CHAPTER: 12 ATOMS

INTRODUCTION
➢ In 1897, the experiments on electric discharge through gases carried out by the English physicist J. J.
Thomson revealed that atoms of different elements contain negatively charged constituents
(electrons) that are identical for all atoms.
➢ Atoms on a whole are electrically neutral. Therefore, an atom must also contain some positive
charge to neutralize the negative charge of the electrons.
➢ 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 and the
negatively charged electrons are embedded in it like seeds in a watermelon. This model was called
plum pudding model of the atom.
➢ Ernest Rutherford in 1906, proposed a classic experiment of scattering of these α-particles by atoms
to investigate the atomic structure. This was well known as Rutherford’s planetary model of atom
(Nuclear Model of Atom). According to this the entire positive charge and most of the mass of the
atom is concentrated in a small volume called the nucleus with electrons revolving around the
nucleus just as planets revolve around the sun.
➢ But, it failed to explain emission of light by atoms by discrete wavelengths.

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

At the suggestion of Ernst Rutherford, in 1911, H. Geiger and E. Marsden performed an experiment.
Observation:
➢ They directed a beam of 5.5 MeV α-particles
emitted from a 214
83Bi radioactive source at a
thin metal foil made of gold.
➢ 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.
➢ These flashes may be viewed through a
microscope and the distribution of the
number of scattered particles may be
studied as a function of angle of scattering.
➢ A graph of the total number of α-particles scattered at different angles, in a given interval of time, is
plotted.
➢ Only about 0.14% of the incident α-particles scatter by more than 1º; and about 1 in 8000 deflect by
more than 90º.

Conclusion:
➢ Graphical representation suggest us that atom has a small, dense, positively charged nucleus.
➢ Rutherford argued that, to deflect the α-particle backwards, it must experience a large repulsive
force. This force could be provided if the greater part of the mass of the atom and its positive
charge were concentrated tightly at its centre.
➢ Thus according to Rutherford’s nuclear model of the atom, the entire positive charge and most of
the mass of the atom are concentrated in the nucleus with the electrons some distance away.

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➢ The electrons would be moving in orbits about the
nucleus just as the planets do around the sun.
➢ Rutherford’s experiments suggested the size of the
nucleus to be about 10–15 m to 10–14 m and the
electrons would seem to be at a distance from the
nucleus of about 10,000 to 100,000 times the size
of the nucleus itself. Thus, most of an atom is
empty space.
➢ By considering α-particles are nuclei of helium
atoms and, therefore, carry two units, 2e, of
positive charge and have the mass of the helium
atom.
➢ The charge of the gold nucleus is Ze, where Z is the
atomic number of the atom; for gold Z=79.
➢ The trajectory of an alpha-particle can be computed by using Newton’s second law of motion and
the Coulomb’s law for electrostatic force of repulsion between the alpha-particle and the positively
charged nucleus.
The magnitude of this force is
1 (2e)(Ze)
F=
4πε0 r2
where r is the distance between the α-particle and the nucleus.
➢ The force is directed along the line joining the α-particle and the nucleus.

Alpha-particle trajectory

• The trajectory traced by a α-particle depends on the impact parameter, b of collision.

• A given beam of α-particles has a distribution of impact parameters b, so that the beam is
scattered in various directions with different probabilities.
• α-particle close to the nucleus suffers large scattering.
• In case of head-on collision, the impact parameter is minimum and the α-particle rebounds
back (θ=π).
• For a large impact parameter, the α-particle goes nearly undeviated and has a small deflection
(θ=0).
• Small fraction of incident particles rebound back indicates that the number of α-particles
undergoing head on collision is small.
• This implies that the mass of the atom is concentrated in a small volume.
• Rutherford scattering therefore, is a powerful way to determine an upper limit to the size of the
nucleus.

Note: The impact parameter is the perpendicular distance of the initial velocity vector of the α-
particle from the centre of the nucleus.
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Electron orbits
The Rutherford nuclear model of the atom which involves classical concept
of the atom as an electrically neutral sphere consisting 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 requisite centripetal force (Fc) to keep them
in their orbits.
Thus, for a dynamically stable orbit in a hydrogen atom
Fe = Fc
mv2 1 e2
=4πε
r 0r2
1 e2
mv 2 =4πε r
………1
0
Thus the relation between the orbit radius and the electron velocity is
1 e2
r=
4πε0 mv2
The kinetic energy (K) and electrostatic potential energy (U) of the electron in hydrogen atom are
1
K= mv2
2
By substituting equation 1
1 e2
K= ………2
8πε0 r
Potential energy of the electron
U= Potential at a distance ‘r’ from the nucleus x charge on the electron
U=Vq
1 e
U= X -e
4πε0 r
1 e2
U=− 4πε r ………3
0
Total energy possessed by the electron
E=K+U
By using equation 2 and 3
1 e2 1 e2
E=8πε − 4πε
0 r 0 r
𝟏 𝐞𝟐
E=− 𝟖𝛑𝛆 𝐫
𝟎
The total energy of the electron is negative.
This implies the fact that the electron is bound to the nucleus.

ATOMIC SPECTRA
• Each element has a characteristic spectrum of radiation.
• 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.
• A spectrum which contains certain specific bright lines on a dark background is termed as
emission line spectrum.
• The spectrum emitted by atomic hydrogen is as shown in figure
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 • 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.
• Spectrum of electromagnetic radiation obtained after passing through certain absorbing
material is called the absorption spectrum.

Spectral series of Hydrogen:

• Different elements emit different frequencies of the light in some regular pattern.
• Similarly Hydrogen also exhibits a pattern of spectrum.
• Spacing between lines within certain sets of the hydrogen spectrum decreases as the
wavelength decreases (Frequency increases).
• Such a set of spectrum is called spectral series.
• Such series was observed by a Swedish school teacher Johann Jakob Balmer in the visible region
of the hydrogen spectrum.
• This series is called Balmer series.
I. Balmer Series:
• This series consists of all wavelength emitted due to the transition of the electron from the
higher allowed orbit to the 2nd orbit.
• The line with the longest wavelength, 656.3 nm in the red is called Hα.
• The next line with wavelength 486.1 nm in the bluegreen is called Hβ.
• The third line 434.1 nm in the violet is called Hγ; and so on.
• As the wavelength decreases, the lines appear closer together and are weaker in intensity.
• Balmer found a simple empirical formula for the observed wavelengths

where λ is the wavelength, R is a constant called the Rydberg constant, and n represents the
allowed orbit which may have integral values 3, 4, 5, etc.
The value of R is 1.097 × 107m-1
This equation is also called Balmer formula.

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 • To obtain the wavelength of the Hα line(656.3 nm): one should take n=3
Similarly for the wavelength of the Hβ line(486.1 nm): one should take n=4
& for the wavelength of the Hγ line(434.1 nm): one should take n=5
• For n =∞, which is called limit of the series, wavelength obtained is λ= 364.6 nm.
This is the shortest wavelength in the Balmer series.
• Beyond this limit, no further distinct lines appear, instead only a faint continuous spectrum is
seen.
II. Lyman series:
• This series consists of all wavelengths emitted due to the transition of the electrons from the
higher allowed orbits to the 1st orbit.
• This series lies in ultraviolet region of the hydrogen spectrum.
• Emperical formula for the observed wavelength is

where λ is the wavelength, R is a constant called the Rydberg constant, and n represents the
allowed orbit which may have integral values 2, 3, 4, 5, etc.
The value of R is 1.097 × 107m-1
• For n =∞, which is called limit of the series, wavelength obtained is λ= 91 nm.
This is the shortest wavelength in the Lyman series.
III. Paschen series:
• This series consists of all wavelengths emitted due to the transition of the electrons from the
higher allowed orbits to the 3rd orbit.
• This series lies in Infrared region of the hydrogen spectrum.
• Emperical formula for the observed wavelength is

where λ is the wavelength, R is a constant called the Rydberg constant, and n represents the
allowed orbit which may have integral values 4, 5, etc.
The value of R is 1.097 × 107m-1
• For n =∞, which is called limit of the series, wavelength obtained is λ= 820 nm.
This is the shortest wavelength in the Paschen series.
IV. Brackett series:
• This series consists of all wavelengths emitted due to the transition of the electrons from the
higher allowed orbits to the 4th orbit.
• This series lies in Infrared region of the hydrogen spectrum.
• Emperical formula for the observed wavelength is

where λ is the wavelength, R is a constant called the Rydberg constant, and n represents the
allowed orbit which may have integral values 5, 6, 7 etc.
The value of R is 1.097 × 107m-1
V. Pfund series:
• This series consists of all wavelengths emitted due to the transition of the electrons from the
higher allowed orbits to the 5th orbit.
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 This series lies in Infrared region of the hydrogen spectrum.
• Emperical formula for the observed wavelength is

where λ is the wavelength, R is a constant called the Rydberg constant, and n represents the
allowed orbit which may have integral values 6, 7, 8 etc.
The value of R is 1.097 × 107m-1
Note:
Balmer formula may be written in terms of frequency as fallows
w.k.t c=υλ
c
λ=ν
1 ν
λ c
=
Hence for Balmer formula
ν 1 1
=𝑅 (22 − n2 )
c
1 1
ν=𝑅𝑐 (22 − n2 )
This above formula holds good for spectrum of hydrogen and hydrogen like elements (Singly ionized
helium, doubly ionized lithium etc)

BOHR MODEL OF THE HYDROGEN ATOM

Niels Bohr in 1913 combined the idea of Rutherford’s Atomic Model and Quantum Concepts to give the
following postulates.
These are:
(i) Bohr’s first postulate was that an electron in an atom could 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.
(ii) Bohr’s second postulate states that the electron revolves around the nucleus only in those orbits
ℎ
for which the angular momentum is some integral multiple of
2𝜋
–34
where h is the Planck’s constant (= 6.6 x10 J s).
𝑛ℎ
Thus the angular momentum (L) of the orbiting electron is quantized. That is L =
2𝜋
(iii) Bohr’s third postulate states that an electron might make a transition from one of its specified
non-radiating orbits to another of lower energy. When it does so, 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 = Ei – Ef
where Ei and Ef are the energies of the initial and final states and Ei > Ef .
Expression for the Orbital Velocity, Radius and Energy of an electron of the Hydrogen Atom:
To calculate r, Bohr’s second postulate about the angular momentum of the electron is used. The
angular momentum L is given by
L = mvr

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Bohr’s second postulate of quantization says that the allowed values of angular momentum are
ℎ
integral multiples of
2𝜋
For nth possible orbit, rn is the radius of an orbit. Then angular momentum is written as
𝑛ℎ
Ln = mvnrn = ………..1
2𝜋
where vn is the speed of moving electron in the nth orbit.
The allowed orbits are numbered 1, 2, 3 ..., according to the values of n, which is called the principal
quantum number of the orbit.
Thus, for a dynamically stable orbit in a hydrogen atom

Fe = Fc [The electrostatic force of attraction, (Fe) between the revolving electrons and the
nucleus provides the requisite centripetal force (Fc) to keep them in their orbits.]

mv2n 1 e2
=4πε 2
rn 0 rn

1 e2
mvn2 =4πε ………2
0 rn

Thus the relation between the orbit radius and the electron velocity is

1 e2
rn =
4πε0 mv2n

2 1 e2
vn =4πε mr
0 n
v
𝐞
𝐯𝐧 = ………3
√𝟒𝛑𝛆𝟎 𝐦𝐫𝐧
-e
Substituting equation 3 in equation 1, we have
e 𝑛ℎ +e
m rn = r
√4πε0 mrn 2𝜋

Taking Square at both sides

e2 𝑛 2 ℎ2
𝑚2 4πε mr r2
n = (2𝜋)2
0 n

𝑛2 ℎ 2 4πε0 mrn
rn2 = (2𝜋)2 𝑚2 e2

𝒏𝟐 𝒉𝟐 𝟒𝛑𝛆
𝐫𝐧 = (𝟐𝝅)𝟐 𝐦𝐞𝟐𝟎 ………4

Thus equation 3 and equation 4 gives orbital speed and radius of the nth orbit.
The radius of the innermost orbit (n=1) can be obtained as
𝒉𝟐 𝛆𝟎
𝐫𝟏 = 𝝅𝐦𝐞𝟐
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This is called the Bohr radius, represented by the symbol a 0.
𝒉𝟐 𝛆𝟎
a0=𝝅𝐦𝐞𝟐
By substituting the values a0=5.29x10-11m.
Thus total energy of the electron in the stationary states of the hydrogen atom can be obtained by
substituting the value of orbital radius
𝟏 𝐞𝟐
E=− 𝟖𝛑𝛆 𝐫 {By Rutherford Atom model}
𝟎

𝐞𝟐 (𝟐𝝅)𝟐 𝐦𝐞𝟐
𝐄𝐧 =− 𝟖𝛑𝛆
𝟎 𝒏𝟐 𝒉𝟐 𝟒𝛑𝛆𝟎

𝐦𝐞𝟒
𝐄𝐧 =− 𝟖𝒏𝟐 𝒉𝟐 𝛆𝟎 𝟐

By substituting the values

𝟐.𝟏𝟖𝐱𝟏𝟎−𝟏𝟖
𝐄𝐧 = − J
𝒏𝟐
Atomic energies are often expressed in electron volt (eV). Therefore by dividing by 1.6x10 -19J
𝟏𝟑.𝟔
𝐄𝐧 = − 𝒏𝟐 eV
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 of a Hydrogen Atom:

• The energy of an atom is the least (largest negative value) when its electron is revolving in an orbit
closest to the nucleus i.e., at n = 1.
• The lowest state of the atom is called the ground
state.
• In ground state electron revolving in the orbit of
smallest radius called the Bohr radius, a0.
• The energy of this state (n = 1), E1 is –13.6 eV.
• Thus, the minimum energy required to free the
electron from the ground state of the hydrogen atom
is 13.6 eV.
• Minimum energy required to free the electron from
the atom is called the ionisation energy of the atom.
• At room temperature, most of the hydrogen atoms
are in ground state.
• When a hydrogen atom receives energy by external
means, 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.
• Energy required by the atom to raise the electron to
higher energy state is called Excitations Energy.
• Energy required to excite an electron in hydrogen
atom to its first excited state, is an energy equal to E2
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 – E1 = –3.40 eV – (–13.6) eV = 10.2 eV.
Similarly, for second excited state, E3 – E1 = 12.09 eV and so on.
• From these excited states the electron can then fall back to a state of lower energy, emitting a
photon in the process.
• The principal quantum number n labels the stationary states in the ascending order of energy.
• In this diagram, the highest energy state corresponds to n =∞ and has an energy of 0 eV.

THE LINE SPECTRA 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 𝑛𝑖 to the lower energy state with quantum number 𝑛𝑓 (𝑛𝑓 < 𝑛𝑖 ),
the difference of energy is carried away by a photon of frequency νif such that
hνif =Eni − Enf ……..1
Using Total energy of the hydrogen atom formula
Energy at higher energy state
𝐦𝐞𝟒
Eni =− ……..2
𝟖𝒏𝟐𝒊 𝒉𝟐 𝛆𝟎 𝟐

Energy at lower energy state

𝐦𝐞𝟒
Enf =− ……..3
𝟖𝒏𝟐𝒇 𝒉𝟐𝛆𝟎 𝟐

Substituting equation 2 and 3 in 1 we get

𝐦𝐞𝟒 𝐦𝐞𝟒
hνif =− 𝟐 − (− )
𝟖𝒏𝟐𝒊 𝒉𝟐 𝛆𝟎 𝟖𝒏𝟐𝒇 𝒉𝟐𝛆𝟎 𝟐

𝐦𝐞𝟒 𝐦𝐞𝟒
hνif = 𝟐 −
𝟖𝒏𝟐𝒇 𝒉𝟐𝛆𝟎 𝟖𝒏𝟐𝒊 𝒉𝟐 𝛆𝟎𝟐

𝐦𝐞𝟒 𝟏 𝟏
hνif = ( − )
𝟖𝒉𝟐 𝛆𝟎 𝟐 𝒏𝟐𝒇 𝒏𝟐𝒊

𝐦𝐞𝟒 𝟏 𝟏
νif =𝟖𝒉𝟑 𝛆 𝟐 (𝒏𝟐 − 𝒏𝟐𝒊
)
𝟎 𝒇
𝑐 𝐦𝐞𝟒 𝟏 𝟏
= ( − )
𝜆𝑖𝑓 𝟖𝒉𝟑 𝛆𝟎 𝟐 𝒏𝟐𝒇 𝒏𝟐𝒊
1 𝐦𝐞𝟒 𝟏 𝟏
𝜆𝑖𝑓
=𝟖𝒉𝟑 𝛆 𝟐 𝐜 ( 𝒏𝟐 − 𝒏𝟐𝒊
)
𝟎 𝒇
1 𝟏 𝟏
=𝐑 (𝒏𝟐 − )
𝜆𝑖𝑓 𝒇 𝒏𝟐𝒊
This equation is called Rydberg formula for the spectrum of the hydrogen atom.
Note:
If we take 𝑛𝑓 = 2 and 𝑛𝑖 = 3, 4, 5...,
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 𝐦𝐞𝟒
Then Rydberg constant R is readily identified to be R =
𝟖𝒉𝟑 𝛆𝟎 𝟐𝐜
and its value is 1.097x107m-1

DE BROGLIE’S EXPLANATION OF BOHR’S SECOND POSTULATE

OF QUANTISATION
Second postulate of the Bohr’s Atom Model states that
“The angular momentum of the electron orbiting around the
𝑛ℎ
nucleus is quantized (that is, 𝐿𝑛 = ; n = 1, 2, 3 …). The French
2𝜋
physicist Louis de Broglie explained this puzzle in 1923, ten
years after Bohr proposed his model.
de Broglie’s hypothesized that material particles, such as
electrons, also have a wave nature and experimentally verified
by C. J. Davisson and L. H. Germer in1927.
• Louis de Broglie argued that the electron in its circular orbit, as proposed by Bohr, must be seen as a
particle wave.
• These particle waves too can lead to standing waves under resonant conditions.
• These wave formations are integral in nature under resonant condition.
• For an electron moving in 𝑛𝑡ℎ circular orbit of radius 𝑟𝑛 , the total distance is the circumference of the
orbit, i.e., 2π𝑟𝑛 .
Thus
2π𝑟𝑛 =nλ 
where ‘λ’ is the de Broglie wavelength of the electron moving in 𝑛𝑡ℎ orbit.
h
• w.k.t  = (
p
h
= (de Broglie relation)
mv
For electron in the nth orbit
h
= 
mvn

Substituting equation 2 in equation 1 we have

h
2π𝑟𝑛 =n
mvn
nh
mvn 𝑟𝑛 =
2π
nh
Ln= 2π
This is the quantum condition proposed by Bohr for the angular momentum of the electron.
Thus de Broglie hypothesis provided an explanation for Bohr’s second postulate for the quantization of
angular momentum of the orbiting electron.

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Limitations of Bohr’s Atom Model:
They are:
(i) The Bohr model is applicable to hydrogen like atoms. It cannot be extended even to mere
two electron atoms such as helium. Because each electron interacts not only with the
positively charged nucleus but also with all other electrons. The formulation of Bohr model
involves electrical force between positively charged nucleus and electron. It does not
include the electrical forces between electrons which necessarily appear in multi-electron
atoms.
(ii) While the Bohr’s model correctly predicts the frequencies of the light emitted by hydrogenic
atoms, the model is unable to explain the relative intensities of the frequencies in the
spectrum.

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