Atomic structure and chemical bonding

The atomic structure of an element refers to the constitution of its nucleus and the arrangement
of the electrons around it. Primarily, the atomic structure of matter is made up of protons,
electrons and neutrons.

Atomic Particles

Atoms consist of three basic particles: protons, electrons, and neutrons. The nucleus (centre) of
the atom contains the protons (positively charged) and the neutrons (no charge). The outermost
regions of the atom are called electron shells and contain the electrons (negatively charged).
Atoms have different properties based on the arrangement and number of their basic particles.

The hydrogen atom (H) contains only one proton, one electron, and no neutrons. This can be
determined using the atomic number and the mass number of the element.

Atomic Mass

Protons and neutrons have approximately the same mass, about 1.67 × 10 -24 grams. Scientists
define this amount of mass as one atomic mass unit (amu) or one Dalton. Although similar in
mass, protons are positively charged, while neutrons have no charge. Therefore, the number of
neutrons in an atom contributes significantly to its mass, but not to its charge.

Electrons are much smaller in mass than protons, weighing only 9.11 × 10 -28 grams, or about
1/1800 of an atomic mass unit. Therefore, they do not contribute much to an element’s overall
atomic mass. When considering atomic mass, it is customary to ignore the mass of any electrons
and calculate the atom’s mass based on the number of protons and neutrons alone.

Electrons contribute greatly to the atom’s charge, as each electron has a negative charge equal to
the positive charge of a proton. Scientists define these charges as “+1” and “-1. ” In an
uncharged, neutral atom, the number of electrons orbiting the nucleus is equal to the number of
protons inside the nucleus. In these atoms, the positive and negative charges cancel each other
out, leading to an atom with no net charge.

Atomic Number and Mass Number

The atomic number is the number of protons in an element, while the mass number is the number
of protons plus the number of neutrons.

An electron is a subatomic particle which bears charge – 1.60 × 10 –19 coulomb and has
mass 9.1 × 10– 28 g
A proton is defined as a subatomic particle which has a mass of 1 amu and
charge + 1 elementary charge unit.
A neutron is a subatomic particle which has a mass almost equal to that of a proton and
has no charge.

The Quantum Mechanical Model of the Atom

The Dual Nature of Light

The branch of physics that deals with the motions of objects under the influence of forces
is called mechanics. Classical mechanics refers to the laws of motion developed by Isaac
Newton in the 1600s.
When the Bohr model of the atom could not predict the energy levels of electrons in atoms
with more than one electron, it seemed a new approach to explaining the behavior of
electrons was necessary. Developed in the early 1900s, this new approach was based on the
work of many scientists. The new approach came to be known as quantum mechanics (also
called wave mechanics). Quantum mechanics is the branch of physics that deals with the
behavior of matter at the atomic and subatomic level.
Properties of Waves

The controversy over the nature of light in the 1600s was partially due to the fact that
different experiments with light gave different indications about the nature of light. Energy
waveforms, such as water waves or sound waves, were found to exhibit certain
characteristics, including diffraction (the bending of waves around corners) and
interference (the adding or subtracting of energies when waves overlap).
Light as a Wave

Light also undergoes diffraction and interference. These characteristics of light can be
demonstrated with what is called a double-slit experiment. A box is sealed on all sides so
that no light can enter. On one side of the box, two very thin slits are cut. A light source
placed in front of the slits will allow light to enter the two slits and shine on the back wall of
the box.

If light behaved like particles, the light would go straight from the slits to the back of the
box and appear on the back wall as two bright spots (see the left side of the image above).
If light behaved like waves, the waves would enter the slits and diffract. On the back wall,
an interference · pattern would appear with bright spots showing areas of constructive
interference and dark spots showing areas of destructive interference (see the right side of the
image above). When this double-slit experiment was conducted, researchers saw an
interference pattern instead of two bright spots, providing reasonably conclusive evidence
that light behaves like a wave.

Light as a Particle

Although the results of the double-slit experiment strongly suggested that light is a wave, a
German physicist named Max Planck found experimental results that suggested light behaved
more like a particle when he was studying black body radiation. A black body is a theoretical
object that absorbs all light that falls on it. It reflects no radiation and appears perfectly black.
Black body radiation is the energy that would be emitted from an ideal black body. In the
year 1900, Planck published a paper on the electromagnetic radiation emitted from a black
object that had been heated. In trying to explain the black body radiation, Planck
determined that the experimental results could not be explained with the wave form of
light. Instead, Planck described the radiation emission as discrete bundles of energy, which
he called quanta. A quantum (singular form of quanta) is a small unit into which certain
forms of energy are divided. These “discrete bundles of energy” once again raised the
question of whether light was a wave or a particle – a question once thought settled by
Maxwell’s work. Planck’s work also pointed out that the energy of a quantum of light was
related only to its frequency. Planck’s equation for calculating the energy of a bundle of
light is

E = hν

whereE is the energy of the photon in joules (J), ν is the frequency in hertz (s−1 ), and h is
Planck’s
constant, 6:63×10−34 J s. (A photon is a particle of light. The word quantum is used for
energy in any form; when the type of energy under discussion is light, the words quantum and
photon become interchangeable.
Planck’s work became the basis for quantum theory. Quantum theory is the theory that
energy can only exist in discrete amounts (quanta).
Quantum theory can also be used to explain the result of this next experiment on light
called the photoelectric effect. The photoelectric effect is a phenomenon in which electrons
are emitted from the surface of a material after the absorption of energy. This experiment
involves having light strike a metal surface with enough force to knock electrons off the
metal surface. The results of the photoelectric effect indicated that if the experimenter used
low frequency light, such as red, no electrons were knocked off the metal. No matter how
many light waves were used and no matter how long the light was shined on the metal, red
light could not knock off any electrons. If a higher frequency light was used, such as blue
light, then many electrons were knocked off the metal. Albert Einstein used Planck’s
quantum theory to provide the explanation for the photoelectric effect. A certain amount of
energy was necessary for electrons to be knocked off a metal surface. If light were
quantized, then only particles of higher frequency light (and therefore higher energy)

5
would have enough energy to remove an electron. Light particles of lower frequency (and
therefore lower energy) could never remove any electrons, regardless of how many of them
were used.

Wave-Particle Duality

At this point, scientists had some experimental evidence (diffraction and interference) that
indicated light was a wave and other experimental evidence (black body radiation and the
photoelectric effect) that indicated light was a particle. The solution to this problem was to
develop a concept known as the wave-particle duality of light. The point of this concept is
that light travels as a wave and interacts with matter like a particle. Thus when light is
traveling through space, air, or other media, we speak of its wavelength and frequency, and
when the light interacts with matter, we switch to the characteristics of a particle (quantum).

Wave Character of Particles

In 1924, the Frenchman Louis de Broglie, suggested that if waves can have particle-like
properties as hypothesized by Planck, then perhaps particles can have some wave-like
properties. This concept received some experimental support in 1937 when investigators
demonstrated that electrons could produce diffraction patterns. (All objects, including
baseballs and automobiles could be considered to have wavep like properties, but this
concept is only measurable when dealing with extremely small particles like electrons.) De
Broglie’s “matter waves” would become very useful in attempts to describe the behavior of
electrons inside atoms.

Standing Waves

In the chapter “The Bohr Model of the Atom,” we considered a rope wave that was created
by tying one end of the rope to a tree and by jerking the other end up and down. When a
wave travels down a rope and encounters an immovable boundary, the wave reflects off the
boundary and travels back up the rope. This causes interference between the wave traveling
toward the tree and the reflected wave traveling back toward the person. If the person
moving the rope up and down adjusts the rhythm just right, the crests and troughs of the
wave moving toward the tree will coincide exactly with the crests and troughs of the reflected
wave. When this occurs, the apparent horizontal motion of the crests and troughs along the
rope will cease. This is called a standing wave. In such a case, the crests and troughs will
remain in the exact same place, while the nodes between the crests and troughs do not
appear to move at all.
In the standing wave shown above, the positions of the crests and troughs remain in the same
positions. The crests and troughs will only appear to exchange places above and below the
rope. The places where the rope does not cross the center axis line are called nodes
(positions of zero displacement). These nodal positions do not change and appear to be
frozen in place. By combining the concept of a standing wave along with de Broglie’s matter
waves, it became possible to describe an electron in an electron cloud as either a particle or a
standing wave.

Planck’s quantum hypothesis ; E= hν

Einstein’s relation ; E=mc2

Equating these 2 equations

hν = mc2

hc/λ = mc2

hence λ = h/mc = h/mc or h/p

Quantisation of angular momentum

Circumference of the orbit 2πr = n λ = nh/mv

Rearranging, mvr = nh/2π

The Heisenberg Uncertainty Principle

In all previous attempts to describe the electron’s behavior inside an atom, including in the
Bohr model, scientists tried to describe the path the electron would follow around the
nucleus. The theorists wanted to describe where the electron was located and how it would
move from that position to its next position.
In 1927, a German physicist named Werner Heisenberg, a German physicist stated what
is now known as the Heisenberg uncertainty principle. This principle states that it is
impossible to know both the precise location and the precise velocity of an electron at the
same time. The reason that we can’t determine both is because the act of determining the
location changes the velocity. In the process of making a measurement, we have actually
changed the measurement.
Heisenberg’s uncertainity principle is expressed as ∆x. ∆p ≥ h/4π
Schrödinger’s Equation

The Heisenberg uncertainty principle treated the electron as a particle. In effect, the
uncertainty principle stated that the exact motion of an electron in an atom could never be
determined, which also meant that the exact structure of the atom could not be determined.
Consequently, Erwin Schrödinger, an Austrian physicist, decided to treat the electron as a
wave in accordance with de Broglie’s matter waves.
Schrödinger, in considering the electron as a wave, developed an equation to describe the
electron wave behavior in three dimensions (shown below). Unfortunately, the equation is
so complex that it is actually impossible to solve exactly for atoms and ions that contain
more than one electron. High-speed computers, however, can produce very, very close
approximations, and these “solutions” have provided a great deal of information about the
possible organization of electrons within an electron cloud.
d2ψ/dx2 + 8π2m/h2 (E-V)ψ = 0- One dimensional time independent wave equation
where ψ- wave function, a function of position co-ordinates of the particle, ψ (xyz)
- h2/8π2m (∂2 /∂x2 + ∂2 /∂y2 + ∂2 /∂z2 )ψ +Vψ] = Eψ – Three dimensional form of Schrodinger
equation
Ĥ ψ = E ψ where Ĥ is the Hamiltonian operator
Ĥ = [- h2/8π2m (∂2 /∂x2 + ∂2 /∂y2 + ∂2 /∂z2 ) +V]

Significance of ψ and ψ2
ψ is a wave function and refers to the amplitude of electron wave i.e., probability amplitude. It
has got no physical significance. The wave function ψ may be positive, negative or imaginary.
[ψ]2 is known as probability density and determines the probability of finding an electron at a
point within the atom.

Problems
1. Calculate the uncertainty in the velocity of an electron if the uncertainty in position is
determined with an accuracy of 0.5% of the radius.
2. The uncertainty in determining the position of an electron in an orbit is 0.6Å. What is the
uncertainty in its momentum?

Quantum Numbers, Orbitals, and Probability Patterns

Atomic orbitals
An atomic orbital is a mathematical function which describes the probability of finding any
electron of an atom around its nucleus. Each orbital in an atom is characterized by three sets of
quantum numbers namely principal quantum number (n), angular momentum quantum number
(l) and magnetic quantum number (m). An orbital can accommodate a maximum of two
electrons and is characterized by its spin quantum numbers.

Quantum numbers
Quantum numbers expresses the various energy levels available for an electron to reside in
an atom. They are the numbers that define completely the electrons in an atom. They are used to
i. Specify the position (or location) of an electron in an atom.
ii. Predicts the direction of spin or self-rotation of the electron
iii. Determine the energy and angular momentum of the electron.

Principal quantum number (n)

These are the numbers that represent the circular energy levels (orbits) suggested by Bohr. The
energy levels are represented by non-zero positive integer values upto infinity (i.e, 1, 2, 3…..).
These energy levels are designated by capital letters K (n=1), L (n=2), M (n=3), N (n=4) and so
on. The value of ‘n’ represents also the distance of electrons from the nucleus. i.e, the L shell
electrons are at a more distance form the nucleus compared with K shell, M shell electrons are
more far compared to K and L shell electrons and so on. Thus in turn the number of ‘n’
represents the size of the atom. The value of ‘n’ can give the maximum number of electrons that
can be held by an energy level. This maximum number is fixed by the mathematical formula 2n 2.
Maximum number of electrons in K-shell with n =1 is 2 x 12 = 2
Maximum number of electrons in L-shell with n=2 is 2 x 22 = 8
Maximum number of electrons in M-shell with n=3 is 2 x 32 = 18
Maximum number of electrons in N-shell with n=4 is 2 x 42 = 32
For the hydrogen like atoms the magnitude of energy for each level can be calculated by
knowing the ‘n’ value. For the nth shell,
En = -2π2me4/n2h2

Azimuthal or subsidiary quantum number (l)

It is found that the individual line spectrum of atoms is not a single line but is observed as
fine spectrum consists of closely packed spectral lines. This split in spectral line will be due to
the sublevels existing in the major energy levels. Inorder to represent these subshells the
principal quantum number (n) is not sufficient. Rather another quantum number which is called
azimuthal or subsidiary quantum number (l) is used to represent the sub-shells of which the
shells are composed.
The value of l is dependent on the value of n. For a given value of n, l can have values from 0 to
(n-1). i.e, l = 0, 1, 2, 3, ……..(n-2), (n-1). Thus l can have n values.
Different values of ‘l’ represent the subshells which are designated as s, p, d, f. The energies of
the subshell in a main shell are increasing in the order s < p < d < f…

Magnetic quantum number (m)

When an excited atom which gives a line emission spectrum is placed in a strong magnetic
field, its spectral lines are further resolved into still thinner (i.e, closely spaced) lines. Linde
assumed that these closely spaced lines come due to the splitting of each sub-shell into sub-shells
in a magnetic field called orbitals which give thinner lines in the spectrum. Inorder to represent
these energy levels the first two quantum numbers n and l are not sufficient. Rather a third
quantum number which is called magnetic quantum number (m) is used to represent the orbitals
of which a given sub-shell is composed.
Different values of m are dependent on the value of l which itself is dependent on the value
of n. m can have integral values ranging from –l to +l.
Consequently:
When l = 0 (s sub-shell), m = 0 (only one value)
When l = 1 (p sub-shell), m = 0, ±1 (Three values)
When l = 2 (d sub-shell), m = 0, ±1, ±2 (Five values)
When l =3 (f sub-shell), m = 0, ±1, ±2, ±3 (Seven values)
It may be seen from the above description that for a given value of l, total number of m values is
(2l + 1).
Different values of m for a given value of l give us the total number of different space orientation
for the given s, p, d etc. sub-shells.

Spin quantum number (s)

Inorder to explain the doublet structure obtained for the spectrum of alkali metals,
Goudsmith and Uhlenbeck suggested that an electron while moving around the nucleus, also
spins on its own axis. The direction of spin is either clockwise or anti-clockwise. Inorder to
represent this spin motion an additional quantum number is introduced, that is spin quantum
number (s). This can have values either +1/2 (for clockwise spin) or -1/2 (for anticlockwise
spin).

Spacial orientation of subshells

The distribution of electron cloud around the nucleus of an atom is different in different
orbitals. They are dependent on the three quantum numbers and the structure is explained as
below.

s sub-shell: In the case of s sub-shell the l value is zero. Since l=0, m is also equal to zero. This
implies that s sub-shell of any energy level has only one space orientation. The shape of s-orbital
is depicted as a sphere, which depicts that the probability of finding an electron (i.e, electron
density) in all the direction from the nucleus is the same in s-orbital. As the n value increases the
size of s-orbital also increases. Thus the 2s sub-shell has more radius than the 1s orbital but the
1s orbital is completely within the 2s orbital. There is a vacant space between 1s and 2s orbital
where the probability of finding an electron is zero which is known as nodal plane. There are (n-
1) such nodal surfaces in s-orbital of nth main energy level.
 Shape of s sub-shells

p sub-shell: p-orbital where l=1 have three m values 0, +1 and -1. Thus the subshell which starts
from the second (n=2) major energy level has three space orientations and are in three different
ways along x, y, z axes. These are designated as p x (m=0), py (m=+1) and pz (m=-1). The three p
orbitals are thus perpendicular to each other. All of them have dumb-bell shape. Thus p-orbitals
are directional which determines the geometry of the molecules. All the p-orbitals in the same
principal energy level have the same energy but increases when the n value increases. The two
lobes of the p-orbital are separated by a plane which contains the nucleus and is perpendicular to
the orbital axis. The probability of finding an electron at the nucleus as well as the plane is zero.
The nucleus is called the node and the plane is called the nodal plane.

Shape of p sub-shells
d sub-shell: Here l=2, have five m values -2, -1, 0, +1 and +2. This orbital has n value starts from
3, thus starts from the third principal energy level. These orbitals have thus five different special
orientations with same energy (degenerate). They are designated as d xy (m=-2), dyz (m=-1), dxz
(m=+1), dx2-y2 (m=+2) and dz2 (m=0). dxz, dyz and dxz orbitals have their greatest electron density
between the axes, thus their lobes are lying symmetrically between the axes. d x2-y2 and dz2 orbitals
have their electron density in the region along the axes.
 Shape of d sub-shells

f sub-shell: For this sub-shell l=3, thus it has seven m values and thus seven different special
orientations. These are represented as below,

Shape of f sub-shells

Problems

3. Calculate the number of angular and radial nodes for the 3d orbital.
 Trend in the periodic properties

Periodic property Across a period Along a group

Atomic or Ionic radii Decreases Increases
Ionisation Potential Increases Decreases
Electron Affinity Increases Decreases
Electronegativity Increases Decreases

Chemical bonding
A chemical bond is the attractive force that holds two or more atoms in a molecule or in
an ion. When atoms combine the electrons in the outermost shells of the atoms are arranged
between themselves in such a way that they achieve an octet of electrons in their valence shells.
The tendency of the atoms to have eight electrons in their outermost shell is known as octet rule.
The atom that attains octet configuration achieves the noble gas configuration and is stable. So
the atoms are combining to achieve stability. There are four types of bonds or linkages which
holds the atoms in a molecule, i) ionic bond, ii) covalent bond, iii) co-ordinate bond and
iv) metallic bond. All these are known as strong bonds. However there are some weak forces that
hold the atoms in a molecule. They are i) hydrogen bond and ii) van der Waals forces.

Ionic or Electrovalent Bond

A chemical bond formed between two atoms by the transfer of one or more valence
electrons from one atom to the other is called ionic bond. It is also called electrovalent or polar
bond. If one of the combining atoms has more electrons than the ns 2p6 outer electronic
configuration and the other has less valence electron, the former gives its extra electron to second
atom and allow it to attain the octet valence electron. The compounds which contain these kinds
of bonds are called electrovalent or ionic compounds.

Illustration of the formation of ionic bond

Consider the atom A to form bond with atom B. Atom A has one electron in its valence
shell while atom B has seven electrons. Thus A has one electron in excess and B has one electron
shorter than the stable octet. Therefore A transfers an electron to B and in this transaction both
the atoms acquire a stable electron octet. This result in the formation of positive ion A + (cation)
and negative ion B- (anion), they are held together by electrostatic attraction and the bond is an
ionic bond.
Schematic representation of ionic bond formation.

Thus an ionic bond is due to the electrostatic force of attraction between cation and anion.
Ionic bonding in NaCl
Sodium (2,8,1) transfers its excess one electron to chlorine (2,8,7) and thus Na attains
configuration of Ne (2,8) and Cl acquires the configuration of Ar (2,8,8). The electron lost by Na
atom is accepted by Cl, therefore Na forms its cation Na + and Cl forms the anion Cl -. The two
ions attract each other by electrostatic force of attraction which leads to the formation of an ionic
bond between them.

Ionic bond formation between sodium and chlorine

Bonding in MgO
Inorder to form a bond between Mg and O, two electrons were transferred from Mg to oxygen.
This leads to the formation of Mg 2+ and O2-. They attract each other by electrostatic force and
form MgO.

Ionic bond formation in MgO molecule

Ionic bonding in CaF2
For forming the bond between Ca and F, Ca atom loses two of its electrons and converted to Ca 2+
ion. Each fluorine atom accepts one electron and is converted to F - ion. One Ca2+ attracts two F-
ions and forms CaF2 molecule.

Bonding in calcium fluoride

Ionic bonding is non directional since the charge on one ion can attract any oppositely charged
ion in any direction. When an ionic compound is dissolved in water the electrostatic force
between the ions are broken by the high dielectric constant of water and thus the ions
constituting the ionic compound separate from each other and form respective ions.

Factors favoring ionic bond formation

Following are the factors that favor the formation of ionic bonds.
1. Number of valence electrons: Cation formation is favored when the valence electron is
1, 2 or 3, and anion formation is favored when the number of valence electrons is equal to
5, 6 or 7. Thus the elements in group I, II and III are susceptible for cation formation. The
group V, VI and VII elements prefer anion formation.
2. Ionization energy: If the ionization energy for the metal is low, the cation formation is
most favored.
3. Electron affinity: The atoms with high electron affinity form anions easily.
4. Lattice energy: It is the energy released when one mole of a crystal is formed from its
gaseous ions. Higher the value of the lattice energy of a crystal, the greater is its
formation.
5. Electronegativity: If the difference between the electronegativities of the constituent
atoms is two or more, the ionic bond formation is favored. For example Na (0.9) and Cl
(3.0) the electronegativity difference is 2.1, thus they form ionic bond.

Electrovalency
Electrovalency of an element is equal to the number of electrons lost by an atom of that
element in forming a positive ion or gained by it in forming a negative ion, both attaining noble
gas configuration in the outermost shell. The element that loses electrons show positive
electrovalency and the elements which gain electrons show negative electrovalency. In CaF 2,
calcium loses two electrons thus its valency is two or is a divalent element. One fluorine gains
one electron thus is a monovalent element.
Examples,
Na, Li, Cl, F, Br……………….Monovalent
Mg, Ca, O, S…………………..Divalent
Al, B…………………………...Trivalent
C, Si……………………………Tetravalent

Properties of Ionic compounds

1. Physical state: Ionic compounds are crystalline solids at room temperature, due to their
well ordered geometrical pattern of arrangement of cations and anions.
 2. Electrical conductivity: They are very low conductors in solid state but are good ionic
conductors when melted or dissolved in a solvent.
3. They are hard, low volatile and have high melting and boiling points due to their
strong electrostatic force of attraction between the ions and three dimensional crystalline
arrangements.
4. Solubility: They are freely soluble in polar solvents like water, liquid ammonia etc. They
are insoluble or slightly soluble in non-polar solvents.
5. Highly brittle: Most of the ionic compounds are highly brittle; a little amount of external
force can break the solid.
6. Density: Because of the strong electrostatic attraction the atoms are so close, thus
decreases the volume. Hence ionic solids have high density.
7. They undergo ionic reactions quickly.
8. Isomorphism: Ionic solids made up of ions with identical electronic configuration show
an identity of crystalline form which is called isomorphism.
Examples, (a) NaF and MgO (b) CaCl2 and K2S
(a) Na + (2,8) F- (2,8) and Mg2+ (2,8) O2- (2,8)
(b) Ca (2,8,8) Cl (2,8,8) and K (2,8,8) S2-(2,8,8)
2+ - +

9. They do not show isomerism.

Lattice energy
Lattice energy of an ionic crystal is defined as the amount of energy released when a
mole of cations and anions combined to form an ionic crystal in its gaseous state. It is
represented as U. Generally it has a negative sign since the formation of an ionic bond is an
exothermic process. Thus in the formation energy is released and hence the energy of the system
is decreased. Greater is the value of lattice energy of an ionic compound, more stable is the ionic
solid.
A+ (g) + B- (g) A+B- (s) + Energy released (lattice energy)

Solvation energy

When an ionic compound is dissolved in a polar solvent, it initially dissociates to its

individual ions, which involves an energy which is equivalent to lattice energy of the molecule.
In the second stage the individual ions interact with solvent molecules to form solvated ions. The
process of which the solvated (or hydrated) ions are produced is called solvation (or hydration)
process. This is accompanied by the release of certain amount of energy which is called solvation
or hydration energy. This is an exothermic process where the energy is released. For an ionic
compound to dissolve in a polar solvent, the magnitude of hydration energy of the solvent should
be such that it should be able to overcome the lattice energy of the ionic solid which is
responsible for holding the ions together in the ionic crystal. Thus for an ionic solid to dissolve in
a polar solvent, the solvation energy of the solvent must be greater than the lattice energy of the
ionic solid so that the solvation energy may overcome the lattice energy.
Covalent Bond

In the previous section we could see an elaborate description on formation and

characteristic features of ‘ionic bond’. We have seen that a huge difference in electronegativity
between the two atoms may result in an ionic bond between them. If the electronegativity
difference between the two atoms involved in bond formation is only moderate or very small, a
covalent bond may result by mutual and equal sharing of a finite number of electrons. In this
section, we shall have a brief description on the concepts and theories on covalent bond
formation.
G.N. Lewis in 1916, suggested that two atoms may combine by sharing electrons from
valance shells, resulting in the formation of a covalent bond, which provides a stable ‘octet’
configuration in the valence shell of both the atoms involved in bonding. The shared pair of
electrons remains common for both the atoms involved in bonding. After the formation of a
covalent bond, it is obvious that, the ‘octet’ around an atom will include a few electrons of the
same atom and a few more electrons which are shared. Electronic structures of a variety of
simple molecules could be satisfactorily explained by this ‘octet rule’ for covalent bond
formation.

A few illustrative examples of covalent bond formation which satisfy the octet rule are given
below:

Example 1: Fluorine molecule (F2)

Number of electrons in the valance shell :7 (1s2, 2s2, 2p5)

of each fluorine atom

Number of electrons from each fluorine, : 1

utilized for sharing

Number of covalent bonds between the : 1

two fluorine atoms in F2 molecule

Fluorine molecule formation from Fluorine atoms

Example 2: Chlorine molecule

Number of electrons in the valance shell
of each Chlorine atom : 7 (1s2, 2s2, 2p6,3s2,3p5)

Number of electrons from each Chlorine,

utilized for sharing :1

Number of covalent bonds between the

two Chlorine atoms in Cl2 molecule :1

Example 3: HF molecule
Number of electrons in the valance shell
of each Hydrogen atom :1 (1s1)

Number of electrons in the valance shell

of each Fluorine atom :7 (1s2, 2s2, 2p5)

Number of electrons from Hydrogen,

utilized for sharing :1

Number of electrons from Fluorine,

utilized for sharing :1

Number of covalent bonds between the

hydrogen and the fluorine in HF :1

Covalent bond formation in HF molecule

Example 4: CCl4 molecule

Number of electrons in the valance shell
of each carbon atom : 4 (1s2, 2s2, 2p2)

Number of electrons in the valance shell

of each Chlorine atom : 7 (1s2, 2s2, 2p6,3s2,3p5)

Number of electrons from Carbon, utilized

for sharing :4
Number of electrons from each Chlorine,
utilized for sharing :1

Number of covalent bonds between the

Carbon and the Chlorine atoms in CCl4 : Total four C - Cl covalent bonds

Covalent bond formation in CCl4 molecule

Example 5: CH4 Molecule

Number of electrons in the valance shell
of each carbon atom : 4 (1s2, 2s2, 2p2)

Number of electrons in the valance shell

of each Hydrogen atom : 1 (1s1)

Number of electrons from Carbon, utilized

for sharing :4

Number of electrons from each Hydrogen,

utilized for sharing :1

Number of covalent bonds between the

Carbon and the Hydrogen atoms in CH4 : Total four C - H covalent bonds
Covalent bond formation in CH4 molecule

Example 6: O2 Molecule
Number of electrons in the valance shell of
each Oxygen atoms : 6 (1s2, 2s2, 2p4)

Number of electrons from each Oxygen

atom, utilized for sharing :2

Number of covalent bonds between the two : 2 (i.e., one double bond between the two
Oxygen atoms in O2 molecule Oxygen atoms)

Example 7: N2 Molecule
Number of electrons in the valance shell : 5 (1s2, 2s2, 2p3)
of each Nitrogen atoms

Number of electrons from each Nitrogen

atom, utilized for sharing
 Number of covalent bonds between the : 3 (i.e., one triple bond between the two
two Nitrogen atoms in N2 molecule Nitrogen atoms)

Covalent bond formation in N2 molecule

Example 8: NH3 Molecule

Number of electrons in the valance shell of
each Nitrogen atom : 5 (1s2, 2s2, 2p3)

Number of electrons in the valance shell of

each Hydrogen atom : 1 (1s1)

Number of electrons from Nitrogen, utilized

for sharing : 3

Number of electrons from each Hydrogen,

utilized for sharing :1

Number of covalent bonds between the

Nitrogen and the Hydrogen atoms in NH3 : Total three N-H covalent bonds

Covalent bond formation in NH3 molecule

The number of electrons contributed by an atom for sharing during the covalent bond
formation, is addressed as covalency of that atom.
Covalent Bond Formation – Concept of Atomic Orbital Overlap
In accordance with atomic orbital overlap concept, sharing of electrons for the
formation of a covalent bond occurs by the overlap of the respective outermost orbitals,
in which the valence electrons are situated. Based on the directive nature of orbital
overlap, sigma or pi bonds may be formed.

Sigma bond
Axial overlap of half-filled atomic orbitals results in the formation of a sigma
bond. The covalent bonds in molecules such as H2, Cl2, F2, HF are examples of this type.
Pi bond
Lateral overlap of half-filled atomic orbitals lead to the formation of pi bonds.
Owing to the higher extend of effective overlap sigma bonds are stronger than pi bonds.

Sigma and Pi bond formation in N2 Molecule (N≡N)

Theories and concepts to explain the formation and geometry of covalent molecules.

There are different theoretical approaches for predicting the formation and the
geometry of the compounds formed by covalent bonding. They are briefed here.

Octet rule
The octet rule, even though applicable to explain the covalent bond formation in
many simple molecules, this rule is broken in a significant number of cases. Owing to
varying reasons, the molecules such as BeF2, BF3, PF5, NO, ClO2 are exceptions to the octet
rule. Octet rule could not give any idea about the Para magnetism of O 2 molecule. And
also it does not give any explanation for geometrical shape of molecules.

Sidgwick and Powell Theory

Nevil Sidgwick and Herbert Marcus Powell of the University of Oxford, in 1940,
suggested that the approximate shape of molecules could be predicted based on the
number of electron pairs in the valence shell of the central atom. The bond pairs (electron
pairs in the valence shell, involved in bond formation) and lone pairs (electron pairs in
the valence shell, not involved in bond formation), as per this theory were considered as
equivalent. In view of this theory, all the electron pairs repel each other and therefore
there is an inherent effect in the molecules to orient these electron pairs as far apart as
possible, so as to minimize the repulsion and maximize the stability and this decides the
geometrical shape of the molecule.

Sidgwick and Powell Theory

Valence electrons Angle between the electron Shape of the molecule
of central atom pairs

2 180c Linear

3 120 c Trigonal planar

4 109o28’ Tetrahedral

120o(within the equatorial Trigonal bypyramidal

5 plane) and 90o (between
equatorial and axial
directions)

6 90o Octahedral

Even though shapes of many molecules were predicted correctly by this theory, a few
molecules, which exhibited deviations from the expected shape, exist as exceptions.

Valence Shell Electron Pair Repulsion (VSEPR) Theory

Ronald Gillespie and Ronald Sydney Nyholm of University College London, in

1957, provided a corrective extension to Sidgwick - Powell theory and this modified
theory was addressed as Gillespie-Nyholm theory or Valence Shell Electron Pair
Repulsion (VSEPR) theory. VSEPR theory also predicts that the number of electron pairs
in the valence shell of the central atom that decides the shape of the molecule.
But on accounting the relative strengths of repulsions, as per the VSEPR theory, the lone
pair- lone pair repulsion is considered as of highest strength and the bond pair – bond pair
repulsion as of lowest strength and the lone pair – bond pair repulsion being with
intermediate strength. This variation in strengths of repulsive interactions leads to slight
deviations in bond angles and hence in geometry.

Geometry of molecules by VSEPR theory

Valence Bond pairs Non bonding
Molecule electron pairs Shape of the molecule
 pairs
BeF2 2 2 0 Linear (F-Be-F angle is
180o)

BF3 3 3 0 Trigonal planar (F-B-F

angles are 120o)

CH4 4 4 0 Tetrahedral (H-C-H angles

are 109o28’)

NH3 4 3 1 Trigonal pyramidal (H-N-H

angles are 107o48’)

H2O 4 2 2 Bent (‘V’) (H-O-H angle is

104o27’)

PCl5 5 5 0 Trigonal bypyramidal (Cl-

P-Cl angles are 120o with
in the equatorial plane and
90o between equatorial and
axial planes )

SF6 6 6 0 Octahedral (F-S-F angles

are 90o)

ClF3 5 3 2 Trigonal bypyramidal

arrangement of the five
electron pairs around the Cl
atom. The ClF2 molecule
is of slightly distorted (due
to the presence of lone
pairs) ‘T’ shape.

I3- 5 2 3 Trigonal bypyramidal

arrangement of the five
electron pairs around the
central Iodine atom. With
three lone pairs in the
equatorial and the two bond
pairs in the axial plane, the
I3- ion is observed as linear
in shape.

Valance Bond Theory and Hybridization

Atoms with unpaired electrons tend to combine with other atoms which also have
unpaired electrons. The shared pair of electrons remains common for both the atoms
involved in bonding. The number of unpaired electrons in an atom may be increased by
promoting electrons from paired ground state to the unpaired excited state.
For example, in H2O molecule, two singly occupied 2p orbitals on oxygen overlap
with a singly occupied 1s orbital each of the two hydrogen atoms. Two pairs of electrons
in the valence shell of oxygen remain as two lone pairs.
In NH3 molecule, three singly occupied 2p orbitals on the central nitrogen atom
overlap with a singly occupied 1s orbital each of the three hydrogen atoms. One pair of
electrons in the valence shell of nitrogen remains as a lone pair.
In CH4, for formation of four covalent C-H bonds, the central carbon should be
predicted as with four unpaired electrons. But the ground state electronic configuration of
carbon (1s2, 2s2, 2px1, 2py1, 2pz0) suggests the existence of only two unpaired electrons.
Therefore in order to explain the existence of four unpaired electrons, we shall consider
the excited state electronic configuration of the central carbon, in which a 2s electron is
promoted to 2pz orbital (1s2, 2s1, 2px1, 2py1, 2pz1). Now each of these four unpaired
electrons may pair with the unpaired electrons from the 1s orbital each of the four
hydrogen atoms; which results in the formation of four C-H bonds and hence the CH 4
molecule. Based on the assumptions in VSEPR theory, four bond pairs in CH 4 molecule
provide it with the tetrahedral shape (refer the section on VSEPR theory).
But all the four C-H bonds in methane are observed to be equivalent (particularly,
energy wise). Fundamental VSEPR theory could not explain this equivalency aspect. If
all the four C-H bonds in a methane molecule are to be energetically the same, they might
have been formed due to the combination of similar types of orbitals. But in fact, as per
the basic orbital overlap concept, one C-H bond is formed due to the overlap of 2s orbital
of carbon and 1s orbital of hydrogen and the other three C-H bonds are due to the
combination of 2p orbitals of Carbon and 1s orbital each of the three hydrogen atoms. If
this would have been the real case, all the four C-H bonds could a have never been
equivalent.
To explain factors such as energy wise equivalency of bonds, deviation from the
expected geometry etc., the concept of hybridization is introduced.
Orbital hybridization is simply a combination of two or more valance atomic
orbitals (s, p, or d) of slightly different energies, on the central atom, to form new hybrid
orbitals of same energy which are used for bonding.( Mathematically we apply the linear
combination method to derive the hybrid orbitals from the simple atomic orbitals).
Number of hybrid orbitals formed is equal to the number of atomic orbitals involved in
hybridization. The most striking feature is that the energy of the combining orbitals may
slightly be different; still the hybridized orbitals are stated as of the same energy.
Spatial orientation of hybrid orbitals on the central atom decides the geometrical
shape of the molecule, as per the suggestions from VSEPR theory.

Example 1:- BeF2 molecule: sp hybridization

Berilliun (ground state) : 1s2, 2s2, 2px0, 2py0, 2pz0

Berillium (excited state) : 1s2, 2s1, 2px1, 2py0, 2pz0

 Hybridization : sp

Number of sp hybrid orbitals on : 2

Berillium
Orientation of the four sp3 hybrid : Linear
orbitals around Nitrogen

Number of bond pairs in BeF2 : 2 (2 sp hybrid orbitals on Berillium

combine
with half filled 2p orbitals each of the two
Fluorine atoms)

Number of lone pairs in BeF2 : 0

Shape of the molecule : Linear (as per VSEPR concept)

F-B-F bond angle : 180oF-Be-F

Example 2:- BF3 molecule - sp2 hybridization

Boron (ground state) : 1s2, 2s2, 2px1, 2py0, 2pz0

Boron (excited state) : 1s2, 2s1, 2px1, 2py1, 2pz0

Hybridization : sp2

Number of sp2 hybrid orbitals on Boron :3

Orientation of the four sp2 hybrid : Trigonal planar.

orbitals around Boron

Number of bond pairs in BF3 : 3 (3 sp2 hybrid orbitals on Boron combine

with half filled 2p orbitals each of the three
Fluorine atoms)

Number of lone pairs in BF3 :0

Shape of the molecule : Trigonal planar (as per VSEPR concept)

F-B-F bond angle :120o

The trigonal planar BF3à

 The vacant unhybridized 2p orbital on boron stands as a feature responsible for the
Lewis acidity and electron pair accepting ability of BF3.

Example 3:- Methane (CH4) molecule : sp3 hybridization

Carbon (ground state ) : 1s2, 2s2, 2px1, 2py1, 2pz0

Carbon (excited state ) : 1s2, 2s1, 2px1, 2py1, 2pz1

Hybridization :sp3

Number of sp3 hybrid orbitals on Carbon :4

Orientation of the four sp3hybrid orbitals : Tetrahedral

around Carbon

Number of bond pairs in CH4 : 4 (4 sp3 hybrid orbitals on Carbon

combine with 1s orbitals each of the four
hydrogen atoms)

Number of lone pairs CH4 : Nil

Geometry of the molecule : Tetrahedral (as per VSEPR concept)

H-C-H bond angle : 109o28’

Tetrahedral CH4à

Example 4:- Ammonia (NH3) - sp3 hybridization

Nitrogen : 1s2, 2s2, 2px1, 2py1, 2pz1

Hybridization :sp3
Number of sp3 hybrid orbitals on : 4
Nitrogen
Orientation of the four sp3 hybrid : Tetrahedral.
orbitals around Nitrogen

Number of bond pairs : 3 (3 sp3 hybrid orbitals on Nitrogen

combine with 1s orbitals each of the three
Hydrogen atoms)

Number of lone pairs : 1 (present in the fourth sp3 hybrid orbital

on
Nitrogen).

Shape of the molecule : Pyramidal (as per VSEPR concept)

:. H-N-H bond angle : 107o48’

Pyramidal shaped NH3 à

Example 5:-Water(H2O) - sp3 hybridization

Oxygen : 1s2, 2s2, 2px2, 2py1, 2pz1

Hybridization : sp3
3
Number of sp hybrid orbitals on : 4
Nitrogen
Orientation of the four sp3 hybrid : Tetrahedral.
orbitals around Oxygen

Number of bond pairs in H2O : 2 (2 sp3 hybrid orbitals on Oxygen

combine with 1s orbitals each of the two
hydrogen atoms)

Number of lone pairs in H2O : 2 (present in the other two sp3 hybrid
orbitals on Oxygen).

Shape of the molecule : ‘V’ shape (as per VSEPR concept)

:. H-O-H bond angle : 104o27’

Bent (/‘V’) shaped H2O à

Example 6:-PF5 Molecule - sp3d hybridization

Phosphorous (ground state) : 1s2, 2s2, 2p6, 3s2,3px1,3py1,3pz1,3d0

Phosphorous (excited state) : 1s2, 2s2, 2p6, 3s1,3px1,3py1,3pz1,3d1

Hybridization :sp3d

Number of sp3d hybrid orbitals on : 5

Phosphorous

Orientation of the fivesp3d hybrid : Trigonalbypyramidal

orbitals around Phosphorous

Number of bond pairs in PF5 : 5 (5 sp3d hybrid orbitals on Phosphorous

combine with half filled 2p orbitals each of
the five Fluorine atoms)
Number of lone pairs in PF5 :0

Shape of the molecule :Trigonalbypyramidal (as per VSEPR

concept)

F-P-F bond angle :120o with in the equatorial plane and 90o
between equatorial and axial planes

The trigonalbypyramidal shape of

PF5à

Example 7:- SF6 molecule - sp3d2 hybridization

 Sulphur (ground state) :1s2, 2s2, 2p6, 3s2,3px2,3py1,3pz1,3d0

Sulphur (excited state) :1s2, 2s2, 2p6, 3s1,3px1,3py1,3pz1,3d2(two3d

orbitals carry one unpaired electron each)

Hybridization : sp3d2

Number of sp3d2hybrid orbitals on : 6

Sulphur
Orientation of the sixsp3d2 hybrid
orbitals around Sulphur : Octahedral

Number of bond pairs in SF6 : 6 (6 sp3d2 hybrid orbitals on Sulphur

combine with half filled 2p orbitals each of
the six fluorine atoms)

Number of lone pairs in SF6 :0

Shape of the molecule : Octahedral (as per VSEPR concept)

F-S-F bond angle : 90o

The octahedral shape of SF6à

Properties of covalent compounds

A few characteristics of covalent compounds are listed below:
 Owing to the weak attractions (compared to ionic and metallic compounds)
between the covalent molecules, generally most of the covalent compounds have
relatively low melting points and boiling points.
 In comparison with ionic compounds, covalent compounds exhibit lower
enthalpies of fusion and vaporization.
 In contrast to ionic compounds, aqueous solutions of covalent compounds,
generally do not conduct electricity.
 Compared to ionic solids, covalent compounds exhibit limited solubility in water.

Polar covalent bond

A polar covalent bond (or simply polar bond) is a covalent bond in which the
bonding electrons spend more time near one atom than the other. If the electronegativities
of the bonded atoms are not equal, the bond is polarized toward the more electronegative
atom. For example, in the case of the HCl molecule, the bonding electrons spend more
time near the chlorine atom than the hydrogen atom. This “unequal sharing” of the
bonding electron pair results in a relatively greater electron density near the chlorine
atom and a correspondingly lower electron density near hydrogen atom. Such type of
bond is called as polar covalent bond.

.
Polar covalent bond in HCl
Non-polar covalent bond
A bond is nonpolar if the bonded atoms have equal electronegativities. In the case of Cl 2
the bonding is nonpolar because the electronegativity difference ∆(EN), between the
chlorine atoms is zero; hence the two chlorine atoms share the bonding electrons equally
between them. The covalent bonds in all homonuclear diatomic molecules are nonpolar
covalent bonds.

Coordinate covalent compounds

A covalent bond is formed by sharing a pair of electrons by two atoms. The atoms
are held together because the electron pair is attracted by both the nuclei. In the formation
of a simple covalent bond, each atom supplies one electron to the bond. A coordinate
bond (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
When ammonia and HCl gases are allowed to mix, a thick white smoke of solid
ammonium chloride is formed.
NH3+HCl→NH4Cl
Ammonium ions, NH4+, are formed by the transfer of a hydrogen ion from hydrogen
chloride to the lone pair of electrons on the ammonia molecule.
Co-ordinate bond formed in ammonium ion.
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.

Representing coordinate bonds

Generally, a coordinate bond is shown by an arrow. The arrow points from the
atom donating the lone pair to the atom accepting it.

Dissolving hydrogen chloride in water to make hydrochloric acid

A hydrogen ion (H+) is transferred from the chlorine to one of the lone pairs on
the oxygen atom.
Co-ordinate bond in hydronium ion
H2O + HCl → H3O+ + Cl−
The H3O+ ion is called the hydroxonium ion, the hydronium ion or the oxonium ion. Once
the coordinate bond has been set up, all the hydrogens attached to the oxygen are exactly
equivalent. When a hydrogen ion breaks away again, it could be any of the three.

Reaction between ammonia and boron trifluoride

Boron trifluoride is a compound that does not have a noble gas configuration
around the boron atom. Boron has only three pairs of electrons in its bonding level,
whereas there would be room for four pairs. BF3 is described as being electron deficient.
The lone pair on the nitrogen of an ammonia molecule can be used to overcome that
deficiency, and a compound is formed involving a coordinate bond.

Dative bond formed between ammonia and boron trifluoride

This could be shown as:

The nitrogen end of the bond has become positive because the electron pair has moved
away from the nitrogen towards the boron - which has therefore become negative.

The structure of aluminum chloride

Aluminum chloride sublimes at about 180 °C. If it is considered a polar
compound, it would have a very high melting and boiling point because of the strong
attractions between the positive and negative ions. The implication is that, when it
sublimes at this relatively low temperature, it must be covalent.
 Lewis dot structure for AlCl3
AlCl3, like BF3, is electron deficient. There is a similarity, because aluminum and
boron are in the same group of the Periodic Table, as well fluorine and chlorine are.
Measurements of the relative formula mass of aluminum chloride show that its
formula is not AlCl3, but Al2Cl6. It exists as a dimer. The bonding between the two
molecules is coordinate, using lone pairs on the chlorine atoms. Each chlorine atom has 3
lone pairs, but only the two important ones are shown.

Dimerization of aluminium chloride

Energy is released when the two coordinate bonds are formed, and so the dimer is more
stable than two separate AlCl3 molecules.

The bonding in hydrated metal ions

Water molecules are strongly attracted to metal ions in solution - the water
molecules clustering around the positive or negative ions. In many cases, the attractions
are so great that formal bonds are made, and this is true of almost all positive metal ions.
Metal Ions with water molecules attached are described as hydrated metal ions.
Although aluminum chloride is a covalent compound, when it dissolves in water,
ions are produced. Six water molecules bond to aluminum to give an ion with the formula
Al(H2O)63+. It is called the hexa aqua aluminum complex ion. The bonding in this is
coordinate (dative covalent) using lone pairs on the water molecules.
Water has two lone pairs of electrons
The electronic configuration of aluminum is 1s 22s22p63s23px1. When it forms an
Al ion it loses the 3-level electrons to leave 1s 22s22p6. That means that all the 3-level
3+

orbitals are now empty. Aluminum reorganizes (hybridizes) six of these (the 3s, three 3p,
and two 3d) to produce six new orbitals all with the same energy. These six hybrid
orbitals accept a lone pair each from six water molecules. Only one lone pair is shown on
each water molecule. The other lone pair is pointing away from the aluminum and so is
not involved in the bonding. The resulting ion looks like this:

Because of the movement of electrons towards the center of the ion, the 3+ charge is no
longer located entirely on the aluminum, but is now spread over the whole of the ion.

Characteristics of coordinate compounds

These compounds possess similar characteristics as covalent compounds.
i) They do not ionize in water and are poor conductors of electricity.
ii) They are very sparingly soluble in water but dissolve in organic solvents.
iii) These compounds possess melting and boiling points higher than those of pure
covalent compounds but lower than the ionic compounds.
iv) The coordinate linkage is rigid and directional and therefore these compounds can
exhibit space isomerism.
v) The coordinate linkage is easily broken when the donor and acceptor are
molecules which are capable of independent existence.
Molecular orbital theory

The MO theory treats molecular bonds as a sharing of electrons between nuclei.

The electrons are spread out over the entire molecule. Molecular orbitals are obtained by
the linear combination of the atomic orbitals on the atoms in the molecule.
The MO Theory has five basic rules:
1. The number of molecular orbitals = the number of atomic orbitals combined
2. Of the two MO's, one is a bonding orbital (lower energy) and one is an anti-bonding
orbital (higher energy)
3. Electrons enter the lowest orbital available
4. The maximum number of electrons in an orbital is 2 (Pauli Exclusion Principle)
5. Electrons spread out before pairing up (Hund's Rule)

Molecular orbital theory for H2 molecule

Consider 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 (bonding molecular orbital, BMO). 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. Placing an electron in this orbital therefore stabilizes the H 2 molecule. Another
orbital is formed by subtracting one of these functions from the other (anti- bonding
molecular orbital, ABMO). Electrons placed in this orbital spend most of their time away
from the region between the two nuclei. This orbital is therefore an anti bonding, or
sigma star (σ *), molecular orbital. Placing an electron in this orbital makes the molecule
less stable.

MO energy level diagram for H2. The up and down arrows represent electrons that are
spin up or spin down.
The molecular orbital configuration of H2 is σ (1s)2. The bond order for H-H bond
is ½ [2-0] = 1. Hence the two hydrogen atoms are bonded together by a single bond. The
bond dissociation energy has been found to be 458kJ mol-1 and bond length to 0.74 Å.

Bond order calculation

Bond Order= ½ [Number of electrons in BMO - Number of electrons in ABMO]
 If the bond order is zero, then no bonds are produced and the molecule is not
stable (for example He2). If the Bond Order is 1, then it is a single covalent bond. The
higher the Bond Order, the more stable the molecule is. An advantage of Molecular
Orbital Theory when it comes to Bond Order is that it can more accurately describe
partial bonds (for example in H 2+, where the Bond Order=1/2). Bond order indicates the
strength of the bond.

Molecular orbital diagram of O2 molecule

There are six valence electrons (2s 2, 2px2, 2py1 2pz1) on a neutral oxygen atom and
therefore 12 valence electrons in an O2 molecule. These electrons are added, one at a
time, starting with the lowest energy molecular orbital. As Hund's rule apply to the filling
of molecular orbitals, molecular orbital theory predicts that there should be two unpaired
electrons on this molecule one electron each in the x* and y* orbitals.
 Molecular orbital energy level diagram for O2 molecule.

The molecular orbital configuration of O 2 is KK σ(2s)2 σ*(2s)2 σ(2pZ)2 π(2px)2

π(2py)2 π*(2px)1 π*(2py)1. The bond order for O-O bond is ½ [8-4] = 2. Thus O 2 molecule
contains a double bond. The bond dissociation energy has been found to be 494.6kJ mol -1
and bond length is larger being 1.21 Å. Since there are two unpaired electrons, O 2
molecule is paramagnetic in nature.

Molecular orbital diagram of N2 molecule

The outer shell of Nitrogen atom contains 5 electrons and therefore 10 valence
electrons in a N2 molecule. The molecular orbital configuration of N 2 is KK σ(2s)2
σ*(2s)2 π(2px)2 π(2py)2 σ(2pZ)2.
Molecular orbital diagram of N2 molecule
Its BO is ½ (8-2) = 3. Thus N 2 contains a triple bond. Only one antibonding MO
is involved, making it highly stable. This is confirmed by its high bond dissociation
energy of 945. 6 kJ/ mol and small bond length of 1.10 Å. Since there are no unpaired
electrons in any orbital, N2 is diamagnetic.
Heteronuclear diatomic molecule - CO

Energy levels in CO molecule

The electronic configuration of C and O atoms are 1s 2 2s2 2p2 and 1s2 2s2 2p4 respectively.
There are 4 electrons in the outer shell of C and 6 electrons in O. The molecular orbitals
have to be filled with 10 electrons. Due to higher electronegativity of oxygen, its AOs are
of lower energy than the corresponding AOs of C. Hence the BMOs have more
characteristics as the AOs of Oxygen and the ABMOs have more characteristics as the
AOs of Carbon.
The electronic configuration of CO molecule is KK σ(2s)2 σ*(2s)2 π(2px)2 π(2py)2 σ(2pZ)2.
Its BO is ½(8-2) = 3. There is one σ bond in which both the electrons are from the C atom
(dative bond) and two π bonds.

Note:
1. Since the electro negativity of oxygen is greater than that of C, the 2s and 2p
 orbitals of oxygen have been placed lower than the 2s and 2p orbitals of C.
2. CO is isoelectronic with N2, it has the same MO configuration as N2 molecule.

Hydrogen bond
In compounds of H with highly electronegative atom such as N, O or F, the electron pair
shared between the two atoms lies far away from H atom. Thus the H atom becomes more
electropositive with respect to the other atom, and the electrostatic force of attraction between
polar molecules occurs. It is a weak force that forms a special type of dipole-dipole attraction,
but is generally stronger than ordinary dipole-dipole and dispersion forces, but weaker than true
covalent and ionic bonds.

Donors and Acceptors: In order to obtain a H bond there must be both a hydrogen donor and an
acceptor present. The donor is the atom to which the hydrogen atom participating is covalently
bonded, and is usually a strongly electronegative atom and the hydrogen acceptor is the
neighbouring electronegative ion or molecule, and must possess a lone electron pair in order to
form a hydrogen bond.

Since the hydrogen donor is strongly electronegative, it pulls the covalently bonded
electron pair closer to its nucleus, and away from the hydrogen atom. The hydrogen atom is then
left with a partial positive charge, creating a dipole-dipole attraction between the hydrogen atom
bonded to the donor, and the lone electron pair on the acceptor. This results in a hydrogen bond.
The hydrogen bond is often described as the attractive force that binds H atom with
electronegative atom of another molecule of the same substance. H bonds are always represented
by dotted line and the solid lines represent the original covalent bond. However, it also has some
features of covalent bonding like directional and strong, produces inter-atomic distances shorter
than the sum of the van der Waals radii, and usually involves a limited number of interaction
partners, which can be interpreted as a type of valence.

The origin of hydrogen bonding

The following molecules which have extra non-bonding electrons

Notice that in each of these above molecules:

 The hydrogen is attached directly to one of the most electronegative elements, causing
the hydrogen to acquire a significant amount of positive charge.
 Each of the elements to which the hydrogen is attached is not only significantly negative,
but also has at least one "active" lone pair.
 Lone pairs at the second level have the electrons contained in a relatively small volume of
space which therefore has a high density of negative charge. Lone pairs at higher levels are more
diffuse and not so attractive to positive things.

Consider cluster of water molecules coming close together. The positive (δ+) H is so
strongly attracted to the lone pair that it is almost as beginning to form a co-ordinate (dative
covalent) bond. It does not go that far, but the attraction is significantly stronger than an ordinary
dipole-dipole interaction. H bonds have about a tenth of the strength of an average covalent
bond, and are being constantly broken and reformed in liquid water.

Types of hydrogen bonding

Intermolecular hydrogen bond: Intermolecular hydrogen bond is formed between two different
molecules of the same or different substances. The following molecules forming inter molecular
H bonds: HF, alcohol (ethanol), water, NH 3, acid, between alcohol (ethanol) and water
molecules, between NH3 and H2O molecules.

Intramolecular hydrogen bond: Intramolecular hydrogen bond is formed between the H atom
and the highly electronegative atom present in the same molecule. This bond results in the
cyclization of the molecules and prevents their association. Intramolecular H bonds are present in
molecules such as o-nitrophenol, o-nitrobenzoic acid, and salicylaldehyde, ethylene glycol.
The extent of both intramolecular and intermolecular hydrogen bonding depends on temperature.
Consider a typical example o-nitrophenol has a lower melting and boiling point than P-
nitrophenol.

Difference between inter and intra molecular H bonds

The interactions between molecules are much stronger when there are inter molecular
hydrogen bonds (as in p-nitrophenol) because the bonds are formed between different molecules
and association takes place result in an increase in molecular weight and hence boiling point
increases. If intramolecular hydrogen bonds are present (as in the case of o-nitrophenol) the
interactions within individual molecules are greater and so there is less attraction between
molecules, no association takes place. This causes less stability thus volatile and lower melting
and boiling points. These two derivatives can easily separated by steam distillation.
Intermolecular H bonds take place only for a short time when two molecules are in each
other vicinity. Shortly after, the molecules separate and the interaction do not exist longer.
Intramolecular H bonds on the other hand are much stronger since the two atoms forming the
hydrogen bond remain in each other proximity due to structure of the molecule. In other words,
they exhibit strain.

Properties and effects of hydrogen bonds

Boiling Point: The boiling points of molecules, usually expect with larger molar masses to have
higher boiling points than molecules with smaller molar masses. This, without taking hydrogen
bonds into account, is due to greater dispersion forces. Larger molecules have more space for
electron distribution and thus more possibilities for an instantaneous dipole moment.
Boiling points of different compounds

Compound Molar mass Boiling Point

(g/mol) (K)
H2O 18.0 373.0
HF 20.0 292.5
NH3 17.0 239.8
H2S 34.0 121.9
HCl 36.4 187.9
PH3 34.0 185.2

H2O, HF, and NH3 each have higher boiling points than the same compound formed
between H and the next element moving down its respective group, indicating that the former
have greater intermolecular forces, and exhibit hydrogen bonding, whereas the others do not.
Furthermore, H2O has a smaller molar mass than HF but takes part in more hydrogen bonds per
molecule, so its boiling point is consequently higher.
Many elements form compounds with hydrogen. For example following the plot of the
boiling points of the compounds of the group four elements with hydrogen, the boiling points
increase as go down the group because the molecules are getting larger with more electrons, and
so van der Waals dispersion forces become greater.
 But the compounds of the elements in Groups 5, 6 and 7 with hydrogen, something odd
happen shown as following graph.
Although for the most part the trend is exactly the same as in group 4 (for same reasons),
the boiling point of the compound of hydrogen with the first element in each group is abnormally
high. In the cases of NH3, H2O and HF there must be some additional intermolecular forces of
attraction, requiring significantly more heat energy to break. These relatively powerful
intermolecular forces are described as hydrogen bonds.

On viscosity: The same effect that is seen on boiling point as a result of hydrogen bonding can
also be observed in the viscosity of certain substances have a higher viscosity than those that do
not. Substances which have the possibility for multiple hydrogen bonds exhibit even higher
viscosities. For e.g. glycol is more viscose than ethanol.

Electronegativity: Hydrogen bonding cannot occur without significant electronegativity

differences between hydrogen and the atom it is bonded to. Thus, molecules such as PH 3, which
do not takes part in hydrogen bonding. PH 3 exhibits a trigonal pyramidal molecular geometry
like that of ammmonia, but unlike NH 3 it cannot hydrogen bond. This is due to the similarity in
the electronegativities of phosphorous and hydrogen. Both atoms have an electronegativity of
2.1, and thus, no dipole moment occurs. This prevents the hydrogen bonding from acquiring the
partial positive charge needed to hydrogen bond with the lone electron pair in another molecule.

Atomic Size: The size of donors and acceptors can also affect the ability to hydrogen bond. This
can account for the relatively low ability of Cl to form hydrogen bonds. When the radii of two
atoms differ greatly or are large, their nuclei cannot achieve close proximity when they interact,
resulting in a weak interaction.
Unique properties of water: the density of solid state is greater than liquid state for most of the
substances but the density of ice is less than liquid water. In ice, the intermolecular H bond
between the water molecules is more extensive, and leads to tetrahedral orientation with respect
to another. Each O atom surrounded by four H atoms, two with covalent bond and other two with
H bond. The H bonds weaker therefore linger than covalent bond. This arrangement leads open
cage like structure with number of holes. These holes are formed because of H bonds holding the
water molecules in ice with definite angles. When ice melts, a large number of H bonds broken,
the molecule come closer results increase in density of liquid water (which is “V” shaped).
When liquid water is heated 0-4 oC, the H bonds broken and the molecules come closer,
so contraction takes place. However, there is some expansion of molecule also due to raise in
temperature in other liquids but contraction is dominant. Raise in temperature above 4 oC,
normal expansion takes place like other liquids.

Importance of H bonding: Without H bonds water will exist as a gas, like H 2S. H bonding also
exists in living organisms, animals and vegetables. It exists in various tissue, blood, skin, bone
etc. It plays important role in making wood fibres more rigid. The rigidity and tensile strength in
cotton, silk or synthetic fibres are due to H bonding. Most of the food material like
carbohydrates, sugar, honey, proteins consists of hydrogen bonds.

Intermolecular attraction or van der Waals Force

Intermolecular attraction force is attraction between one molecule and a neighbouring
molecule. The forces of attraction which hold an individual molecule together and this force are
electrostatic in nature. From solid to liquid and to gaseous state, the magnitude of this force is
decreasing. Apart from the existence of electrical repulsion between electron clouds, these may
arise from interactions between electron clouds that take place when they come close to each
other. This physical force of attraction is termed as van der Waals force.
In neutral polar molecules with permanent dipole, the van der Waal’s force is due to
electrical interaction between dipoles, but this force also exists in non-polar molecules like F 2, O2
and N2 and also inert gases like He, Ne, Ar etc. This attraction is evident from the condensation
of gases into liquid at low temperature and high pressure. This was not understood for several
years until 1930, "London forces" named after Fritz London, who first suggested how they
might arise.

London force: In a neutral molecule, the negative charged electron keep on oscillating with
respect to the positive nucleus and thus the positive charge may be concentrated in one region
and negative charge in another region of the same molecule. Thus a non-polar molecule may
become self polarised and may induce a dipole movement in a neighbouring molecule with
antiparallel orientation as follows:

An attraction between original and induced dipole due to electrostatic force is termed as London
force or dispersive forces.
Factors influencing Vander Waals force
 The number of electrons in a molecule: more the electrons, higher the force.
 The shape of the molecule: long thin molecules have higher forces
 The temperature: higher the temperature, lower the force.
Examples:
 The dipole-dipole attractions are fairly minor compared with dispersion forces, and their
effect of two molecules with the same number of electrons and the same size. For
example, the boiling points of ethane (CH 3CH3), and fluoromethane (CH3F), are as
follows:

Both molecules have identical numbers of electrons, and the sizes were similar. Hence the
dispersion forces in both molecules should be much the same. The higher boiling point of
fluoromethane is due to the large permanent dipole on the molecule because of the high
electronegativity of fluorine. However, even given the large permanent polarity of the molecule,
the boiling point has only been increased by some 10 °C.

The shapes of the molecules also matter. Long thin molecules can develop bigger temporary
dipoles due to electron movement than short fat ones containing the same numbers of electrons.
Long thin molecules can also lie closer together; these attractions are at their most effective if the
molecules are really close. For example, the hydrocarbon molecules butane and 2-methylpropane
both have a molecular formula C4H10, but the atoms are arranged differently. In butane the
carbon atoms are arranged in a single chain, but 2-methylpropane is a shorter chain with a
branch.

Trichloromethane (CHCl3), is a highly polar molecule because of the electronegativity of the

three chlorines. There will be quite strong dipole-dipole attractions between one molecule and its
neighbours. On the other hand, tetrachloro methane (CCl 4), is non-polar. The outside of the
molecule is uniformly - in all directions. CCl4 has to rely only on dispersion forces.
Why CCl4 does have more boiling point than CHCl3?
Ans. Because CCl4 is a bigger molecule with more electrons. The increase in the dispersion
forces more than compensates for the loss of dipole-dipole interactions.
The boiling points are: CHCl3- 61.2°C and CCl4- 76.8°C.

a) Explain how part of the attractions between HCl arise due to Van der Waals dipole-dipole
interactions but these are absent in chlorine gas. Instead, the attractions between chlorine
molecules consist entirely of van der Waals dispersion forces (London forces).
Ans. Cl2 is more electronegative than H and so the bond between the two is polar. The chlorine
end will be slightly negative, and the hydrogen end slightly positive. The molecules have
permanent dipoles. The positive end of one molecule will attract the negative end of another one
close to it. But chlorine-chlorine bond is non-polar obviously the atoms at either end have the
same electronegativity. The electrons moving around in the molecule will cause temporary
fluctuating dipoles. If one end of a chlorine molecule is temporarily positive, this will induce a
dipole in a nearby molecule, and these attract each other. As long as the molecules stay close
together, these fluctuating dipoles will stay synchronised with each other.

Explain the trend in boiling points of the halogens using intermolecular attraction force concept.
Ans: The boiling point of F2, Cl2, Br2, and I2 is 85, 238, 332, and 457(K) respectively. The
increasing boiling points as go down the group mean that the intermolecular attractions are
getting stronger. These attractions are Van der Waals dispersion forces, and depend on setting up
temporary fluctuating dipoles. The more number of electrons in a molecule, the bigger the
dipoles that can be formed and the stronger the attractions. As you go from fluorine to iodine,
there are more and more electrons and bigger molecules. The stronger the intermolecular
attractions, the greater the boiling point of a molecule.