Brilliant STUDY CENTRE RESIDENTIAL -2024 (ONLINE CLASS NOTES)

CHAPTER - 04
STRUCTURE OF ATOM

INTRODUCTION
Atoms are the smallest particle of matter which are having either the same property or different property
of it. John Dalton introduced the word atom from the Greek word (Atomio or Atomos). It’s meaning is indivisible
(cannot be sub-divided)
Fundamental sub atomic particles
There are 36 sub atomic particles are present those are:-

Proton  P  ; Neutron  n  ; Electron  e  ; Positron  e  ; Antiproton 

1
1
1
0
0
1
0
1
1
1 P  ;  mesons     ;  meson

    ; Pions (O). Neutrino and Antineutrino etc. Among these proton, electron and neutron are the fundamental
sub atomic particles.
I. DISCOVERIES OF FUNDAMENTAL SUB ATOMIC PARTICLES
(CATHODE RAY EXPERIMENT)/DISCHARGE TUBE EXPERIMENT (JULIUS PLUCKER)
DISCOVERY OF ELECTRON
Julius Plucker (1889) and J.J. Thomson (1898) studied the discharge of electricity through partially
evacuated tubes (cathode ray discharge tube).
They observed that when a high voltage electric current is passed through a gas at low pressure,
negatively charged particles (called cathode rays) travelled from the cathode towards the anode.
A cathode ray discharge tube, Crooks tube, consists of a long glass tube fitted with metal electrodes
on both ends across which a high voltage can be applied. The tube is connected to a vacuum pump
for controlling the pressure of gas inside.

Cathode ray discharge tube

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Electrical discharge through gases is possible only at very low pressures and very high voltages.
When the pressure of gas inside the tube is reduced to about 10-4 atmospheres and a potential
difference of 10000 volts is applied, (the tube glows with a faint greenish light) current starts flowing
through a stream of particles moving in the tube from the negative electrode (cathode) towards the
positive electrode (anode).
The flow of current was further checked by making a hole in the anode and coating the tube behind the
anode with a phosphorescent material (zinc sulphide). These rays, after passing through the anode
developed a bright spot on the zinc sulphide coating.

Cathode ray discharge tube with perforated anode

Characteristic features of cathode rays
1. These rays are negatively charged and move along straight line
2. They are massive particles and deflect in magnetic and electric field.
3. They affect photographic plate
4. These rays ionise gases, which kept inside the discharge tube.
5. They produce heat and light, when hit on the tungsten filament.
6. They produce X-rays, when it hit on the tungsten metal.
7. They produce fluorescence and phosphorescence, when it hit on the corresponding material.
8. The e/m value of cathode rays doesn’t depend on the nature of the gas.
Millikans oil drop experiment
 This experiment is used to find the quantity of electronic charge (q)
 The Principle behind of the experiment is comparing the terminal velocities of oil drop which is adsorbed
with electron, with electric field and without electric field.
Charge on the Electron
Thomson’s experiment led to the determination of e/me value of the electron. The charge (e) on the
electron was determined by American scientist, Robert Millikan in 1909, by his ‘oil drop’ experiment.
Millikan’s oil drop apparatus consists of a chamber containing two charged plates, anode with a hole
in the centre and a cathode placed below. The chamber is provided with an atomiser, a telescope and
a source of X-rays. The downward motion of oil droplets produced by the atomiser and entering
through the small hole can be viewed with the microscope. By measuring the rate of fall of the drops,
it is possible to measure the mass of the oil droplets.

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The air between the electrodes is ionised by passing X-rays. Oil drops acquire one or more electrons
to become negatively charged which are attracted by the positive plate which affects their fall. The
rate of fall of the charged ions can be controlled by varying the applied voltage.
Millikan found that the magnitude of charge ‘q’ on the droplets is always an integral multiple of the
electrical charge, e (1.60 × 10-19C).
q = ne
where n = 1, 2, 3.......(quantized)

Millikan’s oil drop apparatus

J.J. Thomson experiment to determine the specific charge of electron (e/m)
CHARGE TO MASS RATIO OF ELECTRON
In 1897, British physicist J.J. Thomson measured the ratio of charge (e) to mass of electron(me) using
cathode ray tube by applying electrical and magnetic fields perpendicular to each other and the path of
the electrons. He observed that deviation of the particles from their path depended on the magnitude of
negative charge on the particle, mass of the particle and strength of the electrical or magnetic field.
1. Greater the magnitude of charge, greater is the interaction with the field and hence higher the deviation.
2. Heavier the particle lesser the deviation
3. Greater the strength of the magnetic field or the voltage applied, greater will be the deviation.

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Apparatus to determine charge to mass ratio of electron

The magnetic and electric fields deflect the beam in opposite directions (A and C) from point B. From
the amount of charge required to balance the effect of the magnetic field, Thomson calculated the e/
me of cathode ray particle as 1.758820 × 1011 C kg-1.

e
 1.758820 1011 C kg1
me
The e/me ratio for cathode rays was found to be the same irrespective of the nature of the cathode or
the gas taken in the discharge tube, thus indicating that electrons are basic constituents of all atoms.
 e/m value of cathode rays independent of gases inside the discharge tube.
 e/m value of electron is the highest one among all particles
 From the experimental observations, e/m value obtained from the relation

e E

m rB2
Where E and B are the electric and magnetic field strength and r is the radius of an arc developed on
a photographic plate.

 e/m value of electron = 1.76  1011 C /kg

Mass of the Electron

The mass of the electron was calculated by combining these results with Thomson’s e/me value

e 1.6022 10 19 C

me   =  9.1094  10 28 g
e/m e 1.75882 108 C 1g

 9.1094  10 31 kg
The mass of the electron is approximately 1/1837 of the mass of the hydrogen atom.

Anode ray experiemnt / Discovery of canal rays

 Origin of anode rays are the gases present in the discharge tube.
 e/m value of anode rays depend on gases inside the discharge tube and its value was found to be
9.58  107 C /kg , when H2 gas is taken in the discharge tube.
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 Mass of proton = 1.673  1027 kg

Characteristic features of anode rays

 Unlike the charge all the properties of cathode rays are similar to anode rays.
Discovery of Neutrons/James Chadwick experiment
 -particles bombarded on a beryllium foil, it transmutted to carbon atom and releasing chargeless and
massive particles are known as neutrons.

9 12
4 Be 24 He 6 C 10 n

Mass of neutron = 1.675  1027 Kg

Characteristic features of Neutron

1. They are highly penetrating
2. They remain unaffected in electric and mangetic field
3. Neutrons mainly take part in nuclear reactions.
J.J. THOMSON’S MODEL
 Plum pudding model or watermelon model / Raisin pudding model

MERITS
He could clearly explained:-
1. Neutrality of atom
2. When metal is heated, only electrons are emitted
3. Positive sphere is immovable
4. Mass of an atom is uniformly distributed
DEMERIT
1. This model could not satisfy the facts obtained from the Rutherford experiments.
RADIOACTIVITY
Wilhalm Roentgen in 1895 observed that when electrons strike a material in the cathode ray tube
produce fluorescence due to X-rays. It was noticed that X-rays were produced more effectively when
cathode rays strike dense metal anode (target). X-rays are not deflected by electric or magnetic fields
and have very high penetrating power. They have very short wavelengths (  0.1 nm) and are
electromagnetic in character. In 1896, French physicist, Henry Baqueral discovered radioactivity, which

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is the spontaneous emission of radiations by certain elements like uranium. Such elements are said
to be radioactive.
Further investigations by Marie Curie, Piere Curie, Rutherford and Fredrick Soddy showed that three
types of rays, i.e.  ,  and  emanated from radioactive elements.

Characteristics of ,  particles and   rays

rays   rays rays

Mass 6.67 10 27 kg 9.11 1031 kg

Charge 2 1 0

Type/nature Helium nucleus (He2  ) Electron High energy Radiation

1 Nearly the same
Velocity Nearly th of that of light
as that of light Same as that of light
10

Deflected towards Deflected towards

Effect of electric field negative plate positive plate No effect

Penetrating power High (100 times that Very high (1000 times
Low of -rays) that of rays)

RUTHERFORD MODEL OF AN ATOM

 - scattering experiment

 Inference of this experiment is the most of the space in an atom is empty.

Rutherford Model
 Planetary model/solar system model
 Atom is sub divided into two parts :-
Nuclear part and Extra nuclear part
Nuclear part :
 Nucleus : It is positive centre core which contain positive charge. Most of the mass is concentrated in
it.
1
 Radius of nucleus : rn  R 0  A 3 , R0 is the proportionally constant and is equal to 1.3  1015

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1015
 Radio of radius of nucleus to atom = 10
 10 5
10

 Density of nucleus is remains constant for all elements and is equal to 2.3  1017 kgm 3

Extra nuclear part

 Other than the nucleus in an atom is extra nuclear part. In which electrons are revolving round the
nucleus in a circular path
 Centrifugal force is counter balanced by electrostatic force of attraction between nucleus and electron.
Limitations
1. Stability of atom could not clearly explained.
According to the classical theory of electromagnetism proposed by Maxwell, every accelerated charged
particle must emit radiations in the form of electromagnetic waves and lose its total energy. Since
energy of electrons keep on decreasing, the radius of the circular path should also decrease (a spiral
path) and ultimately it should fall into the nucleus.

Electron emitting energy and spiralling into the nucleus.

Calculations showed that it will take only 10-8 seconds for the electron to spiral into the nucleus.
2. Spectrums of atoms could not clearly explained
3. He could not clearly explain the electronic arrangement of atoms.
Atomic number (Z) = Number of protons = Number of electrons
Mass number
The mass of the atom is mainly concentrated in the nucleus. The nucleus contains protons and
neutrons which are collectively called nucleons.
The total number of protons and neutrons in the nucleus is called mass number of the atom.
Mass number (A) = Number of protons + Number of neutrons = Number of nucleons.
The atomic number (Z) and mass number (A) of an element are usually represented along with the
symbol of that element as shown below:

A
Z X
3.1 ISOTOPES, ISOBARS AND ISOTONES
Isotopes: All atoms of an element have the same number of protons in their nuclei, however, the
number of neutrons may vary. Atoms having same atomic number but different mass numbers are
known as isotopes. For example, hydrogen has three isotopes namely protium

 H ,deuterium D andtritium T .
1
1
2
1
3
1
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12 13 14 35 37
Similarly, the three isotopes of carbon are 6 C, 6 C and 6 C. Chlorine has two isotopes, 17 Cl and 17 Cl.
Chemical properties of atoms are controlled by the number of electrons and therefore, all isotopes of
a given element exhibit same chemical behaviour.
Isotones: Sometimes atoms of different elements contain the same number of neutrons. Such atoms
are known as isotones. Thus, isotones are atoms of different elements containing the same number
13 30 31 32
of neutrons. E.g. 6 C and 14
7 N
; 14 Si, 15 P and 16 S.
Isodiaphers: They are atoms of different elements which have the same difference between the
11 13 15 19
number of neutrons and protons (same n - p value). Eg. 5 B and 6 C, 7 N and 9 F
Isosters: Molecules which have the same number of atoms and electrons are alled isosters. E.g. CO
and N2O, CaO and KF, OF2 and HClO.
LIGHT
I. Newtons Corpusular Theory : Particle nature could clearly explained by Newtons corpusular theory.
 Limitations of Newtons corpusular theory
Diffraction, Interference etc could not clearly explained.
II. Wave theory
Electromagnetic wave theory :
Accelerated charged particles like electron which emit radiation/energy in the form of wave component.
Which resolve into two component, ie., electrical component wave and magnetic component wave.
Those waves are mutually particular to each other and are perpendicular to the propagation.

The electric and magnetic field components of electromagnetic wave

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The electromagnetic spectrum (visible region is only a small part of the spectrum)
Characteristic features of wave

1. Wavelength    : Distance between the two consecutive crests or troughs

2. Frequency    : Number of waves passing through a point per second.

c
 ; c is the velocity of light


1

T
3. Amplitude A : The maximum height of crests or the maximum depth of trough.

 = 1 T , T = Time in second.

4. Wave number  = Number of waves passing per unit length .

1


Relation between  and 

  c

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2. Plancks quantum theory

Postulate
1. Atom absorbs and liberate energy not continuously discontinuously in the form of small packets called
quanta (photon)
2. E = h - (1 photon or 1 quanta)

hc
3. E=


hc
4. E=n n = no. photons

 1 Photon breaks 1 molecule where as 1 mole photon breaks 1 mole molecule.
Limitations of wave theory
1. Black body radiation
An ideal black body is expected to absorb completely the radiant energy falling on it is known as a
black body. The radiation emitted by a black body kept at high temperature is called black body radiation.
A black body radiation is the visible glow that the solid object gives off, when heated.
A graph is obtained by plotting the intensity of radiation against wave length gives the following details.

Wave length - intensity relationship.

1. The naure of the radiation depends upon the Temperature of the black body.
2. At given temperature, the intensity of radiation increases with the wavelength, reaches maximum and
then decreases.
3. As the temperature increases peak of maximum intensity shifts towards the shorter wavelength.

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Photo electric effect

When light fall on low ionisation energised metals like Cs and K electrons are ejected
E - incident energy , E0 threshold energy

Equipment for studying photoelectric effect.

 E0  h0  0 = Threshold frequency

E1 = E0  photoelectric effect is formed
E1 < E0  No photo electric effect
E1 > E0  K.E. of photoelectrons are present

E  E1  E0  KE  h  h0

KE  h    0 
KE  
Iincident light  no ejected electrons

Graphical explanation of photoelectric effect

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Cs K Na

K.E.

K.E.

slope  h
0 

I3
I
I2
I1

Stopping potential :
The external potential is required to stop the K.E. of ejected electrons.

KE = h  h0

eV = h  h0

h h0
V 
e e
y  mx  c

Where V is the stopping potential.

Bohr atomic model
Bohr’s atomic theory
Postulates
1. Electron is revolving round the nucleus in a circular stationary energy path called Orbit.
2. As long as electron revolve round the nucleus in a circular path, it neither loose energy nor absorb.

nh
3. Angular momentum of an orbit is quantised. It is integral multiple of some constant values mvrn =
2
or mVrn =
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4. When an electron absorb energy from external source, it get excited to the higher energy level. That
electron has no stability, it de-excited to lower levels by releasing absorbed energy. That energy
corresponds to the spectrum.
MERITS
1. He could clearly derived the relations of K.E., P.E., En (total) velocity of electron in the nth Bohr orbit and
radius of nth Bohr orbit.
1. Relation of KE and PE

KZe2 1
1. K.E.  , K ; 0  permitivity in free space
2rn 40

KZe2
2. P.E. =
rn
If KE is x, PE = –2x.
 Hydrogen like species are He+1, Li+2, Be+3 . Those species contain one electron in ground state.
2 Relation of Radius of Bohr orbit

n2h2
rn 
4 2KZe 2 m

n2 0 n2
rn  0.529 A or rn  52.9 pm
Z Z

n2 x
rnx  r1H  x = Hydrogen like species
Zx
3. Relations of total energy of Bohr orbit
K.E. + P.E. = En

2 4 2 2
E = 2 me z k
n 2h 2

Z2
E n  1312 2 kJ / mol
n

Z2
E n  13.6 2 eV /atom
n

18 Z2
En  2.18  10 J /atom
n2

Z2
En  313.6 Kcal / mol
n2

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Z2 x
En x  E1H  ; Where x is the hydrogen like species.
n2 x
4. Relation of velocity of Bohr orbit

nh 2KZe2
V= ; Vn 
2mrn nh

Z
Vn  2.18  106 m /s
n

Zx
Vnx  V 1H 
N x ; where x is the Hydrogen like species

Ionisation energy
The energy required to eject electron from the outermost shell of neutral gaseous atom in a ground
state.
5. Relations of ionisation energy of Bohr orbit

E  E1  E    E1   E

Z2
E n  1312 kJ / mol
n2

Z2
E n  13.6 eV / atom
n2

Z2
E n  2.18  10 18 J / atom
n2

Z2
E n  313.6 Kcal / mol
n2

Z 2x
I.Enx  I.E1H  where x is the H like species.
n2x

HYDROGEN SPECTRUM

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1. Number of possible spectral lines obtained from the de excitation of electron from excited (n) level to
n  n  1
ground level =
2
2. Number of possible spectral lines obtained from the de excitation of electron from excited (n) level to
 n2  n1  n2  n1  1
lower level other than the ground level =
2
3. Number of spectral lines obtained from the excited level (n) to
1. U.V. region only = n – 1
2. Visible region only = n – 2

 n  3  n  3  1
3. I.R. region only =
2
Rydberg equation (Ritz combination principle)
1. The principle states that, spectral lines of any element include frequencies that are either the sum or
the difference of the frequencies of two other lines.

1 1
  1  R H  2  2  Z 2 ; n = 1; n = 2, 3, 4 etc

 n1 n2  1 2

R H  109677 cm 1 or 1.09677  10 7 m 1 ; n1 = 1; n2 = 1, 2, 3 etc

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 Ionisation energy in terms of RH

I.E.  R H .hc  Z 2x ; x = H like species

Spectrum

Emission spectrum Absorption spectrum

Continuous spectrum Discontinuous spectrum

(Solar spectrum)

(Atomic spectrum)
Line spectrum
Finger print of an atom

Limitations
1. Fine spectrum could not clearly explained.
Fine spectrum is the normal spectral line split in several by observing the spectrum through fine
spectro scope.
2. Multi electron spectrums could not clearly explained
3. Zeeman effect and Stark effect could not clearly explained.
Zeeman effect - Splitting of spectral line, when magnetic field is introduced.
Stark effect - Splitting of spectral line, when electric field is introduced.
4. Dualism of sub-atomic particle could not clearly explained.
5. Uncertainities are the inherent property of the system that results from the dualism of matter. Those
uncertainities could not clearly explained.
Davisson and Germer experiment
This experiment could clearly proved that wave nature of electron in the nth Bohr orbit by the x-ray
diffraction experiment conducted on Nickel metal.
Mosley’s experiment
He could clearly proved that, the identity of element is the atomic number by an x-ray diffraction
experiment and derived relations.

  a Z  b

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 = frequency of radiation
Z = atomic number
a = proportionality constant
b = constant for lines of X-ray
De-brogle relation
According to Einstein’s mass energy relation and Planck’s quantum theory . He derived a relation

h
 .............(1) for light wave
mc

h
 .............(2) for matter wave
mv
Relation between KE and 

h

2mKE

 Number of waves or wavelength produced by an electron when it is revolve round the nucleus in the
2rn
nth Bohr orbit is equal to its principle quantum number n


Vn
 Number of revolutions made by electron in the nth orbit per sec  
2rn

1  2rn
 The time required for the revolution of electron in the nth Bohr orbit T =  Vn

150
 Relation between  and potential =  o 
A V
Heinsenbergs uncertainity principle
It is impossible to determine both position and momentum of sub atomic particles simultaneously with
accuracy.

h
x. p 
4

h
x.mv  ; where x and p are uncertainity position and uncertainity momentum respectively..
4

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h
E. t  ; where E uncertainity energy and t uncertainity in time
4
Quantum mechanical model of an atom (Erwin Schrodinger)
Based on De-Broglie relation and Heisenberg uncertainity principle, Erwin Schrodinger put forward
an equation,. Through that equation he could clearly explained the quantum mechanical model of an
atom.
Schrodinger wave equation

Ĥ  E

2  2  2 82m
   E  v    0
x 2 y 2 z 2 h2

82m
2  E  v   0
h2

Ĥ  Hamiltonion 
 Mathematical operator
 2  Laplacian 

Significance of 
 has no independent significance.  is a solution of Schrodinger equation.  is a wave function
only.

 2 has significance, it is the region in space where the probability of finding electron is maximum.
ie orbital.

ie.    radial .  angular ;  nlm   r .   .

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O rbit O rbital
Electrons revolving round the
It is the region in space where the probability
1 nucleus in a stationary
of finding of electron is m axim um
circular path

2 It is 2-Dimensional It is 3-Dim ensional

Orbitals have:-
S-orbital - spherically sym m etrical
3 It is circular in shape P-orbital - dum b bell
d-orbital - double dumb bell
f - Three dim ensional complicated structure

It doesn't obey Heisenberg's

4 It obeys Heisenberg's uncertainity principle
uncertainity principle

Quantum numbers
These are the numbers which designate size/energy of orbit, shape of orbitals, orientation /direction
of orbitals and spinning of electrons in its own axis.
Mainly three quantum number n, l, m are used to construct an orbital.
I. Principal quantum number (n) Bohr
It gives the size or energy of shell or orbit
It denoted by the letter n
n can have values 1, 2, 3, 4 etc represents K, L, M, N shells.
 Maximum number of subshells present in shell = n
 Maximum number of orbitals present in shell = n2
 Maximum number of electrons can occupy in the shell = 2n2
II. Azimuthal Quantum number / Subsidiary quantum number - Angular Quantum Number
(Somerfield)
 It gives shapes of sub shells
 Its value is obtained by l = 0 to n – 1
 It denoted by l
l = O - s = subshell
l = 1 - p - subshell
l = 2 - d - subshell
l = 3 - f - subshell
 If n = 1, K shell; l = 0 1s subshell
n = 2, L shell; l=0 2s subshell
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l=1 2p subshell
So on

Angular momentum of orbital =     1 h

2
Sommerfield model of an atom
 He could clearly explained atom with sub shells
ie. motion of electron in closed circular orbit is influenced by its own nucleus and is set up into closed
elliptical path.

III. Magnetic Quantum Number  m  Lande / Zeeman

 It gives orientation or direction of orbitals

 Its value obtained by the relation , 0,  

 It denoted by the letter m

n  1 K shell   0 1s subshell 1s orbital

(l  0) (ml  0)
n2 0 2s subshell m  0 2s orbital
-1 0 +1
 1 2p subshell m 

Px Pz Py

n=3 l=0 s subshells ml = 0 3s orbital

l=1 p subshell ml = -1 0 +1

3Py 3Pz Px
ml = -2 -1 0 +1 +2
l=2 d

3dxy 3dyz 3dz2 3dxz 3dx2-y2

 Maximum number of orbitals in subshell =  2  1 

 Maximum number of electron can occupy the sub shell = 2  2  1  4  2

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Brilliant STUDY CENTRE RESIDENTIAL -2024 (ONLINE CLASS NOTES)

IV. Spin quantum number (m(s)) (Uhlenbeck Goudsmit)

 It gives the spinning of electron in its own axis
 Its values are –1/2, +1/2
 Maximum two electrons with opposite spin can be placed in an orbital.


SHAPES OF SUB SHELLS
S-orbital

p-orbital

d-orbital

Node:
The region space where the probability of finding electron is zero. There are two types of nodes:-
1. Radial node / spherical node

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2. Nodal plane / angular node

 Radial node or spherical node = n    1

 Angular node/nodal plane =  value
 Total number of nodes = n – 1
Radial Probability Distrubution Curves

 = radial wavefunction,  2 radial probability density 2

4 r2dr  -radial probability
function

Number of minima = no.of radial node = n    1

Number of maxima = no.of radial node + 1 = n  

Rules for writing the electronic configuration
1. Pauli’s exclusion principle : No two electrons in an atom can have same set of 4 quantum numbers.
2. Aufbau principle: Electrons are filling in the increasing order of energy of atomic orbitals. It is based
on  n    rule

Rule-I : The orbitals having higher  n    value higher will be the energy..

Rule-II : If the orbitals having same  n    value, higher the n value orbital higher will be the energy..

In single electron system (Orbit is considered) : 1s < 2s = 2p < 3s = 2p = 3d

In multiple electron system : 1s < 2s < 2p < 3s < 3p < 3d (orbital is considered)
Hunds rule of maximum multiplicity
In a degenerate orbitals like p, d and f, electrons are filling first singly occupied after that pairing will
occur.

For example : p4

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Brilliant STUDY CENTRE RESIDENTIAL -2024 (ONLINE CLASS NOTES)

Exceptional configuration

Cr = 24  Ar  4s 3d
1 5

18

Cu  29  Ar  4s1 3d10
18

This is due to half filled and fully filled stable configuration

Reason for half filled and fully filled stable configuration
1. Symmetrical arrangement
2. Exchange energy
The energy released, when electrons are exchange in orbitals. Exchange energy increases, stability
increases. Number of exchanges directly proportioal to stability.
Number of exchanges increases also stability increases.

P3 P6

No of exchanges = 3 No.of exchanges = 6

 Stability order of half filled/fully filled orbitals : d5 < p3 < d10 < p6
Reason
First consider the orbital stability then exchange energy.
 Spectrum will not produce, when an electron exchange takes place in degenerate orbitals.

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