CHEMICAL BONDING

Atoms are the basic building blocks of all types of matter. Atoms link to other atoms through
chemicals bonds resulting from the strong attractive forces that exist between the atoms. A
chemical bond is a region that forms when electrons from different atoms interact with each
other. The electrons that participate in chemical bonds are the valence electrons, which are
the electrons found in an atom's outermost shell.

Main Types of Chemical Bonds

The two main types of bonds formed between atoms are ionic bonds and covalent bonds.
An ionic bond is formed when one atom accepts or donates one or more of its valence
electrons to another atom. A covalent bond is formed when atoms share valence electrons.

Other types of bonds include metallic bonds and hydrogen bonding. The attractive forces
between molecules in a liquid can be characterized as van der Waals bonds.

Ionic Bonds

In chemical bonds, atoms can either transfer or share their valence electrons. In the
extreme case where one or more atoms lose electrons and other atoms gain them in
order to produce a noble gas electron configuration, the bond is called an ionic bond.

Typical of ionic bonds are those in the alkali halides such as sodium chloride, NaCl.
 Covalent Bonds
Covalent chemical bonds involve the sharing of a pair of valence electrons by two atoms, in
contrast to the transfer of electrons in ionic bonds. Such bonds lead to stable molecules if they
share electrons in such a way as to create a noble gas configuration for each atom.

Hydrogen gas forms the simplest covalent bond in the diatomic hydrogen molecule. The
halogens such as chlorine also exist as diatomic gases by forming covalent bonds. The nitrogen
and oxygen which makes up the bulk of the atmosphere also exhibits covalent bonding in
forming diatomic molecules.

Metallic Bonds

The properties of metals suggest that their atoms possess strong bonds, yet the ease of
conduction of heat and electricity suggest that electrons can move freely in all
directions in a metal. The general observations give rise to a picture of "positive ions
in a sea of electrons" to describe metallic bonding.

Metal Properties

The general properties of metals include malleability and ductility and most are strong
and durable. They are good conductors of heat and electricity. Their strength indicates
that the atoms are difficult to separate, but malleability and ductility suggest that the
atoms are relatively easy to move in various directions. The electrical conductivity
suggests that it is easy to move electrons in any direction in these materials. The
thermal conductivity also involves the motion of electrons. All of these properties
suggest the nature of the metallic bonds between atoms.

Hydrogen Bonding

Hydrogen bonding differs from other uses of the word "bond" since it is a force of
attraction between a hydrogen atom in one molecule and a small atom of
high electronegativity in another molecule. That is, it is an intermolecular force, not an
intramolecular force as in the common use of the word bond.

When hydrogen atoms are joined in a polar covalent bond with a small atom of high
electronegativity such as O, F or N, the partial positive charge on the hydrogen is
highly concentrated because of its small size. If the hydrogen is close to another
oxygen, fluorine or nitrogen in another molecule, then there is a force of attraction
termed a dipole-dipole interaction. This attraction or "hydrogen bond" can have about
5% to 10% of the strength of a covalent bond.

Hydrogen bonding has a very important effect on the properties of water and ice.
Hydrogen bonding is also very important in proteins and nucleic acids and therefore
in life processes.

Co-ordinate (dative covalent) bonding

A covalent bond is formed by two atoms sharing a pair of electrons. The
atoms are held together because the electron pair is attracted by both of the
nuclei.

In the formation of a simple covalent bond, each atom supplies one electron to
the bond - but that doesn't have to be the case. A co-ordinate bond (also
called a dative covalent bond) is a covalent bond (a shared pair of electrons)
in which both electrons come from the same atom.

The reaction between ammonia and hydrogen chloride

If these colourless gases are allowed to mix, a thick white smoke of solid
ammonium chloride is formed.
Ammonium ions, NH4+, are formed by the transfer of a hydrogen ion from the
hydrogen chloride to the lone pair of electrons on the ammonia molecule.

When the ammonium ion, NH4+, is formed, the fourth hydrogen is attached by
a dative covalent bond, because only the hydrogen's nucleus is transferred
from the chlorine to the nitrogen. The hydrogen's electron is left behind on the
chlorine to form a negative chloride ion.

Once the ammonium ion has been formed it is impossible to tell any
difference between the dative covalent and the ordinary covalent bonds.
Although the electrons are shown differently in the diagram, there is no
difference between them in reality.

Representing co-ordinate bonds

In simple diagrams, a co-ordinate bond is shown by an arrow. The arrow

points from the atom donating the lone pair to the atom accepting it.
Molecular orbital theory
Molecular orbital theory is more powerful than valence-bond theory because the
orbitals reflect the geometry of the molecule to which they are applied.

We assume that the electrons would fill the molecular orbitals of molecules like
electrons fill atomic orbitals in atoms.

 The molecular orbitals are filled in a way that yields the lowest potential
energy for the molecule.
 The maximum number of electrons in each molecular orbital is two. (We
follow the Pauli exclusion principle.)
 Orbitals of equal energy are half filled with parallel spin before they begin to
pair up. (We follow Hund's Rule.)

One common approximation that allows us to generate molecular orbital diagrams

for some small diatomic molecules is called the Linear Combination of Atomic
Orbitals (LCAO) approach. The following assumptions lie at the core of this
model.

 Molecular orbitals are formed from the overlap of atomic orbitals.

 Only atomic orbitals of about the same energy interact to a significant
degree.
 When two atomic orbitals overlap, they interact in two extreme ways to form
two molecular orbitals, a bonding molecular orbital and an antibonding
molecular orbital.

The major draw back is that we are limited to talking about diatomic molecules
(molecules that have only two atoms bonded together), or the theory gets very
complex. The MO theory treats molecular bonds as a sharing of electrons between
nuclei. Unlike the V-B theory, which treats the electrons as localized balloons of
electron density, the MO theory says that the electrons are delocalized. That means
that they are spread out over the entire molecule. Forming Molecular Orbitals
Molecular orbitals are obtained by combining the atomic orbitals on the atoms in
the molecule.
Consider the H2 molecule, for example. One of the molecular orbitals in this
molecule is constructed by adding the mathematical functions for the two 1s
atomic orbitals that come together to form this molecule. Another orbital is formed
by subtracting one of these functions from the other, as shown in the figure below.

One of these orbitals is called a bonding molecular orbital because electrons in

this orbital spend most of their time in the region directly between the two nuclei.
It is called a sigma (σ ) molecular orbital because it looks like an s orbital when
viewed along the H-H bond. Electrons placed in the other orbital spend most of
their time away from the region between the two nuclei. This orbital is therefore an
antibonding, or sigma star (σ *), molecular orbital.

The bonding molecular orbital concentrates electrons in the region directly

between the two nuclei. Placing an electron in this orbital therefore stabilizes the
H2 molecule. Since the * antibonding molecular orbital forces the electron to
spend most of its time away from the area between the nuclei, placing an electron
in this orbital makes the molecule less stable.

Calculating Bond Order

In molecular orbital theory, we calculate bond orders by assuming that two

electrons in a bonding molecular orbital contribute one net bond and that two
electrons in an antibonding molecular orbital cancel the effect of one bond. We can
calculate the bond order in the O2 molecule by noting that there are eight valence
electrons in bonding molecular orbitals and four valence electrons in antibonding
molecular orbitals in the electron configuration of this molecule. Thus, the bond
order is two.

Bond Order= [No. of electrons in bonding state – No. of electrons in antibonding

state] / 2

Although the Lewis structure and molecular orbital models of oxygen yield the
same bond order, there is an important difference between these models. The
electrons in the Lewis structure are all paired, but there could be unpaired electrons
in the molecular orbital description of a molecule. As a result, we can test the
predictions of these theories by studying the effect of a magnetic field on certain
molecules.

Homo Nuclear Diatomic Molecules Molecular Orbitals of the Second Energy

Level (1s and 2s only) Molecular Orbitals for Period 1 Diatomic Molecules
Electrons are added to molecular orbitals, one at a time, starting with the lowest
energy molecular orbital. The two electrons associated with a pair of hydrogen
atoms are placed in the lowest energy, or bonding, molecular orbital, as shown in
the figure below. This diagram suggests that the energy of an H2 molecule is lower
than that of a pair of isolated atoms. As a result, the H2 molecule is more stable
than a pair of isolated atoms.
Molecular Orbital Diagram of Nitrogen

Molecular Orbital Diagram of Oxygen