Introduction

Democritus was the first to theorize that matter was made of small
pieces.
Leucippus was the first to use the term atom (atomon), which meant
"indivisible" in Greek. The existence of atoms has been proposed since the
time of early Indian and Greek philosophers (400 B.C.) who were of the view
that atoms are the fundamental building blocks of matter. According to them,
atoms are indivisible.
The word ‘atom’ has been derived from the Greek word ‘a-tomio’ which
means ‘uncut-able’ or ‘non-divisible’.

Dalton’ atomic theory :

The atomic theory of matter was first proposed on a firm scientific basis
by John Dalton, a British school teacher in 1808.
Dalton’s atomic theory was able to explain the law of conservation of
mass, law of constant composition and law of multiple proportion very
successfully.
Failed to explain the results of many experiments, for example, it was
known that substances like glass or ebonite when rubbed with silk or fur get
electrically charged.

Atoms are made of sub-atomic particles,

i.e., electrons, protons and neutrons
Experiment No.1 : Cathode ray discharge tube experiment :
Discovery of Electron (1897)
When sufficiently high voltage is applied through an inert gas (He, Ar)
across the electrodes, current starts flowing through a stream of particles
moving in the Cathode ray discharge tube from the negative electrode
(cathode) to the positive electrode (anode). These were called cathode rays
or cathode ray particles.
 Properties of Cathode Rays :

1. Cathode rays travel in a straight line.

2. Cathode rays produces mechanical effect, because they rotate a light
paddle wheel placed in their path.
3. Cathode rays produces Heating effect when they hit a heavy metal.
4. Cathode rays produce flourescent effect on fluorescent material.
5. Cathode rays are Negatively charged.
6. Cathode rays deflect towards a positive terminal in an electric field.
7. Cathode rays deflect towards the direction determined by Fleming’ left
hand rule.
8. Cathode rays can ionize gasses.
9. Cathode rays can produce X rays.
10. Cathode rays do not depend upon the nature of the gas and material.

Charge to mass (e/m) ratio determination of an electron :

This experiment measures e/m, the charge to mass ratio of the
electron.This ratio was first measured by J. J. Thomson in 1897. He
won a Nobel prize for his study of electrons.

Procedure :

(i) In the present experiment a beam of electrons is accelerated

through a known potential, so the velocity of the electrons is known.
(ii)A pair of Helmholtz coils produces a uniform and measurable
magnetic field at right angles to the electron beam. This magnetic
field deflects the electron beam in a circular path. By measuring
the accelerating potential, the current to the Helmholtz coils, and
 the radius of the circular path of the electron beam, the ratio e/m is
calculated.
In 1897, British physicist J.J. Thomson measured the ratio of
electrical charge (e) to the mass of electron (me ) by using cathode ray
tube and applying electrical and magnetic field perpendicular to each
other as well as to the path of electrons

Arguements :
Thomson argued that the amount of deviation of the particles
from their path in the presence of electrical or magnetic field depends
upon:
(i) the magnitude of the negative charge on the particle, greater the
magnitude of the charge on the particle, greater is the interaction
with the electric or magnetic field and thus greater is the deflection.
(ii)the mass of the particle — lighter the particle, greater the
deflection.
(iii)the strength of the electrical or magnetic field — the deflection of
electrons from its original path increases with the increase in the
voltage across the electrodes, or the strength of the magnetic field.

Conclusion :
By carrying out accurate measurements on the amount of
deflections observed by the electrons on the electric field strength or
field strength,
 Thomson was able to determine the value of e/me as:
e /me = 1.758820 × 1011 C kg–1
Where me is the mass of the electron in kg and e is the magnitude
of the charge on the electron in coulomb (C). Since electrons are
negatively charged, the charge on electron is – e.

Charge of an electron(Millikan oil drop experiment) :

In 1909, Robert Millikan and Harvey Fletcher conducted the oil

drop experiment to determine the charge of an electron.
• They suspended tiny charged droplets of oil between two metal
electrodes by balancing downward gravitational force with upward
drag and electric forces. The density of the oil was known, so
Millikan and Fletcher could determine the droplets’ masses from
their observed radii (since from the radii they could calculate the
volume and thus, the mass). Using the known electric field and the
values of gravity and mass, Millikan and Fletcher determined the
charge on oil droplets in mechanical equilibrium.
• They calculated this value to be 1.5924 × 10−19 Coulombs (C),
which is within 1% of the currently accepted value of -1.602176487
× 10−19 C.

At the time of Millikan and Fletcher’s oil drop experiments, the

existence of subatomic particles was not universally accepted.
George FitzGerald and Walter Kaufmann found similar results.
In 1923, Millikan won the Nobel Prize in physics in part because
of this experiment.
 Experiment No.2 : Discovery of Proton (1919)

Eugene Goldstein noted stream of particles in Cathode rays in 1886.

These particles move in opposite direction to Cathode rays are called
Canal rays because they passed through holes drilled through a negative
plate (Cathode)
When sufficiently high voltage is applied through an inert gas (He, Ar)
at low pressure across the electrodes, he observed a new type of rays
carrying a positive charge streaming behind the cathode moving from the
positive electrode (Anode) to the negative electrode (cathode). These
were called Anode rays or Anode ray particles.

Properties of Anode rays :

1. Anode rays travel in a straight line.

2. Anode rays produces mechanical effect, because they rotate a light
paddle wheel placed in their path.
3. Anode rays produces Heating effect when they hit a heavy metal.
4. Anode rays produce flourescent effect on fluorescent material.
5. Anode rays are Positively charged.
6. Anode rays deflect towards a Negative terminal in an electric field.
7. Anode rays deflect towards the direction determined by Fleming’ left
hand rule.
8. Anode rays can ionize gasses.
9. Anode rays can produce X rays.
10. Anode rays do not depend upon the nature of the gas and material,
 but mass of positively charged particles depends upon the nature of
gas present in the cathode ray tube.

Experiment.3 : Discovery of Neutron (1932) :

 James Chadwick fired alpha radiation at beryllium sheet from a

polonium source. This led to the production of an uncharged,
penetrating radiation.
 This radiation was made incident on paraffin wax, a hydrocarbon
having a relatively high hydrogen content.
 The protons ejected from the paraffin wax (when struck by the
uncharged radiation) were observed with the help of an ionization
chamber.
 The range of the liberated protons was measured and the interaction
between the uncharged radiation and the atoms of several gases was
studied by Chadwick.
 He concluded that the unusually penetrating radiation consisted of
uncharged particles having (approximately) the same mass as a
proton. These particles were later termed ‘neutrons’.

Characteristics of sub atomic particles :

Electron Proton Neutron

Symbol e / e-- p / p+ N
Nature Negatively Positively Neutral
charged charged
Relative mass 1 /1840 of a Equal to H atom Equal to H atom
H atom
Actual mass 9.1 x 10 -28 g 1.67 x 10-24 g 1.67 x 10-24 g
Charge -1 unit +1 unit No charge
Charge in C - 1.602 x 10-19 C 1.602 x 10-19 C No charge
 Atomic models

An atomic model represents what the structure of an atom could look

like, based on what we know about how atoms behave.
The structure of an atom, theoretically consisting of a positively
charged nucleus surrounded and neutralized by negatively charged
electrons revolving in orbits at varying distances from the nucleus, the
constitution of the nucleus and the arrangement of the electrons differing with
various chemical elements.

Postulates of Thomson’s atomic model

Postulate 1: An atom consists of a positively charged sphere with electrons

embedded in it
Postulate 2: An atom as a whole is electrically neutral because the negative
and positive charges are equal in magnitude
Thomson atomic model is compared to watermelon. Where he considered:

Watermelon seeds as negatively charged particles

The red part of the watermelon as positively charged

Limitations of Thomson’s atomic model

 It failed to explain the stability of an atom because his model of atom

failed to explain how a positive charge holds the negatively charged
electrons in an atom. Therefore, This theory also failed to account for
the position of the nucleus in an atom.
 Thomson’s model failed to explain the scattering of alpha particles by
thin metal foils.
 No experimental evidence in its support.
Although Thomson’s model was not an accurate model to
account for the atomic structure, it proved to be the base for the
development of other atomic models.
Shortcomings and achievements

An important feature of this model is that the mass of the atom is

assumed.
• It failed to explain the stability of an atom because his model of atom
failed to explain how a positive charge holds the negatively charged
electrons in an atom.
• Thomson’s model failed to explain the scattering of alpha particles by
thin metal foils.
• Thomson’ model does not account for the existence of nucleus.
• No experimental evidence.
J.J.Thomson was awarded the Nobel prize in 1906 for discovery of
electron. He also received Knighthood from British Empire.

Rutherford’ alpha ray - scattering experiment :

Objective:
To demonstrate the scattering of alpha particles by gold foil.
Ernest Rutherford was interested in knowing how the electrons
are arranged within an atom.
In this experiment, fast moving alpha alpha-particles were made
to fall on a thin gold foil. He selected a gold foil because he wanted as
thin a layer as possible of about 1000 atoms thick, around it a circular
fluorescent ZnS screen is present. alpha-particles are doubly-charged
helium ions (He+2 ) having a mass of 4µ, the fast-moving alpha particles
have a considerable amount of energy.
It was expected that α-particles would be deflected by the sub-
atomic particles in the gold atoms. Since the alpha particles were much
heavier than the protons, he did not expect to see large
deflections. But, the alpha particle scattering experiment gave totally
unexpected results .
Observations of Rutherford's scattering experiment :

1.Most of the fast moving alpha articles passed straight through the gold foil.
2.Some of the alpha particles were deflected by the foil by small angles.
3. Surprisingly one out of every 20,000 alpha particles appeared to rebound.
Conclusions of Rutherford's alpha ray scattering experiment :

• Most of the space inside the atom is empty because most of the alpha
particles passed through the gold foil without getting deflected.
• Very few particles were deflected from their path, indicating that the
positive charge of the atom occupies very little space.
• A very small fraction of α-particles were deflected by very large angles,
indicating that all the positive charge and mass of the gold atom were
concentrated in a very small volume within the atom.
• From the data he also calculated that the radius of the nucleus
(10–15 m ) is about 105 times less than the radius of the atom (10-10 m)

Rutherford’ Nuclear model of an atom :

On the basis of above observations and conclusions, Rutherford
proposed the nuclear model of atom.
According to this model:
(i) Atom is assumed to be hollow sphere.
(ii) The positive charge and most of the mass of the atom was
densely concentrated in extremely small region. This very small
portion of the atom was called nucleus by Rutherford.
(iii) The nucleus is surrounded by electrons that move around the
nucleus with a very high speed in circular paths called orbits, like
the planets revolve around the Sun in Solar family.
(iv) Electrons and the nucleus are held together by electrostatic
forces of attraction.

Atomic number :

The number of protons in the nucleus of an atom, which is

characteristic of a chemical element and determines its place in the
periodic table. It was discovered by This was Henry Gwyn-Jefferies
Moseley's. Or
The number of positive charges or protons in the nucleus of
an atom of a given element, and therefore also the number of
electrons normally surrounding the nucleus. It is represented by the
letter “Z.” The atomic number symbol, Z, stands for “Zahl,” meaning
German number.
Mass number :

Mass number is an integer (whole number) equal to the

sum of the number of protons and neutrons of an atomic nucleus. In
other words, it is the sum of the number of nucleons in an atom. It is
represented by the letter “A.” Symbol A, from the German word
Atomgewicht [atomic weight]

Isotopes :

Isotopes are the atoms of same element have same atomic

number, but have different mass numbers. They have same chemical
properties as they have same electron and proton number.

Ex :
1 2
1H (protium) 1H (Duterium) 1H3 (Tritium)
12 13 14
6C 6C 6C (Radioactive)
 • In 1913 radio chemist Frederick Soddy while experimenting with
the products of radioactive decay discovered that there appeared to be
more than on element at each position on the periodic table.
• The term isotope was coined by Margaret Todd.
• In the same year , J.J.Thomson conducted an experiment in
which he channeled a stream of Neon ions through magnetic and
electric fields, striking a photographic plate at the other end. He
observed two glowing patches on the plate, which suggested two
different deflection trajectories. Thomson concluded this was because
some of the Neons had a different mass.

Isobars :

Isobars are the atoms of different elements with same mass

number, but have different atomic numbers. They have different
chemical properties as they have different electron and proton number.

The name was given by Alfred Walter Stewart in 1918. It is

originally taken from the combination of Greek words- isos means
equal and bar means weight.
Examples
40 40 40
18Ar 19K 20Ca

32 Ce76 34Se
76

24 24
11Na 12Mg

58 Ni58
26Fe 27

64 64
27Co 28Ni
Drawbacks of Rutherford’ atomic model :

1. Rutherford could not explain the stability of an atom.

According to the electromagnetic theory of Maxwell, charged
particles when accelerated should emit electromagnetic radiation (This
feature does not exist for planets since they are uncharged). Therefore,
an electron in an orbit will emit radiation, the energy carried by radiation
comes from electronic motion. The orbit will thus continue to shrink and
ultimately electron fall into the ground of Nucleus.
2. If the electron loss energy continuously the observed spectrum
should be continuous, but the actual observed spectrum consists of
well defined lines of definite frequencies (i.e. discontinuous). Hence
the loss of energy by electron is not continuous in an atom.

3. Rutherford model failed to say nothing about distribution of the

electrons around the nucleus and the energies of these electrons.

DEVELOPMENTS LEADING TO THE BOHR’S MODEL OF ATOM :

Two developments played a major role in the formulation of

Bohr’s model of atom. These were:
(i) Dual character of the electromagnetic radiation which means that
radiations possess both wave like and particle like properties.
(ii) Experimental results regarding atomic spectra.
 1. Dual nature of electromagnetic radiation

Introduction
James Maxwell (1870) was the first to give a comprehensive
explanation about the interaction between the charged bodies and the
behaviour of electrical and magnetic fields on macroscopic level. He
suggested that when electrically charged particle moves under
accelaration, alternating electrical and magnetic fields are produced
and transmitted. These fields are transmitted in the forms of waves
called electromagnetic waves or electromagnetic radiation.
Electromagnetic radiation is a form of energy that is transmitted
through space in the form of a wave. It can be treated as discrete
packets of energy or particles called photons or quanta.
Light is the form of radiation known from early days and it was
supposed to be made of particles (corpuscules) by Newton.
Maxwell was again the first to reveal that light waves are
associated with oscillating electric and magnetic character.

General properties of electromagnetic radiation :

1. The oscillating electric and magnetic fields produced by oscillating

charged particles are perpendicular to each other and also
perpendicular to the direction of propagation of the wave.
2. Electromagnetic waves are transverse.
3. Unlike sound waves or waves produced in water, electromagnetic
waves do not require medium and can travel in vacuum.
4. Electromagnetic waves can travel at the speed of light in vaccum.
5. Electromagnetic waves can bounce off from a surface.(i.e
reflected)
 6. Electromagnetic waves can change direction (i.e. can be refracted)
7. Electromagnetic waves can spread around corners.(i.e. diffracted)

Electromagnetic spectrum :

Electromagnetic spectrum consists of different electromagnetic

radiations which are arranged in the increasing order of their
wavelengths and decreasing order their frequencies.

Characteristics of a wave

1. Wavelength

Wavelength can be defined as the distance between two successive

crests or troughs of a wave. It is measured in the direction of the wave.
Wavelength is represented by the Greek letter lambda (λ).
Units : Wavelength can be measured in meters, centimeters,
or nanometers (1 m = 109 nm)
2. Frequency

Wave frequency is the number of waves that pass a fixed point

in a given amount of time.
SI unit for wave frequency is the hertz (Hz), where 1 hertz equals
1 wave passing a fixed point in 1 second.
A higher-frequency wave has more energy than a lower-
frequency wave with the same amplitude.

3. Amplitude

The amplitude of a wave refers to the maximum amount of

displacement of a particle on the medium from its rest position. or
The amplitude of a wave is the maximum disturbance or
displacement of the medium from the equilibrium (rest) position.
The SI unit of amplitude is the metre (m).

4. Wavenumber

Wavelength is defined as the number of wavelengths per unit

length.
 The wavenumber (k) is simply the reciprocal of the wavelength,
given by the expression. k = 1 / λ The wavenumber (k) is therefore
the number of waves or cycles per unit distance.
Units for wavenumber are (1/distance), such as 1/m (m-1), 1/cm
(Cm-1) or 1/mm (mm-1) .

Drawbacks of the Wave nature of Electromagnetic radiations :

Some of the experimental phenomenon such as diffraction and

interference can be explained by the wave nature of the electromagnetic
radiation. However, following are some of the observations which could
not be explained with the help of even the electromagentic theory of 19th
century physics (known as classical physics):

1. Black body radiation

2. Photoelectric effect
3. Heat capacity of solids as a function of temperature
4. Line spectra of atoms

1. Black body Radiation :

Phenomenon of the black body radiation mentioned above was

given by Max Planck in 1900.
Ordinary objects are as a rule imperfect absorbers of radiation.
An ideal body, which emits and absorbs radiations of all frequencies
uniformly, is called a black body and the radiation emitted by such a
body is called black body radiation.
When a black body is at a uniform temperature,
its emission has a characteristic frequency distribution that depends
on the temperature. Its emission is called black-body radiation.
Or
An ideal body, which emits and absorbs radiations of all
frequencies uniformly, is called a black body and the radiation emitted
by such a body is called black body radiation.
Example of a body :
Carbon black approximates fairly closely to black body. A good
physical approximation to a black body is a cavity with a tiny hole,
which has no other opening. Any ray entering the hole will be reflected
 by the cavity walls and will be eventually absorbed by the walls. A black
body is also a perfect radiator of radiant energy.

According to Planck’s quantum theory,

Different atoms and molecules can emit or absorb energy in discrete

quantities only. The smallest amount of energy that can be emitted or
absorbed in the form of electromagnetic radiation is known as
quantum.

1. Matter radiate or absorb energy in discrete quantities discontinuously

in the form of small packets or bundles called ‘quanta’. In case of light,
a quantum light radiation is called ‘photon’.
2. The energy of the quantum absorbed or emitted s directly proportional
to the frequency of the light radiation.

The energy of radiation is expressed in terms of frequency as,

E=hν
Where,
E = Energy of the radiation
h = Planck’s constant (6.626×10–34 J.s)
ν= Frequency of radiation
3. A body or matter radiate or absorb energy in whole number multiples
of a quantum as nhʋ. Where n is a positive integer. So energy can be
absorbed or radiated as hʋ, 2hʋ, 3hʋ, 4hʋ --------- etc.

Planck was able to explain the distribution of intensity in the radiation

from black body as a function of frequency or wavelength at different
temperatures.

Evidences in support of Planck’ quantum theory :

1. A prism can separate the light accordinig to their wavelengths. If
light behaves only as a wave, then a prism should give a
continuous rainbow, but in reality it does not.
2. Emission spectrum of nitrogen gas.
Applications of Planck’ quantum theory :
Planck’ quantum theory is the foundamental theory of Quantum
smechanics.
It has many applications in electrical appliances, medical field,,
quantum computing, lasers et.
After Max Planck, German physicist, Albert Einstein revisited the
theory and could interpret the explanation for Photoelectric effect.

Photoelectric effect :
In 1887, H. Hertz performed a very interesting experiment in
which electrons (or electric current) were ejected when certain metals
(for example potassium, rubidium, caesium etc.) were exposed to a
beam of light. The phenomenon is called Photoelectric effect.

(i) The electrons are ejected from the metal surface as soon as the beam of
light strikes the surface, i.e., there is no time lag between the striking of
light beam and the ejection of electrons from the metal surface.
(ii) The number of electrons ejected is proportional to the intensity or
brightness of light.
(iii) For each metal, there is a characteristic minimum frequency, ʋ0 (also
known as threshold frequency) below which photoelectric effect is not
observed. At a frequency ʋ > ʋ 0, the ejected electrons come out with
certain kinetic energy. The kinetic energies of these electrons increase
with the increase of frequency of the light used.
Threshold energy :

“The minimum amount of energy, that is required to eject an

electron from the surface of a metal is called threshold energy or
photoelectric work function".
Although the work function specifically refers to
the energy that needs to be put in, and the threshold energy refers
to the frequency required to eject an electron, they are the same thing
when calculating with the equation.

Threshold frequency :

Threshold frequency is the minimum frequency of incident

light which can cause emission of photo-electrons from the metal
surface. Photo-emission of electrons is not possible below threshold
frequency.

Kinetic energy of the photo electron :

hv = Energy of the striking photon

hv0 = threshold energy
hv - hv0 = Kinetic energy of the photoelectron

Conclusion :
The energy content of the beam of light depends upon the
brightness of the light. In other words, number of electrons ejected and
kinetic energy associated with them should depend on the brightness
of light. It has been observed that though the number of electrons
ejected does depend upon the brightness of light, kinetic energy of the
elecrons does not.
 more intense beam of light consists of larger number of photons,
consequently the number of electrons ejected is also larger.

Atomic spectrum :

Spectrum :

Meaning : The spectrum is the range of different colours which is

produced when light passes through a glass prism or through
a drop of water. A rainbow shows the colours in the spectrum.

Atomic spectra is the study of atoms (and atomic ions) through

their interaction with electromagnetic radiation.

 Whenever electromagnetic radiation interacts with atoms and

molecules of matter, the electrons in these atoms may absorb energy
and jump to a higher energy state, losing their stability.
 In order to regain their stability, they need to move from the higher
energy state to the previous lower energy state.
 To accomplish this job, these atoms and molecules emit radiation in
various regions of the electromagnetic spectrum.
 This spectrum of radiation emitted by electrons in the excited atoms or
molecules is known as an emission spectrum.
Emission spectrum : The spectrum of radiation emitted by a substance
that has absorbed energy is called an emission spectrum. Atoms,
molecules or ions that have absorbed radiation are said to be “excited”.

The emission spectra of atoms in the gas phase, on the other

hand, do not show a continuous spread of wavelength from red to
violet, rather they emit light only at specific wavelengths with dark
spaces between them. Such spectra are called line spectra or atomic
spectra because the emitted radiation is identified by the appearance
of bright lines in the spectra.

Line emission spectra are of great interest in the study of

electronic structure.
Each element has a unique line emission spectrum. The
characteristic lines in atomic spectra can be used in chemical analysis
to identify unknown atoms in the same way as fingerprints are used to
 identify people. The exact matching of lines of the emission spectrum
of the atoms of a known element with the lines from an unknown
sample quickly establishes the identity of the latter, German chemist,
Robert Bunsen (1811-1899) was one of the first investigators to use
line spectra to identify elements.

Elements like rubidium (Rb), caesium (Cs) thallium (Tl), indium

(In), gallium (Ga) and scandium (Sc) were discovered when their
minerals were analysed by spectroscopic methods. The element
helium (He) was discovered in the sun by spectroscopic method.

Absorption spectrum :

A spectrum of electromagnetic radiation transmitted through a

substance, showing dark lines or bands due to absorption at specific
wavelengths.

Continuous spectrum :

Is an emission spectrum that consists of a continuum of

wavelengths.

Line spectrum of Hydrogen :

When an electric discharge is passed through gaseous
hydrogen, the H2 molecules dissociate and the energetically excited
hydrogen atoms produced emit electromagnetic radiation of discrete
frequencies.
 Balmer showed in 1885 on the basis of experimental
observations that if spectral lines are expressed in terms of
wavenumber ( ), then the visible lines of the hydrogen spectrum obey
the following formula:

where n is an integer equal to or greater than 3 (i.e., n = 3,4,5,.... )

The Swedish spectroscopist, Johannes Rydberg, noted that all

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

The value 109,677 cm–1 is called the Rydberg constant for

hydrogen. The first five series of lines that correspond to n1 = 1, 2, 3,
4, 5 are known as Lyman, Balmer, Paschen, Bracket and Pfund series,
respectively.
Electron transitions in the Hydrogen atomic spectrum :

Line Spectrum of Hydrogen

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
followingexpression:
 Rydberg in 1890, and has given a simple theoretical equation for the
calculation of wavelengths and wave numbers of the spectral lines in different
series of hydrogen spectrum. The equation is known as Rydberg formula (or
equation).

This relation is valid for hydrogen atom only. For other species,

Where Z is the atomic number of the species.

Here RH = constant, called Rydberg constant for hydrogen and n1, n2 are
integers (n2 > n1)
For any particular series, the value of n1 is constant while that of n2 changes.
For example,
For Lyman series, n1 = 1, n2 = 2, 3, 4, 5 ………..
For Balmer series, n1 = 2, n2 = 3, 4, 5, 6 ………..
For Paschen series, n1 = 3, n2 = 4, 5, 6, 7 ………..
For Brackett series, n1 = 4, n2 = 5, 6, 7, 8 ………..
For Pfund series, n1 = 5, n2 = 6, 7, 8, 9 ………..

Thus, by substituting the values of n1 and n2 in the above equation,

wavelengths and wave number of different spectral lines can be calculated.
When n1 = 2, the expression given above is called Balmer’s formula.
 Bohr’s Model of Atom

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

Planck’s Quantum Theory. The main points of his model are:

(i) In an atom, the electrons revolve around the nucleus in certain definite
circular paths called orbits.
(ii)Each orbit is associated with definite energy and therefore these are known
as energy levels or energy shells. These are numbered as 1, 2, 3, 4………..
or K, L, M, N………..
(iii) Only those energy orbits are permitted for the electron in which angular
momentum of the electron is a whole number multiple of h/2π
Angular momentum of electron (mvr) = nh/2π (n = 1, 2, 3, 4 etc).
m = mass of the electron.
v = tangential velocity of the revolving electron.
r = radius of the orbit.
h = Planck’s constant.
n is an integer.
(iv) As long as electron is present in a particular orbit, it neither absorbs nor
loses energy and its energy, therefore, remains constant.
(v) When energy is supplied to an electron, it absorbs energy only in fixed
amounts as quanta and jumps to higher energy state away from the nucleus
known as excited state. The excited state is unstable, the electron may jump
back to the lower energy state and in doing so, it emits the same amount of
energy. (∆E = E2 – E1).

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. The mathematical expression for the energy in
the nth orbit is,
Bohr’s theory has explained the atomic spectrum of hydrogen atom.

Limitations of Bohr’s Model

(i) The theory could not explain the atomic spectra of the atoms containing
more than one electron or multielectron atoms.
(ii) Bohr’s theory failed to explain the fine structure of the spectral lines.
(iii) Bohr’s theory could not offer any satisfactory explanation of Zeeman effect
and Stark effect.
(iv)Bohr’s theory failed to explain the ability of atoms to form molecule formed
by chemical bonds.
(v) It was not in accordance with the Heisenberg’s uncertainty principle.

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.
From this analogy, de Broglie gave the following relation between wavelength
(λ) and momentum (p) of a material particle.
Heisenberg’s Uncertainty Principle

It states that, “It is impossible to determine simultaneously, the exact

position and exact momentum (or velocity) of an electon.

Significance of Uncertainty Principle

(i) It rules out existence of definite paths or trajectories of electrons and other
similar particles.
(ii)The effect of Heisenberg’s uncertainty principle is significant only for
microscopic objects and is negligible for macroscopic objects.

Reasons for the Failure of Bohr Model

(i) The wave character of the electron is not considered in Bohr Model.
(ii) According to Bohr Model an orbit is a clearly defined path and this path can
completely be defined only if both the position and the velocity of the
electron are known exactly at the same time. This is not possible according
to the Heisenberg’s uncertainty principle.

Quantum Mechanical Model of Atom

Quantum mechanics: Quantum mechanics is a theoretical science that

deals with the study of the motions of the microscopic objects that have both
observable wave like and particle like properties.
Important Features of Quantum Mechanical Model of Atom

(i) The energy of electrons in atom is quantized i.e., can only have certain
values.
(ii) The existence of quantized electronic energy level is a direct result of the
wave like properties of electrons.
(iii) Both the exact position and exact velocity of an electron in an atom cannot
be determined simultaneously.
(iv) An atomic orbital has wave function φ. There are many orbitals in an atom.
Electron occupy an atomic orbital which has definite energy. An orbital
cannot have more than two electrons. The orbitals are filled in increasing
order of energy. All the information about the electron in an atom is stored
in orbital wave function φ.
(v) The probability of finding electron at a point within an atom is proportional
to square of orbital wave function i.e., |φ2|at that point. It is known as
probability density and is always positive.

From the value of φ2 at different points within atom, it is possible to predict

the region around the nucleus where electron most probably will be found.

Quantum Numbers

Atomic orbitals can be specified by giving their corresponding energies

and angular momentums which are quantized (i.e., they have specific values).
The quantized values can be expressed in terms of quantum number. These
are used to get complete information about electron i.e., its location, energy,
spin etc.

1. Principal Quantum Number (n)

It is the most important quantum number since it tells the principal energy level
or shell to which the electron belongs. It is denoted by the letter V and can
have any integral value except zero, i.e., n = 1, 2, 3, 4……….. etc.
The various principal energy shells are also designated by the letters, K, L, M,
N, O, P ….. etc. starting from the nucleus.
The principal quantum number gives us the following information
(i) It gives the average distance of the electron from the nucleus.
(ii) It completely determines the energy of the electron in hydrogen atom and
hydrogen like particles.
(iii) The maximum number of electrons present in any principal shell is given
by 2n2 where n is the number of the principal shell.
2. Azimuthal or Subsidiary or Orbital Angular Quantum Number (l)

It is found that the spectra of the elements contain not only the main
lines but there are many fine lines also present. This number helps to explain
the fine lines of the spectrum.
The azimuthal quantum number gives the following information:
(i) The number of subshells present in the main shell.
(ii) The angular momentum of the electron present in any subshell.
(in) The relative energies of various subshells.
(iv) The shapes of the various subshells present within the same principal
shell.
This quantum number is denoted by the letter T. For a given value of n, it can
have any value ranging from 0 to n – 1. For example,
For the 1st shell (k), n = 1, l can have only one value i.e., l = 0 For n = 2, the
possible value of l can be 0 and 1.
Subshells corresponding to different values of l are represented by the
following symbols:
value of l 0 1 2 3 4 5 ……………..
Notation for subshell s p d f g h ………………..

3. Magnetic Orbital Quantum Number (m or ml)

The magnetic orbital quantum number determines the number of preferred

orientations of the electrons present in a subshell. Since each orientation
corresponds to an orbital, therefore, the magnetic orbital quantum number
determines the number of orbitals present in any subshell.
The magnetic quantum number is denoted by letter m or ml and for a given
value of l, it can have all the values ranging from – l to + l including zero.
Thus, for energy value of l, m has 2l + 1 values.
For example,
For l = 0 (s-subshell), ml can have only one value i.e., ml = 0.
This means that s-subshell has only one orientation in space. In other words,
s-subshell has only one orbital called s-orbital.

Spin Quantum Number (S or ms)

This quantum number helps to explain the magnetic properties of the

substances. A spinning electron behaves like a micro magnet with a definite
magnetic moment. If an orbital contains two electrons, the two magnetic
moments oppose and cancel each other.
Shapes of s-orbitals

s-orbital is present in the s-subshell. For this subshell, l = 0 and ml = 0.

Thus, s-orbital with only one orientation has a spherical shape with uniform
electron density along all the three axes.
The probability of Is electron is found to be maximum near the nucleus and
decreases with the increase in the distance from the nucleus. In 2s electron,
the probability is also maximum near the nucleus and decreases to zero
probability. The spherical empty shell for 2s electron is called nodal surface or
simply node.

Shapes of p-orbitals

p-orbitals are present in the p-subshell for which l = 1 and m1 can have
three possible orientations – 1, 0, + 1.
Thus, there are three orbitals in the p-subshell which are designated as px,
py and pz orbitals depending upon the axis along which they are directed. The
general shape of a p-orbital is dumb-bell consisting of two portions known as
lobes. Moreover, there is a plane passing through the nucleus along which
finding of the electron density is almost nil. This is known as nodal plane as
shown in the fig.

From the dumb-bell pictures, it is quite obvious that unlike s-orbital, a p-orbital
is directional in nature and hence it influences the shapes of the molecules in
the formation of which it participates.

Shapes of d-orbitals

d-orbitals are present in d-subshell for which l = 2 and ml = -2, -1, 0, +1

and +2. This means that there are five orientations leading to five different
orbitals.

Aufbau Principle
The principle states: In the ground state of the atoms, the orbitals are filled in
order of their increasing energies.
In other words, electrons first occupy the lowest energy orbital available to
them and enter into higher energy orbitals only after the lower energy orbitals
are filled.
The order in which the energies of the orbitals increase and hence the order in
which the orbitals are filled is as follows:
Is, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f,6d, 7p,8s
The order may be remembered by using the method given in fig.
Pauli Exclusion Principle
According to this principle, no two electrons in an atom can have the same set
of four quantum numbers.
Pauli Exclusion Principle can also be stated as: Only two electrons may exist
in the same orbital and these electrons must have opposite spins.

Hund’s Rule of Maximum Multiplicity

It states that: pairing of electrons in the orbitals belonging to the same subshell
(p, d or f) does not take place until each orbital belonging to that subshell has
got one electron each i.e., it is singly occupied.

Electronic Configuration of Atoms

The distribution of electrons into orbitals of an atom is called its electronic
configuration. The electronic configuration of different atoms can be
represented in two ways.
For example:

Causes of Stability of Completely Filled and Half Filled Subshells

The completely filled and half-filled subshells are stable due to the following
reasons:

Symmetrical distribution of electrons: The completely filled or half-filled

subshells have symmetrical distribution of electrons in them and are therefore
more stable.
2. The stabilizing effect arises whenever two or more electrons with same spin
are present in the degenerate orbitals of a subshell. These electrons tend to
exchange their positions
and the energy released due to their exchange is called exchange energy. The
number of exchanges that can takes place is maximum when the subshell is
either half-filled or completely filled.
-As a result the exchange energy is maximum and so is the stability.