Atomic Structure

Atom

The smallest particle of an element which possesses the

properties of that element and take part in chemical
reaction is an atom.

The word atom is derived from the Greek language (a=

absence, tomos= cut) which mean indivisible or uncuttable.
 Historical background

The history of the atom begins around 450 B.C. with a

Greek philosopher named Democritus
He thought that a point would be reached where
matter could not be cut into still smaller pieces. He
called these "uncuttable" pieces atomos. This is
where the modern term atom comes from.

Around 1800, a British chemist named John Dalton

revived Democritus’s early ideas about the atom.
Dalton did many experiments that provided
evidence for atoms. He developed Dalton’s atomic
theory.
Structure of the atom
 Atomic Models

After the discovery of different subatomic particles, the

designation of these subatomic particles in atom became the part
of query. Different types of atomic models were proposed . Some
important models of atoms are.

Thomson’s atomic model

Rutherford atomic model

Bohr’s atomic model

Wave mechanical model

 Thomson’s atomic model (plum
pudding model or watermelon model
of atom)
Proposed by J.J. Thomson in 1898.
This model explained the inner structure of the atom theoretically.
Postulates:
An atom consists of a positively charged sphere with electrons
embedded in it just like plum in the pudding.
An atom as a whole is electrically neutral
Thomson atomic model is compared to watermelon where
Watermelon seeds as negatively charged particles and the
red part of the watermelon as positively charged.
 Limitations of Thomson’s atomic model

• It failed to explain the stability of an atom because his model

of atom failed to explain how a positive charge holds the
negatively charged electrons in an atom. Therefore, This
theory also failed to account for the position of the nucleus in
an atom

• No experimental evidence in its support

 Rutherford’s atomic model
(alpha ray scattering experiment
/ gold foil experiment)

This model was put forward by Ernest

Rutherford in 1911 A.D. He was New
Zealand born British physicist known
as father of nuclear physics .
In 1908, Ernest Rutherford was
awarded the Nobel Prize for Chemistry
for his “investigations into the
disintegration of the elements” or, put
more simply, for helping establish the
principles of radioactivity.
 Rutherford’s atomic model
(Nuclear model )

This model was put forward by Ernest Rutherford in 1911 with

help of α- ray scattering experiment. In this experiment, he
bombarded a thin sheet of pure gold foil (0.00004cm thickness)
with beam of α- particles/rays (Alpha particles are helium nuclei
i.e.2+He4). The α-particles were obtained from radium (radioactive
substance) kept inside a lead box with a small pinhole in it. The
gold foil was surrounded by movable zinc sulphide screen to detect
the scattered α- particles from gold foil. When α- particles struck
zinc sulphide screen they produced tiny flashes or scintillation
which could be observed by movable microscope.
The experimental setup used in the experiment is shown
in figure below

Figure: Rutherford’s α- particles scattering Experiment

The following observations were made from the scattering
experiment.
1. Most of the α- particles (about 99%) passed through the
foil without any deflection.
2. Some or few α- particles (about 1%) were deflected
through small angle i.e. less than 90°.
3. Very few α- particles (about 1 in 100,000) were deflected
back through angle more than 90˚ or even returned back
suffering a deflection of 180°.
He made following conclusion from above mentioned
observations.

1. Most of the α- particles passed through the foil with out any
deflection. This shows that most of the space inside the atom
is empty or hollow.

2. Few α- particles were deflected through small angle. Since α-

particles consist of positive charge they could be deflected
only by some dense positively charged body present within
the atom. The alpha particle deflected were those which
passed very close to this positive body.
3. Very few α- particles were deflected back. Since α- particles
have an appreciable mass they could be deflected back when
they strike some body having an appreciable mass inside the
atom. It means that whole mass of the atom is concentrated in
a small portion of the atom and volume occupied by this
heavier body with in the atom is very small compared to the
total volume of the atom.

This small dense positively charged body with in the atom in

which whole mass of atom is concentrated was called nucleus
by Rutherford.
Figure: Scattering of α- particles by single atom
Based upon the above conclusion, Rutherford put forward his
nuclear model of atom. According to this model,
1. The atom is made up of a positively charged nucleus which is
very small in size compared to atom but carries almost
whole mass of the atom.
2. Most part of atom is empty.
3. The atom as a whole is electrically neutral since the number
of electrons is equal to the number of net positive charge in
the nucleus.
4. Electrons are revolving around the nucleus like planets
revolve around the sun in regularly defined orbit .
5. The centrifugal force of an electron which tends to pull away
electron from its orbit is balanced by electrostatic force of
attraction between nucleus and electrons

Figure: Rutherford’s model of an atom

Limitations/ Drawbacks/ Shortcoming
of Rutherford’s Atomic Model

Although the Rutherford atomic model was based on

experimental observations it failed to explain certain things:
1. This model could not explain the stability of atom.
According to Maxwell, accelerated charged particles emit
electromagnetic radiations and hence an electron revolving
around the nucleus should emit electromagnetic radiation.
This radiation would carry energy from the motion of the
electron. As a result of this motion of the electron falls and
electron moves towards closer and closer to the nucleus
following spiral path and ultimately the electrons would
collapse in the nucleus.
(Calculations have shown that as per the Rutherford model,
an electron would collapse in the nucleus in less than 10-8
seconds).But actually this will not happen because atom is
stable in nature. So Rutherford model was not in accordance
with Maxwell’s theory and could not explain the stability of an
atom.

Figure: Spiral path of the electrons

2. This model could not explain the origin of line spectra of
hydrogen atom
According to Rutherford’s atomic model, electron revolving
around the nucleus is expected to emit continuous energy
spectrum. But atoms such as hydrogen emit discrete line
spectra when it is subjected in the electric field and
magnetic field. This fact could not be explained by
Rutherford’s model.
 Bohr’s atomic
Model

Niels Henrik David Bohr(October 1885 –

18 November 1962) was a Danish
physicist who made foundational
contributions to understanding atomic
structure and quantum theory, for which
he received the Nobel Prize in Physics in
1922.
 Bohr’s atomic Model

In 1913 Niels Bohr proposed an atomic model to overcome

the limitations of Rutherford’s atomic model keeping its
essential spirits. He applied Planck's quantum theory of
radiation to an atom. The basic postulates of Bohr’s atomic
model are as follows.
1. In an atom, electrons revolve around the positively
charged nucleus in a definite circular path called orbits or
shells or energy level.
2. As long as electrons remains in a particular orbit, it neither
emits nor absorbs energy. It means the energy of
revolving electron in a particular orbit remains constant.
Hence these orbits are also called stationary orbit /
stationary energy levels or simply energy levels or energy
shells. Such a state of electron is called stationary state.
This postulate explain the stability of an atom.
3. The energy levels are represented by an integer (n=1, 2,
3…) known as the principal quantum number. Energy
associated with a certain energy level increases with the
increase of its distance from the nucleus. The orbits n=1,
2, 3, 4… are assigned as K, L, M, N…. shells and when an
electron attains the lowest energy level, it is said to be in
the ground state.

Figure. Stationary energy levels around the nucleus

4. Electron can revolve only in those orbit in which the
angular momentum of revolving electron around the
nucleus is an integral multiple of h/2π. That is why only
certain fixed orbit are allowed.
Angular momentum = n h/2π
mvr = nh/2π
where,
m = mass of electron
v = velocity of electron
r= radius of orbit in which electron revolving
n = An integer called principal quantum number
= 1,2,3,…………∞ ( number of orbit)
h = Planck's constant
 The Angular momentum can have value h/2π, 2h/2π,
3h/2π, 4h/2π etc. but it can never have fractional value.
Thus the angular momentum is quantized ( quantization
of angular momentum )

5. The centrifugal force of an electron which tends to pull

away electron from its orbit is balanced by electrostatic
force of attraction between nucleus and electrons
6. Electrons could jump from one orbit to another only by
emitting or absorbing fixed quanta of energy.
When energy is supplied to an electron it may jump from
lower energy level to higher energy level by absorbing
fixed quanta of energy. The new excited state of energy is
called excited state . The excited state of electron is highly
unstable, so electron jump from higher energy level to
lower energy level by emitting fixed quanta of energy in
the form of radiation.
The amount of energy absorbed or emitted is equal to the
energy difference between lower and higher energy level
of the atom.
ΔE = E2-E1 =hυ
Where, ΔE = Energy emitted or absorbed
E2 = Energy of higher energy level
E1 = energy of lower energy level
hυ = photon or quantum of energy
h = Planck's constant ( = 6.626 *10 -34 JS)
υ = frequency of radiation

Figure:
Successes of the Bohr’s atomic model

1. Bohr’s atomic model explained the stability of an atom

According to Bohr as long as electrons remains in a
particular orbit, it neither emits nor absorbs energy. Also,
it can not jump from first orbit to the lower orbit as there
is no orbit less than one. The gradual loss of energy by
electron is not possible . Hence atom is stable.
2. Bohr calculated the radii of various orbits and energy of
an electron in a particular orbit of hydrogen or hydrogen
like system.
Expression for radius (r)
radius of nth orbit (rn) =
where,
m = mass of electron (9.1 *10-31 kg )
e = charge on electron (1.6*10-19 C )
z = atomic number of element
h = Planck's constant
k = 1/4πε0 (ε0 = permittivity of medium)
value of k = 1 (in CGS unit)
k= 9*109 Nm2C-2 (in SI unit)
For hydrogen atom Z =1
rn = 0.53 × n2 A˚ (A ˚ = 10-10 m)

For hydrogen like species ( He+, Li2+ etc.)

rn = A˚
Expression for energy (E)
Energy of electron in nth orbit (En) = -
For hydrogen atom Z=1
En = - KJ mol-1

En = - eV per atom
For hydrogen like species
En = - KJ mol-1

En = - eV per atom
3. Bohr’s atomic model provided satisfactory explanation
about the formation of hydrogen spectrum
According to Bohr when electron jump from higher energy
level to lower energy level it emits the energy in the form
of radiation. Thus emitted radiation is responsible for
formation of atomic spectrum.
Explanation of hydrogen spectrum by
Bohr’s theory

Fig: Hydrogen spectrum experiment

When electric discharge is passed through a tube containing
hydrogen gas at low pressure at first hydrogen molecules
dissociate to form hydrogen atoms. Since the hydrogen gas
contains large number of hydrogen atoms, electrons in
different atoms absorb different amounts of energies. As a
result, electrons in the first energy level( ground state) of
hydrogen atoms get excited to jump into different higher
energy levels 2,3,4,5,etc depending upon the amount of
energy absorbed. The excited electrons in higher energy level
become unstable and jump back to the ground state in one
or more jumps by emitting energy in the form of radiation.
For example, some electrons come back to ground state (n=1 )
and others to n=2, n=3, n= 4 …etc. from higher energy level.
These different downward jumps emit radiations of different
wavelength (or frequencies) and produce different spectral lines
at same time in hydrogen spectrum although hydrogen contains
only one electron. The series of such a spectral lines is called
spectral series.
The wavelength of the radiations associated with different
downward jumps of electrons are given by Rydberg equation

= R( - )
Where, λ =wavelength of the radiation
R= Rydberg’s constant ( R= 1.097 × 107 m-1)
n1 = lower energy level
n2 = higher energy level
n=∞

Fig: Various spectral line in hydrogen spectrum

The different types of spectral series of hydrogen spectrum
are as follows:
(1) Lyman series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 2 to ∞ to
first energy level i.e. n1=1 .This series lies in ultraviolet
region within wavelength range of 92 nm to 120nm
The wavelength for the spectral line in Lyman series are
given by
= R( - )
(2) Balmer series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 3 to ∞ to
second energy level i.e. n1=2 .This series lies in visible
region within wavelength range of 400 nm to 650 nm
The wavelength for the spectral line in Balmer series are
given by
= R( - )
(3) Paschen series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 4 to ∞ to
third energy level i.e. n1=3 .This series lies in infrared
region within wavelength range of 950 nm to 1875 nm.
The wavelength for the spectral line in Paschen series are
given by
= R( - )
(4) Brackett series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 5 to ∞ to
fourth energy level i.e. n1=4 .This series lies in infrared
region within wavelength range of 1945 nm to 4050 nm.
The wavelength for the spectral line in Brackett series are
given by
= R( - )
(5) Pfund series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 6 to ∞ to
fifth energy level i.e. n1=5. This series lies in far infrared
region within wavelength range above 4050 nm.
The wavelength for the spectral line in pfund series are
given by
= R( - )
(6) Humphrey series
The spectral lines in these series are obtained when
electron jumps from higher energy level i.e. n2= 7 to ∞ to
sixth energy level i.e. n1=6. This series lies in far- infrared
region within wavelength range above 4050 nm.
The wavelength for the spectral line in Humphrey series
are given by
= R( - )
 Limitations/ Shortcoming of Bohr’s
Theory
1. Bohr’s theory explained the spectra of single electron system
like hydrogen atom and hydrogen like system i.e. He+, Li++
ions etc. but this theory was unable to explain formation of
spectra of multi-electron system like He, Li etc.
2. Bohr’s theory could not explain about the multiple or fine
structure of spectral line revealed through high resolving
power spectroscope .
3. According Bohr’s theory electron revolves around the nucleus
in circular path which is a simple planar motion but this theory
was unable to explain three dimensional motion of electron
around nucleus(orbital).
4. This model was unable to explain Zeeman effect ( splitting
of spectral line into magnetic field) and stark
effect( electric field).
5. This theory was unable to explain dual nature of electron
i.e. wave particle behavior. Bohr’s considered electron
only as particle.
6. According to Bohr’s concept electron revolved around the
nucleus with a define velocity at defined distance ( fixed
orbit) from nucleus. This is against Heisenberg’s
uncertainty principle which states that it is impossible to
determine simultaneously both the position and velocity
of moving electron with absolute accuracy.