + B F H N B F
H F H F

In this stable compound, boron has an octet of electrons.

More than an Octet

The third and largest class of exceptions consists of molecules or ions in which
there are more than eight electrons in the valence shell of an atom. As an example,
consider PCl5. When we draw the Lewis structure for this molecule, we are forced to
“expand” the valence shell and place 10 electrons around the central phosphorous
atom:
••
: Cl :
••
Cl :
•• ••
: Cl P
•• ••
Cl :
••
: Cl :
••
THE CHEMICAL BOND

The Nature of Chemical Bonding

The attraction between the atoms within a compound, crystal or molecule is a

chemical bond. The chemical bond results from the simultaneous attraction of
electrons to two nuclei. Elements differ widely in the tendencies of their atoms to
combine with other atoms.

Chemical energy is stored in the chemical bond. This chemical energy is equivalent
to potential energy (unreleased energy due to position or condition of the bond).
When a chemical bond is formed in a reaction, energy is released; when a chemical
bond is broken, energy is absorbed.

Bonds between Atoms

The electrons in the incomplete outer shell of an atom, called the valence shell, play
the major role in the chemical bonding of atoms to form compounds. These electrons
called valence electrons, are involved in bond formation, and may be transferred from
one atom to another, or may be shared equally or unequally between two atoms.
Transition elements may have two outermost shells involved in bond formation.

When atoms of elements enter into chemical reactions, they gain, lose, or share
electrons in their valence shell. Their electronic structure (outer shell) becomes more
like the rare gas atoms in that they contain the maximum number of valence
electrons. (With the exception of helium which has 2 electrons in its outer shell, the
rare gases have 8 electrons in their outer shell.) When this occurs, they are in a
condition of lowest energy content and maximum stability.

IONIC BOND

Ionic bonds refer to the electrostatic forces that exist between opposite charge. Ions
may be form from atoms by the transfer of one or more electrons from atom to
another.

For example, when a sodium atom (Na) and a chlorine atom (C1) react, the sodium
atom, which differs from neon (rare gas) by having one electron in its valence shell,
will lose this electron to the chlorine atom, which differs from argon (rare gas), by
having one less electron in its outer shell.

As a result of the transfer of the electron, the sodium atom attains the stable neon
configuration (8 electrons in the outer shell). However, the sodium atom, having lost
a negative electron, becomes positively charged and is called a sodium ion (Na +).
Likewise, the chlorine atom, which has gained an electron, attains the stable argon
configuration (8 electrons in the outer shell). However, the chlorine atom, having
gained a negative electron, becomes negatively charged, and is called a chloride ion
(Cl-).
 • :
Na + : Cl : Na+ +
:

: :
: Cl : Na+ : Cl :
: :

Two ions are held together by the electrostatic attraction of opposite charges in the
sodium chloride crystal lattice. The ionic bond is also called an electrovalent bond
or ionic bond.

Another example of ionic bonding as found in the compound, calcium fluoride, CaF 2
follows:

:
: F :
Ca :
: + Ca++ +
:
: F :
:

: :
: F : - + : F :
: :

: :
: F : - Ca++ : F : -

: :

Ionic compounds include most of the binary compounds which are formed from the
elements of the 2 families preceding the rare gases in the Periodic Table and the 2
families immediately following the rare gases.
COVALENT BOND

Covalent bonds are formed when e-s are shared between 2 or more non-metals which
results in the formation of molecule.

Molecules with Single Bonds

One way to construct a Lewis structural formula for a covalent molecule is to write
first the electron-dot diagrams for each atom of the molecular formula. Then the
atoms are redrawn closer together so that atoms share pairs of electrons to produce
a structure in which all atoms follow the rule of eight or the rule of two. To illustrate
this approach, we will diagram Lewis structures for hydrogen peroxide, H 2O2, ethane,
C2H6, and methyl alcohol, CH3OH. In each of these compounds, hydrogen, with only
one electron in the first main level, forms only one covalent bond with another atom
by sharing a pair of electrons. Hence, the atom other than hydrogen must be bonded
to one another. With this information alone, we can diagram the Lewis structures of
these molecules.

Name Formula
1. Hydrogen peroxide H2O2
2. ethane C2H6,
3. methyl alcohol CH3OH

Formulation
1.
: :
H • + • O • + • O • + • H
: :
2.
H H
• •
+ +
• •
H • + • C • + • C • + • H
• •
+ +
• •
H H
3.
H
•
+
• :
H • + • C • + • O • + • H
• :
+
•
H

Lewis Structure
1.
.. ..
H - O - O - H
.. ..

2.
H H

H - C - C - H

H H

3.
H
..
H - C - O - H
..
H
Nonpolar Covalent Bond

When electrons are shared equally between atoms of equal electronegativity, the
resulting bond is a nonpolar covalent bond. Electronegativity is the tendency of an
atom to attract shared electrons.

An example of a nonpolar covalent bond is the fluorine molecule. The formula for
fluorine is F2 to indicate that it is diatomic and that there are two atoms in each
molecule. Each fluorine atom has 7 valence electrons and needs one more electron
to attain the stable argon electronic configuration. Since the atoms are the same,
each will have the same attraction (equal electronegativity) for electrons; they will
share 2 electrons, equally, so that there will be a complete shell of electrons around
each atom.

x x x x
: x : x x
: F · +x F : F · Fx
x x x x
: x x :
x x

Another example of a nonpolar covalent bond the diatomic hydrogen molecule, H2.
.
H. + xH HxH

It is possible for more than 2 electrons to be shared. An example is the diatomic

molecule nitrogen, N2. In this case, nitrogen atoms share 6 electrons, giving each a
total of 8 electrons. When two atoms share three pairs of electrons, the atoms are
said to be connected by a triple covalent bond.

x . x x x
x N x
: N : + : N. N
x
•
x x x
x
.
x

A shared pair of electrons can also be designated by a dash (-) in lieu of dots, as for
example, F-F. When 2 pairs of electrons are shared, they can be designated by 2
dashes, as for example O=O; when three pairs of electrons are shared, they can be
designated by dashes, as for example N – N.
Polar Covalent Bond

When electrons are shared between atoms which have unequal electronegativity
(attraction for electrons), they are shared unequally, and the resulting bond is polar.
Polar means that the center of the positive charge does not coincide with the center
of the negative charge.

An example of a polar covalent bond is found in the hydrogen chloride molecule, HCl.
The shared pair of electrons is unequally shared, spending more time on the chlorine
atom than on the hydrogen atom. As a result, the chlorine end of the molecule is
negatively charged and the hydrogen end positively charged. However, the molecule
as a whole is electrically neutral since the excess negative charge or the chlorine
atom is balanced by the greater positive charge of the chlorine nucleus.

x
x : :
H + . Cl : . Cl :
: :

One can make a prediction as to whether a diatomic molecule will be polar or

nonpolar. If the atoms of the molecule are alike, the bond will generally be nonpolar
and the molecule will be nonpolar. If the atoms of the molecule are different in bond
it will be generally polar.

Single Bond
H 2O 2

•• ••
H O O H
•• ••

N2H4

•• ••
H N N H

H H
C2H6
H H

H C C H

H H

Double Bond

C2H4

H C C H

H H

CO2

•• ••
O C O
•• ••

HCHO

••
H C O
••

H
SO

•• ••
S O
•• ••

O2

•• ••
O O
•• ••

Triple Bond

C2H2

H C C H
HCN
•
H C N
•

N2
:N N :

Electronegativity: Classifying Bond Type

The modern definition of electronegativity is due to Linus Pauling. It is:

the power of an atom in a molecule to attract electrons to itself.
 A ppli cati ons of Ele c t r one g a t ivit y

Electronegativity of one atom does not tell us much apart from how
much an atom may want another electron. Electronegativity is much more
useful when considering how atoms interact with one another. Differences in
electronegativity can help us determine what kind of bond may be found
between two atoms. Electronegativity values are useful in determining if a
bond is to be classified as nonpolar covalent, polar covalent or ionic.

What you should do is look only at the two atoms in a given bond.
Calculate the difference between their electronegativity values. Only the
absolute difference is important.

I. Nonpolar Covalent: This type of bond occurs when there is equal sharing
(between the two atoms) of the electrons in the bond. Molecules such
as Cl2, H2 and F2 are the usual examples.

Textbooks typically use a maximum difference of 0.2 - 0.5 to indicate

nonpolar covalent. Since textbooks vary, make sure to check with your
teacher for the value he/she wants. However, most of the Chemistry classes
use 0.5.

One interesting example molecule is CS2. This molecule has nonpolar

bonds. Sometimes a chemistry instructor will only use diatomics as examples
in lecture and then spring CS2 as a test question. Since the electronegativities
of C and S are both 2.5, you have a nonpolar bond.

II. Polar Covalent: This type of bond occurs when there is unequal sharing
(between the two atoms) of the electrons in the bond. Molecules such
as NH3 and H2O are the usual examples.

The typical rule is that bonds with an electronegativity difference less

than 1.6 are considered polar. (Some textbooks or web sites use 1.7.)
Obviously there is a wide range in bond polarity, with the difference in a C-Cl
bond being 0.5 -- considered just barely polar -- to the difference the H-O
bonds in water being 1.4 and in H-F the difference is 1.9. This last example
is about as polar as a bond can get.

III. Ionic: This type of bond occurs when there is complete transfer (between
the two atoms) of the electrons in the bond. Substances such as NaCl
and MgCl2 are the usual examples.

The rule is that when the electronegativity difference is greater than 2.0,
the bond is considered ionic.

So, let's review the rules:

1. If the electronegativity difference (usually called ΔEN) is less than 0.5,

then the bond is nonpolar covalent.
 2. If the ΔEN is between 0.5 and 1.6, the bond is considered polar
covalent
3. If the ΔEN is greater than 2.0, then the bond is ionic.

That, of course, leaves us with a problem. What about the gap between
1.6 and 2.0? So, rule #4 is:

4. If the ΔEN is between 1.6 and 2.0 and if a metal is involved, then the
bond is considered ionic. If only nonmetals are involved, the bond is
considered polar covalent.

Here is an example: Sodium bromide (formula = NaBr; ENNa = 0.9,

ENBr = 2.8) has a ΔEN = 1.9. Hydrogen fluoride (formula = HF; ENH = 2.1,
ENF = 4.0) has the same ΔEN. We use rule #4 to decide that NaBr has ionic
bonds and that HF has a polar covalent bond in each HF molecule.

A warning: rule #4 may not exist in other chembooks. Often, the 1.6
value is used and the 1.6-2.0 range is lumped into the ionic category.

Electronegativity is related to ionization energy and electron affinity. For

example, an atom with a strongly negative electron affinity and a high
ionization energy will be highly electronegative. That is, it will attract electrons
from other atoms and will resist having its own electrons taken from it. An
atom with a positive electron affinity and a low ionization energy, on the other
hand, will have a very low electronegativity, as it does not want more electrons
and willingly gives up the valence one(s) it has.

Electronegativity is assigned based on a unit less system that assigns

the most electronegative atom, fluorine, an electronegativity of 4. Cesium, the
least electronegative atom, is given an electronegativity of 0.7. All other atoms
have electronegativities between the two.

W h a t a r e th e g en eral tren ds of electr onega tivity?

o In general, electronegativity increases from left to right across a period.

This is due to increasing effective nuclear charge which accounts for
increasing ionization energy and increasing (more negative) electron
affinity. The chart shows electronegativities from sodium to chlorine,
except for Argon for it does not have electronegativity, because it does
not form bonds.
o In general, electronegativity decreases from top to bottom down a group.
This is due to decreasing effective nuclear charge that accounts for
decreasing ionization and energy and the small decreases we see in
electron affinity.
 VSEPR and MOLECULAR GEOMETRY

VSEPR stands for Valence Shell Electron Pair Repulsion, which is a theory
that chemists use to predict the shape and bond angles of different molecules.
Basically, the theory says that the valence electron pairs around an atom repel each
other mutually. This implies that the electrons will arrange themselves in such a way
that this repulsion is minimized. The arrangement of electrons determines their
molecular geometry (also known as shape). Keep in mind that this theory is a
prediction, and though it is almost entirely accurate, you still must keep in mind
that there is some room for variation in reality. This means that, if we could see all
of the electrons in every atom, they may differ slightly from this predicted model.

The table on the next page contains several columns. We already have a
concept of bonding pair of electrons and non-bonding pairs of electrons. Bonding
pairs of electrons are those electrons shared by the central atom and any atom to
which it is bonded. Non-bonding pairs of electrons are those pairs of electrons on an
individual atom that are not shared with another atom. In the table the term bonding
groups/domains (second from the left column) is used in the column for the bonding
pair of electrons. The term electron-pair geometry is the name of the geometry of the
electron-pair/groups/domains on the central atom, whether they are bonding or
non-bonding. Molecular geometry is the name of the geometry used to describe the
shape of a molecule. The electron-pair geometry provides a guide to the bond angles
of between a terminal-central-terminal atom in a compound. The molecular geometry
is the shape of the molecule. So when asked to describe the shape of a molecule we
must respond with a molecular geometry. If asked for the electron-pair geometry on
the central atom we must respond with the electron-pair geometry. Notice that there
are several examples with the same electron-pair geometry, but different molecular
geometries. You should note that to determine the shape (molecular geometry) of a
molecule you must write the Lewis structure and determine the number of bonding
groups of electrons and the number of non-bonding pairs of electrons on the central
atom, then use the associated name for that shape.

When using the VSEPR theory, the following rules apply:

1. Draw the electron-dot structure of the compound.
2. Count the number of atoms bonded to the central atom.
3. Count the number of non-bonded electron pairs on the central atom.

4. Add the number of atoms bonded to the central atom to the number of non-bonded
electron pairs. This total will indicate the shape (molecular geometry), as shown
below. The table below summarizes the molecular and electron-pair geometries for
different combinations of bonding groups and nonbonding pairs of electrons on the
central atom.

# of bonding # of lone pair

groups/domains on electrons on Electron-pair Molecular Bond
'central' atom 'central' atom Geometry Geometry Angle
2 0 linear linear 180
trigonal trigonal
3 0 120
planar planar
 less
trigonal
2 1 bent than
planar
120
4 0 tetrahedral tetrahedral 109.5
less
trigonal
3 1 tetrahedral than
pyramidal
109.5
less
2 2 tetrahedral bent than
109.5
90, 120
trigonal trigonal
5 0 and
bipyramidal bipyramidal
180
90, 120
trigonal
4 1 seesaw and
bipyramidal
180
trigonal 90 and
3 2 T-shaped
bipyramidal 180
trigonal
2 3 linear 180
bipyramidal
90 and
6 0 octahedral octrahedral
180
square 90 and
5 1 octahedral
pyramidal 180
square 90 and
4 2 octahedral
planar 180

Exercise 1

Determine the shape of CH4.

Solution

▪ Step 1 The electron-dot structure is

▪ Step 2 The number of atoms bonded to the central atom is 4.

▪ Step 3 The number of nonbonded electron pairs on the central atom is 0.
▪ Step 4 The total of Steps 2 and 3 is 4.

The predicted shape should be tetrahedral.

Exercise 2

Determine the structure of NH3..

Solution

▪ Step 1 The electron – dot structure is

H
..
H: N: H
..

▪ Step 2 The number of atoms bonded to the central atom is 3.

▪ Step 3 The number of nonbonded electron pairs on the central atom is
1.
▪ Step 4 The total of Step 2 and 3 is 4 (3+1), which corresponds to a
predicted pyramidal shape, or

H H

Exercise 3

Determine the shape of H2O

Solution

▪ Step 1 The electron- dot structure is

..
H: O :H
..

▪ Step 2 The number of atoms bonded to the central atom is 2.

▪ Step 3 The number of nonbonded electron pairs on the central atom is
2.

▪ Step 4 The total of Steps 2 and 3 is 4 (2+2), which corresponds to a

predicted shape of bent, or

H H
Exercise 4

Determine the shape of CO2.

Solution

▪ Step 1 The electron-dot structure is

.. ..
:O: :C: :O:

▪ Step 2 The number of atoms bonded to the central atom is 2.

▪ Step 3 The number of non-bonded electron pairs on the central atom is
0.
▪ Step 4 The total of Step 2 and 3 is 2, which predicts a linear shape, or

O=C=O

Exercise 5

Draw the electron-dot structure for the sulfate ion (SO4 2-).

Solution

Structures for ions are similar to compounds except we must add or subtract
electrons to account for charge. Sulfur has six valence electrons and can be written
as
..
:S:
..

Oxygen has six valence electrons and can be written as

..
:O:

The ionic charge of –2 means that there are two extra electrons that can be placed
around the sulfur.
..
:S:
..
Sulfur now has eight electrons and needs no more electrons. Each oxygen atom
needs two more electrons and sulfur provides them as shown.

..
.. :O: ..
:O: :S: :O:
.. .. ..
:O:
..

Exercise 6

Draw the electron-dot structure for NH4 +.

Solution
+
H
..
H : N: H
..
H