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INDIA’S FIRST NOTES WITH MOST
IMPORTANT SUBTOPICS MARKED
ACCORDING TO JEE MAINS
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SAMPLE PROBLEMS FOR

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UNDERSTANDING WHICH ARE

HIGHLY EXPECTED IN JEE MAINS
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EXAM
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 Chapter - 3
ATOMIC STRUCTURE
3.1 Introduction
Matter is constituted by very small particles which can not exist in free state in most of the cases
called atoms. These atoms are constituted further by some fundamental particles called electrons;
protons and neutrons. Present chapter deals with the structure of atom in terms of these fundamental
particles and influence of electronic arrangement on the properties of the molecules.

Nature of cathode rays

(i) They travel in straight lines away from the cathode with very high velocities ranging from
107 – 109 cm per second.

(ii) They produce a green glow when strike the wall beyond anode.
JE

(iii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.
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(iv) They are deflected by the electric and magnetic fields. When the rays are passed between two
electrically charged plates, these are deflected towards the positively charged plate.

(v) When a small pin wheel is placed in their path, the blades of the wheel are set in motion this
indicates cathode rays consists of material particles which have mass and velocity.
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(vi) When they fall on material having high atomic mass, new type of penetrating rays of very small
wavelengths are emitted which are called X-rays.
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(vii)They affect the photographic plate.

(viii) They can penetrate through thin foils of solid materials and cause ionisation in gases through
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which they pass.

(ix) The nature of the cathode rays is independent of:

(a) The nature of the cathode and.
(b) The gas in the discharge tube.

(x) The negatively charged particles which constitute cathode rays are called electrons.

Rest mass of electron: The rest mass of electron is found to be 9.1096 × 10–31 kg.

Mass of moving electron : The mass of moving electron is given by the relation.

rest mass of electron

Mass of moving electron = 2
v
1   
c
Where v is the velocity of the electron and c is the velocity of light. When v becomes equal to c mass
of moving electron becomes infinity.

[ 65 ]
Atomic Structure

Charge on electron : The charge on electron is found to be –1.6022 × 10–19 coulombs. Since the
electron has the smallest charge known, it is designated as unit negative charge.

e/m of electron : Charge to mass ratio of the electron is found to be –1.7588 × 108 C per g.

Nature of Anode Rays

(i) These rays travel in straight lines and cast shadow of the object placed in their path.

(ii) Like cathode rays, they also rotate the wheel placed in their path and also have heating effect.
Thus, the rays possess kinetic energy.

(iii) The rays produce fluorescence on zinc sulphide screen.

(iv) The rays are deflected by electric and magnetic field in the direction opposite to that of cathode
rays. These rays are attracted towards the negatively charged plate showing that they carry
positive charge.

(v) They can pass through thin metal foils.

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(vi) They can produce ionisation in gases.

(vii)They are capable of producing physical and chemical changes.

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(viii) Positive particles in these rays have e/m values much smaller than that of the electron.

(ix) e/m value is dependent on the nature of the gas taken in the discharge tube. Particles of highest
e/m are obtained when hydrogen is taken in the discharge take. These particles of highest e/m
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are called proton.

Mass of proton: Mass of proton is found to be 1.672 × 10–27 kg or 1.0072 amu. (amu = atomic mass
unit)
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Charge on proton : Charge on proton is same as charge on electron (i.e., +1.6022 × 10–19 coulombs)
in magnitude but opposite in sign.

e/m of proton: Charge to mass ratio of proton is found to be +9.579 × 104 coulombs per g. Which
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is very small as compared to electron.

Rutherford’s -scattering experiment

Rutherford carried out a series of experiments using
-particles. A beam of -particles was directed against a
thin foil of gold, platinum, silver or copper. The foil was
surrounded by a circular fluorescent zinc sulphide screen.
Whenever an -particle struck the screen, it produced a
flash of light.
The following observations were made:
(i) Most of the -particles went straight without suffering any deflection.
(ii) A few of them got deflected through small angles.
(iii) A few of them (about one in 20,000) returned back towards its source.

[ 66 ]
Atomic Structure

Following conclusions were drawn from the above observations:

(i) Since most of the particles went straight through the metal foil undeflected, it indicates most of
space of an atom is empty.

(ii) A few of the -particles were deflected from their original paths through moderate angles, it
was concluded that whole of the positive charge is concentrated and the space called nucleus. It
is supposed to be present in the centre of the atom.

(iii) A very few of the -particles suffered strong deflections or even rebound on their path due to
maximum repulsion and minimum Impact parameter.

Mosley’s Experiment and the concept of Atomic Number : Moseley studied the x-ray spectra
of 38 different elements, starting from aluminium to gold. He measured the frequency of principal
lines of a particular series (the -lines in the k-series) of the spectra. He observed that the frequency
of the particular spectral line was related with the serial number of the element in the periodic table
which he termed as atomic number (Z). He suggested the following relationship.
JE

v  a ( Z  b)
(a) (b)
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20 20
v/108 s–1

–1
v/10 s
15 15
8
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10 10

5 5
20 40 60 80 100 10 20 30 40
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Relative Atomic Mass (A) Atomic Number (Z)

Where v = frequency of X-rays, Z = atomic number, a and b are constants. When the values of
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square root of the frequency were plotted against atomic numbers of the elements producing X-rays,
a straight line was obtained.

It was pointed out that the atomic number of an element is equal to the total positive charge contained
in the nucleus.

(i) Atomic number of the element = Serial number of the element in periodic table.
= Charge on the nucleus of the atom of the element
= Number of protons present in the nucleus of the atom of
the element
= Number of extranuclear electrons present in the atom of
the element.

(ii) They produce a green glow when strike the wall beyond anode.

(iii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.

[ 67 ]
Atomic Structure

Chadwick’s Experiment and discovery of Neutron : Chadwick bombarded beryllium with a

stream of -particles. He observed that penetrating radiations were produced which were not affected
by electric and magnetic fields. These radiations consisted neutral particles, which were called
neutrons.

9 Be  4 He  12 C  1n
4 2 6 0
beryllium α- particle carbon neutron

The mass of the neutron was determined. It was 1.675 × 10–24 g, i.e., nearly equal to the mass of
proton.

Thus, a neutron is a sub-atomic particle which has a mass 1.675 × 10–24 g approximately 1
amu or nearly equal to the mass of proton or hydrogen atom and carrying no electrical
charge. The e/m of neutron is zero.

Rutherford’s Model of Atom : Rutherford proposed a model of the atom which is known as
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nuclear atomic model. According to this model.

(i) An atom consists of heavy positively charged nucleus where all the protons and neutrons are
present. The magnitude of the positive charge on the nucleus is different for different atoms.
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(ii) The volume of the nucleus is very small and is only a minute fraction of the total volume of the
atoms.
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Diameter of atom 108 cm

 13  105.
Diameter of the nucleus 10 cm
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Thus, the diameter of an atom is 100,000 times the diameter of the nucleus.

The radius of a nucleus is proportional to the cube root of the mass number.

Radius of the nucleus = 1.33 × 10–13 × A1/3 cm

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where A is the mass number.

(iii) There is an empty space around nucleus called extranuclear part. In this part electrons are
present. The number of electrons in an atom is always equal to number of protons present in the
nucleus. The volume of the atom is about 1015 times the volume of the nucleus.

Volume of the atom (10 8 ) 3 10 24

   1015
Volume of the nucleus (10 13 ) 3 10 39

(iv) Electrons revolve round the nucleus in closed orbits with high speeds. The centrifugal force
acting on the revolving electrons is being counter balanced by the force of attraction between
electrons and the nucleus.

This model was similar to solar system, the nucleus representing the sun and electrons the
planet. The electrons are, therefore, generally referred as planetary electrons.

[ 68 ]
Atomic Structure

Limitations of Rutherford model

(i) According to wave theory, a charged particle when moves under the influence of attractive
force, it loses energy continuously in the form of electromagnetic radiations. Thus, the electron
which moves in an attractive field (created by protons present in the nucleus), must emit radiations.
As a result the electron should lose energy at every turn and move closer and closer to the
nucleus
Nucleus
following a spiral path and fall into the nucleus, thereby making the
atom unstable. Since atom is quite stable, it means the electrons do not
fall into nucleus, and this model does not explain the stability of the
atom. +
(ii) If the electrons lose energy continuously, the observed spectra should
be continuous but the observed spectra consists of well defined lines of Electron
definite frequencies. Hence, the loss of energy by the electrons is not
continuous in an atom.
JE

Electromagnetic radiations (wave theory): Electromagnetic radiation is generated by oscillations

of a charged body in a magnetic field or of a magnet in an electric field. These radiations or waves
have electric and magnetic fields associated with them and travel at right angle to these fields. The
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following are, the important characteristics of electromagnetic radiations.

(i) These consists of electric and magnetic fields that oscillate in directions perpendicular to each
other and perpendicular to the direction in which the wave is travelling.

(ii) All electromagnetic radiations travel with same velocity, i.e., the velocity of light (3 × 108 ms–1 or
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3 × 1010 cm s–1).

(iii) The electromagnetic radiations do not require any medium for transmission.
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Wave
A wave is always characterised by the following five characteristics :
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(i) Wavelength (ii) Frequency (iii) Velocity (iv) Wave number and

(v) Amplitude

(i) Wavelength : The distance between two consecutive crests or troughs is called the wavelength.
It is denoted by .
Crest
Wavelength

Vibrating
source Energy

Trough

(ii) Frequency : It is defined as the number of waves which pass through a point in one second. It
is denoted by the symbol, v and is measured in terms of cycles per second (cps) or Hertz (Hz)
units.

[ 69 ]
Atomic Structure

c
v
λ
or where;  = wavelength
c = velocity of height
v = frequency.

(iii) Velocity : It is defined as the distance covered by wave in one second. It is denoted by the letter
‘c’. All electromagnetic waves travel with same velocity.

Thus, a wave of higher frequency has a shorter wavelength while a wave of lower frequency
has a longer wavelength.

(iv) Wave number: This is reciprocal of wavelength, i.e., It is denoted by the symbol v

1
v Its unit is cm–1 or m–1.
λ
(v) Amplitude: It is defined as the height of the crest of depth of the trough of a wave. It is denoted
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by letter ‘a’. It determines the intensity of the radiation.

The arrangement of various types of electromagnetic radiations in the order of increasing or

decreasing wavelengths or frequencies is known as electromagnetic spectrum.
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Electromagnetic radiation Wavelength range (Å) Frequency range (Hz)

Cosmic rays 0.01 to zero 3 × 1020 to infinity

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Gamma rays 0.1 to 0.01 3 × 1019 to 3 × 1020

X-rays 150 to 0.1 2 × 1016 to 3 × 1019
Ultra-violet radiation (UV) 3800 to 150 7.9 × 1014 to 2 × 1016
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Visible radiation 7600 to 3800 3.95 × 1014 to 7.9 × 1014

Infra-red radiation (IR) 6 × 106 to 7600 5 × 1011 to 3.95 × 1014
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Micra waves 3 × 109 to 6 × 106 1 × 109 to 5 × 1011

Radio waves 3 × 1013 to 3 × 109 1 × 105 to 1 × 109

SAMPLE PROBLEMS 3.1 (MCQ)

Problem 1: Isotopes have
(a) Same number of protons (b) Same number of neutrons
(c) Different number of electrons (d) Different atomic numbers

Solution: (a) Isotopes have same atomic number.

Problem 2: The ratio of mass of an electron to that of the mass of hydrogen atom is:
(a) 1837 : 1 (b) 1 : 2000
(c) 1 : 1837 (d) 1 : 3500

Solution: (c)

[ 70 ]
Atomic Structure

Problem 3: The number of neutrons present in deuterium is:

(a) 3 (b) 0
(c) 2 (d) 1

Solution: (d)

Problem 4: What happens when -rays strike a thin gold foil:

(a) Most of the -rays gets deflected through small angles
(b) Most of the rays do not pass through the foil
(c) Most of the rays passes through without any deviation
(d) Most of the rays gets deflected back

Solution: (c)

Problem 5: Wave number is equal to:

c
(a) (b) λ  ν
λ
1
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(c) (d) 
λ

1
Solution: (c) ν 
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Problem 6: The frequency of microwaves with wavelength 2 × 106 nm is

(a) 2.5 × 106 s–1 (b) 5 × 108 s–1
(c) 1.5 × 1011 s–1 (d) 3.2 × 107 s–1
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c 3  108 ms 1
Solution: (c) ν   3
 1.5 1011 s1
λ 2  10 m
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Problem 7: The diameter of an atom is ______times the diameter of the nucleus

(a) 105 (b) 103
(c) 104 (d) 102
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diameter of atom
Solution: (a)  105
diameter of nucleus

Problem 8: The unit of frequency is/are

(a) Cycles per second (b) Hertz
(c) Metre per second (d) Both (a) and (b)

Solution: (d) Factual

Problem 9: The limitations of Rutherford’s -ray scattering experiment was

(a) It could not explain the stability of atom
(b) It could not explain the position of nucleus
(c) It could not explain the size of atom
(d) Both (a) and (c)

Solution: (a)
[ 71 ]
Atomic Structure

Problem 10: Unit of wavelength can be

(a) cm (b) nm
(c) pm (d) all of these

Solution: (d) Factual

3.2 Atomic Spectrum of Hydrogen

When an electric discharge is passed through hydrogen gas at low pressure, a bluish light is emitted.
When a ray of this light is passed through a prism, a discontinuous line spectrum of several isolated
sharp lines is obtained. The wavelengths of various lines lie in visible, ultraviolet and infra-red regions.
All these lines observed in the hydrogen spectrum can be classified into five series.

Spectral series Discovered by Appearing in

Lyman series Lyman Ultra-violet region

Balmer series Balmer Visible region
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Paschen series Pashcen Infra-red region

Brackett series Brackett Infra-red region
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Pfund series Pfund relation Infra-red region

Ritz presented a mathematical relation to find the wave number of various lines of H-spectrum.

1 v 1 1 
v    
an
λ c  n12 n22 

where R is a universal constant, known as Rydberg constant. It’s value is 109,678 cm –1

(R = 1.097 × 107 m–1) n1 and n2 are integers (such that n2 > n1). For a given spectral series n1 remains
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constant while n2 varies from line to line in the same series.

The value of n1 = 1, 2, 3, 4 and 5 for the Lyman, Balmer, Paschen, Brackett and Pfund series
respectively. n2 is greater than n1 by at least 1.
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Values of n1 and n2 for various series

Spectral Series Value of n1 Value of n2

Lyman series 1 2, 3, 4, 5,.....

Balmer series 2 3, 4, 5, 6,.....
Pashcen series 3 4, 5, 6, 7,.....
Bracket series 4 5, 6, 7, 8,.....
Pfund series 4 6, 7, 8, 9,.....

(i) They produce a green glow when strike the wall beyond anode.

(ii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy.

[ 72 ]
Atomic Structure

Quantum theory of electromagnetic radiations: The wave theory successfully explains many
phenomenon such as reflection, refraction, diffraction, interference, polarisation etc., but fails to
explain phenomenon like black body radiation, photo-electric effect etc.

In order to explain black body radiation and photo-electric effect a new theory was proposed which
is known as quantum theory of radiation. According to this theory, a hot body emits energy not
continuously but discontinuously in the form of small packets of energy called quantum. The energy
associated with each quantum of a given radiation is proportional to the frequency of the emitted
radiation; E 

or E = hv where h is a constant known as Planck’s constant. It’s numerical value is 6.624 × 10–34 Js.
The energy emitted or absorbed by a body can be either one quantum or any whole number multiple
of hv, i.e., 2hv, 3hv, 4hv,...., nhv quanta of energy.

Thus energy emitted or absorbed = nhv, where n can have values 1, 2, 3, 4,...... Thus, the energy
emitted or absorbed is quantised.
JE

Bohr’s Model of an atom

Postulates:
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(i) The atom has a nucleus where all the protons and neutrons are present. It is present at the
centre of the atom.

(ii) Negatively charged electrons are revolving around the nucleus in a same way as the planets are
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revolving around the sun. The path of the electron is circular. The force of attraction between
the nucleus and the electron is equal to centrifugal force of the moving electron.
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(iii) Out of infinite number of possible circular orbits around the nucleus, the electron can revolve

h h
only in those orbits whose angular momentum is an integral multiple of , i.e., mvr  n
2π 2π
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where m = mass of electron, v = velocity of electron, r = radius of orbit and n = 1, 2, 3, .... number
of orbit. Thus the angular momentum is quantized. The specified orbits are called stationary
orbits.

(iv) By the time, the electron remains in any one of the stationary orbits, it does to lose energy. Such
a state is called ground state.

(v) Each stationary orbit is associated with a definite amount of energy. The greater the distance of
the orbit from the nucleus, more shall be the energy associated with it. These orbits are also
called energy levels and are numbered as 1, 2, 3, 4, ..... or K, L, M, N,..... from nucleus outwards.

(vi) The emission or absorption of energy in the form of radiation can only occur when an electron
jumps from one stationary orbit to another.

E = Ehigh –Elow = hv

[ 73 ]
Atomic Structure

Electrons excited
by absorbing energy
(energy absorbed)

+
Nucleus
Energy radiated
when electrons fall
n=1
back
(K) n = 2 n=3
(L) n=4 (Energy emitted)
(M)
(N) n = 0
(O) n = 6
(P)
Energy is absorbed when electron jumps from inner to outer orbit and is emitted when it moves from
outer to an inner orbit.

When the electron moves from inner to outer orbit by absorbing definite amount of energy, the new
state of the electron is said to be excited state.
JE

Radii of various orbits mv2

r Force of
Consider an electron of mass ‘m’ and charge ‘e’ revolving around attraction
v e
the nucleus of charge Ze (Z = atomic number). Let ‘v’ be the
r
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tangential velocity of the revolving electron and ‘r’ the radius of the
orbit. The electrostatic force of attraction between the nucleus and + Ze
kZe 2
electron  2 .
r
an

1
where k is a constant. It is equal to 4πε ,  0 being absolute permittivity of medium. In SI units, the
0

1
ka

numerical value of 4πε is equal to 9 × 109 Nm2/c2.

0

[In C.G.S. units, value of k is equal to 1]

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As force of attraction = centrifugal force

kZe 2 mv 2
So, 
r2 r
kZe 2
v2  ...(i)
rm
According to one of the postulates,

h
Angular momentum  mvr  n
2

nh
or v ...(ii)
2mr

Putting the value of ‘v’ in eq. (i)

n 2h 2 kZe 2

4 2 m 2 r 2 mr

[ 74 ]
Atomic Structure

n 2h 2
or  kZe 2
4 2 mr
n 2h 2
or r ...(iii)
4 2 mkZe 2
n 2h 2
For hydrogen atom Z = 1, so, r 
4 2 mke 2
Now putting the values of h, p, m, e and k
r = 0.529 × 10–8 × n2 cm.

n2
and rn  0.529  Å for hydrogen like species.
Z

Velocity
We know
KZe 2
v2 = .....(i)
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r.m
also we know

nh
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v = 2r m .....(ii)

Dividing (i) by (ii) we get

v2 KZe 2 2   m
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= .m . nh
v

2 KZe 2
v=
nh
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2 Ke 2
v=
h
Z
v = 2.18 × 106 . m/sec.
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Energy of an electron: Let the total energy of the electron be E. It is sum of kinetic energy and
potential energy.

E = kinetic energy + potential energy

1 kZe 2
 mv 2 
2 r
Putting the value of mv2 from eq. (i)

kZe 2 kZe 2 kZe 2

E  
2r r 2r

Putting the value of r from eq. (iii)

2 2 Z 2 k 2 me 4
E ...(iv)
n 2h 2

[ 75 ]
Atomic Structure

For hydrogen atom, Z = 1

2 2 k 2 me 4
so, E
n2h2
Putting the values of p, k, m, e and h

13.6
E  eV / atom
n2

313.6
E kcal/mole
n2

1313
E kJ / mole
n2

E1
En  for hydrogen atom
n2
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Z2
and E n  E1  for hydrogen like species.
n2

Interpretation of hydrogen spectrum

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P
The electron in the hydrogen atom O
resides in the first orbit. When energy N Pashcen
is supplied, the electron moves to series
M
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higher energy shells depending on the L

amount of energy absorbed. When this Balmer K Brackett
series series
electron returns to any of the lower
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energy level, it emits energy. Lyman

series is obtained when the electron Pfund
returns to the lowest energy state while series
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Balmer series is obtained when the

electron returns to second energy shell. Lyman
series
Similarly, Pashcen, Brackett and Pfund
series are obtained when electron returns to the third, fourth and fifth energy shell from higher
energy shells respectively.

Maximum number of lines produced when an electron jumps from nth level to ground level. It is equal

n ( n  1)
to . If the electron comes back from energy level having energy E2 to energy level having
2
energy E1, then the difference may be expressed in terms of energy of photon as :
E2 – E1 = E = h
s or The frequency of the emitted photon is given by

E

h

[ 76 ]
Atomic Structure

Since, E can have only definite values depending on the energies of E2 and E1, v will have only fixed
values in an atom.

c E
or V  
 h

hc
or  
E

Since h and c are constants, E corresponds to definite energy, thus, each transition from one energy
level to another will produce a light of definite wavelength. This is actually observed as a line in the
spectrum of hydrogen atom.

Thus, the different spectral lines in the spectra of atoms correspond to different transitions of electrons
from higher energy levels to lower energy levels.
JE

Let n1 and n2 be the two energy shells in hydrogen atom (n1 < n2).

2 2 me 4 k 2
Energy associated with n1 shell (E1)   n12 h 2
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2 2 me 4 k 2
Energy associated with n2 shell (E2)  
n 22 h 2
2 2 me 4 k 2  2 2 me 4 k 2 
E 2  E1    
n 22 h 2  n12 h 2 
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2 2 me 4 k 2  1 1
E  2  2
 2
h  n1 n 2 
c
E  hv  h.
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
c 2 2 me 4 k 2  1 1
h.   n2  n2 
 h2  1 2
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1 2 me k  1
2 4 2 1
or   n2  n2 
 h 3c  1 2

1 1 1
   RH  2  2 
  n1 n2 
1 1
or   RH c  2  2 
 n1 n2 
where, RH is Rydberg constant for hydrogen. Its value is 109, 679 cm–1. (RH = 1.098 × 107 m–1) for
H like atoms (Li2+, He+, etc.)

1 1
v  Z 2 RH  1  2 
 n1 n2 

1 1
v  Z 2 RH c  1  2 
 n1 n2 

[ 77 ]
Atomic Structure

The following points support Bohr’s theory:

(i) The frequencies of the spectral lines calculated from Bohr’s equation are in the agreement with
the frequencies observed experimentally in hydrogen spectrum.

(ii) The value of Rydberg constant calculated from Bohr’s equation tallies with the determined
experimentally.

(iii) The spectra of hydrogen like species such as

He+, Li+2, Be3+, can be explained with the help of Bohr’s theory.

Limitations of Bohr’s theory

(i) It does not explain the spectra of multi-electron species (due to inter electronic repulsion)

(ii) When a high resolving power spectroscope is used, it is observed that a spectral line in the
hydrogen spectrum is a collection of several lines which are very close to one another. Bohr’s
theory does not explain the fine spectra of even hydrogen atom.
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(iii) It does not explain the splitting of spectral lines into a group of lines under the influence of
magnetic field (Zeeman effect) and electric field (Stark effect).
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(iv) It is not in agreement with Heisenberg’s uncertainty principle.

Photoelectric Effect: The emission of electrons from the surface of a metal when illuminated by
electromagnetic radiation of suitable wavelength of frequency is called photoelectric effect. For a
given material, there exists a minimum frequency or incident radiation which emits photoelectrons. If
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the frequency is less than that no electron can be emitted from the metal surface, no matter how
intense the radiation may be. This minimum value of frequency is called threshold frequency. The
energy of the photoelectrons is proportional to the frequency of the incident radiation and the number
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of photoelectrons emitted per second is proportional to the intensity of the incident radiation.

Accepting to Planck’s idea that radiation consists of photons, Einstein suggest that photon’s energy
is used in two ways:
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(i) A part of energy is used to free the electron from the atom. This energy is known as photoelectric
work function. This is denoted by .

(ii) Rest of the energy is used in giving kinetic energy to the electron. Thus, energy of the photon,

hv    12 mv2 ...(i)

where, v is the velocity of the emitted electron .

When photon’s energy is equal to  the kinetic energy becomes zero. Under this condition, eq. (i)
reduces to
hv0 = 
where, v0 is the threshold frequency, from eq. (i)
1
2 mv2  hv 

Putting the value of 0,

[ 78 ]
Atomic Structure

1 mv 2  hv  hv 0
2

1 mv 2  h (v  v0 )
2

For a definite metal, the value of hv0 is constant

So, 1 mv 2  hv
2

or v2  v
Thus, increase of frequency of the incident radiation causes an increase in the velocity of electron
provided intensity of incident light is constant.

Wave nature of electrons (deBroglie’s hypothesis): de-Broglie proposed that electrons like
light, behaves both as material particle and as a wave.

de-Broglie derived an expression for calculating the wavelength of the wave associated with the
electron. According to Planck’s equation
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c
E  h  h. .....(i)

The energy of a photon on the basis of Einstein’s mass energy relationship is
E = mc2 .....(ii)
ES

where c is the velocity of electron

Equating both the equations
c
h.  mc 2

an

h
or  .....(iii)
mc
The wavelength decreases if the value of mass (m) increases, de-Broglie equation is applicable in
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the case of smaller particles like electron and has no significance for large particles.

SAMPLE PROBLEMS 3.2 (MCQ)

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Problem 1: Bohr’s theory is not applicable to:

(a) Be2+ (b) H
(c) He + (d) Li2+

Solution: (a) Bohr’s theory is applicable only to hydrogen and H-like species.

Problem 2: n1 for Balmer series of hydrogen spectrum where e– falls is:

(a) 3 (b) 2
(c) 4 (d) 1

Solution: (b) For Balmer series n1 = 2, n2 > 2

Problem 3: Radius of Bohr’s orbit of H-atom is

(a) 0.53Å (b) 0.26Å
(c) 1.25Å (d) 2.57Å

n2
Solution: (a) rn  0.53 
Z

[ 79 ]
Atomic Structure

Problem 4: Which of the following transitions in the H-atom will emit most energetic photon as per
Bohr’s theory.
(a) n = 5 to n = 3 (b) n = 6 to n = 5
(c) n = 2 to n = 1 (d) n = 6 to n = 1

Solution: (d) Difference of energy is maximum between orbit 6 and 1

Problem 5: The number of spectral lines observed when an electron falls from n = 5 to n = 1 in visible
region is
(a) 5 (b) 3
(c) 2 (d) 4

Solution: (b) 5  2, 4  2, 3  2 (3 lines)

Problem 6: The energy of the 3rd orbit of H-atom is

(a) –0.342 × 10–19J (b) –0.726 × 10–18 J
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(c) –2.18 × 10–18 J (d) –2.42 × 10–19 J

Solution: (d) E n  R H  Z2 / n 2
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Problem 7: The K.E. of photoelectrons depends upon:

(a) Intensity of incident rays (b) Frequency of incident rays
(c) Number of photons striking (d) Number of photoelectrons ejected
an

Solution: (b) Factual

Problem 8: The work function () of a metal having threshold frequency (0) 5.2 × 1014 s–1 is:
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(a) 2.19 × 10–10 J (b) 1.23 × 10–22 J

(c) 3.44 × 10–19 J (d) 7.64 × 10–15 J

Solution: (c) Work function () = h0

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Problem 9: The ratio of the radii of the three Bohr’s orbit is:
(a) 1 : 5 : 3 (b) 1 : 4 : 9
(c) 1 : 8 : 27 (d) 1 : 3 : 9

n2
Solution: (b) rn  0.529 
Z

Problem 10: A certain metal irradiated to light of frequency 3.2 × 1016 Hz emits photoelectrons with
twice K.E. as did photoelectrons when the same metal is irradiated by light of frequency
2 × 1016 Hz. The threshold frequency of metal is
(a) 1.2 × 1016 Hz (b) 4 × 1015 Hz
(c) 8 × 1015 Hz (d) 9 × 1014 Hz

Solution: (c) Threshold frequency (0) = h0

[ 80 ]
Atomic Structure

3.3 Bohr’s theory versus de-Broglie Equation

One of the postulates of Bohr’s theory is that angular momentum of an electron is an integral

h
multiple of . This postulate can be derived with the help of de-Broglie concept of wave nature of
2
electron.

Consider an electron moving in a circular orbit around nucleus. The wave would be associated with
the circular orbit. If the two ends of the electron wave meet to give regular series of crests and
troughs, the electron wave is said to be in phase, i.e., the circumference of Bohr’s orbit is equal to
whole number multiple of the wavelength of the electron wave.

so, 2r = n

2r
or  .....(i)
n
JE

From de-Broglie Equation (In phase) (Out of phase)

h
 .....(ii)
mv
ES

h 2r
Thus, 
mv n
an

h
or mvr  n. [v = velocity of electron and r = Radius of the orbit]
2

h
Angular momentum  n.
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i.e., ...(iii)
2
This proves that de-Broglie and Bohr-concepts are in perfect agreement with each other.
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Heisenberg Uncertainty Principle: Werner Heisenberg presented a principle known as

Heisenberg uncertainty principle which states: “It is impossible to measure simultaneously the
exact position and exact momentum of a body as small as electron.”

The uncertainty of measurement in position, x, and the uncertainty of momentum, p or mv, are
related by Heisenberg’s relationship as

x.p  h/4
or x.mv  h/4 where, h is Planck’s constant.

For an electron of mass m (9.10 × 10–28 g), the product of uncertainty is quite large.

In the case of bigger particle (having a considerable mass), the value of the product of uncertainty is
negligible.

If the position is known quite accurately i.e., is very small, v becomes large and vice-versa. Thus,
uncertainty principle is important only in the case of smaller moving particles like electrons.

[ 81 ]
Atomic Structure

Quantum Numbers

The four quantum numbers are :

(i) Principal quantum number (ii) Azimuthal quantum number

(iii) Magnetic quantum number (iv) Spin quantum number

Each quantum number refers to a particular character of the electron in an atom. First three quantum
numbers have been deduced from Schrodinger wave equation.

Quantum or Wave mechanical model of atom: This new model of atom was put forward by
Schrodinger in 1920 by taking into account the de Broglie concept of dual nature of matter and
Heisenberg’s uncertainty principle. He described the motion of the electron in three dimensional
space in terms of a mathematical equation called Schrodinger wave equation viz.

 2  2  2 8 2 m
   (E – V)  = 0
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x 2 y 2 z 2 h2

where  is the amplitude of the electron wave at a point with coordinates x, y, z, E = total energy and
V = potential energy of the electron y is also called wave function.  2 gives the probability of finding
ES

the electron at (x, y, z). The acceptable solutions of the above equation for the energy E are called
eigen values and the corresponding wave function  are called eigen functions.

Schrodinger wave equation can be written as

an

 2 2  2  8 2 m
    
 x 2 y 2 z 2  (E – V)  = 0
  h2
8 2 m
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2
or    (E – V) = 0
h2
2 2 2 2
where   2  2  2 is called Laplacian operator
x y z
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The above equation can be rewritten as

8 2 m
 2  – (E – V) 
h2
 2 
 – h 2  V 
or  8 m
2  =E
 
or H = E

h2
where H  – 2
 2  V is called Hamiltonian operator..
8 m

In this operator, first term represents kinetic energy operator (T) and second term represents potential
energy operator (V). Hence Schrodinger wave equation can also be written as

(T + V)  = E 

[ 82 ]
Atomic Structure

Application of Schrodinger wave equation to hydrogen atom: For hydrogen atom, potential
e2
energy, V = – . Replacing mass m of the electron by reduced mass (µ) of hydrogen atom (1/µ)
r
= 1/me + 1/mp), Schrodinger wave equation for hydrogen atom is obtained. As µ = mp me /(mp + me)
and me << mp therefore, µ ~
 me. On solving of E, we get
2 2 me e 4
En = 
n2 h2
1 2 2 me e 4 me e 4
or in S.I. units. En = –   , where 0 is permittivity of vacuum.
(4 0 ) 2 n 2 h 2 8 20 n 2 h 2

Schrodinger wave equation in terms of

spherical polar co-ordinates: Putting x = r sin Z

 cos , y = r sin  sin , z = r cos , Schrodinger P(x, y, z) or (r, )

wave equation in terms of spherical polar co-
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ordinates is obtained, i.e., it now consists of three r

variables, r,  and . Hence, the complete wave

function can be expressed in the form
X
ES


(r, ) = R(r). O
H ().  ()
90°

R (r) which is a function of radical Y

H (q). ()
distance r is called O
an

which depends upon angle  and

 is called Angular wave
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function.

Dependence of Radial and Angular wave functions on quantum numbers:

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 n, l, m(r, ) = Rn, l (r). O

H l, m (). m ()

where n, l and m represent principal, azimuthal and magnetic quantum numbers respectively.

Plots of Radial Wave Function (R), Radial Probability Density (R2) and Radial Probability
Function (4  r2R2): The probability of funding the electron in a spherical shell of thickness dr at
a distance r from the nucleus is equal to the product of the volume of shell of thickness dr at distance
r from the nucleus (4 r2dr) and the radial probability density (R2) per unit volume, i.e., equal to
4r2 dr R2 = P dr where P = 4r2R2 is called radial probability function.

2p
1s 2s
R R
R
(a) NODE
+
r r – r

[ 83 ]
Atomic Structure

2p
1s NODE 2s
R2 R
2
R
2

(b)

r r r
14
12 2p
10 1s 5 5
2s
4r2R2

4r2R2

4r2R2
4 4
6 3 3
4 2 2
(c) 2 1 1 2.1 Å
2.7 Å
0 0 0
2 4 6 8 2 4 6 8 2 4 6 8
r(Å) r(Å) r(Å)
0.529 Å
In the plots of radial probability versus distance from the nucleus, number of peaks, i.e. region of
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maximum probability = n – l, e.g., 2s has two peaks 3s will have 3 peaks, 2p has one peak, 3p has
two peaks and so on.

Note that the nodal surface of 2s orbital exists at a distance of 2a0 from the nucleus where a0 is the
ES

Bohr radius, i.e., 0.529 Å.

H )|2: For any ns

H ) and angular probability density | O
Plots of angular wave function ( O
H  = (1/4)1/2 i.e., it is independent of angles  and . Hence, the plots of O
orbital, O H  as well as
an

H |2 are circular in two dimensions or spherical in three dimensions. The plots of O
|O H  for pz
orbital involves angle  while those for px and py orbitals involve both  and . Hence, in their case,
two tangent spheres are obtained.
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Principle quantum number: It describes the average distance of the electron from the nucleus. It
is designated as ‘n’. The energy of the electron and the volume of the electron cloud are dependent
on this quantum number. Theoretically it may have all integral values from 1 to  but only values
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from 1 to 7 have been established in the atoms of known elements so far,

Higher the value of ‘n’:

(i) Greater is the distance of the shell from nucleus,

(ii) Greater is the magnitude of energy.

The maximum number of electron which can be present in a principal energy shell is equal to 2n2.

No energy shell in the atoms of known elements possess more than 32 electrons.

Azimuthal quantum number : This quantum number is also called secondary or subsidiary quantum
number. It is designated by symbol ‘l’. It describes spatial distribution of electron cloud and the
angular momentum of the electron. It actually tells about the shape of orbital occupied by the electron.
For any given value of principal quantum number ‘n’, the azimuthal quantum number ‘l’ can have all
integral values from 0 to (n – 1). Each value corresponds to an energy sub-shell or sublevel. The total
number of sublevels in each principal shell is numerically equal to the value of ‘n’.
[ 84 ]
Atomic Structure

The sub shells are designated by the letters s, p, d and f.

l=0 s-sub-shell; l=2 d-sub-shell

l=1 p-sub-shell; l=3 f-sub-shell

s, p, d and f are spectral terms and signify sharp, principal, diffuse and fundamental respectively.

The energies of the various sub-shells in the same shell are in order of s < p < d < f. Sub-shells
having equal l values but with different n values have similar shapes but their sizes increase as the
value of ‘n’ increases.

Magnetic quantum number: This quantum number is designated by the symbol ‘m’. To explain
splitting of spectral line into a number of closely spaced lines in the presence of magnetic field
(Zeeman effect), electron producing a single line has several possible space orientations for the
same angular momentum vector in a magnetic field, i.e., under the influence of magnetic field each
sub-shell is further sub-divided into orbitals. Magnetic quantum number describes the orientation or
distribution of electron cloud. For each value of ‘l’, the magnetic quantum number ‘m’ may assume
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2l + 1 values ranging from –l to +l including zero. Each value of “m” represent on ORBITAL, which
contains maximum of two elements, with opposite spins, m for pz is zero.

Characteristics of orbitals
ES

(i) All orbitals of the same shell in the absence of magnetic field possess same energy, i.e., they are
degenerate.

(ii) All orbitals of the same sub-shell differ in the direction of their space orientation.
an

(iii) Total number of orbitals in a main energy shell is equal to n2.

Spin quantum number: When spectral lines were observed by instruments of high resolving power,
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each line was found consisting of a pair of lines. To account for these doublets, it was suggested that
electron while moving around the nucleus in an orbit, is also spinning about its own axis either in
clockwise or in anti-clockwise direction. There are two possible values either. These spins are also
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shown by arrows; upwards () or downwards ().

Spin  12 ­ clockwise

Spin  12 ¯ anti-clockwise

The electrons with the same sign of spin quantum numbers are said to have parallel spins while those
having opposite signs of spin quantum numbers are said to have opposite spins or paired up spins.
N Magnetic field S

+1/2 –1/2

S N

[ 85 ]
Atomic Structure

Since, a spinning charge is associated with a magnetic field, an electron must have a magnetic
moment associated with it.

Pauli’s Exclusion Principle: The principle states that no two electrons in an atom can have
the same set of all the four quantum numbers. In other words, an orbital cannot have more than
two electrons.

Conclusion :

(i) The maximum capacity of a main energy shell is equal to 2n2 electrons.

(ii) The maximum capacity of a sub-shell is equal to 2(2l + 1) electrons.

(iii) Number of sub-shells in a main energy shell is equal to the value of n.

(iv) Number of orbitals in a main energy shell is equal to n2.

(v) One orbital cannot have more than two electrons. If two electrons are present, their spins should
be in opposite directions.
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Aufbau’s Principle: This principle gives us a sequence in which various sub-shells are filled with
electrons. The sequence in which various sub-shells are filled up depends on the relative order of the
energy of sub-shells. The sub-shell with minimum energy is filled up first and when this
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attains maximum quota of electrons, then next sub-shell of higher energy starts filling.

The sequence in which the various sub-shells are filled is the following:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
an
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1s 2s 3s 4s 5s 7s
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2p 3p 4p 5p 7p

3d 4d 5d

4f

The sequence in which various sub-shells are filled up can also be determined with the help of (n +
1) value for a given sub-shell. The sub-shell with lowest (n + l) value is filled up first. When
two or more sub-shells have same (n + l) value, the sub-shell with lowest value of ‘n’ is
filled up first.

Hund’s Rule of Maximum Multiplicity (Orbital Diagrams): It states that electrons are
distributed among the orbitals of a sub-shell in such a way as to give the maximum number
of unpaired electrons with parallel spins. Thus, the orbitals available in a sub-shell are first filled
singly before they begin to pair. This means that pairing of electrons occurs with the introduction of

[ 86 ]
Atomic Structure

second electron in s-orbital, the fourth electron in p-orbitals, sixth electron in d-orbitals and eighth
electron in f-orbitals.

The rule is based on the fact that electrons being of the same charge repel each other and hence try
to keep farther apart from each other as much as possible. The electrons thus, occupy different
orbitals of the sub-shell as to minimise the inter-electronic repulsion and increase the stability of the
atom. Orbitals tend to become half filled or completely filled since such an arrangement will be more
stable on account of symmetry.

All those atoms which consist of at least one of the orbitals singly occupied behave as paramagnetic
materials because these are weakly attracted to a magnetic field, while all those atoms in which all
the orbitals are doubly occupied behave as diamagnetic materials because they have no attraction
for magnetic field. However, these are slightly repelled by magnetic field due to induction.

SAMPLE PROBLEMS 3.3 (MCQ)

Problem 1: In which of the following orbitals, the sum of (n + l) value is lowest?
JE

(a) 4s (b) 4p
(c) 5s (d) 3d

Solution: (a)
ES

Problem 2: The maximum number of electrons that can be accommodated in d x 2  y 2 orbital is

(a) 5 (b) 2
an

(c) 1 (d) 3

Solution: (b) An orbital can accommodate only 2 electrons.

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Problem 3: The maximum value of ‘m’ for a 3p orbital is

(a) +1 (b) +2
(c) +3 (d) +4
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Solution: (a) For a p-orbital m = +1, 0, –1

Problem 4: The correct sequence of energy of orbitals in a multielectron species is:

(a) 4s < 4p < 3d (b) 4s < 3d < 4p
(c) 3d < 4s < 4p (d) 4p < 3d < 4s

Solution: (b) Use (n + l) to calculate the energy.

Problem 5: The number of electrons present in ‘L’ shell of phosphorus (Atomic number = 15) is
(a) 2 (b) 6
(c) 10 (d) 8

Solution: (d) K shell = 2 electrons

L shell = 8 electrons
M shell = 5 electrons

[ 87 ]
Atomic Structure

Problem 6: Which of the following ions contains maximum number of unpaired electrons?
(a) Fe2+ (b) Zn+
(c) Cu+ (d) Ti2+

Solution: (a) Write the electronic configuration of each ion.

Problem 7: In which of the following orbital the four lobes are present along the axis?
(a) d xy (b) d x 2  y 2

(C) d yz (d) d xz

Solution: (b)

Problem 8: The four quantum numbers of an electron present in valence shell of potassium atom are:

1 1
(a) 4,1,0, (b) 4,1,1,
2 2

1 1
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(c) 4,0,0, (d) 4,0,1,

2 2

Solution: (c) Last electron of potassium is present in 4s orbital.

ES

Problem 9: Maximum number of unpaired electrons present in a f-subshell is

(a) 3 (b) 5
(c) 9 (d) 7

Solution: (d) f-subshell has 7-orbitals.

an

Problem 10: Which of the following atom cannot have electrons in d-subshell?
(a) Si (b) Ca
ka
(c) Cu (d) C

Solution: (d)

SOLVED EXAMPLES
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Example 1 : Calculate the radius of the first Bohr orbit of a hydrogen atom. Given that h = 6.63 × 10–27 erg.
sec; m = 9 × 10–28 g and charge of an electron = 4.8 × 10 –10 esu.

Solution: We have, for hydrogen Z = 1, n = 1

h2
r1 
4 2 me 2
27 2
(6.63 10 )
 2 28 10 2
4  (3.14)  9  10  ( 4.8 10 )
= 0.53 × 10–8 cm = 0.53 Å.

Example 2 : Calculate the ionisation energy in eV of a hydrogen atom in the ground state.

Solution : Since ionisation energy is defined as the energy required to remove an electron from outermost
orbit of atom, we can mathematically say that since the hydrogen atom is in ground state,

[ 88 ]
Atomic Structure

ionisation energy will be the energy required to remove the electron from the first orbit to 
orbit (i.e., r1 to r).
Thus,
Ionisation energy = E – E1
= 0 – (2.18 × 10–11) erg.
We know that E1 = – 2.18 × 10–11 erg.
11
2.18  10
 Ionisation energy = 2.18 × 10 –11
erg.  12
 13.60 eV
1.602  10

Example 3 : Calculate the wavelength in angstrom of the photon that is emitted when an electron in Bohr
orbit n = 2 returns to the orbit n = 1 in the hydrogen atom. The ionisation potential of the
ground state of hydrogen atom is 2.17 × 10–11 erg per atom.

Solution : Since the hydrogen atom has only one orbit containing only one electron, the ionisation
potential of the ground state of the, hydrogen atom is the energy of the electron of the first
orbit, i.e.,
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E1 = –2.17 × 10–11 erg.

E
Thus, E2  2
.....(Eqn. 5)
n
ES

2.17  10 11
= – 2
(n = 2)
2
 Energy of the radiation emitted,
an

E = E2 – E1
2.17 1011
= 2
 (2.17 1011 )
2
= 1.627 × 10–11 erg
ka

hc
We know E = h 

lp
hc 11
Thus,  1.627 10

27 10
6.62  10  3  10 5
 11
 1.22  10 cm
1.627  10
= 1220Å (1 Å = 10–8 cm)

Example 4 : The vapour of Hg absorbs some electrons accelerated by a potential difference of 4.5 volt
as a result of which light is emitted. If the full energy of a single incident electron is supposed
to be converted into light emitted by single Hg atom, find the wave number (1/) of the light.

Solution: We know that electron volts = charge in coulombs × potential difference in volts

 Charge of an electron   Potential difference 

4.5 eV =   
 in coulomb   in volt 

= (1.6022 × 10–19) (4.5) joule

[ 89 ]
Atomic Structure

Now,

1 E
wave number = 
 h.c
19
(1.6022  10 ) (4.5)
= 34 8
(6.626  10 ) ( 2.998 10 )
= 3.63 × 106 metres–1.

Example 5 : 13.6 eV is needed for ionisation of a hydrogen atom. An electron in a hydrogen atom in its
ground state absorbs 1.50 times as much energy as the minimum required for it to escape
from the atom. What is the wavelength of the emitted electron? (me = 9.109 × 10–31 kg, e =
1.602 × 10–19 coulomb, h = 6.63 × 10–34 J.s.)

Solution : 1.5 times of 13.6 eV, i.e., 20.4 eV is absorbed by the hydrogen atom out of which 6.8 eV
(20.4 – 13.6) is converted to kinetic energy.
KE = 6.8 eV = 6.8 (1.602 × 10–19 coulomb) (1 volt) = 1.09 × 10–18 J
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1 2
Now, KE  mv
2

KE 2(1.09 10 18 J)

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or, v  2 
m (9.109 10 31 kg )
= 1.55 × 106 metres.
34
h 6.63 10
   = 37 6 = 4.70 × 10–10 meters.
mv
an
(9.109 10 ) (1.55 10 )
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[ 90 ]
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