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ATOMS
Important Points:
a) Most of the α- particles were found to pass through the gold- foil without being deviated
from their paths.
b) Some α- particles were found to be deflected through small angles θ < 90° .
c) Few α- particles were found to be scattered at fairly large angles from their initial path
θ < 90°
d) A very small number of α- particles about in 8000 practically retraced their paths or
suffered deflections of nearly 180°
f) The whole positive charge of the atom must be concentrated in a small space which is at the
centre of the atom called nucleus.
1 (2e)( Ze) 1
2. Distance of Closest Approach: . = mα vα2
4π ∈0 r0 2
k ( Ze)e mV 2
=
r2 r
h
ii) The angular momentum of the electron is an integral multiple of , where h is the
2π
h
Planck’s constant. mvr = n , where n = 1, 2,3, 4.... called principal quantum number.
2π
iii) An electron in a stationary orbit has a definite amount of energy. It possesses kinetic
energy because of its motion and potential energy on account of the attraction of the nucleus.
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iv) Energy is radiated or absorbed when an electron jumps from one stationary orbit to
another stationary orbit. This energy is equal to the energy difference between these
two orbits and emitted or absorbed as one quantum of radiation of frequency v given by
hc
Planck’s equation E2 − E1 = hv =
λ
h 2 n2
Radius of the nth orbit rn = .
4π2 ke2 mZ
In general, the radius of the nth orbit of hydrogen like atom is given by
n2
rn = 0.53 Å where n = 1, 2,3,.......
Z
th 2πke2 Z
The velocity of an electron in n orbit Vn = .
h n
n3 n3
The time period of rotation of electron in nth orbit T = i.e T ∝ .
2πω0 Z 2 Z2
2π2 k 2 e 4 mZ 2 4π2 k 2 e4 mZ 2
Kinetic energy K n = .
n2 and potential energy U = −
h 2 n 2
n
h2
2π2 k 2 e4 mZ 2
Total energy of the electron in nth orbit En = −
h 2 n 2
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1. What is the angular momentum of electron in the second orbit of Bohr’s model of
hydrogen atom?
h
A. The angular momentum L = n , where n = 1, 2,3, 4.... called principal quantum number.
2π
2. What is the expression for fine structure constant and what is its value?
e2
A. The term α = is fine structure constant. Where h is Planck’s constant, C is speed
h
4πε 0 c
2π
of light, e is charge of an electron and ε 0 permittivity of free space. The value of
α =7.2973 ×10–3
4. Sharp lines are present in the spectrum of a gas. What does this indicate?
A. When atomic gas or vapour is excited at low pressure by passing electric current through it the
emitted radiation has a spectrum which contains specific wavelengths. This indicates emission
line spectrum.
5. Name a physical quantity whose dimensions are the same as those of angular momentum.
A. Planck’s constant.
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small deflection (θ ≅ 0 ) .
Ze 2 cot(θ / 2)
Impact parameter b = ⇒ b ∝ cot(θ / 2)
1 2
4πε 0 mv
2
For large b, particles will go un-deviated and for small b the a-particle will suffer large
scattering.
8. Among alpha, beta and gamma radiations, which get affected by the electric field?
A. Alpha and beta radiations are affected by the electric field because they are charged particles.
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11. The Lyman series of hydrogen spectrum lies in the ultraviolet region. Why?
A. The Lyman series of hydrogen spectrum lies in UV region is because of the large energies
involved in the transitions. As an illustration, the energy radiated corresponding to the first line
of Lyman series is
[-3.4 - (- 13.6)] eV i.e., 10.2eV, such high energy photons are in the UV region of the
spectrum.
12. Write down a table giving longest and shortest wavelengths of different spectral series.
912 A0
A. Wavelength of spectral line in Hydrogen spectrum for any series is λ =
1 1
n2 − n2
1 2
13. The wavelengths of some of the spectral lines obtained in hydrogen spectrum are 1216 Å,
6463 Å and 9546 Å. Which one of these wavelengths belongs to the Paschen Series?
A. The Paschen series lies in the infrared region. So, the wavelength of any line in the Paschen
Series has to be in between 8220 Å - 18751 Å. Clearly 9546 Å belongs to the Paschen Series.
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(ii) The electron moving around the nucleus continuously experience centripetal acceleration
and therefore it must lose energy continuously. Hence the atom must be able to emit continuous
energy spectrum. But the observed spectrum from the atom is line spectrum.
1. What is impact parameter and angle of scattering? How are they are related to each
other?
A. Impact Parameter: The impact parameter b is defined as the perpendicular distance of the
velocity vector of the α -particle from the centre of the nucleus when it is far away from the
atom.
Angle of Scattering: The angle between the initial and final directions of motion of a
scattered -particle is called angle of scattering.
Target nucleus
A beam of α -particles have nearly same kinetic energy close to the nucleus. (Small impact
parameter) suffers large scattering. In case of head - on collision, the impact parameter is
minimum and the α -particles rebounds back (θ ≅ π ) . For a large impact parameter, the-
particle goes nearly undeviated and has a small deflection (θ ≅ 0) .
The fact that only a small fraction of the number of incident particles rebound back
indicated that the number of α -particles undergoing head on collision is small. This in turn,
implies that the mass of the atom is concentrated in a small volume.
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2. Derive an expression for potential and kinetic energy of an electron in any orbit of a
hydrogen atom according to Bohr’s atomic model. How does P.E. change with increasing
‘n’?
A. Potential Energy:
An electron possesses some potential energy because it is found in the field of nucleus.
−1 ( Ze ) e
P.E. =
4π ∈0 r
n 2 h 2 ε0
But, r = And for hydrogen atom Z = 1,
πme 2 Z
me 4
P .E . = −
4 ε0 2 n 2 h 2
Kinetic Energy:
The Coulomb’s force of attraction between electron and the positively charged nucleus provides
necessary centripetal force.
mv 2 1 Ze2
= .
r 4πε 0 r 2
1 Ze 2
Or mv 2 = .
4 πε0 r
1 2 1 Ze 2
Or mv = .
2 8πε0 r
n 2 h 2 ε0
But, r = And for hydrogen atom Z = 1,
πme 2 Z
me 4
K .E . =
8ε 0 2 n 2 h 2
As the value of ‘n’ increases, the potential energy of the electron increases.
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(i) The theory could not account the spectra of atoms more complex than hydrogen.
(ii) The theory does not give any information regarding the distribution and arrangement of
electrons in atom.
(iii) It does not explain the experimentally observed variations in intensity of the spectral lines of
an element.
(iv) This theory cannot be used to calculate about transitions from one level to another such as the
rate at which they occur or the selection rules which apply to them.
(v) This theory fails for accounting the fine structure of spectral line. Actually it was found that
when spectral lines emitted by an atom are examined, each line is composed of several lines
closely packed together. Bohr’s theory does not throw any light on it.
(vi) This theory cannot be used for the quantitative explanation of chemical bonding.
(vii) The theory fails to give correct result when an electric or magnetic field is applied to the atom.
It is found that when electric or magnetic field is applied to the atom, each spectral line splits
into several lines. The former effect is called as Stark effect while the later as Zeeman Effect.
The minimum distance from the nucleus up to which the a-particle approach, is called the
Distance of Closest Approach (r0).
As the α- particle approaches the nucleus, the electrostatic repulsive force due to the nucleus
increases and kinetic energy of the alpha particle goes on converting into electrostatic potential
energy. When whole of the kinetic energy is converted into electrostatic potential energy, the
particle cannot further move towards the nucleus but returns back on its initial path i.e.
α- particle is scattered through an angle of 180°. The distance of particle from the nucleus in
this stage is called the distance of closest approach.
1 (2e)( Ze) 1
. = mα vα2
4π ∈0 r0 2
1 4Ze2
∴ r0 =
4π ∈0 mα vα 2
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5. Give a brief account of Thomson model of atom. What are its limitations?
A. Thomson’s Atomic Model:
J.J. Thomson gave the first idea regarding structure of atom. According to this model.
1) An atom is a solid sphere in which entire and positive charge and it’s mass is uniformly
distributed and in which negative charge (i.e. electron) are embedded like seeds in watermelon.
6. Describe Rutherford atom model. What are the draw backs of this model?
A. Postulates: The experiments carried out by Geiger and Marsden gave rise to the Rutheroford’s
nuclear model of atom. This model of the atom is also known as Rutherford’s planetary model
of the atom. This model is based on the following postulates.
i) The whole of the positive charge and nearly the entire mass of the atom is concentrated in a
very small volume of the atom called nucleus. The nuclear radius is about (1/10,000) of the
atomic radius.
(ii) The electrons are distributed around the nucleus. So, there is lot of empty space in the
atom.
(iii) The amount of positive charge in the nucleus is equal to the amount of negative charge on
the electrons. So, the atom, as a whole, is an electrically neutral entity.
(iv) Electrons were continuously revolving around the nucleus in circular orbits. The
electrostatic force of attraction provides the necessary centripetal force.
Merits (i) Large angle scattering of alpha-particles through thin foils could be explained.
(ii) The classification of elements in the periodic table on the basis of their atomic number,
instead of atomic weight, was justified.
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(ii) Rutherford model does not envisage any particular values of the radius of the electronic
orbit. This should mean that an electron can emit radiations of all possible frequencies. In
other words, an atom should have a continuous radiation spectrum. But this is contrary to the
experimental result. The spectrum of an atom is a series of sharp lines. Thus, Rutherford
model could not explain the line spectra of the atoms.
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De Broglie tried to explain Bohr’s criterion to select the allowed orbits in which angular
h
momentum of the electron is an integral multiple of . According to his hypothesis, an
2π
electron revolving round nucleus is associated with certain wavelength ‘ λ ’ which depends on
h h
its momentum mv. It is given by λ = =
mv p
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In an allowed orbit, an electron can have an integral multiple of this wavelength. That is the
nth orbit consists of n complete de-Broglie wavelengths i.e. 2πrn = nλ n , where rn is the radius
2πrn 2π
of nth orbit and λ n is the wavelength of nth orbit λ n = (or) λ n = (0.53 × n2 ) Å (or)
n n
λ n = 2πr1n Å , where r1 is radius of first orbit of H -atom.
Figure (a) shows the waves on a string having a wavelength related to the length of the string
allowing them to interfere constructively. If we imagine the string bent into a closed circle we
get an idea of how electrons in circular orbits can interfere constructively as shown in figure
(b). If the wavelength does not fit in to the circumference, the electron interferes destructively
and it cannot exist in such an orbit.
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1. Describe Geiger - Marsden Experiment on scattering of - particles. How is the size of the
nucleus estimated in this experiment?
A. Geiger - Marsden Experiment:
Figure shows a schematic diagram of this experiment. Alpha-particles emitted by a radioactive
source were collimated into a narrow beam by their passage through lead bricks. The beam was
allowed to fall on a thin foil of gold of thickness 2.1×10 −7 m. The scattered α − 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 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.
Observations:
Experimental Observations:
a) Most of the α- particles were found to pass through the gold- foil without being deviated
from their paths.
b) Some α- particles were found to be deflected through small angles θ < 90° .
c) Few α- particles were found to be scattered at fairly large angles from their initial path
θ > 90°
d) A very small number of α- particles about in 8000 practically retraced their paths or suffered
deflections of nearly 180°.
Conclusions:
i) 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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ii) The electrons would be moving in orbits about the nucleus just as the planets do around the
sun.
iii) The distance of closest approach of the particles corresponding to that maximum value of
kinetic energy for which the particle is not scattered back, will be a measure of the radius of the
nucleus.
iv) Rutherford’s experiments suggested the size of the nucleus to be about 10 −15 m to10 −14 m .
Size of the nucleus: The fact that very small fraction of alpha particles undergoes large
scattering indicates that the size of the nucleus is very small.
The fact that a large fraction of particles passes through the foil without deviation indicates
that there is a large distance or empty space between the revolving e- and the nucleus
Size of nucleus (Distance of Closest Approach): Consider an α- particle of mass m moving
directly towards a nucleus with velocity v at any given time. As this α- -particle approaches
the nucleus, its velocity and hence kinetic energy continues to decrease. At a certain distance d
from the nucleus, the α- -particle will stop and then start retracing its path as depicted. This
distance is called the distance of closest approach. At this distance, the kinetic energy of the
α- -particle is transformed into electrostatic potential energy.
1 1 ( Ze)(2e)
If Z be the atomic number of the nucleus, then mv 2 =
2 4πε 0 d
⇒d
1 4 Ze 2
=
4πε 0 mv 2
1
Here = 9 × 109 N m2 C–2
4πε 0
The distance of closest approach is of the order of 10–14 m. So, the radius of the nucleus should
be less than 10–14 m.
n f ( n f < ni ) , the difference of energy is carried away by a photon of frequency ν if such that
hν if = Eni − En f
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stable hence the electron returns to its ground state in about 10–8 seconds. The excess of
energy is now radiated in the form of radiations of different wavelengths. The different
wavelengths constitute spectral series which are characteristics of atom emitting them.
The wavelength of the different members of the series can be found from the following
derivation
According to Bohr’s frequency condition,
hν if = Eni − En f
me 4
Using the equation En = 2 2 2 for En f and Eni , we get
8n ε 0 h
me4 1 1
hν if = 2 2 2 − 2
8ε 0 h n f ni
me 4 1 1
Or vif = − this equation is called Rydberg formula, for the spectrum of the
8ε 02 h3 n 2f ni2
me 4
hydrogen atom. The Rydberg constant R is given by R =
8ε 02 h3c
If we insert the values of various constants in above equation we get R = 1.03 × 107 m −1
If c is the velocity of light in vacuum and is the wavelength of radiation emitted, then
2
c 1 2π 2 me4 1 1
= 2− 2 [ ν = c/ λ ]
λ 4πε 0 h 3
n1 n2
2
1 1 2π 2 me4 1 1
= 2− 2
λ 4πε 0 ch n1 n2
3
Here 1/ λ is the wave number. It is defined as the number of waves in unit distance. It is
denoted by v
2
1 2π 2 me 4 1 1
v = 2− 2
4πε 0
3
ch n1 n2
1 1
v =R 2− 2
n1 n2
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The term is known as Rydberg constant it is denoted by R. Its value is 1.0974 × 107 m–1.
The above relation, known as Rydberg formula for the spectrum of the hydrogen atom, various
spectral lines of different frequencies are produced for different values n1 and n2.
(i) Lyman Series. The spectral lines of this series correspond to the transition of an electron from
some higher energy state to the innermost orbit (n = 1).
For Lyman series, n1= 1 and n2 = 2, 3, 4, ....
The wave numbers and the wavelengths of the spectral lines constituting the Lyman series are
given by
1 1 1
v= = R 2 − 2
λ 1 n2
Lyman series was first predicted by Bohr. This series lies in the ultra-violet region of the
spectrum.
(ii) Balmer series. The spectral lines of this series correspond to the transition of an electron from
some higher energy state to an orbit having n = 2.
For Balmer series, n1= 2, n2 = 3, 4, 5, ....
The wave numbers and the wavelengths of spectral lines constituting the Balmer series are
given by
1 1 1
v= = R 2 − 2
λ 2 n2
Balmer series is so named because it was discovered by Balmer in 1885. The first four lines of
Balmer series lie in the visible region of the spectrum.
(iii) Paschen Series. The spectral lines of this series correspond to the transition of an electron
from some higher energy state to an orbit having n = 3.
For Paschen series, n1= 3, n2 = 4, 5, 6,
The wave numbers and the wavelengths of the spectral lines constituting the Paschen series are
given by
1 1 1
v= = R 2 − 2
λ 3 n2
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Paschen series is so named because it was discovered by Paschen. Just like other series, this
series was first predicted by Bohr. Paschen series lies in the infrared region of the spectrum
and is invisible.
(iv) Bracket Series: The spectral lines of this series correspond to the transition of an electron
from a higher energy state to the orbit having n = 4. For this series, n1= 4 and n2 = 5, 6, 7, ....
The wave numbers and the wavelengths of the spectral lines constituting the Bracket series are
given by
1 1 1
v= = R 2 − 2
λ 4 n2
The wave numbers and the wavelengths of the spectral lines constituting the Pfund series are
given by
1 1 1
v= = R 2 − 2
λ 5 n2
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3. State the basic postulates of Bohr’s theory of atomic spectra. Hence obtain an expression
for the radius of orbit and the energy of orbital electron in a hydrogen atom?
A. Postulates:
1) Electrons revolve only in certain allowed circular orbits called stationary orbits while in these
orbits they do not radiate energy.
h
2) The angular momentum of an electron is an integer multiple of
2π
nh
∴ mvr =
2π
When m = mass of electron, v = linear velocity of the electron, r = radius of the stationary
orbit, h = Planck’s constant and n = 1, 2,3, 4……. whole number integer. Angular momentum
and energy both are quantized for an electron.
3) An orbiting electron emits energy in the form of electromagnetic waves when it jumps from
outer stationary orbit to the inner orbit.
E2 − E1 = hv Where v is the frequency of radiation.
4) The coulomb force of attraction between the nucleus and the electron supplies the necessary
centripetal force
1 ( Ze)(e) mv 2
=
4π ∈0 r 2 r
Radius of Orbit:
The coulomb force of attraction between the nucleus and the electron supplies the necessary
centripetal force
1 ( Ze )( e ) mv 2 1 Ze2
= Or = mvn2
4π ∈0 rn 2 rn 4π ∈0 rn
nh nh
But, mvrn = (or) vn =
2π 2π nrn
1 Ze 2 n 2 h2
∴ = m×
4π ∈0 rn 4π m 2 rn2
∈0 h 2 n2
( )
2
−10 n
rn = = 0.53 × 10 m
π me Z
2
Z
n2 0
Or rn = 0.53 × A For H 2 atom z = 1
Z
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∴ rn = 0.53n 2 Or rn ∝ n 2
−1 ( Ze ) e
P.E. =
4π ∈0 r
n 2 h 2 ε0
But, r = and for hydrogen atom Z = 1 ,
πme 2 Z
me 4
P .E . = −
4 ε0 2 n 2 h 2
Kinetic Energy:
The Coulomb’s force of attraction between electron and the positively charged nucleus
provides necessary centripetal force.
mv 2 1 Ze2
= .
r 4πε 0 r 2
1 Ze 2
⇒ mv 2 = .
4 πε0 r
1 1 Ze 2
⇒ mv 2 = .
2 8πε0 r
n 2 h 2 ε0
But, r = And for hydrogen atom Z = 1 ,
πme 2 Z
me 4
K .E . =
8ε 0 2 n 2 h 2
Total Energy:
Total energy = P.E. + K.E.
me 4 me 4 me 4
∴T .E . = − + = −
4 ε 0 2 n 2 h 2 8ε 0 2 n 2 h 2 8ε 0 2 n 2 h 2
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PROBLEMS
1. The radius of the first electron orbit of a hydrogen atom is 5.3 × 10 −11 m . what is the radius of
the second orbit?
Sol: r1 = 5.3 × 10−11 m, n1 = 1
n2 = 2, r2 = 2
r2 n22
r ∝ n2 ⇒ =
r1 n12
2
r2 2
⇒ = =4
5.3 × 10−11 1
2. Determine the radius of the first orbit of the hydrogen atom. What’ would be the velocity
and frequency of the electron in the first orbit?
nh
Velocity of electron in nth orbit, v n =
2π mrn
4π 2 m ( 0.53) n 4 4π 2 m ( 0.53) n3
2 2
mr 2 4π 2
f = ⇒ f = ⇒ f = = 6.6 × 1015 Hz (n = 1)
nh nh h
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3. The total energy of an electron in the first excited state of the hydrogen atom is -3.4eV.
What is the potential energy of the electron in this state?
Sol: TE1 = −3.4 ev
= −6.8 ev
4. The total energy of an electron in the first excited state of the hydrogen, atom is -3.4eV.
What is the kinetic energy of the electron in this state?
ke2 ke 2
A. Ek = ,E = − In the first excited state
2r 2r
Ek = - E = - (-3.4) eV = 3.4 eV
5. Find the radius of the hydrogen atom in its ground state. Also calculate the velocity of the
electron in n= 1 orbit?
nh
Velocity of electron in nth orbit, v n =
2π mrn
h
For first orbit, n = 1 ∴ v1 =
2π m × 0.53 × 10−10
En2 = Eα = o
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−13.6 13.6
E = o− 2 = = 3.4 ev.
n 4
8. The wavelength of the first member of Lyman Series is 1216 A. Calculate the wavelength
of second member of Balmer series?
Sol: wavelength of different members of Lyman series is given by
1 1 1
= R 2 − 2
λ 1 n2
( n2 = 2,3, 4,.....)
1 1 1 3 R 4
⇒ = R − = ⇒ λα = = 1216 Ao
λα 1 4 4 3R
1 1 1
= R 2 − 2
λ 2 n2
Where n2 = 3, 4,5,.....
1 1 1 3R 16
∴ = R − = ⇒ λβ =
λβ 4 16 16 3R
16
λβ
∴ = 3R = 4 ⇒ λβ = 4λ α = 4 (1216 ) = 4864 Ao
λα 4
3R
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9. The wavelength of first member of Balmer Series is 6563 Ao. Calculate the wavelength of
second member of Lyman series?
1 1 1
Sol: From = R 2 − 2
λ 2 n2
1 1 1 5R 36
= R − = OR λ α = = 6563 Ao
λα 4 9 36 5R
1 1 1
From = R 2 − 2
λ 1 n2
1 1 8R
= R 1 − =
λβ 9 9
9
9 λβ 8 R 5
∴ λβ = ⇒ = =
8R λα 36 32
5R
5 5
λβ = λβ = × 6563 = 1025.5 Ao
32 32
10. The second member of Lyman Series in hydrogen spectrum has wavelength 5400 Å. Find
the wavelength of first member?
1 1 1
A. = R 2 − 2
λ n1 n2
Let and be the wavelengths of the first and second lines respectively.
1 1 1 1 3
= R 2 − 2 = R 1 − = R
λ1 1 2 4 4
1 1 1 1 8
= R 2 − 2 = R 1 − = R
λ2 1 3 9 9
1 λ1 1 8 4 32
× = = R× =
λ2 1 λ2 9 3R 27
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32 32
λ1 = × λ2 = × 5400 Å = 6400 Å
27 27
11. Calculate the shortest wavelength of Balmer Series. Or calculate the wavelength of the
1 1 1 1 R R
= R 2 − 2 Or = or λ =
λ 2 ∞ λ 4 4
4
λ= m = 3.646 × 10−7 m
10970000
12. Using the Rydberg formula, calculate the wavelength of the first four spectral lines in the
Balmer series of the hydrogen spectrum.
A. The Rydberg formula is
hc 1 2 2 1 1
= mc α 2 − 2
λif 2 n ni
f
The wavelength of the first four lines in the Balmer series correspond to transitions from
hc
λi 2 = m
−19 1 1
21.76 × 10 × − 2
4 ni
3.653ni 2 −7 3653ni 2
× 10 m = Å
(ni 2 − 4) (ni 2 − 4)
Substituting ni = 3, 4, 5 and 6, we get λ32 = 6575 Å , λ32 = 4870 Åλ52 = 4348 Åand λ62 = 4109 Å
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