C-02 Structure of Atom

⟹ An Indian philosopher Maharishi Kanad postulated that if we go on dividing matter (pa

darth) we shall ultimately get the smallest particle beyond which further division will not
be possible. These smallest particles were named parmanu.
⟹ Democritus and Leucippus also suggested that if we keep on dividing matter a stage
will come when particles obtained cannot be divided further. These particles were called
atoms.
⟹ John Dalton for the first time explained the atom by putting forward this theory the
atomic theory. According to this theory atom is the smallest indivisible particle which
participates in a chemical reaction.
⟹ In 1833 Michael Faraday showed that there is a relationship between matter and
electricity. This for the first time suggested that atom is not the smallest indivisible
particle of all matter but was made up of smaller particles.
⟹ The foundation of modern picture of atom was laid by J.J Thomson and Ernest
Rutherford.
⟹ The atom consists of several particle called subatomic particles like electron, proton,
neutron, positron, neutrino, meson etc. Out of these the electron, the proton and the
neutron are called fundamental particles.

Cathode Rays-Discovery of electron.

⟹ In 1859 Julius Plucker started the study of conduction of electricity through gases at a
low pressure in discharge tube.
⟹ The discharge tube in a hard glass tube with two metal electrodes sealed at both the
ends. it is connected to a side tube through which it can be evacuated to any desired
pressure with the help of a vaccum pump.
⟹

1
⟹ Further investigations were made by W.Crookes, J.Perrin, J.J Thomson and othus
Characterstics of Cathode rays:
1. They travel in straight lines away from the cathode with very high velocities. From
109 −1011 cm per second. A shadow of metallic object placed in the path of cathode rays
is casted on th wall opposite to the cathode.
2. They produce heat energy when they collide with metter this can be shown by placing
aluminium foil in the path of cathode rays.
3. When the rays are passed between two electrically charged plates, they are deflected
towards the positively charged plate. This shows that the cathode rays are negatively
charged.
4. Cathode rays are mechanical in nature. This can be proved by placing a spinning wheel
in the path of cathode rays. The wheel starts to move. This shows that cathode rays have
kinetic energy. Thus cathode rays consist of material particles which have mass and
velocity.
⟹ These netgatively charged particles were called negatrons by J.J Thomson and latter
electron by stoney.
⟹ Cathode rays produce X-rays. They effect the photographic plate.
⟹ The nature of cathode rays are independent of
(a) the nature of the cathode
(b) the gas in the discharge tube.

Charge and Mass of electron:-

⟹ JJ Thomosn determined the ratio of the charge (e) of the electron to its mass by
measuring the deflection under the simultaneous influence of electric and magnetic
fields applied perpendicular to each other.
⟹ The apparatus is set up in such a manner that high potential is maintained between
cathode and anode.
⟹ Electrons emitted from the cathode are accelerated by high voltage. The beam emitted
pases through electric and magnetic fields which are perpendicular to each other and
also to the direction of the motion.
⟹ The amount of deviation of the particles form their path in the presence of electrical
and magnetic field depends upon the following.

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(i) Magnitude of negative charge of particles:-
Greater the magnitude of the charge on the particles, greater is the interaction with the
electric or magnetic field and therefore greater is the deflection.
(ii) Mass of the particles:- Lighter the particles greater is the deflection.

(iii) Strength of electric and magnetic field:-

The deflection of the particles increases with increase in voltage.
⟹ When only electric field is applied, the electrons devide form their path and hit the
cathode ray tube at point A.
⟹ When only magnetic field is applied, electrons devide form their path and hit the
cathode ray tube at point C.
⟹ By balancing the electric and the magnetic field it is possible to bring back the electron
to the path followed as in the absence of electric and magnetic field and they hit the
screen at point ‘B’.
⟹ By observing the deflection due to both magnetic and electric field the value of e/m
was calculated
e
= 1.78 × 1011 C kg −1
m
M = mass of the electron in Kg
E = magnitude of charge on the electron in couloumb.

Determination of charge on the electron:-

⟹ The charge on the electron was measured by Millikan in 1909 by oil drop method.
⟹ Small drops of oil are formed by a sprayer and these are allowed to fall in between two
metal plates which may be electrically charged.
⟹ A single drop between the plates is observed by means of a telescope. The oil falls in
rough the air under the influence of gravitational force. The space between the plates is
then irradiated with X-rays. These rays knocked electrons from some molecules of the
air which were caught by oil droplets having electric charge. by charging the upper
plate +ve and lower plate negative the oil droplet in attracted in the upper plate. To
keep the oil droplet in the centre the electric field is so adjusted that it balances the
downward pull due to gravitational force. These force the drop remains stationary.
From the amount of charge on the plates and the mass of the droplet, the charge on the
droplet was determined.
⟹ From his experiments, Mulikan found the charge on the electron to be 1.6022 × 10−19
coulombs.

3
Mass of the electron:-

The mass of the electron can be calculated from the value of e/m and the value of ‘e’
e 1.6022×10−19
m= =
e/m −1.7588×1011
−31
= 9.109610 kg
⟹ This is termed as the rest mass of the electrons.

rest mass of the electron

⟹ Mass of moving electrons 2
V
√1−( )
C
V = velocity of the electron
c = velocity of light.
⟹ When V = c, mass of the moving electrons becomes infinty
⟹ When V>c, mass of electron becomes imaginary.
Mass of electron relative to that of hydrogen atom:
= 1.008 amu = 1.008 X 1.66 X 10−24 g
Mass of hydrogen atom
Mass of hydrogen atom 1.673×10−24
=
Mass of the electron 9.11×10−28
= 1837
1
∴ Mass of an electron = × mass of hydrogen atom
1837
⟹ An electron is thus defined as a subatomic particle which carries charge −1.60 ×
1
10−19 coulomb and has mass 9.1 × 10−28 g i. e th mass of the hydrogen atom.
1837
⟹ Electrons are essential constitution of all atoms, this can be proved as electrons emitted
from different sources have the same mass and same charge

Discovery of Proton:-

⟹ With the discovery of electrons, sceientists started looking for positively charged
particles which were naturally expected as matter is electrically neutral.
⟹ The experimental verification for proton was discovered by Goldstien in 1886
⟹ He used performed cathode in the modified cathode ray tube.
⟹ On applying high potential differnce between the electrons it was observed that not
only cathode rays were produced but also a new type of rays were produced
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 simultaneously form the anode moving towards the cathode and passed through the
holes of the cathode. These were called anode rays or canal rays.
⟹ Thomson studied the properties of anode rays suggesting that these were positively
charged rays.

Characteristics of anode Rays:-

(i) The rays travel in straight line and cast a shadow of the object placed in their path.
(ii) Like cathode rays, these rays rotate the wheel placed in their path and also have
heating effect. Therefore they also have mass particles.
(iii) The rays produce flashes of light on ZnS screen.
(iv) The rays are deflected by electric and magnetic fields in a direction oppisite to that of
cathode rays. These rays are attracted towards the negatively charged plate there by
showing that they are +vely charged.
(v) Positive particles in these rays have e/m values much smaller than that of electron. This
suggested that they have higher masses than electons.
(vi) e/m value is dependent on the nature of the gas taken in the discharge tube i.e positive
particles are different in different gases.
e/m ration of proton = 9.57 × 104
J.J Thomson made there measurements.
⟹ The name proton was given by Rutherford.
⟹ Charge on the proton = +1.602 × 10−19 C
e 1.602×10−19
Mass of proton = =
e/m 9.57×104
= 1.67 × 10−24 g
= 1.67 × 10−27 kg

1.672×10−24
Mass of the proton in amu = = 1.0072
1.66×10−24
⟹ ∴ A proton is defined as a subatomic particle which has mass nearly 1 amu and a
charge of +1 unit.
⟹ Protons, are produced in a number of nuclear reactions. On the basis of such reactions
proton has been recognised as a fundamental building unit of the atom.
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Arrangment of electrons and protons in an atom:

1. Thomson model of atom:-

⟹ The first simple model was proposed by J.J Thomon known as Thomson’s atomic
model.
⟹ He proposed that the positive charge is spread over a sphere in which the electrons are
ambeded to make the atom as a whole neutral. This model was like raisins in a a
pudding and is known as Thomson’s plum pudding model. It was also compared with
water nelon model of positive charge in which seeds (electrons) were ambeded.
⟹ An important feature of this model in that the mass of the atom is considered to be
evenly spread over the atom.
⟹ This model could not explain the Rutherford’s ∝. Scattering experiment. Thus it was
discarded soon.

2. Rutherford’s model of an atom:

⟹ In 1911 Rutherford and his co-workers carried out a series of experiments using ∝-
particles (nuclie of the having mass 4 amu and charge 2 unit +ve charge)
⟹ A beam of these particles was directed against a thin foil of gold, pltinum, silver or
copper. The foil was surrounded by a circular fluoroscent ZnS screen. Whenever an a-
particle stuck the screen, it produced a flash of light.

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The following observations were made:
(i) Most of the ∝-particles went straight without suffering any deflection.
(ii) A few of them were deflected to certain angles.
(iii) A very few (about one in 20,000) did not pass through the foil at all but suffered large
deflections. Some of them also showed deflections of 180o
⟹ Consider an ∝-particle of mass ‘m’ moving directly towards a nucleus with velocity
‘v’ at any given time. As this ∝- particle approaches the nucleus, its velocity hence
kinetic energy continuous to decrease. At a certain distance from the nucleus, the ∝-
particle will stop and starts retracing its path. This distance is called distance of closest
approach. At this distance, the kinetic energy of ∝-particles in transformed into
electrostatic potential energy.
⟹ The distance of closest approach is of the order of 10−14 m. So the radius should be
less than 10−14 m
Following conclusions were made from the Rutherford’s experiment:

(i) As most of the ∝- particles went straight, it suggested that most of the space in the atom
is empty.
(ii) As a few of the ∝-particles were deflected, it was concluded that whole of the positive
charge is concentrated in a very small space in the atom. When ∝- particles are closer
to this point, they suffer forces of repulsion and deviate from their path. The positively
charged heavy mass which occupies only a small volume in an atom is called nucleus.
It is present at the centre of the atom.
(iii) A very few of the ∝-particles bounced cack as they directly collided with the nucleus.

Moosley Experiment→Atomic number:

⟹ Moseley (1912-1913) investigated the x-ray spectra of 38 different elements, starting

from aluminium and ending in gold. It was observed that the frequency of a particular
spectral line gradually increased with increase in atomic mass of the element. But soon
it was suggested that the frequency of particular spectral line was related to the atomic
number ‘z’. He presented the following relation ship:
√𝑣 = 𝑎(𝑧 − 6)
𝑣 = frequency of X − Rays.
Z = atomic number
a and b = constants.
⟹ Thus it was suggested that the atomic number of an element is equal to total +ve
charge contained in the nucleus of its atom.

⟹ Atomic number of the element:-

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= Serial number of the element in the periodic table
= charge on the nucleus of the atom of the element.
= number of protons present.
= number of extranucleal electrons present.

Discovery of neutron:

⟹ The discovery of neutron was made about 20 years often the structures of atom.
⟹ Atomic masses of different atoms could not be explained if the atom consisted of only
electrons and protons.
⟹ Thus Rutherford suggested that in atom there must be present atleast of third type of
fundamental particle which should have no charge and have mass equal to that of
proton. He called these particles as neutrons.
⟹ In 1932 Chadwick bombarded beryllium with ∝-particles to discover ‘neutrons’
⟹ The mass of neutron was 1.675 × 10−24 g i.e nearly equal to that of proton.
⟹ Neutron is a subatomic particle which has mass 1.675 × 10−24 g and has no electrical
charge.
⟹ e/m value of neutron is zero.

Rutherford Model:-
According to this model:-
(i) An atom consists of a heavy positively charged nucleus where all protons and neutrons
are present. These were collectively called nucleons. The +ve charge on the nucleus is
different for different atoms.
(ii) The volume of the nucleus is very small and is only a small fraction of the total volume
of the atom. Nucleus has a diameter of 10−12 to 10−13 cm and an atom has a diameter
of 10−12 to 10−13 cm and an atom has a diameter of 10−8 cm
⟹ The radius of a nucleus is proportional to the cube root of the number of electrons
within it.
(iii) There are empty space around the nucleus called extranuclear part. In this extranuclear
part electrons are present. As the nucleus part of the atom is responsible for the mas of
the atom, the extranuclear mass gives its volume.
(iv) Electrons revolve around the nucleus in closed orbits with high speed
⟹ This model was similar to the solar system, the electrons are therefore called planetary
electrons.

Drawbacks of Rutherford model:-

(i) According to classical electromagnetic theory, when a charged particle moves under the
influence of attractive force, it loses energy continuously in the form of electromagnetic
radiations. Thus, when electron moves in an electric field it must emit radiations. Thus
an electron should loose energy at every turn and should move closer and closer to the

8
 nucleus. Ultimately it should fall in the nucleus thus making the atom unstable.
Therfore this model does not explain the stability of atom.
(ii) If the electron loose energy, the observed spectrum should be continuous but the actual
spectrum consists of well defined lines of definite frequencies. Thus this model could
not give a statisfactory explanation of the actual spectrum.

Electromagnetic radiations:
⟹ Radiations which are simultaneously subjected to electric and magentic fields.
⟹ They are generated by oscillations of a charged body in a magnetic field or a magnet in
an electrical field.
⟹ These radiations do not need any medium for propagation.
⟹ These radiations or waves have electrical and mgnetic fields associated with them and
travel at right angle to these fields.

Characterstrics of electromagnetic radiations.

(i) All electromagnetic radiations travel with the speed of light i.e 3 × 108 ms −1
(ii) These consist of electric and magnetic fields that oscillate in directions perpendicular
to each other and perpendicular to the direction in which the wave is travellig.

A wave is characterized by the following six characterstics

(i) Wavelength →
→ distance between two nearest crsts or two nearest troughs.

Wavelegnth can be measured in the following units:

IÅ = 1018 cm = 10−10 m
IHm = 10−4 cm = 10−6 m
Inm = 10−7 cm = 109 m
1cm = 108 Å = 104 Hm = 107 nm

(ii) Frequency = v
⟹ It is defined as the number of waves which pass through a point in one second.
⟹ Its unit is s −1 or Hz.
(iii) Velocity =’c’
⟹ It is defined as the distance covered in one second by the wave.
⟹ All electromagnetic waves travel with the same velocity i.e 3 × 1010 cm/s

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Relationship between frequency, velocity and wavelength:
𝑐
𝑣=
𝜆
(iv) Wave number:This is the reciprocal of wavelength
𝐼
𝑣̅ =
𝜆
⟹ Its unit is cm−1 or m−1
(v) Amplitude: It is defined as the hight of the crest or depth of the trough of a wave
⟹ It is denoted by ‘a’
⟹ It determines the intensity of the radiation.
(vi) Time period= Time taken by the wave for one complete cycle
1
Electromagnetic spectrum: 𝑇 =
𝑣

The arragement of various types of elctronmagnetic radiation in order of their increasing

frequencies and decresing wavelengths.
𝑣 = 3 × 107 𝑠 −1 ⟶ 3 × 1021
𝜆 = 103 ⟵ 10−11

S.No Name Wavelength(Å) Frequency Source

1 Radio wave 3 × 1014 − 3 × 107 1 × 105 Attending
− 1 × 109 current of high
frequency
2 Microwave 3 × 107 − 6106 1 × 109 Klystron tube
− 5 × 1011
3 Infrared 6 × 106 − 7600 5 × 1011 Incandescent
− 3.95 × 1016 objects
4 Visible 7600 − 3800 3.95 × 1016 Electric bulbs,
− 7.9 × 1014 sun rays.
5 Ultraviolet UV 3800 − 150 7.9 × 1014 Sun rays, area
− 2 × 1016 lamps with
mercury
vapours
6 x-rays 150 − 0.1 2 × 1016 Cathode rays
− 3 × 1019 striking metal
plate.
7 𝛾-rays 0.1 − 0.01 3 × 109 Secondary
− 3 × 1020 effect of
radioactive
decay

10
 8 Cosmic rays 0.01 − zero 3 × 1020 Outer space
− Infinity

Emission spectra-Hydration spectrum:

⟹ the putting up of light into series of color bands is known as dispersion and the series
of colour bonds is called spectrum.
⟹ It is broadly of two types:
(i) Emission spectrum (ii) Absorpton spectrum.

Emission spectrum Absorption spectrum

1. It gives bright lines (coloured on the 1. It gives dark lines on the bright
dark background background.

2. Emission spectrum is obtained when Absorption spectrum is obtained when

radiations emitted by the excited the white light is first passed through the
substance are analysed with substance (in gaseous state or in
spectroscope. solution) and the transmitted light is
analysed with a spectro –scope.

Emission spectra:-
It is obtained form the substance which emit light on excitation i.e either by heating the
substance on flame or by passing electric discharge through gases at low pressure or by
passing electric current discharge through a this filament of high melting point metal.
⟹ There are two types of emission spectrum:-

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 (i) Continuous spectra:-
⟹ when white light is allowed to pass through a prism, it gets resolved to many colour. In
this one colour merges into other just like a rainbow. It gives us VIBGYOR that is colour
of a raibow.
ii) Discontinuous spectra: When gases or vapour of a chemical substance are heated in an
electric arc or in a bbussen flame, light is emitted. If a ray of this light is passed through
a prism, a line spectrum is observed. Every element has a different spectrum therefore
they are known as thumb inpressions of each atom.
⟹ Hydrogen spectrum is an example of emission spectrum. When an electric discharge is
passed through hydrgoen gas at low pressrue, a blue light is emitted. When a ray of this
light is passed through a prism, a discontinuous line spectrum of sharp lines is obtained.
The hydrogen spectrum has the following series:
Spectral Series Discovered by Region
1. Lyman series Lyman Ultraviolet region.
2. Balmer series Balmer Visible region.
3. paschen series Pashen Infra red
4. Brachett series Brackett Infra red
5. Ptund seres Pfund Infra red
6. Hmuphrey series Humphery Far infra red
⟹ Ritz proposed a mathematical formula to find the wavelengths of various hydrogen
lines.
Spectral Series Value of n1 Value of n2
1. Lyman series 1 2,3,4,5____
2. Balmer series 2 3,4,5______
3.Paschen series 3 4,5,6______
4. Brackett series 4 5, 6, 7, 8_____
5.P fund series 5 6, 7, 8, 9_____
⟹ Atoms give the spectrum whereas moelcules give band spectrum
⟹ Four lines of Balmer series are given below:
Electronic Transition Name of line Wave No. Wavelength and color
n2 = 3 ⟶ n1 = 2 Hα (first line) 5𝑅 𝜆 = 6563 Å (𝑅𝑒𝑑)
𝑣=
36
𝑛2 = 4 ⟶ 𝑛1 = 2 Hβ (second line) 3𝑅 𝜆 = 4861 Å (𝐵𝑙𝑢𝑒)
𝑣̅ =
16

12
𝑛2 = 5 ⟶ 𝑛1 = 2 Hγ (third line) 21𝑅 𝜆 = 4340 Å (Indigo)
𝑣̅ =
100
𝑛2 = 6 ⟶ 𝑛1 = 2 HS (fourth line) 8𝑅 𝜆 = 4102 Å(violet)
𝑣̅ =
36

Quatntum Theory of Radiation:-

⟹ The electromagnetic wave theory of radiation believed in continusous generation of

energy. This theory explained the phenomenon of energy. This theory explained the
phenomenon of propagation of light such as diffraction and interference but failed to
explain Black body radiation and photoelectric effect

(a) Black body radiation:

A black body refers to an opaque object that emits thermal radiation. A perfect black
body is one that absorbs all incoming light and does not reflect any. At room
temperature, such an object will appear to be perfectly black. However if heated to
higher temperature black body will begin to glow.
⟹ At the beginning of the 20th century scientists lord Rayleigh and max plank studied the
black body radiation using such a device. Plank empirically described the intensity of
light emitted by a black body as a function of wavelength.
⟹ As the temperature of the black body increases the total amount of light emitted per
second increases, and the wavelength of the spectrum peak shifts to the blue colors.
⟹ For example, an iron bar becomes orange red when heated to high temperatrue and its
color shifts towards blue and white as it is heated further.
⟹ Wavelength of maximum emission form a block body is inversly proportonal to its
temperature. Shorter wavelength (higher frequency) light corresponds to high energy
photons.
⟹ The radiation of black body is determined only by temperature not by body’s shape or
composition.
⟹ In particle no material has been found to absorb all incoming radiation, but carbon in
its graphite form absorbs all but 3%.

(ii) Photoelectric effect:

⟹ Proposed by H.Hertz
⟹ When light shines on a metal, electrons can be ejected form the surface of the metal in
a phenomenon known as phtoelectric effect. The electrons that are ejected form the
metals are called photoelectrons.
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⟹ Based on the classical description of light as a wave they made the following
predictions.
(a) The kinetic energy of emitted photoelectrons should increase with the light amplitude.
(b) The rate of electron-emission should increase as the light frequency is increased.
⟹ Let us compare a light wave to a water wave. Imagine some beach balls sitting at the
dock that extends out in the ocean. The dock represents a metal surface, the beach ball
represents electrons and the ocean waves represent light waves. If a single large wave
were to shake the dock, we would expect the energy form the big wave would send the
beach balls flying off the dock with much move kinetic energy of the dock with much
move kinetic energy compared to a single, small wave.
⟹ Light amplitude was predicted to result in photoelectric with more kinetic energy
⟹ When experiments were performed to look at the effect of light amplitude and
frequency the following results were observed:
(a) The kinetic energy of photoelectrons increases with light frequency
(b) Electric current remains constant as light frequency increases.
⟹ It may be noted that only a few metals such a cesium, rubidium, potassium, in which
the electrons are loosely held by the nucleus show this effect.
⟹ The following observations were made during the experiments:
(i) The electrons are ejected from the metal surface as soon as the beame of light strikes
the surface.
(ii) For each metal, certain minimum frequency of light is needed to eject the electrons this
is called threshold frequency and it is different for different metals. Light of frequency
less than 𝑣0 cannot eject electrons no matter how long it falls on the surface or how
high is its intensity.
(iii) The kinetic energy of the ejected electron is directly proportional to the frequency of
the incident radiation and is independent of its intensity.
(iv) The number of electrons ejected per second from the metal surface depends upon the
intensities of incident radiation but does not depnd upon frequency.

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Plank’s Quantum theory:

⟹ In order to explain black body radiation and photoelectric effect, max Plank in 1901
gave a new theory called quantum theory of radiation.
⟹ According to this theory, a hot body emits radiant energy not continuously but
discontinuously in the form of small packets of energy called quantum. The energy
associated with each quantum of given radiation is directly proportional to the
frequency of emitted radiation
𝐸∝𝑣
𝐸 = ℎ𝑣
Where h = Plank’s constant
ℎ = 6.6 2 × 1034 Js
⟹ According to Einstien ligh consists of a stream of particles called photons.
Energy associated with each photon is
𝐸 = ℎ𝑣
Also
𝐸 = 𝑚𝑐 2
Thus it was pointed out that light has wave as well as particle character.
Bohr’s atomic model:
⟹ To explain the hydrogen spectrum Bohr proposed a quantum mechanical model of an
atom. This model was based on the quantum theory of radiation and classical law of
physics
⟹ The important postulates of Bohr’s model are:
(i) The atom has a nucleus where all protons and neutrons are present. The nucleus is
present at the centre of the atom.
(ii) Negativity charged electrons are revolving around the nucleus in the same way as the
planet are revolving around the nucleus in the same way as the planets are revolving
around the sun. The force of attraction between the nucleus and the electron is
centrifugal force of the moving electron.
(iii) Out of infinite number of circular orbits around the nucleus only those are permissible
ℎ
which have angular momentum equal to the internal multiple of
2𝜋
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
ℎ 2ℎ 3ℎ
The angular momentum can have values, such as , , etc. but it cannot have
2𝜋 2𝜋 2𝜋
fractional values. The specified or circular orbits are quantized and are called stationary
orbits.
(iv) Till the electron ramins in any one of the stationary orbits, it does not loose energy.
This is called the ground state. In the ground state, potential energy of electron will be
minimum, therfore it is the most stable state.
(v) Each stationary orbit is associated with a definite amount of energy. The greater is the
distance of the orbit from the nucleus, more shall be the energy associated with it.

15
 These orbits are also called energy levels and are numbered 1,2,3,4……….or K, L, M,
N ………..from nucleus outwards.
i.e
𝐸1 < 𝐸2 < 𝐸3 < 𝐸4
(𝐸2 − 𝐸1 ) > (𝐸3 − 𝐸2 ) > (𝐸4 − 𝐸3 )….
(vi) The emission or absorption of energy in the form of radiations can occur only when an
electron jumps form one stationary orbit to other
∆𝐸 = 𝐸ℎ𝑖𝑔ℎ − 𝐸𝑙𝑜𝑤
= ℎ𝑣
⟸ The electron absorbs energy when it jumps to enter orbit and emits energy when it
jumps back to inner orbit.
⟹ The new state of the electron is called excited state.
⟹ Using the above postulates, Bohr calculated the radii of various stationary orbits, the
energy associated with each orbit and explained the spectrum of hydrogen atoms.
r = 0.529 × 10−8 × n2 cm
𝑟𝑛 = 𝑟1 × 𝑛2 for hydrogen atom
𝑛
𝑟𝑛 = 0.529 × 2 Å (for hydrogen like species)
𝑍
Energy of an electron:-
E = kinetic energy + potential energy
−2𝜋2 𝑘 2 𝑚𝑒 4
𝐸=
ℎ2 ℎ2
2×(3.14)2 ×(9×10)92 ×(9.1×10)−31 ×(1.6×10−19 )4
𝐸=
𝑛2 ×(6.625×10−34 )2
−13.6
= eV per atom
n2
2.18×10−18
= J/mole
𝑛2
−1312
= 2 kJ/mol
n
For hydrogen like atoms:
−13.6
= 2 × z 2 ev/atom
n

Energy Shell E(Joule per atom) E(ev per atom) E kJ/mol

−19
1 −21.79 × 10 −13.6 −313.6
−19 −3.4 −78.4
2 −5.44 × 10
3 −19 −1.51 −34.84
−2.42 × 10
4 −19 −0.85 −19.6
−1.36 × 10
∞ 0 0 0
⟹ Since, ‘n’ can have only integral values, it follows that total energy of the electron is
quantised. The negative sign indicates that the electron is under attraction towards
nucleus.

16
⟹ At infinity the electron has zero energy which means that it is no longer bend to the
nucleus.
Velocity of an electron;
Centrigugal force on electron
= force of attraction between the nucleus and electron.
𝑚𝑣 2 Ze2
= 2
𝑟 r
The angular momentum of an electron is given as:
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
2.188×108
𝑣= 𝑐𝑚/𝑠
𝑛
𝑣1 2 V3 1
= and =
𝑣2 1 V1 3
Orbit frequency: Number of revolutions per second by an electron in a shell is called
orbital frequency
Velocity 𝑉
Number of revolutions per second = =
Circumterence 2𝜋𝑟
Time period of revolution of electron in the nth orbit(in)
2𝜋𝑟 𝑛3
In = = × 1.5 × 10−16
𝑠
𝑣𝑛 𝑧2
Hydrogen spectrum:
⟹ Under ordinary conditions the electron in hydrogen atom lies in the first orbit.
⟹ When it absorbs energy it goes to the higher energy
Shell depending upon how much energy is absorbed.
⟹ When this electron returns to any of the lower energy shell it emits energy .
⟹ Lyman sereis is formed when the electron returns to lowest energy state while balmer
series is formed when electron returns to second energy state.
⟹ Number of lines produced during transmitions
(𝑛2 −𝑛1 )(𝑛2 −𝑛1 +1)
2
⟹ The difference in energy may be expressed as
𝐸2 − 𝐸1 = ∆𝐸 = ℎ𝑣
∆𝐸
𝑣=
ℎ
𝐶 Δ𝐸
𝑣= =
𝜆 ℎ
ℎ𝑐
𝜆=
Δ𝐸
Since h and c are constants, Δ𝐸 correspnds to difinite energy, so a light of definite
wavelenth its produced. This is absorbed as a line in the spectrum of hydrogen atom.
Modification of Rydberg equation:
According to Rydberg equation:
1 1 1
𝑣̅ = = 𝑅 ( − 2)
𝜆 𝑛 2 𝑛 1 2
It is considered that the electron and the nucleus revolve around this common centre of
mass. Therefore instead of mass of the electron reduced mass of the electron was taken:
17
 2𝜋2 𝑧 2 𝑥𝑒 2 1 1
𝑣̅ = (𝑛 2 − 𝑛2 )
𝑐ℎ3 1 2
Reduced mass h can be calculated as:
1 1 1
= +
𝐻 𝑚 𝑀
M = mass of electron
M = mass of nucleus
𝑚𝑀
𝐻=
𝑚+𝑀
(i) First line of series:→line of longest wavelength
→ or line of shortest energy
For first line:
𝑛2 = 𝑛1 + 1
v̅ 1 1 1
= = R [ 2 − (n ]
first Δfirst n1 1 +1)
2

For second, third, and fourth lines

𝑛2 = 𝑛1 + 2, 𝑛2 = 𝑛1 + 3 𝑎𝑛𝑑 𝑛2 = 𝑛1 + 4
∴ Rydberg equation
1 1 1
𝑣̅ = = 𝑅𝑍 2 [ 2 − (𝑛 2
]
𝜆 𝑛1 1 +𝑥)
(ii) Series limit of last line of a series:
For last line
𝑛2 = ∞
̅̅̅̅̅
𝑣 1 𝑅
= = 2
𝑙𝑎𝑠𝑡 𝜆 𝑒𝑎𝑠𝑡 𝑛1
(iii) Intensities of spectral lines
e.g Lyman series
(2 ⟶ 1) > (3 ⟶ 1) > (4 ⟶ 1) > (5 ⟶ 1)
For Balmer series:
(3 ⟶ 2) > (4 − 2) > (5 − 2) > (6 ⟶ 2)
Ionisation energy and excitation energy:-
⟹ The energy requied to remove and electron from the ground state to form cation, i.e., to
take the electron to infinity is called ionisation energy.
𝐼𝐸 = 𝐸∞ − 𝐸𝑔𝑟𝑜𝑢𝑛𝑑.
= 0 − 𝐸1 (𝐻) = 13.6 𝑒𝑉/𝑎𝑡𝑜𝑚
z2
I. E = × 13.6 eV
n2
2
𝐼1 𝑍1 𝑛2 2
= ×
𝐼2 𝑛1 2 𝑍22
⟹ If an electron is already present in the excited state, then the energy required to remove
that electron is called separation energy.
𝐸𝑠𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 = 𝐸∞ − 𝐸𝑒𝑥𝑐𝑖𝑡𝑒𝑑
Limitations of Bohr’s theory:
(i) It does not explain the spectra of multielectron systems.
(ii) It could not explain fine sepctra of even hydrogen
18
(iii) It could not explain the Zeeman effect i.e influence of magnetic field on hydrogen
spectrum and the stark effect i.e influence of electric field on hydrogen spectrum
(iv) Bohr theory is not in agreement with heisenberg uncertainity principle.
Particle and wave nature of electron:
⟹ In 1924, de-Broglie proposed that an electron like light behave both as material particle
and as a wave.
⟹ Thus a new theory was proposed known as wave mechanical theory of matter.
⟹ This theory suggested that electrons, protons and even atoms when in motion possess
wave properties.
⟹ de- Broglie relation:
According to Plank:
ℎ𝑒
𝐸=
According to Einatien
E = mc 2
hc
∴ = mc 2
λ
ℎ𝑐
𝜆=
𝑚𝑐 2
ℎ
𝜆=
𝑚𝑐
ℎ
𝜆=
𝑝
⟹ de Broglie’s equation is applicable in case of smaller particle like electron and has no
significance for larger particles.
(A) de –Broglie wavelength associated with charged particles:
(i) For electron
12.27
𝜆= Å
√𝑣
(ii) For proton
0.286
𝜆= Å
√𝑉
(iii) For ∝ − particle
0.101
𝜆= Å
√𝑣
Where v = accelerating potential of these particles.

(c) de –Broglie wavelength associated with unchanged particles:

(i) For neutrons:
0.286
λ= Å
√E(eV)

(ii) For gas molecule:

ℎ
𝜆=
√3𝑚𝑅 𝑇
Where k = Boltzmann constant
Bohr’s theory versus de-Broglie equation:-
19
⟹ Consider an electron moving in a circular orbit around nucleus. The wave associated
with the orbit may be such that its two ends meet to give a regular series of crests and
troughs. In such case the electron wave is said to be in phase i.e, the circumference of
Bohr orbit is equal to whole number multiple of wavelength of the electron wave.
So,
2𝜋𝑟 = 𝑛𝜆
2𝜋𝑟
𝜆=
𝑛
From de-Broglie relationship
ℎ
𝜆=
𝑚𝑣
2𝜋𝑟 ℎ
=
𝑛 𝑚𝑣
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
⟹ Therefore de-Broglie and Bohr’s concept are in perfect agreement with each other.
Heisenberg Uncertainity Principle:
⟹ Bohr considered an electron as a material particle therefore its position and momentum
can be determined with accuracy. But as electron was considered as a wave by de-
Broglie it became difficult to ascertain of the electron more precisely at a given instant
as the wave is extending throughout a region of space to locate the electron radiation
with extremly short wavelength is required. Radiation with short wavelength has very
high energy and hence it changes the velocity of the electron. Thus the attempt to locate
the electron changes the momentum of the electron. Photons with longer wavelength
are less energetic and cause less effect on the momentum of the electron but due to
larger wavelengths, the position of the electron is not located accurately.
⟹ In 1927, werner Hisenberg stated that: “it is impossible to measure simultaneously the
exact position and exact momentum of a having microscopic particle such as an
electron.
⟹ Mathematically:
ℎ
∆𝜋. ∆𝑝 ≥
4𝜋
ℎ
∆𝜋. 𝑚∆𝑣 ≥
4𝜋
⟹ In case of bigger particles, the value of uncertainity product is negligible. It ∆𝜋 is small
∆𝑣 becomes large and vice-versa. Thus, uncertainity principle is important only for
microscopic particles, like electrons.
⟹ If energy and time are given:
ℎ
∆𝐸. ∆𝑡 ⟹
4𝜋
⟹ For angular motion
ℎ
∆𝐸. Δ𝑡 ≥
4𝜋
⟹ This principle gave a serious blow to the Bohr’s model.

20
⟹ This gave rise to probability picture i.e, a region of space where the probability of
finding an electron is maximum. This three dimensional space around the nucleus is
called an atomic orbital.
Wave Mechanical model of atom:
⟹ The atomic model which is based on the particle and wave nature of the electron is
known as wave mechanical model of the atom.
⟹ This model was developed by Erow in schrodinger.
⟹ The model describes the electron as a three dimensitional wave in the electronic field
of positively charged nucleus
⟹ The schrodinger wave equation may be given as:
𝑑2𝜑 𝑑2𝜑 𝑑2𝜑 8𝜋2 𝑚
+ + + (𝐸 − 𝑉)𝜑 = 0
𝑑𝑥 2 𝑑𝑧 2 𝑑𝑦 2 𝑛2
m = mass of electron; E = total energy opf electron
V= potential energy of electron. φ = wave function of the electron.
Significance of 𝝋:⟹ The wave function is regarded as the amplitude function expressed
in terms of co-ordinates 𝑥, 𝑦, 𝑧. The wave function may have +ve or –ve values.
⟹ Schorodingous main aim has to calculate the probability of finding an electron but it
was observed that Ψ had both +ve and –ve values. But probability should always be
positive and can not be negative. Therefore Ψ 2 was used instead of ψ
Significance of 𝛙𝟐 ⟹ Ψ 2 is a probability factor. It describes the probability finding an
electron within a small space. The space where the probability of finding an electron is
maximum is called an orbital.
⟹ The schrodinger wave equation gives a set of four numbers called quantum numbers.
These quantum numbers describe energies of electrons in atoms, information about the
shapes and orientations of the most probable distribution of electrons around the
nucleus.
⟹ Node is that point where the probability of finding an electron is zero.
⟹ For hydrogen wave function, number of nodes can be calculated as:
(i) Number of radial nodes = 𝑛 − 𝑙 − 1
(ii) Number of angular nodes = 𝑙
(iii) Total number of nodes = 𝑛 − 1
(iv) Number of nodal planes = 𝑙
For s−orbitals
⟹ (n−1)radial + 𝑎ngular nodes = (n − 1) total nodes.
nodes
⟹ For p-orbitals
(n-2) radial nodes +1 angular node = (𝑛 − 1) total nodes.
⟹ For d-orbitals:
(n − 3) radial nodes+2 angular nodes =(n-1) total nodes
Operator form of schrodinger wave equation:
̂ Ψ = EΨ
H
̂=T
H ̂+V ̂ = Haniltonian operator
̂ = kinetic energy operator
T

21
 ̂ = potential energy operator.
V
Quantum Numbers:
⟹ Four numbers are required to locate a particular electron in an atom. These are called
quantum numbers.
1. Principal quantum number:-
⟹ It was given by Bohr. It is denoted by ‘n’ it represents the name, size and energy of the
shell to which the electron belongs
⟹ Value of ‘n’ = 1 2 3 4 5 6 7
Designation = K L M N O P Q
(i) Higher the value of ‘n’ greater is the distance of the shell from the nucleus.
𝑛2
𝑟1 < 𝑟2 < 𝑟3 < 𝑟4 ………..𝑟 = 0.529 × Å
𝑍
(ii) Higher the value of ‘n’ greater is the energy
𝐸1 < 𝐸2 < 𝐸3 < 𝐸4 ……………
Energy separation between two cells decreases on moving away from the nucleus
(𝐸2 − 𝐸1 ) > (𝐸3 − 𝐸2 ) > (𝐸4 − 𝐸3 )
(iii) Maximum number of electrons = 2(2𝑙 + 1)
Present in the subshell
3. Magnetic Quantum number:-
⟹ designed by ‘m’
⟹ proposed by Linde
⟹ It explains the Zeeman effect i.e splitting of single spectral line into a numbe rof lines
in a magnetic field.
⟹ He proposed that under the influence of magnetic field each sub-shell is further
subdivided into orbitals.
⟹ Magnetic quantum number desribes the orientation or distribution of elecron cloud.
⟹ = −𝑙 to + 𝑙
4. Spin Quantum number:-
⟹ denoted by ‘s’
⟹ proposed by Goldschmidt
ℎ
(i) 𝐻𝑠 = √𝑆(𝑠 + 1)
2𝜋
Where 𝑆 = +1/2
1
Total spin of atom n × (n = number of unpaired electrons
2
Radial wave function R:
The function ‘R’ depends only on ‘r’ the distance from nucleus, therefore they describe
the distribution of the electorn as a function of ‘r’ from the nucleus. These functions
depend upon two quantum numbers, n and i.

22
Plot of Radial wave function ‘R’:

Number of radial nodes = (𝑛 − 𝑙 − 1)

At node, the value of ‘R’ changes from positive to negative.
Plot of Radial Probability density ′𝑹′𝟐 :
The plots of probability i.e 𝑅 2 or Ψ 2 are more meaning ful than the plots of functions
themselves. For both is 1s and 2s the probability has maximum value at r = 0 i.e in the
nucleus

Plot of Radial Probability Function (𝟒𝝅 𝒓𝟐 𝑹𝟐 ):

In order to visualize the elcectron cloud within a spherical shell is placed at radii ‘r’ and r
+dr from the nucleus. Thus radial probability function describes the total probability of
finding the electron in spherical shell of thickness or located at the distance r from the
nucleus.
R.P.F = Volume of spherical shell × Probability density
= 4πr 2 dr × R2

Shapes of orbitals:-
Different values of ‘m’ for a given value of ‘l’ provide the total number of ways in which
a given s, p, d and f subshells in present of magnetic field can be arranged in space along
x,y and z axes or total number of orbitals into which a subshell can be divided.
⟹ When 𝑙 = 0, 𝑚 = 0 i.e one value implies that S-subshell has only one space orientation
and hence it can be arranged in space only in one way along x, y or z axes. Thus ‘s’
orbital has a symmetical spherical shape.
23
⟹ In case of 15-orbital the electron cloud is maximum at the nucleus and decreases with
the distance. The region of maximum electron density is called antinode. The electron in
25-orbital is likely to be found in two regions, one near the nucleus and other in a
spherical shell about the nucleus. Electron density is zero in the nodal region
⟹ When 𝑙 = 1, 𝑚′ has three values −1,0, +1. This implies that ‘p’ subshell has three
orientations i.e, three orbitals
Orbital Pz Px Py
m o ±1 ±1
Modal plane xy yz zx
When 𝑙 = 2, ′𝑚′ has give values −2, −1,0, +1, +2. Therefore d has give orbitals:
𝑂𝑟𝑏𝑖𝑡𝑎𝑙 𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑧𝑥 𝑑𝑥 2 − 𝑦 2 𝑑𝑧 2
𝑚 ±2 ±1 ±1 ±2 0

Orbital Nodal planes

𝑑𝑥𝑦 𝑥𝑧, 𝑦𝑧
𝑑𝑦𝑧 𝑥𝑦, 𝑧𝑥
𝑑𝑥𝑧 𝑥𝑦, 𝑦𝑧
2 2
𝑑𝑥 − 𝑦 𝑥 − 𝑦 = 0, 𝑥 + 𝑦 = 0
2
𝑑𝑧 no nodal plane, it has a ring around the lobe.
⟹ f-has seven orbitals 𝑓𝑥(𝑥 − 𝑦 𝑓𝑦(𝑥 2 − 𝑦 2 ), 𝑓𝑧(𝑥 2 −
2 2 ),

𝑦 2 ), 𝑓𝑥𝑦𝑧, 𝑓𝑥𝑦𝑧, 𝑓𝑧 3 , 𝑓𝑦𝑧 2 and 𝑓𝑥𝑧 2

⟹ +ve values of 𝑚𝑙 describes the orbital angular component in the direction of applied
magnetic field while-ve values of 𝑚𝑙 are for the components in opposite direction to the
applied magnetic field.
Characterstics of orbitals:-
(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 subshell differ in the direction of their space orientation.
Electronic configuration of atoms:-
⟹ The filling up of orbitals in an atom is a hypothetical process in which the atom is buit
up by feeding electrons in orbitals. This distribution of electrons in different orbitals is
known as electronic configuration of the atom.
⟹ The filling up or orbitals is governed by the following principles:
(i) Aufban principle:-
⟹ In the ground state of an atom, an electron enters the orbital of lowest energy first and
subsequent elecrons are filled in order of increasing energies
⟹ The following sequence is observed for orbitals in increasing order of energy:
1𝑠, 2𝑠, 2𝑝, 3𝑠, 3𝑝, 4𝑠, 3𝑑, 4𝑝, 5𝑠, 4𝑑, 5𝑝, 6𝑠, 4𝑡, 5𝑑, 6𝑝
⟹ Bohr Bury’s Rule:

24
Paul’s exclusion principle:
⟹ According to this principle no two electrons in an atom can have same value of all the
four quantum numbers.
⟹ An orbital can accommodate at the maximum of two electron and that two with
opposite spins.
⟹ An electron may have same values of principal, azimuthal and magnetic quantum
numbers but has different values of spin quantum number.
Conclusions:
(i) The maximum capacity of main energy shell is equal to 2𝑛2 electrons.
(ii) The maximum capcity of a subshell is equal to 2(2𝑙 + 1) electrons.
(iii) Number of subshells in 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 and that too with opposite spins.
Hund’s rule of maximum multiplicity:
⟹ One method of representing the electronic configuration is called orbital diagram
⟹ It states that electrons are distributed among the orbitals of a subshell in such a way as
to give maximum number of unpaired electrons with parallel spins.
⟹ In other words pairing will not take place in a set of degenerate orbitals till all electrons
are singly filled.

25
26