1 ATOMS

ATOMS
Introduction: In 1897, the experiments conducted by J. J. Thomson using discharge tube revealed
that atoms of different elements contain negatively charged particles called electrons. However, atoms
on a whole are electrically neutral. Therefore, an atom must also contain some positive charge to
neutralize the negative charge of the electrons. This fact led to the discovery of atoms.

J. J. Thomson model:
The first model of atom was proposed by J. J. Thomson. According to this model, the
positive charge of the atom is uniformly distributed throughout the volume of the atom and the
negatively charged electrons are embedded in it like seeds in a watermelon. This model was called
plum pudding model of the atom. However subsequent studies on atoms showed that the distribution
of the electrons and positive charges are very different from that proposed in this model.

ALPHA-PARTICLE SCATTERING AND RUTHERFORD’S NUCLEAR MODEL OF ATOM

At the suggestion of Ernst Rutherford, H. Geiger and E. Marsden performed the alpha – particle
scattering experiment whose schematic diagram is as shown in the fig.

Alpha-particles emitted by a 214 83𝐵𝑖 radioactive source were confined into a narrow beam by passing
them through lead bricks. The beam was allowed to fall on a thin gold foil. The scattered alpha-
particles were observed through a rotatable detector consisting of zinc sulphide screen and a
microscope. The scattered alpha-particles on striking the screen produced brief light flashes or
scintillations. These flashes were viewed through a microscope and the number of scattered particles
for different angle of scattering θ was noted.
A typical graph of the total number of α-particles scattered at different angles, in a given
interval of time, is shown in Fig. From the graph following observations were made
1) Many of the α-particles pass through the foil. It means that they do not suffer any collisions.
2) Only about 0.14% of the incident α-particles scatter by more than 1º;
3) About 1 in 8000 α-particles deflect by
more than 90º.

From these observations, Rutherford argued that, to

deflect the α-particle backwards, it must experience a
large repulsive force which can be provided only if
most of the mass of the atom and its positive charge is
concentrated at the centre of the atom. Thus when α-
2 ATOMS

particle pass very close to the positive charge, it is deflected at large angle.

Rutherford’s Model of Atom:

According to Rutherford,
1) The entire positive charge and most of the mass of the atom are concentrated in the nucleus.
2) The electrons moves around the nucleus in orbits just as the planets do around the sun.
3) The size of the nucleus is about 10-15 m to 10-14 m whereas the size of an atom is 10-10m. Thus
the size of an atom is 10,000 to 100,000 times larger than nucleus.
4) As most of the α-particles passed through the gold foil un deflected, most of an atom is empty
space.
5) The force of interaction between an α-particle of charge 2e and the gold nucleus of charge Ze
(Z is the atomic no) is given by,
1 (2𝑒)(𝑍𝑒)
F=
4𝜋𝜀0 𝑟2
Where, r → is the distance between α-particle and the nucleus.

Note:
Alpha-particle trajectory:
Impact parameter: The impact parameter is the perpendicular distance of the initial velocity vector of
the α-particle from the centre of the nucleus.

Limitations of Rutherford’s atomic model:

Rutherford’s atomic model assumes that the negatively charged electrons revolve around the positively
charged nucleus in definite orbits. But since electrons and nucleus are charged objects held together by
electrostatic force the model fails to explain the following:
1) Stability of an atom: According to electromagnetic theory, an accelerating charge particle
emits radiation in the form of electromagnetic waves. Thus, the energy of the accelerating electron
should continuously decrease. If electron loses it energy then the electron would spiral inward and
eventually fall into the nucleus and such an atom cannot be stable.
2) Formation of Line spectrum of hydrogen: As the electrons spiral inwards, their angular
velocities and hence their frequencies would change continuously, and so will the frequency of light
emitted. Thus, they would emit a continuous spectrum instead of line spectrum actually observed.

Electron orbits:
The Rutherford nuclear model of an atom assumes that the atom consists of a very small, massive and
positively charged nucleus at the centre surrounded by the revolving electrons in their respective
dynamically stable orbits. The electrostatic force of attraction, Fe between the revolving electrons and
the nucleus provides the centripetal force (Fc) to keep them in their orbits. For the dynamically stable
orbit in hydrogen atom the electrostatic force Fe and the centripetal force Fc balance with each other.

Expression for total energy of the electron in terms of orbital radius:

When the electrons revolve around the nucleus, the electrostatic force between the electron and nucleus
(Fe) and the centripetal force (Fc) are balanced,
i.e Fe = Fc
𝟏 𝒆(𝒆) 𝒎𝒗𝟐
or =
𝟒𝝅𝜺𝟎 𝒓𝟐 𝒓
𝒆𝟐 𝒆𝟐
r= and v2 =
𝟒𝝅𝜺𝟎 𝒎𝒗𝟐 𝟒𝝅𝜺𝟎 𝒎𝒓

Now the kinetic energy (K) of the electron in hydrogen atom is

3 ATOMS

K= ½ mv2
𝑒2
Substituting v2 = in the above eq, we get
𝟒𝝅𝜺𝟎 𝒎𝒓

𝒆𝟐
K=½m( )
𝟒𝝅𝜺𝟎 𝒎𝒓

𝒆𝟐
K= →(1)
𝟖𝝅𝜺𝟎 𝒓

Potential energy (U) of the electron is given by work done in displacing the electron through a distance
equal to radius (r) of its orbit. Thus

𝟏 𝒆𝟐
U =(
𝟒𝝅𝜺𝟎 𝒓𝟐
) (−𝒓)

− 𝒆𝟐
U= →(2)
𝟒𝝅𝜺𝟎 𝒓

Now the total energy E = K + U

𝒆𝟐 𝒆𝟐
E= −
𝟖𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓

− 𝒆𝟐
E= →(3)
𝟖𝝅𝜺𝟎 𝒓

ATOMIC SPECTRA :
Every element is associated with a characteristic spectrum of radiation which the radiation emits and is
called as the atomic spectra.
Types of atomic spectra:
1) Emission line spectrum: When an atomic gas or vapour is excited at low pressure usually by
passing an electric current through it, the emitted radiation has a spectrum which contains
certain specific wavelengths only. This kind of spectrum is called as emission line spectrum. It
consists of bright lines on dark background.
2) Absorption line spectrum: When white light is passed through a gas and if it is viewed using a
spectrometer dark lines can be seen. It is observed that these lines have wavelengths which were
found in the emission line spectrum of the gas. This is called as the absorption spectrum.

The spectrum emitted by hydrogen atom is as shown in fig. The study of emission line spectra of a
material can serve as fingerprint for the identification of the gas.
4 ATOMS

Spectral series:
The spectrum of atoms consist of set of lines showing some regular pattern which are called as Spectral
series. There are five spectral series
1.Lyman series: This series consists of all the wavelength (spectral lines) which are emitted due to
transition of electrons from different higher orbit to the 1st orbit..
The Lyman series is formed in the ultraviolet region of the hydrogen spectrum. The empirical formula
is
𝟏 𝟏 𝟏
= 𝑹( − ) n = 2,3,4…….
𝝀 𝟏𝟐 𝒏𝟐

2.Balmer series: This series consists of all the wave length (spectral lines) which are emitted due to
transition of electrons from different higher orbit to the 2nd orbit.
The series is formed in the visible region of the hydrogen spectrum. The empirical formula is

𝟏 𝟏 𝟏
= 𝑹( − ) n = 3,4,5…….
𝝀 𝟐𝟐 𝒏𝟐

2. The longest wavelength in this region is 656.3nm.

3.Paschen series: This series consists of all the wavelength (spectral lines) which are emitted due to
transition of electrons from different higher orbit to the 3rd orbit.
The series is formed in the infrared region of the hydrogen spectrum. The empirical formula is

1 1 1
= 𝑅 (32 − 𝑛2 ) n = 4,5,6…….
𝜆

4. Brackett series: This series consists of all the wavelength(spectral lines) which are emitted due to
transition of electrons from different higher orbit to the 4th orbit.
The series is also formed in the infrared region of the hydrogen spectrum. The empirical formula is

1 1 1
= 𝑅 (42 − 𝑛2 ) n = 5,6,7…….
𝜆

5. Pfund series: This series consists of all the wave length (spectral lines) which are emitted due to
transmission of electrons from different higher orbit to the 5th orbit.
The empirical formula for pfund series is

1 1 1
= 𝑅 (52 − 𝑛2 ) n = 6,7,8…….
𝜆
Where, R → constant called the Rydberg constant. R=1.097 x 107 m-1.

Balmer series: Johann Jakob Balmer found the first series in 1885 named after him as Balmer series, in
the visible region of the hydrogen spectrum. The Balmer series in the emission spectrum of hydrogen is
as shown in the fig.
• In the series the line with the longest wavelength,
656.3 nm in the red is called Hα.
• The line with wavelength 486.1 nm in the blue-
green is called Hβ.
• The third line 434.1 nm in the violet is called H and
so on.
The empirical formula for Balmer series is
5 ATOMS

𝟏 𝟏 𝟏
= 𝑹( − )
𝝀 𝟐𝟐 𝒏𝟐

Balmer formula in terms of frequency of the light can be written as,

𝟏 𝟏
 = 𝑹𝒄 ( − )
𝟐𝟐 𝒏𝟐
𝟏 𝝊
(∵ = )
𝝀 𝒄

Bohr’s postulates:
(1) Bohr’s first postulate says that an electron in an atom can revolve in certain stable orbits
without the emission of radiant energy. According to this postulate, each atom has certain
definite stable states in which it can exist, and each possible state has definite total energy.
These are called the stationary states of the atom.
(2) Bohr’s second postulate states that the electron revolves around the nucleus only in those
orbits for which the angular momentum is some integral multiple of h/2π i.e. L = mvr = nh/2π
where h is the Planck’s constant (= 6.6 × 10–34 J s). Thus the angular momentum (L) of the
orbiting electron is quantised. This is also called Bohr’s second postulate of quantization.
(3) Bohr’s third postulate states that when an electron makes a transition from higher energy level
to a lower energy, a photon is emitted having energy equal to the energy difference between the
initial and final states. The frequency of the emitted photon is then given by
h = Ei – Ef
where, Ei and Ef are the energies of the initial and final states and Ei > Ef.

Expression for radius of nth orbit of hydrogen atom:

Consider an hydrogen atom consisting of electron of mass ‘m’, revolving with a velocity ‘v’ around the
nucleus. Let the radius of the orbit be ‘r’.
According to Bohr’s second postulate
Angular momentum = Integral multiple of h/2

𝒏𝒉
mvr=
𝟐𝝅
𝒏𝒉
or v = → (1)
𝟐𝝅𝒎𝒓
We know that the electrostatic force(Fe) balances with the centrepetal force (Fc) in the atom,
Fe = Fc
𝟏 𝒆𝟐 𝒎𝒗𝟐
=
𝟒𝝅𝜺𝟎 𝒓𝟐 𝒓

𝒆𝟐
 r=
𝟒𝝅𝜺𝟎 𝒎𝒗𝟐

𝒆𝟐
v2 =
𝟒𝝅𝜺𝟎 𝒎𝒓

𝑒
v= →2
√4𝜋𝜀0 𝑚𝑟

equating (1) and (2)

6 ATOMS

𝒏𝒉 𝒆
=
𝟐𝝅𝒎𝒓 √4𝜋𝜀0 𝑚𝑟

Squaring both sides

𝑛2 ℎ 2 𝑒2
=
4𝜋2 𝑟 2 𝑚2 4𝜋𝜀0 𝑚𝑟

𝒏𝟐 𝒉𝟐 𝜺𝟎
r=
𝝅𝒎𝒆𝟐
This is the expression for the radius of nth orbit hydrogen atom

For innermost orbit n=1

𝒉𝟐 𝜺𝟎
r=
𝝅𝒎𝒆𝟐

Orbital velocity of an electron:

Consider an hydrogen atom consisting of electron of mass ‘m’, revolving with a velocity ‘v’ around the
nucleus. Let the radius of the orbit be ‘r’.
We know that according to Bohr’s theory the electrostatic force(Fe) balances with the centrepetal force
(Fc) in the atom,
Fe = Fc
𝟏 𝒆𝟐 𝒎𝒗𝟐
=
𝟒𝝅𝜺𝟎 𝒓𝟐 𝒓
𝒆𝟐
𝒎𝒗𝟐 = →(1)
𝟒𝝅𝜺𝟎 𝒓
According to Bohr’s second postulate

𝒏𝒉
𝒎𝒗𝒓 =
𝟐𝝅

Divide eq (1) and (2)

𝒆𝟐
𝒎𝒗𝟐 𝟒𝝅𝜺𝟎 𝒓
= 𝒏𝒉
𝐦𝐯𝐫
𝟐𝝅

𝒆𝟐
v=
𝟐𝜺𝟎 𝒏𝒉
This is the velocity of electron in nth orbit.

Total energy of the electron in nth orbit:

When the electrons revolve around the nucleus, the electrostatic force between the electron and nucleus
(Fe) and the centripetal force (Fc) are balanced,
i.e Fe = Fc

𝟏 𝒆𝟐 𝒎𝒗𝟐
or =
𝟒𝝅𝜺𝟎 𝒓𝟐 𝒓
7 ATOMS

𝒆𝟐 𝒆𝟐
r= and v2 =
𝟒𝝅𝜺𝟎 𝒎𝒗𝟐 𝟒𝝅𝜺𝟎 𝒎𝒓

Now the kinetic energy (K) of the electron in hydrogen atom is

𝟏
𝑲 = 𝒎𝒗𝟐
𝟐
𝑒2
Substituting v2 = in the above eq, we get
𝟒𝝅𝜺𝟎 𝒎𝒓

𝑒2
K = ½ m (𝟒𝝅𝜺 𝒎𝒓)
𝟎

𝒆𝟐
K= → (1)
𝟖𝝅𝜺𝟎 𝒓

Potential energy (U) of the electron is given by work done in displacing the electron through a distance
equal to radius (r) of its orbit. Thus

𝟏 𝒆
U =(
𝟒𝝅𝜺𝟎 𝒓
) (−𝒆)

− 𝒆𝟐
U= →(2)
𝟒𝝅𝜺𝟎 𝒓

Now the total energy E = K + U

𝒆𝟐 𝒆𝟐
E= -
𝟖𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓

− 𝒁𝒆𝟐
E= →(3)
𝟖𝝅𝜺𝟎 𝒓

But we know that the radius of nth orbit of an electron is given by

𝒏𝟐 𝒉𝟐 𝜺𝟎
r=
𝝅𝒎𝒆𝟐

Substituting r in eq (3) we get

− 𝒆𝟐
E=
𝒏𝟐 𝒉𝟐 𝜺𝟎
𝟖𝝅𝜺𝟎 𝒓( )
𝝅𝒎𝒆𝟐

−𝒎𝒆𝟒
T.E= E =
𝟖𝜺𝟎 𝟐 𝒏𝟐 𝒉𝟐

−𝟏𝟑.𝟔
T.E= 𝒆𝑽
𝒏𝟐
8 ATOMS

The negative sign of the total energy of an electron moving in an orbit means that the electron is
bound with the nucleus.

Limitations of Bohr’s theory:

1) Bohr’s theory can be applied only for hydrogen atom. It cannot be extended even to two
electron atoms such as helium.
2) It fails to explain the spectrum of multi electron atoms.
3) Bohr’s model involves electrical force between nucleus and electron but does not include
electrical forces between electrons which appear in multi electron atoms.
4) It fails to explain the relative variation in intensities of the frequencies in the spectrum.
5) In Bohr’s model electron is regarded as particle but the wave nature of electrons are ignored.

Energy levels:
• The energy of an atom is the least when its electron is revolving in an orbit closest to the
nucleus i.e., for n = 1.
• For n = 2, 3, ... the energy is progressively larger i.e in the outer orbits.
• The lowest state of the atom is called the ground state. It has the lowest energy and the orbit has
the smallest radius called as the Bohr radius, a0.
• The energy of the ground state (n = 1), E1 is –13.6 eV. Therefore, the minimum energy
required to free the electron from the ground state of the hydrogen atom is 13.6 eV. It is called
the ionisation energy of the hydrogen atom.
• At room temperature, most of the hydrogen atoms are in ground state. When a hydrogen atom
receives energy the atom may acquire sufficient energy to raise the electron to higher energy
states. The atom is then said to be in an excited state.

Note: As the excitation of hydrogen atom increases (that is as n increases) the value of minimum
energy required to free the electron from the excited atom decreases.

Energy level diagram:

The energy level diagram is a convenient form of representing the energies of different orbits and
transition of electron from one orbit to another.

According to the formula En = -13.6/n2 eV

The energy level diagram of hydrogen atom is as shown in the
fig. The various energy levels are represented by horizontal
lines and electron transitions are represented by vertical lines.
The first horizontal line represent the ground state and the other
horizontal lines represent the possible exited state of hydrogen
atom.
Excitation energy: The minimum energy required to free the
electron from its ground state and raise it to an excited state is
called excitation energy.

Ionization energy : The minimum energy required to knock off

an electron from given orbit to an infinite distance from the
nucleus is called ionization energy.
OR
Ionisation Energy: - The energy required to detach an electron
from an atom is called ionization energy of the atom.
9 ATOMS

Electron Volt [eV] : An electron volt is the amount of Kinetic energy an electron acquires when it is
accelerated through an electric potential of 1 volt.

Expression for the frequency of emitted radiation:

According to the third postulate of Bohr’s model, when an atom makes a transition from the higher
energy state with quantum number ni to the lower energy state with quantum number nf (nf < ni ),
photon with frequency if is emitted, carrying energy equal to the difference of energy of initial and
final states.
i.e h = Ei - Ef →(1)
we know that total energy of the electron in nth orbit is given by,
−𝑚 𝑒 4
E = ℎ =
8𝜀0 2 𝑛2 ℎ2

−𝒎 𝒆𝟒 −𝒎 𝒆𝟒
Ei = 𝟐 and Ef =
𝟖𝜺𝟎 𝒏𝒊 𝟐 𝒉𝟐 𝟖𝜺𝟎 𝟐 𝒏𝒇 𝟐 𝒉𝟐

Substituting Ei and Ef in eq (1) we get

−𝒎 𝒆𝟒 𝒎 𝒆𝟒
h = +
𝟖𝜺𝟎 𝟐 𝒏𝒊 𝟐 𝒉 𝟐 𝟖𝜺𝟎 𝟐 𝒏𝒇 𝟐 𝒉𝟐

𝒎 𝒆𝟒 𝟏 𝟏
h = 𝟐 [𝒏 𝟐 − 𝒏𝒊 𝟐
]
𝟖𝜺𝟎 𝒉𝟐 𝒇

𝒎 𝒆𝟒 𝟏 𝟏
= 𝟐 [𝒏 𝟐 − ]
𝟖𝜺𝟎 𝒉𝟑 𝒇 𝒏𝒊 𝟐

This equation is called Rydberg formula.

𝑐
We have, c =  or = 

𝒄 𝒎 𝒆𝟒 𝟏 𝟏

= 𝟐 [𝒏 𝟐 − 𝒏𝒊 𝟐
]
𝟖𝜺𝟎 𝒉𝟑 𝒇

𝟏 𝒎 𝒆𝟒 𝟏 𝟏

= 𝟐 [𝒏 𝟐 − 𝒏𝒊 𝟐
]
𝟖𝜺𝟎 𝒄𝒉𝟑 𝒇

From the above equation Rydberg constant R is given by,

𝒎 𝒆𝟒
R=
𝟖𝜺𝟎 𝟐 𝒄𝒉𝟑

Spectral series:
We have Rydberg formula given by
1 𝑚 𝑒4 1 1
= [ − ]
 8𝜀0 2 𝑐ℎ3 𝑛𝑓 2 𝑛𝑖 2
10 ATOMS

1) Lyman series: When an electron jumps from higher orbits to the first orbit Lyman series is
obtained.
If nf =1 and ni = 2,3,4….then Lyman series is
obtained.
2) Balmer series: When an electron jumps from
higher orbits to the second orbit Balmer series is
obtained.
If nf =2 and ni = 3,4,5….then Balmer series is
obtained.
3) Paschen series: When an electron jumps from
heigher orbits to the third orbit Paschen series is
obtained.
If nf =3 and ni = 4,5,6….then Paschen series is
obtained.
4) Brackett series: When an electron jumps from
higher orbits to the fourth orbit Brackett series is
obtained.
If nf 4 and ni = 5,6,7….then Brackett series is
obtained.
5) Pfund series: When an electron jumps from
higher orbits to the fifth orbit Pfund series is
obtained.
If nf 5 and ni = 6,7,8….then Brackett series is
obtained.

DE BROGLIE’S EXPLANATION OF BOHR’S SECOND POSTULATE OF QUANTISATION:

According to Bohr’s second postulate of quantization electrons revolve around the nucleus only in
those orbits for which the angular momentum is some integral multiple of h/2π
i.e. L = mvr = nh/2π where h is the Planck’s constant

Louis de Broglie explained that electron must be seen as a particle wave. While revolving around the
orbit these waves of electrons superimpose over each other to set up stationary standing waves. Thus
circumference of that orbit will be an integral multiple of electron
wavelength given as
2πrn = n, n=1,2,3….. →(1)
The diagram shows the standing particle wave on a circular orbit of radius
‘r’ and wavelength of electron .
We know de Broglie’s wavelength,

𝒉 𝒉
= = →(2)
𝒑 𝒎𝒗
Substitute (2) in (1)
𝑛ℎ
2πrn = ,
𝑚𝑣
Or 𝒏𝒉
mvrn =
𝟐𝝅
The above eq is the quantum condition proposed by bohr for the angular momentum of the
electron. Thus de Broglie hypothesis explains the Bohr’s second postulate for quantization of angular
momentum of the orbiting electron.