Lecture-1

ATOMIC STRUCTURE,
QUANTUM THEORY AND
BOHR ATOM

*** TEXT
“Essentials of Physical Chemistry”
B. S. Bahl, G. D. Tuli and Arun Bahl,
24th ed. (1997), S. Chand & Company Ltd,
ISBN: 81-219-0546-X

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 ATOMIC STRUCTURE

Landmarks in the evolution

of atomic structure are:

1805 Dalton’s atomic theory

1896 Thomson discovery of electron and proton
1909 Rutherford’s nuclear atom
1913 Bohr’s atomic model
1932 Chadwick’s discovery of neutron

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Democritus (400 BC) Aristotle (300 BC-1800’s) John Dalton (1803) J.J Thomson (1897)
Atomos= not to be cut
Death to Atoms are
the field of uncuttable, too
chemistry small to see and
indestructible.

Plum pudding model

Bohr Bohr
1913 1913
Rutherford(1908) Information Atomic Model Analogy
Information Atomic Model Analogy
In 1913, the Danish scientist Niels Bohr Solar System
proposed an improvement. He In 1913,
built the Danish scientist Niels Bohr
on the Solar System
proposed
concept that the mass of an atom is an improvement. He built on the
concept
contained mostly in the nucleus. Hethat
alsothe mass of an atom is
theorized that electrons move contained mostly in the nucleus. He also
in definite
theorized
orbits around the nucleus, much that electrons move in definite
like planets
orbits
circle the sun. These orbits, or around
energy the nucleus, much like planets
levels,
circle the sun.
are located at certain distances from the These orbits, or energy levels,
nucleus. are located at certain distances from the
Atomic nucleus.
Structure 3
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Atomic
Structure

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 Atomic Theory of Dalton: (1805)
• (1) All matter is composed of tiny particles called
atom which can not be created, destroyed or split.
• (2) All atoms of any one element are identical,
have same mass and chemical properties.
• (3) A compound is a type of matter composed of
atoms of two or more elements.
• (4) A chemical reaction consists of rearranging
atoms from one combination to another.

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 Dalton’s Contribution:
British Chemist John Dalton provided the basic
theory: all matter- whether element, compound, or
mixture- is composed of small particles called
atoms.

Limitations of Dalton’s Model:

(1) Atom can be divided into subatomic particle
namely electron, proton and neutron.
(2) All atoms of any elements are not identical, have
different mass and chemical properties. This property
is known as isotopes.
Exercise
What is atom and how can you define the atomic number?

The number of protons in the nucleus of an atom is the atomic number of that atom
 Rutherford’s experiment

Observations
➢ A major fraction of the α-particles bombarded towards the gold sheet passed through
the sheet without any deflection, and hence most of the space in an atom is empty.
➢ Some of the α-particles were deflected by the gold sheet by very small angles, and
hence the positive charge in an atom is not uniformly distributed. The positive
charge in an atom is concentrated in a very small volume.
➢ Very few of the α-particles were deflected back, that is only a few α-particles had nearly
180o angle of deflection. So the volume occupied by the positively charged
particles in an atom is very small as compared to the total volume of an atom
 Postulates of Rutherford atomic model
• Most of the space in the atom is empty

• The positively charged particles and most of the mass of an atom were concentrated
in an extremely small volume. He called this region of the atom as a nucleus.

• Rutherford’s model proposed that the negatively charged electrons surround the
nucleus of an atom. He also claimed that the electrons surrounding the nucleus
revolve around it with very high speed in circular paths. He named these circular
paths as orbits. Thus, Rutherford’s model of atom resembles the solar system in
which the nucleus plays the role of sun and the electrons that of revolving
planets.

• Electrons being negatively charged and nucleus being a densely concentrated mass
of positively charged particles are held together by strong electrostatic force of
attraction.
Exercise

Question : Which sub-atomic particle was discovered by Rutherford

through his Alpha (α) Particle Scattering Experiment?
 Limitations of Rutherford atomic model
Although Rutherford’s atomic model was based on experimental observations it failed to
explain certain things.

• Rutherford proposed that the electrons revolve around the nucleus in fixed paths called
orbits. According to Maxwell, accelerated charged particles emit electromagnetic
radiations and hence an electron revolving around the nucleus should emit
electromagnetic radiation. This radiation would carry energy from the motion of the
electron which would come at the cost of shrinking of orbits. Ultimately the electrons
would collapse in the nucleus. Calculations have shown that as per Rutherford’s model
an electron would collapse in the nucleus in less than 10-8 seconds. So Rutherford’s
model was not in accordance with Maxwell’s theory and could not explain the
stability of an atom.

• This model does not exactly same as the solar system because the planets are
neutral but electrons are negatively charged.

• One of the drawbacks of Rutherford’s model was also that he did not say
anything about the arrangement of electrons in an atom which made his theory
incomplete.
 Rutherford’s Model of Atom (contd.):

Rutherford’s
Atomic Model

Contribution of Rutherford’s model:

⚫ Rutherford laid the foundation of the model
picture of atom.

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 Three subatomic particles or principal
fundamental particles:
Mass Charge
Particle Simbol
Amu grams Units Coloumbs

Electron e- 1/1835 9.110-28 -1 -1.610-19

Proton p+ 1 1.67210-24 +1 +1.610-19

Neutron N or no 1 1.67410-24 0 0

Electrons are very small in mass compared with protons

and neutrons. It takes more than 1,800 electrons to equal the
mass of 1 proton. In fact, the mass of an electron is so small that it is usually
considered to be zero.

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Atomic Number, Mass Number & Isotopes

• An atom consists of three particles- electron,

proton and neutron. The charge of proton is positive,
electron is negative and neutron no charge.
• In a neutral atom, number of proton is equal to that
of the electron and a proton has mass more than
1800 times that of the electron.
• The atomic number is the number of protons in the
nucleus of an atom.

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 Atomic Number, Mass Number & Isotopes…

⚫ The neutron is a nuclear particle having a mass almost

identical to that of the proton.
⚫ The mass number is the total number of protons and
neutrons in a nucleus.
⚫ All nuclei of the atoms of a particular element have the
same atomic number, but the nuclei may have different
mass numbers. These atoms are known as Isotopes.
⚫ That is, isotopes have the same number of protons but
different numbers of neutrons.

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 Quantum Theory and Bohr Atom:
(1913)

To understand the Bohr theory, we need to learn-

⚫the nature of electromagnetic radiations,

⚫the atomic spectra
 Electromagnetic Radiations:
Electromagnetic radiation can be described as
a wave (carrier of energy) occurring
simultaneously in electrical and magnetic fields
and consists of particles called quanta or
photons.
Energy can be transmitted through space by
electromagnetic radiations.
Some forms of electromagnetic radiations are:

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 Electromagnetic Radiations (contd.)
⚫ radio waves
⚫ visible light
⚫ infrared light
⚫ ultraviolet light
⚫ x-rays etc.

These radiations have both the properties of a wave as well

as a particle, now become familiar for their uses. The X-rays
are used in medicine, the ultraviolet rays lead to sunburns
and radio and radar waves used in communication and
visible light.
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 Electromagnetic radiations or waves…

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 Characteristics of Waves:

Wave Length
Crest

Vibrating
Source
Energy

Trough
Wavelength (, lambda):
The wavelength is defined as the distance
between two successive crests or troughs of a
wave.
Units: cm, m or Å (angstrom).
(1 Å = 10-8 cm = 10-10 m, 1 nm = 10-9 m)

Frequency (, nu):

The frequency is defined as the number of complete
cycles (oscillations) per second.
Units: hertz (hz), one cycle per second.
A wave of high frequency has a shorter wavelength, while a wave of low
frequency has a longer wavelength.

Speed (c):
The speed (or velocity) of a wave is the distance
through which a particular wave travels in one
second.
Speed = Frequency  Wavelength
i. e. c=

Wave Number:
This is reciprocal of the wavelength and is given
the symbol (nu bar). i. e.  = 1/
 Problems:
1# The wavelength of a violet light is 400 nm. Calculate
its frequency and wave number. (Given, c = 3×108m
sec-1) (Answer:  = 7.5 × 1014 sec-1,  = 25 × 105 m-1)

2# The frequency of a strong yellow line in the

spectrum of sodium is 5.09  1014 sec-1. Calculate the
wavelength of light in nanometers. (Answer:  = 589
nm)

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 Spectra:
A spectrum is an arrangement of waves or particles
spread out according to the increasing or decreasing
of some property like wavelength or frequency.

An increase in frequency or a decrease in

wavelength represents an increase in energy.
 Continuous Spectrum:
White light is radiant energy coming from the sun or
from incandescent lamps. It is composed of light
waves in the range 4000-8000 Å.
When a beam of white light is passed through a
prism, a continuous series of colour bands
(rainbow) is received on a screen with different
wavelengths called Continuous Spectrum.
VIBGYOR -violet
-indigo
-blue
-green
-yellow
-orange and
-red
The violet component of the spectrum has
shorter wavelengths (4000-4250Å) and higher
frequencies.

The red component has longer wavelengths

(6500-7500Å) and lower frequencies.

The invisible region beyond the violet is called

ultraviolet region and the one below the red is
called infrared region.
 Atomic Spectra:
When an element in the vapor or the gaseous state is heated in
a flame or a discharge tube, the atoms are excited and emit light
radiations of a characteristic colour. The colour of light produced
indicates the wavelength of the radiation emitted. The spectrum
obtained on the photographic plate is found to consists of bright
lines.
 Atomic Spectra:

Na

3500 4000 4500 5000 5500 6000 6500 7000

F ig. E m is s ion s pec tra of K , Na and H

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Atomic Spectrum of Hydrogen:
In 1884 J. J. Balmer observed the following four
prominent coloured lines in the visible hydrogen
spectrum:
(1) a red line with a wavelength of 6563 Å
(2) a blue-green line with a wavelength of 4861 Å
(3) a blue line with a wavelength of 4340 Å
(4) a violet line with a wavelength of 4102 Å
The series of four lines in the visible spectrum
of hydrogen is known as Balmer series.

PHOTOGRAPHIC
FILM
o
6563 A
o
HYDROGEN 4861 A
o
DISCHARGE TUBE 4340 A
GLASS PRISM
o
4102 A

LENS
SLIT

Figure: The examination of the atomic spectrum of hydrogen with a spectroscope.

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Balmer equation:
Balmer was able to give an equation which relate the wavelengh () of the
observed lines. The Balmer equation is,

where R is a constant called Rydberg constant which has the value 109,677
cm-1 and n = 3, 4, 5, 6, etc.
Five Spectral Series:
In addition to Balmer series, four other spectral series were
discovered in the infrared (ir) and ultraviolet (uv) regions of the
hydrogen spectrum. These bear the names of discoverers.
(1) Lyman series (uv)
(2) Balmer series (visible)
(3) Paschen series (ir)
(4) Brackett series (ir)
(5) Pfund series (ir)
 Quantum Theory of Radiation:
(1) When atoms or molecules absorb or emit radiant energy,
they do so in separate ‘units of waves’ called quanta or
photons.

Continuous Wave
Quantum Theory of Radiation (contd.):
(2) The energy, E, of a quantum or photon
is given by the relation.
E = h (h, Planck’s constant
= 6.62  10–27 erg sec.
or 6.62  10-34 J sec.)
c =  (c = velocity of radiation)

hc
E =

Quantum Theory of Radiation (contd.):
(3) An atom or molecule can emit (or
absorb) either one quantum of energy
(h) or any whole number multiple of
this unit.
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Bohr Model of the Atom:
1. Electrons travel around the nucleus in specific permitted
circular orbits and in no others.
2. While in these specific orbits, an electron does not radiate
(or lose) energy.
3. An electron can move from one energy level to another by
quantum or photon jumps only.
4. The angular momentum (mvr) of an electron orbiting
around the nucleus is an integral multiple of Planck’s
constant divided by 2.
where m = mass of electron,
nh v = velocity of electron,
 mvr = r = radius of the orbit,
2 n = 1, 2, 3…..etc and
h = Planck’s constant.
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 Bohr Model of the Atom (contd.):

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Shortcoming of the Bohr Atom:
• It is unsuccessful for every other atom containing more
than one electron.
• In view of modern advances, like dual nature of matter,
uncertainty principle etc. any mechanical model of the
atom stands rejected.
• Bohr’s model of electronic structure could not account
for the ability of atoms to form molecules through
chemical bonds.
• Bohr’s theory could not explain the effect of magnetic
field (Zeeman effect) and electric field (Stark effect) on
the spectra of atoms.
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 Calculation of Radius of Orbits:

Calculation of Energy of Electron in each Orbit:

Consider, an electron of m v 2

charge e revolving around a r

nucleus of charge Ze, where v F o rc e o f
e
Z is the atomic number and e A t t ra c t io n
the charge on a proton. Let m
r
be the mass of the electron, r
the radius of the orbit and v Ze
the tangential velocity of the
revolving electron.

F
i
g
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or
c
e
sk
ee
pi
n
g
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le
c
tr
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ni
no
r
bi
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Calculation of Radius of Orbits…
The electrostatic force of attraction between the nucleus and
the electron (Coulomb’s Law),
= Ze e
r2

The centrifugal force acting on the electron

2
= mv
r
Bohr assumed that these two opposing forces must be
balancing each other exactly to keep the electron in orbit.
Thus, Ze 2 2
mv
=
r2 r

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 Calculation of Radius of Orbits…
For hydrogen Z=1, therefore,
e2 mv 2
r2
=
r

multiplying both sides by r

e2
= mv2 --- --- --- (1)
r
According to Bohr’s theory, angular momentum of the
revolving electron is given by the expression:
nh nh
mvr = or v= --- --- --- (2)
2 2 mr

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 Calculation of Radius of Orbits…
Substituting the value of v in equation (1) 1C= 3 x 10^9 esu
2 h= 6.626 x 10-27 erg s
e2  nh 
m   e= 4.8 x 10^10 esu
r =  2 mr  m= 9.11 x 10^-28 g
Solving for r,
n2h2
r= 2 2 --- --- --- (3)
4 me
Since the value of h, m and e had been determined
experimentally, substituting these values in (3), we have
8
r = n  0.529 10
2
cm --- --- --- (4)
where n is the principal quantum number and hence
the number of the orbit.
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 Calculation of Energy of Electron in each orbit…
For hydrogen atom, the energy of the revolving electron, E is
the sum of its kinetic energy  1 mv  and potential energy.  e
2
2


2   r 

(Hints: P.E.=kq1q2/r; attractive force, so negative)
1 2 e2
E= mv --- --- --- (5)
2 r
From equation (1) e2
mv = 2

r
Substituting the value of mv2 in (5),
1 e2 e2 e2
E= 2 r r , E= --- --- --- (6)
2r

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 Calculation of Energy of Electron in each
orbit…
Substituting the value of r from equation (3) in (6),

e 2 4 2 me 2 2 2 me4
E=  2 2 = --- --- --- (7)
2 n h n2 h2

Substituting the values of m, e and h in (7),

2.179 10 −11
E= erg / atom
n2 ,
2.179 10 −18
or E = J per atom --- --- --- (8)
n2

By using proper integer for n, we can get the energy for

each orbit.
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Problems:
• Problem-3: Calculate the first five Bohr radii of the hydrogen
atom.
• Problem-4: Calculate the radius of the third orbit of hydrogen
atom.
• Problem-5: Calculate the five lowest energy levels of the
hydrogen atom.
• Problem-6: Calculate the energy of electron of the second orbit
of the hydrogen atom.

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Bohr Explanation of Hydrogen Spectrum:
• The solitary electron in hydrogen atom at ordinary
temperature resides in the first orbit (n =1) and is in the
lowest energy state (ground state).
• When energy is supplied to hydrogen gas in the discharge
tube, the electron moves to higher energy levels viz., 2, 3, 4,
5, etc., depending on the quantity of energy absorbed.
• From these high energy levels, the electron returns by jumps
to one or other lower energy level. In doing so the electron
emits the excess energy as a photon.
• This gives an excellent explanation of the various spectral
series of hydrogen.

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Lyman series is obtained when the electron
returns to the ground state i.e., n = 1 from higher
levels (n2 = 2, 3, 4, 5, etc.).

Similarly, Balmer, Paschen, Brackett and Pfund

series are produced when the electron returns to
the second, third, fourth and fifth energy levels
respectively as shown in figure below:
 Table: Spectral series of hydrogen

Series n1 n2 Region Wavelength 

(Å)
Lyman 1 2, 3, 4, 5, etc. Ultraviolet 920-1200

Balmer 2 3, 4, 5, 6, etc. Visible 4000-6500

Paschen 3 4, 5, 6, 7, etc. Infrared 9500-18750

Brackett 4 5, 6, 7 Infrared 19450-40500

Pfund 5 6, 7 Infrared 37800-75000

1  1 1 
= R 2 − 2 
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Hydrogen spectral series:

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 1  1 1 
= R 2 − 2 
Questions:   n1 n2 
1. Explain- ‘values of Rydberg’s constant is the same as in the
original empirical Balmer’s equation’.
2. How do you calculate the wavelengths of the spectral lines of
hydrogen in the visible region using Balmer equation?
 1  1 1 
= R 2 − 2 
Problems:  2 n 
Problem-7: Calculate the wavelength in Å of the line in
Balmer series that is associated with drop of the electron
from the fourth orbit. The value of Rydberg constant is
109,676 cm-1.
Problem-8: Calculate the wavelength in Å of the third line in
Balmer series that is associated with drop of the electron.
(Rydberg constant =109,676 cm-1).
Problem-9: The energy of the electron in the second and
third orbits of the hydrogen atom is -5.42 ×10-12 erg and -
2.41×10-12 erg respectively. Calculate the wave length of the
emitted radiation. (Hints: E=hc/, Answer: 6653Å)
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 Possible Question????

1. Discuss the contribution and limitation of each atomic model ( Dalton, Rutherford &

Bohr)

2.Extablish the Bohr atomic radius calculation equation for hydrogen atom.

3. Show the derivation of the Bohr atomic radius or energy expression equation.

4. What is spectrum and electromagnetic radiation.

5.Calculation of radius of certain orbit/ energy of electron orbiting in certain orbit. (

Mathematical Problem)
6. Draw a labelled energy level diagram and explain the different series of spectral
lines for hydrogen atom.

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 next class
QUIZ-1

Thank you

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