ATOMIC STRUCTURE

AND CHEMICAL
BONDS

Atomic structure and Chemical bonds: -

Structure of an atom, electrons and
Quantum numbers, orbitals, shapes of
orbitals, s, p, d, and f subshells, K, L, M, N,
UNIT - 2
O, P, and Q shells. Illustration of Pauli`s
exclusion principle, Aufbau principle, and
Hund`s rule, electron configuration, octet
rule. Formation and properties of
noncovalent and covalent bonds,
hydrogen bonds, ionic bonds, van der
Waals interactions, London forces, dipole-
dipole interactions, electrostatic
interactions, and hydrophobic
interactions. Sigma, pi and co-ordinate
bonds, back bonding. Corresponding
energy associated, outline of theories of
bonding.
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 Atomic Structure and Chemical Bonds

UNIT - 2

Atomic Structure and Chemical Bonds:

ATOM:
Atoms are the smallest building blocks of matter/s. They are the
fundamental unit of all matter that is composed of three sub-atomic particles:
like, proton, neutron and electron.

The history of atomic structure and quantum mechanics goes back to the time
of Democritus, the man who first proposed that matter is composed of atoms.
The study of the structure of an atom gives great insight into the entire class of
chemical reactions, bonds, and their physical properties. The first scientific
theory of atomic structure was proposed by John Dalton in the 1800s. Advances
in atomic structure and quantum mechanics have led to the discovery of other
fundamental particles. The discovery of subatomic particles has been the basis
for many other discoveries and inventions.

ATOMIC STRUCTURE:
The atomic structure of an element refers to the nature of its nucleus and the
arrangement of electrons around it. Primarily, the atomic structure of matter
consists of protons, electrons, and neutrons.

The protons and neutrons form the nucleus of the atom, which is surrounded by
the electrons belonging to the atom. The atomic number of an element describes
the total number of protons in
its nucleus.

Neutral atoms have the same

number of protons and
electrons. However, atoms
can gain or lose electrons to
increase their stability, and
the resulting charged entity is
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called an ion.
 Atomic Structure and Chemical Bonds

The atoms of different elements have different atomic structures because they
contain different numbers of protons and electrons. This is the reason for the
unique properties of the different elements.

ATOMIC MODELS:
In the 18th and 19th centuries, many scientists attempted to explain the
structure of the atom using atomic models. Each of these models had its own
merits and drawbacks and was crucial to the development of the modern atomic
model. The most notable contributions in this field came from scientists such as
John Dalton, J.J. Thomson, Ernest Rutherford, and Niels Bohr.

DALTON’S ATOMIC POSTULATE (THEORY):

The English chemist John Dalton claimed that all matter is composed of atoms,
which are indivisible and indestructible. He also stated that all atoms of one
element are exactly the same, but atoms of different elements differ in size and
mass.
Chemical reactions, according to Dalton's atomic theory, involve
rearrangement of atoms to form products. According to Dalton's postulates, the
atomic structure consisted of atoms, the smallest particles responsible for
bringing about chemical reactions.

Below are the postulates of Dalton’s theory:

➢ All matter is composed of atoms. Atoms are indivisible.

➢ Certain elements have only one kind of atoms in them.
Each atom has its own constant mass, which varies from element to
element.
➢ Atoms will undergo rearrangement during a chemical reaction.
➢ Atoms can neither be created nor be destroyed, but they can be
transformed from one form to another.
➢ Dalton's atomic theory successfully explained the Laws of chemical
reactions, namely the law of conservation of mass, the law of constant
properties, the law of multiple proportions, and the law of reciprocal
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proportions.
 Atomic Structure and Chemical Bonds

DEMERITS OF DALTON’S ATOMIC THEORY:

➢ The theory was failed to explain the existence of isotopes.
➢ Nothing about the structure of the atom was adequately explained.
➢ Later, scientists discovered particles inside the atom, which proved that
atoms are divisible.

The discovery of the particles inside the atoms led to a better understanding of
the chemical species, these particles inside the atoms are called subatomic
particles. The discovery of the different subatomic particles is as follows:

THOMSON ATOMIC MODEL:

The English chemist Sir Joseph John Thomson presented his model for
describing atomic structure in the early 1900s.

He later received the Nobel Prize for the discovery of "electrons." His work was
based on an experiment called the cathode ray experiment. The operation of the
experiment is as follows:

CATHODE RAY EXPERIMENT

It consists of a glass tube that has two openings, one for the vacuum pump and
the other for the inlet through which a gas is pumped in. The function of the
vacuum pump is to maintain a "partial vacuum" inside the glass chamber. A high
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 Atomic Structure and Chemical Bonds

voltage power supply is connected across electrodes, i.e., cathode and Anode
is fitted inside the glass tube.

OBSERVATIONS:

➢ When a high voltage supply is turned on, rays leak from the cathode to the
anode. This was confirmed by the "fluorescent spots' on the ZnS screen
used. These rays were called "cathode rays."
➢ When an external electric field is applied, the cathode rays are deflected
toward the positive electrode, but in the absence of an electric field they
travel in a straight line.
➢ When rotor blades are placed in the path of the cathode rays, they appear
to rotate. This proves that the cathode rays consist of particles with a
certain mass, so they have some energy.

The direction of Cathode rays in the absence of an Electric Field

➢ From all this evidence, Thompson concluded that cathode rays consist of
negatively charged particles called "electrons."
➢ Applying an electric and magnetic field to the cathode rays (electrons),
Thomson found the charge to mass ratio (e/m) of the electrons. (e/m) for
electron: 17588 × 1011 e/bg.
➢ Using this ratio, the charge of Mullikin's electron was determined by the
oil drop experiment. (Charge of e- = 1.6 × 10-16 C and mass of e- = 9.1093
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× 10-31 kg).
 Atomic Structure and Chemical Bonds

CONCLUSIONS:
Based on the conclusions from his cathode ray experiment, Thomson described
the atomic structure as a positively charged sphere in which negatively charged
electrons were embedded.

This model is commonly referred to as the "plum pudding model" because it can
be visualized as a plum pudding shell, with the pudding describing the positively
charged atom and the plum pieces describing the electrons.

Thomson's atomic structure described the atoms as electrically neutral,

meaning that the positive and negative charges were of equal magnitude.

LIMITATIONS OF THOMSON'S ATOMIC

STRUCTURE:

Thomson's atomic model does not clearly explain the stability of an atom. Also,
further discoveries of other subatomic particles could not be fitted into his
atomic model.

RUTHERFORD ATOMIC THEORY:

Rutherford, a student of J. J. Thomson, modified the atomic structure with the

discovery of another subatomic particle, called "Nucleus". His atomic model
was based on the experiment of alpha ray scattering experiment.

ALPHA RAY SCATTERING EXPERIMENT:

CONSTRUCTION:

➢ A very thin gold foil of 1000 atoms thickness is taken.

➢ Alpha rays (doubly charged Helium He2+) were made to bombard the gold
foil.
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➢ A Zn S screen is placed behind the gold foil.

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 Atomic Structure and Chemical Bonds

OBSERVATION:

➢ Most of the beams simply passed through the gold foil and caused
scintillations (bright spots) on the ZnS screen.
➢ A few beams were reflected after hitting the gold foil.
➢ One out of 1000 beams were reflected at an angle of 180° (retraced path)
after hitting the gold foil (returned path).

CONCLUSIONS:

➢ Since most of the rays got through, Rutherford concluded that most of the
space inside the atom was empty.
➢ Only a few rays were reflected because their positive charge was repelled
by another positive charge inside the atom.
➢ 1/1000th of the rays were strongly deflected because of a very strong
positive charge in the center of the atom. He referred to this strong
positive charge as the "Nucleus."
➢ He said that most of the charge and mass of the atom resides in the
Nucleus

RUTHERFORD STRUCTURE ATOM:

Based on the above observations and conclusions, Rutherford proposed his

own atomic structure, which is as follows.

➢ The nucleus is located in the center of an atom, where most of the charge
and mass are concentrated.
➢ The atomic structure is spherical.
➢ Electrons revolves around the nucleus in a circular path, much like the
planets orbit around the sun.

LIMITATIONS OF RUTHERFORD ATOMIC MODEL:

➢ When the electrons have to revolve around the nucleus, they will spend
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energy, and that too against the strong force of attraction from the
 Atomic Structure and Chemical Bonds

nucleus, a lot of energy will be spent by the electrons and eventually they
will lose all their energy and fall into the nucleus, so the stability of the
atom cannot be explained.
➢ If the electrons are constantly orbiting the nucleus, we would expect to
see a continuous spectrum. But in reality, what we see is a line spectrum.

ATOMIC STRUCTURE – RUTHERFORD’S

MODEL, J.J THOMSON MODEL:

SUBATOMIC PARTICLES:

PROTONS

Protons are positively charged subatomic particles. The charge of a proton is 1e, which
is about 1.602 × 10-19.

The mass of a proton is about 1.672 × 10-24

Protons are over 1800 times heavier than electrons.

The total number of protons in the atoms of an element is always equal to the atomic
number of the element.

NEUTRONS

The mass of a neutron is almost the same as that of a proton, i.e., 1.674×10-24
Neutrons are electrically neutral particles and carry no charge.
The different isotopes of an element have the same number of protons, but differ
in the number of neutrons in their respective nuclei.

ELECTRONS

The charge of an electron is -1e, which is approximately -1.602 × 10-19

The mass of an electron is approximately 9.1 × 10-31. Because of the relatively

small mass of electrons, they are ignored when calculating the mass of an atom.
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 Atomic Structure and Chemical Bonds

ATOMIC STRUCTURE OF ISOTOPES

Nucleons are the constituents of the nucleus of an atom. A nucleon can be either
a proton or a neutron. Each element has a unique number of protons in it, which
is described by its unique atomic number. However, there can be several atomic
structures of an element that differ in the total number of nucleons.

These variants of elements with a different nucleon number (also known as the
mass number) are called isotopes of the element. Thus, the isotopes of an
element have the same number of protons but differ in the number of neutrons.

The atomic
structure of an
isotope is
described using
the chemical
symbol of the
element, the
atomic number of
the element, and the mass number of the isotope. For example, there are three
well known naturally occurring isotopes of hydrogen, namely protium,
deuterium and tritium. The atomic structures of these hydrogen isotopes are
illustrated below.

The isotopes of an element differ in their stability. The half-lives of the isotopes
are also different. However, they generally have similar chemical behaviour
because they have the same electronic structures.

ATOMIC STRUCTURE OF SOME ELEMENTS:

The atomic structure of an element can be simply represented by the total

number of protons, electrons, and neutrons present in it. The atomic structures
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of a few elements are shown below.

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 Atomic Structure and Chemical Bonds

HYDROGEN

The most abundant isotope of hydrogen on planet Earth is protium. The atomic
number and mass number of this isotope are 1 and 1, respectively.

Structure of the hydrogen atom: This implies that it contains one proton, one
electron and no neutrons (total number of neutrons = mass number - atomic
number)

CARBON

Carbon has two stable isotopes - 12C and 13C. Of these isotopes, 12C occurs in
a 98.9% abundance. It contains 6 protons, 6 electrons and 6 neutrons.

Structure of Carbon atom: The electrons are distributed on two shells and the
outermost shell (valence shell) has four electrons. The tetravalence of carbon
allows it to form a variety of chemical bonds with different elements.

OXYGEN

There are three stable isotopes of oxygen - 18O, 17O, and 16O. However,
oxygen-16 is the most abundant isotope.

Structure of the oxygen atom: Since the atomic number of this isotope is 8 and
the mass number is 16, it consists of 8 protons and 8 neutrons. 6 of the 8
electrons in an oxygen atom are in the valence shell.

BOHR’S ATOMIC THEORY

Neils Bohr put forth his model of the atom in the year 1915. This is the most
widely used atomic model to describe the atomic structure of an element, which
is based on Planck's theory.

POSTULATES:

The electrons inside atoms are in discrete orbits called "stationary orbits."
The energy levels of these shells can be represented by quantum numbers.
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 Atomic Structure and Chemical Bonds

Electrons can jump to higher levels by absorbing energy, and move to lower
energy levels by losing or emitting its energy.

As long as an electron remains in its own shell, there is no energy absorption or

release.

Electrons revolve around the nucleus only in these stationary orbits.

The energy of the stationary orbits is quantized.

LIMITATIONS OF BOHR’S ATOMIC THEORY:

Bohr's atomic structure works only for single-electron species such as H, He+,
Li2+, Be3+,..

Observing the emission spectrum of hydrogen with a more accurate

spectrometer, it was found that each line spectrum is a combination of several
smaller discrete lines. Both the Stark and Zeeman effects couldn't be explained
by Bohr's theory.

HEISENBERG’S UNCERTAINTY PRINCIPLE:

Heisenberg stated that no two conjugate physical quantities can be measured

simultaneously with 100% accuracy. There will always be some error or
uncertainty in the measurement.

DRAWBACK: Position and momentum are two such conjugate

quantities that were (theoretically) accurately measured by Bohr.

STARK EFFECT: The phenomenon of deflection of electrons in the

presence of an electric field.

ZEEMAN EFFECT: The phenomenon of deflection of electrons in

the presence of a magnetic field.

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 Atomic Structure and Chemical Bonds

DUAL NATURE OF MATTER

Electrons, which have been considered as particles, also have a wave nature,
as shown by the photoelectric effect. This was proved by Thomas Young with
the help of his double-slit experiment.

De-Broglie concluded that since nature is symmetrical, light or any other matter
wave should also be symmetrical.

QUANTUM NUMBERS

The set of numbers used to describe the position and energy of the electron in
an atom are called quantum numbers. There are four quantum numbers, namely
the principal quantum number, the azimuthal quantum number, the magnetic
quantum number and the spin quantum number.

PRINCIPAL QUANTUM NUMBER (n):

The principal quantum numbers are denoted by the symbol 'n'. They designate
the principal electron shell of the atom. Since the most probable distance
between the nucleus and the electrons is described by them, a larger value of
the principal quantum number implies a larger distance between the electron
and the nucleus (which, in turn, implies a larger atomic size).

The value of the principal quantum number can be any integer with a positive
value equal to or greater than one. The value n=1 denotes the innermost electron
shell of an atom, which corresponds to the lowest energy state (or ground state)
of an electron. Thus, it can be understood that the principal quantum number n
cannot have a negative value or be equal to zero, since it is not possible for an
atom to have a negative value or no value for a principal shell. When energy is
added to a particular electron (excited state), it can be observed that the
electron jumps from one principle shell to a higher shell, causing the value of n
to increase. Similarly, when electrons lose energy, they jump back to lower
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shells and the value of n also decreases. The increase in the value of n for an
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electron is called absorption and emphasizes the photons or energy being

 Atomic Structure and Chemical Bonds

absorbed by the electron. Similarly, the decrease in the value of n for an electron
is called emission, where the electrons radiate their energy.

AZIMUTHAL QUANTUM NUMBERS/ ORBITAL

ANGULAR MOMENTUM QUANTUM NUMBER (L):

➢ The azimuthal (or orbital angular momentum) quantum number describes

the shape of a particular orbital. It is denoted by the symbol 'l' and its value
is equal to the total number of angular nodes in the orbital.
➢ A value of the azimuthal quantum number can indicate either an s, p, d, or
f subshell, which differ in shape. This value depends on (and is bounded
by) the value of the principal quantum number, i.e., the value of the
azimuthal quantum number is between 0 and (n-1).
➢ For example, when n =3,
the azimuthal quantum
number can take the
following values: 0, 1, and
2. When l=0, the resulting
subshell is an 's' subshell.
Similarly, when l=1 and
l=2, the resulting
subshells are 'p' and 'd'
subshells, (respectively).
Thus, if n=3, the three
possible subshells are 3s,
3p, and 3d.
➢ In another example,
where the value of n is 5,
the possible values for l
are 0, 1, 2, 3, and 4. If l = 3,
then there are a total of
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three angular nodes in the

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atom.
 Atomic Structure and Chemical Bonds

The allowed subshells under various combinations of 'n' and 'l' are listed above.
It is clear that the orbital '2d' cannot exist, since the value of 'l' is always smaller
than that of 'n'.

MAGNETIC QUANTUM NUMBER (m): The total number of

orbitals in a subshell and the orientation of these orbitals are determined by the
magnetic quantum number. It is denoted by the symbol 'ml'. This number gives

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 Atomic Structure and Chemical Bonds

the projection of the angular momentum corresponding to the orbital along a

given axis.

The value of the magnetic quantum number depends on the value of the
azimuthal quantum number (or orbital angular momentum). For a given value of
l, the value of ml lies between the interval -l to +l. Therefore, it depends indirectly
on the value of n.

For example, if n = 4 and l = 3 in an atom, the possible values of the magnetic

quantum number are -3, -2, -1, 0, +1, +2, and +3.

Azimuthal Quantum Corresponding Number Possible Values of ml

Number Value of Orbitals (2l + 1)

0 (‘s’ subshell) 2*0 + 1 = 1 0

1 (‘p’ subshell) 2*1 + 1 = 3 -1, 0, and 1
2 (‘d’ subshell) 2*2 + 1 = 5 -2, -1, 0, 1, and 2
3 (‘f’ subshell) 2*3 + 1 = 7 -3, -2, -1, 0, 1, 2, and 3

The total number of orbitals in a given subshell is a function of the 'l' value of that
orbital. It is given by the formula (2l + 1). For example, the '3d' subshell (n=3, l=2)
contains 5 orbitals (2*2 + 1). Each orbital can accommodate 2 electrons.
Therefore, the 3d subshell can accommodate a total of 10 electrons.

ELECTRON SPIN QUANTUM NUMBER ( m S):

➢ The electron spin quantum number is independent of the values of n, l, and

ml. The value of this number gives information about the direction in which

the electron is spinning, and is denoted by the symbol mS.

➢ The possible values of the electron spin quantum number are +½ and -½.
The positive value of mS means that the electron has an upward spin, also

known as "spin up' and denoted by the symbol ↑. When mS has a negative
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 Atomic Structure and Chemical Bonds

value, the electron in question is said to have a downward spin, indicated

by the symbol ↓.
➢ The value of the electron spin quantum number determines whether the
atom in question has the ability to generate a magnetic field. The value of

mS can be generalized to ±½.

ATOMIC ORBITALS:
Atomic orbitals are mathematical functions that describe the wave nature of
electrons (or electron pairs) in an atom.

There are four different kinds of orbitals, denoted s, p, d and f each with a
different shape. Of the four, s and p orbitals are considered because these
orbitals are the most common in organic and biological chemistry. An s-orbital
is spherical with the nucleus at its centre, a p-orbitals is dumbbell-shaped and
four of the five d orbitals are cloverleaf shaped. The fifth d orbital is shaped like
an elongated dumbbell with a doughnut around its middle. The orbitals in an
atom are organized into different layers or electron shells.

According to the quantum atomic model, an atom can have many possible
numbers of orbitals. These orbitals can be categorized on the basis of their size,
shape or orientation. A smaller sized orbital means there is a greater chance of
getting an electron near the nucleus. The orbital wave function or ϕ is a
mathematical function used for representing the coordinates of an electron. The
square of the orbital wave function represents the probability of finding an
electron.

This wave function also helps us in drawing boundary surface diagrams.

Boundary surface diagrams of the constant probability density for different
orbitals help us understand the shape of orbitals.

The Shape of s Orbitals

• The boundary surface diagram for the s orbital looks like a sphere having
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the nucleus as its centre which in two dimensions can be seen as a circle.
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 Atomic Structure and Chemical Bonds

• Hence, we can say that s-orbitals

are spherically symmetric having
the probability of finding
the electron at a given distance
equal in all the directions.

• The size of the s orbital is also found

to increase with the increase in the
value of the principal quantum
number (n), thus, 4s > 3s> 2s > 1s.

The Shape of p Orbitals

• Each p orbital consists of two sections better known as lobes which lie on
either side of the plane passing through the nucleus.

• The three p orbitals differ in the way the lobes are oriented whereas they
are identical in terms of size, shape, and energy.

• As the lobes lie along one of the x, y or z-axis, these three orbitals are
given the designations 2px, 2py, and 2pz. Thus, we can say that there are
three p orbitals whose axes are mutually perpendicular.

• Similar to s orbitals the size, and energy of p orbitals increase with an

increase in the principal quantum number (4p > 3p > 2p).

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 Atomic Structure and Chemical Bonds

The Shape of d Orbitals

• The magnetic orbital quantum number for d orbitals is given as (-2,-1,0,

1,2). Hence, we can say that there are five d-orbitals.

• These orbitals are designated as dxy, dyz, dxz, dx2–y 2 and dz2.

• Out of these five d

orbitals, the shapes of
the first four d-orbitals
are similar to each
other, which is
different from the
dz2 orbital whereas the
energy of all five d
orbitals is the same.

The Shape of f Orbitals

• The shape of the f orbital is tetrahedral. Though the shape of the f orbital
is more
complex
than the
other
orbitals, the
rule of filling
the orbital
remains the
same as that
of p and the d
orbitals. The
alignment of
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the electrons
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is also found to be the same as that of the other two orbitals.

 Atomic Structure and Chemical Bonds

ELECTRON SHELL:
In chemistry and atomic physics, an electron shell may be thought of as
an orbit followed by electrons around an atom's nucleus. The closest shell to
the nucleus is called the "1 shell" (also called the "K shell"), followed by the "2
shell" (or "L
shell"), then the "3
shell" (or "M
shell"), and so on
farther and farther
from the nucleus.
The shells
correspond to
the principal
quantum
numbers (n = 1, 2, 3, 4 ...) or are labeled alphabetically with the letters used in X-
ray notation (K, L, M, ...). A useful guide when understanding electron shells in
atoms is to note that each row on the conventional periodic table of elements
represents an
electron shell.

Each shell can

contain only a fixed
number of
electrons: the first
shell can hold up to
two electrons, the
second shell can
hold up to eight (2 + 6)
electrons, the third shell can hold up to 18 (2 + 6 + 10) and so on. The general
formula is that the nth shell can in principle hold up to 2(n2) electrons. For an
explanation of why electrons exist in these shells, see electron configuration.
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Each shell consists of one or more subshells, and each subshell consists of one
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or more atomic orbitals.

 Atomic Structure and Chemical Bonds

RULES FOR FILLING THE ELECTRONS IN

VARIOUS ORBITALS:

The electrons must be occupied in the s, p, d, f according to the following rule.

1. Aufbau's principle: The Aufbau principle dictates the way in which the

electrons are filled in the atomic

orbitals of an atom in its ground state.

It states that the electrons are filled

into the atomic orbitals in the
ascending order of the energy level of
the orbitals. According to the Aufbau
principle, the available atomic
orbitals with the lowest energy levels
are filled before those with higher
energy levels.The word 'Aufbau' has
German roots and can be roughly
translated as 'to construct' or 'to build
up'. Below is a diagram illustrating the
order in which the atomic orbitals are
filled. Here 'n' refers to the principal
quantum number and 'l' is the azimuthal
quantum number.

The Aufbau Principle can be used to

understand the location of electrons in
an atom and their corresponding energy
levels. Carbon, for example, has 6
electrons and its electronic configuration
is 1s22s22p2.
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It is important to know that each orbital can hold a maximum of two electrons
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(according nto the orbitalto the Pauli exclusion principle). Also, the way the
 Atomic Structure and Chemical Bonds

electrons are filled is of a single subshell must follow Hund's rule, i.e., each
orbital in a given subshell must be individually filled with electrons before two
electrons pair in an orbital.

Main features of the Aufbau Principle

According to the Aufbau principle, electrons first occupy the orbitals whose
energy is lowest. This means that the electrons do not enter the orbitals with
higher energies until the orbitals with lower energies are fully occupied. The
order in which the energy of the orbitals increases can be determined using the
(n+l) rule, where the sum of the principal and azimuthal quanta numbers
determines the energy level of the orbital.

Lower (n+l) values correspond to lower orbital energies. If two orbitals share
equal (n+l) values, the orbital with the lower n value is said to have lower energy
associated with it. The order in which the orbitals are filled with electrons is: 1s,
2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, and so on.

Exceptions

The electron configuration of

chromium is [Ar]3d54s1 and not
[Ar]3d44s2 (as suggested by the
Aufbau principle). This
exception is attributed to
several factors such as the
increased stability provided by
half-filled subshells and the
relatively low energy gap
between the 3d and the 4s
subshells.

The energy gap between the

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different subshells is illustrated below.

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 Atomic Structure and Chemical Bonds

Half-filled subshells feature lower electron-electron repulsions in the orbitals,

thereby increasing the stability. Similarly, completely filled subshells also
increase the stability of the atom. Therefore, the electron configurations of some
atoms disobey the Aufbau principle (depending on the energy gap between the
orbitals). For example, copper is another exception to this principle with an
electronic configuration corresponding to [Ar]3d104s1. This can be explained by
the stability provided by a completely filled 3d subshell.

2. Pauli's exclusion principle:

Pauli’s Exclusion principle is one of the important principles along with Aufbau’s
Principle and Hund’s Rule in chemistry. Pauli’s Exclusion principle basically
helps us to understand the electron arrangements in atoms and molecules and
it also gives an explanation for the classification of elements in the periodic table

The Pauli exclusion principle states that in a single atom no two electrons will
have an identical set or the same quantum numbers (n, l, ml, and ms). To put it in
simple terms, every electron should have or be in its own unique state (singlet
state). There are two salient rules that the Pauli Exclusion Principle follows:

• Only two electrons can occupy the same orbital.

• The two electrons that are present in the same orbital must have opposite
spins or they should be antiparallel.

However, Pauli’s Exclusion Principle does not only apply to electrons. It applies
to other particles of half-integer spin such as fermions. It is not relevant for
particles with an integer spin such as bosons which have symmetric wave
functions. Moreover, bosons can share or have the same quantum states, unlike
fermions. As far as the nomenclature goes, fermions are named after the Fermi–
Dirac statistical distribution that they follow. Bosons, on the other hand, get their
name from the Bose-Einstein distribution function.

Example:
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 Atomic Structure and Chemical Bonds

We can take a neutral helium atom as a common Pauli Exclusion Principle example. The
atom has 2 bound electrons and they occupy the outermost shell with opposite spins. Here,
we will find that the two electrons are in the 1s subshell where n = 1, l = 0, and ml = 0.

Their spin moments will also be different. One will be ms = -1/2 and the other will be +1/2. If
we draw a diagram then the subshell of the helium atom will be represented with 1 “up”
electron and 1 “down” electron. In essence, 1s subshell will consist of two electrons, which
have opposite spins.

Similarly, if we take Hydrogen, it will have 1s subshell with 1 “up” electron (1s1). Lithium will
have the helium core (1s2) and then
one more “up” electron (2s1). What
we are trying to depict here is that
the electron configuration of the
orbitals is written in this manner.No
two electrons can have all the
four quantum numbers to be
the same, or if two electrons
have to be placed in one energy
state, they should be placed
with opposite spins.

From this example, we can

further deduce that successive
larger elements will have shells of successively higher energy. The number
of electrons in the outermost shell is also directly related to the different
chemical properties that elements possess. Elements with the same number of
electrons in the outermost shell will have similar properties.

Nuclear stability and Pauli’s exclusion principle

The nuclei in an atom consist of neutrons and protons which are held together
by the nuclear force. However, protons tend to repel each other via
electromagnetic force as a result of their positive charge. Basically, these two
forces are working against (competing) each other thereby leading to the
22

stability of nuclei. Meanwhile, you will find only certain sets or combinations of
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protons and neutrons that form stable nuclei. The nucleus is mostly stabilized
 Atomic Structure and Chemical Bonds

by the neutrons as attract each other and protons. This further helps
counterbalance the electrical repulsion between protons. When this happens,
the number of protons goes up. In essence, an increasing ratio of neutrons to
protons is needed to form a stable nucleus.

In case if there are a larger number of (neutrons also obey the Pauli exclusion
principle) or too few neutrons for a given number of protons, the nucleus of the
atom is not stable. This will lead to radioactive decay. Meanwhile, Pauli’s
exclusion principle also has an effect on the critical energy of fissile and
fissionable nuclei. For example, if we look at actinides that have an odd neutron
number, they are usually fissile or in other words fissionable with slow neutrons.
On the other hand, actinides that have even neutron number they are usually not
fissile or we can say that are fissionable with fast neutrons. Similarly, due to the
Pauli exclusion principle, heavy nuclei with an even number of protons and
neutrons are very stable due to the presence of ‘paired spin’. Alternatively,
nuclei with an odd number are unstable.

Importance and applications of Pauli’s exclusion principle

• The Pauli exclusion principle helps to explain a wide variety of physical

phenomena such as the electron shell structure of atoms and the way
atoms share electrons.

• It helps in describing the various chemical elements and how they

participate in forming chemical bonds.

• The periodic table can also be defined with the help of this principle.

• Solid-state Properties: Many electrical, optical, magnetic, mechanical

and chemical properties of solids are the direct consequence of Pauli
exclusion.

• The principle helps in describing the stability of large systems with many
electrons and many nucleons.

• Apart from chemistry, the principle is a fundamental principle in quantum

23

mechanics which is mainly studied in physics.

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• It is also used in astrophysics.

 Atomic Structure and Chemical Bonds

3. Hund's rule:

Aufbau principle tells us that the lowest energy orbitals get filled by electrons
first. After the lower energy orbitals are filled, the electrons move on to higher
energy orbitals. The problem with this rule is that it does not tell about the three
2p orbitals and the order that they will be filled in.

According to Hund’s rule: Before the

double occupation of any orbital, every
orbital in the sub level is singly occupied.

• For the maximization of total spin,

all electrons in a single occupancy
orbital have the same spin.

An electron will not pair with another

electron in a half-filled orbital as it has the
ability to fill all its orbitals with similar
energy. Many unpaired electrons are
present in atoms which are at the ground
state. If two electrons come in contact,
they would show the same behaviour as two magnets do. The electrons first try
to get as far away from each other as possible before they have to pair up.

Hund's rule of maximum multiplicity:

Hunds Rule of Maximum Multiplicity rule states that for a given electron
configuration, the term with maximum multiplicity falls lowest in energy.
According to this rule electron pairing in p, d and f orbitals cannot occur until
each orbital of a given subshell contains one electron each or is singly occupied.
It is a rule which depends on the observation of atomic spectra, which is helpful
in predicting the ground state of a molecule or an atom with one or more than
one open electronic shells. This rule was discovered in the year 1925
24

by Friedrich Hund.
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 Atomic Structure and Chemical Bonds

Explanation of Hund’s rule:

The electrons enter an empty orbital before pairing up. The electrons repel each
other as they are negatively charged. The electrons do not share orbitals to
reduce repulsion.

When we consider the second rule,

the spins of unpaired electrons in
singly occupied orbitals are the
same. The initial electrons spin in the
sub-level decides what the spin of
the other electrons would be. For
instance, a carbon atom’s electron
configuration would be 1s22s22p2.
The same orbital will be occupied by
the two 2s electrons although different orbitals will be occupied by the two 2p
electrons in reference to Hund’s rule.

This image helps in understanding the electronic configuration and its

purpose. The valence shells of two atoms that come in contact with each other
will interact first. When valence shells are not full then the atom is the least
stable. The chemical characteristics of an element are largely dependent on the
valence electrons. Similar chemical characteristics can be seen in elements
that have similar valence numbers.

The stability can also be predicted by the electron configuration. When all the
orbitals of an atom are full it is most stable. The orbitals that have full energy
level are the most stable, for example, noble gases. These types of elements do
not react with other elements.

Use of Hund’s rule:

It has wide applications in the following –

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It is majorly used in atomic chemistry, quantum chemistry, and spectroscopy,

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etc
 Atomic Structure and Chemical Bonds

ELECTRONIC CONFIGURATION:

Definition: The systematic

distribution of electrons in the
various atomic orbitals is called its
electronic configuration. In the
electronic configuration, electrons
are distributed in various energy
levels (various shells) of an atom,
such as K shell, L shell, M shell, N
shell, etc.

Example:

HOW TO WRITE
ELECTRONIC CONFIGURATION TO
DIFFERENT ATOMS

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 Atomic Structure and Chemical Bonds

OCTET RULE:

The octet rule dictates that atoms are most stable when their valence shells are
filled with eight electrons. It is based on the observation that the atoms of the
main group elements have a tendency to participate in chemical bonding in such
a way that each atom of the resulting molecule has eight electrons in the valence
shell. The octet rule is only applicable to the main group elements.

The molecules of the halogens, oxygen, nitrogen, and carbon are known to obey
the octet rule. In general, the elements that obey this rule include the s-block
elements and the p-block elements (except hydrogen, helium, and lithium).

The octet rule can be observed in the

bonding between the carbon and
oxygen atoms in a carbon dioxide
molecule, as illustrated via a Lewis dot
structure here.

The shared electrons fulfil the valency requirements of both the bonded atoms.
Thus, it can be noted that both the oxygen atoms and the carbon atom have an
octet configuration in the CO2 molecule.

Upon observing that the noble gases were chemically inert, the electronic
theory of valency was proposed by the German physicist Walther Kossel and

the American chemist Gilbert Lewis. It was based on the tendency of atoms
to assume the most stable state possible.

Examples:

NaCl (Sodium Chloride)

• This compound features an ionic bond between the sodium ion (Na +) and
27

the electronegative chloride ion (Cl–).

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 Atomic Structure and Chemical Bonds

• The chlorine atom holds 7 electrons in its valence shell and can attain an
octet configuration by gaining an electron.

• The outermost shell of sodium has one electron. If it loses this electron,
the second shell would become the valence shell (which is already filled
with 8 electrons). Thus, the Na+ ion is more stable than metallic sodium.

• The sodium cation and the chloride anion now form an ionic bond, and the
resulting molecule features octet configurations for both the participating
atoms.

MgO (Magnesium Oxide)

• The bond between magnesium and oxygen in magnesium oxide is ionic in

nature.

• The magnesium atom readily loses two electrons to obtain the stable
electronic configuration of neon. This leads to the formation of the Mg 2+

• Similarly, oxygen gains two electrons to form the O2-

• The electrostatic attraction that arises between these two ions leads to
the formation of an ionic bond between them.

• Both the atoms in a molecule of MgO have stable octet configurations.

Exceptions to the Octet Rule

Not all elements and compounds follow the octet rule. Some of the exceptions to
this rule are listed below.

• An ion, atom, or a molecule containing an unpaired valence electron is

called a free radical. These species disobey the octet rule. However, they
are very unstable and tend to spontaneously dimerize.

• Since the first shell can only accommodate two electrons, elements such
as lithium, helium, and hydrogen obey the duet rule instead of the octet
rule. For example, lithium can lose an electron to have a stable
28

configuration in which the valence shell holds two electrons.

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 Atomic Structure and Chemical Bonds

• Due to the presence of a d-orbital, the transition elements do not obey the
octet rule. The valence shells of these atoms can hold 18 electrons.

• Aromatic compounds involve a delocalization of pi electrons. These

electrons obey Huckel’s rule

It can be noted that some electron deficient molecules such as boranes and
carboranes follow Wade’s rules in order to obtain stability. These molecules
feature 3c-2e bonds (three centred bonds) in which two electrons are shared by
three atoms.

The Expanded Octet Rule - Hypervalency

Some main group elements have the ability to form hypervalent compounds.
Examples include sulfur hexafluoride (SF6) and phosphorus pentachloride
(PCl5). If all the phosphorus-chlorine bonds in a PCl5 molecule are covalent, it
would imply that the phosphorus molecule is violating the octet rule by holding
a total of 10 valence electrons.

The formation of five bonds by the phosphorus molecules can be explained by

the sp3d hybridization in PCl5. Here, one ‘s’ orbital, three ‘p’ orbitals, and one ‘d’
orbital undergo hybridization to form a sp3d hybrid. This hybrid orbital forms five
covalent bonds with the five chlorine atoms.

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 Atomic Structure and Chemical Bonds

The structure of the hypervalent PCl5 molecule is trigonal bipyramidal, as

illustrated above.

CHEMICAL BONDING:

Chemical Bonding refers to the formation of a chemical bond between two or

more atoms, molecules, or ions to give rise to a chemical compound. These
chemical bonds are what keep the atoms together in the resulting compound. In
other words, the attractive force which holds various constituents (atom, ions,
etc.) together and stabilizes them by the overall loss of energy is known as
chemical bonding. Therefore, it can be understood that chemical
compounds are reliant on the strength of the chemical bonds between its
constituents; The stronger the bonding between the constituents, the more
stable the resulting compound would be.

The opposite also holds true; if the chemical bonding between the constituents
is weak, the resulting compound would lack stability and would easily undergo
another reaction to give a more stable chemical compound (containing stronger
bonds). To find stability, the atoms try to lose their energy.

Whenever matter interacts with another form of matter, a force is exerted on one
by the other. When the forces are attractive in nature, the energy decreases.
When the forces are repulsive in nature, the energy increases. The attractive
force that binds two atoms together is known as the chemical bond.

SOME IMPORTANT CHEMICAL BOND THEORIES:

LEWISE THEORY OF CHEMICAL BONDING:

• An atom can be viewed as a positively charged ‘Kernel’ (the nucleus plus

the inner electrons) and the outer shell.

• The outer shell can accommodate a maximum of eight electrons only.

• The eight electrons present in the outer shell occupy the corners of a cube
30

which surround the ‘Kernel’.

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 Atomic Structure and Chemical Bonds

• The atoms having octet configuration, i.e., 8 electrons in the outermost

shell, thus symbolize a stable configuration.

• Atoms can achieve this stable configuration by forming chemical bonds

with other atoms. This chemical bond can be formed either by gaining or
losing an electron(s) (NaCl, MgCl2) or in some cases due to the sharing of
an electron (F2).

• Only the electrons present in the outer shell, also known as the valence
electrons take part in the formation of chemical bonds. Gilbert Lewis used
specific notations better known as Lewis symbols to represent these
valence electrons.

• Generally, the valency of an element is either equal to the number of dots

in the corresponding Lewis symbol or 8
minus the number of dots (or valence
electrons).

Lewis symbols for lithium (1 electron), oxygen (6

electrons), neon (8 electrons) are given below:

Here, the number of dots that surround the

respective symbol represents the number of valence electrons in that atom.

Kossel’s theory of Chemical Bonding

• Noble gases separate the highly electronegative halogens and the highly
electropositive alkali metals.

• Halogens can form negatively charged ions by gaining an electron.

Whereas alkali metals can form positively charged ions by losing an
electron.

• These negatively charged ions and positively charged ions have a noble
gas configuration that is 8 electrons in the outermost shell. The general
electronic configuration of noble gases (except helium) is given by ns2np6.

• As unlike charges attract each other these unlike charged particles are
31

held together by a strong force of electrostatic attraction existing

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between them. For example, MgCl2, the magnesium ion, and chlorine ions
 Atomic Structure and Chemical Bonds

are held together by force of electrostatic attraction. This kind of

chemical bonding existing between two unlike charged particles is known
as an electrovalent bond.

Explanation of Kossel Lewis Approach

In 1916 Kossel and Lewis succeeded in giving a successful explanation based
upon the concept of an electronic configuration of noble gases about why atoms
combine to form molecules. Atoms of noble gases have little or no tendency to
combine with each other or with atoms of other elements. This means that these
atoms must be having stable electronic configurations.

Due to the stable configuration, the noble gas atoms neither have any tendency
to gain or lose electrons and, therefore, their combining capacity or valency is
zero. They are so inert that they even do not form diatomic molecules and exist
as monoatomic gaseous atoms.

Types of Chemical Bonds

When substances participate in chemical bonding and yield compounds, the
stability of the resulting compound can be gauged by the type of chemical bonds
it contains.

The type of chemical bonds formed vary in strength and properties. There are 4
primary types of chemical bonds which are formed by atoms or molecules to
yield compounds. These types of chemical bonds include:

• Ionic Bonds

• Covalent Bonds

• Hydrogen Bonds

• Polar Bonds

These types of bonds in chemical bonding are formed from the loss, gain, or
sharing of electrons between two atoms/molecules.
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 Atomic Structure and Chemical Bonds

IONIC BOND

Ionic bonding is a type of chemical bonding which involves a transfer of

electrons from one atom or molecule to another. Here, an atom loses an electron
which is in turn gained by another atom. When such an electron transfer takes
place, one of the atoms develops a negative charge and is now called the anion.

The other atom develops a positive charge and is called the cation. The ionic
bond gains strength from the difference in charge between the two atoms, i.e.,
the greater the charge disparity between the cation and the anion, the stronger
the ionic bond.

In other words, these bonds are also called as electrovalent Bonds, these are
produced when electrons are transferred from atoms of one element to atoms
of another element, producing positive and negative ions. The bond which is
formed by the transfer of electrons between the atoms is called electrovalent
bond or ionic bond. Electrovalent bonds are only formed between metals and
non-metals. Electrovalent bonds are
not formed between two non-metals.

In simple words electrovalent bond

involves the transference of a
certain number of electrons to
another dissimilar atom which has a
tendency to gain electrons so that
both acquire stable inert gas configurations. The electrostatic attraction always
tends to decrease the potential energy. Hence, the potential energy of the
system is much less than it was before the formation of an ionic bond.

Electronegativity and Ionic Bonding

• An Ionic bond is the bond formed by the complete transfer of valence

electron to attain stability.
33

• This type of bonding leads to the formation of two oppositely charged ions
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– positive ions known as cations and negative ions known as anions.

 Atomic Structure and Chemical Bonds

• The presence of two oppositely charged ions results in a strong attractive

force between them. This force is an ionic or electrovalent bond.

• Ionic bonds form between atoms with large differences

in electronegativity, whereas covalent bonds formed between atoms with
smaller differences in electronegativity.

• The compound formed by the electrostatic attraction of positive and

negative ions is called an ionic compound.

Ionic Bond Properties

Due to the presence of a strong force of attraction between cations and anions
in ionic bonded molecules, the following properties are observed:

1. The ionic bond has charge separation, and so they are the most reactive
of all the bonds in the proper medium.
2. The ionic bonded molecules have high melting and boiling point.
3. The ionic bonded molecules in their aqueous solutions or in the molten
state are good conductors of electricity. This is due to the presence of
ions which acts as charge carriers.

Examples of Ionic Bonds

Element Electronic config. Reaction Formed ion

Na (11) 2,8,1 Na → Na+ + e– Na+

Ca (20) 2,8,8,2 Ca → Ca2+ + 2e– Ca2+

Cl (17) 2,8,7 Cl + e–→ Cl– Cl–

O (8) 2,6 O + 2e–→ O2- O2-

COVALENT BOND
A covalent bond indicates the sharing of electrons between atoms. Compounds
34

that contain carbon (also called organic compounds) commonly exhibit this type
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 Atomic Structure and Chemical Bonds

of chemical bonding. The pair of electrons which are shared by the two atoms
now extend around the nuclei of atoms, leading to the creation of a molecule.

The covalent bonds are also termed as molecular bonds. Sharing of bonding
pairs will ensure that the atoms achieve stability in their outer shell which is
similar to the atoms of noble gases.

Covalent Bonding can be Achieved in two Ways:

• Sharing of electrons between atoms of the same kind E.g. Formation of

H2, Cl2, O2, etc.

• Sharing of electrons between atoms of different kind E.g. Formation of

CH4, H2O, NH3, etc.

COVALENT BONDING between different kids of atoms

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COVALENT BONDING between same atoms

 Atomic Structure and Chemical Bonds

Properties of Covalent Bond

If the normal valence of an atom is not satisfied by sharing a single electron pair
between atoms, the atoms may share more than one electron pair between
them. Some of the properties of covalent bonds are:

• Covalent bonding does not result in the formation of new electrons. The
bond only pairs them.

• They are very powerful chemical bonds that exist between atoms.

• A covalent bond normally contains the energy of about ~80 kilocalories

per mole (kcal/mol).

• Covalent bonds rarely break spontaneously after it is formed.

• Covalent bonds are directional where the atoms that are bonded
showcase specific orientations relative to one another.

• Most compounds having covalent bonds exhibit relatively low melting

points and boiling points.

• Compounds with covalent bonds usually have lower enthalpies of

vaporization and fusion.

• Compounds formed by covalent bonding don’t conduct electricity due to

the lack of free electrons.

• Covalent compounds are not soluble in water.

SIGMA BONDS
Sigma and pi bonds are types of
covalent bonds that differ in the
overlapping of atomic orbitals.
Covalent bonds are formed by
the overlapping of atomic
orbitals.

“Sigma bonds are a result of the

36

head-to-head overlapping of
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 Atomic Structure and Chemical Bonds

atomic orbitals whereas pi bonds are formed by the lateral overlap of two atomic
orbitals.”

The Sigma (σ) Bond

This type of covalent bond is formed by head-on positive (same phase) overlap
of atomic orbitals along the internuclear axis. Sigma bonds are the strongest
covalent bonds, owing to the direct overlapping of the participating orbitals.
The electrons participating in a σ bond are commonly referred to as σ electrons.

Generally, all single bonds are sigma bonds. They can be formed via the
following combinations of atomic orbitals.

s-s Overlapping

In this kind of overlapping, one ‘s’ orbital from each participating atom
undergoes head-on overlapping along the internuclear axis. An s orbital must be
half-filled before it overlaps with another.

THE Pi BONDS:

Pi bonds are chemical bonds that are covalent in nature and involve the lateral
overlapping of two lobes of an atomic orbital with two lobes of another atomic
orbital that belongs to a different atom. Pi bonds are often written as ‘𝛑 bonds’,
37

where the Greek letter ‘𝛑’ refers to the similar symmetry of the pi bond and the
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p orbital.
 Atomic Structure and Chemical Bonds

The two orbitals which are bonded share the same nodal plane at which the
electron density is zero. Commonly, pi bonding involves p orbitals. However, d
orbitals also have the ability to participate in 𝛑 bonding and these types of bonds
involving d orbitals can be found in the multiple bonds formed between two
metals.

Examples:

Ethene (C2H2) is often considered the

simplest alkene since it contains only 2
carbon atoms (that are doubly bonded
to each other) and four hydrogen atoms.
The electronic configuration of carbon
is 1s22s22p2. However, in its excited
state, an electron is promoted from the
2s orbital to the 2p orbital.

Now, the 2s orbital and one 2p

orbital undergo hybridization to
form a sp hybridized orbital. This
orbital contains the 2s electron and
the 2px electron. The 2py and
2pz electrons of the carbon atoms
now form pi bonds with each other.

Strength of Pi Bonds

The pi bonds are almost always weaker than sigma bonds. For example, two
times the bond energy of a carbon-carbon single bond (sigma bond) is greater
than a carbon-carbon double bond containing one sigma and one pi bond. This
observation on the bond strength of 𝛑 bonds suggests that they do not add as
much stability as sigma bonds do.

The relative weakness of these bonds, when compared to sigma bonds, can be
38

explained with the help of the quantum mechanical perspective that there is a
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significantly lower degree of overlapping of p orbitals in pi bonds due to the fact

 Atomic Structure and Chemical Bonds

that they are oriented parallel to each other. Sigma bonds, however, have a far
greater degree of overlapping and hence tend to be stronger than the
corresponding 𝛑 bonds.

Pi Bonding in Multiple Bonds

The following multiple bonds can be broken down into sigma, pi, and delta
bonds:

➢ Generally, double bonds consist of a single sigma bond and a single pi

bond. An example of such a bond can be seen in ethylene (or ethene).
➢ Typically, triple bonds consist of a single sigma bond and two 𝛑 bonds
which are placed in planes that are perpendicular to each other and
contain the bond axis.
➢ Quadruple bonds are very rare bonds which can only be found in the
bonds between two transition metal atoms. It can be broken down into one
sigma, two pi, and one delta bond.
➢ The combination of pi and sigma bonds in multiple bonds are always
stronger than a single sigma bond. The reduction in bond lengths in
multiple bonds points towards this statement. This contraction in the bond
length can be observed in the length of the carbon-carbon bond in ethane,
ethylene, and acetylene, which are equal to 153.51 pm, 133.9 pm, and
120.3 pm respectively.
➢ Therefore, it can be understood that multiple bonds shorten the total bond
length and strengthen the overall bond between the two atoms. To learn
more about sigma and pi bonds, register with BYJU’S and download the
mobile application on your smartphone

CO-ORDINATE BONDS:

Co-ordinate bond is a type of alternate covalent bond that is formed by sharing of electron
pair from a single atom. Both shared electrons are donated by the same atom. It is also
39

called dative bond or dipolar bond.

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 Atomic Structure and Chemical Bonds

Co-ordinate covalent bonds are usually formed in reactions that involve two non-metals
such as a hydrogen atom or during bond formation between metals ions and ligands.

Characteristics Of Coordinate Covalent Bond

➢ In this type of bonding, the atom that shares an electron pair from itself is
termed as the donor.
➢ The other atom which accepts these shared pair of electrons is known as
a receptor or acceptor.
➢ The bond is represented with an arrow →, pointing towards acceptor from
the donor atom.
➢ After sharing of electron pain each atom gets stability.
➢ This type of bonding is central to the Lewis theory.
➢ Getting a good understanding of co-ordinate covalent bonds can help in
properly designing complex organic molecules.

Example:

AMMONIUM ION:

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 Atomic Structure and Chemical Bonds

HYDRONIUM ION:

Properties Of Coordinate Compounds

➢ These have lower melting and boiling points than ionic compounds.
➢ Some of these compounds exhibit isomerism.
➢ Sharing of electrons takes place in a definite direction, hence, it is a
directional bond.
➢ It is weaker than Ionic bonding.

VALENCE BOND THEORY

Valence bond theory is a fundamental concept in chemistry that provides an

explanation for the formation of chemical bonds between atoms. It was first
proposed by Linus Pauling in the 1930s and has since become an essential part
of understanding the nature of chemical bonding. The theory is based on the
idea that covalent bonds are formed when atomic orbitals overlap, leading to
the sharing of electrons between atoms. In valence bond theory, a covalent
bond is formed when two atomic orbitals, each containing a single electron,
overlap and the electrons have opposite spins. This results in the formation of a
new molecular orbital that is localized between the two atoms. The strength of
41

the bond is determined by the extent of overlap between the atomic orbitals, with
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 Atomic Structure and Chemical Bonds

greater overlap leading to a stronger bond. One of the key strengths of valence
bond theory is its ability to explain the directional nature of covalent bonds. By
considering the spatial orientation of atomic orbitals and their overlap, the
theory can account for the observed geometry of molecules. Additionally,
valence bond theory can provide insights into the concept of resonance, where
multiple Lewis structures can be used to represent a molecule. Furthermore,
valence bond theory has been instrumental in understanding the concept of
hybridization, where atomic orbitals mix to form new hybrid orbitals that are
better suited for bonding. This has been particularly useful in explaining the
shapes and bonding in molecules with central atoms surrounded by multiple
groups.

MOLECULAR ORBITAL THEORY

Molecular orbital theory is a fundamental concept in chemistry that describes

the behavior of electrons in molecules. It is based on the idea that atomic
orbitals combine to form molecular orbitals, which are the regions of space
where electrons are most likely to be found in a molecule. This theory provides
a powerful framework for understanding and predicting the properties of
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molecules, including their stability, reactivity, and spectroscopic behavior. In

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 Atomic Structure and Chemical Bonds

molecular orbital theory, the combination of atomic orbitals leads to the

formation of bonding and antibonding molecular orbitals. When atomic orbitals
combine in-phase, they form bonding molecular orbitals, which are lower in
energy than the original atomic orbitals. Conversely, when atomic orbitals
combine out-of-phase, they form antibonding molecular orbitals, which are
higher in energy than the original atomic orbitals. The distribution of electrons
into these molecular orbitals determines the stability and properties of the
molecule. One of the key principles of molecular orbital theory is the filling of
molecular orbitals according to the aufbau principle, similar to the filling of
atomic orbitals.
The Pauli
exclusion
principle and
Hund’s rule also
apply to
molecular
orbitals,
governing the
distribution of
electrons within
them. Molecular
orbital theory has
been instrumental
in explaining various phenomena in chemistry, such as bond order, bond length,
and magnetic properties of molecules. It has also provided insights into
chemical reactions and the behavior of complex organic molecules.
Additionally, it has been widely used in computational chemistry to predict and
understand the behavior of molecules.
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