CHEMICAL BONDS

Matter is made up of one or different type of elements. Under normal conditions no other element
exists as an independent atom in nature, except noble gases. However, a group of atoms is found
to exist together as one species having characteristic properties. Such a group of atoms is called a
molecule. Obviously there must be some force which holds these constituent atoms together in the
molecules. The attractive force which holds various constituents (atoms, ions, etc.) together in
different chemical species is called a chemical bond. Since the formation of chemical compounds
takes place as a result of combination of atoms of various elements in different ways, it raises
many questions. Why do atoms combine? Why are only certain combinations possible? Why do
some atoms combine while certain others do not? Why do molecules possess definite shapes?

To answer such questions different theories and concepts have been put forward from time to time.
The evolution of these theories and concepts have closely been related to the developments in the
understanding of the structure of atom, the electronic configuration of elements and the periodic
table. Consequently, the next two lectures are devoted to an overview of some of the basic ideas
concerning bonding and the structure of molecules.

Lewis Symbols
The electrons involved in chemical bonding are the valence electrons, which, for most atoms, are
those residing in the outermost occupied shell of an atom. The American chemist G. N. Lewis
(1875-1946) suggested a simple way of showing the valence electrons in an atom and tracking
them in the course of bond formation, using what are now known as Lewis electron-dot symbols,
or merely Lewis symbols. The Lewis symbol for an element consists of the chemical symbol for
the element plus a dot for each valence electron. Sulfur, for example, has the electron configuration
[Ne]3s23p4; its Lewis symbol therefore shows six valence electrons:

..
. S.
..
The dots are placed on the four sides of the atomic symbol: the top, the bottom, and the left and
right sides.

The Lewis dot structures provide a picture of bonding in molecules and ions in terms of the shared
pairs of electrons and the octet rule. While such a picture may not explain the bonding and

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behaviour of a molecule completely, it does help in understanding the formation and properties of
a molecule to a large extent. For this reason, drawing Lewis structures is an important skill that
you should practice. Procedure:
1. Sum the valence electrons from all atoms. For an anion, add one electron to the
total for each negative charge. For a cation, subtract one electron from the total for
each positive charge.
2. Write the symbols for the atoms to show which atoms are attached to which, and
connect them with a single bond. Chemical formulas are often written in the order
in which the atoms are connected in the molecule or ion. The formula HCN, for
example, tells you that the carbon atom is bonded to the H and to the N. In many
polyatomic molecules and ions, the central atom is usually written first, as in CO32-
and SF4.
3. Complete the octets around all the atoms bonded to the central atom. Remember,
however, that you use only a single pair of electrons around hydrogen.
4. Place any leftover electrons on the central atom, even if doing so results in more
than an octet of electrons around the atom.
5. If there are not enough electrons to give the central atom an octet, try multiple
bonds. Use one or more of the unshared pairs of electrons on the atoms bonded to
the central atom to form double or triple bonds.

EXAMPLES
1. What is the electron configuration and Lewis symbol for B and Si?
Solution:

Element Electron configuration Lewis symbol

B (5) [He] 2s2 2p1 :B·

Si (14) [Ne]3s2 3p2 :Si:

2. Draw the Lewis structure for phosphorus trichloride, PC13 and HCN.
Solution:

a) PC13

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 i. Find the sum of valence electrons of all
atoms in the polyatomic ion or molecule.

i. Write the symbols for the atoms to show

which atoms are attached to which, and
connect them with a single bond, a dash
(representing two electrons).
Keep track of the electrons: 26 − 6 = 20

ii. Complete the octets around all the atoms

bonded to the central atom.

Keep track of the electrons: 20 - 18 = 2

iii. Place any leftover electrons on the

central atom.

Keep track of the electrons: 2 - 2 = 0

b) HCN
i. Find the sum of valence electrons of all
atoms in the polyatomic ion or molecule. HCN

1 + 4 + 5 = 10

iv. Write the symbols for the atoms to show

which atoms are attached to which, and
connect them with a single bond, a dash
(representing two electrons).
Keep track of the electrons: 10 − 4 = 6

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 v. If we then place the remaining six
electrons around N to give it an octet, we
do not achieve an octet on C.

Keep track of the electrons: 6 - 6 = 0

vi. If there are not enough electrons to give

the central atom an octet, try multiple
bonds.

Molecular shapes
Lewis structures, unfortunately, do not show one of the most important aspects of molecules-their
overall shapes. Molecules have shapes and sizes that are defined by the bond angles and distances
between the nuclei of their component atoms. Thus, the bond angles of a molecule, together with
the bond lengths, accurately define the shape and size of the molecule. In this section, we will learn
the relationship between two-dimensional Lewis structures and three-dimensional molecular
shapes.

Most molecules conform to the general formula ABn in which the central atom A is bonded to n B
atoms. For example, both CO2 and H2O are AB2 molecules, whereas SO3 and NH3 are AB3
molecules, and so on. The possible shapes of ABn molecules depend on the value of n. An AB2
molecule must be either linear (bond angle = 180°) or bent (bond angle ≠ 180°) as shown below.
For example, CO2 is linear, and SO2 is bent.

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For AB3 molecules, the two most common shapes place the B atoms at the comers of an equilateral
triangle. If the A atom lies in the same plane as the B atoms, the shape is called trigonal planar,
as shown below. If the A atom lies above the plane of the B atoms, the shape is called trigonal
pyramidal. The shape of any particular ABn molecule can usually be derived from one of the basic
geometric structures shown below.

Linear Bent

Trigonal planar

Trigonal
Pyramid

Tetrahedral

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 Trigonal
bipyramid

Octahedron

Why do so many ABn molecules have shapes related to these basic structures, and can we predict
these shapes? When A is a representative element (one of the elements from the s block or p block
of the periodic table), we can answer these questions by using the valence-shell electron-pair
repulsion (VSEPR) model.

The VSEPR model

Imagine tying two identical balloons together at their ends as shown in (a) below; the balloons
naturally orient themselves to point away from each other-they try to “get out of each other’s way”
as much as possible. If a third balloon is added, the balloons orient themselves toward the vertices
of an equilateral triangle, as shown in (b). If a fourth balloon is added, they adopt a tetrahedral
shape, (c).

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Somehow, electrons in molecules behave like the balloons shown above.

Recall that a single covalent bond is formed between two atoms when a pair of electrons occupies
the space between the atoms. We will refer to the region in which the bonding pair of electrons
will most likely be found as an electron domain. Likewise, a nonbonding pair (or lone pair) of
electrons defines an electron domain that is located principally on one atom. For example, the
Lewis structure of NH3 has four electron domains around the central nitrogen atom (three bonding
pairs and one nonbonding pair):
nonbonding pair
..
H N H

H
bonding electrons

Each multiple bond in a molecule also constitutes a single electron domain. Thus, O3 has three
electron domains around the central oxygen atom (a single bond, a double bond, and a nonbonding
pair of electrons):

.. .. ..
:O.. O O
..
In general, each nonbonding pair, single bond, or multiple bond produces an electron domain
around the central atom.

The main postulates of VSEPR theory are as follows:

 Electron domains are negatively charged and therefore repel one another.

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  The shape of a molecule depends upon the number of electron domains around the central
atom.
 These electron domains tend to occupy such positions in space that minimize repulsion and
thus maximise distance between them.

The arrangement of electron domains about the central atom of an ABn molecule or ion is called
its electron-domain geometry. In contrast, the molecular geometry is the arrangement of only the
atoms in a molecule or ion-any nonbonding pairs are not part of the description of the molecular
geometry. In the VSEPR model, we predict the electron domain geometry. From knowing how
many electron domains are due to nonbonding pairs, we can then predict the molecular geometry
of a molecule or ion from its electron-domain geometry.

For the prediction of geometrical shapes of molecules with the help of VSEPR theory, it is
convenient to divide molecules into two categories as (i) molecules in which the central atom has
no lone pair and (ii) molecules in which the central atom has one or more lone pairs.

EXERCISE
1. Use the VSEPR model to predict the molecular geometry of O3 and SnC13-
Solution:
Molecule Arrangement of electron Electron-domain Molecular
pairs (Lewis structure) geometry geometry (Shape)
O3 Trigonal planar Bent
SnC13- Tetrahedral Trigonal pyramid

2. Predict the electron-domain geometry and the molecular geometry for (a) SeCl2, (b) CO32-
Answers: (a) tetrahedral, bent; (b) trigonal planar, trigonal planar

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