Chapter 12

Atoms
Thomson Model of Atom- (plum pudding model)
The first model of atom was proposed by J. J. Thomson in 1898.
▪ According to this model, the positive charge of the atom is uniformly
distributed throughout the volume of the atom .
▪ The negatively charged electrons are embedded in it like seeds in a
watermelon.
This model is also called plum pudding model of the atom.

Alpha-Particle Scattering and Rutherford’s Nuclear Model of Atom

Ernst Rutherford , a former research student of J. J. Thomson, proposed a
classic experiment of scattering of these α-particles by atoms to investigate
the atomic structure. The explanation of the results led to the birth of
Rutherford’s planetary model of atom (also called the nuclear model of the
atom).

Alpha-Particle Scattering
At the suggestion of Ernst Rutherford, in 1911, H. Geiger and E. Marsden
performed scattering experiment.

Alpha-particles emitted by a 214 83 𝐵𝑖 radioactive source were collimated into a

narrow beam by passing through lead bricks. The beam was allowed to fall
on a thin foil of gold of thickness 2.1 × 10 –7 m. The scattered alpha-particles
were observed through a rotatable detector consisting of zinc sulphide
screen and a microscope.
Observations
▪ Many of the α-particles pass through the foil. It means that
they do not suffer any collisions.
▪ Only 0.14% of the incident α-particles scatter by more than 1º.
▪ About 1 in 8000 of incident α-particles deflect by more than 90º.
Rutherford argued that , greater part of the mass of the atom and its positive
charge were concentrated tightly at its centre. When the incoming α-particle
make a close encounter with the positive charge ,that would result in a large
deflection.
Rutherford’s nuclear model of the atom
▪ Most of an atom is empty space.
▪ The entire positive charge and most of the mass of the atom
are concentrated in the nucleus with the electrons some
distance away.
▪ The electrons would be moving in orbits about the nucleus just
as the planets do around the sun.
▪ The size of the nucleus to be about 10 –15 m to 10–14 m.
▪ The electrostatic force of attraction, between the
revolving electrons and the nucleus provides the
centripetal force to keep them in their orbits.
Impact Parameter (b)

Impact parameter is the perpendicular distance of the initial velocity vector

of the 𝛂 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞 from the centre of the nucleus.
Alpha-particle trajectory
The trajectory traced by an α-particle depends on the impact parameter, b of
collision.
 ▪ For an α-particle close to the nucleus , impact parameter is
small and it suffers large scattering.
▪ For head on collision, the impact parameter b=0 and
α particle rebounds back ie,angle of scattering 𝜃 =180 0.
▪ For large impact parameter, the angle of scattering will be
small ( 𝜃 ≈0 0) and such α particles go undeviated.

Electron orbits
The electrostatic force of attraction(F e), between the revolving electrons and
the nucleus provides the centripetal force (F c) to keep them in their orbits.
F c = Fe
mv 2 1 ⅇ2
=
r 4πε 0 r 2

The kinetic energy (K) of electron

𝟏 𝐞𝟐
K = 𝒎𝒗𝟐 =
𝟐 𝟖𝛑𝛆𝟎 𝐫
The potential energy (U) of electron
−𝐞𝟐
U=
𝟒𝛑𝛆𝟎 𝐫
(The negative sign in U signifies that the electrostatic force is in the –r
direction.)
Thus the total energy E of the electron in a hydrogen atom is
E = K+U
ⅇ2 ⅇ2
E= −
8πε 0 r 4πε 0 r
−𝐞𝟐
E = 𝟖𝛑𝛆
𝟎𝐫

The total energy of the electron is negative. This implies the fact that the
electron is bound to the nucleus. If E were positive, an electron will not
follow a closed orbit around the nucleus.
Limitations of Rutherford Model
Rutherford nuclear model has two main difficulties in explaining the
structure of atom:
(a)It predicts that atoms are unstable because the
accelerated electrons revolving around the nucleus loses
energy and must spiral into the nucleus. This contradicts
the stability of matter.
(b) It cannot explain the characteristic line spectra of atoms of
different elements.
Bohr Model of Hydrogen Atom
Niels Bohr made certain modifications in Rutherford’s model using the
ideas of quantum hypothesis. Bohr combined classical and early quantum
concepts and gave his theory in the form of three postulates.

1) Bohr’s first postulate states that an electron in an atom revolves in

certain stable orbits without the emission of radiant energy.
2) Second postulate states that the electron revolves around the nucleus
only in those orbits for which the angular momentum is an integral multiple
of h/2π where h is the Planck’s constant
𝒏𝒉
L = mvr = ,where n = 1,2,3……….
𝟐𝝅
n is called principal quantum number
3) Third postulate states that when an electron make a transition from
higher energy level to lower energy level 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
hν = 𝑬 𝒊 - 𝑬𝒇
Expression for Radius of Hydrogen Atom
Consider an electron of charge ‘e’ and mass ‘m’ revolving round the
positively charged nucleus in circular orbit of radius ’r’
Centripetal force = Electrostatic force of attraction
mv 2 1 ⅇ2
= --------------(1)
r 4πε 0 r 2
According to Bohr atom model, the angular momentum
nh
mvr =
2π
nh
v= ------------------(2)
2πmr
Substituting eqn (2) in eqn (1)
nh 2 ⅇ2
m( ) = 4πε
2πmr 0r
n2h2 ⅇ2
=
4π 2 mr 2 4πε 0 r
𝐧𝟐 𝐡𝟐 𝛆𝟎
𝐫𝐧 = -----------(3)
𝛑𝐦𝐞𝟐
th
r n is the radius of n orbit of Hydrogen atom
𝐫 𝐧 𝛂 𝐧𝟐
For the first orbit n=1
h 2 ε0
r 1=
πmⅇ 2

This is called the Bohr radius, represented by the symbol a 0

𝐡𝟐 𝛆𝟎
𝐚 𝟎=
𝛑𝐦𝐞𝟐

Bohr radius , 𝐚 𝟎 = 5.29 × 𝟏𝟎−𝟏𝟏 m = 0.53Å

The radius of 𝐧 𝐭𝐡 orbit of Hydrogen atom can also be written as

𝐫 𝐧 =0.53 𝐧𝟐 Å
𝐫 𝟏 =1 x 0.53 Å
𝐫 𝟐 =4 x 0.53 Å
𝐫 𝟑 =9 x 0.53 Å

Energy of Hydrogen Atom

Total energy of 𝒏 𝒕𝒉 energy level
−ⅇ2
En =
8πε 0 r n

The radius of hydrogen atom

n2 h 2 ε0
r n=
πmⅇ 2

Substituting for rn from eqn(3)

−ⅇ2
En = n 2h 2ε 0
8πε 0 ( )
πmⅇ 2

−𝐦𝐞𝟒
𝐄𝐧 =
𝟖𝐧𝟐 𝛆𝟎 𝟐 𝐡𝟐
−𝟏𝟑.𝟔
𝐄𝐧 = eV
𝐧𝟐
𝟏
𝐄𝐧 𝛂
𝐧𝟐
The negative sign of the total energy of an electron moving in an orbit means
that the electron is bound with the nucleus.
Energy levels
The energy of an atom is the least (largest negative value) when its electron
is revolving in an orbit closest to the nucleus for n = 1. The energy is
progressively larger in the outer orbits.

Ground State
The lowest energy state of an atom is called the Ground State, with the
electron revolving in the orbit of smallest radius, the Bohr radius, a 0.
For ground state n=1
−𝟏𝟑.𝟔
𝐄𝟏 = eV = -13.6 eV
𝟏𝟐

At room temperature most of the Hydrogen atoms are in ground state.

Excited States
When Hydrogen atom receives energy by the process such as collisions, the
atoms may acquire sufficient energy to raise the electrons to higher energy
states. Then atom is said to be in an excited state.

For first excited state (second energy level)

−13.6
n =2, E2 = eV = -3.4 eV
22
For second excited state (third energy level)
−13.6
n =3 , E3 = eV = -1.51 eV
32
And so on..
The energy level diagram for the hydrogen atom
Ionisation Energy
The minimum energy required to free the electron from the ground state of
the atom is called the Ionisation energy.

Ionisation energy of an atom is always positive.

Ionisation energy of Hydrogen atom = E ∞ - E1
= 0 – ( -13.6) eV = 13.6 eV.
Ionisation energy of Hydrogen atom is 13.6 eV

The energy required to excite an electron in Hydrogen atom from ground

state to its first excited state is
𝐄 𝟐 -𝐄𝟏 = -3.6 eV – (-13.6) eV = 10.2 eV

The energy required to excite an electron in Hydrogen atom from ground

state to its second excited state is
𝐄 𝟑 -𝐄𝟏 = -1.51 eV – (-13.6) eV = 12.09 eV
And so on…
Atomic Spectra
Each element has a characteristic spectrum of radiation, which it emits.
There are two types of spectra-Emission spectrum and Absorption
spectrum.

Emission Spectrum
When an atomic gas or vapour is excited at low pressure, by passing an
electric current through it, the emitted radiation has a spectrum which
contains certain specific wavelengths only. A spectrum of this kind is termed
as emission line spectrum and it consists of bright lines on a dark
background. Study of emission line spectra of a material is used for
identification of the gas.
Absorption Spectrum
When white light passes through a gas and we analyse the transmitted light
using a spectrometer we find some dark lines in the spectrum. These dark
lines correspond precisely to those wavelengths which were found in the
emission line spectrum of the gas. This is called the absorption spectrum of
the material of the gas.

Spectral series of Hydrogen Atom

Hydrogen is the simplest atom and therefore, has the simplest spectrum.
The spacing between lines within certain sets of the hydrogen spectrum
decreases in a regular way . Each of these sets is called a spectral series. The
first series was observed Johann Jakob Balmer the visible region of the
hydrogen spectrum. This series is called Balmer series .

The line with the longest wavelength, 656.3 nm in the red is called H α
The line with the shortest wavelength, 364.6 nm is called 𝐻 ∞ .

Rydberg formula, for the spectrum of the hydrogen atom

According to the third postulate of Bohr’s model, when an atom makes a
transition from the higher energy state with quantum number n i to the
lower energy state with quantum number n f (nf < ni ),

h𝑣 = E i – Ef
−mⅇ4 −mⅇ4
h𝑣 = 2 −
8n i 2 ε 0 2 h 8n f 2 ε 0 2 h 2
−mⅇ4 1 1
h𝑣 = 2h2 ( n 2 − )
8ε 0 f ni 2
mⅇ 4 1 1
𝑣= 2h3 ( n 2 − )
8ε 0 f ni 2
 c
𝑣=
λ

c mⅇ 4 1 1
= 2h3 ( n 2 − )
λ 8ε 0 f ni 2

1 mⅇ 4 1 1
= 2h3c (n 2 − )
λ 8ε 0 f ni 2
𝟏 𝟏 𝟏
=𝐑( 𝟐 − )
𝛌 𝐧𝐟 𝐧𝐢 𝟐

This is the Rydberg formula, for the spectrum of the hydrogen atom. R is
called the Rydberg constant.
𝐦𝐞𝟒
𝐑=
𝟖𝛆𝟎 𝟐 𝐡𝟑 𝒄
R = 1.03 × 10 7 m–1

Balmer Formula
If we take nf = 2 and ni = 3, 4, 5..., Rydberg formula reduces to Balmer
formula.
𝟏 𝟏 𝟏
= 𝐑 ( 𝟐 − 𝟐 ) where n= 3,4,5,…..
𝛌 𝟐 𝐧

R is Rydberg constant and its value R = 1.03 × 10 7 m–1.

▪ For Hα line, n = 3
1 1 1
=R( − )
λ 22 32
λ = 656.3 nm
This is the longest wavelength of Balmer series

▪ For 𝐻𝛽 line, n = 4
1 1 1
=R( 2 − )
λ 2 42
λ = 486.1 nm.

▪ For 𝐻∞ line, n = ∞
1 1 1
=R( − )
λ 22 ∞2
λ = 364.6 nm
This the shortest wavelength of Balmer series i.e.,the limit of Balmer series.
The formulae for spectral series of Hydrogen atom
Other series of spectra for hydrogen were subsequently discovered. These
are known, after their discoverers. The spectral series of hydrogen atom are
Lyman,Balmer, Paschen, Brackett, and Pfund series.

Lyman Series
𝟏 𝟏 𝟏
=𝐑( 𝟐 − ) where n= 2,3,4,…..
𝛌 𝟏 𝐧𝟐

Balmer Series
𝟏 𝟏 𝟏
=𝐑( − ) where n= 3,4,5,…..
𝛌 𝟐𝟐 𝐧𝟐

Paschen Series
𝟏 𝟏 𝟏
=𝐑( 𝟐 − ) where n=4,5,6,…..
𝛌 𝟑 𝐧𝟐

Brackett Series
𝟏 𝟏 𝟏
=𝐑( − ) where n=5,6,7,.…..
𝛌 𝟒𝟐 𝐧𝟐

Pfund Series
𝟏 𝟏 𝟏
=𝐑( 𝟐 − ) where n= 6,7,8,…..
𝛌 𝟓 𝐧𝟐

The Lyman series is in the ultraviolet,Balmer series in the Visible region and
the Paschen and Brackett series are in the infrared region.

The Balmer formula in terms of frequency of the light,

c = νλ
1 𝑣
=
𝜆 𝑐
𝑣 1 1
= R( − )
𝑐 22 n2
𝟏 𝟏
𝛎 = 𝐑𝐜 ( 𝟐 − 𝟐 ) where n=3,4,5,….
𝟐 𝐧
The Line Spectra of The Hydrogen Atom

De Broglie’s Explanation of Bohr’s second postulate of Quantisation

De Broglie argued that electron in its circular orbit behaves as a particle
wave. The particle wave can produce standing wave under resonant
condition.

For 𝒏𝒕𝒉 orbit of radius 𝑟𝑛 , the resonant condition is

2 π 𝑟𝑛 = n λ----------- (1) where n=1,2,3…..

But by de Broglie hypothesis , for matter waves

𝐡
λ= ---------------(2)
𝐦𝐯
Substituing eqn (2) in eqn (1),
𝐡
2 π rn= n
𝐦𝐯
𝐧𝐡
mv 𝐫𝐧 = where n=1,2,3……
𝟐𝛑
This Bohr’s second postulate of Quantisation.
Limitations of Bohr Atom Model

(i) The Bohr model is applicable to hydrogenic atoms. It cannot be

extended two or more electron atoms. Difficulty lies in the fact that
each electron interacts not only with the positively charged nucleus
but also with all other electrons.

(ii) While the Bohr’s model correctly predicts the frequencies of the
light emitted by hydrogenic atoms, the model is unable to explain
the intensity variations of the frequencies in the spectrum.