Introduction

In the previous chapter, we have discussed about Some Basic Concept

of Chemistry but in this chapter, we shall study about Structure of
Atom. Atom is made up of still smaller particles like electrons, protons
and neutrons. The arrangement of these particles within the atom was
put forward by Rutherford (in 1911) on the basis of his "Scattering
experiments".

The word "atom" has been derived from the Greek word 'atomos’
which mans 'indivisible’. These early ideas were mere speculation and
there was no way to test them experimentally.

Atomic Structure

Atom is made up of smaller units like proton, neutron and electron.

Some other particles like positron, neutrino, antineutrino, π-meson, μ-
meson, k meson etc are also present which are very short lived.

Discovery of Electron

In 1879, William Crooks studied the conduction of electricity through

gases at low pressure. He performed the experiment in a discharge
tube which is a cylindrical hard glass tube about 60 cm in length. It is
sealed at both the ends and fitted with two metal electrodes. The
electrical discharge through the gases could be observed only at very
low pressures and at very high voltages.

J.J. Thomson took a discharge tube and applied a voltage of a 10000

volt potential difference across it at a pressure of 10 –2 mm of Hg. He
found some glowing behind anode. It means some invisible rays
produced at cathode strike behind anode and produce fluorescence.
He named them cathode rays.

Properties of Cathode Rays

1. These rays have mechanical energy and travel in straight line.

2. These rays are deflected towards positive plate of electric field. It

means these are made up of negatively charged particle
called electron.

3. Colour observed is independent from nature of gas.

4. Mulliken determined the charge on electron which is 1.602 × 10

–

19
C.

5. Specific charge on electron is calculated by J.J. Thomson.

Charge to mass ratio

J.J. Thomson for the first time experimentally determined charge/mass

ratio called e/m ratio for the electrons. For this, he subjected the beam
of electrons released in the discharge tube as cathode rays to
influence the electric and magnetic fields. These were acting
perpendicular to one another as well as to the path followed
by electrons.

According to Thomson, the amount of deviation of the particles from

their path in presence of electrical and magnetic field depends on
 1. Magnitude of the negative charge on particle
2. Mass of particle
3. Strength of magnetic field

When electric field is applied, deviation from path takes place. If only
electric field is applied, cathode rays strike at A. If only magnetic field is
applied, cathode rays strike at C. In absence of any field, cathode rays
strike at B.

By carrying out accurate measurements on the amount of deflections

observed by the electrons on the electric field strength or magnetic
field strength, Thomson was able to determine the value of

e/me = 1.758820 x 1011 C kg-1

where me = Mass of the electron in kg

e = magnitude of charge on the electron in coulomb (C).

Discovery of anode rays

In 1886, Goldstein modified the discharge tube by using a perforated

cathode. On reducing the pressure, he observed a new type of
luminous rays passing through the holes or perforations of the
cathode and moving in a direction opposite to the cathode rays. These
rays were named as positive rays or anode rays or as canal rays. Anode
rays are not emitted from the anode but from a space between anode
and cathode.

Properties of anode rays

1. These rays deflect towards negative plate of applied electric field.

It means these are made up of positively charged particle.
2. Property of anode rays depends on nature of gas.
3. These rays travel in straight line and have mechanical energy.

Discovery of Neutron
Chadwick in 1932 found the evidence for the production of neutron in
given reaction.

4Be9 + 2He4 ⟶ 6C12 + 0n1

Neutron is chargeless particle and have mass equal to proton.

Millikan’s Oil Drop Experiment

In this experiment, some fine oil droplets were allowed to enter

through a tiny hole into the upper plate of electrical condenser. These
oil droplets were produced by atomiser. The air in the chamber was
subjected to the ionization by X-rays. The electrons produced by the
ionization of air attach themselves to the oil drops

Thus oil droplets acquire negative charge. When sufficient amount of

electric field is applied, the motion of the droplets can be accelerated,
retarded or made stationary. Millikan observed that the smallest
charge found on them was –1.6 × 10–19 coulomb and the magnitude of
electrical charge, q on the droplets is always an integral multiple of the
electrical charge ‘e’ i.e., q = ne

Thomson’s Model of Atom

J.J. Thomson in 1898, proposed a model of atom which looked more or

less like plum pudding or raisin pudding. He assumed atom to be a
spherical body in which electrons are unevenly distributed in a sphere
having positive charge which balance the electron’s charge. It is called
Plum pudding model.

Important Feature of This Model : The mass of the atom is assumed

to be uniformly distributed over whole atom.
Failure : This model was able to explain the overall neutrality of the
atom, it could not satisfactorily, explain the results of scattering
experiments carried out by Rutherford in 1911.

Rutherford's Model

Rutherford in 1911, performed some scattering experiments in which

he bombarded thin foils of metals like gold, silver, platinum or copper
with a beam of fast moving a-particles. The thin gold foil had a circular
fluorescent zinc sulphide screen around it. Whenever a-particles struck
the screen, a tiny flash of light was produced at that point.

From these experiments, he made the following observations:

1. Most of the α-particles pass without any deviation.

2. Few particles deviate with small angle.
3. Rare particles retrace its path or show deflection greater than
90°.

On the basis of these observation, he proposed a model.

1. Atom is of spherical shape having size of order 10–10 meters.

2. Whole mass is concentrated in centre called nucleus having size
of order 10–15 meters.
3. Electron revolves around the nucleus in circular path like planets
revolve around sun.

Limitation : This model could not explain stability of atom. According

to Maxwell's classic theory, an accelerated charged particle liberates
energy. So, during revolution, it must radiate energy and by following
the spiral path it should comes on nucleus.

Atomic number
It is equal to the number of protons present in the nucleus of an atom.
Atomic number is designated by the letter ‘Z’. In case of neutral atom
atomic number is equal to the number of protons and even equal to
the number of electrons in atom.

Z = Number of protons (p) = Number of electrons (e)

Mass number

It is equal to the sum of the positively charged protons (p) and

electrically neutral neutrons (n). Mass number of an atom is
designated by the letter ‘A’.

Mass number (A) = Number of protons (p or Z) + Number of neutrons

(n)

Note : The atom of an element X having mass number (A) and atomic
number (Z) may be represented by a symbol ZXA.

Isotopes

Atoms with identical atomic number but different atomic mass number
are known as Isotopes. Isotopes of Hydrogen 1H1, 1H2 and 1H3

Isobars

Isobars are the atom with the same mass number but different atomic
number, for example 6C14 and 7N14

Electromagnetic Waves Theory

This theory was put forward by James Clark Maxwell in 1864.

Electromagnetic Waves are the waves which are produced by varying
electric field and magnetic field which are perpendicular to each other
in the direction perpendicular to both of them.
The main points of this theory are as follows:

1. The energy is emitted from any source continuously in the form

of radiations and is called the radiant energy.

2. The radiations consist of electric and magnetic fields oscillating

perpendicular to each other and both perpendicular to the
direction of propagation of the radiation.

3. The radiations possess wave character and travel with the

velocity of light 3 x 108 m/sec.

4. These waves do not require any material medium for

propagation. For example, rays from the sun reach us through
space which is a non-material medium.

Characteristics of a Wave

Wavelength (λ) : It is the distance between two consecutive crests or

troughs and is denoted by λ.

Frequency (v) : It is the number of waves passing through a given

point in one second. The unit frequency is hertz or cycle per second.

Wave number : It is the number of waves in a unit cycle. wave

number =1λ=1λ

Velocity : Velocity of a wave is defined as the linear distance travelled

by the wave in one second. It is represented by c and is expressed in
m/sec.

Amplitude : Amplitude of a wave is the height of the crest or the depth

of the through. It is represented by V and is expressed in the units of
length.
Black Body Radiations

Black-body is an ideal body which emits and absorbs radiations of all

frequencies. The radiation emitted by these bodies is called black-
body radiation.

At a given temperature, the intensity and frequency of the emitted

radiation depends is temperature. At a given temperature, the
intensity of radiation emitted increases with decrease of wavelength.

Photoelectric Effect

When light of a suitable frequency is allowed to incident on a metal,

ejection of electrons take place. This phenomenon is known as photo
electric effect.

Observations in Photoelectric Effect

1. Only photons of light of certain minimum frequency called

threshold frequency (v0) can cause the photoelectric effect. The
value of v0 is different for different metals.

2. The kinetic energy of the electrons which are emitted is directly

proportional to the frequency of the striking photons and is quite
independent of their intensity.

3. The number of electrons that are ejected per second from the
metal surface depends upon the intensity of the striking photons
or radiations and not upon their frequency.

Explanation of Photoelectric Effect

Einstein in (1905) was able to give an explanation of the different
points of the photoelectric effect using Planck’s quantum theory as
under:

1. Photoelectrons are ejected only when the incident light has a

certain minimum frequency (threshold frequency v0).

2. If the frequency of the incident light (v) is more than the

threshold frequency (v0), the excess energy (hv–hv0) is imparted
to the electron as kinetic energy.

3. On increasing the intensity of light, more electrons are ejected

but the energies of the electrons are not altered.

K.E. of the ejected electron.

12mv2=hv–hv012��2=ℎ�–ℎ�0

Planck's Theory

According to this theory, energy cannot be absorbed or released

continuously but it is emitted or released in the form of small packets
called quanta. In case of light this quanta is known as photon. This
photon travels with speed of light. Energy of the photon is directly
proportional to frequency.

E∝ν�∝�
E=hν�=ℎ�

h is Planck's constant, value is 6.62 × 10–34 Js

Bohr’s Model

Niels Bohr in 1913, proposed a new model of atom on the basis of

Planck’s Quantum Theory. The main points of this model are as
follows:
 1. Atom is of spherical shape having size (of order 10
–10
metre).

2. Whole mass is concentrated in centre called nucleus (having

order of size 10–15 metre).

3. Electron revolves around nucleus only in limited circular path and

he assumed that electron does not radiate energy during its
revolution in permitted paths.

4. Only those orbits are allowed whose orbit angular momentum is

integral multiple of h2πℎ2�.
mvr=nh2π���=�ℎ2�, where n = 1, 2, 3, 4...

5. When electron absorbs energy, it jumps to higher orbit and when

it comes back, it radiates energy. This postulate explain spectra.

Achievements of Bohr’s Theory

1. Bohr’s theory has explained the stability of an atom.

2. Bohr’s theory has helped in calculating the energy of electron in

hydrogen atom and one electron species.

3. Bohr’s theory has explained the atomic spectrum of hydrogen

atom.

Limitations of Bohr’s Model

1. The theory could not explain the atomic spectra of the atoms
containing more than one electron or multielectron atoms.

2. Bohr's theory failed to explain the fine structure of the spectral

lines.

3. Bohr’s theory could not offer any satisfactory explanation of

Zeeman effect and Stark effect.
 4. Bohr’s theory failed to explain the ability of atoms to form
molecule formed by chemical bonds.

5. It was not in accordance with the Heisenberg’s uncertainty

principle.

Spectra

The most compelling evidence for the quantization of energy comes

from spectroscopy. Spectrum word is taken from Latin word which
means appearance. The record of the intensity transmitted or
scattered by a molecule as a function of frequency or wavelength is
called its spectrum.

Cosmic rays < gamma rays < x rays < ultraviolet rays < visible rays <
infra red < micro waves < radio waves

Line Spectrum of Hydrogen Atom

When electric discharge is passed through hydrogen gas enclosed in

discharge tube under low pressure and the emitted light is analysed by
a spectroscope, the spectrum consists of a large number of lines which
are grouped into different series. The complete spectrum is known as
hydrogen spectrum.

On the basis of experimental observations, Johannes Rydberg noted

that all series of lines in the hydrogen spectrum could be described by
the following expression:

Zeeman Effect

When spectral line (source) is placed in magnetic field, spectral lines

split up into sublines. This is known as zeeman effect.
Stark Effect

If splitting of spectral lines take place in electric field, then it is known

as stark effect.

Dual Behaviour of Matter (de Broglie Equation)

de Broglie in 1924, proposed that matter, like radiation, should also

exhibit dual behaviour i.e., both particle like and wave like properties.
This means that like photons, electrons also have momentum as well
as wavelength.

Assume light have wave nature, then its energy should be given by
Planck's theory

E=hν�=ℎ� …(i)

If it have particle nature, then its energy should be given by Einstein

relation

E = mc2 …(ii)

On comparing equation (i) and (ii),

hν=mc2ℎ�=��2
λ=hmc�=ℎ�� (for light) …(iii)

For other matter,

λ=hmv�=ℎ�� …(iv)
λ=hp�=ℎ� …(v)

where p = momentum

This equation is called de Broglie equation.

Heisenberg’s Uncertainty Principle

It states that, "It is impossible to measure simultaneously the exact

position and exact momentum of a microscopic particle".

If uncertainty in position = Δx and

Uncertainty in momentum = ΔP

When both are measured simultaneously, According to this principle,

Δx.ΔP≥h4π