CHAPTER 12 ATOMS

 THOMSON'S MODEL OF AN ATOM The α-particles from this source are collimated into a
narrow beam through a narrow slit. The beam is
In 1898, J.J. Thomson proposed that an atom is a allowed to fall on a thin gold foil. Tire α-particles
sphere of positively charged matter with electrons scattered in different directions are observed with the
embedded in it. The positive charge is uniformly help of a rotatable detector which consists of a zinc
distributed over the entire atom. The arrangement of sulphide screen and a microscope. Whenever an alpha
electrons inside the continuous positive charge is particle strikes the screen, it produces a tiny flash, or
similar to that of the seeds in a watermelon or the scintillation, which is viewed through the microscope.
plums in a pudding. The electrons are arranged in such In this way, the number of α-particles scattered at
a manner that their mutual repulsions are balanced by different angles can be counted. The whole apparatus
their attractions with the positively charged matter. is enclosed in an evacuated chamber to avoid
Thus the atom as a whole is stable and neutral. scattering of α-particles by air molecules.
To explain the observed spectra of elements,
Thomson assumed that slight perturbations of atoms
cause vibrations of the electrons

Fig. - Plum pudding model of an atom. Fig. : α-particle scattering experiment.

about their equilibrium positions. These vibrating Observations. As shown in the graph, drawn
electrons emit electromagnetic radiations of their own between the scattering angle θ and the number N(θ) of
frequency of oscillations. the α-particles scattered at an angle θ, for a very
large number of α-particles.
Failure of Thomson's model.

1. It could not explain the origin of several spectral

series in the case of hydrogen and other atoms.
2. It failed to explain the large angle scattering of
α-particles in Rutherford's experiment.

 ALPHA PARTICLE SCATTERING

EXPERIMENT: (Geiger-Marsden experiment)

On the suggestion of Rutherford, H. Geiger and E.

Marsden, in 1911, performed experiments on the
scattering of α-particles from thin foils and obtained an
important insight into the structure of the atom.
Experimental arrangement:
A schematic arrangement is shown in Figure. A
radioactive source of α-particles like 214 Fig. : Graph of the total number of α-particles
83 Bi is enclosed
in thick lead block, provided with a narrow opening. scattered at different angles θ.

1
The above graph reveals the following facts: and then begins to retrace its path, i.e., it is scattered
1. Most of the α-particles pass straight through the through an angle of 180°. The distance r0 is called the
gold foil or suffer only small deflections. distance of closest approach. At this distance r0, the
2, A few α-particles, about 1 in 8,000, get deflected entire initial kinetic energy of the α-particle gets
through 90° or more. converted into electrostatic potential energy.
3. Occasionally, an α-particle gets rebounded from
the gold foil, suffering a deflection of nearly 180°.
Significance of the result. Rutherford concluded the
following important facts about an atom:
1. As most of the α-particles pass straight through the
foil, so most of the space within atoms must be
empty.
2. To explain large angle scattering of α-particles,
Rutherford suggested that all the positive charge
and the mass of the atom is concentrated in a very Fig: Distance of closest approach.
small region, called the nucleus of the
Now, charge on an α-particle, q1 = + 2e
atom.
Charge on a scattering nucleus, q2= +Ze
3. The nucleus is surrounded by a cloud of electrons
where Z is the atomic number of foil atoms.
whose total negative charge is equal to the total
Initial kinetic energy of α-particle, Ka = 1 mv2
positive charge on the nucleus so that the atom as a
whole is electrically neutral. 2
Electrostatic P.E. of α-particle and nucleus at
distance r0,
The scattering of the α-particles is due to the
𝑈 = 𝑘. = 𝑘𝑞1 𝑞2 = 𝑘 . 2𝑒. 𝑍𝑒
Coulombic repulsion between the positively charged
α-particles and the nuclei. 𝑟0 𝑟0
By conservation of energy, 𝐾𝛼 = 𝑈
1 2𝑍𝑒 2
or 𝐾𝑎 = 2 𝑚𝑣 2 = 𝑘 𝑟0
2𝑘𝑍𝑒 2 4𝑘𝑍𝑒 2
𝑟0 = =
𝐾𝛼 𝑚𝑣 2
1
where 𝑘 = 4𝜋𝜀 = 9 × 109 𝑁𝑚2 𝐶 −2
0
Clearly, the radius of the nucleus must be smaller than
𝑟0 .

 IMPACT PARAMETER

The scattering of an α-particle from a

Fig. : Scattering of α-particles on the Rutherford nucleus depends on its distance of closest approach to
model. the nucleus or on an equivalent length,
called the impact parameter 'b‘ as shown in Fig below
 DISTANCE OF CLOSEST APPROACH:
ESTIMATION OF NUCLEAR SIZE

Suppose an α-particle of mass m and initial

velocity v moves directly towards the centre of the
nucleus of an atom. As it approaches the positive
nucleus, it experiences Coulombic repulsion and its
kinetic energy gets progressively converted into Fig : Impact parameter b and scattering
electrical energy. At a certain distance r0 from the angle θ.
nucleus, the α-particle stops for a moment

2
“The impact parameter is defined as the perpendicular atom as a whole is electrically neutral.
distance of the velocity vector of the α-particle from 4. The electrons revolve around the nucleus in
the centre of the nucleus, when it is far away from the various orbits just as planets revolve around the
atom.” sun. The centripetal force required for their
revolution is provided by the electrostatic
From experiments, it is noticed that: attraction between the electrons and the nucleus.

1. For large impact parameters, the repulsive force Limitations of Rutherford's atomic model:
experienced by the α-particle is weak (because of
its inverse square law character) and the α-particle 1. According to electromagnetic theory, an
passes almost undeflected. accelerated charged particle must radiate
electromagnetic energy. An electron revolving
2. For small impact parameter, the repulsive force is around the nucleus is under continuous acceleration
large and so the α-particle is scattered through towards the centre. It should continuously lose
large angle. energy and move in orbits of gradually decreasing
radii. The electron should follow a spiral path and
3. For a head-on collision, when the α-particle just finally it should collapse into the nucleus. Thus the
aims at the centre of the nucleus, the impact Rutherford's model cannot explain the stability of
parameter b = 0, scattering angle θ =180°, i.e., the an atom.
α-particle is reversed back along its original path.
2. As the electrons spiral inwards, their angular
Thus the shape of the trajectory of the scattered velocities and frequencies would change
α-particles depends on the impact parameter and the continuously, and so the frequency of emitted light
nature of the potential field. will also change. They would emit a continuous
spectrum instead of the actually observed line
Rutherford deduced the following relationship spectrum.
between the impact parameter b and the scattering
angle θ:
θ
1 𝑍𝑒 2 cot2
𝑏=
4𝜋𝜀0 𝐾
Where, K is kinetic energy of alpha particle when it is
far away from atom.
θ
1 𝑍𝑒 2 cot
2
or 𝑏= . 1
4𝜋𝜀0
2
𝑚𝑣 2

 RUTHERFORD’S MODEL OF AN ATOM

AND ITS LIMITATIONS Fig: Spiral path of an accelerated electron.
On the basis of the α-particle scattering experiment,  BOHR'S QUANTISATION CONDITION
Rutherford proposed the following model of an atom :
1. An atom consists of a small and massive central Consider the motion of an electron in a circular
core in which the entire positive charge and almost orbit of radius r around the nucleus of the atom.
the whole mass of the atom are concentrated. This According to de Broglie hypothesis, this electron is
core is called the nucleus. also associated with wave character. Hence a circular
2. The size of the nucleus (≈10-15 m) is very small as orbit can be taken to be a stationary energy state only if
compared to the size of the atom (≈10-10 m). it contains an integral number of de-Broglie
3. The nucleus is surrounded by a suitable number of wave-lengths, i.e., we must have
electrons so that their total negative charge is equal 2πr = n
to the total positive charge on the nucleus and the

3
 𝑛ℎ
........ L = mvr = 2 , n = 1, 2, 3…..
where L, m and v are the angular momentum, mass
and speed of the electron, r is the radius of the
permitted orbit and n is positive integer called
principal quantum number. The above equation is
Bohr's famous quantum condition.
3. Stationary orbits. While revolving in the
permissible orbits, an electron does not radiate
energy. These non-radiating orbits are called
stationary orbits.
Fig.: de Broglie waves and hydrogen atom
4. Frequency condition. An atom can emit or absorb
(a) Only a certain number of (de Broglie)
radiation in the form of discrete energy photons
wavelengths would fit in the electron orbits,
only when an electron jumps from a higher to a
(b) discrete standing waves (characteristic
lower orbit or from a lower to a higher orbit,
frequencies or wavelengths) correspond
respectively. If E1 and E2 are the energies associated
to the discrete orbits in Bohr's theory.
with these permitted orbits, then the frequency v of
𝒉 the emitted or absorbed radiation is given by
But de Broglie wavelength,  = 𝒎𝒗 hv = E2 – E1
𝒏𝒉
∴ 2 r = This is Bohr's frequency condition.
𝒎𝒗
The angular momentum L of the electron must be  BOHR'S THEORY OF HYDROGEN ATOM
𝒏𝒉
L = mvr = , n = 1, 2, 3…..
𝟐  Radii of permitted orbits:
According to Bohr's theory, a hydrogen atom
This is the Bohr's quantisation condition for angular consists of a nucleus with a positive charge Ze, and
momentum. so only those circular orbits can be the a single electron of charge -e, which revolves
allowed stationary states of an electron in around it in a circular orbit of radius r. Here Z is the
which its angular momentum is an integral multiple of atomic number and for hydrogen Z = 1. The
h/2π. electrostatic force of attraction between the
nucleus and the electron is
 BOHR'S ATOMIC MODEL:(POSTULATES) k Ze.e kZe2
F= =
r2 r2
Postulates of Bohr's theory of hydrogen atom.
Bohr proposed an atomic model to explain the spectra
emitted by hydrogen atoms. Bohr's atomic model, so
called Planetary model of the atom, is based on the
following postulates:
1. Nuclear concept. An atom consists of a small and
massive central core, called nucleus around which
planetary electrons revolve. The centripetal force
required for their rotation is provided by the Fig: Bohr's model of hydrogen atom.
electrostatic attraction between the electrons and To keep the electron in its orbit, the centripetal
the nucleus. force on the electron must be equal to the electrostatic
2. Quantum condition. Of all the possible circular attraction.
orbits allowed by the classical theory, the electrons 𝑚𝑣 2 𝑘𝑍𝑒2
are permitted to circulate only in those orbits in Therefore, = 2
𝑟 𝑟
which the angular momentum of an electron is an 𝑘𝑍𝑒 2
ℎ or 𝑚𝑣 2 = ⋯(1)
integral multiple of ; h being Planck's constant. r
2 𝑘𝑍𝑒 2
Therefore, for any permitted orbit, or 𝑟= …(2)
𝑚𝑣 2

4
where 𝑚 is the mass of the electron and 𝑣, its speed 𝑚 and is called fine structure constant. Its value is
an orbit of radius 𝑟. 2𝜋 × 9 × 109 × (1.6 × 10−19 )2 1
Bohr’s quantisation condition for angular momentum 𝛼= 8 −34
=
3 × 10 × 6.63 × 10 137
𝑛ℎ 1 𝑐
𝐿 = 𝑚𝑣𝑟 = ∴ v = 137 . 𝑛
2𝜋 𝐜
𝑛ℎ For first orbit (𝑛 = 1), 𝐯 =
or r= …(3) 𝟏𝟑𝟕
2𝜋𝑚𝑣
From equations (2) and (3), we get Thus the speed of the electron in the innermost
𝑘𝑍𝑒 2 𝑛ℎ orbit is 1/137 of the speed of light in vacuum, while the
= speed in the outer orbits varies inversely with n.
𝑚𝑣 2 2𝜋 𝑚𝑣

2𝜋𝑘𝑍𝑒 2  Energy of the electron.

Or 𝑣= ...(4)
𝑛ℎ
Substituting this value of 𝑣𝑚 equation (3), we get It includes the electron's kinetic energy and the
electrostatic potential energy of the two charges.
𝑛ℎ 𝑛ℎ
𝑟= . Kinetic energy of the electron in nth orbit is
2 𝜋𝑚 2𝜋𝑘𝑍𝑒 2 1 𝑘𝑍𝑒 2
K.E. = 𝑚𝑣 2 = [Using equation (1)]
𝒏𝟐 𝒉𝟐 2 2𝑟
or 𝒓= ...(5) Potential energy of the electron in nth orbit is
𝟒𝝅𝟐 𝒎𝒌𝒁𝒆𝟐 𝑞1 𝑞2 𝑘 𝑍𝑒.(𝑒) 𝑘𝑍𝑒 2
P.E. = 𝑘 = = = −
𝟏 𝑟 𝑟 𝑟
𝒓α & 𝒓 α n2 Hence total energy of the electron in nth orbit is
𝒁
En = K.E. + P.E.
Clearly, the radii of the permitted orbits are
proportional to n2 and increase in the ratio of 𝑘𝑍𝑒 2 𝑘 𝑍𝑒 2 𝑘𝑍𝑒 2
𝑘= − =−
1:4:9:16.... The parameter n is called the principle 2𝑟 𝑟 2𝑟
quantum number.
The radius of the innermost orbit of the hydrogen 𝑘𝑍𝑒 2 4𝜋 2 𝑚𝑘 𝑍𝑒 2
= .
atom, called Bohr's radius can be determined by 2 𝑛2 ℎ2
putting Z = 1 and n = 1 in equation (5) and it is denoted
by r0. [Using equation (5)]
𝒉𝟐
𝒓𝟎 = 𝟐𝝅𝟐 𝒎𝒌𝟐 𝒁𝟐 𝒆𝟒
𝟒𝝅𝟐 𝒎𝒌𝒆𝟐 or 𝑬𝒏 = − …(6)
𝒏𝟐 𝒉𝟐

(6.63 × 10−34 )2 The negative value of the total energy indicates

= 𝑚 that the electron is bound to the nucleus by means of
4𝜋 2 × 9.11 × 10−31 × 9 × 109 × (1.6 × 10−19 )2
electrostatic attraction and some work is required to be
= 5.29 × 10−11 𝑚 ≃ 0.53 Å. done to pull it away from the nucleus.

 SPECTRAL SERIES OF HYDROGEN ATOM

 Speed of electron :
Acc to Bohr's theory, the energy of an electron in
From equation (4), the orbital speed of electron is
the nth orbit of hydrogen atom is given by
𝟐𝝅𝒌𝒁𝒆𝟐
𝒗=
𝒏𝒉 𝟐𝝅𝟐 𝒎𝒌𝟐 𝒁𝟐 𝒆𝟒 𝟏
For hydrogen, 𝑍 = 1, therefore, 𝑬𝒏 = − .
2𝜋𝑘𝑒 2 2𝜋𝑘𝑒 2 𝑐 𝒉𝟐 𝒏𝟐
𝑣= =( )
𝑛ℎ 𝑐ℎ 𝑛 According to Bohr's frequency condition,
𝑐
or 𝑣 = 𝛼. 𝑛 whenever an electron makes a transition from a higher
2𝜋𝑘𝑒 2 energy level n2 to a lower energy level n1, the
The quantity 𝛼 = , is a dimensionless constant difference of energy appears in the form of a photon.
𝑐ℎ

5
 higher energy level n2 = 2, 3, 4 to a lower energy
level n1 =1, we get a set of spectral lines called
Lyman series which belong to the ultraviolet
region of the electromagnetic spectrum.
This series is given by
1 1 1
V = = 𝑅[ 2− ] , 𝑛2 = 2, 3, 4……
𝜆 1 𝑛22
(ii) Balmer series. The spectral series corresponding
Fig: Emission of a spectral line by a to the transitions n2 = 3, 4, 5 to n1, = 2, lies in the
hydrogen atom. visible region and is called Balmer series. For this
series,
The frequency v of the emitted photon is given by 1 1 1
V = = 𝑅[ − ], 𝑛2 = 3, 4, 5…..
𝜆 22 𝑛22
ℎ𝑣 = 𝐸𝑛2 − 𝐸𝑛1 (iii) Paschen series. If n2 = 4,5,6 . and n2 = 3, we get a
2𝜋𝑚𝑘 2 𝑒 4 1 1 spectral series in the infrared region which is called
or ℎ𝑣 = [ − ] Paschen series.
ℎ2 𝑛12 𝑛22
1 1 1
2𝜋 2 𝑚𝑘 2 𝑒 4 1 1 V = = 𝑅[ − ] , 𝑛2 = 4, 5, 6…..
or 𝑣= [ − ] 𝜆 32 𝑛22
ℎ3 𝑛12 𝑛22 (iv) Brackett series. If n2 = 5, 6, 7……and n1 = 4, we
As 𝑐 = 𝑣𝜆, get a spectral series in the infrared region which is
called Brackett series.
therefore wave number v, which ιs the reciprocal of 1 1 1
wavelength λ, is given by V = = 𝑅[ − ] , 𝑛2 = 5, 6, 7…..
𝜆 42 𝑛22
(v) Pfund series. If n2 = 6,7,8…… and n1 = 5, we get a
𝟏 𝒗 𝟐𝝅𝟐 𝒎𝒌𝟐 𝒆𝟒 𝟏 𝟏 spectral series in the infrared region which is called
𝐯= = = [ − ] Pfund series.
𝝀 𝒄 𝒄𝒉𝟑 𝒏𝟐𝟏 𝒏𝟐𝟐 1 1 1
V = = 𝑅[ − ] , 𝑛2 = 6, 7,8…..
𝜆 5 2 𝑛22
𝟐𝝅𝟐 𝒎𝒌𝟐 𝒆𝟒
where R= , is the Rydberg constant and its The greatness of Bohr's theory lies in the fact that it
𝒄𝒉𝟑
7 -1
value is 1.0973 × 10 m . The above equation is the not only successfully explained the already known
Rydberg formula for the spectrum, of hydrogen atom. series of Lyman, Balmer and Paschen but also
This formula indicates that the radiation emitted by predicted two new series in the infrared region which
the excited hydrogen atom consists of certain specific were later on discovered by Brackett (in 1922) and
wavelengths or frequencies, the values of which Pfund in (1924). Neil Bohr was awarded the 1922
depend on quantum numbers n1 and n2. Nobel prize in physics for this work.

Note:
 For any spectral series of H-atom :
n2 = n1 + 1 is called Hα line (Minimum frequency)
n2 = ∞ is called series limit (Maximum frequency)

 ENERGY LEVEL DIAGRAM FOR

HYDROGEN:

It is a diagram in which the energies of the different

stationary states of an atom are represented by parallel
Fig. Spectral series of hydrogen atom. horizontal lines, drawn according to some suitable
As shown in Fig, the origin of the various series in energy scale. Such a diagram illustrates more clearly
the hydrogen spectrum can be explained as follows : the known facts about the stationary states and the
(i) Lyman series. If an electron jumps from any emission or absorption of various spectral lines.

6
 Energy levels of hydrogen. From Bohr's theory, the the ascending order of energy.
total energy of an electron in nth orbit is given by
2𝜋 2 𝑚𝑘 2 𝑍 2 𝑒 4
En =
𝑛2 ℎ2

2𝜋 2 𝑚𝑘 2 𝑒 4 1
En = .
ℎ2 𝑛2
For hydrogen Z = 1, therefore,

Energy of the electron in the first orbit (n = 1) is given

by
E1 =
2 ×(3.14)2 ×9.11×10−31 ×(9×109 )2 ×(1.6×10−19 )4 1
(6.63×10−34 )2
. 2
1
21.76 × 10−19
−19
= −21.76 × 10 𝐽= 𝑒𝑉
1.6 × 10−19
= −13.6𝑒𝑉 [∵ 1𝑒𝑉 = 1.6 × 10−19 J]
Hence we can write,
𝐸1 13.6
𝐸𝑛 = 2 = − 2 𝑒𝑉
𝑛 𝑛

for 𝑛 = 2, 3, 4, etc., we get the energies for the higher

orbits as follows:
−13.6
𝐸2 = = −3.4𝑒𝑉
22
−13.6
𝐸3 = = −1.51𝑒𝑉 Fig: Energy level diagram of hydrogen atom and
32 its various spectral series.
−13.6
𝐸4 = = −0.8𝑆 𝑒𝑉
42
−13.6  LIMITATIONS OF BOHR'S THEORY
𝐸5 = = −0.54𝑒𝑉 Although Bohr's theory could successfully
52
−13.6 explain the spectrum of hydrogen, yet it had the
𝐸6 = = −0.38𝑒𝑉 following shortcomings:
62
Clearly, an electron can have only certain definite 1. This theory is applicable only to hydrogen-like
values of energy while revolving in different orbits. single electron atoms and fails in the case of
This is called energy quantization. atoms with two or more electrons.
The energy state corresponding to n-1, has the 2. In the spectrum of hydrogen, certain spectral lines
lowest energy equal to -13.6 eV. This state or orbit is are not single lines but a group of closed lines
called the ground or normal state of the atom. with slightly different frequencies. Bohr's theory
Normally the electron in the hydrogen atom remains in could not explain these fine features of
the ground state. When the hydrogen atom receives the hydrogen spectrum.
energy from outside by processes such as electron 3. It does not explain why only circular orbits should
collisions, the electron may make transition to some be chosen when elliptical orbits are also possible.
higher energy state like E2, E3, E4, etc. which are called 4. As electrons exhibit wave properties also, so
the excited states. orbits of electrons cannot be exactly defined as in
Figure shows the energy level diagram of the Bohr's theory.
hydrogen atom in which the energies of the various 5. Bohr's theory does not tell anything about the
permitted orbits have been represented by parallel relative intensities of the various spectral lines.
horizontal lines according to some energy scale. The Bohr's theory predicts only the frequencies of
principal quantum number n labels the energy states in these lines.

7
6. It does not explain the further splitting of -particles led to the estimation of the size of the nucleus.
spectral lines in a magnetic field Zeeman effect) or 4. What is meant by impact parameter? How does it
in an electric field (Stark effect). influence the shape of the trajectory of an alpha-particle
in its scattering from a heavy nucleus? What is the
 EXCITATION AND IONISATION POTENTIALS: value of impact parameter for a head-on collision?
5. Calculate the velocity of electron in Bohr's first orbit of
Excitation energy: hydrogen atom. How many times does the electron go
in Bohr's first orbit in one second?
The excitation energy of an atom is defined as
6. Show that the speed of an electron in the innermost
the energy required by its electron to jump from the orbit of H-atom is 1/137 times the speed of light in
ground state to any one of the excited states. vacuum.
First excitation energy of hydrogen 7. Figure shows energy level diagram of hydrogen atom.
= E2 – E1 = -3.4 - (-13.6) = 10.2 eV
Second excitation energy of hydrogen
= E3 – E1 = -1.51 - (-13. 6) = 12.09 eV.

Ionisation Energy:
It is defined as the energy required to knock an
electron completely out of the atom, i.e., the energy
required to take an electron from its ground
(i) Find out the transition which results in the emission
state to the outermost orbit (n = ∞). After the removal of a photon of wavelength 496 nm.
of the electron, the atom is left with positive charge (ii) Which transition corresponds to the emission of
and it is said to ionised. radiation of maximum wavelength? Justify your
Ionisation energy of hydrogen, answer.
= E∞ - E1 = 0 - (-13.6) = 13.6 eV. 8. Calculate the shortest wavelength in the Balmer series
of hydrogen atom. In which region (infrared, visible,
Excitation potential: ultraviolet) of hydrogen spectrum does this
It is that accelerating potential which gives to a wavelength lie?
bombarding electron, sufficient energy to excite the 9. Using the Rydberg formula, calculate the wavelength of
target atom by raising one of its electrons from an the first four spectral lines in the Balmer series of the
hydrogen spectrum.
inner to an outer orbit.
10. Using Rydberg formula, calculate the longest
First excitation potential of hydrogen, wavelengths belonging to Lyman and Balmer series. In
= -3.4-(-13.6) = 10.2 V which region of hydrogen spectrum do these transitions
Second excitation potential of hydrogen, lie?
= -1.51-(-13.6) = 12.09 V
.
Ionisation potential:
It is that accelerating potential which gives to a
bombarding electron, sufficient energy to ionise the
target atom by knocking one of its electrons
completely out of the atom.
Ionisation potential of hydrogen,
= 0-(-13.6) = 13.6 V.

QUESTIONS:

1. Describe Thomson's model of an atom. Why was this

model discarded later on?
2. Describe Rutherford's experiment on the scattering of
a-particles by a nucleus. Explain the observations and
conclusions of the experiment.
3. Explain how Rutherford's experiment on scattering of α